Switching CO2 Electroreduction Selectivity Between C1 and C2 Hydrocarbons on Cu Gas-Diffusion Electrodes

Zhang, Jianfang; Li, Zhengyuan Y.; Cai, Rui; Zhang, Tianyu; Yang, Shize; Ma, Lu; Wang, Yan; Wu, Yucheng; Wu, Jingjie J.

doi:10.1002/eem2.12307

Title: Switching CO₂ Electroreduction Selectivity Between C₁ and C₂ Hydrocarbons on Cu Gas-Diffusion Electrodes

Journal Article · Tue Nov 02 00:00:00 EDT 2021 · Energy & Environmental Materials

DOI:https://doi.org/10.1002/eem2.12307· OSTI ID:1890212

^[1]; Li, Zhengyuan Y. ^[2]; Cai, Rui ^[3]; Zhang, Tianyu ^[2]; Yang, Shize ^[4]; Ma, Lu ^[5]; Wang, Yan ^[3];

^[3]; Wu, Jingjie J. ^[2]

Hefei University of Technology (China); University of Cincinnati, OH (United States)
University of Cincinnati, OH (United States)
Hefei University of Technology (China)
Arizona State University, Tempe, AZ (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO₂ electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C₁ or C₂ hydrocarbons. The selectivity toward C₂H₄ progressively increases, while CH₄ decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu^δ+/Cu⁰ ratio favors the pathways of hydrogenation to form CH₄ with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm^-2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu^δ+/Cu⁰ ratio prefers C–C coupling to form C₂₊ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C₂H₄ accounts for 46.4% and the partial current density of C₂H₄ achieves 279 mA cm^-2. This work demonstrates that the selectivity from CH₄ to C₂H₄ is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC); Central Universities; Key R&D Projects of Anhui Province; Arizona State University

Grant/Contract Number:: SC0012704; CBET-2033343; 52172293; 51772072; 51672065; JZ2021HGQB0282; PA2021GDSK0088; 202104b11020016; NNCI-ECCS-1542160

OSTI ID:: 1890212

Report Number(s):: BNL-223518-2022-JAAM

Journal Information:: Energy & Environmental Materials, Vol. 6, Issue 2; ISSN 2575-0356

