Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Effect of co-existing organic compounds on adsorption of perfluorinated compounds onto carbon nanotubes

Co-existing organic compounds may affect the adsorption of perfluorinated compounds (PFCs) and carbon nanotubes in aquatic environments. Adsorption of perfluorooctane sulfonate (PFOS), perfluorooctane acid (PFOA), perfluorobutane sulfonate (PFBS), and perfluorohexane sulfonate (PFH_xS) on the pristine multi-walled carbon nanotubes (MWCNTs-Pri), carboxyl functionalized MWCNTs (MWCTNs-COOH), and hydroxyl functionalized MWCNTs (MWCNTs-OH) in the presence of humic acid, 1-naphthol, phenol, and benzoic acid was studied. Adsorption kinetics of PFOS was described well by the pseudo-second-order model and the sorption equilibrium was almost reached within 24 h. The effect of co-existing organic compounds on PFOS adsorption followed the decreasing order of humic acid>1-naphthol>benzoic acid>phenol. Adsorbed amounts of PFOS decreased significantly in the presence of co-existing or preloaded humic acid, and both adsorption energy and effective adsorption sites on the three MWCNTs decreased, resulting in the decrease of PFOS adsorption. With increasing pH, PFOS removal by three MWCNTs decreased in the presence of humic acid and phenol. The adsorbed amounts of different PFCs on the MWCNTs increased in the order of PFBSxS相似文献   

Utilization of nano/micro-size iron recovered from the fine fraction of automobile shredder residue for phenol degradation in water

Phenol removal by n/m Fe in the presence of H₂O₂ was highly effective. Increasing the amounts of n/m Fe and H₂O₂?increased the phenol removal rate. Phenol removal was decreased with an increase in the concentration of phenol. The natural pH (6.9) of the solution was highly effective for phenol removal. The pseudo-first-order kinetics was best fitted for the degradation of phenol. The study investigates the magnetic separation of Fe from automobile shredder residue (ASR) (<0.25 mm) and its application for phenol degradation in water. The magnetically separated Fe was subjected to an ultrasonically assisted acid treatment, and the degradation of phenol in an aqueous solution using nano/micro-size Fe (n/m Fe) was investigated in an effort to evaluate the possibility of utilizing n/m Fe to remove phenol from wastewater. The prepared n/m Fe was analyzed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The effects of the dosages of n/mFe, pH, concentration of phenol and amount of H₂O₂ on phenol removal were evaluated. The results confirm that the phenol degradation rate was improved with an increase in the dosages of n/mFe and H₂O₂; however, the rate is reduced when the phenol concentration is higher. The degradation of phenol by n/mFe followed the pseudo-first-order kinetics. The value of the reaction rate constant (k) was increased as the amounts of n/m Fe and H₂O₂ increased. Conversely, the value of k was reduced when the concentration of phenol was increased. The probable mechanism behind the degradation of phenol by n/m Fe is the oxidation of phenol through hydroxyl radicals which are produced during the reaction between H₂O₂ and n/m Fe.     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.     

Deposition of copper nanoparticles on multiwalled carbon nanotubes modified with poly (acrylic acid) and their antimicrobial application in water treatment

A novel hybrid material, Cu-PAA/MWCNTs (copper nanoparticles deposited multiwalled carbon nanotubes with poly (acrylic acid) as dispersant, was prepared and expected to obtain a more effective and well-dispersed disinfection material for water treatment. X-ray energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), the X-ray fluorescence (XRF), X-ray photoelectron spectra (XPS), Fourier transform infrared spectra (FT-IR), Raman spectroscopy, and thermal gravimetric analyzer (TGA) were used to characterize the Cu-PAA/MWCNTs. Escherichia coli (E. coil) was employed as the target bacteria. The cell viability determination and fluorescence imaging results demonstrated that Cu-PAA/MWCNTs possessed strong antimicrobial ability on E. coil. The deposited Cu was suggested to play an important role in the antimicrobial action of Cu-PAA/MWCNTs.     

