Adsorption of HCN molecules on Ni,Pd and Pt-doped (7, 0) boron nitride nanotube: a DFT study

We studied affinity of pure and Ni, Pd and Pt-doped (7, 0) boron nitride nanotubes (BNNTs) to toxic HCN molecules using density functional theory calculations. The results indicated that the pure (7, 0) BNNTs can weakly adsorb HCN molecules with adsorption energy of ?0.2474 eV. Upon adsorption of HCN molecules on this nanotube, the band gap energy was decreased from 3.320 to 2.960 eV. The more negative adsorption energy between these transition metal-doped (7, 0) BNNTs and HCN molecules indicated that doping of (7, 0) BNNTs with Ni, Pd and Pt elements can significantly improve the affinity of BNNTs toward this gas. Additionally, it was found that the interaction energy between HCN molecules and Pt-doped BNNTs is more negative than those of the Ni and Pd-doped BNNTs. These observations suggested that the Pt-doped (7, 0) BNNTs are strongly sensitive to HCN molecules and therefore it may be used in gas sensor devices for detecting this toxic gas.     

Theoretical investigation of CO adsorption on TM-doped (MgO)12 (TM = Ni, Pd, Pt) nanotubes

CO adsorption on TM-doped magnesia nanotubes (TM = Ni, Pd and Pt) have been studied by using density functional theory. Our calculation results show that CO favors adsorption on TM-doped magnesia nanotubes in the form of C atom bonding with TM atom. Fukui indices analysis clearly exhibits that doping of impurity TM atom allows for a noticeably enhancement of nucleophilic reactivity ability of magnesia nanotube. The adsorption energies demonstrate that CO molecule is more strongly bound on the 3-fold TM atoms than the 4-fold TM atoms. This finding is well confirmed by TM-C bond length, charge transfer and C-O vibrational frequency. The high adsorption energy of 2.55 eV is found when CO adsorbs on 3-fold Pt in Pt-doped magnesia nanotubes, implying the kind of the doping TM atom has a significant influence on the chemical reactivity.     

Electronic structures and magnetic properties of rare-earth-atom-doped BNNTs

Stable geometries, electronic structures, and magnetic properties of (8,0) and (4,4) single-walled BN nanotubes (BNNTs) doped with rare-earth (RE) atoms are investigated using the first-principles pseudopotential plane wave method with density functional theory (DFT). The results show that these RE atoms can be effectively doped in BNNTs with favorable energies. Because of the curvature effect, the values of binding energy for RE-atom–doped (4,4) BNNTs are larger than those of the same atoms on (8,0) BNNTs. Electron transfer between RE-5d, 6s, and B-2p, N-2p orbitals was also observed. Furthermore, electronic structures and magnetic properties of BNNTs can be modified by such doping. The results show that the adsorption of Ce, Pm, Sm, and Eu atoms can induce magnetization, while no magnetism is observed when BNNTs are doped with La. These results are useful for spintronics applications and for developing magnetic nanostructures.     

A first-principles study on the interaction of CO molecules with VIII transition metals-embedded graphitic carbon nitride as an excellent candidate for CO sensor

We studied the adsorption behavior of CO molecules over graphitic carbon nitride (gCN) and VIII transition metals (TM)-embedded gCN systems (TM=Ni, Pd, and Pt atoms) using density functional theory. The results indicated that the Pt-embedded gCN is excellent candidate for adsorption of CO molecules with adsorption energy of −2.77 eV, which is much better than those of the other adsorbents. Furthermore, it was observed that the band gap energies of TM-embedded systems were less than that of pristine gCN and decoration of transition metal atoms leads to the formation of mid gap impurity states, resulting in increase of electrical conductivity. Additionally, the Lowdin charges displayed that upon adsorption of CO molecules, this molecule acts as an electron acceptor and gCN systems behave as an electron donor with electron transfer from d-orbitals of transition metal atoms to the states of CO molecule. The results of spin polarized band structure indicated that the pristine gCN, Ni and Pd-embedded systems are non-magnetic, whereas Pt-embedded gCN induces non-zero magnetic moment equal to 1.35 μB. Therefore, our results revealed that among the TM-embedded systems, Pt-embedded gCN is more effective than those of the other adsorbents in sensing and removing of this gas from the atmosphere.     

