Fluorescence Sensing Properties of a Bibranched Cyanostilbene Derivative Containing -NH2 for Trace Water and Picric Acid Determination.

In order to design organic small molecule fluorescent materials with multiple sensing, a bibranched -NH2 modified cyanostilbene derivative (AM) was synthesized. It exhibits solvent and aggregation-induced emission effects, with a solid-state quantum yield of 28%, which is seven times higher than that in THF. The synthesized sample AM demonstrated high sensitivity to trace water via a fluorescence "turn-off" response, achieving a low detection limit of 0.41 µM in THF and 0.80 µM in EtOH. AM also exhibits a "turn-off" response to picric acid, attributed to the photo-induced electron transfer effect it induces. The recognition of picric acid by AM demonstrates specificity and resistance to interference from nitro explosives, with a detection limit of 300 ppb and a linear relationship (R2 = 0.9981) at the range of 0-4 equivalents AM. Such acid recognition can facilitate the design of qualitative test papers and safety inks. Additionally, AM can function as a temperature sensor with a linear relationship (R2 = 0.9976) within the temperature range of 25-110 °C. Leveraging these unique characteristics, a series of methods were proposed for the direct quantitative determination of trace water in nonaqueous solvents, picric acid, and temperature.

Speciation Characterization and Environmental Stability of Arsenic in Arsenic-Containing Copper Slag Tailing.

The increasing presence of arsenic-containing impurities within Cu ores can adversely affect the smelting process and aggravate the environmental impact of slag tailing. This study investigates the geochemical, mineralogical, and chemical speciation characteristics to better understand the association and environmental stability of metal(loid)s in copper slag tailing. The results indicate that the predominant chemical compositions of the selected slag tailing are Fe2O3 (54.8%) and SiO2 (28.1%). These tailings exhibit potential for multi-elemental contamination due to elevated concentrations of environmentally sensitive elements. Mineral phases identified within the slag tailings include silicate (fayalite), oxides (magnetite and hematite), and sulfides (galena, sphalerite, arsenopyrite, and chalcopyrite). The consistent presence of silicate, iron, arsenic, and oxygen in the elemental distribution suggests the existence of arsenic within silicate minerals in the form of Si-Fe-As-O phases. Additionally, arsenic shows association with sulfide minerals and oxides. The percentages of arsenite (As(III)) and arsenate (As(V)) within the selected slag tailings are 59.4% and 40.6%, respectively. While the slag tailings are deemed non-hazardous due to the minimal amounts of toxic elements in leachates, proper disposal measures should be taken due to the elevated carbonate-bound levels of As and Cu present in these tailings.

Chemical Speciation, Leaching Behavior, and Environmental Risk Assessment of Trace Elements in the Bottom Ash from Biomass Power Plant.

Biomass combustion for power generation stands as a pivotal method in energy utilization, offering a promising approach for renewable energy utilization. However, the substantial volume of slag produced by biomass burning plants poses environmental challenges, impeding sustainable energy practices. This article systematically studies the characteristics of ash generated from typical biomass direct combustion power plant ash and analyzes the chemical composition, trace element content characteristics, leaching characteristics, and chemical forms of biomass bottom ash. Furthermore, it assesses the environmental ecology and bioavailability of trace elements in bottom ash using the ecological risk assessment method and RAC method. The results demonstrate that the biomass bottom ash contains plant nutrients, such as K, Ca, Mg, and P, while the content of harmful trace elements is lower than the relevant Chinese standards. In dissolution experiments, the leaching rate of nearly all elements remains exceptionally low, primarily due to the distribution of trace elements within the lattice structure of stable minerals. Trace elements predominantly exist in the residual phase, Cu and Zn primarily found in organic compounds and sulfide bound states, while other elements mostly exist in the form of iron manganese oxide bound states. Ecological risk assessment indicates a significant risk level for Cd, contrasting with the slight risk associated with other elements. RAC results indicated no ecological risk of all of the trace elements. Consequently, the utilization of bottom ash in agricultural and forestry soils is deemed to be viable. These findings serve as a crucial foundation for biomass bottom ash resource utilization and underpin the sustainable utilization of biomass energy.

