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1.
The adsorption and thermal decomposition of alkanethiols (R-SH, where R = CH3, C2H5, and C4H9) on Pt(111) were studied with temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) with synchrotron radiation. Dissociation of sulfhydryl hydrogen (RS-H) of alkanethiol results in the formation of alkanethiolate; the extent of dissociation at an adsorption temperature of 110 K depends on the length of the alkyl chain. At small exposure, all chemisorbed CH3SH, C2H5SH, and C4H9SH decompose to desorb hydrogen below 370 K and yield carbon and sulfur on the surface. Desorption of products containing carbon is observed only at large exposure. In thermal decomposition, alkanethiolate is proposed to undergo a stepwise dehydrogenation: R'-CH2S --> R'-CHS --> R'-CS, R' = H, CH3, and C3H7. Further decomposition of the R'-CS intermediate results in desorption of H2 at 400-500 K and leaves carbon and sulfur on the surface. On the basis of TPD and XPS data, we conclude that the density of adsorption of alkanethiol decreases with increasing length of the alkyl chain. C4H9SH is proposed to adsorb mainly with a configuration in which its alkyl group interacts with the surface; this interaction diminishes the density of adsorption of alkanethiols but facilitates dehydrogenation of the alkyl group.  相似文献   

2.
A general method for the determination of the activation (ka), deactivation (kd), and initiation (ki) rate constants in atom transfer radical processes is reported. The method involves the monomer trapping techniques and the analytical solution of the persistent radical effect. For tert-butyl 2-bromopropionate, using ATRP catalyst [CuI(dNbpy)2][Br] and methyl methacrylate in CH3CN at 22 degrees C, the values of ka, kd, and ki were determined to be (9.4 +/- 0.6) x 10-3 M-1 s-1, (8.5 +/- 1.2) x 106 M-1 s-1 and (5.5 +/- 0.9) x 104 M-1 s-1, respectively. The determined initiation rate constant was in good agreement with the literature value (6.0 x 104 M-1 s-1), confirming the validity of the proposed approach. For methyl 2-bromopropionate, under the same conditions, ka, kd, and ki values were found to be (26 +/- 5.9) x 10-3 M-1 s-1, (29 +/- 7.3) x 106 M-1 s-1, and (5.7 +/- 1.6) x 104 M-1 s-1, respectively.  相似文献   

3.
A series of alkanethiol monolayers (CH 3(CH 2) n-1 SH, n = 4, 6, 8, 10, 12, 14, 16) were used to modify gold source-drain electrode surfaces for bottom-contact poly(3,3'-didodecylquaterthiophene) (PQT-12) thin-film transistors (TFTs). The device mobilities of TFTs were significantly increased from approximately 0.015 cm (2) V (-1) s (-1) for bare electrode TFTs to a maximum of approximately 0.1 cm (2) V (-1) s (-1) for the n = 8 monolayer devices. The mobilities of devices with alkanethiol-modified Au electrodes varied parabolically with alkyl length with values of 0.06, 0.1, and 0.04 cm (2) V (-1) s (-1) at n = 4, 8, and 16, respectively. Atomic force microscopy investigations reveal that alkanethiol electrode surface modifications promote polycrystalline PQT-12 morphologies at electrode/PQT-12 contacts, which probably increase the density of states of the PQT-12 semiconductor at the interfaces. The contact resistance of TFTs is strongly modulated by the surface modification and strongly varies with the alkanethiol chain length. The surface modifications of electrodes appear to significantly improve the charge injection, with consequent substantial improvement in device performance.  相似文献   

4.
The reaction of vapor-phase alkyl isocyanates (O=C=N-(CH2)n-1CH3) with OH-terminated alkanethiol template monolayers on Au produces well-organized self-assembled monolayers, containing intrachain carbamate linkages (Au/S(CH2)16O(C=O)NH(CH2)n-1CH3, where n = 1-8, 11, and 12). X-ray photoelectron spectroscopy, contact angle goniometry, and reflection absorption infrared spectroscopy suggest that the template surface completely reacts with the isocyanates yielding a monolayer that contains an interchain hydrogen-bonded carbamate network. Spectroscopic data indicates that the alkyl underlayer remains well ordered following reaction with the isocyanates. The order of the overlayer and the hydrogen-bonding interactions between adjacent chains increase as a function of the alkyl isocyanate chain length, n. The overlayer appears to be well ordered for n > or = 5.  相似文献   

