First-principles study towards the reactivity of the Pd(111) surface with low Zn deposition

Methanol steam reforming (MSR) is an important means to produce hydrogen. While metal Pd shows no selectivity to MSR, PdZn alloy exhibits both high selectivity and activity towards this process. Recently a high temperature desorption peak of formaldehyde is observed when methanol is dosed onto Pd(111) surfaces on which 0.03-0.06 monolayer Zn is deposited. Strikingly such surface which is predominated by Pd atoms was suspected to be active for MSR. To determine the structure on which the high desorption peak is observed and its performance to MSR, we studied adsorption and dehydrogenation of formaldehyde on various models. It is demonstrated that the high desorption peak of CH(2)O may originate from the supported surface clusters. The calculated energy barriers of CH(2)O dehydrogenation show that while formaldehyde can decompose easily into formyl on the supported PdZn and Pd(2) clusters, this process is kinetically difficult on the surface Zn(3) clusters. It is further revealed that formation of dioxymethylene, the proposed precursor for CO(2) production, from formaldehyde and oxygen is feasible on the surface Zn cluster. Based on these calculations we predict that compared with 1:1 PdZn alloy, the activity of the Zn clusters to MSR is lower, though its selectivity may be higher.     

Zn modification of the reactivity of Pd(111) toward methanol and formaldehyde

The adsorption and reaction of methanol and formaldehyde on two-dimensional PdZn alloys on a Pd(111) surface were studied as a function of the Zn content in the alloy in order to understand the role of Zn in Pd/ZnO catalysts for the steam reforming of methanol (SRM). Temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) data show that Zn atoms incorporated into the Pd(111) surface dramatically decrease the dehydrogenation activity and alter the preferred bonding sites for adsorbed CO, CH3O, and CH2O intermediates. The experimental results obtained in this study are consistent with previous theoretical studies of this system and provide new insight into how Zn alters the reactivity of Pd.     

CH3O decomposition on PdZn(111), Pd(111), and Cu(111). A theoretical study

Methanol steam re-forming, catalyzed by Pd/ZnO, is a potential hydrogen source for fuel cells, in particular in pollution-free vehicles. To contribute to the understanding of pertinent reaction mechanisms, density functional slab model studies on two competing decomposition pathways of adsorbed methoxide (CH(3)O) have been carried out, namely, dehydrogenation to formaldehyde and C-O bond breaking to methyl. For the (111) surfaces of Pd, Cu, and 1:1 Pd-Zn alloy, adsorption complexes of various reactants, intermediates, transition states, and products relevant for the decomposition processes were computationally characterized. On the surface of Pd-Zn alloy, H and all studied C-bound species were found to prefer sites with a majority of Pd atoms, whereas O-bound congeners tend to be located on sites with a majority of Zn atoms. Compared to Pd(111), the adsorption energy of O-bound species was calculated to be larger on PdZn(111), whereas C-bound moieties were less strongly adsorbed. C-H scission of CH(3)O on various substrates under study was demonstrated to proceed easier than C-O bond breaking. The energy barrier for the dehydrogenation of CH(3)O on PdZn(111) (113 kJ mol(-)(1)) and Cu(111) (112 kJ mol(-)(1)) is about 4 times as high as that on Pd(111), due to the fact that CH(3)O interacts more weakly with Pd than with PdZn and Cu surfaces. Calculated results showed that the decomposition of methoxide to formaldehyde is thermodynamically favored on Pd(111), but it is an endothermic process on PdZn(111) and Cu(111) surfaces.     

Catalytic Conversion of Methanol by Oxidative Dehydrogenation

This study investigates the effects of addition of oxygen on the oxidative dehydrogenation (ODH) of methanol when a fluorotetrasilicic mica ion-exchanged with palladium (Pd2 -TSM) was used as the catalyst. The reaction proceeded at a very low temperature in the presence of oxygen, and HCOOCH3 was obtained at high selectivity. By calculating the equilibrium conversion, it has been shown that substantial ODH took place for HCOOCH3 production. Consequently, this reaction would make dehydrogenation the dominant reaction at equilibrium. Not all the H dissociated from CH3OH was converted to H2O by oxidation. It has been shown that the H2O was not produced from oxidative dehydrogenation by the direct reaction of CH3OH and O2 when an attempt was made to carry out oxidative dehydrogenation using an isotope oxygen trace method in the gas phase. Therefore, when CH3OH was converted to CO2 and dehydrogenated to HCOOCH3, the C—O bonds were not dissociated.     

