RESUMEN
Lead halide perovskite nanocrystals with excellent photophysical properties are promising electrochemiluminescence (ECL) candidates, but their poor stability greatly restricts ECL applications. Herein, hydrogen-bonded cocrystal-encapsulated CsPbBr3 perovskite nanocrystals (PeNCs@NHS-M) were synthesized by using PeNCs as nuclei for inducing the crystallization of melamine (M) and N-hydroxysuccinimide (NHS). The as-synthesized composite exhibits multiplicative ECL efficiencies (up to 24-fold that of PeNCs) without exogenous coreactants and with excellent stability in the aqueous phase. The enhanced stability can be attributed to the well-designed heterostructure of the PeNCs@NHS-M composite, which benefits from both moiety passivation and protection of the peripheral cocrystal matrix. Moreover, the heterostructure with covalent linkage facilitates charge transfer between PeNCs and NHS-M cocrystals, realizing effective ECL emission. Meanwhile, the NHS and M components act as coreactants for PeNCs, shortening the electron-transport distance and resulting in a significant increase in the ECL signal. Furthermore, by taking advantage of the specific binding effect between NHS-M and uranyl (UO22+), an ECL system with both a low detection limit (1 nM) and high selectivity for monitoring UO22+ in mining wastewater is established. The presence of UO22+ disrupted the charge-transfer effect within PeNCs@NHS-M, weakening the ECL signals. This work provides an efficient design strategy for obtaining stable and efficient ECLs from perovskite nanocrystals, offering a new perspective for the discovery and application of perovskite-based ECL systems.
RESUMEN
Uranium poses severe health risks due to its radioactivity and chemical toxicity if released into the environment. Therefore, there is an urgent demand to develop sensing materials in situ monitoring of uranium with high sensitivity and stability. In this work, a fluorescent Eu3+-TFPB-Bpy is synthesized by grafting Eu3+ cation onto TFPB-Bpy covalent organic framework (COF) synthesized through Schiff base condensation of monomers 1,3,5-tris(4-formylphenyl)benzene (TFPB) and 5,5'-diamino-2,2'-bipyridine (Bpy). The fluorescence of Eu3+-TFPB-Bpy is enhanced compared with that of TFPB-Bpy, which is originated from the intramolecular rotations of building blocks limited by the bipyridine units of TFPB-Bpy coordinated with Eu3+. More significantly, Eu3+-TFPB-Bpy is a highly efficient probe for sensing UO22+ in aqueous solution with the luminescence intensity efficiently amplified by complexation of UO22+ with Eu3+. The turn-on sensing capability was derived from the resonance energy transfer occurring from UO22+ to the Eu3+-TFPB-Bpy. The developed probe displayed desirable linear range from 5 nM to 5 µM with good selectivity and rapid response time (2 s) for UO22+ in mining wastewater. This strategy provides a vivid illustration for designing luminescence lanthanide COF hybrid materials with applications in environmental monitoring.
RESUMEN
Developing new electrochemiluminescence (ECL) luminators with high stability, wide applicability, and strong designability is of great strategic significance to promote the ECL field to the frontier. Here, driven by the I···N bond, 1,3,5-trifluoro-2,4,6-triiodobenzene (TFTI) and 2,4,6-trimethyl-1,3,5-triazine (TMT) self-assembled into a novel halogen cocrystal (TFTI-TMT) through slow solution volatilization. Significant difference of charge density existed between the N atoms on TMT and the σ-hole of the I atoms on TFTI. Upon the induction of σ-hole effect, high-speed and spontaneous charge transferring from TMT to the σ-hole of TFTI occurred, stimulating exciting ECL signals. Besides, the σ-hole of the I atoms could capture iodine ions specifically, which blocked the original charge transfer from the N atoms to the σ-hole, causing the ECL signal of TFTI-TMT to undergo a quenching rate as high as 92.9%. Excitingly, the ECL sensing of TFTI-TMT toward I- possessed a wide linear range (10-5000 nM) and ultralow detection limit (3 nM) in a real water sample. The halogen cocrystal strategy makes σ-hole a remarkable new viewpoint of ECL luminator design and enables ECL analysis technology to contribute to addressing the environmental and health threats posed by iodide pollution.
