杉木活性炭吸附处理水溶液中的尼古丁

用不同孔径及化学性质的活性炭对尼古丁水溶液进行吸附研究. 以杉木屑为原料, 分别用氯化锌化学活化法和水蒸气物理活化法制备活性炭, 并分别命名为AC-Z和AC-H. 同时选用椰壳基商品活性炭作为对比吸附剂, 命名为AC-C. 采用比表面积孔径测定分析仪及Boehm滴定法对活性炭进行表征, 分别测定其比表面积、孔径分布和表面官能团含量. 吸附实验主要考虑吸附时间、温度和尼古丁溶液的初始浓度三个因素, 实验数据分析结果表明微孔有利于物理吸附的进行, 而表面酸性官能团及金属原子作为吸附活性位的作用更加重要. 由改变温度对各样品的吸附量影响也能说明活性位在吸附中的作用. AC-Z拥有较多的活性位, 温度变化时尼古丁的吸附量先升高后减小, 这主要是由于适合的温度能加快尼古丁分子的离解并促使其与活性位相结合, 而过高的温度会造成尼古丁分子动能增加, 导致分子间碰撞的机率和强度增大, 使吸附在活性炭表面的尼古丁分子脱落. AC-H和AC-C由较多的微孔和不同程度的活性位组成, 优先发生物理吸附, 并且伴随发生吸附剂表面分子团簇现象, 其吸附趋势与AC-Z相反. 动力学研究表明活性炭对尼古丁的吸附反应非常迅速, 并且符合准二阶动力学程模型. 各热力学参数ΔG⁰, ΔH⁰和ΔS⁰的计算结果表明吸附剂对尼古丁的吸附为吸热和自发性过程.AC-Z和AC-H的ΔH⁰值远低于AC-C, 说明吸附剂表面的活性位对尼古丁分子有强烈的吸引作用, 所以吸附相同数量吸附质分子所需的吸附热更小, 这也说明了活性位在吸附过程中发生作用.     

Conduction mechanism of Aviram-Ratner rectifiers with single pyridine-sigma-C(60) oligomers

We present the electron transport of pyridyl aza[60]fulleroid oligomers, abbreviated as C(60)NPy, which is based on the donor-barrier-acceptor (D-sigma-A) architecture, at a single molecular scale using scanning tunneling microscopy. A rectifying effect is observed in the current-voltage characteristics. The theoretical calculation shows that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are well localized either on the Py moiety (donor) or on the C(60) moiety (acceptor), indicating the sigma-bridge decouples the LUMO and the HOMO of the donor and the acceptor, respectively. This structure accords well with the unimolecular rectifying model proposed by Aviram and Ratner [Chem. Phys. Lett. 1974, 29, 277]. The mechanism of the rectifying effect is understood by analyzing in detail the electron transport through energy levels of the donor and the acceptor of the C(60)NPy molecules. By directly comparing the experimental conductance peaks and the calculated density of states of the C(60)NPy, we find that the observed rectification is attributed to the asymmetric positioning of the LUMOs and the HOMOs of both sides of the acceptor and the donor of the C(60)NPy molecules with respect to the Fermi level of the electrodes. When a main voltage drop is over the molecule-electrode vacuum junction but a small fraction over the molecule itself, the shift of the energy levels between the donor and the acceptor will be small. This behavior deviates from the original proposal by Aviram and Ratner in which a large shift of the energy level is expected.     

Water vapor adsorption and microporous structure of carbon adsorbents. 18. Effect of surface chemistry of activated carbons on water vapor adsorption

This investigation has been devoted to a study of the chemical composition of the surfaces of activated carbons. A study has been made of the way in which changes in the surface chemistry of a series of carbons, as a result of heat treatment, affects the nature of their adsorption of water vapor. A differentiation has been made between oxygen-containing groups found on the surface of activated carbons before and after their heat treatment. It has been established that the original adsorption centers, which play a determining role in water vapor adsorption by activated carbons, comprise functional groups like strongly acidic free hydrogen ions, carboxylic and phenolic groups, situated on on the pore surface of the activated carbons. The number of these functional groups on the pore surface of the activated carbons has been correlated with the parametera ₀ (the number of original adsorption centers) in the isotherm equation for water vapor adsorption. The relative pressure corresponding to the formation of an adsorption layer on the surface of the activated carbons has been shown to depend on the number of original adsorption centers, the acidic functional groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1991.     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

