High-quality steel production requires superior-performance refractories.To meet the requirements of quality enhancement and efficiency improvement in the steelmaking industry,the application of the novel microporous ...High-quality steel production requires superior-performance refractories.To meet the requirements of quality enhancement and efficiency improvement in the steelmaking industry,the application of the novel microporous magnesia with high strength,remarkable slag resistance,and excellent thermal insulation is promoted.The interface reaction between H13 steel and novel microporous magnesia castable was investigated by using the crucible method,to elucidate the molten steel purification mechanism.The interface microstructure was observed by scanning electron microscopy,and the composition,size,and amount of inclusions were statistically analyzed.A thermal calculation was conducted to gain a deeper understanding of the modification process of inclusions.Fused magnesia castables were used as the blank control.The results show that the average number density and size of inclusions were reduced by 5.99 mm^(−2) and 0.28μm respectively after the same reaction time because the micropores enhanced the inclusion adsorption.The size of inclusions caused by erosion decreased.Also,more[Mg]dissolved into molten steel over 60 min reaction time and resulted in a 0.49 wt.%increase in inclusion Mg content,which modified the inclusion by decreasing their melting point.Therefore,applying novel microporous magnesia was beneficial for purifying H13 steel.展开更多
As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen e...As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.展开更多
The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant ch...The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant challenges.This work presents the low-coordination PtBi nanosheets(LC-PtBi NSs),featuring a unique amorphous-crystalline heterostructure with a low coordination number of 2.3-2.5.They can exhibit exceptional mass activity(8.3 A mg_(Pt)^(-1))and stability(maintaining 88.7%of initial activity after running for 3600 s)of the EG oxidation reaction(EGOR).They also achieve over 90%apparent selectivity for EG-to-GA conversion at low potentials(<0.7 V vs.RHE)and even more than 100-h continuous electrolysis.Density fu nctional theory(DFT)calculations reveal that the low-coordination PtBi heterogeneous interface is responsible for the high coverage of OH_(ad) species and weakened adsorption of carbonaceous intermediates on LC-PtBi NSs,thereby promoting the direct oxidation of C_(2) intermediates to GA.This work demonstrates a strategy of doping-mediated catalytic interface regulation and electron density rearrangement,offering insights for designing efficient Pt-based electrocatalysts toward selective oxidation of small molecules.展开更多
Additive manufacturing(AM)methods have garnered considerable attention owing to their flexibility in fabricating complex parts with desirable mechanical properties.However,the poor surface quality of the resulting met...Additive manufacturing(AM)methods have garnered considerable attention owing to their flexibility in fabricating complex parts with desirable mechanical properties.However,the poor surface quality of the resulting metal parts remains a severe challenge for the applications.Here,a novel dual-additive synergy strategy is presented,which simultaneously enhances material removal efficiency and regulates electrode surface reactions during electrochemical polishing(ECP)of AM AlSi10Mg.Theoretical studies and experimental characterizations confirm that NaF promotes selective dissolution at the peaks,while glucose acts as a stabilizer for the surface valleys.This approach effectively facilitates the selective removal of surface protrusions,achieving a smoother and more uniform surface finish,resulting in a surface roughness reduction of approximately 86%,compared to a 63%reduction without additives.This study not only provides a new approach for optimizing surface quality of AM AlSi10Mg but also offers new insights into electrolyte design and the stabilization of metal anodes.展开更多
Hydrogen evolution reaction(HER)catalytic electrodes under actual working conditions show interesting mass transfer behaviors at solid(electrode)/liquid(electrolyte)/gas(hydrogen)three-phase interfaces.These behaviors...Hydrogen evolution reaction(HER)catalytic electrodes under actual working conditions show interesting mass transfer behaviors at solid(electrode)/liquid(electrolyte)/gas(hydrogen)three-phase interfaces.These behaviors are essential for forming a continuous and effective physical contact region between the electrolyte and the electrode and require further detailed understanding.Here,a case study on 1 T-2 H phase molybdenum disulfide(Mo S_(2))/carbon fiber paper(CFP)catalytic electrodes is performed.Rapid gas-liquid mass transfer at the interface for enhancing the working area stability and capillarity for increasing the electrode working area is found.The real scenario,wherein the energy utilization efficiency of the as-prepared non-noble metal catalytic electrode exceeds that of the noble metal catalytic electrode,is disclosed.Specifically,a fluid dynamics model is developed to investigate the behavior mechanism of hydrogen bubbles from generation to desorption on the catalytic electrode surface with different hydrophilic and hydrophobic properties.These new insights and theoretical evidence on the non-negligible three-phase interface behaviors will identify opportunities and motivate future research in high-efficiency,stability,and low-cost HER catalytic electrode development.展开更多
