A dual Z-scheme heterojunction Cu-CuTCPP/Cu2O/CoAl-LDH for photocatalytic CO2 reduction to C1 and C2 products.

In this research, a ternary Cu-CuTCPP/Cu2O/CoAl-LDH composite with a dual Z-scheme heterostructure was fabricated based on a Cu2O photocatalyst and applied in photocatalytic CO2 reduction. The physicochemical properties of the prepared catalysts and the possible reaction mechanism in CO2 reduction were analyzed and studied by various characterization methods. The activity of CO2 reduction significantly increased, especially forming C2 products. The optimal yield of C2H4 and C2H6 reached 1.56 and 1.92 µmol g-1 h-1 respectively, which was 14.45 and 17.45 times that from using the Cu2O monomer. In addition, the selectivity of C2 products reached 37.4%. The satisfactory C2 yield was mainly due to the fact that Cu1+δ2(COO)3 nodes in Cu-CuTCPP contained adjacent Cu sites, which effectively promoted the C-C coupling reaction. Moreover, the dual Z-scheme heterojunction stimulated the separation of photogenerated electron-hole pairs and diminished the recombination rate. This work contributes to the development of novel photocatalysts with a dual Z-scheme heterojunction and facilitates the generation of valuable C2 products.

Recent Progress of Covalent Organic Frameworks-Based Materials in Photocatalytic Applications: A Review.

Covalent organic frameworks (COFs) are one type of porous organic materials linked by covalent bonds. COFs materials exhibit many outstanding characteristics such as high porosity, high chemical and thermal stability, large specific surface area, efficient electron transfer efficiency, and the ability for predesigned structures. These exceptional advantages enable COFs materials to exhibit remarkable performance in photocatalysis. Additionally, the activity of COFs materials as photocatalysts can be significantly upgraded by ion doping and the formation of heterojunctions. This paper summarizes the latest research progress on COF-based materials applied in photocatalytic systems. Initially, typical structures and preparation methods of COFs are analyzed and compared. Moreover, the essential principles of photocatalytic reactions over COFs-based materials and the latest research developments in photocatalytic hydrogen production, CO2 reduction, pollutants elimination, organic transformation, and overall water splitting are indicated. At last, the outlook and challenges of COF-based materials in photocatalysis are discussed. This review is intended to permit instructive guidance for the efficient use of photocatalysis based on COFs in the future.

Ti3 C2 -modified g-C3 N4 /MoSe2 S-Scheme Heterojunction with Full-Spectrum Response for CO2 Photoreduction to CO and CH4.

Energy shortage and global warming caused by the extensive use of fossil fuels are urgent problems to be solved at present. Photoreduction of CO2 is considered to be a feasible solution. The ternary composite catalyst g-C3 N4 /Ti3 C2 /MoSe2 was synthesized by hydrothermal method, and its physical and chemical properties were studied by an array of characterization and tests. In addition, the photocatalytic performance of this series of catalysts under full spectrum irradiation was also tested. It is found that the CTM-5 sample has the best photocatalytic activity, and the yields of CO and CH4 are 29.87 and 17.94 µmol g-1 h-1 , respectively. This can be ascribed to the favorable optical absorption performance of the composite catalyst in the full spectrum and the establishment of S-scheme charge transfer channel. The formation of heterojunctions can effectively promote charge transfer. The addition of Ti3 C2 materials provides plentiful active sites for CO2 reaction, and its superior electrical conductivity is also favorable for the migration of photogenerated electrons.

Fabrication and characterization of Z-scheme BiOCl/C/Cu2O heterojunction nanocomposites as efficient catalysts for the photocatalytic reduction of CO2.

The photocatalytic reduction of CO2 to hydrocarbons is expected to simultaneously alleviate the energy crisis and greenhouse effect. Herein, the ternary BiOCl/C/Cu2O catalysts with different mass ratios were compounded using a simple hydrothermal method, revealing better photocatalytic activity than the monomer. In the absence of sacrificial agents and photosensitizers, 25% BiOCl/C/Cu2O showed optimal photocatalytic performance. The CO and CH4 yields over 25% BiOCl/C/Cu2O reached 26.77 and 9.86 µmol g-1 h-1, which is 2.9 and 8.7 times higher than that of the pristine Cu2O, respectively. The ameliorative activity can be attributed to the construction of the Z-scheme heterostructure and carbon layer, which are conducive to the transfer and separation of photogenerated carriers. This study offers valuable references for the design and investigation of a Z-scheme heterojunction using a carbon layer as an electron transfer medium.

