title: Understanding the Reaction Mechanism of Glycerol Hydrogenolysis over a CuCr2O4Catalyst.
abstract: The reaction mechanism of glycerol hydrogenolysis to 1,2-propanediol over a spinel CuCr2O4catalyst was investigated by using DFT calculations. Theoretical models were developed from the results of experimental characterization. Adsorption configurations and energetics of the reactant, intermediates, final product, and transition states were calculated on Cu(1 1 1) and CuCr2O4(1 0 0). Based on our DFT results, we found that the formation of acetol is preferred to that of 3-hydroxypropionaldehyde thermodynamically and kinetically on both surfaces. For glycerol hydrogenolysis to 1,2-propanediol, the CuCr2O4surface is less exothermic but more kinetically favorable than the Cu surface. The low activation barrier during the reaction on the CuCr2O4surface is attributed to the unique surface structure; the cubic spinel structure provides a stable adsorption site on which reactants are allowed to be dehydrated and hydrogenated easily with the characteristic adsorption configuration. The role of the Cu and Cr atoms in a CuCr2O4surface were revealed. The results of reaction tests supported our theoretical calculations.
authors.affiliation: World Class University Program of Chemical Convergence for Energy&Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul, 151-742, Republic of Korea.
authors.forename: Yang Sik
authors.initials: YS
authors.lastname: Yun
authors.affiliation: World Class University Program of Chemical Convergence for Energy&Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul, 151-742, Republic of Korea.
authors.forename: Tae Yong
authors.initials: TY
authors.lastname: Kim
authors.affiliation: World Class University Program of Chemical Convergence for Energy&Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul, 151-742, Republic of Korea.
authors.forename: Danim
authors.initials: D
authors.lastname: Yun
authors.affiliation: World Class University Program of Chemical Convergence for Energy&Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul, 151-742, Republic of Korea.
authors.forename: Kyung Rok
authors.initials: KR
authors.lastname: Lee
authors.affiliation: Department of Chemical Engineering, University of Seoul, Seoul, 130-743, Republic of Korea.
authors.forename: Jeong Woo
authors.initials: JW
authors.lastname: Han
authors.affiliation: World Class University Program of Chemical Convergence for Energy&Environment, Institute of Chemical Processes, School of Chemical and Biological Engineering, Seoul National University, Seoul, 151-742, Republic of Korea.
authors.forename: Jongheop
authors.initials: J
authors.lastname: Yi
mesh_terms: D000096:Acetone / Q000031:analogs & derivatives / Q000737:chemistry; D000327:Adsorption; D002384:Catalysis; D017608:Chromium Compounds / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D005990:Glycerol / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D019946:Propylene Glycol / Q000737:chemistry; D011789:Quantum Theory; D013499:Surface Properties
chemical_list: D017608:Chromium Compounds; D000096:Acetone; D019946:Propylene Glycol; D003300:Copper; C004433:acetol; D006859:Hydrogen; D005990:Glycerol
keywords: 1,2-propanediol; copper chromite; density functional theory; glycerol; reaction mechanisms; surface reactions