CH3（ad）在清洁及预吸附氧Pd（100）表面的热脱附性能

用高分辨电子能量损失谱，热脱附谱，紫外光电子能谱研究了ＣＨ３在清洁及预吸附氧Ｐｄ表面上的热稳定性。ＣＨ３由ＣＨ３Ｉ在Ｐｄ表面的热分解来产生。ＣＨ３Ｉ的ＨＲＥＥＬＳ表明，ＣＨ３中的Ｃ－Ｈ键近似与表面平行，ＣＨ３Ｉ在Ｐｄ表面低于１１０Ｋ时已裂解为ＣＨ３和Ｉ，大量的ＣＨ３在２００－２１０Ｋ的温度范围内的Ｈ结合并以ＣＨ４的形式脱附，但在氧改性表面，ＣＨ４脱附的温度范围变宽，脱附温度有所提高，可能是由于表面     

The role of Oad in the decomposition of NH3 adsorbed on Ir(110): a combined TPD and high-energy resolution fast XPS study

High energy resolution fast XPS combined with TPD experiments were used to study the effect of chemisorbed oxygen on the adsorption and dissociation of NH(3) on Ir(110). Below 250 K the presence of O(ad) does not influence NH(3) decomposition. Above 250 K O(ad) enhances NH(3) dissociation, which results in three times as much N(2) formation and less molecular NH(3) desorption compared to the experiments without O(ad). The effect of O(ad) can be attributed to destabilization of NH(ad) on the surface, resulting in a further dehydrogenation towards N(ad). The presence of O(ad) on the surface lowers the temperature at which the N(ad) combination reaction takes place by as much as 200 K, due to repulsive interaction between N(ad) and O(ad). NO is formed above 450 K if both N(ad) and O(ad) are present on the surface.     

Catalytic oxidation of ammonia on RuO2(110) surfaces: mechanism and selectivity

The selective oxidation of ammonia to either N2 or NO on RuO2(110) single-crystal surfaces was investigated by a combination of vibrational spectroscopy (HREELS), thermal desorption spectroscopy (TDS) and steady-state rate measurements under continuous flow conditions. The stoichiometric RuO2(110) surface exposes coordinatively unsaturated (cus) Ru atoms onto which adsorption of NH3 (NH3-cus) or dissociative adsorption of oxygen (O-cus) may occur. In the absence of O-cus, ammonia desorbs completely thermally without any reaction. However, interaction between NH3-cus and O-cus starts already at 90 K by hydrogen abstraction and hydrogenation to OH-cus, leading eventually to N-cus and H2O. The N-cus species recombine either with each other to N2 or with neighboring O-cus leading to strongly held NO-cus which desorbs around 500 K. The latter reaction is favored by higher concentrations of O-cus. Under steady-state flow condition with constant NH3 partial pressure and varying O2 pressure, the rate for N2 formation takes off first, passes through a maximum and then decreases again, whereas that for NO production exhibits an S-shape and rises continuously. In this way at 530 K almost 100% selectivity for NO formation (with fairly high reaction probability for NH3) is reached.     

Ethanol adsorption, decomposition and oxidation on Ir(111): a high resolution XPS study.

Ethanol (C(2)H(5)OH) adsorption, decomposition and oxidation is studied on Ir(111) using high-energy resolution, fast XPS and temperature-programmed desorption. During heating of an adsorbed ethanol layer a part of the C(2)H(5)OH(ad) desorbs molecularly, and another part remains on the surface and decomposes around 200 K; these two decomposition pathways are identified, as via acetyl (H(3)C--C=O) and via CO(ad)+CH(3ad), respectively. Acetyl and CH(3ad) decompose around 300 K into CH(ad) (and CO(ad)). CH(ad) decomposes forming C(x) and H(2) around 520 K. In the presence of O(ad) an acetate intermediate is formed around 180 K, as well as a small amount of CH(3ad) and CO(ad). Acetate decomposes between 400-480 K into CO(2), H(2)(/H(2)O) and CH(ad).     

SiO2—Al2O3和MgO催化剂上吸附CH3NO2的TPD和IR研究

用TPD和IR方法研究了CH_3NO_2在典型固体酸SiO_2-Al_2O_3和固体碱MgO催化剂上的吸附分解。结果表明,在SiO_2-Al_2O_3表面CH_3NO_2吸附转化为表面甲酰胺物种,后者在高温下分解为CO_2和NH_3。在MgO表面CH_3NO_2吸附形成多种表面化学物种,它们在升温过程中脱附,并通过表面亚硝基甲烷物种分解为NO、C_2H_4、C_2H_6和N_2O.讨论了CH_3NO_2分解过程中表面酸、碱中心的作用。     

Cyanoacetylene adsorption on amorphous and crystalline water ice films: investigation through matrix isolation and quantum study.

