H2O and Cation Structure and Dynamics in Expandable Clays: 2H and 39K NMR

Investigations of Hectorite

Geoffrey M. Bowers,*,†,§ David L. Bish,‡ and R. James Kirkpatrick†, ⊥

Department of Geology, UniVersity of Illinois Urbana-Champaign, Urbana, Illinois 61801, and Department of
Geological Sciences, Indiana UniVersity, Bloomington, Indiana 47405
ReceiVed: December 19, 2007; In Final Form: February 13, 2008

Variable temperature 39K and 2H nuclear magnetic resonance (VT NMR) spectroscopy of K+-saturated hectorite,
a prototypical smectite clay, provides new insight into the relationships between the structural and dynamical
behavior of K+ and H2O in confinement and at surfaces. In d ) 10 Å K-exchanged hectorite, interlayer K+
is rigidly held by the silicate rings, probably in 12-coordinate inner-sphere sites as in muscovite mica. In a
1/1.5 by weight hectorite/water paste, K+ occurs on interlayer and external surface sites that are indistinguishable
by 39K NMR. The K+ environments experience changes in dynamical behavior over the temperature range
from -50 to 60 °C that are directly related to H2O dynamics. 39K NMR of the paste sample shows dynamic
line narrowing at low temperatures due to modulation of the electric field gradient (EFG) at frequencies of
the order of the static line width (≈20 kHz) and two “melting”-type dynamic transitions near -10 °C, one
for surface and one for confined K+. At and above 0 °C, K+ remains closely associated with the clay surfaces
and experiences motion at frequencies greater than 200 kHz and less than 10 MHz, as revealed by 39K T1
relaxation behavior, nutation behavior, and the 39K quadrupolar product. These data are consistent with rapid
exchange between inner- and outer-sphere K+ sites reported previously for K-montmorillonite based on
molecular dynamics simulations. Deuterium NMR shows the presence of two unique H2O environments in
the system: one structurally and dynamically consistent with bulk water between particles and one attributable
to H2O confined in the interlayer. Confined H2O experiences anisotropic motion between -50 and 0 °C via
fast rotation (>2 MHz) about a single axis oriented 127.5 ( 0.5° from the principal axis of the 2H EFG,
potentially due to C2 rotation. This motion does not affect the 39K EFG significantly. Melting of free and
confined H2O occurs between -10 and 0 °C and near 0 °C, respectively, similar to the melting behavior of
K+ and likely reflecting the onset of molecular diffusion. At and above 10 °C, all H2O environments experience
motion near or in excess of 300 kHz through at least three NMR-indistinguishable mechanisms, including
Brownian motion of free water, exchange of free and confined H2O near particle edges, and diffusive motion
of H2O that remains confined on the experimental time scale. The correlation between the rates of 2H and 39K
motion and the observed melting transitions for both spin populations strongly suggest that 39K melting and
dynamics above the melting transition are linked to an increase in the motional freedom of H2O.

Introduction space of phyllosilicates. Differences between the structural and

The dynamic behavior of H2O and ionic species in two- and
three-dimensional confinement plays a variety of important roles
in processes such as ion transport and adsorption,1-5 water
storage in hostile environments,6,7 dissolution/precipitation
reactions in aqueous environments,8,9 and the swelling of
smectite clays (low charge 2:1 type phyllosilicates with expand-
able interlayers).3,10,11 Historically, the structure and dynamics
of ions and water in confined spaces and at solid-fluid
interfaces have been difficult to characterize on the molecular
scale, but the continued evolution of molecular modeling,
neutron scattering, and nuclear magnetic resonance (NMR)
spectroscopy has permitted ever more detailed theoretical and
experimental investigations, particularly regarding the special
case of H2O in the two-dimensional, nanometer-scale interlayer
* Corresponding author. E-mail: bowersg@msu.edu.
† University of Illinois Urbana-Champaign.
‡ Indiana University.
§ Current address: Department of Chemistry, Michigan State University,
East Lansing, MI 48824.
⊥ Current address: College of Natural Science, Michigan State University,
East Lansing, MI 48824.
dynamical properties of bulk water and H2O confined in low-
charge 2:1 phyllosilicate interlayers were recognized as early
as 1971 based on quasi-elastic neutron scattering studies of a
Li+-vermiculite.12 Recent neutron,13-17 NMR,18-27 and mo-
lecular modeling19,28-42 studies show that H2O within one to
two statistical monolayers from a phyllosilicate surface (in the
interlayer or at the particle exterior) exhibits structural, diffu-
sional, rotational, and vibrational properties that differ from bulk
water. Unfortunately, much less is known regarding the structure
and dynamics of charge-balancing ions in these systems and
how the dynamics of confined H2O and ions are related. These
are essential components for a complete understanding of ion
sequestration and transport in porous materials.
