3D printed hierarchical spinel monolithic catalysts for highly efficient semi-hydrogenation of acetylene
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Porous monolithic catalysts with high specific surface areas, which can not only facilitate heat/mass transfer, but also help to expose active sites, are highly desired in strongly exothermic or endothermic gas–solid phase reactions. In this work, hierarchical spinel monolithic catalysts with a porous woodpile architecture were fabricated via extrusion-based three-dimensional (3D) printing (direct ink writing, DIW in brief) of aluminate-intercalated layered double hydroxide (AI-LDH) followed by low temperature calcination. The intercalation of aluminate in LDH is found crucial to tailor the M2+/Al3+ ratio, integrate LDH nanosheets into monolithic catalyst, and enable the conversion of LDH to spinel at the temperature as low as 500 °C with high specific surface areas (> 350 m2/g). The rapid mass/heat transfer resulted from the versatile 3D network at macroscale and the highly dispersed and fully exposed active sites benefited from the porous structure at microscale endow the 3D-printed Pd loaded spinel MgAl-mixed metal oxide (3D-AI-Pd/MMO) catalyst with excellent catalytic performance in semi-hydrogenation of acetylene, achieving 100% conversion at 60 °C with more than 84% ethylene selectivity.
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3D printed hierarchical spinel monolithic catalysts for highly efficient semi-hydrogenation of acetylene
Abstract
Porous monolithic catalysts with high specific surface areas, which can not only facilitate heat/mass transfer, but also help to expose active sites, are highly desired in strongly exothermic or endothermic gas–solid phase reactions. In this work, hierarchical spinel monolithic catalysts with a porous woodpile architecture were fabricated via extrusion-based three-dimensional (3D) printing (direct ink writing, DIW in brief) of aluminate-intercalated layered double hydroxide (AI-LDH) followed by low temperature calcination. The intercalation of aluminate in LDH is found crucial to tailor the M2+/Al3+ ratio, integrate LDH nanosheets into monolithic catalyst, and enable the conversion of LDH to spinel at the temperature as low as 500 °C with high specific surface areas (> 350 m2/g). The rapid mass/heat transfer resulted from the versatile 3D network at macroscale and the highly dispersed and fully exposed active sites benefited from the porous structure at microscale endow the 3D-printed Pd loaded spinel MgAl-mixed metal oxide (3D-AI-Pd/MMO) catalyst with excellent catalytic performance in semi-hydrogenation of acetylene, achieving 100% conversion at 60 °C with more than 84% ethylene selectivity.
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Acknowledgements
We thank Prof. Yixiang Shi and Haohong Duan from Tsinghua University, Prof. Dianqing Li, Xue Duan and Junfeng Liu from Beijing University of Chemical Technology and Prof. Zhiyi Lu from Chinese Academy of Sciences (Ningbo Institute of Materials Technology and Engineering) for the helpful discussion and the help on the facilities. This research was supported by the National Natural Science Foundation of China (Nos. 21935001, 22005022 and 22175012), the Program for Changjiang Scholars and Innovation Research Team in the University (No. IRT1205), the starting-up foundation from Beijing University of Chemical Technology (No. BUCTRC202025), the fellowship of China Postdoctoral Science Foundation (No. 2020M670107), the Natural Science Foundation of Beijing, China (No. 2214062), the Fundamental Research Funds for the Central Universities, and the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC.
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