Bimetallic In_(2)O_(3)/Bi_(2)O_(3) Catalysts Enable Highly Selective CO_(2) Electroreduction to Formate within Ultra-Broad Potential Windows

CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.

Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Self-derivation and reconstruction of silver nanoparticle reinforced cobalt-nickel bimetallic hydroxides through interface engineering for overall water splitting

Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.

Elucidating the structure-activity relationship of Cu-Ag bimetallic catalysts for electrochemical CO_(2) reduction

Developing bimetallic catalysts is an effective strategy for enhancing the activity and selectivity of electrochemical CO_(2) reduction reactions,where understanding the structure-activity relationship is essential for catalyst design.Herein,we prepared two Cu-Ag bimetallic catalysts with Ag nanoparticles attached to the top or the bottom of Cu nanowires.When tested in a flow cell,the Cu-Ag catalyst with Ag nanoparticles on the bottom achieved a faradaic efficiency of 54%for ethylene production,much higher than the catalyst with Ag nanoparticles on the top.The catalysts were further studied in the H-cell and zero-gap MEA cell.It was found that placing the two metals in the intensified reaction zone is crucial to triggering the tandem reaction of bimetallic catalysts.Our work elucidates the structure-activity relationship of bimetallic catalysts for CO_(2) reduction and demonstrates the importance of considering both catalyst structures and cell characteristics to achieve high activity and selectivity.

Performance enhancement and active sites identification of Cu-Cd bimetallic oxide derived catalysts for electrochemical CO_(2) reduction

The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.

Constructing fast mass-transfer channels with efficient catalytic ozonation activity in 2D manganese dioxide membranes by intercalating Fe/Mn bimetallic MOF

Two-dimensional(2D)catalytic ozonation membranes are promising for the treatment of micropollutants in wastewater due to simultaneous ozone-catalyzed degradation and membrane filtration processes.However,it remains challenging for 2D catalytic ozonation membranes to efficiently degrade micropollutants due to low mass-transfer efficiency and poor catalytic activity.Herein,Fe/Mn bimetallic metal-organic framework(MOF)intercalated lamellar MnO_(2) membranes with fast and robust ozone-catalyzed mass-transfer channels were developed on the surface of the hollow fiber ceramic membrane(HFCM)to obtain 2D Fe/Mn-MOF@MnO_(2)-HFCM for efficiently degrading micropollutants in wastewater.The intercalation of Fe/Mn-MOF expanded the interlayer spacing of the MnO_(2) membrane,thereby providing abundant transport channels for rapid passage of water.More notably,the Fe/Mn-MOF provided enriched reactive sites as well as high electron transfer efficiency based on the redox cycling between Mn^(3+)/Mn^(4+) and Fe^(2+)/Fe^(3+),ensuring the effective catalytic oxidative degradation of micropollutants including tetracycline hydrochloride(TCH),methylene blue,and methyl blue.Moreover,the carboxyl groups on the MOF formed covalent bonds(-COO-)with the hydroxyl groups in MnO_(2) between layers,which increased the interaction between MnO_(2) nanosheets to form stable interlayer channels.Specifically,the optimal composite membrane achieved a high removal rate of TCH micropollutant(93.4%),high water treatment capacity(282 L·m^(-2)·h^(-1)·MPa^(-1)),and excellent longterm stability(1200 min).This study provides a simple and easily scalable strategy to construct fast,efficient,and stable 2D catalytic mass-transfer channels for the efficient treatment of micropollutants in wastewater.

Improvement of ionic conductivity of solid polymer electrolyte based on Cu-Al bimetallic metal-organic framework fabricated through molecular grafting

A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Microstructure evolution,mechanical properties and fracture behavior of Al-xSi/AZ91D bimetallic composites prepared by a compound casting

In this paper,the effect of the Si content on microstructure evolution,mechanical properties,and fracture behavior of the Al-xSi/AZ91D bimetallic composites prepared by compound casting was investigated systematically.The obtained results showed that all the Al-xSi/AZ91D bimetallic composites had a metallurgical reaction layer(MRL),whose thickness increased with increasing Si content for the hypoeutectic Al-Si/AZ91D composites,while the hypereutectic Al-Si/AZ91D composites were opposite.The MRL included eutectic layer(E layer),intermetallic compound layer(IMC layer)and transition region layer(T layer).In the IMC layer,the hypereutectic Al-Si/AZ91D composites contained some Si solid solution and flocculent Mg_(2)Si+Al-Mg IMCs phases not presented in the hypoeutectic Al-Si/AZ91D composites.Besides,increasing Si content,the thickness proportion of the T layer increased,forming an inconsistent preferred orientation of the MRL.The shear strengths of the Al-xSi/AZ91D bimetallic composites enhanced with increasing Si content,and the Al-15Si/AZ91D composite obtained a maximum shear strength of 58.6 MPa,which was 73.4% higher than the Al-6Si/AZ91D composite.The fractures of the Al-xSi/AZ91D bimetallic composites transformed from the T layer into the E layer with the increase of the Si content.The improvement of the shear strength of the Al-xSi/AZ91D bimetallic composites was attributed to the synergistic action of the Mg_(2)Si particle reinforcement,the reduction of oxidizing inclusions and the ratio of Al-Mg IMCs as well as the orientation change of the MRL.

