不同催化剂可见光催化H2O2降解莠去津的性能研究

以锐钛矿型TiO2(记为A)以及Fe3+改性后的锐钛矿型TiO2(记为Fe-A)为光催化剂,以内分泌干扰物莠去津为目标污染物,研究了H2O2加入前后对两种不同催化剂可见光催化降解莠去津的影响,及其可见光催化降解莠去津的反应机理。结果表明:在H2O2存在的条件下,锐钛矿型TiO2可见光催化降解莠去津的光催化性能有了一定的提高,而Fe3+改性过后的锐钛矿型TiO2可见光催化降解莠去津的性能却得到显著提高,反应1h,降解率便达到98%。形成这种结果的原因可以初步判定为前者是H2O2吸附于锐钛矿型TiO2表面形成特殊结构,产生的O2-.主要起氧化降解作用,而后者则由于其溶出的Fe3+与H2O2作用在可见光下发生光芬顿反应,进而对莠去津起到良好的降解效果。     

Fe2O3/γ-Al2O3催化剂的制备表征及其催化活性的研究

采用浸渍法制备用于常温常压下催化湿式过氧化氢氧化工艺(CWPO)的负载型Fe2O3/γ-Al2O3催化剂,采用BET,SEM,XRD,XPS和XRF对其进行了表征,并以偶氮染料酸性橙为特征污染物,考察了Fe2O3/γ-Al2O3催化剂的催化活性和稳定性.研究表明,Fe2O3/γ-Al2O3催化剂中的活性组分Fe是以α-Fe2O3的形式存在,且Fe的负载量为1.907%(质量分数).对于初始浓度为500mg/L的酸性橙模拟废水,当Fe2O3/γ-Al2O3催化剂和H2O2氧化剂的投加量分别为30g/L和330mg/L时,处理3h时染料的脱色率、COD去除率和TOC去除率可分别达到82.10%,80.14%和74.2%.与传统Fenton试剂法相比,以Fe2O3/γ-Al2O3为催化剂的CWPO工艺具有矿化程度高和催化剂易回收再用的优点.     

Pt/Fe_2O_3/TiO_2的制备、表征及其光催化活性研究

报道了担载不同贵金属或过渡金属氧化物的TiO2 催化剂对空气中微量甲醛的光催化氧化的研究结果。实验发现 ,TiO2 上担载Fe2 O3 或Pt时对甲醛均有较高的光催化氧化活性。同时担载双组分的光催化剂Pt Fe2 O3 TiO2 ,由于 2种组分的协同作用 ,具有更高的光催化活性。研究了催化剂制备因素、催化剂的结构及表面特性对催化活性的影响     

平炉尘合成超细铁氧体催化性能研究

平炉尘提纯得到超细Fe2O3, 利用同晶型间的拓扑转化原理, 使平炉尘转化为超细铁氧体MnFe2O4、CoFe2O4催化剂, 并对催化剂进行了BET、XRD、H2-TPR、TEM和电导技术表征, 研究了其对丙烷氧化脱氢制丙烯反应的催化性能.实验结果表明由平炉尘转化得到的超细铁氧体CoFe2O4为p型半导体催化剂,对丙烷氧化脱氢制丙烯反应表现出优异的催化性能,当丙烷转化率在10%和20%时,丙烯的选择性分别为40.34%和35.23%.为资源综合利用及减少环境污染提供了新方法.     

废SCR脱硝催化剂中砷元素赋存形态与氧化碱浸脱除

以燃煤电厂废SCR脱硝催化剂为研究对象,通过XPS、ICP等检测方法研究废催化剂中杂质As元素的含量及赋存形态,发现废SCR催化剂中As元素存在形态为As2 O3与As2 O5.采用氧化碱浸技术,将难与NaOH反应的As2 O3氧化为更易反应的As2 O5,实现不同价态As元素的深度脱除.分别研究了氧化剂种类、氧化剂浓度、浸出剂浓度、反应温度、时间、液固比等因素对As元素脱除率的影响规律.结果表明,当反应温度为30℃、反应时间为4 h、H2 O2浓度为5％(质量分数)、NaOH浓度为10％(质量分数)、液固比为2 mL/g时脱砷效果最佳,废催化剂中As含量由1334×10-6降低至50×10-6,脱除率达到98.5％.所得产物为脱砷后催化剂,主要由锐钛矿型TiO2与少量WO3组成.通过EPR、XPS技术对H2 O2强化浸出的反应机理进行研究,发现废SCR催化剂中V元素主要以V4+、V5+两种价态存在,其与NaOH反应生成的HV2 O5-、VO43-和H2 O2引发的类Fenton反应,可产生具有强氧化性的羟基自由基,将难以脱除的As3+氧化为更易溶于碱液的As5+,提高As元素的脱除率.     

