Differential contributions of the glycosylphosphatidylinositol (GPI)-anchor and GPI-anchored proteins (GPI-AP) to signalling remain poorly understood. Here we show that GPI-AP deficient murine clones produce on averag...Differential contributions of the glycosylphosphatidylinositol (GPI)-anchor and GPI-anchored proteins (GPI-AP) to signalling remain poorly understood. Here we show that GPI-AP deficient murine clones produce on average 18 and 181-fold more IL-2 mRNA and protein, respectively, upon T cell receptor (TCR) stimulation, in a cell-intrinsic fashion. This phenotype is formally attributed to a mutation within the transferase complex that predicates the initial step in GPI-anchor biosynthesis. Conditional disruption of the transferase complex enabled the generation of primary GPI-AP deficient CD4<sup>+</sup> T cells, which produce on average 10- and 23-fold more IL-2 mRNA and protein, respectively, upon TCR stimulation. Conditional disruption of the transamidase complex yields GPI-sufficient, GPI-AP deficient primary CD4<sup>+</sup> T cells. TCR stimulation of these cells yields levels of IL-2 mRNA and protein ranging from 1 - 3 and 3-fold, respectively, of controls. These results provide the first evidence of a profound impact of GPI in the regulation of TCR signalling.展开更多
Objective:To investigate the regulatory effect of aqueous extract of leaves of Ocimum sanctum on IL-2 cytokine production in vivo and in vitro,and the effect of leaves extract on general blood picture including T&...Objective:To investigate the regulatory effect of aqueous extract of leaves of Ocimum sanctum on IL-2 cytokine production in vivo and in vitro,and the effect of leaves extract on general blood picture including T& B lymphocytes.Methods:For in vivo studies albino Wistar rats were treated with aqueous crude leaves extract of Ocimum sanctum for 20 consecutive days.Spleen cells were harvested and assayed for IL-2 production by using sandwich enzyme-linked immunosorbent assay(ELISA) and mRNA expression methods.For in vitro study aqueous Ocimum sanctum leaves extract= in different concentrations(25-500μ/mL) was added into culture plates containing ConA stimulated splenocytes.To study the overall effect on blood picture,density gradient purified lymphocytes analysis and conventional methodology for total and differential leukocyte count and hemoglobin level were also done.Results:It indicated that the rats treated with Ocimum sanctum leaves extract had significantly enhanced(P【0.001) ability of spleen cells to secrete IL-2.Investigation in vitro also showed regulation of IL-2 production.Blood study exhibited leucocytosis and augmentation of T& B lymphocytes by 25%approximately.4-5%increase in Hemoglobin value was also noticed.Conclusion:Aqueous Ocimum sanctum leaves extract may have stimulatory effect on T & B lymphocytes particularly on Th 1 subset of lymphocytes as shown by enhancement in IL-2 production.展开更多
It is observed that Ge-132 can increase human interleukin-2（IL-2）productionby the peripheral blood mononuclear cells（PBMC）under PHA induction in vitro.TraceGe-132(10<sup>-3</sup>-1μg/ml)can obviously ...It is observed that Ge-132 can increase human interleukin-2（IL-2）productionby the peripheral blood mononuclear cells（PBMC）under PHA induction in vitro.TraceGe-132(10<sup>-3</sup>-1μg/ml)can obviously increase the IL-2 production;even utmost minimalGe-132 (10<sup>-4</sup>-10<sup>-1</sup>μg/ml)can promote the reactivity of lymphocyres to IL-2.The proba-ble anticancer mechanism of Ge-132 was discussed.展开更多
Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to en...Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.展开更多
NH_(2)-MIL-125 and its derivatives are receivingmore attention in various aspects of photocatalytic reactions,especially in the photocatalytic hydrogen peroxide(H_(2)O_(2))production from water(H_(2)O)and oxygen(O_(2)...NH_(2)-MIL-125 and its derivatives are receivingmore attention in various aspects of photocatalytic reactions,especially in the photocatalytic hydrogen peroxide(H_(2)O_(2))production from water(H_(2)O)and oxygen(O_(2)),which is a promising and sustainable strategy.However,the generation of H_(2)O_(2) from NH_(2)-MIL-125 is far from satisfactory due to rapid photo-generated carriers recombination and poor surface electron transfer.In the work,the composite photocatalyst CQDs/TiO_(2)/NH_(2)-MIL-125(C/T/NM)was designed for the first time by one-step hydrothermal method.TiO_(2) was in situ converted from partial NH_(2)-MIL-125(NM)during the successful loaded of Carbon quantum dots(CQDs)by hydrothermal process.The results indicated the typeⅡheterojunction was successfully constructed between the NM and TiO_(2) interface,which could promote the transmission of photo-generated electrons.In addition,the successful loaded of CQDs could effectively transfer and stored the photo-generated electrons to the photocatalyst surface to participate in the reaction,and further avoiding the recombination of photo-generated carriers.The C/T/NM composite photocatalyst achieved a H_(2)O_(2) generation of 455μmol/L for 5 hours under visible light without oxygen bubbling,whichwas 7.1 times superior to that of NM.The H_(2)O_(2) generation rate reached 645.4μM/(g·h),which was in priority in the reported literature under the same conditions.Finally,based on the active species capture experiments,energy band structure analysis and the photoelectrochemicalmeasurements,a possiblemechanism for the efficientH_(2)O_(2) generation through C/T/NM had been proposed.This work provided new ideas for designing NH_(2)-MIL-125 based composite photocatalysts for the production of H_(2)O_(2).展开更多
Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy convers...Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.展开更多
S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists ...S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.展开更多
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
Photocatalytic H_(2)production from water splitting is a promising candidate for solving the increasing energy crisis and environmental issues.Herein we report a novel g-C_(3)N_(4)/Ag In_(x)S_(y)S-scheme heterojunctio...Photocatalytic H_(2)production from water splitting is a promising candidate for solving the increasing energy crisis and environmental issues.Herein we report a novel g-C_(3)N_(4)/Ag In_(x)S_(y)S-scheme heterojunction photocatalyst for water splitting into stoichiometric H_(2)and H_(2)O_(2)under visible light.The catalyst was prepared by depositing 3D bimetallic sulfide(Ag In_(x)S_(y))nanotubes onto 2D g-C_(3)N_(4)nanosheets.Owing to the special 3D-on-2D configuration,the photogenerated carriers could be rapidly transferred and effectively separated through the abundant interfacial heterostructures to avoid recombination,and therefore excellent performance for visible light-driven water splitting could be obtained,with a 24-h H_(2)evolution rate up to 237μmol g^(-1)h^(-1).Furthermore,suitable band alignment enables simultaneous H_(2)and H_(2)O_(2)production in a 1:1 stoichiometric ratio.H_(2)and H_(2)O_(2)were evolved on the conduction band of g-C_(3)N_(4)and on the valance band of Ag In_(x)S_(y),respectively.The novel 3D-on-2D configuration for heterojunction construction proposed in this work provided alternative research ideas toward photocatalytic reaction.展开更多
H_(2)O_(2)is an excellent green oxidant with important applications in many fields.The conventional anthraquinone process for synthesizing H_(2)O_(2)is usually accompanied by high economic costs and stringent process ...H_(2)O_(2)is an excellent green oxidant with important applications in many fields.The conventional anthraquinone process for synthesizing H_(2)O_(2)is usually accompanied by high economic costs and stringent process requirements.The photocatalytic production of H_(2)O_(2)via heterojunction semiconductors has proven to overcome these limitations,which is a promising alternative to the conventional anthraquinone process.In this review,we provide a comprehensive summary of the semiconductor heterojunction materials that have been attempted to be used in the photocatalytic generation of H_(2)O_(2)in recent years.Firstly,a brief description of the photoreaction mechanisms of different types of heterojunctions in the photocatalytic process is presented,focusing on the generation pathways and competing reactions for the photoproduction of H_(2)O_(2).Then,the types of heterojunctions applied for photoproduction of H_(2)O_(2)are comprehensively summarized.Among them,the four most widely used types of heterojunctions,including type-Ⅱ heterojunctions,Z-scheme systems,S-scheme systems,and Schottky heterojunctions,and their current applications in the reaction of photoproduction of H_(2)O_(2)are highlighted.By comparing the differences in the internal electric fields of different types of heterojunctions,different charge transfer pathways of various types of heterojunctions in the photoproduction of H_(2)O_(2)are distinguished.Furthermore,the great potential of other types of heterojunctions,such as p-n heterojunctions,in photocatalysis is further outlined.Finally,the challenges as well as opportunities for the development of novel heterostructural photocatalysts for H_(2)O_(2)production are outlined.We sincerely hope this minireview can attract more attention from scientific research workers in the field of photocatalytic H_(2)O_(2)generation,making them valuable for environmental remediation and industrial applications in the future.展开更多
Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen ...Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen production and CO_(2) conversion into value-added products.Among the materials explored for photocatalysis,nickel-based photocatalysts have emerged as highly promising due to their low cost,abundance,stability,and efficiency.This review summarizes recent advancements in Ni-based photocatalysts,highlighting their role in improving photocatalytic performance by enhancing light absorption,charge separation,and reducing charge recombination.Key challenges and future directions for optimizing these materials are also discussed,offering insights into their potential for advancing clean energy technologies.展开更多
