通过边缘活性位点调控解析光热催化中析氢与二氧化碳还原的界面竞争

doi:10.1016/j.actphy.2025.100099

Abstract

Abstract:

Solar-driven photothermal catalytic CO₂ conversion with H₂O is a promising approach to produce sustainable fuels and chemicals. However, the competition between hydrogen evolution reaction (HER) and CO₂ reduction reaction (CO₂RR) results in unsatisfactory product selectivity. Noble metal nanoparticles (NMNPs) are widely used cocatalysts to introduce active sites on semiconductors, with unique active sites at the metal-semiconductor interfacial edges playing a critical role in the competitive mechanisms. Herein, we prepared a series of NMNPs loaded on Al-doped SrTiO₃ with abundant interfacial edge sites for continuous photothermal catalytic CO₂ and H₂O conversion. Different NMNPs demonstrated distinct CO₂-induced effects on hydrogen evolution. The key intermediate interactions were investigated by in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results revealed that bidentate carbonate (b-CO₃²⁻) tended to occupy the edge sites at the metal-semiconductor interfaces, competitively consuming the active sites for *H adsorption and altering the energy barrier of hydrogen evolution. The predominant site-blocking effect of b-CO₃²⁻ on Rh-loaded catalysts was verified through establishing a simplified geometric model to quantify the correlation of particle sizes, active site proportions and CO₂-induced hydrogen production variations. Controlling Rh nanoparticle size can tune the proportion of edge sites, which involves a trade-off between *H coverage and CO₂ activation and promotes the CO₂RR process toward methane production. This work initially unravels the interfacial competitive mechanism between HER and CO₂RR via edge-active-site modulation, hoping to provide valuable insights for the rational catalyst design and offer potential strategies to enhance CO₂ conversion efficiency.

Key words: Photothermal catalysis, Hydrogen evolution, CO₂ reduction, Active site, Interfacial competition

Jianan Hong, Chenyu Xu, Yan Liu, Changqi Li, Menglin Wang, Yanwei Zhang. Decoding the interfacial competition between hydrogen evolution and CO₂ reduction via edge-active-site modulation in photothermal catalysis[J]. Acta Phys. -Chim. Sin. 2025, 41(9), 100099. doi: 10.1016/j.actphy.2025.100099

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Decoding the interfacial competition between hydrogen evolution and CO₂ reduction via edge-active-site modulation in photothermal catalysis

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