Chinese Journal of Catalysis ›› 2025, Vol. 68: 177-203.DOI: 10.1016/S1872-2067(24)60177-4
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Bailing Zhonga, Jundie Hua, Xiaogang Yanga, Yinying Shua, Yahui Caib, Chang Ming Lia,*(), Jiafu Qua,*(
)
Received:
2024-08-23
Accepted:
2024-10-24
Online:
2025-01-18
Published:
2025-01-02
Contact:
* E-mail: About author:
Chang Ming Li (School of Materials Science and Engineering, Suzhou University of Science and Technology) received his B.S. degree from University of Science and Technology of China in 1970, and Ph.D. degree from Wuhan University in 1987. He worked at Nanyang Technological University (from 2003 to 2012) and Southwest University (from 2012 to 2016). Since 2017, he has been working in Suzhou University of Science and Technology. His research interests mainly focus on cross-field sciences including functional nanomaterials and green energies. He has published 800 more peer-reviewed journal papers and H-index of 107 as well as 240 patents. He is the Chief Editor of Mater. Rep.: Energy.Supported by:
Bailing Zhong, Jundie Hu, Xiaogang Yang, Yinying Shu, Yahui Cai, Chang Ming Li, Jiafu Qu. Metal species confined in metal-organic frameworks for CO2 hydrogenation: Synthesis, catalytic mechanisms, and future perspectives[J]. Chinese Journal of Catalysis, 2025, 68: 177-203.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60177-4
Fig. 1. The quantity of published articles (a) and references (b) pertaining to metal species constrained within MOFs during the period spanning 2014 to 2024.
Fig. 3. (a) Conventional solvothermal synthesis of MOF structures. Reprinted with permission from Ref. [57]. Copyright 2013, Springer Nature. (b) A perspective view of HKUST-1 illustrates its nanochannels arranged in a fourfold symmetry (the structure depicts copper atoms in blue, carbon atoms in grey, and oxygen atoms in red). Reprinted with permission from Ref. [61]. Copyright 1999, American Association for the Advancement of Science. (c) MOF-5's architecture features Zn4O tetrahedra (depicted as blue polyhedra) connected by benzene dicarboxylate linkers (where oxygen is red and carbon is black), forming an expansive three-dimensional cubic framework. Reprinted with permission from Ref. [62]. Copyright 1999, Springer Nature.
Fig. 6. (a) Diagram illustrating various synthetic pathways for dual-metal MOFs alongside their strengths and weaknesses. Reprinted with permission from Ref. [83]. Copyright 2022, Royal Society of Chemistry. (b) Metal exchange after synthesis to incorporate reduced metal cations into MOF-5 networks. Reprinted with permission from Ref. [89]. Copyright 2013, American Chemical Society.
Fig. 7. (a) The ‘‘one-pot” approach. Reprinted with permission from Ref. [93]. Copyright 2017, MDPI. (b) Integration of Pt nanoparticles into MOFs via a direct one-step technique (top) and a dynamically controlled one-step approach (bottom). Reprinted with permission from Ref. [97]. Copyright 2016, John Wiley and Sons. (c) Preparation of Pd0-in-UiO-67. Color legend: cyan represents secondary building units of MOFs; grey denotes organic connectors; orange indicates metal precursors or nanoparticles; red signifies stabilizing agents. Reprinted with permission from Ref. [98]. Copyright 2014, Royal Society of Chemistry.
Fig. 8. (a) The ‘‘ship-in-a-bottle’’ approach. (b) The ‘‘bottle-around-ship” approach. Reprinted with permission from Ref. [93]. Copyright 2017, MDPI.
Fig. 9. (a) Diagram illustrating the fabrication process of Ni NPs@MOF. (b) TEM micrograph of Ni-MOF-74 treated at 350 °C for 12 h, with an inset showing electron diffraction. Reprinted with permission from Ref. [107]. Copyright 2015, Royal Society of Chemistry. (c) Methodology for synthesizing Pd@ZIF-8 using mechanochemistry assistance. (d) TEM visuals depicting Pd@ZIF-8 structures. (e) XRD spectra comparing Pd/ZnO and Pd@ZIF-8. Reprinted with permission from Ref. [108]. Copyright 2019, Royal Society of Chemistry.
