Effects of carrier and Mn loading on supported manganese oxide catalysts for catalytic combustion of methane

Supported manganese oxide catalysts were prepared by incipient wetness impregnation method for methane catalytic combustion, and effects of the support （Al2O3, SiO2 and TiO2） and Mn loading were investigated. These catalysts were characterized with N2 adsorption, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Methane conversion varied in a large range depending on supports or Mn loading. Al2O3 supported 15% Mn catalyst exhibited better activity toward methane catalytic oxidation. The manganese state and oxygen species played an important role in the catalytic performance,

Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming

The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.

Synergetic effect between sulfurized Mo/γ-Al_2O_3 and Ni/γ-Al_2O_3 catalysts in hydrodenitrogenation of quinoline

An evidence for the synergetic effect between the stacked bed of Mo/γ-Al2O3 and Ni/γ-Al2O3 in the hydrodenitrogenation （HDN） reaction of quinoline has been provided in this paper. The synergism factor decreases when the reaction temperature increases （280？340 ？C）. The synergetic effect leads to improve the hydrogenation activity for the stacked bed compared with the single Mo/γ-Al2O3 bed, which may be attributed to the generation of hydrogen spillover on the Ni/γ-Al2O3 catalyst.

Effect of the Ni size on CH4/CO2 reforming over Ni/MgO catalyst：A DFT study

Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.

Doping effects of manganese on the catalytic performance and structure of NiMgO catalysts for controllabe synthesis of multi-walled carbon nanotubes

Doping effects of manganese （Mn） on catalytic performance and structure evolution of NiMgO catalysts for synthesis of multi-walled carbon nanotubes （MWCNTs） from methane were investigated for the first time. Addition of Mn in NiMgO catalyst can greatly improve the MWCNTs yield. Mno.2NiMgO catalyst among the tested ones gives the highest MWCNTs yield as 2244%, which is two times higher than that of the catalyst without Mn. The structure evolution, reduction behaviors and surface chemical properties of MnNiMgO catalysts with various Mn contents were studied in detail. It was found that the stable solid solution of NiMgO2 formed in NiMgO catalyst was disturbed by the addition of Mn. Instead, another solid solution of MnMg608 is formed. More amount of Ni can be reduced and dispersed on the catalyst surface to be acted as active sites. Importantly, the changes of Ni content on the surface are correlated with the Ni particle size and the outer diameter of MWCNTs, suggesting the controllable synthesis of MWCNTs over MnNiMgO catalysts.

Inhibiting effect of tungstic compounds on glucose hydrogenation over Ru/C catalyst

The effect of acid component including various conventional acids and tungstic compounds on glucose hydrogenation over a series of binary catalyst system containing Ru/C catalyst was investigated. The results showed that HC1, H2SO4, H3BO3, H3PO4, and HNO3 had negligible effect, while all the tungstic compounds imposed inhibiting effects on the hydrogenation of glucose over Ru/C catalyst, and the suppressing effect followed the order of H2WO4〉HPW〉WO3〉AMT〉HSiW. This order is the same as the order of ethylene glycol （EG） yields in the one-pot conversion of glucose to EG, suggesting the important role of competition between glucose hydrogenation and retro-aldol condensation in controlling the selectivity of EG.

AN EFFECTIVE ORGANO-BIMETALLIC Rh-Co CLUSTER CATALYST FOR HYDROFORMYLATION

s: RhCo3(CO) 12/Sio2 aller decarbonylated is regenerable under CO, and catalyzes ethylene hydrofornlylation with high activity and stability.

ISOTHERMAL EFFECTIVENESS FACTORS FOR NONUNIFORM ACTIVE CATALYST

Isothermal effectiveness factors for slab,cylinder and sphere shaped catalysts with uniform or nonuni-form intrinsic activity profiles have been investigated.In the case of zero-,first- and second-order kinetics,the effectiveness factors of pellets with increasing activity towards the pellet surface are larger than that ofuniform active catalyst,and they are proportional to the square root of the activity at the pellet surfacewith significant diffusion effect.The effectiveness factor-Thiele modulus curves which are valid for bothuniform and nonuniform catalysts have been obtained with the Thiele modulus modified by equivalent thick-hess of effective layer of the catalyst.Thus,the effectiveness factor for nonuniform active catalyst could bepredicted with a maximun deviation of 5% in the case of significant or insignificant diffusion effect but 10%in general.

