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. 2025 Oct 16;10(42):49583–49590. doi: 10.1021/acsomega.5c04141

CO2 Hydrogenation over MOF-74-Based Catalysts: Role of Physical Mixing and Mg-MOF-74 as a Support

Shunsaku Yasumura 1, Mone Yamazaki 1, Masaru Ogura 1,*
PMCID: PMC12573148  PMID: 41179211

Abstract

MOF-derived catalysts were prepared by physical mixing of Ni-MOF-74 and Mg-MOF-74. Catalytically active Ni metal particles were generated upon thermal treatment of Ni-MOF-74 (acting as a precursor), while Mg-MOF-74 functions as a stable catalyst support with a high CO2 adsorption capacity. The resulting 50Ni50Mg-MOF-74-derived catalyst exhibited superior performance in CO2 hydrogenation to CH4 at 350 °C compared to catalysts derived solely from Ni-MOF-74. The thermal stability of Mg-MOF-74 was confirmed through X-ray diffraction and TG-DTA, while the formation of well-dispersed Ni metal particles was shown by transmission electron microscopy and HAADF-STEM measurements. Molecular dynamics simulation also indicates the formation of Ni metal particles from Ni-MOF-74 and the high stability of Mg-MOF-74. The catalyst prepared by physical mixing demonstrated high activity and durability for the CO2 hydrogenation reaction over 50 h.

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1. Introduction

CO2 capture has received significant interest as a pivotal technology for achieving carbon neutrality. Solid organo-amine-based and physisorption-based adsorbers have been utilized within the systems. − The captured CO2 is converted into valuable chemicals and fuels (methane, methanol, ammonia, jet fuel, etc.), so-called carbon capture and utilization. ,, Recently, CO2 capture and reduction with H2 (CCR) has been investigated. − In unsteady-state reactor systems, low-concentration CO2 and H2 are alternately introduced, enabling the transformation of adsorbed CO2 into CH4 and CO. Dual-functional materials that integrate CO2 capture and hydrogenation capabilities have recently gained significant attention, as they facilitate isothermal CCR processes. −

Metal–organic framework (MOF) is a functional porous material comprising metal cations (Mnn+) and organic linkers. − Its diverse and tunable structural properties have led to extensive research into applications such as adsorption, separation, chemical sensing, and biomedical delivery. MOF has also been widely investigated as a promising adsorber for CO2 due to its ability to adsorb CO2 selectively. −

MOFs are also widely investigated as precursors of heterogeneous catalysts. − Thermal decomposition of MOFs under inert gas provides size-selective metal nanoparticles working as effective active sites for many catalytic reactions. − Zurrer et al. prepared CO2 hydrogenation catalysts by thermal decomposition of mixed-NiMg-MOF-74-derived catalysts, where Ni and Mg species serve as the catalytic active site (Ni metal nanoparticle) and catalyst support (Mg-MOF-74 derived material), respectively.

Functional groups are introduced into the pore of the MOF to tune the CO2 capacity, adsorption/desorption kinetics, and stability under varying atmospheric conditions. For example, it is reported that Mg-MOF-74, functionalized with ethylenediamine, showed increased CO2 capacity at low concentrations and enhanced stability during thermal swing operations compared to the unmodified MOF. − Su et al. conducted a study on the functionalization of Mg-MOF-74 with tetraethylenepentamine to enhance CO2 adsorption. Their findings indicate that optimal modification of Mg-MOF-74 significantly improves the performance and stability.

Herein, MOF-derived catalysts with CO2 hydrogenation activities were developed using a simple physical mixing method of MOFs. Ni-MOF-74 and Mg-MOF-74 served as the precursors for catalytic active sites and the catalyst support, respectively. The resultant 50Ni50Mg-MOF-74-derived catalyst demonstrated excellent performance in the CO2 hydrogenation reaction and durability for long-term tests.

2. Experimental Section

2.1. Catalyst Preparation

Ni- and Zn-MOF-74 were synthesized by using solvothermal procedures. Briefly, metal nitrates and 2,5-dihydroxyterephthalic acid were dissolved in DMF, stirred, and heated in a Teflon-lined autoclave at 120 °C for 24 h. The resulting solids were washed with DMF and ethanol, followed by solvent exchange in ethanol for several days to activate the pores. Mg-MOF-74 was obtained commercially from Atomis Inc.