5.
利用自组装技术在金电极表面构造了具有不同前端健长度偶氮苯功能化的单分子膜体系:Au/S(CH2)nNHCO-N=N-OCH2CH3(n=2,3,4,6).研究结果表明,仍氮苯到金电极的表现电子转移速率随它们之间的距离长度的增加而呈指数性的下降趋势.基于Marcus电子隧穿理论,得到了此自组装膜体系的长程电子隧穿系数ρ=(1.35±0.2)/CH2在和可逆电活性分子自组装膜体系及理论计算相比较的基础上,从偶氮苯分子自组装膜结构与电子转移过程的关系角度对这一结果进行了分析和说明.  相似文献   

6.
The kinetics and mechanism of the reaction Cl + CH3(CH2)3CHO was investigated using absolute (PLP-LIF) and relative rate techniques in 8 Torr of argon or 800-950 Torr of N2 at 295 +/- 2 K. The absolute rate experiments gave k[Cl+CH3(CH2)3CHO] = (2.31 +/- 0.35) x 10(-10) in 8 Torr of argon, while relative rate experiments gave k[Cl+CH3(CH2)3CHO] = (2.24 +/- 0.20) x 10(-10) cm3 molecule(-1) s(-1) in 800-950 Torr of N2. Additional relative rate experiments gave k[Cl+CH3(CH2)3C(O)Cl] = (8.74 +/- 1.38) x 10(-11) cm3 molecule-1 s(-1) in 700 Torr of N2. Smog chamber Fourier transform infrared (FTIR) techniques indicated that the acyl-forming channel accounts for 42 +/- 3% of the reaction. The results are discussed with respect to the literature data and the importance of long range (greater than or equal to two carbon atoms along the aliphatic chain) effects in determining the reactivity of organic molecules toward chlorine atoms.  相似文献   

7.
The physical adsorption of formic (HC(O)OH) and acetic (CH(3)C(O)OH) acid on ice was measured as a function of concentration and temperature. At low concentrations, the gas-ice interaction could be analysed by applying Langmuir adsorption isotherms to determine temperature dependent partition constants, K(Lang). Using temperature independent saturation coverages (N(max)) of (2.2 +/- 0.5) x 10(14) molecule cm(-2) and (2.4 +/- 0.6) x 10(14) molecule cm(-2) for HC(O)OH and CH(3)C(O)OH, respectively, we derive K(Lang)(HC(O)OH) = 1.54 x 10(-24) exp (6150/T) and K(Lang)(CH(3)C(O)OH) = 6.55 x 10(-25) exp (6610/T) cm(3) molecule(-1). Via a van't Hoff analysis, adsorption enthalpies were obtained for HC(O)OH and CH(3)C(O)OH. Experiments in which both acids or HC(O)OH and methanol interacted with the ice surface simultaneously were adequately described by competitive adsorption kinetics. The results are compared to previous measurements and used to calculate the equilibrium partitioning of these trace gases to ice surfaces under conditions relevant to the atmosphere.  相似文献   

8.
The electronic properties of alkanethiolate [CH3(CH2)nS-, n = 9 and 11] and alkaneselenolate [CH3(CH2)nSe-, n = 9 and 11] self-assembled monolayers on Au{111} have been quantitatively compared. Simultaneously acquired apparent tunneling barrier height (ATBH) and scanning tunneling microscopy (STM) images reveal that alkanethiolate molecules have a lower barrier to tunneling, and therefore a higher conductance than alkaneselenolates of the same alkyl chain length. Molecular and contact conductance differences were elucidated by using observed STM topographic tunneling height differences between the analogous species. This apparent topographic difference combined with comparative ATBH data indicate that the observed decrease in conductance for alkaneselenolates compared to alkanethiolates originates exclusively from the Au-chalcogenide physical, chemical, and electronic contact.  相似文献   

9.
10.
Huang M  Shen D  Chow LM  Yang M 《The Analyst》2002,127(7):940-946
This paper describes the measurement of the kinetics of adsorption of sodium dodecyl sulfate (SDS), an anionic surfactant, onto a quartz surface with a pre-adsorbed layer of Ca2+ as an ion bridge, using an electrode-separated piezoelectric sensor (ESPS). An impedance analysis method was employed to characterize the responses of the ESPS. The impedance and frequency parameters of the ESPS were examined as functions of the conductivity, permittivity, viscosity and density of the liquid. The adsorption process of SDS onto the quartz surface resulted in an increase in both the mass and energy dissipation of the oscillating quartz crystal. The adsorption densities could be estimated by the ESPS method after taking into consideration the effects of surface viscosity and roughness. The adsorption and desorption rate constants of SDS onto the quartz surface were calculated as ka = (88.1 +/- 0.26) mol(-1) L s(-1) and kd = (4.92 +/- 0.53) x 10(-3) s(-1), respectively, based on the Langmuir model. ESPS was shown to be a powerful means of examining anionic surfactant adsorption to the solid/liquid interface.  相似文献   

