Plasma treated M1 MoVNbTeO_(x)-CeO_(2) composite catalyst for improved performance of oxidative dehydrogenation of ethane

High activity and productivity of MoVNbTeO_(x) catalyst are challenging tasks in oxidative dehydrogenation of ethane(ODHE)for industrial application.In this work,phase-pure M1 with 30 wt%CeO_(2) composite catalyst was treated by oxygen plasma to further enhance catalyst performance.The results show that the oxygen vacancies generated by the solid-state redox reaction between M1 and CeO_(2) capture active oxygen species in gas and transform V^(4+)to V^(5+)without damage to M1 structure.The space-time yield of ethylene of the plasma-treated catalyst was significantly increased,in which the catalyst shows an enhancement near~100% than that of phase-pure M1 at 400℃ for ODHE process.Plasma treatment for catalysts demonstrates an effective way to convert electrical energy into chemical energy in catalyst materials.Energy conversion is achieved by using the catalyst as a medium.

Synthesis and Photocatalytic Activity of TiO_2/V_2O_5 Composite Catalyst Doped with Rare Earth Ions

TiO2/V2O5 catalyst doped with rare earth ions was prepared by sol-gel method. Titanium tetrapropoxide and vanadium pentoxide were used as precursor of the composite catalyst and rare earth ions were used as dopant. The crystal phases, crystalline sizes, microstructure, absorption spectra of doped composite catalyst were studied by XRD, EDS, FT-IR and UV-Vis. Photoactivity of the prepared catalyst under ultraviolet irradiation were evaluated by degradation of methyl orange （MO） in aqueous solution. It is shown that the prepared catalyst is composed of anatase and futile. The rare earth ions are highly dispersed in composite catalyst. All the doped catalysts appear higher photocatalytic activity than TiO2/V2O5 catalyst and catalyst doped with Ce^4＋ present the best activity to MO.

Improved ethane conversion to ethylene and aromatics over a Zn/ZSM-5 and CaMnO^(3-δ) composite catalyst

Ethane conversion to ethylene and aromatics over Zn/zeolite catalysts is a promising technology for efficient exploitation of light alkanes. However, the reaction faces two major hurdles including the limited ethane conversion due to thermodynamics and the drastic catalyst deactivation by kinetical coke accumulation. Here we present a route to improve ethane conversion using a composite catalyst, involving Zn/HZSM-5 for ethane dehydroaromatization and CaMnO3-δperovskite for in situ selective hydrogen oxidation. The in situ H2 consumption shifts ethane dehydrogenation equilibrium to the desired side and can obviously increase the yield of target product. Furthermore, it is found that the in situ generated H2 O through H2 combustion can significantly suppress the coke formation and consequently enhance the stability of the composite catalyst. After 400 min reaction, a product yield of 23% was retained over the composite catalyst, almost a threefold increase with respect to the Zn/HZSM-5 reference(8%). It is anticipated that this novel composite catalyst combined with an efficient reactor technology may improve the viability of ethane aromatization in utilization.

Photocatalytic degradation of imidacloprid by composite catalysts H_3PW_(12)O_(40)/La-TiO_2

A series of La-doped TiO2 with different mass fractions were prepared by sol-gel method. Composite catalysts H3PW12O40/La-TiO2 with different loading levels were synthesized using impregnation method. The prepared samples were charac- terized by foutler transform infrared spectroscopy （FT-IR）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, UV vis diffuse reflectance spectroscopy （DRS） and nitrogen adsorption-desorption analysis. The Keggin structure of H3PWI2040 （HPW） re- mained intact on the surface of the composites, they had relatively uniform spherical grains of diameter less than 20 nm. The visible light activity of prepared composites were improved by loading HPW and doping La. The prepared composites were used as photo- catalysts in degradation of pesticide imidacloprid. Results revealed that 20%H3PWL204o/0.3%La-TiO2 possessed the best photocata- lyric activity. Thus, the degradation conversion of imidacloprid reached 98.17% after 60 rain irradiation when 20%H3PW12O4/0.3% La-TiO2 was used as catalysts. The degradation of imidacloprid corresponded with first-order kinetic reaction, and the half life of the degradation of imidacloprid was 9.35 min in the optimal conditions.

