The reactivity and auger chemical shift of oxygen adsorbed on platinum

The reaction of carbon monoxide with oxygen chemisorbcd on polycrystalline platinum has been studied using Auger spectroscopy. Two types of chemisorbed oxygen are distinguished on the basis of Auger electron chemical shifts and reactivity towards carbon monoxide. When the substrate is below 800 K, a single very reactive type of chemisorbed oxygen is formed. Above 800 K a new species begins to form which is characterized by an Auger chemical shift of about 6 eV and by low reactivity. The decay of the oxygen Auger signal using several fixed pressures of carbon monoxide was measured. The reaction is first order in carbon monoxide pressure but no clear decision can be made about the order with respect to oxygen coverage. With the reaction $\text{CO +}\text{1}\text{20}{}_2\text{→ CO}{}_2$ operating at steady-state, the oxygen coverage was measured as a function of CO pressure. In the region 363–600 K, the steady state oxygen coverage began to decline measurably when reached 0.1. When p_CO>p_O2the oxygen coverage became immeasurably small. A simple model is used to relate these phenomena to observed carbon dioxide production rates.     

The adsorption and decomposition of formaldehyde by tungsten

A hot, clean tungsten surface was highly effective in decomposing formaldehyde vapour to carbon monoxide and hydrogen. At temperatures above 1300 K about 30% of the impinging molecules decomposed. At lower temperatures the reactivity was reduced, probably as the result of inhibition by the adsorbed carbon monoxide. Pre-adsorbed oxygen affected the reactivity in an unusual way. At low coverages of oxygen (θ < 0.4) and intermediate filament temperatures (T < 1000 K) no effect was observed, whereas under more extreme conditions (θ > 0.5 or T > 1200 K) a nearly linear decline in activity was recorded. These results are attributed to a similarity between the inhibiting effects of adsorbed oxygen and carbon monoxide.     

An Auger spectroscopic study of the kinetic behavior of adsorbed oxygen on palladium

The adsorption of oxygen on polycrystalline palladium, the kinetics of the reaction of adsorbed oxygen with carbon monoxide and the amount of adsorbed oxygen present during the catalyzed reaction, $\text{CO +}\text{1}\text{2}\text{O}{}_2\text{→ CO}{}_2$, were studied by Auger electron spectroscopy. At temperatures below 783 K, the initial sticking probability is high (~0.8). Adsorbed oxygen and CO react with high probability and low activation energy to form carbon dioxide. The reaction is first order with respect to carbon monoxide pressure and zero order in oxygen coverage. Oxygen coverages measured during the CO-oxidation reaction decrease sharply around P_CO ? P_O2 and are very small when P_CO >P_O2. The reaction kinetics are discussed using a modified Eley-Rideal mechanism involving strongly adsorbed oxygen atoms and surface carbon monoxide in a short-lived state. The oxygen adsorption phenomena are correlated with the reaction kinetics.     

钙基复合载氧体的化学链燃烧循环实验研究

在固定床实验台架上,研究了用浸渍制备的CaSO4复合载氧体与一氧化碳的反应特性。循环实验结果表明添加助剂可大幅度提高CaSO4的反应活性;随着温度的升高,SO2急剧增加,而COS无明显变化;在850℃时含Ni—Fe的载氧体在等生成CO2能力下的硫损失率最小。通过一系列的表征手段,分析了反应前后载氧体组分,表面结构的变化...     

Coadsorption de l'oxygène et du monoxyde de carbone sur des surfaces de rhénium

Temperature programmed desorption ($\text{2.65}\text{K}\text{sec}$) has been used to study carbon monoxide and mixed layers of carbon monoxide and oxygen on rhenium ribbons, strongly oriented parallel to the (0001) plane. Four binding states, populated in decreasing energy have been detected. Interpretation of the results on β states agrees qualitatively with King's model postulating dissociation of carbon monoxide molecules and a repulsive interaction energy between carbon and oxygen atoms. However, in the coadsorbed layers studies, it is shown that all the oxygen atoms do not play a part in the recombination process, during desorption, and that when oxygen is adsorbed after carbon monoxide, a displacement reaction occurs, due to apparent transfer from β states towards molecular α states. Optimization of the results on pure carbon monoxide layers leads to an interactional energy ω, equal to 3 $\text{kcal}\text{mole}$, and is only possible if is assumed that β states are formed on alternatively filled and empty rows.     