11.
The kinetics and mechanism of the reactions of Cl atoms and OH radicals with CH3CH2CHO were investigated at room temperature using two complementary techniques: flash photolysis/UV absorption and continuous photolysis/FTIR smog chamber. Reaction with Cl atoms proceeds predominantly by abstraction of the aldehydic hydrogen atom to form acyl radicals. FTIR measurements indicated that the acyl forming channel accounts for (88 +/- 5)%, while UV measurements indicated that the acyl forming channel accounts for (88 +/- 3)%. Relative rate methods were used to measure: k(Cl + CH3CH2CHO) = (1.20 +/- 0.23) x 10(-10); k(OH + CH3CH2CHO) = (1.82 +/- 0.23) x 10(-11); and k(Cl + CH3CH2C(O)Cl) = (1.64 +/- 0.22) x 10(-12) cm3 molecule(-1) s(-1). The UV spectrum of CH3CH2C(O)O2, rate constant for self-reaction, and rate constant for cross-reaction with CH3CH2O2 were determined: sigma(207 nm) = (6.71 +/- 0.19) x 10(-18) cm2 molecule(-1), k(CH3CH2C(O)O2 + CH3CH2C(O)O2) = (1.68 +/- 0.08) x 10(-11), and k(CH3CH2C(O)O2 + CH3CH2O2) = (1.20 +/- 0.06) x 10(-11) cm3 molecule(-1) s(-1), where quoted uncertainties only represent 2sigma statistical errors. The infrared spectrum of C2H5C(O)O2NO2 was recorded, and products of the Cl-initiated oxidation of CH3CH2CHO in the presence of O2 with, and without, NO(x) were identified. Results are discussed with respect to the atmospheric chemistry of propionaldehyde.  相似文献   

12.
Product distribution studies of the OH radical and Cl atom initiated oxidation of CF3CH2CH2OH in air at 1 atm and 298 +/- 5 K have been carried out in laboratory and outdoor atmospheric simulation chambers in the presence and absence of NOx. The results show that CF3CH2CHO is the only primary product and that the aldehyde is fairly rapidly removed from the system. In the absence of NOx the major degradation product of CF3CH2CHO is CF3CHO, and the combined yields of the two aldehydes formed from CF3CH2CH2OH are close to unity (0.95 +/- 0.05). In the presence of NOx small amounts of CF3CH2C(O)O2NO2 were also observed (<15%). At longer reaction times CF3CHO is removed from the system to give mainly CF2O. The laser photolysis-laser induced fluorescence technique was used to determine values of k(OH + CF3CH2CH2OH) = (0.89 +/- 0.03) x 10(-12) and k(OH + CF3CH2CHO) = (2.96 +/- 0.04) x 10(-12) cm3 molecule(-1) s(-1). A relative rate method has been employed to measure the rate coefficients k(OH + CF3CH2CH2OH) = (1.08 +/- 0.05) x 10(-12), k(OH + C6F13CH2CH2OH) = (0.79 +/- 0.08) x 10(-12), k(Cl + CF3CH2CH2OH) = (22.4 +/- 0.4) x 10(-12), and k(Cl + CF3CH2CHO) = (25.7 +/- 0.4) x 10(-12) cm3 molecule(-1) s(-1). The results from this investigation are discussed in terms of the possible importance of emissions of fluorinated alcohols as a source of fluorinated carboxylic acids in the environment.  相似文献   

13.
In this paper, we describe a new method of measuring alkanethiol monolayer formation on a gold surface. A gold-coated millimeter-sized rectangular-shaped lead zirconate titanate (PZT) cantilever of dimensions 3.5 x 2 x 0.05 mm, previously shown to detect a picogram level of mass change, was used to measure the adsorption kinetics of 1-hexadecanethiol in ethanol over six orders of concentration range (1 nM to 10 mM) in real time. The flexural mode of cantilever vibration, 45.5 +/- 0.01 kHz, was monitored during the self-assembly. The total resonant frequency change obtained for the 1 nM, 10 nM, 100 nM, 1 microM, 4 mM, 8 mM, and 10 mM thiol concentrations were 116 +/- 2 (n = 2), 225 (n = 1), 270 +/- 10 (n = 2), 440 +/- 10 (n = 2), 900 +/- 10 (n = 2), 900 +/- 10 (n = 2), and 900 +/- 10 (n = 2) Hz, respectively. These results compare favorably to literature results in that the rate of the monolayer formation is concentration-dependent and the exponential change during adsorption follows the reversible first-order Langmuir kinetic model. The rate constants of adsorption and desorption were 0.061 M(-1) s(-1) and 3.61 x 10(-4) s(-1), respectively. The significance of the results is that millimeter-sized PZT cantilevers can be used in real-time for characterizing self-assembly of monolayer formation at nanomolar concentration levels. In addition, at 1 nM, the adsorption was found not to be diffusion limited.  相似文献   