Recent Progress of Three-dimensionally Ordered Macroporous (3DOM) Materials in Photocatalytic Applications: A Review.

In recent years, three-dimensionally ordered macroporous (3DOM) materials have attracted tremendous interest in the field of photocatalysis due to the periodic spatial structure and unique physicochemical properties of 3DOM catalysts. In this review, the fundamentals and principles of 3DOM photocatalysts are briefly introduced, including the overview of 3DOM materials, the photocatalytic principles based on 3DOM materials, and the advantages of 3DOM materials in photocatalysis. The preparation methods of 3DOM materials are also presented. The structure and properties of 3DOM materials and their effects on photocatalytic performance are briefly summarized. More importantly, 3DOM materials, as a supported catalyst, are extensively employed to combine with various common materials, including metal nanoparticles, metal oxides, metal sulfides, and carbon materials, to enhance photocatalytic performance. Finally, the prospects and challenges for the development of 3DOM materials in the field of photocatalysis are presented.

Recent Advances and Perspectives of Core-Shell Nanostructured Materials for Photocatalytic CO2 Reduction.

Photocatalytic CO2 conversion into solar fuels is a promising technology to alleviate CO2 emissions and energy crises. The development of core-shell structured photocatalysts brings many benefits to the photocatalytic CO2 reduction process, such as high conversion efficiency, sufficient product selectivity, and endurable catalyst stability. Core-shell nanostructured materials with excellent physicochemical features take an irreplaceable position in the field of photocatalytic CO2 reduction. In this review, the recent development of core-shell materials applied for photocatalytic reduction of CO2 is introduced . First, the basic principle of photocatalytic CO2 reduction is introduced. In detail, the classification and synthesis techniques of core-shell catalysts are discussed. Furthermore, it is also emphasized that the excellent properties of the core-shell structure can greatly improve the activity, selectivity, and stability in the process of photocatalytic CO2 reduction. Hopefully, this paper can provide a favorable reference for the preparation of efficient photocatalysts for CO2 reduction.

A review on TiO2-x-based materials for photocatalytic CO2 reduction.

Photocatalytic CO2 reduction technology has a broad potential for dealing with the issues of energy shortage and global warming. As a widely studied material used in the photocatalytic process, titanium dioxide (TiO2) has been continuously modified and tailored for more desirable application. Recently, the defective/reduced titanium dioxide (TiO2-x) catalyst has attracted broad attention due to its excellent photocatalytic performance for CO2 reduction. In this perspective review, we comprehensively present the recent progress in TiO2-x-based materials for photocatalytic CO2 reduction. In detail, the review starts with the fundamentals of CO2 photocatalytic reduction. Then, the synthesis of a defective TiO2 structure is introduced for the regulation of its photocatalytic performance, especially its optical properties and dissociative adsorption properties. In addition, the current application of TiO2-x-based photocatalysts for CO2 reduction is also highlighted, such as metal-TiO2-x, oxide-TiO2-x and TiO2-x-carbon-based photocatalysts. Finally, the existing challenges and possible scope of photocatalytic CO2 reduction over TiO2-x-based materials are discussed. We hope that this review can provide an effective reference for the development of more efficient and reasonable photocatalysts based on TiO2-x.

Carbon quantum dots-modified Z-scheme Bi12O17Cl2/NiAl-LDH for significantly boosting photocatalytic CO2 reduction.

Photocatalytic reduction of CO2 to high-energy products is an effective way to utilize solar energy and mitigate the greenhouse effect. In this paper, a series of CQDs/Bi12O17Cl2/NiAl-LDH (C/BOC/LDH) photocatalysts were prepared via a one-pot hydrothermal method, demonstrated excellent photocatalytic CO2 reduction performance. In the case of only water without any photosensitizer and sacrificial agent, the CO production rate on C/0.3BOC/LDH reached 16.4 µmol·g-1h-1, which is 6.7 times higher than that of the original LDH. The construction of Z-scheme heterojunctions inhibited the recombination of electrons with holes. The unique up-conversion PL behavior of CQDs benefitted the absorption of energy in the NIR by the photocatalyst. This study provides meaningful assistance for the design and construction of a ternary photocatalytic system with Z-scheme heterojunction and carbon-based co-catalyst.

