Abstract Emissive covalent organic frameworks (COFs) have recently emerged as next‐generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so‐called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well‐defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.8%) substoichiometric 2D‐COF (COF‐SMU‐1) featuring free uncondensed aldehyde groups is reported. In particular,COF‐SMU‐1features a dual‐pore architecture with an overallbexnet topology, tunable emission in various organic solvents, and distinct colorimetric changes in the presence of water. To gain further insights into its photoluminescence properties, the charge transfer, excimer emission, and excited state exciton dynamics ofCOF‐SMU‐1are investigated using femtosecond transient absorption spectroscopy in different organic solvents. Additionally, highly enhanced atmospheric water‐harvesting properties ofCOF‐SMU‐1are revealed using FT‐IR and water sorption studies.The findings will not only lead to in‐depth understanding of structure–property relationships in emissive COFs but also open new opportunities for designing COFs for potential applications in solid‐state lighting and water harvesting.
more »
« less
Covalent Organic Frameworks as a Decorating Platform for Utilization and Affinity Enhancement of Chelating Sites for Radionuclide Sequestration
Abstract The potential consequences of nuclear events and the complexity of nuclear waste management motivate the development of selective solid‐phase sorbents to provide enhanced protection. Herein, it is shown that 2D covalent organic frameworks (COFs) with unique structures possess all the traits to be well suited as a platform for the deployment of highly efficient sorbents such that they exhibit remarkable performance, as demonstrated by uranium capture. The chelating groups laced on the open 1D channels exhibit exceptional accessibility, allowing significantly higher utilization efficiency. In addition, the 2D extended polygons packed closely in an eclipsed fashion bring chelating groups in adjacent layers parallel to each other, which may facilitate their cooperation, thereby leading to high affinity toward specific ions. As a result, the amidoxime‐functionalized COFs far outperform their corresponding amorphous analogs in terms of adsorption capacities, kinetics, and affinities. Specifically, COF‐TpAb‐AO is able to reduce various uranium contaminated water samples from 1 ppm to less than 0.1 ppb within several minutes, well below the drinking water limit (30 ppb), as well as mine uranium from spiked seawater with an exceptionally high uptake capacity of 127 mg g−1. These results delineate important synthetic advances toward the implementation of COFs in environmental remediation.
more »
« less
- Award ID(s):
- 1706025
- PAR ID:
- 10055324
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 30
- Issue:
- 20
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Tuning the topology of two‐dimensional (2D) covalent organic frameworks (COFs) is of paramount scientific interest but remains largely unexplored. Herein, we present a site‐selective synthetic strategy that enables the tuning of 2D COF topology by simply adjusting the molar ratio of an amine‐functionalized dihydrazide monomer (NH2−Ah) and 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzaldehyde (Tz). This approach resulted in the formation of two distinct COFs: a clover‐like 2D COF with free amine groups (NH2−Ah−Tz) and a honeycomb‐like COF without amine groups (Ah−Tz). Both COFs exhibited good crystallinity and moderate porosity. Remarkably, the clover‐shaped NH2−Ah−Tz COF, with abundant free amine groups, displayed significantly enhanced adsorption capacities toward crystal violet (CV, 261 mg/g) and congo red (CR, 1560 mg/g) compared to the non‐functionalized honeycomb‐like Ah−Tz COF (123 mg/g for CV and 1340 mg/g for CR), underscoring the pivotal role of free amine functional groups in enhancing adsorption capacities for organic dyes. This work highlights that the site‐selective synthetic strategy paves a new avenue for manipulating 2D COF topology by adjusting the monomer feeding ratio, thereby modulating their adsorption performances toward organic dyes.more » « less
-
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 (β-cyclodextrin (β-CD)-based polymer network) and activated carbon under the same conditions. Furthermore, PAF-1-NDMB exhibits the highestk2value of 24,000 g mg−1h−1among 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.more » « less
-
Abstract Copper ions in wastewater present substantial environmental hazards, toxic to aquatic species and prone to bioaccumulation. Addressing this, we present a novel cross‐linked polythiourethane (C‐PTU) as a promising chelating adsorbent for the effective removal of copper ions from wastewater. A new monomer, 5‐(2,2,2‐trifluoroacetamide) benzene‐1,3‐bis(carbonyl) isothiocyanate (TFA‐ITC), was synthesized and further condensed with a 1,4‐butane diol to produce a trifluoroacetamide functionalized polythiourethane (TFA‐PTU) and subsequently generating amine functionalized polythiourethane (A‐PTU). The cross‐linking reaction was carried out through amino groups present on the polymer backbone with terephthaloyl chloride, resulting in the formation of C‐PTU. The monomer and polymers underwent characterization using Fourier transform infrared,1H, and13C nuclear magnetic resonance spectroscopy, with X‐ray diffraction analyzing the resin's chain alignment. Thermogravimetric and differential scanning calorimetry assessed C‐PTU's thermal properties. The adsorption process for Cu(II) ions was studied using atomic absorption spectroscopy, optimizing conditions for maximal uptake. Results revealed that C‐PTU exhibited a significant adsorption capacity for Cu(II) ions, reaching 67% after a 2 h contact time, with optimal adsorption occurring at pH 6. The Langmuir adsorption isotherm described the sorption mechanism, indicating favorable monolayer cation adsorption via coordination with donor sites on C‐PTU. This research presents a viable solution for copper ion contamination in wastewater, illustrating C‐PTU as an efficient, environmentally friendly adsorbent, marking progress toward cleaner water resources.more » « less
-
Abstract The first synthesis and comprehensive characterization of two vinyl tetrazine‐linked covalent organic frameworks (COF), TA‐COF‐1 and TA‐COF‐2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2g−1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light‐driven applications. These advantages enable TA‐COFs to act as reusable metal‐free photocatalysts in the arylboronic acids oxidation and light‐induced coupling of benzylamines. In addition, these TA‐COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HCl solution, HCl vapor, and NH3vapor. Further, the TA‐COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA‐COFs can also degrade 5‐nitro‐1,2,4‐triazol‐3‐one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight‐driven photocatalytic process; thus, revealing dual functionality of the protonated TA‐COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF‐based materials, facilitating advances in catalysis, sensing, and other related fields.more » « less
An official website of the United States government
