Highly dispersed MgInCe-mixed metal oxides catalyzed direct carbonylation of glycerol and CO_(2)into glycerol carbonate

Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

3D printing of poly(ethyleneimine)-functionalized Mg-Al mixed metal oxide monoliths for direct air capture of CO_(2)

Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.

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.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

Highly Dispersed Pd Nanoparticles Supported on Zr-Doped MgAl Mixed Metal Oxides for 2-Ethylanthraquinone Hydrogenation

In this study,Pd-Mg(Al)-LDH/γ-Al2O3 and Pd-Mg(Al)Zr-LDH/γ-Al2O3 precursors were synthesized by impregnating Na2PdCl4 on Mg(Al)-LDH/γ-Al2O3 and Mg(Al)Zr-LDH/γ-Al2O3,and then the precursors were calcinated and reduced to obtain Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalysts.Compared with Pd/γ-Al2O3 catalyst,the hydrogenation efficiency of Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 increased by 15.7%and 24.0%,respectively.Moreover,the stability of Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalyst was also higher than that of Pd/γ-Al2O3.After four runs,the hydrogenation efficiency of Pd/γ-Al2O3 decreased from 12.1 to 10.0 g/L,while that of Pd-Mg(Al)Zr-MMO/γ-Al2O3 decreased from 15.0 to 14.3 g/L.The active aquinones selectivities of all catalysts were almost 99%.The structures of the catalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 adsorption–desorption,inductively coupled plasma-atomic emission spectrometry(ICP-AES),CO chemisorption analysis,transmission electron microscopy(TEM),temperature-programmed reduction with hydrogen(H2-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicate that the improved catalytic performance is attributed to the stronger interaction between Pd and Mg(Al)Zr-MMO/γ-Al2O3,smaller Pd particle size and higher Pd dispersion.This work develops an effective method to synthesize highly dispersed Pd nanoparticles based on the layered double hydroxides(LDHs)precursor.

Bifunctional nanozyme activities of layered double hydroxide derived Co-A1-Ce mixed metal oxides for antibacterial application

Marine biofouling is an expensive problem that needs evolved chemical or physical antifouling strategies.However,most of the current antifouling materials that would damage the environment through metal leaching and bacteria resistance are being halted.Nanozyme is one kind of environmental antifouling materials through generating reactive oxygen species(ROS).We prepared various contents of CeO2 that could uniform disperse compounding with Co3 O4 and CoAl2 O4 to form a stable Co-Al-Ce mixed metal oxide(MMO) by a layered double hydroxide derived method.We find that coupling with CeO2 can improve the peroxidase(POx) activity.When the molar ratio of Ce is 2.5% and the calcination temperature is 200℃,the POx activity of Co-Al-Ce MMO is the best caused by the good dispersion of catalytically active components and the high specific area(150.10±4.95 m2/g).This novel Co-Al-Ce MMO also exhibits an antibacterial mode of action Gram-negative bacteria in near-neutral pH solution through generating ROS(mainly ·O2-)in the presence of H2 O2.Ce containing MMO can be utilized as potential green marine antifouling material.

Electron Donating Property and Catalytic Activity ofPerovskite-type Mixed Oxides (ABO_3) Consisting of Rare Earth and 3d Transition Metals

The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have been correlated with the surface electron donor properties of these mixed oxides

Dehydrogenation of methylcyclohexane over Pt supported on Mg–Al mixed oxides catalyst:The effect of promoter Ir

To enhance the hydrogen release during hydrogen storage,several Pt-Ir supported on Mg-Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane(MCH)in this study.The effects of iridium content,reduction temperature on the activity and stability of the catalysts were studied in detail.In the presence of Ir,metal particle size was decrea sed and electron transfer between Ir and Pt was observed.High reduction temperature increased the metallic Ir content but enlarged the particle size of active site s.During the dehydrogenation reaction on Pt-Ir bimetallic catalyst,MCH was efficiently converted into toluene and PtIr-5/Mg-Al-275 exhibited the highe st activity.After prolonging the residence time and raising the reaction temperature to 350℃the conversion and hydrogen evolution rate were increased to 99.9%and 578.7 mmol·(g Pt)^-1·min^-1,respectively.Moreover,no carbon deposition was observed in the spent catalyst,presenting a high anti-coking ability and good potential for industrial application.

