|
|||||
|
|
Molecular Engineering of a Metal-Organic Polymer for Enhanced Electrochemical Nitrate-to-Ammonia Conversion and Zinc Nitrate Batteries |
|
| Authors: | 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 |
| Institution: | 1. Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, 999077 China
These authors contributed equally to this work.;2. Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, 999077 China;3. Department of Materials Science and Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, 999077 China Hong Kong Center for Cerebro-Cardiovascular Health Engineering (COCHE), 999077 Shatin, NT, HKSAR, China;4. College of Materials Science and Engineering, Shenzhen University, 518060 Shenzhen, Guangdong, China |
| 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 |