Ammonia is a crucial feedstock for the chemical industry, a carbon-free energy source, and a safe source for hydrogen storage. The electrochemical nitrate reduction reaction (NO₃RR) is one promising strategy for greener ammonia synthesis due to high water solubility and low N═O bond dissociation energy of NO₃^–. More importantly, polluted water is a source of NO₃^–. Herein, we rationally designed a bifunctional covalent organic framework catalyst (Ru-Tta-Dfp) having a triazine- and pyridine-rich backbone with inherent Ru-nanocluster sites to control both NO₃^– and H⁺ diffusion and interactions to achieve selective conversion of NO₃^– to ammonia monitored by operando Raman spectroscopy (93.93% faradaic efficiency and yield rate of 1.16 mg h^–1cm^–2 at −0.4 V vs RHE). Moreover, we have developed a strategy for the first time to couple the anodic glucose oxidation reaction (GOR) to facilitate the cathodic NO₃RR with reduced energy consumption and to achieve value-added products at both electrodes. Notably, NO₃RR-GOR full cell studies generate a ∼2.5 times higher NH₃ yield rate than that of NO₃RR-OER.

中文翻译：

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共价有机框架双功能催化剂用于硝酸盐与氨电解耦合的葡萄糖氧化反应

氨是化学工业的重要原料、无碳能源和安全的储氢来源。由于NO ₃ ^–的高水溶性和低N=O键解离能，电化学硝酸盐还原反应（NO ₃ RR）是一种有前景的绿色氨合成策略。更重要的是，受污染的水是NO ₃ ^–的来源。在此，我们合理设计了一种双功能共价有机骨架催化剂（Ru-Tta-Dfp），其主链富含三嗪和吡啶，具有固有的Ru纳米簇位点，可以控制NO ₃ ^-和H ^{+ 的}扩散和相互作用，从而实现选择性转化NO ₃ ^–通过操作拉曼光谱监测氨（法拉第效率为 93.93%，产率为 -0.4 V vs RHE 时为 1.16 mg h ^–1 cm ^–2）。此外，我们首次制定了一种策略，将阳极葡萄糖氧化反应（GOR）耦合起来，以促进阴极NO ₃ RR，降低能耗，并在两个电极上实现增值产品。值得注意的是，NO _{3 RR-GOR 全细胞研究产生的 NH 3}产率比 NO ₃ RR-OER高约 2.5 倍。