Preparation of Biporous Adsorbents with Controlled Structure

A new procedure was developed for the preparation of the adsorbents with a biporous structure by mixing metal hydroxides with fine- and coarse-porous structures. It was shown that structural parameters of the biporous samples can be changed significantly by varying the aging time of initial hydroxides or preparing them from salt solutions of different concentrations. This is confirmed by the positions of maxima on the curves of pore volume distribution over effective radii. It was found that the regularities of structural changes directly depend on the conditions of preparation of mixing hydroxides. A suggested mechanism of structural variations allowed us to explain the results obtained.     

Geopolymeric adsorbents from fly ash for dye removal from aqueous solution

Adsorbents from coal fly ash treated by a solid-state fusion method using NaOH were prepared. It was found that amorphous aluminosilicate geopolymers would be formed. These fly ash-derived inorganic polymers were assessed as potential adsorbents for removal of some basic dyes, methylene blue and crystal violet, from aqueous solution. It was found that the adsorption capacity of the synthesised adsorbents depends on the preparation conditions such as NaOH:fly-ash ratio and fusion temperature with the optimal conditions being at 1.2:1 weight ratio of Na:fly-ash at 250-350 degrees C. The synthesised materials exhibit much higher adsorption capacity than fly ash itself and natural zeolite. The adsorption isotherm can be fitted by Langmuir and Freundlich models while the two-site Langmuir model producing the best results. It was also found that the fly ash derived geopolymeric adsorbents show higher adsorption capacity for crystal violet than methylene blue and the adsorption temperature influences the adsorption capacity. Kinetic studies show that the adsorption process follows the pseudo second-order kinetics.     

Adsorption kinetics of hemoglobin onto silicate adsorbents

A comparative study was performed of the adsorption kinetics of hemoglobin onto four silicate adsorbents that differed in parameters of porous structure: industrial silochrome, and three silicates obtained by template synthesis. The existence of a reversible stage of the process preceding irreversible protein binding was shown by kinetic analysis. Rate constants for the reversible stage of the process and the effective constants of first order rate were calculated. It was concluded that the adsorption rate is the highest on silochrome and the lowest on silicate of MCM-41 type, the pore size of which is comparable to the diameter of a hemoglobin molecule. The constant of the desorption rate for the first reversible stage of the process was shown in the case of mesoporous silicates to be lower by a factor of 3.5–4 than in the case of silochrome.     

The special features of protein adsorption isotherms on silica adsorbents

The adsorption isotherms of hemoglobin, peroxidase, and β-galactosidase on silochrome and mesoporous and biporous silicas were comparatively studied. Adsorption developed in two stages, including fast “reversible” protein adsorption (equilibrium was reached in t ≤ 1–2 h) and a “slow stage” of irreversible binding in t ≫ 24 h (multipoint adsorption). The corresponding equilibrium constants were determined. The mechanism of unlimited linear association of peroxidase in the adsorption layer on the surface of silochrome was established.     

硅铝酸盐聚合反应的研究

应用NMR技术、激光拉曼光谱和硅钼酸方法研究了碱性硅铝酸盐聚合反应中铝酸根离子和硅酸根离子的存在状态及其变化.发现聚合反应是低分子量硅铝酸根离子之间或低分子量硅铝酸根离子与低分子量硅酸根离子之间的反应.     

Pd/PdO在MCM-41介孔材料孔表面的溶液移植

利用PdCl~2溶液与介孔结构硅酸铝合成原粉反应,把Pd/PdO多用途催化剂移植到MCM-41材料孔表面。产物用XRD,热分析(TG/DTA),TEM,N~2吸附及FT-IR光谱等手段进行表征。结果表明,钯经由Si-O-Pd键负载在硅酸铝骨架及孔表面上。在有序介孔材料外表面沿着孔道方向粘附着直径为10-30nm的Pd/PdO晶粒。研究表明,采用这种液相移植的方法可以有效负载金属催化剂,并防止孔道堵塞。     

