Pore chemistry

Although an increase in meso pore surface area and activity will result in an increase in conversion and resid conversion, Table IV also shows that there is no simple correlation between the observed catalyst properties and these results. Apparently other aspects such as pore size distribution and pore chemistry also play an important role. 

New developments were done concerning gas separation (GS) membranes and membranes for gaseous diffusion. The tailorable pore sizes and pore chemistry of... 

Understanding the pore chemistry and physics of complicated materials such as coal can make a significant long-term contribution to advanced coal conversion technology. 

To enhance the adsorptive and catalytic performance, both tailoring the pore structure and tuning the pore chemistry should be considered. The former is related to the internal mass-transfer resistance, while the latter contributes to selective adsorption and nature of the active center. High-efficiency porous heterogeneous catalysts could be produced on the basis of the synergistic effect of the high surface area, uniform pore channel, and the reactivity. 

As a general rule, adsorbates above their critical temperatures do not give multilayer type isotherms. In such a situation, a porous absorbent behaves like any other, unless the pores are of molecular size, and at this point the distinction between adsorption and absorption dims. Below the critical temperature, multilayer formation is possible and capillary condensation can occur. These two aspects of the behavior of porous solids are discussed briefly in this section. Some lUPAC (International Union of Pure and Applied Chemistry) recommendations for the characterization of porous solids are given in Ref. 178. 

The pore systems of solids are of many different kinds. The individual pores may vary greatly both in size and in shape within a given solid, and between one solid and another. A feature of especial interest for many purposes is the width w of the pores, e.g. the diameter of a cylindrical pore, or the distance between the sides of a slit-shaped pore. A convenient classification of pores according to their average width originally proposed by Dubinin and now officially adopted by the International Union of Pure and Applied Chemistry is summarized in Table 1.4. 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

A detailed examination of the correlation between Vj and M is discussed in references on analytical chemistry such as Ref. 6. We shall only outline the problem, with particular emphasis on those aspects which overlap other topics in this book. To consider the origin of the calibration curve, we begin by picturing a narrow band of polymer solution being introduced at the top of a solvent-filled column. The volume of this solvent can be subdivided into two categories the stagnant solvent in the pores (subscript i for internal) and the interstitial liquid in the voids (subscript v) between the packing particles ... 

Eactors that could potentiaHy affect microbial retention include filter type, eg, stmcture, base polymer, surface modification chemistry, pore size distribution, and thickness fluid components, eg, formulation, surfactants, and additives sterilization conditions, eg, temperature, pressure, and time fluid properties, eg, pH, viscosity, osmolarity, and ionic strength and process conditions, eg, temperature, pressure differential, flow rate, and time. 

Mlcrofiltra.tlon, Various membrane filters have been used to remove viral agents from fluids. In some cases, membranes which have pores larger than the viral particle can be used if the filtration is conducted under conditions which allow for the adsorption of the viral particle to the membrane matrix. These are typically single-pass systems having pore sizes of 0.10—0.22 lm. Under situations which allow optimum adsorption, between 10—10 particles of poHovims (28—30 nm) were removed (34—36). The formation of a cake layer enhanced removal (35). The titer reduction when using 0.10—0.22 p.m membrane filters declined under conditions which minimized adsorption. By removal standards, these filters remove vimses at a rate on the low end of the desired titer reduction and the removal efficiency varies with differences in fluid chemistry and surface chemistry of viral agents (26). 

The design and manufacture of adsorbents for specific appHcations involves manipulation of the stmcture and chemistry of the adsorbent to provide greater attractive forces for one molecule compared to another, or, by adjusting the size of the pores, to control access to the adsorbent surface on the basis of molecular size. Adsorbent manufacturers have developed many technologies for these manipulations, but they are considered proprietary and are not openly communicated. Nevertheless, the broad principles are weU known. 

The stmcture of activated carbon is best described as a twisted network of defective carbon layer planes, cross-linked by aHphatic bridging groups (6). X-ray diffraction patterns of activated carbon reveal that it is nongraphitic, remaining amorphous because the randomly cross-linked network inhibits reordering of the stmcture even when heated to 3000°C (7). This property of activated carbon contributes to its most unique feature, namely, the highly developed and accessible internal pore stmcture. The surface area, dimensions, and distribution of the pores depend on the precursor and on the conditions of carbonization and activation. Pore sizes are classified (8) by the International Union of Pure and AppHed Chemistry (lUPAC) as micropores (pore width <2 nm), mesopores (pore width 2—50 nm), and macropores (pore width >50 nm) (see Adsorption). 

In addition to surface area, pore size distribution, and surface chemistry, other important properties of commercial activated carbon products include pore volume, particle size distribution, apparent or bulk density, particle density, abrasion resistance, hardness, and ash content. The range of these and other properties is illustrated in Table 1 together with specific values for selected commercial grades of powdered, granular, and shaped activated carbon products used in Hquid- or gas-phase appHcations (19). 

Separation media, with bimodal chemistry, are generally designed for the complete separation of complex samples, such as blood plasma serum, that typically contain molecules differing in properties such as size, charge, and polarity. The major principle of bifunctional separation relies on the pore size and functional difference in the media. For example, a polymer bead with hydrophilic large pores and hydrophobic small pores will not interact with and retain large molecules such as proteins, but will interact with and retain small molecules such as drugs and metabolites. 

Given a polymer to separate, it is important to select an appropriate solvent and appropriate surface chemistry on the pore wail for the optimal separation. In particular, adsorption of the polymer onto the pore surface needs to be prevented. If adsorption occurs, it will favor high MW components, a phenome-... 

Wallace, B. A., 1990. Gramicidin channels and pores. Annual Review of Biophysics and Biophysical Chemistry 19 127—157. 

When mature concrete is contaminated by chloride, e.g. by contact with deicing salts, the cement chemistry is more complex, and less chloride is taken up by the cement hydrate minerals and a larger proportion is free in the pore solutions and can therefore pose a greater hazard. When embedded steel corrodes, the production of a more voluminous corrosion product pushes the concrete from the steel with resultant cracking and spalling of the concrete. 

---