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8

Researchers at the Los Alamos National Laboratory, USA have

developed a completely new class of organic nanoporous
polymers with narrow pore size distributions using cyclodextrins
as basic building blocks. DeQuan Li and Min Ma provide more
details of the polymers that are proving very eJicient in
absorbing organic molecules in water.

_Later is a critical many of them to a desirable degree such completely new class of nanoporous
resource that is as low parts-per-billion (ppb) levels. polymers. These nanoporous polymers
responsible for the Other materials, such as zeolites, have not only remove many organic
existence of life on interesting well-defined porosity but contaminants from water to parh-per-
* 4% earth and the show little affinity to organic compounds trillion levels (ppt), but they also offep
removal of organic contamfnants from in water and therefore have proven flexibility, cost-effectiveness, and ease of
water is an important municipal problem ineffective. Moreover, both activated use. These materials are based on
as well as a crucial industrial issue. The carbons and zcolites absorb moisture molecular building blocks known as
challenge is how to remove inert organic from air and lose their effectiveness cyclodextrins. Cyclodextrins have a well-
molecules, which typically have little unless they are regenerated by heating. defined cylindrical cavity -- in essence, a
affinity to most chemical compounds, Secondly, reverse osmosis requires high “cage” structure as shown in Figure 1. The
from water. pressure, typically 20- 100 bar, in order to nanometer-sized cavity has multiple
The Semiconductor Industry overcome the higher hydrodynamic hydroxyi groups on either end. Efficient
Association’s Technology Roadmap resistance produced by a denser cross-linkers convert the molecular
identifies the generation and recycling of membrane. In addition, it is difficult to nanocavity into three-dimensional,
ultrapure water as critical to the future of recover 100% of water, and a low nanoporous polymers. By tuning the
semiconductor manufacturing. concentration of small molecules typically degree of crossimking, the tailored
Conventional water purification processes leaks into the permeate side because the structure results are either hydrophilic or
involve either filtration through activated membrane is not perfectly hydrophobic (reject water but attract
carbons or reverse osmosis. First, semipermeable. organic molecules) polymers with
activated carbon has some affinity to Researchers at Los Aiamos National ‘Molecular hosts” that trap targeted
organic compounds, but it fails to remove Laboratory have recently developed a organic compounds.

26 December 1999 Filtration & Separation

 Formation constant K
(M“) I x104 3x 105 -0.0 -0.0
Equilibrium concentration 4 pptr* 1 ppm** 53 ppb*** N/A N/A
Loading Level
(mg/cm3) 40 29 26 -0.0 -0.0
Leaching organics No Yes Yes Yes Yes
Thin-film formation Yes No NO No No

*pptr-ports per trillion by moles or number.

**ppm-parts per million by moles or number.
***ppb-parts per billion by moles or number.

The environment of the cyclodextrin inclusion that results from the optimized nanoporous polymers have much higher
cage is lipophilic and provides a perfect non-covalent mutual attractions between affinity to organ& and will absorb
fit for most small organic molecules to the host cavity and the guest molecules. organic molecules in the concentration
optimize their van der Waals interactions These attractions are exceptionally ranges well below that of activated
with the inner wall of the cyclodextrin favorable non-covalent bindings that are carbon. The researchers expect that these
cage. Whereas, water tends to form extremely effective in removing organics nanoporous polymers will absorb
hydrogen bonds and is hydrophilic and even at very low concentrations. organics to low ppt concentrations,
therefore provides a hostile environment The quantitative performances of these making them suitable for ultrapure water
for organic molecules. When the solid nanoporous polymers are listed in Table 1 applications.
powders of nanoporous polymeric along with the tested results on activated The interactions between the polymer
materials are introduced into carbons and molecular sieves, There are cavities and the organic contaminates
contaminated water7 guest organic several features that distinguish these strongly depend on the medium, that is
molecules are taken in by the “friendly” polymers from activated carbons or the solvent they are in. A hydrophilic
host, resulting in two separate phases molecular sieves. First, the nanoporous medium (for example, water solution)
with completely different properties: an polymer has a low surface area (l-2 will drive the organic guest molecules
organic solid phase and an aqueous phase. l&/g) when compared to that of into the hydrophobic cavities, while an
The organic guest molecules are inside activated carbon (-600 m2/g), but it has organic solvent such as ethanol tends to
the solid lipophillic polymers and the a loading capacity for organic molecules release those organic molecules that were
aqueous phase is organic free. The similar to that of activated carbons. This trapped in the nanopores. Based on this
inclusion of coloured organic compounds implies that organic molecules are not phenomenon known as regeneration, Los
can be identified with the naked eye just adsorbed on the surface of Alamos National Laboratory (LANL) has
because the polymers are transparent cyclodextrin polymers but are designed and synthesized nanoporous
glass-like solids and serve as a transported into the bulk of the polymeric materials that remove trace
concentrator for these organic samples nanoporous polymers. The absorption amounts of organic contamination from
For example, the absorption of rather than adsorption of organic water and regenerate these polymers
nitrophenol yields a yellow solid and the molecules is due to the effect of inclusion under ethanol rinsing or washing. Once
inclusion of p-nitrothiolphenol results in between cyclodextrins and organic regenerated, the polymer is ready for use
an orange solid. This process is molecules. The inclusion phenomenon is again and again. LANL has also designed
thermodynamically “down hill” because also verified with circular dichroism (vide and synthesized a suite of nanoporous
both the cyclodextrin and water gain inja). Secondly, the formation constants polymers for a large variety of organic
more stability through lowering their between organic molecules and contaminants, including trichloroethylenc
interaction energies. In other words, an nanoporous polymers are a few orders of (“ICE), toluene, acetone, chloroacetic
inclusion phenomenon takes place when magnitude larger than those formation acid, p-hydroxy-benzosulfonate, and
strong mutual attractions between host constants between organic molecules and phenol derivatives.
and guest occur. The organic molecules activated carbon. Although these are The advantage that nanoporous
are absorbed by means of physical equilfbrium constants, they suggest that polymers have over inorganic materials is

