The global concern surrounding the advancement of methods for treating wastewater and polluted soil has markedly increased over time.While electrochemical advanced oxidation processes(EAOPs)and biotreatments are commo...The global concern surrounding the advancement of methods for treating wastewater and polluted soil has markedly increased over time.While electrochemical advanced oxidation processes(EAOPs)and biotreatments are commonly employed technologies for remediating wastewater and polluted soil,their widespread adoption is hindered by their limitations,which include high costs associated with EAOPs and prolonged remediation time of biotreatments.In the review,we provided an overviewof EAOP technology and biotreatment,emphasizing the critical aspects involved in building a combined system.This review systematically evaluates recent research that combines EAOPswith bioremediation for treating wastewater or contaminated soil as pretreatment or post-treatment process.Research findings suggest that the combined treatment method represents a promising and competitive technology that can overcome some of the limitations of individual treatments.Additionally,we discussed the potential applications of this technology in varying levels of wastewater and soil pollution,as well as the underlying combination mechanisms.展开更多
A new perspective was reported to design the self-densified plasma electrolytic oxidation(SDF-PEO)coat-ings on magnesium alloys based on the dissolution-ionization-diffusion-deposition(DIDD)model.The main consideratio...A new perspective was reported to design the self-densified plasma electrolytic oxidation(SDF-PEO)coat-ings on magnesium alloys based on the dissolution-ionization-diffusion-deposition(DIDD)model.The main considerations of the new PEO electrolyte include the establishment of a thermodynamics diagram,the construction of a liquid-solid sintering system and the regulation of plasma sparkling kinetics.The SDF-PEO coating exhibited a homogeneous and dense microstructure,superior corrosion resistance and good technological adaptability.This work offers a novel theory to design surface treatment solutions with superior corrosion resistance and promising application prospects.展开更多
Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality...Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality,hidden contamination,and complex treatment requirements.Current research focuses on advanced treatment technologies,among which the advanced oxidation process(AOPs) of peroxomonosulfate(PMS) has great potential.Although there are many reviews of PMS-based AOP,most of them focus on surface water.This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation(ISCO) technology,further study the reaction mechanism,compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park,propose new activation methods and catalyst selection,and provide guidance for future groundwater treatment research.展开更多
The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale in...The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).展开更多
Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with...Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with exposed{100}-rich facets were synthesized by a glucose-assisted solvent-thermal method,in which alloying W not only can facilitate the formation of such specific nanostructures to expose more active sites for AOR,but also modulate the electronic structure of PtIr to promote the kinetics of AOR.The PtIrW-NCBs featuring the small nanoparticle size of 5.05±0.07 nm exhibit superior AOR performance,wherein the onset potential is down to 0.319 V and the mass activity is 30.15 A g_((PGM=Pt,Ir))^(-1)at 0.50 V vs.RHE,significantly higher than those of reported majority of AOR catalysts and even commercial PtIr/C.Meanwhile,in situ Fourier transform infrared spectroscopy measurement further reveals that AOR on PtIrW-NCBs dominantly undergoes the dimerization path of NH_(x)(1≤x≤2).In addition,the theoretical calculations also identify that alloying W into PtIr can contribute additional electrons to 5d orbitals of PtIr,enabling the d-band center approaching the Femi level,which in turn induces the high-filling of bonding orbitals of N-N bond in^(*)N_(2)H_(4),promoting the dimerization of^(*)NH_(2)to^(*)N_(2)H_(4)and thus leading to high AOR activity of PtIrW.This work provides new insights for designing efficient AOR electrocatalysts.展开更多
To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomat...Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.展开更多