Wastewater treatment by catalytic wet air oxidation process over Al-Fe pillared clays synthesized using microwave irradiation

Microwave irradiation has been used to prepare Al, Fe-pillared clays from a natural Tunisian smectite from the El Hicha deposit (province of Gabes). Chemical analysis, XRD spectra and surface properties evidenced the success of pillaring process. The obtained solids present higher surface area and pore volume than conventionally prepared Al-Fe pillared clays. The main advantages of the microwave methodology are the considerable reduction of the synthesis time and the consumption of water. The microwave-derived Al-Fe pillared clays have been tested for catalytic wet air oxidation (CWAO) of phenol in a stirred tank at 160°C and 20 bar of pure oxygen pressure. These materials are efficient for CWAO of phenol and are highly stable despite the severe operating conditions (acidic media, high pressure, high temperature). The catalyst deactivation was also significantly hindered when compared to conventionally prepared clays. Al-Fe pillared clays prepared by microwave methodology are promising as catalysts for CWAO industrial water treatment.

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ZnO-MgO/Al2O3吸附-臭氧催化氧化处理难降解有机废水

以活性氧化铝为载体,采用浸渍法制备催化剂,对甲基橙及草酸模拟废水进行处理.在中性条件下,臭氧催化氧化比单独臭氧氧化能提前30 min使得甲基橙溶液褪色,反应105 min时,臭氧催化氧化对TOC的去除率高达96.53%,比单独使用臭氧氧化对甲基橙TOC去除率提高了47.19%,在处理草酸废水时臭氧催化氧化对TOC去除率高达80.59%,比单独使用臭氧氧化对草酸TOC去除率提高了59.14%.在处理甲基橙及草酸的小试实验中催化剂对有机污染物的吸附作用起到了加快反应进行的作用.在对垃圾渗滤液超滤出水时,O₃与COD质量比为1:1时,臭氧催化氧化对COD去除率为49.09%,比单独使用臭氧氧化提高36.37%,臭氧催化氧化对TOC的去除率是单独使用臭氧氧化的2.54倍,在处理垃圾渗滤液纳滤浓水时,臭氧催化氧化对COD去除率高达88.72%,比单独使用臭氧氧化提高37.60%,并且臭氧催化氧化对TOC的去除率是单独臭氧氧化的1.6倍.臭氧催化氧化反应过程中产生的羟基自由基对有机物更快的反应速率.     

The abatement of major pollutants in air and water by environmental catalysis

This review reports the research progress in the abatement of major pollutants in air and water by environmental catalysis. For air pollution control, the selective catalytic reduction of NO _x (SCR) by ammonia and hydrocarbons on metal oxide and zeolite catalysts are reviewed and discussed, as is the removal of Hg from flue gas by catalysis. The oxidation of Volatile organic compounds (VOCs) by photo- and thermal-catalysis for indoor air quality improvement is reviewed. For wastewater treatment, the catalytic elimination of inorganic and organic pollutants in wastewater is presented. In addition, the mechanism for the procedure of abatement of air and water pollutants by catalysis is discussed in this review. Finally, a research orientation on environment catalysis for the treatment of air pollutants and wastewater is proposed.     

Phenolic compounds removal by wet air oxidation based processes

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, we especially reviewed the WAO and CWAO processes for phenolic compounds degradation. It provides a comprehensive introduction to the CWAO processes that could be beneficial to the scientists entering this field of research. The influence of different reaction parameters, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail; Homogenous catalysts and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed, among which Cu based catalysts and Ru catalysts were shown to be the most active. Three different kinds of the reactor implemented for the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degradation efficiency and reduce the cost of the CWAO process, biological degradation can be combined to develop an integrated technology.

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CuO/zeolite catalyzed oxidation of gaseous toluene under microwave heating

The development of a combined process of catalytic oxidation and microwave heating for treatment of toluene waste gas was described in this work. Toluene, a typical toxic volatile organic compound, was oxidized through a fixed bed reaction chamber containing zeolite-supported copper oxide (CuO/zeolite) catalyst mixed with silicon carbide (SiC), an excellent microwave-absorbing material. The target compound was efficiently degraded on the surface of the catalyst at high reaction temperature achieved by microwave-heated SiC. A set of experimental parameters, such as microwave power, air flow and the loading size of CuO etc., were investigated, respectively. The study demonstrated these parameters had critical impact on toluene degradation. Under optimal condition, 92% toluene was removed by this combined process, corresponding to an 80%–90% TOC removal rate. Furthermore, the catalyst was highly stable even after eight consecutive 6-h runs. At last, a hypothetical degradation pathway of toluene was proposed based on the experimental data obtained from gas chromatography-mass spectrum and Fourier transform infrared spectroscopy analyses.     

