A systematic study of CO oxidation on metals and metal oxides: density functional theory calculations

CO oxidation on Ru(0001), Rh(111), Pd(111), Os(0001), Ir(111), Pt(111), and their corresponding metal oxides is studied using density functional theory. It is found that (i) the reactivity of metal oxide is generally higher than that of the corresponding metal, and (ii) on both metals and metal oxides, the higher the chemisorption energy is in the initial state, the larger the reaction barrier. The barriers are further analyzed by decomposing them into electronic and geometric effects, and the higher reactivity of metal oxides is attributed mainly to the surface geometric effect. Moreover, the electronic effect on both metals and metal oxides follows the same pattern: the shorter the OC-O bond distance in the TS, the higher the barrier.     

Density functional theory study of CO adsorption on molybdenum sulfide

CO adsorption on four MoSx (stoichiometric and nonstoichiometric) clusters has been investigated by using density functional method. It is found that CO prefers adsorption on the coordinatively unsaturated (1010) surface. The adsorption energy of high coverage shows the additivity as compared with that of one CO adsorption, and there is no significant repulsive interaction between the end-on adsorbed CO probes. The computed CO stretching frequencies (2000-2080 cm(-1)) agree perfectly with the experimental data (a broad band centered at 2070 cm(-1) with a tail extent to 2000 cm(-1)). No bridged CO adsorption is favored energetically under high CO concentration, and this might explain the catalytic ability of MoSx for C1 products instead of higher hydrocarbons and alcohols.     

Density functional theory of complex transition densities

We present an extension of Hohenberg-Kohn-Sham density functional theory to the domain of complex local potentials and complex electron densities. The approach is applicable to resonance (Siegert) [Phys. Rev. 56, 750 (1939)] states and other scattering and transport problems that can be described by a normalized state of a Hamiltonian containing a complex local potential. Such Hamiltonians are non-Hermitian and their eigenvalues are in general complex, the imaginary part being inversely proportional to the lifetime of the system. The one-to-one correspondence between complex local potentials nu and complex electron densities rho is established provided that the complex variables are sufficiently close to real local potentials and densities of nondegenerate ground states. We show that the exchange-correlation functionals, contributing to the complex energy, are determined through analytic continuation of their ground-state-theory counterparts. This implies that the exchange-correlation effects on the lifetime of a resonance are, under appropriate conditions, already determined by the functionals of the ground-state theory.     

Pre-combustion CO2 capture by transition metal ions embedded in phthalocyanine sheets

Transition metal (TM) embedded two-dimensional phthalocyanine (Pc) sheets have been recently synthesized in experiments [M. Abel, S. Clair, O. Ourdjini, M. Mossoyan, and L. Porte, J. Am. Chem. Soc. 133, 1203 (2010)], where the transition metal ions are uniformly distributed in porous structures, providing the possibility of capturing gas molecules. Using first principles and grand canonical Monte Carlo simulations, TMPc sheets (TM = Sc, Ti, and Fe) are studied for pre-combustion CO(2) capture by considering the adsorptions of H(2)/CO(2) gas mixtures. It is found that ScPc sheet shows a good selectivity for CO(2), and the excess uptake capacity of single-component CO(2) on ScPc sheet at 298 K and 50 bar is found to be 2949 mg/g, larger than that of any other reported porous materials. Furthermore, electrostatic potential and natural bond orbital analyses are performed to reveal the underlying interaction mechanisms, showing that electrostatic interactions as well as the donation and back donation of electrons between the transition metal ions and the CO(2) molecules play a key role in the capture.     

Density functional study of ammonia activation by late first-row transition metal cations

Density functional theory (DFT) in its B3LYP implementation is used to investigate the reaction of ammonia with the late (Co(+), Ni(+), and Cu(+)) first-row transition metal cations in both high- and low-spin states. The potential energy surfaces (PES's) leading to three different exit channels are closely examined. The binding energies for the reaction products are calculated and compared with the corresponding experimental values. A comparison with our earlier works covering the reactivity of the Sc-Fe series of cations is made in order to underline similarities and differences of the reaction mechanisms as well as to establish trends along the row.     