Unraveling the surface reactions during liquid-phase oxidation of benzyl alcohol on Pd/Al2O3: an in situ ATR-IR study

The palladium-catalyzed liquid-phase reaction of benzyl alcohol to benzaldehyde was investigated in the presence and absence of oxygen by attenuated total reflection infrared (ATR-IR) spectroscopy. The 5 wt % Pd/Al2O3 catalyst was fixed in a flow-through ATR-IR cell serving as a continuous-flow reactor. The reaction conditions (cyclohexane solvent, 323 K, 1 bar) were set in the range commonly applied in the heterogeneous catalytic aerobic oxidation of alcohols. The in situ ATR-IR study of the solid-liquid interface revealed a complex reaction network, including dehydrogenation of benzyl alcohol to benzaldehyde, decarbonylation of benzaldehyde, oxidation of hydrogen and CO on Pd, and formation of benzoic acid catalyzed by both Pd and Al2O3. Continuous formation of CO and its oxidative removal by air resulted in significant steady-state CO coverage of Pd during oxidation of benzyl alcohol. Unexpectedly, benzoic acid formed already in the early stage of the reaction and adsorbed strongly (irreversibly) on the basic sites of Al2O3 and thus remained undetectable in the effluent. This observation questions the reliability of product distributions conventionally determined from the liquid phase. The occurrence of the hydrogenolysis of the C-O bond of benzyl alcohol and formation of toluene indicates that Pd was present in a reduced state (Pd0) even in the presence of oxygen, in agreement with the dehydrogenation mechanism of alcohol oxidation.     

Comparative theoretical study of formaldehyde decomposition on PdZn, Cu, and Pd surfaces

Methanol steam reforming, catalyzed by Pd/ZnO (PdZn alloy), is a potential source of hydrogen for on-board fuel cells. CO has been reported to be a minor side product of methanol decomposition that occurs in parallel to methanol steam reforming on PdZn catalysts. However, fuel cells currently used in vehicles are very sensitive to CO poisoning. To contribute to the understanding of pertinent reaction mechanisms, we employed density functional slab model calculations to study the decomposition of formaldehyde, a key intermediate in methanol decomposition and steam reforming reactions, on planar surfaces of Pd, Cu, and PdZn as well as on a stepped surface of PdZn. The calculated activation energies indicate that dehydrogenation of formaldehyde is favorable on Pd(111), but unfavorable on Cu(111) and PdZn(111). On the stepped PdZn(221) surface, the dehydrogenation process was calculated to be more competitive to formaldehyde desorption than on PdZn(111). Thus, we ascribe the experimentally observed small amount of CO, formed during steam reforming of methanol on the Pd/ZnO catalyst, to occur at metallic Pd species of the catalyst or at defect sites of PdZn alloy.     

Discrimination of active palladium sites in catalytic liquid-phase oxidation of benzyl alcohol

Knowledge of the structure of active sites is a prerequisite for the rational design of solid catalysts. Using site-selective blocking by CO and isotope labeling combined with in situ attenuated total reflection infrared (ATR-IR) spectroscopy, we were able to discriminate the different sites involved in the liquid-phase oxidation of benzyl alcohol on Pd/Al(2)O(3). The main reaction, that is, the oxidative dehydrogenation of the alcohol to the corresponding aldehyde, showed only little dependence on structure and occurred on all exposed Pd faces, whereas the undesired product decarbonylation occurred preferentially on hollow sites on (111) Pd faces. This explains why specific blocking of the latter sites, as realized in the industrially used Pd-Bi/Al(2)O(3) catalysts, leads to improved catalytic performance.     

