Density Functional Theory Study of Selectivity Considerations for C–C Versus C–O Bond Scission in Glycerol Decomposition on Pt(111)

Glycerol decomposition via a combination of dehydrogenation, C?CC bond scission, and C?CO bond scission reactions is examined on Pt(111) with periodic Density Functional Theory (DFT) calculations. Building upon a previous study focused on C?CC bond scission in glycerol, the current work presents a first analysis of the competition between C?CO and C?CC bond cleavage in this reaction network. The thermochemistry of various species produced from C?CO bond breaking in glycerol dehydrogenation intermediates is estimated using an extension of a previously introduced empirical correlation scheme, with parameters fit to DFT calculations. Br?nsted?CEvans?CPolanyi (BEP) relationships are then used to estimate the kinetics of C?CO bond breaking. When combined with the previous results, the thermochemical and kinetic analyses imply that, while C?CO bond scission may be competitive with C?CC bond scission during the early stages of glycerol dehydrogenation, the overall rates are likely to be very low. Later in the dehydrogenation process, where rates will be much higher, transition states for C?CC bond scission involving decarbonylation are much lower in energy than are the corresponding transition states for C?CO bond breaking, implying that the selectivity for C?CC scission will be high for glycerol decomposition on smooth platinum surfaces. It is anticipated that the correlation schemes described in this work will provide an efficient strategy for estimating thermochemical and kinetic energetics for a variety of elementary bond breaking processes on Pt(111) and may ultimately facilitate computational catalyst design for these and related catalytic processes.     

Structure sensitivity of alcohol reactions on (110) and (111) palladium surfaces

A temperature programmed reaction/desorption (TPD) study of decomposition pathways of methanol, ethanol, 1-propanol and 2-propanol was conducted on the clean Pd(110) surface under ultra-high vacuum conditions. No alcohol underwent C-O scission. Alcohols appear to react on this clean surface via the same dehydrogenation and decarbonylation steps observed on the Pd(111) surface. In contrast to previous reports noting substantial differences in methanol chemistry on the Pt(110) and (111) surfaces, the reactions of methanol and ethanol were found to be the same on the Pd(110) and (111) surfaces, giving rise to H₂ plus CO from methanol, and H₂, CO, and CH₄ from ethanol. The C₃ alcohols, 1- and 2-propanol, did produce somewhat different products on the Pd(110) and (111) surfaces, but these differences can be accounted for by differences in the chemistry of intermediate reaction products, rather than different reaction pathways of the parent alcohols.     

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

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, CH₃O 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 sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O 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 CH₃OH and CH₂OH, 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 CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

In situ X-ray studies of crotyl alcohol selective oxidation over Au/Pd(1 1 1) surface alloys

The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys.     

The kinetics of methanol oxidation on a supported Pd model catalyst: molecular beam and TR-IRAS experiments

Combining a multi-molecular-beam approach and in situ time-resolved IR reflection absorption spectroscopy (TR-IRAS), we investigate the kinetics of methanol oxidation on a well-defined supported Pd model catalyst. The model catalyst is prepared under ultra-high-vacuum (UHV) conditions by Pd deposition onto a well-ordered Al₂O₃ film grown on NiAl (110). In previous studies, this system has been characterized in detail with respect to its geometric and electronic structure and its adsorption properties. Crossing molecular beams of methanol and oxygen on the sample surface, we systematically probe the rate of total methanol oxidation to CO₂ as a function of surface temperature and reactant fluxes. The results are compared with equivalent experiments for the related CO oxidation reaction. Pronounced differences are observed in the kinetics of the two processes, both under steady state and under transient conditions. The dissimilarities can be related to the dehydrogenation step of methanol, which is found to be strongly inhibited at high oxygen coverage. At low oxygen fluxes, CO is formed as the main product of methanol decomposition. Via a three-beam isotope-exchange experiment combined with TR-IRAS, the kinetics of CO formation is investigated as a function of reactant fluxes and surface temperature. Mean-field simulations of the kinetics are performed in a two-step procedure. First, the kinetics of CO oxidation is described, both under steady state and transient conditions. In a second step the microkinetic model is extended to include the formation of CO formed by methanol dehydrogenation. A comparison with the experimental data indicates that the transient kinetics cannot be fully described by a mean-field approach.     

