Fan Hao, Yang Qian Qian, Fang Song Ru, Xu Yi Ning, Lv Yao, Lin Hao Yang, Lin Miao Yu, Liu Ji Kai, Wu Yi Xiao, Yuan Hai Yang, Dai Sheng, Liu Peng Fei, Yang Hua Gui
Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, 130 Meilong Road, 200237, Shanghai, China.
Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, 200237, Shanghai, China.
Angew Chem Int Ed Engl. 2024 Dec 16;63(51):e202412080. doi: 10.1002/anie.202412080. Epub 2024 Oct 25.
Proton exchange membrane (PEM) electrolysis holds great promise for green hydrogen production, but suffering from high loading of platinum-group metals (PGM) for large-scale deployment. Anchoring PGM-based materials on supports can not only improve the atomic utilization of active sites but also enhance the intrinsic activity. However, in practical PEM electrolysis, it is still challenging to mediate hydrogen adsorption/desorption pathways with high coverage of hydrogen intermediates over catalyst surface. Here, operando generated stable palladium (Pd) hydride nanoclusters anchored on tungsten carbide (WC) supports were constructed for hydrogen evolution in PEM electrolysis. Under PEM operando conditions, hydrogen intercalation induces formation of Pd hydrides (PdH) featuring weakened hydrogen binding energy (HBE), thus triggering reverse hydrogen spillover from WC (strong HBE) supports to PdH sites, which have been evidenced by operando characterizations, electrochemical results and theoretical studies. This PdH-WC material can be directly utilized as cathode electrocatalysts in PEM electrolysis with ultralow Pd loading of 0.022 mg cm, delivering the current density of 1 A cm at the cell voltage of ~1.66 V and continuously running for 200 hours without obvious degradation. This innovative strategy via tuning the operando characteristics to mediate reverse hydrogen spillover provide new insights for designing high-performance supported PGM-based electrocatalysts.
