General rules for predicting where a catalytic reaction should occur on metal surfaces: A density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces

To predict where a catalytic reaction should occur is a fundamental issue scientifically. Technologically, it is also important because it can facilitate the catalyst's design. However, to date, the understanding of this issue is rather limited. In this work, two types of reactions, CH4 CH3 + H and CO C + 0 on two transition metal surfaces, were chosen as model systems aiming to address in general where a catalytic reaction should occur. The dissociations of CH4 - CH3 + H and CO --> C + O and their reverse reactions on flat, stepped, and kinked Rh and Pd surfaces were studied in detail. We find the following: First, for the CH4 Ch(3) + H reaction, the dissociation barrier is reduced by similar to0.3 eV on steps and kinks as compared to that on flat surfaces. On the other hand, there is essentially no difference in barrier for the association reaction of CH3 + H on the flat surfaces and the defects. Second, for the CO C + 0 reaction, the dissociation barrier decreases dramatically (more than 0.8 eV on Rh and Pd) on steps and kinks as compared to that on flat surfaces. In contrast to the CH3 + H reaction, the C + 0 association reaction also preferentially occurs on steps and kinks. We also present a detailed analysis of the reaction barriers in which each barrier is decomposed quantitatively into a local electronic effect and a geometrical effect. Our DFT calculations show that surface defects such as steps and kinks can largely facilitate bond breaking, while whether the surface defects could promote bond formation depends on the individual reaction as well as the particular metal. The physical origin of these trends is identified and discussed. On the basis of our results, we arrive at some simple rules with respect to where a reaction should occur: (i) defects such as steps are always favored for dissociation reactions as compared to flat surfaces; and (ii) the reaction site of the association reactions is largely related to the magnitude of the bonding competition effect, which is determined by the reactant and metal valency. Reactions with high valency reactants are more likely to occur on defects (more structure-sensitive), as compared to reactions with low valency reactants. Moreover, the reactions on late transition metals are more likely to proceed on defects than those on the early transition metals.

The Y-procedure: How to extract the chemical transformation rate from reaction-diffusion data with no assumption on the kinetic model

The paper presents a new method to extract the chemical transformation rate from reaction–diffusion data with no assumption on the kinetic model (“kinetic model-free procedure”). It is a new non-steady-state kinetic characterization procedure for heterogeneous catalysts. The mathematical foundation of the Y-procedure is a Laplace-domain analysis of the two inert zones in a TZTR followed by transposition to the Fourier domain. When combined with time discretization and filtering the Y-procedure leads to an efficient practical method for reconstructing the concentration and reaction rate in the active zone. Using the Y-procedure the concentration and reaction rate of a non-steady state catalytic process can be determined without any pre-assumption regarding the type of kinetic dependence. The Y-procedure is the basis for advanced software for non-steady state kinetic data interpretation. The Y-procedure can be used to relate changes in the catalytic reaction rate and kinetic parameters to changes in the surface composition (storage) of a catalyst.

Miniaturization of heterogeneous catalytic reactors: Prospects for new developments in catalysis and process engineering

This paper gives an overview of the research done since 1999 at Eindhoven University of Technology in the Netherlands in the field of miniaturization of heterogeneous catalytic reactors. It is described that different incentives exist for the development of these microstructured reaction systems. These include the need for efficient research instruments in catalyst development and screening, the need for small-scale reactor devices for hydrogen production for low-power electricity generation with fuel cells, and the recent quest for intensified processing equipment and novel process architectures (as in the fine chemicals sector). It is demonstrated that also in microreaction engineering, catalytic engineering and reactor design go hand-in-hand. This is illustrated by the design of an integrated microreactor and heat-exchanger for optimum performance of a highly exothermic catalytic reaction, viz. ammonia oxidation. It is argued that future developments in catalytic microreaction technology will depend on the availability of very active catalysts (and catalyst coating techniques) for which microreactors may become the natural housing.

Femtosecond lasers for mass spectrometry: Proposed application to catalytic hydrogenation of butadiene

Mass spectra from the interaction of intense, femtosecond laser pulses with 1,3-butadiene, 1-butene, and n-butane have been obtained. The proportion of the fragment ions produced as a function of intensity, pulse length, and wavelength was investigated. Potential mass spectrometry applications, for example in the analysis of catalytic reaction products, are discussed.

Facet-Dependent Catalytic Activity of Platinum Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells

Platinum (Pt) nanocrystals have demonstrated to be an effective catalyst in many heterogeneous catalytic processes. However, pioneer facets with highest activity have been reported differently for various reaction systems. Although Pt has been the most important counter electrode material for dye-sensitized solar cells (DSCs), suitable atomic arrangement on the exposed crystal facet of Pt for triiodide reduction is still inexplicable. Using density functional theory, we have investigated the catalytic reaction processes of triiodide reduction over {100}, {111} and {411} facets, indicating that the activity follows the order of Pt(111) > Pt(411) > Pt(100). Further, Pt nanocrystals mainly bounded by {100}, {111} and {411} facets were synthesized and used as counter electrode materials for DSCs. The highest photovoltaic conversion efficiency of Pt(111) in DSCs confirms the predictions of the theoretical study. These findings have deepened the understanding of the mechanism of triiodide reduction at Pt surfaces and further screened the best facet for DSCs successfully.

