Recent advancements in thermal conductivity modulating strategies have shown promising enhancements to the thermal management capabilities of two-dimensional materials.In this article,both the iterative Boltzmann tran...Recent advancements in thermal conductivity modulating strategies have shown promising enhancements to the thermal management capabilities of two-dimensional materials.In this article,both the iterative Boltzmann transport equation solution and the two-temperature model were employed to investigate the efficacy of targeted phonon excitation applied to hexagonal boron nitride(hBN).The results indicate significant modifications to hBN's thermal conductivity,achieving increases of up to 30.1%as well as decreases of up to 59.8%.These findings validate the reliability of the strategy,expand its scope of applicability,and establish it as a powerful tool for tailoring thermal properties across a wider range of fields.展开更多
High-entropy materials possess high hardness and strong wear resistance,yet the key bottleneck for their practical applications is the poor corrosion resistance in harsh environments.In this work,the high-entropy nitr...High-entropy materials possess high hardness and strong wear resistance,yet the key bottleneck for their practical applications is the poor corrosion resistance in harsh environments.In this work,the high-entropy nitride(HEN)coatings of(MoNbTaTiZr)1-x Nx(x=0-0.47)were fabricated using a hybrid di-rect current magnetron sputtering technique.The research focus was dedicated to the effect of nitrogen content on the microstructure,mechanical and electrochemical properties.The results showed that the as-deposited coatings exhibited a typical body-centered cubic(BCC)structure without nitrogen,while the amorphous matrix with face-centered cubic(FCC)nanocrystalline grain was observed at x=0.17.Further increasing x in the range of 0.35-0.47 caused the appearance of polycrystalline FCC phase in structure.Compared with the MoNbTaTiZr metallic coating,the coating containing nitrogen favored the high hard-ness around 13.7-32.4 GPa,accompanied by excellent tolerance both against elastic and plastic deforma-tion.Furthermore,such N-containing coatings yielded a low corrosion current density of about 10−8-10−7 A/cm^(2) and high electrochemical impedance of 10^(6)Ωcm^(2) in 3.5 wt.%NaCl solution,indicating the supe-rior corrosion resistance.The reason for the enhanced electrochemical behavior could be ascribed to the spontaneous formation of protective passive layers over the coating surface,which consisted of the domi-nated multi-elemental oxides in chemical stability.Particularly,noted that the(MoNbTaTiZr)_(0.83) N0.17 coat-ing displayed the highest hardness of 32.4±2.6 GPa and H/E ratio at 0.09,together with remarkable cor-rosion resistance,proposing the strongest capability for harsh-environmental applications required both good anti-wear and anti-corrosion performance.展开更多
Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporti...Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.展开更多
Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid ...Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.展开更多
Graphitic carbon nitride(g-C_(3)N_(4))exhibits great mechanical as well as thermal characteristics,making it a valuable ma-terial for use in photoelectric conversion devices,an accelerator for synthesis of organic com...Graphitic carbon nitride(g-C_(3)N_(4))exhibits great mechanical as well as thermal characteristics,making it a valuable ma-terial for use in photoelectric conversion devices,an accelerator for synthesis of organic compounds,an electrolyte for fuel cell applications or power sources,and a hydrogen storage substance and a fluorescence detector.It is fabricated using dif-ferent methods,and there is a variety of morphologies and nanostructures such as zero to three dimensions that have been designed for different purposes.Ther e are many reports about g-C_(3)N_(4) in recent years,but a comprehensive review which covers nanostructure dimensions and their properties are missing.This review paper aims to give basic and comprehensive understanding of the photocatalytic and electrocatalytic usages of g-C_(3)N_(4).It highlights the recent progress of g-C_(3)N_(4) nano-structure designing by covering synthesis methods,dimensions,morphologies,applications and properties.Along with the summary,we will also discuss the challenges and prospects.Scientists,investigators,and engineers looking at g-C_(3)N_(4) nanostructures for a variety of applications might find our review paper to be a useful resource.展开更多
Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),...Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.展开更多
Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))an...Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))and specific capacity(1675 mAh·g^(-1)).Currently,various strategies have been proposed to overcome the technical barriers,e.g.,“shuttle effect”,capacity decay and volumetric change,which impede the successful commercialization of lithium-sulfur batteries.This paper reviews the applications of metal nitrides as the cathode hosts for high-performance lithium-sulfur batteries,summa-rizes the design strategies of different host materials,and discusses the relationship between the properties of metal nitrides and their electrochemical performances.Finally,reasonable suggestions for the design and development of metal nitrides,along with ideas to promote future breakthroughs,are proposed.We hope that this review could attract more attention to metal nitrides and their derivatives,and further promote the electrochemical performance of lithium-sulfur batteries.展开更多
Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline el...Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline electrolytes,the electrochemical instability and capacity degradation of VN electrode materials present significant challenges for practical applications.Herein,the capacitance decay mechanism of VN is investigated and a simple strategy to improve cycling stability of VN supercapacitor electrodes is proposed by introducing VO_(4)^(3-)anion in KOH electrolytes.Our results show that the VN electrode is electrochemical stabilization between-1.0and-0.4 V(vs.Hg/Hg O reference electrode)in 1.0 MKOH electrolyte,but demonstrates irreversible oxidation and fast capacitance decay in the potential range of-0.4 to0 V.In situ electrochemical measurements reveal that the capacitance decay of VN from-0.4 to 0 V is ascribed to the irreversible oxidation of vanadium(V)of N–V–O species by oxygen(O)of OH^(-).The as-generated oxidization species are subsequently dissolved into KOH electrolytes,thereby undermining the electrochemical stability of VN.However,this irreversible oxidation process could be hindered by introducing VO_(4)^(3-)in KOH electrolytes.A high volumetric specific capacitance of671.9 F.cm^(-3)(1 A.cm^(-3))and excellent cycling stability(120.3%over 1000 cycles)are achieved for VN nanorod electrode in KOH electrolytes containing VO_(4)^(3-).This study not only elucidates the failure mechanism of VN supercapacitor electrodes in alkaline electrolytes,but also provides new insights into enhancing pseudocapacitive energy storage of VN-based electrode materials.展开更多
Integrating photocatalysis technology with peroxymonosulfate oxidation possesses huge potential for degrading stubborn pollutant.Herein,a porous ultra-thin carbon nitride with C-defect O-doping and advanced n-π^(∗)tr...Integrating photocatalysis technology with peroxymonosulfate oxidation possesses huge potential for degrading stubborn pollutant.Herein,a porous ultra-thin carbon nitride with C-defect O-doping and advanced n-π^(∗)transition was customized by one-pot thermalinduced polymerization of molten urea assisted with paraformaldehyde.Via visible-light coupling peroxymonosulfate activation,the DCN-100 can completely photodegrade 2,4-dichlorophenol,and rate constant is 136.6 and 37.9 times that of CN and DCN-100 without peroxymonosulfate.The light-absorption of DCN-100 surpasses 550 nm,specific surface area rises from 45.03 to 98.58m^(2)/g,and charge behaviors are significantly improved.The effects of paraformaldehyde amount,PMS dosage,pH,2,4-dichlorophenol concentration,different water-body,wavelength and recycling times on photodegradation performance were explored in detail.Via capture experiments,ESR,LC-MS,Fukui-function,TEXT toxicity assessment and DFT theoretical calculation,themain active substances,degradation pathway,intermediate toxicity and enhanced activity mechanism of DCN-100 were clarified.The research provides a cost-effective,high-efficiency and environmental-friendly photocatalysts to activate peroxymonosulfate for water remediating.展开更多
The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising ...The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising approach,but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers.In this study,we introduce a novel photoresponsive carbon-based antibacterial agent,Ce6/g-C_(3)N_(4),which combines the photocatalytic properties of graphite-phase carbon nitride(g-C_(3)N_(4))with the photodynamic attributes of chlorin e6(Ce6).This agent,with an average particle size of 250.7 nm,demonstrates significantly enhanced photocatalytic activity.Additionally,the strong affinity of Ce6/g-C_(3)N_(4)for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99%against Gram-positive bacteria and excellent biofilm eradication under light irradiation.In vivo experiments reveal that Ce6/gC_(3)N_(4)effectively inhibits bacterial growth on wounds,and promotes wound healing post-light treatment,while maintaining good biocompatibility.Overall,the Ce6/g-C_(3)N_(4)antibacterial agent synergizes photodynamic and photocatalytic mechanisms,offering a new avenue for the photo-mediated,multi-strategic treatment of bacterial infections and wound healing.展开更多
Graphitic carbon nitride(g-C_(3)N_(4)),known for its green and abundant nature and composed of carbon and nitrogen in a two-dimensional structure,has emerged as a significant area of interest across various discipline...Graphitic carbon nitride(g-C_(3)N_(4)),known for its green and abundant nature and composed of carbon and nitrogen in a two-dimensional structure,has emerged as a significant area of interest across various disciplines,particularly in energy conversion and storage.Its recent demonstrations of high potential in supercapacitor applications mark it as a promising alternative to graphene within the realm of materials science.Numerous favorable features,such as chemical and thermal stability,abundant nitrogen content,eco-friendly attributes,and gentle conditions for synthesis,are shown.This review summarizes recent advancements in the use of g-C_(3)N_(4)and its composites as electrodes for supercapacitors,highlighting the advantages and issues associated with g-C_(3)N_(4)in these applications.This emphasizes situations where the composition of g-C_(3)N_(4)with other materials,such as metal oxides,metal chalcogenides,carbon materials,and conducting polymers,overcomes its limitations,leading to composite materials with improved functionalities.This review discusses the challenges that still need to be addressed and the possible future roles of g-C_(3)N_(4)in the research of advanced supercapacitor technology,such as battery-hybrid supercapacitors,flexible supercapacitors,and photo-supercapacitors.展开更多
The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multip...The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.展开更多
Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen.However,developing efficient electrocataly...Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen.However,developing efficient electrocatalyst towards this technology remains challenging.Herein,a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam(Co@Mo_(2)N/NF)for the glycerol oxidation reaction(GOR)and hydrogen evolution reaction(HER).Remarkably,the obtained Co@Mo_(2)N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm^(2)for HER and high Faradaic efficiency of formate of 95.03%at 1.35 V vs.RHE for GOR,respectively.The systematic in-situ experiments reveal that the Co@Mo_(2)N heterostructure promotes the cleavage of C-C bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product.Moreover,the density functional theory(DFT)calculations confirm the strong interaction at Co@Mo_(2)N interface,which contributes to the optimized water dissociation and the transformation of H^(*)to H^(2).Benefiting from those advantages,the built HER||GOR electrolyzer delivers a low voltage of 1.61 V at 50 mA/cm^(2),high Faradaic efficiency,and robust stability over 120 h for sustained and stable electrolysis.展开更多
Negatively charged boron vacancy(V_(B)^(-))spin defects are stable in nanoscale hexagonal boron nitride(hBN)flakes,which can be easily integrated into two-dimensional materials and devices to serve as both sensors and...Negatively charged boron vacancy(V_(B)^(-))spin defects are stable in nanoscale hexagonal boron nitride(hBN)flakes,which can be easily integrated into two-dimensional materials and devices to serve as both sensors and protective materials.Ion irradiation is frequently employed to create V_(B)^(-)spin defects in hBN.However,the optimal ion irradiation parameters remain unclear,even though they play a crucial role in determining the depth and density of the defects,which in turn affect sensing sensitivity.In this work,we optimize the carbon ion irradiation parameters for creating V_(B)^(-)spin defects by varying the irradiation dose and the incident angle.For 30 keV carbon ion irradiation,the optimal irradiation dose to create a V_(B)^(-)ensemble is determined to be 4×10^(13)ions/cm^(2),and both continuous and pulsed optically detected magnetic resonance measurements are used to estimate the magnetic sensitivity and spin coherence properties.Moreover,the incident angle of energetic ions is found to influence both the depth and density distributions of the V_(B)^(-)ensemble,a factor that is often overlooked.These results pave the way for improving the performance of quantum sensors based on hBN spin defects by optimizing the irradiation parameters.展开更多
The photocatalytic hydrogen peroxide(H_(2)O_(2))production by graphitic carbon nitride is a sustainable and environment-benign alternative approach of conventional anthraquinone autoxidation technology,but it is great...The photocatalytic hydrogen peroxide(H_(2)O_(2))production by graphitic carbon nitride is a sustainable and environment-benign alternative approach of conventional anthraquinone autoxidation technology,but it is great challenges to promote two-electron O_(2)reduction and water oxidation.Herein,we present the well-dispersed graphitic carbon nitride quantum dots decorated with cyano groups(Na-CNQD and K-CNQD)by thermal polymerization of melamine in the presence of metal fluoride.The quantum confinement and edge effect have endowed the photocatalysts with rich active sites,wide light absorption range and the inhibited charge recombination.The cyano moieties function as O_(2)reduction centers to accept the photogenerated electrons and facilitate their rapid transfer to O_(2)molecules.This process enables the selective two-electron reduction of O_(2),leading to the production of H_(2)O_(2).Concurrently,the valence band holes on the heptazine moiety oxidize water into H_(2)O_(2).These synergistic effects promote photocatalytic H_(2)O_(2)production from O_(2)and H_(2)O without the need for additional photosensitizers,organic scavengers and co-catalysts.In contrast,pristine carbon nitride nanosheets remain inactive under the same conditions.This study offers new strategies for rational design of carbon-based materials for solar-to-chemical energy conversion.展开更多
Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water spli...Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.展开更多
The huge carrier transfer resistance caused by large-sized"nitrogen pot"severely limits the photocatalytic performance of carbon nitride(CN).This study aims to explore the selection principle of metal ion br...The huge carrier transfer resistance caused by large-sized"nitrogen pot"severely limits the photocatalytic performance of carbon nitride(CN).This study aims to explore the selection principle of metal ion bridges for constructing dual carrier-transfer channels to delivery carriers to respectively active sites using photodegradation of phenol as the model reaction.Density functional theory(DFT)calculation was used to optimize the structure model of nitrogen vacancies(Nv,provide active sites for reduction of O_(2) and oxidation of phenol)and metal ions(Fe^(3+),Co^(2+),Ni^(2+)or Cu^(2+))co-modified CN,and screen metal ion bridges based on the three parameters including bonding state of metal ion and"nitrogen pot",electrostatic potential(ESP)distribution around the active sites,and three-electron bond length.Both calculation results and activity data show that Fe^(3+),Co^(2+)and Ni^(2+)can construct dual carrier-transfer channels to promote the degradation of phenol while Cu^(2+)cannot Ny and Fe^(3+)co-modified CN(Fe/N_(v)-CN)showed the best catalytic performance among various catalysts and was used as the model catalyst for the detailed characterization to verify the calculation results.This work provides not only the novel strategy for constructing dual carrier-transfer channels in CN,but also the crucial basis for computer simulation as a prediction tool of catalyst structure design rationality.展开更多
