Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

Effect of Cu loading content on the catalytic performance of Cu-USY catalysts for selective catalytic reduction of NO with NH3

Series of Cu-USY zeolite catalyst with different Cu loading content were synthesized through simple impregnation method. The obtained catalysts were subjected to selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) performance evaluation, structural/chemical characterizations such as X-ray diffraction (XRD), N₂ adsorption/desorption, H₂ temperature-programmed reduction (H₂-TPR), NH₃ temperature-programmed desorption (NH₃-TPD) as well as detailed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments including CO adsorption, NH₃ adsorption and NO+O₂ in situ reactions. Results show that Cu-USY with proper Cu loading (in this work 5Cu-USY with 5 wt.% Cu) could be promising candidates with highly efficient NH₃-SCR catalytic performance, relatively low byproduct formation and excellent hydrothermal stability, although its SO₂ poisoning tolerability needs alleviation. Further characterizations reveal that such catalytic advantages can be attributed to both active cu species and surface acid centers evolution modulated by Cu loading. On one hand, Cu species in the super cages of zeolites increases with higher Cu content and being more conducive for NH₃-SCR reactivity. On the other hand, higher Cu loading leads to depletion of Brønsted acid centers and simultaneous formation of abundant Lewis acid centers, which facilitates NH₄NO₃ reduction via NH₃ adsorbed on Lewis acid centers, thus improving SCR reactivity. However, Cu over-introduction leads to formation of surface highly dispersed CuO_x, causing unfavorable NH₃ oxidation and inferior N₂ selectivity.     

Pt/CeO2催化氧化甲苯反应机制研究

采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.     

Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C3H6

Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Nano-sized alumina supported palladium catalysts for methane combustion with excellent thermal stability

Pd/Al₂O₃ catalysts supported on Al₂O₃ of different particle sizes were synthesized and applied in methane combustion. These catalysts were systematically characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), high resolution-transmission electron microscopy (HR-TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), H₂-temperature-programmed reduction (H₂-TPR), O₂-temperature-programmed oxidation (O₂-TPO), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS). The characterization results indicated that nano-sized Al₂O₃ enabled the uniform dispersion of palladium nanoparticles, thus contributing to the excellent catalytic performance of these nano-sized Pd/Al₂O₃ catalysts. Among them, Pd/Al₂O₃-nano-10 (Pd/Al₂O₃ supported by alumina with an average particle size of 10 nm) showed superior catalytic activity and stability for methane oxidation under harsh practical conditions. It maintained excellent catalytic performance for methane oxidation for 50 hr and remained stable even after harsh hydrothermal aging in 10 vol.% steam at 800°C for 16 hr. Characterization results revealed that the strong metal-support interactions and physical barriers provided by Al₂O₃-nano-10 suppressed the coalescence ripening of palladium species, and thus contributed to the superior sintering resistance of the Pd/Al₂O₃-nano-10 catalyst.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

纳米CeO2催化氧化甲苯的形貌效应研究

采用水热法合成CeO2纳米棒、纳米颗粒和纳米立方体,利用XRD、BET-N2、TEM/HRTEM、Raman、O2-TPD和H2-TPR等表征手段进行表征,并利用连续流固定床反应法研究各催化剂对甲苯的催化氧化性能.结果表明,CeO2纳米棒因具有高比表面积和细颗粒尺寸,且表面主要暴露高活性的{100}/{110}晶面,拥有更多的氧空位和高活性氧物种,因此,催化活性最高,CeO2纳米颗粒次之,立方体最低.原位红外甲苯催化氧化机理分析进一步表明,CeO2纳米颗粒和纳米立方体上生成的羧酸盐物质难以进一步深度氧化,而纳米棒能在贫氧和低温条件下诱导甲苯的完全氧化和产物脱附,使甲苯得以快速降解.     

Promoting effect of vanadium on catalytic activity of Pt/Ce–Zr–O diesel oxidation catalysts

A series of Pt–V/Ce–Zr–O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt–V/Ce–Zr–O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer–Emmett–Teller method,X-ray diffraction, H2temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce–Zr–O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation.     

Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

The effect of pretreatment on Pd/Al₂O₃ catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al₂O₃ catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al₂O₃ activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al₂O₃ pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al₂O₃, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al₂O₃ catalyst for the catalytic oxidation of o-xylene at low temperature.     

Structures and catalytic performances of Me/SAPO-34 (Me = Mn, Ni, Co) catalysts for low-tem perature SCR of NOx by ammonia

Me/SAPO-34 (Me = Mn, Ni, Co) series of catalysts were prepared by a wetness impregnation method and investigated for the selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR). Among them, Mn/SAPO-34 catalyst was found as the most promising candidate based on its superior low-temperature activity. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy images (TEM), nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and desorption (TPR and TPD), and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) of NH₃/NO_x adsorption. Mn/SAPO-34 is obviously different from Ni/SAPO-34 and Co/SAPO-34 in the active species state and distribution. Surface MnO_x species which play an essential role in NO oxidation and NO₂ adsorption, act as better active sites than nickel and cobalt mostly in the form of the aluminates and silicates.     

Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3

Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction （SCR） of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.     

Role of NO in Hg oxidation over a commercial selective catalytic reduction catalyst V2O5–WO3/TiO2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V₂O₅–WO₃/TiO₂, to investigate mercury oxidation in the presence of NO and O₂. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O₂. With NO and O₂ pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg⁰ oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O₂. Although NO promoted Hg⁰ oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg⁰ oxidation; NO in the gaseous phase may directly react with the adsorbed Hg⁰, but excessive NO hinders Hg⁰ adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO₂) with oxygen, which facilitated the adsorption and oxidation of Hg⁰. Hg⁰ was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg⁰ temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O₂.     

