Metal-Organic Framework-Based Composites for the Adsorption Removal of Per- and Polyfluoroalkyl Substances from Water.

The increasing health risks posed by per- and polyfluoroalkyl substances (PFASs) in the environment highlight the importance of implementing effective removal techniques. Conventional wastewater treatment processes are inadequate for removing persistent organic pollutants. Recent studies have increasingly demonstrated that metal-organic frameworks (MOFs) are capable of removing PFASs from water through adsorption techniques. However, there is still constructive discussion on the potential of MOFs in adsorbing and removing PFASs for large-scale engineering applications. This review systematically investigates the use of MOFs as adsorbents for the removal of PFAS in water treatment. This primarily involved a comprehensive analysis of existing literature to understand the adsorption mechanisms of MOFs and to identify factors that enhance their efficiency in removing PFASs. We also explore the critical aspects of regeneration and stability of MOFs, assessing their reusability and long-term performance, which are essential for large-scale water treatment applications. Finally, our study highlights the challenges of removing PFASs using MOFs. Especially, the efficient removal of short-chain PFASs with hydrophilicity is a major challenge, while medium- to long-chain PFASs are frequently susceptible to being captured from water by MOFs through multiple synergistic effects. The ion-exchange force may be the key to solving this difficulty, but its susceptibility to ion interference in water needs to be addressed in practical applications. We hope that this review can provide valuable insights into the effective removal and adsorption mechanisms of PFASs as well as advance the sustainable utilization of MOFs in the field of water treatment, thereby presenting a novel perspective.

Portable smartphone-assisted highly sensitive detection of mercury ions based on gold nanoparticle-modified NH2-UiO-66 metal-organic framework.

A novel portable smartphone-assisted colorimetric method was reported for the determination of Hg2+ with good analytical performance. A Zr(IV)-based metal-organic framework functionalized with amino groups (NH2-UiO-66) has been adopted as a supporting platform to anchor gold nanoparticles (AuNPs), avoiding the migration and aggregation of AuNPs. With the addition of Hg2+, the formation of gold amalgam proved possible to enhance peroxidase-like activity of the composite (AuNPs/NH2-UiO-66), accelerating the oxidization of zymolyte 3,3',5,5'-tetramethylbenzidine (TMB). In the meantime, the color of the reaction solution turned a vivid blue, and the red, green, and blue (RGB) values of the solution color changed accordingly. On account of this strategy, the quantitative detection of Hg2+ could be achieved. After the optimization of the experiment conditions, the average color intensity (Ic) resulting from RGB values was linear related to the concentration of Hg2+ from 10 to 100 nM, accompanied with a detection limit (LOD) down to 5.4 nM calculated by 3σ/S. The successful application of the designed method has been promoted to detect Hg2+ in some water samples, displaying a great potential in practical application. Furthermore, the use of a smartphone made our proposed method simple and accurate, and thus puts forward a possible way for in situ and real-time monitoring.

Two-Site Enhanced Porphyrinic Metal-Organic Framework Nanozymes and Nano-/Bioenzyme Confined Catalysis for Colorimetric/Chemiluminescent Dual-Mode Visual Biosensing.

The rational design of efficient nanozymes and the immobilization of enzymes are of great significance for the construction of high-performance biosensors based on nano-/bioenzyme catalytic systems. Herein, a novel V-TCPP(Fe) metal-organic framework nanozyme with a two-dimensional nanosheet morphology is rationally designed by using V2CTx MXene as a metal source and iron tetrakis(4-carboxyphenyl)porphine (FeTCPP) ligand as an organic linker. It exhibits enhanced peroxidase- and catalase-like activities and luminol-H2O2 chemiluminescent (CL) behavior. Based on the experimental and theoretical results, these excellent enzyme-like activities are derived from the two-site synergistic effect between V nodes and FeTCPP ligands in V-TCPP(Fe). Furthermore, a confined catalytic system is developed by zeolitic imidazole framework (ZIF) coencapsulation of the V-TCPP(Fe) nanozyme and bioenzyme. Using the acetylcholinesterase (AChE) as a model, our constructed V-TCPP(Fe)/AChE@ZIF confined catalytic system was successfully used for the colorimetric/CL dual-mode visual biosensing of organophosphorus pesticides. This work is expected to provide new insights into the design of efficient nanozymes and confined catalytic systems, encouraging applications in catalysis and biosensing.

