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Conversion of carbon dioxide into useful chemicals has attracted great attention. However, the significant bottlenecks facing in the field are the poor conversion efficiency of CO2 and low selectivity of products. Herein, hierarchical BiOBr hollow microspheres are fabricated by a solvothermal method using ethylene glycol (EG) as solvent in presence of polyvinyl pyrrolidone (PVP). The hollow BiOBr microspheres prepared at 120 °C exhibit the best performance for CO2 photoreduction. The evolution rates of product CO and CH4 are up to 88.1 µmol g-1h−1 and 5.8 µmol g-1h−1, which are 8.8 times and 5.8 times higher than that of plate-like BiOBr respectively. The hollow microspheres possess larger specific area and generate multiple reflections of light in the cavity, thus enhancing the utilization efficiency of light. The modulated electronic structure by oxygen vacancy (OVs) is beneficial to the transfer of photogenerated electrons and holes. Especially, the enriched charge density of BiOBr by OVs is conductive to the adsorption and activation of CO2, which could lower the overall activation energy barrier of CO2 photoreduction. In summary, the synergistic effect of the hollow structure with OVs plays a vital role in boosting the photoreduction of CO2 for BiOBr. This work provides a new opportunity for designing the high efficiency catalyst by morphology engineering with defects at the atomic level for CO2 photoreduction.

Photocatalytic overall water splitting is considered as an ideal solution to the energy crisis by converting inexhaustible solar energy into hydrogen energy. However, the practical application of p...

Silicon is one of the most promising candidates for anode materials for next-generation lithium-ion batteries due to its high theoretical capacity. However, the catastrophic volume change upon lith...

Monolayer nanosheets of Bi₂W₁–ₓMoₓO₆ solid solutions, possessing an average thickness of 0.98 nm, have been rationally designed and constructed by a facile bottom-up route of a hydrothermal reaction. The tiptop photocatalytic efficiency of Bi₂W₁–ₓMoₓO₆ monolayer nanosheets can be achieved for effective reduction conversion of nitrobenzene into anilines under visible light, in conspicuous contrast to the homologous pristine Bi₂WO₆ and Bi₂MoO₆ components. The optimal Bi₂W₀.₂₅Mo₀.₇₅O₆ monolayer nanosheets exhibit a high selectivity and stability for photocatalytic nitrobenzene reduction, affording a high aniline generating rate of 650 μmol g–¹.h–¹, in excess of the previously reported ordinary photocatalysts. The good photocatalytic property could be due to the lattice distortion in solid solutions for structural polarity by the more electronegative W substitution, leading to the efficient interfacial and interior separation of photogenerated carriers. The structure–activity relationship of Bi₂W₁–ₓMoₓO₆ demonstrates a novel insight to devise property-controllable photocatalysts at the atomic level with high efficiency for organic photocatalytic reactions.

Sesamin, a lignan compound, exhibits a variety of biological activities and possesses potent anticancer properties on some human cancers. However, its effect on human colorectal cancer (CRC) remains to be elucidated. To investigate the effects of sesamin on CRC cells and further to explore the mechanisms, cell viability, cell cycle and apoptosis assays were performed in this study. We found that sesamin had a selective antiproliferation of CRC cell line HCT116 in a dose- and time-dependent manner, but no obvious effect on human normal colorectal mucosa epithelial cell FHC. Further study showed that sesamin-induced cell cycle arrest and decreased the expression of Cyclin D1 significantly and dose-dependently in HCT116 cells. Moreover, sesamin dose-dependently triggered apoptosis of HCT116 but not FHC, and promoted the expression levels of proapoptotic biomarkers Bax, cleaved caspase-3 and cleaved PARP-1 and inhibited the expression of antiapoptotic biomarker Bcl-2. Western blot analysis was used to reveal the possible signaling pathways, and we found that sesamin upregulated the phosphorylation expression levels of C-Jun N-terminal kinase (JNK) and p38 except ERK1/2 in a dose-dependent way in both HCT116 and another CRC cell line SW480. Moreover, we found that the apoptosis effect induced by sesamin was partially eliminated by inhibiting JNK or p38 activation. Finally, we showed that sesamin effectively reduced the growth of xenograft tumors derived from cell lines with limited toxicity. Taken together, the potential ability of sesamin to induce cell cycle arrest and apoptosis was shown to be via the p38 and JNK mitogen-activated protein kinase signaling pathways, which may be one of the mechanisms of the anticancer activity of this low-toxic agent.

The design and synthesis of two semiconducting bis (4-ethynyl-bridging 1, 8-naphthalimide) bolaamphiphiles (BENI-COO- and BENI-NH3 + ) to fabricate supramolecular metal-insulator-semiconductor (MIS) nanostructures for biomimetic hydrogen evolution under visible light irradiation is presented. A H2 evolution rate of ca. 3.12 mmol g-1 ⋅h-1 and an apparent quantum efficiency (AQE) of ca. 1.63 % at 400 nm were achieved over the BENI-COO- -NH3 + -Ni MIS photosystem prepared by electrostatic self-assembly of BENI-COO- with the opposite-charged DuBois-Ni catalysts. The hot electrons of photoexcited BENI-COO- nanofibers were tunneled to the molecular Ni collectors across a salt bridge and an alkyl region of 2.2-2.5 nm length at a rate of 6.10×108 s-1 , which is five times larger than the BENI-NH3 + nanoribbons (1.17×108 s-1 ). The electric field benefited significantly the electron tunneling dynamics and compensated the charge-separated states insufficient in the BENI-COO- nanofibers.

Sun-light driven water splitting to produce hydrogen and oxygen gases in a large scale is a promising method for solar energy conversion. However, it is still a challenge to explore photocatalytic materials for overall water splitting due to the limited choice of a single semiconductor with suitable band energy levels (matching with water redox splitting potentials) while with minimized band gap for light harvesting. Here, we report a one-photon excitation pathway by coupling polymeric carbon nitride (PCN) with LaOCl semiconductor to achieve overall water splitting. This artificial photosynthesis composite catalyzes the decomposition of H2O into H2 and O2, with evolution rates of 22.3 and 10.7 µmol h-1, respectively, outperforming most of the PCN-based materials. The high photocatalytic performance of PCN/LaOCl can be ascribed to the simultaneously accomplished reduction and oxidation of water on LaOCl and PCN domains, respectively, as well as the fast charge separation and migration induced by the interfacial electric field related to LaOCl modification. This study provides new insights on the development of composite photocatalysts for pure water splitting on the basis of polymer-based materials via charge modulation.

