Ruta Vincenzo, Cipriano Luis A, Di Liberto Giovanni, Wojcieszak Robert, Vilé Gianvito
Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, Piazza Leonardo da Vinci 32, IT-20133, Milano, Italy.
Department of Material Sciences, University of Milan Bicocca, Via R. Cozzi 55, IT-20125, Milano, Italy.
ChemSusChem. 2025 May 5;18(9):e202402641. doi: 10.1002/cssc.202402641. Epub 2025 Jan 17.
The conversion of bio-based molecules into valuable chemicals is essential for advancing sustainable processes and addressing global resource challenges. However, conventional catalytic methods often demand harsh conditions and suffer from low product selectivity. This study introduces a series of bifunctional PdPt catalysts supported on TiO, designed for achieving selective and mild-temperature catalysis in biomass conversion. Synthesized via a sol immobilization method and characterized by XRF, N physisorption, HRTEM, HAADF-STEM, and XPS, these catalysts demonstrate superior selectivity and activity over monometallic counterparts. In fact, at 20 bar H, Pt/TiO show a low selectivity in benzophenone hydrodeoxygenation, favoring the benzhydrol hydrogenation product; similarly, Pd/TiO preferentially form the diphenylmethane hydrodeoxygenation (HDO) product, but with slow conversion rates. The synergistic combination of the two metals in PdPt/TiO drastically improve performance, with 100 % benzophenone conversion and 73 % diphenylmethane selectivity. DFT calculations confirm the synergy between Pd and Pt as the key to drive the activity and selectivity. Additionally, the catalysts also demonstrate high recyclability with minimal performance loss, and have been generalized for the HDO of vanillin and furfural, and in HMF oxidation. Overall, this work highlights the potential of bimetallic catalysts in enabling efficient and selective bio-based molecule conversion under mild conditions.
将生物基分子转化为有价值的化学品对于推进可持续发展进程和应对全球资源挑战至关重要。然而,传统的催化方法通常需要苛刻的条件,且产品选择性较低。本研究介绍了一系列负载在TiO上的双功能PdPt催化剂,旨在实现生物质转化中的选择性温和温度催化。这些催化剂通过溶胶固定法合成,并通过XRF、N物理吸附、HRTEM、HAADF-STEM和XPS进行表征,与单金属催化剂相比,它们表现出卓越的选择性和活性。事实上,在20 bar H下,Pt/TiO在二苯甲酮加氢脱氧反应中选择性较低,更倾向于生成苯甲醇加氢产物;同样,Pd/TiO优先形成二苯甲烷加氢脱氧(HDO)产物,但转化率较低。PdPt/TiO中两种金属的协同组合显著提高了性能,二苯甲酮转化率达到100%,二苯甲烷选择性达到73%。DFT计算证实Pd和Pt之间的协同作用是驱动活性和选择性的关键。此外,这些催化剂还表现出高可回收性,性能损失最小,并已推广应用于香草醛和糠醛的HDO以及HMF氧化反应。总体而言,这项工作突出了双金属催化剂在温和条件下实现高效、选择性生物基分子转化的潜力。