The burgeoning field of nanoscience has stimulated an intense interest in properties that depend on particle size. For transition metal particles, one important property that depends on size is catalytic reactivity, in which bonds are broken or formed on the surface of the particles. Decreased particle size may increase, decrease, or have no effect on the reaction rates of a given catalytic system. This Account formulates a molecular theory of the structure sensitivity of catalytic reactions based on the computed activation energies of corresponding elementary reaction steps on transition metal surfaces. Recent progress in computational catalysis, surface science, and nanochemistry has significantly improved our theoretical understanding of particle-dependent reactivity changes in heterogeneous catalytic systems. Reactions that involve the cleavage or formation of molecular pi-bonds, as in CO or N(2), must be distinguished from reactions that involve the activation of sigma-bonds, such as CH bonds in methane. The activation of molecular pi-bonds requires a reaction center with a unique configuration of several metal atoms and step-edge sites, which can physically not be present on transition metal particles less than 2 nm. This is called class I surface sensitivity, and the rate of reaction will sharply decrease when particle size decreases below a critical size. The activation of sigma chemical bonds, in which the activation proceeds at a single metal atom, displays a markedly different size relationship. In this case, the dependence of reaction rate on coordinative unsaturation of reactive surface atoms is large in the forward direction of the reaction, but the activation energy of the reverse recombination reaction will not change. Dissociative adsorption with cleavage of a CH bond is strongly affected by the presence of surface atoms at the particle edges. This is class II surface sensitivity, and the rate will increase with decreasing particle size. Reverse reactions such as hydrogenation typically show particle-size-independent behavior. The rate-limiting step for these class III reactions is the recombination of an adsorbed hydrogen atom with the surface alkyl intermediate and the formation of a sigma-type bond. Herein is our molecular theory explaining the three classes of structure sensitivity. We describe how reactions with rates that are independent of particle size and reactions with a positive correlation between size and rate are in fact complementary phenomena. The elucidation of a complete theory explaining the size dependence of transition metal catalysts will assist in the rational design of new catalytic systems and accelerate the evolution of the field of nanotechnology.

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The mechanism of the oligomerization reaction of silica, the initial step of silica formation, has been studied by quantum chemical techniques. The solvent effect is included by using the COSMO model. The formation of various oligomers (from dimer to tetramer) was investigated. The calculations show that the anionic pathway is kinetically preferred over the neutral route. The first step in the anionic mechanism is the formation of the SiO-Si linkage between the reactants to form a five-coordinated silicon complex, which is an essential intermediate in the condensation reaction. The rate-limiting step is water removal leading to the oligomer product. The activation energies for dimer and trimer formation ( approximately 80 kJ/mol) are significantly higher than those of the subsequent oligermerization. The activation energies for the ring closure reaction ( approximately 100 kJ/mol) are even higher. The differences in activation energies can be related to the details in intra- and intermolecular hydrogen bonding of the oligomeric complexes.

The mechanism of CO dissociation is a fundamental issue in the technologically important Fischer-Tropsch (F-T) process that converts synthesis gas into liquid hydrocarbons. In the present study, we propose that on a corrugated Ru surface consisting of active sixfold (i.e., fourfold + twofold) sites, direct CO dissociation has a substantially lower barrier than the hydrogen-assisted paths (i.e., via HCO or COH intermediates). This proves that the F-T process on corrugated Ru surfaces and nanoparticles with active sixfold sites initiates through direct CO dissociation instead of hydrogenated intermediates.