Decomposition of carbon monoxide on a (110) nickel surface

New investigations of the (110) nickel/carbon monoxide system have been made using low energy electron diffraction (LEED), Auger electron spectroscopy (AES), mass spectroscopy and work function measurements. Room temperature adsorption of CO on the surface was reversible with the CO easily removable by heating in vacuum to 450°K. The CO formed a double-spaced structure on the surface which, however, was unstable at room temperature for CO pressures less than 1×10^?7 torr. Work function changes greater than + 1.3 eV accompany this reversible CO adsorption. Irreversible processes leading to the build-up of carbon, and under certain circumstances oxygen, on the surface were the primary concern of the measurements reported here. These processes could be stimulated by the electron beams used in LEED and AES, or by heating the clean surface in CO. The results of AES investigations of this carbon (and oxygen) build-up, together with CO desorption results could be explained on the basis of two surface reactions. The primary reaction was the dissociation of chemisorbed CO leaving carbon and oxygen atomically dispersed on the surface. The second reaction was the reduction of the surface oxygen by CO from the gas phase. The significance of the dissociation reaction to COdesorption studies is discussed.     

Vibrational characterization of carbon monoxide oxidation on the Pt(111) surface

The surface reaction between coadsorbed carbon monoxide and atomic oxygen has been characterized using high resolution electron energy loss spectroscopy, coupled with temperature programmed reaction spectroscopy on a Pt(111) surface characterized using Auger electron spectroscopy and low energy electron diffraction. Preferential oxidation of bridge bonded CO is not observed despite the fact that bridge bonded CO is adsorbed less vigorously than linearly bound CO. Saturation of the Pt(111) surface with one quarter of a monolayer of atomic oxygen completely suppresses the adsorption of bridge bonded CO. However, substantial coverages of bridge bonded CO can be coadsorbed if the Pt(111) surface is only partially saturated with atomic oxygen. The vibrational data for reaction of coadsorbed CO and atomic oxygen is consistent with a reaction mechanism involving reaction of mobile CO along oxygen island perimeters.     

Low energy electron diffraction studies of chemisorbed gases on stepped surfaces of platinum

The chemisorption of hydrogen, oxygen, carbon, carbon monoxide and ethylene was studied by low-energy electron diffraction on ordered stepped surfaces of platinum which were cut at angles less than 10° from the (111) face. The chemisorption characteristics of stepped platinum surfaces are markedly different from those of low index platinum surfaces and they are also different from each other. Hydrogen and oxygen which do not chemisorb easily on the (111) and (100) crystal faces chemisorb readily and at relatively low temperatures and pressures on the stepped platinum surfaces used in this study. In contrast to the ordered adsorption of carbon monoxide and ethylene on low index faces, the adsorption was disordered on the stepped surfaces and there is evidence for dissociation of the molecule. Carbon formed several ordered surface structures and caused faceting on the stepped surface, which are not observed on low index platinum surfaces. There appears to be a much stronger interaction of chemisorbed gases with stepped surfaces than with low index planes that must be caused by the differing atomic structures at the steps. Evidence for the differing reactivities of the two stepped surfaces are also discussed.     

Investigation of oxygen states and reactivities on a nanostructured cupric oxide surface

Nanostructured copper (II) oxide was formed on clean copper foil at room temperature using activated oxygen produced by RF discharge. CuO particles of approximately 10-20 nm were observed on the surface by Scanning Tunneling Microscopy (STM). The copper states and oxygen species of the model cupric oxide were studied by means of X-ray Photoelectron Spectroscopy (XPS). These oxide particles demonstrated abnormally high reactivity with carbon monoxide (CO) at temperatures below 100 °C. The XPS data showed that the interaction of CO with the nanostructured cupric oxide resulted in reduction of the CuO particles to Cu₂O species. The reactivity of the nanostructured cupric oxide to CO was studied at 80 °C using XPS in step-by-step mode. The initial reactivity was estimated to be 5 × 10⁻⁵ and was steadily reduced down to 5 × 10⁻⁹ as the exposure was increased. O1s spectral analysis allowed us to propose that the high initial reactivity was caused by the presence of non-lattice oxygen states on the surface of the nanostructured CuO. We established that reoxidation of the partially reduced nanostructured cupric oxide by molecular oxygen O₂ restored the highly reactive oxygen form on the surface. These results allowed us to propose that the nanostructured cupric oxide could be used for low temperature catalytic CO oxidation. Some hypotheses concerning the nature of the non-lattice oxygen species with high reactivity are also discussed.     