Developing high-efficiency photocatalysts for water decomposition is one of the major challenges in converting solar energy to chemical energy. In this paper, Ni(OH)2 modified Mn0.5Cd0.5S solid solution without the use of precious metals is successfully synthesized via hydrothermal method followed by precipitation, the photocatalytic activity for hydrogen evolution and stability of composite samples present significant improvement with respect to the pristine Mn0.5Cd0.5S. These improvements are attributed to that Mn0.5Cd0.5S CB potential (−0.7 V vs. NHE) is more negative than the potential of Ni2+/Ni (−0.23 V vs. NHE), which promotes the transfer of photo-generated electrons from Mn0.5Cd0.5S CB to Ni(OH)2 for H2 production as well as partial reduction of Ni2+ to Ni0, leaving VB holes to oxidize the sacrificial reagents. The metal Ni atoms with conductivity and Ni(OH)2 nanoparticles not only boost the segregation and transfer of photo-induced carriers but also act as water-reduction promoter, thereby promoting the photocatalytic activity for hydrogen release. A novel visible light responsive MnxCd1-xS-based photocatalytic material promising for practical applications is provided in this subject.

In a previous study we identified EARLY BUD BREAK 1 (EBB1), an ERF transcription factor, in peach (Prunus persica var. nectarina cultivar Zhongyou 4); however, little is known of how PpEBB1 may regulate bud break. To verify the function of PpEBB1 in bud break, PpEBB1 was transiently transformed into peach buds, resulting in early bud break. Bud break occurred earlier in PpEBB1-oe poplar (Populus trichocarpa) obtained by heterologous transformation than in wild type (WT), consistent with the peach bud results, indicating that PpEBB1 can promote bud break. To explore how PpEBB1 affects bud break, differentially expressed genes (DEGs) between WT and PpEBB1-oe poplar plants were identified by RNA-sequencing. The expression of DEGs associated with hormone metabolism, cell cycle, and cell wall modifications changed substantially according to qRT-PCR. Auxin, ABA, and total trans-zeatin-type cytokinin levels were higher in the PpEBB1-oe plants than in WT plants, while the total N6-(Δ 2-isopentenyl)-adenine-type cytokinins was lower. Yeast two-hybrid and bimolecular fluorescence complementation assays verified that a cell wall modification-related protein (PpEXBL1) interacted with PpEBB1 suggesting that PpEBB1 could interact with these cell wall modification proteins directly. Overall, our study proposed a multifaceted explanation for how PpEBB1 regulates bud break and showed that PpEBB1 promotes bud break by regulating hormone metabolism, the cell cycle, and cell wall modifications., The transcription factor EBB1 plays important roles in regulating bud break in peach trees by regulating hormone metabolism, the cell cycle, and cell wall modifications.

The diverse nature of organic precursors offers a versatile platform for precisely tailoring the electronic properties of semiconducting polymers. In this study, three fully conjugated sp2 carbon-linked polymers have been designed and synthesized for photocatalytic hydrogen evolution under visible-light illumination, by copolymerizing different C3 -symmetric aromatic aldehydes as knots with the 1,4-phenylene diacetonitrile (PDAN) linker through a C=C condensation reaction. The hydrogen evolution (HER) is achieved at a maximum rate of 30.2 mmol g-1 h-1 over a polymer based on 2,4,6-triphenyl-1,3,5-triazine units linked by cyano-substituted phenylene, with an apparent quantum yield (AQY) of 7.20 % at 420 nm. Increasing the degree of conjugation and planarity not only extends visible-light absorption, but also stabilizes the fully conjugated sp2 -carbon-linked donor-acceptor (D-A) polymer. Incorporating additional electron-withdrawing triazine units into the D-A polymer to form multiple electron donors and acceptors can greatly promote exciton separation and charge transfer, thus significantly enhancing the photocatalytic activity.

Carbon coated core-shell structured anode has been reported with advantages to enhance conductivity and partly buffer the volume expansion. However, huge mechanical stress and long lithium/sodium transmission distance also hinder the lithium/sodium storage performances. For maximum buffer effect, we herein design a multicore-shell CoSn@C nanocages with decreased particle size and enhanced extra space in comparison with the monocore-shell sample. This unique structure can effectively buffer the volume expansion in the deintercalation process, alleviate electrode pulverization and improve cyclic stability. Electrochemical tests show that multicore-shell CoSn@C nanocubes have excellent discharge capacities of 1010.9 mAh g−1 at 0.5 A g−1 after 160 cycles and 818 mAh g−1 at 1 A g−1 after 300 cycles for lithium ion battery anode, much higher than that of the monocore-shell sample. The sodium storage performance of the multicore-shell CoSn@C is also far more than the monocore-shell one. Above results suggests that fabrication of multicore-shell structure is an excellent design to buffer volume expansion and enhance performance for lithium and sodium storage.

MALAT1-associated small cytoplasmic RNA (mascRNA) is a highly conserved transfer RNA–like (tRNA-like) noncoding RNA whose function remains largely unknown. We show here that this small RNA molecule played a role in the stringent control of TLR-mediated innate immune responses. mascRNA inhibited activation of NF-κB and mitogen-activated protein kinase (MAPK) signaling and the production of inflammatory cytokines in macrophages stimulated with LPS, a TLR4 ligand. Furthermore, exogenous mascRNA alleviated LPS-induced lung inflammation. However, mascRNA potentiated the phosphorylation of IRF3 and STAT1 and the transcription of IFN-related genes in response to the TLR3 ligand poly(I:C) both in vitro and in vivo. Mechanistically, mascRNA was found to enhance K48-linked ubiquitination and proteasomal degradation of TRAF6, thereby negatively regulating TLR-mediated MyD88-dependent proinflammatory signaling while positively regulating TRIF-dependent IFN signaling. Additionally, heterogeneous nuclear ribonucleoprotein H (hnRNP H) and hnRNP F were found to interact with mascRNA, promote its degradation, and contribute to the fine-tuning of TLR-triggered immune responses. Taken together, our data identify a dual role of mascRNA in both negative and positive regulation of innate immune responses.

