Catalytic effect in lithium metal batteries: From heterogeneous catalyst to homogenous catalyst

Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Synthesis of Co Nanoparticles and Their Catalytic Effect on the Decomposition of Ammonium Perchlorate

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.

Catalytic Effect of Activated Carbon and Activated Carbon Fiber in Non-Equilibrium Plasma-Based Water Treatment

Catalysis and regeneration efficiency of granular activated carbon （GAC） and activated carbon fiber （ACF） were investigated in a non-equilibrium plasma water treatment reactor with a combination of pulsed streamer discharge and GAC or ACF. The experimental results show that the degradation efficiency of methyl orange （MO） by the combined treatment can increase 22% （for GAC） and 24% （for ACF） respectively compared to pulsed discharge treatment alone, indicating that the combined treatment has a synergetic effect. The MO degradation efficiency by the combined treatment with pulsed discharge and saturated GAC or ACF can increase 12% and 17% respectively compared to pulsed discharge treatment alone. Both GAC and ACF show catalysis and the catalysis of ACF is prominent. Meanwhile, the regeneration of GAC and ACF are realized in this process. When H202 is introduced into the system, the utilization efficiency of ozone and ultraviolet light is improved and the regeneration efficiency of GAC and ACF is also increased.

THE PREPARATION OF ISOPOLYMOLYBDIC ACID-POLYANILINE FILM MODIFIED ELECTRODE AND ITS CATALYTIC EFFECTS ON CHLORATE IONS

The preparation method of H_4MoO_(26)-polyaniline film modified electrode and its voltammetric behaviour are described. The modified electrode has high electrocatalytic activity on chlorate ions.

Catalytic Effect of SCN^- on Electrodeposition of Zinc-Nickle Alloy

The electrodeposition of zinc nickle alloy was obtained on a copper cathode of 1×1cm 2. The deposited alloys are quantitatively analyzed by atomic absorption spectrometry. The morphology of the deposits was observed by means of scanning electron microscopy(SEM).We observed that the electrodeposition of zinc nickle alloy is an anomalous codeposition. The catalytic effects of SCN - on the electrochemical behavior of Ni deposition and hydrogen discharge are obvious. SEM analysis shows that the surface morphology of the coating appears to be more compact and homogeneous with the increase of SCN - concentration.

Kinetics of Carbothermic Reduction of MnO_2 and Catalytic Effect of La_2O_3

Kinetics of carbothermic reduction of manganese oxide and the catalyticeffect of La_2O_3 on the reduction have been studied by the measurement of mass loss in N_2atmosphere at different temperatures and followed by SEM analysis. It is concluded that the kineticsof carbothermic reduction of manganese oxide is divided into three stages: gas diffusioncontrolling stage, carbon gasification con-trolling stage and solid state diffusion controllingstage. La_2O_3 has catalytic effect on the reduction. The catalytic effect of La_2O_3 increases withthe added amount of La_2O_3. SEM analysis shows that the catalytic mechanism is that La_2O_3promotes the transfer of oxygen ions so that carbon gasifying is catalyzed and thus carbothermicreduction of MnO_2 is catalyzed.

Catalytic Effect Analysis of Metallic Catalyst During Diamond Single Crystal Synthesis

By transition metals （Fe, Ni, Mn, Co） and their alloys as catalysts during the diamond synthesis, some transition phases will be formed, such as FeaC type carbides and y solid solutions. Based on the empirical electron theory of the solid and molecules, the valence electron structures of different kinds of carbides and y solid solutions and the relative electron density differences of various diamond/carbide and y solid solution/carbide interfaces were calculated and analyzed in this paper. The electron structure conditions of the ideal catalyst were presented by analyzing the different catalytic effects of the catalysts, which provide a new theoretical path to the optimal design of the catalyst composition

Catalytic effect of carbon-based electrode materials in energy storage devices

The catalytic effect of electrode materials is one of the most crucial factors for achieving efficient electrochemical energy conversion and storage.Carbon-based metal composites were widely synthesized and employed as electrode materials because of their inherited outstanding properties.Usually,electrode materials can provide a higher capacity than the anticipated values,even beyond the theoretical limit.The origin of the extra capacity has not yet been explained accurately,and its formation mechanism is still ambiguous.Herein,we first summarized the current research progress and drawbacks in energy storage devices(ESDs),and elaborated the role of catalytic effect in enhancing the performance of ESDs as follows:promoting the evolution of the solid electrolyte interphase(SEI),accelerating the reversible conversion of discharge/charge products,and improving the conversion speed of the intermediate and the utilization rate of the active materials,thereby avoiding the shuttling effect.Additionally,a particular focus was placed on the interaction between the catalytic effect and energy storage performance in order to highlight the efficacy and role of the catalytic effect.We hope that this review could provide innovative ideas for designing the electrode materials with an efficient catalytic effect for ESDs to promote the development of this research field.

