Recent advances in multi-metallic-based nanozymes for enhanced catalytic cancer therapy

Nanozymes have emerged as a promising alternative to natural enzymes,effectively addressing natural enzymes'inherent limitation.Versatility and potential applications of nanozyme span across various fields,with catalytic tumor therapy being one prominent area.This has sparked significant interest and exploration in the utilization of nanozymes for targeted cancer treatment.Recent advancements in interdisciplinary research,nanotechnology,biotechnology,and catalytic technology have led to the emergence of multi-metallicbased nanozymes,which exhibit tremendous potential for further development.This review focuses on investigating the synergistic effects of multimetallicbased nanozymes,aiming to enhance our understanding of their catalytic activities and facilitate their broader applications.We comprehensively survey the remarkable achievements in the synthesis,catalytic mechanisms,and the latest applications of multi-metallic-based nanozymes in cancer catalytic therapy.Furthermore,we identify the current limitations and prospects of multi-metallic-based nanozymes in the development of new materials and the application of novel technologies,along with the potential challenges associated with catalytic cancer therapy.This review underscores the significance of multi-metallic-based nanozymes and emphasizes the need for continued exploration as well as their potential impact on the development of novel materials and the realization of breakthroughs in catalytic tumor therapy.

Fe-lnduced Electronic Transfer and Structural Evolution of Lotus Pod-Like CoNiFeP_(x)@P,N-C Heterostructure for Sustainable Oxygen Evolution

Transition metal phosphides with metallic properties are a promising candidate for electrocatalytic water oxidation,and developing highly active and stable metal phosphide-based oxygen evolution reaction catalysts is still challenging.Herein,we present a facile ion exchange and phosphating processes to transform intestine-like CoNiP_(x)@P,N-C into lotus pod-like CoNiFeP_(x)@P,N-C heterostructure in which numerous P,N-codoped carboncoated CoNiFeP_(x)nanoparticles tightly anchors on the 2D carbon matrix.Meanwhile,the as-prepared CoNiFeP_(x)@P,N-C enables a core-shell structure,high specific surface area,and hierarchical pore structure,which present abundant heterointerfaces and fully exposed active sites.Notably,the incorporation of Fe can also induce electron transfer in CoNiP_(x)@P,IM-C,thereby promoting the oxygen evolution reaction.Consequently,CoNiFeP_(x)@P,IM-C delivers a low overpotential of 278 mV(vs RHE)at a current density of10 mA cm^(-1)and inherits excellent long-term stability with no observable current density decay after 30 h of chronoamperometry test.This work not only highlights heteroatom induction to tune the electronic structure but also provides a facile approach for developing advanced and stable oxygen evolution reaction electrocatalysts with abundant heterointerfaces.

Two Isostructural Multi-metal Borates: Syntheses, Crystal Structures and Characterizations of M_3LiNa_4Be_4B_(10)O_(24)F(M = Sr, Cd)

Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallography. The compounds crystallize in the trigonal space group R 3, with a = b = 9.4645（1） A, c = 38.842（8） A, V = 3013.2（6） A3, Z = 6, F（000） = 2568, Dc = 3.005 g/cm^3, Mr = 908.9, R = 0.0327, w R = 0.0678, μ = 8.160 mm-1 for Sr3 Li Na4Be4B10O24F and a = b = 9.3019（8） A, c = 37.782（7） A, V = 2831.12（9） A3, Z = 6, F（000） = 2748, Dc = 3.459 g/cm^3, Mr = 983.24, R = 0.0158, w R = 0.0455, μ = 3.586 mm-1 for Cd3 Li Na4Be4B10O24F. The structures are characterized by an infinite two-dimensional [Be8B16O40F2]∞ double layer bridged by [B12O24] groups like a sandwich structure, while the cations reside in tunnels along different directions. UV-vis-IR diffuse reflectance spectroscopy demonstrates that their cut-off edges are below 200 nm. Thermal analysis shows that they melt incongruently and their melting points are around 740-770 ℃.

Dissolution kinetics of copper from multi-metal copper alloy roasted in oxygen

A kinetic study on the sulfuric acid leaching of multi-metal oxide, which is the product of multi-metal copper alloy with iron trioxide roasted in oxygen, was carried out. The effects of leaching time, stirring speed, sulfuric acid concentration, reaction temperature, and particle size of the multi-metal oxide on the kinetics and mechanism of copper extraction were studied. It was found that the reaction kinetic model about the copper extraction from multi-metal oxide follows the mixed kinetic shrinking core mode： 1/31n（1-X）＋（1-X）-l/3-1=680.5C（H2SO4）0.4297dp0.75115exp（-Ea/RT）t.