Type of catalysis | Typical catalyst | Selectivity | Yield | Ref. |
---|---|---|---|---|
Photocatalysis | Ag⊂Re-UiO-67 | — | 0.94/h | [ |
Co-ZIF-9 | — | TON:180 h−1 | [ | |
MIL-101(Cr)-Ag | — | CO: 808.2 µmol g−1 h−1, CH4: 427.5 µmol g−1 h−1 | [ | |
Cu NCs@UiO-66-NH2 | HCOOH: 86% | 128 µmol·h−1·g−1 | [ | |
Cu2O@Cu@UiO-66-NH2 | CH4: 61.4% | CO: 20.9 μmol g−1 h−1, CH4: 8.3 μmol g−1 h−1 | [ | |
MOF-525-Co | CH4: 15.4% | CO: 200.6 mmol g−1 h−1, CH4: 36.67 mmol g−1 h−1 | [ | |
Cu SAs/UiO-66-NH2 | — | methanol: 5.33 μmol g−1 h−1, ethanol: 4.22 μmol g−1 h−1 | [ | |
Thermocatalysis | microCu@Al‐bpydc | 100% | — | [ |
Cu⊂UiO-66 | 100% | TOF: 3.7 × 103 s−1 | [ | |
10Ni@MOF-5 | — | conversion: 75.1% CO2 | [ | |
Ni-Co@CMOF-74 | — | conversions: 65%CO2, 57% CH4 | [ | |
Ni@C/MCF-T | — | conversion: 53.4% CO2 | [ | |
Ru@MIL-101 | CH4:99% | TOF: 3257 h−1 | [ | |
Photothermal catalysis | AuPt@UiO-66-NH2 | 91% | 1451 μmol g metal−1 h−1 | [ |
Ag/MIL-100 (Fe) | 86%−92% | — | [ | |
Au&Pt@ZIF | 100% | TOF: 1522 h−1 | [ | |
Au@Pd@UiO-66-NH2-0.5 | — | 3737 μmol g metal−1 h−1 | [ |
Table 1 CO2 hydrogenation applications of catalysts with different catalytic modes.
Type of catalysis | Typical catalyst | Selectivity | Yield | Ref. |
---|---|---|---|---|
Photocatalysis | Ag⊂Re-UiO-67 | — | 0.94/h | [ |
Co-ZIF-9 | — | TON:180 h−1 | [ | |
MIL-101(Cr)-Ag | — | CO: 808.2 µmol g−1 h−1, CH4: 427.5 µmol g−1 h−1 | [ | |
Cu NCs@UiO-66-NH2 | HCOOH: 86% | 128 µmol·h−1·g−1 | [ | |
Cu2O@Cu@UiO-66-NH2 | CH4: 61.4% | CO: 20.9 μmol g−1 h−1, CH4: 8.3 μmol g−1 h−1 | [ | |
MOF-525-Co | CH4: 15.4% | CO: 200.6 mmol g−1 h−1, CH4: 36.67 mmol g−1 h−1 | [ | |
Cu SAs/UiO-66-NH2 | — | methanol: 5.33 μmol g−1 h−1, ethanol: 4.22 μmol g−1 h−1 | [ | |
Thermocatalysis | microCu@Al‐bpydc | 100% | — | [ |
Cu⊂UiO-66 | 100% | TOF: 3.7 × 103 s−1 | [ | |
10Ni@MOF-5 | — | conversion: 75.1% CO2 | [ | |
Ni-Co@CMOF-74 | — | conversions: 65%CO2, 57% CH4 | [ | |
Ni@C/MCF-T | — | conversion: 53.4% CO2 | [ | |
Ru@MIL-101 | CH4:99% | TOF: 3257 h−1 | [ | |
Photothermal catalysis | AuPt@UiO-66-NH2 | 91% | 1451 μmol g metal−1 h−1 | [ |
Ag/MIL-100 (Fe) | 86%−92% | — | [ | |
Au&Pt@ZIF | 100% | TOF: 1522 h−1 | [ | |
Au@Pd@UiO-66-NH2-0.5 | — | 3737 μmol g metal−1 h−1 | [ |
Type of catalysis | Typical catalyst | Metal specie | Size (nm) | Pore volume/size | Stability | Ref. |
---|---|---|---|---|---|---|
Photocatalysis | Ag⊂Re-UiO-67 | Ag NCs | 16 | — | 48 h | [ |
Co-ZIF-9 | Co | — | — | 5 cycles | [ | |
MIL-101(Cr)-Ag | Ag NPs | 80-800 | — | — | [ | |
