Details

Autor(en) / Beteiligte

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

Titel

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

Ist Teil von

• Nature communications, 2023-07, Vol.14 (1), p.3944-3944, Article 3944

Ort / Verlag

London: Nature Publishing Group UK

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. Noble metals have been extensively employed in a variety of hydrotreating catalyst systems. Here, the authors demonstrate that coordinating Pd with alkenyl-type ligands creates an electron-rich environment for Pd entity to weaken the interaction between Pd and unsaturated C for selective hydrogenation.