Chemical state study of palladium powder and ceria-supported palladium during low-temperature CO oxidation

The chemical state of Pd at the surfaces of two sizes of Pd powders and ceria-supported Pd during low-temperature CO oxidation has been studied using X-ray photoelectron spectroscopy (XPS). During oxidation in O(2), metallic Pd powder is converted into PdO, and the thickness of the PdO layer increases with increasing reaction temperature. A similar Pd oxidation process occurs during the catalytic CO oxidation reaction, but the extent of the Pd oxidation is less due to the presence of CO which is a reducing agent. The reaction rate data indicate that the larger size Pd powder is about three times more active than the smaller size Pd powder on a surface area basis at 160 degrees C. Catalytic CO oxidation data obtained from 10 wt % Pd supported on nanocrystalline ceria powder indicate that there is a strong chemical interaction between the ceria and the supported Pd. The Pd is present as PdO on the fresh catalyst. During reaction, small amounts of Pd metal and PdO(2) are formed at 50 degrees C while less Pd metal and only a small amount of PdO(2) are present after running the reaction at 110 degrees C. At 50 degrees C, the catalytic activity decays rapidly due to accumulation of carbonate or bicarbonate species on the surface. This decay does not occur at 110 degrees C due to decomposition of the bicarbonate species.     

Influence of CeO2 and La2O3 on properties of palladium catalysts used for emission control of natural gas vehicles

Pd/YZ-Al2O3 (Y and Zr modified Al2O3, and hereafter, labelled as Al) catalysts with 4 wt% additive CeO2 and/or La2O3 were prepared and characterized by X-ray photoelectron spectroscopy (XPS), NO-temperature programmed desorption (NO-TPD), N2-adsorption/desorption (Brunauer-Emmet-Teller BET method), X-ray diffraction (XRD) and CO-chemisorption. Catalytic activities for CH4, CO and NO conversion were tested in a gas mixture simulated the emissions from natural gas vehicles (NGVs) operated under stoichiometric conditions. The results indicated that all catalysts exhibited excellent catalytic performances for CH4 and CO oxidation and the promoting effect of CeO2 or La2O3 was significant for NO conversion. XPS results showed that the electron density around Pd was increased by CeO2 and/or La2O3, the binding energy of Pd 3d decreased as the order: Pd/Al>Pd/Ce/Al>Pd/La/Al>Pd/CeLa/Al. The electron-rich Pd showed Rh-like catalytic properties which exhibited good activity for the reduction of NO. NO-TPD results showed that the addition of CeO2 and/or La2O3 increased NO adsorption on surface, and promoted the conversion of NO.     

Temperature-programmed desorption study of the selective oxidation of alcohols on silica-supported vanadium oxide

The partial oxidation of methanol and ethanol on silica-supported vanadium oxide catalysts was studied using temperature-programmed desorption (TPD), Raman spectroscopy, and diffuse reflectance infrared spectroscopy (DRIFTS). Methanol TPD results for V2O5/SiO2 samples as a function of vanadia loading in conjunction with X-ray diffraction data and Raman spectra indicated that dispersed vanadia on silica agglomerates into vanadia crystallites during a CH3OH TPD experiment. For ethanol-dosed samples, agglomeration of the dispersed vanadia was less severe, and it was possible to measure the activation energy for the dehydrogenation of adsorbed ethoxides to produce CH3CHO. Assuming a preexponential factor of 10(13) s(-1), the activation energy for this reaction was estimated to be 132 kJ/mol. The results of this study further demonstrate that there is a relatively weak interaction between vanadia and silica and suggest that adsorbed methoxide species help facilitate agglomeration of dispersed vanadia.     

Study of the elementary processes involved in the selective oxidation of methane over MoOx/SiO2

