Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr...Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr （χ= 0, 5, 10, 20）, they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation （TPO） in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270℃, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40℃ under loose contact condition.展开更多
Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn...Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn,Cr,Fe,Cu) oxides modified CZ were prepared by incipient wetness impregnation method to improve the oxygen storage capacity of CZ-based materials.To clearly illustrate the influence of TM oxides,N2 adsorption-desorption,X-ray diffraction(XRD),oxygen storage capacity(OSC),temperature programmed reduction by H2(H2-TPR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the physical and chemical properties of samples.It is found that,all modified CZ have higher OSC,lower reduction temperatures than those of pristine CZ.Interaction between TMOs and CZ take precedence over specific surface to influence OSC.Notably,FeOx/CZ has the highest OSC,which is about 1.9 times that of CZ and it could be attributed to synergistic effect between FeOx and CZ;CuOx/CZ has the lowest reduction temperature which is 168℃lower than that of CZ,and it can be explained by hydrogen spillover effect.展开更多
CeZr, CeYZr, LaCeZr, LaCePrZr, LaCePrYZr, and LaCePr solid solutions were prepared via the coprecipitation method, and characterized by means of X-Ray Diffraction （XRD） and Brunauer-Emmett-Teller （BET） techniques....CeZr, CeYZr, LaCeZr, LaCePrZr, LaCePrYZr, and LaCePr solid solutions were prepared via the coprecipitation method, and characterized by means of X-Ray Diffraction （XRD） and Brunauer-Emmett-Teller （BET） techniques. The oxygen storage capacity （OSC） of the solid solutions was evaluated by the pulse technique and the catalytic activity was assessed using a 4-channel catalysis device. It was seen that the solid solutions presented cubic structure. The specific surface area and thermal stability could be enhanced by doping Y into the solid solutions. Doping a small amount of La had a positive effect on the thermal durability while doping a large amount of La decreased the specific surface area and the thermal stability. LaCePrZr and LaCePrYZr solid solutions synthesized using Baotou rare earth mineral residue enriched with LaCePr after Nd extraction presented a certain higher value in specific surface area and thermal stability, thereby enabling to be used as economic catalysts for automobile exhaust purification. Coating Al2O3 or SiO2 layer on the surface of ceria-zirconia solid solutions increased the specific surface area and thermal resistance.展开更多
Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentar...Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.展开更多
The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materi...The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materials in the presence of H_(2)O or SO_(2)were evaluated for the oxidation of ethylbenzene(EB).The PdPtVO_(x)/CZO sample exhibited high catalytic activity,good hydrothermal stability,and reversible sulfur dioxide-poisoning performance,over which the specific reaction rate at 160℃,turnover frequency at 160℃(TOF_(Pd or Pt)),and apparent activation energy were 72.6 mmol/(g_(Pt)·sec)or 124.2 mmol/(g_(Pd)·sec),14.2 sec^(-1)(TOF_(Pt))or 13.1 sec^(-1)(TOF_(Pd)),and 58 k J/mol,respectively.The large EB adsorption capacity,good reducibility,and strong acidity contributed to the good catalytic performance of PdPtVO_(x)/CZO.Catalytic activity of PdPtVO_(x)/CZO decreased when 50 ppm SO_(2)or(1.0 vol.%H_(2)O+50 ppm SO_(2))was added to the feedstock,but was gradually restored to its initial level after the SO_(2)was cut off.The good reversible sulfur dioxide-resistant performance of PdPtVO_(x)/CZO was associated with the facts:(i)the introduction of SO_(2)leads to an increase in surface acidity;(ii)V can adsorb and activate SO_(2),thus accelerating formation of the SO_(x)^(2-)(x=3 or 4)species at the V and CZO sites,weakening the adsorption of sulfur species at the PdPt active sites,and hence protecting the PdPt active sites to be not poisoned by SO_(2).EB oxidation over PdPtVO_(x)/CZO might take place via the route of EB→styrene→phenyl methyl ketone→benzaldehyde→benzoic acid→maleic anhydride→CO_(2)and H_(2)O.展开更多