Synergistic effects of bimetallic Cu-Fe/SiO_2 nanocatalysts in selective hydrogenation of diethyl malonate to 1,3-propanediol

Cu-x-Fe-y/SiO2 catalysts were prepared using urea-assisted sol-gel method. The structure and physicochemical properties of the catalysts were characterized using N-2 adsorption-desorption, transmission electron microscopy, H-2-temperature-programmed reduction, powder X-ray diffraction, and X-ray photoelectron spectroscopy. Compared with monometallic Cu or Fe catalysts, the bimetallic Cu-x-Fe-y/SiO2 catalysts exhibited enhanced catalytic performance for the selective hydrogenation of diethyl malonate to 1,3-propanediol. The bimetallic catalyst with an optimal Cu/Fe atomic ratio of 2 exhibited the highest activity, which yielded 96.3% conversion to diethyl malonate and 93.3% selectivity to 1,3-propanediol under the optimal reaction conditions. Characterization results revealed that interactions between Cu and Fe contributed to the improvement of diethyl malonate conversion and selectivity to 1,3-propanediol. The X-ray photoelectron spectroscopy results revealed that the addition of appropriate amount of Fe species enhanced the reduction of Cu2+ species, thereby increasing the Cu-0 species on the surface of bimetallic catalyst. It led to a better chemisorption capacity of hydrogen and further promoted of the activation of hydrogen molecule. The ethyl acetate temperature-programmed desorption results indicated that the FeOx species provided the additional adsorption sites for substrate molecules, and they activated the C=O bond. The improved catalytic performance of bimetallic Cu-x-Fe-y/SiO2 catalyst was mainly attributed to the synergistic effect between Cu-0 and FeOx species. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Electronic Effect of Carbon Support on Pt Catalyst Supported on Graphite Intercalation Compound

Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.

Solvent effects on Pt-Ru/C catalyst for methanol electro-oxidation

Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.

Fischer–Tropsch synthesis on impregnated cobalt-based catalysts:New insights into the effect of impregnation solutions and pH value

The Co-based catalysts were prepared with different cobalt acetate solutions. Effects of pH value were studied deeply on Fischer–Tropsch synthesis (FTS) through a semi-batch reactor. Among all impregnation solutions (water, butanol, amyl alcohol, acetic acid, nitric acid and ammonium nitrate), the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree. However, the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS. According to FT-IR spectra results, the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity. Whereas, the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts. The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value. © 2016 Science Press

Effect of Steam on the Oxidative Coupling of Methane over La-Ba System Catalysts

The influence of steam on catalytic performance for the oxidative coupling of methane(OCM) over Ba 2+ promoted La 2 O 3 catalysts was studied. It was shown that the presence of a suitable amount of steam led to a significant increase of the yield and selectivity to C 2 hydrocarbons, a decrease of selectivity to carbon monoxide and some increase of selectivity to carbon dioxide with increasing the amount of water in the feed was also observed. The activity and selectivity of the catalysts are more sensitive to the effect of steam with the variation of Ba 2+ content in the catalysts at a relatively low temperature(650℃). The comparative experiments for OCM with methane oxygen mixture diluted with nitrogen or steam were carried out in order to investigate the role of steam.

Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H_2

Activated carbon （AC） supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation （PROX） in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures （≤200 ℃） following heat treatment in He at 200 ℃ （He200H200）, exhibited the best catalytic properties. Temperature-programmed desorption （TPD）, X-ray diffraction （XRD） and temperature-programmed reduction （TPR） results indicated that silver oxides were produced during heat treatment in He at 200 ℃ which were reduced to metal silver nanoparticles in H2 at low temperatures （≤200 ℃）, simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 ℃. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.

Enhanced CO oxidation over potassium-promoted Pt/Al_2O_3 catalysts:Kinetic and infrared spectroscopic study

A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.

