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.
© 2023 Wiley-VCH GmbH.