Stabilizing the interface wave of the molten aluminum(metal)-electrolyte(bath)is beneficial to shorten the anode-cathode distance(ACD)which is critical to the energy saving.A coupled mathematical model was developed t...Stabilizing the interface wave of the molten aluminum(metal)-electrolyte(bath)is beneficial to shorten the anode-cathode distance(ACD)which is critical to the energy saving.A coupled mathematical model was developed to study the impact of the novel cathode protrusion on the molten fluid motion as well as the metal-bath interface deformation.The molten fluid motion in the aluminum reduction ceils is under the combined effect of the electro-magnetic forces(EMFs)and the gas bubbles generated at the anode.A transient inhomogeneous three-phase model(metal-bath-gas bubble)was established in order to calculate more accurate.The results indicate that the metal-bath interface deformation can be reduced significantly by the novel cathode protrusion which is beneficial to the electric energy saving.Besides,The EMFs decreases as a result of the optimizing of the magnetic field due to the novel cathode convex which is an important driving force for the deformation of the interface.In addition,large vortex in the metal flow field is break up into the small vortex by the cathode protrusion and then dissipated due to the viscous force and the hindering effect of the cathode protrusion.The quantity of the vortex as well as the strength of the vortex reduces significantly in the reduction cell with novel cathode protrusion.展开更多
Ta/NiFe film is deposited on Si substrate precoated with SiO_2 by magnetron sputtering.SiO_2/Ta interface and Ta_5Si_3 standard sample are investigated by using X-ray photoelectron spectroscopy (XPS) and peak decompos...Ta/NiFe film is deposited on Si substrate precoated with SiO_2 by magnetron sputtering.SiO_2/Ta interface and Ta_5Si_3 standard sample are investigated by using X-ray photoelectron spectroscopy (XPS) and peak decomposition technique.The results show that there is a thermodynamically favorable reaction at the SiO_2/Ta interface:37Ta+15SiO_2=5Ta_5Si_3+6Ta_2O_5.The more stable products Ta_5Si_3 and Ta_2O_5 may be beneficial to stop the diffusion of Cu into SiO_2.展开更多
Ta/NiO/NiFe/Ta multilayers were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field (Hex) between NiO and NiFe reached 120O e. The composition and chemical states at the interface region o...Ta/NiO/NiFe/Ta multilayers were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field (Hex) between NiO and NiFe reached 120O e. The composition and chemical states at the interface region of NiO/NiFe were studied using the X-ray photoelectron spectroscopy (XPS) and peak decomposition technique. The results show that there are two thermodynamically favorable reactions at NiO/NiFe interface: NiO+Fe=Ni+FeO and 3NiO+2Fe=3Ni+Fe2O3. The thickness of the chemical reaction as estimated by angle-resolved XPS was about 1-1.5 nm. These interface reaction products are magnetic defects, and we believe that the Hex and the coercivity (Hc) of NiO/NiFe are affected by these defects. Moreover, the results also show that there is an intermixing layer at the Ta/NiO (and NiO/Ta) interface due to a thermodynamically favorable reaction: 2Ta+5NiO+Ta2O5. This interface reaction has an effect on the exchange coupling as well. The thickness of the intermixing layer as estimated by XPS depth-profiles was about 8-10 nm.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically re...Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically reduce CO_(2) emission and contribute to carbon-neutral cycle. E cient electrocatalytic reduction of chemically inert CO_(2) is challenging from thermodynamic and kinetic points of view. Therefore,low-cost,highly e cient,and readily available electrocatalysts have been the focus for promoting the conversion of CO_(2). Very recently,interface engineering has been considered as a highly e ective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation,regulations of electron/proton/mass/intermediates,and the control of local reactant concentration,thereby achieving desirable reaction pathway,inhibiting competing hydrogen generation,breaking binding-energy scaling relations of intermediates,and promoting CO_(2) mass transfer. In this review,we aim to provide a comprehensive overview of current developments in interface engineering for CO_(2) RR from both a theoretical and experimental stand-point,involving interfaces between metal and metal,metal and metal oxide,metal and nonmetal,metal oxide and metal oxide,organic molecules and inorganic materials,electrode and electrolyte,molecular catalysts and electrode,etc. Finally,the opportunities and challenges of interface engineering for CO_(2) RR are proposed.展开更多
The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting p...The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.展开更多
