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61.
The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite (host) frameworks displaying different pore sizes, have been studied as solid hosts: mazzite (MAZ), AIPO-8 (AET), UTD-1F (DON), faujasite (FAU), and VPI-5 (VFI). Intermediates and transition states involved in the ethylene trimerization reaction catalyzed by a Ti-based catalyst [(η(5)-C(5)H(4)CMe(2)C(6)H(5))TiCl(3)/MAO] have been used as sorbates (guests). We have demonstrated linear correlations with slope a(H,j) between the adsorption enthalpy and the molecular volume V(m) of the sorbates, each holding for a given microporous host below a host-specific threshold V(mmax,j). Beyond this maximal molecular volume, the adsorption vanishes due to steric exclusion. a(H,j) increases, and V(mmax,j) decreases with decreasing host pore size, in line with the confinement concept. We moreover showed that, in the limit of vanishing loading (Henry regime), the enthalpies and entropies of adsorption in a given host are linearly correlated. We have defined a host-specific confinement compensation temperature a(j), which refers to a temperature where the stabilizing adsorption enthalpic interactions are canceled out against the loss in entropy. However, calculated a(j) are much larger than the operating temperatures. With a setup microkinetic model, we predict that the activity and selectivity of the confined Ti-catalyst in ethylene oligomerization can be significantly altered with respect to homogeneous phase conditions, since the adsorption free energies of transition states and intermediates also become functions of a(H,j) and V(m). We have applied this theory to predict the optimum host pore size to get maximum α-octene production, instead of α-hexene, which is primarily produced in the homogeneous phase. We also predict a significantly increased activity for confined catalysts. 相似文献
62.
The absorption spectra of 5 nm noble metal nanoparticles (Ag, Au, and Cu) with typical morphologies of multiply twinned particles (MTPs) and single crystals are calculated by using the discrete dipole approximation method. Among the considered morphologies, it is found that icosahedral, cuboctahedral and truncated octahedral particles behave like quasispherical particles whereas the optical response of the decahedral particles significantly differs from the others. This result, which originates from the shape anisotropy of the decahedron, points out the capacity to discriminate decahedral MTPs from a population of particles with mixed crystallinities and related quasispherical shapes. 相似文献
63.
Besson C Mirebeau JH Renaudineau S Roland S Blanchard S Vezin H Courillon C Proust A 《Inorganic chemistry》2011,50(6):2501-2506
The scope of N-atom transfer from the electrophilic ruthenium(VI) nitrido containing polyoxometalate [PW(11)O(39)Ru(VI)N](4-) has been extended to the N-heterocyclic carbene {CH(2)(Mes)N}(2)C and the coupling product {CH(2)(Mes)N}(2)CNH(2)(+) characterized by (1)H NMR and high-resolution mass spectrometry. Because guanidines display many fields of applications ranging from biology to supramolecular chemistry, this could afford an original route to the synthesis of cyclic guanidines. This also enlarges the potential of nitrido complexes in the synthesis of heterocycles, mainly illustrated in the literature through the formation of aziridines through N-atom transfer to alkenes. In the course of the reaction, the ruthenium(III)-containing polyoxometallic intermediate [PW(11)O(39)Ru(III){NC{N(Mes)CH(2)}(2)}](5-) has been thoroughly characterized by continuous-wave and pulsed electron paramagnetic resonance, which nicely confirms the presence of the organic moiety on the polyoxometallic framework, Ru K-edge X-ray absorption near-edge structure, and electrochemistry. 相似文献
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66.
High sensitive matrix-free mass spectrometry analysis of peptides using silicon nanowires-based digital microfluidic device 总被引:1,自引:0,他引:1
Lapierre F Piret G Drobecq H Melnyk O Coffinier Y Thomy V Boukherroub R 《Lab on a chip》2011,11(9):1620-1628
We present for the first time an electrowetting on dielectric (EWOD) microfluidic system coupled to a surface-assisted laser desorption-ionization (SALDI) silicon nanowire-based interface for mass spectrometry (MS) analysis of small biomolecules. Here, the transfer of analytes has been achieved on specific locations on the SALDI interface followed by their subsequent mass spectrometry analysis without the use of an organic matrix. To achieve this purpose, a device comprising a digital microfluidic system and a patterned superhydrophobic/superhydrophilic silicon nanowire interface was developed. The digital microfluidic system serves for the displacement of the droplets containing analytes, via an electrowetting actuation, inside the superhydrophilic patterns. The nanostructured silicon interface acts as an inorganic target for matrix-free laser desorption-ionization mass spectrometry analysis of the dried analytes. The proposed device can be easily used to realize several basic operations of a Lab-on-Chip such as analyte displacement and rinsing prior to MS analysis. We have demonstrated that the analysis of low molecular weight compounds (700 m/z) can be achieved with a very high sensitivity (down to 10 fmol μL(-1)). 相似文献
67.
Zhuoying Chen Brice Nadal Benoit Mahler Hervé Aubin Benoit Dubertret 《Advanced functional materials》2014,24(3):295-302
The first functional light‐emitting diodes (LEDs) based on quasi 2D colloidal core/shell CdSe/CdZnS nanoplatelets (NPLs). The solution‐processed hybrid devices are optimized with respect to their electroluminescent characteristics, first, by improving charge injection through exchanging the as‐synthesized NPL long‐chain ligands to shorter ones such as 3‐mercaptopropionic acid, and second, by comparing different hole‐transporting layers. NPL‐LEDs exhibit a maximum luminance of 4499 cd m‐2 and external quantum efficiencies of 0.63%. In particular, over different applied voltages, systematically narrow electroluminescence of full width at half maximum (FWHM) in the range of 25–30 nm is observed to be independent from the choice of device configuration and NPL ligands. As spectrally narrow electroluminescence is highly attractive in terms of color purity in the context of LED applications, these results emphasize the unique potential of this new class of colloidal core/shell nanoplatelet in achieving bright and functional LEDs of superior color purity. 相似文献
68.
Mérièm Anouti Amina Mirghani Johan Jacquemin Laure Timperman Hervé Galiano 《Ionics》2013,19(12):1783-1790
Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV–visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs. 相似文献
69.
Martin Me Court Eric Imbert Pascale Vincensini-fort Jérôme Mars Hervé Ribot Dominique Persegol Thierry Jacquemin Josette Toussan-berger Denis Trystram José Camargo da Costa Mahmoud Helal Atman Guerchaoui Noureddine Mhaya Ignacio Jesus Ania de Briseno Chien Nguyen Duc Laurent Chety 《电信纪事》1989,44(3-4):194-197
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