In recent years,machine learning(ML)techniques have demonstrated a strong ability to solve highly complex and non-linear problems by analyzing large datasets and learning their intrinsic patterns and relationships.Par...In recent years,machine learning(ML)techniques have demonstrated a strong ability to solve highly complex and non-linear problems by analyzing large datasets and learning their intrinsic patterns and relationships.Particularly in chemical engineering and materials science,ML can be used to discover microstructural composition,optimize chemical processes,and create novel synthetic pathways.Electrochemical processes offer the advantages of precise process control,environmental friendliness,high energy conversion efficiency and low cost.This review article provides the first systematic summary of ML in the application of electrochemical oxidation,including pollutant removal,battery remediation,substance synthesis and material characterization prediction.Hot trends at the intersection of ML and electrochemical oxidation were analyzed through bibliometrics.Common ML models were outlined.The role of ML in improving removal efficiency,optimizing experimental conditions,aiding battery diagnosis and predictive maintenance,and revealing material characterization was highlighted.In addition,current issues and future perspectives were presented in relation to the strengths and weaknesses of ML algorithms applied to electrochemical oxidation.In order to further support the sustainable growth of electrochemistry from basic research to useful applications,this review attempts to make it easier to integrate ML into electrochemical oxidation.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/ca...Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/catalyst photoelectrode assemblies are used to achieve reasonable efficiencies.At the same time,unlike in dark electrochemical processes,the role of the catalyst is not straightforward in photoelectrochemistry,where the onset potential of the redox process should be mostly determined by the flatband potential of the semiconductor.In addition,the energy of holes(i.e.,the surface potential)is independent of the applied bias;it is defined by the valence band(VB)position.In this study,we compared PdAu,Au,and Ni on Si photoanodes in the photoelectrochemical(PEC)oxidation of glycerol at record high current densities(>180 mA cm^(‒2)),coupled to H_(2) evolution at the cathode.We successfully decreased the energy requirement(i.e.,the cell voltage)of the paired conversion of glycerol and water by 0.7 V by exchanging the widely studied Ni catalyst with PdAu.The catalyst choice also dictates the product distribution,resulting mainly in C3 products on PdAu,glycolate(C2 product)on Au,and formate(C1 product)on Ni,without complete mineralization of glycerol(CO_(2) formation)that is difficult to rule out in dark electrochemical processes(as demonstrated by comparative measurements).Finally,we achieved a bias‐free(standalone)operation with PdAu/Si and Au/Si photoanodes by combining the PEC oxidation of glycerol with oxygen reduction reaction(ORR).展开更多
Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production...Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.展开更多
A comprehensive understanding of the dynamic processes at the catalyst/electrolyte interfaces is crucial for the development of advanced electrocatalysts for the oxygen evolution reaction(OER).However,the chemical pro...A comprehensive understanding of the dynamic processes at the catalyst/electrolyte interfaces is crucial for the development of advanced electrocatalysts for the oxygen evolution reaction(OER).However,the chemical processes related to surface corrosion and catalyst degradation have not been well understood so far.In this study,we employ LiCoO_(2) as a model catalyst and observe distinct OER activities and surface stabilities in different alkaline solutions.Operando X-ray diffraction(XRD)and online mass spectroscopy(OMS)measurements prove the selective intercalation of alkali cations into the layered structure of LiCoO_(2) during OER.It is proposed that the dynamic cation intercalations facilitate the chemical oxidation process between highly oxidative Co species and adsorbed water molecules,triggering the so-called electrochemical-chemical reaction mechanism(EC-mechanism).The results of this study emphasize the influence of cations on OER and provide insights into new strategies for achieving both high activity and stability in high-performance OER catalysts.展开更多
The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical pr...The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.展开更多
Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materi...Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.展开更多
Gibberellins(GAs)and auxin play central regulatory roles in seed germination and root system development,respectively,so that the application of these phytohormones to crops would be worthwhile,with an increasing pote...Gibberellins(GAs)and auxin play central regulatory roles in seed germination and root system development,respectively,so that the application of these phytohormones to crops would be worthwhile,with an increasing potential demand in agriculture.However,there are few effective chemicals that simultaneously enhance both GA and auxin signaling.Here,we report on an artificial thiourea derivative chemical,Y21,that serves as both a GA-signaling agonist and an auxin analog,promoting seed germination and root development,as well as low-phosphorus tolerance.Phenotypic,biochemical,and genetic evidence demonstrated that Y21 enhances the interaction between GA and its receptor GID1C via the Val239 amino acid residue and consequently promotes degradation of the DELLA proteins REPRESSOR OF ga1-3(RGA)and RGA-LIKE 2.Furthermore,we found that Y21 interacts with the auxin receptor TIR1 via the Cys405 residue and thus promotes the turnover of the auxinresponsive Aux/IAA proteins.Consequently,Y21significantly increases low-phosphorus tolerance of treated plants by positively regulating lateral root development.To our knowledge,Y21 is the first GA-signaling agonist to be identified,and our results also demonstrate that this potent synthetic chemical,identified by chemical genetic screening,is effective at modulating plant development and stress tolerance.展开更多