Decomposition of Ethanol Over Ru(0001): A DFT Study

We studied decomposition pathways of ethanol on Ru(0001) with periodic slab-model calculations using a DFT-GGA approach. We calculated the adsorption modes of ethanol and several of its dehydrogenation products and we evaluated reaction energies as well as activation barriers of pertinent dehydrogenation, C–C, and C–O cleavage steps. The calculated barrier heights of C–C and C–O scission steps can be related to the number of hydrogen atoms bound to the C1–C2 and C1–O moieties of the intermediates, respectively. Two counteracting effects are at work, increasing with each dehydrogenation: (i) higher order of the pertinent bond of the adsorbate, and (ii) stronger substrate-surface interaction and thus better stabilization of the transition state. For most intermediates we determined C–O cleavage to be both kinetically and thermodynamically favored over C–C scission, except for the highly dehydrogenated species CH _k CO (k = 1, 2). Based on the calculated energetics, the most likely decomposition pathway, with a rate-determining barrier at 77 kJ·mol^?1, leads to the formation of ketene CH₂CO and subsequent C–C cleavage yielding methylene and CO.     

Combined UHV and ambient pressure studies of 1,3-butadiene adsorption and reaction on Pd(1 1 1) by GC,IRAS and XPS

The hydrogenation of 1,3-butadiene on Pd(1 1 1) at 300 K was studied at atmospheric pressure by infrared reflection absorption spectroscopy (IRAS) and gas chromatography (GC). Kinetic measurements showed 1-butene, trans-2-butene and cis-2-butene as primary products. Once 1,3-butadiene had been completely consumed, 1-butene was re-adsorbed on the surface producing trans-/cis-2-butene through isomerization and n-butane through hydrogenation. These results were corroborated by in situ IRAS spectroscopy. Post-reaction analysis by X-ray photoelectron spectroscopy (XPS) in the C1s region revealed a band at 284.2 eV, corresponding to adsorbed butadiene and/or carbonaceous deposits. Quantification of this peak revealed a total carbon coverage of 0.3 ML. Nevertheless, deactivation due to carbon deposition was a minor effect under our reaction conditions, as indicated by the kinetics of the subsequent butene hydrogenation reaction. Temperature-dependent XPS experiments after butadiene adsorption at 100 K indicated a high stability of the diene molecule with hardly any desorption and/or decomposition up to 500 K. Above this temperature, butadiene decomposed to carbon species that eventually dissolved in the Pd bulk above 700 K.     

The study of photochemical reactions in polyoximurethane

Summary The irradiation of polyoximurethane at 77K yields only iminoxy radicals. The gaseous products are CO and CO₂. The mechanism of photodegradation, including 2 initial processes of N-O and C-O bond scission is discussed. The ratio between the initial processes depends on the wavelength of the light used. Only the C-O bond cleavage results in polymer degradation.     

Reaction kinetics and in situ sum frequency generation surface vibrational spectroscopy studies of cycloalkene hydrogenation/dehydrogenation on Pt(111): Substituent effects and CO poisoning

The influence of substituent effects and CO poisoning were examined during the hydrogenation/dehydrogenation of cycloalkenes (cyclohexene and 1- and 4-methylcyclohexene) on a Pt(111) single crystal. Reaction rates for both hydrogenation and dehydrogenation decreased when a methyl group was added to the cycloalkene ring. The location of a methyl group relative to the CC double bond was influential in the overall kinetics for both reaction pathways. All cycloalkenes demonstrated “bend-over” Arrhenius behavior, after which rates for hydrogenation and dehydrogenation decreased with increasing temperature (inverse Arrhenius behavior). This is explained in terms of a change in surface coverage of the reactive cycloalkene. The potential importance of hydrogen effects is discussed. Introduction of CO in the Torr pressure range (0.015 Torr) led to a decrease in turnover frequency and increase in apparent activation energy for both the hydrogenation and dehydrogenation of all cycloalkenes. Sum frequency generation (SFG) surface vibrational spectroscopy revealed that upon adsorption, the three cycloalkenes form a surface species with similar molecular structure. SFG results under reaction conditions in the presence of CO demonstrated that the cycloalkene coverage is low on a CO-saturated surface. Substituted cyclohexenes were more sensitive than cyclohexene to the presence of adsorbed CO, with larger increases in the apparent activation energy, especially in the case of dehydrogenation. A qualitative explanation for the changes in activity with temperature and the increase in apparent activation energy for cycloalkene hydrogenation/dehydrogenation in the presence of CO is presented from a thermodynamic and kinetic perspective.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Effect of Carbon Deposits on Reactivity of Supported Pd Model Catalysts

