Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Theoretical study of the adsorption of benzene on coinage metals.

ABSTRACT: The adsorption of benzene on the M(111), M(100) and M(110) surfaces of the coinage metals copper (M = Cu), silver (M = Ag) and gold (M = Au) is studied on the basis of density functional theory (DFT) calculations with an empirical dispersion correction (D3). Variants of the Perdew-Burke-Ernzerhof functionals (PBE, RPBE and RevPBE) in combination with different versions of the dispersion correction (D3 and D3(BJ)) are compared. PBE-D3, PBE-D3(BJ) and RPBE-D3 give similar results which exhibit a good agreement with experimental data. RevPBE-D3 and RevPBE-D3(BJ) tend to overestimate adsorption energies. The inclusion of three-center terms (PBE-D3(ABC)) leads to a slightly better agreement with the experiment in most cases. Vertical adsorbate-substrate distances are calculated and compared to previous theoretical results. The observed trends for the surfaces and metals are consistent with the calculated adsorption energies.

SUBMITTER: Reckien W

PROVIDER: S-EPMC4142854 | biostudies-literature | 2014

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Theoretical study of the adsorption of benzene on coinage metals.

Reckien Werner W Eggers Melanie M Bredow Thomas T

Beilstein journal of organic chemistry 20140804

The adsorption of benzene on the M(111), M(100) and M(110) surfaces of the coinage metals copper (M = Cu), silver (M = Ag) and gold (M = Au) is studied on the basis of density functional theory (DFT) calculations with an empirical dispersion correction (D3). Variants of the Perdew-Burke-Ernzerhof functionals (PBE, RPBE and RevPBE) in combination with different versions of the dispersion correction (D3 and D3(BJ)) are compared. PBE-D3, PBE-D3(BJ) and RPBE-D3 give similar results which exhibit a g ...[more]

PMID: 25161736

Similar Datasets

A (μ-hydrido)diborane(4) anion and its coordination chemistry with coinage metals.

Project description:A tetra(o-tolyl) (μ-hydrido)diborane(4) anion 1, an analogue of [B2H5]- species, was facilely prepared through the reaction of tetra(o-tolyl)diborane(4) with sodium hydride. Unlike common sp2-sp3 diborane species, 1 exhibited a σ-B-B bond nucleophilicity towards NHC-coordinated transition-metal (Cu, Ag, and Au) halides, resulting in the formation of η2-B-B bonded complexes 2 as confirmed by single-crystal X-ray analyses. Compared with 1, the structural data of 2 imply significant elongations of B-B bonds, following the order Au > Cu > Ag. DFT studies show that the diboron ligand interacts with the coinage metal through a three-center-two-electron B-M-B bonding mode. The fact that the B-B bond of the gold complex is much prolonged than the related Cu and Ag compounds might be ascribed to the superior electrophilicity of the gold atom.

| S-EPMC8905795 | biostudies-literature

Theoretical Study of As?O? Adsorption Mechanisms on CaO surface.

Project description:Emission of hazardous trace elements, especially arsenic from fossil fuel combustion, have become a major concern. Under an oxidizing atmosphere, most of the arsenic converts to gaseous As?O?. CaO has been proven effective in capturing As?O?. In this study, the mechanisms of As?O? adsorption on CaO surface under O? atmosphere were investigated by density functional theory (DFT) calculation. Stable physisorption and chemisorption structures and related reaction paths are determined; arsenite (AsO?3-) is proven to be the form of adsorption products. Under the O? atmosphere, the adsorption product is arsenate (AsO?3-), while tricalcium orthoarsenate (Ca?As?O?) and dicalcium pyroarsenate (Ca?As?O?) are formed according to different adsorption structures.

| S-EPMC6416740 | biostudies-literature

Relevance of Orbital Interactions and Pauli Repulsion in the Metal-Metal Bond of Coinage Metals.