Performance tests of multi-metal zincate solutions with zinc sulfate and zinc oxide

Morphology of zinc alloy layer,from zincate solution with zinc sulfate and zinc oxide respectively,together with the consequent deposit was observed with SEM and back scattering electron image.EDS was applied to analyze the components of zinc alloy layer and the interface of high-Si aluminum alloy substrate-zinc alloy-deposit.Besides,the surface morphology of the zincated aluminum alloy after immersing in 3.5% NaCl solution for 7 d,is observed and the corrosion rate was calculate.Finally,tension test is conducted to quantify the adhesion between high-Si aluminum cast substrate and the deposit.The results show that,the zinc oxide contained zincating solution with sodium potassium tartrate and sodium citrate is a better one in multi-metal zincating solutions.The zinc alloy layer from this one gets stable performance,perfect adhesion with deposit,and good corrosion resistance.

Harnessing dimethyl ether and methyl formate fuels for direct electrochemical energy conversion

In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.

MOF-derived Zn-Co-Ni sulfides with hollow nanosword arrays for high-efficiency overall water and urea electrolysis

Water electrolysis is a promising technology to produce hydrogen but it was severely restricted by the slow oxygen evolution reaction(OER).Herein,we firstly reported an advanced electrocatalyst of MOF-derived hollow Zn-Co-Ni sulfides(ZnS@Co_(9)S_(8)@Ni_(3)S_(2)-1/2,abbreviated as ZCNS-1/2)nanosword arrays(NSAs)with remarkable hydrogen evolution reaction(HER),OER and corresponding water electrolysis performance.To reach a current density of 10 mA cm^(-2),the cell voltage of assembled ZCNS-1/2//ZCNS-1/2 for urea electrolysis(1.314 V)is 208 mV lower than that for water electrolysis(1.522 V)and stably catalyzed for over 15 h,substantially outperforming the most reported water and urea electrolysis electrocatalysts.Density functional theory calculations and experimental result clearly reveal that the properties of large electrochemical active surface area(ECSA)caused by hollow NSAs and fast charge transfer resulted from the Co_(9)S_(8)@Ni_(3)S_(2) heterostructure endow the ZCNS-1/2 electrode with an enhanced electrocatalytic performance.

Attapulgite nanorods assisted surface engineering for separator to achieve high-performance lithium–sulfur batteries

Lithium-sulfur(Li-S)batteries have been recognized as one of the most promising candidates for nextgeneration portable electronic devices,owing to their extremely high energy density and low cost.However,the dissolution of lithium polysulfides(LiPSs)and consequent"shuttle effect"seriously hinder the practical deployment of Li-S batteries.Herein,multi-metal oxide nanorods named attapulgite are proposed as multifunctional ionic sieve to immobilize LiPSs and further promote the regulation of LiPSs.Attapulgite,consisting of Al,Mg,Fe,Si and O ions,possesses more polar sites to immobilize LiPSs in comparison with single metal oxides.In addition,the catalytic nature(Fe ions)of attapulgite avails the LiPSs conversion reaction,which is further confirmed by the linear sweep voltammetry and electrochemical impedance spectroscopy.Benefited from the synergistic effect of multi-metal oxide and conductive carbon,the Li-S battery with the modified separator delivers remarkable discharge capacities of 1059.4 mAh g-1 and 792.5 mAh g-1 for the first and 200th cycle at 0.5 C,respectively.The work presents an effective way to improve the electrochemical performance of Li-S batteries by employing attapulgite nanorods assisted separator surface engineering.

Electrochemical tests on zincating solution with zinc sulfate and zinc oxide

In order to find out a multi-metal zincate solution to get good micromorphology and fine adhesion of coatings, sulfate zincate and zinc oxide zincate with different chelating agents combinations, of which there are 8 solutions are designed. CHI630 electrochemical test system is applied to measure the φ—t curves of zincate process and Tafle curves of zincated plates in 3.5% NaCl medium. The analyzed results show that when molar ratio of sodium hydroxide to zinc ions is constant, the better chelating agents combination for multi-metal zincation solution is the combination of sodium potassium tartrate and sodium citrate in zinc oxide solution, from which zinc alloy is high in potential and perfect in corrosion resistance. After the second zincate immersion for 60s, the immersion potential is -1.606V(vs SCE). The corrosion current density is 6.612, J_ corr/(A·cm -2); and the corrosion potential is -1.381, φ_ corr(I=0)/V.

Highly efficient multi-metal catalysts for carbon dioxide reduction prepared from atomically sequenced metal organic frameworks

The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.

