Genome-wide identification of HSP90 gene family in Rosa chinensis and its response to salt and drought stresses.

Heat shock protein 90 (HSP90) is important for many organisms, including plants. Based on the whole genome information, the gene number, gene structure, evolutionary relationship, protein structure, and active site of the HSP90 gene family in Rosa chinensis and Rubus idaeus were determined, and the expression of the HSP90 gene under salt, and drought stresses in two rose varieties Wangxifeng and Sweet Avalanche were analyzed. Six and eight HSP90 genes were identified from R. chinensis and Ru. idaeus, respectively. Phylogenetic analysis revealed that the analyzed genes were divided into two Groups and four subgroups (Classes 1a, 1b, 2a, and 2b). Although members within the same classes displayed highly similar gene structures, while the gene structures and conserved domains of Group 1 (Class 1a and 1b) and the Group 2 (Class 2a and 2b) are different. Tandem and segmental duplication genes were found in Ru. idaeus, but not in R. chinensis, perhaps explaining the difference in HSP90 gene quantity in the two analyzed species. Analysis of cis-acting elements revealed abundant abiotic stress, photolight-response, and hormone-response elements in R. chinensis HSP90s. qRT-PCR analysis suggested that RcHSP90-1-1, RcHSP90-5-1 and RcHSP90-6-1 in Sweet Avalanche and Wangxifeng varieties played important regulatory roles under salt and drought stress. The analysis of protein structure and active sites indicate that the potential different roles of RcHSP90-1-1, RcHSP90-5-1, and RcHSP90-6-1 in salt and drought stresses may come from the differences of corresponding protein structures and activation sites. These data will provide information for the breeding of rose varieties with high stress resistance. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-024-04052-0.

A Universal In-Situ Interfacial Growth Strategy for Various MXene-Based van der Waals Heterostructures with Uniform Heterointerfaces: The Efficient Conversion from 3D Composite to 2D Heterostructures.

Two-dimensional (2D) van der Waals heterostructures endow individual 2D material with the novel functional structures, intriguing compositions, and fantastic interfaces, which efficiently provide a feasible route to overcome the intrinsic limitations of single 2D components and embrace the distinct features of different materials. However, the construction of 2D heterostructures with uniform heterointerfaces still poses significant challenges. Herein, a universal in-situ interfacial growth strategy is designed to controllably prepare a series of MXene-based tin selenides/sulfides with 2D van der Waals homogeneous heterostructures. Molten salt etching by-products that are usually recognized as undesirable impurities, are reasonably utilized by us to efficiently transform into different 2D nanostructures via in-situ interfacial growth. The obtained MXene-based 2D heterostructures present sandwiched structures and lamellar interlacing networks with uniform heterointerfaces, which demonstrate the efficient conversion from 3D composite to 2D heterostructures. Such 2D heterostructures significantly enhance charge transfer efficiency, chemical reversibility, and overall structural stability in the electrochemical process. Taking 2D-SnSe2/MXene anode as a representative, it delivers outstanding lithium storage performance with large reversible capacities and ultrahigh capacity retention of over 97% after numerous cycles at 0.2, 1.0, and 10.0 A g-1 current density, which suggests its tremendous application potential in lithium-ion batteries.

Harnessing antimicrobial peptide-coupled photosensitizer to combat drug-resistant biofilm infections through enhanced photodynamic therapy.

Bacterial biofilm-associated infection was one of the most serious threats to human health. However, effective drugs for drug-resistance bacteria or biofilms remain rarely reported. Here, we propose an innovative strategy to develop a multifunctional antimicrobial agent with broad-spectrum antibacterial activity by coupling photosensitizers (PSs) with antimicrobial peptides (AMPs). This strategy capitalizes on the ability of PSs to generate reactive oxygen species (ROS) and the membrane-targeting property of AMPs (KRWWKWIRW, a peptide screened by an artificial neural network), synergistically enhancing the antimicrobial activity. In addition, unlike conventional aggregation-caused quenching (ACQ) photosensitizers, aggregation-induced emission (AIE) PSs show stronger fluorescence emission in the aggregated state to help visualize the antibacterial mechanism. In vitro antibacterial experiments demonstrated the excellent killing effects of the developed agent against both Gram-positive (G+) and Gram-negative (G-) bacteria. The bacterial-aggregations induced ability enhanced the photoactivatable antibacterial activity against G- bacteria. Notably, it exhibited a significant effect on destroying MRSA biofilms. Moreover, it also showed remarkable efficacy in treating wound infections in mice in vivo. This multifunctional antimicrobial agent holds significant potential in addressing the challenges posed by bacterial biofilm-associated infections and drug-resistant bacteria.

