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Insights into the Mechanism of Nitrobenzene Reduction to Aniline by Phosphomolybdic Acid Supported TM1 Single-Atom Catalysts.
Zhao, Cong Cong; Wang, Shuang; Yan, Li Kai; Su, Zhong Min.
Afiliación
  • Zhao CC; Institute of Functional Material Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China.
  • Wang S; Institute of Functional Material Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China.
  • Yan LK; Institute of Functional Material Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China.
  • Su ZM; Institute of Theoretical Chemistry, Jilin University, Changchun 130023, PR China.
Inorg Chem ; 63(4): 1784-1792, 2024 Jan 29.
Article en En | MEDLINE | ID: mdl-38232070
ABSTRACT
Catalytic hydrogenation of nitrobenzene (Ph-NO2) to aniline (Ph-NH2) is a model reaction in the field of catalysis, in which the development of efficient catalysts remains a great challenge due to the lack of strategies to solve activity and selectivity problems. In this work, the mechanism of Ph-NO2 hydrogenation over Pt1 supported on phosphomolybdic acid (α-PMA) was proposed by density functional theory (DFT) calculations. The results show that the dissociation of the first and second N-O bonds is triggered by single H-induced and double H-induced mechanisms, respectively. The limiting potential of the reaction process is -0.19 V, which is the smallest potential in the field of Ph-NO2 reduction reaction to date. In the whole reaction process, the catalytic active site is the Pt atom, and polyoxometalate plays the role of an electronic sponge in the reaction. Additionally, based on experimentally confirmed Pt1/Na3PMA, the reduction capacity of Pd1/Na3PMA toward Ph-NO2 was predicted by DFT calculation. The distinctive adsorption patterns of Ph-NO2 on Pt1/Na3PMA and Pd1/Na3PMA were elucidated using the DOS diagram and fragment molecular orbital analysis. We anticipate that our theoretical calculations can provide novel perspectives for experimental researchers.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article Pais de publicación: Estados Unidos