Li Yun-Wu, Zhang Wen-Jie, Li Chun-Xia, Gu Lin, Du Hong-Mei, Ma Hui-Yan, Wang Su-Na, Zhao Jin-Sheng
Shandong Provincial Key Laboratory/Collaborative Innovation Center of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University Liaocheng 252000 P. R. China
RSC Adv. 2019 Dec 23;9(72):42554-42560. doi: 10.1039/c9ra08068f. eCollection 2019 Dec 18.
Dinuclear metal clusters as metalloenzymes execute efficient catalytic activities in biological systems. Enlightened by this, a dinuclear {Co } cluster was selected to survey its ORR (Oxygen Reduction Reaction) catalytic activities. The crystalline {Co } possesses defined structure and potential catalytic active centers of {CoNO} sites, which was identified by X-ray single crystal diffraction, Raman and XPS. The appropriate supramolecular porosity combining abundant pyridinic-N and triazole-N sites of {Co } catalyst synergistically benefit the ORR performance. As a result, this non-noble metal catalyst presents a nice ORR electrocatalytic activity and abides by a nearly 4-electron reduction pathway. Thus, this unpyrolyzed crystalline catalyst clearly provide precise active sites and the whole defined structural information, which can help researcher to design and fabricate efficient ORR catalysts to improve their activities. Considering the visible crystal structure, a single cobalt center-mediated catalytic mechanism was also proposed to elucidate the ORR process.
双核金属簇作为金属酶在生物系统中执行高效的催化活性。受此启发，选择了一种双核{Co}簇来研究其氧还原反应（ORR）催化活性。晶体{Co}具有明确的结构和潜在的{CoNO}位点催化活性中心，这通过X射线单晶衍射、拉曼光谱和X射线光电子能谱得以确定。{Co}催化剂丰富的吡啶-N和三唑-N位点与适当的超分子孔隙率协同作用，有利于ORR性能。结果，这种非贵金属催化剂表现出良好的ORR电催化活性，并遵循近乎4电子还原途径。因此，这种未热解的晶体催化剂清楚地提供了精确的活性位点和完整的明确结构信息，这有助于研究人员设计和制造高效的ORR催化剂以提高其活性。考虑到可见的晶体结构，还提出了一种单钴中心介导的催化机制来阐明ORR过程。
