TiO2-SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical characteristics and catalytic behavior in selective catalytic reduction of NO by NH3

TiO₂-SiO₂ with various compositions prepared by the coprecipitation method and vanadia loaded on TiO₂-SiO₂ were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH₃ and in the undesired oxidation of SO₂ to SO₃, using BET, XRD, XPS, NH₃-TPD, acidity measurement by the titration method and activity test. TiO₂-SiO₂, compared with pure TiO₂, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V₂O₅. The SCR activity and N₂ selectivity are found to be more excellent over vanadia loaded on TiO₂-SiO₂ with 10–20 mol% of SiO₂ than over that on pure TiO₂, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH₃ adsorbed on the catalysts. With increasing SiO₂ content, the remarkable activity decrease in the oxidation of SO₂ to SO₃, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V⁴⁺ on TiO₂-SiO₂, while V⁵⁺ exists on TiO₂, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO₂-SiO₂ with low SiO₂ content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NO_x activity but also the low SO₂ oxidation performance.     

TiO2–g-C3N4/BMMS光催化氧化脱硫催化剂

为了提高TiO₂的光催化氧化脱硫(PODS)活性,利用负载和复合的协同作用,将TiO₂与g-C₃N₄复合,并负载于双介孔二氧化硅(BMMS)上,制备了TiO₂–g-C₃N₄/BMMS。以含二苯并噻吩(DBT)的十二烷溶液为模拟油,评价了催化剂的催化性能;优化了反应条件并提出了催化反应机理。结果表明:TiO₂–g-C₃N₄/BMMS具有明显的双介孔结构,TiO₂与g-C₃N₄已实现复合并负载于BMMS上,TiO₂–g-C₃N₄活性组分在载体上分散良好,与单一TiO₂相比对光的吸收能力增强,催化活性有明显提高,优化后的反应条件为,催化剂用量3%(质量分数),O/S摩尔比为10:1,萃取剂与模拟油体积比为1:1,此时脱硫率可达96.6%,且重复使用8次后脱硫率仍保持85%以上,PODS过程中的主要活性中间物种是·O₂^–和h⁺。     

Effect of promoters including tungsten and barium on the thermal stability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

The effect of tungsten and barium on the thermal stability of V₂O₅/TiO₂ catalyst for NO reduction by NH₃ was examined over a fixed bed flow reactor system. The activity of V₂O₅/sulfated TiO₂ catalyst gradually decreased with respect to the thermal aging time at 600 °C. The addition of tungsten to the catalyst surface significantly enhanced the thermal stability of V₂O₅ catalyst supported on sulfated TiO₂. On the basis of Raman and XRD measurements, the tungsten on the catalyst surface was identified as suppressing the progressive transformation of monomeric vanadyl species into crystalline V₂O₅ and of anatase into rutile phase of TiO₂. However, the NO removal activity of V₂O₅/sulfated TiO₂ catalyst including barium markedly decreased after a short aging time, 6 h at 600 °C. This may be due to the transformation of vanadium species to inactive V–O–Ba compound by the interaction with BaO which was formed by the decomposition of BaSO₄ on the catalyst surface at high reaction temperature of 600 °C. The addition of SO₂ to the feed gas stream could partly restore the NO removal activity of thermally aged V₂O₅/sulfated TiO₂ catalyst containing barium.     

SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

Hydrogenation of CO2 over sprayed Ru/TiO2 fine particles and strong metal–support interaction

Ru/TiO₂ catalysts were prepared by spray reaction (SPR) and conventional impregnation (IMP) methods. The catalytic activities of SPR fine particles were much higher than those of IMP catalysts for CO₂ hydrogenation. A high temperature reduction greatly promoted the activity of SPR catalyst. A model of surface structure was proposed which exhibits the enhancement of decoration and the formation of more boundaries over spr-Ru/TiO₂. The high activity of SPR catalyst is attributed to the occurrence of new active sites at the metal–support perimeters and not any SMSI phenomenon. EXAFS reveals that the Ru atom was interacting with TiO₂ by oxygen atom so strongly on the SPR catalysts that a part of the Ru atoms, located near the internal interface between Ru particles and TiO₂ support, existed as Ruⁿ⁺ (n<4) cations even if SPR catalyst was subjected to a high temperature reduction. These Ruⁿ⁺ cations are responsible for the inhibition of SMSI formation over SPR catalysts.     

