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Abstract
Copper (Cu) is the most promising catalyst for electrochemical CO2-to-C2+ conversion, whereas performance remains below practical thresholds due to the high energy barrier of C−C coupling and lack of effective approaches to steer the reaction pathway. Recent advances show that metal-organic frameworks (MOF) could be a promising platform as support, pre-catalyst, and co-catalyst to modify the electronic structure and local reaction environment of Cu catalysts for promoting CO2-to-C2+ reduction by virtue of their great tunability over compositions and pore architectures. In this review, we discussed general design principles, catalytic mechanisms, and performance achievements of MOF-based Cu catalysts, aiming to boost catalyst refinement for steering CO2 reduction pathway to C2+ products. The fundamentals and challenges of CO2-to-C2+ reduction are first introduced. Then, we summarized design conceptions of MOF-based Cu catalysts from three aspects: engineering the electronic properties of Cu, regulating the local reaction environment, and managing site exposure and mass transport. Further, the latest progress of CO2 reduction to C2+ products over MOF-based Cu catalysts, namely Cu-based MOF, MOF-derived Cu, and Cu@MOF hybrid catalysts, are discussed. Finally, future research opportunities and strategies are suggested to innovate the rational design of advanced MOF-based Cu catalysts for electrifying CO2-to-C2+ transformation.
Keywords
catalyst design
/
C−C coupling
/
CO2 reduction
/
copper
/
metal-organic frameworks
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Chen Qin, Xuheng Li, Ting Wang, Zhen Xu, Kai-Jie Chen, Fuping Pan.
Metal-Organic Frameworks-Based Copper Catalysts for CO2 Electroreduction Toward Multicarbon Products.
Exploration, 2025, 5(3): 270011 DOI:10.1002/EXP.70011
| [1] |
F. Guo and G. J. He, “Size, Alloy and Interface Effects on Cu-Based Catalysts for Enhancing Electrochemical Reduction of CO2,” Results in Engineering 20 (2023): 101510.
|
| [2] |
P. De Luna, C. Hahn, D. Higgins, S. A. Jaffer, T. F. Jaramillo, and E. H. Sargent, “What Would It Take for Renewably Powered Electrosynthesis to Displace Petrochemical Processes?,” Science 364 (2019): 3506.
|
| [3] |
Y. Yang, S. Louisia, S. Yu, et al., “Operando Studies Reveal Active Cu Nanograins for CO2 Electroreduction,” Nature 614 (2023): 262-269.
|
| [4] |
Y. Wu, Z. Jiang, X. Lu, Y. Liang, and H. Wang, “Domino Electroreduction of CO2 to Methanol on a Molecular Catalyst,” Nature 575 (2019): 639-642.
|
| [5] |
F. Pan, L. Fang, B. Li, et al., “N and OH-Immobilized Cu3 Clusters In Situ Reconstructed From Single-Metal Sites for Efficient CO2 Electromethanation in Bicontinuous Mesochannels,” Journal of the American Chemical Society 146 (2024): 1423-1434.
|
| [6] |
Y. Shang, M. Zheng, H. Liu, et al., “Mimicking Frustrated Lewis Pairs on Graphitic Carbon Nitride for CO2 Photoreduction,” ACS Catalysis 13 (2023): 14530-14539.
|
| [7] |
J. Strunk, “Separating Fiction From Fact for Photocatalytic CO2 Reduction,” Nature Chemistry 15 (2023): 1209-1211.
|
| [8] |
A. Ramirez, X. Gong, M. Caglayan, et al., “Selectivity Descriptors for the Direct Hydrogenation of CO2 to Hydrocarbons During Zeolite-Mediated Bifunctional Catalysis,” Nature Communications 12 (2021): 5914.
|
| [9] |
L. Xiao, X. Xu, Y. Jia, et al., “Pyroelectric Nanoplates for Reduction of CO2 to Methanol Driven by Temperature-Variation,” Nature Communications 12 (2021): 318.
|
| [10] |
T. Zheng, M. Zhang, L. Wu, et al., “Upcycling CO2 into Energy-Rich Long-Chain Compounds via Electrochemical and Metabolic Engineering,” Nature Catalysis 5 (2022): 388-396.
|
| [11] |
J. Y. T. Kim, C. Sellers, S. Hao, T. P. Senftle, and H. Wang, “Different Distributions of Multi-Carbon Products in CO2 and CO Electroreduction Under Practical Reaction Conditions,” Nature Catalysis 6 (2023): 1115-1124.
|
| [12] |
D. Gao, R. M. Arán-Ais, H. S. Jeon, and B. R. Cuenya, “Rational Catalyst and Electrolyte Design for CO2 Electroreduction Towards Multicarbon Products,” Nature Catalysis 2 (2019): 198-210.