Recent advances and perspectives of g-C3N4-based materials for photocatalytic dyes degradation.

Photocatalytic degradation technology is regarded as a promising technology for dye-contained wastewater treatment due to its superior efficiency and recycling. The key to the implementation of photocatalytic degradation technology is the selection of sunlight-active photocatalyst. Graphitic carbon nitride (g-C3N4) photocatalyst has been put into a lot of research in the field of organic pollutant degradation because of its low cost, suitable electronic structure and high chemical stability. In this perspective review, we comprehensively discuss the recent advance of photocatalytic dyes degradation over g-C3N4-based materials. The properties, structure and preparation methods of g-C3N4 are briefly introduced. Furthermore, the progress in improving the degradation efficiency of g-C3N4-based photocatalyst is highlighted in the article. The possible pathways and different active species for dyes decomposition are also summarized. We expect this review can provide instructive application of g-C3N4-based catalysts for environmental remediation.

Research progress on photocatalytic reduction of CO2 based on LDH materials.

Converting CO2 to renewable fuels or valuable carbon compounds is an effective way to solve the global warming and energy crisis. Compared with other CO2 conversion methods, photocatalytic reduction of CO2 is more energy-saving, environmentally friendly, and has a broader application prospect. Layered double hydroxide (LDH) has attracted widespread attention as a two-dimensional material, composed of metal hydroxide layers, interlayer anions and water molecules. This review briefly introduces the basic theory of photocatalysis and the mechanism of CO2 reduction. The composition and properties of LDH are introduced. The research progress on LDH in the field of photocatalytic reduction of CO2 is elaborated from six aspects: directly as a catalyst, as a precursor for a catalyst, and by modification, intercalation, supporting with other materials and construction of a heterojunction. Finally, the development prospects of LDH are put forward. This review could provide an effective reference for the development of more efficient and reasonable photocatalysts based on LDH.

Toxicity effects of ciprofloxacin on biochemical parameters, histological characteristics, and behaviors of Corbicula fluminea in different substrates.

Antibiotic toxicity and antibiotic resistance have become significant challenges to human health. However, the potential ecotoxicity of sediment-associated antibiotics remains unknown. In this study, biochemical responses, histological changes, and behavioral responses of Corbicula fluminea exposed to sediment-associated ciprofloxacin (CIP) were systemically investigated. Special attention was paid to the influence of different substrate types. Biochemical analyses revealed that the balance of the antioxidant system was disrupted, eventually leading to oxidative damage to the gills and digestive gland with increasing CIP concentration. Severe histopathological changes appeared along with the oxidative damage. An enlargement of the tubule lumen and thinning of the epithelium in the digestive gland were observed under exposure to high CIP concentrations (0.5 and 2.5 µg/g CIP). In a behavioral assay, the filtration rate of C. fluminea in high concentration exposure groups was clearly inhibited. Moreover, from the integrated biomarker response (IBR) index, the toxicity response gradients of the digestive gland (no substrate--NOS > Sand > Sand and kaolinite clay-- SKC > Sand, kaolinite clay, and organic matter--SCO) and gills (NOS > SCO > SKC > Sand) were different among substrate exposure groups. The most serious histopathological damage and highest siphoning inhibition were observed in the NOS group. The changes in the morphological structure of digestive gland cells in C. fluminea were similar in the other three substrate groups. The inhibition of the filtration rate in the higher concentration groups decreased in the order Sand > SKC > SCO.

Sampling and analysis of airborne ammonia in workplaces of China.

