Surface-enhanced Raman scattering of pyridine on platinum and nickel electrodes in nonaqueous solutions

Surface-enhanced Raman scattering (SERS) spectra of pyridine adsorbed onto bare platinum and nickel electrodes in nonaqueous solutions are reported in this Letter. There are similarities and differences between the SERS from aqueous and nonaqueous solutions. The surface enhancement factor for platinum in acetonitrile solution has been calculated to decrease by a factor of ca. 10 compared with that in the aqueous media. The double-band character for the ring breathing mode is observed at 1009 and 1019 cm⁻¹. Two adsorption modes of pyridine on the platinum surface were assumed. Part of the pyridine molecules may be chemisorbed onto the surface, with the ring plane oriented vertical to the surface; other pyridine molecules may co-adsorb with lithium cations onto the surface.     

The interaction of pyridine with the surface of active carbons

The adsorption and desorption of pyridine on the surface of granulated active carbons was studied. It was shown that pyridine was extracted from aqueous solutions because of physical adsorption and specific adsorption with the formation of H-bonds with oxygen-containing surface groups. The desorption of pyridine at temperatures up to 400°C did not cause its complete removal from the surface of adsorbents. The fraction of pyridine remaining on the surface was proportional to the amount of oxygen-containing surface groups of active carbons of the acid type.     

电化学粗糙银电极表面上共吸附体系的SERS研究

自1974年发现表面增强喇曼散射(SERS)光谱以来,人们不但对其进行实验和理论上的探讨,还开展了应用方面的研究,如用于痕量分析、催化和腐蚀等,并已开始用于研究物质的吸附状态以及多物种共存体系。本文通过对吡啶、苯甲酸共存体系的SERS谱及其随外加电位变化的实验研究,运用镜像场等理论探讨了在电化学粗糙银电极表面上吡啶和苯甲酸共存体系中的吸附状态。     

Surface enhanced Raman scattering at Ag electrodes in non-aqueous pyridine solutions

The surface enhanced Raman scattering (SERS) of interfacial pyridine and Br⁻ species at Ag electrodes from neat pyridine solutions containing tetra-n-butylammonium bromide is presented. The potential dependence of the SERS peak frequencies, bandwidths, and relative intensities is reported and interpreted in terms of pyridine reorientation in the double layer. A band at 221 cm⁻¹ is observed at certain potentials and is assigned to the AgN stretch for Ag surface pyridine species.     

Role of conformation in the electronic properties of chemisorbed pyridine on Cu(110): an STM/STS study

Pyridine was chemisorbed on Cu(110) at 10 K and observed using STM at 5 K as dosed and after annealing to temperatures between 20 and 300 K. At very low coverage, two molecular species with different apparent heights are observed to coexist. The higher species is assigned to a pyridine molecule bonded with its symmetry axis perpendicular to the surface plane, while the lower species is assigned to a pyridine molecule that is tilted down toward the surface plane. At low coverage, the tilted pyridine species predominates on the surface, but as the total surface coverage of pyridine increases, the molecules stand up until the upright geometry becomes favored. Measurements of the STS of the two species show different molecular resonances derived from the lowest unoccupied pyridine pi* orbitals. The tilted pyridine species has a peak in the unoccupied local density of states at 2.6 +/- 0.1 eV, whereas the upright pyridine species has a peak at 2.3 +/- 0.1 eV.     

Control of adhesion and surface forces via potential-dependent adsorption of pyridine