Simple high-performance liquid chromatography-ultraviolet method for simultaneous separation and detection of 14 bisphenol pollutants in building materials.

A high-performance liquid chromatography-ultraviolet method was developed for rapidly and simultaneously analyzing novel and typical bisphenols in building materials, including bisphenol S, diphenolic acid, bisphenol F, bisphenol E, bisphenol A, bisphenol B, bisphenol AF, bisphenol AP, bisphenol C, bisphenol FL, bisphenol Z, bisphenol BP, bisphenol M, and bisphenol P. By using a Kromasil 100-5 C18 column, these bisphenols were completely separated in 40 min via gradually increasing the concentration of methanol in the mobile phase from 45 to 80% during the elution process. In particular, this method achieved the synchronous analysis of bisphenol S, diphenolic acid, bisphenol FL, bisphenol BP, and bisphenol M through HPLC, which were difficult to separate and had to be identified and detected through mass spectrometry. The limits of detection of the method ranged from 0.002 to 0.040 mg/L for these 14 bisphenols, with a precision of less than 4.9% (n = 7, c = 0.05 mg/L). The analytical results for five types of building materials (phenolic, epoxy, polycarbonate, polyester, and polysulfone resins) indicated that the proposed method is appropriated for the rapid measurement of bisphenols in real samples.

Cationic metal-organic frameworks as an efficient adsorbent for the removal of 2,4-dichlorophenoxyacetic acid from aqueous solutions.

Metal-organic frameworks (MOFs) material with high surface area, good chemical stability and multi-functionality, has become an emerging adsorbent for water treatment. A novel kind of quaternary amine anionic-exchange MOFs UiO-66 namely UiO-66-NMe3+ was firstly synthesized for adsorptive removal of a widely used toxic herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions. The well-prepared UiO-66-NMe3+ MOFs were fully characterized, and then the main parameters affecting the adsorption process including solution pH, adsorbent dosage and coexisting anions were systematically investigated. The maximum adsorption capacity of UiO-66-NMe3+ toward 2,4-D reached as high as 279 mg g-1, much higher than that of pristine UiO-66 and aminated UiO-66. The adsorption mechanism could be attributed to the electrostatic interactions efficiently enhanced by the functionalization of quaternary amine groups, combining with the π-π conjugations between the linkers in MOFs and 2,4-D molecules, leading to the better adsorption performance of UiO-66-NMe3+. Additionally, the UiO-66-NMe3+ could be well regenerated by simple solvent washing and exhibited a slight decline of adsorption capacity after seven successive recycle. Furthermore, satisfactory adsorption capacity and reusability of the MOFs in environmental water samples were attained. Comparing with reported activated carbon and resin materials, the UiO-66-NMe3+ MOFs possessed higher adsorption capacity and shorter equilibrium time, as well as good reusability and practicality. The developed ion-exchange functionalized MOFs provided an ideal alternative for efficient adsorptive-removal of 2,4-D from complicated aqueous environment.

Speciation analysis of mercury by dispersive solid-phase extraction coupled with capillary electrophoresis.

A pretreatment method of dispersive solid-phase extraction (DSPE) along with back-extraction followed by CE-UV detector was developed for the determination of mercury species in water samples. Sulfhydryl-functionalized SiO2 microspheres (SiO2 -SH) were synthesized and used as DSPE adsorbents for selective extraction and enrichment of three organic mercury species namely ethylmercury (EtHg), methylmercury (MeHg), and phenylmercury (PhHg), along with L-cysteine (L-cys) containing hydrochloric acid as back-extraction solvent. Several main extraction parameters were systematically investigated including sample pH, amount of adsorbent, extraction and back-extraction time, volume of eluent, and concentration of hydrochloric acid. Under optimal conditions, good linearity was achieved with correlation coefficients over 0.9990, in the range of 4-200 µg/L for EtHg, and 2-200 µg/L for MeHg and PhHg. The LODs were obtained of 1.07, 0.34, and 0.24 µg/L for EtHg, MeHg, and PhHg, respectively, as well as the LOQs were 3.57, 1.13, and 0.79 µg/L, respectively, with enrichment factors ranging from 109 to 184. Recoveries were attained with tap and lake water samples in a range of 62.3-107.2%, with relative standard deviations of 3.5-10.1%. The results proved that the method of SiO2 -SH based DSPE coupled with CE-UV was a simple, rapid, cost-effective, and eco-friendly alternative for the determination of mercury species in water samples.

Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines.

Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and ß-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.

Speciation analysis of mercury in water samples by dispersive liquid-liquid microextraction coupled to capillary electrophoresis.

In this study, a method of pretreatment and speciation analysis of mercury by dispersive liquid-liquid microextraction along with CE was developed. The method was based on the fact that mercury species including methylmercury (MeHg), ethylmercury (EtHg), phenylmercury (PhHg), and Hg(II) were complexed with 1-(2-pyridylazo)-2-naphthol to form hydrophobic chelates and l-cysteine could displace 1-(2-pyridylazo)-2-naphthol to form hydrophilic chelates with the four mercury species. Factors affecting complex formation and extraction efficiency, such as pH value, type, and volume of extractive solvent and disperser solvent, concentration of the chelating agent, ultrasonic time, and buffer solution were investigated. Under the optimal conditions, the enrichment factors were 102, 118, 547, and 46, and the LODs were 1.79, 1.62, 0.23, and 1.50 µg/L for MeHg, EtHg, PhHg, and Hg(II), respectively. Method precisions (RSD, n = 5) were in the range of 0.29-0.54% for migration time, and 3.08-7.80% for peak area. Satisfactory recoveries ranging from 82.38 to 98.76% were obtained with seawater, lake, and tap water samples spiked at three concentration levels, respectively, with RSD (n = 5) of 1.98-7.18%. This method was demonstrated to be simple, convenient, rapid, cost-effective, and environmentally benign, and could be used as an ideal alternative to existing methods for analyzing trace residues of mercury species in water samples.

Alkaline Modified Mesoporous Silica Supported Ruthenium Catalyst for Improved α-Amino Acid Synthesis.

Amino acids are a class of compounds with wide-ranging applications. The synthesis of amino acids from biomass-derived α-keto acids and ammonia is a sustainable way but the unstable primary imine intermediates (R-C=NH) easily form oligomers. Herein, targeting this problem, alkaline modified mesoporous silica was employed as a support for ruthenium (Ru/M-MCM-41), which could be used as a bifunctional catalyst in the reductive amination of α-keto acids to synthesize α-amino acids. The incorporation of Sr improved the dispersion of Ru nanoparticles and enhanced metal-support interactions via electron transfer from Sr to Ru, and the active Ru sites could efficiently hydrogenate primary imine intermediates to α-amino acids, thus prohibiting the formation of oligomers. Moreover, the Sr-dopant introduces base sites that could catalyze the hydrolysis of oligomers back to primary imine intermediates and finally hydrogenated to α-amino acids. As a result, >99 % yield of glycine was achieved from glyoxylic acid over Ru/Sr-MCM-41, which is nearly three times that achieved over Ru/MCM-41 (32.2 %).

Organic conjugated polymer nanoparticles enhanced tyrosinase electrochemical biosensor for selective, sensitive and rapid detection of bisphenol A.

Bisphenol A (BPA) has been widely used in the production of polycarbonate (PC) plastics, flame retardants and epoxy resins, which is one of the most important endocrine disrupting chemicals and can cause damage to the estrogen system of human. In this work, organic conjugated polymer nanoparticles (CPNPs) were synthesized through nanoprecipitation method using liposome 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy (polyethylene glycol)-2000] (DSPE-mPEG2000) coated poly[(4,4'-bis(2-ethylhexyl)-dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-4,7-di(4-hexyl-2-thienyl)-5,6-difluoro-2,1,3-benzothiadiazole] (PDTS-hDTBT) and poly[(4,4'-bis(2-ethylhexyl)-dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-4,7-di(4-(2-ethylhexyl)-2-thienyl)-5,6-difluoro-2,1,3-benzothiadiazole] (PDTS-ehDTBT). These two polymers have different side chains, which can affect the configuration of the polymers, thereby affecting the π-π interaction between BPA and CPNPs. The resultant two CPNPs were explored as extremely attractive matrix for tyrosinase immobilization to construct electrochemical biosensing platforms for sensitive and rapid detection of BPA in water environments. The electrochemical performance of these two biosensors was significantly enhanced, benefiting from the large specific surface area and excellent biocompatibility of CPNPs, as well as the strong π-π interaction between CPNPs and BPA. The current response of PDTS-ehDTBT-Tyr-Chi/GCE exhibited a good linear relationship with BPA concentration ranging from 0.02 to 3.0 µM with a low detection limit of 11.83 nM and a high sensitivity of 0.9724 µA µM-1 cm-2. The fabricated biosensor was further used for BPA detection in actual samples with a recovery rate of 92.0 %-99.4 %. With the remarkable advantages, CPNPs-based biosensor provides a highly sensitive detection tool for rapid detection of BPA in actual samples, which has broad application prospects.

