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1.
Small ; 20(25): e2310791, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38214692

ABSTRACT

The evolution of porous membranes has revitalized their potential application in sustainable osmotic-energy conversion. However, the performance of multiporous membranes deviates significantly from the linear extrapolation of single-pore membranes, primarily due to the occurrence of ion-concentration polarization (ICP). This study proposes a robust strategy to overcome this challenge by incorporating photoelectric responsiveness into permselective membranes. By introducing light-induced electric fields within the membrane, the transport of ions is accelerated, leading to a reduction in the diffusion boundary layer and effectively mitigating the detrimental effects of ICP. The developed photoelectric-responsive covalent-organic-framework membranes exhibit an impressive output power density of 69.6 W m-2 under illumination, surpassing the commercial viability threshold by ≈14-fold. This research uncovers a previously unexplored benefit of integrating optical electric conversion with reverse electrodialysis, thereby enhancing energy conversion efficiency.

2.
Angew Chem Int Ed Engl ; 62(11): e202216724, 2023 Mar 06.
Article in English | MEDLINE | ID: mdl-36538551

ABSTRACT

Water pollution is a growing threat to humanity due to the pervasiveness of contaminants in water bodies. Significant efforts have been made to separate these hazardous components to purify polluted water through various methods. However, conventional remediation methods suffer from limitations such as low uptake capacity or selectivity, and current water quality standards cannot be met. Recently, advanced porous materials (APMs) have shown promise in improved segregation of contaminants compared to traditional porous materials in uptake capacity and selectivity. These materials feature merits of high surface area and versatile functionality, rendering them ideal platforms for the design of novel adsorbents. This Review summarizes the development and employment of APMs in a variety of water treatments accompanied by assessments of task-specific adsorption performance. Finally, we discuss our perspectives on future opportunities for APMs in water purification.

3.
Nat Commun ; 13(1): 3386, 2022 Jun 13.
Article in English | MEDLINE | ID: mdl-35697704

ABSTRACT

Increasing the charge density of ionic membranes is believed to be beneficial for generating high output osmotic energy. Herein, we systematically investigated how the membrane charge populations affect permselectivity by decoupling their effects from the impact of the pore structure using a multivariate strategy for constructing covalent-organic-framework membranes. The thermo-osmotic energy conversion efficiency is improved by increasing the membrane charge density, affording 210 W m-2 with a temperature gradient of 40 K. However, this enhancement occurs only within a narrow window, and subsequently, the efficiency plateaued beyond a threshold density (0.04 C m-2). The complex interplay between pore-pore interactions in response to charge variations for ion transport across the upscaled nanoporous membranes helps explain the obtained results. This study has far-reaching implications for the rational design of ionic membranes to augment energy extraction rather than intuitively focusing on achieving high densities.

4.
Nat Commun ; 13(1): 2132, 2022 04 19.
Article in English | MEDLINE | ID: mdl-35440580

ABSTRACT

Herein, we report a strategy to construct highly efficient perfluorooctanoic acid (PFOA) adsorbents by installing synergistic electrostatic/hydrophobic sites onto porous organic polymers (POPs). The constructed model material of PAF-1-NDMB (NDMB = N,N-dimethyl-butylamine) demonstrates an exceptionally high PFOA uptake capacity over 2000 mg g-1, which is 14.8 times enhancement compared with its parent material of PAF-1. And it is 32.0 and 24.1 times higher than benchmark materials of DFB-CDP (ß-cyclodextrin (ß-CD)-based polymer network) and activated carbon under the same conditions. Furthermore, PAF-1-NDMB exhibits the highest k2 value of 24,000 g mg-1 h-1 among all reported PFOA sorbents. And it can remove 99.99% PFOA from 1000 ppb to <70 ppt within 2 min, which is lower than the advisory level of Environmental Protection Agency of United States. This work thus not only provides a generic approach for constructing PFOA adsorbents, but also develops POPs as a platform for PFOA capture.


