Influence of preparation method on performance of Ni-CeO2 catalysts for reverse water-gas shift reaction

This study investigated 1 wt.% Ni-CeO₂ catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift (RWGS) reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller (BET), atomic absorption spectrophotometer (AAS), X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and temperature programmed reduction (TPR). The results showed that the Ni-CeO₂ catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO₂ catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.     

Effect of coating modification of cordierite carrier on catalytic performance of supported NiMnO3 catalysts for VOCs combustion

NiMnO_3 perovskite catalysts supported on cordierite modified by Ce_xZr_(1-x)O_2 coatings were prepared using impregnation and sol-gel methods for catalytic combustion of single/double component VOCs at different concentrations and GHSV of 15,000 h~(-1), which were characterized by BET, XRD, SEM, FT-IR, H_2-TPR and O_2-TPD. After coating modification, the specific surface area of catalysts is improved obviously.Among the catalysts, the Ce_(0.75)Zr_(0.25)O_2 coating modified NiMnO_3 catalyst exhibits the best catalytic activity for VOCs combustion with 95.6% conversion at 275 ℃ and has stable activity when catalyst is embalmed at 800 ℃. In addition, the catalyst also presents the excellent water-resistant and conversion stability over time-on-stream condition. The reason is that Ce_(0.75)Zr_(0.25)O_2 coating can promote more lattice distortion and defects and smaller crystal size, which improve oxygen transfer capability and dispersion of active component.     

Catalytic wet oxidation of N,N-dimethyl formamide over ruthenium supported on CeO2 and Ce0.7Zr0.3O2 catalysts

A series of Ru supported on CeO₂ and Ce_0.7Zr_0.3O₂(CeZrO) was prepared by incipient-wet impregnation method and investigated in the catalytic wet oxidation of N,N-dimethyl formamide (DMF) in batch reactor. The physicochemical property of the catalysts was characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). Compared with 3%Ru/CeO₂, 3%Ru/Ce_0.7Zr_0.3O₂ catalyst exhibits much higher performance for DMF degradation due to the promotion of Ru dispersion and the transfer of active oxygen, and 99% DMF conversion and 97% COD elimination are obtained at 453 K, 2.5 MPa oxygen pressure after 5 h. The reaction mechanism of DMF degradation was suggested. The carbonaceous species deposition and oxidation of Ru can be responsible for catalyst deactivation. And the catalyst activity can be recovered by air calcination and H₂ reduction.     

Effect of manganese and/or ceria loading on V_2O_5-MoO_3/TiO_2 NH_3 selective catalytic reduction catalyst

The effect of manganese and/or ceria loading of V_2 O_5-Mo_O_3/TiO_2 catalysts was investigated for selective catalytic reduction(SCR) of NO_x by NH_3.The manganese and/or ceria loaded V_2 O_5-MoO_3/TiO_2 catalysts we re prepared by the wetness impregnation method.The physicochemical characteristics of the catalysts were thoroughly characterized.The catalytic performance of 1.5 wt% V_2 O_5-3 wt% MoO_3/TiO_2(V1.5 Mo3/Ti) is greatly enhanced by addition of 2.5 wt% MnO_x and 3.0 wt% CeO_2(V1.5 Mo3 Mn2.5 Ce3/Ti) below450℃.Compared with the V1.5 Mo3/Ti catalyst with NO_x conversion of 75% at 275 ℃,V1.5 Mo3 Mn2.5 Ce3/Ti exhibits higher NO_x conversion of 84% with good resistance to SO_2 and H_2 O at a gas hourly space velocity value of 150000 h~(-1).The active manganese,cerium,molybdenum,and vanadium oxide species are highly dispersed on the catalyst surface and some synergistic effects exist among these species.Addition of MnO_x significantly enhances the redox ability of the cerium,vanadium,and molybdenum species.Addition of Ce increases the acidity of the catalyst.More active oxygen species,including surface chemisorbed oxygen,form with addition of Mn and/or Ce.Because of the synergistic effects,appropriate proportions of manganese in different valence states exist in the catalysts.In summary,the good redox ability and the strong acidity contribute to the high NH3-SCR activity and N2 selectivity of the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst in a wide temperature range.And the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst shows good resistance to H_2 O and SO2 in long-time catalytic testing,which can be ascribed to the highly sulfated species adsorbed on the catalyst.     