|
| [13] |
W. Ma, S. Xie, B. Zhang, et al., “Copper Lattice Tension Boosts Full-Cell CO Electrolysis to Multi-Carbon Olefins and Oxygenates,” Chemistry 9 (2023): 2161-2177.
|
| [14] |
S. Nitopi, E. Bertheussen, S. B. Scott, et al., “Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte,” Chemical Reviews 119 (2019): 7610-7672.
|
| [15] |
F. Pan, B. Li, W. Deng, et al., “Promoting Electrocatalytic CO2 Reduction on Nitrogen-Doped Carbon With Sulfur Addition,” Applied Catalysis B 252 (2019): 240-249.
|
| [16] |
J. Moutet, J. M. Veleta, and T. L. Gianetti, “Symmetric, Robust, and High-Voltage Organic Redox Flow Battery Model Based on a Helical Carbenium Ion Electrolyte,” ACS Applied Energy Materials 4 (2020): 9-14.
|
| [17] |
T. Wang, X. Duan, R. Bai, et al., “Ni-Electrocatalytic CO2 Reduction Toward Ethanol,” Advanced Materials 36 (2024): 2410125.
|
| [18] |
M. Kunitski, N. Eicke, P. Huber, et al., “Double-Slit Photoelectron Interference in Strong-Field Ionization of the Neon Dimer,” Nature Communications 10 (2019): 1.
|
| [19] |
Y. Lin, T. Wang, L. Zhang, et al., “Tunable CO2 Electroreduction to Ethanol and Ethylene with Controllable Interfacial Wettability,” Nature Communications 14 (2023): 3575.
|
| [20] |
F. Li, A. Thevenon, A. Rosas-Hernández, et al., “Molecular Tuning of CO2-to-Ethylene Conversion,” Nature 577 (2019): 509-513.
|
| [21] |
F. Pan, W. Deng, C. Justiniano, and Y. Li, “Identification of Champion Transition Metals Centers in Metal and Nitrogen-Codoped Carbon Catalysts for CO2 Reduction,” Applied Catalysis B 226 (2018): 463-472.
|
| [22] |
F. Pan, B. Li, E. Sarnello, et al., “Boosting CO2 Reduction on Fe-N-C with Sulfur Incorporation: Synergistic Electronic and Structural Engineering,” Nano Energy 68 (2020): 104384.
|
| [23] |
R. I. Masel, Z. Liu, H. Yang, et al., “An Industrial Perspective on Catalysts for Low-Temperature CO2 Electrolysis,” Nature Nanotechnology 16 (2021): 118-128.
|
| [24] |
T. F. Yeh, J. M. Syu, C. Cheng, T. H. Chang, and H. Teng, “Graphite Oxide as a Photocatalyst for Hydrogen Production From Water,” Advanced Functional Materials 20 (2010): 2255-2262.
|
| [25] |
J. W. Wang, S. C. Fan, H. P. Li, X. Bu, Y. Y. Xue, and Q. G. Zhai, “De-Linker-Enabled Exceptional Volumetric Acetylene Storage Capacity and Benchmark C2H2/C2H4 and C2H2/CO2 Separations in Metal-Organic Frameworks,” Angewandte Chemie International Edition 62 (2023): e202217839.
|
| [26] |
S. Yuan, L. Feng, K. Wang, et al., “Stable Metal-Organic Frameworks: Design, Synthesis, and Applications,” Advanced Materials 30 (2018): 1704303.
|
| [27] |
T. A. Al-Attas, N. N. Marei, X. Yong, et al., “Ligand-Engineered Metal-Organic Frameworks for Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide,” ACS Catalysis 11 (2021): 7350-7357.
|
| [28] |
A. Mahmood, W. Guo, H. Tabassum, and R. Zou, “Metal-Organic Framework-Based Nanomaterials for Electrocatalysis,” Advanced Energy Materials 6 (2016): 1600423.
|
| [29] |
X. L. Cui, K. J. Chen, H. B. Xing, et al., “Pore Chemistry and Size Control in Hybrid Porous Materials for Acetylene Capture From Ethylene,” Science 353 (2016): 141-144.
|
| [30] |
K. J. Chen, D. G. Madden, S. Mukherjee, et al., “Synergistic Sorbent Separation for One-Step Ethylene Purification From a Four-Component Mixture,” Science 366 (2019): 241-246.
|
| [31] |
T. Zhang, K. Manna, and W. Lin, “Metal-Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations,” Journal of the American Chemical Society 138 (2016): 3241-3249.