The influence of active elements C and Hf on the interface reactions and wettability between a Ni3Albased superalloy and the ceramic mould material was studied by using a sessile drop experiment, The microstructure of...The influence of active elements C and Hf on the interface reactions and wettability between a Ni3Albased superalloy and the ceramic mould material was studied by using a sessile drop experiment, The microstructure of the alloy interface was investigated by scanning electron microscopy analysis and the phase identification was performed by X-ray diffraction analysis, The results show that interface reactions occur as C and Hf contents reach a critical value, The critical values for C and Hf to cause interface reactions are 0,12 wt% and 1,17 wt%, respectively, The reaction products contain HfO2 and 9Al2OH,Cr2O3, Adsorptions of Hf and interface reactions improve the wettability obviously,展开更多
Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inhere...Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves,and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR.Therefore,we optimized and designed a Ni_(2)P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity.Density functional theorycalculations first predict a regular charge transfer from CoP to Ni_(2)P,which creates a built-in electric field between Ni_(2)P and CoP interface.Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity.Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni_(2)P/CoP interface.Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs.RHE,at 10 mA cm^(-2),respectively.Furthermore,Ni_(2)P/CoP achieves industrial-grade current densities(500 mA cm^(−2))at 1.75 V and 1.87 V in the overall urea electrolyzer(UOR||HER)and overall human urine electrolyzer(HUOR||HER),respectively,and demonstrates considerable durability.展开更多
The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing...The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.展开更多
Insertion of species A into species B forms a product P through two kinetic processes, namely, （1） the chemical reaction between A and B that occurs at the B-P interface, and （2） the diffusion of species A in prod...Insertion of species A into species B forms a product P through two kinetic processes, namely, （1） the chemical reaction between A and B that occurs at the B-P interface, and （2） the diffusion of species A in product P. These two processes are symbiotic in that the chemical reaction provides the driving force for the diffusion, while the diffusion sustains the chemical reaction by providing sufficient reactant to the reactive interface. In this paper, a math- ematical framework is developed for the coupled reaction- diffusion processes. The resulting system of boundary and initial value problem is solved analytically for the case of interface-reaction controlled diffusion, i.e., the rate of diffu- sion is much faster than the rate of chemical reaction at the interface so that the final kinetics are limited by the interface chemical reaction. Asymptotic expressions are given for the velocity of the reactive interface and the concentration of diffusing species under two different boundary conditions.展开更多
The microstructure together with the formation and growth ofreaction phases in the interfacial diffusion zone of the explosive cladding TA2/A3 has been investigated by means of OM, SEM, AES and XRD techniques. When th...The microstructure together with the formation and growth ofreaction phases in the interfacial diffusion zone of the explosive cladding TA2/A3 has been investigated by means of OM, SEM, AES and XRD techniques. When the specimen annealed at temperature under the βTi→αTi transformation, i. e. below 1173 K, only TiC forms along TA2 side of interface and hinders the interdiffusion of Fe and Ti atoms, thus Fe2Ti or FeTi is unable to occur. While heated up to the transformation temperature of βTi, e. g, over 1223 K, the parabolic growth of intermetallic compounds of Fe2Ti and FeTi with layer structure may form intergranularly and the formation of βTi or βTi+αTi structure at the Fe enriched side of TA2 and the martensitic transformation products at the Fedepleted side are observed owing to the diffusion of Fe. Furthermore, the growth of βTi transformation layer is revealed to follow the parabolic rule.展开更多
Designing a durable lithium metal anode for solid state batteries requires a controllable and uniform deposition of lithium, and the metal lithium layer should maintain a good interface contact with solid state electr...Designing a durable lithium metal anode for solid state batteries requires a controllable and uniform deposition of lithium, and the metal lithium layer should maintain a good interface contact with solid state electrolyte during cycles. In this work, we construct a robust functional interface layer on the modified LiB electrode which considerably improves the electrochemical stability of lithium metal electrode in solid state batteries. It is found that the functional interface layer consisting of polydioxolane, polyiodide ion and Li TFSI effectively restrains the growth of lithium dendrites through the redox shuttle reaction of I-/I3-and maintains a good contact between lithium anode and solid electrolyte during cycles. Benefit from these two advantages, the modified Li-B anode exhibits a remarkable cyclic performance in comparison with those of the bare Li-B anode.展开更多
