胶原纤维为模版制备TiO2及La/TiO2纳米纤维及光催化活性研究

以胶原纤维为模版分别负载钛(Ti4+)或钛(Ti4+)和镧(La3+),在高温下煅烧制得TiO2和La/TiO2纳米纤维。通过扫描电镜(SEM)、场发射扫描电镜(FESEM)、X-射线衍射(XRD)、比表面积和孔径分析、X-射线光电子能谱(XPS)、紫外可见光谱(UV-Vis)等对这2种纳米纤维的结构和物理性能进行了表征。结果表明,TiO2和La/TiO2较完整地保持了胶原纤维的纤维状结构。在600~800℃范围内随着煅烧温度的升高,TiO2和La/TiO2的晶粒尺寸逐渐增大,晶格常数发生各相异性的变化。La/TiO2的相变温度在700~800℃之间,明显高于未掺杂TiO2的相变温度。N2吸附-脱附等温线按Langmiur分类为Ⅳ类,表明TiO2和La/TiO2纳米纤维具有介孔结构。与Degussa P25相比,TiO2和La/TiO2吸收光谱范围明显红移。当以可见光为光源进行酸性橙Ⅱ光助催化降解反应时,TiO2和La/TiO2纳米纤维均表现出比Degussa P25更高的催化活性。     

CoOx-CeOx/ZrO2催化氧化NO性能及抗SO2毒化研究

采用浸渍法制备了一系列CoO_x-CeO_x/ZrO₂催化剂,探讨了催化剂载体、Co含量、Co/Ce配比等对Co基催化剂催化氧化NO活性的影响及其机理。ZrO₂负载的Co氧化物具有优良的低温NO催化氧化活性,铈的添加进一步提高了催化剂的低温活性。其促进机制主要是提高了催化剂吸附氧的能力及改善了Co在催化剂表面的分散。同时,掺杂铈使得催化剂抗SO₂能力有一定增强,呈现出选择性毒化机制。     

贵金属负载TiO2对光催化还原CO2选择性的影响

利用光沉积方法在TiO₂表面分别负载1%(质量分数) Pt、Pd、Au和Ag助催化剂.用TEM、XRD、UV-vis等技术对催化剂进行了表征,并利用连续瞬态电流时间响应和线性扫描伏安法等电化学方法,对贵金属负载的TiO₂光催化剂在光照条件下的电流响应强度及电催化析氢电位等特性加以测试.分析了贵金属助催化剂对光催化还原CO₂性能的差异.结果表明,负载贵金属助催化剂能显著加速光生电子空穴的分离,降低复合率;另外,助催化剂对还原CO₂选择性的顺序为Ag>Au>Pd>Pt.贵金属助催化剂还原CO₂的加氢选择性和析氢过电位存在相关性,即越不利于析氢过程的助催化剂,其催化CO₂加氢还原产物的选择性越高.     

铌元素改性V2O5-WO3/TiO2催化剂降低脱硝过程SO2的氧化率

本文采用浸渍法制备了Nb改性的V₂O₅-WO₃/Ti O₂催化剂,研究了脱硝反应中Nb负载量对催化剂SO₂氧化活性的影响。结果表明,在350℃下,Nb2O5负载量为2%的Nb₂O₅-V₂O₅-WO₃/Ti O₂催化剂上的SO₂氧化率最低（0.6%）,而同时NOx的转化率仍能达到95%。采用TGA、氮吸附、XRD、H2-TPR、CO₂-TPD、XPS和in-situ DRIFTS等对催化剂进行了表征分析,结果显示,Nb改性后V2O5-WO₃/Ti O₂催化剂的晶体结构没有发生明显改变,但是其比表面积小幅度下降,有助于减少对SO₂的吸附;同时,改性后催化剂表面的吸附氧含量下降,氧化还原性能也稍微减弱,这有利于降低其对SO₂...     