Effect of nitrobenzene on the performance and bacterial community in an expanded granular sludge bed reactor treating high-sulfate organic wastewater

Less than 50 mg/L nitrobenzene brought little effect on anaerobic sulfate reduction. Kinetics of sulfate reduction under different nitrobenzene contents was studied. Increased nitrobenzene contents greatly changed the bacterial community structure. Genus Desulfovibrio played the key role in anaerobic sulfate reduction process. Nitrobenzene (NB) is frequently found in wastewaters containing sulfate and may affect biological sulfate reduction process, but information is limited on the responses of sulfate reduction efficiency and microbial community to the increased NB contents. In this study, a laboratory-scale expanded granular sludge bed reactor was operated continuously to treat high-sulfate organic wastewater with increased NB contents. Results successfully demonstrated that the presence of more than 50 mg/L NB depressed sulfate reduction and such inhibition was partly reversible. Bath experiments showed that the maximum specific desulfuration activity (SDA) decreased from 135.80 mg SO₄^2?/gVSS/d to 30.78 mg SO₄^2?/gVSS/d when the NB contents increased from none to 400 mg/L. High-throughput sequencing showed that NB also greatly affected bacterial community structure. Bacteroidetes dominated in the bioreactor. The abundance of Proteobacteria increased with NB addition while Firmicutes presented an opposite trend. Proteobacteria gradually replaced Firmicutes for the dominance in response to the increase of influent NB concentrations. The genus Desulfovibrio was the dominant sulfate-reducing bacteria (SRB) with absence or presence of NB, but was inhibited under high content of NB. The results provided better understanding for the biological sulfate reduction under NB stress.     

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII). • Pb(II) enhanced Mn(VII) oxidation performance over a wide pH range. • Pb(II) did not alter the pH-rate profile for contaminants oxidation by Mn(VII). • Mn(VII) alone cannot oxidize Pb(II) effectively at pH below 5.0. • Pb(III) plays important roles on enhancing Mn(VII) decontamination process. The permanganate (Mn(VII)) oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds. Nonetheless, only a few studies have been conducted to explore the role of the heavy metals (especially the redox-active ones) during the Mn(VII) oxidation process. In this study, taking Pb(II) as an example, its influence on the Mn(VII) decontamination performance has been extensively investigated. It was found that, with the presence of Pb(II), Mn(VII) could degrade diclofenac (DCF), 2,4-dichlorophenol, and aniline more effectively than without. For instance, over a wide pH range of 4.5–8.0, the dosing of 10 μmol/L Pb(II) accelerated the DCF removal rate from 0.006–0.25 min⁻¹ to 0.05–0.46 min⁻¹ with a promotion factor of 1.9–9.4. Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII) could react with Pb(II) to produce Mn(IV) and Pb(IV) at pH 6.0–8.0, further experiments revealed that Pb(II) did not exert its enhancing effect through promoting the generation of MnO₂, as the reactivity of MnO₂ was poor under the employed pH range. At pH below 5.0, it was interesting to find that, a negligible amount of MnO₂ was formed in the Mn(VII)/Pb(II) system in the absence of contaminants, while once MnO₂ was generated in the presence of contaminants, it could catalyze the Pb(II) oxidation to Pb(IV) by Mn(VII). Collectively, by highlighting the conversion process of Pb(II) to Pb(IV) by either Mn(VII) or MnO₂, the reactive Pb(III) intermediates were proposed to account for the Pb(II) enhancement effect.     

Adsorption of toluene, ethylbenzene and xylene isomers on multi-walled carbon nanotubes oxidized by different concentration of NaOCl

Multi-walled carbon nanotubes (MWCNTs) were fabricated and oxidized by different concentrations of sodium hypochlorite (NaOCl) solutions. The untreated MWCNTs and modified MWCNTs were employed as adsorbents to study their characterizations and adsorption performance of toluene, ethylbenzene and xylene isomers (TEX) in an aqueous solution. The physicochemical properties of MWCNTs were greatly affected after oxidation, which influences TEX adsorption capacity. The 3% NaOCl-oxidized MWCNTs shows the greatest enhancement in TEX adsorption, followed by the 30% NaOCl. More interestingly, the 15% NaOCl-oxidized MWCNTs has lower adsorption capacities than untreated MWCNTs. The adsorption mechanism of TEX on treated MWCNTs is attributed to the combined action of hydrophobic interaction, π-π bonding interaction between the aromatic ring of TEX and the oxygen-containing functional groups of MWCNTs and electrostatic interaction. 3% NaOCl solution could not only introduce much oxygen-containing functional groups on MWCNTs, but also lead to less damage for the pore structure. This suggests that the CNTs-3% NaOCl is efficient adsorbent for TEX and that they may possess good potential for TEX removal in wastewater treatment.     