Interface reaction of SiC w/6061Al aluminium matrix composite subjected to laser welding was studied. It is pointed out that the main reason for bad weldability of the material is concerned with the interface reaction...Interface reaction of SiC w/6061Al aluminium matrix composite subjected to laser welding was studied. It is pointed out that the main reason for bad weldability of the material is concerned with the interface reaction during the welding. Effects of welding parameters on interface reaction were also investigated. The results show that the interface bonding state can be improved by laser beam, and the main welding parameter affecting the strength of weld is laser output power. The smaller the output power, the lower the extent of interface reaction and the better the mechanical properties.展开更多
The ceramic filter in continuous casting tundish can effectively improve the cleanliness of high-performance steel by regulating tundish flow field to promote the removal of inclusions and adsorbing or blocking fine i...The ceramic filter in continuous casting tundish can effectively improve the cleanliness of high-performance steel by regulating tundish flow field to promote the removal of inclusions and adsorbing or blocking fine inclusions in the molten steel into the mold.The interaction between microporous magnesia refractories used as tundish filter and molten interstitial-free(IF)steel at 1873 K was investigated to reveal the formation mechanism of their interface layer and its effect on steel cleanliness by laboratory research and thermodynamic calculations.The results show that the magnesium–aluminum spinel layer at the interface between the molten IF steel and the microporous magnesia refractories is formed mainly by the reaction of MgO in the refractory with the[Al]and[O]in the molten steel,significantly reducing the total O content,the size and amount of inclusions of the molten steel.In addition,the interparticle phases of microporous magnesia refractories at high temperature can adsorb Al_(2)O_(3) and TiO_(2) inclusions in the molten steel into interparticle channels of the refractories to form high melting point spinel,impeding the further penetration of the molten steel.As a result,the consecutive interface layer of high melting point spinel between microporous magnesia refractories and molten steel can improve the cleanliness of the molten steel by adsorbing inclusions in the molten steel and avoid the direct dissolution of refractories of the tundish ceramic filter immersed in the molten steel,increasing their service life.展开更多
Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still ...Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still unclear.Hence,using combined molecular dynamics and quantum chemistry methods,the heterogeneous chemistry of AcAc at the air-droplet interface was investigated,including the attraction of AcAc isomers by the droplets,the distribution of isomers at the air-droplet interface,and the hydration reactions of isomers at the air-droplet interface.The results reveal that the preferential orientation of two AcAc isomers(keto-and enol-AcAc)to accumulate and accommodate at the acidic air-droplet interface.The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the“water bridge”structure is destroyed by H_(3)O^(+),especially for the isomerization from keto-Ac Ac to enol-AcAc.At the acidic air-droplet interface,the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration.Keto-diol is the dominant products to accumulate at the air-droplet interface,and excessive keto-diol can enter the droplet interior to engage in the oligomerization.The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface,which indirectly facilitate the uptake and formation of more keto-diol.Our results provide an insight into the heterogeneous chemistry ofβ-diketones and their influence on the environment.展开更多
基金support of this study by the National Natural Science Foundation of China(Grant Nos.U22A20173 and U21A2058).
文摘High-quality steel production requires superior-performance refractories.To meet the requirements of quality enhancement and efficiency improvement in the steelmaking industry,the application of the novel microporous magnesia with high strength,remarkable slag resistance,and excellent thermal insulation is promoted.The interface reaction between H13 steel and novel microporous magnesia castable was investigated by using the crucible method,to elucidate the molten steel purification mechanism.The interface microstructure was observed by scanning electron microscopy,and the composition,size,and amount of inclusions were statistically analyzed.A thermal calculation was conducted to gain a deeper understanding of the modification process of inclusions.Fused magnesia castables were used as the blank control.The results show that the average number density and size of inclusions were reduced by 5.99 mm^(−2) and 0.28μm respectively after the same reaction time because the micropores enhanced the inclusion adsorption.The size of inclusions caused by erosion decreased.Also,more[Mg]dissolved into molten steel over 60 min reaction time and resulted in a 0.49 wt.%increase in inclusion Mg content,which modified the inclusion by decreasing their melting point.Therefore,applying novel microporous magnesia was beneficial for purifying H13 steel.
