Molecular surface studies of adsorption and catalytic reaction on crystal (Pt,Rh) surfaces under high pressure conditions (atmospheres) using sum frequency generation (SFG) – surface vibrational spectroscopy and scanning tunneling microscopy (STM)

Sum frequency generation (SFG) – surface vibrational spectroscopy and the scanning tunneling microscope (STM) have been used to study adsorption and catalyzed surface reactions at high pressures and temperatures using (111) crystal surfaces of platinum and rhodium. The two techniques and the reaction chambers that were constructed to make these studies possible are described. STM and SFG studies of CO at high pressures reveal the high mobility of metal atoms, metal surface reconstruction, ordering in the adsorbed molecular layer, and new binding states for the molecule. CO oxidation occurs at high turnover rates on Pt(111). Different adsorbed species are observed above and below the ignition temperature. Some inhibit the reaction, and others are reaction intermediates since their surface concentration is proportional to the reaction rate. The dehydrogenation of cyclohexene on Pt(100) and Pt(111) proceeds through a 1,3‐cyclohexadiene surface intermediate. The higher dehydrogenation rate is related to the higher surface concentration of these molecules on the (100) crystal face. This revised version was published online in August 2006 with corrections to the Cover Date.     

Einfluss der natur der alkohole auf den mechanismus ihrer elektrooxidation

The electochemical behaviour of alcohols with different numbers of C atoms and different structure depends strongly on the number of H atoms bonded to the C atom with the OH group. All other structure properties are of less importance. This experimental observations, obtained at platinum in H₂SO₄, leads to a mechanism of anodic oxidation as follows: a preceding dehydrogenation is followed by chemical and/or electrochemical oxidation of the reaction products. Depending on the state of the electrode surface, the dehydrogenation occurs via adsorption or through a chemical reaction with the oxygen coverage of the electrode.The mechanism discussed is not limited to alcohols, but it can be applied to molecules of similar kind (aldehydes, formic acid, etc.) also.     

Conversion of 2-propanol over chromium aluminum orthophosphates

The catalytic conversion (dehydration/dehydrogenation) of 2-propanol on a series of CrPO₄-AlPO₄ (CrAlP) catalysts, which were differently prepared and thermally treated at 773–1073 K, has been studied by microcatalytic pulse reactor technique at different temperatures (473–573 K). Kinetic parameters for conversion of 2-propanol to propene have been obtained by analysis of the data through the Bassett-Habgood equation for first-order reaction processes. The influence of the reaction temperature upon alcohol conversion and product selectivities was also investigated. Catalytic performance was affected by the precipitation agent. Catalysts obtained in propylene oxide-aqueous ammonia showed the highest activity towards propene compared to other catalysts. Calcination at increasing temperatures caused a decrease in the activity due to the decrease in surface acid character. The results of dehydration to propene can be well interpreted through the differences in the number and strength of acid sites, which were gas-chromatographically measured using pyridine and 2,6-dimethylpyridine chemisorbed at different temperatures (573 and 673 K). Dehydrogenation to 2-propanone occurred to a small extent at all reaction temperatures and, besides, its conversion changed slightly with reaction temperature. Propene selectivity strongly increased with increasing reaction temperature.     

Reaction of Formic Acid on Zn-Modified Pd(111)

The decomposition of formic acid on Zn/Pd(111) was studied using Temperature Programmed Desorption and High Resolution Electron Energy Loss Spectroscopy. On Pd(111), HCOOH decomposes via both dehydration and dehydrogenation pathways to produce CO, CO₂, H₂ and H₂O. Small amounts of Zn (<0.1 mL) incorporated the Pd(111) surface were found to increase the stability of formate species and alter their decomposition selectivity to favor dehydrogenation, resulting in an increase in CO₂ production. This difference in reactivity appears to be caused by relatively long range electronic interactions between surface Pd and Zn atoms and may be important in Pd/ZnO methanol steam reforming catalysts which exhibit high selectivities to CO₂ and H₂.     

Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

The reaction of sulfur and oxygen with the gold surface is important in many technological applications, including heterogeneous catalysis, corrosion, and chemical sensors. We have studied reactions on Au(111) using scanning tunneling microscopy (STM) in order to better understand the surface structure and the origin of gold’s catalytic activity. We find that the Au(111) surface dynamically restructures during deposition of sulfur and oxygen and that these changes in structure promote the reactivity of Au with respect to SO₂ and O₂ dissociation. Specifically, the Au(111) herringbone reconstruction lifts when either S or O is deposited on the surface. We attribute this structural change to the reduction of tensile surface stress via charge redistribution by these electronegative adsorbates. This lifting of the reconstruction was accompanied by the release of gold atoms from the herringbone structure. At high coverage, clusters of gold sulfides or gold oxides form by abstraction of gold atoms from regular terrace sites of the surface. Concomitant with the restructuring is the release of gold atoms from the herringbone structure to produce a higher density of low-coordinated Au sites by forming serrated step edges or small gold islands. These undercoordinated Au atoms may play an essential role in the enhancement of catalytic activity of gold in reactions such as oxygen dissociation or SO₂ decomposition. Our results further elucidate the interaction between sulfur and oxygen and the Au(111) surface and indicate that the reactivity of Au nanoclusters on reducible metal oxides is probably related to the facile release of Au from the edges of these small islands. Our results provide insight into the sintering mechanism which leads to deactivation of Au nanoclusters and into the fundamental limitation in the edge definition in soft lithography using thiol-based self-assembled monolayers (SAMs) on Au. Furthermore, the enhanced reactivity of Au after release of undercoordinated atoms from the surface indicate a relatively insignificant role of an oxide support for high reactivity.     

Formic acid decomposition on Au catalysts: DFT,microkinetic modeling,and reaction kinetics experiments

A combined theoretical and experimental approach is presented that uses a comprehensive mean‐field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self‐consistent, generalized gradient approximation (GGA‐PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO₂ + H₂) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is ≤4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1303–1319, 2014     

Towards understanding the bifunctional hydrodeoxygenation and aqueous phase reforming of glycerol

Kinetically coupled reactions of glycerol in water over bifunctional Pt/Al₂O₃ catalysts are explored as a function of the Pt particle size and the reaction conditions. Detailed analysis of the reaction network shows that “reforming” and hydrodeoxygenation require the presence of a bifunctional catalyst, i.e., the presence of an acid–base and a metal function. The initial reaction steps are identified to be dehydrogenation and dehydration. The dehydrogenation of hydroxyl groups at primary carbon atoms is followed by decarbonylation and subsequent water gas shift or by disproportionation to the acid (and the alcohol) followed by decarboxylation. Hydrogenolysis of the C–O and C–C bonds in the alcohols does not occur under the present reaction conditions. Larger Pt particles favor hydrodeoxygenation over complete deconstruction to hydrogen and CO₂.     

Atom-resolved noncontact atomic force microscopic and scanning tunneling microscopic observations of the structure and dynamic behavior of CeO2(1 1 1) surfaces

Atomic-scale structures and dynamic behaviors of CeO₂(1 1 1) surfaces were imaged by noncontact atomic force microscopy (NC-AFM) and scanning tunneling microscopy (STM). Hexagonally arranged oxygen atoms, oxygen point vacancies, multiple oxygen vacancies, and hydrogen adatoms at the surfaces were visualized by atom-resolved NC-AFM observations. Multiple defects were stabilized by displacement of the surrounding oxygen atoms around the multiple defects, which gave enhanced brightness in the NC-AFM image due to a geometric reason. Multiple defects without reconstruction of the surrounding oxygen atoms were reactive and were healed by exposure to O₂ gas and methanol at RT. Successive NC-AFM and STM measurements of slightly reduced CeO₂(1 1 1) surfaces revealed that hopping of surface oxygen atoms faced to the metastable multiple defects was thermally activated even at room temperature (RT) and more promoted at higher temperatures. Heterogeneous feature of the reactivity of surface oxygen atoms with methanol was imaged by successive NC-AFM observations. These observations gave a new insight for understanding the surface structures and behavior of CeO_2−x with the facile oxygen reservoir and oxidation–reduction properties related to the unique catalysis.     

Scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) of heteropolyacid (HPA) self-assembled monolayers (SAMS): connecting nano properties to bulk properties

Nanoscale investigation of Keggin-type heteropolyacid (HPA) self-assembled monolayers (SAMs) was performed by scanning tunneling microscopy (STM) and tunneling spectroscopy (TS) in order to relate surface properties of nanostructured HPA monolayers to bulk redox and acid properties of HPAs. Cation-exchanged, polyatomsubstituted, and heteroatom-substituted HPAs were examined to see the effect of different substitutions. HPA samples were deposited on HOPG surfaces in order to obtain images and tunneling spectra by STM before and after pyridine adsorption. All HPA samples formed well-ordered monolayer arrays, and exhibited negative difference resistance (NDR) behavior in their tunneling spectra. NDR peaks measured for fresh HPA samples appeared at less negative potentials for higher reduction potentials of the HPAs. These changes could also be correlated with the electronegativities of the substituted atoms. Introduction of pyridine into the HPA arrays increased the lattice constants of the two-dimensional HPA arrays by ca. 6 A. Exposure to pyridine also shifted NDR peak voltages of HPA samples to less negative values in the tunneling spectroscopy measurements. The NDR shifts of HPAs obtained before and after pyridine adsorption were correlated with the acid strengths of the HPAs. This work demonstrates that tunneling spectra measured by STM can fingerprint acid and redox properties of HPA monolayers on the nanometer scale. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Oxygen chemisorption at Cu(110) at 120 K: dimers, clusters and mono-atomic oxygen states

Three distinct states of oxygen have been observed at a Cu(110) surface at 120 K by scanning tunnelling microscopy (STM): isolated oxygen adatoms; pairs or dimers, separated by about 6 Å and clusters of five or six atoms arranged anisotropically. There is also evidence for oxygen atoms undergoing ballistic motion as might be expected from “hot” oxygen atoms. Such states of oxygen have been central to the mechanistic models proposed earlier, and based on surface spectroscopic studies, for the oxidation of ammonia at copper surfaces under ammonia-rich conditions.     

Using scanning tunneling microscopy to characterize adsorbates and reactive intermediates on transition metal oxide surfaces

Scanning tunneling microscopy (STM) is demonstrated to be a powerful tool to characterize adsorption and reaction on oxide surfaces by imaging molecular adsorbates and reactive intermediates. The molecules were used to probe surface structure and to study surface reactivity spatially at the atomic level. Results for three systems are presented: alcohol adsorption on WO₃(0 0 1), carboxylates on the anatase polymorph of TiO₂, and propene adsorption on a PdO monolayer on Pd(1 0 0). When the alcohols were exposed to the WO₃(0 0 1)-c(2×2) surface at room temperature the molecules could not be imaged. Heating the surface to temperatures above a water desorption peak associated with alcohol deprotonation, however, allowed 1-propoxide to be imaged. The images reveal that the alkoxide has no preference for defects, rather it binds to W⁶⁺ ions exposed on the fully oxidized c(2×2) surface. Temperature-programmed desorption revealed that alkoxides at these sites undergo only dehydration reactions. To probe the structure of the unusual (1×4) reconstruction on anatase (0 0 1), formic and acetic acid adsorption were used. Following dissociative adsorption, both formate and acetate adsorb solely centered atop the bright rows that define the surface reconstruction, and the molecules are always at least two lattice constants apart. This result may be attributed to carboxylates bridge-bonded to Ti atoms at the center of the bright rows. This finding eliminates several suggested models of the reconstruction and suggests that a recently proposed ad-molecule model is a good representation of the surface structure. Propene was observed to initially randomly adsorb on the PdO monolayer. At higher coverages, however, the adsorbates cluster, disrupting the surface structure and causing the adsorption rate adjacent to the clusters to increase. Temperature-programmed reaction revealed that once propene adsorbs, the oxide monolayer catalyzes its oxidation at lower temperatures than metallic Pd, but that the propene sticking coefficient on the ordered oxide layer is a factor of 5 lower.     

