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.

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.

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.

Catalytic reduction of SO_2 by CO over CeO_2-TiO_2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

Catalytic performance for methane combustion of supported Mn-Ce mixed oxides

A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, laser Raman spectrum （LRS）, and temperature programmed reduction （TPR） techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarkably promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3：7, methane conversion reached 92% at a temperature as low as 470 ℃.

Effect of Manganese Doping on Oxygen Storage Capacity of Ceria-Zirconia Mixed Oxides

CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （OSC） of the samples. The doping method brought about strong interactions between manganese oxide and ceria, both in the bulk and on the surface. Only a small part of Mn cations are incorporated into the ceria lattice to form solid solutions and the remaining are left on the surface as finely dispersed Mn3O4. The OSC behaviors of the materials are influenced by the doping amount of Mn and the solubility of Mn in the CeO2 lattice. The OSC is more easily affected by available contents of oxygen storage components when the measurement frequency is low. Comparatively, the concentration of lattice defects, which affects the mobility of bulk oxygen, is the determining factor under high frequency.

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.

Co–Cr–O mixed oxides for low–temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation

A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxides.The catalyst with a Co/Cr molar ratio of 1:2(1 Co2 Cr)and a spinel structure has the best activity(with a reaction rate of 1.38μmol g^–1 s^–1 at 250℃),which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility,as evidenced by the temperature-programmed desorption of ammonia,reduction of hydrogen,and surface reaction of propane.Kinetic study shows that the reaction orders of propane and oxygen on the 1 Co2 Cr catalyst(0.58±0.03 and 0.34±0.05,respectively)are lower than those on the 2 Co1 Cr catalyst(0.77±0.02 and 0.98±0.16,respectively)and 1 Co5 Cr(0.66±0.05 and 1.30±0.11,respectively),indicating that the coverages of propane and oxygen on 1 Co2 Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility.In addition,in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1 Co2 Cr during the reaction are polydentate carbonate species,which accumulate on the surface at low temperatures(<250℃)but decompose at relatively high temperatures.

Ethylbenzene to styrene over ZrO_2-based mixed metal oxide catalysts with CO_2 as soft oxidant

ZrO2-based mixed metal oxide catalysts for the industrially important dehydrogenation process of ethylbenzene to styrene monomer have been explored by our group for the past 20 years.These efforts were subjected to the activation of CO2 over mixed metal oxide catalysts and resulted in several promising benefits to the dehydrogenation processes,such as stabilized conversion and selectivity,suppressed coke formation and commercially-acceptable longevity.In this review,we summarize the most recent developments on ZrO2-based mixed metal oxide catalysts,including the further optimization of sol-gel process in the synthesis of catalysts,rationalizing acid-base properties by doping,co-operative properties between redox and acid-base active sites and additional promoters towards the effective improvement of the longevity of catalysts.

Synthesis of mesoporous cerium-zirconium mixed oxides by hydrothermal templating method

Mesoporous cerium-zirconium mixed oxides were prepared by hydrothermal method using cetyl trimethyl ammonium bromide (CTAB) as template. The effects of amount of template, pH value of solution and hydrothermal temperature on mesostructure of samples were systematically investigated. The final products were characterized by XRD, TEM, FT-IR, and BET. The results indicate that all the cerium-zirconium mixed oxides present a meso-structure. At molar ratio of n(CTAB)/n((Ce)+(Zr))= 0.15, pH value of 9, and hydrothermal temperature of 120 ℃, the samples obtained possess a specific surface area of 207.9 m2/g with pore diameter of 3.70 nm and pore volume of 0.19 cm3/g.

Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

Cu-Ce-La mixed oxides were prepared by three precipitation methods （coprecipitation, homogeneous precipitation, and deposition precipitation） with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 （111） framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3＋ or Ce^4＋ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide （crystalline） and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.

