The effects of manganese precursors on Mn-based/TiO2 catalysts for catalytic reduction of NO with NH3

Manganese acetate (MnAc) and manganese nitrate (MnN) were employed as precursors for the preparation of MnAc)/TiO2, Mn (N)/TiO2, Mn(Ac)-Ce/TiO2, and Mn(N)-Ce/TiO2 by impregnation. These complexes were used as catalysts in the low-temperature selective catalytic reduction of NO with NH3. The influence of manganese precursors on catalyst characteristics, the reduction activity, and the stability of the catalysts to poisoning by H2O and SO2 were studied. Experiments showed that Mn(N) produced MnO2 with large grain sizes in Mn(N)/TiO2 catalyst. On the contrary, Mn(Ac) led to highly dispersed and amorphous Mn2O3 in Mn (Ac)/TiO2 catalyst, which had better catalytic activity and stability to SO2 at low temperatures. The doping of cerium reduced the differences in catalytic performance between the catalysts derived from different Mn precursors.     

Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: an experimental and theoretical examination of hydrazine derivatives

The photocatalytic oxidation of oxalyldihydrazide, N,N'-bis(hydrazocarbonyl)hydrazide, N,N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N2 gas, NH4+ (and/or NO3-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrazo group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrazo groups were photoconverted mainly into N2 gas (in mineralization yields above 70%) and partially to NH4 ions (below 10%). The formation of NO3- ions was scarcely recognized.     

Catalytic wet oxidation of ammonia: why is N2 formed preferentially against NO3 -?

The role of catalyst and the reason for the preferential formation of N(2) in the catalytic oxidation reaction of ammonia in water over a Ru (3wt.%)/TiO(2) catalyst were elucidated. It was verified that the catalyst in the reaction had no direct relevance to the selective formation of N(2), but was responsible only for the oxidation of aqueous ammonia, NH(3)(aq), finally giving a molecule of nitrous acid. The preferential production of N(2) was experimentally demonstrated due to the homogeneous aqueous phase reaction of the nitrous acid-dissociated NO(2)(-) with NH(4)(+) ions. Even under the highly oxidizing condition, NO(2)(-) was much more likely to react with NH(4)(+) to form N(2) than being oxidized over the catalyst to NO(3)(-) as long as NH(4)(+) was available in solution.     

Mo-N-TiO2光催化剂的制备、表征及其活性提高机制

以钼酸铵和氨水分别为钼源和氮源,采用溶胶-凝胶法制备了Mo-N-TiO2光催化剂,并对其进行了XRD、XPS和UV-visDRS表征。XRD结果表明,Mo、N共掺杂有效抑制了TiO2晶粒的生长,提高了TiO2由锐钛矿向金红石相的转变温度。UV-vis表明,Mo-N-TiO2光催化剂可见光吸收能力增强,吸收带边明显"红移",且钼酸铵添加量(相对TiO2)为0.5%的样品"红移"程度最大,最大吸收带边为550 nm。XPS分析结果表明,Mo取代了TiO2晶格中的部分Ti4+,以Mo6+形式存在的,而N以Ti—N及N—Ti—O形式存在。以罗丹明B为模型污染物,重点考察了钼酸铵添加量与焙烧温度对Mo-N-TiO2光催剂性能的影响。结果表明,400℃焙烧下、钼酸铵添加量为0.5%的样品催化活性最好。模拟太阳光下光照120min对罗丹明B的降解率达到96.8%,是纯TiO2的2.42倍。     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Degradation of short-chain alkyl- and alkanolamines by TiO2- and Pt/TiO2-assisted photocatalysis

The photooxidation of C2H5NH2, (C2H5)2NH, HOC2H4NH2, (HOC2H4)2NH and (HOC2H4)3N using TiO2 and Pt/TiO2 as photocatalysts has been investigated. A laboratory set up was designed and a study on the influence of the concentration of the photocatalyst, the pH-value and the structure of the amine performed. The photocatalytic process was optimized with respect to the concentrations of the model substances during degradation. The decrease of the amine concentrations was found to be maximum at a pH of 10. The time-dependence of the formation of cationic breakdown products, such as NH3/NH4 and short-chain alkyl- and alkanolamines was studied by analyses with single column ion chromatography. The experimental data show that the photodegradation follows a Langmuir-Hinshelwood kinetic. The mineralization of the model substances also was monitored by measurements of the decrease of the TOC and of the formation of NO2 and NO3. The different mineralization efficiencies for the model substances studied are discussed with regard to their structure and adsorption behaviour on the photocatalyst. A possible breakdown mechanism involving the electrophilic attack of the hydroxyl radical is given. The applicability of the TiO2-assisted photocatalytic degradation of C2H5NH2 and (C2H5)2NH was tested at the pilot plant-scale with real solar radiation. The degradation rates and products obtained were similar to those found in the laboratory experiments.     

