INTERFACIAL ACTIVITY BEHEAVIOR OF FLUX DURING ALUMINIUM BRAZING

A study on the interfacial activity behavior of flux during aluminium brazing has been made by using metallography,SEM and electron prob techniques.The results show that the activity, of a flux is caused by the wetting of base metal with the liquid heavy metal reduced from the flux,thus,some regions of liquid alloy created,at which no aluminium oxide film covers on the surfaces.The reduced metal drops are finally trapped in the fillet.The size of the metal drops increases with the decrease of brazing temperature.

Ni nanoparticles as electron-transfer mediators and NiS_x as interfacial active sites for coordinative enhancement of H_2-evolution performance of TiO_2

The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.

Janus membrane with enhanced interfacial activation for solar evaporation

Low solar spectrum coverage,high evaporation enthalpy,and undesired salt deposition severely limited the solar-driven interfacial evaporation technology for further sewage purification and seawater desalination.To overcome these problems,we designed an amphiphilic Janus-structured polyaniline(PANI)/ZrC/cellulose acetate(CA)(J-PZCA) membrane.Firstly,the interfacial interaction between PANI and ZrC enhances the photoabsorption and photothermal conversion efficiency.Secondly,low thermal conductivity reduces the heat lost at the interface.Most importantly,ZrC could facilitate interfacial activation,which weakens the intermolecular forces of water by affecting the hydrogen bond.Under 1 solar irradiation(1 sun),the composite membrane exhibits a high evaporation rate of 1.31 kg m^(-2)h^(-1) and an excellent efficiency of 79.4%.In addition,the sewage purification and seawater desalination experiments reveal a remarkable purification capability of J-PZCA membrane.Especially for the treatment of high-concentration salt solution,it realizes a long-term stable evaporation performance due to the excellent salt deposition resistance.Therefore,the J-PZCA membrane constructed in this study provides a new perspective for the design of efficient interfacial evaporation devices.

PREPARATION,IDENTIFICATION AND INTERFACIAL ACTIVITIES OF PETROLEUM CARBOXYLATE AS SURFACTANT FOR CHEMICAL FLOODING

Petroleum carboxylate that may be suitable for tertiary oil recovery have been produced inexpensively from the fractions of Daqing crude oil by a two step process.The feed stock was first oxidized in the vapor phase,followed by reaction of the oxidized products with sodium hydroxide.Dilute solutions of sodium carboxylates were produced and show ultralow(10^(-2)mN/m)interfacial tensions(IFTs)against a variety of hydrocarbons with a wide range of ACN(Alkane Carbon Number).Infrared spectroscopy was used to identify the functional groups in the oxidized and the saponified products.

Recent Advances in Constructing Interfacial Active Catalysts Based on Layered Double Hydroxides and Their Catalytic Mechanisms

The interaction between the metal and the support of supported metal catalysts, which are widely used in industry, is the primary focus of the study of such catalysts. With the developing understanding of the metal–support interaction, the intrinsic factor that influences the catalytic performance has been determined to be the structure of interfacial sites. Layered double hydroxides(LDHs, a class of two-dimensional layered anion clay) possess several unique characteristics, such as the following:(1) tunable elemental component, homogeneous distribution of metal cations.(2) anchoring eff ect.(3) multiple layered structure for exfoliation or intercalation and special memory eff ect;and(4) internal/external confinement eff ects during topological transformation. Taking LDHs and their derivatives as precursors or supports shows superior advantages in designing interfacial active catalysts with tunable properties. Therefore, this review is mainly focused on constructing interfacial active catalysts by LDHs and revealing the interfacial eff ects(including electronic, geometric, and bifunctional eff ects) on the catalytic performance that will provide new perspectives and approaches for the development of heterogeneous catalysis.

