Improvement of low-temperature catalytic activity over hierarchical Fe-Beta catalysts for selective catalytic reduction of NO_x with NH_3

Hierarchical Fe-Beta obtained by hydrothermal synthesis exhibited higher low-temperature NH_3-SCR activity than conventional Fe-Beta. In order to identify the main factors leading to the difference in catalytic activity, we investigated the pore structure, acidity and Fe sites of the hierarchical Fe-Beta and conventional Fe-Beta. The enhanced activity of hierarchical Fe-Beta was mainly due to the increase of the quantity of active Fe species. NH_3-TPD and DRIFTS results of NH_3 adsorption clearly verified that hierarchical Fe-Beta had more Lewis acid sites, which is beneficial to the adsorption and activation of NH_3. The H_2-TPR, UV–vis DRS, and EPR results confirmed that the hierarchical Fe-Beta had more isolated active Fe species, which may be associated with that the hierarchical structure introduced more structural defects as ion-exchange sites. Based on the analysis of kinetics experiments and the abovementioned characterizations, it can be concluded that the improvement of NH_3-SCR activity was not due to an intrinsic effect of the specific structural characteristics, but was related to more Fe active sites and better dispersion of Fe species in the hierarchical Fe-Beta.

Understanding the Pt-like Catalytic Activity of Transition Metal Carbide Ta4C_(3) for I_(3)^(-) Reduction

This paper attempts to understand the Pt-like catalytic activity of transition metal carbide Ta4C_(3) for IRR(I_(3)^(-)reduction reaction)based on the correlation of adsorption energy to d-band center(εd).Ta4C_(3) was prepared by carbothermal reduction method with a template.Its photoelectrochemical properties were investigated as a CE(counter electrode)in DSSC(dye-sensitized solar cell).Its surface electronic structures,including DOS(density of state)andεd,and adsorption energy were computed by first-principle DFT(density functional theory).In TMC(transition metal carbide)Ta4C_(3),the interaction between Ta and C atoms makes the d-band of Ta broaden and results in the downward shift of itsεd.A moderate absorption energy corresponding to theεd is achieved,which is the nature of the Pt-like catalytic activity of Ta4C_(3).Appropriate change of adsorption energy by adjustingεd is a promising strategy to improve catalytic activity.This work is of great significance to the fundamental and application researches.

Low-Temperature Denitrification Performance of Cu2O/Activated Carbon Catalysts for Selective Catalytic Reduction of NOx by CO

To improve the denitrification performance of carbon-based materials for sintering flue gas,we prepared a composite catalyst comprising coconut shell activated carbon(AC)modified by thermal oxidation air.The microstructure,the specific surface area,the pore volume,the crystal structure,and functional groups presented in the prepared Cu2O/AC catalysts were thoroughly characterized.By using scanning electron microscopy(SEM),nitrogen adsorption/desorption isotherms,Fourier-transform infrared(FTIR)spectroscopy and X-ray diffractometry(XRD),the effects of Cu2O loading and calcination temperature on Cu2O/AC catalysts were investigated at low temperature(150℃).The research shows that Cu on the Cu2O/AC catalyst is in the form of Cu2O with good crystalline performance and is spherical and uniformly dispersed on the AC surface.The loading of Cu2O increases the active sites and the specific surface area of the reaction gas contact,which is conducive to the rapid progress of the carbon monoxide selective catalytic reduction(CO-SCR)reaction.When the loading of Cu2O was 8%and the calcination temperature was 500℃,the removal rate of NOx facilitated by the Cu2O/AC catalyst reached 97.9%.These findings provide a theoretical basis for understanding the denitrification of sintering flue gas.

Effects of Co_3O_4 nanocatalyst morphology on CO oxidation:Synthesis process map and catalytic activity

This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.

Effect of Precipitation Method and Ce Doping on the Catalytic Activity of Copper Manganese Oxide Catalysts for CO Oxidation

The influence of Ce doping and the precipitation method on structural properties and the catalytic activity of copper manganese oxides for CO oxidation at ambient temperature have been investigated. The catalysts were characterized by means of the powder X-ray diffraction and N2 adsorption-desorption, the inductively coupled plasma atomic emission spectrometry, the temperature programmed reduction, diffuse reflectance UV-Vis spectra, and the X-ray photoelectron spectroscopy. It was found that after doping little amount of Ce in copper manganese oxide, CeO2 phase was highly dispersed and could prevent sintering and aggregating of the catalyst, the size of the catalytic material was decreased, the reducibility was enhanced, the specific surface area was increased and the formation of the active sites for the oxidation of CO was improved significantly. Therefore, the activity of the rare earth promoted catalyst was enhanced remarkably.