Studies on the Decomposition of Carbon Dioxide in a Low-Temperature Plasma

The decomposition of carbon dioxide was studied in an argon plasma jet, generated by a direct-current arc discharge. The decomposition degree of carbon dioxide was up to 0,4 at an effective energy consumption lower than 1 MJ/mole CO. The efficiency of high-temperature decomposition of carbon dioxide to carbon monoxide and oxygen is essentially dependent both on the quenching intensity of the products, which prevents from the reverse oxidation reaction in the system, as well as on the proper conditions of plasma-substrate mixing.     

Poisoning and non-poisoning oxygen on Cu(410)

We have investigated ethene and oxygen co-adsorption on Cu(410) by high resolution electron energy loss spectroscopy. We find that these two species compete for the adsorption sites and that pre-exposure to oxygen affects ethene adsorption more or less strongly depending on oxygen coverage and the kind of occupied sites. The c(2 × 2) O overlayer is inert with respect to ethene adsorption, while when some oxygen is removed by thermally induced subsurface incorporation, ethene chemisorption is restored. The latter species also adsorbs on the disordered oxygen phase formed when O(2) is dosed at low crystal temperature. Contrary to the bare surface case, most of the ethene ends up in a π-bonded configuration. Dehydrogenation occurs, too, albeit as a minority channel. The so-produced carbon reacts already at low temperature with adsorbed oxygen to yield carbon monoxide, which desorbs around 190 K.     

The interaction of hydrogen and carbon monoxide with oxygen on Cu(111)-Fe Surfaces

The interaction of hydrogen and carbon monoxide with oxygen adsorbed on Cu(111)-Fe surfaces containing different amounts of iron has been studied with ellipsometry, Auger electron spectroscopy and low energy electron diffraction. With carbon monoxide copper can be reduced completely and if, at larger iron deposits, γ-Fe₂O₃ is present, γ-Fe₂O₃ can be reduced to Fe₃O₄. The maximum reaction rate is proportional to the square of the total copper surface. With hydrogen all oxygen can be removed. The reduction proceeds via a number of different stages. This is explained by the subsequent occurrence of γ-Fe₂O₃, Fe₃O₄ Fe_0.95O and Fe.     

The adsorption and decomposition of methanol on tungsten. II

A clean tungsten filament adsorbs methanol rapidly at room temperature, the initial sticking probability being 0.8. At saturation, the composition of the adsorbed layer is roughly CO:H = 1:1 and it is suggested that the hydrogen may be in the form of a surface complex. The continuous decomposition of methanol by the hot filament under steady-state conditions, or when the filament had been previously oxygenated, followed a different course from that previously reported for the newly-cleaned filament. Rather than a rapid rise in the rate of decomposition (to CO + H₂) for 600 < T_fil < 1300 K to a high plateau above 1300 K, decompositon to formaldehyde, carbon monoxide and methane was observed. The rates at which these products appeared passed through low maxima between 900 and 1100 K. The change in the relative importance of formaldehyde and carbon monoxide production with filament temperature within this range is attributed to a temperature-dependent life-time of formaldehyde molecules on the oxygenated surface. At the highest temperature (> 1500 K) the reactivity increased rapidly to join that of the clean surface, probably due to the desorption of surface oxygen.     

Carbon monoxide dissociation on polycrystalline cobalt

The dissociation reaction of carbon monoxide was studied on a polycrystalline cobalt foil between room temperature and 470 K, at pressures below 10^-5 Torr. Dissociation kinetics were monitored mainly by the variation of the work function, while the surface composition was studied with AES, UPS and TDS. Kinetics of oxygen uptake at 300 and 470 K were also obtained in order to ascertain the state of surface oxygen. The dissociation of CO on polycrystalline material is well detectable above 350 K and leads to a surface covered by both carbon and oxygen atoms in a 1:1 atomic ratio, each atomic species reaching about half the coverage corresponding to saturation of the chemisorption when adsorbed separately. Adsorbed oxygen atoms do not react with CO in the range of temperatures and pressures investigated. The rate of the dissociation process is determined by the coverage of CO molecules adsorbed in equilibrium with the gas and by the availability of active sites for the dissociation of adsorbed CO molecules, which are mobile on the surface. Values of the rate constant of the dissociation process were obtained for different temperatures and pressures, from which an activation energy of 17±2 kcal/mol was derived.     

