CdBi2S4-Decorated Aminated Polyacrylonitrile Nanofiber for Photocatalytic Treatment of Cr(VI) and Tetracycline Wastewater.

The significant threat posed by the high toxicity of heavy metals and antibiotics in water pollutants has prompted a growing emphasis on the development of highly efficient removal methods for these pollutants. In this paper, flexible electrospinning polyacrylonitrile (PAN) nanofiber-supported CdBi2S4 was synthesized via a hydrothermal method, followed by amination treatment with diethylenetriamine (DETA). The as-prepared CdBi2S4/NH2-PAN nanofiber, enriched with sulfur vacancies, demonstrated outstanding visible-light trapping ability and a suitable band gap, leading to efficient separation and transport of photogenerated carriers, ultimately resulting in exceptional photocatalytic capability. The optimal 3-CdBi2S4/NH2-PAN nanofiber achieved impressive reduction rates of 92.26% for Cr(VI) and 96.45% for tetracycline hydrochloride (TCH) within 120 min, which were much higher than those for CdS/NH2-PAN, Bi2S3/NH2-PAN, and CdBi2S4/PAN nanofibers. After five cycles, the removal rate of the CdBi2S4/NH2-PAN nanofiber consistently remained above 90%. Their ease of separation and recovery from the application environment contributes to their practicality. Additionally, compared with conventional suspended particle catalyzers, the composite nanofiber exhibited remarkable flexibility and self-supporting properties.

Ultrathin LayCoOx Nanosheets with High Porosity Featuring Boosted Catalytic Oxidation of Benzene: Mechanism Elucidation via an Experiment-Theory Combined Paradigm.

Designing transition-metal oxides for catalytically removing the highly toxic benzene holds significance in addressing indoor/outdoor environmental pollution issues. Herein, we successfully synthesized ultrathin LayCoOx nanosheets (thickness of ∼1.8 nm) with high porosity, using a straightforward coprecipitation method. Comprehensive characterization techniques were employed to analyze the synthesized LayCoOx catalysts, revealing their low crystallinity, high surface area, and abundant porosity. Catalytic benzene oxidation tests demonstrated that the La0.029CoOx-300 nanosheet exhibited the most optimal performance. This catalyst enabled complete benzene degradation at a relatively low temperature of 220 °C, even under a high space velocity (SV) of 20,000 h-1, and displayed remarkable durability throughout various catalytic assessments, including SV variations, exposure to water vapor, recycling, and long time-on-stream tests. Characterization analyses confirmed the enhanced interactions between Co and doped La, the presence of abundant adsorbed oxygen, and the extensive exposure of Co3+ species in La0.029CoOx-300 nanosheets. Theoretical calculations further revealed that La doping was beneficial for the formation of oxygen vacancies and the adsorption of more hydroxyl groups. These features strongly promoted the adsorption and activation of oxygen, thereby accelerating the benzene oxidation processes. This work underscores the advantages of doping rare-earth elements into transition-metal oxides as a cost-effective yet efficient strategy for purifying industrial exhausts.

Hydroxyl-Decorated Pt as a Robust Water-Resistant Catalyst for Catalytic Benzene Oxidation.

In catalytic oxidation reactions, the presence of environmental water poses challenges to the performance of Pt catalysts. This study aims to overcome this challenge by introducing hydroxyl groups onto the surface of Pt catalysts using the pyrolysis reduction method. Two silica supports were employed to investigate the impact of hydroxyl groups: SiO2-OH with hydroxyl groups and SiO2-C without hydroxyl groups. Structural characterization confirmed the presence of Pt-Ox, Pt-OHx, and Pt0 species in the Pt/SiO2-OH catalysts, while only Pt-Ox and Pt0 species were observed in the Pt/SiO2-C catalysts. Catalytic performance tests demonstrated the remarkable capacity of the 0.5 wt % Pt/SiO2-OH catalyst, achieving complete conversion of benzene at 160 °C under a high space velocity of 60,000 h-1. Notably, the catalytic oxidation capacity of the Pt/SiO2-OH catalyst remained largely unaffected even in the presence of 10 vol % water vapor. Moreover, the catalyst exhibited exceptional recyclability and stability, maintaining its performance over 16 repeated cycles and a continuous operation time of 70 h. Theoretical calculations revealed that the construction of Pt-OHx sites on the catalyst surface was beneficial for modulating the d-band structure, which in turn enhanced the adsorption and activation of reactants. This finding highlights the efficacy of decorating the Pt surface with hydroxyl groups as an effective strategy for improving the water resistance, catalytic activity, and long-term stability of Pt catalysts.

Anion-π Interaction in a Diketopyrrolopyrrole Derivative.

