Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands

Zhang, Jianghao; Hu, Wenda; Qian, Binbin; Li, Houqian; Sudduth, Berlin; Engelhard, Mark; Zhang, Lian; Hu, Jianzhi; Sun, Junming; Zhang, Changbin; He, Hong; Wang, Yong

doi:10.1038/s41467-023-39478-2

Title: Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands

Journal Article · 03 July 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-39478-2 · OSTI ID:1988108

; Hu, Wenda; Qian, Binbin; Li, Houqian; Sudduth, Berlin;

;

; Sun, Junming;

;

Abstract Noble metals have been extensively employed in a variety of hydrotreating catalyst systems for their featured functionality of hydrogen activation but may also bring side reactions such as undesired deep hydrogenation. It is crucial to develop a viable approach to selectively inhibit side reactions while preserving beneficial functionalities. Herein, we present modifying Pd with alkenyl-type ligands that forms homogeneous-like Pd-alkene metallacycle structure on the heterogeneous Pd catalyst to achieve the selective hydrogenolysis and hydrogenation. Particularly, a doped alkenyl-type carbon ligand on Pd-Fe catalyst is demonstrated to donate electrons to Pd, creating an electron-rich environment that elongates the distance and weakens the electronic interaction between Pd and unsaturated C of the reactants/products to control the hydrogenation chemistry. Moreover, high H ₂ activation capability is maintained over Pd and the activated H is transferred to Fe to facilitate C-O bond cleavage or directly participate in the reaction on Pd. The modified Pd-Fe catalyst displays comparable C-O bond cleavage rate but much higher selectivity (>90%) than the bare Pd-Fe (<50%) in hydrotreating of diphenyl ether (DPE, modelling the strongest C-O linkage in lignin) and enhanced ethene selectivity (>90%) in acetylene hydrogenation. This work sheds light on the controlled synthesis of selective hydrotreating catalysts via mimicking homogeneous analogues.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1988108

Report Number(s):: PNNL-SA-186598; 3944; PII: 39478

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Title: Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands

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