To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only ...To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only a few elements have been examined.This study proposes guidelines for the selection of Cu catalyst dopants to promote ethylene production.It was hypothesized that the dopant chemical state highly influences the CO_(2)RR catalytic activity.In the case of dopants possessing a standard reduction potential within the CO_(2)RR potential region(e.g.,Mn and Ni),low Faradaic efficiency(FE)toward ethylene production was obtained owing to the presence of a metallic dopant(10.7%for Ni dopant).In contrast,a low standard reduction potential led to a stable high oxidation state for the dopant,yielding abundant Cu^(δ+)species with modified electronic structures and enhancing the CO_(2)RR catalytic activity for ethylene production(42.1%for Hf dopant).We expected that a dopant with a low standard reduction potential is difficult to reduce,which leads to a stable Cu-O-X bond and induces a stable Cu^(δ+)species.Our study provides insights into how to select dopant for various catalyst to enhance CO_(2)RR catalytic activity.展开更多
Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of Z...Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.展开更多
Hydrogen generation and related energy applications heavily rely on the hydrogen evolution reaction(HER),which faces challenges of slow kinetics and high overpotential.Efficient electrocatalysts,particularly single-at...Hydrogen generation and related energy applications heavily rely on the hydrogen evolution reaction(HER),which faces challenges of slow kinetics and high overpotential.Efficient electrocatalysts,particularly single-atom catalysts (SACs) on two-dimensional (2D) materials,are essential.This study presents a few-shot machine learning (ML) assisted high-throughput screening of 2D septuple-atomic-layer Ga_(2)CoS_(4-x)supported SACs to predict HER catalytic activity.Initially,density functional theory (DFT)calculations showed that 2D Ga_(2)CoS4is inactive for HER.However,defective Ga_(2)CoS_(4-x)(x=0–0.25)monolayers exhibit excellent HER activity due to surface sulfur vacancies (SVs),with predicted overpotentials (0–60 mV) comparable to or lower than commercial Pt/C,which typically exhibits an overpotential of around 50 m V in the acidic electrolyte,when the concentration of surface SV is lower than 8.3%.SVs generate spin-polarized states near the Fermi level,making them effective HER sites.We demonstrate ML-accelerated HER overpotential predictions for all transition metal SACs on 2D Ga_(2)CoS_(4-x).Using DFT data from 18 SACs,an ML model with high prediction accuracy and reduced computation time was developed.An intrinsic descriptor linking SAC atomic properties to HER overpotential was identified.This study thus provides a framework for screening SACs on 2D materials,enhancing catalyst design.展开更多
The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limit...The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.展开更多
Hydrogen peroxide(H_(2)O_(2))is an essential environmentally friendly oxidant with a wide range of applications.Compared with traditional anthraquinone processes,the electrochemical synthesis of H_(2)O_(2)via the two-...Hydrogen peroxide(H_(2)O_(2))is an essential environmentally friendly oxidant with a wide range of applications.Compared with traditional anthraquinone processes,the electrochemical synthesis of H_(2)O_(2)via the two-electron oxygen reduction reaction and two-electron water oxidation reaction offers a more promising and sustainable alternative.Carbon-based electrocatalysts playing a crucial role in these processes owing to their abundance and facile functionalization.This review focuses on the strategic design of carbon-based electrocatalysts to enhance H_(2)O_(2)production.We begin by highlighting the significance of H_(2)O_(2)and the fundamental mechanisms of electrochemical process.Subsequently,we present a detailed analysis of key factors affecting catalytic performance,concentrating electronic structure and geometric structure regulation as primary catalyst design approaches to improve H_(2)O_(2)production.Interface engineering and pH effects are also emphasized for their crucial roles.Finally,the major challenges and prospects for advancing H_(2)O_(2)production towards practical applications are discussed.展开更多
CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 wi...CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 with large-scale.However,CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable,which typically requires a harsh reaction temperature above 800℃.In this work,solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO_(2)-free H_(2)relying solely on solar energy as the driving force.A high H_(2)yield of 204.6 mmol g^(–1)h^(–1)was observed over Ni-CeO2 interface under photothermal conditions,along with above 87%reduction in the apparent activation energy(11.2 vs.87.3 kJ mol^(–1))when comparing with the traditional thermal catalysis.Further studies suggested that Ni/CeO_(2)catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition.The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light,which lowered activation energy and improved the photothermal catalytic activity.This work provides a promising photothermal catalytic strategy to produce CO_(2)-free H^(2)under mild conditions.展开更多
