Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites.

ABSTRACT: Supercages of faujasite (FAU)-type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo₂ S₄ ) and tetranuclear (Mo₄ S₄ ) molybdenum sulfide clusters. The FAU-encaged Mo₄ S₄ clusters have a distorted cubane structure similar to the FeMo-cofactor in nitrogenase. Both clusters possess unpaired electrons on Mo atoms. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stable (>150 h) for ethene hydrogenation, while layered MoS₂ structures deactivate significantly under the same reaction conditions.

SUBMITTER: Weindl R

PROVIDER: S-EPMC8252740 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Zeolite-Stabilized Di- and Tetranuclear Molybdenum Sulfide Clusters Form Stable Catalytic Hydrogenation Sites.

Weindl Roland R Khare Rachit R Kovarik Libor L Jentys Andreas A Reuter Karsten K Shi Hui H Lercher Johannes A JA

Angewandte Chemie (International ed. in English) 20210317 17

Supercages of faujasite (FAU)-type zeolites serve as a robust scaffold for stabilizing dinuclear (Mo2 S4 ) and tetranuclear (Mo4 S4 ) molybdenum sulfide clusters. The FAU-encaged Mo4 S4 clusters have a distorted cubane structure similar to the FeMo-cofactor in nitrogenase. Both clusters possess unpaired electrons on Mo atoms. Additionally, they show identical catalytic activity per sulfide cluster. Their catalytic activity is stab ...[more]

PMID: 33576131

Similar Datasets

Hydrogen Activation on Zeolite Stabilized Ni-Mo Sulfide Clusters.

Project description:The activation of H2 on NaY-encapsulated Mo sulfide clusters is significantly influenced by the presence of Ni at ion exchange positions. Ni was incorporated by partially ion exchanging the NaY zeolite with Ni2+ cations. Mo(CO)6 vapors were subsequently deposited on the ion exchanged NiNaY zeolites followed by sulfidation in 10 vol % H2S/H2 at 673 K, leading to the formation of dimeric Mo2S4 clusters connected to Ni2+ via bridging S atoms. In contrast to the monometallic Mo sulfide clusters, which stabilize adsorbed hydrogen primarily as hydrides on Mo atoms, the bimetallic Ni-Mo sulfide clusters bind hydrogen also as sulfhydryl groups on the bridging sulfur atoms. The formation of sulfhydryl groups in Ni-Mo sulfide clusters is attributed to the lower electron density on the cluster due to coordination with more electronegative Ni2+. The ethene hydrogenation rate was significantly higher on the bimetallic Ni-Mo sulfide catalysts compared to monometallic Mo sulfide catalysts because the stabilization of atomic hydrogen as sulfhydryl groups opens a new hydrogenation pathway.

| S-EPMC11862920 | biostudies-literature

Di- and Tetrameric Molybdenum Sulfide Clusters Activate and Stabilize Dihydrogen as Hydrides.

Project description:NaY zeolite-encapsulated dimeric (Mo2S4) and tetrameric (Mo4S4) molybdenum sulfide clusters stabilize hydrogen as hydride binding to Mo atoms. Density functional theory (DFT) calculations and adsorption measurements suggest that stabilization of hydrogen as sulfhydryl (SH) groups, as typical for layered MoS2, is thermodynamically disfavored. Competitive adsorption of H2 and ethene on Mo was probed by quantifying adsorbed CO on partly hydrogen and/or ethene covered samples with IR spectroscopy. During hydrogenation, experiment and theory suggest that Mo is covered predominately with ethene and sparsely with hydride. DFT calculations further predict that, under reaction conditions, each Mo x S y cluster can activate only one H2, suggesting that the entire cluster (irrespective of its nuclearity) acts as one active site for hydrogenation. The nearly identical turnover frequencies (24.7 ± 3.3 molethane·h-1·molcluster -1), apparent activation energies (31-32 kJ·mol-1), and reaction orders (∼0.5 in ethene and ∼1.0 in H2) show that the active sites in both clusters are catalytically indistinguishable.

| S-EPMC8965828 | biostudies-literature

Catalytic hydrogenation of olefins by a multifunctional molybdenum-sulfur complex.