Alumina-supported Pd model catalysts were prepared by Pd evaporation onto a thin alumina film grown on a NiAl(110) substrate. Adsorption and co-adsorption of ethene, CO and hydrogen on Pd/Al₂O₃/NiAl(110) covered by carbon species, formed by ethene dehydrogenation at 550 K, was studied by temperature programmed desorption (TPD). TPD results show that carbon deposits do not prevent adsorption but inhibit dehydrogenation of di- bonded ethene. Carbon species suppress CO adsorption in the highly coordinated sites and also suppress the formation of hydrogen ad-atoms on the surface. The ethene hydrogenation reaction performed by co-adsorption of hydrogen and ethene is inhibited by the presence of carbon deposits. The inhibition is independent of particle size studied (1-3 nm). The effects are rationalized in terms of a site-blocking behavior of carbon species occupying highly coordinated sites on the Pd surface.     

Advances in Infrared Spectroscopy of Catalytic Solid–Liquid Interfaces: The Case of Selective Alcohol Oxidation

Progress in the use of ATR-IR spectroscopy to improve the understanding of liquid-phase heterogeneous catalytic reactions is illustrated using the example of the oxidation of benzyl alcohol over Pd/Al₂O₃ and Bi–Pd/Al₂O₃. The in situ studies performed in both batch and continuous reactor cells provide rich information on the reaction pathway and important facets of the mechanism, such as the nature of active Pd sites and the effect of the Bi-promoter. The combination of CO site blocking prior to reaction and isotopic labeling suggests that alcohol dehydrogenation occurs uniformly over Pd nanoparticles, but only selected sites may allow desorption of the product benzaldehyde thus providing the required selectivity. Promotion of Pd/Al₂O₃ using bismuth produces infrared spectra free of adsorbed CO. This information demonstrates that Bi is deposited on selected adsorption sites (terraces rather than defects) and simultaneously confirms that open terraces favor product decomposition. Experiments performed in the continuous reactor cell using different catalyst film thickness show that reactions can be studied under kinetic or mass transfer limited conditions depending on catalyst film thickness. This allowed to study the alcohol oxidation under conditions of oxygen diffusion limitation, which are preferably applied in praxis in order to prevent catalyst deactivation by over-oxidation.     

Understanding the Catalytic Conversion of Automobile Exhaust Emissions Using Model Catalysts: CO + NO Reaction on Pd(111)

The CO + NO reaction is one of the profoundly important reactions that take place on Pd-based industrial three-way catalysts (TWC). In this review, we discuss results from polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and conventional IRAS experiments on CO adsorption, NO adsorption and the CO + NO reaction on a Pd(111) model catalyst surface within a wide range of pressures (10^?6–450 Torr) and temperatures (80–650 K). It will be shown that these studies allow for a detailed understanding of the adsorption behavior of these species as well as the nature of the products that are formed during their reaction under realistic catalytic conditions. CO adsorption experiments on Pd(111) at elevated pressures reveal that CO overlayers exhibit similar adsorption structures as found for ultrahigh vacuum (UHV) conditions. On the other hand, in the case of the CO + NO reaction on Pd(111), the pressure dependent formation of isocyanate containing species' was observed. The importance of this observation and its effects on the improvement of the catalytic NO _x abatement is discussed. The kinetics of the CO + NO reaction on Pd(111) were also investigated and the factors affecting its selectivity are addressed.     

Effects of Alloying Pd and Au on the Hydrogenation of Ethylene: An ab initio-Based Dynamic Monte Carlo Study

