Directing the Surface Atomic Geometry on Copper Sulfide for Enhanced Electrochemical Nitrogen Reduction

Haneul Jin; Hee Soo Kim; Chi Ho Lee; Yongju Hong; Jihyun Choi; Hionsuck Baik; Sang Uck Lee; Sung Jong Yoo; Kwangyeol Lee; Hyun S. Park

doi:10.1021/acscatal.2c03680

Directing the Surface Atomic Geometry on Copper Sulfide for Enhanced Electrochemical Nitrogen Reduction

Haneul Jin, Hee Soo Kim, Chi Ho Lee, Yongju Hong, Jihyun Choi, Hionsuck Baik, Sang Uck Lee, Sung Jong Yoo, Kwangyeol Lee, Hyun S. Park

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

14 Citations (Scopus)

Abstract

Understanding catalytic-conversion determinants will blueprint an efficient electrocatalyst design for electrochemical nitrogen reduction. In metal chalcogenide-based catalysts, metal-site nitrogen adsorption initiates nitrogen fixation, and successive hydrogen supply from nearby chalcogen sites hydrogenates the nitrogen to ammonia. However, surface geometry-dependent reaction kinetics are rarely studied because the reaction is very fast. Here, we investigate the relationship between catalyst geometrical features and their electrochemical nitrogen reduction kinetics using surface atomic geometry-regulated copper sulfide (Cu_1.81S) nanocatalysts with exposed (100)- and (010)-type facets for flat and zigzag planes, respectively. The exposed facet densities of the nanocatalysts are varied via their aspect ratios. Nanocrystals with highly exposed (010)-type surfaces exhibit the best nitrogen reduction kinetics. Density functional theory calculation reveals that the protruded Cu and S atomic arrangement on the zigzag (010)-type surface promotes N₂adsorption and facilitates proton transfer from near the S site to*N₂at the Cu site, thus fast-forwarding electrochemical nitrogen reduction.

Original language	English
Pages (from-to)	13638-13648
Number of pages	11
Journal	ACS Catalysis
Volume	12
Issue number	21
DOIs	https://doi.org/10.1021/acscatal.2c03680
Publication status	Published - 2022 Nov 4

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea (NRF-2022M3I3A1094160, NRF-2021M3D1A2051389 (Creative Materials Discovery Program), NRF-2019R1A6A1A11044070, NRF-2020R1A2B5B03002475, NRF-2018M1A2A2061975, NRF-2021M3H4A1A02042948, NRF-2018M3D1A1058714, NRF-2021R1A2B5B01002879, and NRF-2022R1C1C2005786). This work was also supported by the Korea Institute of Science and Technology (2E31871). Y.H. acknowledges the Global Ph.D. Fellowship (NRF-2018H1A2A1062618).

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

Keywords

ammonia production
catalytic conversion
electrochemical nitrogen reduction
metal chalcogenide-based catalyst
surface atomic geometry

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.2c03680

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title = "Directing the Surface Atomic Geometry on Copper Sulfide for Enhanced Electrochemical Nitrogen Reduction",

abstract = "Understanding catalytic-conversion determinants will blueprint an efficient electrocatalyst design for electrochemical nitrogen reduction. In metal chalcogenide-based catalysts, metal-site nitrogen adsorption initiates nitrogen fixation, and successive hydrogen supply from nearby chalcogen sites hydrogenates the nitrogen to ammonia. However, surface geometry-dependent reaction kinetics are rarely studied because the reaction is very fast. Here, we investigate the relationship between catalyst geometrical features and their electrochemical nitrogen reduction kinetics using surface atomic geometry-regulated copper sulfide (Cu1.81S) nanocatalysts with exposed (100)- and (010)-type facets for flat and zigzag planes, respectively. The exposed facet densities of the nanocatalysts are varied via their aspect ratios. Nanocrystals with highly exposed (010)-type surfaces exhibit the best nitrogen reduction kinetics. Density functional theory calculation reveals that the protruded Cu and S atomic arrangement on the zigzag (010)-type surface promotes N2adsorption and facilitates proton transfer from near the S site to*N2at the Cu site, thus fast-forwarding electrochemical nitrogen reduction.",

keywords = "ammonia production, catalytic conversion, electrochemical nitrogen reduction, metal chalcogenide-based catalyst, surface atomic geometry",

author = "Haneul Jin and Kim, {Hee Soo} and Lee, {Chi Ho} and Yongju Hong and Jihyun Choi and Hionsuck Baik and Lee, {Sang Uck} and Yoo, {Sung Jong} and Kwangyeol Lee and Park, {Hyun S.}",