Development of SDS-Modified PbO2 Anode Material Based on Ti3+ Self-Doping Black TiO2NTs Substrate as a Conductive Interlayer for Enhanced Electrocatalytic Oxidation of Methylene Blue.

Efficient and stable electrode materials are urgently required for wastewater treatment in the electrocatalytic degradation of toxic and refractory organic pollutants. Ti3+ self-doping black TiO2 nanotube arrays (Ti/B-TiO2-NTs) as an interlayer were used for preparing a novel PbO2 electrode via an electrochemical reduction technology, and a sodium dodecyl sulfate (SDS)-modified PbO2 catalytic layer was successfully achieved via an electrochemical deposition technology. The physicochemical characterization tests showed that the Ti/B-TiO2-NTs/PbO2-SDS electrodes have a denser surface and finer grain size with the introduction of Ti3+ in the interlayer of Ti/TiO2-NTs and the addition of SDS in the active layer of PbO2. The electrochemical characterization results showed that the Ti3+ self-doping black Ti/TiO2-NTs/PbO2-SDS electrode had higher oxygen evolution potential (2.11 V vs. SCE), higher electrode stability, smaller charge-transfer resistance (6.74 Ω cm-2), and higher hydroxyl radical production activity, leading to it possessing better electrocatalytic properties. The above results indicated that the physicochemical and electrochemical characterization of the PbO2 electrode were all enhanced significantly with the introduction of Ti3+ and SDS. Furthermore, the Ti/B-TiO2-NTs/PbO2-SDS electrodes displayed the best performance on the degradation of methylene blue (MB) in simulated wastewater via bulk electrolysis. The removal efficiency of MB and the chemical oxygen demand (COD) could reach about 99.7% and 80.6% under the optimal conditions after 120 min, respectively. The pseudo-first-order kinetic constant of the Ti/B-TiO2-NTs/PbO2-SDS electrode was 0.03956 min-1, which was approximately 3.18 times faster than that of the Ti/TiO2-NTs/PbO2 electrode (0.01254 min-1). In addition, the Ti/B-TiO2-NTs/PbO2-SDS electrodes showed excellent stability and reusability. The degradation mechanism of MB was explored via the experimental identification of intermediates. In summary, the Ti3+ self-doping black Ti/TiO2-NTs/PbO2-SDS electrode is a promising electrode in treating wastewater.

Synthesis of Ag3PO4/Ag/g-C3N4 Composite for Enhanced Photocatalytic Degradation of Methyl Orange.

In this study, we have successfully constructed Ag3PO4/Ag/g-C3N4 heterojunctions via the hydrothermal method, which displays a wide photo-absorption range. The higher photocurrent intensity of Ag3PO4/Ag/g-C3N4 indicates that the separation efficiency of the photogenerated electron-hole pairs is higher than that of both Ag3PO4 and Ag/g-C3N4 pure substances. It is confirmed that the efficient separation of photogenerated electron-hole pairs is attributed to the heterojunction of the material. Under visible light irradiation, Ag3PO4/Ag/g-C3N4-1.6 can remove MO (~90%) at a higher rate than Ag3PO4 or Ag/g-C3N4. Its degradation rate is 0.04126 min-1, which is 4.23 and 6.53 times that of Ag/g-C3N4 and Ag3PO4, respectively. After five cycles of testing, the Ag3PO4/Ag/g-C3N4 photocatalyst still maintained high photocatalytic activity. The excellent photocatalysis of Ag3PO4/Ag/g-C3N4-1.6 under ultraviolet-visible light is due to the efficient separation of photogenerated carriers brought about by the construction of the Ag3PO4/Ag/g-C3N4 heterostructure. Additionally, Ag3PO4/Ag/g-C3N4 specimens can be easily recycled with high stability. The effects of hydroxyl and superoxide radicals on the degradation process of organic compounds were studied using electron paramagnetic resonance spectroscopy and radical quenching experiments. Therefore, the Ag3PO4/Ag/g-C3N4 composite can be used as an efficient and recyclable UV-vis spectrum-driven photocatalyst for the purification of organic pollutants.

High Sensitivity Electrochemical As (III) Sensor Based on Fe3O4/MoS2 Nanocomposites.