Photocatalytic and photoelectrocatalytic H_(2)O_(2)production has been identified as a significant pathway within environmental pollution control,green energy,medical treatment,sterilization and disinfection.However,c...Photocatalytic and photoelectrocatalytic H_(2)O_(2)production has been identified as a significant pathway within environmental pollution control,green energy,medical treatment,sterilization and disinfection.However,conventional single-material photocatalysts struggle to fulfill the stringent criteria of high efficiency,stability,cost-effectiveness,and responsiveness to visible light.The elevated recombination rates of photogenerated charge carriers,coupled with the suboptimal utilization of visible light,have collectively constrained the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.Heterojunction catalysts for the production of H_(2)O_(2)has become a focal point of research.This review commences by elucidating the fundaments underlying the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.Subsequently,it delineates the distinctive electron transfer mechanisms of Z-scheme and S-scheme heterojunctions,which exhibit enhanced efficiency in the photocatalytic and photoelectrocatalytic H_(2)O_(2)production,along with a summary of strategies for the improvement of photocatalyst and photoelectrocatalyst performance.Furthermore,this review also outlines the latest fabrication strategies,state-of-the-art in-situ characterization techniques,machine learning and density functional theory(DFT)simulations for Z-scheme or Sscheme catalysts for the photocatalytic and photoelectrocatalytic H_(2)O_(2)production,and briefly describes the multifunctional applications in H_(2)O_(2)production.Ultimately,the review contemplates the prospective developmental trajectories and application potential of these heterojunction configurations for the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.展开更多
Using the ultra-low permeability reservoirs in the L block of the Jiangsu oilfield as an example,a series of experiments,including slim tube displacement experiments of CO_(2)-oil system,injection capacity experiments...Using the ultra-low permeability reservoirs in the L block of the Jiangsu oilfield as an example,a series of experiments,including slim tube displacement experiments of CO_(2)-oil system,injection capacity experiments,and high-temperature,high-pressure online nuclear magnetic resonance(NMR)displacement experiments,are conducted to reveal the oil/gas mass transfer pattern and oil production mechanisms during CO_(2) flooding in ultra-low permeability reservoirs.The impacts of CO_(2) storage pore range and miscibility on oil production and CO_(2) storage characteristics during CO_(2) flooding are clarified.The CO_(2) flooding process is divided into three stages:oil displacement stage by CO_(2),CO_(2) breakthrough stage,CO_(2) extraction stage.Crude oil expansion and viscosity reduction are the main mechanisms for improving recovery in the CO_(2) displacement stage.After CO_(2) breakthrough,the extraction of light components from the crude oil further enhances oil recovery.During CO_(2) flooding,the contribution of crude oil in large pores to the enhanced recovery exceeds 46%,while crude oil in medium pores serves as a reserve for incremental recovery.After CO_(2) breakthrough,a small portion of the crude oil is extracted and carried into nano-scale pores by CO_(2),becoming residual oil that is hard to recover.As the miscibility increases,the CO_(2) front moves more stably and sweeps a larger area,leading to increased CO_(2) storage range and volume.The CO_(2) full-storage stage contributes the most to the overall CO_(2) storage volume.In the CO_(2) escape stage,the storage mechanism involves partial in-situ storage of crude oil within the initial pore range and the CO_(2) carrying crude oil into smaller pores to increase the volume of stored CO_(2).In the CO_(2) leakage stage,as crude oil is produced,a significant amount of CO_(2) leaks out,causing a sharp decline in the storage efficiency.展开更多
文摘Differential contributions of the glycosylphosphatidylinositol (GPI)-anchor and GPI-anchored proteins (GPI-AP) to signalling remain poorly understood. Here we show that GPI-AP deficient murine clones produce on average 18 and 181-fold more IL-2 mRNA and protein, respectively, upon T cell receptor (TCR) stimulation, in a cell-intrinsic fashion. This phenotype is formally attributed to a mutation within the transferase complex that predicates the initial step in GPI-anchor biosynthesis. Conditional disruption of the transferase complex enabled the generation of primary GPI-AP deficient CD4<sup>+</sup> T cells, which produce on average 10- and 23-fold more IL-2 mRNA and protein, respectively, upon TCR stimulation. Conditional disruption of the transamidase complex yields GPI-sufficient, GPI-AP deficient primary CD4<sup>+</sup> T cells. TCR stimulation of these cells yields levels of IL-2 mRNA and protein ranging from 1 - 3 and 3-fold, respectively, of controls. These results provide the first evidence of a profound impact of GPI in the regulation of TCR signalling.
