PDF
Abstract
Electrochemical CO2 reduction reaction (CO2RR) has received great attention to solve CO2- induced global warming and carbon neutrality. It is essential to enhance the electrochemical CO2RR selectivity, activity, and long-term stability for sustainable manufacturing of specific chemicals via CO2RR. To produce multi-carbon (C2+) chemicals, Cu-based heterogeneous catalysts have been developed in terms of defect engineering, morphological design, and facet control. Despite the substantial efforts for the design of efficient Cu-based heterogeneous catalysts, there exist inevitable structural changes of catalysts with continuous dissolution and redeposition during CO2RR. This reconstruction modifies the as-synthesized catalysts into an unpredictable structure and leads to changes in active site. Here, we review the reconstruction of Cu-based catalysts during CO2RR, which occurs via continuous dissolution and redeposition process. This includes fundamental principles of reconstruction and the effect of microenvironment on reconstruction during CO2RR. We offer research progress about the reconstruction of Cu-based electrocatalysts, analysis methodologies to track the reconstruction, and the insight to improve the activity, selectivity, and stability of CO2RR. We provide perspective to understand and harness the reconstruction for the development of efficient CO2RR catalysts.
Keywords
carbon neutrality
/
CO2 reduction reaction
/
electrocatalysts
/
heterogeneous catalysts
/
reconstruction
Cite this article
Download citation ▾
Woosuck Kwon, Dohun Kim, Yujin Lee, Jinoh Jung, Dae-Hyun Nam.
Advancements in Understanding Catalyst Reconstruction During Electrochemical CO2 Reduction.
Exploration, 2025, 5(4): e20240019 DOI:10.1002/EXP.20240019
| [1] |
D. Gao, I. Sinev, F. Scholten, et al., “Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring,” Angewandte Chemie (International ed in English) 58 (2019): 17047-17053.
|
| [2] |
B. Zhang, J. Zhang, M. Hua, et al., “Highly Electrocatalytic Ethylene Production From CO2 on Nanodefective Cu Nanosheets,” Journal of the American Chemical Society 142 (2020): 13606-13613.
|
| [3] |
Z. Tang, E. Nishiwaki, K. E. Fritz, T. Hanrath, and J. Suntivich, “Cu(I) Reducibility Controls Ethylene vs Ethanol Selectivity on (100)-Textured Copper during Pulsed CO2 Reduction,” ACS Applied Materials & Interfaces 13 (2021): 14050-14055.
|
| [4] |
R. Kortlever, J. Shen, K. J. P. Schouten, F. Calle-Vallejo, and M. T. M. Koper, “Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide,” The Journal of Physical Chemistry Letters 6 (2015): 4073-4082.
|
| [5] |
A. Loiudice, P. Lobaccaro, E. A. Kamali, et al., “Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction,” Angewandte Chemie International Edition 55 (2016): 5789-5792.
|
| [6] |
P. Iyengar, M. J. Kolb, J. R. Pankhurst, F. Calle-Vallejo, and R. Buonsanti, “Elucidating the Facet-Dependent Selectivity for CO2 Electroreduction to Ethanol of Cu-Ag Tandem Catalysts,” ACS Catalysis 11 (2021): 4456-4463.
|
| [7] |
J. Kim, W. Choi, J. W. Park, C. Kim, M. Kim, and H. Song, “Branched Copper Oxide Nanoparticles Induce Highly Selective Ethylene Production by Electrochemical Carbon Dioxide Reduction,” Journal of the American Chemical Society 141 (2019): 6986-6994.
|
| [8] |
G. Shi, Y. Xie, L. Du, et al., “Constructing Cu−C Bonds in a Graphdiyne-Regulated Cu Single-Atom Electrocatalyst for CO2 Reduction to CH4,” Angewandte Chemie (International ed in English) 61 (2022): e202203569.
|
| [9] |
H. Zou, G. Zhao, H. Dai, et al., “Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way,” Angewandte Chemie (International ed in English) 62 (2023): e202217220.
|
| [10] |
Y. Xu, C. Li, Y. Xiao, et al., “Tuning the Selectivity of Liquid Products of CO2RR by Cu-Ag Alloying,” ACS Applied Materials & Interfaces 14 (2022): 11567-11574.
|
| [11] |
F. Chang, K. Zhu, C. Liu, et al., “Construction of Cu─Ni Atomic Pair With Bimetallic Atom-Cluster Sites for Enhanced CO2 Electroreduction,” Advanced Functional Materials 34 (2024): 2400893.
