Fabrication of highly dispersed carbon doped Cu-based oxides as superior selective catalytic oxidation of ammonia catalysts via employing citric acid-modified carbon nanotubes doping CuAl-LDHs

In this work,the CuAl-LDO/c-CNTs catalyst was fabricated via in situ oriented assembly of layered-double hydroxides(LDHs)and citric acid-modified carbon nanotubes(c-CNTs)followed by annealing treatment,and evaluated in the selective catalytic oxidation(SCO)of NH_(3)to N_(2).The CuAl-LDO/c-CNTs catalyst presented better catalytic performance(98%NH_(3)conversion with nearly 90%N_(2)selectivity at 513 K)than other catalysts,such as CuAlO_(x)/CNTs,CuAlO_(x)/c-CNTs and CuAl-LDO/CNTs.Multiple characterizations were utilized to analyze the difference of physicochemical properties among four catalysts.XRD,TEM and XPS analyses manifested that CuO and Cu_(2)O nanoparticles dispersed well on the surface of the Cu Al-LDO/c-CNTs catalyst.Compared with other catalysts,larger specific surface area and better dispersion of CuAl-LDO/c-CNTs catalyst were conducive to the exposure of more active sites,thus improving the redox capacity of the active site and NH_(3)adsorption capacity.In-situ DRIFTS results revealed that the internal selective catalytic reduction(iSCR)mechanism was found over CuAl-LDO/c-CNTs catalyst.

Low-temperature catalytic oxidation of NO over Mn-Ce-O_x catalyst

A series of manganese-cerium oxide catalysts were prepared by different methods and used for low-temperature catalytic oxidation of NO in the presence of excess O2.Their surface properties were evaluated by means of BET and were characterized by using scanning electron microscopy(SEM) and X-ray diffractometer(XRD).The activity test of Mn-Ce-Ox catalysts showed that addition of Ce enhanced the activities of NO oxidation.The most active catalysts with a molar Ce/(Mn+Ce) ratio of 0.3 were prepared by co-precip...

Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

The selective catalytic oxidation （SCO） of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica （MPS） with different Mn/Fe ratios. Effects of the amount of manganese and iron, oxygen, and calcination temperature on NO conversion were also investigated. It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of 1 showed the highest activity at the calcination temperature of 400 °C. The results showed that over this catalyst, NO conversion reached 70% under the condition of 280 °C and a space velocity of 5000 h-1. SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240 °C. In addition, the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240 °C, and such an effect was reversible after heating treatment.

Selective catalytic oxidation of NO with O_2 over Ce-doped MnO_x/TiO_2 catalysts

A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.

2,5-Furandicarboxylic acid production via catalytic oxidation of 5-hydroxymethylfurfural:Catalysts,processes and reaction mechanism

Biomass conversion to value-added chemicals has received tremendous attention for solving global warming issues and fossil fuel depletion.5-Hydroxymethylfurfural(HMF)is a key bio-based platform molecule to produce many useful organic chemicals by oxidation,hydrogenation,polymerization,and ring-opening reactions.Among all derivatives,the oxidation product 2,5-furandicarboxylic acid(FDCA)is a promising alternative to petroleum-based terephthalic acid for the synthesis of biodegradable plastics.This review analytically discusses the recent progress in the thermocatalytic,electrocatalytic,and photocatalytic oxidation of HMF into FDCA,including catalyst screening,synthesis processes,and reaction mechanism.Rapid fundamental advances may be possible in non-precious metal and metal-free catalysts that are highly efficient under the base-free conditions,and external field-assisted processes like electrochemical or photoelectrochemical cells.

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO_2/MgO and SnO_2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether （DME） in the temperature range of 275 to 300 ℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate （MF） and dimethoxyethane （DMET） of 19.1% and 59.0% respectively were obtained at 275 ℃.

