4.8 Article

Kinetically Controlled Synthesis of Rhodium Nanocrystals with Different Shapes and a Comparison Study of Their Thermal and Catalytic Properties

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 16, Pages 6293-6302

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c02734

Keywords

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Funding

  1. NSF [CHE-1804970, ECCS-1542174]
  2. Georgia Institute of Technology
  3. NSF Graduate Research Fellowship [DGE-1650044]
  4. Georgia Tech-ORNL Fellowship

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The synthesis of Rh nanocrystals with different shapes was achieved by controlling the kinetics involved in the growth process, and the resulting nanocrystals showed various facet-dependent properties in thermal and catalytic applications.
We report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable reduction kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temperature to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500 degrees C, respectively. When tested as catalysts for hydrazine decomposition, the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H-2 selectivity relative to the cubic counterpart. As for ethanol oxidation, the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.

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