Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst

A series of CeO₂ promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N₂O). Addition of CeO₂ to Co₃O₄ led to an improvement in the catalytic activity for N₂O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N₂O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O₂, H₂O or NO. Methods of XRD, FE-SEM, BET, XPS, H₂-TPR and O₂-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO₂ could increase the surface area of Co₃O₄, and then improve the reduction of Co³⁺ to Co²⁺ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N₂O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO₂, are responsible for the enhancement of catalytic activity of Co₃O₄.     

动物骨源羟磷灰石负载Co3O4用于N2O催化分解

通过焙烧猪骨和鸡骨获得羟磷灰石(nHAP)载体,并采用浸渍法制备Co3O4/nHAP催化剂。采用XRD、N2物理吸附-脱附、FT-IR和H2-TPR等对催化剂进行表征,在连续流动微反装置上考察催化剂催化分解N2O的性能。结果表明,相比于鸡骨源Co3O4/nHAP催化剂,以猪骨源HAP为载体的催化剂因其较大的比表面积以及较小的Co3O4粒径尺寸,提供了更多的活性位点。特别是猪骨源Co3O4/nHAP催化剂中适量的K、Na等元素促进了Co^3+到Co^2+的还原,削弱了Co-O键,使催化剂的催化活性显著提高。     

沉淀方式对沉淀法制备Co_3O_4催化N_2O直接分解性能的影响

以Co(NO_3)_2·6H_2O为钴源,K_2CO_3为沉淀剂,采用沉淀法制备Co_3O_4催化剂,用于催化N_2O直接分解反应。利用N_2~-物理吸附、XRD、FT-IR、TEM、TPR和ICP等对其进行表征,考察沉淀方式对Co_3O_4催化剂结构及其催化性能的影响。结果表明,沉淀方式对制备的Co_3O_4催化剂织构性质、物相组成和晶粒尺寸等影响不大,但显著影响其K残留量和还原性能,进而决定催化剂直接催化分解N_2O的催化性能。反加法制得的催化剂中K残留量为1.43%,明显高于正加法,同时催化剂中Co~(3+)较正加法更易还原,因而表现出更高的催化性能。在空速10 000 h~(-1)和N_2O体积分数0.1%的条件下,反加法制备的催化剂可在280℃催化N_2O完全分解,较正加法低20℃。     

Promotion effect of residual K on the decomposition of N2O over cobalt–cerium mixed oxide catalyst

A series of cobalt–cerium mixed oxide catalysts (Co₃O₄–CeO₂) with a Ce/Co molar ratio of 0.05 were prepared by co-precipitation (with K₂CO₃ and KOH as the respective precipitant), impregnation, citrate, and direct evaporation methods and then tested for the catalytic decomposition of N₂O. XRD, BET, XPS, O₂-TPD and H₂-TPR methods were used to characterize the catalysts. Catalysts with a trace amount of residual K exhibited higher catalytic activities than those without. The presence of appropriate amount of K in Co₃O₄–CeO₂ may improve the redox property of Co₃O₄, which is important for the decomposition of N₂O. When the amount of K was constant, the surface area became the most important factor for the reaction. The co-precipitation-prepared catalyst with K₂CO₃ as precipitant exhibited the best catalytic performance because of the presence of ca. 2 mol% residual K and the high surface area. We also discussed the rate-determining step of the N₂O decomposition reaction over these Co₃O₄–CeO₂ catalysts.     

Co3O4 with ordered pore structure derived from wood vessels for efficient Hg0 oxidation

Catalytic oxidation of Hgo to Hg^O is an efficient way to remove Hg⁰ from coal-fired flue gas.The catalyst with ordered pore structure can lower mass transfer resistance resulting in higher Hg⁰ oxidation efficiency.Therefore,in the present work,wood vessels were used as sacrificial template to obtain Co₃O₄with ordered pore structure.SEM and BET results show that,when the mass concentrations of Co(NO₃)₂·6H₂O wa...     