基于密度泛函理论研究掺杂Pd石墨烯吸附O2及CO

基于第一性原理的密度泛函理论研究了单个O₂和CO气体分子吸附于本征石墨烯和掺杂钯(Pd)的石墨烯的体系, 通过石墨烯掺Pd前后气体分子的吸附能、电荷转移及能带和态密度的计算, 发现掺Pd后气体分子吸附能和电荷转移显著增大, 这是由于Pd的掺杂, 在本征石墨烯能带中引入了杂质能级, 增强了石墨烯和吸附气体分子间的相互作用; 氧化性气体O₂和还原性气体CO吸附对石墨烯体系能带结构和态密度的影响明显不同, 本征石墨烯吸附O₂后, 费米能级附近态密度变大, 掺Pd后在一定程度变小; 吸附还原性的CO后, 石墨烯费米能级附近态密度几乎没有改变, 表明掺杂Pd不会影响石墨烯对CO的气体灵敏度, 但由于CO对石墨烯的吸附能增大, 可以提高石墨烯对还原性气体的气敏响应速度.     

Structure and reactivity of Pd doped Ag surfaces

We have performed first principles calculations for clean and Pd doped Ag(1 1 1) and Ag(1 0 0) surfaces, with and without adsorbed O and CO. Our results for the structure of the Pd doped Ag surfaces indicate that Pd atoms are located lower than the surrounding Ag surface atoms. We find that O atoms adsorbed on Pd doped Ag(1 1 1) reside at the fcc hollow sites, the site next to Pd being slightly favored. Moreover, we provide results for O and CO co-adsorption on the clean and Pd doped Ag(1 1 1) surfaces, indicating that Pd can act as an electronic promoter for the CO oxidation reaction.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH2分子相互作用

本研究采用密度泛函理论研究了纯的及V, Fe, Ni, Pd, Si, P, S和Cl掺杂原子对石墨烯和CaH2分子之间相互作用. 研究结果发现CaH2分子与所有石墨烯表面均具有较大的相互作用, 而CaH2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用, 在所有掺杂原子中, 其中与Pd掺杂石墨烯具有最大的相互作用, S次之, 其它掺杂石墨烯与CaH2分子相互作用能力相差不大. 这些结果表明虽然所有石墨烯均有助于CaH2中H原子的脱附, 但掺杂石墨烯脱附能力仍然大于纯的石墨烯. 在掺杂原子中, Pd和S掺杂石墨烯对CaH2中H原子的脱附效果最好, 其它的掺杂原子脱附效果相差不明显. 此研究结果将有望为CaH2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH_2分子相互作用

本研究采用密度泛函理论研究了纯的及V,Fe,Ni,Pd,Si,P,S和Cl掺杂原子的石墨烯和CaH_2分子之间相互作用.研究结果发现CaH_2分子与所有石墨烯表面均具有较大的相互作用,而CaH_2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用,在所有掺杂原子中,其中与Pd掺杂石墨烯具有最大的相互作用,S次之,其它掺杂石墨烯与CaH_2分子相互作用能力相差不大.这些结果表明虽然所有石墨烯均有助于CaH_2中H原子的脱附,但掺杂石墨烯脱附能力仍然大于纯的石墨烯.在掺杂原子中,Pd和S掺杂石墨烯对CaH_2中H原子的脱附效果最好,其它的掺杂原子脱附效果相差不明显.此研究结果将有望为CaH_2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

Effects of metal-support interactions on the electronic structures of metal atoms adsorbed on the perfect and defective MgO(1 0 0) surfaces

