Reversed Charge Transfer and Enhanced Hydrogen Spillover in Pt Nanoclusters Anchored on Titanium Oxide with Rich Oxygen Vacancies Boost Hydrogen Evolution Reaction.

The catalytic activity of metal clusters is closely related with the support, while the knowledge about the influence of support on the catalytic activity is scarce. Herein, we show that, Pt nanoclusters (NCs) anchored on porous TiO 2 nanosheets with rich oxygen vacancies ( V O -rich Pt/TiO 2 ) and deficient oxygen vacancies ( V O -deficient Pt/TiO 2 ), display significantly different catalytic activity for hydrogen evolution reaction (HER), in which V O -rich Pt/TiO 2 shows a mass activity of 45.28 A mg Pt -1 at -0.1 V vs. RHE, 16.7 and 58.8 times higher than those of V O -deficient Pt/TiO 2 and commercial Pt/C, respectively. DFT calculations and in-situ Raman spectra suggest that porous TiO 2 with rich oxygen vacancies can simultaneously achieve the reversed charge transfer (electrons transfer from TiO 2 to Pt NCs) and enhanced hydrogen spillover from Pt NCs to TiO 2 support, which bring to electron-rich Pt NCs being favorable for proton reduction to absorbed H*, as well as the acceleration of hydrogen desorption at Pt catalytic sites, both promoting the HER. Our work provides a new strategy for rational design of highly efficient HER catalysts.