[Determination of three dechloranes in environmental water by magnetic solid-phase extraction-gas chromatography-negative chemical ionization mass spectrometry based on the covalent organic framework material].

Dechloranes are additive-type chlorine flame retardants that are widely used in processing industrial products, such as electronic equipment and textiles. Dechloranes, which can enter the human body through various routes, pose significant health risks because of their toxicity, persistence, and bioaccumulation. In 2023, dechlorane plus was listed in the Stockholm Convention on Persistent Organic Pollutants. In the same year, China recognized this compound as a priority-controlled substance. Dechloranes are commonly found at trace levels in water, which is extremely harmful to the environment and human health. Therefore, the development of detection methods for dechloranes is crucial. Magnetic solid-phase extraction (MSPE) has attracted considerable attention because of its low organic solvent consumption, simplicity of adsorbent separation, and ease of operation. In general, the selectivity and efficiency of MSPE depend on the characteristics of the adsorbent. Covalent organic frameworks (COFs) have regular porosity, structural predictability and stability, high specific surface areas, and adjustable pore sizes, which are advantageous for a wide range of separation and analysis applications. In this study, Fe3O4 magnetic nanoparticles and a COF material (TpBD) were combined to prepare Fe3O4@TpBD as an adsorbent for dechloranes. Subsequently, an effective method for analyzing dechlorane in environmental water was established by coupling MSPE with gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The successful synthesis of Fe3O4@TpBD was confirmed using transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and vibrating sample magnetometry. A single-factor method was used to optimize the extraction conditions, including the Fe3O4@TpBD dosage, pH of water sample, elution solvent type and volume, extraction time, elution time, and ionic strength. The target analytes were separated on a TG-5SILMS column (30 m×0.25 mm×0.25 µm) and quantified using the external standard method in the selected-ion monitoring (SIM) mode. Under the optimal extraction conditions, the method validation results showed a linear range of 2-1000 ng/L. The limits of detection (LODs) and quantification (LOQs) were 0.18-0.27 ng/L and 0.60-0.92 ng/L, respectively, for the three analytes. The intra-day and inter-day precisions at three spiked levels were 4.2%-16.2% and 6.9%-15.7%, respectively. This method was successfully applied to the determination of dechloranes in environmental water samples (laboratory tap water, reservoir water, wastewater treatment plant effluent, and landfill leachate treatment effluent). The recoveries of the three dechloranes at different spiked levels ranged from 77.8% to 113.3% with relative standard deviations (RSDs) of 2.5%-16.3% (n=3). With the advantages of operational simplicity, high sensitivity, and good reproducibility, the proposed method is suitable for the qualitative and quantitative determination of dechloranes in environmental water.

Spark plasma sintered porous Ni as a novel substrate of Ni3Se2@Ni self-supporting electrode for ultra-durable hydrogen evolution reaction.

Developing efficient and durable self-supporting catalytic electrodes is an important way for industrial applications of hydrogen evolution reaction. Currently, commercial nickel foam (NF)-based electrode has been widely used due to its good catalytic performance. However, the NF consisting of smooth skeleton surface and large pores not only exhibits poor conductivity but also provides insufficient space for catalyst decoration and sufficient adhesion, resulting in inadequate catalytic performance and poor durability of NF-based electrodes. In this paper, a novel three-dimensional porous Ni substrate with multangular skeleton surface and small pore structure was prepared by a modified spark plasma sintering technique, and subsequently Ni3Se2@Porous Ni electrode with a large number of Ni3Se2 nanosheets uniformly distributed on the surface was obtained by one-step in-situ selenization. The electrode exhibits outstanding conductivity and catalytic hydrogen evolution reaction, providing a low overpotential of 183 mV at a current density of 100 mA cm-2. Due to the strong interfacial bonding between Ni and Ni3Se2, the Ni3Se2@Porous Ni electrode shows strong durability, which can work stably at 85 mA cm-2 for more than 200 h. This work provides an effective strategy for the rational preparation of metal substrates for efficient and durable self-supporting catalytic electrodes.

[Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials].