基金supported by the National Natural Science Foundation of China(U21A20332,52103226,52202275,52203314,and 12204253)the Distinguished Young Scholars Fund of Jiangsu Province(BK20220061)the Fellowship of China Postdoctoral Science Foundation(2021 M702382)。
文摘As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.
基金supported by the National Natural Science Foundation of China(NSFC,No.22172121)the Fundamental Research Funds for the Central Universities(No.ZYN2025267)Southwest Minzu University。
文摘The electrocatalytic oxidation of ethylene glycol(EG)into high-value chemicals like glycolic acid(GA)is a crucial step for upcycling waste plastics.However,catalyst deactivation and low selectivity pose significant challenges.This work presents the low-coordination PtBi nanosheets(LC-PtBi NSs),featuring a unique amorphous-crystalline heterostructure with a low coordination number of 2.3-2.5.They can exhibit exceptional mass activity(8.3 A mg_(Pt)^(-1))and stability(maintaining 88.7%of initial activity after running for 3600 s)of the EG oxidation reaction(EGOR).They also achieve over 90%apparent selectivity for EG-to-GA conversion at low potentials(<0.7 V vs.RHE)and even more than 100-h continuous electrolysis.Density fu nctional theory(DFT)calculations reveal that the low-coordination PtBi heterogeneous interface is responsible for the high coverage of OH_(ad) species and weakened adsorption of carbonaceous intermediates on LC-PtBi NSs,thereby promoting the direct oxidation of C_(2) intermediates to GA.This work demonstrates a strategy of doping-mediated catalytic interface regulation and electron density rearrangement,offering insights for designing efficient Pt-based electrocatalysts toward selective oxidation of small molecules.
基金financially supported by the National Natural Science Foundation of China(Nos.52175444,51905506,21871065 and 22071038)the Sichuan Science and Technology Program(No.2021JDJQ0014).
文摘Additive manufacturing(AM)methods have garnered considerable attention owing to their flexibility in fabricating complex parts with desirable mechanical properties.However,the poor surface quality of the resulting metal parts remains a severe challenge for the applications.Here,a novel dual-additive synergy strategy is presented,which simultaneously enhances material removal efficiency and regulates electrode surface reactions during electrochemical polishing(ECP)of AM AlSi10Mg.Theoretical studies and experimental characterizations confirm that NaF promotes selective dissolution at the peaks,while glucose acts as a stabilizer for the surface valleys.This approach effectively facilitates the selective removal of surface protrusions,achieving a smoother and more uniform surface finish,resulting in a surface roughness reduction of approximately 86%,compared to a 63%reduction without additives.This study not only provides a new approach for optimizing surface quality of AM AlSi10Mg but also offers new insights into electrolyte design and the stabilization of metal anodes.
基金supported by the National Natural Science Foundation of China(No.62004051)the Natural Science Foundation of Heilongjiang province(No.LH2020F013)+1 种基金the China Postdoctoral Science Fund(No.2020M670909)the Heilongjiang Postdoctoral Science Fund(No.LBH-Z19017)。
文摘Hydrogen evolution reaction(HER)catalytic electrodes under actual working conditions show interesting mass transfer behaviors at solid(electrode)/liquid(electrolyte)/gas(hydrogen)three-phase interfaces.These behaviors are essential for forming a continuous and effective physical contact region between the electrolyte and the electrode and require further detailed understanding.Here,a case study on 1 T-2 H phase molybdenum disulfide(Mo S_(2))/carbon fiber paper(CFP)catalytic electrodes is performed.Rapid gas-liquid mass transfer at the interface for enhancing the working area stability and capillarity for increasing the electrode working area is found.The real scenario,wherein the energy utilization efficiency of the as-prepared non-noble metal catalytic electrode exceeds that of the noble metal catalytic electrode,is disclosed.Specifically,a fluid dynamics model is developed to investigate the behavior mechanism of hydrogen bubbles from generation to desorption on the catalytic electrode surface with different hydrophilic and hydrophobic properties.These new insights and theoretical evidence on the non-negligible three-phase interface behaviors will identify opportunities and motivate future research in high-efficiency,stability,and low-cost HER catalytic electrode development.
