Reversed Charge Transfer and Enhanced Hydrogen Spillover in Platinum 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; however, knowledge on the influence of the support on the catalytic activity is scarce. We demonstrate that Pt nanoclusters (NCs) anchored on porous TiO2 nanosheets with rich oxygen vacancies (V-O-rich Pt/TiO2) and deficient oxygen vacancies (V-O-deficient Pt/TiO2), display significantly different catalytic activity for the hydrogen evolution reaction (HER), in which V-O-rich Pt/TiO2 shows a mass activity of 45.28 A mg(Pt)(-1) at -0.1 V vs. RHE, which is 16.7 and 58.8 times higher than those of V-O-deficient Pt/TiO2 and commercial Pt/C, respectively. DFT calculations and in situ Raman spectra suggest that porous TiO2 with rich oxygen vacancies can simultaneously achieve reversed charge transfer (electrons transfer from TiO2 to Pt NCs) and enhanced hydrogen spillover from Pt NCs to the TiO2 support, which leads to electron-rich Pt NCs being amenable to proton reduction of 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.

Automated summary

The study demonstrates that Pt nanoclusters supported on porous TiO2 nanosheets with rich oxygen vacancies exhibit significantly higher catalytic activity for the HER compared to those supported on TiO2 with deficient oxygen vacancies. This is attributed to the ability of the TiO2 support with rich oxygen vacancies to facilitate reversed charge transfer and enhanced hydrogen spillover, promoting proton reduction and hydrogen desorption at Pt catalytic sites. This work provides a new strategy for the rational design of highly efficient HER catalysts.