Effect of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation

This study was focused on the influence of active oxygen on the performance of Pt/CeO_2 catalysts for CO oxidation. A series of CeO_2 supports with different contents of active oxygen were obtained by adding surfactant at different synthesis steps. 0.25 wt% Pt was loaded on these CeO_2 supports by incipientwetness impregnation methods. The catalysts were characterized by N2 adsorption, X-ray diffraction(XRD), high-resolution transmission electron microscopy(HRTEM), H_2 temperature-programmed reduction(H_2-TPR), dynamic oxygen storage capacity(DOSC) and in-situ DRIFTS technologies. For S-f supports, the surfactant was added into the solution before spray-drying in the synthesis process, which facilitates more active oxygen formation on the surface of CeO_2. After loading Pt, the more active oxygen on CeO_2 contributes to dispersing Pt species and enhancing the CO oxidation activity. As for the aged samples,Pt-R-h shows the highest activity above 190 ℃ because of the presence of more partly oxidized Pt~(δ+) species. Thus the activity is also influenced by the states of Pt and the Pt~(δ+) species may contribute to the high activity at elevated temperature.     

Structural Studies of Dispersoids in Fe–15 wt% Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–5 wt% Ti Model ODS Alloys During Milling and Subsequent Annealing

Oxide dispersion strengthened (ODS) steels have very high thermal stability and creep resistance due to reinforcement of hard and stable nano-sized ceramic dispersoids in metallic matrix which act as barriers to dislocation motion. This study established the role of Ti in the structural evolution of yttria during mechanical milling and subsequent annealing in a Fe–15 wt% Y₂O₃–5 wt% Ti model ODS alloy, using electron microscopy and XRD techniques. The alloy was synthesized in a high energy planetary ball mill in Ar atmosphere by varying the milling durations in the range of 0 (un-milled) to 60 h. The XRD result revealed amorphisation of Y₂O₃/Ti during milling and evolution of YTiO₃ complex oxide upon annealing at 1273 K for 1 h. The electron microscopy studies revealed the refinement of alloy powders from ~50  μm to few nanometers during milling. Electron diffraction analysis and high resolution transmission electron microscopy of 60 h milled as well as and annealed powder showed formation of different types of Y–Ti–O complex oxides such as Y₂Ti₂O₇, Y₂TiO₅ and YTiO₃.     

Preparation of M/Ce1–xTixO2 (M=Pt,Rh, Ru) from sol-gel method and their catalytic oxidation activity for diesel soot

A series of Ce_1–xTi_xO₂ mixed oxide catalysts were synthesized by sol-gel method and then loading of noble metal (M = Pt, Rh, Ru) was used for soot oxidation. Ti-doped Ce_1–xTi_xO₂ catalysts (x is the molar ratio of Ti/(Ti + Ce) and ranges from 0.1 to 0.5) exhibit much better oxidation performance than CeO₂ catalyst, and the Ce_0.9Ti_0.1O₂ catalyst calcined at 500 °C has the best catalysis activity. Each noble metal (1 wt%) was supported on Ce_0.9Ti_0.1O₂ (M/C9T1) and the properties of the catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, Brunauer–Emmett–Teller (BET) method, and H₂-temperature programmed reduction (H₂-TPR) results. Results show that the introduction of Ti into CeO₂ forming Ti-O-Ce structure enhances the catalytic activity and increases the number of oxygen vacancies at the catalyst surface. The noble metal is highly dispersed over Ce_0.9Ti_0.1O₂, and M/C9T1 catalysts present enhanced activity in comparison to Ce_0.9Ti_0.1O₂. It is found that noble metals can greatly increase the activity of the catalyst and the corresponding oxidation rate of soot can enhance the electron transfer capacity and oxygen adsorption capacity of the catalyst. A small amount of Ti doping in CeO₂ can significantly improve the activity of the catalyst, while a large amount of Ti reduces the performance of the catalyst because a large amount of Ti is enriched on the surface of the catalyst, which hinders the contact and reaction between the catalyst and the soot.     

