Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion

Shiyuan Lin; Yongjie Chen; Huayong Li; Wenhang Wang; Yang Wang; Mingbo Wu

doi:10.1016/j.isci.2024.109656

. 2024 Apr 2;27(5):109656. doi: 10.1016/j.isci.2024.109656

Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion

Shiyuan Lin ^1,³, Yongjie Chen ^1,³, Huayong Li ^1,³, Wenhang Wang ^1,², Yang Wang ^1,^∗, Mingbo Wu ^1,^∗∗

PMCID: PMC11033205 PMID: 38650984

Summary

One-carbon (C1) catalysis refers to the conversion of compounds with a single carbon atom, especially carbon monoxide (CO), carbon dioxide (CO₂), and methane (CH₄), into clean fuels and valuable chemicals via catalytic strategy is crucial for sustainable and green development. Among various catalytic strategies, thermal-driven process seems to be one of the most promising pathways for C1 catalysis due to the high efficiency and practical application prospect. Notably, the rational design of thermal-driven C1 catalysts plays a vital role in boosting the targeted products synthesis of C1 catalysis, which relies heavily on the choice of ideal active site support, catalyst fabrication precursor, and catalytic reaction field. As a novel crystalline porous material, metal-organic frameworks (MOFs) has made significant progress in the design and synthesis of various functional nanomaterials. However, the application of MOFs in C1 catalysis faces numerous challenges, such as thermal stability, mechanical strength, yield of MOFs, and so on. To overcome these limitations and harness the advantages of MOFs in thermal-driven C1 catalysis, researchers have developed various catalyst/carrier preparation strategies. In this review, we provide a concise overview of the recent advancements in the conversion of CO, CO₂, and CH₄ into clean fuels and valuable chemicals via thermal-catalytic strategy using MOFs-based catalysts. Furthermore, we discuss the main challenges and opportunities associated with MOFs-based catalysts for thermal-driven C1 catalysis in the future.

Subject areas: Physical chemistry, Materials chemistry

Physical chemistry; Materials chemistry

Introduction

In today’s society, the manufacture of fuels and petrochemical commodities relies heavily on petroleum resources. However, due to the non-renewable nature of petroleum resources and the environmental pollution it brings, we urgently call for a cleaner and more sustainable way to synthesize fuels and petrochemical commodities. The utilization of compounds containing a single carbon atom (C1 molecules), such as CO, CO₂, and CH₄, for essential chemicals and clean fuels production possesses great potential for energy consumption upgrade and sustainable development.¹^,² The current main conversion pathways for C1 molecules into valuable chemicals and fuels are shown in Figure 1.³ Syngas (CO + H₂) from the gasification of coal, biomass, and natural gas can be converted into platform chemicals (e.g., methanol, alkanes, and alkenes) via the direct pathway, as well as value-added products (e.g., aromatics, transportation fuels, light olefins, etc.) via the indirect process. It is obvious that the transformation of syngas can not only realize the clean utilization of coal and natural gas resources but also be employed as a bridging process to connect sustainable biomass resources and valuable products. Syngas conversion can also pave the way for the utilization of greenhouse gases CO₂ and CH₄ because these two greenhouse gases can be converted into syngas via the reverse water-gas shift reaction (CO₂ + H₂ → CO + H₂O) and reforming strategy (dry reforming by CO₂, steam reforming by H₂O, and oxidative reforming by O₂), respectively. Additionally, C₂₊ hydrocarbons or oxygenates production from CO₂ hydrogenation, selective CH₄ oxidation, or CH₄ coupling opens a new window to eliminate the greenhouse gases in the atmosphere.

The conversion pathways for different C1 molecules to valuable chemicals

Reproduced with permission from Wang et al.³ Copyright © 2023, American Chemical Society.

The highly efficient conversion of C1 molecules into valuable chemicals heavily relies on the catalysis strategy (denoted as C1 catalysis).⁴^,⁵ Due to the inert property of C-O or C-H bond in C1 molecules and sluggish behavior of C-C coupling during products synthesis, external energy (e.g., photo/thermal/electro-driven) should be added into the system to facilitate the C1 molecules transformation process. Among various strategies, the thermal-driven process seems to be more promising for practical application due to the high C1 molecules activation capability and targeted products yield.⁶^,⁷^,⁸ Significant progress has been made in fundamental and applied research toward the development of C1 catalysis processes based on key catalytic systems. However, the current C1 conversion processes in the industry are characterized by high energy consumption and complicated procedures involving multi-step reactions and product separations, which encourages significant innovations in highly efficient catalyst design. Metallic catalysts with different scales, such as nanoparticles, clusters, and even single atoms, have been thoroughly investigated to realize the oriented conversion of C1 molecules into targeted products. The choice of ideal active site support, catalyst fabrication precursor, and even catalytic reaction field is essential to boost the catalytic performance of C1 catalysts.

Metal-organic frameworks (MOFs) have emerged as a highly promising new class of porous materials, which are composed of metal ions or clusters (also known as secondary building units, or SBUs) and bridging organic linkers.⁹^,¹⁰^,¹¹^,¹² Since the discovery, MOFs and MOFs-derived materials have garnered significant attention due to their remarkable features, including structural versatility and tunability,¹³^,¹⁴^,¹⁵^,¹⁶^,¹⁷ low density,¹⁸ high porosity,¹⁹ and enormous specific surface area.²⁰ The unique characteristics of MOFs endow them as excellent support, precursor, and even reaction fields for the rational design of C1 catalysts. On the one hand, MOFs have unique and well-defined periodic crystal structures that allow for the uniform distribution of active sites throughout the framework. This feature facilitates efficient interactions between the catalyst and the substrates, resulting in a more uniform distribution of reaction intermediates and products. The tailorable porosity of MOFs further allows for the transportation of intermediates and products, therefore enhancing the overall reaction rate and selectivity. On the other hand, MOFs can serve as excellent templates/precursors to prepare various carbon/metal-based porous materials by means of pyrolysis. The obtained derivates inherit the characteristics of pristine MOFs to a large degree, such as large surface area, high porosity, composition diversity and dispersion, and excellent tailorability.

Under this background, MOFs have gained increasing attention from researchers as new catalytic materials for the transformation of C1 compounds, especially CO, CO₂, and CH₄. In recent years, significant progress has been made in the development of MOFs-based heterogeneous catalysts for the conversion of these C1 compounds. Many reviews on the conversion of CO, CO₂, and CH₄ to value-added chemicals with MOFs-based catalysts have been published.²¹^,²²^,²³^,²⁴^,²⁵ In particular, Bu et al. reviewed studies of MOFs-based catalysts that catalyzed the conversion of CO, CO₂, and CH₄ to chemicals and clean fuels from the perspective of C1 chemistry in 2019.²⁶ The review highlighted the unique properties and advantages of these catalysts compared to traditional porous materials. It emphasized their potential for future research and development in this area. However, it should be noted that in recent years, numerous new advancements have been made in the primary and applied research of MOFs-based catalysts for the production of high-value chemicals via C1 catalysis. Accordingly, in this review, we briefly summarize the latest achievements of MOFs-based catalysts in the conversion of C1 molecules (mainly including CO, CO₂, and CH₄) into valuable chemicals via thermal-catalytic strategy, as illustrated in Figure 2. By outlining these examples, we aim to provide a comprehensive understanding of the progress made in this field and the potential of MOFs-based C1 catalysts for future research and practical application.

C1 molecules to valuable chemicals via MOFs-based catalysts

CO conversion

Carbon monoxide is a colorless, odorless, and tasteless gas, highly toxic, and primarily produced through partial oxidation or incomplete combustion of carbon-containing compounds. From an environmental perspective, CO is an atmospheric pollutant, necessitating its removal through catalytic oxidation in applications such as automotive emission control and air purification.²⁷^,²⁸ Conversely, from the standpoint of energy security and industrial production, CO holds immense value as a primary chemical raw material for valuable chemicals and liquid fuels production. CO comes from a wide range of sources and can be produced from coal, biomass and organic waste gasification, or methane (CH₄) conversion. The main product of these production processes is synthesis gas (CO + H₂), which can be used directly as a chemical feedstock to produce clean fuels and value-added chemicals. By converting natural gas, coal, biomass, and other non-petroleum carbon resources into high-value-added chemicals and clean fuels, an attractive alternative non-petroleum pathway is provided for the production of hydrocarbons. There are two main routes for syngas conversion, namely the Fischer-Tropsch Synthesis (FTS) and methanol routes. Fischer-Tropsch Synthesis (FTS) refers to the conversion of syngas (CO + H₂) into hydrocarbon fuels and chemicals by adsorption and activation of CO/H₂ and C-C coupling in the presence of a metal catalyst.⁶^,²⁹^,³⁰^,³¹ On the other hand, syngas can be converted to the critical intermediate methanol on suitable catalysts (usually copper-based or reducible metal oxide) in the methanol route. The resulting methanol can be further converted to compounds such as dimethyl ether (DME), light olefins, aromatics etc., in the presence of acid catalysts (mainly zeolites). The syngas-to-methanol route tends to involve more complex catalytic systems and reaction conditions.³²^,³³^,³⁴^,³⁵

This section focuses on the conversion of CO to high-value chemicals via FTS and methanol routes using MOFs and their derivates as catalysts or carriers.

MOFs-based catalysts for FTS

The FTS process requires demanding reaction conditions. Limited by relatively low thermal, hydrothermal, and chemical stability, pristine MOFs usually cannot perform well in FTS. In order to overcome this limitation, the study of MOFs-derived catalysts, the synthesis of carbon-based materials with unique structures by high-temperature pyrolysis using pristine MOFs as templates and/or precursors, has recently become a hot spot. The obtained MOFs-derived materials retain some of the specific properties of MOFs-precursors and can also be adapted to the reaction conditions of FTS.³⁶^,³⁷ In this review, we focus on two types of FTS catalysts reported so far: Fe-MOFs-derived FTS catalysts and Co-MOFs-derived FTS catalysts. The catalytic activities of MOFs-based catalysts for FTS reported in recent years are summarized in Table 1.

Table 1.

Summary of the catalytic performance of MOFs-derived FTS catalysts reported in recent years

