Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction

Herzog, Antonia; Luna, Mauricio Lopez; Jeon, Hyo Sang; Rettenmaier, Clara; Grosse, Philipp; Bergmann, Arno; Cuenya, Beatriz Roldan

doi:10.1038/s41467-024-48052-3

Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO₂ electroreduction

Journal Article · Sat May 11 00:00:00 EDT 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-48052-3· OSTI ID:2470824

^[1]; Luna, Mauricio Lopez ^[2]; Jeon, Hyo Sang ^[3]; ^[4]; Grosse, Philipp ^[4]; ^[4]; ^[4]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
Korea Institute of Science and Technology (KIST), Seoul (Korea, Republic of); Fritz Haber Institute of the Max Planck Society, Berlin (Germany)
Fritz Haber Institute of the Max Planck Society, Berlin (Germany)

Pulsed CO₂ electroreduction (CO₂RR) has recently emerged as a facile way to in situ tune the product selectivity, in particular toward ethanol, without re-designing the catalytic system. However, in-depth mechanistic understanding requires comprehensive operando time-resolved studies to identify the kinetics and dynamics of the electrocatalytic interface. Here, we track the adsorbates and the catalyst state of pre-reduced Cu₂O nanocubes (~30 nm) during pulsed CO₂RR using sub-second time-resolved operando Raman spectroscopy. By screening a variety of product-steering pulse length conditions, we unravel the critical role of co-adsorbed OH and CO on the Cu surface next to the oxidative formation of Cu-O_ad or CuO_x/(OH)_y species, impacting the kinetics of CO adsorption and boosting the ethanol selectivity. However, a too low OH_ad coverage following the formation of bulk-like Cu₂O induces a significant increase in the C₁ selectivity, while a too high OH_ad coverage poisons the surface for C-C coupling. Thus, we unveil the importance of co-adsorbed OH on the alcohol formation under CO₂RR conditions and thereby, pave the way for improved catalyst design and operating conditions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2470824

