Cu‐WO_x‐TiO₂ Catalysts by Modified Evaporation‐Induced Self‐Assembly Method for Glycerol Hydrogenolysis to 1, 3‐Propanediol

Abstract

A series of Cu-WO x -TiO 2 catalysts for heterogeneous catalysis with different molar ratios of copper and tungsten species loadings were prepared by modified evaporation-induced selfassembly method. Their physical and chemical properties were characterized by X-ray diffraction, liquid N 2 sorption, Py-IR, Raman, inductive coupled plasma, X-ray photoelectron spectroscopy, scanning electron microscope-energy dispersive X-ray spectroscopy and transmission electron microscope techniques, and their catalytic performances were investigated in the hydrogenolysis of glycerol. The mesoporous framework for Cu-WO x -TiO 2 materials can be kept well when the molar ratio of tungsten species is lower than 6%. Although the tungsten species loading is the same, the 2Cu-6WO x -TiO 2 sample has distinctly more Brønsted acid sites than the 2Cu-6WO x /TiO 2 -I sample prepared by impregnation method, which is owing to homogeneous tetrahedrally WO x species dispersion resulting in the formation of W 5 + species. The 2Cu-6WO x -TiO 2 sample has a higher catalytic performance than other samples, and the glycerol conversion of 12.7%, 1, 3-Propanediol selectivity of 32.3% and the ratio of 1, 3-Propanediol to 1, 2-Propanediol of 1.17 can be obtained. The 2Cu-6WO x -TiO 2 sample shows good catalytic reusability, whose glycerol conversion 12.1% and 1, 3-PDO selectivity 30.8% can be reached even though after repeated reaction for 5 times.[a] Dr.

Supported MoOx and WOx Solid Acids for Biomass Valorization: Interplay of Coordination Chemistry, Acidity, and Catalysis

“…Satisfactory results (12.7% glycerol conversion and 32.3% 1,3-PDO selectivity) from the hydrogenolysis of glycerol were achieved over noble-metal free Cu−WO x −TiO 2 catalysts. 175 More Brønsted acid sites were found in the catalyst prepared by a modified evaporationinduced self-assembly method (EISAM) than the impregnated catalyst. This is due to the formation of the homogeneous dispersion of tetrahedrally WO x species, giving more W 5+ species in the EISAM catalyst.…”

Glycerol Transformation to Value-Added 1,3-Propanediol Production: A Paradigm for a Sustainable Biorefinery Process

“…Later extensive research work was carried out based on noble metaland tungsten-based catalysts (Pt-WOx) [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]. While Pt/WOx catalysts stand out to be the most outstanding high-performance catalysts for selective hydrogenolysis of glycerol to 1,3-PDO compared to other noble metals, Cu-based WOx supported on titania catalyst has also been investigated and was found to efficient in the production of 1,3-PDO [42]. Though the mechanism is still uncertain, it is obvious from previous research that the addition of tungsten as a cocatalyst has very well enhanced the acid strength especially the number of Brønsted acid sites which favors the formation of 1,3-PDO [11].…”

On the effect of Alkaline Earth Metal Cations in the Hydrogenolysis of Glycerol over Pt/C – an Experimental and Theoretical Study

“…Glycerol (GLY), a bio-based polyol and the major side product of biodiesel production, can be converted to several value added chemicals such as propylene glycol (PG), [1] 1,3propanediol, [2][3][4][5][6][7] n-propanol [8] and propyl acetate. [9] In particular PG finds wide application in cosmetics, as monomer, anti-freeze and food additive.…”