Highly Sensitive Ammonia Gas Sensors at Room Temperature Based on the Catalytic Mechanism of N,C Coordinated Ni Single-Atom Active Center

Significant challenges are posed by the limitations of gas sensing mechanisms for trace-level detection of ammonia(NH3).In this study,we propose to exploit single-atom catalytic activation and targeted adsorption properties to achieve highly sensitive and selective NH3 gas detection.Specifically,Ni singleatom active sites based on N,C coordination(Ni-N-C)were interfacially confined on the surface of two-dimensional(2D)MXene nanosheets(Ni-N-C/Ti_(3)C_(2)Tx),and a fully flexible gas sensor(MNPE-Ni-N-C/Ti_(3)C_(2)Tx)was integrated.The sensor demonstrates a remarkable response value to 5 ppm NH3(27.3%),excellent selectivity for NH3,and a low theoretical detection limit of 12.1 ppb.Simulation analysis by density functional calculation reveals that the Ni single-atom center with N,C coordination exhibits specific targeted adsorption properties for NH3.Additionally,its catalytic activation effect effectively reduces the Gibbs free energy of the sensing elemental reaction,while its electronic structure promotes the spill-over effect of reactive oxygen species at the gas-solid interface.The sensor has a dual-channel sensing mechanism of both chemical and electronic sensitization,which facilitates efficient electron transfer to the 2D MXene conductive network,resulting in the formation of the NH3 gas molecule sensing signal.Furthermore,the passivation of MXene edge defects by a conjugated hydrogen bond network enhances the long-term stability of MXene-based electrodes under high humidity conditions.This work achieves highly sensitive room-temperature NH3 gas detection based on the catalytic mechanism of Ni single-atom active center with N,C coordination,which provides a novel gas sensing mechanism for room-temperature trace gas detection research.

Size-dependent peroxidase-like catalytic activity of Fe_3O_4 nanoparticles

Peroxidase-like catalytic properties of Fe3O4 nanoparficles （NPs） with three different sizes, synthesized by chemical coprecipitation and sol-gel methods, were investigated by UV-vis spectrum analysis. By comparing Fe3O4 NPs with average diameters of 11, 20, and 150 nm, we found that the catalytic activity increases with the reduced nanoparticle size. The electrochemical method to characterize the catalytic activity of Fe3O4 NPs using the response currents of the reaction product and substrate was also developed.

The catalytic activity of transition metal oxide nanoparticles on thermal decomposition of ammonium perchlorate

The catalytic proficiency of three MONs for AP thermal decomposition was studied in this work.A chemical co-precipitation method was used for synthesis of MONs(CuZnO,CoZnO,and NiZnO)and their characterization carried out by utilizing XRD,FTIR,and SEM.The TGA/DSC technique was employed for the investigation of the catalytic proficiency of MONs on the AP.The DSC data were used for measuring activation energy of catalyzed AP by using Ozawa,Kissinger,and Starink method.The MONs were much sensitive for AP decomposition,and the performance of AP decomposition was further improved.Among all the MONs,the CuZnO exhibits higher catalytic action than others and decomposition temperature of AP is descending around 117℃ by CuZnO.The reduction in the activation energy was noticed after the incorporation of MONs in AP.

Preparation of SO_4^(2-)/TiO_2-WO_3 solid superacid and its catalytic activity in acetalation and ketaltion

SO_4^(2-)/TiO_2-WO_3 was prepared and its catalytic activity under differentsynthetic conditions was discussed with esterification of n-butanoic acid and n-butyl alcohol asprobing reaction. The optimum conditions are found that the mass fraction of H_2WO_4 used in thecompound is 12.5 percent, the calcination temperature is 580 deg C, the calcination time is 3 h, andthe soaked consistency of H_2SO_4 is 1.0 mol centre dot L^(-1). Then SO_4^(2-)/TiO_2-WO_3 wasapplied as the catalyst in the catalytic synthesis of eight similar important ketals and acetalsunder the optimum conditions and revealed high catalytic activity. On condition that the molar ratioof aldehyde/ketone to glycol is 1:1.5, the mass fraction of the catalyst used in the reactants is0.5 percent, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 64.2percent-95.1 percent. Moreover, it can be easily recovered and reused.

