Oxidative dehydrogenation of ethylbenzene to styrene with CO2 over SnO2–ZrO2 mixed oxide nanocomposite catalysts

SnO₂–ZrO₂ nanocomposite catalysts with different compositions ranging from 0 to 100% of SnO₂ were prepared at room temperature by co-precipitation method using aqueous ammonia as a hydrolyzing agent. X-ray diffraction, transmission electron microscopic characterization revealed the SnO₂–ZrO₂ nanocomposite behavior. Acid–base properties of these catalysts were ascertained by temperature-programmed desorption (TPD) of NH₃ and CO₂. Both acidic and basic sites distribution of the nanocomposite catalysts is quite different from those of respective single oxides (SnO₂ or ZrO₂). Catalytic activity of these nanocomposite catalysts for ethylbenzene dehydrogenation (EBD) to styrene in the presence of excess CO₂ was evaluated. The change in the acid–base bi-functionality of the nanocomposite catalysts in comparison with single oxides had profound positive influence in enhancing the catalytic activity.     

Impact of surface mobility in selective oxidation. Isotopic exchange of O2 with O2 on various oxides: MoO3, SnO2 and Sb2O4. Effect of a reducer gas

Isotopic oxygen exchange experiments were carried out on simple oxides (Sb₂O₄, MoO₃ and SnO₂) and mechanical mixtures of MoO₃ or SnO₂(acceptor phase) with Rh//Al₂O₃ or Sb₂O₄ (donor phase). With Rh//Al₂O₃ a synergy effect is found: the amount of oxygen exchanged on the mixture is higher than the sum of oxygen exchanged on the two separate phases. This is a prove of oxygen mobility between donor and acceptor phases. With Sb₂O₄ this effect is less marked suggesting that the presence of a reducer gas is required. In presence of hydrocarbon, no isotopic exchange is observed: only total oxidation occurs. The presence of Sb₂O₄ decreases the rate of total oxidation by blocking, by oxygen spillover, the most active sites for oxidation.     

Solid-state reaction of Cr2O3 and SnO2

Various mixtures of SnO₂---Cr₂O₃ and SnO₂---K₂Cr₂O₇, were subjected to different thermal treatments. The crystalline phases in the calcination products have been identified by X-ray diffraction. The non-formation of definite compounds was also proved by diffuse reflectance: The structural environment of the cation Cr(III) was also studied.     

Activity enhancement of SnO2-doped Ga2O3–Al2O3 catalysts by coexisting H2O for the selective reduction of NO with propene

Catalytic reduction of NO by propene in the presence of oxygen was studied over SnO₂-doped Ga₂O₃–Al₂O₃ prepared by sol–gel method. Although SnO₂-doped Ga₂O₃–Al₂O₃ gave lower NO conversion than Ga₂O₃–Al₂O₃ in the absence of H₂O, the activity was enhanced considerably by the presence of H₂O and much higher than that of Ga₂O₃–Al₂O₃. The presence of SnO₂ and Ga₂O₃–Al₂O₃ species having intimate Ga–O–Al bondings was found to be essential for the promotional effect of H₂O. The promotional effect of H₂O was interpreted by the following two reasons. The first one is the removal of carbonaceous materials deposited on the catalyst surface by H₂O. The other is the selective inhibition by H₂O of the reaction steps resulting in propene oxidation to CO_x without reducing NO.     

The influence of F doping on the activity of PbO2 film electrodes in oxygen evolution reaction

The PbO₂ and F⁻-doped PbO₂ (F-PbO₂) film electrodes have been prepared by an electrodeposition process onto platinum substrate. The changes of their electrochemical activity for oxygen evolution (OE) reaction with accelerated electrolysis time have been studied. The results show that the activity of the electrodes decreases with increasing electrolysis time. This can be attributed to the conductivity variations, which are caused by the decrease of the oxygen vacancy concentration in PbO₂ films during OE. The mechanism of the decrease of the oxygen vacancies has been investigated. For F-PbO₂ film electrodes, though its electrochemical activity is somewhat lower than that of undoped one, its activity stability is much higher in comparison with that of PbO₂. The influence of F⁻ doping on the activity of PbO₂ film electrodes has been also discussed.     