Experimental and DFT insights into nitrogen and sulfur co-doped carbon nanotubes for effective desulfurization of liquid phases: Equilibrium & kinetic study

• Synthesis of NS-CNTS is used in a high desulfurization performance. • Synthesizing NS-CNT is considered as a novel adsorbent from low-cost precursors. • A high sulfur removal capacity for NS-CNT is attained compared with recent works. Herein, nitrogen and sulfur co-doped carbon nanotubes (NS-CNT) adsorbents were synthesized via the chemical vapor deposition technique at 1000°C by employing the camphor, urea and sulfur trioxide pyridine. In this study, desulfurization of two types of mercaptans (dibenzothiophene (DBT) and tertiary butyl mercaptan (TBM) as nonlinear and linear forms of mercaptan) was studied. In this regard, a maximum capacity of NS-CNT was obtained as 106.9 and 79.4 mg/g and also the removal efficiencies of 98.6% and 88.3% were achieved after 4 h at 298K and 0.9 g of NS-CNT for DBT and TBM, respectively. Characterization of the NS-CNTs was carried out through exploiting scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and elemental analysis (CHN). The isotherm equilibrium data could be ascribed to the Freundlich nonlinear regression form and the kinetic data was fitted by nonlinear form of the pseudo second order model. The negative values of ΔS⁰, ΔH⁰ and ΔG⁰ specify that the adsorption of both types of mercaptans was a natural exothermic process with a reduced entropy. Maintenance of more than 96% of the adsorption capacity even after nine cycles suggest the NS-CNT as a superior adsorbent for mercaptans removal in the industry. Density functional theory (DFT) calculations were also performed to peruse the effects of S/N co-doping and carbon monovacancy defects in CNTs toward the adsorption of DBT and TBM.     

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru–Ce/Al₂O₃ on catalytic activity.     

Interaction of carbonaceous nanomaterials with wastewater biomass

Increasing production and use of carbonaceous nanomaterials (NMs) will increase their release to the sewer system and to municipal wastewater treatment plants. There is little quantitative knowledge on the removal of multi-walled carbon nanotubes (MWCNTs), graphene oxide (GO), or few-layer graphene (FLG) from wastewater into the wastewater biomass. As such, we investigated the quantification of GO and MWCNTs by UV-Vis spectrophotometry, and FLG using programmable thermal analysis (PTA), respectively. We further explored the removal of pristine and oxidized MWCNTs (O-MWCNTs), GO, and FLG in a biomass suspension. At least 96% of pristine and O-MWCNTs were removed from the water phase through aggregation and 30-min settling in presence or absence of biomass with an initial MWCNT concentration of 25 mg·L⁻¹. Only 65% of GO was removed with biomass concentration at or above 1,000 mg·L⁻¹ as total suspended solids (TSS) with the initial GO concentration of 25 mg·L⁻¹. As UV-Vis spectrophotometry does not work well on quantification of FLG, we studied the removal of FLG at a lower biomass concentration (50 mg TSS·L⁻¹) using PTA, which showed a 16% removal of FLG with an initial concentration of 1 mg·L⁻¹. The removal data for GO and FLG were fitted using the Freundlich equation (R² = 0.55, 0.94, respectively). The data presented in this study for carbonaceous NM removal from wastewater provides quantitative information for environmental exposure modeling and life cycle assessment.     