Mortierella alpina has a strong capacity for lipid accumulation. Isocitrate dehydrogenase (IDH) plays an important role in affecting the flow of intracellular carbon sources and reducing power NADPH for lipid biosynthesis. In this study, the effect of various IDHs (NAD+- and NADP+-specific) in M. alpina on the lipid accumulation was investigated through homologous overexpression. The results showed that the transcription level and enzyme activity of the IDHs from M. alpina (MaIDHs) in homologous overexpressing strains were higher than those of the control strain, but that their biomass was not significantly different. Among the various NAD+-specific MaIDH1/2/3 overexpression, NAD+-MaIDH3 reduced total lipid content by 12.5%, whereas overexpression NAD+-MaIDH1 and NAD+-MaIDH2 had no effect on fatty acid content. Intracellular metabolites analysis indicated that the overexpression NAD+-MaIDH3 strain had reduced the fatty acid accumulation, due to its greater carbon flux with the tricarboxylic acid cycle and less carbon flux with fatty acid biosynthesis. For the NADP+-MaIDH4/5/6 recombinant strains overexpressing only NADP+-MaIDH4 enhanced the total fatty acid content by 8.2%. NADPH analysis suggested that this increase in lipid accumulation may have been due to the great reducing power NADPH is produced in this recombinant strain. This study provides theoretical basis and guidance for the analysis of the mechanism of IDH function and the potential to improve lipid production in M. alpina.

A novel microbial fuel cell-assisted electro-permanganate process (MFC-PM) was proposed for enhanced diclofenac degradation compared to that of the permanganate oxidation process. By utilizing eco-friendly bio-electricity in situ, the MFC-PM process could activate the simultaneous anodic biological metabolism of urea and the cathodic electro-permanganate process. Density functional analysis and experimental evidence revealed the reactive manganese species (Mn(VII)aq, Mn(VI)aq, Mn(V)aq, and Mn(III)aq), generated via single electron transfer, contributed to diclofenac degradation in the cathodic chamber. The sites of diclofenac with a high Fukui index were preferable to be attacked by reactive manganese species, and diclofenac degradation was mainly accomplished through the ring hydroxylation, ring opening, and decarboxylation processes. Biological detection revealed clostridia were the primary electron donor in the anode chamber in an anaerobic environment. Furthermore, maximum output power density of 1.49 W m−3 and the optimal removal of 94.75% diclofenac were obtained within 20 min under the conditions of pH = 3.0, [DCF]0 = 60 µM, and [PM]0 = 30 µM. Diclofenac removal efficiency increased with external resistance, higher PM dosage, and lower catholyte pH. In addition, the MFC-PM process displayed excellent applicability in urine and other background substances. The MFC-PM process provided an efficient and energy-free bio-electricity catalytic permanganate oxidation technology for enhancing diclofenac degradation.

The dormancy-associated MADS-box (DAM) genes PpDAM5 and PpDAM6 have been shown to play important roles in bud endodormancy; however, their molecular regulatory mechanism in peach is unclear. In this study, by use of yeast one-hybrid screening, we isolated a TEOSINTE BRANCHED1/CYCLOIDEA/PROLIFERATING CELL FACTOR transcription factor, PpTCP20, in the peach cultivar ‘Zhongyou 4’ (Prunus persica var. nectarina). The protein was localized in the nucleus and was capable of forming a homodimer. Electrophoretic mobility shift assays demonstrated that PpTCP20 binds to a GCCCR element in the promoters of PpDAM5 and PpDAM6, and transient dual luciferase experiments showed that PpTCP20 inhibited the expression of PpDAM5 and PpDAM6 as the period of the release of flower bud endodormancy approached. In addition, PpTCP20 interacted with PpABF2 to form heterodimers to regulate bud endodormancy, and the content of abscisic acid decreased with the release of endodormancy. PpTCP20 also inhibited expression of PpABF2 to regulate endodormancy. Taken together, our results suggest that PpTCP20 regulates peach flower bud endodormancy by negatively regulating the expression of PpDAM5 and PpDAM6, and by interacting with PpABF2, thus revealing a novel regulatory mechanism in a perennial deciduous tree., PpTCP20 controls the release of endodormancy in peach flower buds by negatively regulating the expression of PpDAM5 and PpDAM6, and by interacting with PpABF2.

Designing controllable porous structures with hybrid components is of widespread interest for lithium sulfur batteries (LSBs), which is helpful to selecting an optimal sulfur host. Here, we establish a facile route to three-dimensional hierarchical porous structures based on the dopamine surface-functionalization of silica nanoparticles. This strategy enables in-situ transformation of molybdenum dioxide particles into building blocks owing to the ability of dopamine coordinated with molybdate ions. Through aperture analysis and electrochemical measurements, these hosts manifest their respective superiority in sulfur fixation By contrast, the hierarchical porous structure with inner pores of 50 nm and interlocking pores exhibits a superior comprehensive performance than the other samples. Our work also proposes a universal and highly controllable strategy in constructing more powerful porous structures for LSBs or other applications.

Surface frustrated Lewis pairs (SFLPs) have been implicated in the gas-phase heterogeneous (photo)catalytic hydrogenation of CO2 to CO and CH3 OH by In2 O3-x (OH)y . A key step in the reaction pathway is envisioned to be the heterolysis of H2 on a proximal Lewis acid-Lewis base pair, the SFLP, the chemistry of which is described as In⋅⋅⋅In-OH + H2 → In-OH2 + ⋅⋅⋅In-H- . The product of the heterolysis, thought to be a protonated hydroxide Lewis base In-OH2 + and a hydride coordinated Lewis acid In-H- , can react with CO2 to form either CO or CH3 OH. While the experimental and theoretical evidence is compelling for heterolysis of H2 on the SFLP, all conclusions derive from indirect proof, and direct observation remains lacking. Unexpectedly, we have discovered rhombohedral In2 O3-x (OH)y can enable dissociation of H2 at room temperature, which allows its direct observation by several analytical techniques. The collected analytical results lean towards the heterolysis rather than the homolysis reaction pathway.