A comparative study of Ag/Al2O3 and Cu/Al2O3 catalysts for the selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by C₃H₆ in excess oxygen was evaluated and compared over Ag/Al₂O₃ and Cu/Al₂O₃ catalysts. Ag/Al₂O₃ showed a high activity for NO reduction. However, Cu/Al₂O₃ showed a high activity for C₃H₆ oxidation. The partial oxidation of C₃H₆ gave surface enolic species and acetate species on the Ag/Al₂O₃, but only an acetate species was clearly observed on the Cu/Al₂O₃. The enolic species is a more active intermediate towards NO + O₂ to yield—NCO species than the acetate species on the Ag/Al₂O₃ catalyst. The Ag and Cu metal loadings and phase changes on Al₂O₃ support can affect the activity and selectivity of Ag/Al₂O₃ and Cu/Al₂O₃ catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al₂O₃ catalyst for NO reduction is higher than that of the Cu/Al₂O₃ catalyst.     

Low temperature oxidation of methane over Pd/SnO2 catalyst

Catalytic activities of supported Pd were investigated for low temperature oxidation of methane. Pd/SnO₂ catalysts demonstrated excellent activity for methane oxidation in spite of their low surface area. The catalytic activity of Pd/SnO₂ was strongly affected by the preparation procedure. Impregnation of Pd on SnO₂ using aqueous solution of Pd(CH₃COO)₂ was most effective in enhancing the catalytic activity. The catalytic activity was also improved when well-crystallized SnO₂ was employed as a support material. TEM observations revealed that catalytic activity is strongly influenced by the dispersion state of Pd. For the active catalysts, strong interaction between Pd and SnO₂ support was observed in the adsorption of oxygen.     

Studies on SnO2–ZrO2 solid solution

The solubilities of Sn in ZrO₂ and Zr in SnO₂ are investigated. The X-ray diffraction (XRD) studies show the solubility limit for Sn in zirconia to be 20 mol% whereas Zr in SnO₂ is around 25 mol%. All the compositions were prepared by the coprecipitation method. The average particle size for a typical composition was 25 nm as revealed by the transmission electron microscopy (TEM).     

Ag掺杂Ti/PbO2电极的制备及其在苯酚降解中的应用

使用化学还原和电沉积的方法制备了单质银（Ag）掺杂的Ti/PbO₂电极（Ti/Ag-PbO₂）。在保持镀银液浓度一定的条件下,通过改变镀银的时长制备出三种银含量的钛基体二氧化铅电极（Ti/Ag1-PbO₂、Ti/Ag2-PbO₂、Ti/Ag3-PbO₂）。利用X射线光电子能谱（XPS）和X射线荧光光谱分析（XRF）确定了PbO₂电极中Ag的价态和掺杂量。扫描电子显微镜（SEM）和X射线衍射（XRD）结果表明,Ag掺杂未明显改变电极的表面形态和晶型。根据涂层附着力测试试验发现,掺银PbO₂电极与基底之间有更好的结合力,电极使用寿命提高了约2.5倍。电化学交流阻抗谱（EIS）和循环伏安法（CV）测试结果表明,Ag的掺杂大幅降低了PbO₂电极的电荷转移电阻,提高了电极的电催化活性。利用掺银量2.7%（质量分数）的Ti/PbO₂电极降解100mg/L的苯酚水溶液,相较常规Ti/PbO₂电极,完全降解时间缩短了33.3%,降解能耗下降了34%。     

Physico-chemical characteristics and CO oxidation studies over Pd/(Mn2O3 + SnO2) catalyst