Currently, heavy metal ion pollution in water is becoming more and more common, especially As (III), which is a serious threat to human health. In this experiment, a glassy carbon electrode modified with Fe3O4/MoS2 nanocomposites was used to select the square wave voltammetry (SWV) electrochemical detection method for the detection of trace As (III) in water. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) showed that Fe3O4 nanoparticles were uniformly attached to the surface of MoS2 and were not easily agglomerated. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) showed that Fe3O4/MoS2 has higher sensitivity and conductivity. After optimizing the experimental conditions, the Fe3O4/MoS2-modified glassy carbon electrode exhibited high sensitivity (3.67 µA/ppb) and a low detection limit (0.70 ppb), as well as excellent interference resistance and stability for As (III).

Chemical speciation and bioavailability of potentially toxic elements in surface sediment from the Huaihe River, Anhui Province, China.

In order to understand the characteristics of speciation and ecological risk of potentially toxic element (PTE) pollution in the surface sediment of huaihe river (Anhui province), 23 surface sediment samples were collected. The occurrence characteristics of PTEs (As, Cr, Zn, Cu, Cd, Pb, Mn) were analyzed by modified continuous extraction method (BCR), and the pollution status and potential ecological risk of PTEs were comprehensively evaluated by Pollution Load Index (PLI), Geoaccumulation Index (Igeo), Enrichment Factor (EF) and the risk assessment code (RAC). Results showed that the total concentrations of As, Mn, Cd, Cr, Cu, Pb, and Zn in sediment were 14.98 ± 2.32, 936.02 ± 144.48, 0.32 ± 0.08, 161.73 ± 124.83, 40.44 ± 9.67, 15.46 ± 6.67, and 74.85 ± 26.43 mg/kg, respectively. The mean concentrations of PTEs with the increasing order of Zn < Mn < Cr < Pb < Cu < As < Cd. Most PTEs appeared to mainly associate with a dominant proportion of residual fraction suggesting lower mobility whereas Cd and Mn presented a relative higher exchangeable fraction indicating a great degree of bioavailability and easily ingested by aquatic organism. Results of pollution degree showed that 3 sampling sites belong to the pollution degree of strong pollution, and the other sampling sites belonged to the medium pollution level. The indexes EF revealed moderately enrichment of Cr, minor enrichment of Cd, Mn and As, no enrichment of Cu, Zn and Pb. The values of the Igeo and RAC demonstrated that Cd and Mn pose a high ecological risk, which deserves further attention.

Adsorption properties of pyramidal superatomic molecules based on the structural framework of the Au20 cluster.

The pyramidal Au20 cluster is a highly inert and stable superatomic molecule, but it is not suitable as a potential catalyst for covalent bond activations, e.g., CO oxidation reaction. Herein, the adsorption and electronic properties of CO molecules on various pyramidal clusters based on the structural framework of Au20 are investigated using density functional theory. According to the SVB model, we constructed isoelectronic superatomic molecules with different pyramid configurations by replacing the vertex atoms of the Au20 using metal M atoms (M = Li, Be, Ni, Cu, and Zn group atoms). After the CO molecules are adsorbed on the vertex atoms of these metal clusters, we analyzed the CO adsorption energies, C-O bond stretching frequencies, and electronic properties of the adsorption structures. It was found that the adsorption of CO molecules results in minimal changes in the parent geometries of the pyramidal clusters, and most adsorption structures are consistent with the geometry of CO adsorption at the vertex site of the Au20 cluster. There are significant red shifts when CO molecules are adsorbed on the Ni/Pd/Pt atoms of the clusters, and their CO adsorption energies were also greater. The molecular orbitals and density of states reveal that there are overlaps between the frontier orbitals of the clusters and CO, and the electronic structure of NiAu19- is not sensitive to CO. The ETS-NOCV analysis shows that the increase in the density of the bonding area caused by the orbital interactions between the fragments is higher than the decrease in the density of the bonding area caused by Pauli repulsion, presenting that the direction of charge flow in the deformation density is from CO → clusters. From energy decomposition analysis (EDA) and NPA charge, we find a predominant covalent nature of the contributions in CO⋯M interactions (σ-donation). Our study indicates that the SVB model provides a new direction to expand the superatomic catalysts from the superatom clusters, which also provides inference for the extension of the single atom catalysis.

