Self-catalytic induced interstitial C-doping of Pd nanoalloys for highly selective electrocatalytic dehydrogenation of formic acid

Light-metalloid-atom-doped Pd interstitial nanoalloy is promising candidate for electrocatalysis because of the favorable electronic effect.Herein,an innovative method was developed to synthesize C-doped Pd interstitial nanoalloy using palladium acetate both as metal precursor and C dopant.Elaborate characterizations demonstrated that C atoms were successfully doped into the Pd lattice via self-catalytic decomposition of acetate ions.The as-synthesized C-doped Pd catalysts showed excellent activity and durable stability for formic acid electrooxidation.The mass activity and specific activity at 0.6 V of C-doped Pd were approximately 2.59 A/mg and 3.50 mA cm^(-2),i.e.,2.4 and 2.6 times of Pd,respectively.DFT calculations revealed that interstitial doping with C atoms induced differentiation of Pd sites.The strong noncovalent interaction between the Pd sites and the key intermediates endowed Pd with high-selectivity to direct routes and enhanced CO tolerance.This work presents a sites-differentiation strategy for metallic catalysts to improve the electrocatalysis.

Surface composition dominates the electrocatalytic reduction of CO2 on ultrafine CuPd nanoalloys

Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivity.However,the synthesis of ultrafine nanoalloys and tuning their surface composition remain challenging.In this report,ultrafine CuPd nanoalloys with the particle size of ca.2 nm are synthesized based on the galvanic replacement reaction between presynthesized Cu nanoparticles and Pd2+precursors,and the tuning of their surface compositions is also achieved by changing the atom ratios of Cu/Pd.For the electrocatalytic reduction of CO2,Cu5Pd5 nanoalloys show the CO Faradaic efficiency(FE)of 88%at−0.87 V,and the corresponding mass activity reaches 56 A/g that is much higher than those of Cu8Pd2 nanoalloys,Cu3Pd7 nanoalloys and most of previously reported catalysts.Density functional theory uncovers that with the increase of Pd on the surface of the ultrafine CuPd nanoalloys,the adsorbed energy of both of intermediate COOH*and CO*to the Pd sites is strengthened.The Cu5Pd5 nanoalloys with the optimal surface composition better balance the adsorption of COOH*and desorption of CO*,achieving the highest selectivity and activity.The difficult liberation of absorbed CO*on the surface of Cu3Pd7 nanoalloys provides carbon source to favor the production of ethylene,endowing the Cu3Pd7 nanoalloys with the highest selectivity for ethylene among these ultrafine CuPd nanoalloys.

Sputtering FeCu nanoalloys as active sites for alkane formation in CO_(2) hydrogenation

Catalytic conversion of CO_(2) to high-value products is a crucial method to achieve targets of carbon dioxide emissions peak and carbon neutralization.However,realizing a controllable product distribution in a single CO_(2) hydrogenation process is of great challenge.Herein,we prepared the CuFe nanoalloy catalyst that directly transforms CO_(2) to alkanes using physical sputtering method in mild condition.The characteristic results show that the proximity between Cu and Fe is the crucial factor to tunable products among the different catalysts.The formation of unique coordination of FeCu4 nanoalloys from high-energy sputtering process provides close interaction between Cu and Fe,which is favorable to formation of low carbon paraffin,however,a distant proximity and weak interaction will increase the selectivity of olefins and alcohols.This work provides a general strategy for tuning target chemicals and enriches the viewpoints in CO_(2) hydrogenation.

Heating rate effects for the melting transition of Pt-Ag-Au nanoalloys

The classical molecular dynamics simulations in canonical NVT ensemble conditions are used to investigate the melting transition in different heating rates of Pt-Ag-Au ternary nanoalloys.In order to obtain the initial configurations used in the molecular dynamics simulations,optimizing the chemical ordering of Pt_(13)AgnAu_(42−n)(n=0-42)ternary nanoalloys was performed using the Basin-Hopping algorithm which would not allow changes in the icosahedron structure.The Gupta many-body potential was used to model interatomic interactions in both molecular dynamics simulations and optimization simulations.The melting transitions of selected Pt-Ag-Au nanoalloys were explored using caloric curves and Lindemann parameters.There have been two identified types of melting mechanisms,one includes sudden jump behavior in the caloric curve and the other is an isomerization while melting transition.The temperature range in which the isomerization takes place depends on the heating rate value.