Entry	Catalyst	T (^oC)	P (MPa)	GHSV^a (mL g_cat⁻¹ h⁻¹)	H₂/CO	X_CO (%)	S_CO2 (%)	S_CH4 (%)	Desired product (%)	Reference
1	Co/MnO_x@quasi-MOF-74	200	3.0	4500	2	6.7	0.0	3.4	45.4 of S_ROH, 93.1 of C₂₊OH/ROH	Cui et al., 2020³⁹
2	Co/MnO_x@quasi-MOF-74	220	3.0	4500	2	12.1	0.0	7.0	42.4 of S_ROH, 92.5 of C₂₊OH/ROH	Cui et al., 2020³⁹
3	Co/MnO_x@quasi-MOF-74	230	3.0	4500	2	21.4	0.8	10.0	39.0 of S_ROH, 92.1 of C₂₊OH/ROH	Cui et al., 2020³⁹
4	CoPCN-920	220	2.5	5300	2	18.3	–	10.9	8.9 of S_C2-C4, 80.2 of S_C5+	Lü et al., 2020⁴⁰
5	ZIF-67-920	220	2.5	5300	2	4.8	–	4.8	29.4 of S_C2-C4, 28.6 of S_C5+	Lü et al., 2020⁴⁰
6	Co@C@SiO₂-0	230	2.0	6750	2	35.6	2.1	26.1	11.0 of S_C2-C4, 62.9 of S_C5+	Chen et al., 2020⁴⁴
7	Co@C@SiO₂-1	230	2.0	6750	2	29.2	1.4	22.2	11.9 of S_C2-C4, 65.9 of S_C5+	Chen et al., 2020
8	Co@C@SiO₂-2	230	2.0	6750	2	22.2	1.0	17.3	8.6 of S_C2-C4, 74.1 of S_C5+	Chen et al., 2020
9	Co@C@SiO₂-4	230	2.0	6750	2	13.3	1.0	15.7	6.7 of S_C2-C4, 77.6 of S_C5+	Chen et al., 2020
10	Co₃O₄/Al₂O₃-I	230	2.0	12(SL·g⁻¹·h⁻¹)	2	35.5	0.3	7.9	4.4 of S_C2-C4, 87.7 of S_C5+	Zhao et al., 2021⁴⁵
11	Co₃O₄/Al₂O₃-II	230	2.0	12(SL·g⁻¹·h⁻¹)	2	33.5	0.3	7.6	4.1 of S_C2-C4, 88.3 of S_C5+	Zhao et al., 2021⁴⁵
12	Co₃O₄/Al₂O₃-III	230	2.0	12(SL·g⁻¹·h⁻¹)	2	62.6	1.3	12.3	5.9 of S_C2-C4, 81.8 of S_C5+	Zhao et al., 2021⁴⁵
13	Co@SiO₂-3	210	2.0	17500	1	49.2	1.2	3.4	93.1 of S_C5+	Qin et al., 2022⁴⁶
14	Co@SiO₂-3	210	2.0	17500	2	98.3	1.3	7.0	89.9 of S_C5+	Qin et al., 2022⁴⁶
15	Co@C/CW-100	240	2.0	10000	2	92.6	–	∼12.0	∼30.0 of S_C2-C4, 58.1 of S_C5+	47
16	Co@C/CW-100	240	2.0	40000	2	89.6	–	∼13.0	∼32.5 of S_C2-C4, 53.5 of S_C5+	Qin et al., 2021⁴⁷
17	Co@C/CW-100	240	2.0	50000	2	81.2	–	∼22.5	∼35.0 of S_C2-C4, 48.5 of S_C5+	Qin et al., 2021⁴⁷
18	CoPNP-600	220	2.5	5300	2	71.6	<6.0	22.0	12.1 of S_C2-C4, 65.9 of S_C5+	Luo et al., 2021⁵¹
19	CoPNP-700	220	2.5	5300	2	62.5	<6.0	14.5	15.3 of S_C2-C4, 70.2 of S_C5+	Luo et al., 2021⁵¹
20	CoPCN-920	220	2.5	5300	2	18.3	<6.0	10.9	8.9 of S_C2-C4, 80.2 of S_C5+	Luo et al., 2021⁵¹
21	Co4.7Mo@C	275	3.0	15000	2	48.0	–	–	19.7 of S_MeOH 80.3 of S_C2+OH	54
22	CoMn-350	240	3.0	3750	2	51.5	0.5	7.7	57.5 of S_ROH, 47.4 of S_C2+OH	Guo et al., 2023⁵⁵
23	FeC(4,700)	300	2.0	8000	∼2	88.9	34.4	8.9	15.4 of S_C2-C4, 75.7 of S_C5+	Cho et al., 2020⁶⁰
24	FeC(4,800)	300	2.0	8000	∼2	84.6	32.8	8.9	16.3 of S_C2-C4, 74.8 of S_C5+	Cho et al., 2020⁶⁰
25	FeC(4,900)	300	2.0	8000	∼2	73.1	31.8	10.8	17.6 of S_C2-C4, 71.6 of S_C5+	Cho et al., 2020⁶⁰
26	Fe-MIL-88B-T/C	280	2.0	4200	1	94	43.0	17.0	40 of S_C2-C4, 43 of S_C5+	Rashed et al., 2022⁶¹
27	R-1	300	2.0	36000	1	14.1	7.5	4.2	10.41 of S_C2-C4, 85.36 of S_C5+	Mehar et al., 2020⁶²
28	R-2	300	2.0	36000	1	12.2	8.2	8.2	13.03 of S_C2-C4, 81.79 of S_C5+	Mehar et al., 2020⁶²
29	R-3	300	2.0	36000	1	8.0	5.4	5.4	9.59 of S_C2-C4, 86.36 of S_C5+	Mehar et al., 2020⁶²
30	R-4	300	2.0	36000	1	5.2	6.8	5.2	12.78 of S_C2-C4, 82.06 of S_C5+	Mehar et al., 2020⁶²
31	R-5	300	2.0	36000	1	5.4	4.0	3.3	8.56 of S_C2-C4, 88.19 of S_C5+	Mehar et al., 2020⁶²
32	Fe/CNS(900)	340	1.0	9000	1	33.9	31.9	26.5	28.4 of S_C2-C4, 28.4 of S_C5+	Zhao et al., 2021⁶⁶
33	Fe/CNS(950)	340	1.0	9000	1	40.2	32.2	24.3	23.2 of S_C2-C4, 35.6 of S_C5+	Zhao et al., 2021⁶⁶
34	Fe/CNS(1000)	340	1.0	9000	1	51.2	33.0	23.6	22.0 of S_C2-C4, 36.3 of S_C5+	Zhao et al., 2021⁶⁶
35	Fe/CNS(1100)	340	1.0	9000	1	31.0	31.2	28.4	23.0 of S_C2-C4, 31.6 of S_C5+	Zhao et al., 2021⁶⁶
36	Fe@C	340	2.5	5000	1	27.0	20.0	17.0	20 of S_C2-C4, 63 of S_C5+	Wang et al., 2021⁶⁸
37	Na/Fe@C	340	2.5	5000	1	51.0	34.0	16.0	18 of S_C2-C4, 66 of S_C5+	Wang et al., 2021⁶⁸
38	Cu/Fe@C	340	2.5	5000	1	91.0	40.0	29.0	36 of S_C2-C4, 35 of S_C5+	Wang et al., 2021⁶⁸
39	Ru/Fe@C	340	2.5	5000	1	60.0	35.0	41.0	30 of S_C2-C4, 29 of S_C5+	Wang et al., 2021⁶⁸
40	Fe@C	340	2.5	5000	1	94.0	42.0	22.0	36 of S_C2-C4, 42 of S_C5+	Wang et al., 2022⁶⁹
41	FeCo@C	340	2.5	5000	1	99.0	40.0	40.0	29 of S_C2-C4, 31 of S_C5+	Wang et al., 2022⁶⁹
42	FeNi@C	340	2.5	5000	1	87.0	40.0	53.0	17 of S_C2-C4, 30 of S_C5+	Wang et al., 2022⁶⁹
43	FeMn@C	340	2.5	5000	1	73.0	40.0	18.0	31 of S_C2-C4, 51 of S_C5+	Wang et al., 2022⁶⁹
44	FeZn@C	340	2.5	5000	1	94.0	42.0	28.0	34 of S_C2-C4, 38 of S_C5+	Wang et al., 2022⁶⁹

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Gas hourly space velocity.

Co-MOFs derived FTS catalysts

In 2016, Isaeva et al. prepared novel nanohybrid materials by immobilizing cobalt nanoparticles on a microporous framework, MIL-53(Al), which serves as a porous host matrix. The catalytic properties of Co@MIL-53(Al) nanohybrids were investigated in Fischer-Tropsch Synthesis (FTS).³⁸ For MOFs materials, structural stability and suitable active sites are essential for achieving a high C₂₊OH selectivity in FTS.²¹ However, these MOFs-derived materials usually have a lower surface area and collapsed skeletal structure after high-temperature decomposition, resulting in a large amount of active metal sites being embedded into the bulk phase and coated with graphite carbon.³⁶^,³⁷ Hu et al. constructed a core-shell Co/MnO_x@quasi-MOF-74 catalyst by controlling the delocalization of bimetallic CoMn-MOF-74 through a partial pyrolysis strategy, which largely preserved the original skeleton of MOFs and generated many highly active Co/MnO_x nanoparticles in situ.³⁹ At 200°C, 3.0 MPa (CO/H₂ = 1/2) and 4500 mL g⁻¹ h⁻¹ of GHSV, the alcohol selectivity reached 48.7 wt %, of which 93.1 wt % was C₂₊ alcohols. Mechanistically, the porosity and skeletal structure of the core-shell catalysts ensured that the reactants were able to diffuse into the active sites even though Co⁰, Co²⁺, and Co₂C, where the metal Co was used for CO dissociation and chain growth of the C₂₊ alkyl chains, while the CUS of Co²⁺ and Co₂C were used for CO insertion to generate C₂₊OH (Figure 3). Luo et al. reported a strategy for the preparation of highly dispersed Co-embedded porous carbon nanocage (CoPCN) structures derived from ZIF-8@ZIF-67 precursor.⁴⁰ By pyrolyzing the core-shell ZIF-8@ZIF-67 precursor at high temperatures, the metallic zinc in the ZIF-8 core was vaporized by high-temperature pyrolysis to form the nanocages, which resulted in the formation of a well-developed porous structure and the realization of high Co loading with a weight percentage of more than 30%. The porous channels and hollow structure of CoPCN enhanced the diffusion of reactants and hydrocarbon products and improved the selectivity of C₅₊ and CO conversion.

Schematic illustration of the calcination-induced structure changes of the CoMnMOF-74

Reproduced with permission from Cui et al.³⁹ Copyright © 2020, Elsevier.

The presence of graphitic carbon layers after pyrolysis can cover the active sites and inhibit the adsorption and activation of reactants, resulting in a decrease in the FTS activity of the catalyst. Calcination of Co@C catalysts in air removes the graphitic carbon layer, but without the constraining effect of the carbon skeleton, the Co particles will be agglomerated, thus inducing catalyst deactivation.⁴¹^,⁴²^,⁴³ Therefore, some researchers have worked on improving the FTS performance of MOFs-derived catalysts through the role of a cladding hydrophobic layer or the support. Li et al. prepared Co@C catalysts using zeolite imidazolium hydrochloride framework-67 with MOFs structure as precursors with high cobalt loading of 55.6 wt % and small cobalt crystal size of 8.6 nm.⁴⁴ Co@C@SiO₂-X core-shell catalysts with different SiO₂ shell thicknesses were successfully prepared by coating different amounts of TEOS (tetraethyl orthosilicate) on the outer surface of Co@C to change the product selectivity. In follow-up research, Li et al. used an in situ doping method to introduce an aluminum source during the synthesis of ZIF-67 to obtain a high-performance Co₃O₄/Al₂O₃-x catalyst.⁴⁵ The effects of different Al precursors (including AlCl₃·6H₂O, Al(C₃H₇O)₃, and Al (NO₃)₃·9H₂O) on the catalytic performance were also investigated. The prepared Co₃O₄/Al₂O₃-x catalysts showed better FTS activity and lower CH₄ selectivity than the Co@C catalysts obtained by direct carbonization. The Co₃O₄/Al₂O₃-x catalysts with different aluminum sources showed different FTS performances, among which the catalysts using Al (NO₃)₃·9H₂O as the aluminum source showed the best performance, with stronger metal-support interactions, smaller Co particle sizes, and a higher number of active sites. Ding et al. synthesized a hollow Co@SiO₂ catalyst with cobalt species highly dispersed within a mesoporous hollow silica shell with the help of cobalt MOFs materials (Figure 4), which showed a high selectivity of 93.3% for C₅₊ hydrocarbons and only 3.4% for CH₄.⁴⁶ Compared with conventional encapsulated catalysts, the hollow core-shell structure provided an inner-cavity environment, which shortened the diffusion distance and contact area between cobalt metal and support. It improved the residence time of the exposed active cobalt sites and intermediates, thus enhancing the catalytic activity and the selectivity for long-chain hydrocarbons. Using natural macro-porous wood combined with microporous MOFs, Jiang et al. prepared Co@C/CW, a monolithic 3D catalyst for Fischer-Tropsch synthesis application, by growing Co-MOF in-situ on a wood monolith and carbonizing it.⁴⁷ In general, Co@C/CW showed higher CO conversion and C₅₊ selectivity, attributed to its 3D multi-channel reactor structure and more contact surfaces. In the three-dimensional structure of tracheal cells, Co-MOF was well separated, yielding more contact surfaces. In addition, the mesoporous structure of Co@C/CW-100 facilitates the diffusion, adsorption, reaction, and dissociation of synthesis gas on the Co@C surface, resulting in higher C₅₊ selectivity.

Illustration of the synthesis of hollow Co@SiO₂-3 catalyst

Reproduced with permission from Qin et al.⁴⁶ Copyright © 2022, Elsevier.

The impregnation method is widely used to prepare industrial FTS catalysts, often yielding Co loadings below 20 wt %. At the same time, the support usually has strong metal-support interactions with the Co species, leading to irreversible catalyst deactivation.⁴⁸^,⁴⁹^,⁵⁰ Layered double hydroxide (LDH) is a typical inorganic layered substrate, and active Co can be used as a component of the LDH substrate to achieve higher metal loadings. Lv et al. prepared ZIF-67 MOFs grown in situ on CoAl LDH and subsequently prepared highly dispersed Co-embedded porous nanoparticle (CoPNP) catalysts for FTS by pyrolysis.⁵¹ The CoPNP showed a hierarchical structure with a high specific surface area. The CoPNP showed a hierarchical structure with a high specific surface area, and the porous channels could enhance syngas diffusion and hydrocarbon production and improve CO conversion and C₅₊ selectivity, with CO conversion up to 71.6% and C₅₊ long-chain hydrocarbon selectivity up to 70.2% (Figure 5). Due to the unsaturated coordination state provided by the Co cation on the LDH surface, ZIF-67 can be grown in situ on the LDH surface to form CoAl-LDH/ZIF-67. The pyrolysis of CoAl-LDH/ZIF-67 mainly leads to two structural transformations: the transformation of the ZIF-67 crystals into porous graphitic carbon and the transformation of CoAl-LDH nanoparticles into Co nanoparticles.

Schematic of the preparation of CoPNP catalysts and the production of C₅₊ long-chain hydrocarbons from syngas

Reproduced with permission from Luo et al.⁵¹ Copyright © 2021, American Chemical Society.

Recently, the selective conversion of syngas to higher alcohols (HA) has been of great interest. Modified Co-based catalysts have attracted much attention due to their excellent activity, relatively high HA selectivity, and low water-gas shift capability.⁵²^,⁵³ Wang et al. reported a special MOFs-assisted strategy to prepare well-contained Co-Mo bimetallic refiners based on MOFs pyrolysis, with an optimal ratio of Co⁰ and Co₆Mo₆C to Co_4.7Mo@C at 275°C and 3.0 MPa, which resulted in a 48% CO conversion and a C₂₊OH time space yield (STY) of 99 mg g_cat⁻¹ h⁻¹.⁵⁴ Ma et al. prepared a series of catalysts by partially thermally decomposing CoMn-MOF materials with layered structures.⁵⁵ The MOFs framework could be partially retained after calcination at 350°C under nitrogen flow, where Co²⁺ species could provide additional non-dissociatively adsorbed CO sites, thus improving alcohol selectivity. The addition of manganese promotes cobalt dispersion and Co₂C formation. The synergistic catalytic effect of these actives resulted in higher selectivity of the optimal CoMn-350 catalyst for higher alcohols.

