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

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

Journal Article · Tue Dec 02 00:00:00 EST 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.

View Accepted Manuscript (DOE)

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

Alternate ID(s):: OSTI ID: 3009130

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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