基金Item Sponsored by the National Natural Science Foundation of China[NO.50934005 and NO.50904014]
文摘Stabilizing the interface wave of the molten aluminum(metal)-electrolyte(bath)is beneficial to shorten the anode-cathode distance(ACD)which is critical to the energy saving.A coupled mathematical model was developed to study the impact of the novel cathode protrusion on the molten fluid motion as well as the metal-bath interface deformation.The molten fluid motion in the aluminum reduction ceils is under the combined effect of the electro-magnetic forces(EMFs)and the gas bubbles generated at the anode.A transient inhomogeneous three-phase model(metal-bath-gas bubble)was established in order to calculate more accurate.The results indicate that the metal-bath interface deformation can be reduced significantly by the novel cathode protrusion which is beneficial to the electric energy saving.Besides,The EMFs decreases as a result of the optimizing of the magnetic field due to the novel cathode convex which is an important driving force for the deformation of the interface.In addition,large vortex in the metal flow field is break up into the small vortex by the cathode protrusion and then dissipated due to the viscous force and the hindering effect of the cathode protrusion.The quantity of the vortex as well as the strength of the vortex reduces significantly in the reduction cell with novel cathode protrusion.
文摘Ta/NiFe film is deposited on Si substrate precoated with SiO_2 by magnetron sputtering.SiO_2/Ta interface and Ta_5Si_3 standard sample are investigated by using X-ray photoelectron spectroscopy (XPS) and peak decomposition technique.The results show that there is a thermodynamically favorable reaction at the SiO_2/Ta interface:37Ta+15SiO_2=5Ta_5Si_3+6Ta_2O_5.The more stable products Ta_5Si_3 and Ta_2O_5 may be beneficial to stop the diffusion of Cu into SiO_2.
基金supported by the National Natural Science Foundation of China and Beijing under grant No.19890310 and 2012011,respectively
文摘Ta/NiO/NiFe/Ta multilayers were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field (Hex) between NiO and NiFe reached 120O e. The composition and chemical states at the interface region of NiO/NiFe were studied using the X-ray photoelectron spectroscopy (XPS) and peak decomposition technique. The results show that there are two thermodynamically favorable reactions at NiO/NiFe interface: NiO+Fe=Ni+FeO and 3NiO+2Fe=3Ni+Fe2O3. The thickness of the chemical reaction as estimated by angle-resolved XPS was about 1-1.5 nm. These interface reaction products are magnetic defects, and we believe that the Hex and the coercivity (Hc) of NiO/NiFe are affected by these defects. Moreover, the results also show that there is an intermixing layer at the Ta/NiO (and NiO/Ta) interface due to a thermodynamically favorable reaction: 2Ta+5NiO+Ta2O5. This interface reaction has an effect on the exchange coupling as well. The thickness of the intermixing layer as estimated by XPS depth-profiles was about 8-10 nm.
基金supported by the National Natural Science Foundation of China (22071172)the Ministry of Science and Technology of China (2016YFB0401100,2017YFA0204503,and 2018YFA0703200)Shandong Provincial Natural Science Foundation (No. ZR2019BB025)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2) RR) can store and transform the intermittent renewable energy in the form of chemical energy for industrial production of chemicals and fuels,which can dramatically reduce CO_(2) emission and contribute to carbon-neutral cycle. E cient electrocatalytic reduction of chemically inert CO_(2) is challenging from thermodynamic and kinetic points of view. Therefore,low-cost,highly e cient,and readily available electrocatalysts have been the focus for promoting the conversion of CO_(2). Very recently,interface engineering has been considered as a highly e ective strategy to modulate the electrocatalytic performance through electronic and/or structural modulation,regulations of electron/proton/mass/intermediates,and the control of local reactant concentration,thereby achieving desirable reaction pathway,inhibiting competing hydrogen generation,breaking binding-energy scaling relations of intermediates,and promoting CO_(2) mass transfer. In this review,we aim to provide a comprehensive overview of current developments in interface engineering for CO_(2) RR from both a theoretical and experimental stand-point,involving interfaces between metal and metal,metal and metal oxide,metal and nonmetal,metal oxide and metal oxide,organic molecules and inorganic materials,electrode and electrolyte,molecular catalysts and electrode,etc. Finally,the opportunities and challenges of interface engineering for CO_(2) RR are proposed.