Influence of chromium modification on the properties of MnO_x-FeO_x catalysts for the low-temperature selective catalytic reduction of NO by NH_3

Catalytic properties of MnOx-FeOx complex oxide （hereafter denoted as Mn-Fe） catalysts modified with different loadings of chromium oxide were investigated by using the combination of physico-cbemical techniques, such as N2 physisorption, X-ray diffraction （XRD）, high-resolution transmission electron microscope （HRTEM）, in situ Fourier transform infrared spectroscopy （in situ FT-IR） and temperature-programmed reduction （TPR） and their catalytic activities were evaluated with the selective catalytic reduction （SCR） of NOx by NH3. It was found that with the addition of Cr, more NO could be removed in the low-temperature window （below 120 ℃）. Among the tested catalysts, Mn-Fe- Cr （2 ： 2 ： 1） catalyst exhibited the best catalytic performance at 80 ℃ with the NO conversion higher than 90%. The combination of the reaction and characterization results indicated that （1） the strong interaction among tertiary metal oxides existed in the catalysts when Cr was appropriately added, which made the active components better dispersed with less agglomeration and sintering and the largest BET specific surface area could be obtained; （2） Cr improved the low-temperature reducibility of the catalyst and promoted the formation of the active intermediate （-NH3＋）, which favored the low-temperature SCR reaction.

Synthesis of novel MnO_x@TiO_2 core-shell nanorod catalyst for low-temperature NH_3-selective catalytic reduction of NOx with enhanced SO_2 tolerance

In this study,a MnOx@TiO2 core‐shell catalyst prepared by a two‐step method was used for the low‐temperature selective catalytic reduction of NOx with NH3.The catalyst exhibits high activity,high stability,and excellent N2 selectivity.Furthermore,it displays better SO2 and H2O tolerance than its MnOx,TiO2,and MnOx/TiO2 counterparts.The prepared catalyst was characterized systematically by transmission electron microscopy,high‐resolution transmission electron microscopy,X‐ray diffraction,Raman,BET,X‐ray photoelectron spectroscopy,NH3 temperature‐programmed desorption and H2 temperature‐programmed reduction analyses.The optimized MnOx@TiO2 catalyst exhibits an obvious core‐shell structure,where the TiO2 shell is evenly distributed over the MnOx nanorod core.The catalyst also presents abundant mesopores,Lewis‐acid sites,and high redox capability,all of which enhance its catalytic performance.According to the XPS results,the decrease in the number of Mn4+active centers after SO2 poisoning is significantly lower in MnOx@TiO2 than in MnOx/TiO2.The core‐shell structure is hence able to protect the catalytic active sites from H2O and SO2 poisoning.

Synthesis of Hierarchically Porous CaFe204/Carbon Fiber Hybrids and Microwave Induced Catalytic Activity

Hierarchically porous CaFe204/carbon fiber hybrids with enhanced microwave induced cat- alytic activity for the degradation of methyl violet （MV） from water were synthesized from kapok by a novel two-step process coupling pore-fabricating and nanoparticles assembling. The as-prepared samples exhibited characteristic hollow fiber morphology, CaFe204 nanopar- ticles dispersed uniformly on the surface of hollow carbon fibers （HCF）. The effects of various factors such as CaFe204 loading, microwave power, catalyst doses, initial concen- tration of MV solution and pH value on the microwave induced degradation of MV over CaFe204/HCF were evaluated. It was found that the microwave induced degradation of MV over CaFe204/HCF had high reaction rate and short process time. The kinetic study indicated that the degradation of MV over CaFe204/HCF followed pseudo-first-order kinet- ics model. The high catalytic activity of CaFe204/HCF was facilitated by the synergistic relationship between microwave induced catalytic reaction and adsorption characteristics.

TiO_2-Supported Binary Metal Oxide Catalysts for Low-temperature Selective Catalytic Reduction of NO_x with NH_3

Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.

Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

Theoretical Study on the Catalytic Activity and Sulfur Resistibility of Amorphous Alloy Ni-B-P

In the present paper, one hundred cluster models NinBP （n = 1-6） have been designed and studied by density functional theory （DFT） to get an insight into the local structure, catalytic properties and sulfur resistibility of amorphous alloy Ni-B-P. The configurations in triplet state are found more stable than those in the singlet state. It is found： that as the content of Ni in the clusters increases, the value of Fermi level in clusters fluctuated, which shows that the content of Ni can influence the Fermi level to a certain extent. Based on the Fermi level and DOS, we consider the activity of catalyst in hydrogenation reaction is the best in cluster Ni3BP. On the basis of the charge of clusters NinBP （n = 1 -6）, we conclude the amorphous alloy Ni-B-P with high Ni content has better sulfur resistibility and the best hydrogenation activity, strong sulfur resistibility appears in clusters Ni3BP, and the amorphous alloy Ni60B20P20 with similar proportion is expected to prepare in the future.

Study on Hydrothermal Stability and Catalytic Activity of Al-SBA-15 Mesoporous Materials Prepared by Impregnation Method

The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.

Surface density of synthetically tuned spinel oxides of Co^(3+) and Ni^(3+) with enhanced catalytic activity for methane oxidation

Spinel oxides containing Co and Ni are a promising substitute as a noble metal catalyst for methane combustion.Achieving a complete oxidation of methane under 400°C remains challenging,andhydrothermal 60 h NiClittle impact on activity,especially at high space velocities due to the long hydrothermal time with less absorbed oxygen species and crystal defects.Overall,these results help clarify methane activa-tion mechanisms and aid the development of more efficient low-cost catalysts.

One-step fabrication of TiO2/graphene hybrid mesoporous film with enhanced photocatalytic activity and photovoltaic performance

We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.

Phospholipase C from Pseudomonas aeruginosa and Bacillus cereus:characterization of catalytic activity

Objective:To study characteristics of phospholipases C(PLCs),their importance for producing microorganisms us well us the potential of their use for industrial purposes.Methods:PLC from Bacillus cereus(B.cereus) D101 was selected as an example of Gram-positive PLCs and PLC from Pseudomanas aeruginosa(P.aeruginosa) D183 of Gram-negative ones.Enzymes were partially purified by ammonium sulfate precipitation followed by membrane dialysis.Partially purified preparations were used to study effect of different factors on activities as well as in substrate specificity tests which were conducted using a turbidimetric assay method.Results:Maximum activity was at pH 7 and 8 and 40 ℃ for P.aeruginosa PLC,and pH 8-10 and 37 ℃ for B.cereus PLC.Both PLCs were inhibited by Pi at 5 mM or higher,whereas,PLC from B.cereus only was inhibited by EDTA.Activity of P.aeruginosa PLC was not affected by removing Zn^(2+) ions from reaction mixture or their replacement with Ca^(2+),Ba^(2+),Mg^(2+) or Mn^(2+)ions.Vis-a-vis,activity of B.cereus PLC was found to be metal ion dependent PLCs from both isolates were relatively thermostable and showed maximum affinity toward phosphatidylcholine.Sphingomyelin and phosphatidylethanolamine were not good substrates and phosphatidylinositol,phosphatidylserine,phosphatidylglycerol and cardiolipin could be considered nonsubstrates.Conclusions:Human body physiological conditions could favor activity of P.aeruginosa and B.cereus PLCs.These enzymes may participate in phosphate scavenging and virulence of producing isolates but not in autolysis.PLCs from both isolates are potential candidates for industrial use.

A new method to improve surface morphology of Ni-Fe-Mo-Co alloy electrode and its catalytic activity for HER

A new pretreatment method has been developed to improve the catalytic activity of the Ni-Fe-Mo-Co alloy electrode for hydrogen evolution reaction （HER）. The procedure involves pre-electrolyzing the Ni-Fe-Mo-Co alloy electrode in 30% KOH solution containing 10% potassium sodium tartrate at 70℃ for 2 h, until some of the Mo and Fe elements are leached out. The surface morphology of the Ni-Fe-Mo-Co alloy demonstrates a unique hive-like structure after the pre- treatment, which has the pore size in a nanometer range （about 50 nm）, a very large real surface area, and good stability. The results of the electrochemical studies show that compared to other similar electrode materials and the treated Ni-Fe-Mo-Co electrode by leaching method, the pre-treated Ni-Fe-Mo-Co electrode has a much lower overpotential and much higher exchange current density for HER. In addition, a long-term continuous electrolysis test with a current interruption shows that the Ni-Fe-Mo-Co alloy has excellent catalytic stability.