Tian Han, Yu Xu, Huang Weimin, Chang Ziwei, Pei Fenglai, Zhou Jiangdong, Dai Ningning, Meng Ge, Chen Chang, Cui Xiangzhi, Shi Jianlin
State Key Lab of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China.
Small. 2023 Oct;19(42):e2303061. doi: 10.1002/smll.202303061. Epub 2023 Jun 21.
Developing anode catalysts with substantially enhanced activity for hydrogen oxidation reaction (HOR) and CO tolerance performance is of great importance for the commercial applications of proton exchange membrane fuel cells (PEMFCs). Herein, an excellent CO-tolerant catalyst (Pd-WO /C) has been fabricated by loading Pd nanoparticles on WO via an immersion-reduction route. A remarkably high power density of 1.33 W cm at 80 °C is obtained by using the optimized 3Pd-WO /C as the anode catalyst of PEMFCs, and the moderately reduced power density (73% remained) in CO/H mixed gas can quickly recover after removal of CO-contamination from hydrogen fuel, which is not possible by using Pt/C or Pd/C as anode catalyst. The prominent HOR activity of 3Pd-WO /C is attributed to the optimized interfacial electron interaction, in which the activated H* adsorbed on Pd species can be effectively transferred to WO species through hydrogen spillover effect and then oxidized through the H species insert/output effect during the formation of H WO in acid electrolyte. More importantly, a novel synergetic catalytic mechanism about excellent CO tolerance is proposed, in which Pd and WO respectively absorbs/activates CO and H O, thus achieving the CO electrooxidation and re-exposure of Pd active sites for CO-tolerant HOR.
开发对氢氧化反应(HOR)具有大幅增强活性和抗CO性能的阳极催化剂对于质子交换膜燃料电池(PEMFC)的商业应用至关重要。在此,通过浸渍还原路线将钯纳米颗粒负载在WO上制备了一种优异的抗CO催化剂(Pd-WO /C)。使用优化后的3Pd-WO /C作为PEMFC的阳极催化剂,在80°C时可获得1.33 W cm的极高功率密度,并且在CO/H混合气体中适度降低的功率密度(仍保留73%)在从氢气燃料中去除CO污染后能够迅速恢复,而使用Pt/C或Pd/C作为阳极催化剂则无法做到这一点。3Pd-WO /C突出的HOR活性归因于优化的界面电子相互作用,其中吸附在Pd物种上的活化H*可通过氢溢流效应有效地转移到WO物种上,然后在酸性电解质中形成H WO的过程中通过H物种插入/输出效应被氧化。更重要的是,提出了一种关于优异抗CO性能的新型协同催化机制,其中Pd和WO分别吸收/活化CO和H O,从而实现CO的电氧化以及使Pd活性位点重新暴露以进行抗CO的HOR。