[EN] The selective hydrogenation of alkynes to alkenes is a crucial step in the synthesis of fine chemicals. However, the widely utilized palladium (Pd)-based catalysts often suffer from poor selectivity. In this work, we ...[+]
[EN] The selective hydrogenation of alkynes to alkenes is a crucial step in the synthesis of fine chemicals. However, the widely utilized palladium (Pd)-based catalysts often suffer from poor selectivity. In this work, we demonstrate a carbonization-reduction method to create palladium carbide subnanometric species within pure silicate MFI zeolite. The carbon species can modify the electronic and steric characteristics of Pd species by forming the predominant Pd-C-4 structure and, meanwhile, facilitate the desorption of alkenes by forming the Si-O-C structure with zeolite framework, as validated by the state-of-the-art characterizations and theoretical calculations. The developed catalyst shows superior performance in the selective hydrogenation of alkynes over mild conditions (298 K, 2 bar H-2), with 99 % selectivity to styrene at a complete conversion of phenylacetylene. In contrast, the zeolite-encapsulated carbon-free Pd catalyst and the commercial Lindlar catalyst show only 15 % and 14 % selectivity to styrene, respectively, under identical reaction conditions. The zeolite-confined Pd-carbide subnanoclusters promise their superior properties in semihydrogenation of alkynes.[-]
info:eu-repo/grantAgreement/NSFC//21920102005/ info:eu-repo/grantAgreement/NSFC//21835002/ info:eu-repo/grantAgreement/NSFC//22201094/ info:eu-repo/grantAgreement/NSFC//91961119/ info:eu-repo/grantAgreement/NSFC//22288101/ info:eu-repo/grantAgreement/EC//ERC-AdG-2014-671093/ info:eu-repo/grantAgreement/MINECO//SEV-2016-0683/ info:eu-repo/grantAgreement/NKRDPC//2021YFA1501202/ info:eu-repo/grantAgreement/Department of Science and Technology of Jilin Province//20230508189RC/ [-]
Agradecimientos:
The authors thank the National Natural Science Foundation of China (Grant 21920102005, 22288101, 21835002, and 91961119), the National Key Research and Development Program of China (Grant 2021YFA1501202), the 111 Project ...[+]
The authors thank the National Natural Science Foundation of China (Grant 21920102005, 22288101, 21835002, and 91961119), the National Key Research and Development Program of China (Grant 2021YFA1501202), the 111 Project (B17020), the European Union through the European Research Council (Grant ERC-AdG-2014-671093, SynCatMatch), and the Spanish Government through "Severo Ochoa" (SEV-2016-0683, MINECO) for supporting this work. R. B. thanks the National Natural Science Foundation of China (Grant 22201094) and the Jilin Youth Growth Science and Technology Plan Project (Grant 20230508189RC) for funding. The Centre for High-resolution Electron Microscopy (C & hstrok;EM), supported by SPST of ShanghaiTech University under Contract EM02161943 is acknowledged for their help on electron microscopy.[-]