Publisher:: Wiley - Zhengzhou UniversityCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Facet Dependence of CO ₂ Reduction Paths on Cu Electrodes Luo, Wenjia; Nie, Xiaowa; Janik, Michael J. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01967	journal	December 2015
Operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction Lin, Sheng-Chih; Chang, Chun-Chih; Chiu, Shih-Yun Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17231-3	journal	July 2020
Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces Li, Fengwang; Li, Yuguang C.; Wang, Ziyun Nature Catalysis, Vol. 3, Issue 1 https://doi.org/10.1038/s41929-019-0383-7	journal	December 2019
Efficient Methane Electrosynthesis Enabled by Tuning Local CO ₂ Availability Wang, Xue; Xu, Aoni; Li, Fengwang Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b12445	journal	January 2020
Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO ₂ Electroreduction by Process Conditions Kas, Recep; Kortlever, Ruud; Yılmaz, Hasan ChemElectroChem, Vol. 2, Issue 3 https://doi.org/10.1002/celc.201402373	journal	December 2014
Morphology Matters: Tuning the Product Distribution of CO ₂ Electroreduction on Oxide-Derived Cu Foam Catalysts Dutta, Abhijit; Rahaman, Motiar; Luedi, Nicola C. ACS Catalysis, Vol. 6, Issue 6 https://doi.org/10.1021/acscatal.6b00770	journal	May 2016
Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction Li, Jun; Wang, Ziyun; McCallum, Christopher Nature Catalysis, Vol. 2, Issue 12 https://doi.org/10.1038/s41929-019-0380-x	journal	November 2019
On the Oxidation State of Cu ₂ O upon Electrochemical CO ₂ Reduction: An XPS Study Permyakova, Anastasia A.; Herranz, Juan; El Kazzi, Mario ChemPhysChem, Vol. 20, Issue 22 https://doi.org/10.1002/cphc.201900468	journal	July 2019
Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO ₂ over Cu Nanowire Arrays Ma, Ming; Djanashvili, Kristina; Smith, Wilson A. Angewandte Chemie International Edition, Vol. 55, Issue 23 https://doi.org/10.1002/anie.201601282	journal	April 2016
Nanoporous Copper–Silver Alloys by Additive-Controlled Electrodeposition for the Selective Electroreduction of CO ₂ to Ethylene and Ethanol Hoang, Thao T. H.; Verma, Sumit; Ma, Sichao Journal of the American Chemical Society, Vol. 140, Issue 17 https://doi.org/10.1021/jacs.8b01868	journal	April 2018
Subsurface oxide plays a critical role in CO ₂ activation by Cu(111) surfaces to form chemisorbed CO ₂ , the first step in reduction of CO ₂ Favaro, Marco; Xiao, Hai; Cheng, Tao Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1701405114	journal	June 2017
Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO ₂ Reduction to Ethylene Chou, Tsu-Chin; Chang, Chiao-Chun; Yu, Hung-Ling Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b11126	journal	January 2020
Tandem Electrodes for Carbon Dioxide Reduction into C2+ Products at Simultaneously High Production Efficiency and Rate She, Xiaojie; Zhang, Tianyu; Li, Zhengyuan Cell Reports Physical Science, Vol. 1, Issue 4 https://doi.org/10.1016/j.xcrp.2020.100051	journal	April 2020
Understanding Surface-Mediated Electrochemical Reactions: CO ₂ Reduction and Beyond Dunwell, Marco; Luc, Wesley; Yan, Yushan ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02181	journal	July 2018
Controlling the selectivity of CO2 electroreduction on copper: The effect of the electrolyte concentration and the importance of the local pH Varela, Ana Sofia; Kroschel, Matthias; Reier, Tobias Catalysis Today, Vol. 260 https://doi.org/10.1016/j.cattod.2015.06.009	journal	February 2016
Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B. Chemical Reviews, Vol. 119, Issue 12 https://doi.org/10.1021/acs.chemrev.8b00705	journal	April 2019
Spectroscopic Observation of Reversible Surface Reconstruction of Copper Electrodes under CO ₂ Reduction Gunathunge, Charuni M.; Li, Xiang; Li, Jingyi The Journal of Physical Chemistry C, Vol. 121, Issue 22 https://doi.org/10.1021/acs.jpcc.7b03910	journal	May 2017
A review of the aqueous electrochemical reduction of CO₂ to hydrocarbons at copper Gattrell, M.; Gupta, N.; Co, A. Journal of Electroanalytical Chemistry, Vol. 594, Issue 1, p. 1-19 https://doi.org/10.1016/j.jelechem.2006.05.013	journal	August 2006
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A. Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0139-9	journal	October 2018
CO ₂ Reduction on Copper’s Twin Boundary Tang, Can; Shi, Jianjian; Bai, Xiaowan ACS Catalysis, Vol. 10, Issue 3 https://doi.org/10.1021/acscatal.9b03814	journal	January 2020
Electrochemical CO ₂ reduction on Cu ₂ O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons Kas, Recep; Kortlever, Ruud; Milbrat, Alexander Phys. Chem. Chem. Phys., Vol. 16, Issue 24 https://doi.org/10.1039/C4CP01520G	journal	January 2014
Selective increase in CO ₂ electroreduction activity at grain-boundary surface terminations Mariano, Ruperto G.; McKelvey, Kim; White, Henry S. Science, Vol. 358, Issue 6367 https://doi.org/10.1126/science.aao3691	journal	November 2017
Electrochemical Reduction of CO ₂ Toward C ₂ Valuables on Cu@Ag Core‐Shell Tandem Catalyst with Tunable Shell Thickness Zhang, Shuaishuai; Zhao, Shulin; Qu, Dongxue Small, Vol. 17, Issue 37 https://doi.org/10.1002/smll.202102293	journal	August 2021
Grain-Boundary-Dependent CO ₂ Electroreduction Activity Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/ja5130513	journal	April 2015
Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area Wang, Lei; Nitopi, Stephanie; Wong, Andrew B. Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0301-z	journal	June 2019
Electrochemical Reduction of CO ₂ Using Copper Single-Crystal Surfaces: Effects of CO* Coverage on the Selective Formation of Ethylene Huang, Yun; Handoko, Albertus D.; Hirunsit, Pussana ACS Catalysis, Vol. 7, Issue 3 https://doi.org/10.1021/acscatal.6b03147	journal	February 2017
