Creating and Stabilizing an Oxidized Pd Surface under Reductive Conditions for Photocatalytic Hydrogenation of Aromatic Carbonyls.

Autor:	Qiao W; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China.; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China., Fan X; Research Center for Carbon-based Electronics and Key Laboratory for the Physics and Chemistry of Nanodevices, School of Electronics, Peking University, Beijing 100871, China., Liu W; Dipartimento di Chimica Industriale 'Toso Montanari', University of Bologna, Bologna 40136, Italy., Khan FN; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China., Zhang D; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China.; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China., Han F; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China.; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China., Yue H; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China., Li Y; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China., Dimitratos N; Dipartimento di Chimica Industriale 'Toso Montanari', University of Bologna, Bologna 40136, Italy.; Center for Chemical Catalysis-C3, Alma Mater Studiorum University of Bologna, Bologna 40136, Italy., Albonetti S; Dipartimento di Chimica Industriale 'Toso Montanari', University of Bologna, Bologna 40136, Italy.; Center for Chemical Catalysis-C3, Alma Mater Studiorum University of Bologna, Bologna 40136, Italy., Wen X; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China.; State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China., Yang Y; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China.; State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China., Besenbacher F; The Interdisciplinary Nanoscience Center (iNANO), Aarhus University, DK-8000 Aarhus, Denmark., Li Y; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China.; State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China., Niemantsverdriet H; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China.; SynCat@DIFFER, Syngaschem BV, 6336 HH Eindhoven, The Netherlands., Lin H; School of Physics and Information Technology, Shaanxi Normal University, Xi'an 710119, China., Su R; Soochow Institute for Energy and Materials Innovations (SIEMIS), Soochow University, Suzhou 215006, China.; SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No. 1, Beijing 101407, China.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2023 Mar 08; Vol. 145 (9), pp. 5353-5362. Date of Electronic Publication: 2023 Feb 28.
DOI:	10.1021/jacs.2c13196
Abstrakt:	Photocatalysis provides an eco-friendly route for the hydrogenation of aromatic carbonyls to O-free aromatics, which is an important refining process in the chemical industry that is generally carried out under high pressure of hydrogen at elevated temperatures. However, aromatic carbonyls are often only partially hydrogenated to alcohols, which readily desorbs and are hardly further deoxygenated under ambient conditions. Here, we show that by constructing an oxide surface over the Pd cocatalyst supported on graphitic carbon nitride, an alternative hydrogenation path of aromatic carbonyls becomes available via a step-wise acetalization and hydrogenation, thus allowing efficient and selective production of O-free aromatics. The PdO surface allows for optimum adsorption of reactants and intermediates and rapid abstraction of hydrogen from the alcohol donor, favoring fast acetalization of the carbonyls and their consecutive hydrogenation to O-free hydrocarbons. The photocatalytic hydrogenation of benzaldehyde into toluene shows a high selectivity of >90% and a quantum efficiency of ∼10.2% under 410 nm irradiation. By adding trace amounts of HCl to the reaction solution, the PdO surface remains stable and active for long-term operation at high concentrations, offering perspective for practical applications.
Databáze:	MEDLINE
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