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Abstract Noble‐metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag−Ru core−shell nanocubes and then Ru nanoboxes with a hexagonal close‐packed(hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIIIprecursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag−Ru nanocubes with a hollow interior. The released Ag+ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3, the as‐obtained Ag−Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by anhcpstructure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance.
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Facile Synthesis of Palladium‐Based Nanocrystals with Different Crystal Phases and a Comparison of Their Catalytic Properties
Abstract A relatively unexplored aspect of noble‐metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, a method is reported for the facile synthesis of Ru@Pd core–shell nanocrystals featuring polymorphism, with the core made of hexagonally close‐packed (hcp)‐Ru while the Pd shell takes either anhcpor face‐centered cubic (fcc)phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking thehcpphase whereas the thicker ones revert tofcc. The injection rate provides an experimental knob for controlling the phase, with one‐shot and drop‐wise injection of the Pd precursor corresponding tofcc‐Pd andhcp‐Pd shells, respectively. When these nanocrystals are tested as catalysts toward formic acid oxidation, the Ru@Pdhcpnanocrystals outperform Ru@Pdfccin terms of both specific activity and peak potential. Density functional theory calculations are also performed to elucidate the origin of this performance enhancement.
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- Award ID(s):
- 1804970
- PAR ID:
- 10371900
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 33
- Issue:
- 49
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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