Electron deficient Bi3+δ serves as N2 absorption sites and inhibits carriers recombination to enhance N2 photo-fixation in BiOBr/TiO2 S-scheme heterojunction.

Efficient carriers separation and multiple nitrogen (N2) activation sites are essential for N2 photo-fixation. Here, we found that the BiOBr/TiO2 (BBTO) displayed an attractive reversible photochromism (white → grey) due to the generation of electron deficient Bi3+δ, which was produced by the hole trapping of Bi3+ under light irradiation. Interestingly, more Bi3+δ were detected in the BBTO heterojunction than in pure BiOBr, attributing that the hole trapping was promoted by the built-in electric field in the Step scheme (S-scheme) heterojunction. In the BBTO, the electron deficient Bi3+δ enhanced carriers separation and served as the reactive active site to adsorb more N2. Consequently, the BBTO possessed an excellent N2 photo-fixation activity (191 µmol gcat-1 h-1), which was 7.7 and 18 times higher than that of pure BiOBr (24.8 µmol gcat-1 h-1) and TiO2 (10.6 µmol gcat-1 h-1), respectively. Therefore, this work provides a new perspective for enhancing N2 photo-fixation by the electron deficient photocatalysts with S-scheme heterojunction.

New insights into molecular features of the genome-wide AOX family and their responses to various stresses in common wheat (Triticum aestivum L.).

Alternative oxidase (AOX) is an important terminal oxidase involved in the alternative oxidation pathway in plants, which is closely related to various biotic and abiotic stress responses. However, a comprehensive research on AOX gene family of wheat is still lacking. In this study, the members of wheat AOX (TaAOX) family were identified, and their molecular characteristics and gene expression patterns were systematically investigated. Seventeen TaAOX genes were identified from Chinese Spring (CS) genome, which were mapped on 7 chromosomes and mainly clustered on the long arm's distal end of the second homologous groups. Phylogenetic analysis showed that TaAOX genes were classified into four subgroups (Ia, Ib, Ic, and Id), and the Ia subgroup possessed the most members. Tandem duplication and segmental duplication events were found during the evolution of TaAOX genes and they were affected by purifying selection demonstrated by Ka/Ks analysis. The exon numbers of this family gene varied greatly from 1 to 9. Except for Ta3BSAOX14, all the proteins encoded by the other 16 TaAOX genes contained the amino acid residues of the key active sites in the AOX domain (cd01053). The expression patterns of TaAOX genes in various tissues and under abiotic and biotic stresses were analyzed using public transcriptome data, furthermore, qRT-PCR analysis was performed for some selected TaAOX genes, and the results suggested that most members of this gene family play an important role in response to different stresses in common wheat. Our results provide basic information and valuable reference for further exploring the gene function of TaAOX family by using gene editing, RNAi, VIGS, and other technologies.

Identification of acyl-CoA-binding protein gene in Triticeae species reveals that TaACBP4A-1 and TaACBP4A-2 positively regulate powdery mildew resistance in wheat.