Effects of microwaves on selective oxidation of toluene to benzoic acid over a V2O5/TiO2 system

Two series of catalysts, V₂O₅/TiO₂ and modified V₂O₅/TiO₂, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V₂O₅/TiO₂. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V₂O₅/TiO₂ with MoO₃, WO₃, Nb₂O₅ or Ta₂O₅, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.     

The preparation of coupled WO3/TiO2 photocatalyst by ball milling

The coupled photocatalyst WO₃/TiO₂ is prepared by ball milling by doping WO₃ into TiO₂ and using H₂O solution as disperser. The coupled photocatalyst WO₃/TiO₂ is characterized by UV–VIS diffuse reflection spectrum, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Transmission electron microscopy (TEM). The results show that the optimum percentage of WO₃ doped is 3% and that the photocatalytic activity of the coupled WO₃/TiO₂ photocatalyst is much higher than that of TiO₂ and WO₃–TiO₂ with no ball milling. Compared with TiO₂, the photoexcited wavelength range of the WO₃/TiO₂ photocatalyst red-shifts about 50 nm, and the light absorption intensity is also improved. The crystal phase of TiO₂ is not changed and new crystal phases are not found during the process of ball milling. WO₃ and TiO₂ coupled highly, forming the WO₃/TiO₂ photocatalyst. The increased photocatalytic activity of the coupled photocatalyst may be attributed to the enhance charge separation efficiency and the extend wavelength range of photoexcitation.     

水基纳米TiO_2路径制备有序介孔TiO_2-SiO_2及其可见光催化性能

在多巴胺修饰的水基TiO_2纳米微粒(TiO_2NPs)悬浮液中,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,分别采用碱性水热方法或酸性溶胶-凝胶方法,制备了有序介孔TiO_2-SiO_2(TiO_2NPs/MCM-41或TiO_2NPs/SBA-3)。采用XRD、TEM、ICP和N2吸附-脱附实验对样品进行表征。结果表明,制备的介孔TiO_2-SiO_2在TiO_2高负载质量分数(23.98%TiO_2NPs/MCM-41、17.27%TiO_2NPs/SBA-3)时,仍能保持长程有序的介孔氧化硅结构。TiO_2NPs随机地嵌入在有序介孔氧化硅孔道所组成的网络结构中。在可见光下催化甲基橙降解反应中,反应时间120 min时,在P25上甲基橙相对浓度降为57%,在TiO_2NPs/MCM-41上降为33%,而在TiO_2NPs/SBA-3上降为5.7%。     

Reduction of SO2 by CO to elemental sulfur over Co3O4–TiO2 catalysts

Mixed oxides of Co₃O₄–TiO₂ have shown the highest catalytic activity for the reduction of SO₂ by CO among catalysts that have been developed so far. Almost zero conversion was observed with cobalt alone, whereas a high conversion was obtained with TiO₂ especially at high temperatures. There existed a strong synergistic promotional effect in the conversion of SO₂ when cobalt was mixed with TiO₂. The synergistic effect observed with mixed oxides is caused by simultaneous contributions from two different reaction routes via COS intermediate mechanism and modified redox mechanism. The synergistic effect that is caused by the COS mechanism has a smaller amount of contribution in the conversion increase and remains almost constant with an increase in the reaction temperature. A larger portion of the synergistic effect is contributed from the modified redox mechanism especially at low temperatures, but the effect disappears at temperatures above 450°C. It is found that the introduction of cobalt into TiO₂ produces COS by the reaction between sulfided CoS₂ and CO even at low temperatures. The COS intermediate can react with SO₂ to produce an additional sulfur via the COS intermediate mechanism, and also behaves as a strong reductant to keep oxygen vacancies on the TiO₂ in a high concentration for the production of sulfur via modified redox mechanism.     

Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia

The physico-chemical characteristics and the reactivity of sub-monolayer V₂O₅-WO₃/TiO₂ deNO_x catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO₂ surface. The presence of tungsten oxide stabilizes the surface V^IV and modifies the redox properties of V₂O₅/TiO₂ samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V₂O₅-WO₃/TiO₂ catalysts exhibits higher activity than the binary V₂O₅/TiO₂ and WO₃/TiO₂ reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.     