A theoretical study on chemical ordering of 38-atom trimetallic Pd-Ag-Pt nanoalloys

In this study,truncated octahedron(TO)structure is selected for further analysis and we focus on 38-atom Pd-Pt-Ag trimetallic nanoalloys.The best chemical ordering structures of PdnAg32-nPt6 trimetallic nanoalloys are obtained at Gupta level.The structures with the lowest energy at Gupta level are then re-optimized by density functional theory(DFT)relaxations and DFT results confirm the Gupta level calculations with small shifts on bond lengths indicating TO structure is favorable for 38-atom of PdnAg32-nPt6 trimetallic nanoalloys.The DFT excess energy analysis shows that Pd8Ag24Pt6 composition has the lowest excess energy value in common with excess energy analysis at Gupta level.In Pd8Ag24Pt6 composition,eight Pd atoms are central sites of 8(111)hexagonal facets of TO,24 Ag atoms locate on surface,and 6 Pt atoms locate at the core of the structure.It is also obtained that all of the compositions except Pd18Ag14Pt6 and Pd20Ag12Pt6 exhibit a octahedral Pt core.Besides,it is observed that there is a clear tendency for Ag atoms to segregate to the surface and also Pt atoms prefer to locate at core due to order parameter(R)variations.

PdPbBi nanoalloys anchored reduced graphene-wrapped metal-organic framework-derived catalyst for enhancing ethylene glycol electrooxidation

For future clean energy demand,it is essential to develop highly efficient and durable materials for use in renewable energy conversion devices.Herein,we report an electrocatalyst loaded with Pd-Pb-Bi nanoalloys on reduced graphene(rGO)-wrapped In_(2)O_(3)(PdPbBi@rGO/In_(2)O_(3))prepared by a hydrothermal method.PdPbBi@rGO/In_(2)O_(3)exhibits higher forward current density(229.12 mA·cm^(-2)),larger electrochemical active surface area(ECSA)(85.87 m^(2)·g^(-1)Pd),smaller impedance(12.68Ω)and lower E_(onset)(-0.56 V)than commercial Pd/C.Specifically,the current density and ECS A are 8.46 and3.38 times higher than those of commercial Pd/C(27.07 mA·cm^(-2),25.41 m^(2)·g^(-1)Pd),respectively.Furthermore,the oxidation mechanism of ethylene glycol and the removal of carbon monoxide[CO]_(ads)from the surface of Pd are also discussed in detail.The columnar support structure wrapped by rGO provides a huge active surface area for catalysis.Moreover,the electronic effect of Pd-PbBi nanoalloys can accelerate the removal of CO intermediate species,obtain more Pd active sites and improve the electrocatalytic performance.Our first synthesis of this highly electrocatalyst offers promising value for commercial application in direct fuel cells.

Arranging Electronic Localization of PtCu Nanoalloys to Stimulate Improved Oxygen Electroreduction for High-Performance Fuel Cells

Developing exceptionally durable and efficient oxygen reduction reaction(ORR)catalysts is of paramount importance to the widespread commercialization of proton exchange membrane fuel cells(PEMFCs)but is still challenging.Herein,PtCu nanoalloys rooted on nitrogen-doped carbon nanosheets(PtCuNC-700)with fully exposed PtCu nanoalloys and strong metal–support interaction were developed.Benefiting from its structural and compositional merits,PtCuNC-700 showcases superior ORR activity and stability with a specific activity of 1.05mA cm^(−2)and mass activity of 0.45 A mgPt^(−1),4.2-fold and 3.7-fold higher than Pt/C(0.25 mA cm^(−2)and 0.12 A mgPt^(−1)),respectively.Moreover,PtCuNC-700 exhibits first-class performance in H2/air PEMFC assessment and delivers a peak power density of 929.7 mW cm^(−2)and excellent cycling stability up to 30,000 cycles.Theoretical calculations disclose that the synergistic effect of alloying Pt with Cu combined with the strong interaction between PtCu nanoalloys and nitrogen-doped carbon nanosheets can effectively modify the local electron configuration and density of states of Pt sites approaching the Fermi level.Hence,the PtCu-alloy catalysts realized here diminish the energy barrier for ORR and accelerate their reaction kinetics.This work provides a reliable and effective approach to boost the activity and stability of Pt alloy-based ORR electrocatalysts in PEMFCs.