Panax notoginseng(P.notoginseng),a valuable traditional Chinese medicine,is the dried root of plants in Acanthopanax gracilistylus family,with the effect of dispersing blood stasis,eliminating swelling and relieving p...Panax notoginseng(P.notoginseng),a valuable traditional Chinese medicine,is the dried root of plants in Acanthopanax gracilistylus family,with the effect of dispersing blood stasis,eliminating swelling and relieving pain.With the development of modern medicine,the active ingredients and mechanisms of P.notoginseng have been gradually revealed.The present paper systematically reviews the chemical composition and biological activities of P.nologinseng,to provide a scientific basis and reference for detailed research on P.nologinseng.展开更多
The dried fruit of Forsythia suspensa(Oleaceae),also known as Forsythia,is a traditional Chinese medicinal herb known for its heat-clearing and detoxifying properties.It is used to disperse nodules,reduce swelling,rem...The dried fruit of Forsythia suspensa(Oleaceae),also known as Forsythia,is a traditional Chinese medicinal herb known for its heat-clearing and detoxifying properties.It is used to disperse nodules,reduce swelling,remove toxins,clear heat,and alleviate wind-heat syndromes.It also has hepatoprotective,anti-inflammatory,antiviral,antibacterial,anticancer,antioxidant,antiaging,and anti-obesity effects,as well as potential therapeutic effects on Alzheimer’s disease and diabetic nephropathy.It is used to treat scrofula,mastitis,wind-heat common cold,and other ailments.The review summarizes the chemical constituents and pharmacological effects of F.suspensa,aiming to provide a scientific foundation for its future development,research,and clinical utilization.展开更多
The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing...The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing applications has been limited by inherent challenges such as high electrical resistivity,poor aging resistance,and interfacial incompatibility.To address these limitations,hydroxyl-terminated polybutadiene(HTPB)-based polyurethane was chemically modified with acetylferrocene-polyaniline conductive moieties to enhance charge transport properties.Remarkably,this covalent functionalization endowed the resulting ferrocene-polyaniline hybrid polyurethane(FPHP)with a conductivity of2.33 n A at 1 V bias while preserving piezoresistive functionality.The FPHP demonstrated exceptional mechanical-electrical performance,achieving 254% elongation at break with strain-dependent gauge factors of 7.28(0%-12.5% strain,R^(2)=0.9504)and 19.66(12.5%-35.0% strain,R^(2)=0.9929).Further characterization revealed a rapid 0.60 s response time and stability over 3500 strain-release cycles at compression strain,underscoring its durability under repetitive loading.The FPHP sensor was capable of monitoring various human movements and recognizing writing signals.These advances establish a materials design paradigm for fabricating flexible sensors that synergistically integrate high deformability,tunable sensitivity,and robust operational stability,positioning FPHP as a promising candidate for next-generation wearable electronics and soft robotics.展开更多
Real-time health monitoring and ongoing evaluation of physiological conditions are becoming increasingly vital for the advancement of future medical diagnostics and personalized healthcare solutions.Given that certain...Real-time health monitoring and ongoing evaluation of physiological conditions are becoming increasingly vital for the advancement of future medical diagnostics and personalized healthcare solutions.Given that certain illnesses necessitate prompt and accessible detection methods,wearable chemical sensors have garnered considerable interest for their capability to monitor health through physiological signals and chemical indicators.This review delivers a thorough examination of recent developments in four primary categories of wearable chemical sensors:biosensors,humidity sensors,gas sensors,and ion sensors.We explore the representative materials,device structures,operating mechanisms,and various application scenarios for each type of sensor.By investigating the latest innovations in these technologies,we aim to provide a detailed overview of the current research landscape,highlight existing challenges,and present potential future directions of wearable chemical sensors in healthcare monitoring.展开更多
Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more ...Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.展开更多
基金supported by the National Natural Science Foundation of China(No.51709103)the Natural Science Foundation of Hunan Province,China(Nos.2018JJ3242 and 2021JJ30362)the Science and Technology Innovation Leading Plan of High Tech Industry in Hunan Province(No.2021GK4055).
