Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction

Efficient electron communication between molecular catalyst and support is critical for heterogeneous molecular electrocatalysis and yet it is often overlooked during the catalyst design. Taking CO2 electro-reduction on tetraphenylporphyrin cobalt (PCo) immobilized onto graphene as an example, we de...

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Main Authors: Wang, Jiong, Huang, Xiang, Xi, Shibo, Xu, Hu, Wang, Xin
Other Authors: School of Chemical and Biomedical Engineering
Format: Article
Language:English
Published: 2021
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Online Access:https://hdl.handle.net/10356/154566
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1545662021-12-28T07:13:21Z Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction Wang, Jiong Huang, Xiang Xi, Shibo Xu, Hu Wang, Xin School of Chemical and Biomedical Engineering Engineering::Chemical engineering Axial Coordination Carbon Dioxide Reduction Efficient electron communication between molecular catalyst and support is critical for heterogeneous molecular electrocatalysis and yet it is often overlooked during the catalyst design. Taking CO2 electro-reduction on tetraphenylporphyrin cobalt (PCo) immobilized onto graphene as an example, we demonstrate that adding a relay molecule improves the interfacial electron communication. While the directly immobilized PCo on graphene exhibits relatively poor electron communications, it is found that diphenyl sulfide serves as an axial ligand for PCo and it improves the redox activity of PCo on the graphene surface to facilitate the generation of [PCo]C- active sites for CO2 reduction. Thus, the turnover frequencies of the immobilized Co complexes are increased. Systematic structural analysis indicates that the benzene rings of diphenyl sulfide exhibit strong face-to-face stacking with graphene, which is proposed as an efficient medium to facilitate the interfacial electron communication. Ministry of Education (MOE) National Research Foundation (NRF) This project was funded by the National Research Foundation (NRF), Prime MinisterQs Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) program. We acknowledge financial support from the academic research fund AcRF tier 1 (M4012076 RG118/18), Ministry of Education, Singapore. 2021-12-28T07:13:21Z 2021-12-28T07:13:21Z 2020 Journal Article Wang, J., Huang, X., Xi, S., Xu, H. & Wang, X. (2020). Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction. Angewandte Chemie, 132(43), 19324-19329. https://dx.doi.org/10.1002/ange.202008759 0044-8249 https://hdl.handle.net/10356/154566 10.1002/ange.202008759 43 132 19324 19329 en M4012076 RG118/18 Angewandte Chemie © 2020 Wiley-VCH GmbH. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Chemical engineering
Axial Coordination
Carbon Dioxide Reduction
spellingShingle Engineering::Chemical engineering
Axial Coordination
Carbon Dioxide Reduction
Wang, Jiong
Huang, Xiang
Xi, Shibo
Xu, Hu
Wang, Xin
Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
description Efficient electron communication between molecular catalyst and support is critical for heterogeneous molecular electrocatalysis and yet it is often overlooked during the catalyst design. Taking CO2 electro-reduction on tetraphenylporphyrin cobalt (PCo) immobilized onto graphene as an example, we demonstrate that adding a relay molecule improves the interfacial electron communication. While the directly immobilized PCo on graphene exhibits relatively poor electron communications, it is found that diphenyl sulfide serves as an axial ligand for PCo and it improves the redox activity of PCo on the graphene surface to facilitate the generation of [PCo]C- active sites for CO2 reduction. Thus, the turnover frequencies of the immobilized Co complexes are increased. Systematic structural analysis indicates that the benzene rings of diphenyl sulfide exhibit strong face-to-face stacking with graphene, which is proposed as an efficient medium to facilitate the interfacial electron communication.
author2 School of Chemical and Biomedical Engineering
author_facet School of Chemical and Biomedical Engineering
Wang, Jiong
Huang, Xiang
Xi, Shibo
Xu, Hu
Wang, Xin
format Article
author Wang, Jiong
Huang, Xiang
Xi, Shibo
Xu, Hu
Wang, Xin
author_sort Wang, Jiong
title Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
title_short Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
title_full Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
title_fullStr Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
title_full_unstemmed Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
title_sort axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction
publishDate 2021
url https://hdl.handle.net/10356/154566
_version_ 1720447088676831232