Molecular-scale Insights into Cooperativity Switching of xTAB Adsorption on Gold Nanoparticles

Xu, Lang; Ye, Rong; Mavrikakis, Manos; Chen, Peng

doi:10.1021/acscentsci.3c01075

Title: Molecular-scale Insights into Cooperativity Switching of xTAB Adsorption on Gold Nanoparticles

Journal Article · 04 January 2024 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.3c01075 · OSTI ID:2278757

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University of Wisconsin, Madison, WI (United States)
Cornell University, Ithaca, NY (United States); University of Michigan, Ann Arbor, MI (United States)
Cornell University, Ithaca, NY (United States)

Quantifying adsorption behaviors is crucial for various applications such as catalysis, separation, and sensing, yet it is generally challenging to access in solution. Here, we report a combined experimental and computational study of the adsorption behaviors of alkyl-trimethylammonium bromides (xTAB), a class of ligands important for colloidal nanoparticle stabilization and shape control, with various alkyl chain lengths x on Au nanoparticles. We use density functional theory (DFT) to calculate xTAB binding energies on Au{111} and Au{110} surfaces with standing-up and lying-down configurations, which provides insights into the adsorption affinity and cooperativity differences of xTAB on these two facets. We demonstrate the key role of van der Waals interactions in determining the xTAB adsorption behavior. These computational results predict and explain the experimental discovery of xTAB’s adsorption behavior switch from stronger affinity, negative cooperativity to weaker affinity, positive cooperativity when the concentration of xTAB increases in solution. We also show that in the standing-up configuration, bilayer adsorption may occur on both facets, which can lead to different differential binding energies and consequently adsorption crossover between the two facets when the ligand concentration increases. Our combined experimental and computational approaches demonstrate a paradigm for gaining molecular-scale insights into adsorbate–surface interactions.

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Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Army Research Office, Chemical Science, Reactive Chemical Systems,; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15731; W911NF-23-1-0105; AC02-05CH11231; BES-ERCAP0022773

OSTI ID:: 2278757

Alternate ID(s):: OSTI ID: 2341569

Journal Information:: ACS Central Science, Vol. 10, Issue 1; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Alkyls
Cooperativity
Molecular interactions
Molecules

Title: Molecular-scale Insights into Cooperativity Switching of xTAB Adsorption on Gold Nanoparticles

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