Insight to the Catalytic Activity of Atomically Precise Ag4Ni2 Nanoclusters on Silicon Carbide for Nitroarene Reduction

Yutong Xiao; Xiaofei Huang; Hou Li; Qing-Wen Han; Yu Zhang; Fan Tian; Man Xu

doi:10.1021/acs.inorgchem.4c01065

Insight to the Catalytic Activity of Atomically Precise Ag₄Ni₂ Nanoclusters on Silicon Carbide for Nitroarene Reduction

Inorg Chem. 2024 May 13;63(19):8958-8969. doi: 10.1021/acs.inorgchem.4c01065. Epub 2024 Apr 30.

Authors

Yutong Xiao^{1

2}, Xiaofei Huang^{1

3}, Hou Li^{1

3}, Qing-Wen Han⁴, Yu Zhang⁵, Fan Tian^{1

3}, Man Xu^{1

2}

Affiliations

¹ Key Laboratory of Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430205, P. R. China.
² School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205, P. R. China.
³ School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, P. R. China.
⁴ Hubei Three Gorges Laboratory, Yichang, Hubei 443007, P. R. China.
⁵ Department of Water Resources, Shandong Water Conservancy Vocational College, Rizhao, Shandong 276826, P. R. China.

PMID: 38687123
DOI: 10.1021/acs.inorgchem.4c01065

Abstract

Atomically precise Ag₄Ni₂ nanoclusters with 2,4-dimethylbenzenethiol as the ligands were synthesized and characterized as a cocatalyst of SiC for the selective hydrogenation of nitroarenes to arylamine in the presence of NaBH₄. The obtained Ag₄Ni₂/SiC samples exhibited extraordinary catalytic activity, and a self-accelerated catalytic process was observed with the reduction of nitrophenol to aminophenol as the model reaction. Experimental comparison between the Ag₄Ni₂/SiC samples before and after the catalysis showed that the transformation of Ag₄Ni₂ clusters to polydisperse Ag particles as well as amorphous NiO_x on the surface of SiC in the catalysis was the key to their high activity. AIMD calculations revealed that the transformation of Ag₄Ni₂ was driven by the presence of multiple hydrides on the cluster, which induced the detachment of the thiol ligand of the nanoclusters.