Water vapor adsorption onto activated carbons prepared from cattle manure compost (CMC)

Activated carbons were prepared from cattle manure compost (CMC) using zinc chloride activation. The structural and surface chemical characteristics of CMC-based activated carbons were determined by N₂ adsorption-desorption and Boehm titration, respectively. The water vapor adsorption properties of the prepared activated carbons with various pore structure and surface nature were examined, and the mechanism of water adsorbed onto activated carbon was also discussed. The results show that the adsorption of water vapor on carbons begins at specific active sites at low relative humidity (RH), followed by micropore filling at medium RH through the formation of pentamer cluster of water molecules in the narrow micropores. The water vapor adsorption capacity of activated carbon is predominantly dependent on its pore volume and surface area. Although capillary condensation is not the mechanism for water adsorption onto activated carbon, water can adsorb on narrow mesopore to some extent.     

Tailoring the porous texture of activated carbons by CO<Subscript>2</Subscript> reactivation to produce electrodes for organic electrolyte-based EDLCs

Highly microporous carbon obtained by KOH etching of carbohydrates exhibited enhanced specific capacitance due to the increased adsorption of electrolyte ions on its large surface, which renders it a promising electrode material. However, the KOH-activated carbon electrode did not achieve its optimum charge capacity in organic electrolytes due to the limited accessibility of the electrolyte ions to the micropores, which hindered the adsorption of ions. The electrode performance was enhanced by enlarging the micropores of KOH-activated carbon to mesopores via reactivation in a stream of CO₂, which allowed the mesopore/micropore ratio to be increased without compromising the originally high specific surface area. The extended amount of mesopores increased the charge capacity of the electrode by enabling the large organic electrolyte ions to access the porous surface, as compared to untreated KOH-activated carbon.     

Preparation of activated carbons from used tyres by gasification with steam and carbon dioxide

Activated carbons were prepared from waste tyres by gasification with steam and carbon dioxide and their characteristics were investigated. A two-stage activation procedure (pyrolysis at 800 °C in N₂ atmosphere, followed by steam or carbon dioxide activation) was used for the production of activated samples. The effect of the activation temperature (750-900 °C) and the activation time (1-3 h) on the surface characteristics of the prepared carbon was investigated. Carbons produced to different degrees of burn-off were characterized by means of their nitrogen adsorption isotherms at 77 K. In both sets of experiments, the mesopore, micropore volume, and BET surface area increased almost linearly with the degree of activation. For burn-off values lower than 53%, the steam activation produced carbons with a narrower and more extensive microporosity and higher BET and external surface area than the carbon dioxide activation. As the activation proceeds (burn-off > 53%), a strong development of the mesoporosity in the carbons was observed and the micropores size distribution revealed broader micropores, that is, a more heterogeneous distribution.     

辐照还原法制备Au掺杂MF气凝胶

利用辐照还原法在500 kGy辐照剂量下制备了Au掺杂MF有机气凝胶。通过X射线衍射（XRD）、能量色散光谱仪（EDX）和透射电子显微镜（TEM）测试证实了辐照法成功地制备出Au掺杂MF有机气凝胶复合物。EDX和TEM照片表明辐照处理后Au纳米颗粒均匀地分布在MF气凝胶骨架中,并且Au纳米颗粒的平均尺寸为5.8 nm。N2吸附数据分析表明掺入Au纳米颗粒后,MF气凝胶的比表面积、总孔体积、微孔体积和介孔体积都有所下降。     

Study on the silica hollow spheres by experiment and molecular simulation

This paper presents the synthesis, characterization and molecular simulation of the silica hollow spheres (SHSs). The SHSs have been prepared using a double-template method, in which the calcium carbonate nanoparticles (CaCO₃) serve as core templates and the cetyltrimethyl-ammonium bromide (CTAB) as wall structure-directing agents. The TEM, XRD, and nitrogen adsorption have been employed to characterize morphologies and structures of the SHSs. The experimental results indicate that the as-prepared sample has an average external diameter of about 85 nm and has occurrence of disordered mesopores in the walls. In the simulation, the SHSs have been modeled as cylindrical pore with pore size distribution according to the experimental data. A combined method of grand canonical Monte Carlo (GCMC) simulation and statistics integral equation (SIE) has been carried out to determine the pore size distribution (PSD) of the SHSs based on the experimental adsorption data of nitrogen at 77 K. The results show that the PSD simulated data are in a good agreement with the experiment, which means that the proposed model for the SHSs is reliable and the combined method of GCMC and SIE is powerful for evaluation of the PSD of the silica hollow spheres.     