Fe-MOFs derived FTS catalysts

Fe-based catalysts have been widely studied among active transition metals of all types due to their low market cost, easy availability, high water gas shift activity (WGS), flexible product distribution, and tunable engineering properties.⁵⁶^,⁵⁷ For Fe-MOFs materials, the different porosities, and thicknesses of the carbon layers, as well as the particle sizes of the metal nanoparticles, can be easily adjusted by adjusting the pyrolysis conditions to preferentially form highly dispersed smaller metal nanoparticles from the MOFs with a crystalline phase suitable for the FTS reaction.⁵⁸^,⁵⁹ Jong et al. applied iron carbide catalysts derived from MIL-100(Fe) MOFs to the Fischer-Tropsch synthesis reaction by direct pyrolysis, and the obtained iron carbides were easy to form active iron carbide phases due to the small grain size of the obtained iron carbides.⁶⁰ The crystallite sizes of metallic Fe and Fe₃O₄ on FeC increased with increasing pyrolysis temperature (700°C–900°C) and duration (4 h–16 h). Based on the similar pore volume and pore size on FeC, the catalytic activity is closely related to the specific surface area and crystallite size of FeC nanoparticles, and smaller FeC nanoparticles with larger specific surface area and thinner carbon layer seem to allow easier access of reactants to the active sites and thus higher catalytic activity. Ahmed et al. used TEA instead of NaOH as a deprotonation catalyst to synthesize Fe-MIL-88B MOFs, which improved the synthesis yield of MOFs and was conducive to forming smaller crystals.⁶¹ Smaller crystals result in higher activity and olefins yield.

Catalyst pretreatment is another crucial step during the FTS process, which involves catalyst reduction under different reduction atmospheres seeking an active catalyst. Li et al. investigated the effects of different reduction atmospheres on the FTS reaction products of MOFs-derived Fe-based catalysts, revealing a close relationship between reduction atmospheres and FTS catalytic activity (Figure 6).⁶² The reduction atmospheres mainly affected the FTS catalytic activity. At the same time, they had little effect on the product selectivity, where the catalysts reduced in a pure CO atmosphere had the highest CO conversion. In contrast, the catalysts reduced with H₂ and syngas had a more stable reaction but lower activity and a higher C₅₊ selectivity. Li et al. investigated the synthesis of Fe@C catalysts by direct pyrolysis of FeMIL-88B with the structure of MOFs at different elevated temperatures (600, 700, and 800°C), which overcame the problem that the high C₅₊ selectivity usually comes at the cost of lower CO conversion. The catalyst Fe@C-800 decomposed at 800°C showed a very high C₅₊ hydrocarbon selectivity close to 90% and good reaction stability. MOFs-derived Fe-based catalysts have the potential to achieve high C₅₊ selectivity for FTS without lowering the CO conversion.

Schematic diagram displaying phase transformation over reduction and FTS reaction

Reproduced with permission from Nisa et al.⁶² Copyright © 2019, Elsevier

Functionalizing carbon supports with heteroatom doping is known as one type of chemical modification strategy. The framework N atoms, as electronic donors, can enhance the electron density of adjacent metal species and help anchor metal species by strengthening metal support interactions, improving metal dispersion and sintering resistance.⁶³^,⁶⁴^,⁶⁵ Ma et al. used a MOFs-derived class of Fe-based catalysts, and the derived CNS exhibited a higher degree of graphitization and electronic effects to promote Fe carburization, thereby enhancing the intrinsic activity of the catalysts in FTS (Figure 7).⁶⁶ Furthermore, a comparison of the Fe/CNS, Fe/CP, and Fe/AC catalysts reveals that MOFs morphology and N doping significantly affect the CO conversion, and N doping also affects the product distribution. The MOFs-derived N-doped carbon nanosheets as supports show significant advantages in FTS due to their unique morphology and the electronic effect of N species. The presence of sulfur caused pores to form inside the particles during the catalyst preparation. This phenomenon has also sparked the interest of researchers. Iqbal et al. found that the presence of sulfur in Fe₂(SO₄)₃ MOFs provided a significant amount (52.50%) of light hydrocarbons in the carbon chain distribution.⁶⁷ High-temperature annealing made the pores of the MOFs finer, improving the catalytic products' selectivity. High-temperature pyrolysis during catalyst preparation brought iron and carbon into contact more rapidly and promoted the formation of the active phase of iron carbide. Characterized by SEM, the MOFs prepared from iron sulfate showed sulfur particles attached to iron and carbon particles. The presence of sulfur particles decreased after calcination under the tube furnace atmosphere due to the reaction of sulfur with free water molecules to generate heat, leading to the formation of pores inside the particles.

Schematic illustration of the synthesis process for preparing Fe/CNS catalyst

Reproduced with permission from Zhao et al.⁶⁶ Copyright © 2020, Elsevier

Additionally, adding alkali and other metallic promoters to Fe-based FTS catalysts is a good choice for improving catalytic activity, selectivity, and stability. Transition metals can be used as electronic and structural promoters in FeO_x-FeC_x catalysts and concurrently alter the active site distribution. Luo et al. investigated the Fischer-Tropsch synthesis of porous carbon-loaded Fe-based catalysts based on MOFs promoted by Na, Cu, and Ru metals.⁶⁸ Among them, the Cu sample showed the best activity promotion (FTY = 0.154 mol CO g_Fe⁻¹ h⁻¹), the Ru sample showed more than 70% selectivity for C_1-4 hydrocarbons, and the Na sample showed the highest C₅₊ selectivity of 66%. XRD and TEM characterization confirmed that the enhancement of FTS activity and selectivity of the promoted catalysts was related to the reduction of Fe particle size, which improved the FTS performance by stabilizing the small-sized Fe nanoparticles on the surface of the carbon matrix and preventing their further aggregation at high temperature. In follow-up research, Luo et al. synthesized a bimetallic MOFs, FeM-MOF-74.⁶⁹ Then, they prepared bimetallic FT catalysts with high metal loading (Fe+M > 50 wt %) and uniformly dispersed active sites by pyrolysis of bimetallic MOFs. Among them, FeCo@C showed the highest CO conversion, FeMn@C showed a trend toward light olefins, and FeZn@C produced the highest FTY. The bimetallic catalysts showed higher activity compared to the monometallic Fe catalysts. With the addition of Mn, the olefin to paraffin ratio of Fe@C and FeMn@C catalysts was significantly increased from 0.43 to 1.23, the selectivity of long-chain hydrocarbons (C₅₊) was increased from 42% to 51%, and the CH₄ generation was suppressed from 22% to 18%. This behavior can be explained by the electronic effect of Mn species, which can change the valence state of adjacent Fe and promote the dissociation of CO.

In summary, both Fe-MOFs and Co-MOFs belong to MOF materials with a highly ordered pore structure, which can be adjusted regarding pore size and functionality by selecting different organic ligands and metal centers. However, due to the different metal centers, the differences in the electronic structure and surface properties of their active centers lead to different activities and selectivity in the catalytic reactions. Fe-based materials usually have higher conversion rates for CO and tend to produce more olefins and oxides (e.g., CO₂), while Co-based catalysts have relatively lower reaction temperatures and produce more saturated hydrocarbons. In practical industrial applications, the selection of a suitable catalyst needs to be based on the reaction conditions, the desired product distribution, and the requirements for catalyst stability.

MOFs-based catalysts for methanol route of CO conversion

In addition to FTS, syngas can be used to synthesize high-value chemicals via the methanol route. Research on the one-step conversion of syngas to high-value chemicals via a methanol intermediate route through efficient catalysts is attracting the interest of researchers.³²^,³³^,³⁴^,³⁵ DME production has traditionally been realized via a two-step process, where methanol is synthesized from syngas and then dehydrated to DME. Compared with the two-step synthesis of DME, the direct one-step syngas-to-DME (STD) reaction breaks the thermodynamic equilibrium limitation of methanol synthesis from syngas.⁷⁰^,⁷¹^,⁷² The high DME synthesis performance heavily relies on the well-organized structure of the catalysts. MOFs have received increasing attention from researchers worldwide due to their regular crystal structure and well-developed porosity.³³ Liu et al. prepared Cu/ZnO catalysts with a novel octahedral structure by two-step pyrolysis of Zn-doped Cu-BTC MOFs via one-pot solvothermal and two-step calcination methods.³² The homogeneous distribution of Cu and Zn in the unique octahedral morphology significantly reduces the aggregation and migration of the Cu0 nanoparticles, which enhances the activity and stability of DME production. In addition, the partial reduction of ZnO led to the formation of Cu⁺-O-Zn, further promoting the DME production and showing the best DME generation activity (7.74% CO conversion and 70.05% DME selectivity) after 40 h of continuous reaction. Zhao et al. successfully prepared a new type of Cu-embedded porous Al₂O₃ catalyst by filling Al(OH)₃ into a Cu-BTC skeleton via a deposition-precipitation-calcination process.³³ The prepared Cu@Al₂O₃-dp catalyst has a unique embedded structure with higher Cu dispersion, and the CO conversion and DME selectivity in the STD reaction reached 25.7% and 90.4%, respectively, with higher product selectivity and stability than that of the pure Al₂O₃ supported Cu catalyst.

Aromatics are mainly produced from petroleum refining and are essential basic chemicals. It is extremely attractive to utilize MOFs and their derivative materials to build ingenious structures at the molecular level and develop efficient catalysts with desirable properties for hydrogenating CO to aromatics with high activity and selectivity. Li et al. explored a facile "defect-mediated outward shrinkage" strategy using a Zr geometry to replace Zn in MTV-UiO-66 (Figure 8).⁷³ Subsequently, they carbonized to prepare a robust 3D layered carbon framework and ultrafine metal oxide nanoparticles capable of delivering abundant surface oxygen vacancies, a higher density of exposed active sites, and open and continuous channels. And by coupling with layered H-ZSM-5, the tandem catalyst HO-ZnZrO@C/Z5-0.6 was obtained with aromatic selectivity (73.1%) and lower CH₄ selectivity (3.4%), as well as up to 0.302 g g_oxide⁻¹ h⁻¹ aromatic STY at a CO conversion of 35.2%.

Fabrication Strategy of HO-ZnZrO@C and reaction process for direct production of aromatics from syngas over HO-ZnZrO@C/Z5

Reproduced with permission from Wang et al.⁷³ Copyright © 2020, American Chemical Society.

Coal or biomass-based light olefin production routes include methanol to olefin (MTO) based on synthesis of syngas and Fischer-Tropsch synthesis of olefins (FTO). FTO is difficult to achieve high light olefins selectivity due to the Anderson-Schuler-Flory (ASF) distribution.⁷⁴^,⁷⁵ MTO has emerged as the alternate pathway for supplying light olefins. Ying et al. prepared ZnZrO_x nanoparticles by MOFs calcination, and the XPS results showed that the MOFs-derived ZnZrO_x-400 had more oxygen vacancies and Zn-O-Zr structures.³⁴ CO-TPD and in situ DRIFTS indicated that ZnZrO_x-400 had a more robust CO adsorption capacity, which was favorable for CO conversion. Therefore, the MOFs-derived oxides have abundant oxygen vacancies, and Zn-O-Zr localized structures, which are favorable for CO activation and the generation of methanol and dimethyl ether. Moreover, when combined with SAPO-34, the bifunctional catalyst containing MOFs-derived ZnZrO_x achieved a CO conversion of 22.5% and a light olefin selectivity of 79.7% in hydrocarbons.

Due to the excellent CO dissociation and C-C coupling ability, Rh-based catalysts have shown excellent catalytic performance in ethanol synthesis via syngas conversion and have become popular catalysts for this catalytic system.⁷⁶ In order to compare the effects of pore size and junction properties of UiO MOFs on the catalytic performance of Rh-Mn catalysts, Mao et al. selected three UiO MOFs with different cavity sizes and SBUs and further prepared.³⁵ Rh-Mn bimetallic catalysts by impregnation method. Characterization results showed that the topology of the UiO MOFs was favorable for dispersing dense ultra-small Rh-Mn bimetallic nanoparticles. Among them, the Rh-Mn catalysts with Zr-UiO MOFs (UiO-66 and UiO-67) as supports exhibited outstanding catalytic performance, and the Rh/CeO₂ interface formed by the calcification of RM@Ce-UiO-66 facilitated the conversion of adsorbed CO to the stabilized carbonate species, which improved the activity.

Overall, compared with traditional materials, MOFs materials usually have higher specific surface area and tunable pore structure, which can help to improve the dispersion of catalytic active sites and the adsorption of reactant molecules during the Fischer-Tropsch reaction and thus increase the catalytic activity of FTS. On the other hand, through the precise design of MOFs structure and modification, the product distribution of FTS reaction can be modulated to a certain extent, for example, by adjusting the metal active center and functionalized ligands to improve the selectivity of specific hydrocarbon products. However, MOF materials often have the disadvantages of poor thermal stability and high synthesis and processing costs, so MOFs-derived catalysts obtained by pyrolysis/carbonization are often used to obtain good stability, and there is still a need to optimize the synthesis and preparation strategies to improve their competitiveness in large-scale industrial applications.