In this work, an N-substituted diketopyrrolopyrrole (DPP) derivative Ph-DPP was synthesized, showing interaction toward Lewis alkaline anions such as F-. The typical electron-transfer-dominated anion-π interaction product Ph-DPP•- and unexpected isomer product i-Ph-DPP were both observed, and their formation mechanism was studied by density functional theory calculations, suggesting that a deprotonation initiation route is favored, which gives interesting insight for understanding the debatable role of F- in such non-covalent intermolecular interactions.

Self-Doping Naphthalene Diimide Conjugated Polymers for Flexible Unipolar n-Type OTFTs.

The development of high-performance organic thin-film transistor (OTFT) materials is vital for flexible electronics. Numerous OTFTs are so far reported but obtaining high-performance and reliable OTFTs simultaneously for flexible electronics is still challenging. Herein, it is reported that self-doping in conjugated polymer enables high unipolar n-type charge mobility in flexible OTFTs, as well as good operational/ambient stability and bending resistance. New naphthalene diimide (NDI)-conjugated polymers PNDI2T-NM17 and PNDI2T-NM50 with different contents of self-doping groups on their side chains are designed and synthesized. The effects of self-doping on the electronic properties of resulting flexible OTFTs are investigated. The results reveal that the flexible OTFTs based on self-doped PNDI2T-NM17 exhibit unipolar n-type charge-carrier properties and good operational/ambient stability thanks to the appropriate doping level and intermolecular interactions. The charge mobility and on/off ratio are fourfold and four orders of magnitude higher than those of undoped model polymer, respectively. Overall, the proposed self-doping strategy is useful for rationally designing OTFT materials with high semiconducting performance and reliability.

Ultra-Narrowband Near-Infrared Responsive J-Aggregates of Fused Quinoidal Tetracyanoindacenodithiophene.

Narrowband photoresponsive molecules are highly coveted in high-resolution imaging, sensing, and monochromatic photodetection, especially those extending into the near-infrared (NIR) spectral range. Here, a new class of J-aggregating materials based on quinoidal indacenodithiophenes (IDTs) that exhibit an ultra-narrowband (full width half maxima of 22 nm) NIR absorption peak centered at 770 nm is reported. The spectral width is readily tuned by the length of the solubilizing alkyl group, with longer chains resulting in significant spectral narrowing. The J-aggregate behavior is confirmed by a combination of excited state lifetime measurements and single-crystal X-ray diffraction measurements. Their utility as electron-transporting materials is demonstrated in both transistor and phototransistor devices, with the latter demonstrating good response at NIR wavelengths (780 nm) over a range of intensities.

An efficient NiCu@C/Al2O3 catalyst for selective hydrogenation of acetylene.

The development of non-noble metal catalysts for selective hydrogenation still remains a challenge. Herein, NiCu@carbon core-shell nanoparticles supported on Al2O3 (NiCu@C/Al2O3) were prepared, which showed enhanced catalytic performance of acetylene-selective hydrogenation in comparison with NiCu/Al2O3 without carbon encapsulation. In detail, NiCu@C/Al2O3 displayed high ethylene selectivity (>86%) even at an acetylene conversion of 100% and excellent stability (>90 h). Thus, NiCu@C/Al2O3 exhibited great potential as an alternative to Pd-based catalysts for acetylene-selective hydrogenation.

A directly linked COF-like conjugated microporous polymer based on naphthalene diimides for high performance supercapacitors.

In this work, single bond directly linked COF-like conjugated microporous polymer NDTT is constructed via Stille coupling with thiophene-substituted naphthalene diimides and triazine, showing fair crystallinity. NDTT is utilized as an electrode for supercapacitor applications, exhibiting promising performance with excellent capacitance reaching 425.3 F g-1 under a current of 0.2 A g-1.

Room-temperature fabrication of superhydrophobic covalent organic framework (COF) decorated cotton fabric for high-flux water-in-oil emulsion separation.

We report the preparation of a two-dimensional superhydrophobic covalent organic framework (COF)-coated cotton fabric via a rapid one-step method at room temperature. The COF-coated fabric was found to have stable superhydrophobicity and remarkable water-in-oil emulsion separation capacity with ultra-high flux under only gravity.

Stable Zr-UiO-67 constructed through polymeric network assisted post-synthetic modification and its wettability modulation.

Stable Zr-UiO-67 is prepared by introducing a fluorine-containing layer on its surface through a polymeric network assisted post-synthetic modification (PSM) strategy. The stability of the MOFs in acidic, alkaline and saline environments is improved because of the existence of a protective layer. The MOFs are superlyophobic towards liquids with a surface tension threshold of over 48 mN m-1, making them a potential choice for separating various liquid-liquid mixtures and emulsions.