|
| [32] |
C. Pan, J. Xu, Y. Wang, D. Li, and Y. Zhu, “Dramatic Activity of C3N4/BiPO4 Photocatalyst With Core/Shell Structure Formed by Self-Assembly,” Advanced Functional Materials 22 (2012): 1518-1524.
|
| [33] |
Y. Y. Liu, J. R. Huang, H. L. Zhu, P. Q. Liao, and X. M. Chen, “Simultaneous Capture of CO2 Boosting Its Electroreduction in the Micropores of a Metal-Organic Framework,” Angewandte Chemie International Edition 135 (2023): e202311265.
|
| [34] |
Z. H. Zhao, J. R. Huang, P. Q. Liao, and X. M. Chen, “Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C-C Coupling by a Metal-Organic Framework with Heterodimetal Dual Sites,” Journal of the American Chemical Society 145 (2023): 26783-26790.
|
| [35] |
Y. Xue, C. Li, X. Zhou, et al., “MOF-Derived Cu/Bi Bi-Metallic Catalyst to Enhance Selectivity Toward Formate for CO2 Electroreduction,” ChemElectroChem 9 (2022): e202101648.
|
| [36] |
B. An, J. Zhang, K. Cheng, P. Ji, C. Wang, and W. Lin, “Confinement of Ultrasmall Cu/ZnOX Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2,” Journal of the American Chemical Society 139 (2017): 3834-3840.
|
| [37] |
F. Pan, X. Yang, T. O'Carroll, H. Li, K.-J. Chen, and G. Wu, “Carbon Catalysts for Electrochemical CO2 Reduction Toward Multicarbon Products,” Advanced Energy Materials 12 (2022): 2200586.
|
| [38] |
J. T. Feaster, C. Shi, E. R. Cave, et al., “Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes,” ACS Catalysis 7 (2017): 4822-4827.
|
| [39] |
K. Zhao, Y. Liu, X. Quan, S. Chen, and H. Yu, “CO2 Electroreduction at Low Overpotential on Oxide-Derived Cu/Carbons Fabricated from Metal-Organic Framework,” ACS Applied Materials & Interfaces 9 (2017): 5302-5311.
|
| [40] |
Y. Wang, P. Han, X. Lv, L. Zhang, and G. Zheng, “Defect and Interface Engineering for Aqueous Electrocatalytic CO2 Reduction,” Joule 2 (2018): 2551-2582.
|
| [41] |
T. Cheng and H. Xiao, “Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water,” Journal of the American Chemical Society 138 (2016): 13802-13805.
|
| [42] |
L. Ai, S. F. Ng, and W. J. Ong, “Carbon Dioxide Electroreduction into Formic Acid and Ethylene: A Review,” Environmental Chemistry Letters 20 (2022): 3555-3612.
|
| [43] |
S. J. Folkman and R. G. Finke, “Electrochemical Water Oxidation Catalysis Beginning with Co(II) Polyoxometalates: The Case of the Precatalyst Co4V2W18O6810-,” ACS Catalysis 7 (2016): 7-16.
|
| [44] |
X. Lv, Q. Liu, J. Wang, et al., “Grain Refining Enables Mixed Cu+/Cu0 States for CO2 Electroreduction to C2+ Products at High Current Density,” Applied Catalysis B 324 (2023): 12272.
|
| [45] |
F. Pan, B. Li, X. Xiang, G. Wang, and Y. Li, “Efficient CO2 Electroreduction by Highly Dense and Active Pyridinic Nitrogen on Holey Carbon Layers with Fluorine Engineering,” ACS Catalysis 9 (2019): 2124-2133.
|
| [46] |
S. D. Rihm, M. K. Kovalev, A. A. Lapkin, J. W. Ager, and M. Kraft, “On the Role of C4 and C5 Products in Electrochemical CO2 Reduction via Copper-Based Catalysts,” Energy & Environmental Science 16 (2023): 1697-1710.
|
| [47] |
F. Pan, H. Zhang, K. Liu, et al., “Unveiling Active Sites of CO2 Reduction on Nitrogen-Coordinated and Atomically Dispersed Iron and Cobalt Catalysts,” ACS Catalysis 8 (2018): 3116-3122.
|
| [48] |
C. Li, Y. Ji, Y. Wang, et al. “Applications of Metal-Organic Frameworks and Their Derivatives in Electrochemical CO2 Reduction,” Nano-Micro Letters 15 (2023): 113.
|
| [49] |
T. Cheng and H. Xiao, “Full Atomistic Reaction Mechanism with Kinetics for CO Reduction on Cu(100) from Ab Initio Molecular Dynamics Free-Energy Calculations at 298 K,” Proceedings National Academy of Science USA 114 (2017): 1795-1800.
