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. 2024 Mar 18;12(13):5197–5210. doi: 10.1021/acssuschemeng.3c08250

Intermediate Transfer Rates and Solid-State Ion Exchange are Key Factors Determining the Bifunctionality of In2O3/HZSM-5 Tandem CO2 Hydrogenation Catalyst

Fatima Mahnaz †, Jasan Robey Mangalindan †, Balaji C Dharmalingam ‡, Jenna Vito †, Yu-Ting Lin †, Mustafa Akbulut †, Jithin John Varghese ‡, Manish Shetty †,*
PMCID: PMC10988559  PMID: 38577585

Abstract

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Identifying the descriptors for the synergistic catalytic activity of bifunctional oxide-zeolite catalysts constitutes a formidable challenge in realizing the potential of tandem hydrogenation of CO2 to hydrocarbons (HC) for sustainable fuel production. Herein, we combined CH3OH synthesis from CO2 and H2 on In2O3 and methanol-to-hydrocarbons (MTH) conversion on HZSM-5 and discerned the descriptors by leveraging the distance-dependent reactivity of bifunctional In2O3 and HZSM-5 admixtures. We modulated the distance between redox sites of In2O3 and acid sites of HZSM-5 from milliscale (∼10 mm) to microscale (∼300 μm) and observed a 3-fold increase in space-time yield of HC and CH3OH (7.5 × 10–5 molC gcat–1 min–1 and 2.5 × 10–5 molC gcat–1 min–1, respectively), due to a 10-fold increased rate of CH3OH advection (1.43 and 0.143 s–1 at microscale and milliscale, respectively) from redox to acid sites. Intriguingly, despite the potential of a three-order-of-magnitude enhanced CH3OH transfer at a nanoscale distance (∼300 nm), the sole product formed was CH4. Our reactivity data combined with Raman, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) revealed the occurrence of solid-state-ion-exchange (SSIE) between acid sites and Inδ+ ions, likely forming In2O moieties, inhibiting C–C coupling and promoting CH4 formation through CH3OH hydrodeoxygenation (HDO). Density functional theory (DFT) calculations further revealed that CH3OH adsorption on the In2O moiety with preadsorbed and dissociated H2 forming an H–In–OH–In moiety is the likely reaction mechanism, with the kinetically relevant step appearing to be the hydrogenation of the methyl species. Overall, our study revealed that efficient CH3OH transfer and prevention of ion exchange are the key descriptors in achieving catalytic synergy in bifunctional In2O3/HZSM-5 systems.

Keywords: CO2 utilization, sustainable fuels, C−C coupling, zeolite, ion-exchange, methanol, hydrocarbon

Short abstract

Efficient CH3OH transfer and prevention of ion-exchange between zeolitic H+ and Inδ+ drive catalytic synergy over In2O3/HZSM-5 bifunctional admixtures.

Introduction

In 2023, NASA’s Goddard Institute of Space Studies (GISS) in New York reported that the summer marked Earth’s highest temperatures on record since 1880.1 This warming trend was predominantly driven by anthropogenic CO2 emissions.1 As per the United Nations, the atmospheric CO2 level has seen a 50% increase over preindustrial levels, reaching 421 ppm in May 2022.2−4 A potential approach for decreasing CO2 levels in the atmosphere is the conversion of CO2 into value-added hydrocarbons (HC), fuel, and chemicals by tandem catalysis.5−8

While the idea of converting small molecules into larger and more complex ones seems appealing, it often requires reactions occurring over different active sites (e.g., acylation of aldehydes on Lewis acid and base sites, hydrogenation–hydroformylation over central nitrogen in tertiary amine on metal sites, and alkene metathesis on redox and acid sites).9−20 Even so, tandem (cascade or domino) reactions have proven effective in facilitating such complex transformations in a single step by utilizing multifunctional catalysts.21−23 Examples of such reactions include tandem dehydrogenation and olefin cross-metathesis,24−28 tandem ammonia borane dehydrogenation and hydrogenation of amines,29 and tandem hydrogenation of nitroarenes.30 Tandem reactions are further attractive as they promote process intensification, reducing capital and operational costs by consolidating multiple reaction steps in a single reactor.31−37 As such, tandem hydrogenation of carbon dioxide (CO2) with “green H2”, which couples two major reactions: CH3OH synthesis reaction and CH3OH to hydrocarbons conversion (MTH), to produce HC has emerged as an attractive route to advance toward a sustainable and carbon-neutral circular economy.7,38−52

The design of efficient catalysts for the selective hydrogenation of CO2 faces two major challenges, (i) the constituent steps within the tandem reaction require different catalytic active sites, such as acid and redox sites, which are unlikely to be found within a single material53−56 and (ii) a specific reaction sequence needs to be followed to achieve the desired product (e.g., CH3OH synthesis has to occur before MTH).57−60 The former can be addressed by incorporating the necessary active sites in a single material (i.e., bifunctional catalysts). However, designing efficient tandem catalysts requires careful consideration of factors beyond the inclusion of active sites. Specifically, the second constraint suggests that the mere inclusion of necessary active sites in the catalyst is inadequate as efficient conversion requires the transport of reactants and intermediates from and to specific active sites in a specific reaction sequence. This is apparent considering most of the “state-of-the-art” bifunctional catalysts reported for tandem CO2 hydrogenation are simple admixtures, which address the requirement of multiple active sites, e.g., oxygen vacancies (redox sites) on a metal oxide and Bro̷nsted acid sites (BAS) on a zeolite yet exhibit poor control over the spatial arrangements of active sites to synchronize the sequence of reaction steps. However, simple bifunctional admixture catalysts can still exhibit increased selectivity toward hydrocarbon products,5,61−66 making it imperative to decipher the factors that drive catalytic synergy in these admixtures to determine the optimal catalyst heterostructures.

The key challenge in probing the synergy involved in tandem CO2 hydrogenation is the complexity of the overall reaction network.67 While the first step (CH3OH synthesis) causes a few side reactions of reverse water gas shift (RWGS) and CO2 methanation,68,69 the second step (MTH) encompasses a series of reactions such as the formation of C–C bond, formation of lower olefin, olefin methylation, olefin cracking, hydrogen transfer, cyclization, aromatic methylation, aromatic dealkylation, formation of alkanes by secondary hydrogenation, and co-catalytic intermediates formation in the olefin and aromatic cycles of the “dual-cycle mechanism”.70 This complex reaction system poses challenges in identifying the specific steps that can aid in achieving synergistic performance to enhance the selectivity of specific hydrocarbons.