The orientation and extent of adsorption of pyridine on a gold electrode is known to depend on applied potential and is well characterized. By use of the electrochemical surface forces apparatus, we measured the potential dependence of the double-layer interactions and adhesive forces between a gold electrode and a mica surface for different pyridine concentrations. We observed that, unlike mica-mica interactions, the gold-mica interactions were strongly affected by the presence of small concentrations of pyridine. We are able to reach high negative surface potentials (as determined by applying Derjaguin-Landau-Verway-Overbeek theory to our force measurements), which is similar to what is observed in the absence of pyridine. This demonstrates the electronic nature of the forces measured and shows that pyridine does not displace potential-determining ions on the surface. At positive potentials, where the interaction between gold and mica is attractive, pull-off measurements are a strong function of applied potential. The major effect of the presence of pyridine is on the observed shift in the potential of zero force (PZF), moving it to more negative potentials. This effect is caused by the strong dipole of the pyridine molecule. When the applied potential is cast as a deviation from the PZF, the effect of pyridine is to reduce adhesion between gold and mica. We modeled the potential-dependent adhesion of this system using an electrocapillary framework developed previously, and in doing so, we establish the relationship between the gold-liquid and gold-mica surface energies. In addition, we show that pyridine adsorption affects the capacitance of the gold-mica interface.     

Initial hydrogenations of pyridine on MoP(001): a density functional study

The initial hydrogenations of pyridine on MoP(001) with various hydrogen species are studied using self-consistent periodic density functional theory (DFT). The possible surface hydrogen species are examined by studying interaction of H(2) and H(2)S with the surface, and the results suggest that the rational hydrogen source for pyridine hydrogenations should be surface hydrogen atoms, followed by adsorbed H(2)S and SH. On MoP(001), pyridine has two types of adsorption modes, i.e., side-on and end-on; and the most stable η(5)(N,C(α),C(β),C(β),C(α)) configuration of the side-on mode facilitates the hydrogenation of pyridine. The optimal hydrogenation path of pyridine with surface hydrogen atoms in the Langmuir-Hinshelwood mechanism is the formation of 3-monohydropyridine, followed by producing 3,5-dihydropyridine, in which the two-step hydrogenations take place on the C(β) atoms. When adsorbed H(2)S is considered as the source of hydrogen, slightly higher hydrogenation barriers are always involved, while the energy barriers for hydrogenations involving adsorbed SH are much lower. However, the hydrogenation of pyridine should be suppressed by the adsorption of H(2)S, and the promotion effect of adsorbed SH is limited.     

吡啶与Rh(111)面相互作用的EHMO研究

吡啶作为加氢脱氮的模型化合物,与过渡金属Pt(111),Ni(100),Pd(110,111),Mo(110),Rh(111)面的吸附作用已有大量的实验研究,所采用的技术基本上是LEED,TDS,XPS,HREELS等,然而吡啶与Rh(111)面作用的理论研究尚未见报道.本文用EHMO法研究了吡啶与Rh(111)面的吸附作用,得到了最优吸附构型、结合能、集居数以及电荷分布和转移等,为新的脱氮催化剂开发提供了理论依据. 计算采用EHMO法,其中非对角矩阵元采用MWH近似:     

Formation of highly ordered organic monolayers by dative bonding: pyridine on ge(100)

The adsorption of pyridine onto the Ge(100) surface has been studied using both real-time scanning tunneling microscopy (STM) and ab initio pseudopotential density functional calculations. The results show that pyridine molecules adsorb on the electron-deficient down-Ge atoms of the Ge=Ge dimers via Ge-N dative bonding, with the pyridine ring tilted to the surface. The electron-rich up-Ge atoms remaining after adsorption of pyridine induce an asymmetric dimer row, which is mainly reconstructed to the c(4 x 2) structure. At pyridine coverage of 0.25 ML, the adsorbed pyridine molecules form a perfectly ordered monolayer. The entire Ge substrate underlying this organic monolayer rearranges into the c(4 x 2) structure.     

Pyridine adsorption on Ag(110)

The adsorption of pyridine on a clean Ag(110) surface was characterized with ultraviolet photoemission spectroscopy, flash desorption and Auger electron spectroscopy. Pyridine condenses on the silver surface below 190 K and rapidly forms multiple layers. At temperatures above 235 K pyridine is present in submonolayer concentrations. At 275 K pyridine is chemisorbed on Ag(110).     

