Wan Tongtao, Wang Hongyu, Wu Lanlan, Wu Changcheng, Zhang Zisheng, Liu Shuming, Fu Jing, Li Jingde
Hebei Provincial Key Laboratory of Green Chemical Technology and Highly Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China.
Hebei Provincial Key Laboratory of Green Chemical Technology and Highly Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China; Department of Chemical and Biological Engineering, University of Ottawa, Ottawa, ON K1N 6N5, Canada.
J Colloid Interface Sci. 2023 Dec;651:27-35. doi: 10.1016/j.jcis.2023.07.145. Epub 2023 Jul 24.
The development of highly active and durable nonprecious metal-based bifunctional electrocatalysts for oxygen reduction/evolution reaction (ORR/OER) is important for rechargeable zinc-air batteries. Herein, a three-dimensional conductive niobium-doped TiO-TiO heterostructure supported ZIF-67-derived Co-NC bifunctional catalyst was fabricated. In the Co-NC@Nb-TiO catalyst, the Nb doping promoted the formation of TiO-TiO heterojunction support, enhanced its conductivity and stability and provided strong electron metal-support interaction between Co-NC and Nb-TiO. Also, the supported Co-NC nanoparticles provided abundant active sites with excellent ORR/OER activity. Experimental analysis reveals that the high OER activity of Co-NC@Nb-TiO can be attributed to the in-situ generated CoOOH species. It exhibits excellent ORR activity, as shown by its onset potential (0.95 V vs. RHE) and half-wave potential (0.86 V vs. RHE). Its OER overpotential at 10 mA cm is 480 mV. The zinc-air battery realizes outstanding cycling stability over 225 h cycles tested at 10 mA cm. This work demonstrates the importance of designing highly stable metal oxide-supported catalysts in electrochemical energy conversion devices.
开发用于氧还原/析氧反应（ORR/OER）的高活性和耐用的非贵金属基双功能电催化剂对于可充电锌空气电池至关重要。在此，制备了一种三维导电铌掺杂TiO-TiO异质结构负载的ZIF-67衍生Co-NC双功能催化剂。在Co-NC@Nb-TiO催化剂中，Nb掺杂促进了TiO-TiO异质结载体的形成，提高了其导电性和稳定性，并在Co-NC和Nb-TiO之间提供了强电子金属-载体相互作用。此外，负载的Co-NC纳米颗粒提供了丰富的活性位点，具有优异的ORR/OER活性。实验分析表明，Co-NC@Nb-TiO的高OER活性可归因于原位生成的CoOOH物种。它表现出优异 的ORR活性，其起始电位（相对于RHE为0.95 V）和半波电位（相对于RHE为0.86 V）表明了这一点。其在10 mA cm下的OER过电位为480 mV。该锌空气电池在10 mA cm下测试的225 h循环中实现了出色的循环稳定性。这项工作证明了在电化学能量转换装置中设计高度稳定的金属氧化物负载催化剂的重要性。