In this work,several ceria-zirconia based catalysts with very lo w(and equimolar) metal contents were prepared,characterised and tested for the CO oxidatio n reaction(under lean and stoichiometric conditions),trying t...In this work,several ceria-zirconia based catalysts with very lo w(and equimolar) metal contents were prepared,characterised and tested for the CO oxidatio n reaction(under lean and stoichiometric conditions),trying to emulate those conditions found in a diesel oxidation catalyst(DOC) system from a diesel engine and those encountered under gasoline exhaust(λ=1).The metals chosen are Cu,Co,Ag and Pt(as a reliable benchmark).The results reveal enormous differences among reducibility and catalytic activity despite quite similar structural and textural properties of the catalysts,showing differences among dispersion(Ag-catalyst seems to present a low level of dispersion).This catalyst seems to be characterised,as well,by a strong electronic interaction between Ce and Ag centres which is suggested to yield an improved reducibility under H_(2)-TPR conditions.Nevertheless,the order in catalytic activity(Cu>Ag>Co≈Pt>>support) seems not to follow the order found in reducibility and the Cu-catalyst seems to be the most active independently on the reaction conditions,yielding nearly overlapped CO oxidation catalytic curves.Inte restingly,a stro ng correlation between the catalytic activity under the two conditions tested and the OSC values of the Ce_(0.8)Zr_(0.2)O_(2)-supported metal catalysts is found.Therefore,OSC parameter measured at 150℃ can be used as a relevant descriptor to evaluate the CO oxidation activity at low and medium conversions for the investigated catalysts,much better than the H_(2)-TPR measurements.展开更多
Ultra-fine CeO_2-ZrO_2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce_2(CO_3)_3·8H_2O, ZrOCl_2·xH_2O and ammonia were used as reactants. It is found that the cryst...Ultra-fine CeO_2-ZrO_2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce_2(CO_3)_3·8H_2O, ZrOCl_2·xH_2O and ammonia were used as reactants. It is found that the crystalline Ce_2(CO_3)_3·8H_2O and ZrOCl_2·xH_2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce_(0.15)Zr_(0.85)O_2 mixed oxide with pure tetragonal phase structure and medium particle size(D_(50))less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O_2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.展开更多
The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane （POM） was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing （A...The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane （POM） was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing （ATOM）, precipitator mixing （MOL）, and powder mechanically mixing （MECH）, respectively. The test results indicated that among the three samples, Pd/ATOM had the best catalytic activity while Pd/MOL had the best stability in the stability test. Both the activity sequences of the fresh and used samples were consistent with the order of Pd dispersion. According to the X-ray diffraction （XRD） and BET characterization, the interaction of Ce^4＋, Zr^4＋, and Al^3＋ in the ATOM mixed oxide was in favor of performing higher catalytic activity and thermal stability. The stability test indicated that Pd/MOL had the highest Pd dispersion and least coke formation on the active sites calculated by the Hz-chemisorption and TG results, which was considered to relate to its superior activity of POM to other catalysts.展开更多
Mesostructured Ce0.6Zr0.4O2 solid solutions were synthesized by coprecipitation combined with evaporation-induced self-assembly process. The obtained materials were characterized by X-ray diffractometer （XRD）, Raman...Mesostructured Ce0.6Zr0.4O2 solid solutions were synthesized by coprecipitation combined with evaporation-induced self-assembly process. The obtained materials were characterized by X-ray diffractometer （XRD）, Raman, transmission electron microscopy （TEM）, N2 sorption, and hydrogen temperature programmed reduction （H2-TPR）. The results showed that the solid solutions consisted of uniform nanocrystals, which piled homogeneous mesopores of about 4 nm. Furthermore, different surfactants had little influence on the mesoporous structures. All these samples exhibited high thermal stability.展开更多
Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce_(2)Zr_(2)O_(8) phase shows a...Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce_(2)Zr_(2)O_(8) phase shows an excellent oxygen storage capacity,and thus is examined as a promising material for developing TWCs.Considering the remarkable surface Ce/Zr ratio change during the κ-Ce_(2)Zr_(2)O_(8) formation,we investigated the effects of surface Ce/Zr ratio on the formation of κ-Ce_(2)Zr_(2)O_(8) and on the supported Pdonly three-way catalysts.Raman and transmission electron microscopy(TEM) results demonstrate that partial κ-Ce_(2)Zr_(2)O_(8) structure is formed in the three oxides,and the content of κ-Ce_(2)Zr_(2)O_(8) structure increases with increasing surface Ce/Zr ratio,but its stability declines.After thermal aging,the proportions of Ce^(3+) and oxidized palladium(Pd^(δ+)+Pd^(2+)) in the catalysts,which are shown to be positively correlated with catalytic activity,follow the same sequence as the stability of κ-Ce_(2)Zr_(2)O_(8),namely Pd/M0.33 ROa> Pd/M0.4 ROa> Pd/CeM0.33 ROa.In particular,Pd/M0.33 RO,which possesses 100%((Pd^(δ+)+Pd^(2+))/Pd) even after thermal aging at 900℃ for 4 h,owing to the strengthened metal-support interaction by the presence of stable κ-Ce_(2)Zr_(2)O_(8),shows the best catalytic performance.This work is instructive to the application of κ-Ce_(2)Zr_(2)O_(8) in three-way catalysis.展开更多