FeCoCrMnNiN_(x)high entropy nitride ceramics thin films were prepared using the magnetron sputtering method,and the effects of nitrogen content on the thin films’properties were later examined.The addition of N_(2)af...FeCoCrMnNiN_(x)high entropy nitride ceramics thin films were prepared using the magnetron sputtering method,and the effects of nitrogen content on the thin films’properties were later examined.The addition of N_(2)affected the microstructures of the thin films and their mechanical and corrosion properties.Compared with the FeCoCrMnNi thin films with 1-sccm N_(2),the addition of 2 and 3 sccm of N_(2)by as much as 5.45at%and 6.34at%changed the solid solution’s crystalline structure into an amorphous structure.The addition of nitro-gen caused drastic changes to the surface morphology,creating a smoother and more uniform surface without cauliflower units.The atomic force microscopy image analysis indicated that the addition of nitrogen reduced the surface roughness from 5.58 to 1.82 nm.Adding N_(2)to the CoCrFeMnNi thin film helped increase its mechanical properties,such as hardness and strength,while the Young’s modulus decreased.The hardness of(8.75±0.5)GPa and the reduced Young’s modulus of(257.37±11.4)GPa of the FeCoCrMnNi thin film reached(12.67±1.2)and(194.39±12.4)GPa,respectively,with 1 sccm N_(2).The applied coating of the CoCrFeMnNi thin film on 304SUS increased the corrosion resistance,whereas the addition of nitrogen to the CoCrFeMnNi thin film also improved its corrosion res-istance compared with that of the CoCrFeMnNi thin film without nitrogen.展开更多
The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-a...The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-atom anchored on the defective carbon nitride structure(Cu SA/Def-CN)is designed for selective photocatalytic oxidation of methane into methanol using O_(2) under mild conditions.The Cu SA/Def-CN catalyst exhibits a high methanol selectivity of 92.8%under optimized conditions.Mechanistic studies reveal a synergistic effect between Def-CN and Cu SA,where Def-CN is responsible for the in-situ generation of hydrogen peroxide,which is subsequently decomposed by the Cu SA sites to produce·OH radicals that play a key role in the rate-determining step of methane activation to form methanol.Additionally,the presence of Cu SA not only enhances the electron-hole separation efficiency and improves the transfer of the photo-generated charges,but also increases the number of active sites for methane adsorption and activation.These insights provide valuable guidance for designing efficient catalysts for the highly selective photocatalytic oxidation of methane to methanol.展开更多
Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and...Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.展开更多
基金supported by the National Key Research and Development Project of China(Grant No.2018YFE0127800)。
文摘Recent advancements in thermal conductivity modulating strategies have shown promising enhancements to the thermal management capabilities of two-dimensional materials.In this article,both the iterative Boltzmann transport equation solution and the two-temperature model were employed to investigate the efficacy of targeted phonon excitation applied to hexagonal boron nitride(hBN).The results indicate significant modifications to hBN's thermal conductivity,achieving increases of up to 30.1%as well as decreases of up to 59.8%.These findings validate the reliability of the strategy,expand its scope of applicability,and establish it as a powerful tool for tailoring thermal properties across a wider range of fields.
基金supported by the National Science Fund for Distinguished Young Scholars of China(No.52025014)Zhejiang Provincial Natural Science Foundation of China(Nos.LZJWY23E090001 and LD24E010003)the Natural Science Foundation of Ningbo(No.2022J305).
文摘High-entropy materials possess high hardness and strong wear resistance,yet the key bottleneck for their practical applications is the poor corrosion resistance in harsh environments.In this work,the high-entropy nitride(HEN)coatings of(MoNbTaTiZr)1-x Nx(x=0-0.47)were fabricated using a hybrid di-rect current magnetron sputtering technique.The research focus was dedicated to the effect of nitrogen content on the microstructure,mechanical and electrochemical properties.The results showed that the as-deposited coatings exhibited a typical body-centered cubic(BCC)structure without nitrogen,while the amorphous matrix with face-centered cubic(FCC)nanocrystalline grain was observed at x=0.17.Further increasing x in the range of 0.35-0.47 caused the appearance of polycrystalline FCC phase in structure.Compared with the MoNbTaTiZr metallic coating,the coating containing nitrogen favored the high hard-ness around 13.7-32.4 GPa,accompanied by excellent tolerance both against elastic and plastic deforma-tion.Furthermore,such N-containing coatings yielded a low corrosion current density of about 10−8-10−7 A/cm^(2) and high electrochemical impedance of 10^(6)Ωcm^(2) in 3.5 wt.%NaCl solution,indicating the supe-rior corrosion resistance.The reason for the enhanced electrochemical behavior could be ascribed to the spontaneous formation of protective passive layers over the coating surface,which consisted of the domi-nated multi-elemental oxides in chemical stability.Particularly,noted that the(MoNbTaTiZr)_(0.83) N0.17 coat-ing displayed the highest hardness of 32.4±2.6 GPa and H/E ratio at 0.09,together with remarkable cor-rosion resistance,proposing the strongest capability for harsh-environmental applications required both good anti-wear and anti-corrosion performance.
