Effect of praseodymium additive on CeO_2(ZrO_2)/TiO_2 for selective catalytic reduction of NO by NH_3

A series of praseodymium added CeO_2(ZrO_2)/TiO_2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction(XRD), N_2-brumauer-emmett-teller(N_2-BET), NH_3-temperature programmed desorption(NH_3-TPD), H_2-temperature programmed reduction(H_2-TPR), PL spectra, Raman spectra, electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS), respectively. Influence of preparation method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO_2(ZrO_2)/TiO_2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO_2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO_2 forming the structure of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce~(3+) species, which was favourable for higher catalytic activity.     

Influence of CeO_2 loading on structure and catalytic activity for NH_3-SCR over TiO_2-supported CeO_2

A series of supported CeO_2/TiO_2 catalysts were prepared to explore the influence of CeO_2 loading on these catalysts for the selective catalytic reduction of NO_3 by NH_3(NH_3-SCR).The catalysts were investigated in detail by means of XRD,Raman,H_2-TPR,NH_3-TPD,XPS,in situ DRIFTS,and NH3-SCR reaction.The activity of the catalyst is closely related to the content of CeO_2.When the loading of CeO_2 is near the dispersion capacity(1.16 mmol Ce~(4+)/100 m~2 TiO_2),the catalytic activity is better.This may be because that the dispersed CeO_2 is the active species and the catalyst has appropriate redox property,along with the larger amounts of surface Ce content and surface adsorbed oxygen species.Finally,a possible reaction mechanism via the Langmuir-Hinshelwood(L-H) mechanism is tentatively proposed to further understand the NH_3-SCR reaction.     

Modification of Cu/ZSM-5 catalyst with CeO_2 for selective catalytic reduction of NO_x with ammonia

Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction(SCR) activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction(XRD), nitrogen physisorption, inductively coupled plasma optical emission spectrometry(ICP-OES), X-ray photoelectron spectroscopy(XPS), electron paramagnetic resonance(EPR), H_2 temperature-programmed reduction(TPR) and NH_3 temperature-programmed desorption(TPD). The results showed that more CuO clusters instead of isolated Cu~(2+) species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.     

New insights into MnCe(Ba)O_x/TiO_2 composite oxide catalyst:Barium additive accelerated ammonia conversion

MnCeO_x/TiO_2 has been widely used in selective catalytic reduction(SCR) of NO_x at low temperature.However,it is often poisoned in the presence of water vapor and sulfur dioxide.In this work,the promotion mechanism of Ba modification was investigated.Results show that the doped BaO reacts with CeO_2 and forms BaCeO_3.This unique perovskite structure of BaCeO_3 significantly enhances NO oxidation and NH_3 activation of MnCeO_x/TiO_2 catalyst so that the NO conversion and the resistances to SO_2 improve.It is found that Ba species obviously promotes the NO adsorption ability and improve the redox properties of MnCeO_x/TiO_2 catalyst.While the acid properties of the catalyst are inhibited by Ba modification and among which Lewis acid sites are dominant for both MnCeO_x/TiO_2 and MnCe(Ba)O_x/TiO_2 catalysts.Furthermore,in situ DRIFT experiments reveal that the NO reduction upon MnCeO_x/TiO_2 and MnCe(Ba)O_x/TiO_2 catalysts follows both E-R and L-H mechanisms,in which L-H is preferred.Ba species enhances the formation of active nitrate species,which accelerates the NO reduction through L-H mechanism.It is interesting that although Ba species weakens the NH_3 adsorption,it induces the ammonia conversion to coordination ammonia,which in turn accelerates the catalytic reaction.     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.     

