Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries

Rong ZHANG; Hu HONG; Xinghui LIU; Shaoce ZHANG; Chuan LI; Huilin CUI; Yanbo WANG; Jiahua LIU; Yue HOU; Pei LI; Zhaodong HUANG; Ying GUO; Chunyi ZHI

doi:10.1002/anie.202309930

Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries

Rong ZHANG, Hu HONG, Xinghui LIU, Shaoce ZHANG, Chuan LI, Huilin CUI, Yanbo WANG, Jiahua LIU, Yue HOU, Pei LI, Zhaodong HUANG, Ying GUO, Chunyi ZHI^*

^*Corresponding author for this work

Research output: Journal Publications › Journal Article (refereed) › peer-review

21 Citations (Scopus)

Abstract

Metal–organic framework-based materials are promising single-site catalysts for electrocatalytic nitrate (NO₃⁻) reduction to value-added ammonia (NH₃) on account of well-defined structures and functional tunability but still lack a molecular-level understanding for designing the high-efficient catalysts. Here, we proposed a molecular engineering strategy to enhance electrochemical NO₃⁻-to-NH₃ conversion by introducing the carbonyl groups into 1,2,4,5-tetraaminobenzene (BTA) based metal-organic polymer to precisely modulate the electronic state of metal centers. Due to the electron-withdrawing properties of the carbonyl group, metal centers can be converted to an electron-deficient state, fascinating the NO₃⁻ adsorption and promoting continuous hydrogenation reactions to produce NH₃. Compared to CuBTA with a low NO₃⁻-to-NH₃ conversion efficiency of 85.1 %, quinone group functionalization endows the resulting copper tetraminobenzoquinone (CuTABQ) distinguished performance with a much higher NH₃ FE of 97.7 %. This molecular engineering strategy is also universal, as verified by the improved NO₃⁻-to-NH₃ conversion performance on different metal centers, including Co and Ni. Furthermore, the assembled rechargeable Zn−NO₃⁻ battery based on CuTABQ cathode can deliver a high power density of 12.3 mW cm⁻². This work provides advanced insights into the rational design of metal complex catalysts through the molecular-level regulation for NO₃⁻ electroreduction to value-added NH₃.

Original language	English
Article number	e202309930
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	48
Early online date	12 Oct 2023
DOIs	https://doi.org/10.1002/anie.202309930
Publication status	Published - 27 Nov 2023
Externally published	Yes

Bibliographical note

This work was supported by the National Key R&D Program of China under Project 2019YFA0705104. This work was supported in part by InnoHK Project on [Project 1.3 ‐ Flexible and Stretchable Technologies (FAST) for monitoring of CVD risk factors: Sensing and Applications] at Hong Kong Centre for Cerebro‐cardiovascular Health Engineering (COCHE). We thank Dr. M. K. TSE from the Department of Chemistry of the City University of Hong Kong for the NMR measurements.

Keywords

Metal–Organic Framework
NH3 Synthesis
NO3− Reduction
Zinc Batteries

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10.1002/anie.202309930

Cite this

ZHANG, R., HONG, H., LIU, X., ZHANG, S., LI, C., CUI, H., WANG, Y., LIU, J., HOU, Y., LI, P., HUANG, Z., GUO, Y., & ZHI, C. (2023). Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries. Angewandte Chemie - International Edition, 62(48), Article e202309930. https://doi.org/10.1002/anie.202309930

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title = "Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries",

abstract = " Metal–organic framework-based materials are promising single-site catalysts for electrocatalytic nitrate (NO3−) reduction to value-added ammonia (NH3) on account of well-defined structures and functional tunability but still lack a molecular-level understanding for designing the high-efficient catalysts. Here, we proposed a molecular engineering strategy to enhance electrochemical NO3−-to-NH3 conversion by introducing the carbonyl groups into 1,2,4,5-tetraaminobenzene (BTA) based metal-organic polymer to precisely modulate the electronic state of metal centers. Due to the electron-withdrawing properties of the carbonyl group, metal centers can be converted to an electron-deficient state, fascinating the NO3− adsorption and promoting continuous hydrogenation reactions to produce NH3. Compared to CuBTA with a low NO3−-to-NH3 conversion efficiency of 85.1 %, quinone group functionalization endows the resulting copper tetraminobenzoquinone (CuTABQ) distinguished performance with a much higher NH3 FE of 97.7 %. This molecular engineering strategy is also universal, as verified by the improved NO3−-to-NH3 conversion performance on different metal centers, including Co and Ni. Furthermore, the assembled rechargeable Zn−NO3− battery based on CuTABQ cathode can deliver a high power density of 12.3 mW cm−2. This work provides advanced insights into the rational design of metal complex catalysts through the molecular-level regulation for NO3− electroreduction to value-added NH3. ",