We present here a 2H and 39K NMR study of the structure
and dynamics of H2O and K+ in the prototypical smectite clay
mineral, hectorite, that has been saturated with K+. The focus
of this work is to determine how H2O dynamics in the kilohertz
to megahertz range (“intermediate” regime) affects the behavior
of interlayer and surface K+ via line-shape analysis of 2H and
39K variable temperature (VT) NMR spectra and NMR relax-

10.1021/jp7119087 CCC: $40.75 © xxxx American Chemical Society

Published on Web 03/28/2008 PAGE EST: 8.8
B J. Phys. Chem. C
ation rates. NMR spectroscopy is an attractive approach for
molecular-level structural and dynamical studies of confined
and surface-associated water and ions because it is the only
experimental method capable of identifying, characterizing, and
quantifying structural environments while simultaneously prob-
ing molecular-scale dynamic behavior over a wide frequency
range (hertz to megahertz). However, 39K NMR of inorganic
solids can be challenging because of its low gyromagnetic ratio
(γ/2π ) 1.994259 MHz/T) and moderate nuclear electric
quadrupole moment43 (I ) 3/2, Q ) 0.06 × 10-24 cm2;
comparable to 23Na). Despite these limitations, 39K is 93%
naturally abundant and can be readily observed with modern
spectrometers. Including this work, there have been three
published 39K NMR studies of K+ binding in clays or micas to
date.44-46 Prior studies have focused principally on probing the
structural properties of bound K+ under anhydrous conditions
and as a function of hydration and hydration cycling. This
publication represents the first instance where 39K VT NMR is
used to examine the dynamic properties of K+-exchanged clay
minerals and also the first use of 39K and 2H VT NMR to
correlate the dynamics of K+ and H2O in confinement and at
surfaces, providing important new insights into the behavior of
K+ and H2O in these environments.
Materials and Methods
Materials. The hectorite used in this study was obtained from
the Clay Minerals Society Source Clays Repository currently
housed at Purdue University (sample SHCa-1). Hectorite is ideal
for NMR investigations of smectite clays because the San
Bernardino county sample used here contains a low concentra-
tion of paramagnetic impurities (0.28 wt % Fe and Mn).47,48 A
sample of hectorite was saturated with K+ by exposure to 1 or
0.01 M aqueous KNO3 in three separate ion-exchange reactions.
After the final exchange period, the clay was dried at 110 °C
for 25 h. The aggregated hectorite was gently ground in an agate
pestle and mortar and sieved to a particle size of <177 µm.
The mineralogical composition and structure of K-hectorite
powder and a 1/1.5 by weight hectorite/H2O paste were
characterized at Indiana University using a Bruker D8 Advance
X-ray diffractometer equipped with an environmental chamber.
Additional details regarding sample preparation and the XRD
experiments can be found in the Supporting Information.
39K NMR Experiments. Static 39K echo, nutation echo, and
T1 inversion-recovery echo experiments were performed at
room temperature for atmosphere-equilibrated powder and at
temperatures from -50 to 60 °C for a 1/1.5 by weight
K-hectorite/H2O paste using a Varian 4 mm HXY MAS probe
equipped with a low-γ accessory on a Varian Infinity Plus 14.1
T standard-bore spectrometer. It was necessary to incorporate
an inversion pulse and echo acquisition in each type of
experiment to minimize the effects of acoustic ringing while
maximizing the signal intensity. For the paste, sample temper-
ature was controlled to (1 °C using an FTS TC-84 temperature
controller paired with an AirJet XR1185 chiller unit and Varian
L950 variable temperature stack. The actual sample temperature
was calibrated against the VT thermocouple using the 207Pb
chemical shift of Pb(NO3)2 according to the procedure of
Bielckei and Burum.49 Room temperature static echo experi-
ments were also performed on the paste using the 17.6 T Varian
Unity Plus instrument located at the Pacific Northwest National
Laboratory to provide an estimate of the 39K quadrupolar
parameters and isotropic chemical shift. All 39K spectra were
referenced to the resonance obtained from a 1 M aqueous
solution of KCl.