Conjugation of a zwitterionic polymer with dimethyl chains to lipase significantly increases the enzyme activity and stability

Enzyme-polymer conjugates are complex molecules with great practical significance.This work was designed to develop a novel enzyme-polymer conjugate by covalently coupling a zwitterionic polymer with side dimethyl chains(pID)to Candida rugosa lipase(CRL)via the reaction between the anhydrides of polymer chains with the amino groups of the enzyme.The resulting two CRL-pID conjugates with different pID grafting densities were investigated in term of the catalytic activity,stability and structural changes.In comparison with native CRL,both the CRL conjugates displayed 2.2 times higher activity than the native enzyme,and showed an increase in the maximum reaction rate(V_(max))and a decrease in the Michaelis constant(K_(m)),thus resulting in about three-fold increases in the catalytic efficiency(k_(cat)/K_(m)).These are mainly attributed to the activation of lipase by the hydrophobic alky side chains.Moreover,the thermostability and pH tolerance of the lipase conjugates were significantly enhanced due to the stabilizing effect of the zwitterion moieties.For instance,a five-fold increase of the enzyme half-life at 50℃ for the high-pID conjugated CRL was observed.Spectroscopic studies reveal that the pID conjugation protected the enzyme in the changes in its microenvironment and conformation,well correlating with enhanced activity and stability of lipase conjugates.The findings indicate that enzyme conjugation to the zwitterionic polymer is promising for improving enzyme performance and deserves further development.

Fabrication and characterization of epoxylated zwitterionic copolymergrafted silica nanoparticle as a new support for lipase immobilization

Our previous work proved that the thermal stability of Candida rugosa lipase(CRL)immobilized on zwitterionic polymer(poly(carboxybetaine methacrylate))grafted silica nanoparticle(SNP)was much higher than that on poly(glycidyl methecrylate)(pGMA)grafted SNP,while the latter showed significantly increased activity.Inspired by the research,we have herein proposed to synthesize copolymers of zwitterionic sulfobetaine methacrylate(SBMA)and GMA for CRL immobilization.The copolymers were grafted onto SNP surface at three GMA/SBMA(G/S)molar ratios(G100/S0,G50/S50,G10/S90),followed by the covalent coupling of CRL to the surface copolymers.The immobilized CRLs on the corresponding supports were denoted as p(G100-S0)-CRL,p(G50-S50)-CRL and p(G10-S90)-CRL.The enzyme loading increased with the increase of GMA content in the copolymer,while the activity varied with the grafted copolymer composition.Kinetic study proved the improvement of enzyme-substrate affinity after immobilization.In comparison to p(G100-S0)-CRL,p(G50-S50)-CRL and p(G10-S90)-CRL presented remarkably enhanced thermal stability and pH tolerance,and p(G10-S90)-CRL showed the highest stability.These results suggest that the copolymer design is promising for development as a versatile platform for enzyme immobilization.

Selective adsorption of thiocyanate anions on Ag-modified g-C_3N_4 for enhanced photocatalytic hydrogen evolution

Silver‐modified semiconductor photocatalysts typically exhibit enhanced photocatalytic activitytoward the degradation of organic substances.In comparison,their hydrogen‐evolution rates arerelatively low owing to poor interfacial catalytic reactions to producing hydrogen.In the presentstudy,thiocyanate anions(SCN–)as interfacial catalytic active sites were selectively adsorbed ontothe Ag surface of g‐C3N4/Ag photocatalyst to promote interfacial H2‐evolution reactions.The thiocyanate‐modified g‐C3N4/Ag(g‐C3N4/Ag‐SCN)photocatalysts were synthesized via photodepositionof metallic Ag on g‐C3N4and subsequent selective adsorption of SCN– ions on the Ag surface by animpregnation method.The resulting g‐C3N4/Ag‐SCN photocatalysts exhibited considerably higherphotocatalytic H2‐evolution activity than the g‐C3N4,g‐C3N4/Ag,and g‐C3N4/SCN photocatalysts.Furthermore,the g‐C3N4/Ag‐SCN photocatalyst displayed the highest H2‐evolution rate(3.9μmolh?1)when the concentration of the SCN– ions was adjusted to0.3mmol L?1.The H2‐evolution rateobtained was higher than those of g‐C3N4(0.15μmol h?1)and g‐C3N4/Ag(0.71μmol h?1).Consideringthe enhanced performance of g‐C3N4/Ag upon minimal addition of SCN– ions,a synergistic effectof metallic Ag and SCN– ions is proposed―the Ag nanoparticles act as an effective electron‐transfermediator for the steady capture and rapid transportation of photogenerated electrons,while theadsorbed SCN– ions serve as an interfacial active site to effectively absorb protons from solution andpromote rapid interfacial H2‐evolution reactions.Considering the present facile synthesis and itshigh efficacy,the present work may provide new insights into preparing high‐performance photocatalytic materials

