Pan Bingxin, Peng Xu, Wang Yifan, An Qi, Zhang Xu, Zhang Yuexing, Teets Thomas S, Zeng Ming-Hua
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials , Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules , College of Chemistry & Chemical Engineering , Hubei University , Wuhan , 430062 , P. R. China . Email:
Department of Chemistry , University of Houston , 3585 Cullen Boulevard, Room 112 , Houston , Texas 77204-5003 , USA.
Chem Sci. 2019 Mar 12;10(17):4560-4566. doi: 10.1039/c9sc00505f. eCollection 2019 May 7.
Efficient oxygen evolution reaction catalysts can be prepared controlled pyrolysis of molecular platforms, and there is still minimal mechanistic understanding of such pyrolysis processes. Here, we introduce a 3-MeOsalophen-ligated cobalt complex as a precursor to obtain a Co-based OER electrocatalyst controlled pyrolysis under an inert atmosphere. In our case, the unique N, O chelation mode of the 3-MeOsalophen ligand (bis[3-methoxysalicylydene]-1,2 iminophenylenediamine) was used to synthesis a complex [Co(3-MeOsalophen)(Cl)(CHOH)]. By regulating the pyrolysis conditions, we successfully obtained a N-doped carbon Co/CoO core-shell nanostructure. More importantly, TG-MS was first adopted for tracking the decomposition products of the complex in the pyrolysis process, further finding out the evolution mechanism from to the core-shell nanostructure. As an electrocatalyst for the oxygen evolution reaction, the core-shell Co/CoO @NC-800 nanostructure achieves an ultralow overpotential of 288 mV at 10 mA cm in 1 M KOH solution. This work offers guiding insight into controlled pyrolysis TG-MS analysis, using a novel complex precursor for precise regulation of heteroatom-doped (3d) transition metal-based electrocatalysts.
通过对分子平台进行可控热解可以制备高效的析氧反应催化剂，然而对此类热解过程的机理了解仍然很少。在此，我们引入一种3-甲氧基水杨醛缩邻苯二胺配位的钴配合物作为前驱体，以在惰性气氛下通过可控热解获得一种钴基析氧反应电催化剂。在我们的研究中，3-甲氧基水杨醛缩邻苯二胺配体（双[3-甲氧基水杨亚基]-1,2-亚氨基苯二胺）独特的N、O螯合模式被用于合成配合物[Co(3-甲氧基水杨醛缩邻苯二胺)(Cl)(CHOH)]。通过调节热解条件，我们成功获得了一种氮掺杂碳包覆的Co/CoO核壳纳米结构。更重要的是，首次采用热重-质谱联用技术跟踪配合物在热解过程中的分解产物，进一步探明了从配合物到核壳纳米结构的演变机理。作为析氧反应的电催化剂，核壳结构的Co/CoO@NC-800纳米结构在1 M KOH溶液中10 mA cm时实现了288 mV的超低过电位。这项工作为可控热解和热重-质谱分析提供了指导性见解，利用一种新型配合物前驱体对杂原子掺杂的（3d）过渡金属基电催化剂进行精确调控。
