Title: Copper Single Atoms Anchored in Porous Nitrogen-Doped Carbon as Efficient pH-Universal Catalysts for the Nitrogen Reduction Reaction

Abstract

Artificial nitrogen fixation through the nitrogen reduction reaction (NRR) under ambient conditions is a potentially promising alternative to the traditional energy-intensive Haber–Bosch process. For this purpose, efficient catalysts are urgently required to activate and reduce nitrogen into ammonia. Herein, by the combination of experiments and first-principles calculations, we demonstrate that copper single atoms, attached in a porous nitrogen-doped carbon network, provide highly efficient NRR electrocatalysis, which compares favorably with those previously reported. Benefiting from the high density of exposed active sites and the high level of porosity, the Cu SAC exhibits high NH₃ yield rate and Faradaic efficiency (FE), specifically ~53.3 μg$$_{NH_3}$$ h^–1 mg_cat^–1 and 13.8% under 0.1 M KOH, ~49.3 μg$$_{NH_3}$$ h^–1 mg_cat^–1 and 11.7% under 0.1 M HCl, making them truly pH-universal. They also show good stability with little current attenuation over 12 h of continuous operation. Cu–N₂ coordination is identified as the efficient active sites for the NRR catalysis.

Authors:

Zang, Wenjie  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-0604-9131"

Yang, Tong ^[2]; Zou, Haiyuan ^[3]; Xi, Shibo ^[4]; Zhang, Hong ^[1]; Liu, Ximeng  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-6168-8473"

Kou, Zongkui  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5377-2376"

Du, Yonghua ^[5]; Feng, Yuan Ping  ^[2];

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• Search DOE PAGES for ORCID "0000-0003-2190-2284"

Shen, Lei  ^[6];

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• Search DOE PAGES for ORCID "0000-0001-6198-5753"

Duan, Lele  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-1662-5817"

Wang, John  ^[1];

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• Search DOE PAGES for ORCID "0000-0001-6059-8962"

Pennycook, Stephen J.  ^[1]

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• Search DOE PAGES for ORCID "0000-0002-3210-6323"

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+ Show Author Affiliations

1. National Univ. of Singapore, Singapore (Singapore). Dept. of Materials Science and Engineering
2. National Univ. of Singapore, Singapore (Singapore). Dept. of Physics
3. Southern Univ. of Science and Technology (SUSTech), Shenzhen (China)
4. Inst. of Chemical and Engineering Sciences, Agency for Science, Technology and Research (A*STAR), Jurong Island (Singapore)
5. Inst. of Chemical and Engineering Sciences, Agency for Science, Technology and Research (A*STAR), Jurong Island (Singapore)
6. National Univ. of Singapore, Singapore (Singapore). Dept. of Mechanical Engineering

Publication Date:

Mon Oct 14 00:00:00 EDT 2019

Research Org.:

Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1570669

Report Number(s):

BNL-212188-2019-JAAM
Journal ID: ISSN 2155-5435

Grant/Contract Number:  

SC0012704

Resource Type:

Accepted Manuscript

Journal Name:

ACS Catalysis

Additional Journal Information:

Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2155-5435

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cu single atom catalysts; nitrogen-doped porous carbon; nitrogen