The structure and energy properties of the 1:1 complexes formed between cyanoacetylene and H2O (D2O) are investigated using FT-IR matrix isolation spectroscopy and ab initio calculations at the MP2/ 6-31G(d,p) level. Cyanoacetylene adsorption and desorption on amorphous ice film are monitored by FT-IR using the temperature-programmed desorption method. In an argon matrix, two types of 1:1 complexes are observed. The first one corresponds to the NH structure, which involves a hydrogen bond with the terminal nitrogen of cyanoacetylene. The second corresponds to the HO form, which involves a hydrogen bond from the cyanoacetylene to the oxygen of water. This last complex is the more stable (DeltaE = -8.1 kJ/mol.). As obtained in argon matrixes, two kinds of adsorption site are observed between HC3N and ice. The first one, stable between 25 and 45 K is characterized by a nu(OH) shift similar to the one observed in matrix for the NH complex. The second, stable at higher temperatures (between 45 and 110 K), corresponds to an interaction with the dangling oxygen site of ice and is similar to the HO complex observed in matrix. From theoretical calculations (DFT method combined with a plane wave basis set and ultrasoft pseudopotentials), it is shown that, for this adsorption site, the HC3N moiety is flattened on the ice surface and stabilized by a long-distance interaction ( approximately 3 A) between one dangling OH and the pi system of the C triple bond C triple bond. The HC3N desorption occurs between 110 and 140 K, and the associated desorption energy is 39 kJ/mol. This value is in good agreement with the first principle calculation based on density functional theory and ultrasoft pseudopotentials (34 kJ/mol). These calculations confirm the electrostatic nature of the interaction forces. A small amount of cyanoacetylene is incorporated into the bulk and desorbs at the onset of the ice crystallization near 145 K. In these two kinds of experiments, HC3N acts as both an electrophilic and a nucleophilic molecule.     

Hydrazine decomposition over Irn/Al2O3 model catalysts prepared by size-selected cluster deposition

Hydrazine decomposition chemistry was probed over a temperature range from 100 to 800 K for a series of model catalysts prepared by mass-selected Ir(n)(+) deposition on planar Al(2)O(3)/NiAl(110). Two sets of experiments are reported. Temperature-programmed desorption (TPD) was used to study hydrazine desorption and decomposition on Al(2)O(3)/NiAl(110) and on a model catalyst prepared by deposition of Ir(+) on Al(2)O(3)/NiAl(110) at a density large enough (5 x 10(14) cm(-2)) that formation of a distribution of small Ir(n) clusters on the surface is expected. This model catalyst was found to have hydrazine decomposition properties qualitatively similar to those observed on single-crystal Ir and polycrystalline Rh. This catalyst was also studied by X-ray photoelectron spectroscopy (XPS), to probe TPD-induced changes in the samples. A substantial decrease in the Ir XPS intensity suggests that considerable sintering takes place when the samples are heated to 800 K. In addition, a significant fraction of the nitrogen contained in the hydrazine is converted to an aluminum nitride (or mixed Al(x)O(y)N(z)) compound. Continuous flow experiments were used to probe relative reactivity at 300 and 400 K of samples prepared by depositing differently sized Ir(n)(+) clusters. At 300 K, samples prepared with preformed Ir(n)(+) (n = 5, 7, 10) are about twice as active, per Ir atom, as samples prepared with Ir(+) deposition, and there is a weaker trend to higher activity with increasing cluster size. At 400 K the trends are similar, but weaker, suggesting that thermal modification of the samples is already significant.     

The collimation angle shift of desorbing product N2 in a steady-state N2O+CO reaction on Rh(110)

The angular distribution of desorbing product N2 was studied in N2O decompositions on Rh(110) in the temperature range of 60-700 K. The N2 desorption collimates along 62 degrees -68 degrees off normal toward either the [001] or [001] direction in a transient N2O decomposition below ca. 470 K or in the steady-state N2O+CO reaction above 540 K. In the steady-state reaction at the temperature from ca. 470 to 540 K, however, the collimation angle shifts from 62 degrees to 45 degrees with decreasing surface temperature. This angle shift is ascribed to the steric hindrance by coadsorbed CO because the N2 collimation in transient N2O decomposition at around 65 degrees is recovered in the range of 380-500 K by an abrupt CO pressure drop followed by the decrease in CO coverage. N2O is oriented along the [001] direction before dissociation. A scattering model of the nascent N2 by adsorbed CO is proposed, yielding smaller collimation angles.     

