Pires Bruno M, Dos Santos Pãmyla L, Katic Vera, Strohauer Stefan, Landers Richard, Formiga André L B, Bonacin Juliano A
Institute of Chemistry, University of Campinas, P. O. Box 6154, 13083-970, Campinas, SP, Brazil.
Dalton Trans. 2019 Apr 9;48(15):4811-4822. doi: 10.1039/c8dt04660c.
The search for earth-abundant metal-based catalysts for the oxygen evolution reaction (OER) that operates under neutral conditions is a challenge in the field of sustainable energy. Many strategies have been used, and coordination polymers with structures similar to Prussian blue appear to be interesting electrocatalysts due to their efficiency, stability and tunable properties. In this paper, a novel catalyst produced from a cobalt-pentacyanidoferrate precursor is presented and applied in studies of the OER. This material showed a high surface active area and electrocatalytic activity comparable to traditional cobalt hexacyanidoferrate. According to the theoretical calculations, the improvement of these properties is an effect of the framework arrangement and it is not caused by changes of the electronic structure. Further experimental evidence is necessary to determine the active species. However, our results of spin densities obtained from DFT calculations suggest that the active species for water oxidation is the radical Fe(iii)-CN-Co(iii)-O˙.
寻找在中性条件下运行的用于析氧反应（OER）的富含地球元素的金属基催化剂是可持续能源领域的一项挑战。人们已经采用了许多策略，结构类似于普鲁士蓝的配位聚合物因其效率、稳定性和可调性质似乎是有趣的电催化剂。本文介绍了一种由五氰基铁酸钴前驱体制备的新型催化剂，并将其应用于OER研究。这种材料表现出高表面活性面积和与传统六氰基铁酸钴相当的电催化活性。根据理论计算，这些性质的改善是框架排列的结果，并非由电子结构的变化引起。需要进一步的实验证据来确定活性物种。然而，我们从密度泛函理论（DFT）计算获得的自旋密度结果表明，水氧化的活性物种是自由基Fe(iii)-CN-Co(iii)-O˙ 。