Synthesis, physicochemical characterizations and catalytic performance of Pd/carbon-zeolite and Pd/carbon-CeO2 nanocatalysts used for total oxidation of xylene at low temperatures

In this work, xylene removal from waste gas streams was investigated via catalytic oxidation over Pd/carbon-zeolite and Pd/carbon-CeO₂ nanocatalysts. Activated carbon was obtained from pine cone chemically activated using ZnCl₂ and modified by H₃PO₄. Natural zeolite of clinoptilolite was modified by acid treatment with HCl, while nano-ceria was synthesized via redox method. Mixed supports of carbon-zeolite and carbonceria were prepared and palladium was dispersed over them via impregnation method. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller surface area (BET), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) techniques. Characterization of nanocatalysts revealed a good morphology with an average particle size in a nano range, and confirmed the formation of nano-ceria with an average crystallite size below 60 nm. BET analysis indicated a considerable surface area for catalysts (～1000 m²·g^?1). FTIR patterns demonstrated that the surface groups of synthesized catalysts are in good agreement with the patterns of materials applied in catalyst synthesis. The performance of catalysts was assessed in a low-pressure catalytic oxidation pilot in the temperature range of 100° C-250°C. According to the reaction data, the synthesized catalysts have been shown to be so advantageous in the removal of volatile organic compounds (VOCs), representing high catalytic performance of 98% for the abatement of xylene at 250°C. Furthermore, a reaction network is proposed for catalytic oxidation of xylene over nanocatalysts.     

Ce0.7Zr0.3O2纳米棒的制备及其对柴油车尾气碳颗粒的催化净化性能

本研究以硝酸铈、硝酸锆为原料使用溶剂热合成法,制备了CeO₂-ZrO₂纳米棒催化剂(Ce_0.7Zr_0.3O₂(NR)),并用于柴油车尾气碳颗粒催化净化.催化活性检测证实:Ce_0.7Zr_0.3O₂(NR)纳米棒催化剂可有效净化柴油车尾气碳烟颗粒.在Ce_0.7Zr_0.3O₂(NR)存在下,碳颗粒净化率为10%、50%和90%时,所需温度分别仅为375℃、414℃和455℃,比商用Ce_0.7Zr_0.3O₂和Ce0.3Zr0.7O2催化剂性能更优.采用氮吸附-脱附、X射线光电子能谱(XPS)、H2程序升温还原(H₂-TPR)、X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术对催化剂进行表征.XRD和Raman结果证实,Ce_0.7Zr_0.3O₂(NR)主要由立方相CeO₂构成,并掺杂了少量四方相氧化锆.SEM和TEM结果则显示,Ce_0.7Zr_0.3O₂(NR)催化剂颗粒明显由纳米棒堆积而成,特定的纳米形貌会影响其对碳颗粒的催化氧化活性.XPS结果证明Ce_0.7Zr_0.3O₂(NR)催化剂主要具有晶格氧、化学氧和表面吸附氧等氧物种;晶格氧是碳颗粒氧化的活性氧物种,其溢流到催化剂表面可与碳颗粒接触从而提高反应活性;化学氧和表面吸附氧均为表面氧物种,极易与表面固体碳颗粒直接接触,从而可在较低温度下促进碳颗粒的净化.H₂-TPR结果进一步证实了XPS结果,Ce_0.7Zr_0.3O₂(NR)催化剂的低温还原温度比商用Ce_0.7Zr_0.3O₂催化剂更低,且含有更多的易还原氧物种,这些低温易还原氧物种可以在较低温度下参与催化反应,促进柴油车尾气颗粒物的低温催化净化.     

Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Aqueous solutions of phenol were oxidized by hydrogen peroxide assisted by microwave (MW) irradiation. A simple kinetic model for the overall degradation of phenol in the presence of excess H₂O₂ is proposed in which the degradation rate of phenol is expressed as a linear function of the concentrations of phenol and H₂O₂. A detailed parametric study showed that the degradation rate of phenol increased with increasing [H₂O₂] until saturation was observed. Phenol degradation followed apparent zero-order kinetics under MW radiation or H₂O₂ oxidation. However, after 90 min of irradiation, the observed kinetics shifted to pseudo first order. The overall reaction rates were significantly enhanced in the combined MW/H₂O₂ system, mainly because microwave could accelerate H₂O₂ to generate hydroxyl radical (^·OH) and other reactive oxygen intermediates. The observed synergetic effects of the MW/H₂O₂ process resulted in an increased in the net reaction rate by a factor of 5.75. When hydrogen peroxide is present in a large stoichiometric excess, the time required to achieve complete mineralization is reduced significantly.