Isolated molybdate species supported on silica are reported to have the highest specific activity and selectivity for the direct oxidation of methane to formaldehyde. The present investigation was undertaken to understand the elementary redox processes involved in the formation of formaldehyde over such species. A MoO(x)/SiO(2) catalyst was prepared with a Mo loading of 0.44 Mo/nm(2). On the basis of evidence from extended X-ray absorption fine structure (EXAFS) and Raman spectroscopy, the Mo atoms in this catalyst are present as isolated, pentacoordinated molybdate species containing a single Mo=O bond. Isotopic labeling experiments in combination with in-situ Raman spectroscopy were used to examine the reducibility of the dispersed molybdate species and the exchange of O atoms between the gas phase and the catalyst. It was established that treatment of MoO(x)/SiO(2) at 873 K under pure methane reduces the dispersed molybdate species to only a limited extent and results mainly in the deposition of amorphous carbon. During CH(4) oxidation to formaldehyde, the catalyst undergoes only a very small degree of reduction and typically only approximately 50-500 ppm of Mo(VI) is reduced to Mo(IV). Reactions carried out using CH(4) and (18)O(2) show that there is extensive scrambling of O atoms between the species in the gas phase and the catalyst. Additional experiments revealed that H(2)O formed in the reaction is the principal species responsible for the exchange of O atoms between the gas phase and the SiO(2) support. Low concentrations of H(2)O were observed to enhance the activity of MoO(x)/SiO(2) for CH(4) oxidation to formaldehyde. A mechanism for the oxidation of CH(4) over MoO(x)/SiO(2) was formulated in light of the observations made here and is discussed in the light of previous studies. It is proposed that peroxides are produced by the reaction of O(2) with a small concentration of reduced molybdate species and that the reaction of CH(4) with these peroxide species leads to the formation of formaldehyde. The proposed mechanism also accounts for the positive effects of low concentrations of H(2)O on the rate of formaldehyde formation.     

还原剂对Au-Pd/CeO2催化剂甲醇部分氧化性能的影响

以PVP为保护剂,乙醇(ER)、乙二醇(GR)和水合肼(HR)为还原剂制备了一系列Au-Pd/CeO2催化剂,考察了还原剂对甲醇部分氧化性能的影响,并运用XRD、TPD和TPR等手段对催化剂进行了表征。结果表明,Au-Pd/CeO2(ER)催化剂具有较大的比表面积,形成的AuxPdy量较多、粒径较小、分散度较高、活性组分与载体的相互作用较强,同时对甲醇的吸附量较大和吸附温度较低。因此,该催化剂具有较高的催化活性和氢气选择性以及较低的CO质量分数。     

Rh-promoted methanol decomposition on cerium oxide thin films

Methanol adsorption and reaction have been studied on Rh-deposited cerium oxide thin films under UHV conditions using temperature-programmed desorption and synchrotron soft X-ray photoelectron spectroscopy. The methanol behavior was examined as a function of the Ce oxidation state, methanol exposure, and Rh particle size and coverage. When Rh nanoparticles were deposited on the ceria films, methanol decomposed on Rh to CO and H below 200 K. H atoms recombined and desorbed between 200 and 300 K. CO evolved from Rh deposited on fully oxidized ceria between 400 and 500 K. However, on reduced ceria films, the CO on Rh further decomposed to atomic C. Methanol adsorbed on the ceria films deprotonated to form methoxy as the only intermediate on the surface. This methoxy decomposed and desorbed as CO and H2 at higher temperatures regardless of the ceria oxidation state. Compared with the methanol reaction on Rh-free ceria thin films, formaldehyde formation from methoxy was completely suppressed after Rh deposition. Our results indicate that Rh can promote the decomposition of methoxy adsorbed on the ceria and that decomposition of methoxy intermediates occurred at the metal/oxide interfaces. On the other hand, the reduced ceria can promote total methanol decomposition on Rh.     

Active surfaces for CO oxidation on palladium in the hyperactive state

Hyperactivity was previously observed for CO oxidation over palladium, rhodium, and platinum surfaces under oxygen-rich conditions, characterized by reaction rates 2-3 orders higher than those observed under stoichiometric reaction conditions [Chen et al. Surf. Sci. 2007, 601, 5326]. In the present study, the formation of large amounts of CO(2) and the depletion of CO at the hyperactive state on both Pd(100) and polycrystalline Pd foil were evidenced by the infrared intensities of the gas phase CO(2) and CO, respectively. The active surfaces at the hyperactive state for palladium were characterized using infrared reflection absorption spectroscopy (IRAS, 450-4000 cm(-1)) under the realistic catalytic reaction condition. Palladium oxide on a Pd(100) surface was reduced eventually by CO at 450 K, and also under CO oxidation conditions at 450 K. In situ IRAS combined with isotopic (18)O(2) revealed that the active surfaces for CO oxidation on Pd(100) and Pd foil are not a palladium oxide at the hyperactive state and under oxygen-rich reaction conditions. The results demonstrate that a chemisorbed oxygen-rich surface of Pd is the active surface corresponding to the hyperactivity for CO oxidation on Pd. In the hyperactive region, the CO(2) formation rate is limited by the mass transfer of CO to the surface.     