基金financially supported by Woman Scientist Scheme-A to the first author from the Department of Science and Technology,New Delhi
文摘Objective:To investigate the regulatory effect of aqueous extract of leaves of Ocimum sanctum on IL-2 cytokine production in vivo and in vitro,and the effect of leaves extract on general blood picture including T& B lymphocytes.Methods:For in vivo studies albino Wistar rats were treated with aqueous crude leaves extract of Ocimum sanctum for 20 consecutive days.Spleen cells were harvested and assayed for IL-2 production by using sandwich enzyme-linked immunosorbent assay(ELISA) and mRNA expression methods.For in vitro study aqueous Ocimum sanctum leaves extract= in different concentrations(25-500μ/mL) was added into culture plates containing ConA stimulated splenocytes.To study the overall effect on blood picture,density gradient purified lymphocytes analysis and conventional methodology for total and differential leukocyte count and hemoglobin level were also done.Results:It indicated that the rats treated with Ocimum sanctum leaves extract had significantly enhanced(P【0.001) ability of spleen cells to secrete IL-2.Investigation in vitro also showed regulation of IL-2 production.Blood study exhibited leucocytosis and augmentation of T& B lymphocytes by 25%approximately.4-5%increase in Hemoglobin value was also noticed.Conclusion:Aqueous Ocimum sanctum leaves extract may have stimulatory effect on T & B lymphocytes particularly on Th 1 subset of lymphocytes as shown by enhancement in IL-2 production.
文摘It is observed that Ge-132 can increase human interleukin-2（IL-2）productionby the peripheral blood mononuclear cells（PBMC）under PHA induction in vitro.TraceGe-132(10<sup>-3</sup>-1μg/ml)can obviously increase the IL-2 production;even utmost minimalGe-132 (10<sup>-4</sup>-10<sup>-1</sup>μg/ml)can promote the reactivity of lymphocyres to IL-2.The proba-ble anticancer mechanism of Ge-132 was discussed.
基金support from the National Key Technologies R&D Program of China(2022YFE0114800)National Natural Science Foundation of China(22075047),and the 111 Project(D16008)。
文摘Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.
基金supported by the National Natural Science Foundation of China(NSFC)(No.52100101)and the National Scholarship Fund.
文摘NH_(2)-MIL-125 and its derivatives are receivingmore attention in various aspects of photocatalytic reactions,especially in the photocatalytic hydrogen peroxide(H_(2)O_(2))production from water(H_(2)O)and oxygen(O_(2)),which is a promising and sustainable strategy.However,the generation of H_(2)O_(2) from NH_(2)-MIL-125 is far from satisfactory due to rapid photo-generated carriers recombination and poor surface electron transfer.In the work,the composite photocatalyst CQDs/TiO_(2)/NH_(2)-MIL-125(C/T/NM)was designed for the first time by one-step hydrothermal method.TiO_(2) was in situ converted from partial NH_(2)-MIL-125(NM)during the successful loaded of Carbon quantum dots(CQDs)by hydrothermal process.The results indicated the typeⅡheterojunction was successfully constructed between the NM and TiO_(2) interface,which could promote the transmission of photo-generated electrons.In addition,the successful loaded of CQDs could effectively transfer and stored the photo-generated electrons to the photocatalyst surface to participate in the reaction,and further avoiding the recombination of photo-generated carriers.The C/T/NM composite photocatalyst achieved a H_(2)O_(2) generation of 455μmol/L for 5 hours under visible light without oxygen bubbling,whichwas 7.1 times superior to that of NM.The H_(2)O_(2) generation rate reached 645.4μM/(g·h),which was in priority in the reported literature under the same conditions.Finally,based on the active species capture experiments,energy band structure analysis and the photoelectrochemicalmeasurements,a possiblemechanism for the efficientH_(2)O_(2) generation through C/T/NM had been proposed.This work provided new ideas for designing NH_(2)-MIL-125 based composite photocatalysts for the production of H_(2)O_(2).
文摘Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.
基金financially supported by the National Key Re-search and Development Program of China(Nos.2022YFB3803600 and 2022YFE0115900)the National Natural Science Foundation of China(Nos.U24A2071,22278324,22238009,22361142704,22202187,and U23A20102)+1 种基金the National Science Foundation of Hubei Province of China(No.2022CFA001)Key R&D Program Projects in Hubei Province(No.2023BAB113).