Preparation and application of ZnO doped Pt-CeO2 nanofibers as electrocatalyst for methanol electro-oxidation

ZnO doped Pt/CeO₂ nanocomposites were prepared by electrospinning and reduction impregnation. X-ray diffraction (XRD), transmission electron microscopy (TEM), energy disperse spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the nanocomposites. It is observed that ZnO and CeO₂ form the hexagonal wurtzite phase and cubic fluorite phase in the nanocomposite, respectively, whilst Pt nanoparticles (NPs) with the number-averaged size of ca. 3.1 nm are uniformly distributed on the surface of nanofibers. The mass fraction of Pt NPs in the nanocomposites is about 10 wt%. The doping of ZnO is effective to promote reactive oxygen species, surface reaction sites and the interaction between Pt and oxides. The catalytic performance of nanocomposites was evaluated by the methanol electro-oxidation, indexed with the catalytic activity, stability of catalyst. As a result, it is found that the nanocomposite exhibits much higher activity and stability for methanol oxidation than the undoped Pt/CeO₂ catalyst.     

Hydrothermal stability of MOx-Ce0.75Zr0.25O2 catalysts for NOx reduction by ammonia

Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in air containing 10 vol.% H2 O to obtain the aged catalysts.The catalysts were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,H2 programmed-reduction,NH3 adsorption and deNOx activity measurements.The results showed that,among the catalysts investigated,the phosphated Ce0.75 Zr0.25 O2 catalyst showed the highest hydrothermal stability.The remained high acidity of the phosphated catalyst with moderate redox property helped to maintain the excellent NH3-SCR activity of hydrothermally aged catalyst.Cerium tungstate led to the poor redox property of the tungstated catalyst although the acidity of catalyst was still high.The decomposition of sulfates at temperatures higher than 600 °C restrained the usage of sulfated catalysts in high temperature conditions.The overall dehydration of niobate to niobium oxides led to the low acidity of hydrothermally aged Nb2 O5-Ce0.75 Zr0.25 O2 catalyst.     

Catalytic combustion of toluene on Pt/Al2O3 and Pd/Al2O3 catalysts with CeO2,CeO2-Y2O3 and La2O3 as coatings

CeO₂,La₂O₃,and CeO₂-Y₂O₃ oxides were coated on the surface of spherical granular AI₂O₃(3-5 mm)through impregnation method,and proved as better supports of Pd and Pt catalysts.The influences of rare earth metal doping on the adsorption rates of Pd and Pt ions,as well as the catalytic performance,were investigated.Results show that the H₂PtCl₆·6H₂O adsorption rates of the Al     

Nitric oxide(NO) decomposition on catalysts,containing oxides of lanthanum and cerium,supported on γ-alumina

The present work was devoted to study the catalytic activity of lanthanum and cerium oxides separately,deposited on g-alumina in the reaction of decomposition of nitric oxide. The catalyst samples were prepared by the method of impregnation of g-Al_2 O_3 using solutions, containing nitrates of lanthanum and cerium. The prepared samples were calcined for 4 h at temperature 650℃ in an oven in air atmosphere. The catalysts were characterized by: chemical analysis by inductively coupled plasma atomic emission spectrometry(ICP-AES), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM) combined with energy-dispersive X-ray spectroscopy(EDS), electron paramagnetic resonance(EPR) and infrared(IR) spectroscopy, as well as measurement of the specific surface area. The results show that the catalysts based on lanthanum oxide and cerium oxide deposited on alumina display high catalytic activity over 60% conversion degree with respect to decomposition of nitric oxide in the absence of reducing agent. In the presence of reducer the activity reaches 90% conversion degree.     

Structure and catalytic property of CeO2-ZrO2-Fe2O3 mixed oxide catalysts for diesel soot combustion： Effect of preparation method

A series of Ce0.5Fe0.30Zr0.20O2 catalysts were prepared by different methods(co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrothermal method) and characterized by X-ray diffraction(XRD), Raman spectroscopy, Brunauer-Emmett-Teller(BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation(TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incorporated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases existed in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.2O2 catalyst presented the lowest Ti(251 °C, ignition temperature of soot oxidation) and Tm(310 °C, maximum oxidation rate temperature) for soot combustion(with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 °C for 10 h, the Ti and Tm were still relatively low, at 273 and 361 °C, respectively, indicating high catalytic stability.     