Synthesis of La_2MoO_6@MWCNTs composite catalysts as Pt-free counter electrodes for dye-sensitized solar cell

Pt-free counter electrode(CE) composed of La2 MoO(LaO-MoO) was successfully synthesized by simple pyrolysis of lanthanum acetate(CHOLa·xHO) and hexaammonium heptamolybdate tetrahydrate((NH4)6 MoO·4 HO). Furthermore,three proportions composites catalysts of La2 MoO@MWCNTs based on La2 MoOand multiwall carbon nanotubes(MWCNTs) were prepared and characterized as Ptfree catalyst for CE in dye-sensitized solar cells(DSSCs). The morphology and structure of La2 MoO@MWCNTs composites were determined by scanning electron microscopy, transmission electron microscope and X-ray diffraction. The electrochemical performance of La2 MoO@MWCNTs composite catalysts for CEs was determined by photocurrent-voltage measurements, cyclic voltammetry,electrochemical impedance spectroscopy, and Tafel polarization. The power conversion efficiencies of4.68%, 4.87% and 5.06% are obtained for La2 MoO:MWCNTs with the mass ratios of 5:1, 3:1 and 1:1 towards the reduction of I~-to I~-under the same conditions,respectively,which are superior to those of MWCNTs(3,94%) and La2 MoO(1.71%) electrodes. The experimental results reveal that the presence of MWCNTs results in an augmented active catalytic surface area and enhanced charge transfer from CE to the electrolyte.

Preparation and reaction mechanism of novel Ce_(x)Co_(y)Cuz oxide composite catalysts towards oxidation of o-xylene

Ce_(x)Co_(y)Cuzoxide composite catalysts were prepared by using polyethylene glycol, citrate sol-gel method combined with PMMA template for the oxidation of o-xylene. The catalysts were characterized by the Xray diffraction(XRD), H2-temperature programmed reduction(H2-TPR), X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared spectroscopy(FT-IR), etc. The catalytic activity for o-xylene was investigated. The catalytic degradation pathway and mechanism of o-xylene were inferred. The results show that Ce O_(2)is mainly present on the surface of all catalysts. The surface area of Ce_(2)Co1Cu1is up to 77.2 m^(2)/g, and the average pore size is 10.62 nm. It exhibits redox and sufficient Ce^(4+)and Ce^(^(3+)), and reactive oxygen species, and has maximum O-H and C=O in the five catalyst samples. The catalytic activity of Ce2Co1Cu1is the best at low temperature, with the T50and T90values of 235 and 258°C at a space velocity of 32000 h-1, respectively. The o-xylene is oxidized to o-methyl benzaldehyde, and then further oxidized to o-methylbenzoic acid, and finally CO_(2)and H2O are formed.

SYNTHESIS AND PROPERTIES OF A NOVEL COMPOSITE ZSM-5 ZEOLITE/VERMICULITE CATALYST

The composite ZSM—5 zeolite/vermiculite catalyst,in which tiny ZSM—5 zeolite parti- cles embedded in the vermiculite substrate,has been synthesized by hydrothermal method with vermiculite as silicon source.The catalytic behavior of resulting catalyst for xylene isomerization,propylene aromatization and toluene disproportionation is better than that of HZSM—5 zeolite.

Preparation and characterization of the TiO_2-V_2O_5 photocatalyst with visible-light activity

Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline （PANI） by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 dusters during the calcination process was avoided because of the wrap of polyaniline. The surface mor- phology, the crystal phases, the structure, and the absorption spectra of （PANI）,/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FT-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue （MB） solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2： V2O5 = 10：1 presented the best photocatalytic activity.