Ultrasound-assisted co-precipitation synthesis of mesoporous Co3O4–CeO2 composite oxides for highly selective catalytic oxidation of cyclohexane

The one-step highly selective oxidation of cyclohexane into cyclohexanone and cyclohexanol as the essential intermediates of nylon-6 and nylon-66 is considerably challenging. Therefore, an efficient and low-cost catalyst must be urgently developed to improve the efficiency of this process. In this study, a Co₃O₄–CeO₂ composite oxide catalyst was successfully prepared through ultrasound-assisted co-precipitation. This catalyst exhibited a higher selectivity to KA-oil, which was benefited from the synergistic effects between Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ redox pairs, than bulk CeO₂ and/or Co₃O₄. Under the optimum reaction conditions, 89.6% selectivity to KA-oil with a cyclohexane conversion of 5.8% was achieved over Co₃O₄–CeO₂. Its catalytic performance remained unchanged after five runs. Using the synergistic effects between the redox pairs of different transition metals, this study provides a feasible strategy to design high-performance catalysts for the selective oxidation of alkanes.     

Co3O4/CeO2 composite oxides for methane emissions abatement: Relationship between Co3O4–CeO2 interaction and catalytic activity

Co₃O₄/CeO₂ composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co₃O₄) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co₃O₄ and CeO₂ were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out.

An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co₃O₄ in correspondence of Co₃O₄–CeO₂ containing 30% by weight of Co₃O₄. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co₃O₄ phase and promoting the efficiency of the Co³⁺–Co²⁺ redox couple. The presence in the sample Co₃O₄(30 wt.%)–CeO₂ of a high relative amount of Ce³⁺/(Ce⁴⁺ + Ce³⁺) as detected by XPS confirms the enhanced oxygen mobility.

The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co₃O₄ phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co₃O₄ and Co₃O₄(30 wt.%)–CeO₂, performing the tests in the presence of 5 vol.% H₂O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H₂O + 5 vol.%O₂ in He) of the Co₃O₄(30 wt.%)–CeO₂ sample was also performed. All the results confirm the superiority of this composite oxide.     

Co3O4 based catalysts for NO oxidation and NOx reduction in fast SCR process

Reaction activities of several developed catalysts for NO oxidation and NO_x (NO + NO₂) reduction have been determined in a fixed bed differential reactor. Among all the catalysts tested, Co₃O₄ based catalysts are the most active ones for both NO oxidation and NO_x reduction reactions even at high space velocity (SV) and low temperature in the fast selective catalytic reduction (SCR) process. Over Co₃O₄ catalyst, the effects of calcination temperatures, SO₂ concentration, optimum SV for 50% conversion of NO to NO₂ were determined. Also, Co₃O₄ based catalysts (Co₃O₄-WO₃) exhibit significantly higher conversion than all the developed DeNO_x catalysts (supported/unsupported) having maximum conversion of NO_x even at lower temperature and higher SV since the mixed oxide Co-W nanocomposite is formed. In case of the fast SCR, N₂O formation over Co₃O₄-WO₃ catalyst is far less than that over the other catalysts but the standard SCR produces high concentration of N₂O over all the catalysts. The effect of SO₂ concentration on NO_x reduction is found to be almost negligible may be due to the presence of WO₃ that resists SO₂ oxidation.     

NO decomposition and reduction by CH4 over Sr/La2O3

Both NO decomposition and NO reduction by CH₄ over 4%Sr/La₂O₃ in the absence and presence of O₂ were examined between 773 and 973 K, and N₂O decomposition was also studied. The presence of CH₄ greatly increased the conversion of NO to N₂ and this activity was further enhanced by co-fed O₂. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH₄ in the absence of O₂, and reduction with 1% O₂ in the feed were 8.3·10⁻⁴, 4.6·10⁻³, and 1.3·10⁻² μmol N₂/s m², respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N₂ formation by decomposition was inhibited by O₂ in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH₄ continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O₂ with equal activation energies of 26 kcal/mol. The addition of O₂ increased the reaction order in CH₄ at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O₂ was 0.26 up to 0.5% O₂ during which time the CH₄ concentration was not decreased significantly. N₂O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10⁻⁴ μmol N₂/s m² at 623 K and 1220 ppm N₂O and an activation energy of 24 kcal/mol. The addition of CH₄ inhibits this decomposition reaction. Finally, the use of either CO or H₂ as the reductant (no O₂) produced specific activities at 773 K that were almost 5 times greater than that with CH₄ and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H₂ to reduce NO to N₂ over these REO catalysts.     

