DFT‐Based Coverage‐Dependent Model of Pt‐Catalyzed NO Oxidation

Getman, Rachel B.; Schneider, William F.

doi:10.1002/cctc.201000146

Cited by 96 publications

(100 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After NO adsorption on O 2 /Ov surface, a structure as shown in Fig. 7 Fajin et al (2010);Getman and Schneider (2010) and Fajin et al (2011) studied the adsorption of NO and O 2 at Au and Pt surface, they stated that ONOO* structure is the most stable configuration and reaction intermediate. It is suggested that ONOO* can decompose to NO 2 * and O*, and even direct desorption of NO 2 could be feasible (Fajin et al, 2011).…”

Section: Co-adsorption Of No and O 2 On Defective Mn-doped Ceo 2 (111mentioning

confidence: 99%

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

Liu¹,

Zheng²,

Wang³

et al. 2018

Aerosol Air Qual. Res.

View full text Add to dashboard Cite

The adsorption of NO molecules on Mn-doped CeO 2 (111) surfaces for NO oxidation has been studied by employing the periodic density functional theory plus U (DFT+U) method. Through our calculations, it is demonstrated how Mn-doped CeO 2 with superior NO oxidation activity benefits from the high mobility of the oxygen near the Mn cations. On unreduced Mn-doped CeO 2 (111) surfaces, the NO molecule preferentially interacted with the first neighboring O of the Mn cation, with the N also bonding to an Mn cation (E ads = -3.30 eV) or Ce cation (E ads = -2.90 eV). When NO adsorbs on the surface of defective Mn-doped CeO 2 with O 2 adsorbed in advance, an ONOO* four atoms species is formed on the surface (E ads = -2.51 eV and -2.02 eV), which is an intermediate and can decompose into NO 2 , NO 2 * and O*. The adsorption structure with higher adsorption energy has a closer geometry to NO 2 , indicating a deeper oxidation of NO. The calculation results indicate that the presence of Mn only has a strong effect on the nearby oxygen atoms and that the Mndoped CeO 2 surface has similar properties to a noble metal in NO oxidation catalysis. In DOS plots, the spin of the electron state of the adsorption structures involving the oxidation of NO is symmetric, indicating that electron transfer occurs from the slab to NO and strong covalent bonds are formed between N and O on the slab, which can also be confirmed by the charge density difference plots.

show abstract

Section: Co-adsorption Of No and O 2 On Defective Mn-doped Ceo 2 (111mentioning

confidence: 99%

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

Liu¹,

Zheng²,

Wang³

et al. 2018

Aerosol Air Qual. Res.

View full text Add to dashboard Cite

show abstract

“…This process is exothermic for θ O b 0. 25 [46,48]. The dissociation is exothermic (−0.39 eV) with a relatively low barrier (0.66 eV) on the triangle configuration (θ O = 0.25 ML) due to the availability of a "free" fcc site, i.e., a vacancy in the p(2 × 2)-O lattice due to one O atom in that lattice being out of place.…”

Section: O 2 Adsorption and Dissociationmentioning

confidence: 98%

“…Associative O 2 adsorption, O 2 + * → O 2 * (reactions 3, 5, and 30) depends strongly on the local coverage of oxygen atoms [46,47]. This process is exothermic for θ O b 0.…”

Section: O 2 Adsorption and Dissociationmentioning

confidence: 99%

“…We considered two 1-butanol formation reactions starting from a 1-butoxy intermediate, C 4 H 9 O* + H* → C 4 H 9 OH* + * (reactions 12, 21, and 35) and C 4 H 9 O* + OH* → C 4 H 9 OH* + O* (reactions [44][45][46], as well as one reaction starting from a 1-butyl intermediate, C 4 H 9 * + OH* → C 4 H 9 OH* + * (reactions 13, 22, and 34). For the oxygen overlayer configurations considered in this work, we find that the reactions originating from C 4 H 9 O* are exothermic (by 0.14-1.15 eV) with small barriers (0.14-0.43).…”