Synthesis and study of λ-MnO_2 supported Pt nanocatalyst for methanol electro-oxidation

A λ-MnO2 supported Pt nanocatalyst（5 wt.% Pt/λ-MnO2） was synthesized using a facile approach.X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, scanning electronic microscope（SEM）, transmission electron microscopy（TEM）, and energy disperse spectroscopy（EDS） were used for catalyst structure and morphology characterization, which showed that the metallic Pt particles were attached on a λ-MnO2 surface through the interaction between Pt and λ-MnO2.Cyclic voltammetry（CV） was used to test the catalytic activity of Pt/λ-MnO2 toward methanol oxidation, which showed that Pt/λ-MnO2 catalyst has much higher catalytic activity than baseline Pt/C catalyst.

Insight into the boosted activity of TiO2–CoP composites for hydrogen evolution reaction:Accelerated mass transfer,optimized interfacial water,and promoted intrinsic activity

The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.

Polymer-encapsulated metal complex catalysts:An emerging and efficient platform for electrochemical CO_(2) reduction

Over the past decade,electrocatalytic reduction of CO_(2)has gained substantial attention.However,hardly any of the previous reviews have focused on the systematic discussion of polymer-molecular catalyst composites as an emerging system for the electrochemical transformation of CO_(2)to value-added products.In this review,we first give a brief overview of the general features of solid-state and molecular catalysts,and then advance the discussion to polymer-catalyst composite systems,with particular emphasis on polymer-encapsulated molecular catalysts,where the coordination environment surrounding molecular catalysts can be modified via polymer encapsulation to promote the overall performance of CO_(2)electrocatalysis.The elucidation of the possible reaction mechanisms of this emerging electrocat-alytic system along with proposed optimization strategies is also summarized and discussed based on recently published reports,followed by the challenges and prospects of their industrial applications at the end of this review.From this review,we hope the audience can gain a comprehensive understanding of the electrocatalytic mechanism of the coordinating polymers and valuable insights into engineering the microenvironment surrounding the metal complexes for potential future research directions.

丁基多苷合成的影响因素探讨及其合成动力学研究(英文)

[ Objective ] The paper was to study the factors influencing the synthesis of butyl polyglycosides and its synthesis kineties. [ Method ] In the synthesis process of alkyl polyglycosides by transglyeosidation method, p-toluenesulfonie acid and stearie acid were used as composite catalyst, intermediate product butyl polyglycosides was prepared via reactive distillation technology. [ Result ] The suitable preparation conditian of butyl polyglyeasides was as follows： catalyst usage, 1.2 g（ p-toluenesulfoni ：stearie acid = 6：1 ） ; reaction temperature, 110 ℃ ; the ratio of butanol and glucose, 8： 1. The results showed that the larger the molar ratio of butanol and glucose was,the more the butyl monoside content was, and the less the polymerizatian degree of butyl glyeasides was. The catalyst usage and reaction temperature had little influence on the component of butyl polyglyeesides. With the increase of catalyst usage or reaction temperature,the reaction time was shortened dramatically. The kinetic equation for the synthesis of butyl glueeside was finally obtained as follows： -dCA/dt =0.163 7exp（ -1. 968×10^3/RT）CA -0.003 49 exp （ -2.727×10^3/RT） Ce. [ Conclusionl The suitable condition for the preparation of butyl polyglyeasides and its synthesis kinetic equation obtained in the study could provide theoretical basis for the synthesis of long-chain alkyl polyglyeasides.

