Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2)production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study ...Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2)production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study reports Ir-doped NiFe_(2)O_(4)(NFI,~5 at%Ir)spinel layer with TiO_(2)overlayer(NFI/TiO_(2)),as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell.In dilute(0.1 M)NaCl solutions,the NFI/TiO_(2)marks superior activity and selectivity for chlorine evolution reaction,outperforming the benchmark IrO_(2).Robust operation in near-neutral pH was confirmed.Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO_(2) which serves both as the primary site for Cl−chemisorption and a protective layer for NFI as an ohmic contact.Galvanostatic electrolysis of NH4+-laden synthetic wastewater demonstrated that NFI/TiO_(2)not only achieves quasi-stoichiometric NH_(4)^(+)-to-N_(2)conversion,but also enhances H_(2)generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine.The scaled-up WEC with NFI/TiO_(2)was demonstrated for electrolysis of toilet wastewater.展开更多
For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a...For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.展开更多
The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interfa...The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia(NH_(3)).The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co_(3)O_(4)composite,which certifies that the CuO/Co_(3)O_(4)heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural.In situ electrochemical impedance spectroscopy further shows that CuO/Co_(3)O_(4)has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation.Moreover,CuO/Co_(3)O_(4)also has a good reduction effect on NO_(3)^(-).The ex-situ Raman spectroscopy shows that under the reduction potential,the metal oxide is reduced,and the generated Cu_(2)O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO_(3)^(-)to NH_(3) synthesis.This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO_(3)^(-)while efficiently producing NH_(3).展开更多
The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(...The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
Synthesizing a stable and efficient photocatalyst has been the most important research goal up to now. Owing to the dominant performance of g-C3N4 (graphitized carbonitride), an ordered assemble of a composite photoca...Synthesizing a stable and efficient photocatalyst has been the most important research goal up to now. Owing to the dominant performance of g-C3N4 (graphitized carbonitride), an ordered assemble of a composite photocatalyst, Zn-Ni-P@g-C3N4, was successfully designed and controllably prepared for highly efficient photocatalytic H2 evolution. The electron transport routes were successfully adjusted and the H2 evolution was greatly improved. The maximum amount of H2 evolved reached about 531.2 μmol for 5 h over Zn-Ni-P@g-C3N4 photocatalyst with a molar ratio of Zn to Ni of 1:3 under illumination of 5 W LED white light (wavelength 420 nm). The H2 evolution rate was 54.7 times higher than that over pure g-C3N4. Moreover, no obvious reduction in the photocatalytic activity was observed even after 4 cycles of H2 production for 5 h. This synergistically increased effect was confirmed through the results of characterizations such as XRD, TEM, SEM, XPS, N2 adsorption, UV-vis DRS, transient photocurrent, FT-IR, transient fluorescence, and Mott-Schottky studies. These studies showed that the Zn-Ni-P nanoparticles modified on g-C3N4 provide more active sites and improve the efficiency of photogenerated charge separation. In addition, the possible mechanism of photocatalytic H2 production is proposed.展开更多
Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to real...Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.展开更多
In this study,CuBi2O4 photocathodes were prepared using a simple electrodeposition method for photoelectrochemical(PEC)hydrogen production.The prepared photocathodes were modified with amorphous TiO2 and a Pt co‐cata...In this study,CuBi2O4 photocathodes were prepared using a simple electrodeposition method for photoelectrochemical(PEC)hydrogen production.The prepared photocathodes were modified with amorphous TiO2 and a Pt co‐catalyst,which resulted in the formation of CuBi2O4/TiO2 p‐n heterojunctions,and enhanced the activities of the as‐prepared photocathodes.The novel Pt/TiO2/CuBi2O4 photocathode exhibited a photocurrent of 0.35 mA/cm2 at 0.60 V vs.Reversible Hydrogen Electrode(RHE),which was nearly twice that of the Pt/CuBi2O4 photocathode.The present study provides a facile method for increasing the efficiency of photocathodes and provides meaningful guidance for the preparation of high‐performance CuBi2O4 photocathodes.展开更多
Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In t...Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In this study,we attempted to construct sediment samples with different residual CH_(4) hydrate amounts and reservoir conditions,and then investigate the potentials of both CO_(2) storage and enhanced CH_(4) recovery in depleted gas hydrate deposits in the permafrost and ocean zones,respectively.The results demonstrate that CO_(2) hydrate formation rate can be significantly improved due to the presence of residual hydrate seeds;However,excessive residual hydrates in turn lead to the decrease in CO_(2) storage efficiency.Affected by the T-P conditions of the reservoir,the storage amount of liquid CO_(2) can reach 8 times that of gaseous CO_(2),and CO_(2) stored in hydrate form reaches 2-4 times.Additionally,we noticed two other advantages of this method.One is that CO_(2) injection can enhance CH_(4) recovery rate and increases CH_(4) recovery by 10%-20%.The second is that hydrate saturation in the reservoir can be restored to 20%-40%,which means that the solid volume of the reservoir avoids serious shrinkage.Obviously,this is crucial for protecting the goaf stability.In summary,this approach is greatly promising for high-efficient CO_(2) storage and safe exploitation of gas hydrate.展开更多
Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride...Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.展开更多
To effectively solve the agglomeration problems in the solid state reaction process,pre-adding glucose is adopted to the synthesis of Li Fe PO4/C energy materials using Fe–P waste slag. The average particle grain siz...To effectively solve the agglomeration problems in the solid state reaction process,pre-adding glucose is adopted to the synthesis of Li Fe PO4/C energy materials using Fe–P waste slag. The average particle grain size of Li FeP O4/C decreases,and the impurities in Li Fe PO4/C composites reduce to a great extent. It makes great sense to the mass industrial production. The optimum synthesis conditions determined in this work are based on the orthogonal experiments. The samples synthesized in a scale of 500 g exhibit high purity,excellent electrochemical performance,high reaction activity,good reversibility,and low polarization level.The discharge capacities are 145,134,117,and 102 m Ah/g at the current densities of 0.1 C,0.2 C,0.5 C and1 C,respectively. This work puts forward a practical suggestion for mass producing environmental benign and low cost Li FeP O4/C as cathode materials of lithium ion batteries.展开更多
The calculation time in the Monte Carlo simulations consistently represents an essential issue. It is often very long, and its decrease constitutes a challenge for the simulator. Generally, an MC simulation is qualifi...The calculation time in the Monte Carlo simulations consistently represents an essential issue. It is often very long, and its decrease constitutes a challenge for the simulator. Generally, an MC simulation is qualified as quality or not according to two main criteria: the calculation time and the accuracy of the results. However, in most cases, the optimization of one criterion affects negatively the other. Therefore, a compromise between both of them is always required in this kind of simulation. The present work aims at studying the impact of the production threshold(or cut) of the GEANT4 toolkit on the calculation of the power deposition in the MEGAPIE spallation target.The production threshold of secondaries is a GEANT4 intrinsic parameter. It indicates the limit of energy we can reach in the production of secondary particles. This study has allowed us to make the following conclusions. First,the influence of the cut on the calculation of the deposited power depends on the volume size, its arrangement and the importance of the electromagnetic processes occurring within. Second, the accuracy of the calculations can be acceptable only below a given value of the cut energy.Third, this accuracy remains almost unchangeable from a certain value of the cut. The study has also made it possible to explore the prevalence of certain interactions in the zone of spallation in the MEGAPIE target.展开更多
The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out ...The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.展开更多
A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differentia...A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.展开更多
2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the t...2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324(2),b = 0.6454(3),c = 0.7062(3) nm,α= 111.550(4),β= 95.505(4),γ= 113.395(4)°,V = 0.23595(16) nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F(000) = 126,R = 0.0304 and wR = 0.0907.展开更多
