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Nano Research

Article Title

A facile method to synthesize water-soluble Pd8 nanoclusters unraveling the catalytic mechanism of p-nitrophenol to p-aminophenol

Authors

Pan An, Beijing National Laboratory for Molecular Sciences (BNLMS) and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China University of Chinese Academy of Sciences (UCAS), Beijing 100049, China
Rajini Anumula, Beijing National Laboratory for Molecular Sciences (BNLMS) and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Chaonan Cui, Beijing National Laboratory for Molecular Sciences (BNLMS) and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Yang Liu, Beijing National Laboratory for Molecular Sciences (BNLMS) and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Fei Zhan, Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Ye Tao, Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
Zhixun Luo, Beijing National Laboratory for Molecular Sciences (BNLMS) and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China University of Chinese Academy of Sciences (UCAS), Beijing 100049, China

Keywords

water-soluble, Pd, nanoclusters, catalysis, p-nitrophenol

Abstract

Hydrogenation of p-nitrophenol (PNP) towards the conversion to p-aminophenol (PAP) by metal catalysis is known as a simple and eco-friendly technique for the production of corresponding industrial and pharmaceutical intermediates. While continuous efforts are paid for more sustainable and greener procedures by using transition metal catalysts, atomic-precise reaction mechanism for the PNP-to-PAP is still illusive to be fully understood. Utilizing a dry-wet combined strategy, here we have synthesized water-soluble Pd8 nanoclusters (NCs) with mercaptosuccinic acid (H2SMA) as the ligand, and the Pd8 NCs found high catalytic performance for the conversion of PNP-to-PAP, as identified by the electrospray ionization mass spectrometer (ESI-MS) measurement. The gradual changes over time of ultraviolet–visible (UV–vis) spectra of PNP really display the catalytic reduction by NaBH4 in presence of Pd8 NCs. Further, in-depth charge transfer interactions between PNP and the Pd8 clusters at the proton-rich conditions are investigated by natural bond orbital (NBO) analysis and electron density difference (EDD) analysis. The exothermic and kinetic-favorable reaction pathways are addressed, based on successive PNP hydrogenation and H2O removal processes, clarifying the reaction mechanism of Pd catalysts. It is worth noting that this solid-state synthetic route for such Pd8 clusters enables gram-scale quantity of production in likely practical use.

Graphical Abstract

Publisher

Tsinghua University Press

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