Advanced preparation and application of bimetallic materials in lithium-sulfur batteries:A review

Lithium-sulfur(Li-S)batteries are considered highly promising as next-generation energy storage systems due to high theoretical capacity(2600 Wh kg^(-1))and energy density(1675 mA h g^(-1))as well as the abundant natural reserves,low cost of elemental sulfur,and environmentally friendly properties.However,several challenges impede its commercialization including low conductivity of sulfur itself,the severe“shuttle effect”caused by lithium polysulfides(LiPSs)during charge–discharge processes,volume expansion effects and sluggish reaction kinetics.As a solution,polar metal particles and their compounds have been introduced as the main hosts for sulfur cathode due to their robust catalytic activity and adsorption capability,effectively suppressing the“shuttle effect”of Li PSs.Bimetallic alloys and their compounds with multi-functional properties exhibit remarkable electrochemical performance more readily when compared to single-metal materials.Well-designed bimetallic materials demonstrate larger specific surface areas and richer active sites,enabling simultaneous high adsorption capability and strong catalytic properties.The synergistic effect of the“adsorption-catalysis”sites accelerates the adsorptiondiffusion-conversion process of Li PSs,ultimately achieving a long-lasting Li-S battery.Herein,the latest progress and performance of bimetallic materials in cathodes,separators,and interlayers of Li-S batteries are systematically reviewed.Firstly,the principles and challenges of Li-S batteries are briefly analyzed.Then,various mechanisms for suppressing“shuttle effects”of Li PSs are emphasized at the microscale.Subsequently,the performance parameters of various bimetallic materials are comprehensively summarized,and some improvement strategies are proposed based on these findings.Finally,the future prospects of bimetallic materials are discussed,with the hope of providing profound insights for the rational design and manufacturing of high-performance bimetallic materials for LSBs.

Research Progress of Nickel Iron Bimetallic Series Electrocatalytic Materials

Hydrogen energy has become one of the recognized clean energy sources worldwide due to its advantages such as low cost,renewable energy,and green environmental protec-tion.Electrolytic water is currently one of the most promising solutions for providing hydrogen fuel.Nickel iron bimetallic electrocatalysts have abundant sources,low cost,clean and pollution-free properties,and strong catalytic performance,This article mainly reviews the development and research of bimetallic nickel iron oxides and nickel iron alloys in recent years,and explores their synthesis methods,properties,and stability in depth.

Effect of manganese on the catalytic performance of an iron-manganese bimetallic catalyst for light olefin synthesis

A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst samples were characterized by N2 physisorption, transmis- sion electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, powder X-ray diffraction （XRD）, Mossbauer spectroscopy, H2- differential thermogravimetric analysis （H2-DTG）, CO temperature-programmed reduction （CO-TPR） and CO2 temperature-programmed des- orption （CO2-TPD）. The Fischer-Tropsch synthesis （FTS） performance of the catalyst was measured at 1.5 MPa, 250 ℃ and syngas with H2/CO ratio of 2.0. The characterization results indicated that the addition of manganese decreases the catalyst crystallite size, and improves the catalyst BET surface area and pore volume. The presence of manganese suppresses the catalyst reduction and carburization in H2, CO and syngas, respectively. The addition of manganese improves the catalytic activity of water-gas shift reaction and suppresses the oxidation of iron carbides in the FTS reaction. The incorporation of manganese improves the catalyst surface basicity and results in a significant improvement in the selectivities to light olefins and heavy hydrocarbons （C5＋）, and furthermore an inhibition of methane formation in FTS. The pure iron catalyst （Mn-00） has the highest initial FTS catalytic activity （65%） and the lowest selectivity （17.35 wt%） to light olefins （C2=-C4=）. The addition of an appropriate amount of manganese can improve the catalyst FTS activity.

Highly effective direct synthesis of DMC from CH_3OH and CO_2 using novel Cu-Ni/C bimetallic composite catalysts

Novel Cu-Ni/C has been prepared and utilized as an efficient catalyst system in direct synthesis of DMC from CH3OH and CO2.

Rapid treatment of atrazine-contaminated water by nickel/iron bimetallic system

The utility of nickel/iron in the remediation of atrazine-contaminated water was investigated. The experimental results showed that nickel/iron had effective catalytic activity in dechlorinating atrazine under acidic conditions. The dechlorination reaction approximately followed the first-order kinetics under the experimental conditions(nickel/iron:1.0 g/250 ml;C atrazine=20.0 mg/L), the reaction rate increased with decreasing pH value of the reaction solution and increasing the proportion of Ni:Fe within 2.95%. For condition with 2.95% nickel/iron, the reaction rate constants were 0.07518(R=0.9927), 0.06212(R=0.9846) and 0.00131 min -1(R=0.9565) at pH=2.0, 3.0 and 4.0, respectively. HPLC analysis was used to monitor the decline of atrazine concentration.