|
| [12] |
Y. Wang, Z. Wang, C.-T. Dinh, et al., “Catalyst Synthesis Under CO2 Electroreduction Favours Faceting and Promotes Renewable Fuels Electrosynthesis,” Nature Catalysis 3 (2020): 98-106.
|
| [13] |
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.
|
| [14] |
J. Vavra, T.-H. Shen, D. Stoian, V. Tileli, and R. Buonsanti, “Real-Time Monitoring Reveals Dissolution/Redeposition Mechanism in Copper Nanocatalysts During the Initial Stages of the CO2 Reduction Reaction,” Angewandte Chemie International Edition 60 (2021): 1347-1354.
|
| [15] |
P. Grosse, A. Yoon, C. Rettenmaier, A. Herzog, S. W. Chee, and B. R. Cuenya, “Dynamic Transformation of Cubic Copper Catalysts During CO2 Electroreduction and Its Impact on Catalytic Selectivity,” Nature Communications 12 (2021): 6736.
|
| [16] |
Z. Han, D. Han, Z. Chen, et al., “Steering Surface Reconstruction of Copper With Electrolyte Additives for CO2 Electroreduction,” Nature Communications 13 (2022): 3158.
|
| [17] |
J. Huang, N. Hörmann, E. Oveisi, et al., “Potential-induced Nanoclustering of Metallic Catalysts During Electrochemical CO2 Reduction,” Nature Communications 9 (2018): 3117.
|
| [18] |
J. Vavra, G. P. Ramona, F. Dattila, et al., “Solution-Based Cu+ Transient Species Mediate the Reconstruction of Copper Electrocatalysts for CO2 Reduction,” Nature Catalysis 7 (2024): 89-97.
|
| [19] |
S. Y. Lee, H. Jung, N.-K. Kim, H.-S. Oh, B. K. Min, and Y. J. Hwang, “Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production From CO2 Reduction,” Journal of the American Chemical Society 140 (2018): 8681-8689.
|
| [20] |
C. Xia, F.-M. Li, C. He, S. Zaman, W. Guo, and B. Y. Xia, “Structural Reconstruction of Electrocatalysts,” Fundamental Research (2024).
|
| [21] |
H. Wu, H. Yu, Y. L. Chow, P. A. Webley, and J. Zhang, “Toward Durable CO2 Electroreduction With Cu-Based Catalysts via Understanding Their Deactivation Modes,” Advanced Materials 36 (2024): 2403217.
|
| [22] |
J. Chen and L. Wang, “Effects of the Catalyst Dynamic Changes and Influence of the Reaction Environment on the Performance of Electrochemical CO2 Reduction,” Advanced Materials 34 (2022): 2103900.
|
| [23] |
C. Chen, X. Yan, Y. Wu, et al., “The in Situ Study of Surface Species and Structures of Oxide-Derived Copper Catalysts for Electrochemical CO2 Reduction,” Chemical Science 12 (2021): 5938-5943.
|
| [24] |
K. Rossi and R. Buonsanti, “Shaping Copper Nanocatalysts to Steer Selectivity in the Electrochemical CO2 Reduction Reaction,” Accounts of Chemical Research 55 (2022): 629-637.
|
| [25] |
M. Munz, J. Poon, W. Frandsen, B. R. Cuenya, and C. S. Kley, “Nanoscale Electron Transfer Variations at Electrocatalyst-Electrolyte Interfaces Resolved by in Situ Conductive Atomic Force Microscopy,” Journal of the American Chemical Society 145 (2023): 5242-5251.
|
| [26] |
Y.-G. Kim, J. H. Baricuatro, A. Javier, J. M. Gregoire, and M. P. Soriaga, “The Evolution of the Polycrystalline Copper Surface, First to Cu(111) and Then to Cu(100), at a Fixed CO2RR Potential: A Study by Operando EC-STM,” Langmuir 30 (2014): 15053-15056.
|
| [27] |
Z. Li, L. Wang, T. Wang, L. Sun, and W. Yang, “Steering the Dynamics of Reaction Intermediates and Catalyst Surface During Electrochemical Pulsed CO2 Reduction for Enhanced C2+ Selectivity,” Journal of the American Chemical Society 145 (2023): 20655-20664.
|
| [28] |
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.
|
| [29] |
H. Shi, L. Luo, C. Li, et al., “Stabilizing Cu+ Species in Cu2 O/CuO Catalyst via Carbon Intermediate Confinement for Selective CO2 RR,” Advanced Functional Materials 34 (2024): 2310913.