Laser-optimized Pt-Y alloy nanoparticles embedded in Pt-Y oxide matrix for high stability and ORR electrocatalytic activity

The development of active yet stable catalysts for oxygen reduction reaction(ORR)is still a major issue for the extensive permeation of fuel cells into everyday technology.While nanostructured Pt catalysts are to date the best available systems in terms of activity,the same is not true for stability,particularly under operating conditions.In this work,Pt_(Х)Y alloy nanoparticles are proposed as active and durable electrocatalysts for ORR.Pt_(Х)Y nanoalloys are synthesized and further optimized by laser ablation in liquid followed by laser fragmentation in liquid.The novel integrated laser-assisted methodology succeeded in producing Pt_(Х)Y nanoparticles with the ideal size(<10 nm)of commercial Pt catalysts,yet resulting remarkably more active with E_(1/2)=0.943 V vs.RHE,specific activity=1095μA cm^(-2) and mass activity>1000 A g^(-1).At the same time,the nanoalloys are embedded in a fine Pt oxide matrix,which allows a greater stability of the catalyst than the commercial Pt reference,as directly verified on a gas diffusion electrode.

Sulfur-modulated FeNi nanoalloys as bifunctional oxygen electrode for efficient rechargeable aqueous Zn-air batteries

Currently,FeNi nanoalloys have received considerable attention for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)in rechargeable aqueous zinc(Zn)-air batteries(ZABs)because of their high content and good chemical stability.However,their poor electronic conductivity,small surface area,and sluggish activity seriously hinder their catalytic performance.Herein,S-modulated FeNi nanoalloys supported by hierarchically porous carbon(SFeNi/PC)are synthesized through the thermal treatment of metal-organic precursors for efficient bifunctional oxygen catalysis.S decoration endows S-FeNi/PC with a superior OER performance while maintaining an ORR performance that is comparable to that of Pt/C.Hence,S-FeNi/PC exhibits excellent bifunctional oxygen catalytic activity,outperforming the noble-metal-based composite catalysts of Pt/C and RuO_(2).Notably,the ZABs assembled with S-FeNi/PC exhibit high specific capacity(792 mA h g^(-1)),high peak power density(123.5 mW cm^(-2)),and remarkable durability for 700 charge/discharge cycles at 10 mA cm^(-2),which surpasses the performance of commercially available Pt/C-RuOand other catalysts in previously reported studies.This study will provide not only new bifunctional oxygen electrodes for efficient ZAB devices but also new insights into the design of FeNi-based materials for a wide range of catalytic applications.

New understanding of phase segregation of bimetallic nanoalloys

In a recent online publication of Science,Professor Peter Strasser of the Technical University of Berlin,Germany,and his collaborators reported element-specific anisotropic growth of Pt and Ni in shaped Pt alloy synthesis[1].They showed that the surface steps in the Pt3Ni concave hexapod alloy formed in the initial stage of the synthesis were crucial in the segregation of an M-rich(M=Ni,Co,

Nickel Sulfide Modified NiCu Nanoalloy with Excellent Oxygen Evolution Reaction Properties Prepared through Electrospinning and Heat Treatment

Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).

CO oxidation on supported platinum group metal(PGM) based nanoalloys

The oxidation of carbon monoxide is widely investigated for realistic and potential uses in energy production and environmental processes.As a probe reaction to the surface properties,it gives an insight into the relationship between the structure of active phase and catalytic performance.Noble metals alloyed with certain transition metals in the form of a nanoalloy exhibit enhanced catalytic activity for various reactions,especially when simultaneous activation of oxygen and CO is involved.This article highlights some of these insights into nanoalloy catalysts in which platinum group metal(PGM)is alloyed with a second and/or third transition metal(M/M′=Co,Fe,V,Ni,Ir,etc.),for catalytic oxidation of carbon monoxide in a gas phase.Recent studies have provided important insights into how the atomic-scale structures of the nanoalloy catalysts operate synergistically in activating oxygen and maneuvering surface oxygenated species.The exploration of atomic-scale chemical/structural ordering and coordination in correlation with the catalytic oxidation properties based on findings from ex-and in-situ synchrotron X-ray techniques is emphasized;for example,high-energy X-ray diffraction coupled to atomic-pair distribution function and X-ray absorption fine-structure spectroscopic analysis.The understanding of the detailed active sites of the nanoalloys has significant implications for the design of low-cost,active,and durable catalysts for sustainable energy production and environmental processes.