Dioxygen Affinities and Catalytic Oxidation Performance of Cobalt (Ⅱ)Complexes with N—Aryl Hydroxamic Acid

The oxygenation of cobalt (II) hydroxamates (CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined. The effects of X and Y bonded to hydroxamate group on dioxygen affinities and catalytic oxidation performance were also investigated.

Titanium-Containing Mesoporous Materials: Synthesis and Application in Selective Catalytic Oxidation

Titanium-containing mesoporous molecular sieves are of great significance in selective catalytic oxidation processes with bulky molecules. Recent researches and developments on the designing and synthesis of Ti-containing mesoporous materials have been reviewed. Various strategies for the preparation of Ti-containing mesoporous materials, such as direct synthesis and post-synthesis, are described. Modifications of Ti-containing mesoporous materials by surface-grafting and atom-planting are also discussed. All approaches aimed mainly at the improving of the stability, the hydrophobicity, and mostly the catalytic activity. Structural and mechanistic features of various synthetic systems are discussed. Ticontaining mesoporous materials in liquid phase catalytic oxidation of organic compounds with H2O2 as an oxidant is briefly summarized, showing their broad utilities for green synthesis of fine chemicals by catalytic oxidative reactions.

Gas Phase Selective Catalytic Oxidation of Toluene to Benzaldehyde on V_2O_5-Ag2O/η-Al_2O_3 Catalyst

Gas phase selective catalytic oxidation of toluene to benzatdehyde was studied on V_2O_5-Ag_2O/η-Al_2O_3 catalyst prepared by impregnation. The catalyst was characterized by XRD, XPS, TEM, and FT-IR. The catalytic results showed that toluene conversion and selectivity for benzaldehyde on catalyst sample No.4 (V/(V+Ag)=0.68) was higher than other catalysts with different V/Ag ratios. This was attributed to the higher surface area, larger pore volume and pore diameter of the catalyst sample No. 4 than the other catalysts. The XRD patterns recorded from the catalyst before and after the oxidation reaction revealed that the new phases were developed, and this suggested that silver had entered the vanadium lattice. XPS results showed that the vanadium on the surface of No.4 and No.5 sample was more than that in the bulk, thus forming a vanadium rich layer on the surface. It was noted that when the catalyst was doped by potassium promoter, the toluene conversion and selectivity for benzaldehyde were higher than those on the undoped catalyst. This was attributed to the disordered structure of V_2O_5 lattice of the K-doped catalyst and a better interracial contact between the particles.

Study on Property of Salicylaldehyde Schiff Base Metal Complexes for Catalytic Oxidation of Model Sulfides

Seven kinds of Schiff base metal complexes(C1-C7)were synthesized by the reaction of substituted salicylaldehyde Schiff base with cobalt nitrate,nickel nitrate,and copper nitrate,respectively.The oxygen carrying performance,and the catalytic property of complexes for the oxidation of model sulfides 1-hexanethiol,dibutyl sulfide,and 2-methylthiophene along with their influencing factors were explored,while the oxidized products of the model sulfides were also analyzed and characterized.The results show that the catalytic oxidation property of the complexes is determined by their oxygen carrying performance and solubility in n-octane.The oxygen carrying performance of the complexes is mainly affected by the central ion species,the electronic effects,and the spatial effects of the substituents as well as the degree of conjugation.More specifically,the oxygen carrying performance can be improved by enhancing the oxygenation capacity of the central metal ions,increasing the electron donating ability of the ligand substituent,and diminishing the steric hindrance as well as extending the conjugated chain.Complexes C7 were found to be with high oxygen carrying capacity and high solubility in n-octane,which shows the best catalytic oxidation property,and the oxidation conversion rates for 1-hexylthiol,dibutyl sulfide,and 2-methylthiophene are 74.2%,65.1%,and 22.7%,respectively.Upon using the oxidation catalyst of Schiff base metal complexes,three sulfides can be oxidized by oxygen to form sulfones and sulfoxides.1-Hexanethiol and dibutyl sulfide will continue to be oxidized to form sulfates and sulfites.