Bowers et al.
MAS rotor-synchronized 39K echo experiments were per-
formed on room temperature powder and at temperatures of
-38, -22, -7, and 23 °C (all (1 °C) for a 1/1.5 by weight
K-hectorite/H2O paste packed in 4 mm zirconia rotors using
the same 14.1 T spectrometer/probe arrangement as the static
experiments. The sample temperature was recalibrated against
the VT thermocouple under 10 kHz MAS conditions (identical
to those used in the 39K MAS NMR experiments) using Pb-
(NO3)2, as the change in air flow and friction associated with
MAS will change the sample/set point relationship from that
observed in the static case. Room temperature MAS NMR
experiments were also performed on the atmosphere-equilibrated
powder and a paste prepared from deionized-H2O washed
K-hectorite using a Varian 5 mm double-resonance T3 MAS
probe equipped with a low-γ accessory and the 9.4 T Varian
Infinity Plus spectrometer at Michigan State University. Ad-
ditional details for the 39K static and MAS NMR experiments
can be found in the Supporting Information.
2H NMR Experiments. A 1/1.5 by weight solid/liquid paste
was prepared in a 4 mm NMR tube using D2O rather than H2O.
The deuterated paste sample was immediately sealed with water-
tight epoxy to minimize H2O-for-D2O exchange during the
NMR experiments. Static 2H solid echo VT NMR experiments
were performed on the deuterated paste using a Chemagnetics
4 mm double-resonance T3 magic angle spinning probe mated
with the 14.1 T Varian Infinity Plus wide-bore spectrometer at
the University of Illinois. Experiments were performed at
temperatures of -50, -30, -10, 0, 10, 25, and 40 °C to correlate
deuteron/water motion with the observed K+ behavior. At 10,
25, and 40 °C, a strong isotropic signal overwhelmed the
dynamic range of the instrument, which was corrected by left
shifting and then back-predicting the first 70 data points. All
spectra are referenced with respect to the 2H resonance in pure
D2O liquid at room temperature. Additional experimental details
are reported in the Supporting Information.
The broad deuterium resonance at -50 °C was initially fit
with a rigid powder pattern calculated using the SIMPSON
solid-state NMR simulation package.50 The effects of motion
on the spectra were calculated in Mathematica using functions
originally written by Benesi et al.51 that were modified for
alternative models of motion and to include the effects of T2
relaxation and the quadrupolar asymmetry parameter. The code
calculates spectra based on the derivation and formalism of Vega
and Luz.52 At and above 10 °C, both narrow 2H NMR
resonances were well fit with simple Lorentzian line shapes
using the NUTS NMR processing software by Acorn NMR Inc.
Results and Discussion
XRD Results. The XRD patterns from the powder sample
equilibrated at 53% relative humidity (Figure 1) reveal the
presence of broad diffraction peaks indicative of predominantly
10 Å hectorite and the natural disorder expected in smectite
clays. A basal spacing of 10 Å corresponds to that observed
for muscovite mica, a high-charge 2:1 phyllosilicate that bears
an interlayer containing only K+ and no H2O molecules,
suggesting that a similar “collapsed” interlayer gallery and K+
binding environment exists in the K-exchanged hectorite
powder. The presence of diffraction bands near 19.6 and 34.6°
2θ reflects stacking disorder of the clay layers (due to the low
layer charge) and disorder related to the expandability of
smectites in the c crystallographic dimension. There are indica-
tions of some low-angle scattering associated with partially
expanded layers in the powder, but these represent a negligible
fraction of the overall sample contents, and there is no XRD
2H and 39K NMR Investigations of Hectorite
Figure 1. XRD patterns of a 1/1.5 by weight K-hectorite/water paste
at 98% relative humidity (a) and the K-hectorite powder at 52% relative
humidity (b). The broad, low-intensity basal reflection for the paste
indicates a distribution of randomly interstratified d-spacings, with a
median that corresponds to the 12.5 Å (so-called one-layer hydrate) of
K-hectorite illustrated schematically in (c). Parts (d) and (e) show the
schematic representations of the Mg/Li octahedra and Si tetrahedra
(respectively) that make up the T-O-T layers of hectorite. The blue
spheres represent the possible K+ locations in the hectorite interlayer
based on the MD results of Chang, Skipper, and Sposito37 for the related
smectite clay, montmorillonite.
evidence of mineral species other than hectorite. We denote this
sample as 10 Å hectorite in the remainder of this paper.
