Nitrogen‐doped C60 as a robust catalyst for CO oxidation

The O₂ activation and CO oxidation on nitrogen‐doped C₅₉N fullerene are investigated using first‐principles calculations. The calculations indicate that the C₅₉N fullerene is able to activate O₂ molecules resulting in the formation of superoxide species ( ) both kinetically and thermodynamically. The active superoxide can further react with CO to form CO₂ via the Eley–Rideal mechanism by passing a stepwise reaction barrier of only 0.20 eV. Ab initio molecular dynamics (AIMD) simulation is carried out to evidence the feasibility of the Eley–Rideal mechanism. In addition, the second CO oxidation takes place with the remaining atomic O without any activation energy barrier. The full catalytic reaction cycles can occur energetically favorable and suggest a two‐step Eley–Rideal mechanism for CO oxidation with O₂ catalyzed by the C₅₉N fullerene. The catalytic properties of high percentage nitrogen‐doped fullerene (C₄₈N₁₂) is also examined. This work contributes to designing higher effective carbon‐based materials catalysts by a dependable theoretical insight into the catalytic properties of the nitrogen‐doped fullerene. © 2017 Wiley Periodicals, Inc.     

Geometric stability of PtFe/PdFe embedded in graphene and catalytic activity for CO oxidation

The direct methanol fuel cell (DMFC) is considered as a promising power source, because of its abundant fuel source, high energy density and environmental friendliness. Among DMFC anode materials, Pt and Pt group metals are considered to be the best electrocatalysts. The combination of Pt with some specific transition metal can reduce the cost and improve the tolerance toward CO poisoning of pure Pt catalysts. In this paper, the geometric stabilities of PtFe/PdFe atoms anchored in graphene sheet and catalytic CO oxidation properties were investigated using the density functional theory method. The results show that the Pt (Pd) and Fe atoms can replace C atoms in graphene sheet. The CO oxidation reaction by molecular O₂ on PtFe–graphene and PdFe–graphene was studied. The results show that the Eley–Rideal (ER) mechanism is expected over the Langmuir–Hinshelwood mechanism for CO oxidation on both PtFe–graphene and PdFe–graphene. Further, complete CO oxidation on PtFe–graphene and PdFe–graphene proceeds via a two‐step ER reaction: CO(gas) + O₂(ads) → CO₂(ads) + O(ads) and CO(gas) + O(ads) → CO₂(ads). Our results reveal that PtFe/PdFe commonly embedded in graphene can be used as a catalyst for CO oxidation. The microscopic mechanism of the CO oxidation reaction on the atomic catalysts was explored.     

A Comparative Study of CO Oxidation on Nitrogen‐ and Phosphorus‐Doped Graphene

The geometry, electronic structure, and catalytic properties of nitrogen‐ and phosphorus‐doped graphene (N‐/P‐graphene) are investigated by density functional theory calculations. The reaction between adsorbed O₂ and CO molecules on N‐ and P‐graphene is comparably studied via Langmuir–Hinshelwood (LH) and Eley–Rideal (ER) mechanisms. The results indicate that a two‐step process can occur, namely, CO+O₂→CO₂+O_ads and CO+O_ads→CO₂. The calculated energy barriers of the first step are 15.8 and 12.4 kcal mol^?1 for N‐ and P‐graphene, respectively. The second step of the oxidation reaction on N‐graphene proceeds with an energy barrier of about 4 kcal mol^?1. It is noteworthy that this reaction step was not observed on P‐graphene because of the strong binding of O_ads species on the P atoms. Thus, it can be concluded that low‐cost N‐graphene can be used as a promising green catalyst for low‐temperature CO oxidation.     