Adsorption of pyridine on a polycrystalline gold electrode surface studied by infrared reflection absorption spectroscopy

The adsorption behavior of pyridine on a smooth polycrystalline gold electrode surface was investigated over a wide wavenumber region (2000–500 cm⁻¹) by in situ infrared reflection absorption spectroscopy (IRAS). The reversible adsorption/desorption of pyridine was observed upon the change in applied electrode potential, and the adsorption state at positive potentials was found to depend strongly on the kind of halide ion used as a supporting electrolyte. Symmetry analysis of absorption bands observed revealed that pyridine molecules adsorb with the molecular axis (C₂ axis) perpendicular to the electrode surface (vertical configuration) at positive potentials in 0.5 M KF, KCl and KBr solutions. A band due to the out-of-plane bending mode of the adsorbed pyridine molecule was observed at potentials more negative than ca. 0 V for 0.5 M KF solution containing 100 mM pyridine. We concluded that even in the 100 mM pyridine solution, adsorbed pyridine forms a monolayer and that the molecules reorient from a flat (parallel) to the vertical configuration as the potential becomes less negative. No bands due to adsorbed pyridine were detected for 0.5 M KI solution. The amount of adsorbed pyridine was found to depend strongly on the strength of specific adsorption of halide ions.     

吡啶在几种Y型沸石上的吸附量热研究

用微量量热计测定了在室温至600 K范围内吡啶在NaY、CaY、R_EY和HY这几种Y型沸石上的吸附热。实验结果表明, 在这四种沸石上, 存在两种不同类型的酸中心, 一种是B酸中心; 另一种是非活化的L酸中心。B酸中心的酸强度随温度的升高而增加, 而非活化的L酸中心则随温度的升高而减小。在NaY沸石表面上, 只有Na~+一种非活化的L酸中心; 在HY沸石表面上则只有一种B酸中心。在R_EY和CaY表面上, 同时存在着B酸中心和非活化的L酸中心。高温时, 吡啶先吸附在强酸中心H~+上。室温时吡啶在所有试样上的吸附量均在3.0～3.2 mmolg~(-1)之间, 该值正好对应于超笼和β笼中的吸附中心数。     

吡啶-氯化钾水溶液/n型硫化镉电极界面上的表面增强喇曼散射

本文研究了在吡啶-KC1水溶液中吡啶吸附在n-CdS电极上的表面增强喇曼散射(SERS)。在光照下,CdS电极经过正极化予处理数分钟,就能观察到吡啶吸附在CdS电极上的很强的SERS谱。其特征峰是1010和1036cm^-1与纯吡啶的喇曼特征峰991,1030cm^-1相比有了明显位移。又SERS谱随着吡啶浓度的增加而增强。外加电位对SERS也有一定影响,其曲线形状与CdS的I～V曲线很相似。对这些实验结果,本文用n型CdS电极的光电化学特性进行了初步的考察和讨论。     

Raman spectroscopy as a probe of adsorption on rhodium particles

Raman spectroscopy has been used as a probe of the adsorption of pyridine onto small particles of rhodium. The band energies of the surface phase correspond with those found on roughened silver electrodes. Chemical experiments indicate that the pyridine is stronyly chemisorbed. The similarity with the spectrum of pyridine on Ag presumably means that the predominant surface species is the same on each metal. This work represents the first report of an enhanced Raman spectrum on metallic rhodium.     

Theoretical investigation of formation mechanism of bipyridyl molecule on Ni(111) surface: implication for synthesis of N-doped graphene from pyridine

The formation mechanism of bipyridyl molecule catalyzed by nickel catalyst with pyridine precursor has been studied using density functional theory calculations. The formation of bipyridyl on Ni(111) surface from two pyridine molecules is considered as the initial process of N-doped graphene growth, and the minimum energy pathway for the formation has been investigated in detail. The whole formation processes mainly includes three steps, i.e., the dehydrogenation of the first pyridine, adsorption and dehydrogenation of the second pyridine, and formation of the bipyridyl molecule. It is found that the C-H bond of pyridine could be selectively dissociated while the C-C and C-N bond connections are retained during the catalytic processes. The N-doped graphene formed by pyridine only contains pyridine-like nitrogen atoms, suggesting a possible way to produce N-doped graphene with pure pyridine-like nitrogen atoms. The comparison of formation mechanisms between bipyridyl and biphenyl molecules was carried out, and the results imply a lower temperature process for synthesis of N-doped graphene from pyridine than that for graphene from benzene.     