Reversibility Iteration Method to Understand Reaction Networks and to Solve Micro-Kinetics in Heterogeneous Catalysis

Solving microkinetics of catalytic systems, which bridges microscopic processes and macroscopic reaction rates, is currently vital for understanding catalysis in silico. However, traditional microkinetic solvers possess several drawbacks that make the process slow and unreliable for complicated catalytic systems. In this paper, a new approach, the so-called reversibility iteration method (RIM), is developed to solve microkinetics for catalytic systems. Using the chemical potential notation we previously proposed to simplify the kinetic framework, the catalytic systems can be analytically illustrated to be logically equivalent to the electric circuit, and the reaction rate and coverage can be calculated by updating the values of reversibilities. Compared to the traditional modified Newton iteration method (NIM), our method is not sensitive to the initial guess of the solution and typically requires fewer iteration steps. Moreover, the method does not require arbitrary-precision arithmetic and has a higher probability of successfully solving the system. These features make it ∼1000 times faster than the modified Newton iteration method for the systems we tested. Moreover, the derived concept and the mathematical framework presented in this work may provide new insight into catalytic reaction networks.

The effects of stepped sites and ruthenium adatom decoration on methanol dehydrogenation over platinum-based catalyst surfaces

A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.

Density Functional Theory Studies of Ethanol Decomposition on Rh(211)

Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(3)CO -> CH(3) + CO -> CH(2) + CO -> CH + CO -> C + CO and (2) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(2)COH -> CHCOH -> CHCO -> CH + CO -> C + CO. Both pathways have a common intermediate of CH(3)COH, and the key step is the formation of CH(3)CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH(3)COH rather than an oxametallacycle species (-CH(2)CH(2)O- for Rh( 111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial C(alpha)-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

NO Oxidation on Platinum Group Metals Oxides:First Principles Calculations Combined with Microkinetic Analysis

By combining density functional theory calculation and microkinetic analysis, NO oxidation on the platinum group metal oxides (PtO(2), IrO(2), OsO(2)) is investigated, aiming at shedding light on the activities of metal oxides and exploring the activity variations of metal oxides compared to their corresponding metals. A microkinetic model, taking into account the possible low diffusion of surface species on metal oxide surfaces, is proposed for NO oxidation. The resultant turnover frequencies of NO oxidation show that under the typical experimental condition, T = 600 K, p(O2) = 0.1 atm, p(NO) = 3 x 10(-4) atm, p(NO2) = 1.7 x 10(-4) atm; (i) IrO(2)(110) exhibits higher activity than PtO(2)(110) and OsO(2)(110), and (ii) compared to the corresponding metallic Pt, Ir, and Os, the activity of PtO(2) to catalyze NO oxidation is lower, but interestingly IrO(2) and OsO(2) exhibit higher activities. The reasons for the activity differences between the metals and oxides are addressed. Moreover, other possible reaction pathways of NO oxidation on PtO(2)(110), involving O(2) molecule (NO + O(2) -> OONO) and lattice bridge-O(2c), are also found to give low activities. The origin of the Pt catalyst deactivation is also discussed.

Insight into CO Activation over Cu(100) under Electrochemical Conditions

The reduction of CO₂ on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO₂ reduction process, the electron transfer to CO_ads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COH_ads and CHO_ads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COH_ads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of CHO_ads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COH_ads is more favored than that of CHO_ads, while CHO_ads is thermodynamically more stable. This work reveals that CO activation via COH_ads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO₂ electroreduction over Cu electrodes.

Phosphorylation Mechanism of Phosphomevalonate Kinase: Implications for Rational Engineering of Isoprenoid Biosynthetic Pathway Enzymes

Mevalonate pathway is of important clinical, pharmaceutical and biotechnological relevance. However, lack of the understanding of the phosphorylation mechanism of the kinases in this pathway has limited rationally engineering the kinases in industry. Here the phosphorylation reaction mechanism of a representative kinase in the mevalonate pathway, phosphomevalonate kinase, was studied by using molecular dynamics and hybrid QM/MM methods. We find that a conserved residue (Ser106) is reorientated to anchor ATP via a stable H-bond interaction. In addition, Ser213 located on the α-helix at the catalytic site is repositioned to further approach the substrate, facilitating the proton transfer during the phosphorylation. Furthermore, we elucidate that Lys101 functions to neutralize the negative charge developed at the β-, γ-bridging oxygen atom of ATP during phosphoryl transfer. We demonstrate that the dissociative catalytic reaction occurs via a direct phosphorylation pathway. This is the first study on the phosphorylation mechanism of a mevalonate pathway kinase. The elucidation of the catalytic mechanism not only sheds light on the common catalytic mechanism of GHMP kinase superfamily, but also provides the structural basis for engineering the mevalonate pathway kinases to further exploit their applications in the production of a wide range of fine chemicals such as biofuels or pharmaceuticals. 

Insight into electron-mediated reaction mechanisms: Catalytic CO oxidation on a ruthenium surface

Ruthenium is one of the poorest catalysts for CO oxidation under normal conditions (low or medium O coverage and normal temperature). However, a recent study [Science 285, 1042 (1999)] reveals that, under femtosecond laser irradiation, CO2 can be formed on the Ru surface, and the reaction follows an electron-mediated mechanism. We carried out density functional theory calculations to investigate CO oxidation via an electron-mediated mechanism on Ru(0001). By comparison to the reaction under normal conditions, following features emerge in the electron-mediated mechanism: (i) more reaction channels are open; (ii) the reaction barrier is significantly lowered. The physical origins for these novel features have been analyzed. (C) 2001 American Institute of Physics.

Catalytic Mo2C coatings for the water gas shift reaction: Electrosynthesis in molten salts

Electrosynthesis methods using molten salts are suggested for obtaining a new catalytic system based on the Mo2C/Mo composition for the water gas shift reaction. The coatings obtained by the discharge of the carbonate ion on a molybdenum substrate and by the simultaneous reduction of the electroactive species MoO42 and CO32- are catalytically more active than bulk Mo2C or the commercial catalyst Cu-ZnO-Al2O3 by one and three orders of magnitude, respectively.