Carbon coated LaFe0.92Pd0.08O3 composites for catalytic transfer hydrogenation: Balance in the ability of substrates adsorption and conversion
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Junjiang Zhu1(
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Catalytic transfer hydrogenation (CTH) is a green and efficient pathway for selective hydrogenation of unsaturated aldehydes and ketones. However, managing the abilities of solid catalysts to adsorb substrates and to convert them into desired products is a challenging task. Herein, we report the synthesis of carbon coated LaFe0.92Pd0.08O3 composites (LFPO-8@C) for CTH of benzaldehyde (BzH) into benzyl alcohol (BzOH), using isopropanol (IPA) as hydrogen source. The coating with carbon improves the ability to adsorb/transfer reactants from solution to active sites, and the doping of Pd2+ at Fe3+ site strengthens the ability of LaFeO3 to convert BzH into BzOH. A balanced point between them (i.e., abilities to adsorb BzH and to convert BzH into BzOH) is obtained at LFPO-8@C, which exhibits a BzOH formation rate of 3.88 mmol·gcat−1·h−1 at 180 °C for 3 h, which is 1.50 and 2.72 times faster than those of LFPO-8 and LaFeO3@C. A reaction mechanism is proposed, in which the acidic sites (e.g., Fe4+, oxygen vacancy) are used for the activation of C=O bond of BzH and O–H bond of IPA, and the basic sites (e.g., lattice oxygen) for the activation of α–H (O–H) bond of IPA.
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Carbon coated LaFe0.92Pd0.08O3 composites for catalytic transfer hydrogenation: Balance in the ability of substrates adsorption and conversion
), Junjiang Zhu1(
)
Abstract
Catalytic transfer hydrogenation (CTH) is a green and efficient pathway for selective hydrogenation of unsaturated aldehydes and ketones. However, managing the abilities of solid catalysts to adsorb substrates and to convert them into desired products is a challenging task. Herein, we report the synthesis of carbon coated LaFe0.92Pd0.08O3 composites (LFPO-8@C) for CTH of benzaldehyde (BzH) into benzyl alcohol (BzOH), using isopropanol (IPA) as hydrogen source. The coating with carbon improves the ability to adsorb/transfer reactants from solution to active sites, and the doping of Pd2+ at Fe3+ site strengthens the ability of LaFeO3 to convert BzH into BzOH. A balanced point between them (i.e., abilities to adsorb BzH and to convert BzH into BzOH) is obtained at LFPO-8@C, which exhibits a BzOH formation rate of 3.88 mmol·gcat−1·h−1 at 180 °C for 3 h, which is 1.50 and 2.72 times faster than those of LFPO-8 and LaFeO3@C. A reaction mechanism is proposed, in which the acidic sites (e.g., Fe4+, oxygen vacancy) are used for the activation of C=O bond of BzH and O–H bond of IPA, and the basic sites (e.g., lattice oxygen) for the activation of α–H (O–H) bond of IPA.
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Acknowledgements
Financial support provided by the National Natural Science Foundation of China (Nos. 42277485, 21976141, and 22102123), the Department of Science and Technology of Hubei Province (No. 2021CFA034), the Department of Education of Hubei Province (Nos. T2020011 and Q20211712), and the Opening Project of Hubei Key Laboratory of Biomass Fibers and Eco-Dyeing & Finishing (Nos. STRZ202202 and STRZ202101) is gratefully acknowledged. S. A.C. C. acknowledges Fundação para a Ciência e a Tecnologia (FCT), Portuqal for Scientific Employment Stimulus-Institutional Call (CEEC-INST/00102/2018), and Associate Laboratory for Green Chemistry-LAQV financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/5006/2020).
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