Highly Dense Cu Nanowires for Low-Overpotential CO₂ Reduction Raciti, David; Livi, Kenneth J.; Wang, Chao Nano Letters, Vol. 15, Issue 10, p. 6829-6835 https://doi.org/10.1021/acs.nanolett.5b03298	journal	September 2015
Dual-Facet Mechanism in Copper Nanocubes for Electrochemical CO ₂ Reduction into Ethylene Mangione, Giulia; Huang, Jianfeng; Buonsanti, Raffaella The Journal of Physical Chemistry Letters, Vol. 10, Issue 15 https://doi.org/10.1021/acs.jpclett.9b01471	journal	July 2019
Morphology-Directed Selective Production of Ethylene or Ethane from CO ₂ on a Cu Mesopore Electrode Yang, Ki Dong; Ko, Woo Ri; Lee, Jun Ho Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201610432	journal	December 2016
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts Ren, Dan; Deng, Yilin; Handoko, Albertus Denny ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs502128q	journal	March 2015
Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels Birdja, Yuvraj Y.; Pérez-Gallent, Elena; Figueiredo, Marta C. Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0450-y	journal	September 2019
Tailoring Copper Nanocrystals towards C ₂ Products in Electrochemical CO ₂ Reduction Loiudice, Anna; Lobaccaro, Peter; Kamali, Esmail A. Angewandte Chemie International Edition, Vol. 55, Issue 19 https://doi.org/10.1002/anie.201601582	journal	April 2016
Active and Selective Ensembles in Oxide-Derived Copper Catalysts for CO ₂ Reduction Dattila, Federico; Garcı́a-Muelas, Rodrigo; López, Núria ACS Energy Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsenergylett.0c01777	journal	September 2020
Time-resolved observation of C–C coupling intermediates on Cu electrodes for selective electrochemical CO ₂ reduction Kim, Younghye; Park, Sojung; Shin, Seung-Jae Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE01690J	journal	January 2020
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
Calculation for the cathode surface concentrations in the electrochemical reduction of CO2 in KHCO3 solutions Gupta, N.; Gattrell, M.; MacDougall, B. Journal of Applied Electrochemistry, Vol. 36, Issue 2 https://doi.org/10.1007/s10800-005-9058-y	journal	October 2005
Formation of Copper Catalysts for CO ₂ Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy Eilert, André; Roberts, F. Sloan; Friebel, Daniel The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00367	journal	April 2016
Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface Wang, Hongxia; Tzeng, Yan-Kai; Ji, Yongfei Nature Nanotechnology, Vol. 15, Issue 2 https://doi.org/10.1038/s41565-019-0603-y	journal	January 2020
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12123	journal	June 2016
Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes Chen, Xinyi; Chen, Junfeng; Alghoraibi, Nawal M. Nature Catalysis, Vol. 4, Issue 1 https://doi.org/10.1038/s41929-020-00547-0	journal	December 2020
Potential Dependence of the Local pH in a CO₂ Reduction Electrolyzer Henckel, Danielle A.; Counihan, Michael J.; Holmes, Hannah E. ACS Catalysis, Vol. 11, Issue 1 https://doi.org/10.1021/acscatal.0c04297	journal	December 2020
Controllable CO adsorption determines ethylene and methane productions from CO2 electroreduction Bai, Haipeng; Cheng, Tao; Li, Shangyu Science Bulletin, Vol. 66, Issue 1 https://doi.org/10.1016/j.scib.2020.06.023	journal	January 2021
Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO ₂ Reduction Lee, Si Young; Jung, Hyejin; Kim, Nak-Kyoon Journal of the American Chemical Society, Vol. 140, Issue 28 https://doi.org/10.1021/jacs.8b02173	journal	June 2018
Strategies in catalysts and electrolyzer design for electrochemical CO ₂ reduction toward C ₂₊ products Fan, Lei; Xia, Chuan; Yang, Fangqi Science Advances, Vol. 6, Issue 8 https://doi.org/10.1126/sciadv.aay3111	journal	February 2020
Enhance CO2-to-C2+ products yield through spatial management of CO transport in Cu/ZnO tandem electrodes Zhang, Tianyu; Li, Zhengyuan; Zhang, Jianfang Journal of Catalysis, Vol. 387 https://doi.org/10.1016/j.jcat.2020.05.002	journal	July 2020
The role of in situ generated morphological motifs and Cu(i) species in C2+ product selectivity during CO2 pulsed electroreduction Arán-Ais, Rosa M.; Scholten, Fabian; Kunze, Sebastian Nature Energy, Vol. 5, Issue 4 https://doi.org/10.1038/s41560-020-0594-9	journal	March 2020
A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes Schouten, K. J. P.; Kwon, Y.; van der Ham, C. J. M. Chemical Science, Vol. 2, Issue 10 https://doi.org/10.1039/c1sc00277e	journal	January 2011
Accelerated discovery of CO2 electrocatalysts using active machine learning Zhong, Miao; Tran, Kevin; Min, Yimeng Nature, Vol. 581, Issue 7807 https://doi.org/10.1038/s41586-020-2242-8	journal	May 2020
pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper Liu, Xinyan; Schlexer, Philomena; Xiao, Jianping Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07970-9	journal	January 2019
Oxidation State and Surface Reconstruction of Cu under CO ₂ Reduction Conditions from In Situ X-ray Characterization Lee, Soo Hong; Lin, John C.; Farmand, Maryam Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c10017	journal	December 2020
Operando Spectroscopic Investigation of a Boron-Doped CuO Catalyst and Its Role in Selective Electrochemical C–C Coupling Patra, Kshirodra Kumar; Park, Sojung; Song, Hakhyeon ACS Applied Energy Materials, Vol. 3, Issue 11 https://doi.org/10.1021/acsaem.0c02284	journal	November 2020
Tuning the Catalytic Activity and Selectivity of Cu for CO ₂ Electroreduction in the Presence of Halides Varela, Ana Sofia; Ju, Wen; Reier, Tobias ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.5b02550	journal	February 2016