The increasing availability of quantum-chemical data on surface reaction intermediates invites one to revisit unresolved mechanistic issues in heterogeneous catalysis. One such issue of particular current interest is the molecular basis of the Fischer-Tropsch reaction. Here we review current molecular understanding of this reaction that converts synthesis gas into longer hydrocarbons where we especially elucidate recent progress due to the contributions of computational catalysis. This perspective highlights the theoretical approach to heterogeneous catalysis that aims for kinetic prediction from quantum-chemical first principle data. Discussion of the Fischer-Tropsch reaction from this point of view is interesting because of the several mechanistic options available for this reaction. There are many proposals on the nature of the monomeric single C atom containing intermediate that is inserted into the growing hydrocarbon chain as well as on the nature of the growing hydrocarbon chain itself. Two dominant conflicting mechanistic proposals of the Fischer-Tropsch reaction that will be especially compared are the carbide mechanism and the CO insertion mechanism, which involve cleavage of the C-O bond of CO before incorporation of a CHx species into the growing hydrocarbon chain (the carbide mechanism) or after incorporation into the growing hydrocarbon chain (the CO insertion mechanism). The choice of a particular mechanism has important kinetic consequences. Since it is based on molecular information it also affects the structure sensitivity of this particular reaction and hence influences the choice of catalyst composition. We will show how quantum-chemical information on the relative stability of relevant reaction intermediates and estimates of the rate constants of corresponding elementary surface reactions provides a firm foundation to the kinetic analysis of such reactions and allows one to discriminate between the different mechanistic options. The paper will be concluded with a short perspective section dealing with the needs for future research. Many of the current key questions on the physical chemistry as well as computational study of heterogeneous catalysis relate to particular topics for further research on the fundamental aspects of Fischer-Tropsch catalysis.

The mechanism of the initial stage of silicate oligomerization from solution is still not well understood. Here we use an off-lattice kinetic Monte Carlo (kMC) approach called continuum kMC to model silicate oligomerization in water solution. The parameters required for kMC are obtained from density functional theory (DFT) calculations. The evolution of silicate oligomers and their role in the oligomerization process are investigated. Results reveal that near-neutral pH favors linear growth, while a higher pH facilitates ring closure. The silicate oligomerization rate is the fastest at pH 8. The temperature is found to increase the growth rate and alter the pathway of oligomerization. The proposed pH and temperature-dependent mechanism should lead to strategies for the synthesis of silicate-based materials.

The Horiuti−Polanyi mechanism for ethylene hydrogenation over Pd(111) is examined using first-principle density functional quantum chemical calculations. Cluster and periodic slab DFT-GGA calculations were carried out to determine the modes and energies of chemisorption for a sequence of proposed intermediates, along with overall reaction energies and activation barriers for each of the speculated elementary steps. The DFT-calculated binding energies for ethylene (π), ethylene (di-σ), ethyl, vinyl, ethylidyne, atomic oxygen, and atomic carbon on the Pd19 cluster (and the Pd(111) slab) were found to be −30 (−27), −60 (−62), −130 (−140), −237 (−254), −620 (−636), −375 (−400), and −610 (−635) kJ/mol. The slab results were found to be within 20 kJ/mol of the cluster results. Frequency calculations along with predicted chemisorption energies indicate that ethylene adsorbs in both π- and di-σ-configurations. At moderate temperatures, the binding energies for π- and di-σ-bound ethylene are comparable. At low surface coverages, the predicted intrinsic activation barriers are +72 kJ/mol for the hydrogenation of ethlyene to surface ethyl and +71 kJ/mol for ethyl to ethane. The corresponding overall reaction energies for these two steps are +3 and −5 (without lateral interactions) kJ/mol, respectively. At low surface coverages, the di-σ-intermediate appears to be the precursor to reaction. At low coverage the π-bound intermediate is first converted to the di-σ-species before it will react with hydrogen. The apparent activation barrier for ethylene hydrogenation to surface ethyl is 26 kJ/mol which is significantly lower than the intrinsic activation barrier. The apparent barrier is measured with respect to the gas-phase rather than the adsorbed ethylene state. Higher surface coverages alter the favored reaction state. At higher coverages, the activation barriers for ethylene hydrogenation to surface ethyl were calculated to be +82 and +36 kJ/mol for the di-σ- and π-bound intermediates, respectively. Higher surface coverages weaken both the metal−hydrogen and metal−carbon bonds. This promotes hydrogenation from the π-bound state. The calculated barrier of +36 kJ/mol (from the π-bound state) at higher surface coverages is consistent with experimentally reported ethylene hydrogenation barriers.