|
| [50] |
G. Liu, M. Lee, S. Kwon, et al., “CO2 Reduction on Pure Cu Produces Only H2 After Subsurface O is Depleted: Theory and Experiment,” Proceedings National Academy of Science USA 118 (2021): e2012649118.
|
| [51] |
J. Yu, J. Wang, Y. Ma, et al., “Recent Progresses in Electrochemical Carbon Dioxide Reduction on Copper-Based Catalysts toward Multicarbon Products,” Advanced Functional Materials 31 (2021): 210251.
|
| [52] |
J. D. Goodpaster, A. T. Bell, and M. Head-Gordon, “Identification of Possible Pathways for C-C Bond Formation During Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model,” Journal of Physical Chemistry Letters 7 (2016): 1471-1477.
|
| [53] |
P. Wei, D. Gao, T. Liu, et al., “Coverage-Driven Selectivity Switch from Ethylene to Acetate in High-Rate CO2/CO Electrolysis,” Nature Nanotechnology 18 (2023): 299-306.
|
| [54] |
R. De, S. Gonglach, S. Paul, et al., “Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex,” Angewandte Chemie International Edition 59 (2020): 10527-10534.
|
| [55] |
J. M. Huang, X. D. Zhang, J. Y. Huang, D. S. Zheng, M. Xu, and Z. Y. Gu, “MOF-Based Materials for Electrochemical Reduction of Carbon Dioxide,” Coordination Chemistry Reviews 494 (2023): 215333.
|
| [56] |
Y. Zhao, L. Zheng, D. Jiang, et al., “Nanoengineering Metal-Organic Framework-Based Materials for Use in Electrochemical CO2 Reduction Reactions,” Small 17 (2021): e2006590.
|
| [57] |
A. Brito-Ravicini and F. Calle-Vallejo, “Interplaying Coordination and Ligand Effects to Break or Make Adsorption-Energy Scaling Relations,” Exploration 2 (2022): 20210062.
|
| [58] |
L. Xiong, X. Zhang, H. Yuan, et al., “Breaking the Linear Scaling Relationship by Compositional and Structural Crafting of Ternary Cu-Au/Ag Nanoframes for Electrocatalytic Ethylene Production,” Angewandte Chemie International Edition 60 (2021): 2508-2518.
|
| [59] |
F. Abild-Pedersen, J. Greeley, F. Studt, et al., “Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces,” Physical Review Letters 99 (2007): 016105.
|
| [60] |
Z. Jin, D. Jiao, Y. Dong, et al., “Boosting Electrocatalytic Carbon Dioxide Reduction via Self-Relaxation of Asymmetric Coordination in Fe-Based Single Atom Catalyst,” Angewandte Chemie International Edition 63 (2024): e202318246.
|
| [61] |
C. F. Wen, M. Zhou, P. F. Liu, et al., “Highly Ethylene-Selective Electrocatalytic CO2 Reduction Enabled by Isolated Cu−S Motifs in Metal-Organic Framework Based Precatalysts,” Angewandte Chemie International Edition 61 (2021): e202111700.
|
| [62] |
Z. Z. Niu, L. P. Chi, R. Liu, Z. Chen, and M. R. Gao, “Rigorous Assessment of CO2 Electroreduction Products in a Flow Cell,” Energy & Environmental Science 14 (2021): 4169-4176.
|
| [63] |
Q. Chen, X. Wang, Y. Zhou, et al., “Engineering a Dynamic Solvent-Phobic Liquid Electrolyte Interphase for Long-Life Lithium Metal Batteries,” Advanced Materials 36 (2023): e2303902.
|
| [64] |
T. Lu, T. Xu, S. Zhu, et al., “Electrocatalytic CO2 Reduction to Ethylene: From Advanced Catalyst Design to Industrial Applications,” Advanced Materials 35 (2023): 2310433.
|
| [65] |
Y. Zhang, Y. Chen, X. Wang, Y. Feng, H. Zhang, and G. Zhang, “Self-Polarization Triggered Multiple Polar Units Toward Electrochemical Reduction of CO2 to Ethanol with High Selectivity,” Angewandte Chemie International Edition 62 (2023): e202302241.
|
| [66] |
S. Li, A. Guan, C. Yang, et al., “Dual-Atomic Cu Sites for Electrocatalytic CO Reduction to C2+ Products,” ACS Materials Letters 3 (2021): 1729-1737.
|
| [67] |
K. Zhao, X. Nie, H. Wang, et al., “Selective Electroreduction of CO2 to Acetone by Single Copper Atoms Anchored on N-Doped Porous Carbon,” Nature Communications 11 (2020): 2455.
|
| [68] |
H. Huo, J. Wang, Q. Fan, Y. Hu, and J. Yang, “Cu-MOFs Derived Porous Cu Nanoribbons with Strengthened Electric Field for Selective CO2 Electroreduction to C2+ Fuels,” Advanced Energy Materials 11 (2021): 2102447.