This study investigated the effect of advanced glycation end products(AGEs) on differentiation of na ve CD4+T cells and the role of the receptor of AGEs(RAGE) and peroxisome proliferator-activated receptors(PPAR...This study investigated the effect of advanced glycation end products(AGEs) on differentiation of na ve CD4+T cells and the role of the receptor of AGEs(RAGE) and peroxisome proliferator-activated receptors(PPARs) activity in the process in order to gain insight into the mechanism of immunological disorders in diabetes. AGEs were prepared by the reaction of bovine serum albumin(BSA) with glucose. Human na ve CD4+T cells, enriched from blood of healthy adult volunteers with negative selection assay, were cultured in vitro and treated with various agents including AGEs, BSA, high glucose, PGJ2 and PD68235 for indicated time. In short hairpin(sh) RNA knock-down experiment, na ve CD4+T cells were transduced with media containing shRNA-lentivirus generated from lentiviral packaging cell line, Lent-XTM293 T cells. Surface and intracellular cytokine stainings were used for examination of CD4+T cell phenotypes, and real-time PCR and Western blotting for detection of transcription factor mRNA and protein expression, respectively. The suppressive function of regulatory T(Treg) cells was determined by a [3H]-thymidine incorporation assay. The results showed that AGEs induced higher pro-inflammatory Th1/Th17 cells differentiated from na ve CD4+T cells than the controls, whereas did not affect anti-inflammatory Treg cells. However, AGEs eliminated suppressive function of Treg cells. In addition, AGEs increased RAGE mRNA expression in na ve CD4+T cells, and RAGE knock-down by shRNA eliminated the effect of AGEs on the differentiation of CD4+T cells and the reduction of suppressive function of Treg cells. Furthermore, AGEs inhibited the mRNA expression of PPARγ, not PPARα; PPARγ agonist, PGJ2, inhibited the effect of AGEs on na ve CD4+T cell differentiation and reversed the AGE-reduced suppressive function of Treg cells; on the other hand, PPARγ antagonist, PD68235, attenuated the blocking effect of RAGE shRNA on the role of AGEs. It was concluded that AGEs may promote CD4+T cells development toward pro-inflammatory state, which is associated with increased RAGE mRNA expression and reduced PPARγ activity. +展开更多
Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet...Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet points of electrons using a photochemical method, which is beneficial for the following photocatalytic hydrogen production reaction. H2PO2^– has been used in the photochemical reduction of transition metals because of its special properties. However, the particles formed in the presence of H2PO2^– are very large and highly crystalline, which may inhibit the activity of photocatalysts. In this study, we designed a new method for synthesizing photocatalysts by photodeposition using some other phosphates, aiming to prepare controllable weakly crystalline and small-size cocatalysts to improve the hydrogen production activity. The cocatalyst prepared using H2PO3^– as an inorganic sacrificial agent has an amorphous structure and an average size of about 10 nm. The optimal photocatalytic hydrogen production rate of the obtained Ni(OH)2/g-C3N4(4.36 wt%) is 13707.86 μmol·g^-1·h^-1, which is even higher than the activity of Pt-4.36 wt%/g-C3N4(11210.93 μmol·g^-1·h^-1). Mechanistic studies show that loading of Ni(OH)2 can efficiently accelerate the separation and transfer efficiency of photogenerated charge carriers.展开更多
In this study,phosphoenolpyruvate and erythrose-4-phosphate are efficiently supplied by collaborative design of Embden-Meyerhof-Parnas(EMP)pathway and pentose phosphate(PP)pathway in Escherichia coli,thus increasing t...In this study,phosphoenolpyruvate and erythrose-4-phosphate are efficiently supplied by collaborative design of Embden-Meyerhof-Parnas(EMP)pathway and pentose phosphate(PP)pathway in Escherichia coli,thus increasing the L-tryptophan production.Firstly,the effects of disrupting EMP pathway on L-tryptophan production were studied,and the results indicated that the strain with deletion of phosphofructokinase A(i.e.,E.coli JW-5ΔpfkA)produced 23.4±2.1 g/L of L-tryptophan production.However,deletion of phosphofructokinase A and glucosephosphate isomerase is not conducive to glucose consumption and cell growth,especially deletion of glucosephosphate isomerase.Next,the carbon flux in PP pathway was enhanced by introduction of the desensitized glucose-6-phosphate dehydrogenase(zwf)and 6-phosphogluconate dehydrogenase(gnd)and thus increasing the L-tryptophan production(i.e.,26.5±3.2 g/L vs.21.7±1.3 g/L)without obviously changing the cell growth(i.e.,0.41 h^(-1) vs.0.44 h^(-1))as compared with the original strain JW-5.Finally,the effects of co-modifying EMP pathway and PP pathway on L-tryptophan production were investigated.It was found that the strain with deletion of phosphofructokinase A as well as introduction of the desensitized zwf and gnd(i.e.,E.coli JW-5 zwf243 gnd361ΔpfkA)produced 31.9±2.7 g/L of L-tryptophan,which was 47.0%higher than that of strain JW-5.In addition,the glucose consumption rate of strain JW-5 zwf243 gnd361ΔpfkA was obviously increased despite of the bad cell growth as compared with strain JW-5.The results of this study have important reference value for the following application of metabolic engineering to improve aromatic amino acids producing strains.展开更多
基金supported by the National Research Foundation of Korea(NRF)grants(2022R1A2C4001228,2022M3H4A4097524,2022M3I3A1082499,and 2021M3I3A1084818)the Technology Innovation Program(20026415)of the Ministry of Trade,Industry&Energy(MOTIE,Korea)the supports from Nanopac for fabrication of scaled-up reactor.