An investigation of the energetics of peptide ion dissociation by laser desorption chemical ionization fourier transform mass spectrometry

The energy dependence of competing fragmentation pathways of protonated peptide molecules is studied via laser desorption—chemical ionization in a Fourier transform ion cyclotron resonance spectrometer. Neutral peptide molecules are desorbed by the technique of substrate-assisted laser desorption, followed by post-ionization with a proton transfer reagent ion species. The chemical ionization reaction activates the protonated peptide molecules, which then fragment in accordance with the amount of excess energy that is deposited. Chemical ionization forms a protonated molecule with a narrower distribution of activation energy than can be formed by activation methods such as collision activated dissociation. Furthermore, the upper limit of the activation energy is well defined and is approximately given by the enthalpy of the chemical ionization reaction. Control over the fragmentation of peptide ions is demonstrated through reactions between desorbed peptide molecules with different reagent ion species. The fragmentation behavior of peptide ions with different internal energies is established by generation of a breakdown curve for the peptide under investigation. Breakdown curves are reported for the peptides Val-Pro, Val-Pro-Leu, Phe-Phe-Gly-Leu-Met NH₂, and Arg-Lys-Asp-Val-Tyr. The derived breakdown curve of Val-Pro has been fitted by using quasi-equilibrium Rice-Ramsperger-Kassel-Marcus theory to model the unimolecular dissociation of the protonated peptide to provide a better understanding of the mechanisms for the formation of fragment ions that originate from protonated peptides.     

Adsorption phenomena on glass surfaces. III. a microcalorimetric study of adsorption of n-butanol on heat treated surfaces of controlled pore glass

Flow microcalorimetry was used to study the adsorption of butanol on controlled pore glass (CPG) surfaces. Heats of adsorption and some thermodynamic data are reported for the adsorption process at the original, hydroxylated and hydrated surfaces and for those heat treated at temperatures of 450. 650 and 900°C. It was found that the molar free energy of adsorption is the same, 17 kJ mole^?1 for all the surfaces studied. The molar enthalpy and entropy of adsorption are indicative of steric effects caused by water molecules. For surfaces heat treated to 650°C monolayer coverage of butanol is close to 5 molecules per nm², the same figure as reported for the total number of vicinal and isolated silanol groups on the surface of silica.     

Molecular dynamics study of selective adsorption of PCB on activated carbon

The selectivity of PCB adsorption from fish oil onto activated carbon (AC) was investigated by means of molecular dynamics to determine the importance of molecular planarity. PCB congeners 77 and 118 were selected for comparison purposes due to pronounced differences in mean adsorption efficiency and molecular geometry; triolein, a triacylglycerol of oleic acid (C18:1), was used as the representative fish oil component. Graphitic carbon structure was set up to serve as activated carbon model. Molecular force fields employed in the simulations combined short-range parameters from the OPLS with partial atomic charges obtained via quantum chemical calculations using DFT/B3LYP/6-31**G+ and Solvation Model 6. We modified the dihedral angle potential between the PCB aromatic rings and applied Schrödinger's Jaguar package to evaluate the required force field constants. Our complete system comprised a number of PCB molecules dissolved in triacylglycerol that overlaid and filled the pores of an AC structure. The production run of 4 ns provided strong indications that smaller pores will be conductive to better selectivity though also resulted in certain doubts concerning the estimation and assignment of partial atomic charges on the activated carbon. The majority of PCB molecules trapped in pores were attached via cl-AC “bonding”, leaving the main part of the PCB molecule free to interact with triolein. The cl-AC adsorption energy was found to surpass the energy criteria conventionally used for hydrogen bonds. Planar orientation assumed by a PCB molecule in a very energetically favored position on top of the graphite sheet clearly supported the π-cloud overlap hypothesis.     

