Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction

CO2 electroreduction using renewable electricity is a promising pathway for CO2 utilization. However, the development of highly active and selective catalysts for CO2 reduction still poses significant challenges. Here, we report the use of an amino-functionalized metal-organic framework as a precurs...

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Main Authors: Wang, Haojing, Liu, Guanyu, Chen, Chunping, Tu, Wenguang, Lu, Yan, Wu, Shuyang, O'Hare, Dermot, Xu, Rong
Other Authors: School of Chemical and Biomedical Engineering
Format: Article
Language:English
Published: 2022
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Online Access:https://hdl.handle.net/10356/159950
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-1599502022-07-06T04:08:32Z Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction Wang, Haojing Liu, Guanyu Chen, Chunping Tu, Wenguang Lu, Yan Wu, Shuyang O'Hare, Dermot Xu, Rong School of Chemical and Biomedical Engineering Cambridge Centre for Advanced Research and Education in Singapore Engineering::Chemical engineering Electrocatalysis Metal−Organic Framework CO2 electroreduction using renewable electricity is a promising pathway for CO2 utilization. However, the development of highly active and selective catalysts for CO2 reduction still poses significant challenges. Here, we report the use of an amino-functionalized metal-organic framework as a precursor to derive Ni-N-C active sites embedded in multilayer graphene shells as the dominant active sites for CO2 electroreduction. During the process of high-temperature annealing and acid washing, the -NH2 groups in the MOF precursors exhibit a greater tendency to generate structural defects on graphene layers and derive abundant Ni-N-C sites by Ni migration. Aggregated Ni particles, which incline to catalyze the competitive hydrogen evolution reaction, are successfully removed during the posttreatment, exposing numerous Ni-N-C active sites to facilitate the CO2 electroreduction. The resulting catalyst displays excellent electrochemical CO2 reduction activity to CO with Faradaic efficiencies above 90% in a wide range of potentials from -0.6 to -1.2 V versus reversible hydrogen electrode. The maximum Faradaic efficiency of 97% can be achieved at a low overpotential of 0.79 V with a CO partial current density of 27.2 mA cm-2, which is among the best performance of Ni-based electrocatalysts reported so far. This work provides useful insights into the tuning of the metal sites by the coordination environment of MOFs toward the fabrication of highly active and selective electrocatalysts for CO2 reduction. Nanyang Technological University National Research Foundation (NRF) This work is supported by Nanyang Technological University, Singapore (Grant RG116/16) and by the Singapore National Research Foundation under its Campus for Research Excellence and Technological Enterprise (CREATE) program through the Cambridge Center for Advanced Research and Education in Singapore (CARES) Cambridge Center for Carbon Reduction in Chemical Technology (C4T) and through CARES and the Berkeley Educational Alliance for Research in Singapore (BEARS) eCO2P program. 2022-07-06T04:08:32Z 2022-07-06T04:08:32Z 2021 Journal Article Wang, H., Liu, G., Chen, C., Tu, W., Lu, Y., Wu, S., O'Hare, D. & Xu, R. (2021). Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction. ACS Sustainable Chemistry and Engineering, 9(10), 3792-3801. https://dx.doi.org/10.1021/acssuschemeng.0c08749 2168-0485 https://hdl.handle.net/10356/159950 10.1021/acssuschemeng.0c08749 2-s2.0-85103414859 10 9 3792 3801 en RG116/16 ACS Sustainable Chemistry and Engineering © 2021 American Chemical Society. 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
Electrocatalysis
Metal−Organic Framework
spellingShingle Engineering::Chemical engineering
Electrocatalysis
Metal−Organic Framework
Wang, Haojing
Liu, Guanyu
Chen, Chunping
Tu, Wenguang
Lu, Yan
Wu, Shuyang
O'Hare, Dermot
Xu, Rong
Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
description CO2 electroreduction using renewable electricity is a promising pathway for CO2 utilization. However, the development of highly active and selective catalysts for CO2 reduction still poses significant challenges. Here, we report the use of an amino-functionalized metal-organic framework as a precursor to derive Ni-N-C active sites embedded in multilayer graphene shells as the dominant active sites for CO2 electroreduction. During the process of high-temperature annealing and acid washing, the -NH2 groups in the MOF precursors exhibit a greater tendency to generate structural defects on graphene layers and derive abundant Ni-N-C sites by Ni migration. Aggregated Ni particles, which incline to catalyze the competitive hydrogen evolution reaction, are successfully removed during the posttreatment, exposing numerous Ni-N-C active sites to facilitate the CO2 electroreduction. The resulting catalyst displays excellent electrochemical CO2 reduction activity to CO with Faradaic efficiencies above 90% in a wide range of potentials from -0.6 to -1.2 V versus reversible hydrogen electrode. The maximum Faradaic efficiency of 97% can be achieved at a low overpotential of 0.79 V with a CO partial current density of 27.2 mA cm-2, which is among the best performance of Ni-based electrocatalysts reported so far. This work provides useful insights into the tuning of the metal sites by the coordination environment of MOFs toward the fabrication of highly active and selective electrocatalysts for CO2 reduction.
author2 School of Chemical and Biomedical Engineering
author_facet School of Chemical and Biomedical Engineering
Wang, Haojing
Liu, Guanyu
Chen, Chunping
Tu, Wenguang
Lu, Yan
Wu, Shuyang
O'Hare, Dermot
Xu, Rong
format Article
author Wang, Haojing
Liu, Guanyu
Chen, Chunping
Tu, Wenguang
Lu, Yan
Wu, Shuyang
O'Hare, Dermot
Xu, Rong
author_sort Wang, Haojing
title Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
title_short Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
title_full Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
title_fullStr Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
title_full_unstemmed Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction
title_sort single-ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized mof for highly selective co₂ electroreduction
publishDate 2022
url https://hdl.handle.net/10356/159950
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