The mixed oxide catalyst (Mn₂O₃ + SnO₂) prepared by the coprecipitation method has been impregnated with Pd metal and it's catalytic behaviour for CO oxidation reaction has been investigated. In the coprecipitated material, Mn₂O₃ and SnO₂ were found to crystallise at 875 K and 1175 K, respectively, which are significantly higher than the crystallisation temperatures of individual oxides prepared under similar conditions. Results of catalytic oxidation of CO, carried out using the pulse method for the mixed oxide system and the individual oxides, suggest significant synergistic effects between these two oxides. The impregnation of palladium metal facilitated CO oxidation and the catalyst Pd/(Mn₂O₃ + SnO₂) was found to be quite effective for CO oxidation even at room temperature. Further, the CO disproportionation has been observed on palladium sites in the temperature range 350 to 400 K for the individual oxide systems.     

掺杂铁的二氧化铅电极的制备及性能研究

主要研究了不锈钢/PbO₂电极和掺杂的不锈钢/Fe-PbO₂电极的制备,用其对有机废水的处理效果及影响因素来评价该电极的性能。实验结果表明:采用恒流阳极电沉积技术制备的PbO₂电极,掺杂和不掺杂铁的电极主要成分都是β-PbO₂;两电极外观都没有明显的裂纹等缺陷,掺杂铁的二氧化铅镀层颗粒大小镶嵌,很好地清除了内应力,保证了基材与镀层不易脱落,未掺杂铁的二氧化铅镀层颗粒细小、均匀,内应力有些大;将Fe（NO₃）₂添加至电沉积溶液中,致使PbO₂电沉积层的析氧电位向正方向移动,改善了PbO₂电极的电催化活性,以至于更有利于氧化降解有机物。用改性的Fe-PbO₂电极和常规的PbO₂电极分别降解初始浓度相同的邻苯二酚和苯酚有机物废水,改性的Fe-PbO₂电极对苯酚和邻苯二酚的去除率均高于常规的PbO₂电极。掺杂铁的二氧化铅电极较未掺杂电极有更好的电催化活性,更高的析氧电位,更适宜于用作电催化阳极。     

A study on the characteristics of the SO2 reduction using coal gas over SnO2-ZrO2 catalysts

SO₂, which is an air pollutant causing acid rain and smog, can be converted into elemental sulfur in direct sulfur recovery process (DSRP). SO₂ reduction was performed over catalyst in DSRP. In this study, SnO₂-ZrO₂ catalysts were prepared by a co-precipitation method, and CO and coal gas, which contains H₂, CO, CO₂ and H₂O, were used as reductants. The reactivity profile of the SO₂ reduction over the catalysts was investigated at the various reaction conditions as follows: reaction temperature of 300–550 °C, space velocity of 5000–30,000 cm³/g_-cat. h, [reductant]/[SO₂] molar ratio of 1.0–4.0 and Sn/Zr molar ratio of SnO₂-ZrO₂ catalysts 0/1, 2/8, 3/5, 5/5, 2/1, 3/1, 4/1 and 1/0. SnO₂-ZrO₂ (Sn/Zr = 2/1) catalyst showed the best performance for the SO₂ reduction in DSRP on the basis of our experimental results. The optimized reaction temperature and space velocity were 325 °C and 10,000 cm³/g_-cat. h, respectively. The optimal molar ratio of [reductant]/[SO₂] varied with the reductants, that is, 2.0 for CO and 2.5 for coal gas. SO₂ conversion of 98% and sulfur yield of 78% were achieved with the coal gas.     