Plant acyl-CoA-binding proteins (ACBPs), which contain the conserved ACB domain, participate in multiple biological processes, however, there are few reports on wheat ACBPs. In this study, the ACBP genes from nine different species were identified comprehensively. The expression patterns of TaACBP genes in multiple tissues and under various biotic stresses were determined by qRT-PCR. The function of selected TaACBP genes was studied by virus-induced gene silencing. A total of 67 ACBPs were identified from five monocotyledonous and four dicotyledonous species and divided into four classes. Tandem duplication analysis of the ACBPs suggested that tandem duplication events occurred in Triticum dicoccoides, but there was no tandem duplication event in wheat ACBP genes. Evolutionary analysis suggested that the TdACBPs may have experienced gene introgression during tetraploid evolution, while TaACBP gene loss events occurred during hexaploid wheat evolution. The expression pattern showed that all the TaACBP genes were expressed, and most of them were responsive to induction by Blumeria graminis f. sp. tritici or Fusarium graminearum. Silencing of TaACBP4A-1 and TaACBP4A-2 increased powdery mildew susceptibility in the common wheat BainongAK58. Furthermore, TaACBP4A-1, which belonged to class III, physically interacted with autophagy-related ubiquitin-like protein TaATG8g in yeast cells. This study provided a valuable reference for further investigations into the functional and molecular mechanisms of the ACBP gene family.

Functional insights to the development of bioactive material for combating bacterial infections.

The emergence of antibiotic-resistant "superbugs" poses a serious threat to human health. Nanomaterials and cationic polymers have shown unprecedented advantages as effective antimicrobial therapies due to their flexibility and ability to interact with biological macromolecules. They can incorporate a variety of antimicrobial substances, achieving multifunctional effects without easily developing drug resistance. Herein, this article discusses recent advances in cationic polymers and nano-antibacterial materials, including material options, fabrication techniques, structural characteristics, and activity performance, with a focus on their fundamental active elements.

Oxygen vacancies-rich Cu-W18O49 nanorods supported on reduced graphene oxide for electrochemical reduction ofN2to NH3.

High-performance nitrogen fixation is severely limited by the efficiency and selectivity of a catalyst of electrochemical nitrogen reduction reaction (NRR) under ambient conditions. Here, the RGO/WOCu (reduced graphene oxide and Cu-doping W18O49) composite catalysts with abundant oxygen vacancies are prepared by the hydrothermal method. The obtained RGO/WOCu achieves an enhanced NRR performance (NH3 yield rate:11.4 µg h-1 mgcat-1, Faradaic efficiency: 4.4%) at -0.6 V (vs. RHE) in 0.1 mol L-1 Na2SO4 solution. Furthermore, the NRR performance of the RGO/WOCu still keeps at 95% after four cycles, demonstrating its excellent stability. The Cu+-doping increases the concentration of oxygen vacancies, which is conducive to the adsorption and activation of N2. Meanwhile, the introduction of RGO further improves the electrical conductivity and reaction kinetics of the RGO/WOCu due to the high specific surface area and conductivity. This work provides a simple and effective method for efficient electrochemical reduction ofN2.

Electron-transfer pathways insights into contaminants oxidized by Cu-OOSO3- intermediate: Effects of oxidation states of Cu and solution pH values.

The copper-peroxy complex (Cu-OOSO3-) metastable intermediate has been confirmed to oxidize contaminants via a single-electron-transfer pathway or an oxygen-atom-transfer pathway. And the effects of Cu oxidation states and reaction pH conditions on the intermediate properties have not been explored in depth. Here, copper oxide (CuOx) catalysts with different Cu oxidation states were synthesized by a simple precipitation method by controlling the reaction temperature from 0 to 45 °C. CuOx displayed a strong catalytic dependence on the Cu oxidation state, and CuOx-30 with Cu average valence on the catalyst surface of 1.61 was more reactive for catalytic degradation of bisphenol A with peroxymonosulfate (PMS). Notably, CuOx-30, with the best electron-accepting ability, was easier to bonding with PMS to form the Cu-OOSO3- reactive complex, and the generated intermediate exhibited the strongest capacity to obtain electrons from contaminants. Moreover, the electron-transfer pathways were closely related to the average valence of Cu, and the contribution of the oxygen-atom-transfer pathway changed volcanic with increasing Cu valence. Meanwhile, the reaction predominantly involved the oxygen-atom-transfer pathway under acidic conditions (pH=3), while the contribution of the single-electron-transfer pathway raised with increasing pH values. Hence, this work was devoted to providing new insights into the CuOx-inducing PMS activation and vital supplementary to the properties of the Cu-OOSO3- intermediate.