(Fe,Cr)3O4催化剂表面酸性的研究

本文研究了(Fe,Cr)₃O₄催化剂的表面酸性,发现其表面结构具有可变性,表面主要存在Fe²⁺(α位)和Fe³⁺(β位)两种酸中心,β位上吸附吡啶的E_d=278.8±13.8kJ/mol。     

Comparison of the adsorption mechanisms of pyridine in hydrophilic interaction chromatography and in reversed-phase aqueous liquid chromatography

The adsorption isotherms of pyridine were measured by frontal analysis (FA) on a column packed with shell particles of neat porous silica (Halo), using water–acetonitrile mixtures as the mobile phase at 295 K. The isotherm data were measured for pyridine concentrations covering a dynamic range of four millions. The degree of heterogeneity of the surface was characterized by the adsorption energy distribution (AED) function calculated from the raw adsorption data, using the expectation-maximization (EM) procedure. The results showed that two different retention mechanisms dominate in Per aqueous liquid chromatography (PALC) at low acetonitrile concentrations and in hydrophilic interaction chromatography (HILIC) at high acetonitrile concentrations. In the PALC mode, the adsorption mechanism of pyridine on the silica surface is controlled by hydrophobic interactions that take place on very few and ultra-active adsorption sites, which might be pores on the irregular and rugose surface of the porous silica particles. The surface is seriously heterogeneous, with up to five distinct adsorption sites and five different energy peaks on the AED of the packing material. In contrast, in the HILIC mode, the adsorption behavior is quasi-homogeneous and pyridine retention is governed by its adsorption onto free silanol groups. For intermediate mobile phase compositions, the siloxane and the silanol groups are both significantly saturated with acetonitrile and water, respectively, causing a minimum of the retention factor of pyridine on the Halo column.     

Raman spectra of pyridine adsorbed on a copper electrode

The surface enhanced Raman scattering (SERS) of pyridine adsorbed on a copper electrode was observed with 647.1 nm excitation and the dependence of the Raman intensity as a function of electrode potential was obtained for the most intense bands. The results are compared with reported intensity and frequency values for the silver/pyridine system.     

Interaction of pyridine derivatives with sepiolite

In this study, the adsorption behavior of pyridine derivatives, i.e., 2-aminopyridine and 2,2'-bipyridyl, onto sepiolite, a natural clay mineral, has been investigated by bottle adsorption and IR spectroscopic techniques. The results indicate that 2-aminopyridine and 2,2'-bipyridyl molecules adsorb onto sepiolite through hydrogen bonding of the amino groups to the water molecules in the octahedral sheet and to the surface hydroxyls (Si-OH) in the tetrahedral sheet. These findings reveal that pyridine molecules not only adsorb onto the external surface of sepiolite but are also incorporated in its channels and tunnels with adsorption taking place at corners and/or edges, depending on the position of water molecules. A structural model is proposed to account for the orientation of pyridine derivatives in the sepiolite matrix.     

Synthese von 4-Trichlorsilylmethylbenzonitril und 4-(2-Trichlorsilyläthyl)pyridin zur Oberflächenmodifikation von Zinndioxid

Synthesis of 4-Trichlorosilylmethylbenzonitrile and 4-(2-Trichlorosilylethyl)pyridine for Surface Modification of Tin Dioxide We describe the synthesis of 4-(trichlorosilylmethyl)benzonitrile and 4-(2-trichlorosilylethyl)pyridine, starting from 4-(bromomethyl)benzonitrile and trichlorosilane or vinylpyridine and trichlorosilane. Trimethoxysilanes are obtained by reaction of the trichlorosilyl compounds with methyl orthoformate. 4-(Trichlorosilylmethyl)benzonitrile and 4-(2-trichlorosilylethyl)pyridine are used to modify the surface of tin dioxide.