Understanding the air stability of defective MoS2and the oxidation effect on the surface HER activity.

The defective single layer MoS2(SL-MoS2) with high defect concentrations has shown promising electrocatalytic potential, but it is also highly reactive with gas molecules. The study of electro-chemical activity on gas doped defective SL-MoS2is of importance yet still scarcely discussed. Herein, we performed density functional theory calculations to study the adsorption and chemical activity of four major air molecules on the defective SL-MoS2under different defect concentrations, and evaluated the influence on the hydrogen evolution reaction activity. The N2and CO2molecules are in physisorption states, H2O molecule is in molecular chemisorption state, while O2can be strongly captured and dissociated into atomic O*, which repair the S-vacancy and form O-doped structure. Further study showed that compared to the inert S surface of pure MoS2, the O incorporation greatly enhance the surface reactivity. Using H adsorption as the test probe, the adsorption of H becomes stronger with the increasing oxygen concentration. We further unravel the electronic origins underlying the catalytic activity. The lowest unoccupied electronic states are shown to correlate linearly with the activity, and thus can be used as an electronic descriptor to characterize the electrocatalytic activity.

First-principles study of sulfur vacancy concentration effect on the electronic structures and hydrogen evolution reaction of MoS2.

Defect engineering has been widely used in experiments to modulate the electrocatalytic properties of molybdenum disulfide (MoS2). However, the effect of vacancy concentration on the vacancy distribution, electronic properties, and hydrogen evolution reaction (HER) activity remains elusive. Herein, we perform density functional theory (DFT) studies to investigate defective MoS2 with different numbers of sulfur vacancies. In the case of low S-vacancy concentration, the vacancies prefer to agglomerate rather than being dispersed, while at the higher-vacancy concentration, the combination of local point defect and clustered vacancy chain is preferred. The coupling between S-vacancies leads to decreased band gap and increased Mo-H adsorption strength with increasing vacancy concentration. The optimal HER activity is identified to occur below vacancy concentration of 12.50%. Our work provides an atomic-level understanding about the role of S-vacancies in the HER performance of MoS2, and offers useful guidelines for the design of defective MoS2 and other TMDs electrocatalysts.

One-Step Sixfold Cyanation of Benzothiadiazole Acceptor Units for Air-Stable High-Performance n-Type Organic Field-Effect Transistors.

Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3-benzothiadiazole-4,5,6-tricarbonitrile (TCNBT). An n-type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one-step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n-type semiconductor. The electron-deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n-type organic field-effect transistors (OFETs). Solution-processed OFETs based on TCNBT IDT exhibited a charge-carrier mobility of up to µe ≈0.15 cm2 V-1 s-1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.

Microwave-Assisted Solvothermal Synthesis of Covalent Organic Frameworks (COFs) with Stable Superhydrophobicity for Oil/Water Separation.

COFs were synthesized by a microwave-assisted solvothermal route, with the building blocks containing 1,3,5-tris(4-aminophenyl) benzene and 2,3,5,6-tetra-fluoroterephthalaldehyde (or 1,4-phthalaldehyde). The -F groups introduced into the benzene ring promoted hydrophobicity and stability of the COFs. The universality and long effectiveness of oil adsorption can be realized when applying COFs as adsorbent. The powder also exhibited excellent water-in-oil emulsions separation performance, with the separation efficiency no lower than 99.5%. In this work, the use of microwave solvothermal synthesis of superhydrophobic COFs is potential to replace the conventional synthesis process and more suitable for industrial scale-up production. Furthermore, the findings provide a new strategy for solving the problem of oil spill treatment and industrial water-in-oil emulsions separation by using the emerging 2D COFs.

Hard-and-Soft Integration Strategy for Preparation of Exceptionally Stable Zr(Hf)-UiO-66 via Thiol-Ene Click Chemistry.

UiO-66 metal-organic frameworks (MOFs) are unstable in some harsh aqueous environments, which limit their practical applications. We demonstrate a postsynthetic modification methodology to transform hydrophilic Zr(Hf)-UiO-66 into superhydrophobic Zr(Hf)-UiO-66-SH-y (SH = thiol, y = fluoroalkyl) by introducing long fluoroalkyl chains into organic linkers through a thiol-ene click reaction. Water contact angles of the four modified UiO-66 MOFs are all larger than 150°. The grafted low-surface-energy fluorine-containing groups become an effective protective shield for the MOFs, making them exhibit remarkable stability in extreme conditions such as alkaline (pH = 12), saturated HCl, and high concentration of NaCl solution (20 wt %). The Zr-UiO-66 MOFs grafted with 1H,1H,2H-perfluoro-1-hexene have high CO2 adsorption contents of 1.54 and 2.88 mmol·g-1 at 298 and 273 K, respectively. Moreover, the superhydrophobic MOFs also showed potential application in oil/water separation.

