skip to main content

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Thursday, January 16 until 2:00 AM ET on Friday, January 17 due to maintenance. We apologize for the inconvenience.


Title: Facet-dependent Catalysis of CuNi Nanocatalysts toward 4–Nitrophenol Reduction Reaction
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 nano-octahedra (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.  more » « less
Award ID(s):
1808383
PAR ID:
10166219
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
MRS Advances
Volume:
5
Issue:
27-28
ISSN:
2059-8521
Page Range / eLocation ID:
1491 to 1496
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    We present a one‐pot colloidal synthesis method for producing monodisperse multi‐metal (Co, Mn, and Fe) spinel nanocrystals (NCs), including nanocubes, nano‐octahedra, and concave nanocubes. This study explores the mechanism of morphology control, showcasing the pivotal roles of metal precursors and capping ligands in determining the exposed crystal planes on the NC surface. The cubic spinel NCs, terminated with exclusive {100}‐facets, demonstrate superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their octahedral and concave cubic counterparts. Specifically, at 0.85 V, (CoMn)Fe2O4spinel oxide nanocubes achieve a high mass activity of 23.9 A/g and exhibit excellent stability, highlighting the promising ORR performance associated with {100}‐facets of multi‐metal spinel oxides over other low‐index and high‐index facets. Motivated by exploring the correlation between ORR performance and surface atom arrangement (active sites), surface element composition, as well as other factors, this study introduces a prospective approach for shape‐controlled synthesis of advanced spinel oxide NCs. It underscores the significance of catalyst shape control and suggests potential applications as nonprecious metal ORR electrocatalysts.

     
    more » « less
  2. ABSTRACT In this work, we demonstrate a size-controlled synthesis of CuNi octahedral nanocrystals (NCs) using a hot colloidal solution approach. Two different sizes of CuNi nano-octahedra are chosen and investigated. It is determined that the reagent concentration remarkably plays a key role in the formation of the size-defined CuNi octahedral NCs. In terms of the reduction of 4-nitrophenol (4-NP), it uncovers that the obtained CuNi octahedral NCs (in both sizes) exhibit higher catalytic activity than those of CuNi spherical NCs reported previously. It further indicates that the catalytic performance is strongly size-dependent due to their devise specific surface areas of the exposed crystallographic planes. 
    more » « less
  3. Abstract

    Fabrication of 3dmetal‐based core@shell nanocatalysts with engineered Pt‐surfaces provides an effective approach for improving the catalytic performance. The challenges in such preparation include shape control of the 3dmetallic cores and thickness control of the Pt‐based shells. Herein, we report a colloidal seed‐mediated method to prepare octahedral CuNi@Pt‐Cu core@shell nanocrystals using CuNi octahedral cores as the template. By precisely controlling the synthesis conditions including the deposition rate and diffusion rate of the shell‐formation through tuning the capping ligand, reaction temperature, and heating rate, uniform Pt‐based shells can be achieved with a thickness of <1 nm. The resultant carbon‐supported CuNi@Pt‐Cu core@shell nano‐octahedra showed superior activity in electrochemical methanol oxidation reaction (MOR) compared with the commercial Pt/C catalysts and carbon‐supported CuNi@Pt‐Cu nano‐polyhedron counterparts.

     
    more » « less
  4. Abstract

    Fabrication of 3dmetal‐based core@shell nanocatalysts with engineered Pt‐surfaces provides an effective approach for improving the catalytic performance. The challenges in such preparation include shape control of the 3dmetallic cores and thickness control of the Pt‐based shells. Herein, we report a colloidal seed‐mediated method to prepare octahedral CuNi@Pt‐Cu core@shell nanocrystals using CuNi octahedral cores as the template. By precisely controlling the synthesis conditions including the deposition rate and diffusion rate of the shell‐formation through tuning the capping ligand, reaction temperature, and heating rate, uniform Pt‐based shells can be achieved with a thickness of <1 nm. The resultant carbon‐supported CuNi@Pt‐Cu core@shell nano‐octahedra showed superior activity in electrochemical methanol oxidation reaction (MOR) compared with the commercial Pt/C catalysts and carbon‐supported CuNi@Pt‐Cu nano‐polyhedron counterparts.

     
    more » « less
  5. We report the fabrication of Ag–Au cuboctahedral nanoboxes enclosed by {100} and {111} facets, respectively, through the orthogonal deposition of Au on two different facets of Ag cuboctahedra. Specifically, we titrate aqueous HAuCl 4 into an aqueous mixture containing Ag cuboctahedra, ascorbic acid, and NaOH (under basic conditions), in the presence of poly(vinylpyrrolidone) (PVP) and cetyltrimethylammonium chloride (CTAC), respectively. In the case of PVP, the oxidation of Ag was initiated from the {111} facets of the cuboctahedra through the galvanic replacement reaction between Au( iii ) and Ag, accompanied by the deposition of Au onto the {100} facets. Because the dissolved Ag( i ) ions could react with NaOH to form Ag 2 O on the {111} facets and thus terminate the galvanic reaction, the Au( iii ) ions would be further reduced by the ascorbate monoanion (HAsc − ) to generate Au atoms for their continuing deposition on the {100} facets, converting Ag cuboctahedra to Ag@Au {100} cuboctahedra. Upon the etching of Ag from the core, we obtained Ag–Au cuboctahedral nanoboxes enclosed by {100} facets. In contrast, when CTAC was present, the oxidation of Ag through a galvanic reaction could continuously proceed on {100} facets as the dissolved Ag( i ) ions would react with the excessive amount of Cl − ions derived from CTAC to produce soluble AgCl 2 − ions rather than insoluble Ag 2 O. As a result, the dissolved Ag( i ) and Au( iii ) ions would be co-reduced by HAsc − for the generation of Ag and Au atoms, followed by their co-deposition onto {111} facets for the generation of Ag@Au {111} concave cuboctahedra. After the removal of Ag from the core by etching, we obtained Ag–Au {111} cuboctahedral nanoboxes enclosed by {111} facets. Both samples of cuboctahedral nanoboxes exhibited strong optical absorption in the infrared region. Interestingly, the cuboctahedral nanoboxes enclosed by {111} facets showed significantly enhanced catalytic activity toward the reduction of 4-nitrophenol by NaBH 4 relative to their counterparts encased by {100} facets. 
    more » « less