Probing the catalytic synergy is further complex as the proximity and compatibility between the redox sites and BAS in the admixtures are vital for the efficient hydrogenation of CO2. There is a consensus that the HC selectivity could be enhanced by improving the transfer of CH3OH intermediate from redox sites to BAS by reducing the spatial distances between them; in other words, “the closer, the better”.39,71,72 These improvements have only been shown as improved HC selectivity.39,71−75 The influence of the increased CH3OH advection rates on the HC production rate (i.e., HC space-time yields) has not been enumerated yet. Additionally, several studies have shown that the intimate proximity between the active sites was detrimental to CO2 hydrogenation, especially for In2O3 and zeolite admixtures.7,74,76−78 This change in catalytic activity was suggested to be caused by multiple factors, including the destruction of zeolite structure,77 the reduction of metal oxides (e.g., In2O3) by hydrogen during CO2 hydrogenation,40 and/or cation (e.g., Inδ+) migration and exchange with BAS under harsh reaction conditions.76,79 Recently, a few reports have shown the effect of ion exchange on the inhibition of the catalytic rate of HC production.7,74,80 However, systematic investigation of ion-exchange, formation of cationic species inside the zeolite, and their influence on HC yields and the reaction mechanism are yet to be carried out.

Considering all the factors required in designing an effective catalyst, in this study, we seek to establish (1) a comprehensive understanding of how the placement of the active sites manipulates the reaction trajectories in the complex reaction network of CH3OH and HC formation and influences HC space-time yields (2) a quantitative analysis of how the rate of CH3OH advection from redox to BAS influences the yields and selectivity of HC; (3) at what conditions ion exchange may occur and how different extents of ion exchange can influence the product selectivity and yields and (4) if ion exchange can create new active sites in the zeolite framework and promote side reactions during tandem CO2 hydrogenation. We selected In2O3 and HZSM-5 (Si/Al = 40) for their efficacy in CH3OH synthesis,81 and MTH conversion,82,83 respectively, and modulated the placement of redox and BAS in the admixtures (from milliscale to nanoscale) to evaluate the effect of their proximity on the reaction pathways and product yield and selectivity. Overall, we aimed to explore the factors that determine the catalytic synergy in bifunctional admixtures during tandem CO2 hydrogenation.

Experimental Section

Materials

Indium(III) nitrate hydrate (99.999% metal basis, Thermo Scientific chemicals, Richardson, Texas, USA) and ammonium hydroxide (28–30% NH3 basis, Sigma-Aldrich, St. Louis, Missouri, USA) were used to synthesize indium oxide (In2O3). Zeolite Socony Mobil–5 (NH4-ZSM-5, CBV 8014, Si:Al ratio 40) zeolite was purchased from Zeolyst (Kansas City, USA). Sodium nitrate (ReagentPlus, ≥ 99%, Sigma-Aldrich, St. Louis, Missouri, USA) was used for ion exchange with HZSM-5. Fused α-Alumina (100–200 mesh, Sigma-Aldrich, St. Louis, Missouri, US) was used for spacing in stacked bed catalysts.

Catalyst Synthesis

Synthesis of Indium Oxide (In2O3)

Indium oxide (In2O3) was synthesized by the precipitation method.74,76 Briefly, indium(III) nitrate trihydrate (In(NO3)3.3H2O, 5 g) was added to deionized (DI) water (20 mL). The solution was added dropwise to an ammonium hydroxide (NH4OH) solution (60 mL, 0.8 M). The as-prepared mixture was aged overnight (70 °C, 12 h). The mixture was then filtered under a vacuum. The filtrate/precipitate was then washed with ethanol (70%), dried (80 °C, 5 h), and calcined (500 °C, 4 h) with air (50 mL min–1) in a muffle furnace.

Preparation of HZSM-5

NH4-ZSM-5 was calcined (500 °C, 4 h) under air (50 mL min–1) in a muffle furnace to produce HZSM-5. Specifically, the temperature was increased from 20 to 80 °C (ramp rate of 10 °C/min), followed by an isothermal holdup at 80 °C for 6 h for drying, and then ramped up to 500 °C with a ramp of 19 °C/min, followed by an isothermal holdup at 500 °C for 4 h.

Ion-Exchange of HZSM-5 with Indium (xInZSM-5)

Three ion-exchanged xInZSM-5 samples with different In:Al molar ratios (x= 0.3, 0.7, 3.5) were prepared by incipient wetness impregnation (IWI) of freshly calcined HZSM-5 (3.5 g) with a solution of In(NO3)3.3H2O (0.03, 0.08, and 1.5 g in 1 mL H2O for In:Al ratio of 0.3, 0.7, and 3.5, respectively). The mixture was then dried (80 °C, 5 h) and calcined (500 °C, 6 h) with air (50 mL min–1) in a muffle furnace.

Ion-Exchange of HZSM-5 with Sodium (NaZSM-5)

HZSM-5 was ion-exchanged with Na+ using the wetness impregnation method.84 Specifically, a 2 M NaNO3 solution was prepared by adding 6.8 g NaNO3 in 40 g of DI water. Two grams of HZSM-5 were added to the solution, and the mixture was stirred for 2 h at 70 °C. The mixture was filtered and washed with DI water. The zeolite was collected, and the ion exchange procedure was repeated 4 times. The final ion-exchanged zeolite was then washed, dried (80 °C, 5 h), and calcined (500 °C, 6 h) with air (50 mL min–1) in a muffle furnace.

Preparation of Bifunctional In2O3/HZSM-5 Admixtures

Microscale Placement of In2O3 and HZSM-5 (micro_In2O3/HZSM-5)

The admixture was prepared by physically mixing granules of In2O3 and HZSM-5 at a mass ratio of 1:1 (1 g total, unless otherwise specified). To prepare the granules, the powder of In2O3 and HZSM-5 were separately pressed, crushed, and sieved into 30–60 mesh (size 250–560 μm).

