Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published April 2, 2020 | Supplemental Material
Journal Article Open

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

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.

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.

Attached Files

Supplemental Material - jz0c00642_si_001.pdf

Supplemental Material - jz0c00642_si_003.mp4

Supplemental Material - jz0c00642_si_004.mp4

Supplemental Material - jz0c00642_si_005.mp4

Supplemental Material - jz0c00642_si_006.mp4

Supplemental Material - jz0c00642_si_007.mp4

Supplemental Material - jz0c00642_si_008.mp4

Files

jz0c00642_si_001.pdf
Files (189.9 MB)
Name Size Download all
md5:6492d2742d11efee36beb66b367f0fd3
46.8 MB Download
md5:0bbd8d17016b6790fae8f89486d20f72
47.0 MB Download
md5:4883861e465d3e2608e075fe692d1593
35.9 MB Download
md5:2a7e84bdb3f041555916af732cb8df1c
2.7 MB Preview Download
md5:ff21774428a8bc58dff0a7462922b6e8
13.6 MB Download
md5:d7ceb999e6464b42f4fbc4146464ad54
8.9 MB Download
md5:fd1e3a3f241bac2d87d9847e18176801
35.0 MB Download

Additional details

Created:
August 19, 2023
Modified:
October 19, 2023