|
| [30] |
Z. Ma, T. Wan, D. Zhang, et al., “Atomically Dispersed Cu Catalysts on Sulfide-Derived Defective Ag Nanowires for Electrochemical CO2 Reduction,” ACS Nano 17 (2023): 2387-2398.
|
| [31] |
Z. Ma, C. Tsounis, C. Y. Toe, et al., “Reconstructing Cu Nanoparticle Supported on Vertical Graphene Surfaces via Electrochemical Treatment to Tune the Selectivity of CO2 Reduction Toward Valuable Products,” ACS Catalysis 12 (2022): 4792-4805.
|
| [32] |
X. Wang, A. Guo, Y. Wang, et al., “Br-doped Cu Nanoparticle Formed by in Situ Restructuring for Highly Efficient Electrochemical Reduction of CO2 to Formate,” Journal of Colloid and Interface Science 653 (2024): 238-245.
|
| [33] |
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.
|
| [34] |
W. Fang, R. Lu, F.-M. Li, et al., “Low-Coordination Nanocrystalline Copper-Based Catalysts Through Theory-Guided Electrochemical Restructuring for Selective CO2 Reduction to Ethylene,” Angewandte Chemie International Edition 63 (2024): e202319936.
|
| [35] |
J. Vavra, G. P. L. Ramona, F. Dattila, et al., “Solution-based Cu+ Transient Species Mediate the Reconstruction of Copper Electrocatalysts for CO2 Reduction,” Nature Catalysis 7 (2024): 89-97.
|
| [36] |
W. Lai, Y. Qiao, Y. Wang, and H. Huang, “Stability Issues in Electrochemical CO2 Reduction: Recent Advances in Fundamental Understanding and Design Strategies,” Advanced Materials 35 (2023): 2306288.
|
| [37] |
S. Seo, S. Jin, G. Wang, and B. Yoo, “The Effect of Copper Dissolution in Acidic Electrolyte on the Formation of Nanotwin in Pulse Electrodeposited Copper,” Journal of the Electrochemical Society 161 (2014): D425-D428.
|
| [38] |
P. K. Yadav, C. Kochar, L. Taneja, and S. S. Tripathy, “Study on Dissolution Behavior of CuO Nanoparticles in Various Synthetic media and Natural Aqueous Medium,” Journal of Nanoparticle Research 24 (2022): 122.
|
| [39] |
“Corrosion of Copper Alloys in KOH, NaOH, NaCl, and HCl Electrolyte Solutions and Its Impact to the Mechanical Properties,” Alexandria Engineering Journal 60 (2021): 2235-2243.
|
| [40] |
F. D. Speck and S. Cherevko, “Electrochemical Copper Dissolution: A Benchmark for Stable CO2 Reduction on Copper Electrocatalysts,” Electrochemistry Communications 115 (2020): 106739.
|
| [41] |
D. Zhong, D. Cheng, Q. Fang, Y. Liu, J. Li, and Q. Zhao, “Understanding the Restructuring and Degradation of Oxide-derived Copper During Electrochemical CO2 Reduction,” Chemical Engineering Journal 470 (2023): 143907.
|
| [42] |
P. De Luna, R. Quintero-Bermudez, C.-T. Dinh, et al., “Catalyst Electro-redeposition Controls Morphology and Oxidation state for Selective Carbon Dioxide Reduction,” Nature Catalysis 1 (2018): 103-110.
|
| [43] |
H. Jung, S. Y. Lee, C. W. Lee, et al., “Electrochemical Fragmentation of Cu2O Nanoparticles Enhancing Selective C-C Coupling From CO2 Reduction Reaction,” Journal of the American Chemical Society 141 (2019): 4624-4633.
|
| [44] |
Q. Liu, Q. Jiang, L. Li, and W. Yang, “Spontaneous Reconstruction of Copper Active Sites During the Alkaline CORR: Degradation and Recovery of the Performance,” Journal of the American Chemical Society 146 (2024): 4242-4251.
|
| [45] |
A. Yoon, J. Poon, P. Grosse, S. W. Chee, and B. R. Cuenya, “Iodide-mediated Cu Catalyst Restructuring During CO2 Electroreduction,” Journal of Materials Chemistry A: Materials 10 (2022): 14041-14050.
|
| [46] |
D. K. Pattadar and F. P. Zamborini, “Effect of Size, Coverage, and Dispersity on the Potential-Controlled Ostwald Ripening of Metal Nanoparticles,” Langmuir 35 (2019): 16416-16426.
|
| [47] |
J. Huang, N. Hormann, E. Oveisi, et al., “Potential-induced Nanoclustering of Metallic Catalysts During Electrochemical CO2 Reduction,” Nature Communications 9 (2018): 3117.