|
| [69] |
A. J. Medford, A. Vojvodic, J. S. Hummelshøj, et al., “From the Sabatier Principle to a Predictive Theory of Transition-Metal Heterogeneous Catalysis,” Journal of Catalysis 328 (2015): 36-42.
|
| [70] |
Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, and T. F. Jaramillo, “Combining Theory and Experiment in Electrocatalysis: Insights into Materials Design,” Science 355 (2017): eaad4998.
|
| [71] |
F. Pan, B. Li, E. Sarnello, et al., “Pore-Edge Tailoring of Single-Atom Iron-Nitrogen Sites on Graphene for Enhanced CO2 Reduction,” ACS Catalysis 10 (2020): 10803-10811.
|
| [72] |
R. He, Y. C. Wang, X. Wang, et al., “Facile Synthesis of Pentacle Gold-Copper Alloy Nanocrystals and Their Plasmonic and Catalytic Properties,” Nature Communications 5 (2014): 4327.
|
| [73] |
F. Chang, M. Xiao, R. Miao, et al., “Copper-Based Catalysts for Electrochemical Carbon Dioxide Reduction to Multicarbon Products,” Electrochemical Energy Reviews 5 (2022): 4.
|
| [74] |
J. D. Yi, R. Xie, Z. L. Xie, et al., “Highly Selective CO2 Electroreduction to CH4 by in Situ Generated Cu2O Single-Type Sites on a Conductive MOF: Stabilizing Key Intermediates with Hydrogen Bonding,” Angewandte Chemie International Edition 59 (2020): 23641-23648.
|
| [75] |
C. Wang, Z. Lv, X. Feng, W. Yang, and B. Wang, “Recent Advances in Electrochemical CO2 -to-Multicarbon Conversion: From Fundamentals to Industrialization,” Advanced Energy Materials 13 (2023): 2302382.
|
| [76] |
F. Yang, A. Chen, P. L. Deng, et al., “Highly Efficient Electroconversion of Carbon Dioxide into Hydrocarbons by Cathodized Copper-Organic Frameworks,” Chemical Science 10 (2019): 7975-7981.
|
| [77] |
S. J. Kang, J. H. Won, H. Choi, et al., “Compensating the Impurities on the Cu Surface by MOFs for Enhanced Hydrocarbon Production in the Electrochemical Reduction of Carbon Dioxide,” Journal of Energy Chemistry 66 (2022): 68-73.
|
| [78] |
T. Yan, P. Wang, and W. Y. Sun, “Single-Site Metal-Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO2 Electroreduction to C2H4,” Small 19 (2022): e2206070.
|
| [79] |
Y. Hori, A. Murata, and R. Takahashi, “Formation of Hydrocarbons in the Electrochemical Reduction of Carbon Dioxide at a Copper Electrode in Aqueous Solution,” Journal of the Chemical Society, Faraday Transactions 85 (1989): 2309-2326.
|
| [80] |
Y. Cao, S. Chen, S. Bo, et al., “Single Atom Bi Decorated Copper Alloy Enables C−C Coupling for Electrocatalytic Reduction of CO2 into C2+ Products**,” Angewandte Chemie International Edition 62 (2023): e202303048.
|
| [81] |
Y. Yan, Z. Zhao, J. Zhao, W. Tang, W. Huang, and J. M. Lee, “Atomic-Thin Hexagonal CuCo Nanocrystals with D-Band Tuning for CO2 Reduction,” Journal of Materials Chemistry A 9 (2021): 7496-7502.
|
| [82] |
D. Wei, Y. Wang, C. L. Dong, et al., “Decrypting the Controlled Product Selectivity Over Ag−Cu Bimetallic Surface Alloys for Electrochemical CO2 Reduction,” Angewandte Chemie International Edition 62 (2023): e202217369.
|
| [83] |
M. Liu, S. Liu, Q. Xu, et al., “Dual Atomic Catalysts from COF-Derived Carbon for CO2 RR by Suppressing HER Through Synergistic Effects,” Carbon Energy 5 (2023): e300.
|
| [84] |
C. Du, J. P. Mills, A. G. Yohannes, et al., “Cascade Electrocatalysis via AgCu Single-Atom Alloy and Ag Nanoparticles in CO2 Electroreduction Toward Multicarbon Products,” Nature Communications 14 (2023): 6142.
|
| [85] |
F. Pan, H. Zhang, Z. Liu, et al., “Atomic-Level Active Sites of Efficient Imidazolate Framework-Derived Nickel Catalysts for CO2 Reduction,” Journal of Materials Chemistry A 7 (2019): 26231-26237.