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Role of the Adsorbed Oxygen Species in the Selective Electrochemical Reduction of CO ₂ to Alcohols and Carbonyls on Copper Electrodes Le Duff, Cécile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201706463	journal	September 2017
Operando Investigation of Ag‐Decorated Cu ₂ O Nanocube Catalysts with Enhanced CO ₂ Electroreduction toward Liquid Products Herzog, Antonia; Bergmann, Arno; Jeon, Hyo Sang Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202017070	journal	February 2021
Sub‐Second Time‐Resolved Surface‐Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO ₂ Reduction on Copper An, Hongyu; Wu, Longfei; Mandemaker, Laurens D. B. Angewandte Chemie International Edition, Vol. 60, Issue 30 https://doi.org/10.1002/anie.202104114	journal	June 2021
Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction Zhou, Yixiang; Yao, Yebo; Zhao, Rui Angewandte Chemie International Edition, Vol. 61, Issue 31 https://doi.org/10.1002/anie.202205832	journal	June 2022
In Situ Raman Study of Potential‐Dependent Surface Adsorbed Carbonate, CO, OH, and C Species on Cu Electrodes During Electrochemical Reduction of CO ₂ Moradzaman, Mozhgan; Mul, Guido ChemElectroChem, Vol. 8, Issue 8 https://doi.org/10.1002/celc.202001598	journal	March 2021
Controlled Selectivity of CO ₂ Reduction on Copper by Pulsing the Electrochemical Potential Kimura, Kevin W.; Fritz, Kevin E.; Kim, Jiyoon ChemSusChem, Vol. 11, Issue 11 https://doi.org/10.1002/cssc.201800318	journal	May 2018
Copper(I) Oxide Nanocrystals - One Step Synthesis, Characterization, Formation Mechanism, and Photocatalytic Properties: Copper(I) Oxide Nanocrystals Singhal, Anshu; Pai, Mrinal R.; Rao, Rekha European Journal of Inorganic Chemistry, Vol. 2013, Issue 14 https://doi.org/10.1002/ejic.201201382	journal	March 2013
Vibrational modes of CO adsorbed on disordered copper films Akemann, W.; Otto, A. Journal of Raman Spectroscopy, Vol. 22, Issue 12 https://doi.org/10.1002/jrs.1250221212	journal	December 1991
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
Surface-enhanced Raman spectroscopic observation of two kinds of adsorbed OH− ions at copper electrode Niaura, Gediminas Electrochimica Acta, Vol. 45, Issue 21 https://doi.org/10.1016/S0013-4686(00)00434-5	journal	July 2000
Pulse check: Potential opportunities in pulsed electrochemical CO2 reduction Casebolt, Rileigh; Levine, Kelsey; Suntivich, Jin Joule, Vol. 5, Issue 8 https://doi.org/10.1016/j.joule.2021.05.014	journal	August 2021
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
Optimizing C–C Coupling on Oxide-Derived Copper Catalysts for Electrochemical CO ₂ Reduction Lum, Yanwei; Yue, Binbin; Lobaccaro, Peter The Journal of Physical Chemistry C, Vol. 121, Issue 26 https://doi.org/10.1021/acs.jpcc.7b03673	journal	June 2017
Roughening of Copper (100) at Elevated CO Pressure: Cu Adatom and Cluster Formation Enable CO Dissociation Roiaz, Matteo; Falivene, Laura; Rameshan, Christoph The Journal of Physical Chemistry C, Vol. 123, Issue 13 https://doi.org/10.1021/acs.jpcc.8b07668	journal	October 2018
Selective Electrochemical CO ₂ Reduction during Pulsed Potential Stems from Dynamic Interface Kimura, Kevin W.; Casebolt, Rileigh; Cimada DaSilva, Jessica ACS Catalysis, Vol. 10, Issue 15 https://doi.org/10.1021/acscatal.0c02630	journal	June 2020
Impact of Pulsed Electrochemical Reduction of CO ₂ on the Formation of C ₂₊ Products over Cu Kim, Chanyeon; Weng, Lien-Chun; Bell, Alexis T. ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c02915	journal	September 2020
Revealing the CO Coverage-Driven C–C Coupling Mechanism for Electrochemical CO ₂ Reduction on Cu ₂ O Nanocubes via Operando Raman Spectroscopy Zhan, Chao; Dattila, Federico; Rettenmaier, Clara ACS Catalysis, Vol. 11, Issue 13 https://doi.org/10.1021/acscatal.1c01478	journal	June 2021
Understanding the Roles of Hydroxide in CO₂ Electroreduction on a Cu Electrode for Achieving Variable Selectivity Sun, Mingxu; Staykov, Aleksandar; Yamauchi, Miho ACS Catalysis, Vol. 12, Issue 24 https://doi.org/10.1021/acscatal.2c03650	journal	November 2022
In Situ Raman Spectroscopy of Copper and Copper Oxide Surfaces during Electrochemical Oxygen Evolution Reaction: Identification of Cu ^III Oxides as Catalytically Active Species Deng, Yilin; Handoko, Albertus D.; Du, Yonghua ACS Catalysis, Vol. 6, Issue 4 https://doi.org/10.1021/acscatal.6b00205	journal	March 2016
Improved CO ₂ Electroreduction Performance on Plasma-Activated Cu Catalysts via Electrolyte Design: Halide Effect Gao, Dunfeng; Scholten, Fabian; Roldan Cuenya, Beatriz ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01416	journal	July 2017
Prism-Shaped Cu Nanocatalysts for Electrochemical CO ₂ Reduction to Ethylene Jeon, Hyo Sang; Kunze, Sebastian; Scholten, Fabian ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b02959	journal	December 2017
Existence of an Electrochemically Inert CO Population on Cu Electrodes in Alkaline pH Gunathunge, Charuni M.; Ovalle, Vincent J.; Li, Yawei ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b01552	journal	July 2018
Role of a Hydroxide Layer on Cu Electrodes in Electrochemical CO ₂ Reduction Iijima, Go; Inomata, Tomohiko; Yamaguchi, Hitoshi ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b00896	journal	June 2019
Effects of Surface Roughness on the Electrochemical Reduction of CO ₂ over Cu Jiang, Kun; Huang, Yufeng; Zeng, Guosong ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00482	journal	March 2020
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
The Role of the Copper Oxidation State in the Electrocatalytic Reduction of CO ₂ into Valuable Hydrocarbons Velasco-Vélez, Juan-Jesús; Jones, Travis; Gao, Dunfeng ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 1 https://doi.org/10.1021/acssuschemeng.8b05106	journal	November 2018