基金support for this work by Hebei Education Department(No.JZX2024004)Central Guidance on Local Science and Technology Development Fund of Hebei Province(No.236Z1404G)+3 种基金the National Natural Science Foundation of China(Nos.22301060 and 21272053)China Postdoctoral Science Foundation(No.2023M730914)the Natural Science Foundation of Hebei Province(Biopharmaceutical Joint Fund No.B2022206008)Project of Science and Technology Department of Hebei Province(No.22567622H)。
文摘Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.
基金supported by the National Natural Science Foundation of China(No.51972162)the Fundamental Research Funds for the Central Universities(No.2024300440).
文摘Lowering the synthesis temperature of boron nitride nanotubes(BNNTs)is crucial for their development.The primary reason for adopting a high temperature is to enable the effective activation of highmelting-point solid boron.In this study,we developed a novel approach for efficiently activating boron by introducing alkali metal compounds into the conventional MgO–B system.This approach can be adopted to form various low-melting-point AM–Mg–B–O growth systems.These growth systems have improved catalytic capability and reactivity even under low-temperature conditions,facilitating the synthesis of BNNTs at temperatures as low as 850℃.In addition,molecular dynamics simulations based on density functional theory theoretically demonstrate that the systems maintain a liquid state at low temperatures and interact with N atoms to form BN chains.These findings offer novel insights into the design of boron activation and are expected to facilitate research on the low-temperature synthesis of BNNTs.
基金M Tahir is funded by EU H2020 Marie Skłodows-ka-Curie Fellowship(1439425).
文摘Graphitic carbon nitride(g-C_(3)N_(4))exhibits great mechanical as well as thermal characteristics,making it a valuable ma-terial for use in photoelectric conversion devices,an accelerator for synthesis of organic compounds,an electrolyte for fuel cell applications or power sources,and a hydrogen storage substance and a fluorescence detector.It is fabricated using dif-ferent methods,and there is a variety of morphologies and nanostructures such as zero to three dimensions that have been designed for different purposes.Ther e are many reports about g-C_(3)N_(4) in recent years,but a comprehensive review which covers nanostructure dimensions and their properties are missing.This review paper aims to give basic and comprehensive understanding of the photocatalytic and electrocatalytic usages of g-C_(3)N_(4).It highlights the recent progress of g-C_(3)N_(4) nano-structure designing by covering synthesis methods,dimensions,morphologies,applications and properties.Along with the summary,we will also discuss the challenges and prospects.Scientists,investigators,and engineers looking at g-C_(3)N_(4) nanostructures for a variety of applications might find our review paper to be a useful resource.
基金National Natural Science Foundation of China(21806023)Natural Science Foundation of Hunan Province(2021JJ40199)+2 种基金Education Department Foundation of Hunan Province(20C0813)Hunan University of Science and Technology Fundamental Research FundsPostgraduate Scientific Research Innovation Project of Hunan Province(CX20240877)。
文摘Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.
文摘Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density(2600 Wh·kg^(-1))and specific capacity(1675 mAh·g^(-1)).Currently,various strategies have been proposed to overcome the technical barriers,e.g.,“shuttle effect”,capacity decay and volumetric change,which impede the successful commercialization of lithium-sulfur batteries.This paper reviews the applications of metal nitrides as the cathode hosts for high-performance lithium-sulfur batteries,summa-rizes the design strategies of different host materials,and discusses the relationship between the properties of metal nitrides and their electrochemical performances.Finally,reasonable suggestions for the design and development of metal nitrides,along with ideas to promote future breakthroughs,are proposed.We hope that this review could attract more attention to metal nitrides and their derivatives,and further promote the electrochemical performance of lithium-sulfur batteries.