Eu2O3修饰对纳米TiO2热稳定性及光催化活性的影响

通过浸渍过程实现了Eu2O3对溶胶水热法合成的锐钛矿相TiO2纳米粒子的表面修饰改性.重点研究了表面修饰对纳米锐钛矿相热稳定性及光催化活性的影响.结果表明,Eu2O3表面修饰抑制了锐钛矿相向金红石相的转变,相变温度由550℃左右升高到700℃左右,提高了纳米锐钛矿相TiO2的热稳定性,这与Eu2O3修饰在表面而阻碍了锐钛矿纳米粒子的直接接触有关.与未修饰的TiO2相比,经过700℃高温热处理的Eu2O3修饰的TiO2样品表现出了较高的光催化活性,这与其结晶度提高而有利于光生电荷分离有关.     

模板水热法纳米TiO2制备及光催化性能研究

以聚乙烯吡咯烷酮(PVP)为模板剂,钛酸四正丁酯(TBOT)为钛源,水热法制备纳米TiO2。采用XRD,SEM、TEM和UV-Vis DRS等测试手段对其形貌和结构进行表征。通过对甲基橙的光催化降解实验,探讨了焙烧温度、催化剂用量和溶液pH值对光催化性能的影响。结果表明,TiO2具有锐钛矿相,平均晶粒尺寸约为23.2 nm,TiO2颗粒呈片层状或由片层状堆积的疏松圆球形,经超声后即分散为八面体晶粒。550℃焙烧的样品,紫外光照3 h后,对甲基橙的降解率可达84.2%。相比普通水热法,采用模板剂法制得的TiO2吸收带发生红移,因而也具有较好的可见光催化活性。     

TiO2纳米管阵列在环境领域的研究进展

TiO2纳米管阵列是一种新型的无机功能材料,具有化学惰性、气敏、介电效应、良好的生物兼容性、较强的光催化能力以及抗化学腐蚀和光腐蚀的能力,特别是具有很好的光催化活性,使其在太阳能的储存与利用、环境净化、催化剂、光催化降解环境污染物等方面有比较多的研究应用.TiO2纳米管阵列通过一定的修饰可以使其吸收光谱向可见光区迁移,同时它兼具成本低廉、环境友好等优点,是当前环境污染物削减与监控的重要研究方向之一.本文主要对近年来国内外TiO2纳米管阵列作为光催化剂降解环境污染物和作为功能材料在环境分析检测中的应用进行简要综述,为开发新型污染物监控与处理技术及拓展TiO2纳米管阵列的潜能提供重要参考.     

异质结型Er2O3/TiO2复合纳米纤维制备及光催化性能

采用静电纺丝技术与溶剂热法相结合,制备了异质结型Er2O3/TiO2复合纳米纤维光催化材料。利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、高分辨透射电镜(HRTEM)和紫外-可见吸收光谱(UV-Vis)等分析测试手段对材料进行表征,并以罗丹明B(RB)的脱色降解为模式反应,考察了材料的光催化性能。实验结果表明:Er2O3纳米粒子均匀地负载在TiO2纤维上,形成了异质型Er2O3/TiO2复合纳米纤维光催化材料,拓宽了光谱响应范围,有利于TiO2光生电子和空穴的分离,增强了体系的量子效率。与纯TiO2纳米纤维相比光催化活性明显提高,对RB的紫外光降解率达93.93%。     

Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₂Ti₂O₇/TiO₂/Bi₄Ti₃O₁₂复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明：TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂     

焙烧温度对TS/TiO2结构及光催化反应性能的影响

TS/TiO2是一种热稳定的光催化材料.将该样品分别在300、400、500、540、600和700℃下空气中焙烧,并用UV-Raman、XRD、BET及TPD等手段进行了表征.同时,以苯乙烯光催化氧化反应为探针,考察了其光催化氧化反应性能.结果表明,焙烧温度对催化剂的结构与表面性质有较大程度的影响,除TS/TiO2的晶型及比表面积外,其酸量也发生了较大程度的变化;并与催化剂性能进行了关联.     

