skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Rational design and synthesis of bifunctional metal nanocrystals for probing catalytic reactions by surface-enhanced Raman scattering
This report highlights recent progress in the rational design, synthesis, and applications of bimetallic nanocrystals with integrated SERS and catalytic activities. The ultimate goal is to develop bifunctional nanocrystals as a SERS probe for monitoring a catalytic reaction in situ . We first introduce seeded growth as a facile and powerful route to the syntheses of bifunctional nanocrystals with catalytic activities arising from Au or Pd, in addition to plasmonic properties originating from Ag or Au. Specifically, we discuss two distinctive pathways, namely conformal and site-selected deposition of a second metal on the surface of a noble-metal nanocrystal seed, for the fabrication of bifunctional nanocrystals with controlled composition and morphology. We then discuss the application of these bifunctional nanocrystals as unique probes for in situ SERS monitoring of the Au or Pd-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH 4 and the Ag-catalyzed oxidation of 4-aminothiophenol to trans -4,4′-dimercaptoazobenzene by the O 2 from air. We conclude this review with perspectives on the future development.  more » « less
Award ID(s):
1708300
PAR ID:
10063805
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Journal of Materials Chemistry C
Volume:
6
Issue:
20
ISSN:
2050-7526
Page Range / eLocation ID:
5353 to 5362
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. We report a facile route to the synthesis of Ag@Au–Pt trimetallic nanocubes in which the Ag, Au, and Pt atoms are exposed at the corners, side faces, and edges, respectively. Our success relies on the use of Ag@Au nanocubes, with Ag 2 O patches at the corners and Au on the side faces and edges, as seeds for the site-selective deposition of Pt on the edges only in a reaction system containing ascorbic acid (H 2 Asc) and poly(vinylpyrrolidone). At an initial pH of 3.2, H 2 Asc can dissolve the Ag 2 O patches, exposing the Ag atoms at the corners of a nanocube. Upon the injection of the H 2 PtCl 6 precursor, the Pt atoms derived from the reduction by both H 2 Asc and Ag are preferentially deposited on the edges, leading to the formation of Ag@Au–Pt trimetallic nanocubes. We demonstrate the use of 2,6-dimethylphenyl isocyanide as a molecular probe to confirm and monitor the deposition of Pt atoms on the edges of nanocubes through surface-enhanced Raman scattering (SERS). We further explore the use of these bifunctional trimetallic nanoparticles with integrated plasmonic and catalytic properties for in situ SERS monitoring the reduction of 4-nitrothiophenol by NaBH 4 . Upon the removal of Ag via H 2 O 2 etching, the Ag@Au–Pt nanocubes evolve into trimetallic nanoboxes with a wall thickness of about 2 nm and well-defined openings at the corners. The trimetallic nanoboxes embrace plasmon resonance peaks in the near-infrared region with potential in biomedical applications. 
    more » « less
  2. Abstract Facet‐selective etching and deposition, as determined by the landscape of surface energy, represent two powerful methods for the transformation of noble‐metal nanocrystals into nanostructures with complex shapes or morphologies. This review highlights the use of these two methods, including integration of them, for the fabrication of novel monometallic and bimetallic nanostructures with enhanced properties. We start with an introduction to the role of surface capping in controlling the facet‐selective etching or deposition on the surface of Ag nanocrystals, followed by a case study of how to maneuver etching and deposition at different facets of Pd nanocrystals for the fabrication of nanoframes. We then introduce the use of galvanic replacement to accomplish selective etching and deposition on two different facets in an orthogonal manner, transforming Pd nanocubes into Pd−Pt octapods. By complementing galvanic replacement with a chemical reduction reaction, it is also feasible to control the rates of these two reactions for the conversion of Ag nanocubes into Ag@Ag−Au concave nanocubes and Ag@Au core‐shell nanocubes. These transformation methods not only greatly increase the shape diversity of metal nanocrystals but also offer nanocrystals with enhanced plasmonic and/or catalytic properties. 
    more » « less
  3. Abstract Bifunctional nanocrystals with integrated plasmonic and catalytic activities hold great promise for analyzing chemical reactions by in situ surface‐enhanced Raman spectroscopy. This Minireview gives a brief introduction to the general strategies for designing such nanocrystals, followed by four typical examples, including their fabrication, characterization, and potential limitation. We then use the reduction of 4‐nitrothiophenol and oxidation of 4‐aminothiophenol as two model systems to demonstrate the capabilities of these bifunctional nanocrystals to monitor chemical reactions for the elucidation of reaction mechanisms and measurement of kinetics. We conclude with perspectives on further development of these bifunctional nanocrystals into a viable platform for investigating other types of catalytic reactions. 
    more » « less
  4. We report the fabrication of Ag–Pd concave nanocrystals by introducing the Pd( ii ) precursor into an aqueous suspension of Ag nanocubes in the presence of cetyltrimethylammonium chloride (CTAC) under ambient conditions. Different from the previously reported work that involved the oxidation of Ag and deposition of Pd at random sites on the surface for the generation of Ag–Pd hollow nanocrystals, we demonstrate that the Cl − ions from CTAC can confine the oxidation of Ag atoms to the side faces of a nanocube while the resultant Pd atoms are deposited on the edges in an orthogonal manner. By controlling the amount of the Pd( ii ) precursor involved in a synthesis, we can transform Ag nanocubes into Ag–Pd nanocrystals with different degrees of concaveness for the side faces and controllable Pd contents. We characterize the outermost layer of concave surfaces for the as-obtained Ag–Pd nanocrystals by surface-enhanced Raman scattering (SERS) through the use of an isocyanide probe. This facile approach would enable the fabrication of Ag-based concave nanocrystals for applications in plasmonics and catalysis. 
    more » « less
  5. Understanding the catalytic oxidation of propane is important for developing catalysts not only for catalytic oxidation of hydrocarbons in emission systems but also for selective oxidation in the chemical processing industry. For palladium-based catalysts, little is known about the identification of the chemical or intermediate species involved in propane oxidation. We describe herein findings of an investigation of the catalytic oxidation of propane over supported palladium nanoalloys with different compositions of gold (Pd n Au 100−n ), focusing on probing the chemical or intermediate species on the catalysts in correlation with the bimetallic composition and the alloying phase structure. In addition to an enhanced catalytic activity, a strong dependence of the catalytic activity on the bimetallic composition was revealed, displaying an activity maximum at a Pd : Au ratio of 50 : 50 in terms of reaction temperature. This dependence is also reflected by its dependence on the thermochemical treatment conditions. While the activity for nanoalloys with n ∼ 50 showed little change after the thermochemical treatment under oxygen, the activities for nanoalloys with n < 50 and n > 50 showed opposite trends. Importantly, this catalytic synergy is linked to the subtle differences of chemical and intermediate species which have been identified for the catalysts with different bimetallic compositions by in situ measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). For the catalytic oxidation of propane over the highly-active catalyst with a Pd : Au ratio of 50 : 50, the major species identified include acetate and bicarbonate, showing subtle differences in comparison with the identification of bicarbonate and formate for the catalyst with <50% Au (with a lower activity) and the absence of apparent species for the catalyst with >50% Au (activity is largely absent). The alloying of 50% Au in Pd is believed to increase the oxophilicity of Pd, which facilitates the first carbon–carbon bond cleavage and oxygenation of propane. The implications of the findings on the catalytic synergy of Pd alloyed with Au and the design of active Pd alloy catalysts are also discussed. 
    more » « less