An ab initio-based dynamic Monte Carlo simulation was developed and used to examine the kinetics of ethylene hydrogenation over Pd and PdAu alloys. The intrinsic activation barriers, overall reaction energies and chemisorption energies were calculated from first-principles density functional theoretical calculations. Lateral interactions were modeled by fitting ab initio data to semi-empirical bond order conservation and force field models. The results indicate that the intrinsic activation barriers for ethylene hydrogenation were considerably reduced from 15 to 7-8 kcal/mol due to the intermolecular interactions that take place on the surface at higher coverages. At higher temperatures or lower partial pressures of hydrogen, ethylene decomposition paths to the formation of ethylidyne become important. Alloying the surface with Au influences the intrinsic kinetics for hydrogenation by reducing the activation barrier for hydrogenation but increasing the barriers for H₂ dissociation and ethylidyne formation. This is primarily due to geometric effects that result from alloying. Electronic effects, while present, are significantly smaller. Despite its influence on specific elementary steps, Au appears to have little effect on the calculated turnover frequencies for ethane formation. There are relatively minor increases in the activation barrier from 7.0 to 7.2 to 8.0 as we move from Pd(111) to Pd 87.5% Au 12.5% to Pd 66.7% Au 33.3% respectively. The qualitative effects of Au as well as the quantitative apparent activation barriers reported here are consistent with known experimental results. Au reduces the binding energy of ethylene, which increases the surface hydrogenation activity. However, Au also reduces the number of sites that can activate hydrogen. This reduces the hydrogen surface coverage and subsequently decreases the rate of ethylene hydrogenation. These effects (the weaker metal--adsorbate bonds and the decreased hydrogen surface coverage) balance each other out whereby the addition of Au shows little effect on the simulated turnover frequency on a per Pd atom basis. The primary influence of Au therefore is to decrease the ethylene decomposition paths that lead to ethylidyne and CH_x products.     

Oxygen-induced Restructuring of a Pd/Fe3O4 Model Catalyst

We have studied the influence of oxygen on the structure and morphology of a Pd/Fe₃O₄ model catalyst using molecular beam (MB) methods, IR reflection absorption spectroscopy (IRAS) and scanning tunneling microcopy (STM). The model catalyst was prepared under ultrahigh vacuum (UHV) conditions by physical vapor deposition (PVD) and growth of Pd nanoparticles on an ordered Fe₃O₄ thin film on Pt(111). It is found that surface oxides are formed on the Pd nanoparticles even under mild oxidation conditions (temperatures of 500 K and effective oxygen partial pressures of around 10⁻⁶ mbar). These surface oxides are initially generated at the Pd/Fe₃O₄ interface and, subsequently, are formed at the Pd/gas interface. The process of formation and reduction of surface and interface oxides on the Pd particles is fully reversible in that all oxides formed can be fully reduced. As a result, the oxide phase acts like a storage medium for oxygen during oxidation reactions, as probed via CO oxidation. The process of surface and interface oxidation is directly connected with the onset of a non-reversible sintering process of the Pd particles. It is suggested that this sintering process occurs via a mobile Pd oxide species, which is stabilized by interaction with the Fe₃O₄ support. The restructuring is monitored via STM and IRAS using CO as a probe molecule. In addition to a decrease in particle density and Pd surface area, a reshaping of the particles occurs, which is characterized by the formation of well-ordered crystallites and with a relatively large fraction of (100) facets. After a few oxidation/reduction cycles at 500 K, the sintering process becomes very slow and the system shows a stable behavior under conditions of CO oxidation.     

Aqueous Phase Glycerol Reforming with Pt and PtMo Bimetallic Nanoparticle Catalysts: The Role of the Mo Promoter

The turnover rate (TOR, normalized to sites measured by CO chemisorption before reaction) and selectivity for the aqueous phase reforming of glycerol have been determined for Pt/C and PtMo/C catalysts. While the TOR of PtMo/C is higher than that of Pt/C by about 4 times at comparable conversion, the selectivity to C–O bond cleavage is higher, thus reducing the H₂ yield at high conversion. Under reaction conditions on Pt/C, CO is observed as the most abundant Pt surface species with a fractional coverage of about 0.6 using operando X-ray absorption spectroscopy. Since there is little CO in the effluent (CO₂:CO ratios > 100:1, when CO is detected), it is thought that surface CO is converted to H₂ and CO₂ by the water gas shift reaction. DFT calculations suggest that the role of metallic Mo is to alter the electronic properties of Pt lowering the binding energy of CO and reducing the activation energies of dehydrogenation and C–O bond cleavage. Because the activation energy for C–O cleavage is lowered more than for dehydrogenation, the selectivity for C–O bond cleavage is increased, ultimately lowering the H₂ yield compared to Pt/C.     

