Abstract Hybrid materials, such as metal organic nanotubes (MONTs) can possess nanoconfined water molecules within their pore space and the overall behavior of the water within the material may be tuned based upon interactions with the inner channel walls. We have previously developed a range of methods (electron density mapping, kinetic models, and water interaction enthalpies) to evaluate water behavior under nanoconfinement using a uranium‐based metal organic nanotube (UMONT) but have not explored their applicability across a range of materials. In the current study, we test our methodologies on two additional MONT materials (LaMONTandCu‐LaMONT) to determine if the techniques can be utilized in other systems to predict behavior within complex hybrid materials. In addition, we explored how to use Hirshfeld surface maps generated by the CrystalExplorer software in the visualization and prediction of water behavior within complex hybrid materials.
more »
« less
Investigating the Influence of Pore Wall–Water Interactions on Proton Conductivity within Metal‐Organic Nanotubes Using Electrochemical Impedance Spectroscopy
Abstract Water‐mediated proton conductivity in nanoporous materials is influenced by channel water ordering and the hydrophobicity/hydrophilicity of interior walls, making metal‐organic nanotubes (MONTs) useful systems for exploring these relationships due to their high crystallinity and tunable hydrophobicity. In the current study, electrochemical impedance spectroscopy is utilized to explore the proton conductivity on two metal organic nanotubes (UMONT and Cu‐LaMONT) with weak hydrophobic behavior that possess extended water networks within the 1‐D channels. Measurements performed at 95% RH and 20 °C indicate values of 1.63 × 10−4S cm−1for UMONT and 3.80 × 10−4S cm−1for Cu‐LaMONT, which is lower than values for walls with acidic, hydrophilic functional groups or nanotubular materials with strictly hydrophobic behavior. Proton conductivity decreases sharply with lower humidity, with Cu‐LaMONT being more sensitive to humidity changes. At low temperatures, UMONT outperforms LaMONT due to its well‐established hydrogen bonding network and hydrophobic interior. The anisotropic nature of proton conduction is also confirmed through pelletized powder sample analysis, emphasizing that the conductivity occurs through the water networks located within the 1‐D MONT channels. These findings emphasize the importance of understanding water–pore interactions and the resulting proton conductivity mechanisms to understand complex systems and design advanced materials.
more »
« less
- Award ID(s):
- 2004220
- PAR ID:
- 10585616
- Publisher / Repository:
- Wiley Publishing
- Date Published:
- Journal Name:
- Crystal Research and Technology
- Volume:
- 60
- Issue:
- 1
- ISSN:
- 0232-1300
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract A fluorous metal–organic framework [Cu(FBTB)(DMF)] (FMOF‐3) [H2FBTB = 1,4‐bis(1‐H‐tetrazol‐5‐yl)tetrafluorobenzene] and fluorous nonporous coordination polymer [Ag2(FBTB)] (FN‐PCP‐1) are synthesized and characterized as for their structural, thermal, and textural properties. Together with the corresponding nonfluorinated analogues lc‐[Cu(BTB)(DMF)] and [Ag2(BTB)], and two known (super)hydrophobic MOFs, FMOF‐1 and ZIF‐8, they have been investigated as low‐dielectric constant (low‐κ) materials under dry and humid conditions. The results show that substitution of hydrogen with fluorine or fluoroalkyl groups on the organic linker imparts higher hydrophobicity and lower polarizability to the overall material. Pellets of FMOF‐1, FMOF‐3, and FN‐PCP‐1 exhibit κ values of 1.63(1), 2.44(3), and 2.57(3) at 2 × 106Hz, respectively, under ambient conditions, versus 2.94(8) and 3.79(1) for lc‐[Cu(BTB)(DMF)] and [Ag2(BTB)], respectively. Such low‐κ values persist even upon exposure to almost saturated humidity levels. Correcting for the experimental pellet density, the intrinsic κ for FMOF‐1 reaches the remarkably low value of 1.28, the lowest value known to date for a hydrophobic material.more » « less
-
Abstract Nanoparticles and nanofibers are widely used as components of polymer electrolytes for membranes in fuel cells, and many surface modification methods are reported. However, some fabrication techniques are complicated, and it is necessary to develop a simplified and precise control method. Herein, a facile fabrication method is reported for core–shell nanoparticles hierarchically coated with polymeric ionic liquids (PIL) and hydrophobic polymers as a material for polymer electrolytes. A hierarchical polymer layer on the surface of the SiO2nanoparticles is easily constructed by repeating the facile polymer‐coating technique based on precipitation polymerization several times. The highest proton conductivity of the core–shell nanoparticles is 1.3 × 10−2 S cm−1at 80 °C and 95% relative humidity. Although the hydrophobic polymers coated as a protective layer reduce the proton conductivity, the formation of the PIL enhances the proton conductivity in various temperature and humidity environments. Therefore, the proposed method enables the facile fabrication of polymer layers with multiple functions, such as a proton‐conductive PIL layer and hydrophobic polymer layers as protective layers on the surface of the nanoparticles. Furthermore, they are expected to be applied to energy supply and gas separation, including polyelectrolytes, for the realization of a sustainable society.more » « less
-
Abstract To exploit their charge transport properties in transistors, semiconducting carbon nanotubes must be assembled into aligned arrays comprised of individualized nanotubes at optimal packing densities. However, achieving this control on the wafer‐scale is challenging. Here, solution‐based shear in substrate‐wide, confined channels is investigated to deposit continuous films of well‐aligned, individualized, semiconducting nanotubes. Polymer‐wrapped nanotubes in organic ink are forced through sub‐mm tall channels, generating shear up to 10 000 s−1uniformly aligning nanotubes across substrates. The ink volume and concentration, channel height, and shear rate dependencies are elucidated. Optimized conditions enable alignment within a ±32° window, at 50 nanotubes µm−1, on 10 × 10 cm2substrates. Transistors (channel length of 1–5 µm) are fabricated parallel and perpendicular to the alignment. The parallel transistors perform with 7× faster charge carrier mobility (101 and 49 cm2V−1s−1assuming array and parallel‐plate capacitances, respectively) with high on/off ratio of 105. The spatial uniformity varies ±10% in density, ±2° in alignment, and ±7% in mobility. Deposition occurs within seconds per wafer, and further substrate scaling is viable. Compared to random networks, aligned nanotube films promise to be a superior platform for applications including sensors, flexible/stretchable electronics, and light emitting and harvesting devices.more » « less
-
Abstract Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO2reduction reaction (CO2RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm−2at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) of ≈91% toward CO production, and a remarkable turnover frequency as high as ≈20.82 s−1. In the low overpotential range, the obtained CO formation current density is more than 35 and 25 times higher compared to state‐of‐the‐art MOF and MOF‐derived catalysts, respectively. The operando Cu K‐edge X‐ray absorption near edge spectroscopy and density functional theory calculations reveal the existence of reduced Cu (Cu+) during CO2RR which reversibly returns to Cu2+after the reaction. The outstanding CO2catalytic functionality of conductive MOFs (c‐MOFs) can open a way toward high‐energy‐density electrochemical systems.more » « less
An official website of the United States government