Terminal Group-Oriented Self-Assembly to Controllably Synthesize a Layer-by-Layer SnSe2 and MXene Heterostructure for Ultrastable Lithium Storage.

Heterostructured materials integrate the advantages of adjustable electronic structure, fast electron/ions transfer kinetics, and robust architectures, which have attracted considerable interest in the fields of rechargeable batteries, photo/electrocatalysis, and supercapacitors. However, the construction of heterostructures still faces some severe problems, such as inferior random packing of components and serious agglomeration. Herein, a terminal group-oriented self-assembly strategy to controllably synthesize a homogeneous layer-by-layer SnSe2 and MXene heterostructure (LBL-SnSe2 @MXene) is designed. Benefitting from the abundant polar terminal groups on the MXene surface, Sn2+ is induced into the interlayer of MXene with large interlayer spacing, which is selenized in situ to obtain LBL-SnSe2 @MXene. In the heterostructure, SnSe2 layers and MXene layers are uniformly intercalated in each other, superior to other heterostructures formed by random stacking. As an anode for lithium-ion batteries, the LBL-SnSe2 @MXene is revealed to possess strong lithium adsorption ability, the small activation energy for lithium diffusion, and excellent structure stability, thus achieving outstanding electrochemical performance, especially with high specific capacities (1311 and 839 mAh g-1 for initial discharge and charge respectively) and ultralong cycling stability (410 mAh g-1 at 5C even after 16 000 cycles). This work conveys an inspiration for the controllable design and construction of homogeneous layered heterostructures.

High-ratio {100} plane-exposed ZnO nanosheets with dual-active centers for simultaneous photocatalytic Cr(VI) reduction and Cr(III) adsorption from water.

The development of an efficient catalyst for the simultaneous removal of Cr(VI) and Cr(III) from water is required to eliminate the risk of Cr(III) reconversion in the photocatalytic Cr(VI) reduction process. ZnO with large regions of high-energy {001} and {101} surfaces is often used to degrade various pollutants due to its high activity. However, the more readily available low-energy facets have relatively limited its applications. Here, we report a new strategy that employs a high proportion of {100} plane-exposed ZnO nanosheets for simultaneous photocatalytic Cr(VI) reduction and Cr(III) adsorption. The mechanism of Zn-O co-exposed on the {100} plane as the dual-active centers to jointly promote Cr(VI) reduction and Cr(III) adsorption was clarified at the atomic level. ZnO nanosheets with a high exposure ratio of the {100} plane achieve a total Cr removal rate of over 90% within 120 min under simulated sunlight irradiation, neutral conditions, and a negligible difference in the band structure.

Photo-Activable Organosilver Nanosystem Facilitates Synergistic Cancer Theranostics.

Anticancer drug development is important for human health, yet it remains a tremendous challenge. Photodynamic therapy (PDT), which induces cancer cell apoptosis via light-triggered production of reactive oxygen species, is a promising method. However, it has minimal efficacy in subcellular targeting, hypoxic microenvironments, and deep-seated malignancies. Here, we constructed a breast cancer photo-activable theranostic nanosystem through the rational design of a synthetic lysosomal-targeted molecule with multifunctions as aggregation-induced near-infrared (NIR) emission, a photosensitizer (PDT), and organosilver (chemotherapy) for NIR imaging and synergistic cancer therapy. The synthetic molecule could self-assemble into nanoparticles (TPIMBS NPs) and be stabilized with amphiphilic block copolymers for enhanced accumulation in tumor sites through passive targeting while reducing the leakage in normal tissues. Through photochemical internalization, TPIMBS NPs preferentially concentrated in the lysosomes of cancer cells and generated reactive oxygen species (ROS) upon light irradiation, resulting in lysosomal rupture and release of PSs to the cytosol, which led to cell apoptosis. Further, the photoinduced release of Ag+ from TPIMBS NPs could act as chemotherapy, significantly improving the overall therapeutic efficacy by synergistic effects with PDT. This research sheds fresh light on the creation of effective cancer treatments.