Subject(s)
Fluorocarbons , Polymers , Binding Sites , Caprylates , Fluorocarbons/chemistry , Porosity
5.
Angew Chem Int Ed Engl ; 61(18): e202116910, 2022 Apr 25.
Article in English | MEDLINE | ID: mdl-35179288

ABSTRACT

A vast amount of energy can be extracted from the untapped low-grade heat from sources below 100 °C and the Gibbs free energy from salinity gradients. Therefore, a process for simultaneous and direct conversion of these energies into electricity using permselective membranes was developed in this study. These membranes screen charges of ion flux driven by the combined salinity and temperature gradients to achieve thermo-osmotic energy conversion. Increasing the charge density in the pore channels enhanced the permselectivity and ion conductance, leading to a larger osmotic voltage and current. A 14-fold increase in power density was achieved by adjusting the ionic site population of covalent organic framework (COF) membranes. The optimal COF membrane was operated under simulated estuary conditions at a temperature difference of 60 K, which yielded a power density of ≈231 W m-2 , placing it among the best performing upscaled membranes. The developed system can pave the way to the utilization of the enormous supply of untapped osmotic power and low-grade heat energy, indicating the tremendous potential of using COF membranes for energy conversion applications.

6.
ACS Cent Sci ; 7(10): 1650-1656, 2021 Oct 27.
Article in English | MEDLINE | ID: mdl-34729408

ABSTRACT

Mining uranium from seawater is highly desirable for sustaining the increasing demand for nuclear fuel; however, access to this unparalleled reserve has been limited by competitive adsorption of a wide variety of concentrated competitors, especially vanadium. Herein, we report the creation of a series of uranyl-specific "hooks" and the decoration of them into the nanospace of porous organic polymers to afford uranium nanotraps for seawater uranium extraction. Manipulating the relative distances and angles of amidoxime moieties in the ligands enabled the creation of uranyl-specific "hooks" that feature ultrahigh affinity and selective sequestration of uranium with a distribution coefficient threefold higher compared to that of vanadium, overcoming the long-term challenge of the competing adsorption of vanadium for uranium extraction from seawater. The optimized uranium nanotrap (2.5 mg) can extract more than one-third of the uranium in seawater (5 gallons), affording an enrichment index of 3836 and thus presenting a new benchmark for uranium adsorbent. Moreover, with improved selectivity, the uranium nanotraps could be regenerated using a mild base treatment. The synergistic combination of experimental and theoretical analyses in this study provides a mechanistic approach for optimizing the selectivity of chelators toward analytes of interest.

7.
J Am Chem Soc ; 143(25): 9415-9422, 2021 06 30.
Article in English | MEDLINE | ID: mdl-34029064

ABSTRACT

It has long been a challenge to fabricate angstrom-sized functional pores for mimicking the function of biological channels to afford selective transmembrane transport. In this study, we describe a facile strategy to incorporate ionic elements into angstrom-sized channels using de novo encapsulation of charged dye molecules during the interface polymerization of a three-dimensional covalent organic framework (3D COF). We demonstrate that this approach is tailorable as it enables control over both the type and content of the guest and thus allows manipulation of the membrane function. The resulting membranes exhibit excellent permselectivity and low membrane resistance, thereby indicating the potential for harvesting salinity gradient (blue) energy. As a proof-of-concept study, the reverse electrodialysis device coupled with positive and negative dye encapsulated COF membranes afforded a power density of up to 51.4 W m-2 by mixing the simulated seawater and river water, which far exceeds the commercialization benchmark (5 W m-2). We envision that this strategy will pave the way for constructing new multifunctional biomimetic systems.

8.
Nat Commun ; 12(1): 1844, 2021 03 23.
Article in English | MEDLINE | ID: mdl-33758174

ABSTRACT

Thermal sensation, which is the conversion of a temperature stimulus into a biological response, is the basis of the fundamental physiological processes that occur ubiquitously in all organisms from bacteria to mammals. Significant efforts have been devoted to fabricating artificial membranes that can mimic the delicate functions of nature; however, the design of a bionic thermometer remains in its infancy. Herein, we report a nanofluidic membrane based on an ionic covalent organic framework (COF) that is capable of intelligently monitoring temperature variations and expressing it in the form of continuous potential differences. The high density of the charged sites present in the sub-nanochannels renders superior permselectivity to the resulting nanofluidic system, leading to a high thermosensation sensitivity of 1.27 mV K-1, thereby outperforming any known natural system. The potential applicability of the developed system is illustrated by its excellent tolerance toward a broad range of salt concentrations, wide working temperatures, synchronous response to temperature stimulation, and long-term ultrastability. Therefore, our study pioneers a way to explore COFs for mimicking the sophisticated signaling system observed in the nature.

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