Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement
Relationship between the activity for photocatalytic H2O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and spe-cially the d10 electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d10 electronic configuration of In2O3 was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(In ε5p)and descended O 2p-band(O ε2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(In ε4d)to inhibit its backward reaction.A stable STH efficiency of 2.23％under AM 1.5 G irradiation at 65 ℃ has been obtained over the activated d10 electronic configuration with a lowered activation energy for H2 evolution,verified by femtosecond transient absorption spectros-copy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d10 electronic configuration for resolving the reac-tion energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.
d-Band centerp-Band centerLocalized fieldPhotocatalytic water splittingDynamic process
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