Nanoscale Placement of In2O3 and HZSM-5 (nano_In2O3/HZSM-5)

The nanoscale admixture was prepared by mixing In2O3 and HZSM-5 powder (1 g total, 1:1 mass ratio) in an agate mortar and pestle for 15 min, followed by pressing, crushing, and sieving into granules of 30–60 mesh (size 250–560 μm).

Stacked Bed of In2O3 and HZSM-5 (In2O3||HZSM-5 and HZSM-5||In2O3)

In2O3 and H-ZSM-5 (0.5 g each) were separately pressed, crushed, and sieved into granules of 30–60 meshes (250–560 μm). Then, the In2O3 and HZSM-5 granules were stacked as separate beds with fused α-alumina (Al2O3) (0.5 g) in between.

Catalytic Evaluation Methods

The catalytic conversion of CO2 hydrogenation was evaluated on a high-pressure tubular fixed-bed reactor. Typically, the catalyst (1.0 g, 30–60 mesh) was first pretreated in 5% H2 (balance N2) at 300 °C for 1 h and cooled to 40 °C prior to the reaction. We note that blank reaction tests with α-Al2O3 showed no reactivity. The reaction was conducted at a pressure of 500 psig and a temperature of 350 °C, unless otherwise specified. Gas hourly space velocity (GHSV) was calculated using the following equation:

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GHSV was maintained at 9000 mL gcat–1 h–1 with a 3:1 feed ratio of H2:CO2, unless otherwise specified.

The products were analyzed by an online gas chromatograph (SRI-GC Multigas 5) equipped with a flame ionization detector (FID), a methanizer (FIDm), and a thermal conductivity detector (TCD). A Haysep D column was connected to the TCD and FIDm for separating and detecting CO2, CO, CH4, and C2–C4 HC while the MXT-1 column was connected to the FID for analyzing all HC and oxygenate products (e.g., dimethyl ether and CH3OH). The outlet from the reactor was further analyzed by Agilent GCMS (8890 GC system and 5977B GC/MSD) equipped with a GasPro column connected to FID and mass spectrometer for further quantification and identification of the products. The product selectivity was calculated on a molar carbon basis. The carbon balance is given in the SI (Table S7).

The CO2 conversion, CO selectivity, HC distribution, and STY of HC were calculated using the following equations:

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where CCO2, inlet and CCO2, outlet are the concentrations of CO2 at the inlet and outlet, respectively, Finlet and Foutlet are the inlet and outlet gas flow rates of the reactor, RRF is the relative response factor, A is the peak area of the species on the chromatogram, and n and m denote the number of C and H atoms in the HC.

For the catalytic performance evaluation in bar plots, the data were averaged over three points under a specific reaction condition. The carbon balance was done on a carbon mole basis. The carbon balance ranges from 96 to 101% as shown in SI Table S7.

MTH reaction was conducted in the same tubular fixed-bed reactor. The reaction was conducted at a pressure of 200 psi and a reaction temperature of 350 °C. GHSV was 9000 mL gcat–1 h–1 with a 3:1 feed ratio of H2:N2, keeping pH2 the same as in CO2 hydrogenation. CH3OH was injected using a high-pressure syringe pump (Chemyx Fusion 6000X) with a flow rate of 0.012 mL min–1.

Results and Discussion

Sequential Placement of Active Sites in Bifunctional In2O3 and HZSM-5 Admixtures

We assessed the catalytic performances of In2O3 and HZSM-5 for CO2 hydrogenation at 350 °C, 500 psig, and GHSV of 9000 mL gcat–1 h–1 (Figure 1A). In2O3 generated only C1 products, including CH3OH (6.3%), CO (91.8%), and CH4 (1.9%). The formation of CO and CH4 occurs via the RWGS and CO2 methanation, respectively.81,85 Due to the absence of BAS, no C2+ HC was formed over In2O3. On the other hand, HZSM-5 did not show any reactivity, which is consistent with previous reports, as the BAS of HZSM-5 alone does not catalyze CO2 hydrogenation.39

Figure 1.

Figure 1

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Requirement in the sequential placement of active sites in bifunctional In2O3and HZSM-5 admixtures. (A) Catalytic performance including hydrocarbon distribution (left axis), CO2 conversion, CO and CH3OH selectivity (right axis) during CO2 hydrogenation over In2O3, HZSM-5, HZSM-5||In2O3, and In2O3||HZSM-5 (inserts show configurations of the catalyst beds). (B) Space–time yield (STY) of CH3OH and HC over In2O3, HZSM-5, HZSM-5||In2O3, and In2O3||HZSM-5. Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3 and HZSM-5 mass ratio 1:1.

We next assessed the requirements of bifunctionality and sequential placement of active sites by evaluating the catalytic performance of stacked granules (∼ 405 μm) of In2O3 and HZSM-5 with a 3 mm inert layer of fused α-Al2O3 separating each catalyst in two arrangements, (i) In2O3 stacked on top of HZSM-5, denoted as In2O3||HZSM-5, and (ii) HZSM-5 stacked on top of In2O3, denoted as HZSM-5||In2O3 (see insets in Figure 1A). For HZSM-5||In2O3, akin to In2O3, only C1 products were observed (91% CO, 7.1% CH3OH, and 1.9% CH4 in total product selectivity) as In2O3 was solely responsible for CO2 hydrogenation. However, we observed the formation of C2+ HC over In2O3||HZSM-5 (Figure 1A) with an HC distribution of ∼32.6% paraffins (C2–C4), ∼5.4% lower olefins (C2=–C4=), and ∼28.3% longer-chain HCs (C5+) which substantiates the requirement of bifunctionality for the tandem reaction. Taken together, our data suggests that the sequence of active sites in bifunctional catalysts is crucial for the efficient conversion of CO2 to HC.