Aromatic photonitration in homogeneous and heterogeneous aqueous systems

This work describes the nitration of aromatics upon near-UV photolysis of nitrate and nitrite in aqueous solution and upon photocatalytic oxidation of nitrite in TiO2 suspensions. Phenol is used in this work as a model aromatic molecule and as a probe for *NO2/N2O4. The photoinduced nitration of phenol in aqueous systems occurs upon the reaction between phenol and *NO2 or N2O4, and is enhanced by the photocatalytic oxidation of nitrite to *NO2 by TiO2. Aromatic photonitration in the liquid phase can play a relevant role in the formation of nitroaromatics in natural waters and atmospheric hydrometeors, thus being a potential pathway for the condensed-phase nitration of aromatics. Furthermore, the photoinduced oxidation of nitrite to nitrogen dioxide suggests a completely new role for nitrite in natural waters and atmospheric aerosols.     

TiO2纳米管催化活性再生处理技术

采用H2O2、Fe2（SO4）3和Fenton溶液对失活的TiO2纳米管进行再生处理，重点考察了3种溶液的浓度和处理时间等对再生效果的影响，初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明，经H2O2溶液处理后TiO2催化活性能得到有效再生，经Fe2（SO4）3，和Fenton溶液处理后其催化活性不仅得到再生，还能显著增强，这与H2O2和Fenton的强氧化作用，及进入TiO2纳米管的Fe3＋的阻止电子．空穴对再复合作用有关。     

Photodegradation of alachlor with the TiO(2) film immobilised on the glass tube in aqueous solution

Alachlor photodegradation was performed using TiO(2), which was synthesized by a modified sol-gel method. The thickness of a TiO(2) film immobilised by a 5-time dip-coating was 174 nm and the average diameter of TiO(2) particles was about 10-15 nm in SEM images. The crystal structure of a TiO(2) film calcinated at 300 degrees C for 1 h was observed as a typical anatase type. The stability of a TiO(2) film by a modified sol-gel method was 4% better than TiO(2) by a typical sol-gel method.The removal rate of alachlor with both Fe(3+) and UV radiation in the absence of TiO(2) was 0.28 mg/l/h in 10 h and the removal rate of alachlor with Fe(3+)/UV in the presence of TiO(2) was 0.32 g/l/h, which was higher by 14% than that with Fe(3+)/UV system. TOC concentration during the alachlor degradation with both TiO(2) and UV radiation in the absence of added Fe(3+) decreased from 100%, through 81% and 51%, to 44% with time elapses of 4, 8, and 10 h, respectively, while TOC concentration with both added Fe(3+) and UV radiation in the absence of TiO(2) decreased from 100% to 70% in 10 h.     

TiO_2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为：H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。     

Photocatalytic oxidation of gaseous DMF using thin film TiO2 photocatalyst

The heterogeneous photocatalytic oxidation of gaseous N,N'-dimethylformamide (DMF) widely used in the manufacture of synthetic leather and synthetic textile was investigated. The experiments were carried out in a plug flow annular photoreactor coated with Degussa P-25 TiO2. The oxidation rate was dependent on DMF concentration, reaction temperature, water vapor, and oxygen content. Photocatalytic deactivation was observed in these reactions. The Levenspiel deactivation kinetic model was used to describe the decay of catalyst activity. Fourier transform infrared (FTIR) was used to characterize the surface and the deactivation mechanism of the photocatalyst. Results revealed that carbonylic acids, aldehydes, amines, carbonate and nitrate were adsorbed on the TiO2 surface during the photocatalytic reaction. The ions, NH4+ and NO3-, causing the deactivation of catalysts were detected on the TiO2 surface. Several treatment processes were applied to find a suitable procedure for the regeneration of catalytic activity. Among these procedures, the best one was found to be the H2O2/UV process.     

Photo–degradable and recyclable starch/Fe3O4/TiO2 nanocomposites: feasibility of an approach to reduce the recycling labor cost in plastic waste management

Environmental Science and Pollution Research - In this research, a biodegradable starch/Fe3O4/TiO2 bio-nanocomposites (SFT) were produced using different nano Fe3O4/TiO2 (FT) (3, 5, and 10 (wt% dry...     

Mo-N-TiO_2光催化剂的制备、表征及其活性提高机制

以钼酸铵和氨水分别为钼源和氮源,采用溶胶-凝胶法制备了Mo-N-TiO2光催化剂,并对其进行了XRD、XPS和UV-visDRS表征。XRD结果表明,Mo、N共掺杂有效抑制了TiO2晶粒的生长,提高了TiO2由锐钛矿向金红石相的转变温度。UV-vis表明,Mo-N-TiO2光催化剂可见光吸收能力增强,吸收带边明显＂红移＂,且钼酸铵添加量（相对TiO2）为0.5%的样品＂红移＂程度最大,最大吸收带边为550 nm。XPS分析结果表明,Mo取代了TiO2晶格中的部分Ti4＋,以Mo6＋形式存在的,而N以Ti—N及N—Ti—O形式存在。以罗丹明B为模型污染物,重点考察了钼酸铵添加量与焙烧温度对Mo-N-TiO2光催剂性能的影响。结果表明,400℃焙烧下、钼酸铵添加量为0.5%的样品催化活性最好。模拟太阳光下光照120min对罗丹明B的降解率达到96.8%,是纯TiO2的2.42倍。     