文摘Wastewater electrolysis cells(WECs)for decentralized wastewater treatment/reuse coupled with H_(2)production can reduce the carbon footprint associated with transportation of water,waste,and energy carrier.This study reports Ir-doped NiFe_(2)O_(4)(NFI,~5 at%Ir)spinel layer with TiO_(2)overlayer(NFI/TiO_(2)),as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell.In dilute(0.1 M)NaCl solutions,the NFI/TiO_(2)marks superior activity and selectivity for chlorine evolution reaction,outperforming the benchmark IrO_(2).Robust operation in near-neutral pH was confirmed.Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO_(2) which serves both as the primary site for Cl−chemisorption and a protective layer for NFI as an ohmic contact.Galvanostatic electrolysis of NH4+-laden synthetic wastewater demonstrated that NFI/TiO_(2)not only achieves quasi-stoichiometric NH_(4)^(+)-to-N_(2)conversion,but also enhances H_(2)generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine.The scaled-up WEC with NFI/TiO_(2)was demonstrated for electrolysis of toilet wastewater.
基金supported by the National Natural Science Foundation of China(51672081)the Program of Tri-three Talents Project of Hebei Province(China,A202110002)+1 种基金the Young Top Talents Fund Program of Higher Education Institutions of Heibei Province(BJ2020009)the Project of Science and Technology Innovation Team,Tangshan(20130203D)。
文摘For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.
基金the support received from the National Natural Science Foundation of China(Grant No.22372012,22261160640,and 22002009)the Natural Science Foundation of Hunan Province(Grant No.2023JJ20037 and 2021JJ40565)the Scientific Research Project of Hunan Provincial Department of Education(Grant No.22B0293)
文摘The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia(NH_(3)).The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co_(3)O_(4)composite,which certifies that the CuO/Co_(3)O_(4)heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural.In situ electrochemical impedance spectroscopy further shows that CuO/Co_(3)O_(4)has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation.Moreover,CuO/Co_(3)O_(4)also has a good reduction effect on NO_(3)^(-).The ex-situ Raman spectroscopy shows that under the reduction potential,the metal oxide is reduced,and the generated Cu_(2)O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO_(3)^(-)to NH_(3) synthesis.This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO_(3)^(-)while efficiently producing NH_(3).
文摘The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
基金supported by the National Natural Science Foundation of China(21862002,41663012)the Innovation Team Project of North Minzu University(YCX18082)the Scientific Research Project of North Minzu University(2016 HG-KY 06)~~
文摘Synthesizing a stable and efficient photocatalyst has been the most important research goal up to now. Owing to the dominant performance of g-C3N4 (graphitized carbonitride), an ordered assemble of a composite photocatalyst, Zn-Ni-P@g-C3N4, was successfully designed and controllably prepared for highly efficient photocatalytic H2 evolution. The electron transport routes were successfully adjusted and the H2 evolution was greatly improved. The maximum amount of H2 evolved reached about 531.2 μmol for 5 h over Zn-Ni-P@g-C3N4 photocatalyst with a molar ratio of Zn to Ni of 1:3 under illumination of 5 W LED white light (wavelength 420 nm). The H2 evolution rate was 54.7 times higher than that over pure g-C3N4. Moreover, no obvious reduction in the photocatalytic activity was observed even after 4 cycles of H2 production for 5 h. This synergistically increased effect was confirmed through the results of characterizations such as XRD, TEM, SEM, XPS, N2 adsorption, UV-vis DRS, transient photocurrent, FT-IR, transient fluorescence, and Mott-Schottky studies. These studies showed that the Zn-Ni-P nanoparticles modified on g-C3N4 provide more active sites and improve the efficiency of photogenerated charge separation. In addition, the possible mechanism of photocatalytic H2 production is proposed.