Properties of TiO_2-SiO_2 Mixed Oxides and Photocatalytic Oxidation of Heptane and Sulfur Dioxide

A series of TiO 2-XSiO 2[X denotes the molar fraction(%) of silica in the mixed oxides] with different \{n(Ti)\}/n(Si) ratios was prepared with ammonia water as a hydrolysis catalyst. The photocatalysts prepared were characterized by XRD, thermal analysis, FTIR, UV-Vis and SPS. The characterization results of FTIR and UV-Vis spectra show that Ti atoms were gradually changed from octahedral coordination to tetrahedral coordination with the addition of silica, which is not beneficial for obtaining strong Brnsted acidity and higher photocatalytic activity. The photocatalytic activity experiments, which were conducted by using heptane(or SO 2) as the model reactant, showed that TiO 2-SiO 2 containing a suitable amount of silica can exhibit much higher photocatalytic activity than pure TiO 2. The enhanced photocatalytic activity can be attributed to three following factors: (1) smaller crystalline size; (2) higher thermal stability; (3) the new strong Brnsted acidity.

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.

Preparation of Well Dispersed and Ultra-Fine Ce(Zr)O_2 Mixed Oxide by Mechanochemical Processing

Ultra-fine CeO_2-ZrO_2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce_2(CO_3)_3·8H_2O, ZrOCl_2·xH_2O and ammonia were used as reactants. It is found that the crystalline Ce_2(CO_3)_3·8H_2O and ZrOCl_2·xH_2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce_(0.15)Zr_(0.85)O_2 mixed oxide with pure tetragonal phase structure and medium particle size(D_(50))less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O_2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.

Effects of co-precipitation temperature on structure and properties of La and Y doped cerium zirconium mixed oxides

Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,physical and chemical properties of multi-doped cerium zirconium mixed oxides,a series of La and Y doped cerium zirconium mixed oxides(CZLYs)were synthesized via a co-precipitation method,and the physical and chemical properties of CZLYs were systemically characterized by XRD,N_(2) adsorption−desorption,TEM,XPS,oxygen storage capacity(OSC)and hydrogen temperature programmed reduction(H_(2)-TPR).The results show that co-precipitation temperature is an important parameter to influence the crystal size,oxygen storage capacity and thermal stability of CZLYs.When the co-precipitation temperature was 60℃,the best redox properties and thermal stability of CZLYs were obtained.After thermal treatment at 1100℃for 10 h,the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m^(2)/g and 497.7μmol/g,respectively.In addition,a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.

Bioleaching of a kind of alkaline mixed copper oxide and sulphide mineral

We conducted two-stage acidification-bioleaching experiments to probe the feasibility of bioleaching for a kind of mixed alkaline copper oxide and sulphide mineral. We used the uniform design method for data analysis and experimental optimization, with initial pH value, pulp density, inoculation of bacteria and ferrous iron concentration selected as the influential factors. Polynomial regression shows that the four factors sequentially influence the copper recovery by 14.430%, 8.555%, 1.982% and 3.895%. Acid equilibrium in the bioleaching system is mainly influenced by alkaline gangue content, chemical reactions and bacterial activity. A maximal portion of refractory copper extracted reaches 71.08%. The dynamic analysis of copper recovery indicates that bioleaching goes through a lag leaching phase, prime leaching phase and leaching stationary phase corresponding to the growth phases of bacteria. Compared with the predicted value of 80.87%, the confirmatory experiment observes a 78.21% copper recovery under the optimal conditions of pH of 1.5, pulp density of 5%, bacteria inoculation of 30% and initial ferrous iron concentration of 9 g L-1. Results suggest that bioleaching is technically feasible to improving total copper recovery.

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.

Preparation of Mesoporous Ce_(0.5)Zr_(0.5)O_2 Mixed Oxide by Hydrothermal Templating Method

Mesoporous Ce0.5Zr0.5O2 mixed oxide with high specific surface area was synthesized under basic condition in the presence of non-ionic surfactant PEG-4000. The effect of synthesis conditions, such as synthesis temperature and the molar ratio of PEG-4000/（[ Ce] ＋ [ Zr] ）, on specific surface area were investigated. The products were characterized by transmission electron microscopy, powder X-ray diffraction, and nitrogen adsorption-desorption measurements, respectively. The results showed that synthesis temperature and the molar ratio of PEG-4000/（[ Ce] ＋ [ Zr] ） had great influence on specific surface area. Under the optimum synthesis conditions, the prepared Ce0.5Zr0.5O2 mixed oxide presented cubic fluorite-type structure and possessed high surface area of 148.6 m2·g^-1 with wormlike pores.