note = "Funding Information: This work was supported by the National Research Foundation of Korea (NRF-2022M3I3A1094160, NRF-2021M3D1A2051389 (Creative Materials Discovery Program), NRF-2019R1A6A1A11044070, NRF-2020R1A2B5B03002475, NRF-2018M1A2A2061975, NRF-2021M3H4A1A02042948, NRF-2018M3D1A1058714, NRF-2021R1A2B5B01002879, and NRF-2022R1C1C2005786). This work was also supported by the Korea Institute of Science and Technology (2E31871). Y.H. acknowledges the Global Ph.D. Fellowship (NRF-2018H1A2A1062618). Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

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doi = "10.1021/acscatal.2c03680",

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AU - Jin, Haneul

AU - Kim, Hee Soo

AU - Lee, Chi Ho

AU - Hong, Yongju

AU - Choi, Jihyun

AU - Baik, Hionsuck

AU - Lee, Sang Uck

AU - Yoo, Sung Jong

AU - Lee, Kwangyeol

AU - Park, Hyun S.

N1 - Funding Information: This work was supported by the National Research Foundation of Korea (NRF-2022M3I3A1094160, NRF-2021M3D1A2051389 (Creative Materials Discovery Program), NRF-2019R1A6A1A11044070, NRF-2020R1A2B5B03002475, NRF-2018M1A2A2061975, NRF-2021M3H4A1A02042948, NRF-2018M3D1A1058714, NRF-2021R1A2B5B01002879, and NRF-2022R1C1C2005786). This work was also supported by the Korea Institute of Science and Technology (2E31871). Y.H. acknowledges the Global Ph.D. Fellowship (NRF-2018H1A2A1062618). Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/11/4

Y1 - 2022/11/4

N2 - Understanding catalytic-conversion determinants will blueprint an efficient electrocatalyst design for electrochemical nitrogen reduction. In metal chalcogenide-based catalysts, metal-site nitrogen adsorption initiates nitrogen fixation, and successive hydrogen supply from nearby chalcogen sites hydrogenates the nitrogen to ammonia. However, surface geometry-dependent reaction kinetics are rarely studied because the reaction is very fast. Here, we investigate the relationship between catalyst geometrical features and their electrochemical nitrogen reduction kinetics using surface atomic geometry-regulated copper sulfide (Cu1.81S) nanocatalysts with exposed (100)- and (010)-type facets for flat and zigzag planes, respectively. The exposed facet densities of the nanocatalysts are varied via their aspect ratios. Nanocrystals with highly exposed (010)-type surfaces exhibit the best nitrogen reduction kinetics. Density functional theory calculation reveals that the protruded Cu and S atomic arrangement on the zigzag (010)-type surface promotes N2adsorption and facilitates proton transfer from near the S site to*N2at the Cu site, thus fast-forwarding electrochemical nitrogen reduction.

AB - Understanding catalytic-conversion determinants will blueprint an efficient electrocatalyst design for electrochemical nitrogen reduction. In metal chalcogenide-based catalysts, metal-site nitrogen adsorption initiates nitrogen fixation, and successive hydrogen supply from nearby chalcogen sites hydrogenates the nitrogen to ammonia. However, surface geometry-dependent reaction kinetics are rarely studied because the reaction is very fast. Here, we investigate the relationship between catalyst geometrical features and their electrochemical nitrogen reduction kinetics using surface atomic geometry-regulated copper sulfide (Cu1.81S) nanocatalysts with exposed (100)- and (010)-type facets for flat and zigzag planes, respectively. The exposed facet densities of the nanocatalysts are varied via their aspect ratios. Nanocrystals with highly exposed (010)-type surfaces exhibit the best nitrogen reduction kinetics. Density functional theory calculation reveals that the protruded Cu and S atomic arrangement on the zigzag (010)-type surface promotes N2adsorption and facilitates proton transfer from near the S site to*N2at the Cu site, thus fast-forwarding electrochemical nitrogen reduction.

KW - ammonia production

KW - catalytic conversion

KW - electrochemical nitrogen reduction

KW - metal chalcogenide-based catalyst

KW - surface atomic geometry

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U2 - 10.1021/acscatal.2c03680

DO - 10.1021/acscatal.2c03680

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SN - 2155-5435

VL - 12

SP - 13638

EP - 13648

JO - ACS Catalysis

JF - ACS Catalysis

IS - 21

ER -

Directing the Surface Atomic Geometry on Copper Sulfide for Enhanced Electrochemical Nitrogen Reduction

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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