Microcalorimetric Study of Water Adsorption on Initial and Polyfluoroalkylated Silicas

Water adsorption on initial and modified Silochrom samples was studied by the adsorption calorimetry. Integral heats of immersional wetting by water were measured simultaneously. It was shown that hydroxyl groups both free and sterically screened by a modifier remain on the modified Silochrom surface. Concentrations of these groups and OH groups chemically interacted with the modifier were estimated. The heat of reaction of water molecules with a free surface OH groups of modified sorbents was determined (≈60 kJ/mol). It was found that the modifying layers of the sorbents are getting loose under the effect of adsorbed water, and water molecules gain access to the sterically screened OH groups; the heat of water interaction with these groups is 54–55 kJ/mol. The energy is consumed for getting the modifying layers loose and the rupture of point contacts between Aerosil particles of the secondary structure of both initial and modified Silochrom that significantly affects the heat of immersion, the differential heat of adsorption, the form of the heat release curve, and the dependence of the differential heat on the adsorption value.     

载铜活性炭吸附一氧化碳的密度泛函理论计算

应用密度泛函理论和相对论有效核势方法, 用C₁₆H₁₀, C₁₃H₉, C₁₂H₁₂原子簇模型模拟活性炭表面, 计算得到了CO在载铜活性炭上的吸附位、吸附构型和吸附能. 研究表明: 载铜活性炭吸附CO的过程, 本质上是Cu(I)通过σ-π配键与CO络合, 形成Cu—C键的过程. 载铜活性炭对CO的络合吸附能在50～60 kJ/mol之间, 远大于活性炭对CO的物理吸附能(9.15 kJ/mol), 因而络合吸附更稳定, 选择性也更高. Cu(I)选择吸附在活性炭表面的顶位和桥位, 一个Cu(I)至多可以吸附一个到两个CO分子, 但吸附一个CO比吸附两个CO稳定.     

Determination of the heat effects involved during toluene vapor adsorption and desorption from microporous activated carbon

In the present work the adsorption of toluene on microporous activated carbon was chosen as an illustrative example in order to show that different values of the heat effect might be obtained following the procedure used. Values ranging from 85 to 40 KJ/moL were obtained for the isosteric heat of adsorption at different adsorbate loadings using adsorption isotherm data measured under static conditions. However, the application of temperature programmed desorption (TPD) experiments carried out under dynamic conditions yields apparent energy of desorption values that cannot be systematically correlated with the heat of adsorption which is a thermodynamic parameter relevant to the adsorption equilibrium. This issue is of interest because the use of accurate values of the heat of adsorption is important for the correct designing and operating of adsorption facilities.     

同系列电子给体与同系列电子受体CT络合作用的研究 Ⅱ. 几何匹配效应

在研究弱的CT络合物中给体与受体的相对取向时, 认为应更多地考虑分子间的静电作用, 并根据晶体结构分析结果, 提出头并头的几何匹配棋型。用此模型来分析分子间的作用能, 并由平衡常数的测定结果表明, 当同系列给体与同一受体相作用时, 随着同系序数的增加, 由于几何匹配效应, 络合物的基态稳定性不是单调变化的, 而是呈现两头小中间大的现象。在红外光谱中, 某些吸收峰相对强度的变化也有类似的现象。     

Interlayer triplet-triplet energy transfer in nanosized molecular layers

The results of the study of interlayer triplet-triplet energy transfer from anthracene molecules to Nile Red molecules in Langmuir-Blodgett films are presented. The observed sensitized delayed fluorescence of the energy acceptor is shown to be due to annihilation of migrating triplet excitons. It has been found that the decay kinetics of delayed fluorescence of the donor and the acceptor has a complex form and is described by a combination of the power and exponential functions. The dependence of the energy transfer efficiency on the distance between the donor and acceptor layers was studied.     

An S N2-Model for Proton Transfer in Hydrogen-Bonded Systems

A new mechanism of proton transfer in donor–acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution.     