DFT calculations on the catalytic oxidation of CO over Si-doped (6,0) boron nitride nanotubes

The oxidation of carbon monoxide (CO) is important for a series of technological and environmental applications. In this work, the catalytic oxidation of CO on Si-doped (6,0) boron nitride nanotubes (BNNTs) is investigated by using density functional theory calculations. Reaction barriers and corresponding thermodynamic parameters were calculated using the M06-2X, B3LYP and wB97XD density functionals with 6-31G* basis set. Our results indicate that a vacancy defect in BNNT strongly stabilizes the Si adatom and makes it more positively charged. This charging enhances the adsorption of reaction gases (O₂ and CO) and results in the change of the electronic structure properties of the tube. The calculated barrier of the reaction CO + O₂ → CO₂ + O_ads on Si-doped BNNTs following the Langmuir–Hinshelwood is lower than that on the traditional noble metal catalysts. The second step of the oxidation would be the Eley–Rideal reaction (CO + O_ads → CO₂) with an energy barrier of about 1.8 and 10.1 kcal/mol at M06-2X/6-31G* level. This suggests that the CO oxidation catalyzed by the Si-doped BNNTs is likely to occur at the room temperature. The results also demonstrate that the activation energies and thermodynamic quantities calculated by M06-2X, B3LYP and wB97XD functionals are consistent with each other.     

Esterification reaction kinetics of acetic acid and n-pentanol catalyzed by sulfated zirconia

This study reports experimental data and kinetic modeling of acetic acid esterification with n-pentanol using sulfated zirconia as a catalyst. Reactions were carried out in an isothermal well-mixed batch reactor at different temperatures (50-80°C), n-pentanol to acid molar ratios (1:1-3:1), and catalyst loadings (5-10 wt% in relation to the total amount of acetic acid). The reaction mechanism regarding the heterogeneous catalysis was evaluated considering pseudo-homogeneous, Eley–Rideal, and Langmuir–Hinshelwood model approaches. The reaction mixture was considered a nonideal solution and the UNIQUAC thermodynamic model was used to take into account the nonidealities in the liquid phase. The results obtained indicated that increases in the temperature and catalyst loading increased the product formation, while changes in the n-pentanol to acetic acid molar ratio showed no significant effect. The estimated enthalpy of the reaction was −8.49 kJ mol⁻¹, suggesting a slightly exothermic reaction. The Eley–Rideal model, with acetic acid adsorbed on the catalyst as the limiting step, was found to be the most significant reaction mechanism.     

Computer Simulation of Eley‐Rideal Reactions Over Rough Surface

The effect of surface roughness on an Eley‐Rideal reaction mechanism is studied. The rough surfaces are generated over a 2‐dimensional square lattice using the random deposition model. In an Eley‐Rideal reaction mechanism, a reacting particle approaches from the bulk and reacts with an active site upon collision with it. Three different rough surfaces are considered for the study. Multifractal scaling analysis is performed where the complex distribution of reaction probabilities is analyzed. Two cases of reactions are considered. 1) The reacting particle reacts at its first contact to the surface and 2) the reacting particle diffuses till it finds the lowest‐height position and reacts. The results obtained from the above two cases are compared. Significant differences between τ(q) and f(α) multifractal spectra for these two cases are found. The larger deviation from linearity in the τ(q) curves for the latter than the former gives wider f(α) spectra, indicating greater heterogeneity in the reaction probability distribution. Dynamic scaling theory is also applied on the Eley‐Rideal reaction mechanism over the surface with different surface roughnesses to obtain the two scaling parameters α_d and β_d. The values of α_d and β_d are found to be negative.     

Theoretical study of the CO catalytic oxidation on Au/SAPO‐11 zeolite

Quantum chemistry calculations were carried out, using ONIOM2 methodology, to investigate the CO adsorption and oxidation on gold supported on Silicoaluminophospates (SAPO) molecular sieves Au/SAPO‐11 catalysts. Two models were studied, one containing one Au atom per site (Au? SAPO‐11), and the other with two Au atoms per site (Au₂? SAPO‐11). The results reveal that the CO adsorption and oxidation are exothermic on Au/SAPO11 with an ΔE of ?41.0 kcal/mol and ΔE = ?52.0 kcal/mol, for the adsorption and oxidation, respectively. On the Au₂? SAPO‐11 model, the CO adsorption and oxidation reaction occur, with a ΔE of ?29.7 kcal/mol and ?52 kcal/mol, respectively. According to our results, the oxidation reaction exhibits an Eley‐Rideal type mechanism with adsorbed CO. The theoretical calculations reveal that this type of material could be interesting to disperse Au and consequently to strengthen its catalytic use for different reactions. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2573–2582, 2010     

Pt/ZrO2:An Efficient Catalyst for Aerobic Oxidation of Toluene in Aqueous Solution

