Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement

doi:10.1016/S1872-2067(24)60119-1

Abstract

Abstract:

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 specially 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 ε₅_p) and descended O 2p-band (O ε₂_p) centers as efficient active sites for chemisorption to *OH and *H during forward HOS, respectively, along with a declined In 4d-band center (In ε₄_d) to inhibit its backward reaction. A stable STH efficiency of 2.23% under AM 1.5 G irradiation at 65 °C has been obtained over the activated d¹⁰ electronic configuration with a lowered activation energy for H₂ evolution, verified by femtosecond transient absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics. These findings devote to activating d¹⁰ electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS, which expands the exploration of high-efficiency catalytic materials.

Key words: d-Band center, p-Band center, Localized field, Photocatalytic water splitting, Dynamic process

Shanshan Lai, Jiakun Su, Shujuan Jiang, Jianjun Zhang, Shaoqing Song. Activating d¹⁰ electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H₂ by surface atomic arrangement[J]. Chinese Journal of Catalysis, 2024, 65: 185-194.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60119-1

https://www.cjcatal.com/EN/Y2024/V65/I10/185

Figures/Tables 4

Fig. 1. (a) High-resolution XPS spectra of O 2p for In2O3 and P2-In2O3?x. (b) High-resolution XPS spectra of In 3d for In2O3 and P2-In2O3?x. (c) FESEM images of In2O3. (d) FESEM images of P2-In2O3?x. (e) HRTEM and TEM images (inset in e) of P2-In2O3?x. (f) Lattice fringes of P2-In2O3?x. (g) XRD patterns. (h) The derived facet proportion from texture coefficient calculation and In-P hybridization percent from XPS profiles.

Fig. 2. PDOS and band center changes for In 5p (a) and O 2p (b) before and after P introduction. The optimized adsorption structure models of *H-In2O3 (c), *OH-In2O3 (d), *H-P-In2O3?x (e) and *OH-P-In2O3?x (f). Adsorption energies of *OH on In ε5p (g) and *H on O ε2p (h) of In2O3 and P-In2O3?x, respectively. (i) The schematic diagram for the effect of the decreased O ε2p and the increased In ε5p on the adsorption of *H and *OH intermediates to active sites of In2O3 and P-In2O3?x.

Fig. 3. (a) fs-TAS of In2O3. (b) fs-TAS of P2-In2O3?x. (c) fs-TAS of In2O3 with K2Cr2O7 and CH3CH(OH)COOH as e? and h+ scavengers, respectively. Fitted transient absorption kinetics of In2O3 (d) and P2-In2O3?x (e) at 480 nm within 1000 ps decay time. (f) The proposed mechanism for charge generation, transfer and separation in space at the aids of LEF force and the tuned d- and p-band center positions.

Fig. 4. (a) Gas evolution performances of samples for 3 h under visible light irradiation. (b) AQE values at different wavelengths with UV-vis DRS plot of P2-In2O3?x. (c) STH efficiencies at different temperatures under AM 1.5 G irradiation. (d) Photocatalytic reaction activation energies of the samples calculated according to their performances at different temperatures (Figs. S6(c)?(e)). (e) Recycle stability tests of P2-In2O3?x system. (f?i) The structure models for calculating the reverse reaction of H2O splitting. (j) The calculated reaction Gibbs free energy (ΔG) on In2O3 and P-In2O3?x. (k) In situ DRIFTS patterns during photocatalytically splitting H2O over P2-In2O3?x. (l) DFT calculations to verify the reaction barriers process of H2O splitting into H2 on O ε2p and O2 on In ε5p of P-In2O3?x.

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Activating d¹⁰ electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H₂ by surface atomic arrangement

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