Catalytic reduction of SO2 by CO over Au4Pt2(CO)n and Au6Pt(CO)n clusters: a first-principles study.

The catalytic properties of the magic gold-platinum bimetallic clusters (Au4Pt2 and Au6Pt) for the reduction of SO2 by CO, without or with preadsorbing CO molecules, are firstly investigated using density functional theory calculations. We find that the catalytic activities improve effectively with the preadsorption of CO onto the catalysts and that the catalytic activities of Au6Pt(CO)n are better than those of Au4Pt2(CO)n as more CO molecules are adsorbed onto the catalysts. During the reaction process, the Au4Pt2(CO)n clusters always keep two-dimensional morphologies except for when n = 5 and the Au6Pt(CO)n clusters have three-dimensional geometries except for when n = 0. The most stable adsorption site for SO2 molecules on the catalysts is the site of preadsorbing the next CO molecule on the corresponding catalysts. The largest activation energy (E) is related to the metal 5d (M-5d) band center and the charge transfer (Ct) as well as the bond length (Rb) between COS and the catalyst contribute to the desorption energy (Ed) of COS corporately. We propose that Au6Pt(CO)6 is a cost-effective gold-platinum bimetallic catalyst for the reduction of SO2 by CO.

Damped oscillation in the NO+CO/Pt(100) reaction system.

Considering the influence of the surface defects formed in the surface restructuring phase transition in the CO+NO/Pt(100) reaction system, we propose a lattice gas model to investigate the damped oscillation in the high-temperature oscillatory regime by means of a Monte Carlo simulation. The simulation results show that the persistent oscillation can change into a damped one when the fraction of the defects increases. The production rate of CO2 is near to the maximum value when the oscillation is damped to the end. Furthermore, it is found, in the early stage of the oscillation, that the NO decomposition mainly occurs in the 1 x 1 phase and the hex phase is inactive for the reaction. However, as the reaction proceeds, defects are gradually formed in the 1 x 1 <==> hex phase transition, the hex phase becomes active and dominative for the NO decomposition, and then the oscillation becomes damping. The simulation results give an explanation for some previous experimental phenomena.

Kinetic phase transition in A2 + B2 -->2AB reaction system.

Three lattice gas models for A2 + B2 -->2AB reaction system are studied by Monte Carlo simulation in two-dimensional triangular lattice surface. When both A2 and B2 adsorb and dissociate on the catalytic surface in the random dimer-filling mechanism or in the end-on dimer-filling mechanism, there is no reactive window in the reaction system and just a discontinuous phase transition appears from a "B+vacancy" poisoned state to an "A+vacancy" poisoned state. However, a reactive window appears when one of the two dimers, A2, dissociates in the random dimer-filling mechanism but another dimer, B2, is in the end-on dimer-filling mechanism and the system exhibits a discontinuous phase transition from the active reaction state to a B+ vacancy poisoned state and a continuous phase transition to an "A+vacancy" poisoned state. Furthermore, we show that the critical behavior of the continuous phase transition with infinitely many absorbing states belongs to the robust directed percolation universality class.

Critical behavior of nonequilibrium continuous phase transition in A+BC catalytic reaction system.

We study two lattice gas models for the A+BC-->AC+ 1/2 B2 reaction system. Model I includes the influences of the adsorbate diffusion and model II includes the effect of the diffusion and position exchange of B and C atoms. Model I exhibits a continuous phase transition with infinitely many absorbing states from a reactive state to a poisoned state of B and C atoms and a discontinuous transition to a poisoned state of A and B atoms when the fraction of A in the gas phase varies. The critical exponents are estimated accurately. The simulation results indicate clearly that the critical behavior of the continuous phase transition in model I belongs to the directed percolation (DP) universality class. Model II, however, exhibits a continuous transition with two absorbing states, and its critical behavior is obviously distinct from the DP universality class.

Effect of inert species in gas phase on oscillatory dynamics of oxidation system of CO on Pt(100).

We present a Monte Carlo simulation for the global oscillation of the CO catalytic oxidation system in the presence of inert species in gas phase, which can adsorb and desorb on the catalytic surface but cannot react with other species. It is found that the impurity has a dramatic effect on the oscillatory dynamics, although it does not involve in the reaction of CO oxidation. The simulation results show that with an increase in the fraction of impurity in gas phase, the periodic oscillation may change into an irregular oscillation and even can be inhibited completely. However, as the desorption rate of the impurity is increased, the regular oscillation will be recovered again.

Nonequilibrium kinetic phase transition of a monomer-dimer reaction model with sequential dimer adsorption in two dimensions.

We study a monomer-dimer reaction model in two dimensions in which the adsorption process of a dimer on the surface sites is separated into two steps (i.e., B2+*-->B2 *, and B2 * +*-->2B*, where * is an empty site), as first introduced by Evans and co-workers. It is clear that the dissociation of a dimer is dependent on the complicated configuration of the adsorbate. We show that the continuous transition from the reactive state to the O-passivated state and the discontinuous transition to the CO-passivated state both shift toward higher values of the fraction p of the monomer in gas phase but the reaction window decreases compared to the Ziff-Gulari-Barshad model. For the model studied here, the critical exponents of the continuous phase transition still exhibit a directed percolation character as expected.

Hysteresis phenomena in CO catalytic oxidation system in the presence of inhomogeneities of the catalyst surface.

The hysteresis phenomena in the CO catalytic oxidation system are studied by Monte Carlo simulation in the presence of the inhomogeneities of the catalyst surface. We show that the O-passivated state is destroyed due to the inhomogeneities of the surface, in contrast to the classical Ziff-Gulari-Barshad model. The defects on the surface have a significant effect on the hysteresis transition points. Most importantly, the supercritical nucleation and growth of the O adatom island during the transition from a low reactivity to a high reactivity states are closely related to the inhomogeneities of the catalyst surface. It is shown that the width of the hysteresis loop shrinks as the scan rate beta(CO) of y(CO) (the fraction of CO in gas phase) decreases, but there exists a finite width of the hysteresis loop even if beta(CO) becomes infinitely small. On the other hand, the width of the hysteresis loop decreases with decreasing the diffusion rate, and even the hysteresis loop may disappear for a slow diffusion. These simulation results are in good consistency with the previous relevant experimental results.