2.2. Characterization

The crystalline structures of the MOFs were examined by powder X-ray diffraction (XRD) with Cu Kα radiation. Cluster sizes and elemental distributions were analyzed by transmission electron microscopy (TEM), HAADF-STEM, and EDS mapping. Thermal stability was evaluated by TG-DTA. Ni K-edge X-ray absorption spectroscopy (XAS) measurements were performed at the SPring-8 synchrotron facility (BL01B1).

2.3. Catalytic Tests

CO2 hydrogenation reactions were conducted in a fixed-bed continuous flow system. Typically, 50 mg of catalyst was loaded into a quartz reactor tube and pretreated under Ar flow at 400 °C before the reaction. A feed gas mixture containing CO2 and H2 (balanced with Ar) was introduced at a total flow rate of 150 mL min–1. Reaction products were analyzed online using a GC instrument equipped with a thermal conductivity detector.

2.4. Molecular Dynamics Simulations

The thermal decomposition of MOF structures was investigated by molecular dynamics simulations using the ASE package combined with the mase-mp potential. , Periodic supercells were equilibrated under NPT conditions at ambient temperature, followed by heating to 1500 K, high-temperature simulations, and controlled cooling. For composite systems, Ni-MOF-74 was positioned on a Mg-MOF-74 slab model, and similar heating–cooling cycles were applied. Structural changes during decomposition were monitored by calculating the Ni–Ni coordination numbers as a function of simulation time.

3. Results and Discussion

3.1. Characterization of MOF-74-Derived Catalysts

Previous papers report that the thermal treatment of MOF under inert gas partially decomposes the structure and generates a catalytic active site for CO2 hydrogenation. ,,− The structural change of M-MOF-74 (M = Ni, Mg, and Zn) was characterized by thermogravimetric–differential thermal analyzer (TG-DTA) analysis and XRD (Figure ). Ni- and Zn-MOF-74 exhibited an endothermic process and a reduction in sample weight around 100 °C during TG-DTA measurements under N2 flow, attributed to desorption of water. After the temperature reached over 300 °C, significant weight loss was observed for Ni-MOF-74, indicating the collapse of the MOF structure. The weight loss was not observed for Zn- and Mg-MOF-74 (Figure a). Figure b exhibits the XRD patterns before/after pretreatment (400 °C, 6 h under Ar flow). All samples before the pretreatment show XRD patterns similar to the reference, indicating the formation of M-MOF-74s (M = Ni, Mg, and Zn). The diffraction pattern for Mg-MOF-74 remained even after high-temperature treatment, even though its crystallinity decreased. In the case of Ni-MOF-74, the pattern of the MOF-74 structure disappeared completely, while the diffraction peaks derived from their metal species appeared. Zn-MOF-74 showed no diffraction peak after pretreatment, indicating the decomposition of the periodic structure. These results indicate that Mg-MOF-74 is the most stable among the tested samples.

1.

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(a) TG-DTA profile of Ni-, Mg-, and Zn-MOF-74s. Solid and dashed lines describe the results of TG and DTA, respectively. (b) XRD patterns of Ni-, Mg-, and Zn-MOF-74 before/after pretreatment at 400 °C for 6 h (described as solid and dashed lines, respectively). In both figures, the results of Ni-, Mg-, and Zn-MOF-74 are shown in red, green, and blue lines.

3.2. CO2 Hydrogenation of MOF-74-Derived Catalyst

The catalytic performance of M-MOF-74-derived catalysts (M = Ni, Mg, and Zn) was examined for the CO2 hydrogenation reaction. Initially, 40 mg of the samples was placed in a quartz tube and pretreated under an Ar flow at 400 °C for 6 h. After the reaction temperature was cooled, the CO2 hydrogenation test was conducted under a reactant gas mixture (10% CO2, 40% H2, and the Ar balance). Figure shows the CO2 conversion of each catalyst. Among the tested samples, the Ni-MOF-74-derived catalyst showed the highest catalytic activity at 350 °C. In the case of catalysts derived from Mg- and Zn-MOF-74, CO2 conversion was minimal in the tested temperature range.

2.

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Catalytic activities over Ni-, Mg-, and Zn-MOF-74-derived catalyst for CO2 hydrogenation reaction in 10%CO2 + 40%H2 flow (total flow: 150 mL/min, Ar balance). The catalysts were pretreated under Ar flow at 400 °C for 6 h, followed by that under 45%H2 flow at 350 °C for 0.5 h. The results of Ni-, Mg-, and Zn-MOF-74 are shown in red, green, and blue lines.