Binary Ce-Zr（CZ）,Pr-Zr（PZ） and ternary Ce-Zr-Pr（CZP） mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction（XRD）,Raman spectr...Binary Ce-Zr（CZ）,Pr-Zr（PZ） and ternary Ce-Zr-Pr（CZP） mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction（XRD）,Raman spectra,X-photon spectra（XPS） and CO temperature programmed reduction（TPR） were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity（OSC） was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.% Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3＋ ions themselves to participate in the oxygen exchange process.展开更多
Ce0.6Zr0.3RE0.1O2(RE = Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite struct...Ce0.6Zr0.3RE0.1O2(RE = Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structure. The different dopant ion radii bring different effect on the cell parameter of Ce0.6Zr0.3RE0 1O2. The X-ray photoelectron spec-troscopy (XPS) results show that the binding energy of Ce3d, Zr3d and O1s for Ce0.6Zr0.3RE0.1O2 rises compared with that for Ce0.6Zr0.4O2, indicating that dopant elements change chemistry environment of solid solutions which is available to improve redox performance. Compared with Pd/Ce0.6Zr0.4O2, doping Y and La does not change air/fuel (A/F) characteristic of TWCs, but doping Pr and Tb widens A/F operating window and makes HC, CO and NO have higher conversion. The light-off temperature of Pd/Ce0.6Zr0.3La0.1O2 is corresponding to that of Pd/Ce0.6Zr0.4O2. However, the light-off temperatures of Pd/Ce0.6Zr0.3M0.1O2(M = Y, Pr, Tb) are lower than that of Pd/Ce0.6Zr0.4O2, which keep much lower after high temperature treatments. Among Pd/Ce0.6Zr0.3RE0.1 O2, Pd/Ce0.6Zr0.3Tb0.1 O2 represents wider A/F operating window, higher conversion, lower light-off temperature and better high-temperature resistance.展开更多
Fully formulated lean NOx trap(LNT)catalysts of the type Pt/Rh/BaO/Al2O3 were prepared with and without incorporation of CeO2-ZrO2 in the washcoat,and their NOx reduction behavior was evaluated in steady-state,continu...Fully formulated lean NOx trap(LNT)catalysts of the type Pt/Rh/BaO/Al2O3 were prepared with and without incorporation of CeO2-ZrO2 in the washcoat,and their NOx reduction behavior was evaluated in steady-state,continuous flow experiments.In the fresh state, the CeO2-ZrO2 addition was found to exert little effect on NOx reduction activity using H2,CO,and NH3 as the reductants.However,after simulated road aging,NOx reduction activity was significantly impaired for the CeO2-ZrO2-free catalyst,whereas the performance of the CeO2-ZrO2-containing analog was affected to only a minor degree.These differences are explained on the basis of high-resolution transmission electron microscopy measurements showing that Pt supported on CeO2-ZrO2 remained highly dispersed after aging,whereas Pt supported on BaO/Al2O3 underwent significant sintering.In addition,the Pt/CeO2-ZrO2 component did not accumulate sulfur during aging, unlike Pt/BaO/Al2O3 for which significant sulfation of the Ba phase occurred.For both catalysts,selectivity to NH3 in NO and NO2 reduction by H2 increased after the catalyst aging,indicative of a change in the relative surface coverages of N and H ad-atoms on the precious metal sites.展开更多
As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a ...As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.展开更多
Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0....Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_(2)mixed oxides was realized via a facile and scalable approach,namely,sulfateaided coprecipitation method was labelled as CZ-S.Sulfate ion(SO_(4)^(2-))was added into raw solution in the form of sulfuric acid and acted as coordination agent.The control sample was prepared by conventional coprecipitation method without sulfuric acid added and labelled as CZ.The promotion effect of sulfate ion was analyzed systematically by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),N_(2)adsorption-desorption,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),OSC and hydrogen temperatureprogrammed reduction(H_(2)-TPR)analysis.XRD and high resolution TEM results reveal that CZ-S have homogeneous distributions of elements.TEM and SEM images show that fresh samples of CZ-S have narrower distributions of grain sizes and larger pore sizes than those of CZ.Through cross analysis of structure and morphology of CZ and CZ-S,we find that the introduction of sulfate ions results in uniform distributions of elements,narrows distributions of grain sizes,and enables the formation of secondary loose packing of sub-particles,which lead to enhanced thermal stability of the samples of CZ-S upon aging process at high temperature.After aging treatment at 1100℃for 10 h,aged samples of CZ-S present larger specific surface areas and pore volumes than the aged sample prepared by conventional coprecipitation method without sulfate ions added.Furthermore,the aged sample of CZ-S2(SO_(4)^(2-)/Zr=1)possesses the highest specific surface area of 21.9 m2/g and the biggest pore volume of 0.035 mL/g among all aged samples.展开更多