Identification of ankyrin-transmembrane-type subfamily genes in Triticeae species reveals TaANKTM2A-5 regulates powdery mildew resistance in wheat.

The ankyrin-transmembrane (ANKTM) subfamily is the most abundant subgroup of the ANK superfamily, with critical roles in pathogen defense. However, the function of ANKTM proteins in wheat immunity remains largely unexplored. Here, a total of 381 ANKTMs were identified from five Triticeae species and Arabidopsis, constituting five classes. Among them, class a only contains proteins from Triticeae species and the number of ANKTM in class a of wheat is significantly larger than expected, even after consideration of the ploidy level. Tandem duplication analysis of ANKTM indicates that Triticum urartu, Triticum dicoccoides and wheat all had experienced tandem duplication events which in wheat-produced ANKTM genes all clustered in class a. The above suggests that not only did the genome polyploidization result in the increase of ANKTM gene number, but that tandem duplication is also a mechanism for the expansion of this subfamily. Micro-collinearity analysis of Triticeae ANKTMs indicates that some ANKTM type genes evolved into other types of ANKs in the evolution process. Public RNA-seq data showed that most of the genes in class d and class e are expressed, and some of them show differential responses to biotic stresses. Furthermore, qRT-PCR results showed that some ANKTMs in class d and class e responded to powdery mildew. Silencing of TaANKTM2A-5 by barley stripe mosaic virus-induced gene silencing compromised powdery mildew resistance in common wheat Bainongaikang58. Findings in this study not only help to understand the evolutionary process of ANKTM genes, but also form the basis for exploring disease resistance genes in the ANKTM gene family.

Co3O4 crystal plane regulation to efficiently activate peroxymonosulfate in water: The role of oxygen vacancies.

Crystal plane effect has attracted remarkable attention in the process of peroxymonosulfate (PMS) activation in water. In this work, nanocube-Co3O4 (Co3O4-NC), nanoplate-Co3O4 (Co3O4-NP) and nanorod-like Co3O4 (Co3O4-NR) with (100), (111) and (110) plane predominant exposure is prepared by a facile hydrothermal method. Co3O4-NR with (110) plane exposed possesses more lattice defects (oxygen vacancies, Ov) and low oxidation state Co (Co2+), consequently, it exhibits a superior activity for PMS activation to efficiently remove bisphenol A (BPA) in water. Furthermore, it could be used in a widely water pH values ranging from 5.0 to 9.0 with an excellent PMS activited effects. During Co3O4-NR/PMS oxidation process, it is found that singlet oxygen (1O2) plays a dominant role in BPA degradation. However, Co3O4-NR treated by H2O2 shows a poor PMS activation performance, confirming Ov acting as the active site during such oxidation process. The important effect of dissolved oxygen is tested by Ar introduction into the reaction system and the Ov-O* metastable intermediate is proposed. In situ Raman proves the interaction between dissolved oxygen and Ov and then the intermediate activates PMS to degrade BPA. This work not only explores the effect of different crystal plane exposures on PMS activation in Co3O4/PMS system, but investigates the evolution of Ov during the PMS activation.

Electrostatic self-assembled layered polymers form supramolecular heterojunction catalyst for photocatalytic reduction of high-stability nitrate in water.

In this work, two polymers are connected by electrostatic self-assembly method to form a supramolecular heterojunction to remove pollutants. g-C3N4-Cl/PANI catalyst can be used for photocatalytic reduction of nitrate in water, and the nitrogen selectivity reaches 98.2%. Specially, charge density analysis and comparative experiments showed that the introduction of covalent chlorine increased in electron transfer conduction between layers. In addition, differential charge density and solid EPR tests reveal high electron density and electron transfer pathways for supramolecular heterostructures. The results of the work function give direct evidence for the high catalytic performance of the supramolecular heterojunction. The reasons and active species of photocatalytic reduction of nitrate by g-C3N4-Cl and g-C3N4-Cl/PANI are compared. The catalyst exhibits the performance of highly reducing nitrate to harmless nitrogen with the contribution of supramolecular heterojunction and covalent chlorine. In short, a new idea of constructing a supramolecular photocatalyst is proposed, which can be applied to efficiency reduce nitrate in water.

