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Modern Chemical Routes for the Controlled Synthesis of Anisotropic Bimetallic Nanostructures and Their Application in Catalysis.

ABSTRACT: Bimetallic nanoparticles (BNPs) have attracted greater attention compared to its monometallic counterpart because of their chemical/physical properties. The BNPs have a wide range of applications in the fields of health, energy, water, and environment. These properties could be tuned with a number of parameters such as compositions of the bimetallic systems, their preparation method, and morphology. Monodisperse and anisotropic BNPs have gained considerable interest and numerous efforts have been made for the controlled synthesis of bimetallic nanostructures (BNS) of different sizes and shapes. This review offers a brief summary of the various synthetic routes adopted for the synthesis of Palladium(Pd), Platinum(Pt), Nickel(Ni), Gold(Au), Silver(Ag), Iron(Fe), Cobalt(Co), Rhodium(Rh), and Copper(Cu) based transition metal bimetallic anisotropic nanostructures, growth mechanisms e.g., seed mediated co-reduction, hydrothermal, galvanic replacement reactions, and antigalvanic reaction, and their application in the field of catalysis. The effect of surfactant, reducing agent, metal precursors ratio, pH, and reaction temperature for the synthesis of anisotropic nanostructures has been explained with examples. This review further discusses how slight modifications in one of the parameters could alter the growth mechanism, resulting in different anisotropic nanostructures which highly influence the catalytic activity. The progress or modification implied in the synthesis techniques within recent years is focused on in this article. Furthermore, this article discussed the improved activity, stability, and catalytic performance of BNS compared to the monometallic performance. The synthetic strategies reported here established a deeper understanding of the mechanisms and development of sophisticated and controlled BNS for widespread application.

SUBMITTER: Bhol P

PROVIDER: S-EPMC7262677 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Modern Chemical Routes for the Controlled Synthesis of Anisotropic Bimetallic Nanostructures and Their Application in Catalysis.

Bhol Prangya P Bhavya M B MB Swain Swarnalata S Saxena Manav M Samal Akshaya K AK

Frontiers in chemistry 20200519

Bimetallic nanoparticles (BNPs) have attracted greater attention compared to its monometallic counterpart because of their chemical/physical properties. The BNPs have a wide range of applications in the fields of health, energy, water, and environment. These properties could be tuned with a number of parameters such as compositions of the bimetallic systems, their preparation method, and morphology. Monodisperse and anisotropic BNPs have gained considerable interest and numerous efforts have bee ...[more]

PMID: 32528924

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Project description:Diarylamines are an important class of widely utilized chemicals, and development of diverse procedures for their synthesis is of great importance. Herein, we have successfully developed novel versatile catalytic procedures for the synthesis of diarylamines through acceptorless dehydrogenative aromatization. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/TiO2), various symmetrically substituted diarylamines could be synthesized starting from cyclohexylamines. The observed catalysis of Au-Pd/TiO2 was heterogeneous in nature and Au-Pd/TiO2 could be reused several times without severe loss of catalytic performance. This transformation needs no oxidants and generates molecular hydrogen (three equivalents with respect to cyclohexylamines) and ammonia as the side products. These features highlight the environmentally benign nature of the present transformation. Furthermore, in the presence of Au-Pd/TiO2, various kinds of structurally diverse unsymmetrically substituted diarylamines could successfully be synthesized starting from various combinations of substrates such as (i) anilines and cyclohexanones, (ii) cyclohexylamines and cyclohexanones, and (iii) nitrobenzenes and cyclohexanols. The role of the catalyst and the reaction pathways were investigated in detail for the transformation of cyclohexylamines. The catalytic performance was strongly influenced by the nature of the catalyst. In the presence of a supported gold nanoparticle catalyst (Au/TiO2), the desired diarylamines were hardly produced. Although a supported palladium nanoparticle catalyst (Pd/TiO2) gave the desired diarylamines, the catalytic activity was inferior to that of Au-Pd/TiO2. Moreover, the activity of Au-Pd/TiO2 was superior to that of a physical mixture of Au/TiO2 and Pd/TiO2. The present Au-Pd/TiO2-catalyzed transformation of cyclohexylamines proceeds through complex pathways comprising amine dehydrogenation, imine disproportionation, and condensation reactions. The amine dehydrogenation and imine disproportionation reactions are effectively promoted by palladium (not by gold), and the intrinsic catalytic performance of palladium is significantly improved by alloying with gold. One possible explanation of the alloying effect is the formation of electron-poor palladium species that can effectively promote the β-H elimination step in the rate-limiting amine dehydrogenation.

Dataset Information

Modern Chemical Routes for the Controlled Synthesis of Anisotropic Bimetallic Nanostructures and Their Application in Catalysis.

Publications

Modern Chemical Routes for the Controlled Synthesis of Anisotropic Bimetallic Nanostructures and Their Application in Catalysis.

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