Reaction mechanism of methanol to formaldehyde over Fe- and FeO-modified graphene.

We employed periodic DFT calculations (PBE-D2) to investigate the catalytic conversion of methanol over graphene embedded with Fe and FeO. Two possible pathways of dehydrogenation to formaldehyde and dehydration to dimethyl ether (DME) over these catalysts were examined. Both processes are initiated with the activation of methanol over the catalytic center through O-H cleavage. As a result, a methoxo-containing intermediate is formed. Subsequently, H-transfer from the methoxy to the adjacent ligand leads to the formation of formaldehyde. Conversely, the activation of the second methanol over the intermediate gives DME and H2O. Over Fe/graphene, the dehydration process is kinetically and thermodynamically preferable. Unlike Fe/graphene, FeO/graphene is predicted to be an efficient catalyst for the dehydrogenation process. Oxidative dehydrogenation over FeO/graphene takes place through two steps with free energy barriers of 5.7 and 10.2 kcal mol(-1).

Theoretical studies on electronic structures and photophysical properties of anthracene derivatives as hole-transporting materials for OLEDs.

The electronic structures and photophysical properties of anthracene derivatives as hole-transporting materials (HTM) in OLEDs have been studied by DFT and TD-DFT methods. Thiophene and triphenylamine (TPA) moieties are used as substituents in anthracene based HTMs providing FATn and FAPn compounds (n=1-2), respectively. The calculated electronic levels by B3LYP show proper energy matching of FAPn and hole-injecting layer (HIL), indicating that the hole-transports of the FAPn compounds are better than the FATn compounds. The photophysical properties calculated by TD-B3LYP elucidate that TPA in FAPn compounds acts as electron donating group and induces charge transfer character in the absorptions. Furthermore, the calculated ionization potential (IP), electron affinity (EA) and reorganization energies also revealed that the extended FAP2 compound has the highest charge-transporting ability among the studied compounds. The calculated results are consistent to our experimental observations showing that FAP2 exhibits bright fluorescence with highest quantum yield in electroluminescent devices. Understanding of these properties is useful for further design of new HTMs of desired properties, such as high efficiency and stability.

Comparison of Cu-ZSM-5 zeolites and Cu-MOF-505 metal-organic frameworks as heterogeneous catalysts for the Mukaiyama aldol reaction: a DFT mechanistic study.

The density functional theory (DFT) model ONIOM(M06L/6-311++G(2df,2p):UFF was employed to reveal the catalytic activity of Cu(II) in the paddle-wheel unit of the metal-organic framework (MOF)-505 material in the Mukaiyama aldol reaction compared with the activity of Cu-ZSM-5 zeolites. The aldol reaction between a silyl enol ether and formaldehyde catalyzed by the Lewis acidic site of both materials takes place through a concerted pathway, in which the formation of the CC bond and the transfer of the silyl group occurs in a single step. MOF-505 and Cu-ZSM-5 are predicted to be efficient catalysts for this reaction as they strongly activate the formaldehyde carbonyl carbon electrophile, which leads to a considerably lower reaction barrier compared with the gas-phase system. Both MOF-505 and Cu-ZSM-5 catalysts stabilize the reacting species along the reaction coordinate, thereby lowering the activation energy, compared to the gas-phase system. The activation barriers for the MOF-505, Cu-ZSM-5, and gas-phase system are 48, 21, and 61 kJ mol(-1) , respectively. Our results show the importance of the enveloping framework by stabilizing the reacting species and promoting the reaction.

Mechanistic studies on the transformation of ethanol into ethene over Fe-ZSM-5 zeolite.

Ethanol, through the utilization of bioethanol as a chemical resource, has received considerable industrial attention as it provides an alternative route to produce more valuable hydrocarbons. Using a density functional theory approach incorporating the M06-L functional, which includes dispersion interactions, a large 34T nanocluster model of Fe-ZSM-5 zeolite in which T is a Si or Al atom is employed to examine both the stepwise and concerted mechanisms of the transformation of ethanol into ethene. For the stepwise mechanism, ethanol dehydration commences from the first hydrogen abstraction of the ethanol OH group to form the ethoxide-hydroxide intermediate with a low activation energy of 17.7 kcal mol(-1). Consequently, the ethoxide-hydroxide intermediate is decomposed into ethene through hydrogen abstraction from the ethoxide methyl carbon to either the OH group of hydroxide or the oxygen of the ethoxide group with high activation energies of 64.8 and 63.5 kcal mol(-1), respectively. For the concerted mechanism, ethanol transformation into the ethene product occurs in a single step without intermediate formation, with an activation energy of 32.9 kcal mol(-1).