文摘The global concern surrounding the advancement of methods for treating wastewater and polluted soil has markedly increased over time.While electrochemical advanced oxidation processes(EAOPs)and biotreatments are commonly employed technologies for remediating wastewater and polluted soil,their widespread adoption is hindered by their limitations,which include high costs associated with EAOPs and prolonged remediation time of biotreatments.In the review,we provided an overviewof EAOP technology and biotreatment,emphasizing the critical aspects involved in building a combined system.This review systematically evaluates recent research that combines EAOPswith bioremediation for treating wastewater or contaminated soil as pretreatment or post-treatment process.Research findings suggest that the combined treatment method represents a promising and competitive technology that can overcome some of the limitations of individual treatments.Additionally,we discussed the potential applications of this technology in varying levels of wastewater and soil pollution,as well as the underlying combination mechanisms.
基金supported by the National Natural Sci-ence Foundation of China(Nos.U21A2045 and 52201066)the Liaoning Revitalization Talents Program(No.XLYC2002071).
文摘A new perspective was reported to design the self-densified plasma electrolytic oxidation(SDF-PEO)coat-ings on magnesium alloys based on the dissolution-ionization-diffusion-deposition(DIDD)model.The main considerations of the new PEO electrolyte include the establishment of a thermodynamics diagram,the construction of a liquid-solid sintering system and the regulation of plasma sparkling kinetics.The SDF-PEO coating exhibited a homogeneous and dense microstructure,superior corrosion resistance and good technological adaptability.This work offers a novel theory to design surface treatment solutions with superior corrosion resistance and promising application prospects.
基金supported by the National Key Research and Development Program of China (No.2023YFC3708005)the National Natural Science Foundation of China (Nos.21872102,22172080)the Fundamental Research Funds for the Central Universities (Nankai University,No.63241208)。
文摘Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality,hidden contamination,and complex treatment requirements.Current research focuses on advanced treatment technologies,among which the advanced oxidation process(AOPs) of peroxomonosulfate(PMS) has great potential.Although there are many reviews of PMS-based AOP,most of them focus on surface water.This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation(ISCO) technology,further study the reaction mechanism,compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park,propose new activation methods and catalyst selection,and provide guidance for future groundwater treatment research.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2024-00340074,RS-2024-00409901,2022M3I3A1081901,and RS-2024-00413272)。
文摘The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).
基金supported by the National Natural Science Foundation of China(22379031)the Guangxi Science and Technology Project of China(AB16380030)+1 种基金the National Research Foundation,SingaporeA*STAR(Agency for Science,Technology and Research)under its LCER Phase 2 Programme Hydrogen&Emerging Technologies FI,Directed Hydrogen Programme(U2305D4003)。
文摘Efficiently utilizing ammonia(carbon-free fuel)via low-temperature fuel cells is severely hindered by the sluggish kinetics of ammonia oxidation reaction(AOR).Herein,platinum-iridium-tungsten nanocubes(PtIrW-NCBs)with exposed{100}-rich facets were synthesized by a glucose-assisted solvent-thermal method,in which alloying W not only can facilitate the formation of such specific nanostructures to expose more active sites for AOR,but also modulate the electronic structure of PtIr to promote the kinetics of AOR.The PtIrW-NCBs featuring the small nanoparticle size of 5.05±0.07 nm exhibit superior AOR performance,wherein the onset potential is down to 0.319 V and the mass activity is 30.15 A g_((PGM=Pt,Ir))^(-1)at 0.50 V vs.RHE,significantly higher than those of reported majority of AOR catalysts and even commercial PtIr/C.Meanwhile,in situ Fourier transform infrared spectroscopy measurement further reveals that AOR on PtIrW-NCBs dominantly undergoes the dimerization path of NH_(x)(1≤x≤2).In addition,the theoretical calculations also identify that alloying W into PtIr can contribute additional electrons to 5d orbitals of PtIr,enabling the d-band center approaching the Femi level,which in turn induces the high-filling of bonding orbitals of N-N bond in^(*)N_(2)H_(4),promoting the dimerization of^(*)NH_(2)to^(*)N_(2)H_(4)and thus leading to high AOR activity of PtIrW.This work provides new insights for designing efficient AOR electrocatalysts.