RESUMEN
At present, poor stability and carrier transfer efficiency are the main problems that limit the development of perovskite-based photoelectric technologies. In this work, hydrogen-bonded cocrystal-coated perovskite composite (PeNCs@NHS-M) is easily obtained by inducing rapid crystallization of melamine (M) and N-hydroxysuccinimide (NHS) with PeNCs as the nuclei. The outer NHS-M cocrystal passivates the undercoordinated lead atoms by forming covalent bonds, thereby greatly reducing the trap density while maintaining good structure stability for perovskite nanocrystals. Moreover, benefiting from the interfacial covalent band linkage and long-range ordered structures of cocrystals, the charge transfer efficiency is effectively enhanced and PeNCs@NHS-M displays superior photoelectric performance. Based on the excellent photoelectric performance and abundant active sites of PeNCs@NHS-M, photocatalytic reduction of uranium is realized. PeNCs@NHS-M exhibits U(VI) reduction removal capability of up to 810.1 mg g-1 in the presence of light. The strategy of cocrystals trapping perovskite nanocrystals provides a simple synthesis method for composites and opens up a new idea for simultaneously improving the stability and photovoltaic performance of perovskite.
RESUMEN
The performance of covalent-organic frameworks (COFs) for the photocatalytic extraction of uranium is greatly limited by the number of adsorption sites. Herein, inspired by electronegative redox reactions, we designed a nitrogen-oxygen rich pyrazine connected COF (TQY-COF) with multiple redox sites as a platform for extracting uranium via combining superaffinity and enhanced photoinduction. The preorganized bisnitrogen-bisoxygen donor configuration on TQY-COF is entirely matched with the typical geometric coordination of hexavalent uranyl ions, which demonstrates high affinity (tetra-coordination). In addition, the presence of the carbonyl group and pyrazine ring effectively stores and controls electron flow, which efficaciously facilitates the separation of e-/h+ and enhances photocatalytic performance. The experimental results show that TQY-COF removes up to 99.8% of uranyl ions from actual uranium mine wastewater under the light conditions without a sacrificial agent, and the separation coefficient reaches 1.73 × 106 mL g-1 in the presence of multiple metal ions, which realizes the precise separation in the complex environment. Importantly, DFT calculations further elucidate the coordination mechanism of uranium and demonstrate the necessity of the presence of N/O atoms in the photocatalytic adsorption of uranium.
RESUMEN
A rapid in situ synthesis of electrochromic covalent organic frameworks (EC-COFs) was proposed by using green electrochemical interface polymerization of N,N,N',N'-tetrakis(p-aminophenyl)p-phenylenediamine (TPDA) and 2,5-dihydroxy-p-phenylenedicarboxaldehyde (DHBD). The synthetized TPDA-DHBD films exhibit stable polymorphic colour variations under different applied potentials, which can be attributed to the redox state changes of bis(triphenylamine) and imine electroactive functional groups within the COFs skeleton. TPDA-DHBD represents markedly different electrochromisms from red to cyan due to the steric hindrance effect caused by the presence of UO22+, demonstrating the unique tunability of COFs materials. This work offers a new feasible idea for rapid EC-COFs synthesis and tunable EC-COFs realization.
RESUMEN
An imidazolyl hydrogen-bonded organic framework (HOF-T) with outstanding thermal and water stability was constructed by C-Hâ¯N hydrogen bonding and C-Hâ¯π interactions. UO22+ can be selectively captured by the imidazole group of HOF-T and rapidly reduced to UO2 under visible light irradiation, realizing exceptional uranium removal with high capacity and fast kinetics.
