Platinum nanoparticles (Pt NPs) with uniform size and high dispersion have been successfully assembled on poly(diallyldimethylammonium chloride) functionalized graphene oxide via a sodium borohydride ...reduction process. The loading concentration of Pt NPs on graphene can be adjusted in the range of 18–78 wt %. The obtained Pt/graphene nanocomposites are characterized by transmission electron microscopy, high resolution transmission electron microscopy, energy dispersive spectrometry, X-ray diffraction, and thermogravimetric analysis. The results show that the Pt NPs with sizes of approximate 4.6 nm uniformly disperse on graphene surface for all Pt loading densities. Electrochemical studies reveal that the Pt/graphene nanocomposites with electrochemically active surface area of 141.6 m2/g show excellent electrocatalytic activity toward methanol oxidation and oxygen reduction. The present method is promising for the synthesis of high performance catalysts for fuel cells, gas phase catalysis, and sensors.
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Lanthanide coordination polymer nanoparticles (Ln-CPNs) have been recently demonstrated as excellent platforms for biomolecule detection. In this work, we synthesized novel cerium coordination ...polymer nanoparticles ATP-Ce-Tris CPNs in a simple and quick way using ATP molecules as the biocompatible ligands to Ce3+ ions in tris(hydroxymethyl)aminomethane hydrochloric (Tris-HCl) solution. In view of the excellent free radical scavenging property of cerium compounds, which is ascribed to the mixed valence state (Ce3+, Ce4+) and the reversible switch from Ce3+ to Ce4+, the synthesized ATP-Ce-Tris CPNs was used as artificial peroxidase to selectively and sensitively detect H2O2. The sensing mechanism depends on the oxidation of the fluorescent ATP-Ce(III)-Tris CPNs to nonfluorescent ATP-Ce(IV)-Tris CPNs by H2O2. Compared with those inorganic cerium oxide sensors, this kind of fluoresence ATP-Ce-Tris CPNs sensor needs no additional organic redox dye, such as ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), TMB (3,3,5,5-tetramethylbenzidine), or fluorescein as signal molecules. Moreover, such ATP-Ce-Tris CPNs sensor exhibited a more sensitive response to H2O2 with a detection limit down to 0.6 nM, which is 2 orders of magnitude lower than those of cerium oxide sensors. This sensing platform was further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) for the oxidation of glucose and formation of H2O2.
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•Zwitterionic COFs were designed and prepared for efficient uptake of fluoroquinolone antibiotics.•More functional binding sites were exposed after initial self-exfoliation to ionic ...covalent organic nanosheets.•Tp-MTABs with multiple binding sites exhibited ultrafast adsorption and superior adsorption capacity for FQs.•Zwitterionic Tp-MTABs showed splendid selectivity for the uptake of FQs in complex systems.•Plausible FQs adsorbed mechanisms were ion-pair binding and π–π interactions.
The effective removal of zwitterionic fluoroquinolone (FQ) antibiotics with high water solubility in wastewater is a key environmental challenge due to the inefficacy of conventional methods of wastewater treatment. In this work, zwitterionic covalent organic frameworks (Tp-MTABs) were synthesized through a solvothermal route using 5,5′,5″-methanetriyltris(2-aminobenzenesulfonic acid) (MTABs) as a zwitterionic linker and 1,3,5-triformylphloroglucinol (Tp) as neutral knots for efficient uptake of FQ antibiotics. Tp-MTABs compose of regular distributions of sulfonic acids and amines that produce zwitterionic binding sites, which produce complementary ion-pair interactions with zwitterionic FQ antibiotics. The charge on Tp-MTABs facilitates its initial self-exfoliation to few-layered ionic covalent organic nanosheets (iCONs) with controlled surface charge, which exposes more surface ionic sites and phenyl groups toward FQ antibiotics, improving ion-pair and π–π interactions between iCONs and FQ antibiotics. These iCONs with multiple active sites highly facilitated the process of antibiotics adsorption, boosting the adsorption kinetics and improving the selectivity towards FQ antibiotics. Tp-MTABs endows ultrafast adsorption rate (<30 s) of FQ antibiotics (average over 99%). In addition, Tp-MTABs exhibit high selectivity to the removal of FQs in complex systems containing multiple competing organic compounds and high-salinity natural seawater. This work explored the structural and functional design of iCONs for the removal of organic molecules in environmental remediation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Herein, a novel fluorescent ionic covalent organic framework (BTTA–BDNP) based on a linked carbazole unit was constructed for the synchronous monitoring and capture of TcO4−/ReO4−. BTTA–BDNP has a ...fast fluorescence response time with a low detection limit (66.7 nM) for ReO4− (a non-radioactive substitute for TcO4−). Meanwhile, the high charge density and hydrophobic skeleton of BTTA–BDNP enable it to exhibit rapid and selective trapping of ReO4− in complex environments.
