Quantum mechanics

Gibbs free energy

Catalysis

Oxygen evolution

Hydrogen spillover

Oxide

Electrochemistry

Photochemistry

Materials science

Nanoclusters

Biochemistry

Titanium

Electron transfer

Inorganic chemistry

Physical chemistry

Hydrogen

Physics

Nanotechnology

Organic chemistry

Oxygen

Chemistry

Electrode

Platinum

Angewandte Chemie International Edition

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 (VO-rich Pt/TiO2) and deficient oxygen vacancies (VO-deficient Pt/TiO2), display significantly different catalytic activity for the hydrogen evolution reaction (HER), in which VO-rich Pt/TiO2 shows a mass activity of 45.28 A mgPt−1 at −0.1 V vs. RHE, which is 16.7 and 58.8 times higher than those of VO-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.

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