负载型CuMnO_x/TiO_2催化剂催化燃烧甲苯

采用沉积-沉淀法制备CuMnO_x/TiO_2新型甲苯燃烧催化剂,考察焙烧温度、Cu与Mn物质的量比、Cu和Mn总负载量、空速及水蒸汽含量对催化甲苯燃烧性能的影响。研究表明,焙烧温度500℃和Cu与Mn物质的量比为1∶1时,催化剂活性最好,反应温度250℃时,甲苯去除率为100%;水蒸汽的出现明显降低了甲苯转化率。XRD和H2-TPR表征结果表明,CuMnO_x/TiO_2催化剂的主要活性相为铜锰尖晶石(Cu1.5Mn1.5O4),它的存在降低了CuMnO_x/TiO_2催化剂的还原温度,是催化活性优良的主要原因。     

Catalytic activity and solid acidity of vanadium oxide thin layer loaded on TiO2, ZrO2, and SnO2

Vanadium oxide spread highly on TiO₂ (anatase, A) and SnO₂, and rather densely on TiO₂ (rutile, R) and ZrO₂ to make the monolayer in less than 4–5 V nm⁻². Profile of acid site of the monolayer was measured by temperature programmed desorption of ammonia, and its relation with the surface oxidation state was studied. The acid site density was high on the V₂O₅/TiO₂ (A) independent of the degree of oxidation. On the other hand, that of V₂O₅/TiO₂ (R) and V₂O₅/ZrO₂ depended on the oxidation state, and the high value of the concentration was observed on the oxidized one. The strength of acid site generated on the V₂O₅ monolayer on TiO₂ was as high as on the HZSM-5 zeolite. Turnover frequency (TOF) of propane conversion, and product selectivity were measured in propane oxidation. Among tested oxides, the V₂O₅/TiO₂ (A) showed the high TOF and selectivity to form propylene, while those loaded on TiO₂ (R) and ZrO₂ the small TOF and poor selectivity. Therefore, the reaction profile of activity and selectivity could be related with the extent of spreading and solid acidity. An idea of limit of the acid site density ca. 1.5 nm⁻² on the monolayer was elucidated.     

A comparative study of TiO2 supported noble metal catalysts for the oxidation of formaldehyde at room temperature

The TiO₂ supported noble metal (Au, Rh, Pd and Pt) catalysts were prepared by impregnation method and characterized by means of X-ray diffraction (XRD) and BET. These catalysts were tested for the catalytic oxidation of formaldehyde (HCHO). It was found that the order of activity was Pt/TiO₂  Rh/TiO₂ > Pd/TiO₂ > Au/TiO₂  TiO₂. HCHO could be completely oxidized into CO₂ and H₂O over Pt/TiO₂ in a gas hourly space velocity (GHSV) of 50,000 h⁻¹ even at room temperature. In contrast, the other catalysts were much less effective for HCHO oxidation at the same reaction conditions. HCHO conversion to CO₂ was only 20% over the Rh/TiO₂ at 20 °C. The Pd/TiO₂ and Au/TiO₂ showed no activities for HCHO oxidation at 20 °C. The different activities of the noble metals for HCHO oxidation were studied with respect to the behavior of adsorbed species on the catalysts surface at room temperature using in situ DRIFTS. The results show that the activities of the TiO₂ supported Pt, Rh, Pd and Au catalysts for HCHO oxidation are closely related to their capacities for the formation of formate species and the formate decomposition into CO species. Based on in situ DRIFTS studies, a simplified reaction scheme of HCHO oxidation was also proposed.     

Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3. An FT-IR study

The adsorption and transformation of ammonia over V₂O₅, V₂O₅/TiO₂, V₂O₅-WO₃/TiO₂ and CuO/TiO₂ systems has been investigated by FT-IR spectroscopy. In all cases ammonia is first coordinated over Lewis acid sites and later undergoes hydrogen abstraction giving rise either to NH₂ amide species or to its dimeric form N₂H₄, hydrazine. Other species, tentatively identified as imide NH, nitroxyl HNO, nitrogen anions N₂⁻ and azide anions N₃⁻ are further observed over CuO/TiO₂. The comparison of the infrared spectra of the species arising from both NH₃ and N₂H₄ adsorbed over CuO/TiO₂ strongly suggest that N₂H₄ is an intermediate in NH₃ oxidation over this active selective catalytic reduction (SCR) and selective catalytic oxidation (SCO) catalysts. This implies that ammonia is activated in the form of NH₂ species for both SCR and SCO, and it can later dimerize. Ammonia protonation to ammonium ion is detected over V₂O₅-based systems, but not over CuO/TiO₂, in spite of the high SCR and SCO activity of this catalyst. Consequently Brönsted acidity is not necessary for the SCR activity.     