|
| [48] |
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.
|
| [49] |
B. Chen, Z. Zhang, S. Kim, et al., “Ostwald Ripening Driven Exfoliation to Ultrathin Layered Double Hydroxides Nanosheets for Enhanced Oxygen Evolution Reaction,” ACS Applied Materials & Interfaces 10 (2018): 44518-44526.
|
| [50] |
K. K. Nanda, A. Maisels, F. E. Kruis, H. Fissan, and S. Stappert, “Higher Surface Energy of Free Nanoparticles,” Physical Review Letter 91 (2003): 106102.
|
| [51] |
M. N. Hossain, L. Zhang, R. Neagu, and E. Rassachack, “Free-Standing Single-Atom Catalyst-Based Electrodes for CO2 Reduction,” Electrochemical Energy Reviews 7 (2024): 1-45.
|
| [52] |
J.-Y. Kim, H. S. Ahn, I. Kim, et al., “Selective Hydrocarbon or Oxygenate Production in CO2 Electroreduction Over Metallurgical Alloy Catalysts,” Nature Synthesis 3 (2024): 452-465.
|
| [53] |
K. Fan, L. Zong, J. Liu, et al., “In Situ Reconstruction to Surface Sulfide Adsorbed Metal Scaffold for Enhanced Electrocatalytic Hydrogen Evolution Activity,” Advanced Energy Materials 14 (2024): 2400052.
|
| [54] |
L. Su, X. Cui, T. He, et al., “Surface Reconstruction of Cobalt Phosphide Nanosheets by Electrochemical Activation for Enhanced Hydrogen Evolution in Alkaline Solution†”, Chemical Science 10 (2019): 2019-2024.
|
| [55] |
H. Jiang, Q. He, X. Li, et al., “Tracking Structural Self-Reconstruction and Identifying True Active Sites Toward Cobalt Oxychloride Precatalyst of Oxygen Evolution Reaction,” Advanced Materials 31 (2019): 1805127.
|
| [56] |
E. W. Lees, B. A. Mowbray, F. G. Parlane, and C. P. Berlinguette, “Gas Diffusion Electrodes and Membranes for CO2 Reduction Electrolysers,” Nature Reviews Materials 7 (2022): 55-64.
|
| [57] |
W. Ma, X. He, W. Wang, S. Xie, Q. Zhang, and Y. Wang, “Electrocatalytic Reduction of CO2 and CO to Multi-carbon Compounds Over Cu-based Catalysts,” Chemical Society Reviews 50 (2021): 12897-12914.
|
| [58] |
Y. Kim, S. Park, S.-J. Shin, et al., “Time-Resolved Observation of C-C Coupling Intermediates on Cu Electrodes for Selective Electrochemical CO2 Reduction,” Energy & Environmental Science 13 (2020): 4301-4311.
|
| [59] |
F. Li, Y. C. Li, Z. Wang, et al., “Cooperative CO2-to-Ethanol Conversion via Enriched Intermediates at Molecule-Metal Catalyst Interfaces,” Nature Catalysis 3 (2020): 75-82.
|
| [60] |
B. Eren, D. Zherebetskyy, L. L. Patera, et al., “Activation of Cu(111) Surface by Decomposition Into Nanoclusters Driven by CO Adsorption,” Science 351 (2016): 475-478.
|
| [61] |
B. Eren, D. Zherebetskyy, Y. Hao, et al., “One-Dimensional Nanoclustering of the Cu (100) Surface Under CO Gas in the Mbar Pressure Range,” Surface Science 651 (2016): 210-214.
|
| [62] |
R. Amirbeigiarab, J. Tian, A. Herzog, et al., “Atomic-scale Surface Restructuring of Copper Electrodes Under CO2 Electroreduction Conditions,” Nature Catalysis 6 (2023): 837-846.
|
| [63] |
S. Popovic, M. Bele, and N. Hodnik, “Reconstruction of Copper Nanoparticles at Electrochemical CO2 Reduction Reaction Conditions Occurs via Two-Step Dissolution/Redeposition Mechanism,” ChemElectroChem 8 (2021): 2634-2639.
|
| [64] |
W. Ni, Z. Yixiang, Y. Yao, et al., “Surface Reconstruction with a Sandwich-like C/Cu/C Catalyst for Selective and Stable CO2 Electroreduction,” ACS Applied Materials & Interfaces 14 (2022): 13261.