OBJECTIVES: With the increasing demand for the detection of occupational hazard factors in workplaces, the national standard determination method for ammonia (sampling with absorbing solution-analysis with Nessler reagent spectrophotometry) in the air of workplace presents many drawbacks during application in China. This review summarized the improvement and the alternate methods of the current sampling and analysis procedures for ammonia, aiming to provide reference to establish an appropriate method for the determination of ammonia in workplace air. METHODS: Scientific publications in English and Chinese and the standard methods of the Deutsche Forschungsgemeinschaft (DFG) in Germany, the National Institute for Occupational Safety and Health (NIOSH) and Occupational Safety and Health Administration (OSHA) in the United States, and Ministry of Health in China for airborne ammonia collection and analysis in the workplace were reviewed. RESULTS: The measures to improve the current sampling and analysis procedures for ammonia in China were firstly summarized. For sampling, the decrease of absorbing solution concentration and the methanesulfonic acid solution as the alternate sampling solution were suggested. For analysis, the anti-interference measures and the optimum reaction condition between ammonia and Nessler reagent were discussed. The alternate methods including sampling conducted using solid sorbent tubes and analysis performed by ion chromatography were then considered for the determination of ammonia. CONCLUSIONS: The methods-sampling with acid-treated solid sorbent tubes and analysis with ion chromatography-were more suitable for the determination of ammonia in workplace air. However, some details about ammonia sampling and analysis still need further investigation.

Electrospray ionization time-of-flight mass spectrum analysis method of polyaluminum chloride flocculants.

Electrospray mass spectrometry has been reported as a novel technique for Al species identification, but to date, the working mechanism is not clear and no unanimous method exists for spectrum analysis of traditional Al salt flocculants, let alone for analysis of polyaluminum chloride (PAC) flocculants. Therefore, this paper introduces a novel theoretical calculation method to identify Al species from a mass spectrum, based on deducing changes in m/z (mass-to-charge ratio) and molecular formulas of oligomers in five typical PAC flocculants. The use of reference chemical species was specially proposed in the method to guarantee the uniqueness of the assigned species. The charge and mass reduction of the Al cluster was found to proceed by hydrolysis, gasification, and change of hydroxyl on the oxy bridge. The novel method was validated both qualitatively and quantitatively by comparing the results to those obtained with the (27)Al NMR spectrometry.

ChAy/Bx, a novel chimeric high-molecular-weight glutenin subunit gene apparently created by homoeologous recombination in Triticum turgidum ssp. dicoccoides.

High-molecular-weight glutenin subunits (HMW-GSs) are of considerable interest, because they play a crucial role in determining dough viscoelastic properties and end-use quality of wheat flour. In this paper, ChAy/Bx, a novel chimeric HMW-GS gene from Triticum turgidum ssp. dicoccoides (AABB, 2n=4x=28) accession D129, was isolated and characterized. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) analysis revealed that the electrophoretic mobility of the glutenin subunit encoded by ChAy/Bx was slightly faster than that of 1Dy12. The complete ORF of ChAy/Bx contained 1,671 bp encoding a deduced polypeptide of 555 amino acid residues (or 534 amino acid residues for the mature protein), making it the smallest HMW-GS gene known from Triticum species. Sequence analysis showed that ChAy/Bx was neither a conventional x-type nor a conventional y-type subunit gene, but a novel chimeric gene. Its first 1305 nt sequence was highly homologous with the corresponding sequence of 1Ay type genes, while its final 366 nt sequence was highly homologous with the corresponding sequence of 1Bx type genes. The mature ChAy/Bx protein consisted of the N-terminus of 1Ay type subunit (the first 414 amino acid residues) and the C-terminus of 1Bx type subunit (the final 120 amino acid residues). Secondary structure prediction showed that ChAy/Bx contained some domains of 1Ay subunit and some domains of 1Bx subunit. The special structure of this HMW glutenin chimera ChAy/Bx subunit might have unique effects on the end-use quality of wheat flour. Here we propose that homoeologous recombination might be a novel pathway for allelic variation or molecular evolution of HMW-GSs.

Molecular characterization of two y-type high molecular weight glutenin subunit alleles 1Ay12 and 1Ay8 from cultivated einkorn wheat (Triticum monococcum ssp. monococcum).