The electronic structures of Ni, Pd, Pt, Cu, and Zn atoms adsorbed on the perfect MgO(1 0 0) surface and on a surface oxygen vacancy have been studied at the DFT/B3LYP level of theory using both the bare cluster and embedded cluster models. Ni, Pd, Pt, and Cu atoms can form stable adsorption complexes on the regular O site of the perfect MgO(1 0 0) surface with the binding energies of 19.0, 25.2, 46.7, and 17.3 kcal/mol, respectively, despite very little electron transfer between the surface and the metal atoms. On the other hand, adsorptions of Ni, Pd, Pt, and Cu atoms show strong interaction with an oxygen vacancy on the MgO(1 0 0) surface by transferring a significant number of electron charges from the vacancy to the adsorbed metal atoms and thus forming ionic bonds with the vacancy site. These interactions on the vacancy site for Ni, Pd, Pt, and Cu atoms increase the binding energies by 25.8, 59.7, 85.2, and 19.1 kcal/mol, respectively, compared to those on the perfect surface. Zn atom interacts very weakly with the perfect surface as well as the surface oxygen vacancy. We observed that the interaction increases from Ni to Pt in the same group and decreases from Ni to Zn in the same transition metal period in both perfect and vacancy systems. These relationships correlate well with the degrees of electron transfer from the surface to the adsorbed metal atom. The changes in the ionization potentials of the surface also correlate with the adsorption energies or degrees of electron transfers. Madelung potential is found to have significant effects on the electronic properties of metal atom adsorptions on the MgO(1 0 0) surface as well as on an oxygen vacancy, though it is more so for the latter. Furthermore, the Madelung potential facilitates electron transfer from the surface to the adsorbed metal atoms but not in the other direction.     

The interaction of ultrathin films of Ni and Pd with W(110): an XPS study

The interaction of ultrathin films of Ni and Pd with W(110) has been examined using X-ray photoelectron spectroscopy (XPS) and the effects of annealing temperature and adsorbate coverage (film thickness) are investigated. The XPS data show that the atoms in a monolayer of Pd or Ni supported on W(110) are electronically perturbed with respect to the surface atoms of Pd(100) and Ni(100). The magnitude of the electronic perturbations is larger for Pd than for Ni adatoms. Our results indicate that the difference in Pd(3d_5/2) XPS binding energies between a pseudomorphic monolayer of Pd on W(110) and the surface atoms of Pd(100) correlates with the variations observed for the desorption temperature of CO (i.e., the strength of the Pd---CO bond) on these surfaces. A similar correlation is seen for the Ni(2p_3/2) XPS binding energies of Ni/W(110) and Ni(100) and the CO desorption temperatures from the surfaces. The shifts in XPS binding energies and CO desorption temperatures can be explained in terms of: (1) variations that occur in the Ni---Ni and Pd---Pd interactions when Ni and Pd adopt the lattice parameters of W(110) in a pseudomorphic adlayer; and (2) transfer of electron density from the metal overlayer to the W(110) substrate upon adsorption. Measurements of the Pd(3d_5/2) XP binding energy of Pd/W(110) as a function of film thickness indicate that the Pd---W interaction affects the electronic properties of several layers of Pd atoms.     

过渡金属Pd掺杂AsP结构及其吸附甲醛和一氧化碳的性能研究

基于第一性原理方法,研究了单层本征磷砷AsP和过渡金属钯（Pd）掺杂磷砷AsP的结构,并对比研究了本征和掺杂后的AsP吸附甲醛（HCHO）和一氧化碳（CO）气体分子的稳定性、能带结构、态密度以及电荷差分密度。研究结果表明：经Pd掺杂后AsP由半导体转变为导体;本征AsP吸附一氧化碳最稳定的位置为P-As键顶上,吸附甲醛最稳定的位置为P原子顶上;本征吸附时气体分子与基底之间的距离在3 Å左右,气体分子与基底之间未形成化学键。过渡金属Pd原子掺杂AsP后形成两种结构,分别为Pd原子替换超胞结构中的As原子或P原子。两种掺杂结构分别吸附一氧化碳或甲醛气体分子时,除了Pd原子替换AsP中的As原子形成的结构吸附甲醛的吸附能未明显增加外,其余掺杂结构吸附一氧化碳或甲醛的吸附能和电荷转移较本征吸附时均显著增强,吸附CO分子时,C原子与Pd原子之间形成了化学键。特别是,Pd原子替换AsP中的P原子形成的结构对一氧化碳和甲醛气体分子的吸附性能明显强于Pd原子替换AsP中的As原子所形成的结构。     