Our study on the synergetic effect of electrolysis and permanganate (E-PM) revealed a novel alternative method for generating active Mn(III)aq heterogeneously by electrochemically activating PM with Mn2+ as promoter and stabilizer. We systematically explored the generation mechanism of Mn(III)aq. It indicated that all three components (electrolysis + PM + Mn2+) were necessary to facilitate the generation of active Mn(III) in the E-PM-Mn2+ process. It was worth noting that Mn2+, as essential promoter and Mn(III)aq stabilizer, could considerably enhance the concentration of Mn(III) in the E-PM-Mn2+ process. Further study revealed that the active Mn(III) was mainly produced on cathode rather than in aqueous solution or on anode. In addition, the soluble Mn(III)aq generated in the E-PM-Mn2+ process was demonstrated to be very efficient for the degradation and mineralization of diclofenac (DCF) as well as methyl blue, carbamazepine, phenol, sulfamethoxazole, and nitrobenzene. Moreover, the effects of the main operating parameters (Mn2+ dosage, PM dosage, applied current density, pH of solution, and contaminant concentration) and different water matrices on the E-PM-Mn2+ process were investigated systematically. Possible degradation pathways of DCF in the E-PM-Mn2+ process were also proposed. The results demonstrated that the E-PM-Mn2+ system based on active Mn(III)aq could create a more efficient, sustainable, and less energy costing technology for water treatment.

The construction of high-performance and stable nanocomposite photocatalyst remains a great challenge toward photocatalytic hydrogen evolution reaction, which is mainly due to the mediocre interfacial contact between the cocatalyst and the host. In this work, ultrasmall NiS is highly dispersed on HNb3O8 2D nanosheet via a facile electrostatic adsorption/self-assembly process. Interestingly, the growth of NiS is greatly suppressed by the interlayered spatial steric inhibition effect and a strong interaction between NiS and HNb3O8 nanosheet is formed. While the modification of NiS by the traditional methods, such as the coprecipitation and mechanical mixing methods, could not generate the sub-nanometer size of NiS with the tight contract between NiS and HNb3O8 nanosheet. As a result, the recombination of the photogenerated carriers is greatly suppressed on the sample prepared by our method. Furthermore, the overpotential of hydrogen evolution reaction could also be reduced significantly. Thus, the as-prepared composite exhibits a markedly improved photocatalytic H2 evolution activity as well as considerable stability. The optimal sample shows the H2 evolution rate of 1519.4 μmol g−1 h−1, which is about 17.4 times higher than that of the bare HNb3O8 nanosheets. The activity is also a magnitude higher than that of the sample prepared by a mechanical mixing method. Additionally, NiS/HNb3O8 prepared by the developed method shows a comparable activity as well as overpotential with Pt/HNb3O8, indicating an alternative to platinum.

Significance Oxidation and reduction steps in catalysis are always in series, and excellent activity can be achieved when they occur in close proximity. Photooxidation and photoreduction are generally separated and rarely in series. This work develops defect engineering at the metal–oxide interface to make photooxidation sites close to photoreduction sites. Taking solar hydrogen production from aqueous alcohols over Pt/ T i O 2 as an example, the proximity effect triggers unusual reactions and thus increases hydrogen yield per photon from 0.046 to 1.28. Our study provides a direction for the development of efficient photocatalysis.

The photocatalytic overall conversion of CO2 with H2O to chemical fuel and oxygen mimicking natural photosynthesis is a huge challenge in photocatalysis. This work shows the achievement of the solar-driven photocatalytic overall CO2 reduction with H2O to CO and O2 over a Persian buttercup-like BiOBrxCl1-x solid solution. A CO generation rate of 15.86 μmol g−1 h−1 with the approximate stoichiometric O2 evolution is yielded on BiOBr0.6Cl0.4 solid solution under simulated solar light irradiation, which was about 7.5 and 10.2 times higher than that of pure BiOCl (2.11 μmol g−1 h−1) and BiOBr (1.55 μmol g−1 h−1), respectively. The enhanced photoactivity is contributed to the mediate band gap and energy level tuned by the formation of BiOBrxCl1-x solid solution to facilitate the separation of photogenerated charges. Besides the unique electron structure, the photoinduced oxygen vacancy (OV) formed on BiOBrxCl1-x solid solution also plays an important role in the CO2 reduction.

Loading noble metal on the surface has been widely used to improve photocatalytic activity of semiconductor photocatalyst. Here, Pt-embedded anatase (A)-rutile (R) TiO2 junction photocatalyst (A/Pt/R) was found to show much more efficient photocatalytic H2 evolution activity than the other TiO2 photocatalysts loading Pt on the outside surface (such as Pt/A/R, Pt/A, Pt/R and Pt/P25), although the as-embedded Pt is unreachable to reactants. The A/Pt/R sample shows a photocatalytic H2 evolution rate as high as 17.9 mmol⋅gcat−1⋅h−1, which is 27.2 and 2.5 times higher than the common A/R and Pt/A/R samples, respectively. The traditional theory fails to explain the unexpected high photoactivity. The reverse tandem Schottky junction is suggested to be possibly responsible for the high photoactivity of A/Pt/R, which allows the photogenerated electrons to transfer more swimmingly from rutile to anatase than the common A/R phasejunction. This finding provides a new strategy for further promoting photocatalytic activity of Pt/TiO2 and other heterophase or heterojunction photocatalysts.