Structures, energetics and reaction mechanisms of nitrous oxide on transition-metal-doped and -undoped single-wall carbon nanotubes.

The catalytic activity of carbon nanotubes (CNTs) for the removal of greenhouse gases, like nitrous oxide (N(2)O), can be fine-tuned by metal doping. We modify the inert surfaces of CNTs with Sc, Ti and V transition metals in order to investigate their capability of converting N(2)O to N(2). The stable composite catalysts of Sc-, Ti- and V-doped (5,5)single-walled carbon nanotubes (SWCNTs), along with the unmodified one were investigated by periodic DFT calculations. Without metal doping, the N(2) O decomposition on the bare tube proceeds over a high energy barrier (54.3 kcal mol(-1)) which in the presence of active metals is reduced to 3.6, 8.0 and 10.2 kcal mol(-1) for V-, Ti- and Sc-doped (5,5)SWCNTs, respectively. The superior reactivity is a result of the facilitated electron transfer between the tube and N(2)O caused by the overlap between the d orbitals of the metal and the p orbitals of N(2)O.

Formaldehyde encapsulated in lithium-decorated metal-organic frameworks: a density functional theory study.

The stability of monomeric formaldehyde encapsulated in the lithium-decorated metal-organic framework Li-MOF-5 was investigated by means of density functional calculations with the M06-L functional and the 6-31G(d,p) basis set. To assess the efficiency of Li-MOF-5 for formaldehyde preservation, we consider the reaction kinetics and the thermodynamic equilibrium between formaldehyde and its trimerized product, 1,3,5-trioxane. We propose that trimerization of encapsulated formaldehyde takes place in a single reaction step with an activation energy of 34.5 kcal mol(-1). This is 17.2 kcal mol(-1) higher than the corresponding activation energy in the bare system. In addition, the reaction energy of the system studied herein is endothermic by 6.1 kcal mol(-1) and the Gibbs free energy (ΔG) of the reaction becomes positive (11.0 kcal mol(-1)). Consequently, the predicted reverse rate for the trimerization reaction in the Li-MOF-5 is significantly faster than the forward rate. The calculations show that the oligomerization of formaldehyde in Li-MOF-5 is a reversible reaction, suggesting that such a zeolite might be a good candidate material for preserving formaldehyde in its monomeric form.

Density functional theory study of the carbonyl-ene reaction of encapsulated formaldehyde in Cu(I), Ag(I), and Au(I) exchanged FAU zeolites.

Carbonyl-ene reactions, which involve C-C bond formation, are essential in many chemical syntheses. The formaldehyde-propene reaction catalyzed by several of the group 11 metal cations, Cu(+), Ag(+), and Au(+) exchanged on the faujasite zeolite (metal-FAU) has been investigated by density functional theory at the M06-L/6-31G(d,p) level. The Au-FAU exhibits a higher activity than the others due to the high charge transfer between the Au and the reactant molecules, even though it is located at a negatively charged site of the zeolite. This site enables it to compensate for the charge of the Au(+) ion. The NBO analysis reveals that the 6s orbital of the Au atom plays an important role, inducing a charge on the probe molecules. Moreover, the effect of the zeolite framework makes the Au-FAU more active than the others by stabilizing the high charge induced transition structure. The activation energy of the reaction catalyzed by Au-FAU is 13.0 kcal/mol whereas that of Cu and Ag-FAU is found to be around 17 kcal/mol. The product desorption needs to be improved for Au-FAU; however, we suggest that catalysts with high charge transfer might provide a promising activity.

Oxidative dehydrogenation of propane over a VO2-exchanged MCM-22 zeolite: a DFT study.

The adsorption and the mechanism of the oxidative dehydrogenation (ODH) of propane over VO(2)-exchanged MCM-22 are investigated by DFT calculations using the M06-L functional, which takes into account dispersion contributions to the energy. The adsorption energies of propane are in good agreement with those from computationally much more demanding MP2 calculations and with experimental results. In contrast, B3LYP binding energies are too small. The reaction begins with the movement of a methylene hydrogen atom to the oxygen atom of the VO(2) group, which leads to an isopropyl radical bound to a HO-V-O intermediate. This step is rate determining with the apparent activation energy of 30.9 kcal mol(-1), a value within the range of experimental results for ODH over other silica supports. In the propene formation step, the hydroxyl group is the more reactive group requiring an apparent activation energy of 27.7 kcal mol(-1) compared to that of the oxy group of 40.8 kcal mol(-1). To take the effect of the extended framework into account, single-point calculations on 120T structures at the same level of theory are performed. The apparent activation energy is reduced to 28.5 kcal mol(-1) by a stabilizing effect caused by the framework. Reoxidation of the catalyst is found to be important for the product release at the end of the reaction.