Adsorption and interaction of ethylene on RuO2(110) surfaces

Ethylene (C2H4) adsorbed on the stoichiometric and oxygen-rich RuO2(110) surfaces, exposing coordinatively unsaturated Ru-cus and O-cus atoms, is investigated by applying high-resolution electron energy-loss spectroscopy and thermal desorption spectroscopy in combination with isotope labeling experiments. On the stoichiometric RuO2(110) surface C2H4 adsorbs and desorbs molecularly. In contrast, on the oxygen-rich RuO2(110) surface ethylene adsorbs molecularly at 85 K and is completely oxidized through interaction with O-cus and O-bridge upon annealing to 500 K. The first couple of reactions are observed at 200 K taking place on Ru-cus: A change from pi- to sigma-bonding, formation of -C=O and -C-O groups, and dehydrogenation giving rise to H2O adsorbed at Ru-cus. Maximum reaction rate is reached for C2H4 chemisorbed at Ru-cus with O-cus neighbors on each side. A model for the first couple of reactions is sketched. For the final combustion, C2H4 reacts both with O-cus and O-bridge. Ethylene oxide is not detected under any circumstance.     

Surface chemistry of CN bond formation from carbon and nitrogen atoms on Pt(111)

The mechanism of CN bond formation from CH3 and NH3 fragments adsorbed on Pt(111) was investigated with reflection absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). The surface chemistry of carbon-nitrogen coupling is of fundamental importance to catalytic processes such as the industrial-scale synthesis of HCN from CH4 and NH3 over Pt. Since neither CH4 nor NH3 thermally dissociate on Pt(111) under ultrahigh vacuum (UHV) conditions, the relevant surface intermediates were generated through the thermal decomposition of CH3I and the electron-induced dissociation of NH3. The presence of surface CN is detected with TPD through HCN desorption as well as with RAIRS through the appearance of the vibrational features characteristic of the aminocarbyne (CNH2) species, which is formed upon hydrogenation of surface CN at 300 K. The RAIRS results show that HCN desorption at approximately 500 K is kinetically limited by the formation of the CN bond at this temperature. High coverages of Cads suppress CN formation, but the results are not influenced by the coadsorbed I atoms. Cyanide formation is also observed from the reaction of adsorbed N atoms and carbon produced from the dissociation of ethylene.     

Kinetics and dynamics of N2 formation in a steady-state N2O + CO reaction on Pd(110)

The N(2)O decomposition kinetics and the product (N(2) and CO(2)) desorption dynamics were studied in the course of a catalyzed N(2)O+CO reaction on Pd(110) by angle-resolved mass spectroscopy combined with cross-correlation time-of-flight techniques. The reaction proceeded steadily above 400 K, and the kinetics was switched at a critical CO/N(2)O pressure ratio. The ratio was about 0.03 at 450 K and reached approximately 0.08 at higher temperatures. Below it, the reaction was first order in CO, and negative orders above it. Throughout the surveyed conditions, the N(2) desorption sharply collimated along about 45 degrees off the normal toward the [001] direction. Desorbing N(2) showed translational temperatures in the range of 2000-5000 K. It is proposed that the decomposition proceeds in N(2)O(a) oriented along the [001] direction. On the other hand, the CO(2) desorption sharply collimated along the surface normal, showing a translational temperature of about 1600 K.     

碘乙醇在Ni(100)表面的化学热反应

利用热脱附(TPD)实验和X射线光电子能谱(XPS)研究了碘乙醇在Ni(100)表面的吸附和热反应过程. 实验结果表明, 碘乙醇在100 K温度下以两种分子的形式吸附在Ni(100)的表面, 既有碘原子端的吸附也有碘原子端和羟基端同时吸附在表面. 热分解反应发生在140 K, 伴有少量的乙烯和水产生. 碘乙醇在150 K经过C—I键断裂形成−O(H)CH2CH2−和羟乙基两种中间产物. 在160 K温度下−O(H)CH2CH2−脱去氢形成−OCH2CH2−氧金属环. 中间产物经过进一步分解氧化反应分别在210和250 K产生乙醛, 一部分乙醛从表面脱出, 而其余的则分解成氢气、水和CO.     