In this study, powder activated carbon (PAC) utilized to activate peroxydisulfate (PDS) was investigated for decolorization of Acid Orange 7 (AO7). The results indicated a remarkable synergistic effect in the PAC/PDS system. The effect of PAC, PDS dosages and initial pH on AO7 decolorization were studied and the processes followed first-order kinetics. Response surface method with central composite design (CCD) model was utilized to optimize these three factors and analyze the combined interaction. The optimum condition for the decolorization rate of AO7 was analyzed as the following: PAC (0.19 g/L), PDS (1.64 g/L), and initial pH (4.14). Cl− and SO42− showed a promoting effect on AO7 decolorization while HCO3− had a slightly inhibiting effect. Quenching experiments confirmed that both sulfate and hydroxyl radicals were the oxidizing species, and the oxidation reaction occurred on the surface of PAC. The results of UV-vis spectrum with 100% decolorization rate and the 50% total organic carbon reduction indicated highly efficient decolorization and mineralization of AO7 in the PAC/PDS system. Finally, the recovery performance of PAC was studied and the result indicated PAC had poor reuse in reactivity.

Photocatalytic CO2 reduction conjugated with H2O oxidation is regarded as a promising artificial photosynthesis system because it can simultaneously solve energy and environment problems. Here, a novel solid solution, Zn2Ti1−xGexO4 (0 ≤ x ≤ 0.15), with high photocatalytic activity for the reaction was successfully synthesized via a facile molten salts route. The Zn-based solid solutions with size about 200 nm have a homogeneous inverted cubic spinel structure (Fd3m) and a continuously modulated band gap with the Ge content. For the CO2 reduction reaction with H2O under simulated solar irradiation, the Zn2Ti1−xGexO4 solid solutions display not only high activity for the conversion of CO2 into CH 4 and CO fuels, but also long-term stability (>60 h of catalytic reaction). Experimental results and theoretical calculations indicated that the conduction and the valence bands of the cubic spinel Zn2TiO4 are positively shifted by introducing Zn2GeO4 with a pseudocubic inverse spinel structure, but the band gaps of solid solutions are simultaneously modulated with the introduction of germanium. Nevertheless, the Zn2TiO4 affords a light-carrier effective mass and strong electron delocalization by forming a solid solution with Zn2GeO4, which is beneficial to improving migration of photogenerated electrons and holes. As a synergistic result of band gap narrowing and high carrier diffusion, good conversion efficiencies for production of solar fuels through the reactions of CO2 reduction with H2O are achieved.

Drought stress is a serious threat to agriculture and the environment. Brassinosteroids (BRs) increase tolerance to drought stress of plant. Autophagy plays important roles in plant responses to drought stress; however, there are few reports on autophagy in peach (Prunus persica). In total, 23 putative autophagy-related genes (ATGs) in peach were identified using ATGs from the Arabidopsis thaliana genome as query in BLASTx algorithm-based searches. Under drought stress, the photosynthetic abilities of peach leaves decreased, while antioxidant enzyme activities, autophagy and ATG expression increased. A correlation analysis showed that antioxidant enzyme activities are inversely correlated to the expression levels of the PpATGs. During drought, the PpATG8s and some PpATG18s had the strongest responses. To investigate enhanced drought-stress tolerance, peach was treated with water, 100 nM 24-epibrassinolide (EBR), 1 μM EBR, 10 μM EBR and 1 μM voriconazole. Exogenous EBR at 1 μM decreased the malondialdehyde (MDA) content under drought stress when compared with water-, 1 μM voriconazole-, 100 nM EBR- and 10 μM EBR-treated peach leaf. The 1-μM EBR application increased superoxide dismutase (SOD), catalase (CAT), peroxidase (POD), ascorbate peroxidase (APX) and glutathione peroxidase (GR) activities during drought stress. In addition, the expression levels of PpATGs were inhibited by EBR. Thus, the 1-μM EBR treatment alleviated drought-stress damage to peach leaves, decreased PpATG expression levels and reduced the number of autophagosomes.

With the purpose to settle the aggregation and conductivity issues of the active materials, the metal disulfides (MS2, M = Fe, Co) nanoparticles in-situ encapsulated by amorphous carbon layers (MS2@C) have been synthesized by directly vulcanizing the iron (III) acetylacetonate or cobalt (II) acetylacetonate, which are both the metal source and carbon source, using sulfur power as S source and dispersant by a facile one-step heating method. A structure that MS2 nanoparticles are well wrapped by amorphous carbon layer uniformly coated by many ultra-small MS2 nanoparticles is obtained. Benefiting from the unique multidimensional structure that integrates the advantages of low-dimensional nanostructures and high-dimensional bulk structure, FeS2@C and CoS2@C composites evaluated as electrode materials for lithium storage exhibit superior electrochemical performance. After 100 charge-discharge cycles, this novel FeS2@C architecture delivers a reversible capacity of 829 mAh g−1 at 100 mA g−1. Moreover, a high specific capacity of 480 mAh g−1 for FeS2@C at 1000 mA g−1 after 500 cycles is obtained. As for CoS2@C composite, a high specific capacity of 481 mAh g−1 at 500 mA g−1 after 300 cycles is still displayed. This remarkable cycling property and superior rate capability demonstrate the potential applications for next-generation lithium-ion batteries.

Pursuing higher energy density and longer lifespan of alkaline ion batteries (i.e., Li+ and Na+) to satisfy the growing demand in the energy market remains challenging. One of the limitations is the graphite anode, which has limited lithium storage capability and is incapable of storing sodium. Herein, a unique metal sulfide-based anode with high capacity and extremely long cycle life was presented; a new concept of a self-breathable structure and hetero-atom doping features was introduced. In detail, a new aurilave-like structure composed of a metal sulfide shell and a nitrogen-doped carbon framework (e.g., N–C@MoS2) was constructed using natural spores as the template. Benefiting from the uniqueness of the bio-inspired structure and components, N–C@MoS2 exhibited extraordinary alkaline-ion storage performance with respect to rate capability, initial coulombic efficiency and cycle life, which were superior to those of most MoS2-based anodes reported before. We found that the inside of the aurilave structure served as a dynamic “electrolyte reservoir”, while the N–C skeleton acted as a “highway” for ion/electron transport, thereby leading to a deeper and faster conversion reaction rate. We hope that the bio-inspired architectures and components can be widely applied to design materials for other applications.