Project description:The importance of relativity and dispersion in metallophilicity has been discussed in numerous studies. The existence of hybridization in the bonding between closed shell d10-d10 metal atoms has also been speculated, but the presence of attractive MO interaction in the metal-metal bond is still a matter of an ongoing debate. In this comparative study, a quantitative molecular orbital analysis and energy decomposition is carried out on the metallophilic interaction in atomic dimers (M+···M+) and molecular perpendicular [H3P-M-X]2 (where M = Cu, Ag, and Au; X = F, Cl, Br, and I). Our computational studies prove that besides the commonly accepted dispersive interactions, orbital interactions and Pauli repulsion also play a crucial role in the strength and length of the metal-metal bond. Although for M+···M+ the orbital interaction is larger than the Pauli repulsion, leading to a net attractive MO interaction, the bonding mechanism in perpendicular [H3P-M-X] dimers is different due to the larger separation between the donor and acceptor orbitals. Thus, Pauli repulsion is much larger, and two-orbital, four-electron repulsion is dominant.

| S-EPMC5842375 | biostudies-literature

Theoretical Study of Hydrogen on LaFeO₃ (010) Surface Adsorption and Subsurface Diffusion.

Project description:Based on density functional theory, this paper studies the adsorption and the subsurface occupation by H on LaFeO₃ (010) surface and their corresponding transition states. As shown from the results, the best storage positions of hydrogen are on the O top position of the LaFeO₃ (010) surface and the interstice near the oxygen of the subsurface. In addition, the position of surface Fe atom can also store hydrogen, but H atom prefers to adsorb on O atom first. Whether the H atom is adsorbed on O or Fe atom, it is easy diffuse to the nearby more stable O atom. However, the diffusion between the Fe atoms is difficult to occur. The main diffusion path of the H atom from the surface to the subsurface is the process of inward layer by layer around the O atom. With the fracture of the old H⁻O bond and the formation of the new H⁻O bond, the H is around O atom to constantly repeat the process of a hopping-rotational diffusion. H diffuses through the nearest neighbor position, which is more favorable than the direct diffusion.

| S-EPMC6316970 | biostudies-literature

Switching Xe/Kr adsorption selectivity in modified SBMOF-1: a theoretical study.

Project description:The separation of Xe/Kr mixtures in used nuclear fuel (UNF) has attracted lots of attention, but no report on the adsorption and separation of Kr from mixed Kr/Xe at room temperature can be found. From grand canonical Monte Carlo (GCMC) simulation, it is found that by replacing the metal center Ca of SBMOF-1 with Mg, due to the appropriate pore size, the adsorption selectivity (S Kr/Xe) was extremely high (250 000) and the adsorption capacity for Kr on Mg-SBMOF-1 modified with -NH2 was increased by 300% to 1.020 from 0.248 mmol g-1. Based on the calculations of density functional theory (DFT), we found that the stronger electron-donating ability of a functional group will increase the polarizability of the ligand, and thus increase the adsorption capacity to Kr. In addition, the analysis of electronic structures with independent gradient model (IGM) and energy decomposition analysis (EDA) indicates that van der Waals forces will be responsible for the interaction of Mg-SBMOF-1 and Kr gas. Among them, the interaction of Mg-SBMOF-1 and Kr gas is mainly an induction force, while that of modifications with -CH3 and -NH2 is mainly a dispersion force. The present theoretical study represents the first report of the separation of Kr from Xe with MOF adsorption at room temperature. We hope this work may promote the experimental synthesis of Mg-SBMOF-1 for efficient separation of Kr and Xe.

| S-EPMC9053438 | biostudies-literature

Benzene effects on leaves: Study of benzene metabolism in higher plants.

Project description:au12-01_detox; Improving the knowledge of the metabolic pathways of benzene in higher plants Cabbages (Brassica oleracea Var. Prover)are directly submitted to a one dose of benzene (3ppm) during 1 hour or 3 hours. The comparison is realized between samples treated and untreated to the benzene for both exhibitions.

2013-07-01 | GSE48179 | GEO

Adsorption of Aspartic Acid on Ni{100}: A Combined Experimental and Theoretical Study.