An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:An indirect utilization of CO2

The utilization of CO2 as rawmaterial for chemical synthesis has the potential for substantial economic and green benefits. Thermal decomposition of hexamethylene-1,6-dicarbamate (HDC) is a promising approach for indirect utilization of CO2 to produce hexamethylene-1,6-diisocyanate (HDI). In this work, a green route was developed for the synthesis of HDI by thermal decomposition of HDC over Co3O4/ZSM-5 catalyst, using chlorobenzene as lowboiling point solvent. Different metal oxide supported catalysts were prepared by incipientwetness impregnation (IWI), PEG-additive (PEG) and deposition precipitation with ammonia evaporation (DP) methods. Their catalytic performances for the thermal decomposition of HDC were tested. The catalyst screening results showed that Co3O4/ZSM-525 catalysts prepared by different methods showed different performances in the order of Co3O4/ZSM-525(PEG) N Co3O4/ZSM-525(IWI) N Co3O4/ZSM-525(DP). The physicochemical properties of Co3O4/ZSM- 525 catalyst were characterized by XRD, FTIR, N2 adsorption-desorption measurements, NH3-TPD and XPS. The superior catalytic performance of Co3O4/ZSM-525(PEG) catalyst was attributed to its relative surface content of Co3+, surface lattice oxygen content and total acidity. Under the optimized reaction conditions: 6.5% HDC concentration in chlorobenzene, 1 wt% Co3O4/ZSM-525(PEG) catalyst, 250 °C temperature, 2.5 h time, 800 ml·min?1 nitrogen flow rate and 1.0 MPa pressure, the HDC conversion and HDI yield could reach 100% and 92.8% respectively. The Co3O4/ZSM-525(PEG) catalyst could be facilely separated from the reaction mixture, and reused without degradation in catalytic performance. Furthermore, a possible reaction mechanism was proposed based on the physicochemical properties of the Co3O4/ZSM-525 catalysts.     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.     

Selective catalytic reduction of N2O in industrial emissions containing O2, H2O and SO2: behavior of Fe/ZSM-5 catalysts

The catalytic behavior in N₂O reduction by propane in the presence of O₂, H₂O and SO₂ of Fe/ZSM-5 catalysts prepared by ion exchange and chemical vapour deposition (CVD) is reported. The catalyst prepared by CVD shows a lower dependence of the rate of selective N₂O reduction on the decrease in C₃H₈ to N₂O ratio in the feed and a higher resistance to deactivation by SO₂ in accelerated durability tests with high SO₂ concentration (500 ppm). This catalyst shows stable catalytic behavior in the presence of SO₂ for more than 600 h of time-on-stream. Characterization of the catalysts by UV–VIS–NIR diffuse reflectance indicates that the poor performances of the sample prepared by ion exchange could be related to the presence of highly clustered Fe³⁺ species, in this catalyst. On the other hand, Fe₂O₃ particles are not present in the sample prepared by CVD while mainly isolated Fe³⁺ ions and iron-oxide nanoclusters are present.     

Role of active oxygen transients in selective catalytic reduction of N2O with CH4 over Fe-zeolite catalysts

Sharp NO and O₂ desorption peaks, which were caused by the decomposition of nitro and nitrate species over Fe species, were observed in the range of 520–673 K in temperature-programmed desorption (TPD) from Fe-MFI after H₂ treatment at 773 K or high-temperature (HT) treatment at 1073 K followed by N₂O treatment. The amounts of O₂ and NO desorption were dependent on the pretreatment pressure of N₂O in the H₂ and N₂O treatment. The adsorbed species could be regenerated by the H₂ and N₂O treatment after TPD, and might be considered to be active oxygen species in selective catalytic reduction (SCR) of N₂O with CH₄. However, the reaction rate of CH₄ activation by the adsorbed species formed after the H₂ and N₂O or the HT and N₂O treatment was not so high as that of the CH₄ + N₂O reaction over the catalyst after O₂ treatment. The simultaneous presence of CH₄ and N₂O is essential for the high activity of the reaction, which suggests that nascent oxygen species formed by N₂O dissociation can activate CH₄ in the SCR of N₂O with CH₄.     