New insights into the role of vanadia species as active sites for selective catalytic reduction of NO with ammonia over VO_x/CeO_2 catalysts

A series of VO_x/CeO_2 catalysts we re synthesized via vanadia supported on ceria with different BET surface areas.The catalysts were employed to investigate the active sites for the selective catalytic reduction of NO with NH_3(NH3-SCR).The kinetic results show that VO_x/CeO_2 catalysts exhibit nearly constant apparent activation energies(E_a),indicating the same SCR reaction mechanism.The V-O-Ce bridging modes and oligomeric VO_x were identified and quantified by Raman,FT-IR and H_2-TPR.The amounts of the V-O-Ce bridging modes calculated by H_2-TPR are correlated to the NH_3-SCR intrinsic reaction rates.The turnover frequencies(TOFs) show a constant value at the same temperature,which were calculated based on the number of V-O-Ce bridging modes of VO_x/CeO_2 catalysts.Therefore,it can be concluded that the V-O-Ce bridging modes are the active sites of VO_x/CeO_2 catalysts for the NH3-SCR reaction.     

Au-Pd/ZnO-CeO_2催化剂甲醇部分氧化制氢性能的研究

采用聚合物保护乙醇还原法制备了Au-Pd/ZnO-CeO_2催化剂,考察了CeO_2对Au-Pd/ZnO催化剂甲醇部分氧化制氢反应性能的影响,并运用BET、XRD、TPR、H_2-TPD和CH_3OH-TPD等手段对催化剂进行了表征.结果表明,CeO_2对Au-Pd/ZnO催化剂具有较好的改性效果,CeO_2的引入能提高Au-Pd/ZnO催化剂的活性和氢气的选择性,归结于CeO_2的加入增加了催化剂的比表面积、分散度和对反应物甲醇的吸附,同时减少了对生成物H_2脱附,这些均有利于甲醇部分氧化制氢反应.     

Effects of support property on the catalytic performance of CeO2-ZrO2-CrOx for 1,2-dichloroethane oxidation

HZSM-5, Al₂O₃, TiO₂ and SiO₂ supported CeO₂-ZrO₂-CrO_x catalysts were prepared by deposition-precipitation method and tested for deep catalytic oxidation of 1,2-dichloroethane（DCE）, as one of the common chlorinated organic pollutants. All the catalysts were characterized by means of N₂ adsorption-desorption, X-ray photoelectron spectroscopy（XPS）, ammonia-temperatureprogrammed desorption（NH₃-TPD） and hydrogen temperature-programmed reduction（H2-TPR）. The characterization results revealed that there was strongly synergistic effect between the oxidizability of CZCr species and the acidity of supports, which obviously promoted the catalytic activity for DCE degradation. 20% CZCr/HZSM-5 showed the highest activity and good durability during the long-term continuous test. The catalytic activity decreased in the order: 20%CZCr/HZSM-5>CZCr>20%CZCr/TiO₂>20%CZCr/Al₂O₃>20%CZCr/SiO₂.     

Cerium,manganese and cerium/manganese ceramic monolithic catalysts.Study of VOCs and PM removal

Ceramic supported cerium, manganese and cerium-manganese catalysts were prepared by direct impregnation of aqueous precursor, and characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Brunauer-Emmett-Teller method(BET), temperature programmed reduction(H_2-TPR), X-ray photoelectron spectroscopy(XPS) acidity measurements and electrical conductivity. The catalytic activity was evaluated for volatile organic compounds(VOC)(ethanol, methyl ethyl ketone and toluene) oxidation. Additionally, catalysts were tested in particulate matter(PM) combustion. The characterization results indicated that Ce was in the form of Ce~(4+) and Ce~(3+), and Mn existed in the form of Mn~(4+) and Mn~(3+) on the surface of the Mn/AC sample and in the form of Mn~(4+) in the Ce/Mn/AC monolith. VOC oxidation results revealed that the Ce/Mn/AC sample showed an excellent performance compared with ceramic supported CeO_2(Ce/AC) and MnO_x(Mn/AC) samples. The PM combustion was also higher on Ce/Mn/AC monoliths. The enhanced catalytic activity was mainly attributed to the Ce and Mn interaction which enhanced the acidity, conductivity and the reducibility of the oxides.     