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
Particle Size Effects in the Catalytic Electroreduction of CO ₂ on Cu Nanoparticles Reske, Rulle; Mistry, Hemma; Behafarid, Farzad Journal of the American Chemical Society, Vol. 136, Issue 19 https://doi.org/10.1021/ja500328k	journal	May 2014
Selectivity Control of Cu Nanocrystals in a Gas-Fed Flow Cell through CO ₂ Pulsed Electroreduction Jeon, Hyo Sang; Timoshenko, Janis; Rettenmaier, Clara Journal of the American Chemical Society, Vol. 143, Issue 19 https://doi.org/10.1021/jacs.1c03443	journal	May 2021
Probing the Dynamics of Low-Overpotential CO₂-to-CO Activation on Copper Electrodes with Time-Resolved Raman Spectroscopy de Ruiter, Jim; An, Hongyu; Wu, Longfei Journal of the American Chemical Society, Vol. 144, Issue 33 https://doi.org/10.1021/jacs.2c03172	journal	August 2022
Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO ₂ over Ag and Cu Singh, Meenesh R.; Kwon, Youngkook; Lum, Yanwei Journal of the American Chemical Society, Vol. 138, Issue 39 https://doi.org/10.1021/jacs.6b07612	journal	September 2016
Early Stages of Electrochemical Oxidation of Cu(111) and Polycrystalline Cu Surfaces Revealed by in Situ Raman Spectroscopy Bodappa, Nataraju; Su, Min; Zhao, Yu Journal of the American Chemical Society, Vol. 141, Issue 31 https://doi.org/10.1021/jacs.9b04638	journal	July 2019
Operando Insight into the Correlation between the Structure and Composition of CuZn Nanoparticles and Their Selectivity for the Electrochemical CO ₂ Reduction Jeon, Hyo Sang; Timoshenko, Janis; Scholten, Fabian Journal of the American Chemical Society, Vol. 141, Issue 50 https://doi.org/10.1021/jacs.9b10709	journal	November 2019
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
Electrochemical Reduction of CO at a Copper Electrode Hori, Yoshio; Takahashi, Ryutaro; Yoshinami, Yuzuru The Journal of Physical Chemistry B, Vol. 101, Issue 36 https://doi.org/10.1021/jp970284i	journal	September 1997
Oxide Film Formation and Oxygen Adsorption on Copper in Aqueous Media As Probed by Surface-Enhanced Raman Spectroscopy Chan, Ho Yeung H.; Takoudis, Christos G.; Weaver, Michael J. The Journal of Physical Chemistry B, Vol. 103, Issue 2 https://doi.org/10.1021/jp983787c	journal	January 1999
Nanostructured electrocatalysts with tunable activity and selectivity Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.9	journal	March 2016
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
Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper Li, Jing; Chang, Xiaoxia; Zhang, Haochen Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23582-2	journal	June 2021
Surface hydroxide promotes CO2 electrolysis to ethylene in acidic conditions Cao, Yufei; Chen, Zhu; Li, Peihao Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-37898-8	journal	April 2023
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
Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction De Luna, Phil; Quintero-Bermudez, Rafael; Dinh, Cao-Thang Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0018-9	journal	January 2018
Steering the structure and selectivity of CO2 electroreduction catalysts by potential pulses Timoshenko, Janis; Bergmann, Arno; Rettenmaier, Clara Nature Catalysis, Vol. 5, Issue 4 https://doi.org/10.1038/s41929-022-00760-z	journal	April 2022
Unveiling CO adsorption on Cu surfaces: new insights from molecular orbital principles Gameel, Kareem M.; Sharafeldin, Icell M.; Abourayya, Amr U. Physical Chemistry Chemical Physics, Vol. 20, Issue 40 https://doi.org/10.1039/C8CP04253E	journal	January 2018
Determining intrinsic stark tuning rates of adsorbed CO on copper surfaces Chang, Xiaoxia; Xiong, Haocheng; Xu, Yifei Catalysis Science & Technology, Vol. 11, Issue 20 https://doi.org/10.1039/D1CY01090E	journal	January 2021
Tracking heterogeneous structural motifs and the redox behaviour of copper–zinc nanocatalysts for the electrocatalytic CO₂ reduction using operando time resolved spectroscopy and machine learning Rüscher, Martina; Herzog, Antonia; Timoshenko, Janis Catalysis Science & Technology, Vol. 12, Issue 9 https://doi.org/10.1039/D2CY00227B	journal	January 2022
New aspects of operando Raman spectroscopy applied to electrochemical CO ₂ reduction on Cu foams Jiang, Shan; Klingan, Katharina; Pasquini, Chiara The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5054109	journal	January 2019
CO ₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface Dinh, Cao-Thang; Burdyny, Thomas; Kibria, Md Golam Science, Vol. 360, Issue 6390 https://doi.org/10.1126/science.aas9100	journal	May 2018
Pulsed Electroreduction of CO 2 on Silver Electrodes Shiratsuchi, Ryuichi; Nogami, Gyoichi Journal of The Electrochemical Society, Vol. 143, Issue 2 https://doi.org/10.1149/1.1836484	journal	February 1996
On the Electrochemical CO ₂ Reduction at Copper Sheet Electrodes with Enhanced Long-Term Stability by Pulsed Electrolysis Engelbrecht, Andreas; Uhlig, Conrad; Stark, Oliver Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0091815jes	journal	January 2018

Similar Records

Operando studies reveal active Cu nanograins for CO₂ electroreduction

Journal Article · Tue Feb 07 23:00:00 EST 2023 · Nature (London) · OSTI ID:2293522

Adsorbate-induced adatom formation on Au-Cu bimetallic alloys and its possible consequences for CO₂ electroreduction

Journal Article · Sat Sep 14 20:00:00 EDT 2024 · Surface Science · OSTI ID:3012296

Pulsed electroreduction of CO{sub 2} on Cu-Ag alloy electrodes

Journal Article · Mon May 01 00:00:00 EDT 2000 · Journal of the Electrochemical Society · OSTI ID:20080583

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electrocatalysis

Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction

Citation Formats

References (50)

Similar Records

Related Subjects

Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO₂ electroreduction