A family of functionalized MIL-68(In) have been successfully synthesized and applied to photoreduction of Cr(VI) aqueous under simulated sunlight (280 nm

Kornblum oxidation (benzyl bromide to benzaldehyde) can be realized efficiently by NaOH-modified graphitic carbon nitride (g-C3N4). Different from the oxidation reaction carried out at high temperature using DMSO as an oxidant, our reaction is eco-friendly because it is carried out at room temperature under LED light irradiation using molecular oxygen as an oxidant, which avoids the problems of toxicity, pollution and purification. Alkali treatment leads to the surface deprotonation of g-C3N4 to form NaOH-modified g-C3N4 (Na/g-C3N4). The modifications of the electronic structure and surface chemical environment of g-C3N4 facilitate light absorption and formation of ˙O2− and therefore make the conversion of benzyl bromide reach up to 99%. This work demonstrates a green and sustainable route for benzaldehyde production and the superiority of g-C3N4 for organic syntheses.

Coupling photocatalytic H2 evolution and phenol degradation have drawn much attention on H2 as clean energy and phenol as an organic pollutant to the environment. Such dual-function reaction can utilize the chemical potential of phenol oxidation to make up the chemical potential required for hydrogen evolution from water splitting. The production of H2 thus was enhanced via the phenol oxidation. However, H2 is still needed to be purified from the reaction products by traditional methods. In this study, we demonstrated the simultaneous separation of H2 using a photo twin-reactor under artificial sunlight, in which the photocatalytic efficiency was substantially increased due to the inhibition of backward reaction by separating H2 from the products directly. Three Rh-doped SrTiO3 (STO) photocatalysts calcined at 900, 1100, 1200 °C (named as STO:Rh900, STO:Rh1100, and STO:Rh1200, respectively) were prepared by solid-state fusion reaction, then photo-deposition method was applied to synthesize Pt loading STO:Rh. All photocatalysts were fully characterized by XRD, XPS, UV–vis, SEM, TEM, and DLS. A single reactor and a twin-reactor (Z-scheme system) were systematically designed by using Pt/STO:Rh for H2 evolution photocatalyst and WO3 for phenol oxidation photocatalyst, where Fe3+/Fe2+ pairs were served as electron transfer mediators to conduct the dual-function reaction. In the single reactor, the stoichiometric of the dual-function reaction was proposed and with high consistency to the experimental data. By using the twin-reactor, H2 production rate increased 2.7 times, reaching 1.90 μmol g−1 h−1, compared to that in the single reactor. Moreover, the H2 concentration of the gas-phase products increased from 70% (in the single reactor) to 94% owing to the separation function of the twin-reactor, which would significantly reduce the cost for further purification. The effect of phenol concentration on H2 production in the twin-reactor was also thoroughly investigated. The results showed that increased phenol initial concentration would enhance the production of H2. With 200 μmol L−1 phenol, the H2 yield (11.37 μmol g−1 in 6-h reaction) was increased by 20% compared to that of pure water splitting.

Coupling hydrogen fuel production with selective oxidative organic synthesis in one cooperative manner offers a promising avenue to enable efficient utilization of photoexcited carriers to achieve sustainable chemistry. Herein, a new Mo2N/Mn0.3Cd0.7S/CoPi photocatalyst is reported for visible-light-driven hydrogen production paired with selectively oxidative C C bond formation. Mo2N acting as electron collectors and reduction sites are adsorbed on the Mn0.3Cd0.7S by interfacial Mo-S bond, while CoPi acting as hole collectors and active sites for oxidation reaction are deposited on Mo2N/Mn0.3Cd0.7S. Remarkably, the synergetic effect of Mo2N and CoPi dual cocatalysts results in the adjustable flexibility of switching benzaldehyde (BAD) production to C C coupling synthesis, thus exhibiting the high selectivity of C C coupling products. Mechanism studies indicate that the C C coupling reaction occurs through a free radical mechanism. The present work gives insight for achieving highly efficient C−C coupling synthesis with hydrogen evolution by loading dual cocatalysts.

Photocatalytic hydrogen generation will benefit from the realization of more active but less expensive cocatalysts compared with noble metal counterparts. Herein we developed a universal vapor deposition method that selectively uses the thermal decomposition products of sodium hypophosphite as a phosphorus source for the fabrication of inexpensive and highly efficient metal phosphate (MPi) modified CdS nanorods. We find that the modification with a bimetal phosphate (i.e., 5 wt % NiCoPi) leads to an activity enhancement by a factor of approximately 52 in boosting visible-light-driven hydrogen evolution relative to the pristine CdS nanorods. The photocatalyst exhibits a high hydrogen generation rate of 13.44 mmol·g-1·h-1, which is much higher than that of its single metal counterparts (NiPi, 8.70 mmol·g-1·h-1; CoPi, 5.79 mmol·g-1·h-1) and 1 wt % Pt modified CdS (1.33 mmol·g-1·h-1). Its apparent quantum efficiency reaches 23.5% at 420 nm. Furthermore, it also shows remarkable photostability for eight consecutive cycles of photocatalytic activity tests with total reaction time of 24 h. The excellent photocatalytic performance of the photocatalyst is believed to be associated with the in situ formed NiICoP and NiCoIIIPi cocatalysts, which not only play an important role in photogenerated charge separation but also provide highly active catalytic reaction sites for the corresponding hydrogen evolution reaction and the sacrificial agent oxidation reaction.

We develop a new PdCu/UTCN hybrid by loading low-crystalline PdCu NPs on large-area ultrathin 2D carbon nitride (UTCN) nanosheets that exfoliated from bulk g-C3N4 using a twice thermal exfoliation and repolymerization method for photocatalytic Suzuki C-C cross coupling reaction. Due to the advantages of 2D structure of the UTCN and the changes in electronic structure and surface structure of low-crystalline PdCu NPs, PdCu/UTCN shows promoted photocatalytic activity with high selectivity for Suzuki coupling reaction. The TOF value for coupling of iodobenzene with phenylboronic acid is 418.2 h−1, which is 8 and 6.2 times higher than that of previously reported Pd-g-C3N4 and Pd based alloy photocatalysts under the same reaction, respectively. Morevoer, this photocatalyst shows a good functional group tolerance as well as good to excellent yield and selectivity for various substrates. This study reports for the first time the PdCu alloy supported UTCN photocatalytic material for enhanced Suzuki reaction.

