硝酸根电化学还原中的传质过程调控机制研究

间歇性可再生电力驱动的电化学硝酸根还原是一种很有前途的水处理策略。然而，低离子强度溶液中硝酸根还原活性低。此外，抑制中间体产物，高选择性地还原硝酸根为氨也是目前电化学硝酸根还原的一大挑战。其中，低离子强度溶液中硝酸根还原活性低，其本质是由于带负电荷的阴极对硝酸根阴离子的静电排斥，导致硝酸根阴离子的低电迁移速率。添加支持电解质是促进低浓度溶液中硝酸根还原的最流行的策略之一。硝酸根还原性能的提高是由于支持电解质对界面电场的屏蔽。另一种可能的策略是在催化剂上锚定阳离子位点。为证明这 一策略，采用热解法制备了Fe−N−C催化剂，并通过与铁原子未配的氮原子的甲基化，引入了阳离子位点。催化剂的甲基化导致零电荷电势的负移，催化剂与硝酸根之间的斥力减弱。在低硝酸根浓度的溶液中测试了电催化硝酸根还原的性能，该溶液的离子强度与实际河水相当。甲基化 Fe−N−C 催化剂展示了更高的硝酸根还原反应活性，其氨的分电流密度是 Fe−N−C 催化剂的 9.4 倍。研究表明，用离子基团修饰催化剂是调节低离子强度溶液中电催化活性的一种有效方法。

针对硝酸根还原选择性的问题，其主要在于亚硝酸根中间体的利用效率受其扩散的影响，利用强制对流调制中间体的扩散过程，探究硝酸根还原机理，进而可以提出针对性的措施来提高电化学硝酸根还原为氨的选择性。本研究基于Cu-RDE和Cu-RCE，通过可控强制对流调制扩散过程，系统性地探究了扩散过程对电化学硝酸根还原产物选择性的影响。本研究表明，硝酸根还原过程经历了溶解的亚硝酸根形成的过程。因此，可以通过抑制中间体亚硝酸根的扩散，来提高硝酸根还原为氨的选择性。

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