Two y-type high molecular weight glutenin subunits (HMW-GSs) 1Ay12 and 1Ay8 from the two accessions PI560720 and PI345186 of cultivated einkorn wheat (Triticum monococcum ssp. monococcum, AA, 2n=2x=14), were identified by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The mobility of 1Ay12 and 1Ay8 was similar to that of 1Dy12 and 1By8 from common wheat Chinese Spring, respectively. Their ORFs respectively consisted of 1812bp and 1935bp, encoding 602 and 643 amino acid residues with the four typical structural domains of HMW-GS including signal peptide, conserved N-, and C-terminal and central repetitive domains. Compared with the most similar active 1Ay alleles previous published, there were a total of 15 SNPs and 2 InDels in them. Their encoding functions were confirmed by successful heterogeneous expression. The two novel 1Ay alleles were named as 1Ay12 and 1Ay8 with the accession No. JQ318694 and JQ318695 in GenBank, respectively. The two alleles were classed into the two distinct groups, Phe-type and Cys-type, which might be relevant to the differentiation of Glu-A1-2 alleles. Of which, 1Ay8 belonged to Cys-type group, and its protein possessed an additional conserved cysteine residue in central repetitive region besides the six common ones in N- and C-terminal regions of Phe-type group, and was the second longest in all the known active 1Ay alleles. These results suggested that the subunit 1Ay8 of cultivated einkorn wheat accession PI345186 might have a potential ability to strengthen the gluten polymer interactions and be a valuable genetic resource for wheat quality improvement.

Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions.

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride (FeCI3), aluminum sulfate (AI2(SO4)3), polyaluminum chloride (PACI) and composite polyaluminum (HPAC), in order to remove dissolved organic matter (DOM). Considering the disinfection byproduct (DBP) precursor treatability, DOM was divided into five chemical fractions based on resin adsorption. Trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP) were measured for each fraction. The results showed that hydrophobic acids (HoA), hydrophilic matter (HiM) and hydrophobic neutral (HoN) were the dominant fractions. Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally, HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation. HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions. DOC removal was highest for enhanced coagulation using FeCI3 while DBPFP was lowest using PACI. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PACI under enhanced coagulation could reach 51% and 59% respectively.

Further treatment of decolorization liquid of azo dye coupled with increased power production using microbial fuel cell equipped with an aerobic biocathode.

A microbial fuel cell (MFC) incorporating a recently developed aerobic biocathode is designed and demonstrated. The aerobic biocathode MFC is able to further treat the liquid containing decolorization products of active brilliant red X-3B (ABRX3), a respective azo dye, and also provides increased power production. Batch test results showed that 24.8% of COD was removed from the decolorization liquid of ABRX3 (DL) by the biocathode within 12 h. Metabolism-dependent biodegradation of aniline-like compound might be mainly responsible for the decrease of overall COD. Glucose is not necessary in this process and contributes little to the COD removal of the DL. The similar COD removal rate observed under closed circuit condition (500 Ω) and opened circuit condition indicated that the current had an insignificant effect on the degradation of the DL. Addition of the DL to the biocathode resulted in an almost 150% increase in open cycle potential (OCP) of the cathode accompanied by a 73% increase in stable voltage output from 0.33 V to 0.57 V and a 300% increase in maximum power density from 50.74 mW/m(2) to 213.93 mW/m(2). Cyclic voltammetry indicated that the decolorization products of the ABRX3 contained in the DL play a role as redox mediator for facilitating electron transfer from the cathode to the oxygen. This study demonstrated for the first time that MFC equipped with an aerobic biocathode can be successfully applied to further treatment of effluent from an anaerobic system used to decolorize azo dye, providing both cost savings and high power output.

Simultaneous decolorization of azo dye and bioelectricity generation using a microfiltration membrane air-cathode single-chamber microbial fuel cell.

Electricity generation from readily biodegradable organic substrates accompanied by decolorization of azo dye was investigated using a microfiltration membrane air-cathode single-chamber microbial fuel cell (MFC). Batch experiment results showed that accelerated decolorization of active brilliant red X-3B (ABRX3) was achieved in the MFC as compared to traditional anaerobic technology. Biodegradation was the dominant mechanism of the dye removal, and glucose was the optimal co-substrate for ABRX3 decolorization, while acetate was the worst one. Confectionery wastewater (CW) was also shown to be a good co-substrate for ABRX3 decolorization and a cheap fuel source for electricity generation in the MFC. Low resistance was more favorable for dye decolorization than high resistance. Suspended sludge (SS) should be retained in the MFC for accelerated decolorization of ABRX3. Electricity generation was not significantly affected by the ABRX3 at 300 mg/L, while higher concentrations inhibited electricity generation. However, voltage can be recovered to the original level after replacement with anodic medium not containing azo dye.