制备因素对PrSrCoO4催化剂的结构及催化活性的影响

采用共沉淀法、柠檬酸络合法和聚乙二醇凝胶法制备了PrSrCoO4催化剂,以CO和C3H8氧化为探针反应及XRD、XPS、TPD、TPR和BET等实验手段对催化剂进行了考察.结果表明,所有样品都具有K2NiF4型结构,不同方法制得的复合氧化物呈现不同的催化活性,聚乙二醇凝胶的焙烧温度对催化剂的结构和催化活性有较大影响.     

High activity of CeO_2-TiO_2 composites for deep oxidation of 1,2-dichloroethane

CeO_2-TiO_2 catalysts prepared by different methods were investigated for deep oxidation of 1,2-dichloroethane(DCE),as a typical representative of the chlorinated volatile organic compounds(CVOCs).Characterization analysis reveals that CeO_2-TiO_2 catalysts prepared by sol-gel and coprecipitation methods exhibit higher specific area,CeO_2 and TiO_2 particles are highly dispersed into each other and the reducibility and mobility of active oxygen species are obviously promoted due to the strong interaction between the two catalysts CeO_2 and TiO_2,resulting in higher catalytic activity for DCE oxidation to and less chlorinated byproduct.The high calcination temperature would lead to the formation of a new monoclinic phase Ce_(0.3)Ti_(0.7)O_2 and sintering,which is the main reason for the catalytic activity for DCE oxidation markedly decreases.     

Catalytic performance of a Pt-Rh/CeO_2-ZrO_2-La_2O_3-Nd_2O_3 three-way compress nature gas catalyst prepared by a modified double-solvent method

A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt~0 species and larger Ce~(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.     

Effects of MO_x(M=Mn,Cu,Sb,La)on V-Mo-Ce/Ti selective catalytic reduction catalysts

A series of MO_x-V_2O_5-MoO_3-CeO_2/TiO_2(M=Mn,Cu,Sb,and La) catalysts were prepared via an impregnation method.The physico-chemical properties of the catalysts were characterized and their NH_3-SCR of NO performance was compared.The Mn-loaded catalyst(Mn5V1Mo3Ce7/Ti) exhibits a large number of acid sites of varying strength,and together with good reducibility of the catalyst,contributes to the optimal SCR performance.The sulphate species formed in the presence of SO_2 significantly enhance the H_2O and SO_2 tolerance of Mn5V1Mo3Ce7/Ti.The Cu-loaded catalyst(Cu5V1Mo3Ce7/Ti)demonstrates potential in flue gas applications in the absence of SO_2 at low temperatures because of the excellent redox ability observed and the high degree of weak acid sites.The Sb and La loaded catalysts(Sb5V1Mo3Ce7/Ti and La5V1Mo3Ce7/Ti),especially La5V1Mo3 Ce7/Ti,exhibit the largest number of acid sites and the lowest reducibility,and therefore,may be suitable for use in high temperature denitrification applications.     

Catalytic oxidation of formaldehyde over CeO_2-Co_3O_4 catalysts

A series of CeO_2-Co_3O_4 mixed oxide catalysts with different Co/(Co+Ce) atomic ratios were synthesized by citric acid sol-gel method and used for catalytic oxidation of formaldehyde(HCHO). Many techniques such as Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(FE-SEM), temperature programmed reduction(H_2-TPR), temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy(XPS) were used to characterize catalysts. The results of catalytic performance tests showed that the catalyst CeO_2-Co_3O_4 with Co/(Co+Ce) ratio of 0.95 exhibited the best performance, and the temperature of complete oxidation of HCHO was 80 oC. The analytical results indicated that the addition of CeO_2 enhanced the specific surface area of Co_3O_4 and the fine dispersion of both of them. Moreover, the strong interaction between CeO_2 and Co_3O_4 resulted in the unique redox properties, which enhanced the available surface active oxygen and led to high valence state of cobalt oxide species. All those effects played crucial roles in the excellent performance of CeO_2-Co_3O_4 for the HCHO oxidation.     