文摘Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.
基金the National Natural Science Foundation of China(51602179,21333006,21573135,11374190)the National Basic Research Program of China(973 Program,2013CB632401)~~
文摘In this study,CuBi2O4 photocathodes were prepared using a simple electrodeposition method for photoelectrochemical(PEC)hydrogen production.The prepared photocathodes were modified with amorphous TiO2 and a Pt co‐catalyst,which resulted in the formation of CuBi2O4/TiO2 p‐n heterojunctions,and enhanced the activities of the as‐prepared photocathodes.The novel Pt/TiO2/CuBi2O4 photocathode exhibited a photocurrent of 0.35 mA/cm2 at 0.60 V vs.Reversible Hydrogen Electrode(RHE),which was nearly twice that of the Pt/CuBi2O4 photocathode.The present study provides a facile method for increasing the efficiency of photocathodes and provides meaningful guidance for the preparation of high‐performance CuBi2O4 photocathodes.
基金financially supported by the National Natural Science Foundation of China,China(22378424,52004136,22127812,U20B6005)the Science Foundation of China University of Petroleum Beijing(2462023BJRC017)Hunan Provincial Department of Education Scientific Research Project(22B0310).
文摘Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In this study,we attempted to construct sediment samples with different residual CH_(4) hydrate amounts and reservoir conditions,and then investigate the potentials of both CO_(2) storage and enhanced CH_(4) recovery in depleted gas hydrate deposits in the permafrost and ocean zones,respectively.The results demonstrate that CO_(2) hydrate formation rate can be significantly improved due to the presence of residual hydrate seeds;However,excessive residual hydrates in turn lead to the decrease in CO_(2) storage efficiency.Affected by the T-P conditions of the reservoir,the storage amount of liquid CO_(2) can reach 8 times that of gaseous CO_(2),and CO_(2) stored in hydrate form reaches 2-4 times.Additionally,we noticed two other advantages of this method.One is that CO_(2) injection can enhance CH_(4) recovery rate and increases CH_(4) recovery by 10%-20%.The second is that hydrate saturation in the reservoir can be restored to 20%-40%,which means that the solid volume of the reservoir avoids serious shrinkage.Obviously,this is crucial for protecting the goaf stability.In summary,this approach is greatly promising for high-efficient CO_(2) storage and safe exploitation of gas hydrate.
基金supported by the National Natural Science Foundation of China(21503096,21407067)the Natural Science Foundation of Educational Committee of Anhui Province(KJ2018A0387),ChinaProject of Anhui Province for Excellent Young Talents in Universities(gxyq2019029),China
文摘Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.
基金supported by the National Science Foundation of China(grant no.21206099)
文摘To effectively solve the agglomeration problems in the solid state reaction process,pre-adding glucose is adopted to the synthesis of Li Fe PO4/C energy materials using Fe–P waste slag. The average particle grain size of Li FeP O4/C decreases,and the impurities in Li Fe PO4/C composites reduce to a great extent. It makes great sense to the mass industrial production. The optimum synthesis conditions determined in this work are based on the orthogonal experiments. The samples synthesized in a scale of 500 g exhibit high purity,excellent electrochemical performance,high reaction activity,good reversibility,and low polarization level.The discharge capacities are 145,134,117,and 102 m Ah/g at the current densities of 0.1 C,0.2 C,0.5 C and1 C,respectively. This work puts forward a practical suggestion for mass producing environmental benign and low cost Li FeP O4/C as cathode materials of lithium ion batteries.