Section: -Butanol Formation/decompositionmentioning

confidence: 99%

See 1 more Smart Citation

Implications of sterically constrained n-butane oxidation reactions on the reaction mechanism and selectivity to 1-butanol

2016

Self Cite

View full text Add to dashboard Cite

Density functional theory (DFT) is used to analyze the reaction network in n-butane oxidation to 1-butanol over a Ag/Pd alloy catalyst under steric constraints, and the implications on the ability to produce 1-butanol selectively using MOF-encapsulated catalysts are discussed. MOFs are porous crystalline solids comprised of metal nodes linked by organic molecules. Recently, they have been successfully grown around metal nanoparticle catalysts. The resulting porous networks have been shown to promote regioselective chemistry, i.e., hydrogenation of trans-1,3-hexadiene to 3-hexene, presumably by forcing the linear alkene to stand "upright" on the catalyst surface and allowing only the terminal C-H bonds to be activated. In this work, we extend this concept to alkane oxidation. Our goal is to determine if a MOF-encapsulated catalyst could be used to selectively produce 1-butanol. Reaction energies and activation barriers are presented for more than 40 reactions in the pathway for n-butane oxidation. We find that C-H bond activation proceeds through an oxygen-assisted pathway and that butanal and 1-butanol are some of the possible products.

show abstract

“…First-principles electronic-structure theory [1][2][3][4][5][6][7][8][9][10][11][12][13] allows to gain unbiased insights into the microscopic, quantum-mechanical effects that are at the heart of modern nanotechnology [14][15][16][17][18][19][20][21][22][23][24] . However, often full ab-initio studies on systems of experimental relevance remain challenging since the computational effort grows immensely with system size 25 .…”

Section: Motivationmentioning

confidence: 99%

Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

Schmidt

Albuquerque

Kempe

et al. 2016

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We investigate the electronic structure of a Palladium nanoparticle that is partially embedded in a matrix of silicon carbonitride. From classical molecular dynamics simulations we first obtain a representative atomic structure. This geometry then serves as input to density-functional theory calculations that allow us to access the electronic structure of the combined system of particle and matrix. In order to make the computations feasible, we devise a subsystem strategy for calculating the relevant electronic properties. We analyze the Kohn-Sham density of states and pay particular attention to d-states which are prone to be affected by electronic self-interaction. We find that the density of states close to the Fermi level is dominated by states that originate from the Palladium nanoparticle. The matrix has little direct effect on the electronic structure of the metal. Our results contribute to explaining why silicon carbonitride does not have detrimental effects on the catalytic properties of palladium particles and can serve positively as a stabilizing mechanical support. MotivationFirst-principles electronic-structure theory 1-13 allows to gain unbiased insights into the microscopic, quantum-mechanical effects that are at the heart of modern nanotechnology [14][15][16][17][18][19][20][21][22][23][24] . However, often full ab-initio studies on systems of experimental relevance remain challenging since the computational effort grows immensely with system size 25 . For instance, in many experiments metal nanoparticles that have a diameter of several nm and contain several hundreds or thousands of atoms are used. For such systems, tens of thousands of electrons have to be taken into account for first-principles studies. Even with modern computers using massive parallelization, geometry optimizations and detailed investigations of the electronic structure of systems of that size are out of reach. Therefore, strategies have to be devised how insights can be gained into large systems despite of these computational limitations. In this work, we take a first step in this direction and investigate a palladium nanoparticle which is partially embedded in a matrix of silicon carbonitride (SiCN).This system is of practical relevance because noble-metal nanoparticles, in particular nanoparticles containing Pd, are effective catalysts for a wide range of chemical reactions [26][27][28][29][30] . In comparison to bulk metals, nanoparticles exhibit a high surface-

show abstract

DFT‐Based Coverage‐Dependent Model of Pt‐Catalyzed NO Oxidation

Cited by 96 publications

References 58 publications

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

NO Adsorption and Oxidation on Mn Doped CeO2 (111) Surfaces: A DFT+U Study

Implications of sterically constrained n-butane oxidation reactions on the reaction mechanism and selectivity to 1-butanol

Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

Contact Info

Product

Resources

About