Direct oxidation of methane to oxygenates over heteropolyanions

Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.     

Density functional theory analysis of the reaction pathway for methane oxidation to acetic acid catalyzed by Pd2+ in sulfuric acid

Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.     

Catalytic activity of Pd ensembles over Au(111) surface for CO oxidation: a first-principles study

Employing the first-principles pseudopotential plane-wave methods and nudged-elastic-band simulations, we studied the reaction of CO oxidation on Pd-decorated Au(111) surface. We found that the contiguous Pd ensembles are required for the CO + O(2) reaction. Interestingly, Pd dimer is an active site for the two-step reaction of CO+O(2)→OOCO→CO(2)+O, and a low energy barrier (0.29 eV) is found for the formation of the intermediate metastable state (OOCO) compared to the barrier of 0.69 eV on Pd trimer. Furthermore, the residual atomic O in the CO + O(2) reaction can be removed by another CO on Pd dimer with the barrier of 0.56 eV close to the value of 0.52 eV on Pd monomer via Langmuir-Hinshelwood mechanism. The higher energy barriers (0.96 and 0.64 eV) are also found for the CO + O reaction on Pd trimers. The calculated results indicate Pd dimer is highly reactive for CO oxidation by O(2) via association mechanism on Pd-decorated Au(111) surface.     

The study of the active surface for CO oxidation over supported Pd catalysts

CO oxidation was investigated on various powder oxide supported Pd catalysts by temperature-programmed reaction.The pre-reduced catalysts show significantly higher activities than the pre-oxidized ones.Model studies were performed to better understand the oxidation state,reactivities and stabilities of partially oxidized Pd surfaces under CO oxidation reaction conditions using an in situ infrared reflection absorption spectrometer(IRAS).Three O/Pd(100)model surfaces,chemisorbed oxygen covered surface,surface oxide and bulk-like surface oxide,were prepared and characterized by low-energy electron diffraction(LEED)and Auger electron spectroscopy(AES).The present work demonstrates that the oxidized palladium surface is less active for CO oxidation than the metallic surface,and is unstable under the reaction conditions with sufficient CO.     

On the Role of Vanadia Species for VOx／SiO2 in the Selective Oxidation of Methane

Various VOx/SiO2 catalysts were prepared by the methods of physical mixing, conventional wetness impregnation and ultrasonication-assistant impregnation. The catalysts were characterized by XRD, UV-Vis DRS, Raman, TPR, ESR and TPSR techniques and the nature of the vanadium species were correlated to their catalytic performance in the reaction of direct conversion of methane to formaldehyde. It is concluded that highly dispersed monomeric and low oligomeric vanadia species are formed on the sample prepared with both traditional wetness impregnation method and ultrasonication-assistant impregnation, whereas in the latter case, the amount of oligomeric vanadia species is much smaller. The V2O5 microcrystallines are the dominant species on the material prepared by physical mixing method. During the selective oxidation of methane, Vv species are reduced to V^IV paramagnetic species and both microcrystalline V205 species and oligomeric vanadia species are found to further disperse and transform into tetrahedral vanadia species. Based on the results of UV Raman spectroscopy and TPSR, C02 is suggested to be formed via two different routes, in which one is from the sequence reaction of CH4→ HCHO→ CO → CO2 over monomeric vanadia species, and the other is from the direct oxidation of methane to CO2 over oligomeric vanadia species. Oligomeric vanadia species is more active than monomeric vanadia species for methane activation.     

丝光沸石负载铂,钯催化剂的NO催化还原性能

丝光沸石负载铂、钯催化剂的ＮＯ催化还原性能１）罗孟飞朱波袁贤鑫（杭州大学催化研究所杭州３１００２８）关键词ＮＯ催化还原丝光沸石铂钯如何消除ＮＯｘ对环境造成的污染是当前人们所关心的课题之一，其中催化还原是消除ＮＯｘ的常用方法［１］．近几年，人们对金属离...