Mathematical Modeling and Experimental Validation of Mixed Metal Oxide Thin Film Deposition by Spray Pyrolysis

The deposition of metal oxide films using Spray Pyrolysis Technique (SPT) is investigated through mathematical and physical modeling. A comprehensive model is developed in the processes including atomization, spray, evaporation, chemical reaction and deposition. The predicted results including particle size and film thickness are compared with the experimental data obtained in a complementary study. The predicted film thickness is in a good agreement with the measurements when the temperature is high enough for the chemical reaction to proceed. The model also adequately predicts the size distribution when the nanocrystals are well-structured at controlled temperature and concentration.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH_(3)-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Spray Pyrolysis Deposition of Single and Mixed Oxide Thin Films

The influence of processing parameters is investigated on the structural characteristics of single and mixed oxides produced by spray pyrolysis technique. The films were synthesized by spraying precursor solutions through a noz-zle onto a heated alumina substrate. The precursor consisted separately of aqueous solutions of tin chloride for SnO2 and zinc chloride for ZnO for single oxide cases, and aqueous solutions of tin chloride and indium nitrate for SnO2 + In2O3 and zinc chloride and indium nitrate solutions for ZnO + In2O3 for mixed oxide cases. The substrate temperature was varied accordingly for each single and mixed case. The films produced were characterized by X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy. The results indicate that a non-homogenous film is formed at low temperature for both single oxides considered. The temperature has significant effect on the composition of the synthesized films of both single oxides below 450℃. The results for mixed oxides show that the best homogeneous films are obtained for 80 wt% ZnO + 20 wt% In2O3, and 80 wt% SnO2 + 20 wt% In2O3.

Sulphuric Acid Bake-Leach Process for the Treatment of Mixed Copper-Cobalt Oxide Ores

A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-cobalt oxide ore was carried out by mixing the sample with sulphuric acid followed by baking of the mixture in a muffle furnace. Baking tests were conducted at different conditions such as temperature, time, and varying amounts of acid. The reacted samples were then subjected to water leaching at room temperature to determine the leachability of copper and cobalt from the baked material. The dissolutions of copper and cobalt were dependent on acid concentration with cobalt showing more sensitivity to the amount of acid. Both copper and cobalt were extracted from the baked material within short leaching times and without the addition of reducing agents. The outcome of this work has shown that the sulphuric acid bake-leach process is a possible alternative to the reductive leaching method for copper-cobalt oxide ores.

Development of bimetallic spinel catalysts for low-temperature decomposition of ammonium dinitramide monopropellants

Ammonium dinitramide(ADN)based liquid monopropellants have been identified as environmentally benign substitutes for hydrazine monopropellant.However,new catalysts are to be developed for making ADN monopropellants cold-start capable.In the present study,performance of Co and Ba doped CuCr_2O_4 nanocatalysts prepared by hydrothermal method was evaluated on the decomposition of aqueous ADN solution and ADN liquid monopropellant(LMP103X).The catalysts were characterized by PXRD(Powder X-ray Diffraction),FTIR(Fourier Transform Infrared spectroscopy),SEM(Scanning Electron Microscopy),TEM(Transmission Electron Microscopy),EDS(Energy Dispersive X-ray Spectroscopy),and XPS(X-ray Photoelectron Spectroscopy).The nanosize was confirmed by SEM and TEM,while the nanoflake morphology was confirmed by the SEM analysis.Further,we obtained the elemental composition from the EDS analysis.We investigated the catalytic activity of the catalysts by thermogravimetric(TG)analysis and the developed catalysts lowered the decomposition temperature of ADN monopropellant by about 55℃.The XPS analysis confirmed the presence of metal ions with different chemical states.Apparently,increase in the surface area of the catalysts and the mixed active sites as well as the development of oxygen vacancy on the catalyst surface introduced by metal doping are influencing the decomposition temperature of ADN samples.

Fe_(2)O_(3)/Al_(2)O_(3)修饰的混合金属氧化物降解维C生化废水

针对维C废水在二级生化处理后很难达到排放标准的问题,以铁铝混合粉末作为载体(Fe_(2)O_(3)/Al_(2)O_(3),FA)与其他金属氧化物粉末混合掺杂,通过滚动造粒法制备混合金属氧化物(MMO)臭氧催化剂,用于降解维C生化废水。结果表明,CuO、Ni_(2)O_(3)协同催化,所制备的MMO臭氧催化剂Cu-Ni/FA具有较好的催化性能和力学性能。通过SEM、TEM、BET、XRD、XPS对样品的理化性能进行表征,发现催化体系中NiFe_(2)O_(3)和Cu_(4)O_(3)发挥了重要作用。在废水COD浓度为248.31 mg/L,pH为7,催化剂投加量35 g/L以及臭氧浓度10 mg/L条件下,60 min时COD去除效率达到70%。超声120 min后催化剂脱落率为2.724%,对每次超声后的催化剂进行催化臭氧氧化实验,COD去除率为65%~69%,表明该催化剂具有良好的抗脱落性和稳定性。

