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.

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.

RuRh Bimetallic Nanoparticles Stabilized by 15-membered Macrocycles-terminated Poly(propylene imine) Dendrimer:Preparation and Catalytic Hydrogenation of Nitrile–Butadiene Rubber

A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.

Selective suppression of toluene formation in solvent-free benzyl alcohol oxidation using supported Pd-Ni bimetallic nanoparticles

The solvent‐free oxidation of benzyl alcohol was studied using supported Pd‐Ni bimetallic nanoparticles.Compared with monometallic Pd,the addition of Ni to Pd was found to be effective in suppressing the nondesired product toluene,thereby enhancing the selectivity towards benzaldehyde.This result was attributed to a dual effect of Ni addition:the weakening of dissociative adsorption of benzyl alcohol and the promotion of oxygen species involved in the oxidation pathway.

Recovery of high-purity Pt from Pt-Au bimetallic nanoparticles using organic aqua regia

Using organic aqua regia,a recently discovered powerful organic leaching agent,an effective process of recovering Pt directly from Pt-Au bimetallic nanoparticles was demonstrated.The purities of the Pt recovered from a mixture of Au and Pt nanoparticles and from Pt-Au core-shell nanoparticle catalyst are as high as (99.49±0.22)%,and (95.02±0.08)%,respectively.The novel recovery process promises applications in catalysis industry.

Metal–Oleate Complex?Derived Bimetallic Oxides Nanoparticles Encapsulated in 3D Graphene Networks as Anodes for Efficient Lithium Storage with Pseudocapacitance

In this manuscript, we have demonstrated the delicate design and synthesis of bimetallic oxides nanoparticles derived from metal–oleate complex embedded in 3D graphene networks(MnO/CoMn_2O_4  GN), as an anode material for lithium ion batteries. The novel synthesis of the MnO/CoMn_2O_4  GN consists of thermal decomposition of metal–oleate complex containing cobalt and manganese metals and oleate ligand, forming bimetallic oxides nanoparticles, followed by a selfassembly route with reduced graphene oxides. The MnO/CoMn_2O_4  GN composite, with a unique architecture of bimetallic oxides nanoparticles encapsulated in 3D graphene networks, rationally integrates several benefits including shortening the di usion path of Li^+ ions, improving electrical conductivity and mitigating volume variation during cycling. Studies show that the electrochemical reaction processes of MnO/Co Mn_2O_4  GN electrodes are dominated by the pseudocapacitive behavior, leading to fast Li^+ charge/discharge reactions. As a result, the MnO/CoMn_2O_4  GN manifests high initial specific capacity, stable cycling performance, and excellent rate capability.

Structural optimization of Au–Pd bimetallic nanoparticles with improved particle swarm optimization method

Due to the dependence of the chemical and physical properties of the bimetallic nanoparticles（NPs） on their structures,a fundamental understanding of their structural characteristics is crucial for their syntheses and wide applications. In this article, a systematical atomic-level investigation of Au–Pd bimetallic NPs is conducted by using the improved particle swarm optimization（IPSO） with quantum correction Sutton–Chen potentials（Q-SC） at different Au/Pd ratios and different sizes. In the IPSO, the simulated annealing is introduced into the classical particle swarm optimization（PSO） to improve the effectiveness and reliability. In addition, the influences of initial structure, particle size and composition on structural stability and structural features are also studied. The simulation results reveal that the initial structures have little effects on the stable structures, but influence the converging rate greatly, and the convergence rate of the mixing initial structure is clearly faster than those of the core-shell and phase structures. We find that the Au–Pd NPs prefer the structures with Au-rich in the outer layers while Pd-rich in the inner ones. Especially, when the Au/Pd ratio is 6：4, the structure of the nanoparticle（NP） presents a standardized Pd（core） Au（shell） structure.

Kinetics of 2,4-dichlorophenol dechlorination by Pd-Fe bimetallic nanoparticles in the presence of humic acid

The remediation of groundwater which contains chlorinated organic compounds (COCs) by nanoscale bimetallic catalysts has received increasing interest in recent years. This report presents the dechlorination of 2,4-dichlorophenol (2,4-DCP) by Pd-Fe bimetallic nanoparticles in the presence of humic acid (HA) to investigate the feasibility of using Pd-Fe for the in situ remediation of contaminated groundwater. Our experimental results indicated that HA had an adverse effect on the dechlorination of 2,4-DCP by Pd-Fe nanoparticles. The rate constant k values of 2,4-DCP dechlorination were 0.017, 0.013, 0.009, 0.006 and 0.004 min?1 for HA concentrations of 0, 5, 10, 15 and 20 mg/L, respectively. The relationship between HA dosage and k values can be described as a linear model.