Filtration & Separation December 1999 27

 p-CD-HDI p-Nitrophenol 5x 109 40 (86%) -13.2
P-CD-HDI Phenol 1 x 10s 30 (82%) -10.9
P-CD-OMe-HDI Trichloroethylene 2 x 10s 2 35 (79%) -11.4
j? Cn ED! ~_h~~r~-)rh~n.,~~~~~~~~~~t~ 5Y 1n* 34 /so%! -11.9

P-CD-~M~-HDI Toluene 1 x10x 2 17 (56%) -10.9

P-CD-HDI Chloroacetic Acid 6x 10’ 25 (80%) -12.0

* Eyuilibriurnforlnatlon constant K is measured by indirect determination ofthe solution analyte concentration at equilibrium.
** Data in parenthesis correspond to the percentage of organics to cyclodextrin units in the polymer.

that they offer flexibility in processing from surface adsorbates such as inclusion complexes. As a result, organic
and can be fabricated into granular solids, activated carbons and explains why molecules are extracted out from aqueous
powders, optical-quality thin films, and nanoporous polymers do not leach solutions by nanoporous polymers and
possibly membranes. Such flexibility organic contaminates once they are water is purified. The hypothesis for
enables these materials to be used for absorbed. removing organic molecules from water is
multiple applications and formats, As shown inTable 2, the nanoporous that a large number of close van der Waals
thereby accommodating different water- polymers have high affinity to several contacts between organics and the
treatment configurations and needs. classes of organic compounds. The cyclodextrin are established at the expense
The mechanism of removal of organic measured equilibrium formation of losing a degree of freedom. In other
molecules from water by nanoporous constants between cyclodextrin polymers words, the entropy changes for the
polymers is completely different from and organic molecules are in the range of inclusion processes are negative, AS < 0.
that of activated carbon. Nanoporous K = 1 07- 1 09. The results in Table 2 As shown inTable 2, the Gibbs free
polymers absorb organics into demonstrate that the absorption of energies (AG) for inclusion processes have
cyclodextrin cavities; whereas activated organics by nanoporous polymers in been measured and are typically in the
carbons rely on their high surface area to water is more general, thus rendering range of - 10 to 13 kcal/mol. This leads us
attract organic molecules. The fact that these polymers suitable for removal of to conclude that the inclusion processes by
organic molecules and cyclodextrin form many organics in water, especially at low the nanoporous polymers are driven
inclusion complexes is proven by circular organic concentrations. It is expected that mostly by enthalpy (AH) - exothcrmic
dichroism. A compound or inclusion strong attractions between host and guest reaction. Most separation processes such as
complex must possess both chirality and molecules depend on optimized chemical membrane filtration require energy to
electron-optical absorption in order to or physical interactions such as mutual drive the process to completion, but the
have a circular dichroic absorption. Chiral matching of polarity, size, hydrophobic separation of organics from water by
cyclodextrins have no absorption in the environment, and structural properties. A nanoporous polymers is an exceptionally
ultraviolet and visible region while most half dozen organic molecules from rare spontaneous process.
~_-.-“-~--I_~_
organic molecules (such as p-nitrophenol) different classes were selected for their
absorb light but are not chiral. An induced structures and properties to test the The developers at Los Alamos welcome
circular dichroism will be observed unIy effcctivcness of the nanoporous polymers. industrial partnership to furtbcr
when the cyclodextrin and the organic Their properties are tutned (1) from develop this technology. The current
molecule form a new inclusion complex strong polar molecules such as nanoporolls polymt~rs arc available but
that possesses both chirality and optical nitrophenol to moderate polar molecules they have a low surface area. The
absorption. P-cyclodextrin polymeric such as toluene and phenol; (2) from developers believe that a high surface-
fihns immersed in p-nitrophenol aqueous chlorinated compounds such as area nanoporous polymer would be
solution, produced a positive induced trichloroethylene to aromatic compounds more effective and should be developed
circular dichroic signal with fine such as toluene; (3) from aliphatic acids for more superior performance. Los
structures at 405 mn. The positive such as chloroacetic acid to aromatic Alamos is interested in developing high
circular dichroic absorption indicates that acids such as p-hydroxybenzosulfonate. surface-area nanoporous polymers
polar nitrophenols are inside and parallel These experimental data show that collaboratively with industry for a wide
to the cyclodextrin’s cylindrical cavities, nanoporous polymers will probably range of water purification applications.
while negative circular dichroic perform well at absorbing most small
absorptions suggest that the nitrophenols organic molecules in water. Chemical Science and Technology (UT-4;
are perpendicular to the cyclodextrin’s The absorption process at water soiid- 6755) , LosAlumos h’ationai Laboratory, I! 0
cylindrical cavities. This feature water interfaces effectively separates the Box 1663, Los Alamos, NM 87545, USA. Gi
distinguishes nanoporous polymers organic component from water by forming -tl 505 665 115X$x: +I 505 667 X021