Zhu Yinlong, Su Chao, Xu Xiaomin, Zhou Wei, Ran Ran, Shao Zongping
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (P.R. China); College of Chemistry and Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (P.R. China).
Chemistry. 2014 Nov 17;20(47):15533-42. doi: 10.1002/chem.201403192. Epub 2014 Sep 29.
Increasing energy demands have stimulated intense research activities on reversible electrochemical conversion and storage systems with high efficiency, low cost, and environmental benignity. It is highly challenging but desirable to develop efficient bifunctional catalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A universal and facile method for the development of bifunctional electrocatalysts with outstanding electrocatalytic activity for both the ORR and OER in alkaline medium is reported. A mixture of Pt/C catalyst with superior ORR activity and a perovskite oxide based catalyst with outstanding OER activity was employed in appropriate ratios, and prepared by simple ultrasonic mixing. Nanosized platinum particles with a wide range of platinum to oxide mass ratios was realized easily in this way. The as-formed Pt/C-oxide composites showed better ORR activity than a single Pt/C catalyst and better OER activity than a single oxide to bring about much improved bifunctionality (ΔE is only ≈0.8 V for Pt/C-BSCF; BSCF=Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ ), due to the synergistic effect. The electronic transfer mechanism and the rate-determining step and spillover mechanism were two possible origins of such a synergistic effect. Additionally, the phenomenon was found to be universal, although the best performance could be reached at different platinum to oxide mass ratios for different oxide catalysts. This work thus provides an innovative strategy for the development of new bifunctional electrocatalysts with wide application potentials in high-energy and efficient electrochemical energy storage and conversion.
不断增长的能源需求激发了人们对具有高效率、低成本和环境友好性的可逆电化学转换与存储系统的深入研究。开发用于氧还原反应(ORR)和析氧反应(OER)的高效双功能催化剂极具挑战性但却十分必要。本文报道了一种通用且简便的方法,用于开发在碱性介质中对ORR和OER均具有出色电催化活性的双功能电催化剂。将具有优异ORR活性的Pt/C催化剂与具有出色OER活性的钙钛矿氧化物基催化剂按适当比例混合,并通过简单的超声混合制备而成。通过这种方式可以轻松实现具有广泛铂与氧化物质量比的纳米级铂颗粒。所形成的Pt/C-氧化物复合材料表现出比单一Pt/C催化剂更好的ORR活性,以及比单一氧化物更好的OER活性,从而带来显著改善的双功能性(对于Pt/C-BSCF;BSCF = Ba0.5Sr0.5Co0.8Fe0.2O3-δ,ΔE仅约为0.8 V),这归因于协同效应。电子转移机制、速率决定步骤和溢流机制是这种协同效应的两个可能来源。此外,尽管对于不同的氧化物催化剂,在不同的铂与氧化物质量比下可达到最佳性能,但发现该现象具有普遍性。因此,这项工作为开发在高能效电化学能量存储和转换中具有广泛应用潜力的新型双功能电催化剂提供了一种创新策略。