应用于海水烟气脱硫的陶瓷负载氧化铁催化剂的制备及表征

以FeSO4为原料,分别采用浸渍沉淀(Ⅰ)和溶胶-凝胶法(Ⅱ)制备了轻质陶瓷负载氧化铁催化剂。研究了制备方法和焙烧温度对负载后氧化铁层的结构、形貌和团聚状况的影响。Ⅱ法制备的催化剂有较高SO2脱除活性,使用SEM-EDS,XRD,XPS和H2-程序升温脱附(H2-TPR)等表征结果可以看出,Ⅱ法制备的催化剂有13.28%(质量分数)的氧化铁负载于陶瓷表面,负载后Fe的价态为+3,还原峰温度分别为380和600℃,依次对应Fe2O3还原为Fe3O4以及Fe3O4还原为FeO的两个过程。由于陶瓷表面具有良好的亲水性,同时负载后的氧化铁在其表面有较高的分散性,使得该催化剂的低温脱硫活性较高,适用于燃用中高硫煤的沿海电厂的海水烟气脱硫过程。     

钛网表面Fe3O4/FeS2膜层制备及其类芬顿降解苯酚研究

为了拓宽类芬顿催化剂的pH适用范围、改善其有机污染物降解性能并解决其分离回收难的问题,本文采用易于大规模制备的电沉积法在钛网表面沉积了Fe3O4/FeS2固定化膜层.通过XRD、SEM及XPS等表征手段研究了所合成催化剂的相组成、形貌及表面元素价态.结果 显示,所合成的材料主要由Fe3 O4与FeS2物相组成,且膜层表面呈现由纳米片间相互交联形成的多孔网状结构.类芬顿降解苯酚性能表明,在0.20 mol/L硫源含量下所得膜层于pH 6.0、H2 O2含量6 mmol/L、苯酚初始质量浓度35 mg/L、反应温度30℃的条件下降解60 min,可将98％的苯酚去除.因而,Fe3O4/FeS2固定化膜层催化剂表现出优异的类芬顿催化活性.分析发现:材料较大的比表面积可增强传质,同时提供更多的活性位点参与苯酚降解;而催化剂表面键合的S22-可促进≡Fe3+/≡Fe2+以及Fe3 +/Fe2的氧化还原循环,同时,以硫酸根形式存在的硫物种可为类芬顿反应提供合适的酸性微环境,从而提高羟基自由基的产生速率及产生量,最终显著改善该催化剂在近中性条件下的催化活性.     

焙烧温度对Cu-Mn/γ-Al_2O_3催化剂催化氧化甲苯性能的影响

采用浸渍法合成了Cu-Mn/γ-Al2O3催化剂,通过XRD、BET、H2-TPR和XPS等方法对经不同温度(300~600℃)焙烧的催化剂进行表征,采用固定床管式反应装置考察了焙烧温度对催化剂催化氧化甲苯的影响,并讨论活性组分、表面Cu+/(Cu++Cu2+)和Mn4+/(Mn4++Mn3+)摩尔比值与催化剂活性的关系。结果发现,550℃焙烧温度的催化剂活性最好,氧化能力最强,其转化率为95%时对应的反应温度T95(286℃)最低,CO2的选择性达100%。在550℃焙烧时生成的Cu1.4Mn1.6O4新相以及催化剂表面中相对含量更高的Cu+和Mn4+是催化剂具有高活性的主要原因。     

碳纳米管负载Fe2O3催化剂的制备及其乙苯脱氢催化活性

采用FeSO4-H2O2体系对碳纳米管氧化修饰的同时,氢氧化铁被吸附在碳纳米管管壁上,然后分别通过氢气、氮气、空气在723K下处理2h,制备了碳纳米管负载的γ-Fe2O3催化剂、γ-Fe2O3和α-Fe2O3复合催化剂和非晶态Fe2O3催化剂。采用XRD、TEM和TG-DSC表征了催化剂结构,采用连续流动乙苯气相脱氢生成苯乙烯反应对催化剂性能进行评价,结果表明：热处理条件对催化剂乙苯脱氢的催化性能影响明显,碳纳米管负载的晶态Fe2O3纳米催化剂对乙苯脱氢具有高的活性与选择性。     