Metal/antiperovskite metal nitride composites Ag/AgNNi_(3)as novel efficient electrocatalysts for hydrogen evolution reaction in alkaline media

Searching for effective hydrogen evolution reaction(HER)electrocatalysts is crucial for water splitting.Transition metal nitrides(TMNs)are very attractive potential candidates since of high electrical conductivity,robust stability,element rich and high activity.Antiperovskite metal nitrides provide chemical flexibility since two different types of transition metal elements are contained,allowing partial substitution both for A-and M-sites.Herein,we report a novel antiperovskite metal nitride Ag_(x)Ni_(1-x)NNi_(3)(0≤x≤0.80)thin film used as highly effective HER electrocatalysts.Pure phase antiperovskite nitride can be successfully obtained for Ag_(x)Ni_(1-x)NNi_(3)with x less than 0.80.The Ag_(0.76)Ni_(0.24)NNi_(3) towards HER shows an overpotential of 122 mV at 10 mA cm^(-2)in alkaline media.Furthermore,considering the role of Ag for adsorbing hydroxyl groups,chemical engineering has been carried out for designing metal/antiperovskite nitride Ag/Ag_(x)Ni_(1-x)NNi_(3)composite electrocatalysts.The 0.18 Ag/Ag_(0.80)Ni_(0.20)NNi_(3)electrocatalyst shows a mere 13 and 81 mV of overpotential to reach 1 and 10 mA cm^(-2),respectively,showing high durability in alkaline media.These results will provide a novel type of HER catalysts based on antiperovskite metal nitrides and a strategic design for metal/antiperovskite metal nitride composite electrocatalysts for HER in alkaline media.

Dysprosium regulated platinum particles as a bimetallic alloy catalyst for oxygen reduction reaction

Pt rare earth compounds have recently been investigated as potential substitutes.In this study,the hydrogen reduction method was used to prepare the Pt-Dy bimetallic catalyst,and a number of characterizations were conducted for structure and morphological research.The high resolutiontransmission electron microscopy(HR-TEM)and X-ray diffraction results show that Pt-Dy composite material exists in the form of various alloys and has a clear spherical shape.The majority of the metals in the composite catalyst appear in the zero valent state,and the binding energy of Pt shifts significantly,according to an X-ray photoelectron spectroscopy measurement.Impressively,Pt-Dy alloy produces excellent mass activity of 594 A/g compared to commercial Pt/C catalyst(162.8 A/g)for oxygen reduction process.Furthermore,after an accele rated durability test,the catalytic activity loss for Pt-Dy alloy catalyst reaches 20%while commercial Pt/C reduces 56%.

Increased utilization and mass activity of PtRu on reduced graphene oxide by heat treatment of its aerogel followed by composite with nanomaterials

The method to increase PtRu utilization and its catalytic activity of PtRu nanoparticles supported on reduced graphene oxide(RGO)by avoiding its restacking was proposed with the aim of developing an active catalyst for a direct methanol fuel cell.The heat treatment at 200◦C of the GO aerogel(GOA)prepared by freeze drying of GO ice was introduced to weaken the attractive force of the hydrogen bonding between the GO sheets followed by the composite with the nanoparticles,i.e.,ketjenblack(KB),TiO_(2)and Ti_(4)O_(7),at different weight ratios.The catalyst supported on the heat-treated GOA(RGOA),PtRu/RGOA,improved the PtRu utilization to some extent and also increased the ECSA and mass activity compared to that of PtRu/RGO.RGOA had fewer oxygen functional groups,especially the epoxy groups.Due to the treatment and composite,the PtRu utilization was increased from 66.5%for PtRu/RGO to 128.6%for PtRu/RGOA+Ti_(4)O_(7)(4:1)and the mass activity was improved from 50.7 A/g-PtRu for PtRu/RGO to 130.5 A/g-PtRu for PtRu/RGOA+Ti_(4)O_(7)(1:1).The Ti_(4)O_(7)nanoparticles showed the best catalytic performance for the composite suggesting that the strong interaction between Ti_(4)O_(7)and the Pt nanoparticles was effective due to its high electronic conductivity.