|
| [65] |
M. C. O. Monteiro, F. Dattila, N. López, and M. T. M. Koper, “The Role of Cation Acidity on the Competition Between Hydrogen Evolution and CO2 Reduction on Gold Electrodes,” Journal of the American Chemical Society 144 (2022): 1589-1602.
|
| [66] |
H.-G. Qin, F.-Z. Li, Y.-F. Du, et al., “Quantitative Understanding of Cation Effects on the Electrochemical Reduction of CO2 and H+ in Acidic Solution,” ACS Catalysis 13 (2023): 916-926.
|
| [67] |
B. Pan, Y. Wang, and Y. Li, “Understanding and Leveraging the Effect of Cations in the Electrical Double Layer for Electrochemical CO2 Reduction,” Chem Catalysis 2 (2022): 1267-1276.
|
| [68] |
C.-T. Dinh, T. Burdyny, M. G. Kibria, et al., “CO2 Electroreduction to Ethylene via Hydroxide-mediated Copper Catalysis at an Abrupt Interface,” Science 360 (2018): 783-787.
|
| [69] |
J. A. Gauthier, Z. Lin, M. Head-Gordon, and A. T. Bell, “Pathways for the Formation of C2+ Products Under Alkaline Conditions During the Electrochemical Reduction of CO2,” ACS Energy Letters 7 (2022): 1679-1686.
|
| [70] |
C. Zhong, Y. Deng, W. Hu, J. Qiao, L. Zhang, and J. Zhang, “A Review of Electrolyte Materials and Compositions for Electrochemical Supercapacitors,” Chemical Society Reviews 44 (2015): 7484-7539.
|
| [71] |
W. X. Wu, L. P. Xu, Q. Lu, et al., “Addressing the Carbonate Issue: Electrocatalysts for Acidic CO2 Reduction Reaction,” Advanced Materials 33 (2024).
|
| [72] |
N. Wang, K. Yao, A. Vomiero, Y. Wang, and H. Liang, “Inhibiting Carbonate Formation Using CO2 -CO-C2+ Tandems,” SmartMat 2 (2021): 423-425.
|
| [73] |
A. Perazio, C. E. Creissen, J. G. Rivera de la Cruz, M. W. Schreiber, and M. Fontecave, “Acidic Electroreduction of CO2 to Multi-Carbon Products With CO2 Recovery and Recycling From Carbonate,” ACS Energy Letters 8 (2023): 2979-2985.
|
| [74] |
F. Bernasconi, N. Plainpan, M. Mirolo, et al., “Operando Observation of (Bi)Carbonate Precipitation During Electrochemical CO2 Reduction in Strongly Acidic Electrolytes,” ACS Catalysis 14 (2024): 8232-8237.
|
| [75] |
M. Zeng, W. Fang, Y. Cen, X. Zhang, Y. Hu, and B. Y. Xia, “Reaction Environment Regulation for Electrocatalytic CO2 Reduction in Acids,” Angewandte Chemie (International ed in English) 63 (2024): e202404574.
|
| [76] |
M. Sassenburg, M. Kelly, S. Subramanian, W. A. Smith, and T. Burdyny, “Zero-Gap Electrochemical CO2 Reduction Cells: Challenges and Operational Strategies for Prevention of Salt Precipitation,” ACS Energy Letters 8 (2023): 321-331.
|
| [77] |
Y. Xu, J. P. Edwards, S. Liu, et al., “Self-Cleaning CO2 Reduction Systems: Unsteady Electrochemical Forcing Enables Stability,” ACS Energy Letters 6 (2021): 809-815.
|
| [78] |
Z.-Q. Liang, T.-T. Zhuang, A. Seifitokaldani, et al., “Copper-on-Nitride Enhances the Stable Electrosynthesis of Multi-Carbon Products From CO2,” Nature Communications 9 (2018): 3828.
|
| [79] |
D. Cheng, Z.-J. Zhao, G. Zhang, et al., “The Nature of Active Sites for Carbon Dioxide Electroreduction Over Oxide-Derived Copper Catalysts,” Nature Communications 12 (2021): 395.
|
| [80] |
T. Shinagawa, G. O. Larrazábal, A. J. Martín, F. Krumeich, and J. Pérez-Ramírez, “Sulfur-Modified Copper Catalysts for the Electrochemical Reduction of Carbon Dioxide to Formate,” ACS Catalysis 8 (2018): 837-844.
|
| [81] |
P. Grosse, D. Gao, F. Scholten, I. Sinev, H. Mistry, and B. Roldan Cuenya, “Dynamic Changes in the Structure, Chemical State and Catalytic Selectivity of Cu Nanocubes During CO2 Electroreduction: Size and Support Effects,” Angewandte Chemie International Edition 57 (2018): 6192-6197.