金属掺杂对纳米管TiO2光催化性能的影响

利用水热法,以Degussa P-25TiO2粉末为原料,AlCl3、Fe(NO3)3·9H2O和ZnCl2为掺杂剂合成金属掺杂纳米管TiO2,并采用透射电镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和BET比表面积分析对催化剂进行表征。结果表明,掺杂金属分别以Al 3+、Fe3+和Zn2+的形式存在。随着煅烧温度的增高,样品的比表面积逐渐降低,锐钛矿含量先增大后减小;金属掺杂后,催化剂比表面积略有降低,锐钛矿含量略有增大。考察紫外光催化臭氧化工艺中TiO2降解腐植酸标志物的催化效果,结果表明,450℃煅烧未掺杂纳米管TiO2对腐植酸的催化降解效率为44%,较P-25TiO2粉末提高了11%;金属掺杂后催化效果提升明显,550℃煅烧Fe掺杂纳米管TiO2的催化效果最为显著,腐植酸去除率达77%。     

双微乳液法制备掺杂Fe~(3+)的纳米TiO_2及其光催化性能

为了研究双微乳液法在制备纳米级光催化剂的应用,以TiCl4和NH3.H2O为原料,采用十六烷基三甲基溴化铵-正丁醇-环己烷-水微乳体系制备Fe3+掺杂纳米TiO2,对粉末的晶体结构进行X射线衍射表征,并以其对p-甲酚的降解考察其光催化活性。结果表明,在较小的掺杂量时,Fe3+掺杂量的提高可以提高TiO2的光催化活性,进一步提高掺杂量将引起光催化活性的降低;掺杂Fe3+可导致纳米TiO2的粒径减小;Fe3+的半径较小以及Fe2O3的熔点较低均有利于TiO2从锐钛矿向金红石的相变;当Fe3+掺杂摩尔分数为0.06%,煅烧温度为550℃时,纳米TiO2的光催化活性最高,此时形成TiO2的锐钛矿和金红石相的混晶;乳液中含水量也会影响晶相的组成和粒径大小,随着含水量增加产物中出现了一定比例的金红石相。     

Green synthesis of uniform magnetite (Fe3O4) nanoparticles and micron cubes

Single-crystalline Fe3O4 microcubes were obtained through a green hydrothermal procedure using Fe3+, Fe2+ and H2O2 as starting materials. The structures and morphologies of the as-prepared samples were characterized in detail by X-ray diffraction (XRD), Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) respectively. Magnetite (Fe3O4) cubes averaging 3 microm in diameter were synthesized by H2O2 oxidation of Fe3+ and Fe2+ under neutral conditions. The contrastive experiments were designed to elucidate the effects of Fe3+, Fe2+ and H2O2 on the morphology of the final products. Irregular and ellipsoidal Fe2O3 structures were obtained by H2O2 oxidation of Fe3+ and Fe2+ respectively. Meanwhile, Fe3O4 nanotubes and nanoparticles were obtained when H2O2 was replaced by NH4HCO3 and urea respectively. The results show that H2O2, Fe3+ and Fe2+ in the reactive system play critical roles in obtaining micrometric cube-like Fe3O4. While, other nanometric Fe2O3 and Fe3O4 particles with tube-like and other morphologies could also be developed by controlling the reaction parameters.     

Novel active heterogeneous Fenton system based on Fe3-xMxO4 (Fe, Co, Mn, Ni): the role of M2+ species on the reactivity towards H2O2 reactions