Genome-Wide Analysis of Serine Hydroxymethyltransferase Genes in Triticeae Species Reveals That TaSHMT3A-1 Regulates Fusarium Head Blight Resistance in Wheat.

Serine hydroxymethyltransferase (SHMT) plays a pivotal role in cellular one-carbon, photorespiration pathways and it influences the resistance to biotic and abiotic stresses. However, the function of SHMT proteins in wheat remains largely unexplored. In the present study, SHMT genes in five Triticeae species, Oryza sativa, and four dicotyledon species were identified based on whole genome information. The origin history of the target gene was traced by micro-collinearity analysis. Gene expression patterns of TaSHMTs in different tissues, various biotic stresses, exogenous hormones, and two biotic stresses were determined by Quantitative real-time reverse transcription polymerase chain reaction (qRT-PCR). The function of the selected TaSHMT3A-1 was studied by barley stripe mosaic virus-induced gene silencing in common wheat Bainong207. A total of 64 SHMT members were identified and further classified into two main classes based on the structure of SHMT proteins. The gene structure and motif composition analyses revealed that SHMTs kept relatively conserved within the same subclasses. Interestingly, there was a gene, TdSHMT7B-1, on chromosome 7B of Triticum dicoccoides, but there was no SHMT gene on chromosome 7 of other analyzed Triticeae species; TdSHMT7B-1 had fewer exons and conserved motifs than the genes in the same subclass, suggesting that the gene of TdSHMT7B-1 has a notable evolutionary progress. The micro-collinearity relationship showed that no homologs of TaSHMT3A-1 and its two neighboring genes were found in the collinearity region of Triticum urartu, and there were 27 genes inserted into the collinearity region of T. urartu. Furthermore, qRT-PCR results showed that TaSHMT3A-1 was responsive to abiotic stresses (NaCl and cold), abscisic acid, methyl jasmonate, and hydrogen peroxide. Significantly, upon Fusarium graminearum infection, the expression of TaSHMT3A-1 was highly upregulated in resistant cultivar Sumai3. More importantly, silencing of TaSHMT3A-1 compromises Fusarium head blight resistance in common wheat Bainong207. Our new findings suggest that the TaSHMT3A-1 gene in wheat plays an important role in resistance to Fusarium head blight. This provides a valuable reference for further study on the function of this gene family.

Activation of peroxymonosulfate by α-MnO2 for Orange â removal in water.

Developing high-efficiency catalysts for peroxymonosulfate (PMS)-based advanced oxidation processes is important for eliminating pollutants in water. Herein, α-MnO2 with major exposed {110} and {100} facets prepared via a hydrothermal method were used as catalysts to activate PMS for the degradation of Orange Ⅰ (OⅠ). α-MnO2-100, with more abundant surface hydroxyl groups and greater reductive ability, performed remarkably better than α-MnO2-110 for degrading OⅠ. OⅠ removal of 86.20% was obtained in the α-MnO2-100/PMS system. The apparent rate constant of OⅠ removal over α-MnO2-100 was 2.11 times higher than that of α-MnO2-110. The effects of PMS concentration, catalyst dosage, OⅠ concentration, initial pH, anions and humic acid (HA) on OⅠ degradation in the α-MnO2-100/PMS system were systematically investigated. Quenching experiments and electron paramagnetic resonance (EPR) demonstrated that SO4•-, •OH, O2•- and 1O2 were the reactive oxygen species (ROS) in the α-MnO2-100/PMS system. Moreover, the possible degradation pathway of OⅠ in the α-MnO2-100/PMS system was proposed. This work provides an ideal metal oxide catalyst for sewage remediation.

Treatment of shale gas produced water by magnetic CuFe2O4/TNTs hybrid heterogeneous catalyzed ozone: Efficiency and mechanisms.