Interfacial Features of Stainless Steel/Titanium Alloy Multi-metal Fabricated by Laser Additive Manufacturing

Laser additive manufacturing(LAM)is promising for fabricating multi-metallic component,but the mechanism of microstructural evolution at the interface of two metals is still needed to research further.In this study,a 316L stainless steel/Ti6Al4V alloy multi-metal was fabricated by LAM,and the mechanism of intermetallic phase transformation was deeply investigated.Results show that a strong reaction zone(SRZ)can be induced at the interface of the multi-metal.The phase constituents at the SRZ vary fromχ(Ti_(5)Fe_(17)Cr_(5))+Fe_(2)Ti+α′-Ti+β-Ti or FeTi to Fe_(2)Ti+χwhen the laser power is increased.When the scanning speed is further decreased,the thickness of the SRZ is significantly increased,andα′-Ti phase is also formed at this region besides Fe_(2)Ti andχphases.Moreover,the micro-hardness at the SRZ is increased,caused by the intermetallic phase transformation and elemental interdiffusion at the interface.

Bioinspired Multi-Metal Structures Produced via Direct Ink Writing

Bioinspired Multi-Metal Structures(MMSs)combine distinct properties of multiple materials,benefiting from improved properties and providing superior designs.Additive Manufacturing(AM)exhibits enormous advantages in applying different materials and geometries according to the desired functions at specific locations of the structure,having great potential in fabricating multi-materials structures.However,current AM techniques have difficulty manufacturing 3D MMSs without material cross-contamination flexibly and reliably.This study demonstrates a reliable,fast,and flexible direct ink writing method to fabricate 3D MMSs.The in-situ material-switching system enables the deposition of multiple metallic materials across different layers and within the same layer.3D Fe-Cu MMSs with complex geometries and fine details are fabricated as proof of concept.The microstructures,chemical and phase compositions,and tensile fracture surfaces of the Fe-Cu interfaces indicate a well-bonded interface without cracks,delamination,or material cross-contamination.We envision this novel method making other metallic combinations and even metal-ceramic components.It paves the way for manufacturing 3D MMSs using AM and establishes the possibilities of numerous MMSs applications in engineering fields.

Ternary ZnO/Co_(3)O_(4)/NiO inherited layered core-shell structure from a double template for high performanced supercapacitor

Relying on seed method,a double template ZIF-8@ZIF-67 with a layered core-shell structure was made,which is used as a sacrificial template in the next steps.After going through loading process with solvent thermal method and calcination process,ZIF-8@ZIF-67 was etched and calcined into ternary ZnO/Co_(3)O_(4)/NiO successfully.Besides,benefiting from right amount of the addition of inorganic salts,the optimized ZnO/Co_(3)O_(4)/NiO-2(ZCN-2)shows the outstanding performance in its morphologic structure and electrochemical performance.In the case of a current density of 1 Ag^(-1),the high specific capacitance of 1119.11 Cg^(-1) can be calculated in ZCN-2.In addition,at 10 Ag^(-1),the capacitance value can maintain 93.75%after experiencing 5000 cycles of charging and discharging.The maximum energy density of the assembled ZCN-2//activated carbon(AC)asymmetric supercapacitor can reach 95.82 Wh kg^(-1),which is really outstanding in the present research achievements.After experiencing charge-discharge cycles with the number of 10,000 times in the case of a current density of 10 Ag^(-1),the cycling stability of this supercapacitor can reach 94.53%of the initial value.And after a charge,the device connected by two supercapacitors can make a light emitting diode(LED)shine up to 30 min successfully.

Metallic wastewater treatment by sulfate reduction using anaerobic rotating biological contactor reactor under high metal loading conditions

This study was aimed at investigating the performance of anaerobic rotating biological cont- reactor treating synthetic wastewater containing a mixture of heavy metals under sulfate redu condition. Statistically valid factorial design of experiments was carried out to understand dynamics of metal removal using this bioreactor system. Copper removal was maximum （〉98% followed by other heavy metals at their respective low inlet concentrations. Metal loading rates than 3.7 mg/L· h in case of Cu（II）; less than 1.69 mg/L· h for Ni（II）, Pb（II）, Zn（II）, Fe（III） and C are favorable to the performance of the An-RBC reactor. Removal efficiency of the heavy metals 1 mixture depended on the metal species and their inlet loading concentrations. Analysis of n precipitates formed in the sulfidogenic bioreactor by field emission scanning electron microscopyalong with energy dispersive X-ray spectroscopy （FESEM-EDX） confirmed metal sulfide precipitationby SRB. All these results clearly revealed that the attached growth biofilm bioreactor is well suited for heavy metal removal from complex mixture.