基金supported by the National Natural Science Foundation of China(Nos.52174277 and 51874077)the Fundamental Funds for the Central Universities,China(No.N2225032)+1 种基金the China Postdoctoral Science Foundation(No.2022M720683)the Postdoctoral Fund of Northeastern University,China。
文摘The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.
基金financial support from the National Natural Science Foundation of China (Grant Nos. U1037601 and 51271186)
文摘The influence of active elements C and Hf on the interface reactions and wettability between a Ni3Albased superalloy and the ceramic mould material was studied by using a sessile drop experiment, The microstructure of the alloy interface was investigated by scanning electron microscopy analysis and the phase identification was performed by X-ray diffraction analysis, The results show that interface reactions occur as C and Hf contents reach a critical value, The critical values for C and Hf to cause interface reactions are 0,12 wt% and 1,17 wt%, respectively, The reaction products contain HfO2 and 9Al2OH,Cr2O3, Adsorptions of Hf and interface reactions improve the wettability obviously,
文摘Interface chemical modulation strategies are considered as promising method to prepare electrocatalysts for the urea oxidation reaction(UOR).However,conventional interface catalysts are generally limited by the inherent activity and incompatibility of the individual components themselves,and the irregular charge distribution and slow charge transfer ability between interfaces severely limit the activity of UOR.Therefore,we optimized and designed a Ni_(2)P/CoP interface with modulated surface charge distribution and directed charge transfer to promote UOR activity.Density functional theorycalculations first predict a regular charge transfer from CoP to Ni_(2)P,which creates a built-in electric field between Ni_(2)P and CoP interface.Optimization of the adsorption/desorption process of UOR/HER reaction intermediates leads to the improvement of catalytic activity.Electrochemical impedance spectroscopy and ex situ X-ray photoelectron spectroscopy characterization confirm the unique mechanism of facilitated reaction at the Ni_(2)P/CoP interface.Electrochemical tests further validated the prediction with excellent UOR/HER activities of 1.28 V and 19.7 mV vs.RHE,at 10 mA cm^(-2),respectively.Furthermore,Ni_(2)P/CoP achieves industrial-grade current densities(500 mA cm^(−2))at 1.75 V and 1.87 V in the overall urea electrolyzer(UOR||HER)and overall human urine electrolyzer(HUOR||HER),respectively,and demonstrates considerable durability.
基金supported by the National Natural Science Foundation of China(Grant No.12375303)the Natural Science Foundation of Guangdong Province(Grants No.2024A1515030034 and 2023A1515140156).
文摘The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.
基金supported in part by an ISEN Booster Award at Northwestern Universityin part by NSF(CMMI-1200075)
文摘Insertion of species A into species B forms a product P through two kinetic processes, namely, （1） the chemical reaction between A and B that occurs at the B-P interface, and （2） the diffusion of species A in product P. These two processes are symbiotic in that the chemical reaction provides the driving force for the diffusion, while the diffusion sustains the chemical reaction by providing sufficient reactant to the reactive interface. In this paper, a math- ematical framework is developed for the coupled reaction- diffusion processes. The resulting system of boundary and initial value problem is solved analytically for the case of interface-reaction controlled diffusion, i.e., the rate of diffu- sion is much faster than the rate of chemical reaction at the interface so that the final kinetics are limited by the interface chemical reaction. Asymptotic expressions are given for the velocity of the reactive interface and the concentration of diffusing species under two different boundary conditions.
基金the+6 种基金Non-ferrousMetal Industry Corperation of China
文摘The microstructure together with the formation and growth ofreaction phases in the interfacial diffusion zone of the explosive cladding TA2/A3 has been investigated by means of OM, SEM, AES and XRD techniques. When the specimen annealed at temperature under the βTi→αTi transformation, i. e. below 1173 K, only TiC forms along TA2 side of interface and hinders the interdiffusion of Fe and Ti atoms, thus Fe2Ti or FeTi is unable to occur. While heated up to the transformation temperature of βTi, e. g, over 1223 K, the parabolic growth of intermetallic compounds of Fe2Ti and FeTi with layer structure may form intergranularly and the formation of βTi or βTi+αTi structure at the Fe enriched side of TA2 and the martensitic transformation products at the Fedepleted side are observed owing to the diffusion of Fe. Furthermore, the growth of βTi transformation layer is revealed to follow the parabolic rule.