CO₂ conversion

Excessive CO₂ emissions from the combustion of fossil fuels have caused enormous environmental issues, such as global warming, ocean acidification, and climate change. Converting CO₂ into high-value-added chemicals is a promising strategy not only to reduce carbon emissions but also to fulfill the needs of sustainable development. Undoubtedly, MOFs have been widely used as a promising and powerful strategy for designing and producing a wide range of porous materials to address current environmental and energy issues worldwide. In the past few years, more and more MOFs have been used for CO₂ capture, regeneration, and conversion. In this section, we present recent research advances in using MOFs-based multiphase catalysts for the hydrogenation of CO₂ to valuable chemicals in three main routes: the methanol route, the modified Fischer-Tropsch route, and CO₂ methanation.

MOFs-based catalysts for CO₂ hydrogenation to CH₃OH

Among many valuable chemicals, methanol is not only a building block chemical but also a promising energy carrier for industry and vehicles. In some bifunctional catalytic systems, methanol can be a reaction intermediate for further conversion to other high-value chemicals. The catalytic activities of MOFs-based catalysts for CO₂ hydrogenation to methanol are summarized in Table 2.

Table 2.

Summary of the catalytic performance of MOFs and MOFs-derived catalysts for CO₂ hydrogenation to methanol reported in recent years

Entry	Catalyst	T (^oC)	P (MPa)	GHSV^a (mL g_cat⁻¹ h⁻¹)	H₂/CO₂	X_CO (%)	S_MeOH (%)	STY (g_MeOH g_cat⁻¹h⁻¹)	Reference
1	Cu/ZnO_x@UiO-66	250	4	12000	3	3.5	86.	1.27^b	Yang et al., 2022⁸⁰
2	CuO–ZnO@ZIF-8	200	2	2400	3	14.6	93.4	1.08	Zhanet al., 2023⁸²
3	ZnO/Zr₁₂-bpdc	250	4	4800	3	7.5	95.0	0.11	Zhang et al., 2021⁸⁴
4	15Cu/6.4ZnO/AlFum MOF	230	5	10000	3	45.6	6.86	0.565	Duma et al., 2022⁸⁵
5	3In@4Co(20)	300	5	15600	4	20.5	87.0	0.65	Pustovarenko et al., 2020⁸⁷
6	12%Cu-ZrO₂-1-3	220	3	15000	3	6.8	64.4	0.288	Yu et al., 2021⁸⁸
7	Cu-ZnO^MOF ⊂ Al₂O₃	240	3	14400	3	9.1	86.9	0.407	Qi et al., 2022⁹⁰
8	Pd@In₂O₃	295	3	19200	3	8.0	81.0	81.1^c	Cai et alk., 2022⁹¹
9	Cu@ZrO₂	220	3	15600	3	5.0	85.0	0.144	Han et al., 2022⁹²
10	Mo-Co (2:1)-C-N (800)	275	2	6000	3	9.2	58.4	0.106	Hu et al., 2021⁹³
11	h-MoS₂/ZnS	260	5	15000	4	9.0	67.3	0.93^days	Zhou et alk., 2021⁹⁴
12	CuZnO-MOF-74-350	190	4	4000	3	7.5	80.0	0.45	Zhou et al., 2023⁹⁵
13	Cu/ZnO_x/ZrO₂	260	4	12000	3	18.7	52.0	0.217	Zhang et al., 2022⁹⁶
14	Cu@ZrO₂-U	260	3	2400	3	12.1	70.5	0.073	Chen et al., 2023¹⁰⁰
15	In–Co–Zn/C–N	300	2	6000	3	7.0	77.0	0.106	Liu et al., 2022¹⁰¹
16	In₂O₃@ZrO₂	290	3	12000	3	10.4	84.6	0.29	Cui et al., 2022¹⁰²
17	Cr₂O₃/C-500-500	350	3	1200	3	16.8	29.9	0.038	Wang et al., 2023¹⁰⁵

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a g g_Cu⁻¹ h⁻¹.

b g g_Pd⁻¹ h⁻¹.

c g g _MoS2⁻¹h⁻¹.

Gas hourly space velocity.

To our knowledge, the first person to use MOFs for CO₂ hydrogenation to methanol was Yaghi. In 2016, Yaghi et al. reported a pioneering work in which they encapsulated 18 nm Cu nanocrystals (NC) into single crystal UiO-66 to obtain Cu ⊂ UiO-66 for CO₂ hydrogenation to methanol.⁷⁷ The reaction was carried out at 175°C and 1 MPa, and the results showed that Cu/ZrO₂, Cu/UiO-66, Cu/ZnO/Al₂O₃, and Cu⊂UiO-66 displayed catalytic activity. Cu⊂UiO-66 possessed the highest methanol-forming transition frequency (TOF) of 3.7 × 10⁻³ s⁻¹ and a 100% methanol selectivity. This work was the first to discover the strong metal-carrier interaction effect of MOFs-derived SBU, providing new insights into developing highly selective and efficient MOFs-based non-homogeneous catalysts. Assaf et al. recently synthesized xCu/MOFs catalysts for CO₂ hydrogenation to methanol by impregnating UiO-66 carriers with varying concentrations of copper precursors.⁷⁸ The Cu NP loading accounted for the missing linker defects in the UiO-66 structure, the highest copper-loaded 20Cu/MOFs catalysts had the highest CO₂ conversion and best methanol yields due to strong metal-support interactions and the highest number of missing linker defects in the MOFs structure. The breakthrough of this work enriches the understanding of the effect of copper loading on the UiO-66 and the influence of defect concentration on the catalytic performance. It contributes to the rational design of catalysts for CO₂ hydrogenation to methanol. Lercher and Gutiérrez prepared MOFs UiO-66 samples with controlled defect concentrations and confined Cu clusters in UiO-66 to obtain Cu/UiO-66 for use in the CO₂ hydrogenation to methanol.⁷⁹ They prepared Cu/UiO-66 by exchanging hydroxyl groups at the Zr₆O₈ node by hydrated hydroxyl Cu cations and finally obtained Cu/UiO-66-a with an optimal Cu loading of 1.4 wt %. At 250°C, 3.2 MPa (Figure 9), the methanol production rate of Cu/UiO-66-a was 4.7 mol_MeOH mol⁻¹_Cu h⁻¹, an order of magnitude higher than the rate using the reference Cu/ZrO₂. DFT and experimental desorption results indicate that the Zr-O-Cu interface is part of the active site that strongly adsorbs CO₂. This strategy supports the design of rational catalysts for CO₂ hydrogenation to methanol.

Using defective nodes to deposit Cu species

(A) A linker missing in the UiO-66 structure is replaced by two –OH/OH₂ species, which are active for ion exchange to deposit metal onto the Zr₆ nodes of the MOF.

(B) Possible reaction for Cu deposition (ion exchange) in aqueous solution.

(C) Adsorption energies (ΔE_ads in kJ/mol) of CO₂ at the Cu/UiO-66-a interface. a Cu only sites, b Zr⁴⁺-O^2- sites on the Zr₆O₈ nodes in a bidentate bridging mode, c Zr⁴⁺-O^2-- Zr⁴⁺ sites on the Zr₆O₈ nodes in a tridentate bridging mode, and d Cu-Zr⁴⁺ interfacial sites. Reproduced with permission from Zhu et al.⁷⁹ Copyright © 2020, Nature Publishing Group.

In recent years, the catalytic performance of Cu-loaded MOFs for CO₂ hydrogenation to methanol has been significantly improved by incorporating other metal additives such as Zn and has been widely used. Li et al. synthesized Cu/ZnO_x/UiO-66 for the first time using the dual-solvent method for CO₂ hydrogenation to methanol.⁸⁰ At 250°C, 4 MPa, for Cu/ZnO_x@UiO-66, the STY of methanol is enhanced by 5.5 and 8.5 times compared with those on the commercialized Cu/ZnO/Al₂O₃ and the Cu/ZnO @UiO-66 prepared with the traditional impregnation method. The double solvent method solves the problem that metal particles are easy to agglomerate, and Cu and ZnO phases can easily separate during the high-temperature reaction process. Thus, the prepared catalyst could show good stability. Kobayashi et al. prepared Cu-ZnO/amUiO-66 composites made of Cu-ZnO nanocomposites and amUiO-66 for CO₂ hydrogenation by spray-drying method (Figure 10A).⁸¹ XRD, EXAFS, and STEM-EDX patterns showed that the Cu-ZnO nanocomplexes were homogeneously distributed in the UiO-66 material. In the CO₂ hydrogenation to methanol reaction, the catalytic activity of Cu/amUiO-66 was three times higher than that of crystalline UiO-66 (Figure 10B). In addition, the methanol yield of Cu-ZnO/amUiO-66 was increased by 1.5 times compared with that of Cu/amUiO-66. This study can help for the next step of MOF research. More recently, San et al. prepared a novel floral CuO-ZnO@ZIF-8 catalyst.⁸² XPS and Raman spectra show that the CuO-ZnO@ZIF-8 surface has more oxygen vacancies than co-precipitated CuO-ZnO. XPS and Raman spectra analyses revealed that the CuO-ZnO@ZIF-8 surface exhibits higher oxygen vacancies (O_V) concentrations than co-precipitated CuO-ZnO. These oxygen vacancies play a crucial role in the hydrogenation reactions that lead to the formation of CH₃OH. The O_V sites facilitate the adsorption of H^∗ species and CO₂, activating the reaction intermediates and reducing the energy barrier. Furthermore, the unique floral structural morphology of CuO-ZnO@ZIF-8 enhances the availability of O_V and exposed active sites, strengthening the coordination between CuO and ZnO, thereby favoring the conversion of CO₂ to CH₃OH. CuO-ZnO@ZIF-8 (1:4) demonstrates impressive performance, achieving 14.64% CO₂ conversion and 93.41% methanol selectivity at 200°C. This work further demonstrates that the combination of metals with MOFs can improve the efficiency of catalytic CO₂ hydrogenation to methanol.

MOFs-based nanocomposites prepared by spray drying for CO₂ hydrogenation

(A) Cu/amUiO-66 and Cu-ZnO/amUiO-66 synthesized by the spray-drying method for highly enhanced catalytic activity of CO₂ hydrogenation for methanol synthesis.

(B) The amount of methanol synthesized from CO₂ and H₂ by Cu/cryUiO-66, Cu/amUiO-66, Cu-ZnO/γ-Al₂O₃, and Cu-ZnO/amUiO-66 catalysts. Reproduced with permission from Mitsuka et al.⁸¹ Copyright © 2021, John Wiley and Sons.

In addition to Cu, other classical catalysts for CO₂ hydrogenation to methanol, such as Zn, Pt, etc., can also be combined with MOFs. Recently, Olsbye et al. investigated the kinetic role of Zr-nodes and the effect of H₂O on the CO₂ hydrogenation reaction on UiO-67-Pt at 170°C (Figure 11).⁸³ Through steady-state and transient isotope exchange experiments, H₂O co-feed measurements, and density-functional-theory (DFT) calculations, they discovered that an increase in the number of defects in the Zr-nodes accelerates the production rates of methanol and CH₄. Additionally, they observed that water promotes methanol desorption but does not alter the steady-state reaction rate of methanol formation. On the other hand, water has a significant inhibitory effect on CH₄ formation. These results suggest that water can be used to improve the selectivity of methanol and encourage further detailed investigation of the catalyst system.

The kinetic role of Zr-nodes and the effect of H₂O on the CO₂ hydrogenation reaction

(A) a Zirconium node with 12 benzoate linkers. b A defective node is created by removing one linker resulting in a Zr-node with 11 linkers. c A defective node with two adjacent missing linkers. d A defective node with two opposite missing linkers. The carbon atoms furthest away from the Zr-node were constrained in all cases in all directions, to simulate the integrity of the UiO-67 MOF.

(B) Reaction-onset comparison of UiO-67-Pt (open symbols) and UiO-67(LD)-Pt having intrinsically less benzoic acid modulator (filled symbols). Left: CO (squares), CH₃OH (triangles), and CH₄ (circles) rate of formation. Right: methanol selectivity versus time on stream. Conditions: CO₂/H₂/inert = 1/3/1, τ = 0.01 g_cat min ml⁻¹, T = 170°C, 8 bar.

(C) Postulated mechanism for methane formation on an open Zr-site at the UiO-67-Pt Zr-node. Reproduced with permission from Gutterød et al.⁸³ Copyright © 2020, American Chemical Society.

Wang et al. loaded ZnO onto Zr-based MOFs to obtain ZnO/Zr₁₂-bpdc for the hydrogenation of CO₂ to methanol.⁸⁴ The Zr-based MOFs contained Zr₁₂(μ₃-OH)₈(μ₃-OH)₈(μ₂-OH)₆ clusters, which were connected by linear biphenyl dicarboxylate (bpdc). The resulting ZnO/Zr₁₂-bpdc catalysts showed STY of up to 110 mg_MeOH g_cat⁻¹ h⁻¹ or 440 mg_MeOH g_Zn⁻¹ h⁻¹ and more than 95% selectivity for methanol at 250°C, 4 MPa. In this work, the ZnO/ZrO₂ interface was replaced by the contact between ZnO and Zr₁₂ clusters in MOFs, providing insights into the chemical structure of the active sites in ZnO/ZrO₂ catalysts. Musyoka et al. used Cu-ZnO catalysts supported on an aluminum fumarate metal-organic framework (AlFum MOF) for CO2 hydrogenation to methanol.⁸⁵ The Cu and Zn active sites of the catalyst showed homogeneous dispersion. SEM, SEM-EDS, and TEM revealed that the morphology of the support is preserved after metal loading. The catalyst exhibited good activity with a doubling of Cu and Zn loading over AlFum MOF, leading to an increase in CO₂ conversion from 10.8% to 45.6% and methanol yield from 34.4 to 56.5 g_MeOH kg_cat⁻¹h⁻¹. The performance of catalysts loaded on AlFum MOF reveals that MOF has great promise for application in thermocatalytic conversion.

