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Facile Aqueous-Phase Synthesis of an Ultrasmall Bismuth Nanocatalyst for the Reduction of 4-Nitrophenol.

ABSTRACT: Bismuth metallic nanoparticles have evoked considerable interest in catalysis owing to their small size, high surface area-to-volume ratio, and low toxicity. However, the need for toxic reductants and organic solvents in their synthesis often limits their desirability for application development. Here, we describe a green strategy to synthesize bismuth nanodots via the redox reactions between bismuth nitrate and d-glucose, in the presence of poly(vinylpyrrolidone) in the basic aqueous phase. Both reagents play a crucial role in the formation of monodisperse bismuth nanodots acting as mild reducing and capping agents, respectively. We further demonstrate that the catalytic activity of these dots via the successful reduction of the environmental contaminant 4-nitrophenol to its useful 4-aminophenol analogue requiring only 36 ?g/mL nanocatalyst for 20 mM of the substrate. Moreover, they can be recovered and recycled in multiple reactions before the onset of an appreciable loss of catalytic activity. The proposed facile synthetic route and inexpensive matrix materials lead the way to access bismuth nanodots for both the fundamental study of reactions and their industrial catalysis applications.

SUBMITTER: Liang Y

PROVIDER: S-EPMC6751691 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Publications

Facile Aqueous-Phase Synthesis of an Ultrasmall Bismuth Nanocatalyst for the Reduction of 4-Nitrophenol.

Liang Yanjie Y Manioudakis John J Macairan Jun-Ray JR Askari Mohammad S MS Forgione Pat P Naccache Rafik R

ACS omega 20190904 12

Bismuth metallic nanoparticles have evoked considerable interest in catalysis owing to their small size, high surface area-to-volume ratio, and low toxicity. However, the need for toxic reductants and organic solvents in their synthesis often limits their desirability for application development. Here, we describe a green strategy to synthesize bismuth nanodots via the redox reactions between bismuth nitrate and d-glucose, in the presence of poly(vinylpyrrolidone) in the basic aqueous phase. Bot ...[more]

PMID: 31552336

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Project description:In this work, we have disclosed the facile syntheses of morphologically diverse Cu2O nanoparticles using our laboratory designed modified hydrothermal reactor employing low-cost copper (II) acetate precursor compounds. The reaction conditions dovetail the effect of ethylene glycol (EG) and glucose to exclusively evolve the morphology tuned Cu2O nanomaterial at different pHs. The morphology tuning produces octahedron (Oh), dwarf hexapod (DHP), and elongated hexapod (EHP) Cu2O structures only with the optimized reagent concentrations. Interestingly, all of them were bestowed with a (111) facet, a superlative facet for facile nitroarene reduction. Thus, the morphology reliant catalytic reaction becomes evident. However, when used individually, EG and glucose evolve ill-defined CuO/Cu2O and Cu2O structures, respectively. We have observed that a change in pH of the medium at the onset of the reaction is obligatory for the evolution of tailor-made morphologically diverse Cu2O nanoparticles. However, preformed Cu2O particles do not suffer further structure/morphology changes under deliberate pH (6.0-9.0) change. With the as-obtained Oh, DHP, and EHP Cu2O structures, we further delve into the realm of catalysis to understand the splendor of the nanocatalyst, morphology and surface area dependence, facet selective reactivity, and other factors affecting the catalytic efficiency. The remarkable rate of catalysis of 4-nitrophenol (4-NP), evident from the catalyst activity parameter (k a = 123.6 g-1 s-1), to produce 4-aminophenol in the presence of a reducing agent like sodium borohydride (NaBH4) of the as-prepared catalysts is evidence of the collaborative effects of the effective surface area, surface positive charge, and active (111) facet of the Cu2O nanocatalyst. We have also studied the effect of other common anions, namely, Cl-, NO2 -, NO3 -, CO3 2-, and SO4 2- on the reduction process. To obtain a general consensus about facets, we compared (100) and (111) faceted Cu2O nanocatalysts not only for 4-NP reduction but also for the reduction of toxic chromium Cr(VI) in the presence of formic acid to further emphasize the importance of facet selectivity in catalysis and the versatility of the morphology tuned as-prepared Cu2O.

Dataset Information

Facile Aqueous-Phase Synthesis of an Ultrasmall Bismuth Nanocatalyst for the Reduction of 4-Nitrophenol.

Publications

Facile Aqueous-Phase Synthesis of an Ultrasmall Bismuth Nanocatalyst for the Reduction of 4-Nitrophenol.

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