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
基金financially supported by the National Natural Science Foundation of China(Nos.22205196 and U1904215)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University
文摘Electrochemically induced surface reconstruction offers a novel approach for in situ modulation of the surface structure of nanomaterials.However,comprehensive studies on the surface reconstruction behavior of nanomaterials under diverse electrochemical operations remain limited.Here,exemplified by three electrochemical operations,including cyclic voltammetry(CV),squarewave potential(SWP)and chronoamperometry(CA),we reveal the structural evolution behavior and the corresponding electrocatalytic activity of bimetallic telluride hollow nanorods(Ir_(1-x)Ru_(x)0Te_(2)HNRs).It was found that the surface Te atoms in Ir_(1-x)Ru_(x)0Te_(2)HNRs undergo preferential leaching during the CV and SWP processes,ultimately leading to the formation of a metal alloy shell.In contrast,during the CA process,the surface reconstruction induced by Te leaching was suppressed by the adsorption of anions on the electrode surface.Electrocatalytic tests show that the CV activated Ir_(0.75)Ru_(0.25)Te_(2)HNRs exhibit excellent activity for the hydrogen oxidation reaction in 0.1 M KOH,with a mass activity of 686 Ag^(-1)at an overpotential of50 mV,which is 2.9 times higher than that of commercialPt/C catalyst.Density functional theory(DFT)computation reveals that the incorporation of Ru optimizes the hydroxyl binding energy of IrRu alloy,thus resulting in the reduced reaction energy barrier of hydrogen oxidation reaction.This work provides a new insight into the design of efficient catalysts through electrochemical surface engineering.
基金funding from the National Natural Science Foundation of China(Nos.22122606,22076142,62276190)National Key Basic Research Program of China(No.2017YFA0403402)+2 种基金National Natural Science Foundation of China(No.U1932119)the Science&Technology Commission of Shanghai Municipality(No.14DZ2261100)the Fundamental Research Funds for the Central Universities。
文摘In recent years,machine learning(ML)techniques have demonstrated a strong ability to solve highly complex and non-linear problems by analyzing large datasets and learning their intrinsic patterns and relationships.Particularly in chemical engineering and materials science,ML can be used to discover microstructural composition,optimize chemical processes,and create novel synthetic pathways.Electrochemical processes offer the advantages of precise process control,environmental friendliness,high energy conversion efficiency and low cost.This review article provides the first systematic summary of ML in the application of electrochemical oxidation,including pollutant removal,battery remediation,substance synthesis and material characterization prediction.Hot trends at the intersection of ML and electrochemical oxidation were analyzed through bibliometrics.Common ML models were outlined.The role of ML in improving removal efficiency,optimizing experimental conditions,aiding battery diagnosis and predictive maintenance,and revealing material characterization was highlighted.In addition,current issues and future perspectives were presented in relation to the strengths and weaknesses of ML algorithms applied to electrochemical oxidation.In order to further support the sustainable growth of electrochemistry from basic research to useful applications,this review attempts to make it easier to integrate ML into electrochemical oxidation.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
基金funding under the European Union's Horizon Europe research and innovation program from the European Research Council(ERC,Grant Agreement No.101043617)(C.J.).Project No.RRF‐2.3.1‐21‐2022‐00009titled National Laboratory for Renewable Energy,was implemented with the support provided by the Recovery and Resilience Facility of the European Union within the framework of the Program Széchenyi Plan Plus(C.J.)support from MICIU/AEI/10.13039/501100011033/(PID2020-116093RB−C41 and PID2023‐152771OB‐I00).European Innovation Council(EIC)(101071010).
文摘Photoelectrochemistry is a promising method for the direct conversion of sunlight into valuable chemicals by combining the functions of solar panels and electrolyzers in one technology.In most studies,semiconductor/catalyst photoelectrode assemblies are used to achieve reasonable efficiencies.At the same time,unlike in dark electrochemical processes,the role of the catalyst is not straightforward in photoelectrochemistry,where the onset potential of the redox process should be mostly determined by the flatband potential of the semiconductor.In addition,the energy of holes(i.e.,the surface potential)is independent of the applied bias;it is defined by the valence band(VB)position.In this study,we compared PdAu,Au,and Ni on Si photoanodes in the photoelectrochemical(PEC)oxidation of glycerol at record high current densities(>180 mA cm^(‒2)),coupled to H_(2) evolution at the cathode.We successfully decreased the energy requirement(i.e.,the cell voltage)of the paired conversion of glycerol and water by 0.7 V by exchanging the widely studied Ni catalyst with PdAu.The catalyst choice also dictates the product distribution,resulting mainly in C3 products on PdAu,glycolate(C2 product)on Au,and formate(C1 product)on Ni,without complete mineralization of glycerol(CO_(2) formation)that is difficult to rule out in dark electrochemical processes(as demonstrated by comparative measurements).Finally,we achieved a bias‐free(standalone)operation with PdAu/Si and Au/Si photoanodes by combining the PEC oxidation of glycerol with oxygen reduction reaction(ORR).