Remediation of sulfidic wastewater by catalytic oxidation with hydrogen peroxide

Oxidation of sulfide in aqueous solution by hydrogen peroxide was investigated in the presence of hydrated ferric oxide catalyst. The ferric oxide catalyst was synthesized by sol gel technique from ferric chloride and ammonia. The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-Ray diffraction analysis, scanning electrom microscope and energy dispersive X-ray analysis. The catalyst was quite effective in oxidizing the sulfide by hydrogen peroxide. The effects of sulfide concentration, catalyst loading, H2O2 dosing and temperature on the kinetics of sulfide oxidation were investigated. Kinetic equations and activation energies for the catalytic oxidation reaction were calculated based on the experimental results.

Enhancement effect of Mn doping on Co_(3)O_(4)derived from Co-MOF for toluene catalytic oxidation

The design of Co-Mn composite oxides catalysts derived from MOF is significant for catalytic combustion of toluene.Here,a series of M-CoaMnfbOx,with enhanced catalytic properties compared with that of MCo_(3)O_(4),were successfully prepared through pyrolysis of Mn-doped Co-MOF.The as-synthesized MCo1Mn1Ox(Co:Mn=1:1)exhibits an optimal catalytic activity with 90%toluene conversion reached at227℃,which benefits from the increase of Co^(3+),Oadsand the synergistic effect between Mn and Co.According to the analysis of the in situ diffuse reflectance infrared Fourier transform spectroscopy,toluene could be degraded easier on M-Co1Mn1Oxwith lower activation energy than M-Co_(3)O_(4).The main intermediate products are benzaldehyde,benzoic acid,anhydride,and maleate species.Those findings reveal the value of Mn doping for improved activity of toluene oxidation on MOF derived Co_(3)O_(4),which provide a feasible method for the construction of toluene-oxidation catalysts.

Dioxygen affinities and catalytic oxidation performance of cobalt(Ⅱ) hydroxamates with benzo-15-crown-5 pendants

The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （ΔH^0 and ΔS^0） were calculated based on these （Ko2） values, Meanwhile, these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δ under normal atmospheric pressure. The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL^4 2.

Liquid Phase Catalytic Oxidation of Low-Concentration H_2S in Cerium Doped Absorption Solution

For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.

A Composite Catalytic Oxidation-fluorescence Sensing System for 2,4-dichlorophenol Analysis based on Fe(Ⅲ)PcTs-BuOOH-CdTe QDs

The active oxygen species in the catalytic oxidation system of Fe(Ⅲ)PcTs-t-BuOOH were identified,and the mechanism of the catalytic oxidation of phenolic substrates was proposed.Quinone imine molecules,the main products of catalytic oxidation reaction,can be adsorbed on the surface of CdTe QDs,resulting in their fluorescence quenching.A dual function of catalytic oxidation and fluorescence sensing was developed for the determination of dichlorophenol(DCP)based on the Fe(Ⅲ)PcTs-BuOOH-CdTe QDs system.The linear detection range of DCP was 1×10^(-6)-1.3×10^(-4) mol/L,and the detection limit 2.4×10^(-7) mol/L.This method was characterized by high selectivity,good repeatability and desirable stability,presenting promising potentials for analyzing DCP concentration in real water samples.

Dioxygen Affinities and Catalytic Oxidation Performance of Co （Ⅱ） Complexes with Phenol Ether Bridged Dihydroxamic Acids

The oxygenation constants and thermodynamic parameter （△H°, △S°） of a series of novel Co （Ⅱ） complexes with phenol ether bridged dihydroxamic acids CoL^1-CoL^6 were measured, their catalytic performance in oxidation of p-xylene to p-toluic acid （PTA） were examined. The modulation of O2-binding capabilities and catalytic oxidation activities by X （X = Cl, OCH3） and Y （Y = H, CH3, Cl） groups bonded to the aromatic rings of the Co （Ⅱ） complexes were investigated.