Density functional theory study of the nematic-isotropic transition in an hybrid cell

We have employed the density functional theory formalism to investigate the nematic-isotropic capillary transitions of a nematogen confined by walls that favor antagonist orientations to the liquid crystal molecules (hybrid cell). We analyze the behavior of the capillary transition as a function of the fluid-substrate interactions and the pore width. In addition to the usual capillary transition between isotropiclike to nematiclike states, we find that this transition can be suppressed when one substrate is wet by the isotropic phase and the other by the nematic phase. Under this condition the system presents interfacelike states which allow us to continuously transform the nematiclike phase to the isotropiclike phase without undergoing a sharp phase transition. Two different mechanisms for the disappearance of the capillary transition are identified. When the director of the nematiclike state is homogeneously planar-anchored with respect to the substrates, the capillary transition ends up in a critical point. This scenario is analogous to the observed in Ising models when confined in slit pores with opposing surface fields which have critical wetting transitions. When the nematiclike state has a linearly distorted director field, the capillary transition continuously transforms in a transition between two nematiclike states.     

Density functional calculation of transition metal cluster energy surfaces

A quantum field mechanics of an electron subsystem in 3D physical space as the topology of compact atomic clusters with spontaneously broken local canonical symmetry is used for investigation of different types of microdefects in the condensed state of transition metals. The theory is illustrated with results of calculation of small compact Fe_n clusters (n = 2, 6, 14).     

Density functional theory study of triangular molybdenum sulfide nanocluster and CO adsorption on it

A systematic density functional theory study has been carried out on the structure and stability of triangular molybdenum sulfide (MoS(x)()) models. On the basis of the structural and energetic comparison, the triangle Mo(28)S(84) (VII) cluster has been identified as a reasonable structure for triangular MoS(x)() model. Under reductive atmosphere, the most stable structure has bridging sulfur on edge sites and two H(2)S at each corner site. It is found that CO adsorption at the corner site represents the most stable conformation. Along with other stretching modes, the computed frequency at 2102 cm(-1) for CO at the corner agrees perfectly with the experimental observation.     

Polyol-modified layered double hydroxides with attenuated basicity for a truly reversible capture of CO2

Dendrimers bearing hydroxyl groups supported by layered double hydroxides (CO₃–LDH) with Mg/Al ratio ranging from 1:1 to 5:1 showed improved properties for the reversible capture of carbon dioxide (CO₂). The adsorption capacity of the starting LDH was due to the intrinsic base-like behavior, and was found to depend on the Mg/Al ratio. When contacted with polyol dendrimers in aqueous media, no intercalation took place. This was explained in terms of low exfoliation grade of LDH and hydrophobic character of the dendrimer molecules. The latter rather adsorb on the external surface of the LDH stacks for low dendrimer loadings, or aggregate into organic clusters for higher contents. Analyses through thermal programmed desorption of CO₂ revealed that dendrimer incorporation advantageously attenuates the basicity strength of the starting LDH support, by lowering the desorption temperature. The OH groups of the organic moiety were found to display an amphoteric character, and act as the main adsorption sites. The weak interactions with CO₂ facilitate easier release of the major part of adsorbed CO₂ at temperature not exceeding 80–100 °C. On polyol organo-LDHs, the reversible CO₂ retention was discussed herein in terms of acid–base interactions. This concept allows envisaging the capture of diverse pollutants and other greenhouse gases by modifying the chemical groups on the dendritic moiety.     