Assessment of the Catalytic Effects of Transforming Industrial Heritage:Case Study of Sanbao Street Industrial Historic District in Changzhou

Transforming industrial heritage will have internal economic and cultural effects and will also catalyse changes in surrounding urban areas.Transforming industrial heritage is therefore an essential part of strategies to regenerate decayed industrial districts.The aim of this study was to attempt to answer three questions.Can all transformed industrial heritage give catalytic effects?How should the potential for catalytic effects be assessed?What factors prevent catalytic effects?The Sanbao Street Industrial Heritage Historic District in Changzhou,China,was used as an example,and three effects catalysed by transforming industrial heritage were assessed.These were(1)reuse of industrial and non-industrial buildings in and near the historic district,(2)new construction in and near the historic district,and(3)revitalisation of the whole historic district.Failure of the catalytic effect caused by a lack of a conversion mechanism,failure to communicate the value of industrial heritage,and limited cultural industrial capacity was assessed.Formal transformation strategies focused on the connotative value of industrial heritage are proposed,and are expected to support future research and planning practices.

A novel route to synthesize diphenylene by the catalytic effect of GaP nanocrystals

Diphenylene was synthesized directly from benzene under the catalytic effect of GaP nanocrystals, and the effect of GaP nanocrystals content was studied. The experimental results showed that no reactions took place without GaP nanocrystals. The more the GaP nanocrystals added, the more the reaction complete. Furthermore, at high temperatures (450–480°C), when the content of GaP nanocrystals was high enough, almost all benzene polymerized and the yield of diphenylene was rather high. On the contrast, even if there are enough GaP nanocrystals in the reaction mixture, almost no polymerization reaction took place at low temperature (for example, 250–300°C), and the yield of diphenylene was very poor. The analytical results of XRD, IR, elemental analysis and NMR proved that the sample was truly diphenylene.

Catalytic mechanism of in-situ Ni/C co-incorporation for hydrogen absorption of Mg

Ni and carbon materials exhibit remarkable catalysis for the hydriding reaction of Mg.But the underlying mechanism of Ni/C hybrid catalysis is still unclear.In this work,density functional theory(DFT)calculation is applied to investigate the effect of Ni/C co-incorporation on the hydriding reaction of Mg crystal.The morphology and crystal structure of the Ni/C co-incorporated Mg sample show that the coincorporated structure is credible.The transition state searching calculation suggests that both the incorporations of Ni and C are beneficial for the H_(2) dissociation.But Ni atom has a dramatic improvement for H_(2) dissociation and makes the H diffusion become limiting step of the hyriding reaction.The Ni dz_(2)orbit and H s orbit accept the electrons and combine together compactly,while the Ni d_(xy) orbit is half-occupied.The catalytic effect of Ni on H_(2) dissociation can be ascribed to the bridging effect of Ni d_(xy) orbit.The incorporation of C can weaken the over-strong interaction between Ni and H which hindered the H diffusion on Mg(0001).The Ni/C co-incorporated Mg(0001)shows the best performance during hyriding reaction compared with the clean and single incorporated Mg(0001).

ELECTROCARBOXYLATION OF ORGANIC COMPOUNDS WITH CARBON DIOXIDE CATALYZED BY METALLOPORPHYRINS(Ⅲ)——EFFECTS OF AXIAL LIGANDS ON CATALYTIC ACTIVITY OF CoTPP

The effects of peptides,amino acids and organic bases as an axial ligand on reaction ac- tivities in the electrocarboxylation of benzyl chloride with CO_2 catalyzed by CoTPP are reported. The imidazole organic base,peptide containing —SH and amino acid containing imidazolyl en- hance the catalytic activity.The effect of imidazole amounts on the catalytic activity of CoTPP is studied.