|
| [86] |
F. Pan, Z. Li, Z. Yang, et al., “Porous FeCo Glassy Alloy as Bifunctional Support for High-Performance Zn-Air Battery,” Advanced Energy Materials 11 (2021): 2002204.
|
| [87] |
L. Zhang, F. Mao, L. R. Zheng, H. F. Wang, X. H. Yang, and H. G. Yang, “Tuning Metal Catalyst with Metal-C3 N4 Interaction for Efficient CO2 Electroreduction,” ACS Catalysis 8 (2018): 11035-11041.
|
| [88] |
Y. Zang, T. Liu, P. Wei, et al., “Selective CO2 Electroreduction to Ethanol Over a Carbon-Coated CuOX Catalyst,” Angewandte Chemie International Edition 61 (2022): e202209629.
|
| [89] |
Z. Li, Y. Yang, Z. Yin, et al., “Interface-Enhanced Catalytic Selectivity on the C2 Products of CO2 Electroreduction,” ACS Catalysis 11 (2021): 2473-2482.
|
| [90] |
Z. Zhang, L. Melo, R. P. Jansonius, F. Habibzadeh, E. R. Grant, and C. P. Berlinguette, “pH Matters When Reducing CO2 in an Electrochemical Flow Cell,” ACS Energy Letters 5 (2020): 3101-3107.
|
| [91] |
A. S. Varela, M. Kroschel, T. Reier, and P. Strasser, “Controlling the Selectivity of CO2 Electroreduction on Copper: The Effect of the Electrolyte Concentration and the Importance of the Local pH,” Catalysis Today 260 (2016): 8-13.
|
| [92] |
N. Sikdar, J. R. C. Junqueira, S. Dieckhofer, et al., “A Metal-Organic Framework Derived CuX Oy CZ Catalyst for Electrochemical CO2 Reduction and Impact of Local pH Change,” Angewandte Chemie International Edition 60 (2021): 23427-23434.
|
| [93] |
M. Liu, Y. Pang, B. Zhang, et al., “Enhanced Electrocatalytic CO2 Reduction via Field-Induced Reagent Concentration,” Nature 537 (2016): 382-386.
|
| [94] |
S. Y. Lee, J. Kim, G. Bak, et al., “Probing Cation Effects on @CO Intermediates from Electroreduction of CO2 through Operando Raman Spectroscopy,” Journal of the American Chemical Society 145 (2023): 23068-23075.
|
| [95] |
M. Moura de Salles Pupo and R. Kortlever, “Electrolyte Effects on the Electrochemical Reduction of CO2,” ChemPhysChem 20 (2019): 2926-2935.
|
| [96] |
J. Resasco, L. D. Chen, E. Clark, et al., “Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide,” Journal of the American Chemical Society 139 (2017): 11277-11287.
|
| [97] |
A. S. Varela, W. Ju, T. Reier, and P. Strasser, “Tuning the Catalytic Activity and Selectivity of Cu for CO2 Electroreduction in the Presence of Halides,” ACS Catalysis 6 (2016): 2136-2144.
|
| [98] |
J. Wang, Y. Qin, S. Jin, et al., “Customizing CO2 Electroreduction by Pulse-Induced Anion Enrichment,” Journal of the American Chemical Society 145 (2023): 26213-26221.
|
| [99] |
Y. Huang, C. W. Ong, and B. S. Yeo, “Effects of Electrolyte Anions on the Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper (100) and (111) Surfaces,” ChemSusChem 11 (2018): 3299-3306.
|
| [100] |
M. N. Jackson, O. Jung, H. C. Lamotte, and Y. Surendranath, “Donor-Dependent Promotion of Interfacial Proton-Coupled Electron Transfer in Aqueous Electrocatalysis,” ACS Catalysis 9 (2019): 3737-3743.
|
| [101] |
F. Pan and Y. Yang, “Designing CO2 Reduction Electrode Materials by Morphology and Interface Engineering,” Energy & Environmental Science 13 (2020): 2275-2309.
|
| [102] |
L. X. Liu, Y. Cai, H. Du, et al., “Enriching the Local Concentration of CO Intermediates on Cu Cavities for the Electrocatalytic Reduction of CO2 to C2+ Products,” ACS Applied Materials & Interfaces 15 (2023): 16673-16679.
|
| [103] |
T. T. Zhuang, Y. Pang, Z. Q. Liang, et al., “Copper Nanocavities Confine Intermediates for Efficient Electrosynthesis of C3 Alcohol Fuels from Carbon Monoxide,” Nature Catalysis 1 (2018): 946-951.