光催化氧化深度处理电镀有机废水的工程化实验

采用光催化氧化联用技术对电镀有机废水进行深度处理工程化实验。探讨了uV、uV＋H2O3、uV＋H2O2＋TiO2、uV＋H2O2＋FeSO4、uV＋H2O2＋FeSO4＋TiO2、uV＋O3＋TiO2和uV＋03＋TiO2＋H2O2等体系对废水有机污染物去除率的影响。结果表明，相较于其他反应体系，uV＋O3＋TiO2＋H2O2体系具有更好的氧化效果，经碳滤处理后去除率达到90％以上，最终出水水质满足GB18918-20O2-级标准（A标准）的要求。实际运行项目偿还期5．33年，NPV〉0，内部收益率大于基准值10％。研究表明，uV＋O3＋TiO2＋H2O，体系能降低加药量，工作量及运行成本。可为电镀企业实际废水处理提供现实依据，为优化电镀废水的处理工艺提供参考。     

Dye decomposition and air de-pollution performance of TiO2/SiO2 and N-TiO2/SiO2 photocatalysts coated on Portland cement mortar substates

Environmental Science and Pollution Research - In this study, the newly synthesized TiO2 and N doped TiO2 clusters were added to silica sol to synthesize N-TiO2/SiO2 composites via the...     

Superior pillared clay catalysts for selective catalytic reduction of nitrogen oxides for power plant emission control

Fe(3+)-, Cr(3+)-, Cu(2+)-, Mn(2+)-, Co(2+)-, and Ni(2+)-exchanged Al2O3-pillared interlayer clay (PILC) or TiO2-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe(3+)-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO2-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H2O and SO2 increase both the activity and the product selectivity to N2. The maximum activity on the Ce-Fe-TiO2-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V2O5-WO3/TiO2 catalyst, the Fe-TiO2-PILC catalysts show higher N2/N2O product selectivities and substantially lower activities (by approximately 85%) for SO2 oxidation to SO3 under the same reaction conditions. A 100-hr run in the presence of H2O and SO2 for the CeO2/Fe-TiO2-PILC catalyst showed no decrease in activity.     

Dissolution studies on TiO2 with organics

In this work the effect of organic reducing reagents, namely, ascorbic acid, oxalic acid and L-cysteine on dissolution of commercial TiO(2) has been investigated. Kinetic studies showed that a maximum of about 45% of TiO(2) was dissolved by ascorbic acid in 4h when oxide:acid molar ratio was kept at 1:2. The dissolution of TiO(2) increased with increase in ascorbic acid and oxalic acid concentration up to 0.15M in 4h (corresponding to molar ratio of oxide to acid of 1:3) and further addition did not affect the dissolution. Nearly 45% TiO(2) dissolution was obtained with ascorbic acid alone while oxalic acid yielded 40% dissolution. When oxalic acid was added along with ascorbic acid in equi-molar concentrations, dissolution of TiO(2) was enhanced to 60% in 2.5h but when cysteine was added to ascorbic acid the dissolution was about 50% in just 1h.     

Effect of ZnFe2O4 doping on the photocatalytic activity of TiO2

The photocatalytic oxidation of the organic pollutants with the TiO2 as photocatalyst has been widely studied in the world, and many achievements have been got. The degradation of pollutants is highly related with the photocatalytic activity of TiO2. It is demonstrated that doping ions or oxides to TiO2 is one way to enhance the photocatalytic activity of TiO2. In this paper, the ZnFe2O4-doped TiO2 nanoparticles were prepared from butyl titanate by a sol-gel method and characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that when TiO2 was doped with ZnFe2O4, its particle size will decrease and its crystal structure will partly transform from anatase to rutile. The photocatalytic activity of the elaborated powders was studied following the degradation of Rhodamine B. The results showed that doping ZnFe2O4 to TiO2 will enhance the photocatalytic activity of TiO2 and that ZnFe2O4-doped TiO2 in the coexistence of anatase and rutile has higher efficiency for the degradation of Rhodamine B than that in the anatase phase alone. Also the different role of O2 in the direct photolysis and photocatalysis of Rhodamine B was discussed.     

TiO2微球光催化降解腐植酸钠

以阳离子交换树脂为模板,采用溶胶-凝胶法以四氯化钛为原料制备TiO2微球,采用XRD,FTIR,SEM对样品进行了表征。微球中主要组分是锐钛矿型TiO2,同时掺杂有少量Na+,SO24-等离子,比TiO2粉末具有更好的光催化性能,具备重复使用的能力,使用寿命较长,可作为一种有实用价值的光催化剂。在300 W高压汞灯下采用二氧化钛微球催化降解腐植酸钠,分析了催化剂投加量和反应时间对降解率的影响。腐植酸钠的光催化降解实验结果表明:初始浓度为10 mg/L的腐植酸钠在碱性条件,催化剂投加量为2.5 g/L,反应时间为3 h时最为适宜,最大降解率可达到96.51%。