THEORETICAL PREDICTION OF THE KINETICS CURVES OFPEARLITIC TRANSFORMATION IN HYPO-PROEUTECTOID STRUCTURAL STEELS

Supposing carbon contents of ferrite phases in pearlite precipitating from austenite in multicomponent steel at temperature T and in Fe-C ystem at T' are the same the pearlite formation temperature diference, can be calculated from the FeX phase diagrams and the equilibrium temperature Al. Using Tp and Fe-C binary thermodynamic model, the driving forces for phase transformation from austenite to pearlite in multicomponent steels have been successfully calculated. Through the combination of simplified Zener and Hillert's model for pearlite growth with Johnson-Mehl equation, using data from known TTT diagrams, the interfacial energy parameter and activation energy for pearlite formation can be determined and expressed as functions of chemical composition in steels by regression analysis. The calculated starting curves of pearlitic transformation in some commercial steels agree well with the experimental data.

Catalytic aquathermolysis of Shengli heavy crude oil with an amphiphilic cobalt catalyst

An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and surface/interfacial tension determination were performed to investigate the properties of the catalyst.Results showed that the synthesized catalyst showed active interfacial behavior,decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m,respectively.The catalyst was not thermally degraded at a temperature of 400 ℃,indicating its high thermal stability.Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis.The viscosity determination showed that the viscosity of the heavy oil decreased by 38%.The average molecular weight,group compositions,and average molecular structure of various samples were analyzed using elemental analysis,FT-IR,electrospray ionization Fourier transform ion cyclotron resonance（ESI FT-ICR MS）,and ～1H nuclear magnetic resonance.Results indicated that the catalyst could attack the sulfur- and O_2-type heteroatomic compounds in asphaltene and resin,especially the compounds with aromatic structure,leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil.Therefore,the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil,especially for the high-aromaticity heavy oil with high oxygen content.

RuO_(2)-PdO nanowire networks with rich interfaces and defects supported on carbon toward the efficient alkaline hydrogen oxidation reaction

Interfacial engineering is a promising approach for enhancing electrochemical performance,but rich and efficient interfacial active sites remain a challenge in fabrication.Herein,RuO_(2)-PdO heterostructure nanowire networks(NWs) with rich interfaces and defects supported on carbon(RuO_(2)-PdO NWs/C) for alkaline hydrogen oxidation reaction(HOR) was formed by a seed induction-oriented attachment-thermal treatment method for the first time.As expected,the RuO_(2)-PdO NWs/C(72.8% Ru atomic content in metal) exhibits an excellent activity in alkaline HOR with a mass specific exchange current density(jo,m) of 1061 A gRuPd-1,which is 3.1 times of commercial Pt/C and better than most of the reported nonPt noble metal HOR electrocatalysts.Even at the high potential(~0.5 V vs.RHE) or the presence of CO(5 vol%),the RuO_(2)-PdO NWs/C still effectively catalyzes the alkaline HOR.Structure/electrochemical analysis and theoretical calculations reveal that the interfaces between RuO_(2) and PdO act as the active sites.The electronic interactions between the two species and the rich defects for the interfacial active sites weaken the adsorption of Had,also strengthen the adsorption of OHad,and accelerate the alkaline HOR process.Moreover,OHadon RuO_(2) can spillover to the interfaces,keeping the RuO_(2)-PdO NWs/C with the stable current density at higher potential and high resistance to CO poisoning.

