No abstract

Polymethylbenzene (polyMB) and alkene cycles are considered as two main routes forming light olefins in the process of methanol to olefins (MTO); however, the contribution that each cycle makes to MTO is still unclear. In this work, density functional theory considering dispersive interactions (DFT-D) was used to elucidate the catalytic roles that the polyMB and the alkene cycles may play in forming ethene and propene from methanol in MTO over H-ZSM-5. The results demonstrated that ethene and propene can be produced in nearly the same probability via the polyMB cycle, as they have a very close free energy height as well as a similar free energy barrier for the rate-determining steps. Via the alkene cycle, however, propene is the dominant product, because the methylation and cracking steps to get propene have a much lower free energy barrier in comparison with those to form ethene. As a result, ethene is predominantly formed via the polyMB cycle, whereas propene is produced via both the polyMB and the alkene cycles. The contribution of the alkene cycle is probably larger than that of the polyMB cycle, resulting in a high fraction of propene in the MTO products. Meanwhile, both cycles are interdependent in MTO, as the aromatic species generated by aromatization via the alkene cycle can also serve as new active centers for the polyMB cycle, and vice versa. Moreover, the catalytic activity of H-ZSM-5 zeolite is directly related to its acid strength; weaker acid sites are unfavorable for the polyMB cycle and then enhance relatively the contribution of the alkene cycle to forming light olefins. These results can well interpret the recent experimental observations, and the theoretical insights shown in this work may improve our understanding of the MTO mechanism, which are conducive to developing better MTO catalysts and reaction processes.

ZSM-5 and ZSM-11 zeolites are similar in their crystalline framework structure, acidity, morphology, and textual properties but considerably different in their catalytic performance for conversion of methanol to olefins (MTO). Such an unexpected but exciting finding was extensively explored by various techniques and density functional theory calculations. A detailed investigation shows that it is the different Al distribution in the ZSM-5 and ZSM-11 framework that causes the significant difference in MTO catalytic performance. In ZSM-5, Al atoms are enriched in the intersection, whereas in ZSM-11, the Al atoms are concentrated in the straight 10-membered ring channel. The acid sites located in the intersection enhance the arene-based cycle that generates more ethene, alkanes, and aromatics. Nevertheless, these hydrocarbon molecules can easily diffuse out of the zeolite channel, hence retarding the deposition of carbonaceous materials and increasing catalytic stability. However, the acid sites located in the straight channel promote the alkene-based cycle, thus preferentially generating higher olefins that could transform into aromatics and carbon precursors that have difficulty in diffusing out of ZSM-11. The fast accumulation of coke species leads to its short catalytic lifetime. Via a shift of the Al atoms of ZSM-11 from the straight channel to the intersection by incorporation of appropriate amounts of B or alteration of silica and alumina sources and addition of sodium cations, its MTO catalytic performance (activity, selectivity, and stability) becomes highly comparable to that of ZSM-5. The insights attained in this work not only help to clarify the relationship of Al siting in zeolite with its MTO catalytic performance but also provide a cue for improving the catalytic properties of zeolites by regulating the sitings of active sites in lattice sites.

We present a novel large-scale synthetic method for well-separated copper nanowires (CuNWs) in a commercial electric pressure cooker under mild reaction conditions. CuNWs (∼2.1 g) can be prepared in a batch with the cost of $4.20/g. Well-dispersed polyvinylpyrrolidone-capped CuNWs were obtained via a ligand-exchange method. The transparent and conductive CuNW networks with excellent electrical conductivity and high optical transmittance (30 Ω/□ at 86% transmittance, respectively) were fabricated by a spin-coating process.