Effect of tungsten oxide on ceria nanorods to support copper species as CO oxidation catalysts

In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at% and 3.2 at%) was introduced to the ceria nanorods via a deposition-precipitation(DP) approach,and copper species of ca.10 at% were sequentially anchored onto the modified ceria support by a similar DP route.The aim of the study was to investigate the effect of the amount of tungsten oxide(0,0.4 at%,2.0 at%,and 3.2 at%) modifier on the copper-ceria catalysts for CO oxidation reaction and shed light on the structure-activity relationship.By the aids of multiple characterization techniques including N_2 adsorption,high-resolution transmission electron microscopy(HRTEM),powder X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),and temperature-programmed reduction by hydrogen(H_2-TPR) in combination with the catalytic performance for CO oxidation reaction,it is found that the copper-ceria samples maintain the crystal structure of the fluorite fcc CeO_2 phase with the same nanorod-like morphology with the introduction of tungsten oxide,while the textural properties(the surface area,pore volume and pore size) of ceria support and copper-ceria catalysts are changed,and the oxidation states of copper and tungsten are kept the same as Cu~(2+)and W~(6+)before and after the reaction,but the introduction of tungsten oxide(WO_3)significantly changes the metal-support interaction(transfer the CuO_x clusters to Cu-[O_x]-Ce species),which delivers to impair the catalytic activity of copper-ceria catalysts for CO oxidation reaction.     

Effect of PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.     

LaSr_2Mn_2O_7 Ruddlesden-Popper manganites for oxygen reduction and electrochemical capacitors

LaSr_2 Mn_2 O_7,a Ruddlesden-Popper type bilayered perovskite,was investigated as oxygen catalyst for oxygen reduction reaction(ORR) and active electrode material for electrochemical capacitors in KOH solutions.XPS results show that Mn takes a mixed Mn~(2+),Mn~(3+)and Mn~(4+)valence state with an average valence of 3.4.As catalyst towards ORR,LaSr_2 Mn_2 O_7 and LaSr_2 Mn_2 O_7/acetylene black composite favor four electron pathways for ORR.LaSr_2 Mn_2 O_7/C composite shows a comparable onset potential for ORR to that of Pt/C electrode.The improved ORR activity of LaSr_2 Mn_2 O_7/acetylene black composite is attributed to the synergy between catalytic LaSr_2 Mn_2 O_7 and conductive acetylene black.As electrode material for electrochemical capacitors,LaSr_2 Mn_2 O_7 exhibits a maximum specific capacitance of 167.2 F/g with 62%faradic contribution at a scan rate of 1 mV/s in cyclic voltammetry test.     

CeO2with diverse morphologies-supported IrOx nanocatalysts for efficient oxygen evolution reaction—Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

IrOx-based catalysts are considered the most promising candidates for oxygen evolution reaction(OER)due to their high efficiency.However,improving their intrinsic catalytic activity is essential for practical application.In this work,CeO₂with three different morphologies(rod,cube,octahedron)and supported IrOx nanoparticles were fabricated,and they display morphology-dependent OER activity.The IrOx/CeO₂-rod shows the highest activity;the catalysts have a catalytic activity sequence of rod>cube>octahedron.A plausible mechanism was proposed:the CeO₂support with different morphologies modulates the electronic structure of IrOx by the synergistic interaction promoted by oxygen vacancies between the active component and the support,thereby altering the catalytic activity of the IrOx/CeO₂catalyst.     

CeO_2/CuO catalysts using different template agent for preferential CO oxidation in H_2-rich stream

The CeO_2/CuO catalysts using different template agent(F68 L64, F127 and P123) were synthesized by the simple template and impregnation method. They were characterized by FESEM, XRD, N2 physisorption and H2-TPR techniques. It is found that the CeO_2/CuO catalysts are double pore distribution, and CeO_2 can enter into the gap of CuO supports and form the contact interface of copper and cerium. Among the asprepared catalysts, the CeO_2/CuO-F127 catalyst displays better activity at lower temperature and the CeO_2/CuO-P123 catalyst presents higher activity at higher temperature. The CeO_2/CuO-P123 catalyst has the smallest crystallite sizes of CuO and CeO_2 as well as the largest size of cubes, which may improve the interaction of copper and cerium and enhance the performance of CO oxidation.