Similar Records

Grain Boundary‐Derived Cu ⁺ /Cu ⁰ Interfaces in CuO Nanosheets for Low Overpotential Carbon Dioxide Electroreduction to Ethylene

Journal Article · Sun May 22 00:00:00 EDT 2022 · Advanced Science · OSTI ID:1890212

Zhang, Jianfang; Wang, Yan; Li, Zhengyuan; +8 more

Planar defect-driven electrocatalysis of CO₂-to-C₂H₄ conversion

Journal Article · Tue Jun 15 00:00:00 EDT 2021 · Journal of Materials Chemistry. A · OSTI ID:1890212

Li, Zhengyuan; Fang, Yanbo; Zhang, Jianfang; +6 more

Directing CO₂ electroreduction pathways for selective C₂ product formation using single-site doped copper catalysts

Journal Article · Thu Feb 08 00:00:00 EST 2024 · Nature Chemical Engineering · OSTI ID:1890212

Li, Zhengyuan; Wang, Peng; Lyu, Xiang; +17 more

Related Subjects

36 MATERIALS SCIENCE
CO2 electroreduction
electrodeposition
C2H4
CH4
switchable selectivity

Title: Switching CO2 Electroreduction Selectivity Between C1 and C2 Hydrocarbons on Cu Gas-Diffusion Electrodes

Citation Formats

References (52)

Similar Records

Related Subjects

Title: Switching CO₂ Electroreduction Selectivity Between C₁ and C₂ Hydrocarbons on Cu Gas-Diffusion Electrodes