Adsorption properties of CO on low-index Pt3Sn surfaces

The adsorption properties of CO on Pt₃Sn were investigated by utilizing quantum mechanical calculations. The (1 1 1), (1 1 0) and (0 0 1) surfaces of Pt₃Sn were generated with all possible bulk terminations, and on these terminations all types of active sites were determined. The adsorption energies and the geometries of the CO molecule at those sites were found. Those results were compared with the results obtained from the adsorption of CO on similar sites of Pt(1 1 1), Pt(1 1 0) and Pt(0 0 1) surfaces. The comparison reveals that adsorption of CO is stronger on Pt surfaces; this may be the reason why catalysts with Pt₃Sn phase do not suffer from CO posioning in experimental works. Aiming to understand the interactions between CO and the metal adsorption sites in detail, the local density of states (LDOS) profiles were produced for atop-Pt adsorption, both for the carbon end of CO for its adsorbed and free states, and for the Pt atom of the binding site. LDOS profiles of C of free and adsorbed CO and Pt for corresponding pure Pt surfaces, Pt(1 1 1), Pt(1 1 0) and Pt(0 0 1) were also obtained. The comparison of the LDOS profiles of Pt atoms of atop adsorption sites on the same faces of bare Pt₃Sn and Pt surfaces showed the effect of alloying with Sn on the electronic properties of Pt atoms. Comparison of LDOS profiles of the C end of CO in its free and atop adsorbed states on Pt₃Sn and LDOS of Pt on bare and CO adsorbed Pt₃Sn surface were used to clear out the electronic changes occurred on CO and Pt upon adsorption. The study showed that (i) inclusion of a Sn atom at the adsorption site structure causes dramatic decrease in stability which limits the number of possible CO adsorption sites on Pt₃Sn surface, (ii) the presence of Sn causes angles different from 180° for M-C-O orientation, (iii) the presence of Sn in the neighborhood of Pt on which CO is adsorbed causes superposition of the 5σ/1π derived-state peaks at the carbon end of CO and changes in adsorption energy of CO, (iv) Sn present beneath the adsorption site strengthens the CO adsorption, whereas neighboring Sn on the surface weakens it for all Pt₃Sn surfaces tested and (v) the most stable site for CO adsorption is the atop-Pt site of the mixed atom termination of Pt₃Sn(1 1 0).     

Interaction of CO with atomically well-defined PtxRuy/Ru(0 0 0 1) surface alloys

The interaction of CO with structurally well-defined Pt_xRu_y surface alloys supported on Ru(0 0 0 1) was investigated by thermal desorption spectroscopy and infrared reflection-absorption spectroscopy. The surface composition and the distribution of the surface atoms were controlled by high resolution scanning tunneling microscopy. On these surfaces, which have a nearly random distribution of the two surface species, the adsorption (and desorption) of CO is strongly modified compared to the pure elemental surfaces, by strain effects and electronic ligand effects. CO adsorbs exclusively in a linear configuration on Pt and Ru atoms for all surfaces investigated. The adsorption energy of CO is lowered on the alloy surfaces with respect to both Pt(1 1 1) and Ru(0 0 0 1), similar as for pseudomorphic monolayer Pt films. For both Pt and Ru sites the adsorption strength decreases with increasing Pt concentration.     