From single crystals to supported nanoparticles in experimental and theoretical studies of H2 oxidation over platinum metals (Pt, Pd): Intermediates, surface waves and spillover

The present paper reviews our investigations concerning the mechanism of H₂ + O₂ reaction on the metal surfaces (Pt, Pd) at different structures: single crystals (Pt(1 1 1), Pt(1 0 0), Pd(1 1 0)); microcrystals (Pt tips); and nanoparticles (Pd–Ti³⁺/TiO₂). Field electron microscopy (FEM), field ion microscopy (FIM), high-resolution electron energy loss spectroscopy (HREELS), XPS, UPS, work function (WF), TDS and temperature-programmed reaction (TPR) methods have been applied to study the kinetics of H₂ oxidation on a nanolevel. The adsorption of both O₂ and H₂ and several dissociative products (H_ads, O_ads, OH_ads) was studied by HREELS. Using the DFT technique the equilibrium states and stretching vibrations of H, O, OH, H₂O, adsorbed on the Pt(1 1 1) surface, have been calculated depending on the surrounding of the metal atoms. Sharp tips of Pt, several hundreds angstroms in radius, were used to perform in situ investigations of the dynamic surface processes. The FEM and FIM studies on the Pt-tip surface demonstrate that the self-oscillations and waves propagations are connected with periodic changes in the surface structure of nanoplane (1 0 0)-(hex) ↔ (1 × 1), varying the catalytic property of metal. The role of defects (Ti³⁺-□_O) in the adsorption centers formation, their stabilization by the palladium nanoparticles, and then the defects participation in H₂ + O₂ steady-state reaction over Pd–Ti³⁺/TiO₂ surface have been studied by XPS, UPS and photodesorption techniques (PhDS). This reaction seems to involve the “protonate” hydrogen atoms (H⁺/TiO_x) as a result of spillover effect: diffusion of H_ads atoms from Pd particles on a TiO_x surface. The comprehensive study of H₂, O₂ adsorption and H₂ + O₂ reaction in a row: single crystals → tips → nanoparticles has shown the same nature of active centers over these metal surfaces.     

The interaction of oxygen with alumina-supported palladium particles

Utilizing a combination of molecular beam techniques and scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions we have studied the interaction of oxygen with an alumina-supported Pd model catalyst as well as the influence of the oxygen pretreatment on the kinetics of the CO oxidation reaction. The Pd particles were deposited by metal evaporation in UHV onto a well-ordered alumina film prepared on a NiAl(110) single crystal. The particle density, morphology and structure are determined by STM both immediately after preparation and after oxygen adsorption and CO oxidation. The oxygen sticking coefficient and uptake in the temperature regime between 100 and 500 K and the kinetics of the CO oxidation reaction are quantitatively probed by molecular beam techniques. It is found that starting at temperatures below 300 K the Pd particles rapidly incorporate large amounts of oxygen, finally reaching stoichiometries of PdO_>0.5. STM shows, that neither the overall particle shape nor the dispersion is affected by the oxygen and CO treatment. Only after saturation of the bulk oxygen reservoir are stable CO oxidation conditions obtained. In the low-temperature regime (<500 K), only the surface oxygen, but not the bulk and subsurface oxygen is susceptible to the CO oxidation. The activation energies for the Langmuir–Hinshelwood step of the CO oxidation reaction were determined both in the regime of high CO coverage and high surface oxygen coverage. A comparison shows that the values are consistent with previous Pd(111) single crystal results. Thus, we conclude that, at least for the particle size under consideration in this study (5.5 nm), the LH activation energies are neither affected by the reduced size nor by the oxygen pretreatment.     

