Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Ito, Takashi; Frenk, S. Erin; Rai, Nikhil; Seifert, Soenke; Lin, Xiao-Min; Nayak, Srikanth

doi:10.1021/acs.langmuir.4c03619

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Journal Article · Mon Dec 16 00:00:00 EST 2024 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.4c03619· OSTI ID:2484139

^[1]; Frenk, S. Erin ^[2]; Rai, Nikhil ^[3]; Seifert, Soenke ^[3]; ^[3]; ^[3]

Kansas State University, Manhattan, KS (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Kansas State University, Manhattan, KS (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Self-assembled organic nanotubes (ONTs) have been actively examined for various applications such as chemical separations and catalysis owing to their well-defined tubular nanostructures with distinct chemical environments at the wall and internal/external surfaces. Adsorption of heavy metal ions onto ONTs plays an essential role in many of these applications, but it has rarely been assessed quantitatively. Herein, we investigated interactions between Cu²⁺ and single-/quadruple-wall bolaamphiphile-based ONTs having inner carboxyl groups with different inner diameters, COOH-ONT_10nm and COOH-ONT_20nm. We first examined the effects of Cu²⁺ on their nanotubular structures using SAXS, STEM, and AFM. COOH-ONT_10nm was stable in aqueous Cu²⁺ solution in contrast to COOH-ONT_20nm owing to the presence of polyglycine-II-type hydrogen bonding networks within its wall. Subsequently, we studied the Cu²⁺ adsorption behavior of COOH-ONT_10nm by monitoring the concentration of unbound Cu²⁺ using linear sweep anodic stripping voltammetry. The Cu²⁺ adsorption was quick, attributable to efficient Cu²⁺ partitioning through the open ends of the ONT, followed by fast Cu²⁺ diffusion in the uniform, relatively large nanochannel. More importantly, the Cu²⁺ adsorption capacity and affinity of COOH-ONT_10nm were measured at different pH using the Langmuir adsorption model. The adsorption capacity was similar at the pH range examined, showing the participation of approximately 25% of the inner carboxyl groups in the adsorption. The adsorption affinity increased with pH, indicating the essential role of the deprotonated carboxyl groups in the Cu²⁺ adsorption. Most interestingly, the Langmuir adsorption constant was significantly higher than those of previously reported synthetic adsorbents and planar monolayer based on carboxyl binding sites. The high Cu²⁺ affinity of the ONT was attributable to the highly dense binding sites on the well-defined nanoscale concave structure of the inner channel. Furthermore, these results provide a valuable guideline to designing self-assembled nanomaterials for efficient chemical separations, detection, and catalysis.

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Research Organization:: Kansas State Univ., Manhattan, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0002362; AC02-06CH11357

OSTI ID:: 2484139

Journal Information:: Langmuir, Vol. 40, Issue 52; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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77 NANOSCIENCE AND NANOTECHNOLOGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Organic nanotube
Bolaamphiphile
Copper (II) ion
Small-angle X-ray scattering
Polyglycine-II-type hydrogen bonding
Voltammetry
Langmuir adsorption model
Adsorption
Carboxyls
Hollow structures
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X-ray scattering

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

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