Ni K-edge XAS, TEM, high-angle annular dark field scanning TEM (HAADF-STEM), and energy dispersive X-ray spectroscopy (EDS) mapping were conducted to gain insights into the active site of the Ni-MOF-74-derived catalyst. The Ni K-edge of the as-prepared sample was located at an energy level comparable to that of NiO, indicating that the Ni in the as-prepared Ni-MOF-74 is in the Ni2+ state (Figure a). Furthermore, EXAFS exhibited only a Ni–O shell (around 1.66 Å), reflecting the structural characteristics of Ni-MOF-74 (Figure b). After pretreatment, the Ni K-edge shifted to an energy level similar to reference Ni foil. Accompanying this shift, the EXAFS showed the disappearance of the Ni–O shell and the appearance of the Ni–Ni shell (around 2.17 Å). TEM and HAADF-STEM images before the pretreatment, Ni is dispersed throughout the sample, reflecting the structure of Ni-MOF-74 (Figure a,c,e). In the TEM and HAADF-STEM images after the pretreatment, aggregated metal Ni particles were observed over the Ni-MOF-derived catalyst (Figure b,d,f). Considering the results of XAS, TEM, HAADF-STEM, and EDS, the active site of the Ni-MOF-74-derived catalyst seems to be Ni metal particles formed by pretreatment under inert gas.

3.

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(a) Ni K-edge XANES spectra of Ni-MOF-74 before and after the pretreatment under Ar flow at 400 °C for 6 h and reference samples (Ni foil and NiO). (b) The corresponding FT-EXAFS.

4.

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TEM images of Ni-MOF-74 (a) before and (b) after the pretreatment. HAADF-STEM images of Ni-MOF-74 (c) before and (d) after the pretreatment. Elemental mapping images of Ni over Ni-MOF-74 (e) before and (f) after the pretreatment.

3.3. Physical Mixing of Ni- and Mg-MOF-74

The previous sections showed that Ni-MOF-74 is a promising precursor for the active site of CO2 hydrogenation. Furthermore, Mg-MOF-74 was found to be a potential catalyst support due to its high thermal stability, while the high CO2 adsorption capacity of Mg-MOF-74 has been extensively reported in previous papers. ,,− Based on the results above, MOFs were physically mixed to develop a catalyst exhibiting high activity for CO2 hydrogenation and capability for CO2 adsorption. The Ni-MOF-74 and Mg-MOF-74 are physically mixed using an agate mortar with different molar ratios of Ni and Mg. These materials are denoted as xNiyMg-MOF-74, where x and y are the molar ratios of Ni and Mg, respectively. The mixtures were placed in a quartz tube and pretreated under Ar flow at 400 °C for 6 h. The CO2 conversion and CH4 yield are shown in Figure a,b, respectively. Despite the Mg-MOF-74-derived catalyst exhibiting low catalytic activity (Figure ), the xNiyMg-MOF-74-derived catalyst demonstrated higher activity than the Ni-MOF-74-derived catalyst. Among the tested samples, the 50Ni50Mg-MOF-74-derived catalyst showed the highest performance. The dispersion of Ni metal cluster over the 50Ni50Mg-MOF-74-derived catalyst was investigated using TEM, HAADF-STEM, and EDS (Figure a,b). It is observed that Ni species are aggregated into Ni particles, while aggregated Mg species were hardly observed (Figure c,d), which aligns with the stable nature of Mg-MOF-74 demonstrated by XRD and TG-DTA measurements (Figure ). Interestingly, the size of Ni particles was smaller than that of the Ni-MOF-74-derived catalyst (Figure a). Figure exhibits the size distribution of the formed Ni metal over Ni-MOF-74-derived (Figures b and S1) and 50Ni50Mg-MOF-74-derived (Figure a) catalysts. The calculated average particle size of 50Ni50Mg-MOF-74-derived catalyst was smaller than that of Ni-MOF-74-derived catalyst (7.6 vs 9.5 nm). To theoretically evaluate the effect of Mg-MOF-74 as a support, a temperature ramping simulation was performed by a molecular dynamics calculation. The periodic models of Ni-MOF-74 and Mg-MOF-74 were first equilibrated at 300 K for 20 ps, and then the temperature ramped up to 1500 K with 5 K/ps. After 100 ps of the simulation at 1500 K, the temperature decreased to 300 K with 10 K/ps (more details can be found in the Supporting Information). After the series of simulations, the periodic structure of Ni-MOF-74 (Figure a) was broken, forming a Ni metal cluster (Figure b), whereas that of Mg-MOF-74 remained (Figure S2), which is consistent with the TG-DTA results (Figure a). Another temperature ramping simulation was performed for Ni-MOF-74 on the Mg-MOF-74 slab under similar conditions (Figure c). In comparison to the Ni metal cluster derived solely from Ni-MOF-74, the Ni clusters on Mg-MOF-74 were found to be highly dispersed (Figure d). The average CN of the Ni–Ni bond during the temperature ramp was plotted as a function of the simulation temperature (Figure ). Although both structures begin to decompose at similar temperatures (1300 K), the average CN of Ni on Mg-MOF-74 at 1500 K is lower than that on Ni-MOF-74 alone. These computational simulations also suggest the potential role of Mg-MOF-74 as an effective catalyst support to maintain Ni metal particles dispersed.