|
| [82] |
Y. Xu, F. Li, A. Xu, et al., “Low Coordination Number Copper Catalysts for Electrochemical CO2 Methanation in a Membrane Electrode Assembly,” Nature Communications 12 (2021): 2932.
|
| [83] |
L. Zhang, X. Yang, Q. Yuan, et al., “Elucidating the Structure-Stability Relationship of Cu Single-Atom Catalysts Using Operando Surface-Enhanced Infrared Absorption Spectroscopy,” Nature Communications 14 (2023): 8311.
|
| [84] |
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.
|
| [85] |
C. Rettenmaier, A. Herzog, D. Casari, et al., “Operando Insights Into Correlating CO Coverage and Cu-Au Alloying With the Selectivity of Au NP-decorated Cu2O Nanocubes During the Electrocatalytic CO2 Reduction,” EES Catalysis 2 (2024): 311-323.
|
| [86] |
G. H. Simon, C. S. Kley, and B. Roldan Cuenya, “Potential-Dependent Morphology of Copper Catalysts during CO2 Electroreduction Revealed by In Situ Atomic Force Microscopy,” Angewandte Chemie International Edition 60 (2021): 2561-2568.
|
| [87] |
Y. Li, F. Cui, M. B. Ross, D. Kim, Y. Sun, and P. Yang, “Structure-Sensitive CO2 Electroreduction to Hydrocarbons on Ultrathin 5-Fold Twinned Copper Nanowires,” Nano Letters 17 (2017): 1312-1317.
|
| [88] |
S. J. Raaijman, N. Arulmozhi, and M. T. M. Koper, “Morphological Stability of Copper Surfaces under Reducing Conditions,” ACS Applied Materials & Interfaces 13 (2021): 48730-48744.
|
| [89] |
Z. Xie, Q. Wang, H. Yang, et al., “Surface Facets Reconstruction in Copper-Based Materials for Enhanced Electrochemical CO2 Reduction,” Small 20 (2024): 2401530.
|
| [90] |
C. Choi, S. Kwon, T. Cheng, et al., “Highly Active and Stable Stepped Cu Surface for Enhanced Electrochemical CO2 Reduction to C2H4,” Nature Catalysis 3 (2020): 804-812.
|
| [91] |
T.-T. Zhuang, Z.-Q. Liang, A. Seifitokaldani, et al., “Steering Post-C-C Coupling Selectivity Enables High Efficiency Electroreduction of Carbon Dioxide to Multi-carbon Alcohols,” Nature Catalysis 1 (2018): 421-428.
|
| [92] |
H.-Y. Wang, M. Soldemo, D. Degerman, et al., “Direct Evidence of Subsurface Oxygen Formation in Oxide-Derived Cu by X-Ray Photoelectron Spectroscopy,” Angewandte Chemie International Edition 61 (2022): e202111021.
|
| [93] |
A. Eilert, F. Cavalca, F. S. Roberts, et al., “Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction,” The Journal of Physical Chemistry Letters 8 (2017): 285-290.
|
| [94] |
W. Wang, Z. Ma, X. Fei, et al., “Joint Tuning the Morphology and Oxygen Vacancy of Cu2O by Ionic Liquid Enables High-Efficient CO2 Reduction to C2 Products,” Chemical Engineering Journal 436 (2022): 135029.
|
| [95] |
M. Favaro, H. Xiao, T. Cheng, W. A. Goddard, J. Yano, and E. J. Crumlin, “Subsurface Oxide Plays a Critical Role in CO2 Activation by Cu(111) Surfaces to Form Chemisorbed CO2, the First Step in Reduction of CO2,” Proceedings of the National Academy of Sciences 114 (2017): 6706-6711.
|
| [96] |
C. Peng, G. Luo, J. Zhang, et al., “Double Sulfur Vacancies by Lithium Tuning Enhance CO2 Electroreduction to n-Propanol,” Nature Communications 12 (2021): 1580.
|
| [97] |
C. Peng, G. Luo, Z. Xu, et al., “Lithiation-Enabled High-Density Nitrogen Vacancies Electrocatalyze CO2 to C2 Products,” Advanced Materials 33 (2021): 2103150.
|
| [98] |
R. Sun, C. Wei, Z. Huang, et al., “Cu2+1O/CuOx Heterostructures Promote the Electrosynthesis of C2+ Products From CO2,” Nano Research 16 (2023): 4698-4705.