|
| [104] |
X. Wang, J. F. de Araujo, W. Ju, et al., “Mechanistic Reaction Pathways of Enhanced Ethylene Yields During Electroreduction of CO2-CO Co-Feeds on Cu and Cu-Tandem Electrocatalysts,” Nature Nanotechnology 14 (2019): 1063-1070.
|
| [105] |
R. Shi, L. Shang, C. Zhou, Y. Zhao, and T. Zhang, “Interfacial Wettability and Mass Transfer Characterizations for Gas-Liquid-Solid Triple-Phase Catalysis,” Exploration 2 (2022): 20210046.
|
| [106] |
F. Pan, B. Li, E. Sarnello, et al., “Atomically Dispersed Iron-Nitrogen Sites on Hierarchically Mesoporous Carbon Nanotube and Graphene Nanoribbon Networks for CO2 Reduction,” ACS Nano 14 (2020): 5506-5516.
|
| [107] |
F. Pan, X. Duan, L. Fang, et al., “Long-Range Confinement-Driven Enrichment of Surface Oxygen-Relevant Species Promotes C−C Electrocoupling in CO2 Reduction,” Advanced Energy Materials 14 (2024): 2303118.
|
| [108] |
Z. Chen, M. R. Gao, Y. Q. Zhang, et al., “Tuning Local Carbon Active Sites Saturability of Graphitic Carbon Nitride to Boost CO2 Electroreduction towards CH4,” Nano Energy 73 (2020): 104833.
|
| [109] |
Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-Vallejo, and M. T. M. Koper, “Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels,” Nature Energy 4 (2019): 732-745.
|
| [110] |
G. Wen, D. U. Lee, B. Ren, et al., “Orbital Interactions in Bi-Sn Bimetallic Electrocatalysts for Highly Selective Electrochemical CO2 Reduction toward Formate Production,” Advanced Energy Materials 8 (2018): 1802427.
|
| [111] |
P. C. Chen, C. Chen, Y. Yang, et al., “Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO2 Reduction,” Journal of the American Chemical Society 145 (2023): 10116-10125.
|
| [112] |
J. Wang, G. Wang, J. Zhang, et al., “Inversely Tuning the CO2 Electroreduction and Hydrogen Evolution Activity on Metal Oxide via Heteroatom Doping,” Angewandte Chemie International Edition 60 (2021): 7602-7606.
|
| [113] |
D. H. Nam, O. Shekhah, G. Lee, et al., “Intermediate Binding Control Using Metal-Organic Frameworks Enhances Electrochemical CO2 Reduction,” Journal of the American Chemical Society 142 (2020): 21513-21521.
|
| [114] |
X. F. Qiu, H. L. Zhu, J. R. Huang, P. Q. Liao, and X. M. Chen, “Highly Selective CO2 Electroreduction to C2H4 Using a Metal-Organic Framework with Dual Active Sites,” Journal of the American Chemical Society 143 (2021): 7242-7246.
|
| [115] |
H. L. Zhu, H. Y. Chen, Y. X. Han, Z. H. Zhao, P. Q. Liao, and X. M. Chen, “A Porous π-π Stacking Framework with Dicopper(I) Sites and Adjacent Proton Relays for Electroreduction of CO2 to C2+ Products,” Journal of the American Chemical Society 144 (2022): 13319-13326.
|
| [116] |
R. Wang, J. Liu, Q. Huang, L. Z. Dong, S. L. Li, and Y. Q. Lan, “Partial Coordination-Perturbed Bi-Copper Sites for Selective Electroreduction of CO2 to Hydrocarbons,” Angewandte Chemie International Edition 60 (2021): 19829-19835.
|
| [117] |
D. H. Nam, O. S. Bushuyev, J. Li, et al., “Metal-Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction,” Journal of the American Chemical Society 140 (2018): 11378-11386.
|
| [118] |
Y. Ouyang, L. Shi, X. Bai, C. Ling, Q. Li, and J. Wang, “Selectivity of Electrochemical CO2 Reduction toward Ethanol and Ethylene: The Key Role of Surface-Active Hydrogen,” ACS Catalysis 13 (2023): 15448-15456.
|
| [119] |
L. Huang, Z. Liu, G. Gao, et al., “Enhanced CO2 Electroreduction Selectivity Toward Ethylene on Pyrazolate-Stabilized Asymmetric Ni-Cu Hybrid Sites,” Journal of the American Chemical Society 145 (2023): 26444-26451.
|
| [120] |
S. Popovic, M. Smiljanic, P. Jovanovic, J. Vavra, R. Buonsanti, and N. Hodnik, “Stability and Degradation Mechanisms of Copper-Based Catalysts for Electrochemical CO2 Reduction,” Angewandte Chemie International Edition 59 (2020): 14736-14746.
