CHAPTER 4


HIGH SURFACE AREA MATERIALS


Donald M. Cox

Exxon Research and Engineering


Introduction

The trend to smaller and smaller structures, that is, miniaturization, is well known in the manufacturing and microelectronics industries, as evidenced by the rapid increase in computing power through reduction on chips of the area and volume needed per transistor (Roher 1993). In the materials area this same trend towards miniaturization also is occurring, but for different reasons. Smallness in itself is not the goal. Instead, it is the realization, or now possibly even the expectation, that new properties intrinsic to novel structures will enable breakthroughs in a multitude of technologically important areas (Siegel 1991; Gleiter 1989).

Of particular interest to materials scientists is the fact that nanostructures have higher surface areas than do conventional materials. The impact of nanostructure on the properties of high surface area materials is an area of increasing importance to understanding, creating, and improving materials for diverse applications. High surface areas can be attained either by fabricating small particles or clusters where the surface-to-volume ratio of each particle is high, or by creating materials where the void surface area (pores) is high compared to the amount of bulk support material. Materials such as highly dispersed supported metal catalysts and gas phase clusters fall into the former category, and microporous (nanometer-pored) materials such as zeolites, high surface area inorganic oxides, porous carbons, and amorphous silicas fall into the latter category.

There are many areas of current academic and industrial activity where the use of the nanostructure approach to high surface area materials may have significant impact:

In catalysis the key goal is to promote reactions that have high selectivity with high yield. It is anticipated that this goal will be more closely approached through tailoring a catalyst particle via nanoparticle synthesis and assembly so that it performs only specific chemical conversions, performs these at high yield, and does so with greater energy efficiency. In the electronics area one may anticipate manufacture of single electron devices on a grand scale. Manufacture of materials with greatly improved properties in one or more areas such as strength, toughness, or ductility may become commonplace. In separations science new materials with well defined pore sizes and high surface areas are already being fabricated and tested in the laboratory for potential use in energy storage and separations technologies. In addition, many laboratories around the world are actively pursuing the potential to create novel thermal barrier materials, highly selective sensors, and novel construction materials whose bonding and strength depend upon the surface area and morphology of the nanoscale constituents. Many are also engaged in developing molecular replication technologies for rapid scaleup and manufacturing.

The nanoscale revolution in high surface area materials comes about for several reasons. First, since the late 1970s the scientific community has experienced enormous progress in the synthesis, characterization, and basic theoretical and experimental understanding of materials with nanoscale dimensions, i.e., small particles and clusters and their very high surface-to- volume ratios. Second, the properties of such materials have opened a third dimension to the periodic table, that is, the number of atoms, N (for a recent example see Rosen 1998). N now becomes a critical parameter by which the properties for "small" systems are defined. As a simple example, for metals we have known for decades that the atomic ionization potential (IP) is typically about twice the value of the bulk work function (Lide 1993). It is only relatively recently that experiments have shown that the IP (and electron affinity) for clusters containing a specific number N of (metal) atoms varies dramatically and non-monotonically with N for clusters containing less than 100-200 atoms. (For examples see Taylor et al. 1992; Rademann et al. 1987; and Rohlfing et al. 1984.) Other properties such as chemical reactivity, magnetic moment, polarizability, and geometric structure, where they have been investigated, are also found to exhibit a strong dependence on N. Expectations for new materials with properties different from the atom or the bulk material have been realized (e.g., see Jena 1996 and reports therein). The opportunity is now open to precisely tailor new materials through atom-by-atom control of the composition (controlling the types as well as the numbers of atoms) in order to generate the clusters or particles of precision design for use in their own right or as building blocks of larger-scale materials or devices-that is, nanotechnology and fabrication at its ultimate.

Such precision engineering or tailoring of materials is the goal of much of the effort driving nanoscale technology. Scientists and engineers typically have approached the synthesis and fabrication of high surface area nanostructures from one of two directions:

  1. The "bottom up" approach in which the nanostructures are built up from individual atoms or molecules. This is the basis of most "cluster science" as well as crystal materials synthesis, usually via chemical means. Both high surface area particles and micro- and mesoporous crystalline materials with high void volume (pore volume) are included in this "bottom up" approach.
  2. The "top down" approach in which nanostructures are generated from breaking up bulk materials. This is the basis for techniques such as mechanical milling, lithography, precision engineering, and similar techniques that are commonly used to fabricate nanoscale materials (see Chapter 6), which in turn can be used directly or as building blocks for macroscopic structures.

A fundamental driving force towards efforts to exploit the nanoscale or nanostructure is based upon two concepts or realizations: (1) that the macroscopic bulk behavior with which we are most familiar is significantly different from quantum behavior, and (2) that materials with some aspect of quantum behavior can now be synthesized and studied in the laboratory. Obviously, quantum behavior becomes increasingly important as the controlling parameter gets smaller and smaller. There are numerous examples of quantum behavior showing up in high surface materials: the fact introduced above that clusters are found to exhibit novel (compared to the bulk) electronic, magnetic, chemical, and structural properties; the fact that the diffusivity of molecules through molecular sieving materials cannot be predicted or modeled by hard sphere molecule properties or fixed wall apertures; and the fact that catalysts with one, two, or three spatial dimensions in the nanometer size range exhibit unique (compared to the bulk) catalytic or chemical activity.


Published: September 1999; WTEC Hyper-Librarian