文摘The calculation time in the Monte Carlo simulations consistently represents an essential issue. It is often very long, and its decrease constitutes a challenge for the simulator. Generally, an MC simulation is qualified as quality or not according to two main criteria: the calculation time and the accuracy of the results. However, in most cases, the optimization of one criterion affects negatively the other. Therefore, a compromise between both of them is always required in this kind of simulation. The present work aims at studying the impact of the production threshold(or cut) of the GEANT4 toolkit on the calculation of the power deposition in the MEGAPIE spallation target.The production threshold of secondaries is a GEANT4 intrinsic parameter. It indicates the limit of energy we can reach in the production of secondary particles. This study has allowed us to make the following conclusions. First,the influence of the cut on the calculation of the deposited power depends on the volume size, its arrangement and the importance of the electromagnetic processes occurring within. Second, the accuracy of the calculations can be acceptable only below a given value of the cut energy.Third, this accuracy remains almost unchangeable from a certain value of the cut. The study has also made it possible to explore the prevalence of certain interactions in the zone of spallation in the MEGAPIE target.
文摘The chemical kinetics of the monoesterification between terephthalic acid(TPA)and 1,4-butanediol (BDO)catalyzed by a metallo-organic compound was studied using the initial rate method.The experiments were carried out in the temperature range of 463-483 K,and butylhydroxyoxo-stannane(BuSnOOH)and tetrabutyl titanate[Ti(OBu)4]were used as catalyst respectively.The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO(or TPA)with the concentration of TPA(or BDO)kept constant.The reaction orders of reagents were determined by the initial rate method.The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively.However,the order for BDO is the same 0.9 for the two catalysts.Furthermore,the effects of temperature and catalyst concentration are investigated,and the activation energies and the reaction rate constants for the two catalysts were determined.
基金Supported by Research Funds from Chinese Education Department (2003406)Bureau of Science and Technology of Jiangsu Province (BG2006025)
文摘A series of tungsten-substituted molybdophosphoric acids(H3PMo12-nWnO40·xH2O) were synthesized and characterized by inductive coupled plasma atomic emission spectroscopy(ICPAES),thermal gravimetry and differential scanning calorimetry(TG-DSC),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),and FTIR pyridine adsorption.The as-prepared heteropoly acids have a Keggin type structure.The synthesis of tetrahydrofuran by reactive distillation and cyclodehydration of 1,4-butanediol was studied using the tungsten-substituted molybdophosphoric acids as catalysts.The results of catalytic test indicated that the catalytic activity increased with the increase in the substitution number(n) of tungsten atom in H3PMo12-nWnO40·xH2O and was constant as the substitution number(n) was more than 8.The catalytic activity increased with the increase in the catalyst loading and the selectivity of tetrahydrofuran was nearly 100%.
基金Supported by the National "973" project (No. 613740102)
文摘2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol(C6H12N2O8) was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324(2),b = 0.6454(3),c = 0.7062(3) nm,α= 111.550(4),β= 95.505(4),γ= 113.395(4)°,V = 0.23595(16) nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F(000) = 126,R = 0.0304 and wR = 0.0907.
