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[Display omitted] • Ir – TiO 2 interaction was dependent on Ir sizes and crystal plane of TiO 2. • Both activity and selectivity of the catalysts increased as the Ir size grew from single atom to nanoparticle. • End-on C O adsorption of crotonaldehyde was favored at the Ir-TiO x interface for Ir nanoparticles. • Crotonaldehyde adsorption geometry depends on H coverage on the catalyst surface. For the supported catalysts for the selective hydrogenation of α, β - unsaturated aldehyde with H 2 , tailoring of metal - support interfacial effect to improve reaction performance is a significant but challenging subject. In this work, we regulated both the size regimes of the Ir deposits (single atom, nanocluster and nanoparticle) and the crystal plane of anatase TiO 2 (TiO 2 (1 0 1), TiO 2 (1 0 0) and TiO 2 (0 0 1)) so as to alter the Ir-TiO x interfacial properties, in order to unravel reaction mechanism of selective hydrogenation of crotonaldehyde over the Ir/TiO 2 catalysts. Both the activity and selectivity to crotyl alcohol increased as the Ir size grew from single atom to nanoparticle, ascribed to high Ir0 content, high concentration of surface defects and prominent H-spillover effect on the Ir nanoparticles. Moreover, the in situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations demonstrated that an end-on C O adsorption mode for crotonaldehyde molecule was favored at the Ir-TiO x interface particularly at high H coverage, which thus facilitated the hydrogenation of C O bond to form crotyl alcohol. Moreover, the highest reactivity of the Ir nanoparticles was evidenced by the lowest reaction barrier. These results explicitly demonstrate that larger metal nanoparticles and adsorption geometry of the reactant at the metal - support interface are vital for improved catalytic performance, which would shed light on the ingenious catalyst design. [ABSTRACT FROM AUTHOR]

[Display omitted] • Surface selenation strategy is performed on metal cocatalysts for enhanced CO 2 -to-CH 3 OH conversion. • Stacked photocatalysts with metal core sandwiched between semiconductor and selenated shell are fabricated. • Metal core accelerates the migration of photoelectrons from semiconductor to selenated shell. • Selenated shell decreases the energy barriers for CH 3 OH production and inhibits the side H 2 evolution. Solar-driven reduction of CO 2 and H 2 O to methanol is highly desirable owing to multiple advantages of green and renewable liquid fuels, whose efficiency and selectivity are restricted by sluggish charge kinetics and unfavorable surface reaction dynamics in conversional semiconductor photocatalysts. This study proposes a surface selenation strategy on metal cocatalysts to improve the photocatalytic performance in CO 2 -to-CH 3 OH conversion. Electron microscopy observation shows the formation of a stacked structure with crystalline Rh core sandwiched between semiconductor substrate and amorphous selenated Rh (RhSe) shell after the treatment. The combination of experimental characterizations with theoretical simulations reveals that Rh core smoothens the migration of photoelectrons from light-harvesting semiconductor to RhSe shell, while the selenation of Rh shell not only reduces the rate-limiting barriers required for CH 3 OH production, but also inhibits the occurrence of side H 2 evolution. Enabled by such a design, significantly enhanced photocatalytic activities (41.2 μmol g cat -1 h-1) and selectivties (91.2%) in CH 3 OH generation are achieved by the Rh@RhSe semi-core-shell cocatalysts, 12.7 and 6.4 times as high as that of pristine Rh, respectively. Moreover, the generalized strategy can be extended to other metal cocatalysts for improved CO 2 -to-CH 3 OH transformation, which opens a new avenue for powering the future with liquid sunshine. [ABSTRACT FROM AUTHOR]

Various supported Ir/TiO2 catalysts were prepared using different Ir precursors (i.e., H2IrCl6, (NH4)2IrCl6 and Ir(acac)3) and tested for vapor phase selective hydrogenation of crotonaldehyde. The choice of Ir precursor significantly altered the Ir-TiOx interaction in the catalyst, which thus had essential influences on the geometric and electronic properties of the Ir species, reducibility, and surface acidity, and, consequently, their reaction behaviors. The Ir/TiO2-N catalyst using (NH4)2IrCl6 as the precursor gave the highest initial reaction rates and turnover frequencies of crotyl alcohol formation. Such high performance was ascribed to the high Ir dispersion and high surface concentration of Ir0 species, as well as a higher surface acidity, in the Ir/TiO2-N catalyst compared to its counterparts, indicating the synergistic roles of the Ir-TiOx interface in the reaction, as the interfacial sites were responsible for the adsorption/activation of H2 and the C=O bond in the crotonaldehyde molecule. [ABSTRACT FROM AUTHOR]