Cu NCs@UiO-66-NH2 | Cu NCs | 80 | — | — | [ | |
Cu2O@Cu@UiO-66-NH2 | Cu NPs | 50 | 0.255 cm3 g−1 | 3 cycles | [ | |
MOF-525-Co | Co NPs | — | — | 3 cycles | [ | |
Cu SAs/UiO-66-NH2 | Cu SAs | — | 0.6109 cm3 g−1 | 4 cycles | [ | |
Thermocatalysis | microCu@Al‐bpydc | Cu NPs | — | 2-12 nm | — | [ |
Cu⊂UiO-66 | Cu NCs | 18 | — | 12 cycles | [ | |
10Ni@MOF-5 | Ni NPs | — | 1.037 cm3 g−1 | 100 h | [ | |
Ni-Co@CMOF-74 | Ni, Co NPs | — | — | 10 h | [ | |
Ni@C/MCF-T | Ni NPs | 4.5 | — | 10 h | [ | |
Ru@MIL-101 | Ru NPs | 2-3 | 0.95 cm3 g−1 | 48 h | [ | |
Photothermal catalysis | AuPt@UiO-66-NH2 | AuPt alloy NPs | 14.8 | — | — | [ |
Ag/MIL-100 (Fe) | Ag NPs | 5-7 | 2.5-2.9 nm | 3 cycles | [ | |
Au&Pt@ZIF | Pt nano-Cubes Au nano-cages | Pt: 6 Au: 31 | — | 6 cycles | [ | |
Au@Pd@UiO-66-NH2-0.5 | Pd skin/Au NPs | Au: 13.8 Pd: 0.5-2 | — | 3 cycles performance becomes 62% | [ |
Table 2 Properties of catalysts in different catalytic modes.
Type of catalysis | Typical catalyst | Metal specie | Size (nm) | Pore volume/size | Stability | Ref. |
---|---|---|---|---|---|---|
Photocatalysis | Ag⊂Re-UiO-67 | Ag NCs | 16 | — | 48 h | [ |
Co-ZIF-9 | Co | — | — | 5 cycles | [ | |
MIL-101(Cr)-Ag | Ag NPs | 80-800 | — | — | [ | |
Cu NCs@UiO-66-NH2 | Cu NCs | 80 | — | — | [ | |
Cu2O@Cu@UiO-66-NH2 | Cu NPs | 50 | 0.255 cm3 g−1 | 3 cycles | [ | |
MOF-525-Co | Co NPs | — | — | 3 cycles | [ | |
Cu SAs/UiO-66-NH2 | Cu SAs | — | 0.6109 cm3 g−1 | 4 cycles | [ | |
Thermocatalysis | microCu@Al‐bpydc | Cu NPs | — | 2-12 nm | — | [ |
Cu⊂UiO-66 | Cu NCs | 18 | — | 12 cycles | [ | |
10Ni@MOF-5 | Ni NPs | — | 1.037 cm3 g−1 | 100 h | [ | |
Ni-Co@CMOF-74 | Ni, Co NPs | — | — | 10 h | [ | |
Ni@C/MCF-T | Ni NPs | 4.5 | — | 10 h | [ | |
Ru@MIL-101 | Ru NPs | 2-3 | 0.95 cm3 g−1 | 48 h | [ | |
Photothermal catalysis | AuPt@UiO-66-NH2 | AuPt alloy NPs | 14.8 | — | — | [ |
Ag/MIL-100 (Fe) | Ag NPs | 5-7 | 2.5-2.9 nm | 3 cycles | [ | |
Au&Pt@ZIF | Pt nano-Cubes Au nano-cages | Pt: 6 Au: 31 | — | 6 cycles | [ | |
Au@Pd@UiO-66-NH2-0.5 | Pd skin/Au NPs | Au: 13.8 Pd: 0.5-2 | — | 3 cycles performance becomes 62% | [ |
Fig. 11. (a) Diagram depicting the sequential stages of photocatalytic CO2 conversion, encompassing light absorption, generation and separation of charges, and surface reactions. (b) Diagram illustrating the material functionalities crucial for photocatalytic CO2 conversion, comprising a light-capturing semiconductor and catalytically active sites. Reprinted with permission from Ref. [114]. Copyright 2020, Royal Society of Chemistry.