Enhanced activity of metal oxide-doped Ga2O3–Al2O3 for NO reduction by propene

Effect of additives, In₂O₃, SnO₂, CoO, CuO and Ag, on the catalytic performance of Ga₂O₃–Al₂O₃ prepared by sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. As for the reaction in the absence of H₂O, CoO, CuO and Ag showed good additive effect. When H₂O was added to the reaction gas, the activity of CoO-, CuO- and Ag-doped Ga₂O₃–Al₂O₃ was depressed considerably, while an intensifying effect of H₂O was observed for In₂O₃- and SnO₂-doped Ga₂O₃–Al₂O₃. Of several metal oxide additives, In₂O₃-doped Ga₂O₃–Al₂O₃ showed the highest activity for NO reduction by propene in the presence of H₂O. Kinetic studies on NO reduction over In₂O₃–Ga₂O₃–Al₂O₃ revealed that the rate-determining step in the absence of H₂O is the reaction of NO₂ formed on Ga₂O₃–Al₂O₃ with C₃H₆-derived species, whereas that in the presence of H₂O is the formation of C₃H₆-derived species. We presumed the reason for the promotional effect of H₂O as follows: the rate for the formation of C₃H₆-derived species in the presence of H₂O is sufficiently fast compared with that for the reaction of NO₂ with C₃H₆-derived species in the absence of H₂O. Although the retarding effect of SO₂ on the activity was observed for all of the catalysts, SnO₂–Ga₂O₃–Al₂O₃ showed still relatively high activity in the lower temperature region.     

新型钛基PbO2阳极电氧化降解 有机污染物的特性研究

用电沉积法制备了PbO2/SnO2+Sb2O3/Ti、Bi-PbO2/SnO2+Sb2O3/Ti、PbO2（超声）/SnO2+Sb2O3/Ti、Bi-PbO2（超声）/SnO2+Sb2O3/Ti等4种二氧化铅电极,用稳态极化曲线表征了它们的电催化性和选择性,分析了电解苯酚废水的处理效果,用加速寿命实验测定了电极寿命,用电子扫描电镜表征了沉积层晶相和形貌。结果表明：掺Bi可以提高电极的电催化性和电氧化苯酚的选择性,超声电沉积可以增大电极比表面积,提高电极的表观催化活性,显著增长电极加速寿命。     

Piezoelectric properties of Pb(Mn1/3Nb2/3)O3–PbZrO3–PbTiO3 ceramics with sintering aid of 2CaO–Fe2O3 compound

Since the electromechanical devices move towards enhanced power density, high mechanical quality factor (Q_m) and electromechanical coupling factor (k_p) are commonly needed for the high powered piezoelectric transformer with Q_m≥2000 and k_p=0.60. Although Pb(Mn_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ (PMnN–PZ–PT) ceramic system has potential for piezoelectric transformer application, further improvements of Q_m and k_p are needed. Addition of 2CaO–Fe₂O₃ has been proved to have many beneficial effects on Pb(Zr,Ti)O₃ ceramics. Therefore, 2CaO–Fe₂O₃ is used as additive in order to improve the piezoelectric properties in this study. The piezoelectric properties, density and microstructures of 0.07Pb(Mn_1/3Nb_2/3)O₃–0.468PbZrO₃–0.462PbTiO₃ (PMnN–PZ–PT) piezoelectric ceramics with 2CaO–Fe₂O₃ additive sintered at 1100 and 1250 °C have been studied. When sintering temperature is 1250 °C, Q_m has the maximum 2150 with 0.3 wt.% 2CaO–Fe₂O₃ addition. The k_p more than 0.6 is observed for samples sintered at 1100 °C. The addition of 2CaO–Fe₂O₃ can significantly enhance the densification of PMnN–PZ–PT ceramics when the sintering temperature is 1250 °C. The grain growth occurred with the amount of 2CaO–Fe₂O₃ at both sintering temperatures.     

Influence of metal oxides on the catalytic behavior of Au/Al2O3 for the selective reduction of NOx by hydrocarbons

The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al₂O₃ with a bulk oxide has been investigated. The oxides studied were: Co₃O₄, Mn₂O₃, Cr₂O₃, CuO, Fe₂O₃, NiO, CeO₂, SnO₂, ZnO and V₂O₅. Under lean C₃H₆-SCR conditions, these oxides (with the exception of SnO₂) convert selectively NO to NO₂. When mechanically mixed with Au/Al₂O₃, the Mn₂O₃ and Co₃O₄ oxides and, to a much greater extent, CeO₂ act synergistically with this catalyst greatly enhancing its SCR performance. It was found that their synergistic action is not straightforwardly related to their activity for NO oxidation to NO₂. The exhibited catalytic synergy may be due to the operation of either remote control or a bifunctional mechanism. In the later case, the key intermediate must be a short-lived compound and not the NO₂ molecule in gas-phase.     

