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

Proc Natl Acad Sci U S A. 2023 Dec 12;120(50):e2311149120. doi: 10.1073/pnas.2311149120. Epub 2023 Dec 8.

Authors

Jingwen Zhou^#^{1

2

3}, Yuecheng Xiong^#^{1

2}, Mingzi Sun^#⁴, Zhihang Xu^#⁵, Yunhao Wang^#¹, Pengyi Lu^{1

2}, Fu Liu¹, Fengkun Hao¹, Tianyi Feng¹, Yangbo Ma¹, Jinwen Yin¹, Chenliang Ye⁶, Biao Chen⁷, Shibo Xi⁸, Ye Zhu⁵, Bolong Huang⁴, Zhanxi Fan^{1

2

9}

Affiliations

¹ Department of Chemistry, City University of Hong Kong, Kowloon 999077, Hong Kong, Special Administrative Region of China.
² Hong Kong Branch of National Precious Metals Material Engineering Research Center, City University of Hong Kong, Kowloon 999077, Hong Kong, Special Administrative Region of China.
³ Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, China.
⁴ Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Kowloon 999077, Hong Kong, Special Administrative Region of China.
⁵ Department of Applied Physics Research Institute for Smart Energy, The Hong Kong Polytechnic University, Kowloon 999077, Hong Kong, Special Administrative Region of China.
⁶ College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, China.
⁷ School of Material Science and Engineering, Tianjin University, Tianjin 300350, China.
⁸ Institute of Sustainability for Chemicals, Energy and Environment, A*STAR, Singapore 627833, Singapore.
⁹ City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057, China.

^# Contributed equally.

PMID: 38064508
PMCID: PMC10723141 (available on 2024-06-08)
DOI: 10.1073/pnas.2311149120

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.

Keywords: electrocatalytic nitrate reduction; metallene; relay catalysis; two-dimensional materials; zinc-nitrate/ethanol batteries.

Abstract

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