Base-free aerobic oxidation of glycerol on TiO_2-supported bimetallic Au–Pt catalysts

The aerobic oxidation of glycerol provides an economically viable route to glyceraldehyde, dihydroxyacetone and glyceric acid with versatile applications, for which monometallic Pt, Au and Pd and bimetallic Au-Pt, Au- Pd and Pt-Pd catalysts on TiO2 were examined under base-free conditions. Pt exhibited a superior activity relative to Pd, and Au-Pd and Pt-Pd while Au was essentially inactive. The presence of Au on the Au-Pt/TiO2 catalysts led to their higher activities （normalized per Pt atom） in a wide range of Au/Pt atomic ratios （i.e. 1/3-7/1 ）, and the one with the Au/Pt ratio of 3/1 exhibited the highest activity. Such promoting effect is ascribed to the increased electron density on Pt via the electron transfer from Au to Pt, as characterized by the temperature-programmed desorption of CO and infra-red spectroscopy for CO adsorption. Meanwhile, the presence of Au on Au-Pt/TiO2, most like due to the observed electron transfer, changed the product selectivity, and facilitated the oxidation of the secondary hydroxyl groups in glycerol, leading to the favorable formation of dihydroxyacetone over glyceraldehyde and glyceric acid that were derived from the oxidation of the primary hydroxyl groups. The synergetic effect between Au and Pt demonstrates the feasibility in the efficient oxidation of glycerol to the targeted products, for example, by rational tuning of the electronic properties of metal catalysts.

Recent advances in understanding the key catalyst factors for Fischer-Tropsch synthesis

Catalytic conversion of synthesis gas （CO＋H2） into hydrocarbons, also known as Fischer-Tropsch （FT） synthesis, is a crucial reaction for the translbrmation of non-petroleum carbon resources such as coal, natural gas, shale gas, coal-bed gas and biogas, as well as biomass into liquid fuels and chemicals. Many factors can influence the catalytic behavior of a FT catalyst. This review highlights recent advances in understanding some key catalyst factors, including the chemical state of active phases, the promoters, the size and the microenvironment of active phase, which determine the CO conversion activity and the product selectivity, particularly the selectivity to C5 ＋ hydrocarbons.

Doping Effect of CuO on CeO_2 for CO Oxidation

Cu-Ce-O catalysts, prepared by the amorphous citrate precursor (ACP) method, wereinvestigated by ICP, XRD and ndcro-reactor techniques. At low copper content of Cu-Ce-Ocatalysts, fluorite structures formed at low calcining temperatures, and Cuo doped into the CeO2matrix; at high copper content, in addition to the fluorite structure, crystalline monoclinic phaseCuO formed as well at high calcining temperatures. There was no other phase formed even calcinedat 1000℃. The results show that only a little CuO dopes into the CeO2 matrix to form complexoxide, which promotes the catalytic activity of CO oxidation greatly. The optimum Cu-Ce-Ocatalyst is composed of 15% copper by Cu/(Ce+Cu) atomic ratio, and calcined at 700℃ for 4h. Thephase compositions include the crystalline CuO and the active complex oxide with fluoritestructure. The formulation of the active complex oxide is Cu0.06Ce0. 94O1.94.

Density functional theory study on hydrogenation mechanism in catalyst-activated Mg(0001) surface

A small amount of Fe3O4 catalyst is known to substantially improve the adsorption and desorption thermodynamics and kinetics of Mg-based materials. Using density functional theory in combination with nudged elastic band method,the dissociative chemisorptions of hydrogen on both pure and Fe-doped Mg(0001) surfaces were studied. The adsorption energy calculations show that a weakly physisorbed state above pure and Fe-doped Mg surface atoms can serve as a precursor state to dissociative chemisorption. Then,the dissociation pathway of H2 and the relative barrier were investigated. The calculated dissociation barrier(1.08 eV) of hydrogen molecule on a pure Mg(0001) surface is in good agreement with comparable experimental and theoretical studies. For the Fe-doped Mg(0001) surface,the activated barrier decreases to 0.101 eV due to the strong interaction between the s orbital of H and the d orbital of Fe.