Transient measurements of lattice oxygen in photocatalytic decomposition of formic acid on TiO2

In the absence of gas-phase O₂, formic acid extracted lattice oxygen from TiO₂ during photocatalytic decomposition (PCD) at room temperature. The amount of oxygen extracted was determined by interrupting PCD of a monolayer of formic acid after various reaction times and measuring O₂ uptake in the dark. After surface oxygen was depleted by PCD, oxygen diffused from the bulk to replenish the surface oxygen vacancies. The rate of oxygen diffusion to the surface was determined by measuring O₂ uptake after various dark times. A small fraction of the CO₂ that formed during PCD remained on the reduced sites of the TiO₂ surface, but this CO₂ was displaced by O₂ adsorption at room temperature.     

Basic oxide-supported Ru catalysts for liquid phase glycerol hydrogenolysis in an additive-free system

Several basic oxide-supported Ru catalysts (Ru/CeO₂, Ru/La₂O₃ and Ru/MgO) were prepared and evaluated for the hydrogenolysis of glycerol. The Ru catalysts were characterized by inductively coupled plasma–atomic emission spectroscopy, nitrogen adsorption, powder X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Ru/CeO₂ showed the best performance in the reaction, which is associated with its smaller metal particle size and the weak surface basicity feature of CeO₂. 1,2-Propanediol is obtained as the main product through a dehydrogenation–dehydration–hydrogenation mechanism. The oxidation product lactic acid can be formed by a Cannizzaro reaction from the pyruvaldehyde intermediate.     

Comparative Theoretical Study of Adsorption and Dehydrogenation of Formic Acid, Hydrazine and Isopropanol on Pd(111) Surface

Abstract  

Adsorption and dehydrogenation of formic acid, hydrazine and isopropanol have been investigated using periodic density functional theory (DFT). All the intermediates and transition states have been optimized and the preferred reaction pathways have been found. The adsorption energies for the most stable mode of formic acid, hydrazine and isopropanol are 38.6 kJ/mol, 63.9 kJ/mol and 46.1 kJ/mol, respectively. The dehydrogenation mechanisms of formic acid, hydrazine and isopropanol on Pd(111) surface are proposed and calculated. According to the calculation results, dehydrogenation of formate is more favorable than those of other molecules/groups, and that can be an explanation for the high reactivity of formats in Pd catalyzed transfer hydrogenation.     

Insights into surface reactivity: formic acid oxidation on Cu(110) studied using STM and a molecular beam reactor

Using a combination of STM and molecular beam reactor data we summarise some important features of a model reaction (formic acid oxidation on Cu(110)) which is of general significance to surface reactivity and to catalysis. Three such features are highlighted here. The first concerns the role of weakly held species (possibly physisorbed) in surface reactions. These species, although of very short lifetime on the surface, can, nevertheless, diffuse over long distances to “find” a sparse distribution of active sites. Thus a very low coverage of oxygen on the surface of Cu(110) increases the sticking probability of all the formic acid molecules which strike the surface to high value (0.82), even though the clean surface is relatively unreactive. The important concept here is the “diffusion circle” or “collection zone” which represents the area of surface visited by the molecule in its short sojourn in the weakly held state. The second theme concerns the concept of the “flexible surface”. We show that the involvement of surface atoms in reactions directs the structure and reactivity for a particular reaction. For formic acid oxidation the liberation of Cu atoms during the removal of oxygen as water leads to gross restructuring of the surface and can lead to “compression” of one reactant (the oxygen in this case) into a lower area, higher local coverage, unreactive state (the c(6×2) oxygen structure). Thirdly, and finally, it is proposed that, for many surface reactions, the surface acts in an analogous way to a solvent, supporting a “dissolved” (highly mobile and fluxional) phase of intermediates at low coverage, which crystallise out above a critical coverage (the 2D “solubility limit”). This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of manganese on Cu/SiO2 catalysts for the dehydrogenation of cyclohexanol to cyclohexanone