Fig. 12. (a) The proposed a possible reaction mechanism of CO2 methanation over 20Ni@MIL-101(DSM) catalyst. (b) Potential energy diagram for CO2 methanation on the Ni (111) surface slab structure. Each reactant, product and intermediate structures are also shown in the inset of the Figure. The label “IM” is the intermediate structure, and “TS” is the transition structure. Reprinted with permission from Ref. [102]. Copyright 2017, Elsevier.
Fig. 13. Ren-MOF structures (a) and Ag?Ren-MOF (b) are employed to enhance plasmon-assisted photocatalytic reduction of CO2. Reprinted with permission from Ref. [134]. Copyright 2017, American Chemical Society. (c) Molecular configuration of Co-ZIF-9. (d) Impact of varying quantities of Co-ZIF-9 on CO and H2 production in the CO2 photoreduction setup. Reprinted with permission from Ref. [136]. Copyright 2013, John Wiley and Sons.
Fig. 14. (a) Evaluating CO2 reduction efficiencies across different catalysts. (b) Diagram depicting electron transfer mechanisms in MIL-101(Cr)-Ag hybrids. Reprinted with permission from Ref. [140]. Copyright 2019, American Chemical Society. (c) Graph showing size reduction of Cu NCs@MOF-801 based on Cu NCs concentration. (d) Comparison of CO2 photocatalysis production using Cu NCs@MOF-801 and Cu NCs@UiO-66-NH2 against control experiments. Reprinted with permission from Ref. [141]. Copyright 2022, John Wiley and Sons.
Fig. 15. (a) High-resolution transmission electron microscopy (HRTEM) analysis of Au/MOF-808-SH (the inset shows crystalline Au nanoparticles). (b) Size distribution of Au nanoparticles in Au/MOF-808-SH. (c) Molecular structure of MOF-808-SH. (d) LEIS spectra of Au/MOF-808-SH before and after sputtering (4 × 1014 cm?2 Ar+ ions). Reprinted with permission from Ref. [145]. Copyright 2019, Royal Society of Chemistry.
Fig. 16. (a) Proposed mechanism of the photocatalysis over MIL-125/Ag/g-C3N4. Reprinted with permission from Ref. [148]. Copyright 2017, Elsevier. (b) Cu2O@Cu@UiO-66-NH2 photocatalytic mechanism of CO2. Reprinted with permission from Ref. [149]. Copyright 2020, American Chemical Society.
Fig. 17. (a) Mechanism diagram of CO2 hydrogenation catalyzed by MOF-525-Co. Reprinted with permission from Ref. [151]. Copyright 2016, John Wiley and Sons. (b) Mechanism diagram of CO2 photocatalytic hydrogenation of Cu SAs/UiO-66-NH2. (c) Synthesis process of the Cu SAs/UiO-66-NH2 photocatalyst. Reprinted with permission from Ref. [152]. Copyright 2020, American Chemical Society.
Fig. 19. (a) Energy schematic depicting the thermal catalytic reaction process. Ea1, Ea2, and Ea3 represent the activation energy for reactants and intermediates at various stages of CO2 hydrogenation. The continuous and dashed lines depict the reaction progression in the absence and presence of a catalyst, respectively. Reprinted with permission from Ref. [155]. Copyright 2020, John Wiley and Sons. (b) Four primary outcomes from thermal catalytic CO2 hydrogenation reactions. Reprinted with permission from Ref. [156]. Copyright 2021, John Wiley and Sons.
Fig. 20. (a) A schematic illustration of the synthesis of PdAg/TiO2@ZIF-8. (b) DFT-optimized configurations for dissociated H atoms and HCO3? ions adsorbed on PdAg (111) and PdAg (111) with the ZIF-8 framework (showing two 2-methylimidazole molecules bonded to a Zn2+ ion) in two different configurations. Reprinted with permission from Ref. [157]. Copyright 2020, American Chemical Society.
Fig. 21. (a) Hypothetical process of cycloaddition between CO2 and epoxides facilitated by CZ‐BDO. (b) Impact of varying reaction duration on conversion and specificity. Reprinted with permission from Ref. [164]. Copyright 2020, Royal Society of Chemistry.