Covalent organic frameworks (COFs) have been proposed for electrochemical energy storage, although the poor conductivity resulted from covalent bonds limits their practical performance. Here, we ...propose to introduce noncovalent bonds in COFs through a molecular insertion strategy for improving the conductivity of the COFs as supercapacitor. The synthesized COFs (MI−COFs) establish equilibriums between covalent bonds and noncovalent bonds, which construct a continuous charge transfer channel to enhance the conductivity. The rapid charge transfer rate enables the COFs to activate the redox sites, bringing about excellent electrochemical energy storage behavior. The results show that the MI−COFs exhibit much better performance in specific capacitance and capacity retention rate than those of most COFs‐based supercapacitors. Moreover, through simply altering inserted guests, the mode and strength of noncovalent bond can be adjusted to obtain different energy storage characteristics. The introduction of noncovalent bonds is an effective and flexible way to enhance and regulate the properties of COFs, providing a valuable direction for the development of novel COFs‐based energy storage materials.
A molecular insertion strategy is used by introducing non‐covalent interactions in COFs to form a continuous charge transfer channel and accelerate the charge transfer rate. Meanwhile, the enhanced conductivity activates the redox sites in the COF skeleton, resulting in excellent energy storage performance. In addition, the energy storage behavior can be accurately regulated by changing the type of insertion guests.
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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.
The CsPbBr3 nanocrystals (PeNCs) are coated with hydrogen‐bonded cocrystals (N‐hydroxysuccinimide‐melamine, NHS‐M) to achieve defect passivation and structural stability enhancement. Moreover, this covalently linked heterostructure further promotes the electron transport of PeNCs and realizes the photocatalytic reduction of uranium through the binding sites on the cocrystal.
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•The imidazolium-based cationic organic polymer (ImCOP) was designed and prepared for efficient removal of TcO4−/ReO4−.•The high acid-base stability was due to the semi-rigid ...structure of ImCOP.•ImCOP with rich adsorption sites exhibited a record uptake capability (1162 mg g−1) and high selectivity for ReO4−.•It showed fast kinetics and high-efficiency removal for ReO4− in simulated wastes.
Rational design of anion-scavenging materials with high selectivity and stability under high acid/base extreme conditions for removing 99TcO4− is still a significant challenge. Herein, we put forward an anion exchange strategy that utilized an imidazolium-based cationic organic polymer (named ImCOP) for efficient capture of perrhenate (ReO4−), a surrogate for TcO4− with nonradioactive. ImCOP was synthesized via the quaternization reaction using tris (4-(1H-imidazol-1-yl) phenyl) amine, a tripodal flexible ligand, and 1,4-bis (bromomethyl) benzene to forming a semi-rigid structure. ImCOP exhibited high chemical stability even under 3 M HNO3 and 3 M NaOH, which was superior to those of most materials. Attributed to the charged imidazolium moieties and tertiary amine groups that produced rich adsorption sites, ImCOP can produce electrostatic interactions with ReO4−, thereby leading to a record uptake capability (1162 mg g−1) of ReO4−. Furthermore, ImCOP exhibited high selectivity for removing ReO4− in the presence of large excess of competitive anions, which was attributed to the hydrophobic surface of ImCOP. These excellent features endowed ImCOP successfully separated ReO4− from simulated Hanford waste with a high adsorption removal of 93.4%. The excellent performance suggested ImCOP would be a promising material for TcO4−/ReO4− removal, which provided a feasible pathway for designing a high-efficiency and durable material for nuclear-related environmental remediation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
We report the first example of vinylene-linked covalent organic framework (Tp-TMT) with enhanced uranium adsorption through combined selective ligand binding, chemical reduction and photocatalytic ...reduction. The dense hydroxyl functional groups on the Tp-TMT framework had good selectivity and excellent chemical reduction performance for U(VI). Meanwhile, the synergistic effect of hydroxyl groups and triazine unit significantly enhanced the photocatalytic reduction activity. Thus Tp-TMT exhibited incredible adsorption kinetics and capacity for uranium.