Peculiarities of the Porous Structure of Aluminosilicate Mesoporous Substances Obtained in The Presence of Biotemplates

Supramolecular structures of lecithin occurred to be the template in the synthesis of mesoporous aluminosilicates; using of various combinations of lecithin and cetyltrimethyl-ammonium bromide or octadecylamine as templating agents allowed to obtain mesoporous substances with pores up to 100 Å, as well as biporous materials in aluminosilicate system. In the presence of glucose oxidase and cetyltrimethyl-ammonium bromide combinations aluminosilicate substances with complex porous structure were shown to be formed (pore size distributions exhibited 3 peaks, corresponding 3 effective size of mesopores in the 30–100 Å range). The investigation of sorption of glucose oxidase on obtained aluminosilicate mesoporous substances was carried out, the results obtained allowus to consider such materials as prospect for creation high capable and selective sorbents for biomolecules sorption, as well as active elements of chemical and biosensors.     

Effects of the composition of the reaction mixture and the nature of the template on the structure of mesoporous aluminosilicates formed in the presence of lecithin

It has been established that supramolecular structures of lecithin can act as templates in the synthesis of mesoporous aluminosilicates. Mesoporous substances, with pore dimensions up to 100 Å and biporous materials can be obtained when various combinations of lecithin with cetyltrimethylammonium bromide or octadecylamine are used as template agents in the aluminosilicate system.     

The Effect of Modification on the Structural,Acidic, and Catalytic Properties of a Layered Aluminosilicate

The effect of modification on the structural, acidic, and catalytic properties of a natural layered aluminosilicate containing 90% montmorillonite was studied. With the use of low-temperature nitrogen adsorption and XRD analysis, it was found that the addition of hydroxo complexes of aluminum prevents the silicate layers of the layered aluminosilicate from closing upon heating and results both in the formation of stable micropores and in a considerable increase in the specific surface area. The acidic properties of the H, Na, and Al forms of the layered aluminosilicate were studied by IR spectroscopy of adsorbed CO molecules and by the indicator method. After modification with hydroxo complexes of aluminum, the number of Lewis acid sites and the accessibility of acidic OH groups to CO adsorption increased. The total number and strength of acid sites increased as the calcination temperature of the layered aluminosilicate was increased. A correlation between catalytic activity in the reaction of acetone dimerization and the number of acid sites in different forms of the layered aluminosilicate was obtained.     

Water vapor adsorption and capillary reactions of silicates

States of disperse silicate systems classified according to their fundamental morphological types were represented by a ternary diagram. Water vapor equilibria of various silicate samples were investigated by energy levels, by equivalent pore number of potential bands determined from adsorption potential curves. The silicate adsorbents were characterized by adsorption energy, equipotential surface area and specific capillary. Electrical properties of adsorbents depending on their water contents were examined. Changes of adsorption properties of mechanical, thermal and by ion exchange treated silicates were observed. Electrical properties of adsorbents depending on their humidity were examined. Capillary reactions were observed causing irreversible adsorption-desorption cycles.     

Residue valorization: Preparation of recyclable organic amine adsorbent using laterite residue

This study focuses on exploiting the main component of traditional nickel metallurgical waste for use as a valuable material that can be applied in the removal of organic amines from water systems. Silicon compounds from metallurgic waste were converted into dissolvable sodium silicate by roasting the waste with alkali. Silica with adsorption capacity was combined with magnetic NiFe cores by the carbonation decomposition of purified silicate solution. The composite magnetic adsorbent was characterized, and its adsorption mechanism for organic amines was investigated. The effects of the initial trimethylamine concentration, contact time and temperature on the adsorption efficiency of the composite adsorbent towards trimethylamine were investigated. It was found that the adsorption fit the Freundlich mode well. The adsorption kinetics can be described by a pseudo-second-order kinetic model. The adsorption capacity reached 55.8 μg/mg at 293 K. The use of metallurgical waste to prepare the magnetic composite adsorbent has three advantages, which include benefiting the environment by reducing the amount of solid waste and costs associated with constructing and maintaining storage facilities, generating valuable products in an economical manner and conveniently recycling used adsorbents to avoid secondary pollution.     