In addition to preparing catalyst support, MOFs can be used as a precursor for direct pyrolysis to prepare MOFs-based catalysts, which form porous carbon nanomaterials by heat treatment. In 2011, Xu et al. prepared nanoporous carbon materials with high specific surface area using zeolite-type MOFs as a precursor and templating agent and furfuryl alcohol as a second precursor.⁸⁶ Gascon et al. first applied this strategy to CO₂ hydrogenation to methanol.⁸⁷ They subjected indium-impregnated ZIF-67 to stepwise pyrolysis-oxidative decomposition to obtain In₂O₃@Co₃O₄ reticulated-shell composites with nanostructures. Under reaction conditions, the material underwent structural reorganization, transforming from Co₃O₄ with an amorphous In₂O₃ shell to layer-covered Co₃InC_0.75 consisting of a mixture of amorphous CoO_x and In₂O₃ oxides. Amorphous mixed cobalt-indium oxide shells lead to high yields and selectivity for methanol. The material can reach a maximum methanol production rate of 0.65 g_MeOH·g_cat⁻¹·h⁻¹.

Recently, Wu et al. prepared a series of ZrO₂@HKUST-1 composites, which were thermally decomposed to obtain Cu-ZrO₂ catalysts with highly dispersed Cu nanoclusters. These catalysts have high dispersion and large Cu-ZrO₂ interfacial area, which provided improved catalytic performance.⁸⁸ The results of experimental and DFT studies showed that the Cu-ZrO₂ interface not only activated CO₂ but also stabilized the intermediates, indicating that the interface plays a crucial role in the conversion of CO₂ and the selective generation of methanol. Jin et al. prepared highly dispersed copper/graphene catalysts using HKUST-1 as a template agent.⁸⁹ The graphene/Cu/Zn catalysts were first prepared and calcined at 800°C in nitrogen to obtain GCZ4-800 catalysts. Calcination resulted in uniform dispersion of Cu active centers on graphene. The synergistic effect of graphene and HKUST-1 enhanced the specific surface area of the catalyst, the reducibility of the Cu active centers, and the adsorption capacity for H₂ and CO₂. Compared with the traditional impregnation method, this strategy solved the problems of uneven distribution of active centers and low loading. It provided a new method to achieve the control of metals on carriers.

The MOFs direct pyrolysis strategy cannot only enable nanoparticles to inherit precursor morphology but also integrate multiple functionalities. Bimetallic MOF templates offer unique advantages, such as interfacing with catalytically active metals and enhancing synergetic effects and stability through "solid solution" or "core-shell" structures. Song et al. synthesized bimetallic CuZn-BTC catalysts by a modified one-pot solvothermal method.⁹⁰ The Cu-ZnO^MOF/Al₂O₃ catalysts achieved 86.9% methanol selectivity and 407.2 g_MeOH⁻¹kg_cat⁻¹h⁻¹ methanol STY at 240°C and 3.0 MPa. Characterization by TEM, XPS, EDX, in-situ DRIFTS, chemisorption and programmed warming desorption showed that the novel Cu-ZnO^MOF/Al₂O₃ catalysts have high Cu dispersion on the surface, surface-enriched ZnO and a high number of Cu-ZnO interfacial sites, which improve the adsorption and activation capacity of the catalysts for CO₂ and H₂. This work provides new ideas for optimizing the activity and selectivity of amorphous Cu/ZnO/Al₂O₃ catalysts in CO₂ hydrogenation to methanol reaction. Li et al. synthesized Pd@In₂O₃ catalysts using TCPP(Pd)@MIL-68(In) as a sacrificial templating agent to enhance the dispersion of Pd⁰ species over In₂O₃ and to prevent the formation of the In-Pd super reduced phase (Figure 12A).⁹¹ Under the conditions of 295°C and 3 MPa, the Pd/In₂O₃ catalyst exhibited a maximum methanol STY of 81.1 g_MeOH g_Pd⁻¹ h⁻¹, with CO₂ conversion of 8.0%, and 81% methanol selectivity (Figure 12B). The experimental results indicate that the degree of reduction of In₂O₃ can be controlled by regulating the electronic interactions between Pd and In₂O₃ to improve the methanol selectivity. This study provides a method for designing highly active methanol synthesis catalysts.

Using MOFs sacrificial templating agent to enhance the dispersion of Pd⁰ species over In₂O₃

(A) Fabrication Routes of Pd²⁺/MIL-68(In) and TCPP(Pd)@MIL-68(In) Composites and the Derived IWI-Pd/In₂O₃ and Pd@In₂O₃ Catalysts (B) a Catalytic performance of various Pd-In₂O₃ catalysts, b catalytic performance of Pd@ In₂O₃ catalysts prepared under varied calcination temperatures, c time of stream of Pd@ In₂O₃-600, and d IWI-Pd/In₂O₃ catalyst under standard reaction conditions. Reproduced with permission from Cai et al.⁹¹ Copyright © 2022, American Chemical Society.

MOFs pyrolysis can also be used to form unique catalyst structures. Ma et al. prepared hollow Cu@ZrO₂ catalysts for CO₂ hydrogenation to methanol by pyrolyzing Cu-loaded Zr-MOFs.⁹² Firstly, MOF808 precursor was prepared, and Cu was loaded on the precursor and then calcined at different temperatures. CM-300 obtained by calcination at 300°C was the best catalyst for CO₂ hydrogenation to methanol, with a CO₂ conversion of 5% and methanol selectivity of 85% at 220°C. The Cu nanoparticles generated by low-temperature pyrolysis had highly dispersed Cu⁰/Cu⁺ equilibrium sites, a large number of surface basic sites, and abundant Cu-ZrO₂ interfaces, which contributed to the enhancement of the catalyst’s CO₂ adsorption/activation and selective hydrogenation to methanol.

Mo-based catalyst is an efficient catalyst for CO₂ hydrogenation to methanol.⁹³^,⁹⁴^,⁹⁵ Li et al. synthesized Mo-Co-C-N catalysts using ZIF-67 as a precursor for CO₂ conversion to methanol.⁹⁶ The highest methanol STY was achieved by Mo-Co (2:1)-C-N (800) catalysts at 275°C and 2 MPa,. The formation of Mo₂C and Co₆Mo₆C₂, formed during catalyst preparation, can be used as active phases for RWGS and methanol synthesis reactions. The experimental results showed that the formation of more oxygen vacancies at higher roasting temperature (800°C) can promote CO₂ desorption and improve methanol selectivity. In-plane sulfur vacancies in MoS₂ nanosheets have been identified as efficient catalytic active sites for methanol synthesis from CO₂, while edge vacancies facilitate CO₂ to methane. Zeng et al. prepared boxlike assemblages of quasi-monolayer MoS₂ nanosheets (h-MoS₂/ZnS) by a solvothermal route of MOFs bonding and subsequent thermal treatment (Figure 13).⁹⁷ With the increased exposure of in-plane sulfur vacancies and decreased occurrence of edge sulfur vacancies, h-MoS₂/ZnS exhibited impressive performance, achieving methanol selectivity of 67.3% and CO₂ conversion of 9.0%, with methanol STY as high as 0.93 g_MeOH g_MoS2⁻¹ h⁻¹ at 260°C, 5 MPa. The presence of ZnS can effectively prevent reacting molecules from accessing the sulfur vacancies at the edges of MoS₂ nanosheets, thus improving the selectivity of the target product methanol. This study not only provides a MOFs-involved route for the preparation of hollow quasi-monolayer MoS₂ nanocartridge catalysts but also develops a new method to block or generate the edge sulfur vacancies, which offers fresh perspectives on enhancing CO₂ hydrogenation to methanol conversions.

Schematic illustration of the hollowing synthetic route: formations of h-ZnMoS_x, h-MoS₂/ZnS, and h-MoS₂, starting from their precursor ZIF-8 nanocubes

Reproduced with permission from Zhou et al.⁹⁷ Copyright © 2022, American Chemical Society.

The Cu-ZnO interface concentration is an essential factor in the hydrogenation of CO₂ to methanol catalyzed by the Cu/ZnO catalyst. Li et al. prepared a Cu/ZnO catalyst (CuxZnO-MOF-74-350) with a Cu-rich-ZnO interface using the Cu-Zn bimetallic MOFs template method (x is the Cu/Zn feed ratio).⁹⁸ At 210°C, 4 MPa, when the feeding Cu/Zn ratio was optimized as 1:1, the catalyst exhibited a CO₂ conversion of 6.3% and a methanol STY of 0.29 g·g_cat⁻¹·h⁻¹. Combined with TEM, HRTEM, chemisorption, and EPR, it was concluded that a suitable Cu/Zn ratio is favorable to improve the adsorption and activation of H₂ and CO₂, and the ordering of Cu and Zn, which results in a rich Cu-ZnO interface and promotes the formation of methanol. Similarly, Li et al. prepared a highly efficient and stable CO₂ hydrogenation to methanol catalyst (Cu/ZnO_x/ZrO₂) by co-precipitation and pyrolysis using UiO-66 as a template agent.⁹⁹ The STY of methanol on the Cu/ZnO_x/ZrO₂ catalysts was as high as 216.7 g_MeOH kg_cat⁻¹ h⁻¹ at 260°C and 4 MPa. The UiO-66-derived ZrO₂ carrier enhanced the interaction between the carrier and Cu/Zn, significantly improving the catalytic performance. In this study, the catalytic effect was enhanced by pyrolysis to decompose the MOFs material to expose more active sites.

The loading of active components in MOFs-based catalysts can be controlled simply by the deposition-precipitation method. Mao et al. prepared a series of Cu@UiO-67 catalysts with different Cu loadings by deposition-precipitation method using, and then the Cu@ZrO₂-U obtained by pyrolysis Cu@UiO-67 was used forCO₂ hydrogenation to methanol.¹⁰⁰ Among them, 20-Cu@ZrO₂-U catalysts exhibited the best catalytic activity at 3 MPa and 260°C, and the STY of CH₃OH reached 2.28 mmol_CH3OH g_cat⁻¹ h⁻¹. The three-dimensional skeleton with UiO-67 in the Cu@ZrO₂-U catalyst immobilized highly dispersed copper nanoparticles, and the CuO₂-ZrO₂ interface was obtained by controlling the copper content, which enhanced the synergistic effect of copper and ZrO₂-U, thus significantly improving the catalytic activity. The in situ DRIFTS results indicate that the methanol synthesis via CO₂ hydrogenation on 20-Cu@ZrO₂-U follows the HCOO^∗ intermediate reaction pathway.

In₂O₃-based catalysts hold promise in CO₂ hydrogenation to methanol with high selectivity, yet low conversion hinders their practical use. He et al. report an In-Co-Zn/C-N catalytic system for hydrogenating CO₂ to methanol.¹⁰¹ The In-Co-Zn/C-N-4 (PM) has high conversion and stability and was found to keep a stable STY of 3.3 mmol g_cat ⁻¹ h ⁻¹ for methanol over a 50 h period at 2 MPa and 300°C. Since cobalt-indium carbide inhibits methanol production, ZnO weakens the interaction between Co and In to some extent and inhibits the formation of Co₃InC_0.75, which enhances the selectivity of methanol. Due to its high activity, the In₂O₃/ZrO₂ catalyst is widely used in methanol synthesis, yet the electronic interactions at its interface remain elusive. Hu et al. obtained In₂O₃@ZrO₂ with a hollow structure and abundant In₂O₃/ZrO₂ heterointerfaces by pyrolysis of the mixed MOFs precursor MIL-68@UiO-66.¹⁰² The In₂O₃@ZrO₂ catalyst exhibited an activity of 0.29 g_MeOH g_cat⁻¹ h⁻¹ at 290°C and 3.0 MPa. Mechanistic studies have shown that the electrons at the In₂O₃@ZrO₂ heterogeneous interface tend to be transferred from ZrO₂ to In₂O₃ due to strong interactions to generate electron-rich In₂O₃, which promotes the conversion of HCOO∼^∗ to CH₃O∼^∗ in the process of methanol synthesis. This work reveals the key role of heterointerfaces in regulating the activity and selectivity of CO₂ hydrogenation to methanol.