PtCo-based nanocatalyst for oxygen reduction reaction:Recent highlights on synthesis strategy and catalytic mechanism

Oxygen reduction reaction over Pt-based catalyst is one of the most significant cathode reactions in fuel cells.However,low reserves and high price of Pt have motivated researchers worldwide seeking enhanced utilization efficiency and durability by doping non-noble metals to form Pt-based alloy catalysts.Alloying Pt with Co has been recognized as one of the most effective approaches to achieve this goal.PtCo bimetal combination is one of the most promising candidates to synthesize highly efficient catalysts for oxygen reduction reaction(ORR)applications,owing to its relatively more suitable oxygen binding energy for four-electron transfer reactions.Recently,impressive strategies have been developed to fabricate more active and stable PtCo-based multimetallic alloys with tailorable size and morphology.This paper aims to summarize the most recent highlights on the study of the relationship between preparation strategies,morphologies,electroactivities of the PtCo-based catalyst at atomic level and further the relevant reaction mechanism.The challenges and opportunities on the further development of electrocatalysts for fuel cells are included to provide reference for the practical application.

Sub-2 nm mixed metal oxide for electrochemical reduction of carbon dioxide to carbon monoxide

Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.

Antimicrobial Activity against Escherichia coli of Cu-Ni Nanoalloy and Combination of Ag Nanoparticles,Obtained by Different Method

Escherichia coli,is a pathogenic bacterium that causes serious infections,whose therapeutic treatment is threatened by the emergence of multiple resistance to conventional antibiotics.In recent years,metal nanoparticles(NPs)have been studied for their antimicrobial capacity and their possible applications as an alternative to antibiotics against different pathogens.NPs also vary in synthesis techniques;either by chemical,physical and biological methods.The objective of this work was to study the possible antimicrobial capacity of Cu-Ni nanoalloys obtained by a method called citrate-gel.The antimicrobial capacity of the NPs mentioned above was evaluated in vitro by the agar diffusion method.Most of the NPs evaluated showed antibacterial activity against the strain of E.coli studied.When combining chemical and biological NP,synergistic effects are observed with an increase in antibacterial activity in some cases.We can conclude that NPs derived from chemical and biological synthesis could be used as antimicrobials against E.coli and when these are combined,antibacterial effects increase.In the future,these applications of nanomaterials could be used as an alternative to the use of antibiotics against infections that have limited treatments.

Engineering and Optimization of Silicon–Iron–Manganese Nanoalloy Electrode for Enhanced Lithium-Ion Battery

The electrochemical performance of a battery is considered to be primarily dependent on the electrode material. However, engineering and optimization of electrodes also play a crucial role, and the same electrode material can be designed to offer significantly improved batteries. In this work, Si–Fe–Mn nanomaterial alloy(Si/alloy) and graphite composite electrodes were densified at different calendering conditions of 3, 5, and 8 tons, and its influence on electrode porosity, electrolyte wettability, and long-term cycling was investigated. The active material loading was maintained very high(~2 mg cm^(-2)) to implement electrode engineering close to commercial loading scales. The densification was optimized to balance between the electrode thickness and wettability to enable the best electrochemical properties of the Si/alloy anodes.In this case, engineering and optimizing the Si/alloy composite electrodes to 3 ton calendering(electrode densification from 0.39 to 0.48 g cm^(-3)) showed enhanced cycling stability with a high capacity retention of ~100% over 100 cycles.

