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https://hdl.handle.net/2440/131257
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Type: | Journal article |
Title: | Tailoring acidic oxygen reduction selectivity on single-atom catalysts via modification of first and second coordination spheres |
Author: | Tang, C. Chen, L. Li, H. Li, L. Jiao, Y. Zheng, Y. Xu, H. Davey, K. Qiao, S. |
Citation: | Journal of the American Chemical Society, 2021; 43(20):4819-4827 |
Publisher: | American Chemical Society (ACS) |
Issue Date: | 2021 |
ISSN: | 0002-7863 1520-5126 |
Statement of Responsibility: | Cheng Tang, Ling Chen, Haijing Li, Laiquan Li, Yan Jiao, Yao Zheng, Haolan Xu, Kenneth Davey, and Shi-Zhang Qiao |
Abstract: | Product selectivity in multielectron electrocatalytic reactions is crucial to energy conversion efficiency and chemical production. However, a present practical drawback is the limited understanding of actual catalytic active sites. Here, using as a prototype single-atom catalysts (SACs) in acidic oxygen reduction reaction (ORR), we report the structure–property relationship of catalysts and show for the first time that molecular-level local structure, including first and second coordination spheres (CSs), rather than individual active atoms, synergistically determines the electrocatalytic response. ORR selectivity on Co-SACs can be tailored from a four-electron to a two-electron pathway by modifying first (N or/and O coordination) and second (C–O–C groups) CSs. Using combined theoretical predictions and experiments, including X-ray absorption fine structure analyses and in situ infrared spectroscopy, we confirm that the unique selectivity change originates from the structure-dependent shift of active sites from the center Co atom to the O-adjacent C atom. We show this optimizes the electronic structure and *OOH adsorption behavior on active sites to give the present “best” activity and selectivity of >95% for acidic H₂O₂ electrosynthesis. |
Rights: | © 2021 American Chemical Society |
DOI: | 10.1021/jacs.1c03135 |
Grant ID: | http://purl.org/au-research/grants/arc/FL170100154 http://purl.org/au-research/grants/arc/DE190100636 |
Published version: | http://dx.doi.org/10.1021/jacs.1c03135 |
Appears in Collections: | Aurora harvest 8 Chemical Engineering publications |
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