The heterogeneous oxidation of toluene in aqueous medium has been investigated. Artificially contaminated water with aromatic compound (toluene) was exposed to a simple platinized zirconia (1% Pt/ZrO₂) catalyst in the presence of molecular oxygen. This selective oxidation of toluene to benzyl alcohol, benzaldehyde and benzoic acid provides a step for removing toluene from wastewater or converting it into less harmful substances. Different parameters, e.g. the reaction time, temperature, pressure, the amount of catalyst and agitation, etc influenced the toluene conversion and selectivity. Typical batch reactor kinetic data were obtained and fitted to the classical Langmuir‐Hinshelwood model, Mars‐van Krevelen model as well as to the Eley‐Rideal model of heterogeneously catalyzed reactions. The Eley‐Rideal model was found to give a better fit. 1% Pt/ZrO₂ was observed to be the most active for oxidation of toluene at 333 K in oxygenated atmosphere [p(O₂) ca. 101 kPa] with a nominal stirring speed ≧900 r/min. It was found that catalytic oxidation may be an effective method for the removal of volatile organic compounds from aqueous solutions and comparable to other advanced oxidation processes.     

Real-Time Atomic-Scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction

By using in situ aberration-corrected environmental transmission electron microscopy, for the first time at atomic level, the dynamic evolution of the Cu surface is captured during CO oxidation. Under reaction conditions, the Cu surface is activated, typically involving 2–3 atomic layers with the formation of a reversible metastable phase that only exists during catalytic reactions. The distinctive role of CO and O₂ in the surface activation is revealed, which features CO exposure to lead to surface roughening and consequently formation of low-coordinated Cu atoms, while O₂ exposure induces a quasi-crystalline CuOx phase. Supported by DFT calculations, it is shown that crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.     

Bent Carbon Surface Moieties as Active Sites on Carbon Catalysts for Phosgene Synthesis

Active sites in carbon‐catalyzed phosgene synthesis from gaseous CO and Cl₂ have been identified using C₆₀ fullerene as a model catalyst. The carbon atoms distorted from sp² coordination in non‐planar carbon units are concluded to generate active Cl₂. Experiments and density functional theory calculations indicate the formation of a surface‐bound [C₆₀???Cl₂] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two‐step Eley–Rideal‐type mechanism.     

First‐principle calculations on CO oxidation catalyzed by a gold nanoparticle

We have elucidated the mechanism of CO oxidation catalyzed by gold nanoparticles through first‐principle density‐functional theory (DFT) calculations. Calculations on selected model show that the low‐coordinated Au atoms of the Au₂₉ nanoparticle carry slightly negative charges, which enhance the O₂ binding energy compared with the corresponding bulk surfaces. Two reaction pathways of the CO oxidation were considered: the Eley–Rideal (ER) and Langmuir–Hinshelwood (LH). The overall LH reaction O_2(ads) + CO_(gas) → O_2(ads) + CO_(ads) → OOCO_(ads) → O_(ads) + CO_2(gas) is calculated to be exothermic by 3.72 eV; the potential energies of the two transition states ( TS_LH1 and TS_LH2 ) are smaller than the reactants, indicating that no net activation energy is required for this process. The CO oxidation via ER reaction Au₂₉ + O_2(gas) + CO_(gas) → Au₂₉–O_2(ads) + CO_(gas) → Au₂₉–CO_3(ads) → Au₂₉–O_(ads) + CO_2(gas) requires an overall activation barrier of 0.19 eV, and the formation of Au₂₉–CO_3(ads) intermediate possesses high exothermicity of 4.33 eV, indicating that this process may compete with the LH mechanism. Thereafter, a second CO molecule can react with the remaining O atom via the ER mechanism with a very small barrier (0.03 eV). Our calculations suggest that the CO oxidation catalyzed by the Au₂₉ nanoparticle is likely to occur at or even below room temperature. To gain insights into high‐catalytic activity of the gold nanoparticles, the interaction nature between adsorbate and substrate is also analyzed by the detailed electronic analysis. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

A Theoretical Study of the Interaction of Hydrogen and Oxygen with Palladium or Gold Adsorbed on Pyridine‐Like Nitrogen‐Doped Graphene