Functional-Group Modification of Kraft Lignin for Enhanced Supercapacitors.

Recent efforts to improve the capacitances of Kraft lignin (KL) in supercapacitors have mainly focused on screening KL substrates, which could either compensate the poor conductivity of KL or directly contribute to the capacitance. However, increasing the pseudocapacitance contributed by KL itself, through hydroquinone/quinone redox cycles, remains a challenge, owing to the roughly fixed content of hydroquinone species in natural KL. In this study, the capacitance of KL is greatly improved by using a functional-group modification strategy in which methoxy groups in KL are selectively converted into phenolic hydroxy groups, which facilitate the formation of additional hydroquinone moieties and thus lead to higher pseudocapacitances. The oxidized KL materials show up to 25.6 % enhancement of the phenolic hydroxy content in comparison to raw KL, which results in 21.9 % capacitance improvement from 322 to 390 F g-1 at 0.5 A g-1 in an acidic system.

A novel RNA aptamer-modified riboswitch as chemical sensor.

In this study, a novel label- and immobilization-free RNA aptamer-modified riboswitch-based biosensor was developed by using RNA aptamer modified secondary-structural scaffolds to control the identity of the ribosomal binding sequence (RBS). In the developed sensor, the duplex RNA aptamers-modified cis-repressor sequence is introduced upstream to the RBS of the indicating gene (gfp gene), leading to formatting an RNA bubble due to the none-complementary state of the RNA aptamers in the hairpin structure of the cis-repressor sequence. Without the presence of the target molecule, the ribosome cannot identify the RBS of the indicating gene as the RBS is hidden by the introduced cis-repressor, consequently, the indicating gene in the sensor would not be expressed, demonstrating the absence of the target. On the contrary, with the presence of the target molecule, the binding of aptamer with the target would induce the enlargement of the RNA bubble, leading to the separation of the cis-repressor sequence and RBS. Hence, the indicating gene would be expressed, manifesting the existence of the target. In addition, the developed sensor can quantitatively report the target concentrations by measuring the gfp gene-encoded GFP (green fluorescent protein) concentration. The approach proposed in this study can be used to construct sensors for detecting various chemicals by introducing the corresponding aptamers, therefore, this strategy can potentially provide a new set of analytical tools in the field of analytical chemistry.

Synthesis of Heterocyclic Core-Expanded Bis-Naphthalene Tetracarboxylic Diimides.

A highly reactive bis-naphthalene tetracarboxylic diimide (bis-NDI) intermediate, TBrDNDI, was designed and synthesized for core-expanded NDIs. Based on this intermediate, we achieved 9- and 11-membered core-expanded bis-NDI derivatives. Through expanding the NDI core and introducing electron-donor or electron-acceptor groups, the frontier energy orbitals, optical and electrical properties of these bis-NDIs can be finely tuned to obtain air-stable ambipolar or n-type materials.

Precise Cross-Dimensional Regulation of the Structure of a Photoreversible DNA Nanoswitch.

In this study, an accurately and digitally regulated allosteric nanoswitch based on the conformational control of two DNA hairpins was developed. By switching between UV irradiation and blue light conditions, the second molecular beacon (H#2) would bind/separate with a repression sequence (RES) via the introduced PTG molecules (a photosensitive azobenzene derivative), resulting in the target aptamer sequence in the first molecular beacon (H#1) not being able/being able to hold the stem-loop configuration, hence losing/regaining the ability to bind with the target. Importantly, we successfully monitor conformation changes of the nanoswitch by an elegant mathematical model for connecting Ki (the dissociation constant between RES and H#2) with Kd (the overall equilibrium constant of the nanoswitch binding the target), hence realizing "observing" DNA structure across dimensions from "structural visualization" to digitization and, accurately, digitally regulating DNA structure from digitization to "structural visualization".

Controllable Synthesis of Hierarchical Rose-Like MnCo2O4 Spinel as Lithium-Ion Anode Materials.

Hierarchical rose-like structured MnCo2O4 spinel was synthesized via a facile solvothermal process using polyvinyl pyrrolidone (PVP) as the soft template, which was characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), etc. When evaluated as the anode materials for lithium ion batteries, the as-synthesized MnCo2O4 spinel exhibited excellent cycling performance and rate capacity. The initial discharge and charge capacity reached 1502 mA·h·g-1 and 1131 mA·h·g-1 at the current density of 100 mA·g-1, respectively.