Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren; Su, Dong; Sun, Xiaojun; Xie, Zhao -Xiong; Qin, Dong

doi:10.1021/acsnano.5b07665

Title: Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

Journal Article · Tue Jan 26 00:00:00 EST 2016 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5b07665· OSTI ID:1246788

Zhang, Jiawei ^[1]; Winget, Sarah A. ^[2]; Wu, Yiren ^[3]; Su, Dong ^[4]; Sun, Xiaojun ^[3]; Xie, Zhao -Xiong ^[5]; Qin, Dong ^[3]

Georgia Institute of Technology, Atlanta, GA (United States); Xiamen Univ., Xiamen (People's Republic of China)
Georgia Institute of Technology, Atlanta, GA (United States); Agnes Scott College, Decatur, GA (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Xiamen Univ., Xiamen (People's Republic of China)

In this paper, we report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au³⁺ by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concave cuboctahedra embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H₂O₂ because of the protection by a complete Au shell. These two unique attributes enable in-situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene (trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H₂O₂.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704

OSTI ID:: 1246788

Report Number(s):: BNL-111939-2016-JA; KC0403020

Journal Information:: ACS Nano, Vol. 10, Issue 2; ISSN 1936-0851

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 108 works

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29 ENERGY PLANNING, POLICY, AND ECONOMY
seed-mediated growth
surface capping
concave nanocrystal
surface-enhanced Raman spectroscopy
Au-catalyzed reduction and oxidation
Center for Functional Nanomaterials

Title: Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

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