Preparation of Anisotropic MnO 2 Nanocatalysts for Selective Oxidation of Benzyl Alcohol and 5-Hydroxymethylfurfural
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RESEARCH ARTICLE
Preparation of Anisotropic MnO2 Nanocatalysts for Selective Oxidation of Benzyl Alcohol and 5‑Hydroxymethylfurfural Huanlin Wang1 · Yu Song1 · Xuan Liu1 · Shiyu Lu1 · Chunmei Zhou1 · Yuguang Jin1 · Yanhui Yang1,2 Received: 27 April 2020 / Revised: 13 May 2020 / Accepted: 16 June 2020 © Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Anisotropic MnO2 nanostructures, including α-phase nanowire, α-phase nanorod, δ-phase nanosheet, α + δ-phase nanowire, and amorphous floccule, were synthesized by a simple hydrothermal method through adjusting the pH of the precursor solution and using different counterions. The catalytic properties of the as-synthesized MnO2 nanomaterials in the selective oxidation of benzyl alcohol (BA) and 5-hydroxymethylfurfural (HMF) were evaluated. The effects of micromorphology, phase structure, and redox state on the catalytic activity of M nO2 nanomaterials were investigated. The results showed that the intrinsic catalytic oxidation activity was mainly influenced by the unique anisotropic structure and surface chemical property of MnO2. With one-dimensional and 2D structures exposing highly active surfaces, unique crystal forms, and high oxidation state of Mn, the intrinsic activities for MnO2 catalysts synthesized in pH 1, 5, and 10 solutions (denoted as MnO2-pH1, MnO2-pH5, and M nO2-pH10, respectively) were twice higher than those of other MnO2 catalysts in oxidation of BA and HMF. With a moderate aspect ratio, the α + δ nanowire of MnO2-pH10 exhibited the highest average oxidation state, most abundant active sites, and the best catalytic oxidation activity. Keywords Manganese dioxide · Anisotropic structure · Catalytic oxidation · Benzyl alcohol · 5-hydroxymethylfurfural
Introduction Given their unique catalytic properties compared with their bulk counterparts, one-dimensional (1D) and 2D metal oxide nanostructures have received significant attention and achieved great progress in the preparation of materials with uniform shape, size, and composition [1–9]. Thermal decomposition is a simple and effective approach for the preparation of nanomaterials [10–12], and numerous 1D/2D anisotropic MnO2 nanomaterials prepared by hydrothermal method exhibit novel properties on electrode material [13–15] and catalysis [16, 17]. Huanlin Wang and Yu Song contributed equally to this work. * Chunmei Zhou [email protected] 1
School of Chemistry and Molecular Engineering (SCME), Institute of Advanced Synthesis (IAS), The Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University, Nanjing 211816, China
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
2
The selective oxidation of biomass 5-hydroxymethylfurfural (HMF) to 2,5-diformyl-furan (DFF) is an important reaction for the efficient convert biomass to chemicals; this process has received significant attention because of the wide range
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