5.

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(a) CO2 conversion and (b) CH4 yield for CO2 hydrogenation over Ni-, Ni5Mg95-, Ni25Mg75-, 50Ni50Mg-, and 75NiMg25-MOF-74-derived catalysts in 10%CO2 + 40%H2 flow (total flow: 150 mL/min, Ar balance). The catalysts were pretreated under Ar flow at 400 °C for 6 h, followed by 45% H2 flow at 350 °C for 0.5 h.

6.

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(a) TEM and (b) HAADF-STEM images of 50Ni50Mg-MOF-74. Elemental mapping images of (c) overlayer, (d) Mg, and (e) Ni.

7.

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Distribution of particle size of Ni particles over (a) Ni-MOF-74-derived and (b) 50Ni50Mg-MOF-74-derived catalysts.

8.

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Computational models of Ni-MOF-74 (a) before and (b) after molecular dynamics simulations (1500 K for 100 ps, followed by cooling to 300 K). Computational models of Ni-MOF-74 on Mg-MOF-74 slab (c) before and (d) after the simulation (1500 K for 100 ps, followed by cooling to 300 K). Silver: Ni, orange: Mg, brown: C, red: O, and white: H.

9.

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Average CN of Ni–Ni bond for Ni-MOF-74 (red) and Ni-MOF-74 on Mg-MOF-74 (green) during temperature ranging from 300 K to 1500 K. For clarity, only the data above 1000 K is shown.

3.4. Long-Term Catalytic Test

A long-term catalytic test (50 h of reaction time) was carried out to examine the durability of the 50Ni50Mg-MOF-74-derived catalyst. Before the long-term test, 50 mg of 50Ni50Mg-MOF-74 was pretreated under an Ar flow at 400 °C for 6 h. Figure a shows the time course of CO2 conversion under the reaction conditions. During the initial period, the CO2 conversion slightly decreased from 30% to 25%, and then, the conversion became stable over the long-term test. In addition, the selectivity for CH4 was stable at 80% in the testing time range of 50 h (Figure b). Figure S3 displays the result of a 10 h catalytic test of 28 mg of Ni-MOF-74-derived catalyst (the same content as the 50Ni50Mg-MOF-74), showing low conversion and selectivity (Figure S3a,b, respectively). These results indicate the high activity of Ni metal particles and the durability of Mg-MOF-74 in the 50Ni50Mg-MOF-74-derived catalyst as the catalyst support.

10.

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(a) CO2 conversion and (b) CH4 selectivity of long-term catalytic test over 50Ni50Mg-MOF-74-derived catalyst, in 10%CO2 + 40%H2 flow (total flow: 150 mL/min, Ar balance) at 350 °C. The catalysts are pretreated under Ar flow at 400 °C for 6 h, followed by 45% H2 flow at 350 °C for 0.5 h.

The demonstrated efficiency and durability of Mg-MOF-74 as a catalytic support encourage further exploration of its application in chemical looping systems, while the steady-state catalytic performance is not superior to those of the other reported catalysts. In particular, we are currently investigating the use of this catalyst for a chemical looping system in which CO2, captured from an O2-containing flow, is directly converted into CH4 under the flow of H2.

