Synthesis of neodymium modified CeO_2-ZrO_2-Al_2O_3 support materials and their application in Pd-only three-way catalysts

Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.

Hydrogen generation from NaBH_(4) for portable proton exchange membrane fuel cell

Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and poor kinetic stability of hydrogen generation from NaBH_(4) hydrolysis limits its application.There are two main factors influencing the kinetics stability of hydrogen generation from NaBH_(4).One factor is that the alkaline byproducts(NaBO_(2)) of the hydrolysis reaction can increase the pH of the solution,thus inhibiting the reaction process.It mainly happens in the NaBH_(4) solution hydrolysis system.Another factor is that the monotonous increase in reaction temperature leads to uncontrollable and unpredictable hydrolysis rates in the solid NaBH_(4) hydrolysis system.This is due to the excess heat generated from this exothermic reaction in the initial reaction of NaBH_(4) hydrolysis.In this perspective,we summarize the latest research progress in hydrogen generation from NaBH_(4) and emphasize the design principles of catalysts for hydrogen generation from NaBH_(4) solution and solid state NaBH_(4).The importance of carbon as catalyst support material for NaBH_(4) hydrolysis is also highlighted.

From concept to commercialization:A review of tubular solid oxide fuel cell technology

The reduced sealing difficulty of tubular solid oxide fuel cells(SOFCs)makes the stacking of tubular cell groups relatively easy,and the thermal stress constraints during stack operation are smaller,which helps the stack to operate stably for a long time.The special design of tubular SOFC structures can completely solve the problem of high-temperature sealing,especially in the design of multiple single-cell series integrated into one tube,where each cell tube is equivalent to a small electric stack,with unique characteristics of high voltage and low current output,which can significantly reduce the ohmic polarization loss of tubular cells.This paper provides an overview of typical tubular SOFC structural designs both domestically and internationally.Based on the geometric structure of tubular SOFCs,they can be divided into bamboo tubes,bamboo flat tubes,single-section tubes,and single-section flat tube structures.Meanwhile,this article provides an overview of commonly used materials and preparation methods for tubular SOFCs,including commonly used materials and preparation methods for support and functional layers,as well as a comparison of commonly used preparation methods for microtubule SOFCs,It introduced the three most important parts of building a fuel cell stack:manifold,current collector,and ceramic adhesive,and also provided a detailed introduction to the power generation systems of different tubular SOFCs,Finally,the development prospects of tubular SOFCs were discussed.

Dynamic mechanical characteristics and application of constant resistance energy-absorbing supporting material

In deep underground engineering,rock burst and other dynamic disasters are prone to occur due to stress concentration and energy accumulation in surrounding rock.The control of dynamic disasters requires bolts and cables with high strength,high elongation,and high energy-absorbing capacity.Therefore,a constant resistance energy-absorbing(CREA)material is developed.In this study,the dynamic characteristics of the new material are obtained via the drop hammer tests and the Split Hopkinson Pressure Bar(SHPB)tests of the new material and two common bolt(CB)materials widely used in the field.The test results of drop hammer test and SHPB test show that the percentage elongation of CREA material is more than 2.64 and 3.22 times those of the CB material,and the total impact energy acting on CREA material is more than 18.50 and 21.84 times,respectively,indicating that the new material has high elongation and high energy-absorbing capacity.Subsequently,the CREA bolts and cables using the new material are developed,which are applied in roadways with high stress and strong dynamic disturbance.The field monitoring results show that CREA bolts and cables can effectively control the surrounding rock deformation and ensure engineering safety.

Layered zirconium phosphate-supported metalloporphyrin:Synthesis and catalytic application

This paper reports a new route for the preparation of layered alpha-zirconium phosphate （α-ZrP）-supported metalloporphyrin MnTMPyP. MnTMPyP was intercalated into α-ZrP using α-ZrP.BA （i.e. pre-intercalated bultylamine was arranged by a monolayer mode in α-ZrP） as a starting material. The catalytic activity of the supported material for homovanillic acid （HVA） oxidation was investigated. The results showed a promising layered material-supported catalyst in catalytic system.

New Sr Isotope Evidence to Support the Material Source of the Mengyejing Potash Deposit in the Simao Basin from Ancient Marine Halite or Residual Sea

Objective The Mengyejing potash deposit in the Simao Basin is the only producing area of solid potash at present in China. There is still controversy about the material source and distribution of the potash in this deposit （Shen Lijian et al., 2017）, which has influenced not only the prospecting direction and efficiency but also the understanding of the control of Tethys tectonic evolution on the formation and distribution of the mineral resources. This work analyzed the Sr isotope geochemical characteristics of evaporites from core samples in the well MZK-3 in order to further clarify the material source and to explore the potash distribution in the Simao Basin.