C-N coupling on transition metal surfaces: a density functional theory study

We have investigated the formation of C-N bonds from individual atoms and single hydrogenated moieties on a series of transition metals. These reactions play a role in HCN formation at high oxygen coverage, also known as Andrussow oxidation, and they are fundamental to understand the ability of other materials to form part of alloys where Pt is the major component. Dehydrogenations take place quite easily under these high oxygen conditions and thus, the C+N, HC+N, and N+CH recombinations to form HCN or its isomer CNH might represent the rate-limiting steps for the reaction. For all the metals in the present study we have found that the activation energy for the reactions between H(x)C and NH(y) (x,y = 0,1) involved in C-N formation follow a linear relationship with the adsorption energy of the N atom. This is due to the common nature of all these transition states, where N-containing fragments get activated from three-fold hollow sites to bridge positions. The slopes of the linear dependence, though, depend on the valence of the N fragment, i.e., smaller slopes are found for NH moieties with respect to N ones.     

Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems

Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.     

V2CO2 MXene负载过渡金属单原子催化剂氧还原和氢氧化活性的DFT研究

开发廉价且高性能的电催化剂对推动燃料电池的商业应用具有重要意义.二维(2D) MXenes和单原子(SAs)催化剂是催化研究中的两个前沿领域.2D MXenes材料具有独特的几何和电子结构,能够有效调节负载SAs的催化性能.而负载的SAs又会反过来影响2D MXenes材料的本征活性,使2D MXenes形成更加丰富的活性位,进而提升其催化性能.为了拓展2D负载SAs催化剂在燃料电池中的应用,本文采用密度泛函理论(DFT)计算,系统地研究了V2CO2 MXenes负载过渡金属(TM,包括一系列3d、部分4d和5d金属)SAs催化剂的稳定结构、电子结构及其催化氧还原(ORR)和氢氧化(HOR)的催化活性,并筛选出潜在的可替代贵金属铂的ORR/HOR的双功能催化剂.稳定结构计算结果表明,3d TM SAs倾向于以锚定的形式负载于V2CO2表面与O原子作用,而4d,5d TM原子倾向于以掺杂的形式负载于含氧空穴的V2CO2表面与V原子作用;同时,Sc,Ti,V,Rh,Pd,Pt,Ag和Au SAs在V2CO2表面因具有较高扩散能垒,不易团聚,具有较高的热力学稳定性.电子结构计算结果表明,锚定型的TM SAs与O形成共价键,伴随发生明显的电荷转移,带较多正电荷;掺杂型的TM SAs与V形成金属键,因TM-V和V-O键间电荷转移的协同影响,导致TM SAs仅带有少量的电荷.TM-V2CO2电子结构与ORR/HOR中间物种的吸附关系为,TM位点为ORR中间物种(O,OH和OOH)的吸附位点,且d电子数为1、5、10的TM比其他TM对ORR物种的吸附更弱;而TM-V2CO2表面的O原子为HOR中间物种(H)的有效吸附位点,且H的吸附强弱与O位点的电荷有关,即O位点负电荷越多,对H的吸附越弱.TM-V2CO2催化剂各活性位对ORR和HOR反应物种的选择性吸附结果表明,催化剂有利于形成丰富多样的活性位,并具备作为双功能催化剂的内在优势.TM-V2CO2催化剂ORR和HOR理论活性筛选发现:与Pt(111)相比,Sc-、Mn-、Rh-和Pt-V2CO2具有较高的ORR活性,而Sc-、Ti-、V-、Cr-和Mn-V2CO2表现出较高的HOR活性.其中,Sc-V2CO2和Mn-V2CO2因同时具有较高的ORR和HOR活性和稳定性,有望成为高效和低成本的燃料电池双功能催化剂.本文从研究TM-V2CO2性质和活性出发,深入研究了SAs与2D MXenes间相互作用及其对ORR与HOR催化活性的影响机制,筛选出了高效、低成本的ORR/HOR双功能催化剂,为合理设计燃料电池双功能催化剂提供了理论指导.     

Silicate coatings on titanium, modified with transition metal oxides and their activity in CO oxidation

CuO+M _x O _y /TiO₂+SiO₂/Ti composites (M = Mn, Fe, Co, Ni) were produced by plasma-electrolytic oxidation and impregnation, followed by annealing. The elemental and phase composition of these composites were examined and their activity series in CO oxidation was determined.     

