A Caltech Library Service

Predictions of Chemical Shifts for Reactive Intermediates in CO₂ Reduction under Operando Conditions

Yang, Hao and Ribeiro Negreiros, Fabio and Sun, Qintao and Xie, Miao and Sementa, Luca and Stener, Mauro and Ye, Yifan and Fortunelli, Alessandro and Goddard, William A., III and Cheng, Tao (2021) Predictions of Chemical Shifts for Reactive Intermediates in CO₂ Reduction under Operando Conditions. ACS Applied Materials & Interfaces, 13 (27). pp. 31554-31560. ISSN 1944-8244. doi:10.1021/acsami.1c02909.

[img] PDF (Atomic structure of the water/Cu(100) electrode, optimized structures of CO₂ and CO₂ + nH₂O, comparison of the calculated binding energy of the C 1s reference to vacuum, and coordinates for all predicted intermediates) - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


The electroreduction of CO₂ into value-added products is a significant step toward closing the global carbon loop, but its performance remains far from meeting the requirement of any practical application. The insufficient understanding of the reaction mechanism is one of the major causes that impede future development. Although several possible reaction pathways have been proposed, significant debates exist due to the lack of experimental support. In this work, we provide opportunities for experiments to validate the reaction mechanism by providing predictions of the core-level shifts (CLS) of reactive intermediates, which can be verified by the X-ray photoelectron spectroscopy (XPS) data in the experiment. We first validated our methods from benchmark calculations of cases with reliable experiments, from which we reach consistent predictions with experimental results. Then, we conduct theoretical calculations under conditions close to the operando experimental ones and predict the C 1s CLS of 20 reactive intermediates in the CO₂ reduction reaction (CO₂RR) to CH₄ and C₂H₄ on a Cu(100) catalyst by carefully including solvation effects and applied voltage (U). The results presented in this work should be guidelines for future experiments to verify and interpret the reaction mechanism of CO₂RR.

Item Type:Article
Related URLs:
URLURL TypeDescription
Yang, Hao0000-0002-8241-6231
Ribeiro Negreiros, Fabio0000-0002-4380-9702
Xie, Miao0000-0002-9797-1449
Stener, Mauro0000-0003-3700-7903
Fortunelli, Alessandro0000-0001-5337-4450
Goddard, William A., III0000-0003-0097-5716
Cheng, Tao0000-0003-4830-177X
Alternate Title:Predictions of Chemical Shifts for Reactive Intermediates in CO2 Reduction under Operando Conditions
Additional Information:© 2021 American Chemical Society. Received: February 11, 2021; Accepted: June 15, 2021; Published: June 29, 2021. TC was supported by the National Natural Science Foundation of China (grant no. 21903058), the Natural Science Foundation of Jiangsu Province (Grant go. BK20190810), Jiangsu Province High-Level Talents (JNHB-106), and China Postdoctoral Science Foundation (no. 2019M660128). This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science and Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and the 111 Project. WAG was supported by the Liquid Sunlight Alliance, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under Award Number DE-SC0021266. Computational support from CINECA Supercomputing Centre within the ISCRA program is gratefully acknowledged. AF and WAG received support from NSF (CBET-1805022). Author Contributions. H.Y. and F.R.N. contributed equally to this work. The authors declare no competing financial interest.
Funding AgencyGrant Number
National Natural Science Foundation of China21903058
Natural Science Foundation of Jiangsu ProvinceBK20190810
Jiangsu Province High-Level TalentsJNHB-106
China Postdoctoral Science Foundation2019M660128
Collaborative Innovation Center of Suzhou Nano Science and TechnologyUNSPECIFIED
Priority Academic Program Development of Jiangsu Higher Education InstitutionsUNSPECIFIED
111 Project of ChinaUNSPECIFIED
Department of Energy (DOE)DE-SC0021266
Subject Keywords:carbon loop, CO2, reduction reaction, chemical shifts, reactive intermediates
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Issue or Number:27
Record Number:CaltechAUTHORS:20210709-212639733
Persistent URL:
Official Citation:Predictions of Chemical Shifts for Reactive Intermediates in CO2 Reduction under Operando Conditions. Hao Yang, Fabio Ribeiro Negreiros, Qintao Sun, Miao Xie, Luca Sementa, Mauro Stener, Yifan Ye, Alessandro Fortunelli, William A. Goddard, and Tao Cheng. ACS Applied Materials & Interfaces 2021 13 (27), 31554-31560; DOI: 10.1021/acsami.1c02909
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109761
Deposited By: George Porter
Deposited On:09 Jul 2021 22:28
Last Modified:16 Nov 2021 19:37

Repository Staff Only: item control page