14.
The reactions of iodine monoxide radical, IO, with alkyl peroxide radicals, RO(2) (R = CH(3), C(2)H(5), and CF(3)), have been studied using cavity ring-down spectroscopy. The rate constant of the reaction of IO with CH(3)O(2) was determined to be (7.0 +/- 3.0) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K and 100 Torr of N(2) diluent. The quoted uncertainty is two standard deviations. No significant pressure dependence of the rate constant was observed at 30-130 Torr total pressure of N(2) diluent. The temperature dependence of the rate constants was also studied at 213-298 K. The upper limit of the branching ratio of OIO radical formation from IO + CH(3)O(2) was estimated to be <0.1. The reaction rate constants of IO + C(2)H(5)O(2) and IO + CF(3)O(2) were determined to be (14 +/- 6) x 10(-11) and (6.3 +/- 2.7) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K, 100 Torr of N(2) diluent, respectively. The upper limit of the reaction rate constant of IO with CH(3)I was <4 x 10(-14) cm(3) molecule(-1) s(-1).  相似文献   

15.
FTIR-smog chamber techniques were used to study the products of the Cl atom and OH radical initiated oxidation of CF3CH=CH2 in 700 Torr of N2/O2, diluent at 296 K. The Cl atom initiated oxidation of CF3CH=CH2 in 700 Torr of air in the absence of NOx gives CF3C(O)CH2Cl and CF3CHO in yields of 70+/-5% and 6.2+/-0.5%, respectively. Reaction with Cl atoms proceeds via addition to the >C=C< double bond (74+/-4% to the terminal and 26+/-4% to the central carbon atom) and leads to the formation of CF3CH(O)CH2Cl and CF3CHClCH2O radicals. Reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CH(O)CH2Cl radicals, kO2/kdiss=(3.8+/-1.8)x10(-18) cm3 molecule-1. The atmospheric fate of CF3CHClCH2O radicals is reaction with O2 to give CF3CHClCHO. The OH radical initiated oxidation of CxF2x+1CH=CH2 (x=1 and 4) in 700 Torr of air in the presence of NOx gives CxF2x+1CHO in a yield of 88+/-9%. Reaction with OH radicals proceeds via addition to the >C=C< double bond leading to the formation of CxF2x+1C(O)HCH2OH and CxF2x+1CHOHCH2O radicals. Decomposition via C-C bond scission is the sole fate of CxF2x+1CH(O)CH2OH and CxF2x+1CH(OH)CH2O radicals. As part of this work a rate constant of k(Cl+CF3C(O)CH2Cl)=(5.63+/-0.66)x10(-14) cm3 molecule-1 s-1 was determined. The results are discussed with respect to previous literature data and the possibility that the atmospheric oxidation of CxF2x+1CH=CH2 contributes to the observed burden of perfluorocarboxylic acids, CxF2x+1COOH, in remote locations.  相似文献   

16.
The kinetics of the reactions of 1-and 2-butoxy radicals have been studied using a slow-flow photochemical reactor with GC-FID detection of reactants and products. Branching ratios between decomposition, CH3CH(O*)CH2CH3 --> CH3CHO + C2H5, reaction (7), and reaction with oxygen, CH3CH(O*)CH2CH3+ O2 --> CH3C(O)C2H5+ HO2, reaction (6), for the 2-butoxy radical and between isomerization, CH3CH2CH2CH2O* --> CH2CH2CH2CH2OH, reaction (9), and reaction with oxygen, CH3CH2CH2CH2O* + O2 --> C3H7CHO + HO2, reaction (8), for the 1-butoxy radical were measured as a function of oxygen concentration at atmospheric pressure over the temperature range 250-318 K. Evidence for the formation of a small fraction of chemically activated alkoxy radicals generated from the photolysis of alkyl nitrite precursors and from the exothermic reaction of 2-butyl peroxy radicals with NO was observed. The temperature dependence of the rate constant ratios for a thermalized system is given by k7/k6= 5.4 x 10(26) exp[(-47.4 +/- 2.8 kJ mol(-1))/RT] molecule cm(-3) and k9/k8= 1.98 x 10(23) exp[(-22.6 +/- 3.9 kJ mol(-1))/RT] molecule cm(-3). The results agree well with the available experimental literature data at ambient temperature but the temperature dependence of the rate constant ratios is weaker than in current recommendations.  相似文献   