文摘This study investigated the effect of advanced glycation end products(AGEs) on differentiation of na ve CD4+T cells and the role of the receptor of AGEs(RAGE) and peroxisome proliferator-activated receptors(PPARs) activity in the process in order to gain insight into the mechanism of immunological disorders in diabetes. AGEs were prepared by the reaction of bovine serum albumin(BSA) with glucose. Human na ve CD4+T cells, enriched from blood of healthy adult volunteers with negative selection assay, were cultured in vitro and treated with various agents including AGEs, BSA, high glucose, PGJ2 and PD68235 for indicated time. In short hairpin(sh) RNA knock-down experiment, na ve CD4+T cells were transduced with media containing shRNA-lentivirus generated from lentiviral packaging cell line, Lent-XTM293 T cells. Surface and intracellular cytokine stainings were used for examination of CD4+T cell phenotypes, and real-time PCR and Western blotting for detection of transcription factor mRNA and protein expression, respectively. The suppressive function of regulatory T(Treg) cells was determined by a [3H]-thymidine incorporation assay. The results showed that AGEs induced higher pro-inflammatory Th1/Th17 cells differentiated from na ve CD4+T cells than the controls, whereas did not affect anti-inflammatory Treg cells. However, AGEs eliminated suppressive function of Treg cells. In addition, AGEs increased RAGE mRNA expression in na ve CD4+T cells, and RAGE knock-down by shRNA eliminated the effect of AGEs on the differentiation of CD4+T cells and the reduction of suppressive function of Treg cells. Furthermore, AGEs inhibited the mRNA expression of PPARγ, not PPARα; PPARγ agonist, PGJ2, inhibited the effect of AGEs on na ve CD4+T cell differentiation and reversed the AGE-reduced suppressive function of Treg cells; on the other hand, PPARγ antagonist, PD68235, attenuated the blocking effect of RAGE shRNA on the role of AGEs. It was concluded that AGEs may promote CD4+T cells development toward pro-inflammatory state, which is associated with increased RAGE mRNA expression and reduced PPARγ activity. +
文摘Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet points of electrons using a photochemical method, which is beneficial for the following photocatalytic hydrogen production reaction. H2PO2^– has been used in the photochemical reduction of transition metals because of its special properties. However, the particles formed in the presence of H2PO2^– are very large and highly crystalline, which may inhibit the activity of photocatalysts. In this study, we designed a new method for synthesizing photocatalysts by photodeposition using some other phosphates, aiming to prepare controllable weakly crystalline and small-size cocatalysts to improve the hydrogen production activity. The cocatalyst prepared using H2PO3^– as an inorganic sacrificial agent has an amorphous structure and an average size of about 10 nm. The optimal photocatalytic hydrogen production rate of the obtained Ni(OH)2/g-C3N4(4.36 wt%) is 13707.86 μmol·g^-1·h^-1, which is even higher than the activity of Pt-4.36 wt%/g-C3N4(11210.93 μmol·g^-1·h^-1). Mechanistic studies show that loading of Ni(OH)2 can efficiently accelerate the separation and transfer efficiency of photogenerated charge carriers.
基金This work as financially supported by the National Key Research and Development Program of China(2021YFC2100900)the Key Laboratory of Industrial Biotechnology,Ministry of Education,Jiangnan University(KLIB-KF 202004)Fundamental Research Funds for the Central Universities[No.JUSRP115A19].
文摘In this study,phosphoenolpyruvate and erythrose-4-phosphate are efficiently supplied by collaborative design of Embden-Meyerhof-Parnas(EMP)pathway and pentose phosphate(PP)pathway in Escherichia coli,thus increasing the L-tryptophan production.Firstly,the effects of disrupting EMP pathway on L-tryptophan production were studied,and the results indicated that the strain with deletion of phosphofructokinase A(i.e.,E.coli JW-5ΔpfkA)produced 23.4±2.1 g/L of L-tryptophan production.However,deletion of phosphofructokinase A and glucosephosphate isomerase is not conducive to glucose consumption and cell growth,especially deletion of glucosephosphate isomerase.Next,the carbon flux in PP pathway was enhanced by introduction of the desensitized glucose-6-phosphate dehydrogenase(zwf)and 6-phosphogluconate dehydrogenase(gnd)and thus increasing the L-tryptophan production(i.e.,26.5±3.2 g/L vs.21.7±1.3 g/L)without obviously changing the cell growth(i.e.,0.41 h^(-1) vs.0.44 h^(-1))as compared with the original strain JW-5.Finally,the effects of co-modifying EMP pathway and PP pathway on L-tryptophan production were investigated.It was found that the strain with deletion of phosphofructokinase A as well as introduction of the desensitized zwf and gnd(i.e.,E.coli JW-5 zwf243 gnd361ΔpfkA)produced 31.9±2.7 g/L of L-tryptophan,which was 47.0%higher than that of strain JW-5.In addition,the glucose consumption rate of strain JW-5 zwf243 gnd361ΔpfkA was obviously increased despite of the bad cell growth as compared with strain JW-5.The results of this study have important reference value for the following application of metabolic engineering to improve aromatic amino acids producing strains.