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•COFs effectively capture uranium through three coordinated mechanisms.•Tp-TMT has excellent visible light conversion efficiency and low band gap.•Tp-TMT enhances uranium adsorption through selective ligand binding and reduction.•Tp-TMT exhibits incredible adsorption kinetics and capacity for uranium.
So far, it remains a challenge to synthesize uranium adsorbents with robust stability, high adsorption capacity, excellent photocatalytic activity and easy regeneration. Herein, we report the first example of vinylene-linked covalent organic framework (Tp-TMT) with enhanced uranium adsorption through combined selective ligand binding, chemical reduction and photocatalytic reduction. The unique structure and excellent photocatalytic activity of Tp-TMT make it very suitable for photo-enhanced uranium adsorption through three synergistic mechanisms, thus exhibiting an outstanding uranium adsorption capacity (2362.4 mg g−1). In the dark, a large number of hydroxyl groups in the Tp-TMT framework serve as selective binding sites for uranium, and reduce part of U(VI) to U(IV), thereby greatly improving the adsorption capacity. Meanwhile, the synergistic effect of the triazine units and hydroxyl groups in the highly conjugated framework greatly decreases the optical band gap of Tp-TMT, and an additional U(VI) photocatalytic reduction process can occur under light irradiation, further increasing the adsorption kinetics and capacity. This work explored the structural and functional design of covalent organic frameworks for the adsorption and reduction of uranium in nuclear industry wastewater.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
This study reports a novel and convenient bimodal method for label-free and signal-off detection of arsenate in environmental samples. Cobalt oxyhydroxide (CoOOH) nanoflakes with facile preparation ...and intrinsic peroxidase-like activity as nanozyme can efficiently catalyze the conversion of chromogenic substrate such as 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) with the presence of H2O2 into green-colored oxidation products. CoOOH nanoflakes can specifically bind with arsenate via electrostatic attraction and As–O bond interaction, which gives rise to inhibition of the peroxidase-like activity of CoOOH. Thus, through arsenate specific inhibition of CoOOH nanozyme toward ABTS catalysis, a simple colorimetric method was developed for arsenate detection with a detection limit of 3.72 ppb. Based on the system of CoOOH nanozyme and ABTS substrate, this colorimetric method can be converted into an electrochemical sensor for arsenate assay by the utilization of CoOOH nanoflake-modified electrode. The electrochemical measurement can be realized by chronoamperometry, which showed more sensitive and a lower limit of detection as low as 56.1 ppt. The applicability of this bimodal method was demonstrated by measuring arsenate and total arsenic in different real samples such as natural waters and soil extracted solutions, and the results are of satisfactory accuracy as confirmed by inductively coupled plasma mass spectrometry analysis. The bimodal strategy offers obvious advantages including a label-free step, convenient operation, on-site assay, low cost, and high sensitivity, which is promising for reliable detection of arsenate and total arsenic in environmental samples.
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Noncovalent and multifunctional hybrids have been generated via π–π stacking and electrostatic interactions by combining the nanometer‐scale graphene structure of graphene quantum dots (GQDs) with ...FeIII 5,10,15,20‐tetrakis(1‐methyl‐4‐pyridyl)porphine (FeTMPyP). The inner filter effect (IFE) of FeTMPyP on the GQDs results in substantial PL quenching of the GQDs. The quenched PL of GQDs by the FeTMPyP can be switched back “on” in response to the reaction between FeTMPyP and H2O2, which causes rupture of the cyclic tetrapyrrolic nucleus with consequential loss of iron from FeTMPyP, and then proceeds further to produce colorless dipyrroles and monopyrroles. This “turn on” system can be applied for simple and convenient H2O2 sensing and can be further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) through the oxidation of glucose and formation of H2O2. Because of the inherent synthetic control available for the design of metalloporphyrins, the GQDs‐based optical sensing approach described here has the potential to be highly versatile for other target analytes.
Self‐absorbed: The inner filter effect (IFE) of metalloporphyrins on assembled graphene quantum dots (GQDs) results in substantial photoluminescence (PL) quenching of the GQDs. The quenched PL of GQDs can be switched back “on” in response to the reaction between the metalloporphyrin FeTMPyP and H2O2, which can be applied to H2O2 sensing and further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx).
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