基金financially supported by the National Natural Science Foundation of China(No.U2004210)Application Foundation Frontier Project of Wuhan Science and Technology Program(No.2020010601012199)City University of Hong Kong Strategic Research Grant,Hong Kong,China(No.7005505)。
文摘Vanadium nitride(VN)is a promising pseudocapacitive material due to the high theoretical capacity,rapid redox Faradaic kinetics,and appropriate potential window.Although VN shows large pseudocapacitance in alkaline electrolytes,the electrochemical instability and capacity degradation of VN electrode materials present significant challenges for practical applications.Herein,the capacitance decay mechanism of VN is investigated and a simple strategy to improve cycling stability of VN supercapacitor electrodes is proposed by introducing VO_(4)^(3-)anion in KOH electrolytes.Our results show that the VN electrode is electrochemical stabilization between-1.0and-0.4 V(vs.Hg/Hg O reference electrode)in 1.0 MKOH electrolyte,but demonstrates irreversible oxidation and fast capacitance decay in the potential range of-0.4 to0 V.In situ electrochemical measurements reveal that the capacitance decay of VN from-0.4 to 0 V is ascribed to the irreversible oxidation of vanadium(V)of N–V–O species by oxygen(O)of OH^(-).The as-generated oxidization species are subsequently dissolved into KOH electrolytes,thereby undermining the electrochemical stability of VN.However,this irreversible oxidation process could be hindered by introducing VO_(4)^(3-)in KOH electrolytes.A high volumetric specific capacitance of671.9 F.cm^(-3)(1 A.cm^(-3))and excellent cycling stability(120.3%over 1000 cycles)are achieved for VN nanorod electrode in KOH electrolytes containing VO_(4)^(3-).This study not only elucidates the failure mechanism of VN supercapacitor electrodes in alkaline electrolytes,but also provides new insights into enhancing pseudocapacitive energy storage of VN-based electrode materials.
基金supported by the Natural Science Foundation Project of Jilin Province(Nos.20230101297JC,YDZJ202201ZYTS347,YDZJ202101ZYTS073,20210101117JC,YDZJ202201ZYTS349,YDZJ202102CXJD049)the National Natural Science Foundation(22004047)+4 种基金China Postdoctoral Science Foundation(No.2023M731299)the Project of Jilin Province Development and Reform Commission(Nos.2023C032-5,2023C032-4,2023C032-2)the Project of Human Resources and Social Security Department of Jilin Province(No.2023337)the National College students’innovation and entrepreneurship training program(No.202310203008)the Project of Education Department of Jilin Province(Nos.JJKH20220429KJ,JJKH20210460KJ).
文摘Integrating photocatalysis technology with peroxymonosulfate oxidation possesses huge potential for degrading stubborn pollutant.Herein,a porous ultra-thin carbon nitride with C-defect O-doping and advanced n-π^(∗)transition was customized by one-pot thermalinduced polymerization of molten urea assisted with paraformaldehyde.Via visible-light coupling peroxymonosulfate activation,the DCN-100 can completely photodegrade 2,4-dichlorophenol,and rate constant is 136.6 and 37.9 times that of CN and DCN-100 without peroxymonosulfate.The light-absorption of DCN-100 surpasses 550 nm,specific surface area rises from 45.03 to 98.58m^(2)/g,and charge behaviors are significantly improved.The effects of paraformaldehyde amount,PMS dosage,pH,2,4-dichlorophenol concentration,different water-body,wavelength and recycling times on photodegradation performance were explored in detail.Via capture experiments,ESR,LC-MS,Fukui-function,TEXT toxicity assessment and DFT theoretical calculation,themain active substances,degradation pathway,intermediate toxicity and enhanced activity mechanism of DCN-100 were clarified.The research provides a cost-effective,high-efficiency and environmental-friendly photocatalysts to activate peroxymonosulfate for water remediating.
基金supported by the Natural Science Foundation of the Jiangsu Higher Education Institutes of China(No.22KJB530006)Hainan Provincial Natural Science Foundation of China(No.824QN267)。
文摘The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising approach,but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers.In this study,we introduce a novel photoresponsive carbon-based antibacterial agent,Ce6/g-C_(3)N_(4),which combines the photocatalytic properties of graphite-phase carbon nitride(g-C_(3)N_(4))with the photodynamic attributes of chlorin e6(Ce6).This agent,with an average particle size of 250.7 nm,demonstrates significantly enhanced photocatalytic activity.Additionally,the strong affinity of Ce6/g-C_(3)N_(4)for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99%against Gram-positive bacteria and excellent biofilm eradication under light irradiation.In vivo experiments reveal that Ce6/gC_(3)N_(4)effectively inhibits bacterial growth on wounds,and promotes wound healing post-light treatment,while maintaining good biocompatibility.Overall,the Ce6/g-C_(3)N_(4)antibacterial agent synergizes photodynamic and photocatalytic mechanisms,offering a new avenue for the photo-mediated,multi-strategic treatment of bacterial infections and wound healing.
