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Subsurface catalysis-mediated selectivity of dehydrogenation reaction.

ABSTRACT: Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This paper describes a facile construction of well-defined Pt-skin catalysts modified by different 3d transition metal (3dTM) atoms in subsurface regions. However, on the catalyst containing both surface and subsurface 3dTMs, the selectivity of propane dehydrogenation decreases in the sequences of Pt ~ PtFe > PtCo > PtNi due to the easier C-C cracking on exposed Co and Ni sites. After the exposed 3dTMs were removed completely, the C3H6 selectivity was found to increase markedly in the row Pt < PtNi@Pt < PtCo@Pt < PtFe@Pt, which is in line with the calculated trend of d-band center shifting. The established relationship between reactivity and d-band center shifting illustrates the role of subsurface catalysis in dehydrogenation reaction.

SUBMITTER: Cai W

PROVIDER: S-EPMC6086612 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Subsurface catalysis-mediated selectivity of dehydrogenation reaction.

Cai Weiting W Mu Rentao R Zha Shenjun S Sun Guodong G Chen Sai S Zhao Zhi-Jian ZJ Li Hao H Tian Hao H Tang Yu Y Tao Franklin Feng FF Zeng Liang L Gong Jinlong J

Science advances 20180810 8

Progress in heterogeneous catalysis is often hampered by the difficulties of constructing active architectures and understanding reaction mechanisms at the molecular level due to the structural complexity of practical catalysts, in particular for multicomponent catalysts. Although surface science experiments and theoretical simulations help understand the detailed reaction mechanisms over model systems, the direct study of the nature of nanoparticle catalysts remains a grand challenge. This pape ...[more]

PMID: 30105302

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Project description:Solid/liquid heterogeneous photocatalysis was often considered to occur on the active sites of a solid catalyst surface. Herein, we report that the selectivity of photocatalytic dehydrogenative oxidations of aliphatic primary alcohols in acetonitrile solution into corresponding aldehydes exhibits an anomalous relationship with adsorption behavior of the alcohols. By using Pt-loaded TiO2 photocatalyst in an inert atmosphere under UV light illumination, primary short-chain alcohols (SCAs) with strong adsorption were dehydrogenated into aldehydes in very poor selectivity, whereas weak-adsorbable long-chain alcohols (LCAs) were transformed into corresponding aldehydes with much higher selectivity. More than 20 examples of primary LCAs (C4-C10) were successfully transformed into their corresponding aldehydes with satisfactory selectivity and yield. Both solid-state magic-angle-spinning 13C NMR and attenuated total reflectance-Fourier transform infrared spectroscopy studies provided concrete differences in adsorption behaviors on the Pt-TiO2 photocatalyst surface between SCA ethanol and LCA n-octanol. To further uncover the mechanism for different selectivities of SCAs and LCAs in photodehydrogenation, in situ electron paramagnetic resonance (EPR) experiments (at 8 K temperature) were employed to observe the oxidation features of photogenerated hole in the valance band of Pt-TiO2 (hvb +). The EPR experimental studies exhibited that unlike ethanol, either n-octanol or solvent acetonitrile alone all could not scavenge photogenerated hvb + on Pt-P25 photocatalyst and only n-octanol dissolved in acetonitrile solvent could smoothly react with photoinduced hole. This indicated that selective oxidations of LCAs were achieved by solvent-delivered oxidation rather than directly destructive oxidation of photogenerated hvb +. Our results may open an alternative way in selective dehydrogenative oxidation of various substrates sensitive to both dioxygen and high-temperature treatments.

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Subsurface catalysis-mediated selectivity of dehydrogenation reaction.

Publications

Subsurface catalysis-mediated selectivity of dehydrogenation reaction.

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