The interaction of H₂ and O₂ molecules in the presence of nitrogen‐doped graphene decorated with either a palladium or gold atom was investigated by using density functional theory. It was found that two hydrogen molecules were adsorbed on the palladium atom. The interaction of these adsorbed hydrogen molecules with two oxygen molecules generates two hydrogen peroxide molecules first through a Eley–Rideal mechanism and then through a Langmuir–Hinshelwood mechanism. The barrier energies for this reaction were small; therefore, we expect that this process may occur spontaneously at room temperature. In the case of gold, a single hydrogen molecule is adsorbed and dissociated on the metal atom. The interaction of the dissociated hydrogen molecule on the surface with one oxygen molecule generates a water molecule. The competitive adsorption between oxygen and hydrogen molecules slightly favors oxygen adsorption.     

DFT Study of Cyanide Oxidation on Ge-Doped Carbon Nanotubes

In recent years, the discovery of efficient catalyst with low price to cyanide (CN) oxidation in normal temperature is a major concern in the industry. In present study, in first step the carbon nanotubes (CNTss) were doped with Ge and the surface of Ge-doped CNTss via O₂ molecule were activated. In second step the CN oxidation on activated Ge-CNTss surface via Langmuir–Hinshelwood (LH) and Eley–Rideal (ER) mechanisms was investigated. Results show that O₂ activated Ge-CNTs surface can oxidize the CN molecule via Ge-CNTs–O–O* + CN → Ge-CNTs–O–O*–CN → Ge-CNTs–O* + OCN and Ge-CNTs–O* + CN → Ge-CNTs + OCN reactions. Results show that CN oxidation on activated Ge-CNTs surface via the LH mechanism has lower energy barrier than ER mechanism. Finally, calculated parameters reveal that activated Ge-CNTss is acceptable catalyst with low price and high performance for CN oxidation in normal temperature.     

An investigation of the catalytic performance of Fe–Mn/Al2O3 nanocatalyst for light olefins production using RSM method and kinetic study

The Fe–Mn/Al₂O₃ nanocatalysts were manufactured via the sol-gel procedure and were evaluated for Fischer–Tropsch synthesis. The impact of different operational parameters of T, P, and H₂/CO ratio on the catalytic performance for light olefins production has been studied using response surface methodology (RSM). Furthermore, the optimization and modeling of selected responses were also carried out via RSM and historical data design type of DOE; and the best process conditions were found to be T = 365°C, H₂/CO = 1.50, and P = 1.50 bar. The mechanism of CO hydrogenation reaction over the Fe–Mn/Al₂O₃ nanocatalysts was also investigated using the non-linear regression method. It was found that the mechanism of the CO hydrogenation reaction is based on the Eley–Rideal type and the best-fitted equation for this mechanism was found to be −r_CO = KP_COP_H2/1+αP_CO. The obtained value of activation energy (85.20 kJ mol⁻¹) affirmed the absence of internal mass transfer limitations. The physico-chemical properties of the samples were investigated by various techniques of XRD, BET, TPR, TGA, and DSC.     

Titration of oxygen chemisorbed on platinum: Experiment and simulation

The titration of chemisorbed oxygen by carbon monoxide to form carbon dioxide has been studied from 373 to 673 K over polycrystalline platinum. The pressure transients for CO and CO₂ have been measured and simulated numerically. A complex Langmuir–Hinshelwood mechanism is found which fits all the data, and it is not necessary to invoke Eley–Rideal kinetics. The results fall into two temperature regimes, above and below 473 K, which are characterized by different Arrhenius parameters. A change in activation energy with oxygen coverage is also found below 473 K.     

Ordered Porous Nitrogen‐Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N‐Heterocycles

Single‐atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single‐atom sites were stabilized on an ordered porous nitrogen‐doped carbon matrix (ISAS‐Co/OPNC). ISAS‐Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N‐heterocycles to release H₂. ISAS‐Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N‐heterocycles to store H₂, using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS‐Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious‐metal catalysts. The reaction mechanisms are systematically investigated using first‐principles calculations and it is suggested that the Eley–Rideal mechanism is dominant.     