The space–time yields (STY) of HC and CH3OH over In2O3, In2O3||HZSM-5, and HZSM-5||In2O3 at 350 °C are shown in Figure 1B. The highest STY was observed over In2O3||HZSM-5 (3.00 × 10–5 molC gcat–1 min–1), compared to In2O3 (2.00 × 10–5 molC gcat–1 min–1) and HZSM-5||In2O3 (1.95 × 10–5 molC gcat–1 min–1), suggesting that the BAS of HZSM-5 converted the CH3OH formed over In2O3 (equilibrium limited under reaction conditions,86 see Section S4.2) via MTH, driving the overall reaction forward (as per Le Chatelier’s principle).36,87

Influence of Active Site Proximity and Intermediate Transfer Rates on Catalytic Activity

We tuned the distance between the active sites of In2O3 and HZSM-5 (In2O3||HZSM-5, micro_In2O3/HZSM-5, and nano_In2O3/HZSM-5) to investigate the influence of their proximity on catalytic activity. The estimated average distances between redox sites and BAS in In2O3||HZSM-5, micro_In2O3/HZSM-5, and nano_In2O3/HZSM-5 (described in Section S2) were ∼9.6 mm, ∼318 μm, and ∼315 nm, respectively.

Micro_In2O3/HZSM-5 exhibited decreased CO selectivity (77%) and a higher C5+ selectivity (51% in HC distribution) as compared to In2O3||HZSM-5 (CO selectivity of 91.0% and C5+ selectivity of 28.3%) at a similar CO2 conversion (20.0%) (see Figure 2A). We observed only branched alkanes and cyclic hydrocarbons and no aromatics in C5+ hydrocarbons over micro_In2O3/HZSM-5 (see Figure S22) likely due to the presence of high-pressure H2 during the reaction, which tends to hydrogenate olefins and aromatics over the BAS of the zeolite.88 This observation is consistent with previous reports for HZSM-5 (with Si:Al ratio 15 to 50) under similar reaction conditions.76,89,90 Interestingly, the combined STY of CH3OH and HC (Figure 2B) was ∼3 times higher over micro_In2O3/HZSM-5 compared to In2O3||HZSM-5. This enhancement in STY over micro_In2O3/HZSM-5 was further observed at 400 and 450 °C (see Figure S3). We hypothesize that the higher STY at the microscale could be related to the rate of CH3OH transfer from redox sites to the BAS. Accordingly, we estimated the rate of CH3OH advection (see Figure 2B, calculations described in Section S4.1 and Table S2) to be ∼10 times higher over micro_In2O3/HZSM-5 than In2O3||HZSM-5. Faster transfer and consumption of CH3OH over micro_In2O3/HZSM-5 likely shifts CH3OH synthesis equilibrium (from CO2 and H2, see Section S4.2) forward,86 consequently suppressing the formation of CO and increasing C5+ selectivity via methylation of lower olefins over BAS of HZSM-5.38,70

Figure 2.

Figure 2

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Influence of the proximity between redox sites of In2O3and Bro̷nsted acid sites (BAS) of HZSM-5 on catalytic activity. (A) Catalytic performance including hydrocarbon (HC) distribution (left axis), CO2 conversion, CO and CH3OH selectivity (right axis) during CO2 hydrogenation over In2O3||HZSM-5 and micro_In2O3/HZSM-5. (B) Space–time yield (STY) of CH3OH and HC (left axis) and rate of CH3OH advection (right axis) over In2O3||HZSM-5 and micro_In2O3/HZSM-5. Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:HZSM-5 mass ratio 1:1.

Since the rate of CH3OH advection depends on the gas flow rate (shown in Section S4.1), we further evaluated the catalytic performance of micro_In2O3/HZSM-5 at different GHSV (from 4800 to 12000 mL gcat–1 h–1) to explore how the rate of CH3OH transfer influences HC selectivity (see Figure 3A) and STY (see Figure 3B). Although CO2 conversion decreased by increasing GHSV, the STY of C2+ HC increased over micro_In2O3/HZSM-5 from 3.8 × 10–5 molC gcat–1 min–1 to 7.5 × 10–5 molC gcat–1 min–1 as the rate of CH3OH advection increased from 1.43 to 3.6 s–1. Concomitantly, the STY of unconverted CH3OH increased (1.3 × 10–5 molC gcat–1 min–1 to 1.9 × 10–5 molC gcat–1 min–1). We note that similar enhancements in C2+ HC STY were observed for In2O3||HZSM-5 (see Figure S5). Taken together, we deduce that the efficient transfer of CH3OH from redox to acid sites is crucial in achieving high HC STY and selectivity.

Figure 3.

Figure 3

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Effect of the rate of advective CH3OH transfer from redox sites of In2O3 and Bro̷nsted acid sites (BAS) of HZSM-5 on the catalytic activity. (A) Catalytic performance including hydrocarbon (HC) distribution (left axis), CO2 conversion, CO and CH3OH selectivity (right axis) during CO2 hydrogenation over micro_In2O3/HZSM-5 at different gas hourly space velocity (GHSV). (B) Space-time yield of CH3OH and HC over micro_In2O3/HZSM-5 (left axis) and rate of CH3OH advection (right axis) at different GHSV. Reaction conditions: 350 °C, 500 psig, GHSV 4800–12000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:HZSM-5 mass ratio 1:1.

Interestingly, in the case of nanoscale admixture of In2O3 and HZSM-5, the combined STY of CH3OH and HC was lower (3.1 × 10–5 molC gcat–1 min–1) compared to micro_In2O3/HZSM-5, even though the rate of CH3OH advection was 3 orders of magnitude higher in nano_In2O3/HZSM-5 (see Figure 4A). Further, the sole hydrocarbon product was CH4 over nano_In2O3/HZSM-5. Additionally, the selectivity to unconverted CH3OH (11%) was found to be higher over nano_In2O3/HZSM-5, as compared to micro_In2O3/HZSM-5 (CH3OH selectivity 4.8%) (see Figure 4B), suggesting lower conversion of the CH3OH intermediate over HZSM-5 in nano_In2O3/HZSM-5.

Figure 4.

Figure 4

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Influence of reducing the length scale between redox sites of In2O3and acid sites of HZSM-5 from microscale to nanoscale on the catalytic activity. (A) Space-time yield of CH3OH and hydrocarbon (HC) over micro_In2O3/HZSM-5 and nano_In2O3/HZSM-5 (left axis) and their respective rate of CH3OH advection (right axis); (B) catalytic performance including HC distribution (left axis), CO2 conversion, CO and CH3OH selectivity (right axis) during CO2 hydrogenation over micro_In2O3/HZSM-5 and nano_In2O3/HZSM-5. Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:HZSM-5 mass ratio 1:1.