Chemisorption of CO and H on Pd, Pt and Au nanoclusters: a DFT approach

We have performed a theoretical study of pure metal nanoparticles (Pd/Pt/Au) and their interaction with CO molecules and atomic hydrogen, in order to investigate chemisorption effects of relevance to catalysis by nanoparticles. First-principles density-functional local relaxations are used to investigate the effect of CO and H adsorption on six structural motifs. The results of the energetic crossover and structural deformations are analyzed in terms of the interplay between metal-metal interactions (including internal and surface stress) and CO-metal and H-metal interactions. It is found that H adsorption releases surface stress, thus favoring 5-fold symmetry motifs, whereas CO adsorption produces a flattening of the potential energy surface of the metal clusters.     

Surface (electro-)chemistry on Pt(1 1 1) modified by a Pseudomorphic Pd monolayer

The formic acid and methanol oxidation reaction are studied on Pt(1 1 1) modified by a pseudomorphic Pd monolayer (denoted hereafter as the Pt(1 1 1)-Pd_1 ML system) in 0.1 M HClO₄ solution. The results are compared to the bare Pt(1 1 1) surface. The nature of adsorbed intermediates (CO_ad) and the electrocatalytic properties (the onset of CO₂ formation) were studied by FTIR spectroscopy. The results show that Pd has a unique catalytic activity for HCOOH oxidation, with Pd surface atoms being about four times more active than Pt surface atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO₂ is observed at low potentials. This indicates that the reaction can proceed on Pd at low potentials without the typical “poison” formation. In contrast to its high activity for formic acid oxidation, the Pd film is completely inactive for methanol oxidation. The FTIR spectra show that neither adsorbed CO is formed on the Pd sites nor significant amounts of CO₂ are produced during the electrooxidation of methanol.     

Mass and lattice effects in trapping: Ar, Kr, and Xe on Pt(1 1 1), Pd(1 1 1), and Ni(1 1 1)

The trapping probabilities of argon, krypton, and xenon on Pd(1 1 1) and Ni(1 1 1) have been investigated using supersonic molecular beam techniques. The trapping probability of argon exhibits normal incident energy in a similar fashion on both Pd(1 1 1) and Pt(1 1 1) because the mass of argon is significantly less than the surface mass of either Pd or Pt. In contrast, dynamic corrugation in the gas-surface potential is observed for krypton trapping on Pt(1 1 1) and Pd(1 1 1), resulting in a decreased angular dependence of the trapping probability compared to argon. For xenon trapping on Pd significant lattice deformation during the gas-surface collision appears to give rise to total energy scaling. The trapping probability of xenon on Pd(1 1 1) remains high at unusually high incident kinetic energies due to the overall enhanced energy transfer from the incident atom to the lattice. Trapping probabilities of Ar, Kr, and Xe are significantly lower on Ni(1 1 1) than on either Pt(1 1 1) or Pd(1 1 1) despite the lower surface mass of the Ni atoms. This result is attributed to the lower binding energy of the rare gases on Ni(1 1 1) and the higher Debye temperature of Ni. The energy scaling of Ar trapping on Ni(1 1 1) is determined by static corrugation, but the energy scaling for Kr and Xe on Ni(1 1 1) may involve the effects of dynamic corrugation. In the latter cases, the greater stiffness of the nickel lattice decreases the dynamic corrugation relative to Pt(1 1 1) and Pd(1 1 1).     

Density-functional study of the CO chemisorption on bimetallic Pd–Sn(1 1 0) surfaces

We study the ordered PdSn c(2 × 2), (2 × 1), and PdSn₂ (3 × 1) overlayers deposited on Pd(1 1 0) by using first-principles density-functional calculations. It appears that the two PdSn structures are almost degenerate in the energy. Pd–Sn surfaces we consider do not display the marked buckling with Sn atoms displaced towards vacuum that is common for Pt–Sn surfaces. Low-coverage CO chemisorption at these overlayers and on analogous surface structures on Pd₃Sn is considered. It is shown that inclusion of an empirical correction to the CO adsorption energy changes the stable adsorption site from the long-bridge to the top one in most cases. The adsorption energy decreases with the number of Sn atoms in the vicinity of the adsorption site, and this property correlates well with the position of the centre of gravity of the local Pd d-electron band, and also with the variation of the local density of d-electron states at the Fermi level. The centre-of-gravity value is used to assess the core-level shifts for Pd atoms in various geometries. Most of the calculated data compare rather well with the recent measurements on Pd–Sn overlayers at Pd(1 1 0) as well as with other data on related bimetallic systems.     