The Properties of an UV Curable Support Material Pre-polymer for Three Dimensional Printing

An ultraviolet（UV） curable support material pre-polymer for three dimensional printing was prepared based on the synergistic effect between PEO-PPO-PEO tri-block copolymer（F127） and polyethylene glycol （400） di-acrylate（SR344）. The effects of jetting conditions, thermal stability, curing time, mechanical properties and shrinking rate on printing models were studied. The situation of removing support material from build model was investigated after building progress was completed. The experimental result shows that when F127 is 6.0wt%, SR344 is 20.0wt%, 4-Methoxy phenol is 0.15wt% and Irgacure 2959 is 1.5wt%, the support material pre-polymer could be jetted out from the nozzles smoothly during building up of three dimensional printing models at 50-55 ℃. In addition, the support material could be removed easily from building model without spoiling the model; furthermore, the forming precision of building model is improved.

Synthesis of TiO2 supported on activated carbon by MOCVD： operation parameters study

A novel metallo-organic chemical vapor deposition (MOCVD) technique has been applied to the preparation of the photocatalytic titanium dioxide supported on activated carbon. The effects of various condition parameters such as carrier gas flow rate, source temperature and deposition temperature on the deposition rate were investigated. The maximum deposition rate of 8.2 mg/(g.h) was obtained under conditions of carrier gas flow rate of 400 ml/min, source temperature of 423 K and deposition temperature of 913 K. The deposition rate followed Arrhenius behavior at temperature of 753 K to 913 K, corresponding to activation energy Ea of 51.09 kJ/mol. TiO2 existed only in anatase phase when the deposition temperature was 773 K to 973 K. With increase of deposition temperature from 1073 K to 1273 K, the rutile content sharply increased from 7% to 70%. It was found that a deposition temperature of 773 K and a higher source temperature of 448 K resulted in finely dispersed TiO2 particles, which were mainly in the range of 10-20 nm.

Plastic zone analysis and support optimization of shallow roadway with weakly cemented soft strata

Based on a shallow roadway with weakly cemented soft strata in western China, this paper studies the range and degree of plastic zones in soft strata roadways with weak cementation. Geological radars were used to monitor the loose range and level of surrounding rocks. A mechanical model of weakly cemented roadway was established, including granular material based on the measured results. The model was then used to determine the plastic zone radium. The predicted results agree well with measured results which provide valuable theoretical references for the analysis of surrounding rock stability and support reinforcing design of weakly cemented roadways. Finally, a combined supporting scheme of whole section bolting and grouting was proposed based on the original supporting scheme. It is proved that this support plan can effectively control the deformation and plastic zone expansion of the roadway surrounding rock and thus ensure the long-term stable and safe mining.

New solid superbases: potassium nitrate supported on porous materials

ACCORDING to Tanabe’s definition, all materials possessing the basic strength （H-） over 26.5 are superbases. However, most of superbases known up to now, including CaO and SrO evacuated at 1173 K, K or Na metal supported on KOH/γ-Al2O3, etc. are extremely sensitive to CO2 or H2O in the atmosphere, which limits their application in industrial scale. In or-

Selective ensemble modeling based on nonlinear frequency spectral feature extraction for predicting load parameter in ball mills

Strong mechanical vibration and acoustical signals of grinding process contain useful information related to load parameters in ball mills. It is a challenge to extract latent features and construct soft sensor model with high dimensional frequency spectra of these signals. This paper aims to develop a selective ensemble modeling approach based on nonlinear latent frequency spectral feature extraction for accurate measurement of material to ball volume ratio. Latent features are first extracted from different vibrations and acoustic spectral segments by kernel partial least squares. Algorithms of bootstrap and least squares support vector machines are employed to produce candidate sub-models using these latent features as inputs. Ensemble sub-models are selected based on genetic algorithm optimization toolbox. Partial least squares regression is used to combine these sub-models to eliminate collinearity among their prediction outputs. Results indicate that the proposed modeling approach has better prediction performance than previous ones.

Plasma-assisted Co/Zr-metal organic framework catalysis of CO_(2)hydrogenation:influence of Co precursors

In this study,Co/Zr-metal organic framework(MOF)precursors were obtained by a roomtemperature liquid-phase precipitation method and the equivalent-volume impregnation method,respectively,using a Zr-MOF as the support,and Co/Zr-MOF-M and Co/Zr-MOF-N catalysts were prepared after calcination in a hydrogen-argon mixture gases(VAr:V_(H_(2))=9:1)at 350℃for 2 h.The catalytic activities of the prepared samples for CO_(2)methanation under atmosphericpressure cold plasma were studied.The results showed that Co/Zr-MOF-M had a good synergistic effect with cold plasma.At a discharge power of 13.0 W,V_(H_(2)):VCO_(2)=4:1 and a gas flow rate of 30 ml·min^(-1),the CO_(2)conversion was 58.9%and the CH4 selectivity reached 94.7%,which was higher than for Co/Zr-MOF-N under plasma(CO_(2)conversion 24.8%,CH4 selectivity 9.8%).X-ray diffraction,scanning electron microscopy,transmission electron microscopy,N_(2)adsorption and desorption(Brunauer-Emmett-Teller)and x-ray photoelectron spectroscopy analysis results showed that Co/Zr-MOF-M and Co/Zr-MOF-N retained a good Zr-MOF framework structure,and the Co oxide was uniformly dispersed on the surface of the Zr-MOF.Compared with Co/Zr-MOF-N,the Co/Zr-MOF-M catalyst has a larger specific surface area and higher Co^(2+)/Cototaland Co/Zr ratios.Additionally,the Co oxide in Co/ZrMOF-M is distributed on the surface of the Zr-MOF in the form of porous particles,which may be the main reason why the catalytic activity of Co/Zr-MOF-M is higher than that of Co/ZrMOF-N.