Ag-Ni alloy nanoparticles for electrocatalytic reduction of benzyl chloride

Ag-based nanocatalysts exhibit good catalytic activity for the electrochemical reduction of organic halides. Ag-Ni alloy nanoparticles（NPs） were facilely prepared by chemical reduction, and the as-prepared nanocatalysts were characterized by X-ray diffraction, ultraviolet-visible spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The electrocatalytic activity of Ag-Ni NPs for benzyl chloride reduction was studied in organic medium using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results show that the addition of Ni element can obviously decrease the size of Ag-Ni NPs, shift the reduction peak potential（φp） of benzyl chloride positively, and increase the catalytic activity of Ag-Ni NPs. However, when the Ni content reaches a certain value, the catalytic activity of Ag-Ni NPs decreases. Meanwhile, the synergistic catalytic effect of Ag-Ni NPs was also discussed.

In Situ Coupling of Highly Dispersed Ni/Fe Metal-NC Sites and N-Doped 3D Carbon Fibers Toward Free-Standing Bifunctional Cathode for Flexible Zinc-Air Battery

Designing flexible free-standing air-electrode with efficient OER/ORR performance is of vital importance for the application of Zinc-air batteries in flexible electronics.Herein,a flexible free-standing electrode(Ni/Fe-NC/NCF/CC)is synthesized by in-situ coupling of binary Ni/Fe-NC nanocubes and N-doped carbon nanofibers(NCF)rooted on carbon cloth.The highly dispersed binary Ni/Fe-NC sites ensure excellent ORR activity and create efficient OER active sites relative to Ni-NC and Fe-NC.The in-situ coupling of Ni/Fe-NC and NCF constructs a 3D interconnected network structure that not only provides abundant and stabilized reactive sites but also guarantees fast electron transfer and gas transportation,thus achieving efficient and fast operation of ORR/OER.Therefore,Ni/Fe-NC/NCF/CC displays a much positive potential(0.952 V)at 4.0 mA cm^(-2)for ORR and a low OER overpotential(310 mV)at 50 mA cm^(-2).The Zinc-air battery with Ni/Fe-NC/NCF/CC air-electrode exhibits excellent battery performance with outstanding discharge/charge durability for 2150 cycles.The flexible Zn-air batteries with foldable mechanical properties display a high power density of 105.0 mW cm^(-2).This work widened the way to prepare flexible bifunctional air-electrode by designing composition/structure and in-situ coupling.

The effect of K2SiF6 on the MgH2 hydrogen storage properties

The catalytic effect of K2SiF6 on MgH2 was first timely studied.The MgH2+5 wt.%K2SiF6 was prepared via the ball milling technique.The catalyst had lessened the initial decomposition temperature by 134℃ and 48℃ as compared to both pristine and milled MgH2 samples,respectively.In 2 minutes,4.5 wt.%of hydrogen was absorbed(250℃)by the doped composite,which was 0.8 wt.%higher than the milled MgH2.Meanwhile,for the desorption kinetics(320℃,1 atm),the amount of desorbed hydrogen was increased by 2.4 wt.%and 2.3 wt.%for the first 10 and 20 minutes.Besides,contracting volume and Johnson-Mehl-Avrami models were used to analyse the kinetics sorptions.The decomposition activation energy calculated based on Kissinger equation was 114 kJ/mol.As for the active species,Mg2Si,MgF2 and KH were formed during the heating process.These active species are speculated to be responsible for the improvement of the hydrogenation properties of the composite.

Measurement of Trace Manganese(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method is developed for the measurement of manganese(Ⅱ) in water. The method is based on the catalytic effect of manganese(Ⅱ) with the oxidation of weak acid brilliant blue dye(RAWL) by KIO4 using the Nitrilo triacetic acid(NTA) as an activation reagent. The optimum conditions obtained are 40 mgL-1 RAWL,1×10-4molL-1 KIO4,2×10-4 molL-1 Nitrilo triacetic acid(NTA),pH = 5.8,the reaction time of 3.00 min and the temperature of 20.0 ℃. Under the optimum conditions,the proposed method allows the measurement of manganese(Ⅱ) in a range of 0-50.0 ng mL-1 and with a detection limit of down to 0.158 ng mL-1. The recovery efficiency in measuring the standard manganese(Ⅱ) solution is in a range of 98.5%-102%,and the RSD is in a range of 0.76%-1.25%. The new method has been successfully applied to the measurement of manganese(Ⅱ) in both fresh water and seawater samples with satisfying results. Moreover,few cations and anions interfere with the measurement of manganese(Ⅱ). Compared with other kinetic catalytic methods and instrumental methods,the proposed method shows fairly good selectivity and sensitivity,low cost,cheapness,low detection limit and rapidity. It can be applied on boats easily.

