Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

ACS Materials Letters

10.1021/acsmaterialslett.3c01156

https://doi.org/10.1021/acsmaterialslett.3c01156

Juan Wang, Haoyi Tan, Hongming Xu, Shibo Xi, Qingbo Wa, Yunhao Wang, Wei Xi, Jingwen Zhou, Jinli Yu, Fengkun Hao, Yuecheng Xiong, Yangbo Ma, Guozhi Wang, Qi Liu, Guangcun Shan, Minhua Shao, Zhanxi Fan

06 November 2023

Wang, J., Tan, H., Xu, H., Xi, S., Wa, Q., Wang, Y., Xi, W., Zhou, J., Yu, J., Hao, F., Xiong, Y., Ma, Y., Wang, G., Liu, Q., Shan, G., Shao, M., & Fan, Z. (2023). Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction. ACS Materials Letters, 5(12), 3212–3221. https://doi.org/10.1021/acsmaterialslett.3c01156

The electrochemical carbon dioxide (CO2) reduction reaction (CO2RR) has been considered as a promising approach to convert atmospheric CO2 to value-added chemicals to promote carbon neutrality. However, developing electrocatalysts with superior activity and high selectivity toward individual products remains a great challenge. Herein we report the electronic structure modulation of unconventional phase metal nanomaterials to achieve highly efficient CO2 electroreduction. It has been found that growing cerium oxide (CeOx) nanostructures on 4H/face-centered cubic (fcc) gold (Au) nanorods can significantly enhance their catalytic activity and selectivity toward the electrochemical conversion of CO2 to carbon monoxide. X-ray analysis indicates the electronic structure change of 4H/fcc Au nanorods after CeOx overgrowth. In-situ attenuated total reflection infrared spectroscopy measurements reveal that the HCO3– concentration near the surface of Au-CeOx heteronanostructures is much higher than that of Au nanorods, facilitating the CO2 reduction process. Density functional theory calculations suggest the activation effect of CeOx on the 4H/fcc Au nanorod surface for the electrocatalytic CO2RR. The synergy between 4H/fcc Au and CeOx promotes the formation of carboxyl (*COOH) species and thus boosts the electrocatalytic CO2RR performance. This work highlights the importance of rational electronic structure regulation of unusual phase nanomaterials toward the electrocatalytic conversion of small molecules.

Publisher Copyright

This research / project is supported by the Agency for Science, Technology and Research (A*STAR) - Low Carbon Energy Research Finding Initiative (LCERFI01-0033 | U2102d2006)
Grant Reference no. : U2102d2006

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Materials Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/acsmaterialslett.3c01156.

https://oar.a-star.edu.sg/communities-collections/articles/22700

2639-4979
2639-4979

Institute of Sustainability for Chemicals, Energy and Environment