Effect of preparation method on the bimetallic NiCu/SAPO-11 catalysts for the hydroisomerization of n-octane

The bimetallic NiCu/SAPO-11 catalysts were prepared by co-impregnation, sequential impregnation, coprecipitation, and mechanical mixing methods. Powder X-ray diffraction, nitrogen adsorption-desorption,temperature-programmed desorption of ammonia, transmission electron microscopy, temperatureprogrammed reduction of hydrogen, and X-ray photoelectron spectroscopy were used to characterize the physicochemical properties of the catalysts. The catalytic performance of the catalysts was assessed by the hydroisomerization of n-octane. Results indicated that the conversion of n-octane and selectivity to n-octane isomers were related to the preparation methods of the catalysts. The catalysts with Ni-Cu alloy effectively restrained the hydrogenolysis reaction that decreases the selectivity of isomerization. The catalyst prepared by the mechanical mixing of NiO and CuO hardly formed Ni-Cu alloy, showing obvious hydrogenolysis and low selectivity to n-octane isomers. The unbalance between the metal and acid sites resulted in the low conversion of n-octane and selectivity to n-octane isomers. Among all the catalysts,the catalyst prepared by the co-impregnation method exhibited high catalytic activity and selectivity to n-octane isomers.

Dechlorination of disinfection by-product monochloroacetic acid in drinking water by nanoscale palladized iron bimetallic particle

Nanoscale palladized iron(Pd/Fe)bimetallic particles were prepared by reductive deposition method.The particles were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM),transmission electron microscope(TEM),and Brunauer-Emmett-Teller-nitrogen(BET-N_2)method.Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles containedα-Fe^0.Detected Pd to Fe ratio by weight(Pd/Fe ratio)was close to theoretical value. Spherical granules with diame...

Simulation and experimental verification of interfacial interactions in compound squeeze cast Al/Al-Cu macrocomposite bimetal

The objective of this work was to investigate the thermal and mechanical interactions between the two components of a compound squeeze cast macrocomposite bimetal. First, an Al/Al-4.5wt.%Cu macrocomposite bimetal was fabricated by compound squeeze casting process. Then, heat transfer, solidification and distribution of the generated stresses along the interface region of the bimetal were analyzed using Thermo-Calc, ProCAST and ANSYS softwares, and structure, copper distribution and microhardness changes across the interface of the bimetal were studied. The results showed no noticeable change in the structure of the Al-4.5wt.%Cu insert and no obvious micromixing and diffusion of copper across the interface. Simulation results were in good agreement with the experimental ones only when an equivalent oxide layer at the interface was defined and its effect on heat transfer was considered. This layer caused up to 50% decrease in local liquid fraction formed on the surface of the insert. Simulation of the generated stresses showed a uniformly distributed stress along the interface which was significantly lower than the compressive strength of the oxide layer, resulting in its good stability during the fabrication process. It was postulated that this continuous oxide layer not only acted as a thermal barrier but prevented the direct metal-metal contact along the interface as well.

Bimetallic NiCo2S4 Nanoneedles Anchored on Mesocarbon Microbeads as Advanced Electrodes for Asymmetric Supercapacitors

Bimetallic Ni–Co sulfides are outstanding pseudocapacitive materials with high electrochemical activity and excellent energy storage performance as electrodes for high-performance supercapacitors.In this study,a novel urchin-like NiCo2S4@mesocarbon microbead(NCS@MCMB) composite with a core–shell structure was prepared by a facile two-step hydrothermal method.The highly conductive MCMBs offered abundant adsorption sites for the growth of NCS nanoneedles,which allowed each nanoneedle to fully unfold without aggregation,resulting in improved NCS utilization and efficient electron/ion transferin the electrolyte.When applied as an electrode material for supercapacitors,the composite exhibited a maximum specific capacitance of 936 Fg-1 at 1 Ag-1 and a capacitance retention of 94% after 3000 cycles at 5 Ag-1,because of the synergistic effect of MCMB and NCS.Moreover,we fabricated an asymmetric supercapacitor based on the NCS@MCMB composite,which exhibited enlarged voltage windows and could power a light-emitting diode device for several minutes,further demonstrating the exceptional electrochemical performance of the NCS@MCMB composite.

PVP-Supported Palladium-Cadmium Bimetallic Catalyst for the Hydrogen Transfer Dechlorination of Aryl Chlorides

PVP-supported bimetallic catalyst, PVP-PdCl2-CdCl2, exhibits extremely high catalytic activity for the hydrogen transfer dechlorination of aryl chlorides in neutral environment. The yields of dechlorination products are high under mild reaction conditions and the operation is simple.

Nitrogen-Doped Carbon-Encased Bimetallic Selenide for High-Performance Water Electrolysis

Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.