Selective catalytic reduction of nitrogen oxides over a modified silicoaluminophosphate commercial zeolite

Nitrogen oxides(NO_x:NO,NO_2)are a concern due to their adverse health effects.Diesel engine transport sector is the major emitter of NO_x.The regulations have been strengthened and to comply with them,one of the two methods commonly used is the selective catalytic reduction of NO_xby NH_3(NH_3-SCR),NH_3being supplied by the in-situ hydrolysis of urea.Efficiency and durability of the catalyst for this process are highly required.Durability is evaluated by hydrothermal treatment of the catalysts at temperature above 800°C.In this study,very active catalysts for the NH_3-SCR of NO_xwere prepared by using a silicoaluminophosphate commercial zeolite as copper host structure.Characterizations by X-ray diffraction(XRD),scanning electron microscopy(SEM)and temperature programmed desorption of ammonia(NH_3-TPD)showed that this commercial zeolite was hydrothermally stable up to 850°C and,was able to retain some structural properties up to950°C.After hydrothermal treatment at 850°C,the NO_xreduction efficiency into NH_3-SCR depends on the copper content.The catalyst with a copper content of 1.25 wt.%was the most active.The difference in activity was much more important when using NO than the fast NO/NO_2reaction mixture.     

Synergistic effect of F and triggered oxygen vacancies over F-TiO2 on enhancing NO ozonation

Oxidation-absorption technology is a key step for NO_x removal from low-temperature gas. Under the condition of low O₃ concentration (O₃/NO molar ratio = 0.6), F-TiO₂ (F-TiO₂), which is cheap and environmentally friendly, has been prepared as ozonation catalysts for NO oxidation. Catalytic activity tests performed at 120°C showed that the NO oxidation efficiency of F-TiO₂ samples was higher than that of TiO₂ (about 43.7%), and the NO oxidation efficiency of F-TiO₂-0.15 was the highest, which was 65.3%. Combined with physicochemical characteristics of catalysts and the analysis of active species, it was found that there was a synergistic effect between F sites and oxygen vacancies on F-TiO₂, which could accelerate the transformation of monomolecular O₃ into multi-molecule singlet oxygen (¹O₂), thus promoting the selective oxidation of NO to NO₂. The oxidation reaction of NO on F-TiO₂-0.15 follows the Eley-Rideal mechanism, that is, gaseous NO reacts with adsorbed O₃ and finally form NO₂.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O₃ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ ? NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the “cold start” problem.     

等离子体场内CeO2催化降解甲醇的表面活性氧物种来源与作用研究

利用水热法制备了3种不同形貌(纳米棒、纳米颗粒、纳米立方体)的CeO_2催化剂,并通过比表面积测试(BET)、扫描电子显微镜(SEM)、拉曼光谱分析(Raman)、O_2程序升温脱附(O_2-TPD)手段表征其物理化学性质,结果发现,CeO_2纳米棒的表面氧空位和氧物种最多.等离子体与催化协同降解甲醇性能评价实验结果显示,CeO_2纳米棒展现出最好的催化性能.进一步设计实验(甲醇-TPD、不同气氛常温催化、催化剂内后置比较、O_3催化氧化)推测在等离子体场内CeO_2表面活性氧物种来源及其作用.结果表明:①在等离子体场内参与CeO_2表面催化反应的活性氧物种有两个来源,一是催化剂本身存在的表面氧物种,二是等离子体区域产生的短寿命物种及长寿命物种(主要是O_3),其中,O_3分解产生的活性氧物种是提高催化性能的主要因素.②不同形貌CeO_2由于表面氧空位含量不同,导致O_3在催化剂上分解产生的活性氧物种的量不同,最终影响等离子体催化性能.     

Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst

CeO2–TiO2composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5–WO3/CeO2–TiO2catalysts for the selective catalytic reduction（SCR） of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV–Vis,Raman and XPS techniques. The results showed that the catalytic activity of V2O5–WO3/TiO2 was greatly enhanced by Ce doping（molar ratio of Ce/Ti = 1/10） in the TiO2 support.The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.     

Investigation of the common intermediates over Fe-ZSM-5 in NH3-SCR reaction at low temperature by in situ DRIFTS

The surface species formed in the reaction of NO and NO₂ with pre-adsorbed NH₃ over a Fe-ZSM-5 catalyst (1.27 wt.% Fe, SiO₂/Al₂O₃ = 25) at low temperature (140°C) were studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Through using a background spectrum of NH₃-saturated Fe-ZSM-5, we clearly observed the formation of common intermediates resulting from the reaction of NO₂ or NO + O₂ with pre-adsorbed NH₃. This presents strong evidence that the oxidation of NO to form surface nitrates and nitrites is the key step for standard SCR at low temperature. In addition, the results suggest that in the SCR reaction at low temperature, the NH₄⁺ ions absorbed on Brønsted acid sites are less active than NH₃ adsorbed on Lewis acid sites related to Fe species.     

以堇青石蜂窝陶瓷为载体的新型钒氧化物脱氮催化剂研究

以TiO₂/Al₂O₃/堇青石蜂窝陶瓷为载体,以V₂O₅-MoO₃-WO₃为活性组分,用于氨法选择性催化还原烟气中NO的新型催化剂,并对该催化剂的活性性能和微观结构进行了评价和表征.同时,将该催化剂的活性性能与其它几种活性组分相同但载体、制备方法、结构不同的催化剂进行了对比.对比结果表明,该新型催化剂能取得最好的选择性催化还原氮氧化物催化性能BET、FT IR、XPS表征实验结果表明,其高催化活性得益于大比表面积及大孔体积,而TiO₂/Al₂O₃/堇青石蜂窝陶瓷载体及其制备方法对获得好的催化剂构型起了至关重要的作用.