Density functional theory study of H and H2 interacting with NiAl(110)

We present results of extensive density functional theory (DFT) calculations for H and H2 interacting with NiAl(110). Continuous representations of the full dimensional potential energy surface (PES) for the H/NiAl(110) and H2/NiAl(110) systems are obtained by interpolation of the DFT results using the corrugation reducing procedure. We find a minimum activation energy barrier of approximately 300 meV for dissociative adsorption of H2, which is consistent with the energy threshold obtained in molecular beam experiments for H2 (nu=0). We explain vibrational enhancement observed in experiments as the consequence of vibrational softening in the entrance channel over the most reactive surface site. The H2/NiAl(110) PES shows a high surface site selectivity: for energies up to 0.1 eV above threshold, H2 adsorption can only take place around top-Ni sites (within a circle of radius approximately 0.3 A). A strong energetic corrugation is observed: energy barriers for dissociation vary by more than 1 eV between the most and the least reactive sites. In contrast, geometric corrugation is much less pronounced and comparable to that of low index single metal surfaces like Cu or Pt.     

Theoretical study of structure and basicity of some alkali metal oxides,hydroxides, and amides

Ab initio (TZV *, SBK *, and 3–21G * or 6–31G * basis sets) calculations were performed to predict the geometries and gas-phase proton affinities of Li₂O, LiOH, LiNH₂, Na₂O, NaOH, NaNH₂, K₂O, KOH, and KNH₂. © 1994 John Wiley & Sons, Inc.     

Density functional theory study of single-wall platinum nanotubes

Single-wall platinum nanotubes (SWPtN) were studied using spin-polarized density functional theory calculations. These nanotubes consist of 5-, 6-, and 8-Pt atoms coiling around the tubular axis forming 3.54–4.73 Å in diameter and 0.7–1.4 nm and infinite in length. Two types of wall structures, square and triangular, were investigated. The results show that triangular nanotubes are more stable. Our results suggest that it is also feasible to synthesize the 5- and 8-atom triangular nanotubes as the 6-atom Pt nanotubes were found experimentally. These SWPtN may provide a new dimension in the catalytic applications of platinum.     

Relativistic DFT study on the reaction mechanism of second-row transition metal Ru with CO2

To estimate the importance of relativistic effects on the reaction mechanisms between Ru and CO2, the potential energy surfaces have been performed in the triplet and quintet electronic states using quasi-relativistic (Pauli), zero-order regularly approximated (ZORA), and nonrelativistic (NR) density functional theory (DFT) at the PW91/TZP level. The results demonstrate that there are two rival reaction mechanisms: one is an addition mechanism and the other is an insertion mechanism in the triplet state. The only mechanism in the quintet state is the insertion mechanism. The most favored reaction mechanism in Ru + CO2 is that the Ru atom in its ground state first attacks the CO bond of CO2, forming q-Ru(CO)O (5A') with the insertion mechanism, and then undergoes an intersystem crossing to t-Ru(CO)O (3A'). Then it crosses t-TS3 to produce t-ORuCO molecule. The relativistic effects are important for reactivity of the second-row transition metal to CO2. In the key step of t-Ru(CO)O via t-TS3 to t-ORuCO, relativistic effects reduce the barrier energy by 10.3 kcal/mol, which is nearly half the nonrelativistic barrier energy.     

Two-path reduction of molecular nitrogen by transition metal hydroxides

The kinetics of the reduction of N₂ to N₂H₄ and NH₃ by Ti^III-Mo^III hydroxide was studied at pH I I and 303-333 K, and the activation energies for these reactions and also for the reaction N₂H₄ 2 NH₃ were determined (29, 70, and 25 kJ mol^– respectively). It was concluded that -90 % of ammonia was formed by the direct reduction of N₂ without intermediate formation of hydrazine. A mechanism of this reaction is suggested, which includes the proton insertion into the N-N bond favored by an enhanced electron density at the nitrogen atoms, according to the data of the quantum-mechanical calculation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1402–1405, June, 1996.