基金financially supported by the National Natural Science Foundation of China(No.22275138 and 22271219)
文摘Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.
基金financially supported by the Shenzhen Science and Technology Innovation Program(Grant No.JCYJ20220530150011024)。
文摘A comprehensive understanding of the dynamic processes at the catalyst/electrolyte interfaces is crucial for the development of advanced electrocatalysts for the oxygen evolution reaction(OER).However,the chemical processes related to surface corrosion and catalyst degradation have not been well understood so far.In this study,we employ LiCoO_(2) as a model catalyst and observe distinct OER activities and surface stabilities in different alkaline solutions.Operando X-ray diffraction(XRD)and online mass spectroscopy(OMS)measurements prove the selective intercalation of alkali cations into the layered structure of LiCoO_(2) during OER.It is proposed that the dynamic cation intercalations facilitate the chemical oxidation process between highly oxidative Co species and adsorbed water molecules,triggering the so-called electrochemical-chemical reaction mechanism(EC-mechanism).The results of this study emphasize the influence of cations on OER and provide insights into new strategies for achieving both high activity and stability in high-performance OER catalysts.
基金supported by the Key R&D Program of Shandong Province,China(No.2025CXGC 010412)the National Key Research and Development Program of China(No.2022YFB3709300)the National Natural Science Foundation of China(No.U21A2048).
文摘The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.
文摘Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.
基金supported by grants from the National Natural Science Foundation of China(32470364,31872850,and 31872804)the Natural Science Basic Research Program of Shaanxi(2025JC-JCQN-056 and 2024JC-YBMS-151)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(2025A1515012749)the China Postdoctoral Science Foundation(2025M774348)the Shaanxi Fundamental Science Research Project for Chemistry&Biology(22JHZ007and 22JHQ054)。
文摘Gibberellins(GAs)and auxin play central regulatory roles in seed germination and root system development,respectively,so that the application of these phytohormones to crops would be worthwhile,with an increasing potential demand in agriculture.However,there are few effective chemicals that simultaneously enhance both GA and auxin signaling.Here,we report on an artificial thiourea derivative chemical,Y21,that serves as both a GA-signaling agonist and an auxin analog,promoting seed germination and root development,as well as low-phosphorus tolerance.Phenotypic,biochemical,and genetic evidence demonstrated that Y21 enhances the interaction between GA and its receptor GID1C via the Val239 amino acid residue and consequently promotes degradation of the DELLA proteins REPRESSOR OF ga1-3(RGA)and RGA-LIKE 2.Furthermore,we found that Y21 interacts with the auxin receptor TIR1 via the Cys405 residue and thus promotes the turnover of the auxinresponsive Aux/IAA proteins.Consequently,Y21significantly increases low-phosphorus tolerance of treated plants by positively regulating lateral root development.To our knowledge,Y21 is the first GA-signaling agonist to be identified,and our results also demonstrate that this potent synthetic chemical,identified by chemical genetic screening,is effective at modulating plant development and stress tolerance.
文摘Panax notoginseng(P.notoginseng),a valuable traditional Chinese medicine,is the dried root of plants in Acanthopanax gracilistylus family,with the effect of dispersing blood stasis,eliminating swelling and relieving pain.With the development of modern medicine,the active ingredients and mechanisms of P.notoginseng have been gradually revealed.The present paper systematically reviews the chemical composition and biological activities of P.nologinseng,to provide a scientific basis and reference for detailed research on P.nologinseng.
文摘The dried fruit of Forsythia suspensa(Oleaceae),also known as Forsythia,is a traditional Chinese medicinal herb known for its heat-clearing and detoxifying properties.It is used to disperse nodules,reduce swelling,remove toxins,clear heat,and alleviate wind-heat syndromes.It also has hepatoprotective,anti-inflammatory,antiviral,antibacterial,anticancer,antioxidant,antiaging,and anti-obesity effects,as well as potential therapeutic effects on Alzheimer’s disease and diabetic nephropathy.It is used to treat scrofula,mastitis,wind-heat common cold,and other ailments.The review summarizes the chemical constituents and pharmacological effects of F.suspensa,aiming to provide a scientific foundation for its future development,research,and clinical utilization.