Structural, Textural, and Morphological Characterizations of Nano_In2O3/HZSM-5

To verify if the reduced reactivity of nano_In2O3/HZSM-5 was caused by any change in HZSM-5 structure, we conducted powder X-ray diffraction (PXRD) of nano_In2O3/HZSM-5, which exhibited characteristic peaks of HZSM-5 (see SI Figure S12A), suggesting that the crystallinity of HZSM-5 was largely retained in nano_In2O3/HZSM-5. Further, a comparison of scanning electron micrographs (Figure S10A) and transmission electron micrographs (TEM) of HZSM-5 (Figure S10B) with SEM and TEM of nano_In2O3/HZSM-5 (Figure S12B,C) revealed similar average particle size for HZSM-5 (∼500 nm) in the admixture, indicating no structural change to HZSM-5 in nano_In2O3/HZSM-5.

To further assess the structural and textural changes of HZSM-5 in nano_In2O3/HZSM-5, N2 physisorption was conducted for microscale and nanoscale admixtures. Both samples exhibited mesoporous type IV isotherm, which could be attributed to the mesoporous structure of In2O3 (Figure S13B).91 Although nano_In2O3/HZSM-5 exhibited a lower BET surface area and pore volume (202 m2/g, 0.25 cc/g) compared to micro_In2O3/HZSM-5 (256 m2/g, 0.29 cc/g), the micropore volume estimated from the t-plot was found to be similar (0.07 cc/g for micro_In2O3/HZSM-5 and 0.06 cc/g for nano_In2O3/HZSM-5) (see Table S3), suggesting the microporous structure of HZSM-5 was largely retained. However, the microporous area of nano_In2O3/HZSM-5 (130 m2/g) was found to be lower than micro_In2O3/HZSM-5 (172 m2/g), likely due to the coverage of the pore surface on HZSM-5 with In2O3.

Taking the PXRD patterns, SEM micrographs, and N2 physisorption data together, we posit that the structural integrity of HZSM-5 was largely retained in nano_In2O3/HZSM-5. We further note that the particle size of In2O3 in microscale admixtures is the same as sole In2O3 (∼20 nm Figure S10G), while in nano admixtures, the particle size is ∼10 nm (Figure S12C) likely induced by the mixing process. However, Lu et al. previously corroborated that the selectivity of CH4 remained similar (1.5–2.1% in the HC distribution) by varying In2O3 particle size from 7 to 28 nm. Hence, the increased CH4 selectivity over nano_In2O3/HZSM-5 was likely caused by the ion exchange of zeolitic BAS with Inδ+ rather than any change in particle size of In2O3,91 or structural change of HZSM-5.

Influence of Ion Exchange between Bro̷nsted Acid Sites (BAS) and Inδ+ on Catalytic Activity

To probe whether the inhibited catalytic activity of nano_In2O3/HZSM-5 toward MTH was a result of ion exchange, zeolitic BAS were exchanged with Inδ+ (δ likely to be 3) ions via incipient wetness impregnation (IWI) at three different In:Al molar ratios of 0.3, 0.7, and 3.5 (represented as xInZSM-5, where x = 0.3, 0.7, 3.5). The catalytic performance of microscale admixtures of In2O3 with xInZSM-5 (denoted as micro_In2O3/xInZSM-5) was studied as shown in Figure 5A. An increase in the In:Al ratio increased CH4 selectivity (10, 14, and 100% in HC distribution for x = 0.3, 0.7, and 3.5, respectively) indicating ion-exchange of BAS with Inδ+ enhanced CH4 selectivity. Furthermore, the increase in In:Al ratio resulted in a marginally higher selectivity of unconverted CH3OH from 3.5 to 8.5%. Notably, the catalytic performance of micro_In2O3/3.5InZSM-5 was found to be similar to nano_In2O3/HZSM-5 (Figure 5A). Importantly, in these microscale admixtures (micro_In2O3/xInZSM-5 with x = 0.3, 0.7, and 3.5), the structural damage to HZSM-5 particles was unlikely as no powder mixing was employed. Further insights could be obtained on the effect of ion exchange by evaluating the STY of C2+ HC over micro_In2O3/xInZSM-5 (x = 0.3,0.7,3.5), as shown in Figure 5B. The STY of C2+ HC decreased (from 3.9 × 10–5 to 0 molC gcat–1 min–1) with the increasing In:Al ratio. Notably, for micro_In2O3/3.5In-ZSM-5 the ion exchange appeared complete as no C–C coupling products were observed, similar to nano_In2O3/HZSM-5 (see Figure 5A,B).

Figure 5.

Figure 5

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Effect of ion exchange of zeolitic H+with Inδ+on catalytic activity. (A) Catalytic performance including hydrocarbon (HC) distribution (left axis), CO2 conversion, and CO and CH3OH selectivity (right axis) of micro_In2O3/0.3InZSM-5, micro_In2O3/0.7InZSM-5, micro_In2O3/3.5InZSM-5, and nano_In2O3/HZSM-5 during CO2 hydrogenation. (B) Space-time yield of CH3OH and HC over micro_In2O3/0.3InZSM-5, micro_In2O3/0.7InZSM-5, micro_In2O3/3.5InZSM-5, and nano_In2O3/HZSM-5. Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:ZSM-5 mass ratio 1:1.

To compare how the reaction would proceed without any BAS, we ion exchanged zeolitic BAS with Na+ (denoted as NaZSM-5 with Na:Al ratio of 1:1) and evaluated the catalytic performance of its microscale admixture with In2O3. Complete ion exchange of BAS with Na+ was confirmed by no MTH reactivity on NaZSM-5 as shown in Figure 6A. Notably, as anticipated, micro_In2O3/NaZSM-5 also showed no C–C coupling products, akin to nano_In2O3/HZSM-5 during tandem CO2 hydrogenation (Figure 6B).92−94 Taken together, our data suggests that in nanoscale admixture, the ion exchange of BAS with Inδ+ causes a complete shutdown of MTH.

Figure 6.