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 µg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 µg/L and 0.03-0.42 µg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 µg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

Molecularly imprinted polymers and porous organic frameworks based analytical methods for disinfection by-products in water and wastewater.

Disinfection by-products (DBPs) with heritage toxicity, mutagenicity and carcinogenicity are one kind of important new pollutants, and their detection and removal in water and wastewater has become a common challenge facing mankind. Advanced functional materials with ideal selectivity, adsorption capacity and regeneration capacity provide hope for the determination of DBPs with low concentration levels and inherent molecular structural similarity. Among them, molecularly imprinted polymers (MIPs) are favored, owing to their predictable structure, specific recognition and wide applicability. Also, metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) with unique pore structure, large specific surface area and easy functionalization, attract increasing interest. Herein, we review recent advances in analytical methods based on the above-mentioned three functional materials for DBPs in water and wastewater. Firstly, MIPs, MOFs and COFs are briefly introduced. Secondly, MIPs, MOFs and COFs as extractants, recognition element and adsorbents, are comprehensively discussed. Combining the latest research progress of solid-phase extraction (SPE), sensor, adsorption and nanofiltration, typical examples on MIPs and MOFs/COFs based analytical and removal applications in water and wastewater are summarized. Finally, the application prospects and challenges of the three functional materials in DBPs analysis are proposed to promote the development of corresponding analytical methods.

A violet light-emitting diode-based gas-phase molecular absorption device for measurement of nitrate and nitrite in environmental water.

A simple and sensitive device for the detection of nitrite and nitrate in environmental waters was developed based on visible light gas-phase molecular absorption spectrometry. By integrating a detection cell (DC), semiconductor refrigeration temperature-controlling system (SRTCY), and nitrite reactor into a sequential injection analysis system, trace levels of nitrite and nitrate in complex matrices were successfully measured. A low energy-consuming light-emitting diode (violet, 400-405 nm) was coupled with a visible light-to-voltage converter (TSL257) to measure the gas-phase molecular absorption. To reduce the interference of water vapor, an SRTCY was used to condense the water vapor on-line before the gas-phase analyte entered the DC. The DC was radiatively heated by the SRTCY to avoid water vapor condensation in the light path. As a result, the obtained baseline noise reduced 3.75 times than that of without SRTCY. Under the optimized conditions, the device achieved limits of detection (3σ/k) of 0.055 and 0.36 mmol/L (0.77 and 5.04 mg N/L) for nitrite and nitrate, respectively, and the linear calibration ranges were 0.1-15 mmol/L (R2 = 0.9946) and 1-10 mmol/L (R2 = 0.9995), respectively. Precisions of 5.2 % and 9.0 % were achieved for ten successive determinations of 0.3 mmol/L nitrite and 1.0 mmol/L nitrate, and the analytical times for nitrite and nitrate determination were 5 and 13 min, respectively. This method was validated against standard methods and recovery tests, and it was applied to the measurement of nitrite and nitrate in environmental waters. Moreover, a device was designed to enable the field measurement of nitrite and nitrate in complex matrices.

One-step Sintering Synthesis of Ni3 Se2 -Ni Electrode with Robust Interfacial Bonding for Ultra-stable Hydrogen Evolution Reaction.

Exploring efficient and robust self-supporting hydrogen evolution reaction (HER) electrodes using simple, accessible, and low-cost synthetic processes is crucial for the commercial application of water electrolysis at high current densities. Ni-based self-supporting electrodes are widely studied owing to their low cost and good catalytic performance. However, to date, the preparation of Ni-based electrodes requires multistep and complex preparation processes. In this study, a novel one-step in situ sintering method to synthesize mechanically stable and highly active Ni3 Se2 -Ni electrodes with well-controlled morphologies and structures is developed. Their excellent performance and durability can be attributed to the numerous highly active nano-Ni3 Se2 catalysts embedded on the surface of the Ni skeleton, the excellent conductivity of the interconnected conductive network, and the strong interfacial bonding between Ni3 Se2 and Ni. As a result, the Ni3 Se2 -Ni600 electrode can operate stably at 85 and 400 mA cm-2 for more than 800 and 300 h, respectively. Moreover, the Ni3 Se2 -Ni600 electrode displays outstanding stability for over 500 h in a commercial two-electrode system. This study provides a feasible one-step synthesis method for low-cost, high-efficiency metal selenide-metal self-supporting electrodes for water electrolysis.

