Lebedeva Olga, Zakharov Valery, Kuznetsova Irina, Kultin Dmitry, Chernyshev Vladimir, Kalmykov Konstantin, Savilov Serguei, Dunaev Sergey, Aslanov Leonid, Kustov Leonid
Department of Chemistry, Lomonosov Moscow State University, 119991, Moscow, Russia.
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119991, Leninsky Prospect 31, Moscow, Russia.
Chemistry. 2024 Oct 1;30(55):e202402075. doi: 10.1002/chem.202402075. Epub 2024 Sep 17.
This work uses green sustainable reactions twice. Firstly, it is microwave synthesis: 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and similar compounds were prepared in a closed microwave reactor in n-octane by the Friedel-Crafts reaction. Second, a hybrid electrocatalyst for the highly demanded electrochemical reaction of nitrate reduction to ammonia (NORR) was prepared based on this material. This reaction has great potential to replace the energy-intensive Haber-Bosch process, and in addition, has independent value for the elimination of nitrate contamination of water resources. As shown in the work, microwave synthesis is an eco-friendly method for the synthesis of complex organic compounds; fast, selective and with a high yield of the target product. The electrocatalyst deposited on the graphite electrode consisted of a layer of 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and related compounds coated with cobalt oxide. The hybrid catalyst was firmly retained on the graphite electrode during NORR and the material showed impressive stability with almost no decrease in catalytic activity even after the fifth cycle. Both 2,4-bis([1,1'-biphenyl]-4-yl)-6-hydroxy-1,3,5-triazine and the catalyst based on this substance were characterized by SEM, XPS, XRD, UV-vis spectra, cyclic (and linear) voltammetry, and chronoamperometry. This work can serve as a starting point for the development of stable and durable electrocatalysts for NORR using triazine derivatives.
这项工作两次采用了绿色可持续反应。首先是微波合成：在封闭的微波反应器中，通过傅克反应在正辛烷中制备了2,4,6-三（联苯-4-基）-1,3,5-三嗪及类似化合物。其次，基于这种材料制备了一种用于将硝酸盐还原为氨（NORR）这一高需求电化学反应的混合电催化剂。该反应极有潜力取代能源密集型的哈伯-博施法，此外，对于消除水资源中的硝酸盐污染具有独立价值。如该工作所示，微波合成是一种合成复杂有机化合物的环保方法；快速、具有选择性且目标产物产率高。沉积在石墨电极上的电催化剂由一层2,4-双（[1,1'-联苯]-4-基）-6-羟基-1,3,5-三嗪及相关化合物组成，并涂覆有氧化钴。在NORR过程中，混合催化剂牢固地保留在石墨电极上，并且该材料表现出令人印象深刻的稳定性，即使在第五个循环后催化活性几乎没有下降。2,4-双（[1,1'-联苯]-4-基）-6-羟基-1,3,5-三嗪及其基于该物质的催化剂均通过扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、X射线衍射（XRD）、紫外可见光谱、循环（和线性）伏安法以及计时电流法进行了表征。这项工作可以作为开发使用三嗪衍生物的稳定且耐用的NORR电催化剂的起点。