Positive and Negative Pulse Etching Method of Porous Silicon Fabrication

We present a new method in which both positive and negative pulses are used to etch silicon for fabrication of porous silicon （PS） monolayer. The optical thickness and morphology of PS monolayer fabricated with different negative pulse voltages are investigated by means of reflectance spectra, scanning electron microscopy and photoluminescence spectra. It is found that with this method the PS monolayer is thicker and more uniform. The micropores also appear to be more regular than those made by common positive pulse etching. This phenomenon is attributed to the vertical etching effect of the PS monolayer being strengthened while lateral etching process is restrained. The explanation we propose is that negative pulse can help the hydrogen cations （H^＋） in the electrolyte move into the micropores of PS monolayer. These H^＋ ions combine with the Si atoms on the wall of new-formed micropores, leading to formation of Si-H bonds. The formation of Silt bonds results in a hole depletion layer near the micropore wall surface, which decreases hole density on the surface, preventing the micropore wall from being eroded laterally by F^- anions. Therefore during the positive pulse period the etching reaction occurs exclusively only at the bottom of the micropores where lots of holes are provided by the anode.     

Influence of surface roughness on water- and oil-repellent surfaces coated with nanoparticles

Various rough surfaces coated with titanium oxide nanoparticles and perfluoroalkyl methacrylic copolymer were conducted to explore the influence of surface roughness on the performance of water- and oil-repellence. Surface characteristics determined from nitrogen physisorption at −196 °C showed that the surface area and pore volume increased significantly with the extent of nanoparticle ratio, indicating an increase of surface roughness. Due to the surface nano-coating, the maximum contact angles of water and ethylene glycol (EG) droplets increased up to 56 and 48%, respectively, e.g. from 105° to 164° for water droplets and from 96° to 144° for EG droplets. The excellent water- and oil-repellence of the prepared surfaces was ascribed to this increase of surface roughness and fluorinated-contained surface. Compared with Wenzel model, the Cassie model yielded a fairly good fit to the simulation of contact angle with surface roughness. However, a derivation of 3°–10° at higher roughness still existed. This phenomenon was very likely due to the surface heterogeneity with different pore size distributions of the fractal surfaces. In this case, it was unfavorable for super repellency from rough surface with larger mesopore fraction because of its capillary condensation, reflecting that micropore provided more air resistance against wettability.     

Pore size distribution calculation from H NMR signal and N2 adsorption–desorption techniques

The pore size distribution (PSD) of nano-material MCM-41 is determined using two different approaches: N₂ adsorption–desorption and ¹H NMR signal of water confined in silica nano-pores of MCM-41. The first approach is based on the recently modified Kelvin equation [J.V. Rocha, D. Barrera, K. Sapag, Top. Catal. 54(2011) 121–134] which deals with the known underestimation in pore size distribution for the mesoporous materials such as MCM-41 by introducing a correction factor to the classical Kelvin equation. The second method employs the Gibbs–Thompson equation, using NMR, for melting point depression of liquid in confined geometries. The result shows that both approaches give similar pore size distribution to some extent, and also the NMR technique can be considered as an alternative direct method to obtain quantitative results especially for mesoporous materials. The pore diameter estimated for the nano-material used in this study was about 35 and 38 Å for the modified Kelvin and NMR methods respectively. A comparison between these methods and the classical Kelvin equation is also presented.     

Pore Structure Analysis of Porous Particles by Modelless and Micropore Method

The modelless (ML) and micropore (MP) methods for the pore structure analysis of porous particles have been studied. Concerning the ML method, it has been shown that the Kiselev equation can only be used to describe condensation and evaporation in capillaries, but cannot be used to describe the increase and decrease of the thickness of the adsorption layer. Strictly speaking, therefore, the ML method is not modelless even for the pore core size distribution. A comparison between the ML method and methods using an equivalent pore model is given. The results of using the ML method in conjunction with a certain pore model are little less accurate than those obtained by adopting the equivalent pore model straightaway. The parameters required for the calculation of both the pore core size and the pore size distribution as well as the conversion between these two calculations are given. Concerning the MP method, it has been shown that the three types of v-t curves, the theoretical foundation of the MP method, are not in one to one correspondance to the three kinds of adsorption mechanism. From the viewpoint of accuracy, the MP method has no advantage over the methods which are based on the condensation mechanism, both have their own merits.     