Methanol can also serve as a reaction intermediate to generate other high-value chemicals. In recent years, many studies have combined MOFs-based catalysts with molecular sieves to modulate the product distribution of CO₂ hydrogenation. Zhang et al. prepared ZnZrO_x/SAPO-34@UiO-n (n = 66, 66-NH₂, and 67) tandem catalysts for the catalytic conversion of CO₂ to light olefins.¹⁰³ They coated UiO-n shells on monodisperse SAPO-34 zeolites and physically mixed them with ZnZrO_x by grinding to obtain ZnZrO_x/SAPO-34@UiO-n catalysts. ZnZrO_x/SAPO-34@UIO-66 showed the highest light olefin selectivity (80%) at 380°C, 3 MPa, and it was found that the type of UiO-n membrane could influence the CO₂ hydrogenation product distribution. Dusselier et al. obtained an In-Zr/zeolite hybrid catalyst by directly calcinating MOFs ((Zr)Ui0-67-bipy-In) in the presence of zeolites.¹⁰⁴ The excellent dispersion and low loading of MOFs-derived In-Zr oxides complemented by the strong acidity of rhodochrosite-type zeolites allowed the combination of the activation of CO₂ with the C-C coupling at the employed GHSV conditions to have high STY of light olefins at 375°C. This work reports for the first time the use of small-pore zeolites as acid catalysts instead of zeolite types, demonstrating the importance of acid strength and acidity control by varying the Si/Al ratio for catalyzing CO₂-methanol-olefin cascades.

More recently, Wu et al. obtained Cr₂O₃ catalysts with high oxygen vacancy (O_v) density by sequential carbonization and oxidation (SCO) of chromium-based MOFs (Figure 14).¹⁰⁵ The methanol selectivity of the Cr₂O₃/C-500-500 catalyst was as high as 98.1% at 350°C, 3 MPa with 16.8% CO₂ conversion due to O_v enrichment. Subsequently, they combined the Cr₂O₃/C catalyst with acidic H-ZSM-5 to realize the direct conversion of CO₂ to aromatics. This work provides a synergistic strategy for improving the performance of CO₂ hydrotreating to aromatics by the cooperation of plenty of O_v in reducible metal oxide, unique accessibility of reactants to O_v active sites, and ingenious Al location in zeolite channels. Later, Wu et al. further combined the above Cr₂O₃/C with Cu-doped H-ZSM-5^T to convert CO₂ directly to paraxylene (PX).¹⁰⁶ The PX selectivity and STY achieved 33.8% and 3.0 g_CH2 kg_cat⁻¹ h⁻¹, respectively, by the bifunctional catalysts Cr₂O₃/C & Cu-ZSM-5^T@SiO₂. This study provides a bifunctional catalyst design strategy for CO₂ hydrogenation into targeted products.

Fabrication procedure of SCO-derived Cr₂O₃ catalyst

Reproduced with permission from Wang et al.¹⁰⁵ Copyright © 2023, John Wiley and Sons.

MOFs-based catalysts for modified-FTS of CO₂ conversion

In addition to the methanol intermediates, the modified Fischer-Tropsch route (RWGS+FTS) is another CO₂ hydrogenation route in which CO₂ is first reduced to CO by the reverse water gas shift (RWGS) reaction. Then, CO is converted by the Fischer-Tropsch synthesis (FTS) reaction. In recent years, breakthroughs have been made in producing high-value chemicals by the modified Fischer-Tropsch route. The catalytic activities of MOFs-based catalysts for CO₂ hydrogenation via the modified Fischer-Tropsch route are summarized in Table 3.

Table 3.

Summary of the catalytic performance of MOFs and MOFs-derived catalysts for CO₂ hydrogenation by modified Fischer-Tropsch route reported in recent years

Entry	Catalyst	T (^oC)	P (MPa)	GHSV (mL g_cat⁻¹ h⁻¹)	H₂/CO	X_CO2 (%)	S_CO (%)	S_CH4 (%)	Desired product (%)	Reference
1	Na-Fe@C& H-ZSM-5-0.2 M	320	3	9000	3	15.5	55.5	49	8.2 of aromatics	Wang et al., 2020¹⁰⁸
2	Na-Fe@C/H-ZSM-5-0.2 M	320	3	9000	3	13.3	13.3	4.8	50.2 of aromatics	Wang et al., 2020¹⁰⁸
3	Na-Fe@C\|\| H-ZSM-5-0.2M	320	3	9000	3	29.5	15	7.3	46.1 of aromatics	Wang et al., 2020¹⁰⁸
4	2%Na-Fe@C/CuZnAl	320	5	4500	3	37.1	9.2	3.5	28.6 of ethanol	Wang et al., 2021¹⁰⁹
5	2%Na-Fe@C/5%K-CuZnAl	320	5	4500	3	39.2	9.4	4.7	35.0 of ethanol	Wang et al., 2021¹⁰⁹
6	MnFe/C	400	2	12000	3	37.6	28.3	16.78	57.9 of C₅₊	Yang et al., 2023¹¹⁰
7	ZnFe/C	400	2	12000	3	40.6	22.9	26.68	40.5 of C₅₊	Yang et al., 2023¹¹⁰
8	NiFe/C	400	2	12000	3	45.9	12.0	52.36	30.8 of C₅₊	Yang et al., 2023¹¹⁰
9	Fe/C	400	2	12000	3	46.1	15.8	15.12	59.6 of C₅₊	Yang et al., 2023¹¹⁰
10	Na-Fe@C-3D-sta	320	3	9000	3	32.1	17.2	23.5	48.5 of C₂⁼∼C₄⁼	ang et al., 2024¹¹¹
11	Na-Fe@C-3D-str	320	3	9000	3	39	15.9	23.8	48.9 of C₂⁼∼C₄⁼	Wang et al., 2024¹¹¹
12	Na-Fe@C-3D-spi	320	3	9000	3	38.5	16.6	23.7	50.7 of C₂⁼∼C₄⁼	Wang et al., 2024¹¹¹
13	Na-Fe@C	320	5	9000	3	25.5	22.2	17.3	12.0 of ethanol	Wang et al., 2023¹¹²
14	Na-ZnFe@C	320	5	9000	3	38.4	7.6	15	20.3 of ethanol	Wang et al., 2023¹¹²
15	Na-CuFe@C	320	5	9000	3	33.9	6.1	11.1	15.0 of ethanol	Wang et al., 2023¹¹²
16	Na-MnFe@C	320	5	9000	3	33.1	10.6	14.9	13.4 of ethanol	Wang et al., 2023¹¹²
17	Na-CoFe@C	320	5	9000	3	30.4	11.3	14.4	12.0 of ethanol	Wang et al., 2023¹¹²

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In 2015, Makkee and Gascon et al. used MOFs-derived Fe-based catalysts for the first time to produce high-value chemicals via the FTS route.³⁶ Subsequently, in 2018, Gascon et al. prepared a highly active, selective, and stable Fe-based catalyst by pyrolysis of MOFs doped with different metal promoters to investigate its CO₂ hydrogenation performance.¹⁰⁷ The promoter-added catalyst achieved a high STY of C₂-C₄ olefins of 33.6 mmol g_cat⁻¹ h⁻¹ and CO₂ conversion of 40%, at 320°C and 3 MPa. The results showed that only K could significantly improve the selectivity of olefins in the reaction products among the different metal promoters.

Recently, Tsubaki et al. prepared Na-modified Fe-based catalysts by pyrolysis of Fe-MOFs and combined them with hollow acidic zeolite H-ZSM-5 to obtain bifunctional catalysts for one-pass conversion of CO₂ hydrotreating to aromatics (Figure 15).¹⁰⁸ The Fe-based catalyst portion of the bifunctional catalyst has abundant high-activity sites and special catalytic interfaces, which is conducive to the enhancement of CO₂ activation efficiency and the formation of olefin intermediates. The generated olefins diffuse into the acidic sites of H-ZSM-5 and are converted into aromatics via a dehydroaromatization reaction. The synergistic effect of the modified Fe-based catalysts and molecular sieves in this strategy significantly improved the selectivity of aromatics synthesis in CO₂ conversion. The carbon layers enhance the dispersion of Fe-based nanoparticles derived from MOFs, preventing aggregation during the catalytic process. It provided experience in catalyst design for the preparation of high-value-added products by CO₂ hydrogenation.

Combining Fe-based catalyst obtained from MOFs pyrolysis and acidic zeolite H-ZSM-5 for CO₂ hydrogenation to aromatics

(A) Catalytic performances of 1-hexene conversion over H-ZSM-5-0.2 M, Na-Fe@C^∗/H-ZSM-5-0.2 M (Na-Fe@C^∗ represents the used Na-Fe@C), and Na-Fe@C^∗/H-ZSM-5 under N₂ or CO₂ atmosphere. Reaction conditions, 320 °C, 2 MPa, catalyst weight 1 g zeolite and 0.33 g Na-Fe@C^∗, liquid 1-hexene flow rate 0.005 mL min−1, TOS = 8 h.

(B) Schematic representation of the cooperative interplay between the multifunctional catalyst for the enhanced aromatics synthesis from CO₂ hydrogenation. Reproduced with permission from Wang et al.¹⁰⁸ Copyright © 2020, Elsevier.

Later, Wang et al. obtained a novel multifunctional catalyst for CO₂ hydrogenation by combining Na-Fe@C with K-doped CuZnAl. (Figure 16).¹⁰⁹ They realized the direct conversion of CO₂ to ethanol and, simultaneously, could generate high-value olefins. The experimental results showed that the unique catalytic interface, close synergy, and aldehyde intermediates of the multifunctional catalyst played essential roles in the efficient conversion of CO₂ to ethanol. In addition, the catalyst has considerable potential for industrial applications due to its advantages of easy preparation, low cost, and easy recycling.

Schematic diagram of the direct conversion of CO₂ to ethanol

Reproduced with permission from Wang et al.¹⁰⁹ Copyright © 2021, American Chemical Society.

In order to study the effect of metal additives on the physicochemical properties and catalytic performance of Fe-based catalyst during CO₂ hydrogenation, Yu et al. prepared a series of transition metal M (M = Zn, Ni, Mn) modified Fe-based catalysts (MFe/C) by pyrolysis of MOFs for CO₂ hydrogenation.¹¹⁰ The Mn-doped Fe-based catalysts exhibited optimal catalytic performance with 37.60% CO₂ conversion and C₅₊ STY of 0.27 mol g_cat⁻¹ h⁻¹ under the reaction conditions of 400°C, 2.0 MPa. The metal additives Zn and Mn were able to promote the formation of the Fe₅C₂ active phase on the Fe-based catalysts, with the difference that Mn inhibited the secondary hydrogenation of olefins, while Zn enhanced the secondary hydrogenation of olefins. In addition, the content of specific Fe sites in Fe₅C₂ was found to be related to O/P and olefin selectivity. This study provides new ideas for designing catalysts with high catalytic performance regarding the effects of different metal additives on the active sites of Fe-based catalysts.

In practical reactions, catalysts often need to be formulated into pellets or monoliths for optimal mass and heat transfer. However, existing MOFs-based catalysts are often carbonaceous powders, making it challenging to shape them into suitable forms. Wang et al. fabricated Fe-based monolithic catalysts with excellent catalytic properties and specific structures by direct ink writing (DIW)-style 3D printing (Figure 17).¹¹¹ The helically structured Fe-based monolithic catalysts exhibited 52.6% light olefin selectivity and 451.8 g_CH2 kg_cat⁻¹ h⁻¹ STY at 320°C, 3 MPa. The mass transfer simulation results indicate that the helically structured channels in the Fe-based monolithic catalysts are able to optimize the mass transfer by reducing the coverage of intermediates and products at the catalytic interfaces. This results in efficient utilization of the active centers and timely termination of the carbon chain growth. Density Functional Theory (DFT) showed that the relatively electron-rich catalytic interface and lower intermediate coverage could promote olefin desorption and inhibit the further growth of carbon chains, thus synergistically enhancing the synthesis performance of low-carbon olefins. As a result, the structure enhances the mass and heat transfer and avoids active site aggregation and carbon deposition, significantly improving the catalytic performance. This strategy also provides a new concept for modulating the CO₂ hydrogenation performance of Fe-based catalysts, and it can be generalized to the rational design of other catalytic materials.

Schematic illustration for the fabrication of Fe-based monolithic catalysts via 3D printing technology

Reproduced with permission from Wang et al.¹¹¹ Copyright © 2023, Elsevier.

The electronic properties of a catalyst play a crucial role in determining the adsorption strength and configuration of key intermediates, thereby influencing the reaction network for targeted synthesis. Wang et al. balanced the electronic properties of Fe species by adding a carbon buffer layer on the ternary catalytic component ZnO_x-Fe₅C₂-Fe₃O₄ (Figure 18).¹¹² This layer neutralizes excessive electrons transferred from ZnO_x to Fe species. The unique electronic properties, characterized by appropriate CO adsorption strength and C-C coupling barrier, facilitate ethanol synthesis via the -CO∗ insertion mechanism. This mechanism differs from the common ZnO_x-Fe₅C₂-Fe₃O₄ catalyst, which primarily produces alkenes or alkanes. The moderate CO adsorption strength on Fe₃O₄ and Fe₅C₂ and the low C-C coupling capacity between -CH₂^∗ and -CO^∗ on Fe₅C₂ synergistically resulted in an ultra-high ethanol STY of up to 366.6 g_EtOH kg_cat⁻¹h⁻¹ for CO₂ hydrogenation with a total addition of 10 Vol % CO. This study’s carbon-based electron buffering strategy provides new ideas for the design of other electronic property-sensitive catalytic materials to achieve efficient catalytic performance.

Theoretical simulation and mechanism analysis of ethanol synthesis via Fe-based catalysts

(A) Differential charge density plots of Fe₅C₂(510)/C, ZnO− Fe₅C₂ (510)/C, and ZnO− Fe₅C₂(510) models. The yellow and cyan electron clouds represent the accumulation and depletion of electrons, respectively.

(B) The valence electron number of Fe species in the three models.

