Butenko Vladislav R, Komova Oksana V, Simagina Valentina I, Lipatnikova Inna L, Ozerova Anna M, Danilova Natalya A, Rogov Vladimir A, Odegova Galina V, Bulavchenko Olga A, Chesalov Yuriy A, Netskina Olga V
Boreskov Institute of Catalysis SB RAS, 5 Akademika Lavrentieva Ave., Novosibirsk 630090, Russia.
Department of Natural Sciences, Novosibirsk State University, 1 Pirogova Str., Novosibirsk 630090, Russia.
Materials (Basel). 2024 Apr 13;17(8):1794. doi: 10.3390/ma17081794.
This work focuses on the comparison of H evolution in the hydrolysis of boron-containing hydrides (NaBH, NHBH, and (CHNHBH)) over the Co metal catalyst and the CoO-based catalysts. The CoO catalysts were activated in the reaction medium, and a small amount of CuO was added to activate CoO under the action of weaker reducers (NHBH, (CHNHBH)). The high activity of CoO has been previously associated with its reduced states (nanosized CoB). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the CoO structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in DO, as well as DFT modeling, reveal differences in water activation between Co and CoO-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.
这项工作聚焦于含硼氢化物（NaBH、NHBH和(CHNHBH)）在钴金属催化剂和基于CoO的催化剂上水解过程中氢的演化比较。CoO催化剂在反应介质中被活化，并且在较弱还原剂（NHBH、(CHNHBH)）的作用下添加少量CuO来活化CoO。CoO的高活性先前已与其还原态（纳米级CoB）相关联。所进行的密度泛函理论（DFT）建模表明，与氢化物活化相比，在类金属表面上活化水需要克服更高的能垒。本研究的新颖之处在于其专注于理解剩余氧化钴相的影响。X射线衍射（XRD）、程序升温还原氢（TPR H）、透射电子显微镜（TEM）、拉曼光谱和衰减全反射傅里叶变换红外光谱（ATR FTIR）证实了反应介质中CoO结构中氧空位的形成，这增加了吸附水的量。在D₂O中的动力学同位素效应测量以及DFT建模揭示了Co和基于CoO的催化剂在水活化方面的差异。可以假定，氧化物相不仅作为还原态纳米级钴活性组分的前驱体和载体，而且作为改善水活化的关键催化剂组分。