Project description:Exploration of molybdenum complexes as homogeneous hydrogenation catalysts has garnered significant attention, but hydrogenation of unactivated olefins under mild conditions are scarce. Here, we report the synthesis of a molybdenum complex, [Cp*Mo(Ph2PC6H4S-CH = CH2)(Py)]+ (2), which exhibits intriguing reactivity toward C2H2 and H2 under ambient pressure. This vinylthioether complex showcases efficient catalytic activity in the hydrogenation of various aromatic and aliphatic alkenes, demonstrating a broad substrate scope without the need for any additives. The catalytic pathway involves an uncommon oxidative addition of H2 to the cationic Mo(II) center, resulting in a Mo(IV) dihydride intermediate. Moreover, complex 2 also shows catalytic activity toward C2H2, leading to the production of polyacetylene and the extension of the vinylthioether ligand into a pendant triene chain.

| S-EPMC10821942 | biostudies-literature

Catalytic ammonia synthesis on HY-zeolite-supported angstrom-size molybdenum cluster.

Project description:The development of new catalysts with high N2 activation ability is an effective approach for low-temperature ammonia synthesis. Herein, we report a novel angstrom-size molybdenum metal cluster catalyst for efficient ammonia synthesis. This catalyst is prepared by the impregnation of a molybdenum halide cluster complex with an octahedral Mo6 metal core on HY zeolite, followed by the removal of all the halide ligands by activation with hydrogen. In this activation, the size of the Mo6 cluster (ca. 7 Å) is almost retained. The resulting angstrom-size cluster shows catalytic activity for ammonia synthesis from N2 and H2, and the reaction proceeds continuously even at 200 °C under 5.0 MPa. DFT calculations suggest that N[triple bond, length as m-dash]N bond cleavage is promoted by the cooperation of the multiple molybdenum sites.

| S-EPMC10882513 | biostudies-literature

Na4.25Mo15S19: a novel ternary reduced molybdenum sulfide containing Mo6 and Mo9 clusters.

Project description:The structure of tetra-sodium penta-deca-molybdenum nona-deca-sulfide, Na4.25Mo15S19, is isotypic with Na3.9Mo15Se19 [Salloum et al. (2013 ▶). Acta Cryst. E69, i67-i68]. It is characterized by Mo6S (i) 8S (a) 6 and Mo9S (i) 11S (a) 6 (where i represents inner and a apical atoms) cluster units that are present in a 1:1 ratio. The cluster units are centered at Wyckoff positions 2b and 2c, and have point-group symmetry -3 and -6, respectively. The clusters are inter-connected through additional Mo-S bonds. The Na(+) cations occupy inter-unit voids formed by six or seven S atoms. One Mo, one S and one Na site [occupancy 0.751 (12)] are situated on mirror planes, and two other S atoms and one Na site (full occupancy) are situated on threefold rotation axes.

| S-EPMC4051007 | biostudies-literature

De Novo Design of Tetranuclear Transition Metal Clusters Stabilized by Hydrogen-Bonded Networks in Helical Bundles.

Project description:De novo design provides an attractive approach to test the mechanism by which metalloproteins define the geometry and reactivity of their metal ion cofactors. While there has been considerable progress in designing proteins that bind transition metal ions including iron-sulfur clusters, the design of tetranuclear clusters with oxygen-rich environments has not been accomplished. Here, we describe the design of tetranuclear clusters, consisting of four Zn2+ and four carboxylate oxygens situated at the vertices of a distorted cube-like structure. The tetra-Zn2+ clusters are bound at a buried site within a four-helix bundle, with each helix donating a single carboxylate (Glu or Asp) and imidazole (His) ligand, as well as second- and third-shell ligands. Overall, the designed site consists of four Zn2+ and 16 polar side chains in a fully connected hydrogen-bonded network. The designed proteins have apolar cores at the top and bottom of the bundle, which drive the assembly of the liganding residues near the center of the bundle. The steric bulk of the apolar residues surrounding the binding site was varied to determine how subtle changes in helix-helix packing affect the binding site. The crystal structures of two of four proteins synthesized were in good agreement with the overall design; both formed a distorted cuboidal site stabilized by flanking second- and third-shell interactions that stabilize the primary ligands. A third structure bound a single Zn2+ in an unanticipated geometry, and the fourth bound multiple Zn2+ at multiple sites at partial occupancy. The metal-binding and conformational properties of the helical bundles in solution, probed by circular dichroism spectroscopy, analytical ultracentrifugation, and NMR, were consistent with the crystal structures.