Ordered mesoporous ceria and ceria-zirconia with high specific surface area were prepared by nanocasting of a mesoporous silica KIT-6 template and used for soot oxidation.The as-synthesized ordered mesoporous ceria an...Ordered mesoporous ceria and ceria-zirconia with high specific surface area were prepared by nanocasting of a mesoporous silica KIT-6 template and used for soot oxidation.The as-synthesized ordered mesoporous ceria and ceria-zirconia were characterized by XRD,TEM,Nitrogen adsorption-desorption,Raman spectroscopy,and XRF.The results indicate that mesoporous ceria and ceria-zirconia possess highly ordered mesoporous structure,and exhibited excellent catalytic performance in soot oxidation.T_（50） of mesoporous ceria and ceria-zirconia are 475 and 470 ℃,respectively.The high catalytic activity of mesoporous materials can be attributed to the mesoporous structure and small crystallite size.Moreover,aged mesoporous materials exhibit high catalytic activity.展开更多
Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate, zirconium nitrate, and urea as raw materials by the microwave irradiation method and characterized by X-ray diffraction, fluorescence spec...Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate, zirconium nitrate, and urea as raw materials by the microwave irradiation method and characterized by X-ray diffraction, fluorescence spectrum, transmission electron microscopy, and infrared spectrum. Its acid catalytic activity was evaluated in the esterification reaction of acetic acid and n-butyl alcohol. The results show that Ce0.5Zr0.5O2 solid solution has cubic fluorite structure, and its particle diameter is in the nanometer scale. As a sort of solid acid, it possesses a higher acid catalytic activity and can be easily separated from reaction liquids. It can be used for several times, and basically, its activity keeps constant. The proton acid sites and Lewis acid sites exist in the structure of Ce0.5Zr0.5O2 solid solution.展开更多
Different nanometer CeO_2-ZrO_2 mixed oxides doped with lanthanum or praseodymium were prepared by coprecipi-tation. The characteristics of all mixed oxides were tested by XRD, SEM, TEM, and XPS. XRD results showed th...Different nanometer CeO_2-ZrO_2 mixed oxides doped with lanthanum or praseodymium were prepared by coprecipi-tation. The characteristics of all mixed oxides were tested by XRD, SEM, TEM, and XPS. XRD results showed thatall oxides were formed solid solution with CaF_2 structure at low temperature and had good thermal stability. MoreCe^(4+) ions were rich on the surface by XPS, which were beneficial to oxygen storage. The particle mediun sizes (d_(50))of all oxides powders were approximately 10～20 nm by small angle scattering goniometer. When doped Zr^(4+) inCeO_2, the specific surface areas were improved at low or high temperature. The area of Ce_(0.6)Zr_(0.3)La_(0.04)Pr_(0.06)O_2powder had excess 110 m^2/g after calcining at 923 K for 4 h, even calcined at 1273 K for 4 h, the area was up to65 m^2/g.展开更多
Ceria-zirconia solid solution has been prepared by the urea grind combustion and citric acid sol-gel methods for catalytic applications as oxygen storage/release materials in this study. The properties and oxygen stor...Ceria-zirconia solid solution has been prepared by the urea grind combustion and citric acid sol-gel methods for catalytic applications as oxygen storage/release materials in this study. The properties and oxygen storage/release capacities of samples with different Zr contents were characterized and evaluated by X-ray diffraction（XRD）, Nadsorption, scanning electron microscopy（SEM）, Raman spectroscopy, and insitu CO–COlooping test. The results demonstrate that the samples prepared by two methods are all of excellent lattice [O] release/storage properties and maintain good long-term cycle stability. But the preparation method significantly impacts the homogeneity of samples related to their redox properties and the content of Zr over 20%, which greatly changed the properties of ceria-zirconia solid solutions and caused their changing of crystalline symmetry from cubic to tetragonal. The samples prepared by citric acid solgel method are of more homogeneous particle sizes and higher specific surface areas than that by urea grind combustion method, which is benefit to the oxygen release rather than oxygen storage. The bulk oxygen amount migrated to surface increases with the increasing Zr content, however, the amount of lattice oxygen migration decreases when Zr content is over 20%. When Zr content is 20%, the differences of storage/release capacities from two different preparation methods are reduced at high temperature in the long-term loop reaction.展开更多
文摘Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr （χ= 0, 5, 10, 20）, they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation （TPO） in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270℃, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40℃ under loose contact condition.
基金supported by the National Key Research and Development Program(2017YFC0211002).