Hydrogen Production from Ethanol over Rh–Pd/CeO2 Catalysts

The work presents a study by temperature programmed desorption, in situ infra red spectroscopy and catalytic steam reforming of ethanol (SRE) over CeO₂ and the bimetallic Pd-Rh/CeO₂; comparison with the monometallic catalysts (Rh/CeO₂ and Pd/CeO₂) was also made for the steam reforming study. Comparing TPD of ethanol over CeO₂ and the bimetallic catalysts indicated two main differences: the direct oxidation route to acetate over CeO₂ is suppressed by the presence of the metal and the lowering of the dehydrogenation reaction temperature by about 100 K. In situ IR study indicated that the bimetallic catalyst breaks the carbon–carbon bond of ethanol at low temperature <400 K, as evidenced by the presence of adsorbed CO species. SRE over ½ wt.% Rh–½ wt.% Pd/CeO₂, at 770 K at realistic conditions showed that maximum conversion and selectivity could be achieved. This high activity considering the very small amounts of transition metals on CeO₂ is discussed in light of their electronic and geometric effects.     

Identification of step-edge sites on Rh nanoparticles for facile CO dissociation

Understanding the dependence of the rate of catalytic reactions on metal nanoparticle size remains one of the great challenges in heterogeneous catalysis. Especially, methods to probe step-edge sites on technical supported nanoparticle catalysts are needed to put structure–activity relations on a surer footing. Herein, we demonstrate that N₂ is a useful IR probe for the semi-quantitative identification of step-edge sites on zirconia-supported metallic Rh nanoparticles. The intensity of the strongly perturbed band at 2205 cm^− 1 correlates with the CO bond dissociation rate under conditions relevant to the Fischer–Tropsch reaction. Due to the intermediate reactivity of Rh, step-edge sites are required to dissociate the strong CO bond. DFT calculations show that N₂ prefers to adsorb on top of low-coordinated surface atoms such as steps, corners and edges. The occurrence of the intensity maximum at intermediate particle size is explained by the presence of surface overlayers on terraces that give rise to step-edges. These step-edge sites are important in the dissociation of di-atomic molecules such as CO, NO and N₂.     

Fabrication of an Effusive Molecular Beam Instrument for Surface Reaction Kinetics—CO Oxidation and NO Reduction on Pd(111) Surfaces

A simple molecular beam instrument (MBI) was fabricated for measuring the fundamental parameters in catalysis such as, sticking coefficient, transient and steady state kinetics and reaction mechanism of gas/vapor phase reactions on metal surfaces. Important aspects of MBI fabrication are given in detail. Nitric oxide (NO) decomposition and NO reduction with carbon monoxide (CO) on Pd(111) surfaces were studied. Interesting results were observed for the above reactions and they support the efficiency of the MBI to derive the fundamental parameters of adsorption and catalysis. Sustenance of CO oxidation at 400 K is dependent mostly on the absence of CO-poisoning; apparently, CO + O recombination is the rate determining step ≤400 K. NO adsorption measurements on Pd(111) surface clearly indicating a typical precursor kinetics. Displacement of the chemisorbed CO by NO on Pd(111) surfaces was observed directly with NO + CO beams in the transient kinetics. It is also relatively easy to identify the rate-determining step directly from the MBI data and the same was demonstrated for the above reactions.     

A DFT Investigation of the Dehydrogenation of Tetrahydropyrrole on Pt(111)

van der Waals (vdW) corrected periodic density functional theory (DFT) calculations and microkinetic modeling were employed to elucidate the mechanism and energetics of dehydrogenation of tetrahydropyrrole, a model organic hydrogen carrier, on Pt(111). The overall dehydrogenation is endothermic while individual dehydrogenation steps can be endothermic or exothermic. The calculations indicate that the first dehydrogenation step proceeds via the C–H scission of an α-carbon (with respect to nitrogen). Subsequently, the remaining α- and two β-C–H bonds can be dissociated via multiple energetically similar pathways, wherein the second dehydrogenation step is rate controlling. The inclusion of vdW forces shifts the potential energy surface (PES) downward by an average 0.6 eV indicating that while the activation barriers remain unaffected, there can be significant influence on the overall rate due to increased coverage of intermediates. N-methylation of tetrahydropyrrole weakens adsorption of initial intermediates, indicating that the PES may generally be shifted up thereby affecting the overall kinetics. Finally, there exists a generally linear relationship between the transition state and final state energies of the dehydrogenation reaction.