(C) Energy profiles of −CO^∗ species evolution, C−C coupling, and the following hydrogenation processes on the three models. Key: transition state (TS), Fe (purple), C (dark gray), Zn (yellow), O (red), H (white).

(D) Schematic diagram of the electron-buffering effect for ethanol synthesis from CO₂ hydrogenation. Reproduced with permission from Wang et al.¹¹² Copyright © 2023, John Wiley and Sons.

MOFs-based catalysts for CO₂ hydrogenation to CH₄

CO₂ methanation, also known as the Sabatier reaction, was initially discovered by Paul Sabatier in 1902 and has since been extensively researched. This process is highly exothermic and thermodynamically favorable. Thermodynamically, the reaction is limited by thermodynamic equilibrium at high temperatures, and low temperature is conducive to positive reaction. Kinetically, however, the reaction rate of CO₂ methanation is relatively slow at lower temperatures, prolonging the production cycle. Consequently, the quest for novel and highly active catalysts is crucial to enhancing the yield of this reaction. Historically, metals such as Ni, Co, Ru, and Rh, supported on diverse supports., have demonstrated remarkable activity in CO₂ methanation.¹¹³^,¹¹⁴ Recently, MOFs have emerged as auspicious porous materials for CO₂ methanation reactions. Their unique properties offer countless possibilities for further enhancement and development, holding great promise for maximizing the production of renewable CH₄.

As far as we know, the initial investigation of the application of MOFs in CO₂ methanation was reported by Zhen et al. in 2015.¹¹⁵ In their study, a series of highly active catalysts xNi@MOF-5 for CO₂ methanation were prepared by impregnation methods. Notably, the 10Ni@MOF-5 catalyst demonstrated unexpectedly superior activity compared to the reference catalyst Ni/SiO₂ at low temperatures ranging from 180°C to 320°C. Comprehensive characterization studies revealed that the uniform dispersion of Ni within the MOF-5 framework is the key factor underlying this remarkable activity enhancement. Furthermore, the 10Ni@MOF-5 catalyst demonstrated remarkable stability, exhibiting minimal deactivation during long-term stability tests lasting up to 100 h. These findings highlight MOF-5 as a promising and innovative support material for preparing CO₂ methanation catalysts.

Ni/CeO₂ is a highly active catalyst for CO₂ methanation, but its performance often suffers from nanocrystal coarsening at high temperatures.¹¹⁶ To overcome this, Feng et al. designed a novel Ni/CeO₂ catalyst using Ce-based MOFs as a template (Figure 19).¹¹⁷ This approach confinement effect of the MOF’s ultra-small pores led to ultrafine Ni nanoparticles, excellent dispersion, and robust thermostability. Among the samples, the catalyst calcined at 600°C emerged as the most effective due to its abundant oxygen vacancies, which helped improve the CO₂ adsorption ability and the catalytic performance toward CO₂ methanation. This study presents a concise method for synthesizing ultrafine metal/metal oxide nanocomposite catalysts with superior catalytic activity and stability for diverse applications.

Simple illustration of the synthesis procedure of Ni/CeO₂.¹¹⁷ Copyright © 2021, Elsevier

Carbon capture and conversion are often separate processes, with sorbents handling CO₂ enrichment and catalysts facilitating its transformation. Zurrer et al. introduced NiMg-CUK-1, a dual-functional MOFs, that seamlessly integrates both tasks.¹¹⁸ By regulating the thermal stability of its Ni and Mg components, Ni nanoparticles are selectively formed within the Mg-rich framework. Optimization of the Ni: Mg ratio and treatment temperature boosts catalytic performance while maintaining CO₂ capture abilities. NiMg-CUK-1 efficiently captures CO₂ at ambient temperature and converts it to CH₄ under mild conditions (250°C) in a dual-mode reactor. After five cycles, it stably captures 1.46 ± 0.24 mmol CO₂ g⁻¹ and produces 1.52 ± 0.23 mmol CH₄ g⁻¹, similar sorbent-based catalysts reliant on the chemical looping of metal oxides and carbonates. This approach offers a new route for combined CO₂ capture and conversion using a dual-functional material for efficient low-temperature CO₂ desorption and CH₄ production.

MOFs' ordered and tunable properties make them promising precursors for CO₂ methanation catalysts. However, the role of promoters still needs to be explored. Li et al. developed a carbon-encapsulated NiFe alloy nanoparticle core-shell catalysts (Ni_xFe@C) prepared by impregnating Ni-MOF-74 in Fe³⁺ solution and subsequent pyrolysis.¹¹⁹ Fe-doped catalysts showed enhanced CO₂ methanation activity over monometallic Ni, with Ni₇Fe@C achieving 72.3% CO₂ conversion and 99.3% CH₄ selectivity at 350°C. At 300°C, CO₂ conversion was 53.3%, double that of Ni@C. Experimental and DFT studies revealed that Fe incorporation improved metal particle dispersion, CO₂ and CO adsorption, leading to superior catalytic performance. This work offers a promising approach for the rational design of MOFs-derived CO₂ methanation catalysts and highlights the influence of promoters.

Regarding oxygen binding energy, Ru is one of the most promising catalysts for CO₂ methanation.¹²⁰ Recently, Loccufier et al. studied a catalytic membrane consisting of a silica nanofibrous structure as a carrier for Ru nanoparticles encapsulated within the MOFs Cr-MIL-101 (Figure 20).¹²¹ This membrane was investigated for the Sabatier methanation reaction. Electrospinning of tetraorthosilicate (TEOS) sol resulted in a thermally stable silica nanofibrous structure (up to 1100°C) with pores in the μm-range, enhancing gas throughput with reduced pressure requirements. A simple dip-coating method was used to deposit Ru@MIL-101 on the carrier, preventing Ru clustering. The catalytic membrane demonstrated an impressive turnover frequency of 3257 h⁻¹ at 250°C, paving the way for structured reactors in efficient CO₂ hydrogenation processes. This system therefore paves the way toward structured reactors for efficient CO₂ hydrogenation processes.

Scheme of the incorporation of silica nanofibrous veils as support for MIL-101 nanostructures loaded with Ru nanoparticles to catalyze the hydrogenation of CO₂ to CH₄.¹²¹ Copyright © 2023, Elsevier

It is well-established that MOFs-derived metal oxides often maintain the morphology of their precursor MOFs. However, Fan et al. demonstrated a novel approach to modulate the morphology of ZIF-67-derived Co₃O₄ from 3D dodecahedrons to 0D nanospheres by growing them over 1D TiO₂ nanowires (NWs).¹²² This transformation is attributed to the disruption caused by the 1D TiO₂ NWs, which decompose the dodecahedral structure and disperse the Co₃O₄ nanoparticles. The nanocomposite Insitu-10N7CT achieves a high CO₂ conversion (97.42%) and CH₄ selectivity (99.29%), surpassing its mechanically assembled counterpart M−10N7CT (X_CO2 = 91.45%, S_CH4 = 98.42%). This enhancement is attributed to the intimate interfacial contact between the multi-dimensional Ni, 0D Co₃O₄, and 1D TiO₂ NWs, achieved by uniform dispersion of Co₃O₄ along the TiO₂ NWs. Due to the strong interfacial contact, metallic/metal oxide Ni-Co throughout the nanocomposite introduces additional oxygen vacancies, enhancing catalytic performance and potentially altering the methanation reaction mechanism.

In summary, MOFs-based catalysts exhibit both noteworthy advantages and challenges in the realm of CO₂ hydrogenation. Their primary advantage lies in the tunable nature of their structure, enabling precise engineering of the active site through the selection of metal ions and organic ligands. This design flexibility is pivotal in enhancing the catalytic activity and selectivity of the CO₂ hydrogenation. Furthermore, MOFs’ exceptional surface area and porosity facilitate reactant diffusion and mass transfer, thereby boosting catalytic performance. However, stability remains a significant challenge for MOF-based catalysts, often trailing behind traditional catalysts. MOFs may collapse or decompose under harsh reaction conditions, such as elevated temperatures and pressures, limiting their widespread application in CO₂ hydrogenation. Thus, they are primarily utilized as sacrificial precursor. Additionally, the synthesis of MOFs is often intricate and costly, demanding precise control of reaction conditions and raw material ratios. In conclusion, while MOF-based catalysts offer unique advantages in CO₂ hydrogenation, their stability and synthesis cost remain key challenges that must be addressed for industrial scalability and widespread implementation.

Methane conversion

Methane (CH₄) is a crucial fossil fuel widely found in various sources such as natural gas, shale gas, coalbed methane, combustible ice, and biogas.¹²³ However, the highest C-H bond strength (434 kJ mol⁻¹) among all alkanes, coupled with the low polarizability and negligible electron affinity, makes CH₄ the least reactive alkane. Therefore, the activation and conversion of methane remain a long-standing challenge in catalysis despite the numerous material classes and process variants that have been explored.¹²⁴^,¹²⁵

The primary strategies for methane conversion have been classified into two categories: the indirect routes via syngas and the direct conversion routes. The current industrial route for methane conversion is indirect. It primarily relies on reforming processes such as steam reforming methane (SRM), carbon dioxide (CO₂) reforming methane (CRM), and partial oxidation reforming methane (PORM). These processes generally require high pressure and high temperature. The direct methane conversion reactions mainly include partial oxidation of methane (POM), oxidative coupling of methane (OCM), and nonoxidative coupling of methane (NOCM). Direct methane conversion routes appear to be more favorable than reforming processes due to lower investment requirements, energy savings, and production costs. However, more efficient catalysts must be developed and utilized to improve their impractically low net yields of desired products. MOFs-based catalysts for POM and OCM have been reviewed elsewhere²⁴ and will not be included in this review. Metal/zeolite catalysts are widely used in NOCM, and a series of single-atom-based catalysts have been developed recently, but MOFs-based catalysts have yet to be reported.¹²⁶ Therefore, this section will mainly focus on the recent research progress of MOFs-based catalysts in methane reforming. The catalytic activities of several MOFs-based catalysts for methane reforming are summarized in Table 4.

Table 4.

Summary of MOFs-based catalysts for methane reforming

Entry	Catalysts	Reaction condition					Conversion (%)		H₂/CO	Reference
Entry	Catalysts	GHSV^a (mL g⁻¹ h⁻¹)	Feed gas ratio	T (^oC)	P (bar)	TOS (h)	CH₄	CO₂	H₂/CO	Reference
1	NiAl_MIL	72000	CH₄:CO₂:Ar = 5/5/90	650	1	100	74.0	80.0	1.03	Karam et al., 2021¹²⁷
2	Ni/Al_MIL	72000	CH₄:CO₂:Ar = 5/5/90	650	1	13	70.0	77.0	1.09	Karam et al., 2021¹²⁷
3	NiCo@C/Al₂O₃	60000	CH₄:CO₂:N₂ = 5/5/90	700	1	8	43.0	57.0	0.87	Liang et al., 2020¹³⁰
4	NiCo₂@C/Al₂O₃	60000	CH₄:CO₂:N₂ = 5/5/90	700	1	8	35.0	41.0	0.80	Liang et al., 2020¹³⁰
5	Ni-Co@CMOF-74	33000	CH₄:CO₂:N₂ = 1/1/1	700	5	10	49.0	58.0	–	Khan et al., 2021¹³¹
6	Ni-Co@CMOF-74	33000	CH₄:CO₂:N₂ = 1/1/1	750	5	10	60.0	69.0	0.82	Khan et al., 2021¹³¹
7	Ni-MgO@mSiO₂^MOF	36000	CH₄:CO₂ = 1/1	700	1	60	75.0	69.0	∼0.87	Wang et al., 2022¹³²
8	Ni-MgO/mSiO₂^NO3	36000	CH₄:CO₂ = 1/1	700	1	60	47.0	43.0	∼0.82	Wang et al., 2022¹³²
9	N₂-pyr	30000	CH₄:CO₂:N₂ = 1/1/2	700	1	24	70.0	83.0	0.98	Alli et al., 2023¹³³
10	H₂-pyr	30000	CH₄:CO₂:N₂ = 1/1/2	700	1	24	58.0	77.0	0.91	Alli et al., 2023¹³³
11	CO₂-pyr	30000	CH₄:CO₂:N₂ = 1/1/2	700	1	24	∼56.0	∼75.0	∼0.90	Alli et al., 2023¹³³
12	Ni/MCF	18000	CH₄:CO₂:N₂ = 1/1/2	600	1	25	∼24.0	∼34.0	∼0.64	Shen et al., 2023¹³⁴
13	Ni@C/MCF-650	18000	CH₄:CO₂:N₂ = 1/1/2	600	1	25	∼21.0	31.0	∼0.53	Shen et al., 2023¹³⁴
14	Ni@C/MCF-750	18000	CH₄:CO₂:N₂ = 1/1/2	600	1	25	∼48.0	52.4	∼0.67	Shen et al., 2023¹³⁴
15	NiCeO₂@C-SIM^b	235200	CH₄:CO₂:N₂ = 8/8/180 H₂O (L) = 0.18 mL h⁻¹	600	1	8	48.0	17.0	1.4	Tu et al., 2023¹³⁵
16	NiCeO₂@C-IM^b	235200	CH₄:CO₂:N₂ = 8/8/180 H₂O (L) = 0.18 mL h⁻¹	600	1	8	40.1	11.8	1.4	Tu et al., 2023¹³⁵

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Gas hourly space velocity.

