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Published on: July 28, 2020
Dual Electronic and Interfacial Microenvironment Modulation on Rare-Earth Doped Ternary Pt Alloys Toward Alkaline
Sijie Chen1, Xueheng Liu1, Wenkang Lu1
1School of Chemistry and Chemical Engineering, Nantong University, Nantong226019, China.
Abstract:
Alkaline hydrogen oxidation reaction (HOR) is the bottleneck restricting the performance of anion-exchange membrane fuel cells (AEMFCs), originating from sluggish Volmer kinetics induced by mismatched adsorption of H* and OH intermediates on commercial Pt/C catalysts, accompanied by high Pt cost, poor durability and inferior CO tolerance. Herein, Pr-doped PtMo ternary nanoparticles anchored on XC-72 carbon (PtMoPr/C) are fabricated via a facile wet chemical reduction strategy, where trace Pr dopant regulates electronic configuration and lattice strain of PtMo via unique 4f-5d orbital hybridization. Operando characterizations and DFT calculations verify that Pr induces downshifted Pt d-band center to weaken excessive Pt-H binding, provides abundant OH adsorption sites to accelerate Volmer step. Electronic modulation by Pr also increases the interfacial water and enhances the connectivity of hydrogen-bond networks within the electric double layers, synergistically boosting alkaline HOR performance. Electrochemical measurements demonstrate that the optimized PtMoPr/C delivers a mass activity of 2656.9 mA mgpt-1 at 50 mV vs RHE in 0.1 M KOH, 16-fold higher than that of benchmark Pt/C, together with outstanding anti-CO poisoning capability when exposed to CO-containing H2 feedstock. This work clarifies rare-earth Pr's multifunctional effects and proposes an orbital modulation route to develop low-Pt HOR catalysts for practical AEMFC.
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