Kinetics of metal organic-ammonia adduct decomposition: implications for group-III nitride MOCVD

We have used infrared spectroscopy to investigate the decomposition of the gas-phase (Me)(3)M:NH(3) (M = Al, Ga, In) adducts from room temperature to 573 K, at reactant concentrations in the nominal range used for Al(Ga,In)N metal organic chemical vapor deposition. At 473-523 K TMAl:NH(3) decomposes quantitatively to yield (Me(2))AlNH(2) and CH(4). Comparison of the experimental and theoretical spectra indicates that the majority of the aluminum metal organic product exists in dimer form, i.e., [(Me(2))AlNH(2)](2). The decomposition reaction exhibits unimolecular decomposition kinetics with rate constant parameters of nu = 1 x 10(12) s(-1) and E(a) = 25.7 kcal/mol. At temperatures <543 K, TMGa + NH(3) and TMIn + NH(3) mixtures are dominated by reversible adduct formation-dissociation with no detectable quantities of CH(4) produced. At 574 K a small amount of decomposition is observed in TMGa + NH(3) mixtures, which can be explained by a simple kinetic model that includes the effect of adduct equilibrium. Results demonstrate that the (Me)(3)Al:NH(3) decomposition rate is fast enough to contribute to the early stages of a concerted parasitic chemical reaction mechanism, but the (Me)(3)Ga:NH(3) decomposition rate is too slow.     

N2 emission in NO and N2O reduction on Rh(100) and Rh(110)

The angular distribution of desorbing N(2) was studied in both the thermal decomposition of N(2)O(a) on Rh(100) at 60-140 K and the steady-state NO (or N(2)O) + D(2) reaction on Rh(100) and Rh(110) at 280-900 K. In the former, N(2) desorption shows two peaks at around 85 and 110 K. At low N(2)O coverage, the desorption at 85 K collimates at about 66 degrees off normal towards the [001] direction, whereas at high coverage, it sharply collimates along the surface normal. In the NO reduction on Rh(100), the N(2) desorption preferentially collimates at around 71 degrees off normal towards the [001] direction below about 700 K, whereas it collimates predominantly along the surface normal at higher temperatures. At lower temperatures, the surface nitrogen removal in the NO reduction is due to the process of NO(a) + N(a) --> N(2)O(a) --> N(2)(g) + O(a). On the other hand, in the steady-state N(2)O + D(2) reaction on Rh(110), the N(2) desorption collimates closely along the [001] direction (close to the surface parallel) below 340 K and shifts to ca. 65 degrees off normal at higher temperatures. In the reduction with CO, the N(2) desorption collimates along around 65 degrees off normal towards the [001] direction above 520 K, and shifts to 45 degrees at 445 K with decreasing surface temperature. It is proposed that N(2)O is oriented along the [001] direction on both surfaces before dissociation and the emitted N(2) is not scattered by adsorbed hydrogen.     

Inclined N2 desorption in N2O reduction by D2 and CO on Pd(110)

Inclined N2 desorption was examined in the course of a catalyzed N2O + D2 (or CO) reaction on Pd(110) by angle-resolved mass spectroscopy combined with cross-correlation time-of-flight techniques. N2 desorption collimated at around 45 degrees off the normal toward the [001] direction in the temperature range of 400-800 K. Its collimation angle and kinetic energy were insensitive to both the surface temperature and surface conditions throughout the kinetic transition. It is proposed that this peculiar N2 desorption is induced by the decomposition of N2O oriented along the [001] direction.     

Mechanism of hydrogenation reaction in the Li-Mg-N-H system

The Li-Mg-N-H system composed of 3 Mg(NH2)2 and 8 LiH reversibly desorbs/absorbs approximately 7 wt % of H2 at 120-200 degrees C and transforms into 4 Li2NH and Mg3N2 after dehydrogenation. In this work, the mechanism of the hydrogenation reaction from 4 Li2NH and Mg3N2 to 8 LiH and 3 Mg(NH2)2 was investigated in detail. Experimental results indicate that 4 Li2NH is first hydrogenated into 4 LiH and 4 LiNH2. At the next step, 4 LiNH2 decomposes into 2 Li2NH and 2 NH3, and the emitted 2 NH3 reacts with (1/2) Mg3N2 and produces the (3/2) Mg(NH2)2 phase, while the produced 2 Li2NH is hydrogenated into 2 LiH and 2 LiNH2 again. Such successive steps continue until all 4 Li2NH and Mg3N2 completely transform into 8 LiH and 3 Mg(NH2)2 by hydrogenation.     