Fig. 22. (a) Diagram depicting the fabrication process of hierarchically porous mesoCu@Al‐bpydc. (b) Comparative catalytic activity of microCu@Al‐bpydc and mesoCu@Al‐bpydc with various epoxides. Reprinted with permission from Ref. [168]. Copyright 2019, John Wiley and Sons.
Fig. 23. (a) TOFs for product generation using Cu?UiO-66 and Cu/ZnO/Al2O3 catalysts at varying reaction temperatures. (b) Initial methanol TOFs comparing Cu?UiO-66 and Cu supported on UiO-66. Reprinted with permission from Ref. [171]. Copyright 2016, American Chemical Society. (c) Stability tests over 10Ni@MOF-5 catalyst for 100 h. Reprinted with permission from Ref. [173]. Copyright 2015, Royal Society of Chemistry. (d) Catalytic outcomes of various M@CMOF-74 catalysts at 750 °C, 5 bar pressure, and a flow rate of 18 L h?1 g?1. Reprinted with permission from Ref. [175]. Copyright 2020, MDPI.
Fig. 24. (a) Schematic illustration of composite pathway at Ni@C/MCF-T. (b) CO2 conversion performance. Reprinted with permission from Ref. [179]. Copyright 2023, Elsevier. (c) Diagram depicting the integration of silica nanofibrous veils as support for MIL-101 nanostructures loaded with Ru nanoparticles for catalyzing CO2 hydrogenation to CH4. Reprinted with permission from Ref. [180]. Copyright 2023, Elsevier. (d) Potential energy landscapes for CO2 hydrogenation to CH3OH on Cu(111) via the HCOO, trans-COOH, and water-enhanced trans-COOH mechanisms. Reprinted with permission from Ref. [183]. Copyright 2011, Elsevier.
Fig. 26. (a) The depiction of energetic carriers produced via nonradiative decay stemming from the LSPR phenomena. (b) Activation of bonds atop plasmonic metals, immediate transformation following absorption of plasmon energy from the metal via an indirect (c) and a direct (d) pathway, respectively. Reprinted with permission from Ref. [188]. Copyright 2018, Springer Nature.
Fig. 27. (a) Calculated free energy diagram for CO2 hydrogenation over Pt@UiO-66-NH2 (Co). (b) Redox potentials of various materials and redox potentials of CO2 reduction to products. Reprinted with permission from Ref. [189]. Copyright 2023, John Wiley and Sons.
Fig. 28. (a) diagram depicting the operational concept of plasmon-induced thermal catalysis for CO2 hydrogenation using AuPt@UiO- 66-NH2. (b) Rates of CO2 hydrogenation over AuPt@UiO-66-NH2 at 150 °C under varied light wavelengths for a duration of 4 h. (c) Relationship between reaction rates and temperature for AuPt@UiO-66-NH2; Reprinted with permission from Ref. [200]. Copyright 2022, John Wiley and Sons. (d) UV-visible absorption spectra of MIL-100 (Fe) and Ag/MIL-100 (Fe) with differing Ag loading levels. (e) Synthetic pathway for Ag/MIL-100 (Fe) and the photothermal conversion process of CO2. Reprinted with permission from Ref. [201]. Copyright 2021, Elsevier.
Fig. 29. (a) Product yields of Pt nanocubes, Pt@ZIF, Au&Pt@ZIF, and Pt@ZIF+Au in CO2 hydrogenation at 150 °C for 3 h. (b) Yield comparison of products from Au&Pt@ZIF under light and dark conditions at various temperatures for 3 h. Reprinted with permission from Ref. [203]. Copyright 2016, John Wiley and Sons. (c) Diagram illustrating the synthesis process of Au@Pd@UiO-66-NH2. (d) Rates of CO production using Au@Pd@UiO-66-NH2-0.5 at different temperatures with light exposure. High-speed TA spectroscopy (e) and temporal evolution of TA signals in kinetic curves (f) of Au@Pd-0.5. (g) Schematic representation of light-induced CO2 hydrogenation over Au@Pd@UiO-66-NH2-0.5. Reprinted with permission from Ref. [39]. Copyright 2021, Elsevier.
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