Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries

Jingwen Zhou; Yuecheng Xiong; Mingzi Sun; Zhihang Xu; Yunhao Wang; Pengyi Lu; Fu Liu; Fengkun Hao; Tianyi Feng; Yangbo Ma; Jinwen Yin; Chenliang Ye; Biao Chen; Shibo Xi; Ye Zhu; Bolong Huang; Zhanxi Fan

doi:10.1073/pnas.2311149120

Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries

Jingwen Zhou (Co-first Author)
, Yuecheng Xiong (Co-first Author)
, Mingzi Sun (Co-first Author)
, Zhihang Xu (Co-first Author)
, Yunhao Wang (Co-first Author)
, Pengyi Lu
, Fu Liu
, Fengkun Hao
, Tianyi Feng
, Yangbo Ma
, Jinwen Yin
, Chenliang Ye
, Biao Chen
, Shibo Xi^*
, Ye Zhu^*
, Bolong Huang^*
, Zhanxi Fan^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

104 Citations (Scopus)

32 Downloads (CityUHK Scholars)

Abstract

Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO₃RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg^-1_cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems. © 2023 the Author(s).

Original language	English
Article number	e2311149120
Number of pages	11
Journal	PNAS: Proceedings of the National Academy of Sciences of the United States of America
Volume	120
Issue number	50
Online published	8 Dec 2023
DOIs	https://doi.org/10.1073/pnas.2311149120
Publication status	Published - 12 Dec 2023

Funding

This work was supported by grants (Project Nos. 22175148, 22005258, and 52102320) from National Natural Science Foundation of China, grant (Project Nos. 21309322 and 15307522) from Research Grants Council of Hong Kong, grant (Project No. JCYJ20220530140815035) from Shenzhen Science and Technology Program, Innovation and Technology Commission via Hong Kong Branch of National Precious Metals Material Engineering Research Center, and grants (Project Nos. 9610480 and 9680301) from City University of Hong Kong. The Transmission Electron Microscope facility is funded by the Research Grants Council of Hong Kong (Project No. C5029-18E).

Research Keywords

electrocatalytic nitrate reduction
metallene
relay catalysis
two-dimensional materials
zinc-nitrate/ethanol batteries

Publisher's Copyright Statement

COPYRIGHT TERMS OF DEPOSITED FINAL PUBLISHED VERSION FILE: This full text is made available under CC-BY-NC-ND 4.0. https://creativecommons.org/licenses/by-nc-nd/4.0/

RGC Funding Information

RGC-funded

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Zhou, J., Xiong, Y., Sun, M., Xu, Z., Wang, Y., Lu, P., Liu, F., Hao, F., Feng, T., Ma, Y., Yin, J., Ye, C., Chen, B., Xi, S., Zhu, Y., Huang, B., & Fan, Z. (2023). Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries. PNAS: Proceedings of the National Academy of Sciences of the United States of America, 120(50), Article e2311149120. https://doi.org/10.1073/pnas.2311149120

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title = "Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries",

abstract = "Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of \textasciitilde{}400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems. {\textcopyright} 2023 the Author(s).",

keywords = "electrocatalytic nitrate reduction, metallene, relay catalysis, two-dimensional materials, zinc-nitrate/ethanol batteries",

author = "Jingwen Zhou and Yuecheng Xiong and Mingzi Sun and Zhihang Xu and Yunhao Wang and Pengyi Lu and Fu Liu and Fengkun Hao and Tianyi Feng and Yangbo Ma and Jinwen Yin and Chenliang Ye and Biao Chen and Shibo Xi and Ye Zhu and Bolong Huang and Zhanxi Fan",

year = "2023",

month = dec,

day = "12",

doi = "10.1073/pnas.2311149120",

language = "English",

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journal = "PNAS: Proceedings of the National Academy of Sciences of the United States of America",

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Zhou, J , Xiong, Y, Sun, M, Xu, Z, Wang, Y , Lu, P , Liu, F , Hao, F, Feng, T, Ma, Y , Yin, J, Ye, C, Chen, B, Xi, S, Zhu, Y, Huang, B & Fan, Z 2023, 'Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries', PNAS: Proceedings of the National Academy of Sciences of the United States of America, vol. 120, no. 50, e2311149120. https://doi.org/10.1073/pnas.2311149120

Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries. / Zhou, Jingwen (Co-first Author); Xiong, Yuecheng (Co-first Author); Sun, Mingzi (Co-first Author) et al.
In: PNAS: Proceedings of the National Academy of Sciences of the United States of America, Vol. 120, No. 50, e2311149120, 12.12.2023.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries

AU - Zhou, Jingwen

AU - Xiong, Yuecheng

AU - Sun, Mingzi

AU - Xu, Zhihang

AU - Wang, Yunhao

AU - Lu, Pengyi

AU - Liu, Fu

AU - Hao, Fengkun

AU - Feng, Tianyi

AU - Ma, Yangbo

AU - Yin, Jinwen

AU - Ye, Chenliang

AU - Chen, Biao

AU - Xi, Shibo

AU - Zhu, Ye

AU - Huang, Bolong

AU - Fan, Zhanxi

PY - 2023/12/12

Y1 - 2023/12/12

N2 - Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems. © 2023 the Author(s).

AB - Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems. © 2023 the Author(s).

KW - electrocatalytic nitrate reduction

KW - metallene

KW - relay catalysis

KW - two-dimensional materials

KW - zinc-nitrate/ethanol batteries

UR - https://www.scopus.com/pages/publications/85179646339

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85179646339&origin=recordpage

U2 - 10.1073/pnas.2311149120

DO - 10.1073/pnas.2311149120

M3 - RGC 21 - Publication in refereed journal

C2 - 38064508

SN - 0027-8424

VL - 120

JO - PNAS: Proceedings of the National Academy of Sciences of the United States of America

JF - PNAS: Proceedings of the National Academy of Sciences of the United States of America

IS - 50

M1 - e2311149120

ER -

Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries

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Research Keywords

Publisher's Copyright Statement

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