SO_2对Mn-Ce/TiO_2低温SCR催化剂的毒化作用研究

考察了SO_2对Mn-Ce/TiO_2低温脱硝催化剂活性的影响,利用XRD、BET、SEM和XPS对其毒化作用的原因进行分析。结果表明,SO_2对催化剂活性有明显的抑制作用,使NO_x去除率由84%降至42%左右。主要是SO_2的加入造成催化剂比表面积减小,孔径为5-10 nm的孔数量减少,且催化剂晶相由锐钛矿型转化成金红石型结构,活性组分MnO_x发生晶化现象,破坏了Mn-Ti间的强相互作用。催化剂理化性质的变化造成吸附态氧转化为晶格氧的路径受阻、MnO_2含量减少和CeO_x储氧功能减弱,并且产生氧阻效应而使NO吸附和解吸受阻,造成催化剂活性降低。同时生成的硫酸铵盐在催化剂表面沉积,覆盖了催化剂表面的Lewis酸性位,使其对NH_3吸附能力减弱。     

Electron beam process for SO2 removal from flue gases with high SO2 content

Flue gases with high SO₂ concentration are emitted from different industrial processes, e.g. combustion of coal with high sulfur content, copper smelting and sintering plant. The application of the electron beam process for SO₂ removal from such flue gases was investigated. A parametric study was carried out to determine the removal efficiency as a function of temperature and humidity of irradiated gases, dose and ammonia stoichiometry. At the dose 11.5 kGy 95% SO₂ removal efficiency was obtained when the temperature and humidity of irradiated flue gases and ammonia stoichiometry were properly adjusted. The synergistic effect of high SO₂ concentration on NO_x removal was observed. The collected by-product was the mixture of (NH₄)₂ SO₄ and NH₄NO₃. The content of heavy metals in the by-product was many times lower than the values acceptable for commercial fertilizer.     

NO气体在TiO2表面的吸附行为

采用TPD (Temperature Programmed Desorption)试验方法测定了NO在TiO₂表面吸附后的脱附谱, 揭示了气体脱附量的变化规律. 结果表明, NO在TiO₂表面吸附后可在两个峰值温度450和980 K脱附出N₂气体, 其活化能分别是0.48 和2.5 eV. TiO₂表面经预覆氧处理后, N₂的脱附量降低. N₂的脱附量随NO气体暴露量增加而增加, 但当气体覆盖度超过一定值后, 脱附量趋于定值. 脱附峰值温度随气体暴露量的增加而降低.     

MnOx-TiO2吸附剂对燃煤烟气中汞的脱除

以锐钛矿型TiO_2为载体,采用浸渍法对其进行MnO_x改性制备脱汞吸附剂,探究了负载量、焙烧温度、反应温度及烟气组分等参数对吸附剂脱汞性能的影响。利用N_2吸附-脱附、TG/DTG、XRD、FT-IR、Hg-TPD、XPS等方法对吸附剂的理化性质进行了表征。结果表明,Mn的最佳负载量为12%,最佳焙烧温度和反应温度分别为450和300℃,在实验条件下MnO_x-TiO_2吸附剂可达到的最佳脱汞效率为98.46%。烟气中少量的O_2及微量的HCl对吸附剂的脱汞有较强的促进作用;SO_2对吸附剂的脱汞有较强的抑制作用,SO_2与Hg~0存在的竞争吸附作用以及脱汞反应中产生的硫酸盐覆盖活性位点表面,是导致脱汞效率下降的主要原因。烟气中的CO_2和NO也会对汞的脱除产生轻微的抑制作用。负载在吸附剂上的MnO_x存在Mn~(4+)、Mn~(3+)两种价态,其中,Mn~(4+)将Hg~0氧化为Hg~(2+),自身被还原为Mn~(3+)。结合实验和分析结果发现,Hg~0的吸附和氧化基本遵循Mars-Maessen和Langmuir-Hinshelwood机理。     

Empirical models for NOx and SO2 removal in a double stage flue gas irradiation process

A multidimensional regression method has been applied to construct empirical model equations of NO_x and SO₂ removal efficiency in e–b process for a two-stage irradiation system based on results achieved for the EPS Kaw czyn pilot plant. The influence of different parameters such as dose, temperature, gas humidity and ammonia stoichiometry have been studied. Model equations describe with satisfactory accuracy experimental results. Therefore obtained models equations can be used for prediction of NO_x and SO₂ removal efficiency in e–b process during two-stage irradiation of flue gases, particularly in the case of scale-up. The results will be implemented in the industrial electron beam flue gas treatment installation being constructed at EPS Pomorzany, Dolna Odra PS Group SA, Poland (flue gas flow 270,000 N m³/h, total beam power of applied accelerators 1.2 MW).     

