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1.
The dehydroxylation and rehydroxylation properties of titania (Degussa P-25) were investigated. FTIR and TPD-MS data indicate that hydroxyl groups are not completely removed at 500 °C in vacuo, and rehydration/rehydroxylation occur under helium (water content < 1 ppm) flow at room temperature. In addition, repeating dehydroxylation/rehydroxylation treatments for ten times does not significantly modify the dehydroxylation/rehydroxylation property of titania surface. Desorption of hydrogen from titania was observed at 535 °C after titania was reduced above 400 °C. The maximum surface density of hydrogen was determined to be 0.75 H atom/nm2. TPD data show four types of hydrogen on 3% titania supported cobalt catalysts: hydrogen adsorbed on cobalt metal (desorption temperature around 100 °C), reverse spillover hydro gen (150-250 °C), hydrogen from H-TiO2-x- Co interacting species (-330 °C), and recombined hydrogen from Ti3+-H on titania (-535 °C). The absence of hydrogen desorption peak at 535 °C for titania supported cobalt reduced above 400 °C can be explained in terms of the migration of H-TiO2-x moieties onto cobalt metal surface during reduction. Removal of hydroxyl groups by thermal treatment before reduction enhanced the amount of hydrogen desorption from normal cobalt surface. This indicates that the hydroxyl groups play a role in the surface migration of H-Ti2-x.  相似文献   

2.
The variations in catalytic properties for CO hydrogenation and adsorptive properties for H2 and CO of silica-supported cobalt catalyst as a function of reduction temperature (400 to 700 °C) were investigated. A mild sintering of cobalt metal from 130 Å to 145 Å occurred only when the reduction temperature was further increased from 600 to 700 °C. However, a monotone decrease in the activity (per gram Co) for CO hydrogenation was observed with increasing reduction temperature. This is accompanied with a decrease in methane and an increase in olefin formation. The decrease in activity can not be accounted for by the variation of crystallite size of cobalt metal. A concurrent suppression in the amount of hydrogen and CO adsorptions was observed after reduction temperature was raised to 700 °C. The turnover frequencies, based on cobalt dispersion estimated from H2 and CO chemisorption, remained, more or less, similar with increasing reduction temperature from 400 to 600 °C, but increased ca. 3 and 1.5 times, respectively, at 700 °C. The relative amount of subcarbonyl species (2062 cm?1) with respect to the linear adsorbed CO (2010 cm?1) was found to increase as well. Furthermore, reduction of silica surface at 700 °C was indicated by the presence of ?Si-H, which was detected by infrared spectroscopy at 2294 cm?1. This shows the presence of metal-support interaction for silica-supported cobalt systems after reduction treatment at 700 °C.  相似文献   

3.
This work reports the preparation of a La2O3-modified Pt/TiO2 (Pt/La-TiO2) hybrid through an excess-solution impregnation method and its application for CO2 hydrogenation catalysis. The Pt/La-TiO2 catalyst is characterized by XRD, H2 temperature-programmed reduction (TPR), TEM, X-ray photoelectron spectroscopy (XPS), Raman, EPR, and N2 sorption measurements. The Pt/La-TiO2 composite starts to catalyze the CO2 conversion reaction at 220 °C, which is 30 °C lower than the Pt/TiO2 catalyst. The generation of CH4 and CO of Pt/La-TiO2 is 1.6 and 1.4 times greater than that of Pt/TiO2. The CO2 temperature-programmed desorption (TPD) analysis confirms the strengthened CO2 adsorption on Pt/La-TiO2. Moreover, the in situ FTIR experiments demonstrate that the enhanced CO2 adsorption of Pt/La-TiO2 facilitates the formation of the active Pt–CO intermediate and subsequently boosts the evolution of CH4 and CO. The cycling tests reveal that Pt/La-TiO2 shows reinforced stability for the CO2 hydrogenation reaction because the La species can prevent Pt nanoparticles (NPs) from sintering. This work may provide some guidance on the development new rare-metal-modified hybrid catalysts for CO2 fixation.  相似文献   

4.
Silca-supported Co3O4 (6 wt% as Co) catalysts were prepared by pore volume impregnation of ethanol or aqueous cobalt nitrate solutions, and calcined in vacuo to 300 °C. The catalytic performances of these catalysts for oxidation and hydrogenation of CO were examined. All Co3O4/SiO2 catalysts were found to be very active in catalyzing oxidation of CO to CO2 as compared to a commercial 1 wt% Pt/Al2O3. The ethanol-prepared catalysts exhibited higher activity than those of the aqua-prepared catalysts. Pre-calcination of the ethanol-prepared catalysts in oxygen at 600 °C resulted in a dramatic decrease in the activity. Temperature programmed oxidation indicated the presence of carbon deposits on the surface of used catalysts. Infrared spectra showed the continuous generation of CO2 when these catalysts were exposed to CO. These indicate the primary role of CO disproportionation in catalytic oxidation of CO on Co3O4 at low temperature and explain the sharp decrease in activity in the initial period. After reduction at 400 °C, the ethanol-prepared catalysts were also found to be more active in catalyzing hydrogenation of CO, and produced less methane and olefin (C2-C4) fraction. Higher turnover frequencies were observed after high temperature reduction (600 °C) as well, at which ethoxyl groups were removed from silica surface. In both reactions, the enhanced activity for the ethanol-prepared catalysts can not be fully accounted for by the increase in the dispersion of Co3O4 or CO metal. This suggests that the surface structures of Co3O4 or CO were further modified by the carbonaceous species derived from ethanol.  相似文献   

5.
Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H2 at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.  相似文献   

6.
This research characterizes the stability of the Al2O3 surface oxide on Al (110) as a function of temperature and within an ultrahigh vacuum environment (p < 5 × 10?12 Torr). Auger electron spectroscopy and temperature desorption spectroscopy were used to correlate the change in oxygen and carbon surface concentration. The surface oxide was observed to remain stable up to 350–400 °C. Above this temperature, the oxide began to dissociate resulting in a CO desorption peak at 425 °C followed by extensive dissolution of the C and O into the Al bulk. A second and much smaller CO desorption peak was observed at 590 °C in concert with complete oxide breakdown and the virtual disappearance of surface carbon and oxygen. Extrapolation of the Auger electron spectral ratios of CKLL and OKLL peaks to the sum of the Al0LVV and Al3+LVV peak suggests that the surface concentration of each approaches zero at ~640 °C. The predominant mechanism for reduction of the surface oxide occurs by dissolution into the bulk instead of desorption. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

7.
Abstract

Novel alumina-supported cobalt phosphide catalysts (designated as CoP-3, CoP-10, CoP-20 and CoP-40) prepared from the precursors with Co loadings of 3, 10, 20 and 40?wt% by H2-temperature-programmed reaction were investigated as potential catalysts for preferential CO oxidation (PROX) in excess H2 at high temperatures. It was found that the catalytic activities of these Co2P/γ-Al2O3 catalysts were related to their Co loadings. The CoP-10 catalyst showed the best PROX performance in temperature range of 220–240?°C, which was attributed to its optimal microstructures (high surface area, small particle size and big amount of active site).  相似文献   

8.
Hydrotalcite-like compounds (HTC) are distinguished by their properties for CO2 capture, like high surface area, basic sites, thermal stability and good adsorption/desorption efficiency. Mg–Al e Zn–Al HTCs with Al3+ molar ratios x = 0.20, 0.28 and 0.33 were synthesized by coprecipitation, and subsequently calcined at 400 °C. For both HTCs, X-ray diffraction patterns have attested the formation of mixed oxides through calcination. The amount of basic sites, measured by temperature-programmed desorption of CO2, decreases as x increases. The CO2 adsorption was performed in a thermogravimetric balance using an adsorption temperature of 50 °C. Mg–Al and Zn–Al samples with x = 0.33 molar composition presented the highest CO2 adsorption, 0.91 and 0.21 mmol g?1, respectively. The Langmuir isotherm fitted well to the experimental data. It was also found that increasing the number of adsorption/desorption cycles the CO2 adsorption decreases, which is associated with the irreversible chemisorption.  相似文献   

9.
Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2adsorption-desorption, temperatureprogrammed reduction(TPR), XPS and TEM techniques. In comparison with the samples prepared with CuO as initial support, the samples with Cu(OH)2as initial support have higher reducibilities and smaller relative TPR peak areas, and also larger specific surface areas at calcination temperatures of 400℃–600℃. As a result, Cu(OH)2is better than CuO as initial support for preferential oxidation of CO in excess H2(CO-PROX). The best catalytic performance was achieved on the sample calcined at 600℃ and with an atomic ratio of Ce/Cu at 40%. XPS analyses indicate that more interface linkages Ce-O-Cu could be formed when it was calcined at 600℃. And the atomic ratio of Ce/Cu at 40%led to a proper reducibility for the sample as illustrated by the TPR measurements.  相似文献   

10.
With various contents, Mn was introduced into carbon nanotubes (CNTs) supported cobalt catalysts and the obtained Mn‐Co/CNTs catalysts were investigated for CO hydrogenation to light alkenes and characterized by N2 adsorption, X‐ray diffraction (XRD), X‐ray photoelectron spectra (XPS), H2 temperature programmed reduction (TPR), CO temperature programmed desorption (TPD) and transmission electron microscope (TEM). The results indicate that the addition of a small amount of Mn (0.3 wt%) to CNTs‐supported Co catalyst significantly increased the selectivity of C2–C4 olefins and decreased the selectivity of CH4. However, with further addition of Mn to the cobalt catalysts, the CH4 selectivity decreased obviously along with the increase of the C5+ selectivity. Compared with the unpromoted catalysts, the Mn‐promoted cobalt catalysts increased the C2?–C4?/C20–C40 molar ratio.  相似文献   

11.
CO adsorption on (0.5–15)%CoO/ZrО2 catalysts has been investigated by temperature-programmed desorption and IR spectroscopy. At 20°С, carbon monoxide forms carbonyl and monodentate carbonate complexes on Co m 2+ O n 2- clusters located on the surface of crystallites of tetragonal ZrO2. With an increasing CoO content of the clusters, the amount of these complexes increases and the temperature of carbonate decomposition, accompanied by CO2 desorption, decreases from 400 to 304°С. On the 5%CoO/ZrО2 sample, the carbonyls formed on the Со2+ and Со+ cations and Со0 atoms decompose at 20, 90, and 200–220°С, respectively, releasing CO. At 20°С, they are oxidized by oxygen to monodentate carbonates, which decompose at 180°С. Adsorbed oxygen decreases the temperature of their decomposition on oxidation sites by ~40°C, and the sample remains in an oxidized state ensuring the possibility of subsequent CO adsorption and oxidation. The rate of the oxidation of 5%CoO/ZrО2 containing adsorbed CO by oxygen is higher than the rate of the oxidation of the same sample reduced by carbon monoxide, because the latter reaction is an activated one. In view of the properties of the complexes, it can be concluded that the carbonates decomposing at 180°С are involved in CO oxidation by oxygen from the gas phase in the presence of hydrogen, a process occurring at 50–200°С. The rate-limiting step of this process the decomposition of the carbonates, which is characterized by an activation energy of 77–94 kJ/mol.  相似文献   

12.
An extensive study of Fischer-Tropsch synthesis on nanostructure supports with high surface area such as nanostructure γ-alumina, single wall carbon nanotubes (SWNTs), and the hybrid of SWNTs/nanostructure γ-alumina has been investigated. The nanostructure γ-alumina was promoted with lanthanum to obtain better performance of catalyst and 15 wt% cobalt loading was the basis of our investigation. Fischer-Tropsch synthesis was performed in a fixed bed reactor under different reaction conditions (220–240 °C, 15–25 bar, H2/CO ratio of 2, GHSV of 900–1400) in order to study the effects of temperature, pressure and gas hourly space velocity (GHSV) changes on hydrocarbon selectivity and catalyst activity. The catalysts were extensively characterized by different methods including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma (ICP), hydrogen (H2) chemisorption and temperature-programmed reduction (TPR). The results showed that the yield of hybrid supported catalyst (55.4%) is higher than that of nanostructure γ-alumina supported catalyst (55.0%) and lower than that of SWNTs supported cobalt catalyst (71.0%). The hybrid supported catalyst showed higher reduction degree and dispersion of cobalt particles. The temperature, pressure and GHSV effects on hybrid supported catalyst were studied and results showed that higher pressure favors the chain growth and temperature increase leads to the increases in methane selectivity and CO conversion. Higher hydrocarbon selectivity and CO conversion showed positive relationship with increasing GHSV while lower hydrocarbon selectivity diminishes.  相似文献   

13.
The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO2(001)-(1×4) surface are quite inert for the reaction of CH3CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH3CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH3CHO on the anatase TiO2(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.  相似文献   

14.
The CO adsorption species on Co3O4 and (0.5-15%)CoO/CeO2 catalysts have been investigated by temperature-programmed desorption and IR spectroscopy. At 20°C, the largest amount of CO is adsorbed on the 5%CoO/CeO2 sample to form, on Com2+On2+ clusters, hydrogen-containing, bidentate, and monodentate carbonate complexes, whose decomposition is accompanied by CO2 desorption at 300 and 450°C (1.1 × 1020 g–1). The formation of the carbonates is accompanied by the formation of Co+ cations and Co0, on which carbonyls form. The latter decompose at 20, 90, and 170°C to release CO (2.7 × 1019 g–1). Part of the carbonyls oxidizes to CO2 upon oxygen adsorption, and the CO2 undergoes desorption at 20°C. Adsorbed oxygen decreases the decomposition temperature of the H-containing and bidentate carbonates from 300 to 100-170°C and maintains the sample in the oxidized state, which is active in subsequent CO adsorption and oxidation. CO oxidation by oxygen of the catalyst diminishes the activity of the sample in these processes and increases the decomposition temperature of the carbonate complexes. Taking into account the properties of the adsorption complexes, we concluded that the H-containing and bidentate carbonates are involved in CO oxidation by oxygen of the catalyst at ~170°C under isothermal conditions. The rate limiting step is the decomposition of the carbonates, a process whose activation energy is 65-74 kJ/mol.  相似文献   

15.
Novel cobalt catalysts were prepared by sol–gel method, and enhanced by plasma treatment, for methane catalytic combustion. These samples were characterized using X-ray diffraction, X-ray photoelactron spectroscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, thermal gravimetrical analysis, N2 Adsorption–desorption, temperature-programmed reduction and hydrogen–oxygen titration technologies. The XPS characterizations suggested that plasma treatment was favorable for the enrichment of surface cobalt, with a value of surface cobalt from 2.2% to 8.5% in mole. The specific surface area of the glow plasma assised sample (Co-Plas-Solgel-2) increased to 320 m2/g comparing with 305 m2/g of the conventional sample (Co-Solgel-1). The ignition temperature (T10%) of Co-Plas-Solgel-2 catalyst was about 50 °C lower than that of Co-Solgel-1, and its CH4 conversion was two times higher than that of Co-Solgel-1 during the whole range of catalytic combustion activity test (340–520 °C). With a better dispersion and more active sites, the plasma assisted sample exhibited significant enhancement in catalytic performances.  相似文献   

16.
PtSn/θ-Al2O3 catalysts with different amounts of K (0.14, 0.22, 0.49, 0.72, and 0.96 wt%) are prepared to investigate the K effects on the PtSn catalyst in propane dehydrogenation (PDH). KPtSn catalyst with 0.xx wt% K, 0.5 wt% Pt and 0.75 wt% Sn is designated as xx-KPtSn. PDH was performed at 873 K and a gas hourly space velocity (GHSV) of 53,000 mL/gcat h. The temperature-programmed desorption (NH3-TPD), temperature-programmed reduction (TPR) and CO chemisorption of the KPtSn catalysts with K added revealed the potassium addition blocked the acid sites, promoted the reduction of Sn oxide and decreased the Pt dispersion. The formations of cracking products and higher hydrocarbons on acid sites were suppressed by the K effect of blocking the acid sites. In contrast, K addition at more than 0.72 wt% rather increased cracking products and the amount of coke, resulting in the severe deactivation of catalysts. The high cracking products on the KPtSn catalysts with the high amount of K should not be related to the acid sites, because the acid sites were monotonously decreased with an increase in the amount of K. Instead, the potassium affected the characteristics of PtSn. The interaction between Pt and Sn could be weakened by enriching the reduced Sn, because the K component promoted the reduction of Sn oxide in the TPR experiments. Therefore, the 14-KPtSn catalyst with the low amount of K exhibits the highest stability and selectivity among the prepared KPtSn catalysts due to the compromise of the advantageous (blocking the acid sites) and bad (weakening the interaction between Pt and Sn) effects of the K addition in PDH.  相似文献   

17.
Effects of the anion type on the structure, thermal stability, and catalytic performance of La-doped Cu-Mn catalysts prepared by co-precipitation were characterized by X-ray diffraction, Brunauer-Emmett-Teller, temperature-programmed reduction, temperature-programmed reduction of oxidized surfaces, and temperature-programmed desorption. The Cu-Mn catalyst was tested for the water-gas shift (WGS) reaction. The main crystalline phase of samples prepared with sulfate, acetate, chloride, and nitrate as the starting materials was a Cu1.5Mn1.5O4 spinel structure, following the WGS reaction, the main crystalline phases were transformed into Cu and MnO. The sample prepared with acetate as the starting material showed the most obvious MnCO3 characteristic diffraction peaks, with better synergistic effects of Cu and MnO, increased adsorption of CO2 and improved dispersion of Cu on the catalyst surface; also, the best thermal stability and the highest low temperature catalytic activity were observed. The sample prepared with nitrate as the starting material maintained high thermal stability and catalytic performance in the range of 400°C to 450°C, but CO conversion decreased below 350°C. Catalytic performance of the sample prepared with sulfate and chloride as the starting materials was poor, ranging from 200°C to 450°C.  相似文献   

18.
The influence of TiO2 nanopowder doping with 4 wt% indium and 2 wt% each of indium and chromium on phase transformation was studied. Samples were heated from ambient temperature to 950 °C in sealed quartz capillaries, and in-situ synchrotron radiation diffraction measurements were obtained. Capillary sealing yielded an increase in capillary gas pressure to 0.42 MPa at 950 °C in proportion to absolute temperature by Gay-Lussac’s Law. The initial synthesized samples were amorphous, and crystalline anatase appeared at 200 °C. Crystalline rutile appeared at 850 °C for the nanomaterials that were doped with In and In and Cr. A change in sealed-capillary oxygen partial pressure yielded a decrease and an increase in crystallization temperature, respectively, for the amorphous-to-anatase and anatase-to-rutile transformations. Crystalline titania (anatase and rutile) formed from the amorphous titania by 800 °C and 900 °C, for materials doped with In and In-Cr, respectively. The anatase concentration that was dominant in the In-doped materials up to 950 °C and the higher rutile concentration for the In-Cr doped materials from 900 to 950 °C results from the defect structure that was induced by doping. Cr-ions in the Ti sub-lattice retarded the transformation of anatase to rutile when compared with the retarding effect of mixed In/Cr ions. The transformation results because of the relatively smaller radius of Cr-ions when compared with the In-ions. The differences in phase-transformation kinetics for In, In-Cr and for undoped nanopowders in the literature agree with the calculated transformation activation energies.  相似文献   

19.
《中国化学快报》2020,31(8):2029-2032
In this paper, the Pt/SnO2 nanostructures were prepared via a facile one-step microwave assisted hydrothermal route. The structure of the introduced Pt/SnO2 and its gas-sensing properties toward CO were investigated. The results from the TEM test reveal that Pt grows on the SnO2 nanostructure, which was not found for bulk in this situ method, constructing Pt/SnO2. The results indicated that the sensor using 3.0 wt% Pt/SnO2 to 100 ppm carbon monoxide performed a superior sensing properties compared to 1.5 wt% and 4.5 wt% Pt/SnO2 at 225 °C. The response time of 3.0 wt% sensor is 16 s to 100 ppm CO at 225 °C. Such enhanced gas sensing performances could be attributed to the chemical and electrical factors. In view of chemical factors, the presence of Pt facilitates the surface reaction, which will improve the gas sensing properties. With respect to the electrical factors, the Pt/SnO2 plays roles in increasing the sensor’s response due to its characteristic configuration. In addition, the one-step in situ microwave assisted process provides a promising and versatile choice for the preparation of gas sensing materials.  相似文献   

20.
采用CO与金属Co在473K反应400h以上合成了Co2C样品,采用X射线衍射、透射电镜和CO程序升温还原对样品进行了表征,并采用CO程序升温脱附和CO程序升温表面反应研究了Co2C对CO的吸附及其加氢活化行为. 结果表明,Co2C微观结构由体相和表面钝化层两部分组成. 表面钝化层可被CO于477K左右去除. CO在Co2C上有2个脱附峰,其中低温脱附峰可能源于Co2C上吸附的CO,而高温脱附峰可能对应于残留于Co2C晶格内的CO. Co2C上吸附的CO可与H2反应生成醇.  相似文献   

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