Figure 6

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Inhibition of methanol to hydrocarbon (MTH) due to ion exchange of BAS with Na+. (A) Catalytic performance of NaZSM-5 including hydrocarbon (HC) distribution (left axis) and CH3OH conversion and CO selectivity (left axis) during MTH conversion confirmed complete ion exchange of BAS with Na+. Reaction conditions: CH3OH injection rate 0.012 mL min–1, 350 °C, GHSV of 9000 mL gcat–1 h–1 with H2:N2 ratio 3:1, total pressure 200 psi, partial pressure of CH3OH ∼6 psi; (B) Comparison between the catalytic performance of nano_In2O3/HZSM-5 and micro_ In2O3/NaZSM-5 during CO2 hydrogenation including HC distribution (left axis), CO2 conversion, CO and CH3OH selectivity (right axis). Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:zeolite mass ratio 1:1.

Influence of Ion-Exchange on MTH and CH3OH Hydrodeoxygenation (HDO)

To investigate whether the ion-exchanged Inδ+ species in micro_In2O3/3.5InZSM-5 and nano_In2O3/HZSM-5 have any influence on the reaction pathways, we compared their STY of C1 products with In2O3 and micro_In2O3/NaZSM-5. The STY toward C1 products were similar over micro_In2O3/3.5InZSM-5 and nano_In2O3/HZSM-5, however, higher than In2O3 and micro_In2O3/NaZSM-5, as shown in Figure 7. This further leads to the question of why the ion-exchanged Inδ+ species enhanced STY of CH3OH and CH4 over nano_In2O3/HZSM-5 and micro_In2O3/3.5InZSM-5.

Figure 7.

Figure 7

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Space–time yield (STY) of hydrocarbon (HC) and CH3OH during CO2hydrogenation over micro_In2O3/3.5InZSM-5, nano_In2O3/HZSM-5, In2O3,and micro_In2O3/NaZSM-5. Higher STY for CH3OH and CH4 was observed over micro_In2O3/3.5InZSM-5 and nano_In2O3/HZSM-5, as compared to In2O3 and micro_In2O3/NaZSM-5. Reaction conditions: 350 °C, 500 psig, 9000 mL gcat–1 h–1, H2:CO2 ratio 3:1, In2O3:ZSM-5 mass ratio 1:1.

For further investigation, we performed MTH over HZSM-5, 0.7InZSM-5, 3.5InZSM-5, and In2O3 (see Figure 8A). In2O3 alone did not exhibit any catalytic activity for MTH, while HZSM-5 showed 82% conversion of CH3OH with 1.6% CH4 selectivity in the HC distribution. Interestingly, 0.7InZSM-5 converted 87% CH3OH with a CH4 selectivity of 20%, and 3.5InZSM-5 converted 3% CH3OH at 100% CH4 selectivity, indicating the role played by ion-exchanged Inδ+ species in CH4 formation during MTH. Several studies have reported that CH3OH hydrodeoxygenation (HDO) (CH3OH + H2 → CH4 + H2O) may occur in the presence of H2 during MTH.95−97 Therefore, we infer that CH4 is likely formed over ion-exchanged Inδ+ species via CH3OH HDO,95,98 as In2O3 alone did not show any activity (see Figure 8A). It is to be noted that CH3OH HDO during MTH (in the absence of CO2) over Inδ+ species is distinct from CO2 methanation observed over micro_In2O3/HZSM-5 (Figure 2A). Taken together, our data suggests that the increased CH4 STY during CO2 hydrogenation over nano_In2O3/HZSM-5 and micro_In2O3/3.5InZSM-5 (in Figure 7), is likely due to CH3OH HDO over the ion-exchanged Inδ+ species (as depicted in the scheme of Figure 8B). However, the question remains on how CH3OH HDO occurs over ion-exchanged Inδ+ sites.

Figure 8.

Figure 8

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Ion exchange of zeolitic BAS with Inδ+promotes methane formation. (A) MTH conversion over HZSM-5, 0.7InZSM-5, 3.5InZSM-5, and In2O3. Reaction conditions: CH3OH injection rate 0.012 mL min–1, 350 °C, GHSV of 9000 mL gcat–1 h–1 with H2:N2 ratio 3:1, total pressure 200 psi, partial pressure of CH3OH ∼6 psi. (B) Ion exchange of zeolitic H+ with Inδ+ in nano_In2O3/HZSM-5 influences the reaction pathways during tandem hydrogenation of CO2.

CH3OH Hydrodeoxygenation (HDO) over Ion-Exchanged Inδ+ (In2O Moieties)

We performed spin-polarized density functional theory (DFT) calculations to assess the likely speciation of In species on BAS, the mechanism for CH3OH HDO, and the formation of CH4 over ion-exchanged Inδ+ in HZSM-5 framework (see SI Section S4.3). To model the ion-exchanged In complex in ZSM5, an In2O moiety which is commonly documented in the literature was considered.99 We incorporated the In2O complex in the ZSM5 model by replacing the BAS. This represented the ion-exchanged extra framework moiety over the Al sites of ZSM-5. This catalyst model is hereafter referred to as In2O/ZSM-5 and is shown in Figure S9. The computed In–O–In stretching band at 361 cm–1 correlates with the In–O–In stretch at 382 cm–1 identified during Raman analysis (vide infra, Figure 10).

Figure 10.

Figure 10

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Probing the ion exchange of zeolitic H+with Inδ+via spectroscopic techniques. (A) XPS of In (3d) energy region for In2O3, nano_In2O3/HZSM-5 (1:1), nano_In2O3/HZSM-5 (1:5), 3.5InZSM-5, and 0.7InZSM-5; (B) Raman spectra for In2O3, nano_In2O3/HZSM-5 (1:1), nano_In2O3/HZSM-5 (1:5), 0.3InZSM-5, 0.7InZSM-5, and 3.5InZSM-5. The inset on the top right shows zoomed-in spectra for nano_In2O3/HZSM-5 (1:5) at 5× intensity. (C) Fourier transform infrared (FTIR) spectra of pristine HZSM-5 (black), 3.5InZSM-5 (blue), and nano_In2O3/HZSM-5 (1:1) (red).

Two mechanisms were investigated. The first mechanism assumed CH3OH adsorption on the In2O complex with preadsorbed and dissociated hydrogen forming an H–In–OH–In moiety. This assumption is reasonable considering the high H2 partial pressure in the feed. The free energy profile along this mechanism is shown in green color in Figure 9A and the structures of the intermediates and transition states are shown in Figure 9B. The second mechanism assumed CH3OH adsorption on the pristine In2O complex. The free energy profile along this mechanism is shown in red color in Figure 9A and the structures of the intermediates and transition states are shown in Figure 9C.