SO_2对甲烷在金属铁表面还原NO的反应影响

采用卧式程序控温电加热陶瓷管反应器,在N2和模拟烟气气氛中、300~1 100℃下,研究了SO2对甲烷在金属铁及其氧化物表面还原NO反应的影响。采用XRD等手段对反应前后铁催化剂样品的组成变化进行了表征,分析了SO2在甲烷-铁脱硝反应中的作用机理。结果表明,甲烷在金属铁及氧化铁表面能够高效率地还原NO,NO还原效率不受烟气中SO2的影响。在SO2体积分数为0.01%~0.04%的N2气氛中,温度高于700℃时,金属铁上NO还原率和SO2脱除率可同时达到100%。在SO2体积分数为0.01%~0.04%的模拟烟气中,当温度高于850℃时,NO还原效率达到90%以上;温度为950℃时,NO还原效率达到98%,SO2对NO还原效率的影响可忽略。当反应温度为1 000℃时,在含0.02%SO2的模拟烟气中,甲烷的体积分数为1.13%时,持续100 h金属铁表面上的NO还原效率都能保持95%以上。     

Selective catalytic oxidation of NO with O2 over Ce-doped MnOx/TiO2 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=1/3 and calcined at 300°C shows a superior activity for NO oxidation to NO2. On Ce(1)Mn(3)Ti catalyst, 58% NO conversion was obtained at 200°C and 85% NO conversion at 250°C with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst (48% at 250°C). Characterization results implied that the higher activity of Ce(1)Mn(3)Ti could be attributed to the enrichment of well-dispersed MnOx on the surface and the abundance of Mn3+ and Ti3+ species. The addition of Ce into MnOx/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.     

Sunlight-activated AlFeO3/TiO2 photocatalyst

A nanocomposite photocatalyst composed of AlFeO₃ and TiO₂ is prepared, and characterized through X-ray diffraction. Application of the nanocomposite for the photodegradations of eosin dye and methyl orange gives an improved photoactivity compared with TiO₂-only nanomaterials. The optimal concentration of AlFeO₃ in the composite is about 1.0 wt% under UV excitation, and 9.0 wt% under sunlight excitation for the improved photoactivity. Furthermore, this nanocomposite is more active for eosin photodegradation if natural sunlight rather than UV is used. This may be due to the reason that adding AlFeO₃ nanoparticles into TiO₂ matrix can promote the separation of photogener-ated charge carriers, and extend the photoresponse of TiO₂ toward visible region, which results in an increase in the solar energy utilization efficiency.     

Photocatalytic removal of the insecticide fenitrothion from water sensitized with TiO2

The photocatalytic removal of the insecticide fenitrothion (IUPAC name: O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), C₉H₁₂NO₅PS, from water suspension of TiO₂, was investigated by following the disappearance of the original substance along with the formation and disappearance of intermediates via recording NMR (¹H and ³¹P) and UV spectra, as well as by pH measurements. Based on the obtained data, a possible reaction mechanism was proposed. It was found that ³¹P-NMR spectrometry can be successfully used to follow the kinetics of transforming organic into inorganic phosphorus in the course of the degradation (k_a=9.2×10⁻⁷ mol dm⁻³ min⁻¹, r=0.980 for the illumination period after 15 h). The rate of fenitrothion aromatic ring decomposition was followed by UV spectrometry during the illumination (k_a=3.1×10⁻⁶ mol dm⁻³ min⁻¹, r=0.989). The complete mineralization was attained after about 66 h of irradiation.