Unveiling the CO Oxidation Mechanism over a Molecularly Defined Copper Single-Atom Catalyst Supported on a Metal–Organic Framework

Elucidating the reaction mechanism in heterogeneous catalysis is critically important for catalyst development, yet remains challenging because of the often unclear nature of the active sites. Using a molecularly defined copper single-atom catalyst supported by a UiO-66 metal–organic framework (Cu/UiO-66) allows a detailed mechanistic elucidation of the CO oxidation reaction. Based on a combination of in situ/operando spectroscopies, kinetic measurements including kinetic isotope effects, and density-functional-theory-based calculations, we identified the active site, reaction intermediates, and transition states of the dominant reaction cycle as well as the changes in oxidation/spin state during reaction. The reaction involves the continuous reactive dissociation of adsorbed O₂, by reaction of O_2,ad with CO_ad, leading to the formation of an O atom connecting the Cu center with a neighboring Zr⁴⁺ ion as the rate limiting step. This is removed in a second activated step.     

Direct Hydrogenation of Dinitrogen and Dioxygen via Eley–Rideal Reactions

Most Eley–Rideal abstraction reactions involve an energetic gas‐phase atom reacting directly with a surface adsorbate to form a molecular product. Molecular projectiles are generally less reactive, may dissociate upon collision with the surface, and thus more difficult to prove that they can participate intact in abstraction reactions. Here we provide experimental evidence for direct reactions occurring between molecular N₂⁺ and O₂⁺ projectiles and surface‐adsorbed D atoms in two steps: first, the two atoms of the diatomic molecule undergo consecutive collisions with a metal surface atom without bond rupture; and second, the rebounding molecule abstracts a surface D atom to form N₂D and O₂D intermediates, respectively, detected as ions. The kinematics of the collisional interaction confirms product formation by an Eley–Rideal reaction mechanism and accounts for inelastic energy losses commensurate with surface re‐ionization. Such energetic hydrogenation of dinitrogen may provide facile activation of its triple bond as a first step towards bond cleavage.     

Surface structure–activity relationships of Cu/ZnGaOX catalysts in low temperature water–gas shift (WGS) reaction for production of hydrogen fuel

A new species’ class of Cu-, Ga- and Zn-based rate catalysts was prepared by a systematic co-precipitation technique at the different related pH values (6.5–8.0) along with calcination functional conditions, influencing components’ physical properties, these were characterized, and their application performance for water–gas shift (WGS) reaction was researched. Substances were analysed by various experimental methods, namely chemisorption, temperature-programmed reduction (TPR) characterisation, diffraction, physisorption and microscopy. A homogenous size dispersion of the compounds with smaller granular particles was obtained for catalysis, implemented with high pH-resulting outputs. H₂ TPR profiles revealed a tailored stronger effect of Cu–Zn on Ga for process, operated with low pH-conditioned forms. Over Cu/ZnGaO_X, WGS was sensitive to Cu, which was primarily active. Catalytic chemical reactivity, activity and selectivity were also found to be critically dependent on material lattice structure, copper surface area and metal–support interaction phenomena. The temperature-programmed surface reaction with mass spectrometry (TPSR–MS) measurements showed that formulations, synthesised at the pH of 8.0, enabled reaching >99% of the equilibrium yield CO conversion at 260 °C. An increase in the converted CO, oxidation and H₂ productivity with the integral steam content in gaseous feed flow was achieved. The heterogeneous phase processing at the correlated pH of 7.6 demonstrated the highest formed CO product at the temperature of 200 °C, compared with literature. This is particularly promising for reagent purity hydrogen-fed fuel cells. The kinetics for each co-precipitated solid was evaluated regarding the efficiency for the WGS in a fixed bed reactor.     

Catalytic Activity of WO<Subscript>3</Subscript> and MoO<Subscript>3</Subscript> with Pt and Pd Additives in Oxidation of Hydrogen

We have shown that WO₃ and MoO₃ with Pt or Pd additives exhibit high catalytic activity in the reaction of H₂ oxidation. In the temperature range 313 K to 353 K, we have studied the kinetic behavior of the reaction on 0.1 mass % Pt(Pd)/WO₃ and Pt(Pd)/MoO₃ samples. We have established that the kinetics of H₂ oxidation on these catalysts correspond to an Eley - Rideal mechanism. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 5, pp. 313–316, September–October, 2005.