Cu-Mn氧化物催化N_2O直接分解性能

分别以Cu(NO_3)_2·3H_2O和50%Mn(NO_3)_2水溶液为铜源和锰源,K_2CO_3为沉淀剂,采用沉淀法和共沉淀法制备单一Cu、Mn氧化物催化剂和Cu-Mn-O复合氧化物催化剂,用于催化N_2O直接分解反应,并利用N_2物理吸附-脱附、XRD、FT-IR和TPR等进行表征。结果表明,单一Cu和Mn氧化物分别以体相CuO和Mn2O_3物相形式存在,Cu-Mn-O复合氧化物中除形成CuMn_2O_4尖晶石物相外,还有一定量小晶粒CuO,较单一氧化物具有更加优异的还原性能,表现出较高的催化N_2O直接分解活性。在空速10 000 h~(-1)和N_2O体积分数0.1%条件下,Cu-Mn-O复合氧化物催化剂可在440℃催化N_2O完全分解,分别较单一Cu和Mn氧化物催化剂降低了40℃和60℃。     

N2O catalytic decomposition over various spinel-type oxides

Various spinel-type catalysts AB₂O₄ (where A = Mg, Ca, Mn, Co, Ni, Cu, Cr, Fe, Zn and B = Cr, Fe, Co) were prepared and characterized by XRD, BET, TEM and FESEM-EDS. The performance of these catalysts towards the decomposition of N₂O to N₂ and O₂ was evaluated in a temperature programmed reaction (TPR) apparatus in the absence and the presence of oxygen. Spinel-type oxides containing Co at the B site were found to provide the best activity. The half conversion temperature of nitrous oxide over the MgCo₂O₄ catalyst was 440 °C and 470 °C in the absence and presence of oxygen, respectively (GHSV = 80,000 h⁻¹).

On the grounds of temperature programmed oxygen desorption (TPD) analyses as well as of reactive runs, the prevalent activity of the MgCo₂O₄ catalyst could be explained by its higher concentration of suprafacial, weakly chemisorbed oxygen species, whose related vacancies contribute actively to nitrous oxide catalytic decomposition. This indicates the way for the development of new, more active catalysts, possibly capable of delivering at low temperatures amounts of these oxygen species even higher than those characteristic of MgCo₂O₄.     

Co-ZSM-5 catalysts for N2O decomposition

The catalytic properties of cobalt containing ZSM-5 zeolites prepared by various methods were compared. TPR, XRD, N₂-BET, XPS, FTIR and UV–vis spectroscopy were used for characterizing the samples. Well-dispersed cobalt oxide-like species and isolated Co²⁺ ions in charge compensation positions were found in the zeolite. Catalysts prepared using a single step cation exchange method showed high activity for N₂O decomposition in a temperature range 300–550°C, in the presence of 0–5% O₂, and high stability in the presence of 10% H₂O to the feed. UV–vis spectra and TPR experiments indicated the presence of some cobalt oxides, not detected by DRX, in a Co-ZSM-5 catalyst containing 3.76 wt% Co, prepared by a solid-state reaction procedure. The N₂O conversion over this catalyst was strongly affected by addition of both O₂ and H₂O to the feed.     

Combined CO/CH4 oxidation tests over Pd/Co3O4 monolithic catalyst: Effects of high reaction temperature and SO2 exposure on the deactivation process

CO and CH₄ combined oxidation tests were performed over a Pd (70 g/ft³)/Co₃O₄ monolithic catalyst in conditions of GHSV = 100,000 h⁻¹ and feed composition close to that of emission from bi-fuel vehicles. The effect of SO₂ (5 ppm) on CO and CH₄ oxidation activity under lean condition (λ = 2) was investigated. The presence of sulphur strongly deactivated the catalyst towards methane oxidation, while the poisoning effect was less drastic in the oxidation of CO. Saturation of the Pd/Co₃O₄ catalytic sites via chemisorbed SO₃ and/or sulphates occurred upon exposure to SO₂. A treatment of regeneration to remove sulphate species was attempted by performing a heating/cooling cycle up to 900 °C in oxidizing atmosphere. Decomposition of PdO and Co₃O₄ phases at high temperature, above 750 °C, was observed. Moreover, sintering of Pd⁰ and PdO particles along with of CoO crystallites takes place.     