4. Conclusions

We have demonstrated that a simple physical mixing approach of Ni-MOF-74 and Mg-MOF-74 can prepare MOF-derived catalysts with a high catalytic activity for CO2 hydrogenation. Ni-MOF-74 serves as a precursor for generating Ni metal nanoparticles as the active sites, while Mg-MOF-74, showing high thermal stability, functions as an effective support of the Ni catalyst. The 50Ni50Mg-MOF-74-derived catalyst exhibited higher CO2 conversion to CH4 at 350 °C than the Ni-MOF-74-derived one. The formation of well-dispersed Ni particles and the thermal stability of Mg-MOF-74 were confirmed by XRD, TG-DTA, TEM, and HAADF-STEM analyses. The temperature ramping simulation also supports these experimental results. The catalyst prepared by physical mixing demonstrated excellent durability over 50 h of reaction time. These results highlight the potential of physically mixed MOF-derived catalysts for efficient CO2 capture and conversion in a chemical looping system.

Supplementary Material

ao5c04141_si_001.pdf (350.8KB, pdf)

Acknowledgments

This research was funded by KAKENHI (23K19175) from the Japan Society for the Promotion of Science (JSPS). S.Y. gratefully acknowledges the support from the Tokuyama Science Foundation and the Award of Excellence, Yayoi Award, Institute of Industrial Science, the University of Tokyo. The data of TEM/HAADF-STEM measurement shown in Figures 4 and 6 were observed at Komaba Analysis Core, Institute of Industrial Science, the University of Tokyo. We thank Prof. T. Mizoguchi for discussing the usage of neural network potential. X-ray absorption measurements were performed at the BL01B1 facility of SPring-8 at the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2024A1756).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.5c04141.

  • Experimental and computational details, TEM image for Ni-MOF-74, and the computational model of Mg-MOF before/after MD simulation (PDF)

The authors declare no competing financial interest.

