Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials
Abstract
Here, electrochemical CO2 reduction to formate provides an avenue to reduce globally accelerating CO2 emissions and produce value-added products. Unfortunately, high selectivity in formate electrosynthesis has thus far only been achieved at highly cathodic potentials. Here we use density functional theory to investigate the effect of alloying Cu and Sn on the activity and selectivity towards formate. A theoretical thermodynamic analysis of the reaction energetics suggests that the incorporation of copper into tin could suppress hydrogen evolution and CO production, thus favouring formate generation. Consistent with theoretical trends, the designed CuSn3 catalysts by co-electrodeposition exhibit a Faradaic efficiency of 95% towards formate generation at –0.5 V versus RHE. Furthermore, the catalysts show no degradation over 50 h of operation. In situ Sn L3-edge and Cu K-edge X-ray absorption spectroscopy indicate electron donation from Sn to Cu, which indicates positive oxidation states of Sn in CuSn3 under operating conditions.
- Authors:
-
- Stanford Univ., Stanford, CA (United States)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1493352
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Catalysis
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2520-1158
- Publisher:
- Springer Nature
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, and Cui, Yi. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. United States: N. p., 2018.
Web. doi:10.1038/s41929-018-0200-8.
Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, & Cui, Yi. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. United States. https://doi.org/10.1038/s41929-018-0200-8
Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, and Cui, Yi. Mon .
"Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials". United States. https://doi.org/10.1038/s41929-018-0200-8. https://www.osti.gov/servlets/purl/1493352.
@article{osti_1493352,
title = {Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials},
author = {Zheng, Xueli and Ji, Yongfei and Tang, Jing and Wang, Jiangyan and Liu, Bofei and Steinrück, Hans-Georg and Lim, Kipil and Li, Yuzhang and Toney, Michael F. and Chan, Karen and Cui, Yi},
abstractNote = {Here, electrochemical CO2 reduction to formate provides an avenue to reduce globally accelerating CO2 emissions and produce value-added products. Unfortunately, high selectivity in formate electrosynthesis has thus far only been achieved at highly cathodic potentials. Here we use density functional theory to investigate the effect of alloying Cu and Sn on the activity and selectivity towards formate. A theoretical thermodynamic analysis of the reaction energetics suggests that the incorporation of copper into tin could suppress hydrogen evolution and CO production, thus favouring formate generation. Consistent with theoretical trends, the designed CuSn3 catalysts by co-electrodeposition exhibit a Faradaic efficiency of 95% towards formate generation at –0.5 V versus RHE. Furthermore, the catalysts show no degradation over 50 h of operation. In situ Sn L3-edge and Cu K-edge X-ray absorption spectroscopy indicate electron donation from Sn to Cu, which indicates positive oxidation states of Sn in CuSn3 under operating conditions.},
doi = {10.1038/s41929-018-0200-8},
journal = {Nature Catalysis},
number = 1,
volume = 2,
place = {United States},
year = {Mon Dec 17 00:00:00 EST 2018},
month = {Mon Dec 17 00:00:00 EST 2018}
}
Web of Science
Works referenced in this record:
Nanostructured Tin Catalysts for Selective Electrochemical Reduction of Carbon Dioxide to Formate
journal, January 2014
- Zhang, Sheng; Kang, Peng; Meyer, Thomas J.
- Journal of the American Chemical Society, Vol. 136, Issue 5
Efficient Reduction of CO 2 into Formic Acid on a Lead or Tin Electrode using an Ionic Liquid Catholyte Mixture
journal, June 2016
- Zhu, Qinggong; Ma, Jun; Kang, Xinchen
- Angewandte Chemie International Edition, Vol. 55, Issue 31
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014
- Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
- Nature, Vol. 508, Issue 7497
Controlling H + vs CO 2 Reduction Selectivity on Pb Electrodes
journal, November 2014
- Lee, Chang Hoon; Kanan, Matthew W.
- ACS Catalysis, Vol. 5, Issue 1
Comparison of the Sn L edge X-ray absorption spectra and the corresponding electronic structure in Sn, SnO, and SnO2
journal, April 2004
- Liu, Zhenlin; Handa, Katsumi; Kaibuchi, Kazuki
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 135, Issue 2-3
Molybdenum x-ray absorption edge spectra. The chemical state of molybdenum in nitrogenase
journal, March 1976
- Cramer, S. P.; Eccles, T. K.; Kutzler, F. W.