Rare earth oxide modified Cu-Mn compounds supported on TiO2 catalysts for low temperature selective catalytic oxidation of ammonia and in lean oxygen

Selective catalytic oxidation (SCO) of ammonia was carried out over Cu-Mn compounds catalysts modified with trivalent rare earth oxide Ce₂O₃ and La₂O₃ respectively. TiO₂ was used as support and different ratio of O₂ were tested in order to find an appropriate O₂ concentration (vol.%), and the results showed that 1%O₂ (vol.%) was propitious to SCO of ammonia. The effects of the two rare earth oxides modified catalysts Ce₂O₃-Cu-Mn/TiO₂ and La₂O₃-Cu-Mn/TiO₂ on the catalytic activity and selectivity of ammonia oxidation were investigated under the reaction condition of 500 ppm ammonia, 1%O₂ (vol.%), at the temperature from 125 to 250 °C. The results revealed the beneficial role of Ce₂O₃ and La₂O₃ in catalytic activity at low temperature and lean oxygen concentration, while the modification with Ce₂O₃ and La₂O₃ led to the negative influence on N₂ selectivity. For the catalysts modified with Ce showed lower NO and N₂O selectivity than the catalysts modified with La, then the effects of different Ce loadings on catalytic activity and selectivity were also considered, in combination with catalysts preparation methods, which include incipient wet impregnation, sol-gel method and co-precipitation. Results revealed that the catalysts prepared by sol-gel method obtained preferable catalytic activity compared with the others, reaching 99% ammonia at 200 °C, whereas 96% NO was detected. It also indicated that different catalyst preparation method significantly determined production distribution.     

CO and C3H8 total oxidation over Pd/La-Al2O3 catalysts： Effect of calcination temperature and hydrothermal treatment

A series of Pd/La-Al2O3（PLA） catalysts with La-Al2O3（LA） support calcined at different temperatures（500, 700, 900 and 1050 oC） were prepared using an incipient wetness impregnation method. The activity of the fresh and hydrothermally aged PLA catalysts were tested for total oxidation of CO and C3H8. The activity of the fresh PLA catalysts for CO and C3H8 oxidation increased with increasing calcination temperature of the support, while the activities of the aged catalysts declined and became essentially the same. CO chemisorption results revealed that the suppressed activities of the aged catalysts were mainly due to the decline of palladium dispersion. The turnover frequency（TOF） of CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 1050 oC having the highest value（0.048 s–1）. However, the TOF of C3H8 total oxidation was affected by not only the redox properties of catalysts but also the size of Pd particle, and large Pd particles possessed higher TOF value of C3H8 oxidation, with the highest value（0.125 s–1） being obtained on an aged catalyst calcined at 500 oC.     

Rare earth metal modified three dimensionally ordered macroporous MnOx-CeO2 catalyst for diesel soot combustion

Three dimensionally ordered macroporous(3 DOM) Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template(CCT) route. The as-synthesized catalysts showed wellordered structures with macropores and small interconnected pore windows. The Raman results indicate that the catalyst persists pure fluorite cubic phases until the molar ratio of Mn exceeds 0.3, therefore MnO_x particles form and impede the contact of the active site and the reagent and restraining soot combustion. The doping of Nd into MnO_x-CeO_2 enhances the catalytic activity because of increased oxygen vacancy, Mn~(4+)content and stronger redox ability. Nd-doping also improves thermal stability of the catalyst due to less sintering and none phase separation after thermal aging. The fresh and aged Mn_(0.3)Ce_(0.6)Nd_(0.1)O_2 catalysts show the maximum oxidation rate for soot at 331 and 355 ℃ in the O_2/N_2 atmosphere, achieving a nearly 100% CO_2 selectivity.     

