A coronene-based semiconducting two-dimensional metal-organic framework with ferromagnetic behavior.

Metal-organic frameworks (MOFs) have so far been highlighted for their potential roles in catalysis, gas storage and separation. However, the realization of high electrical conductivity (>10-3 S cm-1) and magnetic ordering in MOFs will afford them new functions for spintronics, which remains relatively unexplored. Here, we demonstrate the synthesis of a two-dimensional MOF by solvothermal methods using perthiolated coronene as a ligand and planar iron-bis(dithiolene) as linkages enabling a full π-d conjugation. This 2D MOF exhibits a high electrical conductivity of ~10 S cm-1 at 300 K, which decreases upon cooling, suggesting a typical semiconductor nature. Magnetization and 57Fe Mössbauer experiments reveal the evolution of ferromagnetism within nanoscale magnetic clusters below 20 K, thus evidencing exchange interactions between the intermediate spin S = 3/2 iron(III) centers via the delocalized π electrons. Our results illustrate that conjugated 2D MOFs have potential as ferromagnetic semiconductors for application in spintronics.

Toward Activity Origin of Electrocatalytic Hydrogen Evolution Reaction on Carbon-Rich Crystalline Coordination Polymers.

The fundamental understanding of electrocatalytic active sites for hydrogen evolution reaction (HER) is significantly important for the development of metal complex involved carbon electrocatalysts with low kinetic barrier. Here, the MSx Ny (M = Fe, Co, and Ni, x/y are 2/2, 0/4, and 4/0, respectively) active centers are immobilized into ladder-type, highly crystalline coordination polymers as model carbon-rich electrocatalysts for H2 generation in acid solution. The electrocatalytic HER tests reveal that the coordination of metal, sulfur, and nitrogen synergistically facilitates the hydrogen ad-/desorption on MSx Ny catalysts, leading to enhanced HER kinetics. Toward the activity origin of MS2 N2 , the experimental and theoretical results disclose that the metal atoms are preferentially protonated and then the production of H2 is favored on the MN active sites after a heterocoupling step involving a N-bound proton and a metal-bound hydride. Moreover, the tuning of the metal centers in MS2 N2 leads to the HER performance in the order of FeS2 N2 > CoS2 N2 > NiS2 N2 . Thus, the understanding of the catalytic active sites provides strategies for the enhancement of the electrocatalytic activity by tailoring the ligands and metal centers to the desired function.

Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H2 Production.

Carbon electrocatalysts consisting of metal complexes such as MNx or MSx are promising alternatives to high-cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene-diamine (MS2 N2 , M=Co and Ni), metal bis(dithiolene) (MS4 ), and metal bis(diamine) (MN4 ) complexes were selectively incorporated into carbon-rich 2D metal-organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H2 generation. The electrocatalytic HER activity of the 2D MOF-based catalysts with different metal complexes follow the order of MS2 N2 >MN4 >MS4 . Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H2 was favored on the M-N units in the MS2 N2 active centers. The results provide an in-depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon-rich electrode materials for energy generation.

Supported and inserted monomeric niobium oxide species on/in silica: a molecular picture.

The geometry, energetic, and spectroscopic properties of molecular structures of silica-supported niobium oxide catalysts are studied using periodic density functional calculations (DFT) and compared with experimental data. The calculations are done for Nb oxide species inserted or grafted in/on an amorphous hydroxylated silica surface. Different positions of the Nb atom/atoms in the silica structure have been investigated. By means of DFT calculations the geometry and the degree of hydration of Nb oxide species with oxidation state +5 have been studied. The local Nb geometry depends on different parameters such as the number of Nb-O-Si groups vs. Nb-O-H groups, the formation of H bonds and the distance between Nb atoms. The interaction between the oxide and silanol groups occurs by formation of Si-O-Nb bonds with chemically and thermally stable Brønsted and Lewis acid sites. UV-Vis, reflection absorption infrared vibrational spectra (RAIRS) as well as various thermodynamic properties have also been investigated in order to get a better insight into the system studied and to provide support to possible experimental studies.

Ab initio simulations reveal that reaction dynamics strongly affect product selectivity for the cracking of alkanes over H-MFI.

Product selectivity of alkane cracking catalysis in the H-MFI zeolite is investigated using both static and dynamic first-principles quantum mechanics/molecular mechanics simulations. These simulations account for the electrostatic- and shape-selective interactions in the zeolite and provide enthalpic barriers that are closely comparable to experiment. Cracking transition states for n-pentane lead to a metastable intermediate (a local minimum with relatively small barriers to escape to deeper minima) where the proton is shared between two hydrocarbon fragments. The zeolite strongly stabilizes these carbocations compared to the gas phase, and the conversion of this intermediate to more stable species determines the product selectivity. Static reaction pathways on the potential energy surface starting from the metastable intermediate include a variety of possible conversions into more stable products. One-picosecond quasiclassical trajectory simulations performed at 773 K indicate that dynamic paths are substantially more diverse than the potential energy paths. Vibrational motion that is dynamically sampled after the cracking transition state causes spilling of the metastable intermediate into a variety of different products. A nearly 10-fold change in the branching ratio between C2/C3 cracking channels is found upon inclusion of post-transition-state dynamics, relative to static electronic structure calculations. Agreement with experiment is improved by the same factor. Because dynamical effects occur soon after passing through the rate-limiting transition state, it is the dynamics, and not only the potential energy barriers, that determine the catalytic selectivity. This study suggests that selectivity in zeolite catalysis is determined by high temperature pathways that differ significantly from 0 K potential surfaces.