CuI-BiOI/Cu film with effective photocatalytic inactivation of E. coli under visible-light-driven (VLD) were prepared on copper sheet and were characterized by TEM, SEM, XRD, XPS and DRS. The photocatalytic inactivation of E. coli of CuI, BiOI, CuI-BiOI and CuI-BiOI/Cu film were investigated. The results showed that CuI-BiOI/Cu film exhibit the most excellent bacteria disinfection activity, and the quantity of viable bacteria could almost inactivate after being illuminated for 2 h. The Laser Scanning Confocal Microscopy (LSCM) observation exhibits that the morphology of bacteria changed a lot after visible light irradiation, and the UV spectra confirm the leakage of bacterial protein. The antibacterial mechanism was studied by employing photoelectrochemical techniques and scavengers of different reactive species, which reveals that the effect of reactive species on the antibacterial activity decrease in order h+ > e−> H2O2> HO > O2−. The CuI and Cu play the important role in the separation of h+ and e−. During the photocatalytic process, the CuI act as a hole-transport channel and the Cu act as electron transfer for CuI-BiOI heterostructure, which promotes the separation of photogenerated charges and enhances the photocatalytic antibacterial activity of the as-prepared samples.

A marigold-like SiC@MoS2 nanoflower with a unique Z-scheme structure efficiently achieves the overall conversion of gas phase CO2 with H2O (CO2 (g) + 2H2O (g) = CH4 + 2O2) without any sacrificial reagents under visible light (λ ≥ 420 nm) irradiation. The CH4 and O2 evolution are 323 and 621 μL·g-1·h-1, and stable throughout 5 cycle reactions of total 40 h. This work demonstrates a breakthrough in artificial photosynthesis with the Z-scheme 1D heterojunction constructed by combining 2D semiconductor and 3D semiconductor based on the transfer balance of photogenerated electron and hole.

The pursuit of increased energy density and longer lifespan lithium-ion batteries (LIBs) is urgently needed to satisfy a dramatically increased demand in the energy market. Currently, metal-oxide-based anodes are being intensively studied due to their higher capacities over current graphite anodes. This work introduces a sustainable strategy to construct a metal-oxide-based anode with high capacity and an extremely long lifecycle, in which the features of bioinspired architectures and heteroatom doping can contribute greatly to increased performances. In detail, 1D tubelike metal oxide (e.g., MnO) coated on an N-doped carbon framework (i.e. MnO/N-C) has been designed by using the naturally abundant and renewable Metaplexis japonica fibers (MJFs) as the biotemplate and heteroatom source. Benefiting from the uniqueness of structure and compositions, as-prepared MnO/N-C demonstrates extremely high rate capacities of 951, 777, 497, and 435 mAh g-1 at the rates of 0.5, 2, 4, and 5 Ag-1 , respectively, with a good stability of more than 1000 cycles. It was found that the electrochemical performances are superior to most previous MnO-based anodes, in which the faster kinetics of conversion due to the advantage of the ion/electron transportation and morphological evolution has been verified. It is hoped that the concept of bioinspired architectures with heteroatom doping can be applied in wider applications for increased capability.

We developed a simple X−-assisted (X = Cl, Br, I) one-pot hydrothermal reaction to successfully synthesize a series of BiOX/Bi2WO6 heterojunction. The effect of different halogens and their addition amount on the photocatalytic performance of BiOX/Bi2WO6 composites was investigated using benzyl alcohol selective oxidation under visible-light irradiation. All BiOX could enhance the photocatalytic activity of Bi2WO6, but the BiOBr was the optimum for the maximum improvement of Bi2WO6. The match of energy band structure between BiOX and Bi2WO6 resulted in the highly efficient separation of photogenerated charges, which was mainly attributed to their fundamental distinction of the photocatalytic activity. This work clarified the essential distinction in photocatalytic performance of the different halogen of BiOX/Bi2WO6 heterojunction, and also provided guidance for the construction of efficient heterojunction photocatalysts.

Recently, the consumption of greenhouse-grown peaches has declined because of their poor flavor, which makes them unappealing to consumers. In this study, an optimum intensity of 1.44 kJ·m−2·d−1 of ultraviolet B (UV-B) radiation increased the sugar accumulation and the total soluble solid/total acidity in ‘Tainongtianmi’ fruit. In the Lumi 1 peach tree variety, 1.44 kJ·m−2·d−1 of UV-B radiation increased the anthocyanin contents twofold in fruit compared with the control. Additionally, the sucrose level increased before the second fruit-expansion stage, while it tended to decrease after the slow-growth period in ‘Lumi 1’ peach trees. The fundamental mechanism in response to the increased sucrose level prior to the second fruit-expansion stage was the increased transport of sucrose to fruit caused by an enhanced tonoplastic monosaccharide transporter function in leaves. The sorbitol content increased in mature fruit owing to the slight increase in sorbitol transporter activity in leaves. Our study indicates that exposure to 1.44 kJ·m−2·d−1 UV-B radiation before the second fruit-expansion period can transiently increase the sucrose and total sugar contents of peach, while prolonged irradiation with UV-B inhibited the accumulation of sugars.

Photoelectrochemical (PEC) water splitting has been demonstrated as a promising way to acquire clean hydrogen energy. However, the efficiency has been limited by the high recombination rate of photogenerated electron-hole pairs. Herein, we provided a simple approach to construct a novel SnO2 quantum dots (QDs) modified TiO2 nanorod arrays (NAs) by the calcination of SnCl2 -adsorbed TiO2 NAs. The photocurrent density of SnO2 QDs/TiO2 NAs exhibits about 5 times higher than that of parent TiO2 NAs at a bias of 0.4 V vs. Ag/AgCl. SnO2 QDs/TiO2 NAs also show a high photoelectrocatalytic activity for overall water splitting with an actual yield of H2 and O2 to be 27.85 and 11.87 μmol cm-2 h-1 , respectively. The excellent performance of photoanode for PEC water splitting could be attributed to its Z-scheme heterostructure for good separation efficiency and transport rate of photogenerated charge carries.