γ-Al_(2)O_(3)/CuO-ACF电吸附除盐的影响因素及反应动力学

开发脱盐率高、寿命长的电极材料是电容去离子(CDI)水处理技术的研究热点之一。通过一锅水热法将层状CuAl双金属氧化物与活性碳纤维复合,成功制备了CDI电极(γ-Al_(2)O_(3)/CuO-ACF)。采用SEM、XRD、FTIR和CV测试对样品的形貌、结构和电极性能进行了表征。当初始NaCl浓度为500mg/L时,随着电压从0.8V逐渐增加到1.6V,两种电极的比吸附量、脱盐效率、电流效率和电耗均有所增加,γ-Al_(2)O_(3)/CuO-ACF的四项参数依次比ACF提高23.4%~55.3%、44.8%~82.0%、65.5%~90.0%和降低15.0%~21.4%。当腐殖酸浓度为5~10mg/L时,ACF脱盐效率下降明显,而γ-Al_(2)O_(3)/CuO-ACF脱盐效率仅在腐殖酸浓度10mg/L时略有下降。在15次循环后,NaCl溶液体系的脱盐效率保留率为96%;但由于腐殖酸的存在,该值下降为92%。两种电极的电吸附除盐过程遵循Langmuir等温吸附方程,表示盐离子在电极表面为单分子层物理吸附。与传统ACF电极相比,γ-Al_(2)O_(3)/CuO-ACF电极具有优异的可回收性、稳定性和增强的电化学特性。

混合金属氧化物掺杂对锰酸锂性能的影响研究

以低钠钾型二氧化锰、碳酸锂为原料,以不同量纳米三氧化二铝、二氧化钛为添加剂,采用高温固相法制备电池正极材料锰酸锂,研究混合金属氧化物添加量对锰酸锂的物理性能及电性能的影响。通过粒度分布、振实密度、微观结构、容量及容量衰减对材料性能进行表征。结果表明,纳米三氧化二铝掺杂量为0.3%和二氧化钛掺杂量为0.5%的条件下合成的锰酸锂材料0.5 C容量为98.2 mAh/g和1.0 C容量为97.9 mAh/g,50次高温循环容量保持率为98.37%,该产品具有高温循环性能优良,对锰酸锂的生产具有一定参考意义。

高锌含量铅锌氧化渣直接还原试验研究

铅锌氧化渣熔融还原是得到金属铅和锌的重要步骤,但氧化渣中锌含量升高和铅含量降低会导致熔化温度增加,使得还原工艺条件发生较大变化。本文对高锌含量铅锌渣(Zn≈25%)的还原工艺条件和渣型制度进行了研究,主要考察了还原煤量、还原温度、还原时间、Fe/SiO_(2)、CaO/SiO_(2)对铅锌氧化渣中Pb、Zn、Cu回收率的影响。试验结果表明,铅锌渣Pb、Zn、Cu金属回收率随着还原煤量、还原温度、还原时间的增加而增加,但过高的煤比和还原温度不利于Pb、Cu回收率的提高;铅锌渣Pb、Zn、Cu金属回收率随着Fe/SiO_(2)和CaO/SiO_(2)的增加而增加,但Fe/SiO_(2)增加至0.78,CaO/SiO_(2)增加至0.8时,继续增加Fe/SiO_(2)和CaO/SiO_(2)将降低Pb、Zn、Cu金属回收率。试验用铅锌渣的适宜还原条件为煤比1.2~1.4、还原温度1623~1673 K、还原时间90~120 min、Fe/SiO_(2)=0.78~1.17,CaO/SiO_(2)=0.5~0.8。在上述工艺条件下,铅锌氧化渣中Pb、Zn、Cu回收率分别可达84.01%、94.51%、85.8%以上。

Mixed metal oxide catalysts for the selective oxidation of ethylbenzene to acetophenone

MgAl and MgMAl oxides（M = Co,Ni and Cu） with a Mg：M：Al molar ratio = 4：1：1 were synthesized from the calcination of their corresponding layered double hydroxide（LDHs） precursors.Their catalytic activities were examined for the oxidation of ethylbenzene using tert-butylhydroperoxide（TBHP） as an oxidant.The oxidized product was mainly acetophenone.The catalytic activities were in the order of MgCuAlMgNiAl～NiAl～MgCoAl～CoAlCuAlMgAl oxides.Reusability studies show that the catalysts are stable under the reaction conditions.

Effect of Different Dopant in the Mo-V-Te-O Catalyst on the Performance of Selective Oxidation Propane to Acrolein

Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of the Mo-V-Te-O catalyst. The catalysts were examined by XRD and H2-TPR. The XRD characteristic of the Mo-V-Te-P-O showed that the addition of P could aggrandize the (V0.07Mo0.93)5O14 phase. H2-TPR illuminated that the MoV0.3Te0.23P0.15On catalyst took on the best redox ability.

Roles of Oxygen Vacancy and Lower Valence Metallic Ion in Direct Decomposition of NO over La_（2－x）（Sr，Th）_xCuO_（4±λ）

Two systems of La_(2-x)Sr_xCuO_(4±λ) and La_(2-x)Th_xCuO_(4±λ) mixed oxides with K_2NiF_4structure were synthesized.The compositions and structures of the catalysts were characterized by means of XRD,XPS,chemical analysis and so on.The catalytic behavior for the direct decomposition of NO has been investigated.The results show that the catalytic activity is closely related to the oxygen vacancy and lower valence metallic ion in the direct decomposition of NO.The presence of oxygen vacancy is necessary for mixed oxide to have steady activity in NO decomposition.