17.
An investigation based on an ultrasoft pseudopotential density functional theory (DFT) method, using the generalized gradient approximation (GGA) under periodic boundary conditions, has been performed in order to investigate how the presence of a neighboring dopant is affecting the CH 3 adsorption reaction (regarded to be an initial growth process). For this study, both the (100) and (111) diamond surface orientations have been considered, and various dopants in two different hydrogenated forms AH X (A = N, B, S, P, or C; X = 0 or 1 for S, X = 1 or 2 for N, B, and P, and X = 2 or 3 for C) were especially scrutinized. For most of the cases studied, the presence of a coadsorbed dopant was found to disfavor CH 3 adsorption with an efficiency that depends on the surface orientation as well as dopant type and position. The NH 2, PH 2, and SH species have the strongest effect in counteracting the CH 3 adsorption to the diamond (111) surface. This is also the situation with the dopants adsorbed on either of two specific surface sites (out of three positions studied) on the diamond (100)-2 x 1 surface. The main reasons for these observations are induced steric hindrances between the two coadsorbates. The BH 2 species, adsorbed to the third type of surface site on diamond (100), has been found to affect the adsorption reaction by formation of a C surf-B bond prior to CH 3 adsorption. The dopants in their radical forms are generally shown to always strongly disfavor the CH 3 adsorption reaction by formation of a C surf-X bond prior to adsorption. However, the NH radical will only form this new bond with the radical surface C site when it is adsorbed to position 3 on the surface.  相似文献   

18.
Crystalline Si(111) surfaces have been alkylated in a two-step chlorination/alkylation process using sterically bulky alkyl groups such as (CH3)2CH- (iso-propyl), (CH3)3C- (tert-butyl), and C6H5- (phenyl) moieties. X-ray photoelectron spectroscopic (XPS) data in the C 1s region of such surfaces exhibited a low energy emission at 283.9 binding eV, consistent with carbon bonded to Si. The C 1s XPS data indicated that the alkyls were present at lower coverages than methyl groups on CH(3)-terminated Si(111) surfaces. Despite the lower alkyl group coverage, no Cl was detected after alkylation. Functionalization with the bulky alkyl groups effectively inhibited the oxidation of Si(111) surfaces in air and produced low (<100 cm s(-1)) surface recombination velocities. Transmission infrared spectroscopy indicated that the surfaces were partially H-terminated after the functionalization reaction. Application of a reducing potential, -2.5 V vs Ag+/Ag, to Cl-terminated Si(111) electrodes in tetrahydrofuran resulted in the complete elimination of Cl, as measured by XPS. The data are consistent with a mechanism in which the reaction of alkyl Grignard reagents with the Cl-terminated Si(111) surfaces involves electron transfer from the Grignard reagent to the Si, loss of chloride to solution, and subsequent reaction between the resultant silicon radical and alkyl radical to form a silicon-carbon bond. Sites sterically hindered by neighboring alkyl groups abstract a H atom to produce Si-H bonds on the surface.  相似文献   

19.
Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) < 2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.  相似文献   

20.
The interaction of a partially fluorinated alkyl sulfate, sodium 1H,1H,2H,2H-perfluorooctyl sulfate (C6F13CH2CH2OSO3Na), with the polyampholyte gelatin has been examined in aqueous solution using surface tension and small-angle neutron scattering (SANS). The 19F chemical shift of each fluorine environment in the surfactant is unaltered by the addition of gelatin, indicating that there is no contact between the gelatin and the fluorocarbon core of the micelle. The chemical shift of the two methylene groups closest to the headgroup is altered when gelatin is present, disclosing the location of the polymer. The critical micelle concentration (cmc) of the surfactant, cmc = 17+/-1 mM, corresponds to an effective alkyl chain (CnH2n+1) length of n = 11. In the presence of gelatin, the cmc is substantially reduced as expected, cmc(1) = 4+/-1 mM, which is also consistent with an effective alkyl chain length of n = 11. In the presence of the fluorosurfactant, the monotonic decay of the SANS from the gelatin-only system is replaced by a substantial peak at an intermediate Q value mirroring the micellar interaction. At low ionic strengths, the gelatin/micelle complex can be described by an ellipsoid. At higher ionic strengths, the electrostatic interaction between the micelles is screened and the peak in the gelatin scattering disappears. The correlation length describing the network structure decreases with increasing SDS concentration as the bound micelles promote a collapse of the network.  相似文献   

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