- Journal of the American Chemical Society, Vol. 98, Issue 5
Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption
journal, November 2017
- Zheng, Xueli; Zhang, Bo; De Luna, Phil
- Nature Chemistry, Vol. 10, Issue 2
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements
journal, October 1994
- Kresse, G.; Hafner, J.
- Journal of Physics: Condensed Matter, Vol. 6, Issue 40
Relationship between the area of L 2,3 x‐ray absorption edge resonances and the d orbital occupancy in compounds of platinum and iridium
journal, February 1982
- Horsley, J. A.
- The Journal of Chemical Physics, Vol. 76, Issue 3
Pd-Catalyzed Electrohydrogenation of Carbon Dioxide to Formate: High Mass Activity at Low Overpotential and Identification of the Deactivation Pathway
journal, April 2015
- Min, Xiaoquan; Kanan, Matthew W.
- Journal of the American Chemical Society, Vol. 137, Issue 14
A grid-based Bader analysis algorithm without lattice bias
journal, January 2009
- Tang, W.; Sanville, E.; Henkelman, G.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
Metallic tin quantum sheets confined in graphene toward high-efficiency carbon dioxide electroreduction
journal, September 2016
- Lei, Fengcai; Liu, Wei; Sun, Yongfu
- Nature Communications, Vol. 7, Issue 1
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Impact of Surface Area in Evaluation of Catalyst Activity
journal, June 2018
- Sun, Shengnan; Li, Haiyan; Xu, Zhichuan J.
- Joule, Vol. 2, Issue 6
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016
- Liu, Min; Pang, Yuanjie; Zhang, Bo
- Nature, Vol. 537, Issue 7620
Electrochemical CO 2 Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity
journal, October 2017
- Clark, Ezra L.; Hahn, Christopher; Jaramillo, Thomas F.
- Journal of the American Chemical Society, Vol. 139, Issue 44
Electrochemical CO 2 Reduction to Formic Acid at Low Overpotential and with High Faradaic Efficiency on Carbon-Supported Bimetallic Pd–Pt Nanoparticles
journal, June 2015
- Kortlever, Ruud; Peters, Ines; Koper, Sander
- ACS Catalysis, Vol. 5, Issue 7
Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012
- Peterson, Andrew A.; Nørskov, Jens K.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid
journal, December 2015
- Yoo, Jong Suk; Christensen, Rune; Vegge, Tejs
- ChemSusChem, Vol. 9, Issue 4
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010
- Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
- Energy & Environmental Science, Vol. 3, Issue 9
In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction
journal, June 2013
- Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D.
- Journal of the American Chemical Society, Vol. 135, Issue 23
Hierarchical Mesoporous SnO 2 Nanosheets on Carbon Cloth: A Robust and Flexible Electrocatalyst for CO 2 Reduction with High Efficiency and Selectivity
journal, December 2016
- Li, Fengwang; Chen, Lu; Knowles, Gregory P.
- Angewandte Chemie International Edition, Vol. 56, Issue 2
Assessing the reliability of calculated catalytic ammonia synthesis rates
journal, July 2014
- Medford, A. J.; Wellendorff, J.; Vojvodic, A.
- Science, Vol. 345, Issue 6193
Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016
- Gao, Shan; Lin, Yue; Jiao, Xingchen
- Nature, Vol. 529, Issue 7584
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
journal, June 2017
- Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.
- ACS Catalysis, Vol. 7, Issue 7
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces
journal, January 2012
- Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N.
- Energy & Environmental Science, Vol. 5, Issue 5
Ultrahigh Mass Activity for Carbon Dioxide Reduction Enabled by Gold–Iron Core–Shell Nanoparticles
journal, October 2017
- Sun, Kun; Cheng, Tao; Wu, Lina
- Journal of the American Chemical Society, Vol. 139, Issue 44
Dipole correction for surface supercell calculations
journal, May 1999
- Bengtsson, Lennart
- Physical Review B, Vol. 59, Issue 19
Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017
- Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
- Nature Communications, Vol. 8, Issue 1
Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate
journal, December 2017
- Zheng, Xueli; De Luna, Phil; García de Arquer, F. Pelayo
- Joule, Vol. 1, Issue 4
Reversible interconversion of carbon dioxide and formate by an electroactive enzyme
journal, July 2008
- Reda, T.; Plugge, C. M.; Abram, N. J.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 31, p. 10654-10658
Tin Oxide Dependence of the CO 2 Reduction Efficiency on Tin Electrodes and Enhanced Activity for Tin/Tin Oxide Thin-Film Catalysts
journal, January 2012
- Chen, Yihong; Kanan, Matthew W.