References

  1. Akimoto K., Sano F., Oda J., Kanaboshi H., Nakano Y.. Climate Change Mitigation Measures for Global Net-Zero Emissions and the Roles of CO2 Capture and Utilization and Direct Air Capture. Energy Clim. Change. 2021;2:100057. doi: 10.1016/j.egycc.2021.100057. [DOI] [Google Scholar]
  2. Findley J. M., Sholl D. S.. Computational Screening of MOFs and Zeolites for Direct Air Capture of Carbon Dioxide under Humid Conditions. J. Phys. Chem. C. 2021;125:24630–24639. doi: 10.1021/acs.jpcc.1c06924. [DOI] [Google Scholar]
  3. Sinha A., Darunte L. A., Jones C. W., Realff M. J., Kawajiri Y.. Systems Design and Economic Analysis of Direct Air Capture of CO2 through Temperature Vacuum Swing Adsorption Using MIL-101­(Cr)-PEI-800 and Mmen-Mg2(Dobpdc) MOF Adsorbents. Ind. Eng. Chem. Res. 2017;56:750–764. doi: 10.1021/acs.iecr.6b03887. [DOI] [Google Scholar]
  4. Zhu X., Xie W., Wu J., Miao Y., Xiang C., Chen C., Ge B., Gan Z., Yang F., Zhang M., O’Hare D., Li J., Ge T., Wang R.. Recent Advances in Direct Air Capture by Adsorption. Chem. Soc. Rev. 2022;51:6574–6651. doi: 10.1039/D1CS00970B. [DOI] [PubMed] [Google Scholar]
  5. Kumar A., Madden D. G., Lusi M., Chen K. J., Daniels E. A., Curtin T., Perry J. J., Zaworotko M. J.. Direct Air Capture of CO2 by Physisorbent Materials. Angew. Chem., Int. Ed. 2015;54:14372–14377. doi: 10.1002/anie.201506952. [DOI] [PubMed] [Google Scholar]
  6. Férey G.. Hybrid Porous Solids: Past, Present, Future. Chem. Soc. Rev. 2008;37:191–214. doi: 10.1039/B618320B. [DOI] [PubMed] [Google Scholar]
  7. Mertens J., Breyer C., Arning K., Bardow A., Belmans R., Dibenedetto A., Erkman S., Gripekoven J., Léonard G., Nizou S., Pant D., Reis-Machado A. S., Styring P., Vente J., Webber M., Sapart C. J.. Carbon Capture and Utilization: More than Hiding CO2 for Some Time. Joule. 2023;7:442–449. doi: 10.1016/j.joule.2023.01.005. [DOI] [Google Scholar]
  8. Zhang L., Song Y., Shi J., Shen Q., Hu D., Gao Q., Chen W., Kow K. W., Pang C., Sun N., Wei W.. Frontiers of CO2 Capture and Utilization (CCU) towards Carbon Neutrality. Adv. Atmos Sci. 2022;39:1252–1270. doi: 10.1007/s00376-022-1467-x. [DOI] [Google Scholar]
  9. Patel H. A., Byun J., Yavuz C. T.. Carbon Dioxide Capture Adsorbents: Chemistry and Methods. ChemSusChem. 2017;10:1303–1317. doi: 10.1002/cssc.201601545. [DOI] [PubMed] [Google Scholar]
  10. Samanta A., Zhao A., Shimizu G. K. H., Sarkar P., Gupta R.. Post-Combustion CO2 Capture Using Solid Sorbents: A Review. Ind. Eng. Chem. Res. 2012;51:1438–1463. doi: 10.1021/ie200686q. [DOI] [Google Scholar]
  11. Chen J., Xu Y., Liao P., Wang H., Zhou H.. Recent Progress in Integrated CO2 Capture and Conversion Process Using Dual Function Materials: A State-of-the-Art Review. Carbon Capture Sci. Technol. 2022;4:100052. doi: 10.1016/j.ccst.2022.100052. [DOI] [Google Scholar]
  12. Bobadilla L. F., Riesco-garcía J. M., Penelás-pérez G., Urakawa A.. Enabling Continuous Capture and Catalytic Conversion of Flue Gas CO2 to Syngas in One Process. Biochem. Pharmacol. 2016;14:106–111. doi: 10.1016/j.jcou.2016.04.003. [DOI] [Google Scholar]
  13. Pinto D., Minorello S., Zhou Z., Urakawa A.. Integrated CO2 Capture and Reduction Catalysis: Role of γ-Al2O3 Support, Unique State of Potassium and Synergy with Copper. J. Environ. Sci. (China) 2024;140:113–122. doi: 10.1016/j.jes.2023.06.006. [DOI] [PubMed] [Google Scholar]
  14. Kosaka F., Liu Y., Chen S. Y., Mochizuki T., Takagi H., Urakawa A., Kuramoto K.. Enhanced Activity of Integrated CO2 Capture and Reduction to CH4 under Pressurized Conditions toward Atmospheric CO2 Utilization. ACS Sustain. Chem. Eng. 2021;9:3452–3463. doi: 10.1021/acssuschemeng.0c07162. [DOI] [Google Scholar]
  15. Tatsumichi T., Okuno R., Hashimoto H., Namiki N., Maeno Z.. Direct Capture of Low-Concentration CO2 and Selective Hydrogenation to CH4 over Al2O3-Supported Ni-La Dual Functional Materials. Green Chem. 2024;26:10842–10850. doi: 10.1039/d4gc03218g. [DOI] [Google Scholar]
