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Design of a Graphene Nitrene Two-Dimensional Catalyst Heterostructure Providing a Well-Defined Site Accommodating 1 to 3 Metals, with Application to CO₂ Reduction Electrocatalysis for the 2 Metal Case

Chen, Shiqian and Yuan, Hao and Morozov, Sergey I. and Ge, Lei and Li, Li and Xu, Lai and Goddard, William A., III (2020) Design of a Graphene Nitrene Two-Dimensional Catalyst Heterostructure Providing a Well-Defined Site Accommodating 1 to 3 Metals, with Application to CO₂ Reduction Electrocatalysis for the 2 Metal Case. Journal of Physical Chemistry Letters, 11 (7). pp. 2541-2549. ISSN 1948-7185. https://resolver.caltech.edu/CaltechAUTHORS:20200313-142322647

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Abstract

Recently, the reduction of CO₂ to fuels has been the subject of numerous studies, but the selectivity and activity remain inadequate. Progress has been made on single-site two-dimensional catalysts based on graphene coupled to a metal and nitrogen for the CO₂ reduction reaction (CO₂RR); however, the product is usually CO, and the metal–N environment remains ambiguous. We report a novel two-dimensional graphene nitrene heterostructure (grafiN₆) providing well-defined active sites (N₆) that can bind one to three metals for the CO₂RR. We find that homobimetallic FeFe–grafiN₆ could reduce CO₂ to CH₄ at −0.61 V and to CH₃CH₂OH at −0.68 V versus reversible hydrogen electrode, with high product selectivity. Moreover, the heteronuclear FeCu–grafiN₆ system may be significantly less affected by hydrogen evolution reaction, while maintaining a low limiting potential (−0.68 V) for C1 and C2 mechanisms. Binding metals to one N₆ site but not the other could promote efficient electron transport facilitating some reaction steps. This framework for single or multiple metal sites might also provide unique catalytic sites for other catalytic processes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.0c00642DOIArticle
ORCID:
AuthorORCID
Yuan, Hao0000-0003-3323-2855
Morozov, Sergey I.0000-0001-6226-5811
Li, Li0000-0001-9260-823X
Xu, Lai0000-0003-2473-3359
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2020 American Chemical Society. Received: February 28, 2020; Accepted: March 12, 2020; Published: March 12, 2020. The authors acknowledge financial support from the National Natural Science Foundation of China (Grant 91961120), Innovative and Entrepreneurial Doctor (World-Famous Universities) in Jiangsu Province, Talent in Demand in the city of Suzhou, and Scientific Research Startup Funding from the Institute of Functional Nano & Soft Materials (FUNSOM) of Soochow University. This project was also funded by the collaborative Innovation Center of Suzhou Nano Science & Technology, the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), the 111 Project, and the Joint International Research Laboratory of Carbon-based Functional Materials and Devices. S.I.M. is thankful for the support by Act 211 Government of the Russian Federation, under Grant 02.A03.21.0011. W.A.G. is supported by the National Science Foundation (CMMT 18-500, Bob McCabe). Author Contributions: S.C. and H.Y. contributed equally to this work. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China91961120
Innovative and Entrepreneurial Doctor in Jiangsu ProvinceUNSPECIFIED
Talent in Demand in the city of SuzhouUNSPECIFIED
Soochow UniversityUNSPECIFIED
Innovation Center of Suzhou Nano Science and TechnologyUNSPECIFIED
Priority Academic Program Development of Jiangsu Higher Education InstitutionsUNSPECIFIED
111 Project of ChinaUNSPECIFIED
Joint International Research Laboratory of Carbon-Based Functional Materials and DevicesUNSPECIFIED
Russian Federation02.A03.21.0011
NSFCMMT 18-500
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1372
Issue or Number:7
Record Number:CaltechAUTHORS:20200313-142322647
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200313-142322647
Official Citation:Design of a Graphene Nitrene Two-Dimensional Catalyst Heterostructure Providing a Well-Defined Site Accommodating One to Three Metals, with Application to CO2 Reduction Electrocatalysis for the Two-Metal Case. Shiqian Chen, Hao Yuan, Sergey I. Morozov, Lei Ge, Li Li, Lai Xu, and William A. Goddard III. The Journal of Physical Chemistry Letters 2020 11 (7), 2541-2549; DOI: 10.1021/acs.jpclett.0c00642
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101907
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:16 Mar 2020 14:20
Last Modified:11 Jul 2020 09:01

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