Theoretical study of CO and Pb adsorption on the Ni(1 1 1) and Ni3Al(1 1 1) surfaces

Adsorption of CO molecules and Pb atoms on the Ni(1 1 1) and Ni₃Al(1 1 1) substrates is studied theoretically within an ab initio density-functional-theory approach. Stable adsorption sites and the corresponding adsorption energies are first determined for stoichiometric surfaces. The three-fold hollow sites (fcc for Pb and hcp for CO) are found most favourable on both substrates. Next, the effect of surface alloying by a substitution of selected topmost substrate atoms by Pb or Ni atoms on the adsorption characteristics is investigated. When the surface Al atoms of the Ni₃Al(1 1 1) substrate are replaced by Ni atoms, the Pb and CO adsorption energies approach those for a pure Ni(1 1 1) substrate. The Pb alloying has a more substantial effect. On the Ni₃Al(1 1 1) substrate, it reduces considerably adsorption energy of CO. On the Ni(1 1 1) substrate, CO binding strengthens slightly upon the formation of the Ni(1 1 1)p(2×2)-Pb surface alloy, whereas it weakens drastically when the Ni(1 1 1)-Pb surface alloy is formed.     

Collision-induced migration of CO on Pt(9 9 7) surface

Lateral displacement of adsorbates induced by collisions with energy-controlled rare gas atoms was examined in an ultra high vacuum chamber using Fourier-transform infrared (FTIR) spectroscopy and a supersonic molecular beam apparatus. A stepped Pt(9 9 7) surface was exposed to CO molecules and subsequently to energy-controlled Ne or Ar atoms. There was no change in the CO stretching mode region of the FTIR spectrum of the Pt(9 9 7) surface after Ne atoms having an average translational energy of 0.23 eV were collided with it. However, when Ne atoms having an average translational energy of 0.56 eV were collided with the surface, the intensity of the peak assigned to the CO stretching mode at terrace sites decreased, while that at step sites increased with increasing the exposure to the Ne atoms. This is the demonstration of collision-induced migration, showing that CO molecules adsorbed at the terrace sites migrate laterally to the step sites upon collision with high-energy Ne atoms. In addition, the experimental results demonstrate the existence of an additional energy barrier for jumps across the steps. This investigation demonstrates an advantage of using a molecular beam for studying adsorbate migration.     

The adsorption and reaction of CO and O2 on PdAu alloy wires

Temperature programmed desorption (TPD) of CO and O₂ on PdAu alloy wires has been studied. The heat of adsorption, sticking coefficient and maximum coverage of CO were recorded for Pd, 83 Pd 17 Au, 60 Pd 40 Au. For Pd and Pd-rich alloys the heat of adsorption remained fairly constant but the maximum coverage fell markedly from 0.42 for Pd to less than 0.05 for bulk palladium atom fraction X_B^pd ? 0.83. The heat of adsorption, sticking coefficient and maximum coverage of O₂ were investigated for pure Pd. A very limited adsorption was recorded on 83 Pd 17 Au and none on the more Au-rich alloys. The adsorption data are used to discuss the CO + O₂ reaction. Activation energy and frequency factor are estimated on Pd, for the TPD conditions used here. Earlier rate constants (0.2 Torr, 150°C) for CO + O₂ on PdAu as a function of Au content correlates with the maximum coverage of chemisorbed CO, which in turn is correlated with the probability of finding a Pd_9±1 ensemble in the surface. Modern results on the d-band structure of the PdAu alloys suggest that the Pd₉ ensemble, i.e. a surface Pd atom without an Au atom in its coordination shell, would tend to optimise both the donor and acceptor actions of the Pd atoms involved in chemisorbing CO.