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.
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Revitalizing silver nanocrystals as a redox catalyst by modifying their surface with an isocyanide-based compound
Silver is an excellent catalyst for oxidation reactions such as ethylene epoxidation, but it shows limited activity toward reduction reactions. Here we report a strategy to revitalize Ag nanocrystals as a redox catalyst for the production of an aromatic azo compound by modifying their surface with an isocyanide-based compound. We also leverage in situ fingerprint spectroscopy to acquire molecular insights into the reaction mechanism by probing the vibrational modes of all chemical species at the catalytic surface with surface-enhanced Raman spectroscopy. We establish that binding of isocyanide to Ag nanocrystals makes it possible for Ag to extract the oxygen atoms from the nitro-groups of nitroaromatics and then use these atoms to oxidize isocyanide to isocyanate. Concurrently, the coupling between two adjacent deoxygenated nitroaromatic molecules leads to the formation of an aromatic azo compound.
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- Award ID(s):
- 1708300
- NSF-PAR ID:
- 10284034
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 11
- Issue:
- 41
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 11214 to 11223
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Aromatic azo compounds are high‐value chemicals extensively used as pigments, drugs, and food additives, but their production typically requires stoichiometric amounts of environmentally unfriendly metals or nitrites. There is an urgent need to develop a dual catalytic system capable of reducing nitroaromatics to aromatic amines, followed by their oxidation to azo compounds. Here we report such a dual catalyst based on Ag@Pd‐Ag core‐frame nanocubes for the stepwise conversion of 4‐nitrothiophenol to
trans ‐4,4′‐dimercaptoazobenzene under ambient conditions. Our in situ surface‐enhanced Raman spectroscopy study reveals three sequential processes that include the Pd‐catalyzed reduction of 4‐nitrothiophenol to 4‐aminothiophenol by hydrogen, a period during which the 4‐aminothiophenol remain unchanged until all hydrogen has depleted, and the Ag‐catalyzed oxidation of 4‐aminothiophenol totrans ‐4,4′‐dimercaptoazobenzene by the O2from air. This work will lead to an environmentally friendly and sustainable approach to the production of aromatic azo compounds. -
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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.
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Abstract Helical poly(isocyanide)s are an important class of synthetic polymers possessing a static helical structure. Since their initial discovery, numerous examples of these helices have been fabricated. In this contribution, the synthesis of a chiral, azobenzene (azo)‐containing isocyanide monomer is reported. Upon polymerization with nickel(II) catalysts, a well‐defined circular dichroism (CD) trace is obtained, corresponding to the formation of a right‐handed polymeric helix. The helical polymer, dissolved in chloroform and irradiated with UV light (365 nm), undergoes a
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Abstract There is an urgent need to develop cost‐effective electrocatalysts based on Pt for a broad spectrum of applications, including those vital to the operation of fuel cells. Hollowing out the interior of Pt nanocrystals offers a simple and viable strategy for maximizing the utilization efficiency of this precious metal while enhancing the electrocatalytic performance. Herein, we report the synthesis and electrocatalytic evaluation of Pt−Ag icosahedral nanocages with an average wall thickness of 1.6 nm. The Pt atoms are coated on the surface of Ag icosahedral seeds, leading to the formation of Ag@PtnLcore‐shell icosahedral nanocrystals with tunable shell thicknesses. The core‐shell nanocrystals are then converted to icosahedral nanocages by selectively etching away the Ag in the core. The as‐obtained nanocages with a composition of Pt4.5Ag exhibit an almost 3‐fold enhancement in specific activity toward oxygen reduction relative to the commercial Pt/C in acid media.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sc04385k