Lewis acid-driven reaction pathways in synergistic cooperative catalysis over gold/palladium bimetallic nanoparticles for hydrogen autotransfer reaction between amide and alcohol

Metal nanoparticle catalysts, especially gold and its bimetallic nanoparticle catalysts, have been widely used in organic transformations as powerful and green catalysts. The concept of employing two distinct catalysts in one reaction system, such as in cooperative and synergistic catalysis, is a powerful strategy in homogeneous catalysis. However, the adaption of such a strategy to metal nanoparticle catalysis is still under development. Recently, we have found that cooperative catalytic systems of gold/palladium bimetallic nanoparticles and Lewis acid can be used for the N‐alkylation of primary amides through hydrogen autotransfer reaction between amide and alcohol. Herein, the results of a detailed investigation into the effects of Lewis acids on this hydrogen autotransfer reac‐tion are reported. It was found that the choice of Lewis acid affected not only the reaction pathway leading to the desired product, but also other reaction pathways that produced several intermedi‐ates and by‐products. Weak Lewis acids, such as alkaline‐earth metal triflates, were found to be optimal for the desired N‐alkylation of amides.

Synthesis and Enhanced Electrochemical Activity of Ag-Pt Bimetallic Nanoparticles Decorated MWCNTs/PANI Nanocomposites

Ag-Pt bimetallic nanoparticles decorated on MWCNTs/PANI nanocomposites have been synthesized by in-situ chemical oxidative polymerization and chemical co-reduction method. The Fourier transform infrared（FT-IR） spectroscopy, X-ray diffraction（XRD）, ultraviolet-visible（UV-vis） absorption spectroscopy, scanning electron microscopy（SEM） and transmission electron microscopy（TEM） were used to characterize the morphology and structure of the nanocomposites. It can be observed that the PANI was uniformly grown along the MWCNTs to form MWCNsT/PANI fiber-like nanocomposites with diameter about 60 nm, and the Ag-Pt binary nanoparticles were decorated onto MWCNTs/PANI with particle sizes around 6.8 nm. Cyclic voltammetry（CV） and electrochemical impedance spectroscopy（EIS） were used to characterize the electrochemical performance of the prepared electrode. The results demonstrated that the obtained MWCNTs/PANI/Ag-Pt electrode displayed a good electrochemical activity and fast electron transport, which has potential applications in biosensors and supercapacitors.

Nanolarvicidal Effect of Green Synthesized Ag-Co Bimetallic Nanoparticles on <i>Culex quinquefasciatus</i>Mosquito

Synthesis of bimetallic nanoparticles has employed many applications especially as larvicidal agents, these bimetallic nanoparticles therefore need to be produced via a cost-effective and eco-friendly route. Here, green synthesis of Ag-Co hybrid nanoparticles obtained from aqueous root extract of palmyra palm was reported. The hybrid nanoparticles formation was noticed by a colour change from light pink to light brown and further studied using UV-Vis and FT-IR spectrophotometers. The maximum absorption wavelength, λmax as determined by the UV-Visible Spectrophotometer was found to be 420 nm. The FT-IR showed the formation and stabilization of the BMNPs. The nanolarvicidal potency was evaluated by the application of varying concentration ranging from 5 to 50 mg/L against first to fourth instars of larvae and recording the percentage mortality after 24 hours. Probit analysis showed the LC50 and LC90 for 1st instar to be 5.237 mg/L and 49.240 mg/L, 9.310 mg/L and 94.969 mg/L for 2nd instar, 13.626 mg/L and 105.542 mg/L for 3rd/4th instars respectively. This result therefore suggests that the nanoparticles can be used as potential control for larval population growth.

Synthesis and Characterization of Bimetallic Gold-Silver Core-Shell Nanoparticles: A Green Approach

Bimetallic gold-silver core-shell nanoparticles were prepared by chemical reduction in aqueous solution, following a method that was friendly to the environment, allowing us to use this for medicinal purposes. Gold nanoparticles were synthesized, and silver cations were then reduced on the nanoparticles. Using the optical properties of metallic nanoparticles, surface plasmon resonance was determined by UV-Vis spectroscopy, and the values obtained for gold and silver were approximately 520 nm and 400 nm in wavelength, respectively. The absorption peaks of the surface plasmon band show a clear red-shift due to size effect in the case of the silver surface, and a plasmon coupling effect, in the case of gold. To obtain a better understanding of the coating conditions, high resolution transmission electron microscopy was used. The average hydrodynamic size and the size distribution of the synthesized nanoparticles were obtained by dynamic light scattering. The development of this process, which is benign for the environment, opens the possibility for many applications in the areas of renewable energy, medicine and biology.

