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
N1 - Publisher Copyright:
Copyright © 2023 the Author(s).
PY - 2023/12/8
Y1 - 2023/12/8
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.
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.
KW - electrocatalytic nitrate reduction
KW - metallene
KW - relay catalysis
KW - two-dimensional materials
KW - zinc-nitrate/ethanol batteries
UR - http://www.scopus.com/inward/record.url?scp=85179646339&partnerID=8YFLogxK
U2 - 10.1073/pnas.2311149120
DO - 10.1073/pnas.2311149120
M3 - Journal article
C2 - 38064508
AN - SCOPUS:85179646339
SN - 0027-8424
VL - 120
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 50
M1 - e2311149120
ER -