文摘S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.
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financially supported by the National Natural Science Foundation of China(Nos.52362012,42077162,51978323)Natural Science Foundation of Jiangxi Province(No.2022ACB203014)+4 种基金Major Discipline Academic and Technical Leaders Training Program of Jiangxi Province(Nos.20213BCJ22018,20232BCJ22048)Natural Science Project of the Educational Department in Jiangxi Province(No.GJJ2201121)Natural Science Foundation of Nanchang Hangkong University(No.EA202202256)Educational Reform Project of Jiangxi Province(No.JXYJG-2022-135)Nanchang Hangkong University Educational Reform Project(Nos.sz2214,sz2213,JY22017,KCPY1806)。
文摘Photocatalytic H_(2)production from water splitting is a promising candidate for solving the increasing energy crisis and environmental issues.Herein we report a novel g-C_(3)N_(4)/Ag In_(x)S_(y)S-scheme heterojunction photocatalyst for water splitting into stoichiometric H_(2)and H_(2)O_(2)under visible light.The catalyst was prepared by depositing 3D bimetallic sulfide(Ag In_(x)S_(y))nanotubes onto 2D g-C_(3)N_(4)nanosheets.Owing to the special 3D-on-2D configuration,the photogenerated carriers could be rapidly transferred and effectively separated through the abundant interfacial heterostructures to avoid recombination,and therefore excellent performance for visible light-driven water splitting could be obtained,with a 24-h H_(2)evolution rate up to 237μmol g^(-1)h^(-1).Furthermore,suitable band alignment enables simultaneous H_(2)and H_(2)O_(2)production in a 1:1 stoichiometric ratio.H_(2)and H_(2)O_(2)were evolved on the conduction band of g-C_(3)N_(4)and on the valance band of Ag In_(x)S_(y),respectively.The novel 3D-on-2D configuration for heterojunction construction proposed in this work provided alternative research ideas toward photocatalytic reaction.
基金supported by the National Natural Science Foundation of China(Nos.52072153,52202238)the Postdoctoral Science Foundation of China(No.2021M690023)the Zhenjiang Key R&D Programmes(No.SH2021021)。
文摘H_(2)O_(2)is an excellent green oxidant with important applications in many fields.The conventional anthraquinone process for synthesizing H_(2)O_(2)is usually accompanied by high economic costs and stringent process requirements.The photocatalytic production of H_(2)O_(2)via heterojunction semiconductors has proven to overcome these limitations,which is a promising alternative to the conventional anthraquinone process.In this review,we provide a comprehensive summary of the semiconductor heterojunction materials that have been attempted to be used in the photocatalytic generation of H_(2)O_(2)in recent years.Firstly,a brief description of the photoreaction mechanisms of different types of heterojunctions in the photocatalytic process is presented,focusing on the generation pathways and competing reactions for the photoproduction of H_(2)O_(2).Then,the types of heterojunctions applied for photoproduction of H_(2)O_(2)are comprehensively summarized.Among them,the four most widely used types of heterojunctions,including type-Ⅱ heterojunctions,Z-scheme systems,S-scheme systems,and Schottky heterojunctions,and their current applications in the reaction of photoproduction of H_(2)O_(2)are highlighted.By comparing the differences in the internal electric fields of different types of heterojunctions,different charge transfer pathways of various types of heterojunctions in the photoproduction of H_(2)O_(2)are distinguished.Furthermore,the great potential of other types of heterojunctions,such as p-n heterojunctions,in photocatalysis is further outlined.Finally,the challenges as well as opportunities for the development of novel heterostructural photocatalysts for H_(2)O_(2)production are outlined.We sincerely hope this minireview can attract more attention from scientific research workers in the field of photocatalytic H_(2)O_(2)generation,making them valuable for environmental remediation and industrial applications in the future.
文摘Photocatalysis offers a sustainable solution to two pressing global issues:greenhouse gas mitigation and clean energy generation.By harnessing light energy,photocatalytic processes enable water splitting for hydrogen production and CO_(2) conversion into value-added products.Among the materials explored for photocatalysis,nickel-based photocatalysts have emerged as highly promising due to their low cost,abundance,stability,and efficiency.This review summarizes recent advancements in Ni-based photocatalysts,highlighting their role in improving photocatalytic performance by enhancing light absorption,charge separation,and reducing charge recombination.Key challenges and future directions for optimizing these materials are also discussed,offering insights into their potential for advancing clean energy technologies.