Effects of the zeolite framework on the adsorptions and hydrogen-exchange reactions of unsaturated aliphatic, aromatic, and heterocyclic compounds in ZSM-5 zeolite: a combination of perturbation theory (MP2) and a newly developed density functional theory (M06-2X) in ONIOM scheme.

The confinement effect on the adsorption and reaction mechanism of unsaturated aliphatic, aromatic and heterocyclic compounds on H-ZSM-5 zeolite has been investigated by the four ONIOM methods (MP2:M06-2X), (MP2:B3LYP), (MP2:HF), and (MP2:UFF). The H-ZSM-5 'nanoreactor' porous intersection, where chemical reactions take place, is represented by a quantum cluster of 34 tetrahedral units. Ethene, benzene, ethylbenzene, and pyridine are chosen to represent reactions of various adsorbates of aliphatic, aromatic and heterocyclic compounds. Among the four combined methods, (MP2:M06-2X) outperforms the others. The results confirm that the method that takes weak interactions, especially the van der Waals interaction, into account is essential for describing the confinement effect from the zeolite framework. The effects of the infinite zeolitic framework on the cluster model are also included by a set of point charges generated by the embedded ONIOM model. The energies for the adsorption of ethene, benzene, ethylbenzene, and pyridine on H-ZSM-5 from an embedded ONIOM(MP2:M06-2X) calculation are predicted to be -14.0, -19.8, -24.7, and -48.4 kcal/mol, respectively, which are very close to available experimental observations. The adsorption energy of pyridine agrees well with the experiment data of -47.6 kcal/mol. We also applied the same computational methodology on the systematic investigation of the H/H exchange reaction of benzene and ethylbenzene with the acidic H-ZSM-5 zeolite. The H/H exchange reaction was found to take place in a single concerted step. The calculated apparent activation energies for benzene and ethylbenzene are 12.6 and 4.9 kcal/mol, which can be compared to the experimental estimates of 11.0 and 6.9 kcal/mol, respectively. The confinement effect of the extended zeolite framework has been clearly demonstrated not only to stabilize the adsorption complexes but also to improve their corresponding activation energies to approach the experimental benchmark.

Decomposition of nitrous oxide on carbon nanotubes.

In this work, we have suggested the possibility of using carbon nanotubes to remove toxic gas. By taking an advantage of the density functional theory, we have investigated the decomposition of nitrous oxide (N(2)O) on the sidewalls of the perfect and the Stone-Wales defect armchair (5,5)-SWNTs at the B3LYP/6-31G(d) level of theory. There are two reaction mechanisms proposed: stepwise and concerted pathways. Our calculations predict that the former route is kinetically favored on both the perfect and defect SWNTs with barrier heights of the rate-determining steps of 37.23 and 34.38 kcal/mol for the perfect and the defect systems, respectively. In the second pathway, the decomposition of nitrous oxide gas takes place in a single step with higher reaction barriers of 48.60 and 40.27 kcal/mol on the sidewalls of the perfect and the defect SWNTs, respectively. Moreover, we also demonstrated that an encapsulation of electron rich species, such as chloride anion, inside the channel of the SWNT can boost up the reaction rate of the N(2)O decomposition on the SWNT. The chloride ion supplies excess electrons to the SWNT for transferring to the N(2)O molecule causing lower reaction barriers in the reaction pathways.

Structures and reaction mechanisms of propene oxide isomerization on H-ZSM-5: an ONIOM study.

The isomerization mechanisms of propene oxide over H-ZSM-5 zeolite have been investigated via the utilization of 5T and 46T cluster models calculated by the B3LYP/6-31G(d,p) and the ONIOM(B3LYP/6-31G(d,p):UFF) methods, respectively. The reactions are considered to proceed through a stepwise mechanism: (1) the epoxide ring protonation, and concurrently the ring-opening, and (2) the 1,2-hydride shift forming the adsorbed carbonyl compound. Because of the asymmetric structure of propene oxide, two different C-O bonds (more or less substituted carbon atom sides) can be broken leading to two different types of products, propanal and propanone. The ring-opening step of these mechanisms is found to be the rate-determining step with an activation barrier of 38.5 kcal/mol for the propanal and of 42.4 kcal/mol for the propanone. Therefore, the propanal is predicted to be the main product for this reaction.