Figure 9.

Figure 9

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Free energy profiles for CH3OH hydrodeoxygenation (HDO) over In2O moieties inside HZSM5. Two mechanisms for HDO were investigated, indicated by green and red free energy profiles. (A) Mechanism 1 (green profile) assumed CH3OH adsorption on the In2O complex with preadsorbed and dissociated hydrogen forming an H–In–OH–In moiety. Mechanism 2 (red profile) assumed CH3OH adsorption on the pristine In2O complex. (B) Structures of the intermediates and transition states in mechanism 1. (C) Structures of the intermediates and transition states in mechanism 2. Red—O; magenta—Al; orange–yellow—Si; greyish mauve—In, gray—C, white—H.

The heterolytic dissociation of H2 on the In2O moiety is highly exergonic (ΔGads = −1.08 eV). In mechanism 1, CH3OH underwent a bridged hydroxyl Obr-H assisted deoxygenation step to form water and CH3* with an activation-free energy barrier of 2.21 eV (ΔGrxn = 0.44 eV). Following the desorption of the formed water, the In–H migrated to the bridged oxygen as this was highly favorable. Hydrogenation of the methyl species and formation of CH4 had a high activation free energy barrier of 2.39 eV (ΔGrxn = 0.78 eV). In mechanism 2, CH3OH underwent a direct C–O bond cleavage at the In site in the In2O moiety to form a methoxy species (CH3–Obr) and In–OH. This step had a slightly lower activation-free energy barrier of 1.98 eV compared to the proton-assisted step in mechanism 1. A concerted H2 dissociation and CH3 hydrogenation step to form methane followed, with a very high activation-free energy barrier of 3.64 eV. Upon desorption of the formed CH4, the In–H migrated to the bridged oxygen. The subsequent formation of water had an activation-free energy barrier of 1.17 eV. Analysis of the free energy profiles along both these mechanisms suggests that mechanism 1 with the Obr-H-assisted hydrodeoxygenation of CH3OH is kinetically more favorable. However, the kinetically relevant step in this mechanism appears to be the hydrogenation of the methyl species. The high activation-free energy barriers computed here indicate that the CH3OH HDO at the In exchanged sites is likely to be slow. This is consistent with the low conversion of CH3OH on the ZSM-5 in the nano_In2O3/HZSM-5 and the overall lower activity of this catalyst post ion exchange (Figures 5 and 6).

Although our DFT calculations suggested that In2O moieties likely form due to ion exchange at the nanoscale, we further investigated the oxidation state of Inδ+ species via X-ray photoelectron spectroscopy (XPS). Figure 10A shows XPS spectra of pristine In2O3, nano_In2O3/HZSM-5 (1:1), 0.7In-ZSM-5, 3.5InZSM-5, and, in addition, nano_In2O3/HZSM-5 (1:5), which has an equivalent In:Al ratio as 3.5InZSM-5 (see PXRD in Figure S21). No peaks corresponding to metallic In were observed for all samples, consistent with the PXRD patterns in Figures S12A and S14A. Bulk In2O3 (spectra a) exhibited characteristic peaks at binding energy (B.E.) values of 443.9 and 451.4 eV for In 3d5/2 and In 3d3/2, respectively.99−101 Interestingly for nano_In2O3/HZSM-5 (1:1) (spectra b), in addition to In2O3 peaks at 443.9 and 451.4 eV, higher B.E. peaks at 445.3 and 452.8 eV,99,102 and lower B.E. peaks at 442.3 and 449.8 eV were observed. For nano_In2O3/HZSM-5 (1:5) (spectra c), peaks corresponding to In2O3 (443.9 and 451.4 eV) and at higher binding energies (445.6 and 453.2 eV) were observed with no peaks at lower B.E. Therefore, we hypothesize that the lower B.E. peaks seen in the XPS of nano_In2O3/HZSM-5 (1:1) (spectra b) could be associated with oxygen vacancies/partially reduced InxOy. Considering that the nano_In2O3/HZSM-5 (1:5) has a much lower loading of In2O3 than nano_In2O3/HZSM-5 (1:1), we infer that the absence of a lower B.E. peak could be due to low concentration of oxygen vacancies that are beyond the detection limit of the XPS.

Among ion-exchanged xInZSM-5 samples, 3.5InZSM-5 (spectra d) showed peaks corresponding to bulk In2O3 (443.9 and 451.4 eV) and at higher B.E. (444.9 and 452.5 eV). For 0.7InZSM-5 (spectra e), no detectable peaks corresponding to In2O3 were observed. However, the peaks shifted further to higher B.E. (446.2 and 453.7 eV), as compared to 3.5InZSM-5. Due to the low signal-to-noise ratio (i.e., low resolution), XPS was not shown for 0.3InZSM-5 samples.

Overall, the XPS of ion-exchanged xInZSM-5 (x = 0.7,3.5) and nanoscale admixtures (nano_In2O3/HZSM-5 (1:1) and nano_In2O3/HZSM-5 (1:5)) exhibited peaks at higher B.E., as compared to In2O3. This observation is consistent with previous studies where a shift toward higher B.E. (445.5 and 453 eV) was attributed to the ion exchange of BAS with Inδ+.76,77,99 Therefore, these higher B.E. peaks could be associated with ion-exchanged Inδ+ species interacting with the HZSM-5 framework likely leading to In2O moieties.99,103−105

Further evaluation of ion exchange was conducted by Raman spectroscopy on pristine In2O3, nano_In2O3/HZSM-5 (1:1), nano_In2O3/HZSM-5 (1:5), 0.3InZSM-5, 0.7InZSM-5, and 3.5InZSM-5, shown in Figure 10B. In agreement with XPS and PXRD, no samples exhibited bands for metallic In at 250 and 620 cm–1 (RRUFF ID: R060771.2),106,107 and cubic In(OH)3 at 137, 204, 356, 390, and 659 cm–1.108,109 Pure In2O3 exhibited bands at 308, 497, and 632 cm–1, which is attributed to the InO6 vibration of the cubic phase of In2O3, consistent with PXRD patterns. The band at the Raman shift of 370 cm–1 can be assigned to the stretching vibration of the In–O–In bonds.108,110

Raman spectra of nano_In2O3/HZSM-5 (1:1) showed bands at 307, 497, and 632 cm–1 for InO6 octahedra,108,110 along with the In–O–In band at 370 cm–1. Interestingly, a shoulder appeared at ∼382 cm–1, which was not exhibited by bulk In2O3. For nano_In2O3/HZSM-5 (1:5), the Raman spectra had low resolution due to the lower loading of In2O3, however, a similar shoulder was visible (see inset in Figure 10B).

