An ab initio and DFT study of the interaction between ethanethiol and zeolites

Soscún, Humberto; Castellano, Olga; Hernández, Javier; Arrieta, Federico; Bermúdez, Yaneth; Hinchliffe, Alan; Brussin, Marcos Rosa; Sanchéz, Morella; Sierraalta, Aníbal; Ruette, Fernando

doi:10.1016/j.molcata.2007.07.051

Cited by 15 publications

(16 citation statements)

References 14 publications

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“…The DFT geometry optimization at cation sites (Fig.4a) shows how the non-bonding pair electron of the sulfur atom in the ethanethiol molecule contributes to the formation of a strong hydrogen bond with the hydrogen atoms of NH + 4 in ZSM-5. 39 Indeed, the bonds between sulfur and H + in NH + 4 -ZSM-5 (2.1 Å) are the shortest bonds formed in the cavity. The heat of adsorption of propanethiol on homogenous SiO framework of zeolites is higher than the heat of adsorption of ethanethiol by 16% for MFI frameworks ( Table 2).…”

Section: Resultsmentioning

confidence: 99%

Nanocellulose–Zeolite Composite Films for Odor Elimination

Keshavarzi

Rad

Mace

et al. 2015

ACS Appl. Mater. Interfaces

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Free standing and strong odor-removing composite films of cellulose nanofibrils (CNF) with a high content of nanoporous zeolite adsorbents have been colloidally processed. Thermogravimetric desorption analysis (TGA) and infrared spectroscopy combined with computational simulations showed that commercially available silicalite-1 and ZSM-5 have a high affinity and uptake of volatile odors like ethanethiol and propanethiol, also in the presence of water. The simulations showed that propanethiol has a higher affinity, up to 16%, to the two zeolites compared with ethanethiol. Highly flexible and strong free-standing zeolite-CNF films with an adsorbent loading of 89 w/w% have been produced by Ca-induced gelation and vacuum filtration. The CNF-network controls the strength of the composite films and 100 μm thick zeolite-CNF films with a CNF content of less than 10 vol % displayed a tensile strength approaching 10 MPa. Headspace solid phase microextraction (SPME) coupled to gas chromatography-mass spectroscopy (GC/MS) analysis showed that the CNF-zeolite films can eliminate the volatile thiol-based odors to concentrations below the detection ability of the human olfactory system. Odor removing zeolite-cellulose nanofibril films could enable improved transport and storage of fruits and vegetables rich in odors, for example, onion and the tasty but foul-smelling South-East Asian Durian fruit.

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Section: Resultsmentioning

confidence: 99%

Nanocellulose–Zeolite Composite Films for Odor Elimination

Keshavarzi

Rad

Mace

et al. 2015

ACS Appl. Mater. Interfaces

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“…3). [4,6,22,28,[34][35][36][37][38] 4 ] + dibenzothiophene + benzoquinoline (95.762 kcal/mol) systems gave positive interaction energy values, which is again indicating that the dissimilar structure of the molecules also does not guarantee the similarity of the nature of orientation and attraction. [33] However, when these dissimilar and similar structural molecules lose their high lone pair of electron density on the heteroatom and π-electron cloud density around their aromatic ring into their neighboring molecules and then can often have structural orientation through NH (five-membered rings of nitrogen)--π (cation) interaction, π (fivemembered rings of sulfur/nitrogen)-π (cation) interaction, and CH (cation)-π (five-membered rings of sulfur/nitrogen) interaction (Fig.…”

Section: The Nature Of 1-ethyl-3-methylimidazolium Ethylsulfatementioning

confidence: 98%

Simultaneous interaction between similar and dissimilar structures of aromatic sulfur and aromatic nitrogen compounds with imidazolium‐based ionic liquid using quantum chemical method

Ramalingam¹,

Jewaratnam

2015

Asia-Pacific J Chem Eng

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Molecular structure, interaction energy, orbital energy, partial charges, and molecular properties of the complex system of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSo 4 ]) + similar or dissimilar structure of thiophene/ benzothiophene/dibenzothiophene/pyrrole/indole/indoline/carbazole/benzacarbazole/pyridine/quinoline/benzoquinoline were predicted using quantum chemical method with 6-31G* basis set. Subsequently, the sigma profile was generated for the similar molecules in the system in order to explain the cause of solvent selectivity and capacity for simultaneous desulfurization and denitrification of liquid fuels. Furthermore, the activity coefficients at infinite dilution of similar or dissimilar structure of compounds in [EMIM][EtSo 4 ] were predicted using quantum chemical method to understand the chemical behavior of [EMIM][EtSo 4 ] with similar or dissimilar structure of the molecules in the complex system. On the other hand, the solvent selection parameters such as selectivity, capacity, and performance index were calculated from the predicted activity coefficient at infinite dilution for all the studied species. The solvent selection parameters showed high values for low order of aromatic ring compounds (i.e. pyrrole, indole, indoline, carbazole, pyridine, quinoline, and thiophene) but gave low values for high order of aromatic compounds like benzothiophene, dibenzothiophene, benzacarbazole, and benzoquinoline.

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“…Consequently, the study of the electronic properties of zeolites using high level ab initio quantum chemical methods, is often performed for relatively small clusters, usually three tetrahedral units, where the examination is focused on the most important active part of zeolite. [27][28][29][30][31][32][33] These studies have given interesting details of the adsorption process and the catalytic mechanism, but due to the small size of the clusters employed, the e®ect of the framework that plays an important role on the structure and energetics of the system is neglected and not taken into account. As a result, the contribution of the van der Waals interactions between adsorbed species and the zeolite walls in the energetics of adsorption/ desorption process is frequently underestimated.…”

Section: Introductionmentioning

confidence: 99%

Adsorption enthalpies of alkyl halides in a FAU acidic zeolite investigated by the ONIOM2 method

Papayannis

Kosmas

2015

J. Theor. Comput. Chem.

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The adsorption of a series of alkyl halides, RX (X¼Cl, Br, I) over acidic zeolite has been investigated by the ONIOM2 method. A 56T model cluster constructed from 55 Si atoms and one tetrahedral Al atom with one Br€ onsted acid site, has been used to represent the zeolite catalyst. Density functional theory (DFT) and speci¯cally, the two layered schemes B3LYP/6-31þG(d,p) genECP:UFF and M06-2X/6-31þG(d,p)genECP:UFF have been employed, augmented with the addition of extra polarization functions for the proper treatment of the halogen atoms. Examination of selective structural changes and the computed adsorption enthalpies, ÁH ad , of the van der Waals 1:1 adsorption complexes assumingly formed, shows a strong dependence both on the theoretical method and the alkyl radical structure. A modest in°uence of the halogen atom involved is also observed. The comparison of the performance of the two functionals underlines the higher capacity of the M06-2X functional to provide a more satisfactory description of the adsorption process and the contribution of the van der Waals dispersion forces.

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An ab initio and DFT study of the interaction between ethanethiol and zeolites

Cited by 15 publications

References 14 publications

Nanocellulose–Zeolite Composite Films for Odor Elimination

Nanocellulose–Zeolite Composite Films for Odor Elimination

Simultaneous interaction between similar and dissimilar structures of aromatic sulfur and aromatic nitrogen compounds with imidazolium‐based ionic liquid using quantum chemical method

Adsorption enthalpies of alkyl halides in a FAU acidic zeolite investigated by the ONIOM2 method

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