The effect of the addition of manganese to Cu/SiO₂ catalysts for cyclohexanol dehydrogenation reaction was investigated. At reaction temperature of 250 °C, the conversion and the selectivity to cyclohexanone were both increased with the addition of manganese to Cu/SiO₂ catalyst. However, as the reaction temperature was further increased, higher loading of manganese in Cu/SiO₂ catalyst led to a decrease in the conversion of cyclohexanol. Manganese in Cu/ SiO₂ catalyst decreased the reduction temperature of copper oxide, increased the dispersion of copper metal, and decreased the selectivity to cyclohexene. It was found that the dehydration of cyclohexanol to cyclohexene occurred on the intermediate acid sites of catalyst. At high Mn loading, catalyst surface was more enriched with manganese in used catalyst compared to that in freshly calcined or reduced catalyst, which may account for the sharp decrease of the conversion at high temperature of 390 °C. Upon reduction, copper manganate on silica was decomposed into fine particles of copper metal and manganese oxide (Mn₃O₄).     

Effect of preparation method on the acidities of Al-B-O x mixed oxides

A series of Al-B-O _x metal oxides with various Al/B ratios were prepared with impregnation and coprecipitation methods. The surface acidic properties of these catalysts were examined by temperature-programmed desorption (TPD) of ammonia and the dehydration reaction of isopropanol. The dehydration reaction was carried out in a continuous-flow microreactor at 130–260 °C under atmospheric pressure. The results of TPD of ammonia indicated that the surface acidity of Al-B-O _x material is medium-strong. The acidic strengths are approximately the same for all the Al-B-O _x samples, regardless of its preparation method. In addition, their acid strengths are much stronger than that of pure alumina. However, the acid concentration is increased with decreasing the Al/B atomic ratio of the catalyst. The dehydration activities of these catalysts are increased with decreasing the Al/B atomic ratios of the samples. The results also indicated that the addition of boron on alumina, no matter what preparation method is used, could significantly enhance the acidities of the catalysts. A compensation effect was observed in isopropanol dehydration reaction over these catalysts. The preexponential factor decreases and activation energy increases with increasing Al/B ratio of the catalyst. The results can be interpreted in terms of the acidity of the catalyst.     

Study of the low-temperature reaction between CO and O2 over Pd and Pt surfaces

Field electron microscopy (FEM), high-resolution electron energy loss spectroscopy (HREELS), molecular beams (MB) and temperature-programmed reaction (TPR) have been applied to the study of the kinetics of CO oxidation at low temperature, and to determine the roles of subsurface atomic oxygen (O_sub) and surface reconstruction in self-oscillatory phenomena, on Pd(111), Pd(110) and Pt(100) single crystals and on Pd and Pt tip surfaces. It was found that high local concentrations of adsorbed CO during the transition from a Pt(100)-hex reconstructed surface to the unreconstructed 1×1 phase apparently prevents oxygen atoms from occupying hollow sites on the surface, and leads to the appearance of a weakly bound active adsorbed atomic oxygen (O_ads) state in an on-top or bridge position. It was also inferred that subsurface oxygen O_sub on the Pd(110) surface may play an important role in the formation of new active sites for the weakly bound O_ads atoms. Experiments with ¹⁸O isotope labeling clearly show that the weakly bound atomic oxygen is the active form of oxygen that reacts with CO to form CO₂ at T 140–160 K. Sharp tips of Pd and Pt, several hundreds angstroms in diameter, were used to perform in situ investigations of dynamic surface processes. The principal conclusion from those studies was that non–linear reaction kinetics is not restricted to macroscopic planes since: (i) planes as small as 200 Å in diameter show the same non-linear kinetics as larger flat surfaces; (ii) regular waves appear under conditions leading to reaction rate oscillations; (iii) the propagation of reaction–diffusion waves involves the participation of different crystal nanoplanes via an effective coupling between adjacent planes.