| S-EPMC5860638 | biostudies-literature

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide.

Project description:Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13](2-) building blocks. Of the three terminal disulfide (S2(2-)) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.

| S-EPMC5495159 | biostudies-literature

Na2.9KMo12S14: a novel quaternary reduced molybdenum sulfide containing Mo12 clusters with a channel structure.

Project description:The crystal structure of tris-odium potassium dodeca-molybdenum tetra-deca-sulfide, Na2.9 (2)KMo12S14, consists of Mo12S14S6 cluster units inter-connected through inter-unit Mo-S bonds and delimiting channels in which the Na(+) cations are disordered. The cluster units are centered at Wyckoff positions 2d and have point-group symmetry 3.2. The K atom lies on sites with 3.2 symmetry (Wyckoff site 2c) between two consecutive Mo12S14S6 units. One of the three independent S atoms and one Na atom lie on sites with 3.. symmetry (Wyckoff sites 4e and 4f). The other Na atom occupies a 2b position with -3.. symmetry. The crystal studied was a merohedral twin with refined components of 0.4951 (13) and 0.5049 (13).

| S-EPMC3684867 | biostudies-literature

Renewable Cyclopentanol From Catalytic Hydrogenation-Rearrangement of Biomass Furfural Over Ruthenium-Molybdenum Bimetallic Catalysts.

Project description:Biomass furfural-like compounds are chemicals that cannot be extracted from fossil materials, through which a large number of fine chemicals and fuel additives can be opened up, but one big efficiency problem during the transformation is the accumulation of oligomers. Here, we propose a novel and efficient Ru-Mo bimetallic catalyst for selective hydrogenation-rearrangement of furfural-like compounds. The result showed that an unprecedented rearrangement product selectivity of 89.1% to cyclopentanol was achieved under an optimized reaction condition over a 1%Ru-2.5%Mo/CNT catalyst reduced at 600°C. Subsequent characterization suggested that the catalyst presented with weak acidity and strong hydrogenation activity for the reaction, which not only ensures the smooth hydrogenation-rearrangement reaction but also inhibits the accumulation of furan polymers. These findings provide a convenient strategy to tune the catalytic performance of Mo-based catalysts by controlling the reduction and carburization conditions, which appear to be versatile for the rearrangement of furans and similar compounds.

| S-EPMC7775491 | biostudies-literature

Structural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters.

Project description:Copper hydrides are important hydrogenation catalysts, but their poor stability hinders the practical applications. Ligand engineering is an effective strategy to tackle this issue. An amidinate ligand, N,N'-Di(5-trifluoromethyl-2-pyridyl)formamidinate (Tf-dpf) with four N-donors has been applied as a protecting agent in the synthesis of stable copper hydride clusters: Cu11H3(Tf-dpf)6(OAc)2 (Cu11) with three interfacial μ5-H and [Cu12H3(Tf-dpf)6(OAc)2]·OAc (Cu12) with three interstitial μ6-H. A solvent-triggered reversible interconversion between Cu11 and Cu12 has been observed thanks to the flexibility of Tf-dpf. Cu11 shows high activity in the reduction of 4-nitrophenol to 4-aminophenol, while Cu12 displays very low activity. Deuteration experiments prove that the type of hydride is the key in dictating the catalytic activity, for the interfacial μ5-H species in Cu11 are involved in the catalytic cycle whereas the interstitial μ6-H species in Cu12 are not. This work highlights the role of hydrides with regard to catalytic hydrogenation activity.

| S-EPMC9018778 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data