Formation of sulfhydryl (SH) species on the clean and (2 × 2)-S covered Pt(111) surfaces by H2S decomposition

H₂S decomposition on the clean and (2 × 2)-S covered Pt(111) surfaces has been characterized using high-resolution electron energy loss (HREELS) and temperature-programmed desorption (TPD) spectroscopies. On the Pt(111)-(2 × 2)-S surface, a mixture of molecular H₂S and sulfhydryl (SH) species forms following H₂S adsorption at 110 K. The molecular H₂S desorbs at 140 K leaving a (2 × 2)-S overlayer saturated with SH; the SH is stable up to 190 K. On the clean Pt(111) surface, a mixture of atomic sulfur, SH and chemisorbed molecular H₂S is formed following H₂S adsorption at 110 K. On the clean surface, adsorbed SH decomposes near 150 K. We report here the first definitive observation of an adsorbed sulfhydryl species on a metal surface.     

Surface-nitrogen removal in a steady-state NO + H2 reaction on Pd(110)

Surface-nitrogen removal steps were analyzed in the course of a catalyzed NO + H(2) reaction on Pd(110) by angle-resolved mass spectroscopy combined with cross-correlation time-of-flight techniques. Four removal steps, i.e., (i) the associative process of nitrogen atoms, 2N(a) --> N(2)(g), (ii) the decomposition of the intermediate, NO(a) + N(a) --> N(2)O(a) --> N(2)(g) + O(a), (iii) its desorption, N(2)O(a) --> N(2)O(g), and (iv) the desorption as ammonia, N(a) + 3H(a) --> NH(3)(g), are operative in a comparable order. Above 600 K, process (i) is predominant, whereas the others largely contribute below 600 K. Process (iv) becomes significant at H(2) pressures above a critical value, about half the NO pressure. Hydrogen was a stronger reagent than CO toward NO reduction and relatively enhanced the N(a) associative process.     

Hydrogen storage properties of Li-Mg-N-H systems with different ratios of LiH/Mg(NH2)2

In this work, the hydrogen desorption and structural properties of the Li-Mg-N-H systems with different LiH/Mg(NH2)2 ratios are systemically investigated. The results indicate that the system with the LiH/Mg(NH2)2 ratio of 6/3 transforms into Li2NH and MgNH, and then, the mixture forms an unknown phase by a solid-solid reaction, which presumably is the ternary imide Li2Mg(NH)2; the system with the LiH/Mg(NH2)2 ratio of 8/3 transforms into 4Li2NH and Mg3N2 after releasing H2 at T < 400 degrees C; the system with the LiH/Mg(NH2)2 ratio of 12/3 transforms into 4Li3N and Mg3N2 after releasing H2 at T > 400 degrees C, where the LiMgN phase is formed by the reaction between Li3N and Mg3N2. The characteristics of the phase transformations and the thermal gas desorption behaviors in these Li-Mg-N-H systems could be reasonably explained by the ammonia mediated reaction model, irrespective of the difference in the LiH/Mg(NH2)2 ratios.     

Primary thermal degradation processes occurring in poly(phenylenesulfide) investigated by direct pyrolysis–mass spectrometry

The thermal degradation Processes which occur in poly(phenylenesulfide) (PPS) have been studied by direct pyrolysis-mass spectrometry (DPMS). The structure of the compounds evolved in the overall temperature range of PPS decomposition (400–700°C) suggests the occurrence of several thermal decomposition steps. At the onset of the thermal degradation (430–450°C) this polymer decomposes with the formation of cyclic oligomers, generated by a simple cylization mechanism either initiated at the—SH end groups or by the exchange between the inner sulfur atoms along the polymer chain. At higher temperature (> 500°C) another decomposition reaction takes over with the formation of aromatic linear thiols. The formation of thiodibenzofuran units by a subsequent dehydrogenation reaction occurs in the temperature range of 550–650°C; in fact, pyrolysis products with a quasi-ladder structure have also been detected. Ultimately, above 600°C, extrusion of sulfur from the pyrolysis residue occurs with the maximum evolution at the end of decomposition (about 700°C). It appears, therefore, that the residue obtained at high temperature tends to have a crosslinked graphite-like structure from which the bonded sulfur is extruded. © 1994 John Wiley & Sons, Inc.