For ion-exchanged 0.3InZSM-5, 0.7InZSM-5, and 3.5InZSM-5, the InO6 bands at 308, 497, and 632 cm–1 were reduced while the band for In–O–In broadened and shifted toward the higher wavenumber of 382 cm–1. This shift to a higher wavenumber is consistent with previous literature where the band shifted to 400 cm–1 for Inδ+ ion-exchanged HZSM-5.108 Taken together, the band at 370 cm–1 was likely associated with oxygen vacancies, while the broadening and shifting of this band to 382 cm–1 was likely related to the ion exchange of BAS with Inδ+. As mentioned earlier, this is consistent with the In2O moieties (Figure 9) inside the zeolite as suggested by DFT calculations.

Taking the findings from Raman and XPS together, we postulate that the Raman band at 382 cm–1 (Figure 10B), seen in all samples containing HZSM-5 but not seen for In2O3, is related to the ion-exchanged Inδ+ species (likely In2O moieties). This observation further aligns with the higher B.E. peaks seen in the XPS by all samples containing HZSM-5 (Figure 10A) indicating the interaction of Inδ+ species with the HZSM-5 at a higher B.E.

The disappearance of peaks corresponding to the BAS of HZSM-5 at a wavenumber of 3605 cm–1 in the Fourier transform infrared (FTIR) spectroscopy is consistent with the solid-state ion-exchange (SSIE) of BAS with Inδ+ species (as shown in Figure 10C). We suggest that the Inδ+ species may not be In+, as the In+ peaks would have shifted to a lower B.E. than bulk In2O3 (443.9 and 451.4 eV for In 3d5/2 and In 3d3/2, respectively). Interestingly, in ion-exchanged 3.5InZSM-5, the ion exchange (via IWI) appeared incomplete, as revealed by FTIR spectroscopy (see the blue spectrum in Figure 10C) after in situ calcination at 400 °C under air. However, upon reduction (at 400 °C with an H2:N2 ratio of 1:1) the ion exchange was complete as seen from the complete disappearance of peaks corresponding to silanol (Si–OH) and BAS of HZSM-5 at wavenumbers of 3740 and 3605 cm–1, respectively (green spectrum). Therefore, under the reductive reaction conditions, the BAS of zeolites was likely completely ion-exchanged with cationic Inδ+ species. Under reductive conditions similar to our work, Xie et al. have suggested that reducible metal oxides can migrate from zeolite surfaces to micropore channels.77 Furthermore, under the harsh reaction conditions used in our study, metal cations formed from metal oxides could have higher thermal mobility, accelerating ion exchange under reductive conditions.112−114 It has been further suggested that under a reductive environment, InO+ could convert to In+.99,115 From our data, we conclude that these ion-exchanged species inhibit C–C coupling by reducing HZSM-5 acidity and promoting CH4 formation via CH3OH hydrodeoxygenation (HDO).

Conclusions

Overall, the microscale (∼300 μm) placement between the redox sites of In2O3 and Bro̷nsted acid sites (BAS) of HZSM-5 exhibited enhanced catalytic activity (STY of CH3OH and HC ∼3× higher at 350 °C) as compared to milliscale (∼10 mm), which was attributed to the efficient transfer and conversion of CH3OH intermediate (rate of CH3OH advection was 10-fold faster at microscale than milliscale). Although the transfer of CH3OH was more efficient at nanoscale placement (∼300 nm), the occurrence of solid-state ion exchange (SSIE) between Bro̷nsted acid sites (H+) of HZSM-5 and Inδ+ ions from In2O3 was observed, which completely inhibited methanol to hydrocarbons (MTH) reaction and promoted only CH4 formation via CH3OH hydrodeoxygenation (HDO) likely on In2O moieties inside HZSM-5. Based on our data, we infer that the rate of CH3OH advection and the prevention of ion exchange between zeolitic BAS and Inδ+ from In2O3 are the key factors in achieving catalytic synergy in the bifunctional In2O3/HZSM-5 system. Our work enriches the understanding of the structure–activity relationship of bifunctional oxide-zeolite systems and offers valuable insights into the synergistic design of tandem catalysts.

Acknowledgments

We are grateful to the Artie McFerrin Department of Chemical Engineering at Texas A&M University, the College of Engineering, Dr. Mark Barteau, and the Provost for their financial support. This work was funded by Texas A&M University (TAMU), Texas A&M Engineering Experiment Station (TEES), the Governor’s University Research Initiative (GURI), the Oak Ridge Associated Universities through their Ralph E. Powe Junior Faculty Enhancement Award, and the National Science Foundation (NSF) CBET grant number 2245474. We thank Yinying Hua for the assistance with collecting powder X-ray diffraction patterns of pre and postreaction samples. We thank Qiang Hu for the assistance with Raman spectroscopy. We would like to thank Dr. Yordanos Bisrat for her assistance with SEM imaging. We would also like to thank Dr. Jing Wu for her assistance with collecting our XPS data. We also acknowledge that the SEM microscopy and XPS characterization of the catalyst powders was performed in the Texas A&M University Materials Characterization Core Facility (RRID:SCR_022202), TEM characterization was performed at Texas A&M University Microscopy and Imaging Center (MIC) (RRID:SCR_022128). BCD and JJV acknowledge the support of the Carbon Capture Utilization and Storage (CCUS) Centre of Excellence at the Indian Institute of Technology Madras.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.3c08250.

  • Computed distances between redox and BAS, CH3OH advection rates, additional reactivity, N2 physisorption isotherms and BET surface areas, TEM, SEM, Raman, and XPS, and detailed mass balances of the tandem reactions referenced in the text (PDF)

Author Contributions

The manuscript was written through the contributions of all authors. All authors have given approval for the final version of the manuscript.

The authors declare no competing financial interest.

Supplementary Material

sc3c08250_si_001.pdf (4.4MB, pdf)

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