A consistent next-to-leading-order QCD calculation of hadronic diffractive scattering

We calculate the order _s² and order _s³ QCD contributions to colour-singlet exchange in the leading log s approximation. We implement the resulting amplitude at the hadronic level and thus construct the QCD pomeron and odderon to this order of perturbation theory. We show that the structure of the hadronic form factors provides a natural mechanism through which the odderon gets suppressed at t = 0 whereas it dominates the elastic cross section at large t. We also demonstrate that the inclusion of nonperturbative effects through a modification of the gluon propagator accelerates greatly the convergence of the log s expansion, although not enough to provide agreement with the data.     

Search for a reliable methodology for PSD determination based on a combined molecular simulation-regularization-experimental approach: The case of PHTS materials

We present here a methodology for searching a robust pore size distribution (PSD) for adsorbent materials. The method is based on a combination of individual adsorption isotherms, obtained from Grand Canonical Monte Carlo simulations, a regularization procedure to invert the adsorption integral equation (Tikhonov regularization solved by singular value decomposition), and the needed experimental adsorption isotherm. The selection of several parameters from the available choices to start the procedure are discussed here: the size of the kernel (number of individual pores and number of experimental adsorption points to be included), the fulfillment of the Discrete Picard condition, and the L-curve criteria, all leading to find a reliable and robust PSD. The procedure is applied to plugged hexagonal templated silicas (PHTS), synthesized, and characterized in our laboratory.     

Characterization of synthetic carbons activated with phosphoric acid

The structural heterogeneity of synthetic phosphoric acid activated carbons has been analyzed using pore-size distributions (PSDs) obtained from nitrogen at −196 °C and carbon dioxide at 0 °C isotherms. PSDs where obtained by the BET–Kelvin method. It is shown that the BET–Kelvin method is in good agreement with DFT and provides a fast means for assessment of the porous structure of adsorbents. PSDs obtained by the BET–Kelvin method using different adsorbates give results consistent with each other. Due to the restricted pressure range for carbon dioxide adsorption isotherm the PSD gives information only about pores in the micropore range. The agreement between different methods is better for small micropores.     

Grand canonical Monte Carlo and molecular dynamics simulations of capillary condensation and evaporation of water in hydrophilic mesopores

A combination of grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations (GCMD simulations) was performed to investigate the effect of the difference in chemical potential between the pore surface and gas phase on the adsorption and desorption kinetics of water in a hydrophilic mesopore. The chemical potential of water vapour was controlled by the GCMC method and the adsorption/desorption of water to/from a hydrophilic mesopore was simulated by the MD method. The calculation results showed that when the stepwise change in chemical potential of the gas phase was small, the initial rate of adsorption or desorption of water could be well predicted by the kinetic theory of gases. However, the rate greatly varied depending on the transport mechanisms of water in mesopores such as film flow and column flow. On the other hand, when the stepwise change in chemical potential was large, the initial rate was overestimated by the kinetic theory of gases; however, it did not change greatly with time.     

Characterization of PSD of activated carbons by using slit and triangular pore geometries

A mixed geometry model for activated carbons, representing the porous space as a collection of an undetermined proportion of slit and triangular pores, is developed, evaluated theoretically and applied to the characterization of a controlled series of samples of activated carbon obtained from the same precursor material. A method is proposed for the determination of the Pore Size Distribution (PSD) for such a mixed geometry model, leading to the unique determination of the proportion of pores of the two geometries fitting adsorption data. By using the Grand Canonical Monte Carlo (GCMC) simulation method in the continuum space, families of N2 adsorption isotherms are generated both for slit and triangular geometry corresponding to different pore sizes. The problem of the uniqueness in the determination of the PSD by fitting an adsorption isotherm using the mixed geometry model is then discussed and the effects of the addition of triangular pores on the PSD are analyzed by performing a test where the adsorption isotherm corresponding to the known PSD is generated and used as the “experimental” isotherm. It is found that a pure slit geometry model would widen the PSD and shift it to smaller sizes, whereas a pure triangular geometry model would produce the opposite effect. The slit and triangular geometry families of isotherms are finally used to the fit experimental N₂ adsorption data corresponding to a family of activated carbons obtained from coconut shells through a one-step chemical activation process with phosphoric acid in air, allowing for the determination of the micropore volume, the proportion of slit and triangular pores and the PSD corresponding to the mixed geometry. The same experimental data were fit using both the conventional slit pore model and the mixed geometry model. From the analysis of the effect of different preparation procedures on the resulting PSDs, it is concluded that the proposed mixed geometry model may probably better capture the morphology and energetics of activated carbons prepared by chemical activation under mild temperatures.     