Interaction between Pd and Cu nanoparticles in bimetallic CuPdx nanoparticles and its impact on oxidation of 1,2-propanediol to aliphatic acids

Bimetallic CuPdx nanoparticles synthesized by the wet chemical reduction method were used as the catalysts in the catalytic oxidation of 1,2-propanediol with gaseous oxygen to aliphatic acids.The palladium and copper nanoparticles in the bimetallic CuP dxnanoparticles had an alloying trend.The catalytic activity of the palladium nanoparticles in the bimetallic CuP dxnanoparticles was enhanced by the interaction between the palladium and copper nanoparticles.When the bimetallic CuPd7 nanoparticles catalyzed the oxidation of 1,2-propanediol in an alkaline aqueous solution at 100℃for 3h,lactic,formic,and acetic acids were dominantly produced with the total selectivity of above 99%at the 1,2-propanediol conversion of 85.9%.The simulation of the reaction kinetic equation on the CuPd7 catalyst showed that the reaction activation energy was 29.4kJ·mol^-1,indicating that the bimetallic CuPd7 nanoparticles had a high catalytic activity in the oxidation reaction between 1,2-propanediol and gaseous oxygen.

Determination of Hydrodynamic Parameters of Chitosan Stabilized Bimetallic Nanoparticles

The hydrodynamic characteristics of bimetallic Ag/Cu and Co/Ag nanopar­ticles stabilized by chitosan were determined.The polydispersity index and the diameter of nanoparticles were observed to decrease in contrast to the original polymer during the creation of chitosan stabilized bimetallic nanoparticles,decreasing from 0.342 to 0.12±0.04 and 2.5 micron to 180 nm,respectively.However,the diffusion coefficient of chitosan was in­creased from 0.2 cm^(2)/s to 2.71 cm2/s during the production of stable bime­tallic nanoparticles.The lack of absorption bands at 500 nm and 700 nm-900 nm in the UV spectra of the samples suggests that in the presence of a reducing agent,copper(II)and cobalt(II)ions undergo full reduction.The relationship between the synthesis conditions and the kind of structure of bimetallic nanoparticles“core-shell”has been discovered.Silver atoms have been shown to be both a core and a shell,depending on the synthesis conditions and chemical nature of metal ions.

Synthesis of Core-Shell Nanoparticles of Cu-Ag for Application in Electrohydrodynamic Printing Technique

Core-shell nanoparticles of Cu-Ag (Cu core and Ag shell) were synthesized using chemical method. Polyvinyl pyrrolidone (PVP) was used as a surfactant, and ascorbic acid (C6H8O6) and sodium borohydride (NaBH4) were used as reducing agents to reduce the metal complexes [Cu(NH3)4]^2+ and [Ag(NH3)2]^+. The results of transmission electron microscope (TEM) analysis, ultraviolet-visible spectroscopic (UV-Vis) analysis, X-ray diffraction (XRD) analysis showed that the core-shell nanoparticles of Cu-Ag were successfully synthersized. The average particle size was 32 nm. The dispersion of the nanoparticles was still good after 80 days without the formation of the oxides of Cu and Ag. The properties of the nanoparticles suggested that they were suitable to be used as an electrically conductive material for conductive ink-jet printing inks.

Bimetallic nanoparticles as cascade sensitizing amplifiers for low-dose and robust cancer radio-immunotherapy

Radiotherapy(RT)is one of the most feasible and routinely used therapeutic modalities for treating malignant tumors.In particular,immune responses triggered by RT,known as radio-immunotherapy,can partially inhibit the growth of distantly spreading tumors and recurrent tumors.How-ever,the safety and efficacy of radio-immunotherapy is impeded by the radio-resistance and poor immu-nogenicity of tumor.Herein,we report oxaliplatin(IV)-iron bimetallic nanoparticles(OXA/Fe NPs)as cascade sensitizing amplifiers for low-dose and robust radio-immunotherapy.The OXA/Fe NPs exhibit tumor-specific accumulation and activation of OXA(I)and Fe^(2+)in response to the reductive and acidic microenvironment within tumor cells.The cascade reactions of the released metallic drugs can sensitize RT by inducing DNA damage,increasing ROS and O_(2) levels,and amplifying the immunogenic cell death(ICD)effect after RT to facilitate potent immune activation.As a result,OXA/Fe NPs-based low-dose RT triggered a robust immune response and inhibited the distant and metastatic tumors effectively by a strong abscopal effect.Moreover,a long-term immunological memory effect to protect mice from tumor rechal-lenging is observed.Overall,the bimetallic NPs-based cascade sensitizing amplifier system offers an effi-cient radio-immunotherapy regimen that addresses the key challenges.