基金supported by Research Project for‘Carbon Upcycling Project for Platform Chemicals’of the National Research Foundation(NRF)funded by the Ministry of Science and ICT,Republic of Korea(grant number:2022M3J3A1050053)supported by the National Research Council of Science&Technology(NST)grant by the Korean government(MSIT)(No.CAP21011-100)+1 种基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2023-00302697)institutional program grants from the Korea Institute of Science and Technology。
文摘To develop an efficient electrochemical CO_(2)reduction reaction(CO_(2)RR)for the production of C_(2)chemicals,improvements in the Cu catalyst are necessary.Doping is widely used for catalyst enhancement;however,only a few elements have been examined.This study proposes guidelines for the selection of Cu catalyst dopants to promote ethylene production.It was hypothesized that the dopant chemical state highly influences the CO_(2)RR catalytic activity.In the case of dopants possessing a standard reduction potential within the CO_(2)RR potential region(e.g.,Mn and Ni),low Faradaic efficiency(FE)toward ethylene production was obtained owing to the presence of a metallic dopant(10.7%for Ni dopant).In contrast,a low standard reduction potential led to a stable high oxidation state for the dopant,yielding abundant Cu^(δ+)species with modified electronic structures and enhancing the CO_(2)RR catalytic activity for ethylene production(42.1%for Hf dopant).We expected that a dopant with a low standard reduction potential is difficult to reduce,which leads to a stable Cu-O-X bond and induces a stable Cu^(δ+)species.Our study provides insights into how to select dopant for various catalyst to enhance CO_(2)RR catalytic activity.
基金supported by the National Natural Science Foundation of China(NSFC,Grant No.52372063,62204246 and 52401244)the Young Elite Scientists Sponsorship Program by CAST(Grant No.2023QNRC001)+1 种基金the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233001,GZC20233006)the China Postdoctoral Science Foundation(Grant No.2024M753526)。
文摘Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.
文摘Hydrogen generation and related energy applications heavily rely on the hydrogen evolution reaction(HER),which faces challenges of slow kinetics and high overpotential.Efficient electrocatalysts,particularly single-atom catalysts (SACs) on two-dimensional (2D) materials,are essential.This study presents a few-shot machine learning (ML) assisted high-throughput screening of 2D septuple-atomic-layer Ga_(2)CoS_(4-x)supported SACs to predict HER catalytic activity.Initially,density functional theory (DFT)calculations showed that 2D Ga_(2)CoS4is inactive for HER.However,defective Ga_(2)CoS_(4-x)(x=0–0.25)monolayers exhibit excellent HER activity due to surface sulfur vacancies (SVs),with predicted overpotentials (0–60 mV) comparable to or lower than commercial Pt/C,which typically exhibits an overpotential of around 50 m V in the acidic electrolyte,when the concentration of surface SV is lower than 8.3%.SVs generate spin-polarized states near the Fermi level,making them effective HER sites.We demonstrate ML-accelerated HER overpotential predictions for all transition metal SACs on 2D Ga_(2)CoS_(4-x).Using DFT data from 18 SACs,an ML model with high prediction accuracy and reduced computation time was developed.An intrinsic descriptor linking SAC atomic properties to HER overpotential was identified.This study thus provides a framework for screening SACs on 2D materials,enhancing catalyst design.
文摘The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.
基金funding supporting from the National Natural Science Foundation of China(Grant No.22125903,22439003,22309176)National Key R@D Program of China(Grants 2022YFA1504100)+2 种基金DICP(DICP I202471)the State Key Laboratory of Catalysis(No:2024SKL-A-001)Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(Grant E412010508,Grant E411070316)。
文摘Hydrogen peroxide(H_(2)O_(2))is an essential environmentally friendly oxidant with a wide range of applications.Compared with traditional anthraquinone processes,the electrochemical synthesis of H_(2)O_(2)via the two-electron oxygen reduction reaction and two-electron water oxidation reaction offers a more promising and sustainable alternative.Carbon-based electrocatalysts playing a crucial role in these processes owing to their abundance and facile functionalization.This review focuses on the strategic design of carbon-based electrocatalysts to enhance H_(2)O_(2)production.We begin by highlighting the significance of H_(2)O_(2)and the fundamental mechanisms of electrochemical process.Subsequently,we present a detailed analysis of key factors affecting catalytic performance,concentrating electronic structure and geometric structure regulation as primary catalyst design approaches to improve H_(2)O_(2)production.Interface engineering and pH effects are also emphasized for their crucial roles.Finally,the major challenges and prospects for advancing H_(2)O_(2)production towards practical applications are discussed.