Speciation Characteristics and Ecological Risk Assessment of Heavy Metals in Municipal Sludge of Huainan, China.

In order to fully understand the morphological characteristics and pollution status of heavy metals in the dewatered sludge of Huainan Municipal sewage treatment plant, the physical and chemical properties were analyzed, and the content and occurrence forms of heavy metals (As, Cu, Zn, Pb, Cd, Cr, and Ni) in the sludge were studied using the geological accumulation method (Igeo), risk assessment coding method (RAC), and potential ecological risk index method to evaluate the ecological risk. The results showed that the municipal sludge in Huainan was rich in nutrients, with good prospects for agricultural utilization. There were differences in the morphological distributions of different heavy metals. The Igeo values for Ni, As, Cr, and Pb were below 0. The results of RAC indicated that the risk level of Cr in sludge was a low risk, and those of other heavy metals were moderate risks. The potential ecological risk of Cd had the highest potential ecological risk, and the other six metals were of low ecological risk. This conclusion can provide basic data and a theoretical reference for the comprehensive utilization of sludge in sewage treatment plants.

Spatial distribution and potential health risk of fluoride in drinking groundwater sources of Huaibei, Anhui Province.

Fluoride enrichment in drinking groundwater at Huaibei leads to potential health risk to the residents. A total of 49 groundwater samples from groundwater sources were collected to evaluate the potential health risk of fluoride ingestion through drinking water for children and adults in Huaibei. Results shown that the average concentration of fluoride in centralized sources is less than that of decentralized sources, which may be attributed to different geological conditions including fluoride-rich minerals, environmental conditions and high fluoride waste discharge. The corresponding health risk value of fluoride in centralized source is lower than that in decentralized one, and the HI values of fluoride in the three exposed groups varied in the same order: infants > children > adults. Infants and children were more sensitive receptors to the non-carcinogenic health hazards of fluoride than adults. Special care should be taken to infants and children for the highly prone to health risk compared to adults.

Superatomic and adsorption properties of Ni atom doped Au clusters.

Due to their strong relativistic effects, Au clusters exhibit many unusual geometric structures. Among them, Au7-, Au8 and Au9+ have 18 valence electrons satisfying the magic numbers in the jellium model, respectively, but these three non-spherical clusters are not superatoms. In general, a single dopant atom can drastically change the structural and electronic properties of Au clusters. Here, we searched structures of NiAu7-, NiAu8 and NiAu9+ clusters using the genetic algorithm program (GA) combined with density functional theory (DFT). It was found that the alloy clusters are all 3D spherical structures. The molecular orbitals and density of states analysis indicate that they have completely filled superatomic shells (1S21P6), in which the electronic structure of the Ni atom is d10. Then, the electrostatic potential surfaces of the alloy clusters are analyzed, and the calculated results show that the NiAu8 superatom has remarkable σ-holes with positive potential regions. Moreover, these electron-deficient regions can be considered as interaction sites with some electron donors. After a Lewis base CO gas molecule is adsorbed on the Au-based superatom, we found that the C-O bond distance becomes slightly elongated and its stretching frequency presents a significant red-shift. This is due to the fact that 5d electrons of the Au atom of the NiAu8 transfer towards the anti-bond π orbitals of the CO molecule. Hence, this is an effective strategy for finding new types of superatoms and potential catalysts for covalent bond activation.

Combustion characteristics and arsenic retention during co-combustion of agricultural biomass and bituminous coal.

A combination of thermogravimetric analysis (TG) and laboratory-scale circulated fluidized bed combustion experiment was conducted to investigate the thermochemical, kinetic and arsenic retention behavior during co-combustion bituminous coal with typical agricultural biomass. Results shown that ignition performance and thermal reactivity of coal could be enhanced by adding biomass in suitable proportion. Arsenic was enriched in fly ash and associated with fine particles during combustion of coal/biomass blends. The emission of arsenic decreased with increasing proportion of biomass in blends. The retention of arsenic may be attributed to the interaction between arsenic and fly ash components. The positive correlation between calcium content and arsenic concentration in ash suggesting that the arsenic-calcium interaction may be regarded as the primary mechanism for arsenic retention.