基金supported by the National Natural Science Foundation of China (NO. 21805113)the Fundamental Research Funds for the Central Universities (NO. 11618410 and NO. 11619103)the China Postdoctoral Science Foundation (NO. 2019M653271)。
文摘Designing a durable lithium metal anode for solid state batteries requires a controllable and uniform deposition of lithium, and the metal lithium layer should maintain a good interface contact with solid state electrolyte during cycles. In this work, we construct a robust functional interface layer on the modified LiB electrode which considerably improves the electrochemical stability of lithium metal electrode in solid state batteries. It is found that the functional interface layer consisting of polydioxolane, polyiodide ion and Li TFSI effectively restrains the growth of lithium dendrites through the redox shuttle reaction of I-/I3-and maintains a good contact between lithium anode and solid electrolyte during cycles. Benefit from these two advantages, the modified Li-B anode exhibits a remarkable cyclic performance in comparison with those of the bare Li-B anode.
文摘Interface reaction of SiC w/6061Al aluminium matrix composite subjected to laser welding was studied. It is pointed out that the main reason for bad weldability of the material is concerned with the interface reaction during the welding. Effects of welding parameters on interface reaction were also investigated. The results show that the interface bonding state can be improved by laser beam, and the main welding parameter affecting the strength of weld is laser output power. The smaller the output power, the lower the extent of interface reaction and the better the mechanical properties.
基金The authors are grateful to the National Natural Science Foundation of China(Nos.U1860205 and 52174323)Innovation Team Cultivation Funding Project of Wuhan University of Science and Technology(2018TDX08).
文摘The ceramic filter in continuous casting tundish can effectively improve the cleanliness of high-performance steel by regulating tundish flow field to promote the removal of inclusions and adsorbing or blocking fine inclusions in the molten steel into the mold.The interaction between microporous magnesia refractories used as tundish filter and molten interstitial-free(IF)steel at 1873 K was investigated to reveal the formation mechanism of their interface layer and its effect on steel cleanliness by laboratory research and thermodynamic calculations.The results show that the magnesium–aluminum spinel layer at the interface between the molten IF steel and the microporous magnesia refractories is formed mainly by the reaction of MgO in the refractory with the[Al]and[O]in the molten steel,significantly reducing the total O content,the size and amount of inclusions of the molten steel.In addition,the interparticle phases of microporous magnesia refractories at high temperature can adsorb Al_(2)O_(3) and TiO_(2) inclusions in the molten steel into interparticle channels of the refractories to form high melting point spinel,impeding the further penetration of the molten steel.As a result,the consecutive interface layer of high melting point spinel between microporous magnesia refractories and molten steel can improve the cleanliness of the molten steel by adsorbing inclusions in the molten steel and avoid the direct dissolution of refractories of the tundish ceramic filter immersed in the molten steel,increasing their service life.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(No.2019B151502064)the National Natural Science Foundation of China(Nos.42077189,42020104001,and 42277081)+3 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01Z032)the Science and Technology Key Project of Guangdong ProvinceChina(No.2019B110206002)the Guangdong Provincial Key R&D Program(No.2022-GDUT-A0007)。
文摘Acetylacetone(AcAc)is a typical class ofβ-diketones with broad industrial applications due to the property of the keto-enol isomers,but its isomerization and chemical reactions at the air-droplet interface are still unclear.Hence,using combined molecular dynamics and quantum chemistry methods,the heterogeneous chemistry of AcAc at the air-droplet interface was investigated,including the attraction of AcAc isomers by the droplets,the distribution of isomers at the air-droplet interface,and the hydration reactions of isomers at the air-droplet interface.The results reveal that the preferential orientation of two AcAc isomers(keto-and enol-AcAc)to accumulate and accommodate at the acidic air-droplet interface.The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the“water bridge”structure is destroyed by H_(3)O^(+),especially for the isomerization from keto-Ac Ac to enol-AcAc.At the acidic air-droplet interface,the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration.Keto-diol is the dominant products to accumulate at the air-droplet interface,and excessive keto-diol can enter the droplet interior to engage in the oligomerization.The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface,which indirectly facilitate the uptake and formation of more keto-diol.Our results provide an insight into the heterogeneous chemistry ofβ-diketones and their influence on the environment.