Catalytic performance of bi-reforming of methane (BRM).

The methane reforming process generally requires high-temperature oxidation to synthesize syngas. In this regard, direct methane reforming on the original MOFs catalyst seems impossible, given its thermal stability. Therefore, using MOFs as sacrificial templates or catalyst precursors to prepare MOFs-derived catalysts is the main strategy for the application of MOFs-based catalysts in methane reforming. As far as we know, in 2019, Karam et al. were the first to use MOFs-based materials for methane reforming.¹²⁷ The MIL-53 (1130 m² g⁻¹) was used as a support precursor and a hard template, intimately mixed with the Ni precursor at the impregnation step, as depicted in Figure 21. The Al-OH groups and pores in the MOFs anchored the Ni precursor, and after a 500°C calcination in air, a porous Ni-Al solid solution formed. After reduction to a porous lamellar γ-Al₂O₃ material with small Ni nanoparticles homogeneously dispersed and stabilized within the support, leading to an outstanding catalytic stability with no activity loss during a 100 h reaction. This report revealed that MOFs could be used as a sacrificial template and porous host to stabilize metal species and obtain fine Ni particles. In addition, Karam et al. further compared another synthesis strategy of mesoporous Ni-alumina materials based on one-pot synthesis combined with the EISA method and summarized the critical characteristics of preparing efficient and stable Ni-aluminum catalysts for methane dry reforming.¹²⁸

Schematic summarizing the MOFs-based preparation route of the Ni-alumina catalyst (Ni_x-Al₂O_3-MIL-53) Reproduced with permission from Karam et al.¹²⁸ Copyright © 2019, Multidisciplinary Digital Publishing Institute

In addition to synthesizing MOFs as supports and impregnating Ni, MOFs containing Ni can be directly synthesized and then pyrolyzed to obtain MOFs-derived catalysts. Leong et al. synthesized a series of NH₂-MIL-88B with varying molar ratios of Ni:Ce (2:1–1:2), showing high DRM activity.¹²⁹ The addition of Ce promoted a smaller particle size of Ni, ranging from 4.6 nm to 6.88 nm. Within the range of the studied molar ratios, 1Ni2Ce showed the highest CH₄ and CO₂ conversion at 63.5% and 86.8%, respectively, at 800°C, further supporting the promotion of Ce. In addition to NiCo MOFs, Leong et al. also attempted in situ growth of NiCo MOFs on Al₂O₃ support, followed by pyrolysis to obtain NiCo@C/Al₂O₃ catalyst.¹³⁰ The catalyst’s basicity increases by incorporating Co into Ni. This enhancement boosts turnover frequencies, light-off stability, and operation stability toward catalytic dry reforming of methane. Gascon et al. also noted the possibility of Ni-Co bimetallic catalyst application in methane dry reforming.¹³¹ They explored using MOF-74/CPO-27 as precursors for synthesizing Ni, Co, and bimetallic Ni-Co metal nanoparticles. The bimetallic Ni-Co@CMOF-74 catalyst showed better catalytic results than monometallic materials due to the synergistic effect of Ni and Co that impedes the coke formation.

Another bimetallic catalyst, Li et al., using MOFs/SiO₂ composite precursor synthesized mesoporous Ni-MgO solid solution catalyst Ni-MgO@mSiO₂^MOF by one-pot calcination.¹³² The chemical interaction between bimetallic Ni-Mg@H4DOT and mSiO₂ gel was confirmed by ²⁹Si and ¹³C MAS NMR, demonstrating the successful synthesis of a Ni-MgO@mSiO₂ MOFs catalyst with outstanding catalytic activity, stability, and coke tolerance. This work is the first example of MOFs/SiO₂ composite with chemical interaction derived mesoporous silica confined Ni-MgO solid solution catalyst, which exhibits excellent performance and coke resistance for dry reforming of methane (DRM). The enhanced performance and coke resistance of the Ni-MgO@mSiO₂ MOFs catalyst can be attributed to the MOFs-templated strategy, which improves the dispersity of Ni species, enhances the interaction between Ni and Mg species, and inhibits the diffusion of Mg species into mSiO₂, thus preventing the formation of Mg₂SiO₄ and/or Mg-O-Si species. In addition, the MOFs/SiO₂ composite with chemical interaction serves as a precursor that improves the reduction degree of NiO and induces more reducible metallic Ni species with small size and strong metal-support interaction (SMSI) exsoluted from NiO-MgO-mSiO₂ compared with pristine NiO-MgO solid solution. Furthermore, the developed Ni-MgO@mSiO₂ MOFs catalysts exhibit higher reactant adsorption ability and accelerate the generation of more OH^∗ species on the surface of the catalyst, which contributes to the elimination of coke during the reaction process.

Different pyrolysis processes after MOFs synthesis also greatly influence the catalytic performance. Mahinpey et al. developed a novel catalyst synthesis scheme using a bimetallic Ni-Ce-BTC MOFs template to synthesize nanostructured Ni/CeO₂ catalysts.¹³³ Three different environments were used to remove the organic template during the thermal process. In addition, further catalyst thermal pre-treatment under a CO₂ environment was performed. The study results indicate that the catalyst labeled N₂-pyr, which underwent only heat treatment under nitrogen, exhibited the most favorable activity and higher stability. This catalyst showed no decline in activity after 24 h on stream, with CO₂ and CH₄ conversions of 83% and 70%, respectively. Meanwhile the catalysts treated thermally under a CO₂ atmosphere presented the lowest activity, attributed to weaker metal-support interaction, lesser dispersion, larger crystallite size (>10 nm), lesser Ce³⁺, and surface oxygen. These factors can influence the reducibility of the catalyst and its activity. Additionally, a stability test was carried out on the N₂-pyr catalyst for 120 h (5 days) on stream, and the results showed no catalyst deactivation or decline in activity or stability.

Methane dry reforming requires a high reaction temperature (generally above 700°C), and lower temperatures usually result in severe carbon deposition. Wang et al. successfully synthesized a carbon-confined Ni@C/MCF catalyst by carbonizing MOFs on MCF supports.¹³⁴ During the carbonization process in a N₂ flow, metallic Ni NPs were formed without needing a separate H₂ reduction step. The Ni@C/MCF-750 catalyst exhibited excellent catalytic performance at 600°C. The carbon layers effectively protected the Ni NPs from sintering and coking due to the confinement effect, thus effectively mitigating the challenges of deactivation caused by sintering and coking in DRM reactions.

MOFs-based catalysts can also be used for the bi-reforming of methane (BRM). Kung et al. incorporate catalytically active nickel into highly porous cerium(IV)-based MOFs using either conventional impregnation techniques or self-limiting post-synthetic modifications.¹³⁵ Subsequently, nanosized MOFs-derived ceria-supported nickel is prepared by carbonizing nickel-incorporated Ce-based MOFs. The crystallinity, porosity, nanostructural morphology, and surface properties of each MOFs and the resulting MOFs-derived materials are meticulously characterized, and as a demonstration, the MOFs-derived catalysts are used for BRM.

Certain conditions enable MOFs materials to serve as both chemically and thermodynamically stable supports. By loading PtNPs onto UiO-67, Vakili et al. achieved a plasma-assisted dry reforming process that transcended the thermodynamic limitations of dry reforming reactions. (Figure 22).¹³⁶ This breakthrough relies on the utilization of energetic electrons to activate reactive molecules rather than traditional thermal activation methods. The UiO-67, with exceptional porosity and surface area exceeding 2000 m² g⁻¹, exhibits exceptional stability under plasma conditions and promotes optimal dispersion of platinum particles. Furthermore, UiO-67 promotes plasma formation and surface discharges in the discharge zone, synergistically enhancing the conversion of CH₄ and CO₂ and syngas production.

Schematic diagram of the DBD plasma-catalytic reactor

Reproduced with permission from Vakili et al.¹³⁶ Copyright © 2020, Elsevier.

In conclusion, research on the catalytic conversion of methane using MOFs-based materials has only recently begun, and there are relatively few related reports. Compared with other leading catalysts such as zeolites, metal oxides, and metal alloys, there are still significant gaps in the stability and activity of MOFs-based catalysts. However, from the existing reports, the prospects for MOFs-based catalysts are still up and coming. MOFs materials possess several unique intrinsic features not found in other materials, making them particularly advantageous in catalyst design.

Conclusions and perspective

In this review, we provide a brief overview of the existing state of the art on using MOFs and MOFs-derived materials as catalysts or supports for C1 catalysis to produce valuable chemicals. As a relatively new class of porous materials, MOFs have attracted significant interest due to their high surface area, chemical versatility, and structural diversity. At the end of this review, we want to identify key technical challenges and suggest future research directions for MOFs and their derivates for the thermal-catalytic conversion of C1 molecules.

First and foremost, the poor stability of MOFs limits their practical application in C1 catalysis. The instability of MOFs can be attributed to the decomposition of their chemical structure under harsh conditions, making them unsuitable for long-term use. Currently, most research aims to produce MOFs-derived materials with higher thermal stability through thermal decomposition treatment. However, the thermal treatment process often sacrifices many of the properties and functions of the original MOFs. To address this challenge, exploring synthetic methods for more stable MOFs or advanced post-synthetic modifications that preserve the original characteristics of MOFs while enhancing their stability is essential. Additionally, utilizing more advanced reaction processes, such as plasma-assisted methods, to replace traditional thermal processes and maintain the stability of MOFs-based materials during reactions is a promising approach.

Secondly, the practical application of MOFs-based catalysts is challenging due to the difficulties in shaping them into particles with micron or centimeter-scale diameter. In practical reactions, especially in fixed-bed reactors, catalysts often need to be formulated into pellets or monoliths to achieve better mass and heat transfer. However, existing MOFs-based catalysts often exist as carbonaceous powders, making it challenging to architect them into suitable shapes. This problem can be addressed by exploring different shaping methods for MOFs-based catalysts. By employing novel techniques such as 3D printing, it may be possible to enhance the mechanical strength and durability of MOFs-based catalysts, making them more suitable for practical applications.

Additionally, utilizing MOFs as precursors for the preparation of bimetallic or trimetallic catalysts is a promising research direction in MOFs-based C1 catalysts. By combining different metals in a single catalyst, it may be possible to achieve improved catalytic activity and selectivity for the conversion of C1 molecules. This approach may provide a more cost-effective and sustainable alternative to traditional catalyst preparation methods. It could open up new avenues for the development of novel MOFs-based catalysts for C1 catalysis.

Finally, it is important to collaborate and share knowledge across different research fields to promote the development of MOFs-based catalysts for converting C1 resources into clean fuels or valuable chemicals. This collaboration can lead to innovative solutions and new applications in this field. For example, the expert with plentiful materials synthesis experience could increase the yield of MOFs high enough for ton-scale industrial application. During the large-scale synthesis process, chemical engineering issues should be considered thoroughly to ensure the uniform and stable crystal growth.

Even though many challenges remain and our understanding of these porous materials is still incomplete, it is believed that the design and synthesis of more functional MOFs materials with specific properties will promote the rapid development of C1 chemistry in the near future. We hope this review will provide valuable insights and suggestions for future research in this area.

Acknowledgments

This work was supported by the National Key Research and Development Program of China (2023YFB4104500, 2023YFB4104502), National Natural Science Foundation of China (22108310), the Science and Technology Innovation Project of the Shandong Energy Group Co., Ltd. (SNKJ2023A03).

Author contributions

S.Y.L.: Writing-Original Draft and Editing, Visualization. Y.J. C.: Writing-Original Draft and Editing, Visualization. H.Y.L.: Writing-Original Draft and Editing, Visualization. W.H.W.: Writing-Review & Editing. Y.W.: Writing-Review and Editing, Project administration. M.B. W.: Project administration.

Declaration of interests

The authors declare no competing interests.

Contributor Information

Yang Wang, Email: wangyang@upc.edu.cn.

Mingbo Wu, Email: wumb@upc.edu.cn.

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PERMALINK

Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion

Shiyuan Lin

Yongjie Chen

Huayong Li

Wenhang Wang

Yang Wang

Mingbo Wu

Summary

Introduction

Figure 1.

Figure 2.

CO conversion

MOFs-based catalysts for FTS

Table 1.

Co-MOFs derived FTS catalysts

Figure 3.

Figure 4.

Figure 5.

Fe-MOFs derived FTS catalysts

Figure 6.

Figure 7.

MOFs-based catalysts for methanol route of CO conversion

Figure 8.

CO2 conversion

MOFs-based catalysts for CO2 hydrogenation to CH3OH

Table 2.

Figure 9.

Figure 10.

Figure 11.

Figure 12.

Figure 13.

Figure 14.

MOFs-based catalysts for modified-FTS of CO2 conversion

Table 3.

Figure 15.

Figure 16.

Figure 17.

Figure 18.

MOFs-based catalysts for CO2 hydrogenation to CH4

Figure 19.

Figure 20.

Methane conversion

Table 4.

Figure 21.

Figure 22.

Conclusions and perspective

Acknowledgments

Author contributions

Declaration of interests

Contributor Information

References

ACTIONS

PERMALINK

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CO₂ conversion

MOFs-based catalysts for CO₂ hydrogenation to CH₃OH

MOFs-based catalysts for modified-FTS of CO₂ conversion

MOFs-based catalysts for CO₂ hydrogenation to CH₄