  16. Duyar M. S., Treviño M. A. A., Farrauto R. J.. Dual Function Materials for CO2 Capture and Conversion Using Renewable H2 . Appl. Catal., B. 2015;168–169:370–376. doi: 10.1016/j.apcatb.2014.12.025. [DOI] [Google Scholar]
  17. Jeong-Potter C., Farrauto R.. Feasibility Study of Combining Direct Air Capture of CO2 and Methanation at Isothermal Conditions with Dual Function Materials. Appl. Catal., B. 2021;282:119416. doi: 10.1016/j.apcatb.2020.119416. [DOI] [Google Scholar]
  18. Wirner L. C., Kosaka F., Sasayama T., Liu Y., Urakawa A., Kuramoto K.. Combined Capture and Reduction of CO2 to Methanol Using a Dual-Bed Packed Reactor. Chem. Eng. J. 2023;470:144227. doi: 10.1016/j.cej.2023.144227. [DOI] [Google Scholar]
  19. Li L., Miyazaki S., Yasumura S., Ting K. W., Toyao T., Maeno Z., Shimizu K.. Continuous CO2 Capture and Selective Hydrogenation to CO over Na-Promoted Pt Nanoparticles on Al2O3 . ACS Catal. 2022;12:2639–2650. doi: 10.1021/acscatal.1c05339. [DOI] [Google Scholar]
  20. Kondo M., Yoshitomi T., Matsuzaka H., Kitagawa S., Seki K.. Three-Dimensional Framework with Channeling Cavities for Small Molecules: {[M2(4, 4′-bpy)3(NO3)4]·xH2O} n (M = Co, Ni, Zn) Angew. Chem., Int. Ed. Engl. 1997;36:1725–1727. doi: 10.1002/anie.199717251. [DOI] [Google Scholar]
  21. Kitagawa S., Kitaura R., Noro S. I.. Functional Porous Coordination Polymers. Angew. Chem., Int. Ed. 2004;43:2334–2375. doi: 10.1002/anie.200300610. [DOI] [PubMed] [Google Scholar]
  22. Li H., Eddaoudi M., O’Keeffe M., Yaghi O. M.. Design and Synthesis of an Exceptionally Stable and Highly Porous Metal-Organic Framework. Nature. 1999;402:276–279. doi: 10.1038/46248. [DOI] [Google Scholar]
  23. Wang Q., Astruc D.. State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis. Chem. Rev. 2020;120:1438–1511. doi: 10.1021/acs.chemrev.9b00223. [DOI] [PubMed] [Google Scholar]
  24. Konnerth H., Matsagar B. M., Chen S. S., Prechtl M. H. G., Shieh F. K., Wu K. C. W.. Metal-Organic Framework (MOF)-Derived Catalysts for Fine Chemical Production. Coord. Chem. Rev. 2020;416:213319. doi: 10.1016/j.ccr.2020.213319. [DOI] [Google Scholar]
  25. Liu J., Zhang A., Liu M., Hu S., Ding F., Song C., Guo X.. Fe-MOF-Derived Highly Active Catalysts for Carbon Dioxide Hydrogenation to Valuable Hydrocarbons. J. CO2 Util. 2017;21:100–107. doi: 10.1016/j.jcou.2017.06.011. [DOI] [Google Scholar]
  26. Pustovarenko A., Dikhtiarenko A., Bavykina A., Gevers L., Ramírez A., Russkikh A., Telalovic S., Aguilar A., Hazemann J. L., Ould-Chikh S., Gascon J.. Metal-Organic Framework-Derived Synthesis of Cobalt Indium Catalysts for the Hydrogenation of CO2 to Methanol. ACS Catal. 2020;10:5064–5076. doi: 10.1021/acscatal.0c00449. [DOI] [Google Scholar]
  27. Nakatsuka K., Yoshii T., Kuwahara Y., Mori K., Yamashita H.. Controlled Pyrolysis of Ni-MOF-74 as a Promising Precursor for the Creation of Highly Active Ni Nanocatalysts in Size-Selective Hydrogenation. Chem.Eur. J. 2018;24:898–905. doi: 10.1002/chem.201704341. [DOI] [PubMed] [Google Scholar]
  28. Shen K., Chen X., Chen J., Li Y.. Development of MOF-Derived Carbon-Based Nanomaterials for Efficient Catalysis. ACS Catal. 2016;6:5887–5903. doi: 10.1021/acscatal.6b01222. [DOI] [Google Scholar]
  29. Chaikittisilp W., Ariga K., Yamauchi Y.. A New Family of Carbon Materials: Synthesis of MOF-Derived Nanoporous Carbons and Their Promising Applications. J. Mater. Chem. A Mater. 2013;1:14–19. doi: 10.1039/C2TA00278G. [DOI] [Google Scholar]
  30. Zurrer T., Wong K., Horlyck J., Lovell E. C., Wright J., Bedford N. M., Han Z., Liang K., Scott J., Amal R.. Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation. Adv. Funct. Mater. 2021;31:2007624. doi: 10.1002/adfm.202007624. [DOI] [Google Scholar]