The interaction of hydrogen and carbon monoxide with oxygen on Cu(110)-Fe surfaces

The interaction of hydrogen and carbon monoxide with oxygen adsorbed on Cu(110)-Fe surfaces has been studied with ellipsometry, Auger electron spectroscopy and low energy electron diffraction. With carbon monoxide copper can be reduced completely and Fe_0.95O partially. With a model which is only an extension of the scheme for the reduction of pure Cu(110) by CO, the reduction of Cu(110)-Fe can be simulated. The lateral orientation of Fe_0.95O with respect to the copper matrix changes during repetitive oxidation-reduction cycles. At 725 K oxygen deficient iron oxide segregates to the surface. With hydrogen all oxygen can be removed.     

原位DRIFTS研究CH4部分氧化和CO2重整的耦合

8%Ru-5?/γ-Al2O3催化剂对于甲烷的低温活化具有较好的催化活性,在500℃下甲烷、二氧化碳和氧气的耦合反应中,吸热反应二氧化碳重整和放热反应甲烷部分氧化进行耦合强化,使得耦合反应中的甲烷转化率为38.8%。用原位漫反射傅里叶红外光谱法对钌系催化剂耦合甲烷部分氧化和二氧化碳重整反应体系机理进行研究。CO在8%Ru-5?/γ-Al2O3上吸附,表明CO在催化剂表面上波数为2 167 cm-1(2 118 cm-1)和2031 cm-1(2 034 cm-1)处形成孪生态Ru(CO)2和Ce(CO)2吸附物种,而且高温下CO吸附物种很容易从催化剂表面脱附出来。原位漫反射红外实验结果表明甲烷部分氧化反应时催化剂表面上有吸附物种碳酸根、甲酰基(甲酸盐)和一氧化碳的形成,其中表面的甲酰基和甲酸盐物种是甲烷部分氧化反应的主要活性中间物,这些中间活性中间体由甲烷吸附态CHx和催化剂表面的氧吸附态结合而形成的,随后这种中间物种再分解为CO产物;甲烷和二氧化碳重整反应时没有新的吸附物种产生,由此提出重整反应的机理是吸附态的甲烷和二氧化碳在催化剂活性中心上进行活化解离而生成合成气;甲烷、二氧化碳和氧气耦合反应过程中出现新的羟基物种(桥式羟基Ru-(OH)2),耦合反应机理复杂可能是由部分氧化和重整两类反应机理的复合,其中桥式羟基Ru-(OH)2参与了反应的进行。     

Interaction of carbon monoxide and oxygen at the surface of inverse titania/Au model catalyst

Interaction of carbon monoxide and oxygen on the surface of titania/Au(1 1 1) inverse model catalyst held at 200 K has been studied by reflection absorption infrared spectroscopy. It was found that CO adsorbs on the oxide/Au perimeter interface, whereas no or very weak adsorption was observed on Au(1 1 1) or titania surface, respectively. Exposing of such species to oxygen results in their decay possibly due to carbon dioxide formation. Efficiency of this effect is higher at lower CO initial concentration which points at the importance of free surface sites for the reaction process.     

Molecular beam studies of ethanol oxidation on Pd(110)

The adsorption and decomposition of ethanol on Pd(110) has been studied by use of a molecular beam reactor and temperature programmed desorption. It is found that the major pathway for ethanol decomposition occurs via a surface ethoxy to a methyl group, carbon monoxide and hydrogen adatoms. The methyl groups can either produce methane (which they do with a high selectivity for adsorption below 250 K) or can further decompose (which they do with a high selectivity for adsorption above 350 K) resulting in surface carbon. If adsorption occurs above 250 K a high temperature (450 K) hydrogen peak is observed in TPD, resulting from the decomposition of stable hydrocarbon fragments. A competing pathway also exists which involves C---O bond scission of the ethoxy, probably caused by a critical ensemble of palladium atoms at steps, defects or due to a local surface reconstruction. The presence of oxygen does not significantly alter the decomposition pathway above 250 K except that water and, above 380 K, carbon dioxide are produced by reaction of the oxygen adatoms with hydrogen adatoms and adsorbed carbon monoxide respectively. Below 250 K, some ethanol can form acetate which decomposes around 400 K to produce carbon dioxide and hydrogen.     

An electron energy loss study of aluminum single crystals exposed to carbon monoxide

Aluminum single crystals of orientations {111}, {110}, and {100} were exposed at room temperature to carbon monoxide. The electron energy loss spectra of the exposed surfaces (> 20000 L) were essentially the same as those of clean surfaces. Since such spectra are very sensitive to small amounts of absorbate (e.g., 0.001 to 0.01 monolayer of oxygen), it is inferred that carbon monoxide does not adsorb on these clean low-order faces at room temperature. Similar results were obtained on polycrystalline and evaporated film samples. This finding contrasts with previous work on aluminum exposed to carbon monoxide.