THEORETICAL PREDICTION OF PROEUTECTOID FERRITICTRANSFORMATION IN HYPO-PROEUTECTOID STRUCTRAL STEELS

Proeutectoid ferrite with carbon content xo precipitating from austenite in a multicomponent steel at temperature T is supposed to be equivalent to proeutectoid ferrite with the same carbon content precipitating from austenite in Fe-C binary system at temperature T'.is described as the temperature difference of proeutectiod ferrite formation, and can be calculated from the Fe-X diagrams and the equilibrium temperature A3. By introducing Tf and basing on the thermodynamic model for Fe-C binary alloy, the driving force for phase transformation from austenite to proeutectoid ferrite in multicomponent steels has been successfully calculated. Through the Johnson-Mehl equation and using the data hem known TTT diagrams, the relationship between the chemical composition and the intedecial edenly packeter as well as activation energy for proeutectoid ferrite formation can be calculated. The starting curves of proeutectoid ferritic transformation calculated in this way in some hypo-proeutectoid structural steels agree well with the erperimental data.

Interfacial active sites on Co-Co_(2)C@carbon heterostructure for enhanced catalytic hydrogen generation

Designing catalysts with capable dual-active sites to drive catalytic hydrogen generation is necessary for the future hydrogen economy.Herein,the interfacial active sites consisting of Co and Co-C on Co-Co_(2)C@carbon heterostructure are designed through annealing and highpressure carbonization.The operating temperature during the high-pressure carbonization under a CO-reducing environment is responsible for the construction and regulation of Co-Co_(2)C@C heterostructure.The optimal catalyst has a high turnover frequency(TOF) of33.1 min^(-1) and low activation energy(E_a) of27.3 kJ-mol^(-1) during the hydrolysis of NH_(3)BH_(3).The catalytic stability of Co-Co_(2)C@C has no dramatic deterioration even after 5 cyclic usages.The interfacial active sites and the carbon on the catalyst surface enhance hydrogen generation kinetics and catalytic stability.The construction of interfacial active sites in Co-Co_(2)C@C prompts the dissociation of reactants(NH_(3)BH_(3) and H_(2)O molecules),leading to an enhanced catalytic hydrogen generation from NH_(3)BH_(3) hydrolysis(Co activates NH_(3)BH_(3) and Co-C activates H_(2)O).The construction of hetero-structural catalysts provides theoretical direction for the rational design of advanced transition metal carbide materials in the field of energy catalysis and conversion.

Electrochemical converting ethanol to hydrogen and acetic acid for large scale green hydrogen production

Electrochemical coupling hydrogen evolution with biomass reforming reaction(named electrochemical hydrogen and chemical cogeneration(EHCC)),which realizes green hydrogen production and chemical upgrading simultaneously,is a promising method to build a carbon-neutral society.Herein,we analyze the EHCC process by considering the market assessment.The ethanol to acetic acid and hydrogen approach is the most feasible for large-scale hydrogen production.We develop AuCu nanocatalysts,which can selectively oxidize ethanol to acetic acid(>97%)with high long-term activity.The isotopic and in-situ infrared experiments reveal that the promoted water dissociation step by alloying contributes to the enhanced activity of the partial oxidation reaction path.A flow-cell electrolyzer equipped with the AuCu anodic catalyst achieves the steady production of hydrogen and acetic acid simultaneously in both high selectivity(>90%),demonstrating the potential scalable application for green hydrogen production with low energy consumption and high profitability.

Active sites in CO2 hydrogenation over confined VOx-Rh catalysts

Metal oxide-promoted Rh-based catalysts have been widely used for CO2hydrogenation,especially for the ethanol synthesis.However,this reaction usually suffers low CO2conversion and alcohols selectivity due to the formation of byproducts methane and CO.This paper describes an efficient vanadium oxide promoted Rh-based catalysts confined in mesopore MCM-41.The Rh-0.3VOx/MCM-41 catalyst shows superior conversion（～12%）and ethanol selectivity（～24%）for CO2hydrogenation.The promoting effect can be attributed to the synergism of high Rh dispersion by the confinement effect of MCM-41 and the formation of VOx-Rh interface sites.Experimental and theoretical results indicate the formation of til-CO at VOx-Rh interface sites is easily dissociated into*CHx,and then*CHxcan be inserted by CO to form CH3CO*,followed by CH3CO*hydrogenation to ethanol.