- Journal of the American Chemical Society, Vol. 134, Issue 4
An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002
- Bahn, S. R.; Jacobsen, K. W.
- Computing in Science & Engineering, Vol. 4, Issue 3
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water
journal, August 2015
- Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao
- Science, Vol. 349, Issue 6253
Progress in inorganic cathode catalysts for electrochemical conversion of carbon dioxide into formate or formic acid
journal, April 2017
- Du, Dongwei; Lan, Rong; Humphreys, John
- Journal of Applied Electrochemistry, Vol. 47, Issue 6
Atomic layer deposited coatings to significantly stabilize anodes for Li ion batteries: effects of coating thickness and the size of anode particles
journal, January 2014
- Wang, Dongniu; Yang, Jinli; Liu, Jian
- Journal of Materials Chemistry A, Vol. 2, Issue 7
Exclusive Formation of Formic Acid from CO 2 Electroreduction by a Tunable Pd-Sn Alloy
journal, August 2017
- Bai, Xiaofang; Chen, Wei; Zhao, Chengcheng
- Angewandte Chemie International Edition, Vol. 56, Issue 40
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Hierarchical Mesoporous SnO 2 Nanosheets on Carbon Cloth: A Robust and Flexible Electrocatalyst for CO 2 Reduction with High Efficiency and Selectivity
journal, December 2016
- Li, Fengwang; Chen, Lu; Knowles, Gregory P.
- Angewandte Chemie, Vol. 129, Issue 2
Efficient Reduction of CO 2 into Formic Acid on a Lead or Tin Electrode using an Ionic Liquid Catholyte Mixture
journal, June 2016
- Zhu, Qinggong; Ma, Jun; Kang, Xinchen
- Angewandte Chemie, Vol. 128, Issue 31
Exclusive Formation of Formic Acid from CO 2 Electroreduction by a Tunable Pd-Sn Alloy
journal, August 2017
- Bai, Xiaofang; Chen, Wei; Zhao, Chengcheng
- Angewandte Chemie, Vol. 129, Issue 40
Works referencing / citing this record:
Trimetallic Synergy in Intermetallic PtSnBi Nanoplates Boosts Formic Acid Oxidation
journal, August 2019
- Luo, Shuiping; Chen, Wen; Cheng, Yu
- Advanced Materials, Vol. 31, Issue 40
Electrode Materials Engineering in Electrocatalytic CO 2 Reduction: Energy Input and Conversion Efficiency
journal, October 2019
- Song, Rong‐Bin; Zhu, Wenlei; Fu, Jiaju
- Advanced Materials
Electrocatalytic Reduction of Gaseous CO 2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes
journal, July 2019
- Ju, Wenbo; Jiang, Fuze; Ma, Huan
- Advanced Energy Materials, Vol. 9, Issue 32
A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO 2 to Value‐Added Chemicals and Fuel
journal, November 2019
- Daiyan, Rahman; Saputera, Wibawa Hendra; Masood, Hassan
- Advanced Energy Materials, Vol. 10, Issue 11
Catalytic Mechanisms and Design Principles for Single‐Atom Catalysts in Highly Efficient CO 2 Conversion
journal, October 2019
- Gong, Lele; Zhang, Detao; Lin, Chun‐Yu
- Advanced Energy Materials, Vol. 9, Issue 44
Activation of Ni Particles into Single Ni–N Atoms for Efficient Electrochemical Reduction of CO 2
journal, December 2019
- Fan, Qun; Hou, Pengfei; Choi, Changhyeok
- Advanced Energy Materials, Vol. 10, Issue 5
Efficient Electrosynthesis of Syngas with Tunable CO/H 2 Ratios over Zn x Cd 1− x S‐Amine Inorganic–Organic Hybrids
journal, November 2019
- Meng, Nannan; Liu, Cuibo; Liu, Yang
- Angewandte Chemie, Vol. 131, Issue 52
In Situ Reconstruction of a Hierarchical Sn‐Cu/SnO x Core/Shell Catalyst for High‐Performance CO 2 Electroreduction