In this work, the effect of incorporation of M2+ species, i.e. Co2+, Mn2+ and Ni2+, into the magnetite structure to increase the reactivity towards H2O2 reactions was investigated. The following magnetites Fe3-xMnxO4, Fe3-xCoxO4 and Fe3-xNixO4 and the iron oxides Fe3O4, gamma-Fe2O3 and alpha-Fe2O3 were prepared and characterized by M?ssbauer spectroscopy, XRD, BET surface area, magnetization and chemical analyses. The obtained results showed that the M2+ species at the octahedral site in the magnetite strongly affects the reactivity towards H2O2, i.e. (i) the peroxide decomposition to O2 and (ii) the oxidation of organic molecules, such as the dye methylene blue and chlorobenzene in aqueous medium. Experiments with maghemite, gamma-Fe2O3 and hematite, alpha-Fe2O3, showed very low activities compared to Fe3O4, suggesting that the presence of Fe2+ in the oxide plays an important role for the activation of H2O2. The presence of Co or Mn in the magnetite structure produced a remarkable increase in the reactivity, whereas Ni inhibited the H2O2 reactions. The obtained results suggest a surface initiated reaction involving Msurf2+ (Fe, Co or Mn), producing HO radicals, which can lead to two competitive reactions, i.e. the decomposition of H2O2 or the oxidation of organics present in the aqueous medium. The unique effect of Co and Mn is discussed in terms of the thermodynamically favorable Cosurf3+ and Mnsurf3+ reduction by Femagnetite2+ regenerating the active species M2+.     

Effect of Ni+2-substituted Fe2TiO5 on the H2-reduction and CO2 Catalytic Decomposition Reactions at 500℃

CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas, high activity nanosized Ni＋2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method. The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 （iron titanate） phase that has a nanocrystallite size of -80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases （-80 nm） NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only. Samples with Ni^＋2=0 shows the lowest reduction extent （20%）; as the extent of Ni＋2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis （TGA） experiments. The oxidation of the H2-reduced Ni＋2 substituted Fe2TiO5 at 500℃ was investigated. As Ni^＋2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction （XRD） and transmission electron microscopy （TEM） of oxidized samples show also the presence of carbon in the sample containing Ni＋2〉0, which appears in the form of nanotubes （25 nm）.     

Use of EAF dust as heterogeneous catalyst in Fenton oxidation of PCP contaminated wastewaters

In this study, chemical oxidation tests using H2O2 were performed on a solution contaminated with 100 mg l(-1) of pentachlorophenol (PCP). The effectiveness of electric arc furnace dust and hematite as heterogeneous catalysts was evaluated. Reactions were conducted at pH 2 for 24 h. Either H2O2 stabilized with KH2PO4 or un-stabilized H2O2 was used. Total organic carbon (T.O.C.) removal and chloride release from PCP molecule were monitored. Results showed that the maximum removal yields for electric arc furnace (EAF) dust (49.2% T.O.C., 56.7% Cl) were achieved when H2O2:PCP ratio was 10:1 and Fe:H2O2 = 1:5 for unstabilized H2O2 and when H2O2:PCP = 10:1 and Fe:H2O2 = 1:1 for stabilized H2O2 (48% T.O.C., 60.6% Cl). The maximum yield using hematite (45.2% T.O.C., 55.2% Cl) was obtained when H2O2:PCP ratio was 10:1 and Fe:H2O2 was 1:2. When EAF dust was used and Fe:H2O2 > 1:5, Cl release was higher than the one expected from T.O.C. removal.     

Improvement of COD and color removal from UASB treated poultry manure wastewater using Fenton's oxidation

The applicability of Fenton's oxidation as an advanced treatment for chemical oxygen demand (COD) and color removal from anaerobically treated poultry manure wastewater was investigated. The raw poultry manure wastewater, having a pH of 7.30 (+/-0.2) and a total COD of 12,100 (+/-910) mg/L was first treated in a 15.7 L of pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB reactor was operated for 72 days at mesophilic conditions (32+/-2 degrees C) in a temperature-controlled environment with three different hydraulic retention times (HRT) of 15.7, 12 and 8.0 days, and with organic loading rates (OLR) between 0.650 and 1.783 kg COD/(m3day). Under 8.0 days of HRT, the UASB process showed a remarkable performance on total COD removal with a treatment efficiency of 90.7% at the day of 63. The anaerobically treated poultry manure wastewater was further treated by Fenton's oxidation process using Fe2+ and H2O2 solutions. Batch tests were conducted on the UASB effluent samples to determine the optimum operating conditions including initial pH, effects of H2O2 and Fe2+ dosages, and the ratio of H2O2/Fe2+. Preliminary tests conducted with the dosages of 100 mg Fe2+/L and 200 mg H2O2/L showed that optimal initial pH was 3.0 for both COD and color removal from the UASB effluent. On the basis of preliminary test results, effects of increasing dosages of Fe2+ and H2O2 were investigated. Under the condition of 400 mg Fe2+/L and 200 mg H2O2/L, removal efficiencies of residual COD and color were 88.7% and 80.9%, respectively. Under the subsequent condition of 100 mg Fe2+/L and 1200 mg H2O2/L, 95% of residual COD and 95.7% of residual color were removed from the UASB effluent. Results of this experimental study obviously indicated that nearly 99.3% of COD of raw poultry manure wastewater could be effectively removed by a UASB process followed by Fenton's oxidation technology used as a post-treatment unit.     