  31. Mahajan S., Elfving J., Lahtinen M.. Evaluating the Viability of Ethylenediamine-Functionalized Mg-MOF-74 in Direct Air Capture: The Challenges of Stability and Slow Adsorption Rate. J. Environ. Chem. Eng. 2024;12:112193. doi: 10.1016/j.jece.2024.112193. [DOI] [Google Scholar]
  32. Choi S., Watanabe T., Bae T. H., Sholl D. S., Jones C. W.. Modification of the Mg/DOBDC MOF with Amines to Enhance CO2 Adsorption from Ultradilute Gases. J. Phys. Chem. Lett. 2012;3:1136–1141. doi: 10.1021/jz300328j. [DOI] [PubMed] [Google Scholar]
  33. Andirova D., Lei Y., Zhao X., Choi S.. Functionalization of Metal-Organic Frameworks for Enhanced Stability under Humid Carbon Dioxide Capture Conditions. ChemSusChem. 2015;8:3405–3409. doi: 10.1002/cssc.201500580. [DOI] [PubMed] [Google Scholar]
  34. Su X., Bromberg L., Martis V., Simeon F., Huq A., Hatton T. A.. Postsynthetic Functionalization of Mg-MOF-74 with Tetraethylenepentamine: Structural Characterization and Enhanced CO2 Adsorption. ACS Appl. Mater. Interfaces. 2017;9:11299–11306. doi: 10.1021/acsami.7b02471. [DOI] [PubMed] [Google Scholar]
  35. Hjorth Larsen A., Jørgen Mortensen J., Blomqvist J., Castelli I. E., Christensen R., Dułak M., Friis J., Groves M. N., Hammer B., Hargus C., Hermes E. D., Jennings P. C., Bjerre Jensen P., Kermode J., Kitchin J. R., Leonhard Kolsbjerg E., Kubal J., Kaasbjerg K., Lysgaard S.. et al. The Atomic Simulation Environment - A Python Library for Working with Atoms. J. Phys.: Condens. Matter. 2017;29:273002. doi: 10.1088/1361-648X/aa680e. [DOI] [PubMed] [Google Scholar]
  36. Kovács D. P., Batatia I., Arany E. S., Csányi G.. Evaluation of the MACE Force Field Architecture: From Medicinal Chemistry to Materials Science. J. Chem. Phys. 2023;159:044118. doi: 10.1063/5.0155322. [DOI] [PubMed] [Google Scholar]
  37. Batatia, I. ; Kovács, D. P. ; Simm, G. N. C. ; Ortner, C. ; Csányi, G. . MACE: Higher Order Equivariant Message Passing Neural Networks for Fast and Accurate Force Fields. In Advances in Neural Information Processing Systems, 2022; Vol. 35, pp 11423–11436. [Google Scholar]
  38. Han A., Wang B., Kumar A., Qin Y., Jin J., Wang X., Yang C., Dong B., Jia Y., Liu J.. et al. Recent Advances for MOF-Derived Carbon-Supported Single-Atom Catalysts. Catalysts. 2019;3:1800471. doi: 10.1002/smtd.201800471. [DOI] [Google Scholar]
  39. Chen X., Chen X., Yu E., Cai S., Jia H., Chen J., Liang P.. In Situ Pyrolysis of Ce-MOF to Prepare CeO2 Catalyst with Obviously Improved Catalytic Performance for Toluene Combustion. Chem. Eng. J. 2018;344:469–479. doi: 10.1016/j.cej.2018.03.091. [DOI] [Google Scholar]
  40. Wezendonk T. A., Santos V. P., Nasalevich M. A., Warringa Q. S. E., Dugulan A. I., Chojecki A., Koeken A. C. J., Ruitenbeek M., Meima G., Islam H. U., Sankar G., Makkee M., Kapteijn F., Gascon J.. Elucidating the Nature of Fe Species during Pyrolysis of the Fe-BTC MOF into Highly Active and Stable Fischer–Tropsch Catalysts. ACS Catal. 2016;6:3236–3247. doi: 10.1021/acscatal.6b00426. [DOI] [Google Scholar]
  41. Yu J., Balbuena P. B.. Water Effects on Postcombustion CO2 Capture in Mg-MOF-74. J. Phys. Chem. C. 2013;117:3383–3388. doi: 10.1021/jp311118x. [DOI] [Google Scholar]
  42. An H., Tian W., Lu X., Yuan H., Yang L., Zhang H., Shen H., Bai H.. Boosting the CO2 Adsorption Performance by Defect-Rich Hierarchical Porous Mg-MOF-74. Chem. Eng. J. 2023;469:144052. doi: 10.1016/j.cej.2023.144052. [DOI] [Google Scholar]
  43. Alonso G., Bahamon D., Keshavarz F., Giménez X., Gamallo P., Sayós R.. Density Functional Theory-Based Adsorption Isotherms for Pure and Flue Gas Mixtures on Mg-MOF-74. Application in CO2 Capture Swing Adsorption Processes. J. Phys. Chem. C. 2018;122:3945–3957. doi: 10.1021/acs.jpcc.8b00938. [DOI] [Google Scholar]

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