文摘Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn,Cr,Fe,Cu) oxides modified CZ were prepared by incipient wetness impregnation method to improve the oxygen storage capacity of CZ-based materials.To clearly illustrate the influence of TM oxides,N2 adsorption-desorption,X-ray diffraction(XRD),oxygen storage capacity(OSC),temperature programmed reduction by H2(H2-TPR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the physical and chemical properties of samples.It is found that,all modified CZ have higher OSC,lower reduction temperatures than those of pristine CZ.Interaction between TMOs and CZ take precedence over specific surface to influence OSC.Notably,FeOx/CZ has the highest OSC,which is about 1.9 times that of CZ and it could be attributed to synergistic effect between FeOx and CZ;CuOx/CZ has the lowest reduction temperature which is 168℃lower than that of CZ,and it can be explained by hydrogen spillover effect.
基金the National Key Basic Research Program (NKBRP 20047CCA03900)the National Natural Science Foundation of China (50662002)
文摘CeZr, CeYZr, LaCeZr, LaCePrZr, LaCePrYZr, and LaCePr solid solutions were prepared via the coprecipitation method, and characterized by means of X-Ray Diffraction （XRD） and Brunauer-Emmett-Teller （BET） techniques. The oxygen storage capacity （OSC） of the solid solutions was evaluated by the pulse technique and the catalytic activity was assessed using a 4-channel catalysis device. It was seen that the solid solutions presented cubic structure. The specific surface area and thermal stability could be enhanced by doping Y into the solid solutions. Doping a small amount of La had a positive effect on the thermal durability while doping a large amount of La decreased the specific surface area and the thermal stability. LaCePrZr and LaCePrYZr solid solutions synthesized using Baotou rare earth mineral residue enriched with LaCePr after Nd extraction presented a certain higher value in specific surface area and thermal stability, thereby enabling to be used as economic catalysts for automobile exhaust purification. Coating Al2O3 or SiO2 layer on the surface of ceria-zirconia solid solutions increased the specific surface area and thermal resistance.
基金the National Natural Science Foundation of China(20825310,20973011)the National Basic Research Program of China(973 Program,2011CB201400,2011CB808700)
文摘Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.
基金supported by the National Natural Science Foundation Committee of China-Liaoning Provincial People’s Government Joint Fund(No.U1908204)the National Natural Science Foundation of China(21976009)+2 种基金the National Key R&D Program of China(Nos.2022YFB3506200 and 2022YFB3504100)the Beijing Natural Science Foundation(J210006)the R&D Program of Beijing Municipal Education Commisson(No.KZ202210005011)。
文摘The PdPtVO_(x)/CeO_(2)-ZrO_(2)(PdPtVO_(x)/CZO)catalysts were obtained by using different approaches,and their physical and chemical properties were determined by various techniques.Catalytic activities of these materials in the presence of H_(2)O or SO_(2)were evaluated for the oxidation of ethylbenzene(EB).The PdPtVO_(x)/CZO sample exhibited high catalytic activity,good hydrothermal stability,and reversible sulfur dioxide-poisoning performance,over which the specific reaction rate at 160℃,turnover frequency at 160℃(TOF_(Pd or Pt)),and apparent activation energy were 72.6 mmol/(g_(Pt)·sec)or 124.2 mmol/(g_(Pd)·sec),14.2 sec^(-1)(TOF_(Pt))or 13.1 sec^(-1)(TOF_(Pd)),and 58 k J/mol,respectively.The large EB adsorption capacity,good reducibility,and strong acidity contributed to the good catalytic performance of PdPtVO_(x)/CZO.Catalytic activity of PdPtVO_(x)/CZO decreased when 50 ppm SO_(2)or(1.0 vol.%H_(2)O+50 ppm SO_(2))was added to the feedstock,but was gradually restored to its initial level after the SO_(2)was cut off.The good reversible sulfur dioxide-resistant performance of PdPtVO_(x)/CZO was associated with the facts:(i)the introduction of SO_(2)leads to an increase in surface acidity;(ii)V can adsorb and activate SO_(2),thus accelerating formation of the SO_(x)^(2-)(x=3 or 4)species at the V and CZO sites,weakening the adsorption of sulfur species at the PdPt active sites,and hence protecting the PdPt active sites to be not poisoned by SO_(2).EB oxidation over PdPtVO_(x)/CZO might take place via the route of EB→styrene→phenyl methyl ketone→benzaldehyde→benzoic acid→maleic anhydride→CO_(2)and H_(2)O.