The controlled-humidity XRD patterns of the 1/1.5 hectorite/
water paste contain a broad basal diffraction representing a range
of spacings between 10 and 15 Å, with the predominant spacing
occurring at roughly 12.5 Å (Figure 1). The broad basal
diffraction peak likely reflects a heterogeneous H2O content in
the interlayers resulting from the heterogeneous distribution of
charge in smectites53-55 combined with a random interstratifi-
cation of interlayer spacings.56-58 It is unlikely that swelling in
the osmotic regime55,59 (where the basal spacing increases
linearly with increasing H2O uptake) contributes to peak
broadening in the paste because K+ has been shown to inhibit
swelling of other smectites.60,61
39K NMR of 10 Å Hectorite. The room temperature 39K
NMR spectra of atmosphere-equilibrated 10 Å K-hectorite under
static and MAS conditions (Figure 2) are very similar to the
39K NMR spectra of other phyllosilicate minerals44,45 and also
reflect the type of disorder typically observed in clays. The
similarity between the hectorite and mica d-spacings and their
39K NMR spectra confirms that K+ in the hectorite interlayers
is rigidly held, probably in an anhydrous 12-fold inner-sphere
coordination analogous to K+ in muscovite. The 39K NMR
resonances for 10 Å K-hectorite at 14.1 T are nearly featureless,
about 541 ( 6 and 66 ( 9 ppm broad at half-height (in the
static and MAS cases, respectively), and slightly skewed to low
frequencies, suggesting some quadrupolar contribution to the
J. Phys. Chem. C C
Figure 2. 39K NMR spectrum of 10 Å hectorite equilibrated with the
ambient atmosphere near 50% relative humidity under static (a) and
MAS (b) conditions at 14.1 T. Note the tailing to low frequency due
to second-order quadrupolar effects and peak shapes that are very similar
to those obtained by Stebbins et al.44 for natural muscovite.
line shape. Calculations based on peak positions from multiple
field MAS NMR data62 yield a 39K quadrupolar product (PQ )
CQ(1 + η2/3)1/2) of 0.91 ( 0.04 MHz and an isotropic chemical
shift of -37 ( 4 ppm (-1 ( 0.1 kHz). The lack of well-defined
spectral features and skewing to low frequencies is consistent
with a distribution of 39K quadrupolar couplings that is
characteristic of disordered solids such as glasses and clays.44,63
In this case, the distribution in quadrupolar couplings is probably
due to the combined effects of disorder in the octahedral Li/
Mg and F/OH distributions, the associated distribution of Li-
K/Mg-K internuclear distances, and variation in the number
of next-nearest-neighbor K+ in adjacent hexagonal rings (all of
which are related to the heterogeneous distribution of charge
in smectites) as well as a distribution of T-O-T bond angles
in the six-member silicate rings.64,65 The similarity between the
39K NMR spectra of rigid K+ in muscovite and the K+ in 10 Å
hectorite, combined with the absence of a sharp spectral feature,
is consistent with a lack of K+ motion in the atmosphere-
equilibrated clay. Given the apparent K+ rigidity and the long
acquisition period required to obtain a suitable signal-to-noise
ratio for the powder, variable temperature 39K NMR experiments
were not justifiable for this sample.
There is no evidence for two resolvable 39K resonances,
indicating that the K+ environment at the external surface is
not sufficiently different from that in the interlayer to create a
resolvable signal under these experimental conditions or that
the relative population of surface K+ is inadequate to produce
a detectable resonance. The 39K lower limit of detection for a
narrow, solution-like K+ resonance, which was determined using
known volumes of KCl solution under identical experimental
conditions and using central-transition selective pulse widths
(the equivalent of a π/4-π/2 sequence for aqueous K+), is of
the order of 6 × 1016 39K nuclei. Assuming the baseline N2
BET surface area of 35.6 m2/g from the source clay data66
applies to the K-exchanged hectorite, that all the measured
surface area is on the particle exteriors, and a 6% surface
coverage of K+ to satisfy the layer charge, there are a maximum
of (4.9 ( 0.1) × 1018 surface 39K spins in the NMR sample.
This is ∼18% of the total 39K spins in the sample volume
D J. Phys. Chem. C
Figure 3. Static 39K VT NMR spectra of the 1/1.5 wt K-hectorite/
water paste obtained from -50 to 40 °C compared with the static
spectrum of 10 Å K-hectorite at room temperature. Note the central
region of the -10 °C spectrum, which may reflect narrowing of the
small surface 39K population, and the abrupt line narrowing associated
with “interlayer melting” between -10 and 0 °C.