文摘CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 with large-scale.However,CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable,which typically requires a harsh reaction temperature above 800℃.In this work,solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO_(2)-free H_(2)relying solely on solar energy as the driving force.A high H_(2)yield of 204.6 mmol g^(–1)h^(–1)was observed over Ni-CeO2 interface under photothermal conditions,along with above 87%reduction in the apparent activation energy(11.2 vs.87.3 kJ mol^(–1))when comparing with the traditional thermal catalysis.Further studies suggested that Ni/CeO_(2)catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition.The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light,which lowered activation energy and improved the photothermal catalytic activity.This work provides a promising photothermal catalytic strategy to produce CO_(2)-free H^(2)under mild conditions.
基金the financial support provided by the National Natural Science Foundation of China(Nos.22262024,52470078,62004143)Jiangxi Province Academic and Technical Leader of Major Disciplines(No.20232BCJ22008)+4 种基金the Key Project of Natural Science Foundation of Jiangxi Province(Nos.20232ACB204007)Double Thousand Talent Plan of Jiangxi Provincethe Natural Science Foundation of Jiangxi Province(No.2022ACB203014)the Key R&D Program of Hubei Province(No.2022BAA084)the Innovation Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202404)。
文摘Photocatalytic and photoelectrocatalytic H_(2)O_(2)production has been identified as a significant pathway within environmental pollution control,green energy,medical treatment,sterilization and disinfection.However,conventional single-material photocatalysts struggle to fulfill the stringent criteria of high efficiency,stability,cost-effectiveness,and responsiveness to visible light.The elevated recombination rates of photogenerated charge carriers,coupled with the suboptimal utilization of visible light,have collectively constrained the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.Heterojunction catalysts for the production of H_(2)O_(2)has become a focal point of research.This review commences by elucidating the fundaments underlying the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.Subsequently,it delineates the distinctive electron transfer mechanisms of Z-scheme and S-scheme heterojunctions,which exhibit enhanced efficiency in the photocatalytic and photoelectrocatalytic H_(2)O_(2)production,along with a summary of strategies for the improvement of photocatalyst and photoelectrocatalyst performance.Furthermore,this review also outlines the latest fabrication strategies,state-of-the-art in-situ characterization techniques,machine learning and density functional theory(DFT)simulations for Z-scheme or Sscheme catalysts for the photocatalytic and photoelectrocatalytic H_(2)O_(2)production,and briefly describes the multifunctional applications in H_(2)O_(2)production.Ultimately,the review contemplates the prospective developmental trajectories and application potential of these heterojunction configurations for the photocatalytic and photoelectrocatalytic H_(2)O_(2)production.
基金Supported by the National Natural Science Foundation of China(52274053)Natural Science Foundation of Beijing(3232028).
文摘Using the ultra-low permeability reservoirs in the L block of the Jiangsu oilfield as an example,a series of experiments,including slim tube displacement experiments of CO_(2)-oil system,injection capacity experiments,and high-temperature,high-pressure online nuclear magnetic resonance(NMR)displacement experiments,are conducted to reveal the oil/gas mass transfer pattern and oil production mechanisms during CO_(2) flooding in ultra-low permeability reservoirs.The impacts of CO_(2) storage pore range and miscibility on oil production and CO_(2) storage characteristics during CO_(2) flooding are clarified.The CO_(2) flooding process is divided into three stages:oil displacement stage by CO_(2),CO_(2) breakthrough stage,CO_(2) extraction stage.Crude oil expansion and viscosity reduction are the main mechanisms for improving recovery in the CO_(2) displacement stage.After CO_(2) breakthrough,the extraction of light components from the crude oil further enhances oil recovery.During CO_(2) flooding,the contribution of crude oil in large pores to the enhanced recovery exceeds 46%,while crude oil in medium pores serves as a reserve for incremental recovery.After CO_(2) breakthrough,a small portion of the crude oil is extracted and carried into nano-scale pores by CO_(2),becoming residual oil that is hard to recover.As the miscibility increases,the CO_(2) front moves more stably and sweeps a larger area,leading to increased CO_(2) storage range and volume.The CO_(2) full-storage stage contributes the most to the overall CO_(2) storage volume.In the CO_(2) escape stage,the storage mechanism involves partial in-situ storage of crude oil within the initial pore range and the CO_(2) carrying crude oil into smaller pores to increase the volume of stored CO_(2).In the CO_(2) leakage stage,as crude oil is produced,a significant amount of CO_(2) leaks out,causing a sharp decline in the storage efficiency.