基金financial support of the TMA pai scholarship from the Manipal Institute of Technology,Manipal Academy of Higher Education,Manipal,in achieving this milestone。
文摘Graphitic carbon nitride(g-C_(3)N_(4)),known for its green and abundant nature and composed of carbon and nitrogen in a two-dimensional structure,has emerged as a significant area of interest across various disciplines,particularly in energy conversion and storage.Its recent demonstrations of high potential in supercapacitor applications mark it as a promising alternative to graphene within the realm of materials science.Numerous favorable features,such as chemical and thermal stability,abundant nitrogen content,eco-friendly attributes,and gentle conditions for synthesis,are shown.This review summarizes recent advancements in the use of g-C_(3)N_(4)and its composites as electrodes for supercapacitors,highlighting the advantages and issues associated with g-C_(3)N_(4)in these applications.This emphasizes situations where the composition of g-C_(3)N_(4)with other materials,such as metal oxides,metal chalcogenides,carbon materials,and conducting polymers,overcomes its limitations,leading to composite materials with improved functionalities.This review discusses the challenges that still need to be addressed and the possible future roles of g-C_(3)N_(4)in the research of advanced supercapacitor technology,such as battery-hybrid supercapacitors,flexible supercapacitors,and photo-supercapacitors.
基金supported by the National Natural Science Foundation of China(Nos.22379116,U2003130 and U2004210)the Outstanding Youth Foundation of Natural Science Foundation of Hubei Province(No.2020CFA099)+1 种基金the Foundation of Science Research Program from Hubei Provincial Department of Education(No.Q20221101)the Innovation group of Key Research and Development Program of Hubei Province(Nos.2021BAA208 and 2022BCA061).
文摘The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.
基金financially supported by the National Natural Science Foundation of China(No.22205205)the Natural Science Foundation of Zhejiang Province(No.LQ24E040002)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)(Nos.21062337Y,LW-YP2024076)。
文摘Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen.However,developing efficient electrocatalyst towards this technology remains challenging.Herein,a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam(Co@Mo_(2)N/NF)for the glycerol oxidation reaction(GOR)and hydrogen evolution reaction(HER).Remarkably,the obtained Co@Mo_(2)N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm^(2)for HER and high Faradaic efficiency of formate of 95.03%at 1.35 V vs.RHE for GOR,respectively.The systematic in-situ experiments reveal that the Co@Mo_(2)N heterostructure promotes the cleavage of C-C bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product.Moreover,the density functional theory(DFT)calculations confirm the strong interaction at Co@Mo_(2)N interface,which contributes to the optimized water dissociation and the transformation of H^(*)to H^(2).Benefiting from those advantages,the built HER||GOR electrolyzer delivers a low voltage of 1.61 V at 50 mA/cm^(2),high Faradaic efficiency,and robust stability over 120 h for sustained and stable electrolysis.
基金supported by the National Key Research and Development Program Project(2024YFF0726104)Key Laboratory of Modern Optical Technologies of the Education Ministry of China,Soochow University(Grant No.KJS2135)+1 种基金a China Postdoctoral Science Foundation Funded Project(Grant No.2024M751236)the Jiangxi Provincial Natural Science Foundation(Grant No.20232BAB211030).
文摘Negatively charged boron vacancy(V_(B)^(-))spin defects are stable in nanoscale hexagonal boron nitride(hBN)flakes,which can be easily integrated into two-dimensional materials and devices to serve as both sensors and protective materials.Ion irradiation is frequently employed to create V_(B)^(-)spin defects in hBN.However,the optimal ion irradiation parameters remain unclear,even though they play a crucial role in determining the depth and density of the defects,which in turn affect sensing sensitivity.In this work,we optimize the carbon ion irradiation parameters for creating V_(B)^(-)spin defects by varying the irradiation dose and the incident angle.For 30 keV carbon ion irradiation,the optimal irradiation dose to create a V_(B)^(-)ensemble is determined to be 4×10^(13)ions/cm^(2),and both continuous and pulsed optically detected magnetic resonance measurements are used to estimate the magnetic sensitivity and spin coherence properties.Moreover,the incident angle of energetic ions is found to influence both the depth and density distributions of the V_(B)^(-)ensemble,a factor that is often overlooked.These results pave the way for improving the performance of quantum sensors based on hBN spin defects by optimizing the irradiation parameters.
基金supported by the National Natural Science Foundation of China(22361024 and 22471055)Natural Science Foundation of Jiangxi Province(20232ACB203001)+1 种基金Natural Science Foundation of Hebei Province(B2024202021,B2022202039)S&T Program of Hebei(236Z4308G)。
文摘The photocatalytic hydrogen peroxide(H_(2)O_(2))production by graphitic carbon nitride is a sustainable and environment-benign alternative approach of conventional anthraquinone autoxidation technology,but it is great challenges to promote two-electron O_(2)reduction and water oxidation.Herein,we present the well-dispersed graphitic carbon nitride quantum dots decorated with cyano groups(Na-CNQD and K-CNQD)by thermal polymerization of melamine in the presence of metal fluoride.The quantum confinement and edge effect have endowed the photocatalysts with rich active sites,wide light absorption range and the inhibited charge recombination.The cyano moieties function as O_(2)reduction centers to accept the photogenerated electrons and facilitate their rapid transfer to O_(2)molecules.This process enables the selective two-electron reduction of O_(2),leading to the production of H_(2)O_(2).Concurrently,the valence band holes on the heptazine moiety oxidize water into H_(2)O_(2).These synergistic effects promote photocatalytic H_(2)O_(2)production from O_(2)and H_(2)O without the need for additional photosensitizers,organic scavengers and co-catalysts.In contrast,pristine carbon nitride nanosheets remain inactive under the same conditions.This study offers new strategies for rational design of carbon-based materials for solar-to-chemical energy conversion.