(determined from the stoichiometry and sample weight) and
should be readily detectable if the resonance is comparable in
width to the neat solution peak.
39K Structure and Dynamics in a 1/1.5 K-Hectorite/Water
Paste. The static 39K VT NMR spectra for the paste show
evidence of dynamic averaging via 39K electric field gradient
(EFG) modulations at a rate close to 20 kHz over the
temperature range from -50 to -10 °C, an increase in the
motional degrees of freedom analogous to a melting-type phase
transition between -10 and 0 °C, and EFG modulation at rates
g200 kHz between 0 and 50 °C. These conclusions are
consistent with an expanded interlayer containing H2O and K+
where H2O mobility plays a role in the 39K dynamic averaging.
The static 39K VT NMR spectra of the paste at -50 and -30 °C
resemble the room temperature spectrum of 10 Å hectorite,
indicating that a nonzero time-averaged quadrupolar interaction
is present and suggesting a lack of motion. However, the
normalized signal-to-noise ratio at -30 °C is 28 ( 3% higher,
opposite the behavior predicted by the Curie law and suggesting
the presence of slow EFG modulation that fails to fully average
the 39K quadrupolar interactions (Figure 3). Using the rigid 39K
line width of 20 kHz obtained from the 10 Å powder results,
the 39K EFG in the paste must be modulated by a dynamic
process occurring at a rate close to 20 kHz in this temperature
range because partial narrowing of quadrupolar nuclei begins
when the EFG is modulated by motion at frequencies of the
order of the static line width.67-69 The low signal-to-noise ratio
precludes us from determining the specific mechanisms of
Bowers et al.
Figure 4. MAS 39K VT NMR obtained from -38 to 23 °C at 14.1 T
for a 1/1.5 K-hectorite/H2O paste compared with the MAS spectrum
of 10 Å K-hectorite at room temperature. Note the narrow frequency
scale compared to Figure 3 and lack of observable signal at -38 °C.
motion responsible for this narrowing. There is no clear evidence
of a second resolvable resonance at -50 and -30 °C, but the
relatively narrow feature near the reference frequency in the
-10 °C spectrum may represent a small 39K population for
which there is significant dynamical narrowing. This may be
K+ on the external particle surfaces. At 0 °C and above, the
static spectra contain only a single, much narrower resonance
with essentially no low-field tail, consistent with 39K EFG
modulations at a rate at least an order of magnitude larger than
the static central transition line width of 39K in the clay, i.e.,
g200 kHz.67 This peak narrowing does not occur for the 10 Å
K-hectorite and must be related to the presence of water in the
interlayers and on particle surfaces, consistent with a K+/H2O
dynamic dependence. A dynamic dependence of anion/cation
behavior has been reported previously in sodium orthophos-
phate,70 but to our knowledge, this is the first spectroscopic
observation of K+/H2O dynamic coupling in phyllosilicate
minerals. Because some H2O is present on the external surfaces
of atmosphere-equilibrated 10 Å K-hectorite, the paste VT
results provide important evidence of separate melting-type
dynamic transitions for the surface and interlayer 39K species.
There is no evidence of resolvable resonances for surface and
interlayer K+ at 0 °C and above.
Although the static 39K spectra appear to be single, narrow
resonances above the melting transition, the VT MAS NMR
results reveal the presence of two distinct K+ environments at
and above -7 °C. One of these is due to solution-like K+ and
the other to less mobile K+ (Figure 4). The narrow, solution-
like resonance is centered at -6 ( 20 Hz (-0.1 ( 0.6 ppm)
and has a full width at half-height (fwhh) of 34 ( 26 Hz at
both 23 and -7 °C. The line shape and chemical shift are nearly
identical to those of 1 M KCl(aq) (Figure S1), indicating that a
small fraction of the 39K spin population is in a liquid-like state
with isotropic mobility under these conditions. This resonance
contains 11.1 ( 0.1% of the integrated intensity, equivalent to
6.3 ( 0.1% of the 39K spins, assuming a 100% refocusing
efficiency and taking into account that (i) the satellite and central
transitions contribute intensity to the liquid-like peak in a
theoretical ratio of 6:4 for I ) 3/271 and (ii) the initial flip angle
2H and 39K NMR Investigations of Hectorite
TABLE 1: 39K T1 Relaxation Times (in ms) for the Paste
and Neat Solution as a Function of Temperature Based on
the Static NMR Results
0 °C 25 °C 50 °C
K-hectorite paste 1.8 ( 0.2 2.6 ( 0.4 2.4 ( 0.1
1 M KCl(aq) 53.5 ( 4.5
is effectively π/4 for liquid-like 39K. The most likely source of
this 39K population is K+ released by dissolution of KNO3 that
crystallized on the mineral surface from residual ion exchange
solution during the post-exchange drying cycle. A room
temperature MAS NMR spectrum of a K-hectorite paste in
which the clay was prerinsed to remove residual salt crystals
does not contain this liquid-like peak, confirming that the liquid-
like signal arises from non-charge-balancing K+ (Figure S1).