基金Project supported by the Spanish Ministry of Science and Innovation/Research Spanish Agency (PID2019-105 542RB-100/AEI/10.13039/501100011033)the UE-FEDER funding and Generalitat Valenciana (CIPROM/2021/070)。
文摘In this work,several ceria-zirconia based catalysts with very lo w(and equimolar) metal contents were prepared,characterised and tested for the CO oxidatio n reaction(under lean and stoichiometric conditions),trying to emulate those conditions found in a diesel oxidation catalyst(DOC) system from a diesel engine and those encountered under gasoline exhaust(λ=1).The metals chosen are Cu,Co,Ag and Pt(as a reliable benchmark).The results reveal enormous differences among reducibility and catalytic activity despite quite similar structural and textural properties of the catalysts,showing differences among dispersion(Ag-catalyst seems to present a low level of dispersion).This catalyst seems to be characterised,as well,by a strong electronic interaction between Ce and Ag centres which is suggested to yield an improved reducibility under H_(2)-TPR conditions.Nevertheless,the order in catalytic activity(Cu>Ag>Co≈Pt>>support) seems not to follow the order found in reducibility and the Cu-catalyst seems to be the most active independently on the reaction conditions,yielding nearly overlapped CO oxidation catalytic curves.Inte restingly,a stro ng correlation between the catalytic activity under the two conditions tested and the OSC values of the Ce_(0.8)Zr_(0.2)O_(2)-supported metal catalysts is found.Therefore,OSC parameter measured at 150℃ can be used as a relevant descriptor to evaluate the CO oxidation activity at low and medium conversions for the investigated catalysts,much better than the H_(2)-TPR measurements.
文摘Ultra-fine CeO_2-ZrO_2 mixed oxide was successfully synthesized by wet-solid phase mechanochemical processing, Ce_2(CO_3)_3·8H_2O, ZrOCl_2·xH_2O and ammonia were used as reactants. It is found that the crystalline Ce_2(CO_3)_3·8H_2O and ZrOCl_2·xH_2O are changed to amorphous cerium and zirconium hydroxide precursor after milling with ammonia, and Ce_(0.15)Zr_(0.85)O_2 mixed oxide with pure tetragonal phase structure and medium particle size(D_(50))less than 1μm is formed by calcining precursor over 673 K. The XRD patterns indicate that the crystal unite size increases with rising calcining temperature due to crystal growth. However, the particle size and BET surface area of the Ce(Zr)O_2 mixed oxide decreases with rising calcining temperature, which may be attributed to the contract of particles and the vanish of holes inside grains.
基金973 Program (2004CB719503)Key Program of Natural Science Foundation of Tianjin (07JCZDJC01600)Program for New Century Excellent Talents in University (NCET-06-0243)
文摘The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane （POM） was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing （ATOM）, precipitator mixing （MOL）, and powder mechanically mixing （MECH）, respectively. The test results indicated that among the three samples, Pd/ATOM had the best catalytic activity while Pd/MOL had the best stability in the stability test. Both the activity sequences of the fresh and used samples were consistent with the order of Pd dispersion. According to the X-ray diffraction （XRD） and BET characterization, the interaction of Ce^4＋, Zr^4＋, and Al^3＋ in the ATOM mixed oxide was in favor of performing higher catalytic activity and thermal stability. The stability test indicated that Pd/MOL had the highest Pd dispersion and least coke formation on the active sites calculated by the Hz-chemisorption and TG results, which was considered to relate to its superior activity of POM to other catalysts.
基金supported by 973 Project (2004CB719500)the New Century Excellent Talents in University (NCET-05-415)the Natural Science Foundation of China (20673037)
文摘Mesostructured Ce0.6Zr0.4O2 solid solutions were synthesized by coprecipitation combined with evaporation-induced self-assembly process. The obtained materials were characterized by X-ray diffractometer （XRD）, Raman, transmission electron microscopy （TEM）, N2 sorption, and hydrogen temperature programmed reduction （H2-TPR）. The results showed that the solid solutions consisted of uniform nanocrystals, which piled homogeneous mesopores of about 4 nm. Furthermore, different surfactants had little influence on the mesoporous structures. All these samples exhibited high thermal stability.
基金Project supported by the National Natural Science Foundation of China (21972097,21773189)。
文摘Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce_(2)Zr_(2)O_(8) phase shows an excellent oxygen storage capacity,and thus is examined as a promising material for developing TWCs.Considering the remarkable surface Ce/Zr ratio change during the κ-Ce_(2)Zr_(2)O_(8) formation,we investigated the effects of surface Ce/Zr ratio on the formation of κ-Ce_(2)Zr_(2)O_(8) and on the supported Pdonly three-way catalysts.Raman and transmission electron microscopy(TEM) results demonstrate that partial κ-Ce_(2)Zr_(2)O_(8) structure is formed in the three oxides,and the content of κ-Ce_(2)Zr_(2)O_(8) structure increases with increasing surface Ce/Zr ratio,but its stability declines.After thermal aging,the proportions of Ce^(3+) and oxidized palladium(Pd^(δ+)+Pd^(2+)) in the catalysts,which are shown to be positively correlated with catalytic activity,follow the same sequence as the stability of κ-Ce_(2)Zr_(2)O_(8),namely Pd/M0.33 ROa> Pd/M0.4 ROa> Pd/CeM0.33 ROa.In particular,Pd/M0.33 RO,which possesses 100%((Pd^(δ+)+Pd^(2+))/Pd) even after thermal aging at 900℃ for 4 h,owing to the strengthened metal-support interaction by the presence of stable κ-Ce_(2)Zr_(2)O_(8),shows the best catalytic performance.This work is instructive to the application of κ-Ce_(2)Zr_(2)O_(8) in three-way catalysis.
基金Project supported by the National Natural Science Foundation of China (50972069)the Ministry of Science and Technology, China (2009AA064803)the Chinese Ministry of Industry and Information Technology
文摘Binary Ce-Zr（CZ）,Pr-Zr（PZ） and ternary Ce-Zr-Pr（CZP） mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction（XRD）,Raman spectra,X-photon spectra（XPS） and CO temperature programmed reduction（TPR） were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity（OSC） was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.% Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3＋ ions themselves to participate in the oxygen exchange process.
基金Project supported by the Doctoral Foundation of Shandong Province (2004BS08001 ) Science Foundation of Ludong University (042901)
文摘Ce0.6Zr0.3RE0.1O2(RE = Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structure. The different dopant ion radii bring different effect on the cell parameter of Ce0.6Zr0.3RE0 1O2. The X-ray photoelectron spec-troscopy (XPS) results show that the binding energy of Ce3d, Zr3d and O1s for Ce0.6Zr0.3RE0.1O2 rises compared with that for Ce0.6Zr0.4O2, indicating that dopant elements change chemistry environment of solid solutions which is available to improve redox performance. Compared with Pd/Ce0.6Zr0.4O2, doping Y and La does not change air/fuel (A/F) characteristic of TWCs, but doping Pr and Tb widens A/F operating window and makes HC, CO and NO have higher conversion. The light-off temperature of Pd/Ce0.6Zr0.3La0.1O2 is corresponding to that of Pd/Ce0.6Zr0.4O2. However, the light-off temperatures of Pd/Ce0.6Zr0.3M0.1O2(M = Y, Pr, Tb) are lower than that of Pd/Ce0.6Zr0.4O2, which keep much lower after high temperature treatments. Among Pd/Ce0.6Zr0.3RE0.1 O2, Pd/Ce0.6Zr0.3Tb0.1 O2 represents wider A/F operating window, higher conversion, lower light-off temperature and better high-temperature resistance.
基金supported by the U.S.Department of Energy(DOE)under award No.DE-EE0000205
文摘Fully formulated lean NOx trap(LNT)catalysts of the type Pt/Rh/BaO/Al2O3 were prepared with and without incorporation of CeO2-ZrO2 in the washcoat,and their NOx reduction behavior was evaluated in steady-state,continuous flow experiments.In the fresh state, the CeO2-ZrO2 addition was found to exert little effect on NOx reduction activity using H2,CO,and NH3 as the reductants.However,after simulated road aging,NOx reduction activity was significantly impaired for the CeO2-ZrO2-free catalyst,whereas the performance of the CeO2-ZrO2-containing analog was affected to only a minor degree.These differences are explained on the basis of high-resolution transmission electron microscopy measurements showing that Pt supported on CeO2-ZrO2 remained highly dispersed after aging,whereas Pt supported on BaO/Al2O3 underwent significant sintering.In addition,the Pt/CeO2-ZrO2 component did not accumulate sulfur during aging, unlike Pt/BaO/Al2O3 for which significant sulfation of the Ba phase occurred.For both catalysts,selectivity to NH3 in NO and NO2 reduction by H2 increased after the catalyst aging,indicative of a change in the relative surface coverages of N and H ad-atoms on the precious metal sites.
基金Project supported by the Beijing Nova Program(Z181100006218030)Major State Research Development Program of Hebei province(20374202D)。
文摘As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.
基金Project supported by Beijing Nova Program(Z181100006218030)。
文摘Ceria-zirconia based mixed oxides(CZs)have been applied in three-way catalysts(TWCs)for their high surface area and oxygen storage capacity(OSC).In this work,enhanced thermal stability of Ce_(0.33)Zr_(0.55)(LaNdY)_(0.12)O_(2)mixed oxides was realized via a facile and scalable approach,namely,sulfateaided coprecipitation method was labelled as CZ-S.Sulfate ion(SO_(4)^(2-))was added into raw solution in the form of sulfuric acid and acted as coordination agent.The control sample was prepared by conventional coprecipitation method without sulfuric acid added and labelled as CZ.The promotion effect of sulfate ion was analyzed systematically by X-ray diffraction(XRD),transmission electron microscopy(TEM),scanning electron microscopy(SEM),N_(2)adsorption-desorption,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),OSC and hydrogen temperatureprogrammed reduction(H_(2)-TPR)analysis.XRD and high resolution TEM results reveal that CZ-S have homogeneous distributions of elements.TEM and SEM images show that fresh samples of CZ-S have narrower distributions of grain sizes and larger pore sizes than those of CZ.Through cross analysis of structure and morphology of CZ and CZ-S,we find that the introduction of sulfate ions results in uniform distributions of elements,narrows distributions of grain sizes,and enables the formation of secondary loose packing of sub-particles,which lead to enhanced thermal stability of the samples of CZ-S upon aging process at high temperature.After aging treatment at 1100℃for 10 h,aged samples of CZ-S present larger specific surface areas and pore volumes than the aged sample prepared by conventional coprecipitation method without sulfate ions added.Furthermore,the aged sample of CZ-S2(SO_(4)^(2-)/Zr=1)possesses the highest specific surface area of 21.9 m2/g and the biggest pore volume of 0.035 mL/g among all aged samples.