RESUMEN
BACKGROUND: The increasing uranium containing wastes generated during uranium mining and finishing pose a huge threat to the environment and human health, and thus robust strategies for on-site monitoring of uranium pollutant are of great significance for environmental protection around uranium tailings. RESULTS: Herein, a facile "turn-on" colorimetric platform that can achieve uranium detection by spectrometry and naked eyes was developed based on the uranium-enhanced nanozyme activity of covalent organic framework (JUC-505). Thanks to the extended π-conjugated skeleton and donor-acceptor (D-A) structure, JUC-505 exhibited superior photo-activated nanozyme activity, which would be prohibited when the cyano group in JUC-505 skeleton was transformed to the amidoxime group. Further results elucidated that the coordination of uranium with amidoxime groups led to the electron transfer between uranium and the JUC-505-AO skeleton, and thus significantly restored the nanozymatic activity of JUC-505-AO with the subsequent remarkable color changes. Moreover, the uranium concentrations in uranium tailing wastewater detected by the present "turn-on" colorimetric method were well agreed with those by ICP-MS, demonstrating a high accuracy of the present method in real samples. SIGNIFICANCE: The D-A structured JUC-505 with superior photocatalytic property and nanozymatic activity was applied to facilitate colorimetric detection of uranium, which displays the advantages of low detection limit, excellent selectivity, fast response and simple operation for uranium detection in real samples, and shows a great potential in on-site monitoring of uranium pollutant around uranium tailings as well as nuclear power plant.
RESUMEN
Photoreduction of highly toxic U(VI) to less toxic U(IV) is crucial for mitigating radioactive contamination. Herein, a CoWO4/TpDD p-n heterojunction is synthesized, with TpDD serving as the n-type semiconductor substrate and CoWO4 as the p-type semiconductor grown in situ on its surface. The Fermi energy difference between TpDD and CoWO4 provides the electrochemical potential for charge-hole separation. Moreover, the Coulombic forces from the distinct carrier types between the two materials synergistically facilitate the transfer of electrons and holes. Hence, an internal electric field directed from TpDD to CoWO4 is established. Under photoexcitation conditions, charges and holes migrate efficiently along the curved band and internal electric field, further enhancing charge-hole separation. As a result, the removal capacity of CoWO4/TpDD increases from 515.2 mg/g in the dark to 1754.6 mg/g under light conditions. Thus, constructing a p-n heterojunction proves to be an effective strategy for remediating uranium-contaminated environments.
RESUMEN
Extracting rare earth elements (REEs) from wastewater is essential for the growth and an eco-friendly sustainable economy. However, it is a daunting challenge to separate individual rare earth elements by their subtle differences. To overcome this difficulty, we report a unique REE nanotrap that features dense uncoordinated carboxyl groups and triazole N atoms in a two-fold interpenetrated metal-organic framework (named NCU-1). Notably, the synergistic effect of suitable pore sizes and REE nanotraps in NCU-1 is highly responsive to the size variation of rare-earth ions and shows high selectivity toward light REE. As a proof of concept, Pr/Lu and Nd/Er are used as binary models, which give a high separation factor of SFPr/Lu = 796 and SFNd/Er = 273, demonstrating highly efficient separation over a single step. This ability achieves efficient and selective extraction and separation of REEs from mine tailings, establishing this platform as an important advance for sustainable obtaining high-purity REEs.
RESUMEN
Untreated radioactive iodine (129I and 131I) released from nuclear power plants poses a significant threat to humans and the environment, so the development of materials to capture iodine from water media and steam is critical. Here, we report a charge transfer complex (TCNQ-MA CTC) with abundant nitrogen atoms and π-conjugated system for adsorption of I2 vapor and I3- from aqueous solutions. Due to the synergistic binding mechanism of benzene/triazine rings and N-containing groups with iodine, special I-π and charge transfer interaction can be formed between the guest and the host, and thus efficient removal of I2 and I3- can be realized by TCNQ-MA CTC with the adsorption capacity up to 2.42 g/g and 800 mg/g, respectively. TCNQ-MA CTC can capture 92% of I3- within 2.5 min, showing extremely fast kinetics, excellent selectivity and high affinity (Kd = 5.68 × 106 mL/g). Finally, the TCNQ-MA CTC was successfully applied in the removal of iodine from seawater with the efficiency of 93.71%. This work provides new insights in the construction of charge transfer complexes and lays the foundation for its environmental applications.