Project description:Understanding the interaction of amino acids with metal surfaces is essential for the rational design of chiral modifiers able to confer enantioselectivity to metal catalysts. Here, we present an investigation of the adsorption of aspartic acid (Asp) on the Ni{100} surface, using a combination of synchrotron X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure, and density functional theory simulations. Based on the combined analysis of the experimental and simulated data, we can identify the dominant mode of adsorption as a pentadentate configuration with three O atoms at the bridge sites of the surfaces, and the remaining oxygen atom and the amino nitrogen are located on atop sites. From temperature-programmed XPS measurements, it was found that Asp starts decomposing above 400 K, which is significantly higher than typical decomposition temperatures of smaller organic molecules on Ni surfaces. Our results offer valuable insights into understanding the role of Asp as a chiral modifier of nickel catalyst surfaces in enantioselective hydrogenation reactions.

| S-EPMC7458468 | biostudies-literature

A theoretical study of CO adsorption on Cu(211) surface with coverage effects.

Project description:CO adsorption on the Cu(211) surface was investigated using energy, geometry and vibrational data, which were produced through periodic DFT computations. Adsorption on the (111) terrace, as well as the previously reported top and bridge sites of the step-edges, was studied at 0.25, 0.33, 0.50, 0.66, 0.75, and 1.00 monolayer (ML) CO coverage. Results showed that up to and including 0.50 ML, on-top or bridge adsorption is preferred on the step-edges. When 0.50 ML is exceeded, top-bridge alternating patterns become feasible on the step edges along with possible shifts towards the terrace. Several feasible patterns were identified at 0.66, 0.75, and 1.00 ML. Like step-edge adsorptions, alternating patterns on the terrace sites were found feasible at higher coverages. For all the studied cases, highest adsorption energies were found for the step-edge positions. In general, coordination number had a stronger effect than coverage on the calculated properties.

| S-EPMC10395743 | biostudies-literature

Cadmium oxide nanoparticles/graphene composite: synthesis, theoretical insights into reactivity and adsorption study.

Project description:Graphene-based metal oxide nanocomposites are interesting and promising kinds of nanocomposites due to their large specific area, fast kinetics, and specific affinity towards heavy metal contaminants. In this work, a facile and cost-effective route was used to synthesize CdO nanoparticles (CdO NPs) and graphene-based CdO nanocomposite (G-CdO). The prepared nanomaterials were characterized and explored for lead removal from water. Both CdO NPs and G-CdO composite exhibited excellent sorption capacity of 427 and 398 mg g-1, respectively, at pH 4.8 and T = 298 K, which was superior to individual graphene and many other adsorbents. The results indicated that the recovered nanomaterials endure 4 times recyclability retaining up to 89% lead uptake efficiency. To complement the experimental study, DFT calculations were performed to investigate the stability of the formed G-CdO composite compared to CdO NPs; the reactivity of G-CdO compared to plain graphene as well as the interaction insights between graphene and CdO clusters were studied using natural-bond-orbital (NBO), electron-localization-function (ELF) and reduced-density-gradient (RDG) analyses.

| S-EPMC9037664 | biostudies-literature

A theoretical study of formaldehyde adsorption and decomposition on a WC (0001) surface.

Project description:A lot of research attention has been paid to designing and exploring efficient adsorbents for HCHO adsorption and decomposition. Herein, we have demonstrated a highly active material, WC, for HCHO adsorption through first-principles calculations. Due to the exposed three-coordinated W atoms (W3c) of the WC (0001) surface, HCHO molecules can be settled on the WC (0001) surface through newly formed OF-W3c and/or CF-W3c bonds, forming different adsorption configurations. When settled on the WC (0001) surface, the molecular configuration of the HCHO molecule and the corresponding CF-HF and CF-OF bond lengths would be greatly changed. Due to the enlarged CF-HF and CF-OF bond lengths, the adsorbed HCHO molecules tend to dissociate through two possible pathways; these are the two-step CF-HF bond scission or the one-step CF-OF bond scission. The former results in two H adatoms and a CO molecule chemisorbed to the surface and the latter produces an O adatom and a CH2 group on the surface. Further Cl-NEB calculations demonstrate that the pre-adsorbed O atom has little influence on the first CF-HF bond scission and the CF-OF bond scission, while promoting the second CF-HF bond scission. Considering the dissociative products, H and CH2 have the potential to couple into a CH3 group (or even a CH4 molecule) and two CH2 groups may couple into a C2H4 molecule. In the end, we propose that OH ions may couple with the dissociative products of HCHO, so an alkali solution could be used to post-process the WC (0001) surface to restore its surface active sites. These results demonstrated the potential of WC in HCHO sensing and abatement.

| S-EPMC9086214 | 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