Color components determination and full-length comparative transcriptomic analyses reveal the potential mechanism of carotenoid synthesis during Paphiopedilum armeniacum flowering.

Background: Paphiopedilum armeniacum (P. armeniacum), an ornamental plant native to China, is known for its distinctive yellow blossoms. However, the mechanisms underlying P. armeniacum flower coloration remain unclear. Methods: We selected P. armeniacum samples from different flowering stages and conducted rigorous physicochemical analyses. The specimens were differentiated based on their chemical properties, specifically their solubilities in polar solvents. This key step enabled us to identify the main metabolite of flower color development of P. armeniacum, and to complete the identification by High-performance liquid chromatography (HPLC) based on the results. Additionally, we employed a combined approach, integrating both third-generation full-length transcriptome sequencing and second-generation high-throughput transcriptome sequencing, to comprehensively explore the molecular components involved. Results: We combined physical and chemical analysis with transcriptome sequencing to reveal that carotenoid is the main pigment of P. armeniacum flower color. Extraction colorimetric method and HPLC were used to explore the characteristics of carotenoid accumulation during flowering. We identified 28 differentially expressed carotenoid biosynthesis genes throughout the flowering process, validated their expression through fluorescence quantification, and discovered 19 potential positive regulators involved in carotenoid synthesis. Among these candidates, three RCP2 genes showed a strong potential for governing the PDS and ZDS gene families. In summary, our study elucidates the fundamental mechanisms governing carotenoid synthesis during P. armeniacum flowering, enhancing our understanding of this process and providing a foundation for future research on the molecular mechanisms driving P. armeniacum flowering.

Dual cloud point extraction coupled with hydrodynamic-electrokinetic two-step injection followed by micellar electrokinetic chromatography for simultaneous determination of trace phenolic estrogens in water samples.

A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic-electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE-two-step injection-MEKC conditions, detection limits of 7.9-8.9 ng/mL and good linearity in the range from 0.05 to 5 µg/mL with correlation coefficients R(2) ≥ 0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108% were obtained with lake and tap water spiked at 0.1 and 0.5 µg/mL, respectively, with relative standard deviations (n = 6) of 1.3-3.1%. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples.

Colorimetric detection of heavy metal ions with various chromogenic materials: Strategies and applications.

Detection of heavy metal ions has drawn significant attention in environmental and food area due to their threats to the human health and ecosystem. Colorimetry is one of the most frequently-used methods for the detection of heavy metal ions owing to its simplicity, easy operation and rapid on-site detection. The development of chromogenic materials and their sensing mechanisms are the key research direction in the area of colorimetric method. Since each chromogenic material has their unique optical and chemical properties, they have totally different colorimetric sensing mechanisms. This review focuses on the chromogenic materials and their sensing strategies for the colorimetric detection of heavy metal ions. We divide the chromogenic materials into three types, including organic materials, inorganic materials, and other materials. As for each type of chromogenic material, we discuss their detailed sensing strategies, sensing performance, and real sample applications. Moreover, current challenges and perspectives related to the colorimetry of heavy metal ions are also discussed in this review. The aim of this review is to help readers to better understand the principles of colorimetric methods for heavy metal ions and push the development of rapid detection of heavy metal ions.

A Rational Design of a CoS2-CoSe2 Heterostructure for the Catalytic Conversion of Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur batteries are anticipated to be the next generation of energy storage devices because of their high theoretical specific capacity. However, the polysulfide shuttle effect of lithium-sulfur batteries restricts their commercial application. The fundamental reason for this is the sluggish reaction kinetics between polysulfide and lithium sulfide, which causes soluble polysulfide to dissolve into the electrolyte, leading to a shuttle effect and a difficult conversion reaction. Catalytic conversion is considered to be a promising strategy to alleviate the shuttle effect. In this paper, a CoS2-CoSe2 heterostructure with high conductivity and catalytic performance was prepared by in situ sulfurization of CoSe2 nanoribbon. By optimizing the coordination environment and electronic structure of Co, a highly efficient CoS2-CoSe2 catalyst was obtained, to promote the conversion of lithium polysulfides to lithium sulfide. By using the modified separator with CoS2-CoSe2 and graphene, the battery exhibited excellent rate and cycle performance. The capacity remained at 721 mAh g-1 after 350 cycles, at a current density of 0.5 C. This work provides an effective strategy to enhance the catalytic performance of two-dimensional transition-metal selenides by heterostructure engineering.