Facet-dependent Catalysis of CuNi Nanocatalysts toward 4-Nitrophenol Reduction Reaction
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MRS Advances © 2020 Materials Research Society DOI: 10.1557/adv.2020.5
Facet-dependent Catalysis of CuNi Nanocatalysts toward 4–Nitrophenol Reduction Reaction Can Li1, Yiliang Luan1, Bo Zhao2, Amar Kumbhar3, Xiaobo Chen4, David Collins5, Guangwen Zhou4, Jiye Fang1,4* 1
Department of Chemistry, State University of New York at Binghamton, New York, USA.
2
College of Arts & Sciences Microscopy, Texas Tech University, Texas, USA.
3 Chapel Hill Analytical and Nanofabrication Laboratory, University of North Carolina at Chapel Hill, North Carolina, USA.
4 Materials Science and Engineering Program, State University of New York at Binghamton, New York, USA.
5
Department of Geological Sciences and Environmental Studies, State University of New York at Binghamton, New York, USA.
ABSTRACT We report a facile method to fabricate CuNi nano-octahedra and nanocubes using a colloidal synthesis approach. The CuNi nanocrystals terminated with exclusive crystallographic facets were controlled and achieved by a group of synergetic capping ligands in a hot solution system. Specifically, the growth of {111}-bounded CuNi nano-octahedra is derived by a thermodynamic control, whereas the generation of {100}-terminated CuNi nanocubes is steered by a kinetic capping of chloride. Using a reduction of 4-nitrophenol with sodium borohydride as a model reaction, CuNi nano-octahedra and nanocubes demonstrated a strong facet-dependence due to their different surface energies although both exhibited remarkable catalytic activity with the high rate constant over mass (k/m). A kinetic study indicated that this is a pseudo first-order reaction with an excess of sodium borohydride. CuNi nanocubes as the catalysts showed better catalytic performance (k/m = 385 s-1•g-1) than the CuNi nanooctahedra (k/m = 120 s-1•g-1), indicating that 4-nitrophenol and hydrogen were adsorbed on the {100} facets with their molecules parallel to the surface much easier than those on {111} facets.
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INTRODUCTION Bimetallic nano-alloys have attracted growing interest due to their unique catalytic performance including high activity, sensitive selectivity, and excellent durability. These outstanding catalytic characters rely on their surface structures, size, shape, and composition[1-6]. High-performance nanocatalysts have been developed using many strategies in terms of their tuneable ligand effect, geometric effect, and shape effect. Among these, the shape-effect of nanocatalysts with exclusively exposed facets has drawn increased attention for the development of catalytic selectivity and activity, and the relevant applications to electrochemical reactions, small organic molecular reactions including hydrogenation and reduction reaction have been reported[7-11]. The previous study has demonstrated that CuNi nano-octahedra in different sizes, such as
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