文摘The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing applications has been limited by inherent challenges such as high electrical resistivity,poor aging resistance,and interfacial incompatibility.To address these limitations,hydroxyl-terminated polybutadiene(HTPB)-based polyurethane was chemically modified with acetylferrocene-polyaniline conductive moieties to enhance charge transport properties.Remarkably,this covalent functionalization endowed the resulting ferrocene-polyaniline hybrid polyurethane(FPHP)with a conductivity of2.33 n A at 1 V bias while preserving piezoresistive functionality.The FPHP demonstrated exceptional mechanical-electrical performance,achieving 254% elongation at break with strain-dependent gauge factors of 7.28(0%-12.5% strain,R^(2)=0.9504)and 19.66(12.5%-35.0% strain,R^(2)=0.9929).Further characterization revealed a rapid 0.60 s response time and stability over 3500 strain-release cycles at compression strain,underscoring its durability under repetitive loading.The FPHP sensor was capable of monitoring various human movements and recognizing writing signals.These advances establish a materials design paradigm for fabricating flexible sensors that synergistically integrate high deformability,tunable sensitivity,and robust operational stability,positioning FPHP as a promising candidate for next-generation wearable electronics and soft robotics.
基金supported by the Shandong Excellent Young Scientists Fund Program(Overseas)(2023HWYQ-035)the Taishan Scholar Program of Shandong Province(tsqn202306078)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(2024A1515011635)the Natural Science Foundation of Shandong Province(ZR2023MF108)the Jinan Central Hospital(1190022050)。
文摘Real-time health monitoring and ongoing evaluation of physiological conditions are becoming increasingly vital for the advancement of future medical diagnostics and personalized healthcare solutions.Given that certain illnesses necessitate prompt and accessible detection methods,wearable chemical sensors have garnered considerable interest for their capability to monitor health through physiological signals and chemical indicators.This review delivers a thorough examination of recent developments in four primary categories of wearable chemical sensors:biosensors,humidity sensors,gas sensors,and ion sensors.We explore the representative materials,device structures,operating mechanisms,and various application scenarios for each type of sensor.By investigating the latest innovations in these technologies,we aim to provide a detailed overview of the current research landscape,highlight existing challenges,and present potential future directions of wearable chemical sensors in healthcare monitoring.
基金financially supported by the National Natural Science Foundation of China(22478211,22179067,22372017)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10)。
文摘Photoelectrochemical water oxidation(PEC-WO)as a green and sustainable route to produce H_(2)O_(2)has attracted extensive attentions.However,water oxidation to H_(2)O_(2)via a 2e^(-) pathway is thermodynamically more difficult than to O_(2)via a 4e^(-)pathway.Herein,with a series of BiVO_(4)-based photoanodes,the decisive factors determining the PEC activity and selectivity are elucidated,combining a comprehensive experimental and theoretical investigations.It is discovered that the ZnO/BiVO_(4)photoanode(ZnO/BVO)forms a Type-Ⅱheterojunction in energy level alignment.The accelerated photogenerated charge separation/transfer dynamics generates denser surface holes and higher surface photovoltage.Therefore,the activity of water oxidation reaction is promoted.The selectivity of PEC-WO to H_(2)O_(2)is found to be potential-dependent,i.e.,at the lower potentials(PEC-dominated),surface hole density determines the selectivity;and at the higher potentials(electrochemical-dominated),surface reaction barriers govern the selectivity.For the ZnO/BVO heterojunction photoanode,the higher surface hole density facilitates the generation of OH·and the subsequent OH·/OH·coupling to form H_(2)O_(2),thus rising up with potentials;at the higher potentials,the 2-electron pathway barrier over ZnO/BVO surface is lower than over BVO surface,which benefits from the electronic structure regulation by the underlying ZnO alleviating the over-strong adsorption of^(*)OH on BVO,thus,the two-electron pathway to produce H_(2)O_(2)is more favored than on BVO surface.This work highlights the crucial role of band energy structure of semiconductors on both PEC reaction activity and selectivity,and the knowledge gained is expected to be extended to other photoeletrochemical reactions.