Assisting effect of Al_(2)O_(3) on MnO_(x) for NO catalytic oxidation

Various Mn-based catalysts for NO oxidation were prepared using MnO_(x)as active compound,while Ti O_(2)and Al_(2)O_(3)were adopted as catalyst support.The performance of the catalysts was tested to study the effect of support on Mn-based catalyst activity.Performance of the catalysts followed as Mn_(0.4)/Al>Mn_(0.2)/Al>Mn_(0.4)/Ti>Mn_(0.2)/Ti>MnO_(x)>Al_(2)O_(3)on the whole,indicating the synergism of MnO_(x)and Al_(2)O_(3)for NO catalytic oxidation.Results were analyzed according to characterization data.Adsorbed oxygen on catalyst rather than lattice oxygen was detected as the active oxidizer for NO oxidation.As catalyst support,Al_(2)O_(3)provided more sites to carry surface adsorbed oxygen than TiO_(2),resulting in the presence of more active oxygen on Mn O_(x)/Al_(2)O_(3)than on MnO_(x)/TiO_(2).Moreover,MnO_(x)/Al_(2)O_(3)possessed high surface area and pore volume,which greatly benefited the adsorption of NO on catalyst and further favored the oxidation of NO by active oxygen.All these advantages helped Mn_(0.4)/Al exhibited the best catalytic efficiency.

Solution-combustion Synthesized Nano-pellet α-Al_(2)O_(3) and Catalytic Oxidation of Cyclohexane by Its Supported Cobalt Acetate

Nano-pelletα-Al_(2)O_(3) was prepared using aluminum nitrate as precursor and urea as fuel by a fast method of solution combustion synthesis.The formation of the nano material was dependent on the molar ratio of fuel/oxidant,calcination temperature,and foreign metallic ions.The prerequisite conditions of the formation were a suitable fuel/oxidant molar ratio larger than two and calcination temperature higher than 673 K.Foreign ions,Ce^(4+) or Co^(2+),hindered this formation via promoting the generation of stable penta-coordinated Al^(3+) ions due to strong interaction with alumina,were revealed by ^(27)Al NMR spectra.Such Al^(3+) ions were recognized as a critical intermediate state for the phase transformation of alumina and their presence deterred the transformation.The nano-pellet morphology of the product demonstrated a specific surface area of 69 m^(2)/g,of which the external surface area occupied 59 m^(2)/g.It was found that the supported cobalt acetate on such nano-pellets existed as nanoparticles attached to the external surface,evidenced by the TEM characterization.The prepared catalyst could efficiently catalyze the selective oxidation of cyclohexane under the reaction condition of pressure under 0.8 MPa,temperature at 373 K,and time for 4 hours.The conversion of the reaction achieved up to 7.9%;while the cyclohexanone selectivity was 42.7%and the cyclohexanone and cyclohexanol selectivity was 91.6%.This catalytic performance recommends the supported cobalt acetate on the inert nano-pellet a-Al_(2)O_(3) as a promising catalyst for the selective oxidation of cyclohexane.

Catalytic Oxidation of NO over La_(0.8)Sr_(0.2)MnO_3 Perovskite

Catalytic oxidation of NO by O2 over La0.8Sr0.2MnO3 was tested in a tubular reactor.The reaction temperature ranged from 373 to 473 K,space time from 0.090 to 0.720 s,inlet NO concentration from 300 to 2000μL/L, and O2 volume fraction from 3%to 9%.The steady-state conversion of NO was increased significantly with increasing reaction temperature and the space time,slightly with increasing the O2 concentration but decreased with increasing the inlet NO concentration at a lower temperature.Under the conditions of 0.720 s space time,500μL/L NO concentration, 5%O2 volume fraction and 473 K,NO conversion reached 90%.A kinetic model including a network of 12 elementary reactions with the desorption of NO2 as the rate-limiting step is established and fits the experimental data well.The activation energy of NO2 desorption from the catalyst surface is determined to be 101 kJ/mol.