金属酞菁电催化硝酸根还原产羟胺研究

电催化还原含氮废弃物为含氮化学品的生产提供了一条可持续发展的路径。作为反应中间体，羟胺（NH₂OH）的选择性电合成仍具有较大的挑战。本文提出了一种新型的电催化剂设计策略，通过抑制NH₂OH的进一步还原来实现NH₂OH的高选择性、快速合成。通过调控催化剂的本征活性，我们筛选出了具有高NH₂OH还原能垒的酞菁锌（ZnPc）电催化剂。同时，我们还发现碳纳米管（CNT）基底具有较好的还原硝酸根（NO₃⁻）产氨（NH₃）的活性，但通过往其表面覆盖足量的ZnPc分子能有效的抑制这一副反应的发生。原位表征技术揭示了在从NO₃⁻还原至NH₃的过程中会产生NH₂OH和HNO等中间体，而ZnPc电极表面可以发生NH₂OH分子的富集。优化后的ZnPc电催化剂具有增强的还原NO₃⁻产NH₂OH性能，能实现超过270 mA cm^-2的NH₂OH分电流密度，法拉第效率（FE）可达53%，且对应的周转频率（TOF）高达7.5 s^-1。该催化剂还能应用于还原亚硝酸根（NO₂⁻）并原位耦合环已酮来生产环己酮肟，其分电流密度可达320 mA cm^-2且FE高达64%。该工作为开发选择性合成高价值中间体的电催化剂提供了借鉴。

The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. The selective synthesis of high-value hydroxylamine (NH₂OH) is challenging due to the instability of NH₂OH as an intermediate. Here, we present a rational electrocatalyst design strategy for promoting NH₂OH electrosynthesis by suppressing the competing pathways of further reduction. We screen zinc phthalocyanine (ZnPc) with a high energy barrier for NH₂OH reduction by regulating their intrinsic activity. Additionally, we discover that carbon nanotube substrates exhibit significant NH₃-producing activity, which can be effectively inhibited by the high coverage of ZnPc molecules. In-situ characterizations reveal that NH₂OH and HNO are generated as intermediates in the nitrate (NO₃⁻) reduction to NH₃, and NH₂OH can be enriched in the ZnPc electrode. The optimized ZnPc catalyst shows improved performance in electrocatalysis of NO₃⁻ reduction to NH₂OH. It demonstrates a high Faradaic efficiency (FE) of 53% for NH₂OH with a partial current density exceeding 270 mA cm^-2 and a high turnover frequency of 7.5 s^-1. It also enables the rapid electrosynthesis of cyclohexanone oxime from nitrite (NO₂⁻) with a high FE of 64% and a high partial current density of 320 mA cm^-2. This work provides a guiding principle for electrocatalyst design in the electrosynthesis of high-value intermediate chemicals.

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