Adsorption of toluene and toluene–water vapor mixture on almond shell based activated carbons

The aim of work is to study the adsorption of a common volatile organic compound such as toluene using activated carbons prepared by chemical activation with phosphoric acid of a lignocellulosic precursor, almond shell, under different conditions. The Impregnation ratio, temperature and time of activation were modified to obtain activated carbons with different characteristics. Regarding the characteristics of the activated carbons, the effects of porous structure and surface chemistry on the toluene adsorption capacity from toluene isotherms have been analysed. Results show that the control of properties of the activated carbons, particularly porous structure, highly dependent on the preparation conditions, plays a decisive role on the toluene adsorption capacity of the activated carbons. Concerning the experiments of toluene adsorption conducted in dynamic mode, activated carbons prepared at low temperatures of activation show higher breakthrough times than those obtained for activated carbons prepared at higher activation temperatures. The amount of toluene adsorbed in presence of water vapor in the gas stream lead to a decrease ranging from 33 to 46 % except for carbons prepared at higher temperatures activated that show only a slight decrease in the amount of toluene adsorbed. Activated carbons can be regenerated with soft heat treatment showing a slight decrease in the adsorption capacity. The high toluene adsorption capacities as well as the high breakthrough times obtained in presence of water vapor make these activated carbons suitable for commercial applications.     

Mesopore control of high surface area NaOH-activated carbon

Activated carbon with BET surface areas in a narrow range from 2318 to 2474 m2/g was made by soaking the char made from corncob in a concentrated NaOH solution at NaOH/char ratios from 3 to 6; the mesopore volumes of the activated carbon were significantly changed from 21 to 58%. The relationships between pore properties (Sp, Vpore, Vmicro/Vpore, Dp) and NaOH dosage were investigated. Comparisons between the methods of NaOH and KOH activation revealed that NaOH activation can suitably control the mesopore specific volume of the activated carbon. Elemental analysis revealed that the H/C and O/C values of the activated carbons of NaOH/char ratios from 3 to 6 were significantly lower. SEM observation of surface hole variation of the activated carbon ascertained that the reaction process was inner pore etching. Based on the above three measurements and experimental investigations, the assumption made by previous researchers, namely that NaOH and KOH produce similar results, was challenged. Furthermore, the adsorption kinetics was used to investigate the adsorption rate of an Elovich equation to determine the relationships between the adsorption behavior on larger molecules (dyes) and smaller molecules (phenols) and the pore structure of the activated carbon.     

超临界甲烷在活性炭上的吸附平衡分析

为分析由吸附平衡时的热力参数确定吸附量、吸附模型和等量吸附热精度的影响因素,选择在温度268.15~338.15 K和压力0~13.5 MPa测试的甲烷在Ajax活性炭上的吸附平衡数据,通过引入甲烷分子可进入活性炭吸附空间内的容积和可以不考虑甲烷在孔内吸附的临界孔宽的概念,依据甲烷在吸附平衡前后的总量守恒,确定甲烷在吸附池内的总量、绝对吸附量和过剩吸附量三者之间的关系式。结果表明,在引入吸附质分子可进入吸附空间内的容积和临界孔宽后,经由活性炭的孔径分布(PSD),可以准确计算甲烷在活性炭上的过剩吸附量;应用实验数据非线性回归Toth方程参数后,可由Gibbs关于吸附的定义确定甲烷在活性炭上的绝对吸附量。比较结果时发现,由于未考虑本体相中甲烷分子对吸附甲烷分子的影响,采用过剩吸附量的等量吸附线标绘确定的等量吸附热数值偏高,工程应用时应由绝对吸附量来确定等量吸附热。     

A DFT study of H2O dissociation on metal‐precovered Fe (100) surface

The H₂O adsorption and dissociation on the Fe (100) surface with different precovered metals are studied by density functional theory. On both kinds of metal‐precovered surface, H₂O molecules prefer adsorb on hollow sites than bridge and top sites. The impurity energy difference is proportional to the adsorption energy, but the adsorbates are not sensitive to the adsorption orientation and height relative to the surface. The Hirshfeld charge analysis shows that water molecules act as an electron donor while the surface Fe atoms act as an electron acceptor. The rotation and dissociation of H₂O molecule occur on the Co‐ and Mn‐precovered surfaces. Some H₂O molecules are dissociated into OH and H groups. The energy barriers are about 0.5 to 1.0 eV, whose are consistence with the experimental data. H₂O molecules can be dissociated more easily at the top site on Co‐precovered surface 1 than that at bridge site on Mn‐precovered surface 2 because of the lower reaction barrier. The dispersion correction effects on the energies and adsorption configurations on Co‐precovered surface 1 were calculated by OBS + PW91. The dispersion contributions can improve a bit of the bond energy of adsorbates and weaken the hydrogen bond effect between adsorption molecules a little.     