基金Supported by the National Natural Science Foundation of China(No.21476177)
文摘Ordered mesoporous ceria and ceria-zirconia with high specific surface area were prepared by nanocasting of a mesoporous silica KIT-6 template and used for soot oxidation.The as-synthesized ordered mesoporous ceria and ceria-zirconia were characterized by XRD,TEM,Nitrogen adsorption-desorption,Raman spectroscopy,and XRF.The results indicate that mesoporous ceria and ceria-zirconia possess highly ordered mesoporous structure,and exhibited excellent catalytic performance in soot oxidation.T_（50） of mesoporous ceria and ceria-zirconia are 475 and 470 ℃,respectively.The high catalytic activity of mesoporous materials can be attributed to the mesoporous structure and small crystallite size.Moreover,aged mesoporous materials exhibit high catalytic activity.
基金This work was financially supported by the Teaching Reform Study Program of Ludong University (No.Y0715).
文摘Ce0.5Zr0.5O2 solid solution was successfully synthesized using cerium nitrate, zirconium nitrate, and urea as raw materials by the microwave irradiation method and characterized by X-ray diffraction, fluorescence spectrum, transmission electron microscopy, and infrared spectrum. Its acid catalytic activity was evaluated in the esterification reaction of acetic acid and n-butyl alcohol. The results show that Ce0.5Zr0.5O2 solid solution has cubic fluorite structure, and its particle diameter is in the nanometer scale. As a sort of solid acid, it possesses a higher acid catalytic activity and can be easily separated from reaction liquids. It can be used for several times, and basically, its activity keeps constant. The proton acid sites and Lewis acid sites exist in the structure of Ce0.5Zr0.5O2 solid solution.
文摘Different nanometer CeO_2-ZrO_2 mixed oxides doped with lanthanum or praseodymium were prepared by coprecipi-tation. The characteristics of all mixed oxides were tested by XRD, SEM, TEM, and XPS. XRD results showed thatall oxides were formed solid solution with CaF_2 structure at low temperature and had good thermal stability. MoreCe^(4+) ions were rich on the surface by XPS, which were beneficial to oxygen storage. The particle mediun sizes (d_(50))of all oxides powders were approximately 10～20 nm by small angle scattering goniometer. When doped Zr^(4+) inCeO_2, the specific surface areas were improved at low or high temperature. The area of Ce_(0.6)Zr_(0.3)La_(0.04)Pr_(0.06)O_2powder had excess 110 m^2/g after calcining at 923 K for 4 h, even calcined at 1273 K for 4 h, the area was up to65 m^2/g.
基金the financial supports of National Natural Science Foundation of China(21406152)Research Project Supported by Shanxi Scholarship Council of China(2014-028)Shanxi Coal Based Key Scientific and Technological Project(MJH2014-02,MJH2015-04)
文摘Ceria-zirconia solid solution has been prepared by the urea grind combustion and citric acid sol-gel methods for catalytic applications as oxygen storage/release materials in this study. The properties and oxygen storage/release capacities of samples with different Zr contents were characterized and evaluated by X-ray diffraction（XRD）, Nadsorption, scanning electron microscopy（SEM）, Raman spectroscopy, and insitu CO–COlooping test. The results demonstrate that the samples prepared by two methods are all of excellent lattice [O] release/storage properties and maintain good long-term cycle stability. But the preparation method significantly impacts the homogeneity of samples related to their redox properties and the content of Zr over 20%, which greatly changed the properties of ceria-zirconia solid solutions and caused their changing of crystalline symmetry from cubic to tetragonal. The samples prepared by citric acid solgel method are of more homogeneous particle sizes and higher specific surface areas than that by urea grind combustion method, which is benefit to the oxygen release rather than oxygen storage. The bulk oxygen amount migrated to surface increases with the increasing Zr content, however, the amount of lattice oxygen migration decreases when Zr content is over 20%. When Zr content is 20%, the differences of storage/release capacities from two different preparation methods are reduced at high temperature in the long-term loop reaction.