Photodegradation of phenol and 4-chlorophenol by BaO–Li2O–TiO2 catalysts

The catalytic photodegradation of phenol and 4-chlorophenol with white and UV light over TiO₂, BaTi₄O₉ and Hollandite catalysts has been studied in our laboratories. BaTi₄O₉ and Hollandite catalysts were prepared by solid state reaction at 900°C and 1200°C, respectively. All the catalysts were characterized by different techniques such as surface area measurements by the BET method, atomic absorption spectroscopy and XRD. Photodegradation reaction experiments were monitored by HPLC analysis. The reaction intermediates: hydroquinone and 1,4-benzoquinone were identified by GC–MS analysis. The photocatalytic activities of these catalysts in the degradation of phenol and 4-chlorophenol were evaluated in comparison with titanium oxide. Experimental results showed that BaTi₄O₉ and Hollandite catalysts exhibit small photocatalytic activity as compared with TiO₂.     

Catalytic activities of Co(Ni)Mo/TiO2–Al2O3 catalysts in gasoil and thiophene HDS and pyridine HDN: effect of the TiO2–Al2O3 composition

The effect of the TiO₂–Al₂O₃ mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous HDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO₂ into the support, and particularly over rich- and pure-TiO₂-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO₂. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil HDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO₂ content and large differences are observed between the catalysts supported on pure Al₂O₃ and pure TiO₂. In contrast, in the case of the thiophene test, the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al₂O₃- and pure TiO₂-based catalysts is relatively small and dependent on the H₂ pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H₂ partial pressure on the thiophene HDS, and on the effect of H₂S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking.     

新型纳米SO42-/TiO2催化剂制备及催化合成醋酸丁酯

采用高压水热法合成纳米锐钛矿相TiO₂前驱体,通过H₂SO₄溶液浸渍制备系列新型SO₄^2-/TiO₂催化剂,采用XRD、TG-DTG和TEM对其结构和形貌进行表征,并用于催化醋酸与正丁醇的酯化反应,考察H₂SO₄溶液浓度、浸渍时间和反应时间对酯化率的影响。结果表明,在H₂SO₄浓度1 mol·L^-1、浸渍时间12 h和反应时间180 min条件下,酯化率高达99.2%,催化剂具有优异的催化性能和较佳的重复使用性。     

Effect of V2O5 on the catalytic activity of Pt-based diesel oxidation catalyst

We investigated the suppression of SO₂ oxidation activity by vanadium oxide in Pt-based diesel oxidation catalyst using reaction experiments, temperature programmed desorption (TPD), infrared (IR) and X-ray photoelectron spectroscopy (XPS). There was no interaction between Pt and S indicated by the XPS results. SO₂ was not adsorbed on Pt at room temperature indicated by the absence of peak arising from SO₂ in SO₂ TPD spectra. SO₂ molecules were adsorbed on the hydroxyl groups of TiO₂ and migrated to Pt particles to react with oxygen adsorbed on it. V₂O₅ decreased the adsorption of SO₂ on TiO₂ by the blockage of V₂O₅ on TiO₂.     

Fischer–Tropsch synthesis over Re-promoted Co supported on Al2O3, SiO2 and TiO2: Effect of water

The activity and selectivity of rhenium promoted cobalt Fischer–Tropsch catalysts supported on Al₂O₃, TiO₂ and SiO₂ have been studied in a fixed-bed reactor at 483 K and 20 bar. Exposure of the catalysts to water added to the feed deactivates the Al₂O₃ supported catalyst, while the activity of the TiO₂ and SiO₂ supported catalysts increased. However, at high concentrations of water both the SiO₂ and TiO₂ supported catalyst deactivated. Common for all catalysts was an increase in C₅₊ selectivity and a decrease in the CH₄ selectivity by increasing the water partial pressure. The catalysts have been characterized by scanning transmission electron microscope (STEM), BET, H₂ chemisorption and X-ray diffraction (XRD).     

B掺杂对负载型TiO_2光催化剂脱硝性能的影响

采用超声辅助溶胶-凝胶法制备活化半焦负载B掺杂TiO_2光催化剂,即B-TiO_2/ASC。在相同实验条件下,分别在紫外和可见光下研究其对模拟烟气的光催化氧化脱硝性能。结果表明,在紫外和可见光下,B掺杂光催化剂的活性得到提高,在可见光下的活性增加更加显著,反应180 min后仍可保持80%以上的脱硝率。结合XRD和FT-IR分析,可以看出B以取代掺杂的方式存在于TiO_2中并且导致TiO_2表面缺陷。表面缺陷有助于光生载流子的分离,从而延长光生电子的寿命并增加参与光催化反应的光生电子数量,从而产生更多的羟基自由基氧化NO,最终提高光催化脱硝率。