Controlled Fabrication of Cd-Bi Nanoparticles via Sonochemical Method

A sonochemical method for the direct controlled synthesis of Cd-Bi nanoparticles from a bulk Cd-Bi alloy is introduced. The nanoparticles were found to be monodispersed and the size distribution can be easily controlled by adjusting the ultrasonic power. The formation and the constituent of the as-prepared Cd-Bi nanoparticles were revealed by means of X-ray diffraction, differential thermal analysis and thermogravimetry, transmission electron microscopy, and electron diffraction. It was found that the Cd-Bi eutectic alloy nanoparticles are made of the hexagonal phase of metal cadmium and the rhombohedral phase of metal bismuth. In addition, we also found through tribological tests that the powder has an excellent antiwear property.

Liquid Phase Hydrogenation of <i>p</i>-Chloronitrobenzene on Au-Pd/TiO₂Catalysts: Effects of Reduction Methods

The effects of palladium addition and the reduction methods on Au/TiO2 were investigated. Pd was loaded on TiO2 firstly by incipient-wetness impregnation, Au was then loaded by deposition-precipitation method. The nominal loadings of Au and Pd were 1 wt% and 0.01 wt%. The bimetallic catalysts were reduced by heating at 453 K, by flowing H2 at 423 K, or by NaBH4 at 298 K. The catalysts were characterized by ICP, XRD, TEM, HRTEM, TPR and XPS. Hydrogenation of p-chloronitrobenzene was carried out at 1.2 MPa H2 pressure and 353 K. The results showed that even adding very small amount of Pd could enhance activity and selectivity of p-chloroaniline significantly. Pd and Au formed alloy and Pd could donate partial electron to Au. Pd metal on the surface of alloy could adsorb hydrogen and enhanced the activity. The pretreatment methods did not change particle size significantly, all were below 4 nm. The sample reduced by NaBH4 could have higher concentration of Au0 and sustain small Au particle size, resulting in high activity.

Formation of Copper Nickel Bimetallic Nanoalloy Film Using Precursor Inks

Precursor (Metal-organic decomposition (MOD)) inks are used to fabricate 2D and 3D printed conductive structures directly onto a substrate. By formulating a nanoalloy structure containing multiple metals, the opportunity to modify chemical and physical properties exists. In this paper, a copper-nickel bimetallic nanoalloy film was fabricated by mixing copper and nickel precursor inks and sintering them in vacuum. The individual elemental inks were formulated and characterized using SEM, EDS, and XRD. During thermal processing, elemental copper forms first and is followed by the formation of bimetallic copper-nickel alloy. The encapsulation of the underlying copper by the nickel-rich alloy provides excellent oxidation resistance. No change in film resistance was observed after the film was exposed to an oxygen plasma. Nanoalloy films printed using reactive metallic inks have a variety of important applications involving local control of alloy composition. Examples include facile formation of layered nanostructures, and electrical conductivity with oxidative stability.

Regulating surface electron structure of PtNi nanoalloy via boron doping for high‐current‐density Li‐O2 batteries with low overpotential and long‐life cyclability

The realization of high‐efficiency,reversible,stable,and safe Li‐O2 batteries is severely hindered by the large overpotential and side reactions,especially at high rate conditions.Therefore,rational design of cathode catalysts with high activity and stability is crucial to overcome the terrible issues at high current density.Herein,we report a surface engineering strategy to adjust the surface electron structure of boron(B)‐doped PtNi nanoalloy on carbon nanotubes(PtNiB@CNTs)as an efficient bifunctional cathodic catalyst for high‐rate and long‐life Li‐O2 batteries.Notably,the Li‐O2 batteries assembled with as‐prepared PtNiB@CNT catalyst exhibit ultrahigh discharge capacity of 20510 mA·h/g and extremely low overpotential of 0.48 V at a high current density of 1000 mA/g,both of which outperform the most reported Pt‐based catalysts recently.Meanwhile,our Li‐O2 batteries offer excellent rate capability and ultra‐long cycling life of up to 210 cycles at 1000 mA/g under a fixed capacity of 1000 mA·h/g,which is two times longer than those of Pt@CNTs and PtNi@CNTs.Furthermore,it is revealed that surface engineering of PtNi nanoalloy via B doping can efficiently tailor the electron structure of nanoalloy and optimize the adsorption of oxygen species,consequently delivering excellent Li‐O2 battery performance.Therefore,this strategy of regulating the nanoalloy by doping nonmetallic elements will pave an avenue for the design of high‐performance catalysts for metal‐oxygen batteries.