Entropic effects in diffusion-adsorption processes in micropores

We analyze the kinetics of diffusion-adsorption processes of one component systems in micropores. In realistic situations, the pores exhibit irregular forms which give rise to inhomogeneous adsorption with preferred sites for the adsorbing particles. By modeling the tortuosity of the pores by means of entropic barriers, we obtain a kinetic equation for the averaged concentration of particles along the pore and on its surface. The analysis performed yields expressions for the adsorption rate, the effective diffusion coeffcient, the adsorption isotherms and the concentration of the adsorbed particles. It is shown that this last quantity strongly depends on the form of the pore. This feature opens the possibility to design micropores with an optimal adsorption rate at selected sites. Our results show that to consider the geometry of the pore in the reaction-diffusion scheme is crucial to reproduce experimental observations of the concentration of adsorbed particles in micropores.     

Al(OH)3溶胶浓度对TC4钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化(MAO)电源,在保持电学参数和处理时间不变的条件下对TC4钛合金表面进行了MAO处理,研究了Al(OH)₃溶胶浓度对钛合金MAO膜的生长特性、微观结构、相结构和电致变色特性的影响.结果表明:随着Al(OH)₃溶胶浓度(体积分数)C的增加,膜层的生长速率由慢到快逐渐增加,膜表面微孔尺寸和粗糙度逐渐增大,而微孔密度逐渐减小;当C≤10%时,膜层由锐钛矿相TiO₂组成,而当C>10%时,膜层中开始出现金红石相TiO₂并随着C的增加其相对含量逐渐增大,并在C=40%时,膜层全部由金红石相TiO₂组成;在pH＝2.0的HCl溶液中的循环伏安测试结果表明,C≤20%制备试样的膜层颜色变化不明显,随着C的进一步增加,制备试样的膜层颜色变化逐渐明显,并在C=40%时,其着色呈蓝色且色泽均匀;该试样在循环伏安测试过程中还表现出了良好的稳定性和可逆性. 关键词： 微弧氧化 氧化膜 微观结构 电致变色     

Combined MR-relaxation and MR-cryoporometry in the study of bone microstructure.

MR-Relaxation (MRR) of 1H nuclei and MR-Cryoporometry (MRC) are combined to assess their feasibility and their potential in the study of bone microstructure. In principle, both techniques are able to give information on the structure of the pore space confining the fluids. Cow femur samples were carefully cored and cleaned in order to remove the natural fluids inside. For MRR analysis quasi-continuous distributions of T(1) and T(2) were obtained on samples fully saturated with water. Cyclohexane was used as a saturating fluid for MRC analysis. All T(1) and T(2) quasi-continuous distributions of water confined in bone samples are more than three decades wide, showing sufficient details to differentiate the samples. Pore size distributions obtained by MRC also differentiate the samples showing different characteristics of the pore space structure in the range of the highest sensitivity of the method (typically 3 to 100 nm, mesopore range). In particular, in samples where MRR shows a large fraction of signal with relaxation times below 10(2) ms, MRC indicates a large fraction of pore volume with pore sizes in the mesopore range.     

Deposition conditions in tailoring the morphology of highly porous reticular films prepared by electrostatic spray deposition (ESD) technique

Spongy-like reticular structure is a unique morphology fabricated by electrostatic spray deposition (ESD) technique. The effects of solvent, substrate temperature, precursor feeding rate, static electric field strength, and deposition time on tailoring the reticular structure were investigated. Scanning electron microscopy was used to observe the film morphology. MnO_x or LiMn₂O₄ were selected as the model materials. It is found that in addition to the conventional solvent butyl carbitol, other kinds of solvents such as ethylene glycol and propylene glycol can also be used to obtain reticular films at a suitable substrate temperature. Porous films with a low cross-linking degree pore structure can be prepared by increasing precursor feeding rate or decreasing substrate temperature. Increasing the deposition time or the electric field strength helps to obtain reticular films with more homogeneous pore size distribution. In addition, the addition of a high boiling-point solvent in mixed alcohol solvent results in the increase of proper substrate temperature. It is concluded that the fluidity of the spray droplets on the surface of a hot substrate is an important factor to form a reticular film.