Catalytic Mechanism of KCl during Carbothermic Reduction of Pre-Oxidized Ilmenite

As alkali additive,KC1 catalyzes effectively the carbothermic reduction of pre-oxidized ilmenite,and the catalytic effect becomes more remarkable as the amount of KC1 increases.During the carbothermic reduction,the gaseous product consists mainly of CO,and the partial pressure of which increases with reaction temperature.The EPMA and XPS of the partially reduced ilmenite ore and that of the used graphite as reductant showed that the potassium ions enter both ilmenite particles and graphite powders during reduction.The above-mentioned phenomena result in the distortion of ilmenite and carbon structure by potassium ions and reaction activity of carbon and ilmenite was enhanced.As a result,the overall carbothermic reduction was catalyzed by KC1.

A novel indicator system for catalytic spectrophotometric determination and speciation of inorganic selenium species (Se(Ⅳ), Se(Ⅵ)) at trace levels in natural lake and river water samples

A novel catalytic kinetic method is proposed for the determination of Se（Ⅳ）, Se（Ⅵ）, and total inorganic selenium in water based on the catalytic effect of Se（Ⅳ） on the reduction of Celestine blue by sodium sulfide at pH 7.0 phosphate buffer. The fixed-time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the two calibration graphs are linear with a good correlation coefficient in the range 2-20 and 20-200 μg·L-1 of Se（Ⅳ） for the fixed-time method at 30℃. The experimental and theo- retical detection limits of the developed kinetic method were found to be 0.21 and 2.50 μg·L-1 for the fixed-time method （3 min）. All of the variables that affect the sensitivity at 645 nm were investigated, and the optimum conditions were established. The interference effect of various cations and anions on the Se（Ⅳ） determination was also studied. The selectivity of the selenium determination was greatly improved with the use of the strongly cation exchange resin such as Amberlite IR120 plus as long as chelating agents of thiourea and thiosulphate. The proposed kinetic method was validated statistically and through recovery studies in natural water samples. The relative standard deviations （RSDs） for ten replicate measurements of 2, 10, and 20 μg·L-1 of Se（Ⅳ） change between 0.35% and 5.58%, while the RSDs for ten replicate measurements of 3, 6, and 12 μg·L-1 of Se（Ⅵ） change between 0.49% and 1.61%. Analyses of a certified standard reference material （NIST SRM 1643e） for selenium using the fixed-time method showed that the proposed kinetic method has good accuracy. The Se（Ⅳ）, Se（Ⅵ）, and total inorganic selenium in lake and river water samples have been successfully determined by this method after selective reduction of Se（Ⅵ） to Se（Ⅳ）.

Catalytic-kinetic spectrophotometric determination of vanadium (V) based on the Celestine blue-bromate-vanadium (V)-citric acid reaction

A novel sensitive and relatively selective kinetic method is presented for the determination of V（V） based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator. The reaction was monitored spectropho- tometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min （the fixed-time method） in an H3PO4 medium at 45℃. The effect of various parameters such as concentrations of H3PO4, citric acid, potassium bromate and Celestine blue, ionic strength, reaction temperature and time on the rate of V（V） catalyzed reaction was studied. The method is free from the most interferences, especially from large amounts of V（IV）. The decrease in absorbance is proportional to the concentration of V（V） over the entire concentration range tested （0.025-1.25 lag.mL^-1） with a detection limit of 6.80 tag.L^-1 （according to statistical 3Sblank/k criterion） and a coefficient of variation （CV） of 1.78% （for ten replicate measurements at 95% confidence level）. The proposed method suffers from a few interferences such as Cr（VI） and Hg（Ⅱ） ions. The method was successfully applied to the determination of V（V） in river water, lake water, tap water, natural drinking water samples and a certified standard reference material such as SRM-1640 with satis- factory results. The vanadium contents of natural water samples were detected by using both linear calibration curve and standard addition curve methods. The recoveries of spiked vanadium （V） into the certified standard water sample were found to be quantitative, and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.