A pH-responsive TiO_2-based Pickering emulsion system for in situ catalyst recycling

Developing methods for efficient product/catalyst separation and catalyst recycling is meaningful in multi-phase catalytic reactions. Here, we reported a p H-responsive emulsion system stabilized by interfacially active TiO2 nanoparticles for achieving in situ product/catalyst separation and catalyst recycling. In this system, emulsification and demulsification process could be easily engineered through tuning the p H values. The emulsion droplets were destroyed completely at a p H value of 3–4, and the solid catalyst distributed in the aqueous phase could be used to the next reaction cycle after removal of the organic product and adjusting the p H to 7–8. Such a p H triggered switchable Pickering emulsion catalytic system not only shows good recyclability of the solid catalyst but also high catalytic efficiency,and could be recycled more than 10 cycles.

Catalytically active interfaces in titania nanorod-supported copper catalysts for CO oxidation

One-dimensional titanium dioxide nanorod(TNR)-supported Cu catalysts(2.5 wt.%-12.5 wt.%)were synthesized using deposition-precipitation.X-ray photoelectron spectroscopy,temperature programmed reduction and CO chemisorption measurements showed that Cu doping over TNR offered metal-support interactions and interfacial active sites that had a profound impact on the catalytic performance.The role of the Cu-TNR interface was investigated by comparing the catalytic activity of Cu-TNR catalysts with that of pure CuO nanoparticles in CO oxidation.The presence of highly dispersed copper species,a high number of interfacial active sites,CO adsorption capacity and surface/lattice oxygen were found to be responsible for the excellent activity of 7.5CU-TNR(ie,Cu loading of 7.5 wt.%on TNR).Moreover,the Cu-TNR catalysts followed the Langmuir-Hinshelwood reaction mechanism with 7.5CU-TNR,exhibiting an apparent activation energy of 44.7 kJ/mol.The TNR-supported Cu catalyst gave the highest interfacial catalytic activity in medium-temperature CO oxidation(120-240℃)compared to other commonly used supports,including titanium dioxide nanoparticles(TiO2-P25),silica(SiO2)and alumina(Al20g)in which copper species were nonhomogeneously dispersed.This study confirms that medium-temperature CO oxidation is highly sensitive to the morphology and structure of the supporting material.

Ultra-thin ALD CoO_(x)-ZnO heterogenous films as highly sensitive and environmentally friendly H_(2)S sensor

To obtain environmentally friendly,integrated and miniaturized gas sensors for the increasing request for the Internet of Things industry and other relative areas,the ultra-thin CoO_(x)/Zn O heterogeneous film with active interfacial sites was in-situ deposited on micro-electro-mechanical systems(MEMS)as H_(2)S sensor.Atomic layer deposition(ALD)was employed to in-situ fabricate the uniform Zn O thin film.ALD CoO_(x)was deposited on ZnO surface to obtain CoO_(x)/Zn O heterojunction and active interfacial sites.The ultra-thin film(20 nm)with 50 ALD Co O_(x)decorated on 250 ALD Zn O displays excellent sensing performance,including very high response(4.45@200×10^(-9))and selectivity to H_(2)S with a limit of detection(LOD)of 0.38×10^(-9),long-term sensing stability,high response/recovery performance(7.5 s/15.7 s)and mechanical strength at 230。C.Reasons for the high sensing performance of CoO_(x)/Zn O have been confirmed by series of characterizations and density functional theory(DFT)calculation.Heterojunction film thickness with Debye length,the oxygen vacancies and the synergistic effect of active interfacial sites are main reasons for the high sensing performance.The strategy by fabrication of CoO_(x)/Zn O heterogeneous film within Debye length and employing synergistic effect of active interfacial sites offers a promising route for the design of environmentally friendly gas sensors.Furthermore,the ALD technique offers a facile in-situ strategy and high-throughput fabrication of MEMS gas sensors.