|
| [99] |
B. Qiao, A. Wang, X. Yang, et al., “Single-Atom Catalysis of CO Oxidation Using Pt1/FeOx,” Nature Chemistry 3 (2011): 634-641.
|
| [100] |
H. Choi, M. G. Ha, J. Suh, et al., “Effect of the Nitrogen/Carbon Ratio in the Organic Ligand of a Nickel Single-Atom Catalyst on Its Electrochemical Activity in CO2 Reduction,” Applied Catalysis B: Environment and Energy 355 (2024): 124192.
|
| [101] |
Z. Zhang, C. Feng, C. Liu, et al., “Electrochemical Deposition as a Universal Route for Fabricating Single-atom Catalysts,” Nature Communications 11 (2020): 1215.
|
| [102] |
W. Zhong, Z. Wang, S. Han, et al., “Identifying the Active Sites of a Single Atom Catalyst With pH-Universal Oxygen Reduction Reaction Activity,” Cell Reports Physical Science 1 (2020): 100115.
|
| [103] |
L. Yan, X.-D. Liang, Y. Sun, et al., “Evolution of Cu Single Atom Catalysts to Nanoclusters During CO2 Reduction to CO,” Chemical Communications 58 (2022): 2488-2491.
|
| [104] |
C. E. Creissen and M. Fontecave, “Keeping Sight of Copper in Single-atom Catalysts for Electrochemical Carbon Dioxide Reduction,” Nature Communications 13 (2022): 2280.
|
| [105] |
L. G. Verga, P. C. D. Mendes, V. K. Ocampo-Restrepo, and J. L. F. Da Silva, “Exploring the Adsorption Site Coordination as a Strategy to Tune Copper Catalysts for CO2 Electro-Reduction,” Catalysis Science & Technology 12 (2022): 869-879.
|
| [106] |
R. Reske, H. Mistry, F. Behafarid, B. Roldan Cuenya, and P. Strasser, “Particle Size Effects in the Catalytic Electroreduction of CO2 on Cu Nanoparticles,” Journal of the American Chemical Society 136 (2014): 6978-6986.
|
| [107] |
X. Zhang, J.-X. Liu, B. Zijlstra, et al., “Optimum Cu Nanoparticle Catalysts for CO2 Hydrogenation towards Methanol,” Nano Energy 43 (2018): 200-209.
|
| [108] |
K. Liu, M. Ma, L. Wu, et al., “Electronic Effects Determine the Selectivity of Planar Au-Cu Bimetallic Thin Films for Electrochemical CO2 Reduction,” ACS Applied Materials & Interfaces 11 (2019): 16546-16555.
|
| [109] |
S. Nag, K. C. Mahdak, A. Devaraj, S. Gohil, P. Ayyub, and R. Banerjee, “Phase Separation in Immiscible Silver-Copper Alloy Thin Films,” Journal of Materials Science 44 (2009): 3393-3401.
|
| [110] |
Y. Yang, S. Louisia, S. Yu, et al., “Operando Studies Reveal Active Cu Nanograins for CO2 Electroreduction,” Nature 614 (2023): 262-269.
|
| [111] |
S.-C. Lin, C.-C. Chang, S.-Y. Chiu, et al., “Operando Time-Resolved X-ray Absorption Spectroscopy Reveals the Chemical Nature Enabling Highly Selective CO2 Reduction,” Nature Communications 11 (2020): 3525.
|
| [112] |
X. Ren, J. Zhao, X. Li, et al., “In-situ Spectroscopic Probe of the Intrinsic Structure Feature of Single-atom Center in Electrochemical CO/CO2 Reduction to Methanol,” Nature Communications 14 (2023): 3401.
|
| [113] |
N. Han, Y. Wang, H. Yang, et al., “Ultrathin Bismuth Nanosheets From in Situ Topotactic Transformation for Selective Electrocatalytic CO2 Reduction to Formate,” Nature Communications 9 (2018): 1320.
|
| [114] |
W. Sheng, S. Kattel, S. Yao, et al., “Electrochemical Reduction of CO2 to Synthesis Gas With Controlled CO/H2 Ratios,” Energy & Environmental Science 10 (2017): 1180-1185.
|
| [115] |
X. Su, Z. Jiang, J. Zhou, et al., “Complementary Operando Spectroscopy Identification of in-situ Generated Metastable Charge-Asymmetry Cu2-CuN3 Clusters for CO2 Reduction to Ethanol,” Nature Communications 13 (2022): 1322.
