Cetyltrimethylammonium Bromide/Chloride on Gold Nanocrystals Can Be Directly Replaced with Tri-Citrate

Li, Kei Kwan; Song, Ho Chang; Xu, Lang; Ding, Yong; Mavrikakis, Manos; Xia, Younan

doi:10.1021/acsnano.5c13995

Title: Cetyltrimethylammonium Bromide/Chloride on Gold Nanocrystals Can Be Directly Replaced with Tri-Citrate

Journal Article · Tue Dec 02 00:00:00 UTC 2025 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.5c13995 · OSTI ID:3012743

Li, Kei Kwan ^[1];

^[2];

^[2]; Ding, Yong ^[1];

^[2];

^[3]

Georgia Institute of Technology, Atlanta, GA (United States)
Univ. of Wisconsin, Madison, WI (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Emory Univ., Atlanta, GA (United States)

This work demonstrates an effective method for directly exchanging the toxic cetyltrimethylammonium bromide/chloride (CTAB/C) on Au nanocrystals with tri-citrate. Our experimental and computational studies indicate that counterion plays a vital role in the exchange process. Specifically, when citrate species bind to Au surface, they all evolve into tri-citrate with different counterions. In the case of three H⁺ counterions, tri-citrate could readily replace the CTAB/C due to a strong binding of the carboxylate group with the Au surface. The substitution of H⁺ counterion by Na⁺ or K⁺ weakens the binding strength and thus compromises the exchange. Additionally, our quantitative measurements and theoretical calculations indicate that Au nanospheres encased by high-index facets are advantageous over their counterparts enclosed by {111} and/or {100} facets for the exchange owing to the difference in binding strength. The mechanistic insights and experimental control should be extendable to other combinations of surface ligands and metal nanocrystals.

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Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States); Univ. of California, Oakland, CA (United States); Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; FG02-05ER15731

OSTI ID:: 3012743

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 49 Vol. 19; ISSN 1936-0851; ISSN 1936-086X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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