Adsorption isotherms of 2,2,4-trimethylpentane and toluene vapors on hydrocarbon adsorber and light-off catalyst

Two monolithic hydrocarbon adsorbers and a monolithic light-off catalyst were selected as adsorbents, and the adsorptive capacity of a hydrocarbon for the adsorbents was measured by using a precise volumetric adsorption apparatus. 2,2,4-Trimethylpentane and toluene vapors were chosen as adsorbates. Equilibrium experiments were carried out at three different temperatures of 303.15, 323.15, and 343.15 K. Adsorption data of each hydrocarbon was fitted to the well-known isotherms such as the Langmuir equation and the Freundlich equation. The Freundlich isotherm predicted equilibrium data better than the Langmuir isotherm. Furthermore, the surface energetic heterogeneity of the adsorbents was evaluated using the isosteric heat of adsorption based on Clausius-Clapeyron equation. The surface energetic heterogeneity of the adsorbents depended on the precious metal (PM) loading and H-ZSM5 loading.     

Adsorption of hydrogen isotopes on micro- and mesoporous adsorbents with orderly structure

The equilibrium and dynamic adsorption data of H(2) and D(2) on different micro- and mesoporous adsorbents with orderly structure including 3A, 4A, 5A, Y, and 10X zeolites; carbon CMK-3; silica SBA-15; and so forth were collected. Critical effect of the nanodimension of adsorbents on the adsorption behavior of hydrogen and its isotopes is shown. The highest adsorption capacity was observed at pore size 0.7 nm, but equal or even larger isotope difference in the equilibrium adsorption was observed at larger pore sizes, whereas the largest isotope difference in the dynamic adsorption was observed at 0.5 nm. The adsorption rate of D(2) is larger than that of H(2) in microporous adsorbents, but the sequence could be switched over in mesoporous materials. Linear relationship was observed between the adsorption capacity for hydrogen and the specific surface area of adsorbents although the adsorbents are made of different material, which provides a convincing proof of the monolayer mechanism of hydrogen adsorption. The linear plot for microporous adsorbents has a larger slope than that for mesoporous adsorbents, which is attributed to the stronger adsorption potential in micropores.     

Displacement processes on hydrophilic/hydrophobic surfaces in 1-propanol-water mixtures

Selective adsorption of 1-propanol-water mixtures was investigated on adsorbents of various surface character. The enthalpy of displacement of 1-propanol by water was studied on graphitized PRINTEX-80, K-60 silicagel, and n-alkylammonium vermiculites. The free enthalpy and entropy isotherms of displacement were derived. The adsorption between the silicate layers of hydrophobic vermiculites was followed by x-ray measurements, and thermodynamic functions were calculated for the structural changes in the adsorption layers. Formation of alcohol-water clusters on the surfaces plays an important role.     

Efficient adsorbents of nanoporous aluminosilicate monoliths for organic dyes from aqueous solution

Growing public awareness on the potential risk to humans of toxic chemicals in the environment has generated demand for new and improved methods for toxicity assessment and removal, rational means for health risk estimation. With the aim of controlling nanoscale adsorbents for functionality in molecular sieving of organic pollutants, we fabricated cubic Im3m mesocages with uniform entrance and large cavity pores of aluminosilicates as highly promising candidates for the colorimetric monitoring of organic dyes in an aqueous solution. However, a feasible control over engineering of three-dimensional (3D) mesopore cage structures with uniform entrance (~5 nm) and large cavity (~10 nm) allowed the development of nanoadsorbent membranes as a powerful tool for large-quantity and high-speed (in minutes) adsorption/removal of bulk molecules such as organic dyes. Incorporation of high aluminum contents (Si/Al=1) into 3D cubic Im3m cage mesoporous silica monoliths resulted in small, easy-to-use optical adsorbent strips. In such adsorption systems, natural surfaces of active acid sites of aluminosilicate strips strongly induced both physical adsorption of chemically responsive dyes and intraparticle diffusion into cubic Im3m mesocage monoliths. Results likewise indicated that although aluminosilicate strips with low Si/Al ratios exhibit distortion in pore ordering and decrease in surface area and pore volume, enhancement of both molecular converges and intraparticle diffusion onto the network surfaces and into the pore architectures of adsorbent membranes was achieved. Moreover, 3D mesopore cage adsorbents are reversible, offering potential for multiple adsorption assays.     

