Insights into bifunctional active sites of Pt-MoO(3)/TiO(2) catalysts enabling selective hydrogenation of an amino acid

深入了解Pt-MoO(3)/TiO(2)催化剂的双功能活性位点,该催化剂能够选择性加氢氨基酸

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Abstract

Selective hydrogenation of amino acids to amino alcohols is a valuable transformation in the synthesis of pharmaceuticals, fine chemicals, and chiral building blocks. However, achieving high activity and selectivity under mild conditions remains challenging due to the need for simultaneous hydrogen activation and substrate coordination. Here, we report a series of Pt-MoO(3) bifunctional catalysts for the hydrogenation of l-alanine (Ala) to alaninol (AlaOH), with a focus on tuning metal-oxide synergy. Structural and electronic characterization studies by high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy reveal strong Pt-MoO(3) interactions, characterized by partial electron transfer. Catalytic tests reveal a volcano-type dependence on the Pt/Mo ratio, with the 4-Pt-MoO(3) catalyst achieving the highest performance. The experiments of H(2) temperature programmed desorption and in situ diffuse reflectance infrared Fourier transform spectroscopy combined with theoretical calculations support a bifunctional mechanism, in which Pt serves as the primary site for H(2) activation, while MoO(3) facilitates adsorption and stabilization of polar alanine. Further tuning via thermal treatments shows that the moderate treatment at 500 °C optimally balances the redox state of MoO(3) without compromising Pt dispersion, leading to enhanced hydrogenation performance. This work not only advances understanding of metal-oxide interfacial catalysis but also provides a rational design strategy for efficient and selective hydrogenation of amino acids.

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