Revealing the Nature of C-C Coupling Sites on a Cu Surface for CO2 Reduction.

Electrochemical CO2 reduction technology plays an important role in reducing CO2 into valuable chemical fuels. Therein, Cu-based catalysts show superior performance for producing high-value C2+ products. Here, we illustrate the ascendency of high-index facets of Cu catalysts in producing C2+ products and find that two kinds of sites favor C-C coupling on the surface. One is prone to adsorb the C-C coupling structure by spanning stepped coppers with different coordination numbers. The other is to embed the structure along two columns of Cu with similar characteristics through O and C adsorbed simultaneously. Within all research surfaces, the coupling energy barrier is lowest on the Cu(911) facet, which is consistent with the experiment. The less charged sites promote the stabilization of the CO-CO structure as determined by charge analysis. Furthermore, our results suggest that the high selectivity for C2+ products on a Cu surface could significantly come from the contribution of the high-index facet.

[1]  K. Rossi,et al.  Well-Defined Copper-Based Nanocatalysts for Selective Electrochemical Reduction of CO2 to C2 Products , 2022, ACS Energy Letters.

[2]  X. Chang,et al.  C-C Coupling Is Unlikely to Be the Rate-Determining Step in the Formation of C2+ Products in the Copper-Catalyzed Electrochemical Reduction of CO. , 2021, Angewandte Chemie.

[3]  Lei Wang,et al.  Effects of the Catalyst Dynamic Changes and Influence of the Reaction Environment on the Performance of Electrochemical CO2 Reduction , 2021, Advanced materials.

[4]  B. Weckhuysen,et al.  Sub‐Second Time‐Resolved Surface‐Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper , 2021, Angewandte Chemie.

[5]  G. Ozin,et al.  The nature of active sites for carbon dioxide electroreduction over oxide-derived copper catalysts , 2021, Nature communications.

[6]  Yingzhou Li,et al.  Product-Specific Active Site Motifs of Cu for Electrochemical CO2 Reduction , 2020, Chem.

[7]  Jeremy T. Feaster,et al.  Oxidation State and Surface Reconstruction of Cu under CO2 Reduction Conditions from In Situ X-ray Characterization. , 2020, Journal of the American Chemical Society.

[8]  A. Comas‐Vives,et al.  Shape and Surface Morphology of Copper Nanoparticles under CO2 Hydrogenation Conditions from First Principles , 2020, The Journal of Physical Chemistry C.

[9]  P. Kenis,et al.  Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes , 2020, Nature Catalysis.

[10]  N. López,et al.  Active and Selective Ensembles in Oxide-Derived Copper Catalysts for CO2 Reduction , 2020 .

[11]  W. Goddard,et al.  Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4 , 2020, Nature Catalysis.

[12]  F. Calle‐Vallejo,et al.  Elucidating the Structure of Ethanol-Producing Active Sites at Oxide-Derived Cu Electrocatalysts , 2020 .

[13]  T. Jaramillo,et al.  Selective reduction of CO to acetaldehyde with CuAg electrocatalysts , 2020, Proceedings of the National Academy of Sciences.

[14]  K. Cummins,et al.  Selective conversion of CO into ethanol on Cu(511) surface reconstructed from Cu(pc): Operando studies by electrochemical scanning tunneling microscopy, mass spectrometry, quartz crystal nanobalance, and infrared spectroscopy , 2020, Journal of Electroanalytical Chemistry.

[15]  M. Fontecave,et al.  Mechanistic Understanding of CO2 Reduction Reaction (CO2RR) Toward Multicarbon Products by Heterogeneous Copper-Based Catalysts , 2020 .

[16]  Christine M. Gabardo,et al.  Molecular tuning of CO2-to-ethylene conversion , 2019, Nature.

[17]  I. Stephens,et al.  Structure‐Sensitivity and Electrolyte Effects in CO2 Electroreduction: From Model Studies to Applications , 2019, ChemCatChem.

[18]  Adam C. Nielander,et al.  Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area , 2019, Nature Catalysis.

[19]  J. Rossmeisl,et al.  Electrochemical CO2 Reduction: Classifying Cu Facets , 2019, ACS Catalysis.

[20]  W. Goddard,et al.  Identifying Active Sites for CO2 Reduction on Dealloyed Gold Surfaces by Combining Machine Learning with Multiscale Simulations. , 2019, Journal of the American Chemical Society.

[21]  J. Nørskov,et al.  Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte. , 2019, Chemical reviews.

[22]  T. Jaramillo,et al.  What would it take for renewably powered electrosynthesis to displace petrochemical processes? , 2019, Science.

[23]  M. Jaroniec,et al.  Understanding the Roadmap for Electrochemical Reduction of CO2 to Multi-Carbon Oxygenates and Hydrocarbons on Copper-Based Catalysts. , 2019, Journal of the American Chemical Society.

[24]  Chengqin Zou,et al.  Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper , 2019, Nature Catalysis.

[25]  Emily A Carter,et al.  Theoretical Insights into Heterogeneous (Photo)electrochemical CO2 Reduction. , 2018, Chemical reviews.

[26]  Zhi Wei Seh,et al.  Understanding heterogeneous electrocatalytic carbon dioxide reduction through operando techniques , 2018, Nature Catalysis.

[27]  K. Cummins,et al.  Potential-Dependent Adsorption of CO and Its Low-Overpotential Reduction to CH_3CH_2OH on Cu(511) Surface Reconstructed from Cu(pc): Operando Studies by Seriatim STM-EQCN-DEMS , 2018 .

[28]  M. Janik,et al.  Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH , 2018, ACS Catalysis.

[29]  F. Calle‐Vallejo,et al.  A brief review of the computational modeling of CO2 electroreduction on Cu electrodes , 2018, Current Opinion in Electrochemistry.

[30]  Haotian Wang,et al.  Metal ion cycling of Cu foil for selective C–C coupling in electrochemical CO2 reduction , 2018, Nature Catalysis.

[31]  M. Head‐Gordon,et al.  Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper? , 2018, The journal of physical chemistry letters.

[32]  W. Goddard,et al.  Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance. , 2017, Journal of the American Chemical Society.

[33]  Jens K Nørskov,et al.  Understanding trends in electrochemical carbon dioxide reduction rates , 2017, Nature Communications.

[34]  Zachary W. Ulissi,et al.  To address surface reaction network complexity using scaling relations machine learning and DFT calculations , 2017, Nature Communications.

[35]  Marco Favaro,et al.  Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction. , 2017, The journal of physical chemistry letters.

[36]  Christopher H. Hendon,et al.  Tracking a Common Surface-Bound Intermediate during CO2-to-Fuels Catalysis , 2016, ACS central science.

[37]  M. Head‐Gordon,et al.  Identification of Possible Pathways for C-C Bond Formation during Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model. , 2016, The journal of physical chemistry letters.

[38]  André,et al.  Formation of Copper Catalysts for CO2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy. , 2016, The journal of physical chemistry letters.

[39]  Michael J. Janik,et al.  Facet Dependence of CO2 Reduction Paths on Cu Electrodes , 2016 .

[40]  M. Koper,et al.  Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. , 2012, Journal of the American Chemical Society.

[41]  Thomas F. Jaramillo,et al.  New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces , 2012 .

[42]  Y. Hori,et al.  Selective Formation of C2 Compounds from Electrochemical Reduction of CO2 at a Series of Copper Single Crystal Electrodes , 2002 .

[43]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .