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1.
Porous carbon-encapsulated Ni and Ni–Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor. During the catalyst preparation, Sn doping reduces the size of carbon spheres, and the formation of Ni–Sn intermetallic compounds restrain the graphitization, contributing to larger pore volume and pore diameter. Consequently, a more facile mass transfer occurs in carbon-encapsulated Ni–Sn intermetallic compound catalysts than in carbon-encapsulated Ni catalysts. During the in-situ hydrothermal deoxygenation, the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n-pentadecane or is hydrogenated to hexadecanol. At high reaction temperature, hexadecanol undergoes dehydrogenation–decarbonylation, generating n-pentadecane. Also, the C–C bond hydrolysis and methanation are suppressed on Ni–Sn intermetallic compounds, favorable for increasing the carbon yield and reducing the H 2 consumption. The n-pentadecane and n-hexadecane yields reached 88.1% and 92.8% on carbon-encapsulated Ni 3Sn 2 intermetallic compound at 330 °C. After washing and H 2 reduction, the carbon-encapsulated Ni 3Sn 2 intermetallic compound remains stable during three recycling cycles. This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions. 相似文献
2.
The NO x storage-reduction catalysis under oxidizing conditions in the presence of SO 2 has been investigated on Pt/Ba/Fe/Al 2O 3, Pt/Ba/Co/Al 2O 3, Pt/Ba/Ni/Al 2O 3, and Pt/Ba/Cu/Al 2O 3 catalysts compared with Pt/Ba/Al 2O 3, Pt/Fe/Al 2O 3, Pt/Co/Al 2O 3, Pt/Ni/Al 2O 3, Pt/Cu/Al 2O 3 and Pt/Al 2O 3 catalysts. The NO x purification activity of Pt/Ba/Fe/Al 2O 3 catalyst was the highest of all the catalysts investigated in this paper after an aging treatment. That of the aged Pt/Ba/Co/Al 2O 3 and Pt/Ba/Ni/Al 2O 3 catalysts was essentially the same as that of the aged Pt/Ba/Al 2O 3 catalyst, while that of the aged Pt/Ba/Cu/Al 2O 3 and Pt/Cu/Al 2O 3 catalysts was substantially lower than the others. The Fe-compound on the aged Pt/Ba/Fe/Al2O3 catalyst has played a role in decreasing the sulfur content on the catalyst after exposure to simulated reducing gas compared with the Pt/Ba/Al2O3 catalyst without the Fe-compound. XRD and EDX show that the Fe-compound inhibits the growth in the size of BaSO4 particles formed on the Pt/Ba/Fe/Al2O3 catalyst under oxidizing conditions in the presence of SO2 and promotes the decomposition of BaSO4 and desorption of the sulfur compound under reducing conditions. 相似文献
3.
The hydrodehalogenation of halon 1211 over Ni, Pd and Pt supported on γ-alumina was studied. The effect of reaction temperature and hydrogen/halon 1211 input ratio was examined. Steady state catalytic activities of Pd and Pt are very similar, and much higher than that of Ni. Hydrodehalogenation over Pd favours the formation of CH 2F 2, while Pt and Ni produce primarily CH 4 and CH 3F, respectively. Product profiles suggest that the hydrodehalogenation of halon 1211 over Pd and Pt follows a reaction mechanism which is similar to hydrodehalogenation of CFC-12. Over Ni catalysts, the primary hydrodehalogenation reactions are those which first remove one halogen (Cl or Br) and then remove two halogens (one F and either Br or Cl). The higher mobility of hydrogen atom on the surface of Pt is consistent with the observation that only trace amounts of C 2+ hydrocarbons were detected when Pt was used compared with Pd and Ni. Increasing selectivity to CH 2F 2 with time on stream over Pd and Pt is mainly ascribed to the transformation of support alumina to partially fluorinated alumina. 相似文献
4.
In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH 3O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp 3 and hydroxyl-like configurations, respectively. Hence, the C atom of CH 2OH preferentially attaches to the top sites, CHOH and CH 2O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH 3OH and CH 2OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH 3OH → CH 2OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH 3OH decomposition pathway and reduces the noble metal utilization. 相似文献
5.
During the reactions related to oxidative steam reforming and combustion of methane over -alumina-supported Ni catalysts, the temperature profiles of the catalyst bed were studied using an infrared (IR) thermograph. IR thermographical images revealed an interesting result: that the temperature at the catalyst bed inlet is much higher under CH 4/H 2O/O 2/Ar = 20/10/20/50 than under CH 4/H 2O/O 2/Ar = 10/0/20/70; the former temperature is comparable to that over noble metal catalysts such as Pt and Pd. Based on the temperature-programmed reduction and oxidation measurements over fresh and used catalysts, the metallic Ni is recognized at the catalyst bed inlet under CH 4/H 2O/O 2/Ar = 20/10/20/50, although it is mainly oxidized to NiAl 2O 4 under CH 4/H 2O/O 2/Ar = 10/0/20/70. This result indicates that the addition of reforming gas (CH 4/H 2O = 10/10) to the combustion gas (CH 4/O 2 = 10/20) can stabilize Ni species in the metallic state even under the presence of oxygen in the gas phase. This would account for its extremely high combustion activity. 相似文献
6.
The effects of Zr doping on the existence of Cu and the catalytic performance of Ce 0.7−xZr xCu 0.3O 2 for CO oxidation were investigated. The characterization results showed that all samples have a cubic structure, and a small amount of Zr doping facilitates Cu 2+ ions entering the CeO 2 lattice, but excessive Zr doping leads to the formation of surface CuO crystals again. Thus, the number of oxygen vacancies caused by the Cu 2+ entering the lattice (e.g., Cu 2+–□–Ce 4+; □: oxygen vacancy), and the amount of reducible copper species caused by CuO crystals, varies with the Zr doping. Catalytic CO oxidation tests indicated that the oxygen vacancy and the reducible copper species were the adsorption and activation sites of O 2 and CO, respectively, and the cooperative effects between them accounted for the high CO oxidation activity. Thus, the samples x = 0.1 and 0.3, which possessed the most oxygen vacancy or reducible copper species, showed the best activity for CO oxidation, with full CO conversion obtained at 110 °C. The catalyst is also stable and has good resistance to water during the reaction. 相似文献
7.
Ethanol steam reforming was studied over Ni/Al 2O 3 catalysts. The effect of support (- and γ-Al 2O 3), metal loading and a comparison between conventional H 2 reduction with an activation method employing a CH 4/O 2 mixture was investigated. The properties of catalysts were studied by N 2 physisorption, X-ray diffraction (XRD) and temperature programmed reduction (TPR). After activity tests, the catalysts were analyzed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG/DTA). Ni supported on γ-Al 2O 3 was more active for H 2 production than the catalyst supported on -Al 2O 3. Metal loading did not affect the catalytic performance. The alternative activation method with CH 4/O 2 mixture affected differently the activity and stability of the Ni/γ-Al 2O 3 and the Ni/-Al 2O 3 catalyst. This activation method increased significantly the stability of Ni/-Al 2O 3 compared to H 2 reduction. SEM and TG/DTA analysis indicate the formation of filamentous carbon during the CH 4/O 2 activation step, which is associated with the increasing catalyst activity and stability. The effect of temperature on the type of carbon formed was investigated; indicating that filamentous coke increased activity while encapsulating coke promoted deactivation. A discussion about carbon formation and the influence on the activity is presented. 相似文献
8.
The reactions of ethanol over Rh/CeO 2 have been investigated using the techniques of temperature programmed desorption (TPD) and FT-IR spectroscopy, in addition to steady state catalytic tests. A comparison with previous studies of ethanol adsorption over Pd/CeO 2 [J. Catal. 186 (1999) 279] and Pt/CeO 2 [J. Catal. 191 (2000) 30] catalysts is presented. The apparent activation energy for the reaction was 49, 40, and 43 kJ mol −1 for Rh/CeO 2, Pd/CeO 2 and Pt/CeO 2, respectively, while the turnover number (TON) at 400 K was 5.9, 8.6 and 2.6, respectively. Surface compositions of catalysts were characterised by XPS. A decrease of the atomic O(1s)/Ce(3d) ratio of the CeO 2 support indicates its partial reduction upon addition of the noble metal. The extent of reduction per metal atom was in the following order: Pt>Pd>Rh. FT-IR and TPD studies have shown that dehydrogenation of ethanol to acetaldehyde occurred over Pd/CeO 2, Pt/CeO 2 and Rh/CeO 2. Moreover, Rh/CeO 2 readily dissociated the C–C bond of ethanol at room temperature to form adsorbed CO (IR bands at 1904–2091 cm −1). This was corroborated by the low desorption temperature of CH 4 over Rh/CeO 2 (450 K) when compared to that of Pd/CeO 2 (550 K) or Pt/CeO 2 (585 K). 相似文献
9.
制备不同负载量的Pd基和Pt基催化剂,建立催化剂活性评价装置,考察贵金属Pd和Pt负载量对甲烷转化率的影响,结果表明,甲烷转化率最高的Pd和Pt负载质量分数分别为1.25%和2%,相同负载质量分数0.1%时,Pd基催化剂的甲烷转化率优于Pt基催化剂。催化剂的BET比表面积大小不能反映催化剂的催化活性,二者之间无线性关系。 相似文献
10.
Effect of fluorite-like or perovskite-like complex oxide promoters, Pd and Cu on the performance of Ni/8YSZ and Ni/ScCeSZ anode materials in CH 4 steam reforming (SR) or selective oxidation (SO) by O 2 into syngas was studied. The spatial distribution of dopants in composites before and after contact with the reaction feed, features of components mutual interaction and forms of deposited coke were controlled by TEM combined with EDX analysis. The lattice oxygen mobility and reactivity were estimated by CH 4 and H 2 temperature-programmed reduction (TPR), and the amount of deposited carbon after operation in the feed with stoichiometric H 2O/CH 4 ratio was estimated by the temperature-programmed oxidation. Promoters decrease the amount of deposited coke, while doping by Pd or Cu ensures also a good and stable performance at moderate (550 °C) temperatures required for the intermediate-temperature solid oxide fuel cells (IT SOFC) operation. 相似文献
11.
通过浸渍法制备了Al_2O_3负载的Pd和Pt催化剂,考察催化剂的甲烷、乙烷和丙烷催化燃烧活性,以及助剂Ba对催化性能的影响。对于Pd/Al_2O_3催化剂,加入Ba使活性物种PdO颗粒变大和还原温度升高,形成更稳定的PdO活性物种,是Pd-Ba/Al_2O_3催化剂活性提升的主要原因。对于Pt/Al_2O_3催化剂,加入Ba助剂使活性物种Pt0含量降低,PtO_x与Al_2O_3载体相互作用增强,使PtO_x物种更难被还原为Pt~0,导致Pt-Ba/Al_2O_3催化剂活性降低。Pd和Pt催化剂催化烷烃氧化反应活性规律一致:丙烷乙烷甲烷。Pd/Al_2O_3催化剂有利于C—H键活化,Pt/Al_2O_3催化剂有利于C—C键活化。Pt/Al_2O_3催化剂对C1-C3烷烃氧化活性的差别明显大于Pd/Al_2O_3催化剂。Pt/Al_2O_3催化剂对碳比例高的烷烃活性更高。 相似文献
12.
Reaction mechanism of the reduction of nitrogen monoxide by methane in an oxygen excess atmosphere (NO–CH 4–O 2 reaction) catalyzed by Pd/H-ZSM-5 has been studied at 623–703 K in the absence of water vapor, in comparison with the mechanism for Co-ZSM-5. Kinetic isotope effect for the N 2 formation in NO–CH 4–O 2 vs. NO–CD 4–O 2 reactions was 1.65 at 673 K and decreased with a decrease in the reaction temperature. In addition, H–D isotopic exchange took place significantly in NO–(CH 4+CD 4)–O 2 reaction. These results are in marked contrast with the case of Co-ZSM-5, for which the C–H dissociation of methane is the only rate-determining step, and show that the C–H dissociation is slow but not the only rate-determining step in the case of Pd/H-ZSM-5. A reaction scheme was proposed, in which the relative rates of the three steps ((i)–(iii) below) vary depending on the reaction conditions. Further, in contrast to Co-ZSM-5, NO x–CH 4–O 2 reaction was much slower than CH 4–O 2 reaction for Pd/H-ZSM-5; the presence of NO x retards the reaction of CH 4 over the latter catalyst, while it accelerates the reaction over the former. It is suggested that CH 4 is activated directly by the Pd atoms in the case of Pd/H-ZSM-5, but by NO 2 strongly adsorbed on Co ion for Co-ZSM-5. The reaction order of the NO–CH 4–O 2 reaction with respect to NO pressure was consistent with this mechanism; 1.05 for Pd/H-ZSM-5 and 0.11 for Co-ZSM-5. 相似文献
13.
Zirconia supported on alumina was prepared and characterized by BET surface area, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), temperature programmed desorption (TPD), and pulse reaction. 0.2% Pd/ZrO 2/Al 2O 3 catalyst were prepared by incipient wetness impregnation of supports with aqueous solution of Pd(NO 3) 2. The effects of support properties on catalytic activity for methane combustion and CO oxidation were investigated. The results show that ZrO 2 is highly dispersed on the surface of Al 2O 3 up to 10 wt.% ZrO 2, beyond this value tetragonal ZrO 2 is formed. The presence of a small amount of ZrO 2 can increase the surface area, pore volume and acidity of support. CO–TPD results show that the increase of CO adsorption capacity and the activation of CO bond after the presence of ZrO 2 lead to the increase of catalytic activity of Pd catalyst for CO oxidation. CO pulse reaction results indicate that the lattice oxygen of support can be activated at lower temperature following the presence of ZrO 2, but it does not accelerate the activity of 0.2% Pd/ZrO 2/Al 2O 3 for methane combustion. 0.2% Pd/ZrO 2/Al 2O 3 dried at 120 °C shows highest activity for CH 4 combustion, and the activity can be further enhanced following the repeat run. The increase of treatment temperature and pre-reduction can decrease the activity of catalyst for CH 4 combustion. 相似文献
14.
Regeneration of S-poisoned Pd/Al 2O 3 catalysts for the abatement of methane emissions from natural gas vehicles was addressed in this work. Investigations were devoted to determine the temperature threshold allowing for catalyst reactivation under different CH4 containing atmospheres. Under lean combustion conditions in the presence of excess O2, partial regeneration took place only above 750 °C after decomposition of stable sulphate species adsorbed on the support. Short CH4-reducing, O2-free pulses led to partial catalyst reactivation already at 550 °C and to practically complete regeneration at 600 °C. Also in this case reactivation was associated with SO2 release due to the decomposition of stable support sulphates likely promoted by CH4 activation onto the reduced metallic Pd surface. Rich combustion pulses with CH4/O2 = 2 were equally effective to CH4-reducing pulses in catalyst regeneration. These results suggest that a regeneration strategy based on periodical natural gas pulses fed to the catalyst by a by-pass line might be efficient in limiting the effects of S-poisoning of palladium catalysts for the abatement of CH4 emissions from natural gas engine. 相似文献
15.
The activity of mixed steam and CO 2 reforming of CH 4 to produce synthesis gas was investigated and compared with those of steam reforming alone and CO 2 reforming alone at 600–900°C under atmosphere pressure on MgO-supported noble metals. Mixed reforming shows a far lower CH 4 conversion than the value for thermodynamic equilibrium. The activity decreases following the order Ru,Rh> Ir> Pt,Pd. Little deactivation was observed for Ru, Rh and Ir catalysts. An isotope labelled 13CO 2 experiment was carried out in situ for mixed reforming on Rh/MgO and the results suggest that CO 2 dissociates as CO-M and O-M. The results of the temperature program reaction (TPR) of mixed reforming shows that CH 4 adsorbs and dissociates before reaction starts and that CO 2 reforming and steam reforming start simultaneously. A possible reaction mechanism is discussed. 相似文献
16.
采用浸渍-还原法制备了铁、钴、镍、铜和锌催化剂,考察了其催化氨硼烷水解产氢性能,并优化了钴催化剂的制备条件和反应条件。结果发现,铁催化剂中铁以Fe 2B合金相存在,钴催化剂中钴以金属钴存在,镍催化剂中镍以金属镍和Ni(OH) 2·2H 2O存在,铜催化剂中铜以金属铜和氧化亚铜存在,锌催化剂中锌以Zn 4SO 4(OH) 6·4H 2O存在。铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢活性由大到小顺序为钴催化剂、镍催化剂、铜催化剂、铁催化剂、锌催化剂。显然,具有金属钴相的钴催化剂、金属镍相的镍催化剂和金属铜相的铜催化剂催化氨硼烷产氢活性高于具有Fe 2B合金相的铁催化剂。锌催化剂在制备条件下不能被还原为金属相,它几乎没有催化氨硼烷产氢活性。氯化钴与还原剂硼氢化钠的物质的量比为1∶1.3、还原温度为303 K时制备的钴催化剂催化BH 3NH 3水解产氢性能最佳。反应动力学计算表明钴催化剂催化BH 3NH 3水解产氢反应对氨硼烷浓度的反应级数为零级,对钴催化剂浓度的反应级数为一级,活化能为58 kJ/mol。 相似文献
17.
Calcined and reduced catalysts Pd/LaBO 3 (B = Co, Fe, Mn, Ni) were used for the total oxidation of toluene. Easiness of toluene destruction was found to follow the sequence based on the T50 values (temperature at which 50% of toluene is converted): Pd/LaFeO 3 > Pd/LaMnO 3+δ > Pd/LaCoO 3 > Pd/LaNiO 3. In order to investigate the activation process (calcination and reduction) in detail, the reducibility of the samples was evaluated by H 2-TPR on the calcined catalysts. Additionally, characterization of the Pd/LaBO 3 (B = Co, Fe) surface was carried out by X-ray photoelectron spectroscopy (XPS) at each stage of the global process, namely after calcination, reduction and under catalytic reaction at either 150 or 200 °C for Pd/LaFeO 3 and either 200 or 250 °C for LaCoO 3. The different results showed that palladium oxidized entities were totally reduced after pre-reduction at 200 °C for 2 h (2 L/h, 1 °C/min). As LaFeO 3 was unaffected by such a treatment, for the other perovskites, the cations B are partially reduced as B 3+ (B = Mn) or B 2+ even to B 0 (B = Co, Ni). In the reactive stream (0.1% toluene in air), Pd 0 reoxidized partially, more rapidly over Co than Fe based catalysts, to give a Pd 2+/Pd 4+ and Pd 0/Pd 2+/Pd 4+ surface redox states, respectively. Noticeably, reduced cobalt species are progressively oxidized on stream into Co 3+ in a distorted environment. By contrast, only the lines characteristic of the initial perovskite lattice were detected by XRD studies on the used catalysts. The higher activity performance of Pd/LaFeO 3 for the total oxidation of toluene was attributed here to a low temperature of calcination and to a remarkable high stability of the perovskite lattice whatever the nature of the stream which allowed to keep a same palladium dispersion at the different stages of the process and to resist to the oxidizing experimental conditions. On the contrary, phase transformations for the other perovskite lattices along the process were believed to increase the palladium particle size responsible of a lower activity. 相似文献
18.
In the steam gasification of biomass, the additive effect of noble metals such as Pt, Pd, Rh and Ru to the Ni/CeO 2/Al 2O 3 catalyst was investigated. Among these noble metals, the addition of Pt was most effective even when the loading amount of added Pt was as small as 0.01 wt.%. In addition, the catalyst characterization suggests the formation of the Pt–Ni alloy over the Pt/Ni/CeO 2/Al 2O 3. 相似文献
19.
In this work, the detailed oxygen reduction reaction (ORR) catalytic performance of M-N 4−xO x (M= Fe, Co, and Ni; x = 1–4) has been explored via the detailed density functional theory method. The results suggest that the formation energy of M-N 4−xO x shows a good linear relationship with the number of doped O atoms. The adsorption manner of O 2 on M-N 4−xO x changed from end-on ( x = 1 and 2) to side-on ( x = 3 and 4), and the adsorption strength gradually increased. Based on the results for binding strength of ORR intermediates and the Gibbs free energy of ORR steps on the studied catalysts, we screened out two highly active ORR catalysts, namely Co-N 3O 1 and Ni-N 2O 2, which possess very small overpotentials of 0.27 and 0.32 V, respectively. Such activities are higher than the precious Pt catalyst. Electronic structure analysis reveals one of the reasons for the higher activity of Co-N 3O 1 and Ni-N 2O 2 is that they have small energy gaps and moderate highest occupied molecular orbital energy levels. Furthermore, the results of the density of states reveal that the O doping can improve the electronic structure of the original catalyst to tune the adsorption of the ORR intermediates. 相似文献
20.
In this contribution, a commercial spherical SiO 2 was modified with different amounts of La 2O 3, and used as the support of Ni catalysts for autothermal reforming of methane in a fluidized-bed reactor. Nitrogen adsorption, XRD and H 2-TPR analysis indicated that La 2O 3-modified SiO 2 had higher surface area, strengthened interaction between Ni and support, and improved dispersion of Ni. CO 2-TPD found that La 2O 3 increased the alkalescence of SiO 2 and improved the activation of CO 2. Coking reaction (via both temperature-programmed surface reaction of CH 4 (CH 4-TPSR) and pulse decomposition of CH 4) disclosed that La 2O 3 reduced the dehydrogenation ability of Ni. CO 2-TPO, O 2-TPO (followed after CH 4-TPSR) confirmed that only part amount of carbon species derived from methane decomposition could be removed by CO 2, and O 2 in feed played a crucial role for the gasification of the inactive surface carbons. Ni/ xLa 2O 3-SiO 2 ( x = 10, 15, 30) possessed high activity and excellent stability for autothermal reforming of methane in a fluidized-bed reactor. 相似文献
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