Development of Cd-doped Co Nanoparticles Encapsulated in Graphite Shell as Novel Electrode Material for the Capacitive Deionization Technology

Because of the low energy requirement and the environmentally safe byproducts, the capacitive deionization water desalination technology has attracted the attention of many researchers. The important requirements for electrode materials are good electrical conductivity, high surface area, good chemical stability and high specific capacitance. In this study, metallic nanoparticles that are encapsulated in a graphite shell(Cd doped Co/C NPs) are introduced as the new electrode material for the capacitive deionization process because they have higher specific capacitance than the pristine carbonaceous materials. Cd doped Co/C NPs perform better than graphene and the activated carbon. The introduced nanoparticles were synthesized using a simple sol gel technique. A typical sol gel composed of cadmium acetate, cobalt acetate and poly(vinyl alcohol)was prepared based on the polycondensation property of the acetates. The physiochemical characterizations that were used confirmed that the drying, grinding and calcination in an Ar atmosphere of the prepared gel produced the Cd doped Co nanoparticles, which were encapsulated in a thin graphite layer. Overall, the present study suggests a new method to effectively use the encapsulated bimetallic nanostructures in the capacitive deionization technology.

Preparation,characterization and catalytic behavior of Pt-Cu nanoparticles in methane combustion

Fine and well dispersed Pt-Cu bimetallic nanoparticles stabilized by polyvinyl pyrrolidone （PVP） were synthesized by alkaline polyol method. The molar ratio of Pt to Cu was 1 ： 1. Further, the Pt-Cu bimetallic nanoparticles were supported on alumina and their catalytic behavior in methane combustion was investigated. The as-prepared as well as the supported Pt-Cu nanoparticles were characterized by transmission elec- tron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, fractal analysis and X-ray diffraction （XRD）. The dependence of methane combustion on the morphology and surface composition of Pt-Cu nanoparticles was analyzed based on the experimental results.

Reverse Microemulsion Synthesis and Characterization of Pd-Ag Bimetallic Alloy Catalysts Supported on Al_2O_3 for Acetylene Hydrogenation

Pd-Ag bimetallic alloy nanoparticles were synthesized by the reverse microemulsion method, and then deposited on A1203 to form the supported catalyst. The nanoparticles of Pd-Ag and Pd-Ag/AI203 samples were characterized by UV/ Vis, HRTEM, EDX, XRD, and XPS. The test results indicated that Pd-Ag bimetallic alloy nanoparticles with a size of about 2 nm and a face-centered cubic （fcc） structure were formed in the measured area of microemulsion. The growth of nanopar- ticles was effectively limited within the droplet of micoremulsion. TEM image exhibited that the Pd-Ag alloy nanoparticles were well-dispersed on the A1203 support. The catalytic performance of various catalysts for selective hydrogenation of acetylene showed that a higher acetylene conversion and selectivity to ethylene upon acetylene hydrogenation was achieved on a nano-sized Pd-Ag bimetallic catalyst with a Pd/Ag alloy supported molar ratio of 1：1.5.

Structural and thermal stabilities of Au@Ag core-shell nanoparticles and their arrays:A molecular dynamics simulation

Thermal stability of core-shell nanoparticles(CSNPs)is crucial to their fabrication processes,chemical and physical properties,and applications.Here we systematically investigate the structural and thermal stabilities of single Au@Ag CSNPs with different sizes and their arrays by means of all-atom molecular dynamics simulations.The formation energies of all Au@Ag CSNPs we reported are all negative,indicating that Au@Ag CSNPs are energetically favorable to be formed.For Au@Ag CSNPs with the same core size,their melting points increase with increasing shell thickness.If we keep the shell thickness unchanged,the melting points increase as the core sizes increase except for the CSNP with the smallest core size and a bilayer Ag shell.The melting points of Au@Ag CSNPs show a feature of non-monotonicity with increasing core size at a fixed NP size.Further simulations on the Au@Ag CSNP arrays with 923 atoms reveal that their melting points decrease dramatically compared with single Au@Ag CSNPs.We find that the premelting processes start from the surface region for both the single NPs and their arrays.