CO oxidation over CuO catalysts supported on CeO2-ZrO2 prepared by microwave-assisted co-precipitation： The influence of CuO content

CeO2-ZrO2 mixed oxide(Ce0.6Zr0.4O2) prepared by microwave-assisted heating co-precipitation was used as a support to prepare a series of CuO/Ce0.6Zr0.4O2 catalysts with various CuO contents(0 wt.%–15 wt.%) via the method of incipient-wetness impregnation.The obtained CuO/Ce0.6Zr0.4O2 samples were characterized by N2 adsorption,XRD,Raman,TEM and H2-TPR technologies,and their catalytic activities for CO oxidation were investigated.The results showed that the activity of CuO/Ce0.6Zr0.4O2 catalyst was strongly influenced by the content of CuO,and the catalyst with 10 wt.% CuO exhibited the best catalytic activity in CO oxidation,which could be attributed to the high dispersion and reducibility of CuO,and high oxygen vacancy concentration in the catalyst.     

Low-content and highly effective zoned Rh and Pd three-way catalysts for gasoline particulate filter potentially meeting Euro 7

The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_x,which would be challenging for the three-way catalysts(TWCs) utilized commercially to eliminate these pollutants.TWCs with reductive(Rh) and oxidative(Pd) active components on gasoline particulate filters(TWC on GPF) play importantly auxiliary roles in the remediation of CO and NO_x downstream the close coupled TWCs to meet their emission targets.Here,a...     

Active oxygen species and oxidation mechanism over Ce-doped LaMn_(0.8)Ni_(0.2)O_3/hierarchical ZSM-5 in pentanal oxidation

Hierarchical ZSM-5(HZ) molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_xMn_(0.8)-Ni_(0.2)O_3(x ≤ 0.5) perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_2 adsorption,X-ray photoelectron spectroscopy(XPS),NH_3-temperature programmed desoprtion(NH_3-TPD),H_2-temperature programmed reduction(H_2-TPR) and O_2-TPD techniques and investigated regarding pentanal oxidation at 120-390℃ to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_2~-and O~-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_3/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What's more,appropriate Ce substitution can significantly enhance the amount of O_2~-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_2 and H_2 O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H) reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.     

Effect of preparation method on MnOx-CeO2 catalysts for NO oxidation

The NO oxidation reaction was studied over MnO_x-CeO₂ catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60% NO conversion was achieved at 250 °C. X-ray diffraction (XRD), Brumauer-Emmett (BET), H₂-temperature programmed reduction (H₂-TPR) and oxygen storage capacity (OSC) techniques were employed to characterize the physical and chemical properties of the catalysts. XRD results showed that amorphous MnO_x or Mn-O-Ce solid solution existed in co-precipitation and impregnation prepared sample, while crystalline MnO_x was found in mechanical mixing catalyst. A larger surface area was observed on co-precipitation prepared catalyst compared to those prepared by impregnation and mechanical mixing. The strong interaction between MnO_x and CeO₂ enhanced the reducibility of the oxides and increased the amount of Mn⁴⁺ and activated oxygen, which are favorable for NO oxidation to NO₂.     

An egg-shell bifunctional CeO2-modified NiPd/Al2O3 catalyst for petrochemical processes involving selective hydrogenation and hydroisomerization

The catalytic performance during the 1-butyne hydrogenation using two reduced Al₂O₃-supported Pd-based catalysts was carried out in a total recirculation system with an external fixed-bed reactor. The lab-prepared egg-shell NiPd/CeO₂-Al₂O₃ catalyst (NiPdCe) with Pd loading = 0.5 wt%, Ni/Pd atomic ratio = 1 and CeO₂ loading = 3 wt% was synthesized and characterized, and it was compared with an egg-shell Al₂O₃-supported Pd based commercial catalyst (PdCC). The reduced catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The textural characteristics and ammonia temperature-programmed desorption profiles of the fresh (unreduced) catalysts were also obtained. Both catalysts show high 1-butyne conversion and selectivity to 1-butene, but the catalysts also present important differences between hydroisomerizing and hydrogenating capabilities. NiPdCe catalyst shows higher capability for hydroisomerization reactions, while the PdCC catalyst exhibits higher hydrogenating capability. The observed catalytic performances can be interesting for some industrial processes and can provide a guideline for the development of a Pd-based catalyst with specific catalytic properties.