H-MCM-22 zeolite bears three types of pores, supercages, sinusoidal channels, and pockets, and exhibits excellent catalytic performance in the process of methanol to olefins (MTO); however, the catalytic role that each type plays in MTO is still unclear. In this work, density functional theory considering dispersive interactions (DFT-D) was used to elucidate the contributions of various pores in H-MCM-22 to MTO. The results demonstrated that these three types of pores are different in their catalytic action on MTO, because of the large differences in pore size and shape that determine the space confinement and electrostatic stabilization effects. The formation of propene is predicted to take place in the supercages, where propene can be effectively produced through both polyMB and alkene cycles, with a relatively low free energy barrier as well as low enthalpy barrier and entropy loss for the rate-determining steps. In the sinusoidal channels, the free energy barrier of the methylation and cracking steps is elevated due to the space confinement and the reactivity of alkenes is also markedly depressed in the narrow channels, in comparison with those in the supercages; as a result, the contribution of the sinusoidal channels to the entire propene formation is minor. Meanwhile, the pockets are probably detrimental to MTO, as certain large intermediates such as 1,1,2,6-tetramethyl-4-isopropylbenzenium cations are easily formed in the pockets but are difficult to decompose due to the lack of an electrostatic stabilization effect from the zeolite framework, which elevates the total free energy barrier and may lead to a rapid deactivation of these active sites. In comparison with the difference in pore size and structure, the difference of various pores in the acid strength of the active sites exhibits an insignificant effect on their catalytic behaviors in MTO. The theoretical insights in this work are conducive to a subsequent investigation on the MTO mechanism and the development of better MTO catalysts and reaction processes.

Identification of the active copper species, and further illustration of the catalytic mechanism of Cu-based catalysts is still a challenge because of the mobility and evolution of Cu and Cu species in the reaction process. Thus, an unprecedentedly stable Cu-based catalyst was prepared by uniformly embedding Cu nanoparticles in a mesoporous silica shell allowing clarification of the catalytic roles of Cu and Cu in the dehydrogenation of methanol to methyl formate by combining isotope-labeling experiment, in situ spectroscopy, and DFT calculations. It is shown that Cu sites promote the cleavage of the O-H bond in methanol and of the C-H bond in the reaction intermediates CH O and H COOCH which is formed from CH O and HCHO, whereas Cu sites cause rapid decomposition of formaldehyde generated on the Cu sites into CO and H .

On the basis of density functional theory including dispersion correction [ωB97XD/6-311+G(2df,2p)//B3LYP/6-311G(d,p)], the thermodynamics and kinetics of the reactions of CH 3 OH and CH 3 OCH 3 over H-ZSM-5 have been systematically computed. For the reaction of the methylated surface (CH 3 OZ) with CH 3 OH, CH 3 OCH 3 formation is kinetically controlled and the competitive formation of CH 2 O + CH 4 is thermodynamically controlled, in agreement with the observed desorption temperatures of CH 3 OH, CH 3 OCH 3 , and CH 2 O under experimental conditions. For the reaction between ZOCH 3 and CH 3 OCH 3 , the formation of the framework stabilized (CH 3 ) 3 O + is kinetically controlled, consistent with the NMR observation at low temperature, and the competitive formation of surface CH 3 OCH 2 OZ + CH 4 is thermodynamically controlled. On the basis of the thermodynamically more favored CH 2 O and CH 3 OCH 2 OZ, there are two parallel routes for the first C−C bond formation, from the coupling of CH 3 OCH 2 OZ with CH 3 OH and CH 3 OCH 3 as well as from the coupling of CH 2 O with CH 3 OH and CH 3 OCH 3 . The most important species is the methylated surface (CH 3 OZ), which can react with CH 3 OH and CH 3 OCH 3 to form the corresponding physisorbed CH 2 O and chemisorbed CH 3 OCH 2 OZ, and they can further couple with additional CH 3 OH and CH 3 OCH 3 to result in first C−C formation, verifying the proposed formaldehyde (CH 2 O) and methoxymethyl (CH 3 OCH 2 OZ) mechanisms.

We report the molecular dynamics simulations of spontaneous and continuous permeation of water molecules through a single-layer graphyne-3 membrane. We found that the graphyne-3 membrane is more permeable to water molecules than (5, 5) carbon nanotube membranes of similar pore diameter. The remarkable hydraulic permeability of the single-layer graphyne-3 membrane is attributed to the hydrogen bond formation, which connects the water molecules on both sides of the monolayer graphyne-3 membrane and aids to overcome the resistance of the nanopores, and to the relatively lower energy barrier at the pore entrance. Consequently, the single-layer graphyne-3 membrane has a great potential for application as membranes for desalination of sea water, filtration of polluted water, etc.