Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO2

Hengpan Yang; Yu Wu; Qing Lin; Liangdong Fan; Xiaoyan Chai; Qianling Zhang; Jianhong Liu; Chuanxin He; Zhiqun Lin

doi:10.1002/anie.201809255

Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO₂

Hengpan Yang, Yu Wu, Qing Lin, Liangdong Fan, Xiaoyan Chai, Qianling Zhang, Jianhong Liu, Chuanxin He, Zhiqun Lin

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

172 Scopus citations

Abstract

A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400 cm² membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO₂ reduction reaction (CO₂RR). Notably, CO with 94 % Faradaic efficiency and −103 mA cm⁻² current density are readily achieved with only about 1.2 mg catalyst loading, which are among the best results ever obtained by metal-free CO₂RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO₂RR, leading to the ultra-high current density.

Original language	English
Pages (from-to)	15476-15480
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	47
DOIs	https://doi.org/10.1002/anie.201809255
State	Published - 19 Nov 2018

Bibliographical note

Funding Information:
The financial support of the National Natural Science Foundation (NNSF) of China (21574084 and 21571131), the Natural Science Foundation of Guangdong Province (2015A030313554 and 2017A040405066), and Shenzhen Government's Plan of Science and Technology (JCYJ20160308104704791, JCYJ20170817095041212, and JCYJ20170818091657056) are gratefully acknowledged.

Funding Information:
The financial support of the National Natural Science Foundation (NNSF) of China (21574084 and 21571131), the Natural Science Foundation of Guangdong Province (2015A030313554 and 2017A040405066), and Shenzhen Government≫s Plan of Science and Technology (JCYJ20160308104704791, JCYJ20170817095041212, and JCYJ20170818091657056) are gratefully acknowledged.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

CO reduction
electrocatalysis
hierarchical pores
metal-free catalysts
ultrahigh current density

Access to Document

10.1002/anie.201809255

Cite this

Yang, H., Wu, Y., Lin, Q., Fan, L., Chai, X., Zhang, Q., Liu, J., He, C., & Lin, Z. (2018). Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO₂. Angewandte Chemie - International Edition, 57(47), 15476-15480. https://doi.org/10.1002/anie.201809255

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title = "Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO2",

abstract = "A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400 cm2 membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO2 reduction reaction (CO2RR). Notably, CO with 94 % Faradaic efficiency and −103 mA cm−2 current density are readily achieved with only about 1.2 mg catalyst loading, which are among the best results ever obtained by metal-free CO2RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO2RR, leading to the ultra-high current density.",

keywords = "CO reduction, electrocatalysis, hierarchical pores, metal-free catalysts, ultrahigh current density",

author = "Hengpan Yang and Yu Wu and Qing Lin and Liangdong Fan and Xiaoyan Chai and Qianling Zhang and Jianhong Liu and Chuanxin He and Zhiqun Lin",

note = "Funding Information: The financial support of the National Natural Science Foundation (NNSF) of China (21574084 and 21571131), the Natural Science Foundation of Guangdong Province (2015A030313554 and 2017A040405066), and Shenzhen Government's Plan of Science and Technology (JCYJ20160308104704791, JCYJ20170817095041212, and JCYJ20170818091657056) are gratefully acknowledged. Funding Information: The financial support of the National Natural Science Foundation (NNSF) of China (21574084 and 21571131), the Natural Science Foundation of Guangdong Province (2015A030313554 and 2017A040405066), and Shenzhen Government≫s Plan of Science and Technology (JCYJ20160308104704791, JCYJ20170817095041212, and JCYJ20170818091657056) are gratefully acknowledged. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/anie.201809255",

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Yang, H, Wu, Y, Lin, Q, Fan, L, Chai, X, Zhang, Q, Liu, J, He, C & Lin, Z 2018, 'Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO₂', Angewandte Chemie - International Edition, vol. 57, no. 47, pp. 15476-15480. https://doi.org/10.1002/anie.201809255

Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores: Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO₂. / Yang, Hengpan; Wu, Yu; Lin, Qing et al.
In: Angewandte Chemie - International Edition, Vol. 57, No. 47, 19.11.2018, p. 15476-15480.

Research output: Contribution to journal › Article › peer-review

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T1 - Composition Tailoring via N and S Co-doping and Structure Tuning by Constructing Hierarchical Pores

T2 - Metal-Free Catalysts for High-Performance Electrochemical Reduction of CO2

AU - Yang, Hengpan

AU - Wu, Yu

AU - Lin, Qing

AU - Fan, Liangdong

AU - Chai, Xiaoyan

AU - Zhang, Qianling

AU - Liu, Jianhong

AU - He, Chuanxin

AU - Lin, Zhiqun

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PY - 2018/11/19

Y1 - 2018/11/19

N2 - A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400 cm2 membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO2 reduction reaction (CO2RR). Notably, CO with 94 % Faradaic efficiency and −103 mA cm−2 current density are readily achieved with only about 1.2 mg catalyst loading, which are among the best results ever obtained by metal-free CO2RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO2RR, leading to the ultra-high current density.

AB - A facile route to scalable production of N and S co-doped, hierarchically porous carbon nanofiber (NSHCF) membranes (ca. 400 cm2 membrane in a single process) is reported. As-synthesized NSHCF membranes are flexible and free-standing, allowing their direct use as cathodes for efficient electrochemical CO2 reduction reaction (CO2RR). Notably, CO with 94 % Faradaic efficiency and −103 mA cm−2 current density are readily achieved with only about 1.2 mg catalyst loading, which are among the best results ever obtained by metal-free CO2RR catalysts. On the basis of control experiments and DFT calculations, such outstanding CO Faradaic efficiency can be attributed to the co-doped pyridinic N and carbon-bonded S atoms, which effectively decrease the Gibbs free energy of key *COOH intermediate. Furthermore, hierarchically porous structures of NSHCF membranes impart a much higher density of accessible active sites for CO2RR, leading to the ultra-high current density.

KW - CO reduction

KW - electrocatalysis

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KW - metal-free catalysts

KW - ultrahigh current density

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