|
| [121] |
H. Zhang, T. Wang, J. Wang, et al., “Surface-Plasmon-Enhanced Photodriven CO2 Reduction Catalyzed by Metal-Organic-Framework-Derived Iron Nanoparticles Encapsulated by Ultrathin Carbon Layers,” Advanced Materials 28 (2016): 3703-3710.
|
| [122] |
Z. Yang, H. Wang, X. Fei, et al., “MOF Derived Bimetallic CuBi Catalysts with Ultra-Wide Potential Window for High-Efficient Electrochemical Reduction of CO2 to Formate,” Applied Catalysis B 298 (2021): 120571.
|
| [123] |
Y. Zhang, X. Y. Zhang, and W. Y. Sun, “In Situ Carbon-Encapsulated Copper-Doped Cerium Oxide Derived from MOFs for Boosting CO2-to-CH4 Electro-Conversion,” ACS Catalysis 13 (2023): 1545-1553.
|
| [124] |
T. Tang, Z. Wang, and J. Q. Guan, “Highly Selective and Eco-Friendly Dihydroisoquinoline Synthesis via Cu/Co Synergistic Catalysis in Cu NPs@MOFs Catalyst Under Mild Conditions,” Exploration 3 (2023): 20230011.
|
| [125] |
H. Y. Li, F. Pan, C. Qin, T. Wang, and K. J. Chen, “Porous Organic Polymers-Based Single-Atom Catalysts for Sustainable Energy-Related Electrocatalysis,” Advanced Energy Materials 13 (2023): 2301378.
|
| [126] |
X. Zou, A. Li, C. Ma, et al., “Nitrogen-Doped Carbon Confined Cu-Ag Bimetals for Efficient Electroreduction of CO2 to High-Order Products,” Chemical Engineering Journal 468 (2023): 143606.
|
| [127] |
B. Kim, Y. C. Tan, Y. Ryu, et al., “Trace-Level Cobalt Dopants Enhance CO2 Electroreduction and Ethylene Formation on Copper,” ACS Energy Letters 8 (2023): 3356-3364.
|
| [128] |
F. Yang, P. L. Deng, Q. Y. Wang, et al., “Metal-Organic Framework-Derived Cupric Oxide Polycrystalline Nanowires for Selective Carbon Dioxide Electroreduction to C2 Valuables,” Journal of Materials Chemistry A 8 (2020): 12418-12423.
|
| [129] |
B. Y. Guan, X. Y. Yu, H. B. Wu, and X. W. D. Lou, “Complex Nanostructures From Materials Based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion,” Advanced Materials 29 (2017): 1703614.
|
| [130] |
X. Yang, J. Cheng, X. Yang, Y. Xu, W. Sun, and J. Zhou, “MOF-Derived Cu@Cu2O Heterogeneous Electrocatalyst with Moderate Intermediates Adsorption for Highly Selective Reduction of CO2 to Methanol,” Chemical Engineering Journal 431 (2022): 134171.
|
| [131] |
H. Sun, L. Chen, L. Xiong, et al., “Promoting Ethylene Production Over a Wide Potential Window on Cu Crystallites Induced and Stabilized via Current Shock and Charge Delocalization,” Nature Communications 12 (2021): 6823.
|
| [132] |
W. Zhang, C. Huang, J. Zhu, et al., “Dynamic Restructuring of Coordinatively Unsaturated Copper Paddle Wheel Clusters to Boost Electrochemical CO2 Reduction to Hydrocarbons**,” Angewandte Chemie International Edition 61 (2022): e202112116.
|
| [133] |
X. Xie, X. Zhang, M. Xie, et al., “Au-Activated N Motifs in Non-Coherent Cupric Porphyrin Metal Organic Frameworks for Promoting and Stabilizing Ethylene Production,” Nature Communications 13 (2022): 63.
|
| [134] |
R. Yang, Y. Wang, J. W. Cao, et al., “Hydrogen Bond Unlocking-Driven Pore Structure Control for Shifting Multi-component Gas Separation Function,” Nature Communications 15 (2024): 804.
|
| [135] |
P. Du, Y. Zhang, X. Wang, et al., “Control of Zeolite Framework Flexibility for Ultra-Selective Carbon Dioxide Separation,” Nature Communications 13 (2022): 1427.
|
| [136] |
C. Lv, L. Zhong, H. Liu, et al., “Selective Electrocatalytic Synthesis of Urea with Nitrate and Carbon Dioxide,” Nature Sustainability 4 (2021): 868-876.
|
| [137] |
C. Lv, C. Lee, L. Zhong, et al., “A Defect Engineered Electrocatalyst That Promotes High-Efficiency Urea Synthesis Under Ambient Conditions,” ACS Nano 16 (2022): 8213-8222.
|
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