Spray-coated SnO2 electron transport layer with high uniformity for planar perovskite solar cells

SnO₂ has been proven to be an effective electron transport layer(ETL)material for perovskite solar cells(PSCs)owing to its excellent electrical and optical properties.Here,we introduce a viable spray coating method for the preparation of SnO2 films.Then,we employ a SnO₂ film prepared using the spray coating method as an ETL for PSCs.The PSC based on the spray-coated SnO₂ ETL achieves a power conversion efficiency of 17.78%,which is comparable to that of PSCs based on conventional spin-coated SnO₂ films.The large-area SnO₂ films prepared by spray coating exhibit good repeatability for device performance.This study shows that SnO₂ films prepared by spray coating can be applied as ETLs for stable and high-efficiency PSCs.Because the proposed method involves low material consumption,it enables the low-cost and large-scale production of PSCs.     

Influence of Ta2O5 on the electrical properties of ZnO- and CoO-doped SnO2 varistors

SnO₂-based varistors doped with 0.5% cobalt, 0.5% zinc and various tantalum amounts were prepared by the solid-state route. Experimental evidence shows that small quantities of Ta₂O₅ improve the nonlinear properties of the samples significantly. It was found that samples doped with 0.05 mol% Ta₂O₅ exhibit the highest density (98.5%), the lowest electric breakdown field (E_b=1050 V/cm) and the highest coefficient of nonlinearity (=11.5). The effect of Ta₂O₅ dopant could be explained by the substitution of Ta⁵⁺ by Sn⁴⁺.     

Evaluation of substrates for zinc negative electrode in acid PbO_2–Zn single flow batteries

An investigation was performed on the suitability of carbon materials, metallic lead and its alloys as substrates for zinc negative electrode in acid Pb O2–Zn single flow batteries. The zinc deposition process was carried out in the medium of 1 mol·L-1H2SO4 at room temperature. No maximum current appears on the potentiostatic current transients for the zinc deposition on lead and its alloys. With increasing overpotential, the progressive nucleation turns to be a 3D-instantaneous nucleation process for the resin-graphite composite. Hydrogen evolution on the graphite composite is effectively suppressed with the doping of a polymer resin. The hydrogen evolution reaction on the lead is relatively weak, while on the lead alloys, it becomes serious to a certain degree. Although the exchange current density of zinc deposition and dissolution process on the graphite composite is relatively low,the zinc corrosion is weakened to a great extent. With the increase of deposition time, zinc deposits are more compact. The cyclings of zinc galvanostatic charge–discharge on the graphite composite provide more than90% of coulombic and 80% of energy efficiencies, and exhibit superior cycling stability during the first 10 cycles.     

Microwave dielectric properties of rutile (Zn1/3Nb2/3)0.40(Ti1−xSnx)0.60O2 (0.15 ≤ x ≤ 0.30) ceramics

Microwave dielectric properties of (Zn_1/3Nb_2/3)_0.40(Ti_1−xSn_x)_0.60O₂ ceramics were investigated as a function of SnO₂ content (0.15 ≤ x ≤ 0.30). A single phase with tetragonal rutile structure was obtained through the entire composition. The unit-cell volume of the specimens was increased with SnO₂ content, due to the larger ionic radius of Sn⁴⁺ (0.69 Å) than that of Ti⁴⁺ (0.605 Å) for octahedral site. Dielectric constant (K) of the sintered specimens was affected by the dielectric polarizability. Quality factor (Qf) was dependent on the degree of reduction of Ti⁴⁺ ion. With an increase of SnO₂ content, the temperature coefficient of resonant frequency (TCF) of the specimens decreased due to the decrease of the octahedral distortion of rutile structure.