|
| [116] |
X. Tan, K. Sun, Z. Zhuang, et al., “Stabilizing Copper by a Reconstruction-Resistant Atomic Cu-O-Si Interface for Electrochemical CO2 Reduction,” Journal of the American Chemical Society 145 (2023): 8656-8664.
|
| [117] |
V. Okatenko, A. Loiudice, M. A. Newton, et al., “Alloying as a Strategy to Boost the Stability of Copper Nanocatalysts During the Electrochemical CO2 Reduction Reaction,” Journal of the American Chemical Society 145 (2023): 5370-5383.
|
| [118] |
P. P. Albertini, M. A. Newton, M. Wang, et al., “Hybrid Oxide Coatings Generate Stable Cu Catalysts for CO2 Electroreduction,” Nature Materials 23 (2024): 680-687.
|
| [119] |
J. Y. Kim, D. Hong, J. C. Lee, et al., “Quasi-graphitic Carbon Shell-Induced Cu Confinement Promotes Electrocatalytic CO2 Reduction Toward C2+ Products,” Nature Communications 12 (2021): 3765.
|
| [120] |
J. Timoshenko, A. Bergmann, C. Rettenmaier, et al., “Steering the Structure and Selectivity of CO2 Electroreduction Catalysts by Potential Pulses,” Nature Catalysis 5 (2022): 259-267.
|
| [121] |
T. Dou, J. He, S. Diao, et al., “Dynamic Reconstructuring of CuS/SnO2-S for Promoting CO2 Electroreduction to Formate,” Journal of Energy Chemistry 82 (2023): 497-506.
|
| [122] |
J. E. Huang, F. Li, A. Ozden, et al., “CO2 Electrolysis to Multicarbon Products in Strong Acid,” Science 372 (2021): 1074-1078.
|
| [123] |
T. Lee, Y. Lee, J. Eo, and D.-H. Nam, “Acidic CO2 Electroreduction for High CO2 Utilization: Catalysts, Electrodes, and Electrolyzers,” Nanoscale 16 (2024): 2235-2249.
|
| [124] |
A. Ozden, F. P. García de Arquer, J. E. Huang, et al., “Carbon-Efficient Carbon Dioxide Electrolysers,” Nature Sustainability 5 (2022): 563-573.
|
| [125] |
Q. Hao, D.-X. Liu, H.-X. Zhong, Q. Tang, and J.-M. Yan, “Electrocatalytic CO2 Reduction in Acidic Medium,” Chem Catalysis 3 (2023): 100542.
|
| [126] |
B. E. A. Rani and B. B. J. Basu, “Green Inhibitors for Corrosion Protection of Metals and Alloys: An Overview,” International Journal of Corrosion 2012 (2012): 1-15.
|
| [127] |
M. Goyal, S. Kumar, I. Bahadur, C. Verma, and E. E. Ebenso, “Organic Corrosion Inhibitors for Industrial Cleaning of Ferrous and Non-Ferrous Metals in Acidic Solutions: A Review,” Journal of Molecular Liquids 256 (2018): 565-573.
|
| [128] |
B. E. Ibrahimi, J. V. Nardeli, and L. Guo Sustainable Corrosion Inhibitors I: Fundamentals, Methodologies, and Industrial Applications (ACS Publications, 2021), 1-19.
|
| [129] |
E. McCafferty, Introduction to Corrosion Science (Springer, 2010).
|
| [130] |
D. Bae, T. Lee, W. Kwon, S.-H. Oh, and D.-H. Nam, “Porous Cu/C Nanofibers Promote Electrochemical CO2 -to-Ethylene Conversion via High CO2 Availability,” Journal of Materials Chemistry A 12 (2024): 17295-17305.
|
| [131] |
C. Kim, J. C. Bui, X. Luo, et al., “Tailored Catalyst Microenvironments for CO2 Electroreduction to Multicarbon Products on Copper Using Bilayer Ionomer Coatings,” Nature Energy 6 (2021): 1026-1034.
|
| [132] |
R. D. Kent and P. J. Vikesland, “Dissolution and Persistence of Copper-Based Nanomaterials in Undersaturated Solutions with Respect to Cupric Solid Phases,” Environmental Science & Technology 50 (2016): 6772-6781.
|
| [133] |
C. Long, X. Liu, K. Wan, et al., “Regulating Reconstruction of Oxide-Derived Cu for Electrochemical CO2 Reduction Toward n-Propanol,” Science Advances 9 (2023): eadi6119.
|
RIGHTS & PERMISSIONS
2025 The Author(s). Exploration published by Henan University and John Wiley & Sons Australia, Ltd.