journal, February 2020
- Ye, Ke; Zhou, Zhiwen; Shao, Jiaqi
- Angewandte Chemie, Vol. 132, Issue 12
Efficient Electrosynthesis of Syngas with Tunable CO/H 2 Ratios over Zn x Cd 1− x S‐Amine Inorganic–Organic Hybrids
journal, December 2019
- Meng, Nannan; Liu, Cuibo; Liu, Yang
- Angewandte Chemie International Edition, Vol. 58, Issue 52
In Situ Reconstruction of a Hierarchical Sn‐Cu/SnO x Core/Shell Catalyst for High‐Performance CO 2 Electroreduction
journal, February 2020
- Ye, Ke; Zhou, Zhiwen; Shao, Jiaqi
- Angewandte Chemie International Edition, Vol. 59, Issue 12
Structure‐Tunable Copper–Indium Catalysts for Highly Selective CO 2 Electroreduction to CO or HCOOH
journal, August 2019
- Zhu, Minghui; Tian, Pengfei; Li, Jiayu
- ChemSusChem, Vol. 12, Issue 17
Visible-light-switched electron transfer over single porphyrin-metal atom center for highly selective electroreduction of carbon dioxide
journal, August 2019
- Yang, Deren; Yu, Hongde; He, Ting
- Nature Communications, Vol. 10, Issue 1
Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis
journal, December 2019
- Zhang, Xi; Cui, Guoqing; Feng, Haisong
- Nature Communications, Vol. 10, Issue 1
Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction
journal, November 2019
- Li, Jun; Wang, Ziyun; McCallum, Christopher
- Nature Catalysis, Vol. 2, Issue 12
Introduction of Mn( iii ) to regulate the electronic structure of fluorine-doped nickel hydroxide for efficient water oxidation
journal, January 2019
- Lv, Jiaqi; Yang, Xiaoxuan; Li, Ke
- Nanoscale Advances, Vol. 1, Issue 10
Facile synthesis of a bismuth nanostructure with enhanced selectivity for electrochemical conversion of CO 2 to formate
journal, January 2019
- Lu, Peilong; Gao, Denglei; He, Hongyan
- Nanoscale, Vol. 11, Issue 16
Hierarchical heterostructure of SnO 2 confined on CuS nanosheets for efficient electrocatalytic CO 2 reduction
journal, January 2020
- Wang, Xiang; Lv, Jing; Zhang, Jiaxu
- Nanoscale, Vol. 12, Issue 2
Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction
journal, January 2020
- Du, Jing; Lang, Zhong-Ling; Ma, Yuan-Yuan
- Chemical Science, Vol. 11, Issue 11
Theoretical search for novel Au or Ag bimetallic alloys capable of transforming CO 2 into hydrocarbons
journal, January 2019
- Wu, Nian; Xiao, Li; Zhuang, Lin
- Journal of Materials Chemistry A, Vol. 7, Issue 36
Heterostructured intermetallic CuSn catalysts: high performance towards the electrochemical reduction of CO 2 to formate
journal, January 2019
- Wang, Jigang; Zou, Jiasui; Hu, Xiao
- Journal of Materials Chemistry A, Vol. 7, Issue 48
Partial sulfuration-induced defect and interface tailoring on bismuth oxide for promoting electrocatalytic CO 2 reduction
journal, January 2020
- Yang, Xuxiao; Deng, Peilin; Liu, Dongyu
- Journal of Materials Chemistry A, Vol. 8, Issue 5
Current progress in electrocatalytic carbon dioxide reduction to fuels on heterogeneous catalysts
journal, January 2020
- Liu, Anmin; Gao, Mengfan; Ren, Xuefeng
- Journal of Materials Chemistry A, Vol. 8, Issue 7
Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis
journal, December 2019
- Zhang, Xi; Cui, Guoqing; Feng, Haisong
- Nature Communications, Vol. 10, Issue 1
Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks
journal, March 2020
- Zhong, Haixia; Ghorbani-Asl, Mahdi; Ly, Khoa Hoang
- Nature Communications, Vol. 11, Issue 1