Adsorption of sodium dodecylsulfate on modified carbon adsorbents

The adsorption of anionic surfactants on carbon adsorbents modified with water-soluble derivatives of natural polymers, cellulose and chitin, is considered with sodium dodecylsulfate taken as an example. It is shown that such modification leads to changes in the adsorption structural characteristics and the particle size distribution of carbon-water suspensions of the original adsorbent, and to the emergence of new functional groups on its surface that are able to interact selectively with adsorbate molecules. It is assumed that adsorption of anionic surfactant on carbon adsorbents under equilibrium conditions proceeds via stepwise filling of the carbon??s porous structure: we first observe volume filling of micropores according to their sizes, and then the formation of a surfactant??s monolayer in mesopores and on the outer surface of the adsorbate. It is established by thermal analysis that the thermal stability of carbon adsorbents is enhanced through the preferential localization of anionic surfactants in micropores. The filling of mesopores and the outer carbon surface by surfactant molecules leads to a regular decrease in thermal stability and an increase in the adsorbent surface??s hydrophilicity.     

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.     

Characterization of novel adsorbents for radiostrontium reduction in foods

Distribution coefficients, pH dependence, isotherms, kinetics and breakthrough curves of Sr binding have been measured on several types of adsorbents (carbons modified with titanium silicate, crystalline titanium silicate, mixed titanium-manganese oxide, and synthetic zeolites A4 and P) from different water solutions. It is concluded that acid-base properties of the adsorbent is very important for Sr binding. Titanium silicate based adsorbents had reduced chemical stability in an artificial food fluid below pH 2, the mixed titanium manganese oxide below pH 6, zeolite A4 below pH 5 and zeolite P below pH 7. Consideration is given to the feasibility of the adsorbents for food decontamination.     

Quantum-Chemical Investigation of the Interaction of Water and Methanol Molecules with Surface Carboxyl Groups on Graphite

A quantum-chemical investigation made of the adsorption of water and methanol at hydrophilic centers (carboxyl groups) on the partly oxidized surface of graphite was undertaken. The enthalpy of adsorption of water and methanol at such centers was determined. It was shown that water is adsorbed at the surface carboxyl groups in the form of dimers, while methanol is adsorbed in the form of single molecules. It was confirmed that the formation of clusters of water molecules in the vicinity of the hydrophilic center is a characteristic feature of the adsorption of water on the surface of graphite and other adsorbents.     

The role of adsorption compression in nanocapillarity

Influence of adsorption compression on nanocapillarity is discussed. Kelvin's equation for a compressible liquid is written in a form that takes into account not only Laplace's pressure, but also adsorption compression. This leads to a simple analytical equation for pressure in nanocapillaries. It is shown that the ratio of Laplace's pressure to the adsorption compression pressure determines different types of nanocapillary behavior. When the Laplace pressure dominates, it results in classical capillarity that is well studied and understood. There is an intermediate range where Laplace's pressure is partially or fully compensated by adsorption compression, and the resulting pressure in a capillary is an interplay between attraction to walls and repulsions from neighboring molecules in compressed adsorbed fluid. If the adsorption compression pressure dominates, it results in inversion of capillary pressure and the fluid adsorbed in the nanocapillary presses on walls from inside. This phenomenon has been observed experimentally for fluids in nanoporous solids; in particular, high-precision measurements have shown significant expansion of nanoporous adsorbents loaded with various fluids. It is also shown that oscillatory adhesion forces and internal forces in nanoporous adsorbents have a common thermodynamic origin and can be discussed in the framework of adsorption compression mechanisms.