Conversion of N2O to N2 on TiO2(1 1 0)

In this study, we examine the interaction of N₂O with TiO₂(1 1 0) in an effort to better understand the conversion of NO_x species to N₂ over TiO₂-based catalysts. The TiO₂(1 1 0) surface was chosen as a model system because this material is commonly used as a support and because oxygen vacancies on this surface are perhaps the best available models for the role of electronic defects in catalysis. Annealing TiO₂(1 1 0) in vacuum at high temperature (above about 800 K) generates oxygen vacancy sites that are associated with reduced surface cations (Ti³⁺ sites) and that are easily quantified using temperature programmed desorption (TPD) of water. Using TPD, X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS), we found that the majority of N₂O molecules adsorbed at 90 K on TiO₂(1 1 0) are weakly held and desorb from the surface at 130 K. However, a small fraction of the N₂O molecules exposed to TiO₂(1 1 0) at 90 K decompose to N₂ via one of two channels, both of which are vacancy-mediated. One channel occurs at 90 K, and results in N₂ ejection from the surface and vacancy oxidation. We propose that this channel involves N₂O molecules bound at vacancies with the O-end of the molecule in the vacancy. The second channel results from an adsorbed state of N₂O that decomposes at 170 K to liberate N₂ in the gas phase and deposit oxygen adatoms at non-defect Ti⁴⁺ sites. The presence of these O adatoms is clearly evident in subsequent water TPD measurements. We propose that this channel involves N₂O molecules that are bound at vacancies with the N-end of the molecule in the vacancy, which permits the O-end of the molecule to interact with an adjacent Ti⁴⁺ site. The partitioning between these two channels is roughly 1:1 for adsorption at 90 K, but neither is observed to occur for moderate N₂O exposures at temperatures above 200 K. EELS data indicate that vacancies readily transfer charge to N₂O at 90 K, and this charge transfer facilitates N₂O decomposition. Based on these results, it appears that the decomposition of N₂O to N₂ requires trapping of the molecule at vacancies and that the lifetime of the N₂O–vacancy interaction may be key to the conversion of N₂O to N₂.     

Catalytic decomposition of N2O over supported Rh catalysts: effects of supports and Rh dispersion

The study of catalytic decomposition of nitrous oxide to nitrogen and oxygen over Rh catalysts supported on various supports (USY, NaY, Al₂O₃, ZrO₂, FSM-16, CeO₂, La₂O₃) showed that the activities of Rh/Al₂O₃ and Rh/USY (ultrastable Y zeolite) catalysts were comparable to or higher than the other catalysts reported in the literatures. The catalytic activity of N₂O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. A pulsed N₂O experiment over a Rh/USY catalyst suggested that the catalytic N₂O decomposition occurs on oxygen-covered surface and that O₂ may be freed on collision of N₂O molecules with the adsorbed oxygen atoms.     

Catalytic reduction of NOx by hydrocarbons over Co/ZSM-5 catalysts prepared with different methods

Co/ZSM-5 catalysts were prepared by several methods, including wet ion exchange (WIE), its combination with impregnation (IMP), solid state ion exchange (SSI) and sublimation (SUB). FTIR results show that the zeolite protons in H-ZSM-5 are completely removed when CoCl₂ vapor is deposited. TPR shows peaks for Co²⁺ ions at 695–705°C and for Co₃O₄ at 385–390°C, but a peak in the 220–250°C region appears to indicate Co²⁺ oxo-ions.

The catalysts have been tested for the selective reduction of NO_x with iso-C₄H₁₀ under O₂-rich conditions and in the absence of O₂, both with dry and wet feeds. A bifunctional mechanism appears to operate at low temperature: oxo-ions or Co₃O₄ clusters first oxidize NO to NO₂, which is chemisorbed as NO_y (y≥2) and reduced. In this modus operandi catalyst SUB shows the highest N₂ yield 90% near 390°C for dry and wet feeds. It is found to be quite stable in a 52 h run with a wet feed. In contrast, the WIE catalyst, which mainly contains isolated Co²⁺ ions and has poor activity below 400°C, excels at T>430°C. This and the observation that, at high temperature, NO is reduced in O₂-free feeds over Co/MFI catalysts, suggest that NO can be reduced over Co²⁺ ions without intermediate formation of NO₂.

The bifunctional mechanism at low temperature is supported by the fact that a strongly enhanced performance is obtained by mixing WIE with Fe/FER, a catalyst known to promote NO₂ formation.