Preparation of Palladium Supported on Ferric Oxide Nano-catalysts for Carbon Monoxide Oxidation in Low Temperature

Nano-Micro Letters - Catalytic property of Pd/Fe2O3 catalysts on carbon monoxide (CO) oxidation at low temperature were investigated in this paper. Both the as-prepared and H2-pretreated Pd/Fe2O3...     

Fe对Mn/CeO2-TiO2催化剂低温NH3选择性催化还原NO的影响

以锰氧化物为活性组分,CeO2-TiO2为载体制备了Mn/CeO2-TiO2催化剂.考察了Fe的加入对Mn/CeO2-TiO2的低温NH3-SCR活性的影响.并采用BET比表面积,H2程序升温还原(H2-TPR)和X射线光电子能谱(XPS)等手段对催化剂进行了表征.活性结果表明,Fe的引入显著改善了Mn/CeO2-TiO2的NH3-SCR活性,催化剂在113～250℃之间表现出良好的NO去除效率.表征结果表明,Fe的引入促进了锰物种在CeO2-TiO2表面的分散,降低了Mn-Fe/CeO2-TiO2中锰物种的还原温度.XPS分析指出Mn-Fe/CeO2-TiO2表面Mn以+4价存在,而Fe主要以+3价的Fe2O3存在,且Fe与载体表面间存在强相互作用.     

Degradation of C.I. Reactive Red 2 (RR2) using ozone-based systems: comparisons of decolorization efficiency and power consumption

This study investigated the decolorization efficiency of C.I. Reactive Red 2 (RR2) in O3, O3/H2O2, O3/Fe3+, O3/H2O2/Fe3+, UV/O3, UV/O3/Fe3+, UV/O3/H2O2 and UV/O3/H2O2/Fe3+ systems at various pHs. The effective energy consumption constants and the electrical energy per order of pollutant removal (EE/O) were also determined. The experimental results indicated that the energy efficiency was highest at [H2O2]0=1000mg/l and [Fe3+]0=25mg/l. Accordingly, the H2O2 and Fe3+ doses in the hybrid ozone- and UV/ozone-based systems were controlled at these values. This work suggests that the dominant reactant in O3, O3/Fe3+ and O3/H2O2 systems was O3 and that in the O3/H2O2/Fe3+ system was H2O2/Fe3+. The experimental results revealed that the combinations of Fe3+ or H2O2/Fe3+ with O3 at pH 4 and of H2O2 or H2O2/Fe3+ with UV/O3 at pH 4 or 7 yielded a higher decolorization rate than O3 and UV/O3, respectively. At pH 4, the EE/O results demonstrated that the UV/O3/H2O2/Fe3+ system reduced 85% of the energy consumption compared with the UV/O3 system. Moreover, the O3/H2O2/Fe3+ system reduced 62% of the energy consumption compared with the O3 system. At pH 7, the EE/O results revealed that the UV/O3/H2O2/Fe3+ system consumed half the energy of the UV/O3 system.     

Effect of pretreatment conditions on particle size of bimetallic pt-au catalysts supported on ZnO/Al2O3 and its activity for toluene oxidation

Bimetallic Pt-Au catalysts supported on ZnO/Al2O3 were prepared by incipient wetness impregnation (IW-IMP) method with different pretreatment conditions such as flow velocity, calcination temperature, and heating rate under H2 during the calcination procedure, and characterized by X-ray diffraction (XRD), CO chemisorption, and scanning transmission electron microscopy (STEM) equipped energy dispersive spectroscopy (EDS). Furthermore, catalytic activity for complete oxidation of toluene was measured using a flow reactor under atmospheric pressure. Finally, relationship between the particle sizes with pretreatment conditions and catalytic activity for toluene on the bimetallic Pt-Au catalysts was discussed. In these results, nanosized bimetallic Pt-Au particles on ZnO/Al2O3 could be prepared by IW-IMP method. Relationship between the Pt and Au particle size and activity for toluene oxidation was clearly observed.