Two-dimensional morphological (2DM) metal oxides are highly desirable for the improvement of electrochemical performance of lithium-ion batteries (LIBs). Herein, a facile and scalable strategy to fabricate porous 2DM zinc-cobalt oxide (ZCO) plates is reported, with the help of a morphology-maintained annealing treatment of metal organic frameworks (MOFs). Through change the proportion of metal nitrates in the precursors, a series of porous ZCO plates are synthesized. Thanks to the porous structure, 2DM morphological features and nanosized building block of Co3O4 plates, the Co3O4 plates electrode as anode materials for LIBs display the high reversible capacity (1027 mA h g-1 at 100 mA g−1 after 100 cycles), remarkable rate capability (541 mA h g-1 even at 1000 mA g−1). Furthermore, this strategy of synthesizing the ZCO plates with MOFs provides a new approach to design bimetallic transition metal oxides that the ratio of transition metal is continuously adjusted and has great lithium storage properties.

Photocatalytic ammonia synthesis is of great importance but remains very challenging in photocatalysis. Here, we fabricated a photocatalytic reaction system for the efficiently photocatalytic nitrate reduction to ammonia under UV irradiation using PdSn/NiO/NaTaO3:La as a photocatalyst in the presence of formic acid. Several important factors of the photocatalytic performance were investigated, including initial concentration of the nitrate solution, initial pH value and cocatalyst loadings. Nitrate conversion reaches 100% and ammonia selectivity is 72% over the optimum photocatalyst with 5% bimetallic PdSn alloy and 0.2% NiO loadings. The outstanding performance of photocatalyst can be ascribed to both the strong adsorption of nitrite on NiO and the efficient separation of electron-hole pairs by PdSn bimetallic alloy. Besides as the hole scavenger, formic acid also provides not only carboxyl anion radicals for nitrate reduction but also the in-situ buffer effect on ammonia formation. These results give inspiration for designing the reactive system with efficient photocatalytic ammonia synthesis.

Novel hybrid transition metal phosphides with elaborate designed architectures are long pursued to improve their lithium-ion storage properties. Here, nanocomposite of Fe x Ni 2-x P particles and P-doped carbon (P-C) substrate has been successfully synthesized through a one-step low-temperature phosphidation of Fe 2 Ni MIL-88 nanorods. In this nanocomposite, the nano-sized Fe x Ni 2-x P particles are embedded into the P-doped carbon nanorods substrate, integrating the high capacity of Fe x Ni 2-x P and the excellent conductivity of P-doped carbon together. When used as anode material for lithium-ion batteries, the nanocomposite exhibits a high reversible capacity of 775 mA h g −1 after 400 cycles at a current density of 100 mA g −1 . Even at a high current density of 2000 mA g −1 , a discharge capacity of 360 mA h g −1 could still be maintained. This excellent electrochemical performance may be attributed to the nano-sized building blocks of Fe x Ni 2-x P particles and the improved conductivity contributed by P-doped carbon substrate as well as the strong interaction between Fe x Ni 2-x P and carbon. Furthermore, this strategy of synthesizing the Fe x Ni 2-x P/P-C nanorods with metal-organic frameworks as a starting point can be extended to design other bimetallic transition metal phosphides with superior lithium storage properties.

Contamination by heavy metals has become a serious environmental pollution issue today due to its potential threat to plant, wildlife, and human health. Photosynthesis, a process in which light energy is used to produce sugar and other organic compounds, is sensitive to heavy metals. In the present study, the response of photosynthetic process and carbon assimilation of Schima superba was investigated under cadmium (Cd) stress. Three Cd concentrations (0, 300, and 600 mg kg−1) were used designated as control (CK), low Cd (L1), and high Cd treatment (L2) of plants. Results showed that photosystem II (PSII) acceptor and donor side electron transport were more easily blocked in treatment compared to control, and L2 have more significant changes than L1. A substantial decrease of 820 nm reflection curve absorption was observed both in L1 and L2 treatments. Special energy fluxes showed significant difference between the control group and the treated group, which indicated that low concentration Cd stress can cause decrease in quantum yield of PSII in plants studied. Non-stomatal factors resulted in a decrease in net photosynthetic rate and a decrease in photosystem activity. Our results suggested that Cd can damage structure and function of the photosynthesis of S. superba young plants.

This work shows the solar-driven dehydrogenative coupling of methane to ethane at room temperature. A solar-to-C2H6 energy conversion efficiency of 0.08% was achieved on the polar surface of Au/ZnO porous nanosheets (NSs), where methane C–H bonds are polarized and dissociated by the local electric field normal to the polar {001} plane, and finally converted into ethane and hydrogen through a radical coupling pathway. Mechanistic studies suggest that the Au-plasmon-induced resonance energy transfer modulates charge carrier energetics to trigger the stoichiometric conversion. Hot electrons reduce protons to H2, which is the rate-determining step of methane coupling.

Controlling the creation of oxygen vacancies can effectively regulate the optical and electronic properties of metal oxide nanomaterials. Over the past several decades, numerous metal oxides with oxygen vacancies have been developed. However, an investigation about oxygen vacancies leading to the formation of nanosheets with different thicknesses has not been available up to now. Here, we report the oxygen vacancy modulated formation of γ-Ga2O3 nanosheets and demonstrate that the thickness of the nanosheets is not the decisive factor in the photocatalytic hydrogen evolution reaction of ultrathin 2D nanosheets. Detailed structural characterization indicated that γ-Ga2O3 prepared at 160 °C (γ-160) with a morphology of ultrathin nanosheets possesses the highest oxygen vacancy concentration and an optimal thickness of the nanosheets. The enhanced photocatalytic performance could be determined from the synergistic effects between the ultrathin 2D structure and the O-vacancies confined in the ultrathin nanosheets. This work provides an efficient strategy to regulate the formation of nanosheets at the atomic scale and enrich the study on the effect of oxygen vacancies in the photocatalytic water splitting reaction.