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Research Article

Impact of Pd single-site coordination structure on catalytic performance for semihydrogenation of acetylene

Yu Zeng, Minqi Xia, Fujie Gao, Changkai Zhou, Xueyi Cheng, Liwei Liu, Liu Jiao, Qiang Wu, Xizhang Wang( ), Lijun Yang( ), Yining Fan, Zheng Hu( )
Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Laboratory for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
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Graphical Abstract

Two different Pd single-site catalysts are prepared on carbon nanocages by regulating nitrogen sources, which consist of PdN2pyN2pr moieties coordinated by two pyridinic N and two pyrrolic N, and PdN2pyC4−x (x = 1–4) by pyridinic N and C, respectively. The former presents 18-fold increase in C2H2 semihydrogenation activity compared to the latter, demonstrating the impact of Pd coordination structure on catalytic performance.

Abstract

Semihydrogenation of trace acetylene in an ethylene gas stream is a vital step for the industrial production of polyethylene, in which Pd single-site catalysts (SSCs) have great potential. Herein, two Pd SSCs with different coordination structures are prepared on hierarchical nitrogen-doped carbon nanocages (hNCNC) by regulating the nitrogen species with or without using dicyandiamide. With using dicyandiamide, the obtained Pd1-Ndicy/hNCNC SSC features the coordinated Pd by two pyridinic N and two pyrrolic N ( PdN2pyN2pr). Without using dicyandiamide, the obtained Pd1/hNCNC SSC features the coordinated Pd by pyridinic N and C ( PdNxpyC4−x, x = 1–4). The former exhibits an 18-fold increase in catalytic activity compared to the latter. Theoretical results reveal the abundant unoccupied orbital states above the Fermi level of PdN2pyN2pr moiety, which can facilitate the activation of substrate molecules and dynamics of acetylene hydrogenation as supported by the combined theoretical and experimental results. In addition, the PdN2pyN2pr moiety presents a favorable desorption of ethylene. Consequently, the Pd1-Ndicy/hNCNC SSC exhibits high C2H2 conversion (99%) and C2H4 selectivity (87%) at 160 °C. This study demonstrates the impact of Pd single-site coordination structure on catalytic performance, which is significant for the rational design of advanced Pd SSCs on carbon-based supports.

Keywords

coordination structurehierarchical nitrogen-doped carbon nanocagespalladiumsemihydrogenation of acetylenesingle-site catalysts

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Nano Research
Volume 17 Issue 9,
September 2024
Pages 8243-8249
DOI: 10.1007/s12274-024-6843-7
Cite this article:
Zeng Y, Xia M, Gao F, et al. Impact of Pd single-site coordination structure on catalytic performance for semihydrogenation of acetylene. Nano Research, 2024, 17(9): 8243-8249. https://doi.org/10.1007/s12274-024-6843-7
Topics:
CarbonPalladium

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Received: 13 May 2024
Revised: 14 June 2024
Accepted: 24 June 2024
Published: 25 July 2024
© Tsinghua University Press 2024
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