keywords = "Metal–Organic Framework, NH3 Synthesis, NO3− Reduction, Zinc Batteries",

author = "Rong ZHANG and Hu HONG and Xinghui LIU and Shaoce ZHANG and Chuan LI and Huilin CUI and Yanbo WANG and Jiahua LIU and Yue HOU and Pei LI and Zhaodong HUANG and Ying GUO and Chunyi ZHI",

note = "This work was supported by the National Key R&D Program of China under Project 2019YFA0705104. This work was supported in part by InnoHK Project on [Project 1.3 ‐ Flexible and Stretchable Technologies (FAST) for monitoring of CVD risk factors: Sensing and Applications] at Hong Kong Centre for Cerebro‐cardiovascular Health Engineering (COCHE). We thank Dr. M. K. TSE from the Department of Chemistry of the City University of Hong Kong for the NMR measurements.",

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AU - ZHANG, Rong

AU - HONG, Hu

AU - LIU, Xinghui

AU - ZHANG, Shaoce

AU - LI, Chuan

AU - CUI, Huilin

AU - WANG, Yanbo

AU - LIU, Jiahua

AU - HOU, Yue

AU - LI, Pei

AU - HUANG, Zhaodong

AU - GUO, Ying

AU - ZHI, Chunyi

N1 - This work was supported by the National Key R&D Program of China under Project 2019YFA0705104. This work was supported in part by InnoHK Project on [Project 1.3 ‐ Flexible and Stretchable Technologies (FAST) for monitoring of CVD risk factors: Sensing and Applications] at Hong Kong Centre for Cerebro‐cardiovascular Health Engineering (COCHE). We thank Dr. M. K. TSE from the Department of Chemistry of the City University of Hong Kong for the NMR measurements.

PY - 2023/11/27

Y1 - 2023/11/27

N2 - Metal–organic framework-based materials are promising single-site catalysts for electrocatalytic nitrate (NO3−) reduction to value-added ammonia (NH3) on account of well-defined structures and functional tunability but still lack a molecular-level understanding for designing the high-efficient catalysts. Here, we proposed a molecular engineering strategy to enhance electrochemical NO3−-to-NH3 conversion by introducing the carbonyl groups into 1,2,4,5-tetraaminobenzene (BTA) based metal-organic polymer to precisely modulate the electronic state of metal centers. Due to the electron-withdrawing properties of the carbonyl group, metal centers can be converted to an electron-deficient state, fascinating the NO3− adsorption and promoting continuous hydrogenation reactions to produce NH3. Compared to CuBTA with a low NO3−-to-NH3 conversion efficiency of 85.1 %, quinone group functionalization endows the resulting copper tetraminobenzoquinone (CuTABQ) distinguished performance with a much higher NH3 FE of 97.7 %. This molecular engineering strategy is also universal, as verified by the improved NO3−-to-NH3 conversion performance on different metal centers, including Co and Ni. Furthermore, the assembled rechargeable Zn−NO3− battery based on CuTABQ cathode can deliver a high power density of 12.3 mW cm−2. This work provides advanced insights into the rational design of metal complex catalysts through the molecular-level regulation for NO3− electroreduction to value-added NH3.

AB - Metal–organic framework-based materials are promising single-site catalysts for electrocatalytic nitrate (NO3−) reduction to value-added ammonia (NH3) on account of well-defined structures and functional tunability but still lack a molecular-level understanding for designing the high-efficient catalysts. Here, we proposed a molecular engineering strategy to enhance electrochemical NO3−-to-NH3 conversion by introducing the carbonyl groups into 1,2,4,5-tetraaminobenzene (BTA) based metal-organic polymer to precisely modulate the electronic state of metal centers. Due to the electron-withdrawing properties of the carbonyl group, metal centers can be converted to an electron-deficient state, fascinating the NO3− adsorption and promoting continuous hydrogenation reactions to produce NH3. Compared to CuBTA with a low NO3−-to-NH3 conversion efficiency of 85.1 %, quinone group functionalization endows the resulting copper tetraminobenzoquinone (CuTABQ) distinguished performance with a much higher NH3 FE of 97.7 %. This molecular engineering strategy is also universal, as verified by the improved NO3−-to-NH3 conversion performance on different metal centers, including Co and Ni. Furthermore, the assembled rechargeable Zn−NO3− battery based on CuTABQ cathode can deliver a high power density of 12.3 mW cm−2. This work provides advanced insights into the rational design of metal complex catalysts through the molecular-level regulation for NO3− electroreduction to value-added NH3.

KW - Metal–Organic Framework

KW - NH3 Synthesis

KW - NO3− Reduction

KW - Zinc Batteries

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DO - 10.1002/anie.202309930

M3 - Journal Article (refereed)

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SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

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M1 - e202309930

ER -

Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries

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Keywords

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