文摘Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.
基金supported by the National Natural Science Foundation of China(82301052)China Postdoctoral Science Foundation(2023M732151)+3 种基金Shanxi Provincial Science and Technology Department(202303021212131)Health Commission of Shanxi Province(2022XM14)Shanxi Provincial Education Department(2022L165)Shanxi Medical University(XD2232)。
文摘The huge carrier transfer resistance caused by large-sized"nitrogen pot"severely limits the photocatalytic performance of carbon nitride(CN).This study aims to explore the selection principle of metal ion bridges for constructing dual carrier-transfer channels to delivery carriers to respectively active sites using photodegradation of phenol as the model reaction.Density functional theory(DFT)calculation was used to optimize the structure model of nitrogen vacancies(Nv,provide active sites for reduction of O_(2) and oxidation of phenol)and metal ions(Fe^(3+),Co^(2+),Ni^(2+)or Cu^(2+))co-modified CN,and screen metal ion bridges based on the three parameters including bonding state of metal ion and"nitrogen pot",electrostatic potential(ESP)distribution around the active sites,and three-electron bond length.Both calculation results and activity data show that Fe^(3+),Co^(2+)and Ni^(2+)can construct dual carrier-transfer channels to promote the degradation of phenol while Cu^(2+)cannot Ny and Fe^(3+)co-modified CN(Fe/N_(v)-CN)showed the best catalytic performance among various catalysts and was used as the model catalyst for the detailed characterization to verify the calculation results.This work provides not only the novel strategy for constructing dual carrier-transfer channels in CN,but also the crucial basis for computer simulation as a prediction tool of catalyst structure design rationality.
基金the Ahvaz Branch, Islamic Azad University for the financial support
文摘FeCoCrMnNiN_(x)high entropy nitride ceramics thin films were prepared using the magnetron sputtering method,and the effects of nitrogen content on the thin films’properties were later examined.The addition of N_(2)affected the microstructures of the thin films and their mechanical and corrosion properties.Compared with the FeCoCrMnNi thin films with 1-sccm N_(2),the addition of 2 and 3 sccm of N_(2)by as much as 5.45at%and 6.34at%changed the solid solution’s crystalline structure into an amorphous structure.The addition of nitro-gen caused drastic changes to the surface morphology,creating a smoother and more uniform surface without cauliflower units.The atomic force microscopy image analysis indicated that the addition of nitrogen reduced the surface roughness from 5.58 to 1.82 nm.Adding N_(2)to the CoCrFeMnNi thin film helped increase its mechanical properties,such as hardness and strength,while the Young’s modulus decreased.The hardness of(8.75±0.5)GPa and the reduced Young’s modulus of(257.37±11.4)GPa of the FeCoCrMnNi thin film reached(12.67±1.2)and(194.39±12.4)GPa,respectively,with 1 sccm N_(2).The applied coating of the CoCrFeMnNi thin film on 304SUS increased the corrosion resistance,whereas the addition of nitrogen to the CoCrFeMnNi thin film also improved its corrosion res-istance compared with that of the CoCrFeMnNi thin film without nitrogen.
文摘The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-atom anchored on the defective carbon nitride structure(Cu SA/Def-CN)is designed for selective photocatalytic oxidation of methane into methanol using O_(2) under mild conditions.The Cu SA/Def-CN catalyst exhibits a high methanol selectivity of 92.8%under optimized conditions.Mechanistic studies reveal a synergistic effect between Def-CN and Cu SA,where Def-CN is responsible for the in-situ generation of hydrogen peroxide,which is subsequently decomposed by the Cu SA sites to produce·OH radicals that play a key role in the rate-determining step of methane activation to form methanol.Additionally,the presence of Cu SA not only enhances the electron-hole separation efficiency and improves the transfer of the photo-generated charges,but also increases the number of active sites for methane adsorption and activation.These insights provide valuable guidance for designing efficient catalysts for the highly selective photocatalytic oxidation of methane to methanol.
基金the National Natural Science Foundation of China(Nos.52488201,52376209)the Fundamental Research Funds for the Central Universities.Zhenxiong Huang thanks the Key Project of Jiangxi Academy of Science(No.2022YYB05)the Science and Technology Innovation Project for Carbon Peak and Neutrality of Jiangxi Carbon Neutralization Research Center(2022JXST02).
文摘Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