Interaction between water molecules and zinc sulfide nanoparticles studied by temperature-programmed desorption and molecular dynamics simulations

We have investigated the bonding of water molecules to the surfaces of ZnS nanoparticles (approximately 2-3 nm sphalerite) using temperature-programmed desorption (TPD). The activation energy for water desorption was derived as a function of the surface coverage through kinetic modeling of the experimental TPD curves. The binding energy of water equals the activation energy of desorption if it is assumed that the activation energy for adsorption is nearly zero. Molecular dynamics (MD) simulations of water adsorption on 3 and 5 nm sphalerite nanoparticles provided insights into the adsorption process and water binding at the atomic level. Water binds with the ZnS nanoparticle surface mainly via formation of Zn-O bonds. As compared with bulk ZnS crystals, ZnS nanoparticles can adsorb more water molecules per unit surface area due to the greatly increased curvature, which increases the distance between adjacent adsorbed molecules. Results from both TPD and MD show that the water binding energy increases with decreasing the water surface coverage. We attribute the increase in binding energy with decreasing surface water coverage to the increasing degree of surface under-coordination as removal of water molecules proceeds. MD also suggests that the water binding energy increases with decreasing particle size due to the further distance and hence lower interaction between adsorbed water molecules on highly curved smaller particle surfaces. Results also show that the binding energy, and thus the strength of interaction of water, is highest in isolated nanoparticles, lower in nanoparticle aggregates, and lowest in bulk crystals. Given that water binding is driven by surface energy reduction, we attribute the decreased binding energy for aggregated as compared to isolated particles to the decrease in surface energy that occurs as the result of inter-particle interactions.     

Energy transfer and fluorescence quenching in complexes of polymethine dyes with human serum albumin

Electronic excitation energy transfer (EET) between molecules of polymethine dyes bound to human serum albumin (HSA) has been established and studied by absorption and fluorescence spectroscopy as well as by fluorescence decay measurements. In this system, excitation of the donor dye molecule leads to fluorescence of the acceptor dye molecule, both bound to HSA, with donor fluorescence quenching by the acceptor. The short distance between the donor and the acceptor (25-28 A) revealed from the Forster model of EET as well as some spectroscopic data show that both molecules are probably located in the same binding domain of HSA. The role of HSA is to bring donor and acceptor molecules together to a distance adequate to achieve EET as well as to increase the donor and acceptor fluorescence quantum yields. Efficient quenching of the intrinsic HSA fluorescence by some polymethine dyes (oxonols) is observed. The experimental results fit well a model for the formation of a weakly fluorescent dye-HSA complex; the quencher in this complex should be located in the immediate vicinity of the HSA fluorophore group (Trp(214)).     

Charge transfer in the TCNQ-sexithiophene complex

Molecular crystals from thiophene molecules can be doped with TCNQ-F4 molecules for use in all-organic optoelectronic and semiconductor devices. The charge transfer and the molecular orbital energy level formation in between these two organic molecules are investigated here by density functional theory calculations. The isolated molecules are calculated nonbonded and bonded together, forming a charge transfer complex (CTC). The relaxed structure of the complex shows essentially coplanar and centered molecules with the alpha-sexithiophene rings tilted alternatingly by 4.8 degrees. The bond formation of these molecules results in a charge transfer of approximately 0.4 e from the alpha-sexithiophene to the TCNQ-F4 molecule. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap width is reduced as compared to the isolated molecules due to the newly formed orbitals in the CTC. Upon adsorption on a Au(111) surface, electrons are transferred onto the molecule complex, thereby causing the molecular levels to align asymmetric with respect to the charge neutrality level. The theoretical results for the single molecule and CTC layer are compared to experimental photoemission and scanning tunneling spectroscopy results.