The development of MOFs-based nanomaterials in heterogeneous organocatalysis

Metal-organic framework(MOF) is a class of inorganic-organic hybrid material assembled periodically with metal ions and organic ligands. MOFs have always been the focuses in a variety of frontier fields owing to the advantageous properties, such as large BET surface areas, tunable porosity and easyfunctionalized surface structure. Among the various application areas, catalysis is one of the earliest application fields of MOFs-based materials and is one of the fastest-growing topics. In this review, the main roles of MOFs in heterogeneous organocatalysis have been systematically summarized, including used as support materials(or hosts), independent catalysts, and sacrificial templates. Moreover, the application prospects of MOFs in photocatalysis and electrocatalysis frontiers were also mentioned.Finally, the key issues that should be conquered in future were briefly sketched in the final parts of each item. We hope our perspectives could be beneficial for the readers to better understand these topics and issues, and could also provide a direction for the future exploration of some novel types of MOFs-based nanocatalysts with stable structures and functions for heterogeneous catalysis.

Metal-support interactions in designing noble metal-based catalysts for electrochemical CO_(2) reduction: Recent advances and future perspectives

Electrochemical CO_(2) reduction reaction (CO_(2) RR) offers a practical solution to current global greenhouse effect by converting excessive CO_(2) into value-added chemicals or fuels. Noble metal-based nanomaterials have been considered as efficient catalysts for the CO_(2) RR owing to their high catalytic activity, long-term stability and superior selectivity to targeted products. On the other hand, they are usually loaded on different support materials in order to minimize their usage and maximize the utilization because of high price and limited reserve. The strong metal-support interaction (MSI) between the metal and substrate plays an important role in affecting the CO_(2) RR performance. In this review, we mainly focus on different types of support materials (e.g., oxides, carbons, ligands, alloys and metal carbides) interacting with noble metal as electrocatalysts for CO_(2) RR. Moreover, the positive effects about MSI for boosting the CO_(2) RR performance via regulating the adsorption strength, electronic structure, coordination environment and binding energy are presented. Lastly, emerging challenges and future opportunities on noble metal electrocatalysts with strong MSI are discussed.

Attractive nanofiber structure based on Cu-Ti/metal sandwich film with excellent electrocatalytic performance for ethanol oxidation

The support materials are an important part of catalysts and they are the dispersant,adhesive,and support for other components.In this study,three types of thin films with different structures were used as the precursor to prepare loading Pd catalysts.The one-step dealloying method was used to prepare a semiconductor nanofiber film(NFF)support material with upward directional growth from the substrate.Pd/NFF and Pd/Ni O/NFF loaded Pd catalysts were prepared using NFF as the support material,and the electrochemical catalytic properties for ethanol oxidation in alkaline media were studied.Cyclic votammetry showed that the NFF support material effectively inhibited agglomeration of palladium,increased the number of active sites of Pd,and improved the electrocatalytic properties of Pd for ethanol oxidation.In addition,the Pd/Ni O/NFF loaded Pd catalyst obtained by modification with nickel oxide significantly improved the electrocatalytic performance for ethanol oxidation compared with the Pd/NFF loaded Pd catalyst.These results show that Ni O is conductive to absorption of oxygen-containing groups on the surface of the catalyst and can further improve the electrocatalytic ability of Pd for ethanol oxidation.All of the above results demonstrate that the support material prepared by the dealloying method has application prospects in load-type catalysts.

Immobilization of Glucose Oxidase on Ordered Macroporous Silicas Functionalized with Amino Group

A novel glucose oxidase immobilized on three-dimensionally ordered macroporous （3DOM） material has been prepared by firstly preparation of hybrid 3DOM SiO2-NH2 materials using colloidal crystal method, and following covalent immobilization of glucose oxidase on the pore walls of the 3DOM materials. The materials were characterized by SEM, FTIR, DSC and BET techniques. SEM observation shows that the macropores are highly ordered and are interconnected by small windows. FTIR measurement shows that there are amino and organic groups in the pore walls. The surface area of the 3DOM SiO2-NH2 material is about 10.2 m2/g. The loaded amount of enzyme is increased with amino content in the materials. The immobilized enzyme has high activity, thermal stability and can be reused.