自支撑BiCu/碳杂化纳米纤维膜高效促进CO_(2)电还原生成甲酸

二氧化碳电还原有利于二氧化碳高价值利用和间歇性电能的存储,是一种极具应用前景的新技术.自支撑催化剂比粉末催化剂在构建电极方面具有明显优势,但缺乏有效的合成方法.本研究采用电纺丝-碳化法合成了一种自支撑的BiCu/碳杂化纳米纤维膜(BiCu/CHNM),可直接用作工作电极在流动池中将二氧化碳还原为甲酸盐,其法拉第效率为87.67%,分电流密度为142.9 mA cm^(-2).稳定性测试中,甲酸盐的法拉第效率在高偏电流密度(>100 mA cm^(-2))下可在50小时内连续保持在80%以上.原位拉曼光谱和密度泛函理论计算证实,铜掺杂降低了Bi(012)平面上HCOO~-形成的能垒,同时提高了碳纳米纤维网络的导电性.由于同时具有高导电框架结构和高度分散的BiCu活性位点,这种杂化膜同时表现出高活性、高选择性和长时间稳定性.

Fe- and Co-doped lanthanum oxides catalysts for ammonia decomposition:Structure and catalytic performances

In this paper, a series of Fe- and Co-doped lanthanum（hydr）oxides catalysts were prepared by a simple coprecipitationhydrothermal method. The as-prepared catalysts were characterized with various techniques including powder X-ray diffraction（XRD）, N2 adsorption/desorption, inductively coupled plasma（ICP） and transmission electron microscopy（TEM）. The Fe-based catalysts exhibited consecutive phase changes of amorphous Fe Ox→FeLaO3→Fe2N under different stages（as-prepared→calcination→ammonia decomposition reaction）; as for Co-based catalysts, the phase transformation followed a sequence of Co（OH）2→Co3O4→metallic Co. It was revealed that Fe2N and metallic Co were most probably the active crystalline phase respectively for Feand Co-based catalysts in the decomposition of ammonia.

Effects of cerium precursors on surface properties of mesoporous CeMnO_x catalysts for toluene combustion

Mesoporous CeMnOx composite oxides catalysts were prepared by surfactant-assisted co-precipitation method and used for the catalytic oxidation of toluene.The effect of different cerium precursors[Ce(NO3)3 and(NH4)2 Ce(NO3)6] on catalyst structure,surface properties and toluene combustion activities of mesoporous CeMnOx catalysts were investigated.The Ce(Ⅲ)MnOx catalyst prepared from Ce(NO3)3 precursor shows higher catalytic activity,with a 90% conversion temperature of 240℃,which is better than the Ce(Ⅳ)MnOx catalyst derived from[(NH4)2 Ce(NO3)6] precursor.On the basis of characterizations,it reveals that abundant surface content of Mn4+,better redox behavior and larger concentration of surface active oxygen species are responsible for the excellent catalytic performance.

Selective oxidation of benzyl alcohols to benzoic acid catalyzed by eco-friendly cobalt thioporphyrazine catalyst supported on silica-coated magnetic nanospheres

A novel magnetically recoverable thioporphyrazine catalyst（CoPz（S-Bu）8/SiO2@Fe3O4） was prepared by immobilization of the cobalt octkis（butylthio） porphyrazine complex（CoPz（S-Bu）8） on silica-coated magnetic nanospheres（SiO2@Fe3O4）. The composite CoPz（S-Bu）8/SiO2@Fe3O4appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide（H2O2） as oxidant under Xe-lamp irradiation,with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number（TON） of 61.7 at ambient temperature. The biomimetic catalyst CoPz（S-Bu）8was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz（S-Bu）8can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.

Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts.Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance,simultaneously provide a radical analysis of the interrelationship between structure and activity.In this review,the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized.Firstly,the synthetic strategies,characterization,dynamics and types of single atoms coupled with clusters/nanoparticles are introduced,and then the key factors controlling the structure of the composite catalysts are discussed.Next,several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated.Eventually,the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.