Magnetic spinel ferrite (CuFe2O4) has been applied to catalyze ozone for treating the practical shale gas produced water (PW) in our previous study. In this work, CuFe2O4/titanium nanotubes (TNTs) catalyst was successfully prepared by an impregnation-calcination method. Characterization results revealed that the crystal form of CuFe2O4 was bound to the surface of TNTs, the particle size is much smaller than the pure CuFe2O4 crystal particle, which could weaken the influence of the internal diffusion process on its catalytic efficiency. The experimental results showed that the removal ratio of CODCr in the CuFe2O4/TNTs/O3 system was approximately 14% higher than that of the CuFe2O4/O3 system. The dissolution of metal elements decreased to one-third that of the CuFe2O4/O3 system. The inhibition ratio of PW on the growth of E. coli K12 decreased 68% after the CuFe2O4/TNTs catalytic oxidation process. Experimental results of complete capture experiments illustrated that the yield of HO• of the CuFe2O4/TNTs/O3 system was 10-19% higher than that of the CuFe2O4/O3 system. The elemental valence analysis revealed that the transition of Cu(II)-Cu(III) and Fe(II)-Fe(III) coexisted in the catalytic system. Besides, the surface hydroxyl groups promoted the electron transfer process and enhanced the ozone adsorption affinity. The proposed catalytic mechanisms of the CuFe2O4/TNTs/O3 system were proposed via the above analysis.

Electrostatic self-assembly to form unique LiNbO3/ZnS core-shell structure for photocatalytic nitrate reduction enhancement.

Photocatalytic NO3- reduction in water has been regarded as a promising route due to its high efficiency and green feature. Several limiting factors, such as lack of catalytic sites, insufficient light collection, and spatial charge separation capacity photocatalytic denitrification, still need to be overcome for the practical applications. Herein, an innovative LiNbO3/ZnS heterojunction with a unilateral opening core-shell structure was constructed. ZnS was tightly anchored on the surface of LiNbO3 by modified electrostatic self-assembly method. High nitrate removal rate (98.84%) and N2 selectivity (98.92%) were achieved with a molar ratio of LiNbO3 and ZnS of 1:5 (1:5L-ZS) using formic acid as a hole scavenge. The LiNbO3/ZnS degradation kinetics of NO3- was corresponding to the first-order kinetics equation. The nitrate removal rate and N2 selectivity remained stable after three cycles in such photocatalytic NO3- reduction. The outstanding photocatalyst performance can be ascribed to the improved surface active sites, the well-matched band structure, and the unique core-shell structure. It provides an effective strategy for controllable fabrication of core-shell photocatalyst with strong light-harvesting ability and charge separation efficiency to enhance the removal rate of nitrate in water.

N-doping TiO2 hollow microspheres with abundant oxygen vacancies for highly photocatalytic nitrogen fixation.

Photocatalytic fixation of nitrogen to ammonia (NH3) is a green but low-efficiency technology due to the high recombination of photo-generated carriers and poor light absorption of photocatalysts. Generally, the adsorption capacity for N2 and the band position of TiO2 are responsible for bandgap, light-adsorption, and the separation of photocarriers. Therefore, they play crucial roles to improve catalytic activity. Herein, N-doping TiO2 hollow microspheres (NTO-0.5) with oxygen vacancies were synthesized via a hydrothermal method using phenolic resin microsphere as a template. The obtained NTO-0.5 achieves an impressive ammonia yield of 80.09 µmol gcat-1h-1. Oxygen vacancies of NTO-0.5 were confirmed by ESR, Raman, XPS, Zeta potential, and H2O2 treatment for reducing oxygen vacancies. The ammonia yield of NTO-0.5 decreases to 34.78 µmol gcat-1h-1 after reducing oxygen vacancies by H2O2 treatment, which demonstrates the importance of oxygen vacancies. The oxygen vacancies narrow the bandgap from 3.18 eV to 2.83 eV and impede the recombination of photo-generated carriers. The hollow microspheres structure is conducive to light absorption and utilization. Therefore, the synergistic effect between the oxygen vacancies and the hollow microspheres structure boosts the efficiency of photocatalytic nitrogen fixation. After four cycles, the ammonia production yield still maintains at 76.52 µmol gcat-1h-1, meaning high stability. This work provides a new insight into the construction of catalysts with oxygen vacancies to enhance photocatalytic nitrogen fixation performance.