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

作者：Zhang, Rong; Hong, Hu; Liu, Xinghui; Zhang, Shaoce; Li, Chuan; Cui, Huilin; Wang, Yanbo; Liu, Jiahua; Hou, Yue; Li, Pei; Huang, Zhaodong; Guo, Ying; Zhi, Chunyi^*

来源：Angewandte Chemie - International Edition, 2023, 62(48).

DOI：10.1002/anie.202309930

• Metal-Organic Framework
• NH3 Synthesis
• NO3- Reduction
• Zinc Batteries

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.