Highly mobile K+ in the unrinsed hectorite paste is probably
solvated by H2O between crystallites that has liquid-like
properties, as observed in published water adsorption isotherms,
XRD, and NMR data for other smectites.19,56,72,73 A sharp,
narrow resonance is not observed at -22 °C, consistent with a
“freezing” out of 39K dynamical averaging for the liquid-like
K+ population and suggesting that averaging of this fraction at
higher temperatures is related to the melting of interparticle
fluid.
The broader and more intense 39K MAS peak arises from
dynamically averaged K+ in the interlayer and on particle
exteriors that 39K T1, PQ, and nutation data reveal to be strongly
associated with the mineral surfaces. This resonance is 210 (
20 Hz wide at half-height and is centered at -443 ( 17 Hz
(-15.8 ( 0.5 ppm) at 14.1 T and 23 °C. This peak becomes
broader and shifts to lower frequency with decreasing temper-
ature until the resonance can no longer be detected at -38 °C.
This behavior is consistent with a mobile 39K population that
is strongly associated with a mineral surface, where the decrease
in mobility with decreasing temperature leads to increased
surface interactions and thus increased residual quadrupolar
coupling.74-76 The observation of MAS NMR signal at -22 °C
and no signal at -38 °C supports the presence of a slower
dynamic process below melting suggested by the static 39K
results, where the rate of motion enables detection in the first
case and obscures detection in the latter case. (We note that the
signal-to-noise ratio is also poor in the -50 °C static spectrum
and that signal detection in the static case is enabled by the
larger 39K spin population in the coil and improved filling factor
of the cut 4 mm NMR tube vs the water-tight MAS rotor.) A
strong association with the mineral surface is also supported
by the 39K T1 relaxation times above the melting transition
(Table 1). These relaxation times are more than an order of
magnitude less than that of bulk solution, reflecting an increase
in the relaxation rate in the paste. An increase in the T1 relaxation
rate relative to bulk solution is well-known to reflect a surface
association of mobile ionic species63,77,78 because surface
interactions of a mobile ion generally lead to an increase in the
intensity of the power spectrum at the Larmor frequency, thus
increasing the T1 relaxation rate relative to the bulk solution.79
It is somewhat surprising that the 39K population giving rise to
the narrow, solution-like peak does not produce biexponential
relaxation behavior or a bi-Lorentzian line shape in the static
NMR results; however, it is likely that the total overlap of the
two resonances combined with the narrow line width and low
population of liquid-like K+ make it indistinguishable under
these conditions. The time-averaged 39K quadrupolar product
of the broad MAS resonance is 0.45 ( 0.03 MHz, which is
between the value for rigid K+ in the 10 Å hectorite (0.91 (
0.04 MHz) and the near-zero coupling expected for solution-
J. Phys. Chem. C E
like K+. This observation also supports strong K+/surface
interactions and some level of K+ mobility. The nutation
dynamics (Figure S2) show that a majority of the 39K spins
experience a room temperature 39K nutation maximum at 5.5-6
µs, much closer to the 5 µs maximum predicted for the central
transition of rigid 39K than the 10 µs maximum observed for
the solution-like K+ fraction. The solid-like nutation behavior
of 39K above the melting transition must be a consequence of
residual 39K quadrupolar coupling due to nonzero time-averaged
electric field gradients at 39K, in agreement with the relatively
broad peaks described above and the PQ data. Furthermore, the
observation of a central-transition-like nutation maximum
establishes an upper bound on the rate of 39K EFG modulation
at room temperature because modulation at rates at or in excess
of 10 MHz would be expected to fully narrow the satellite
contributions and lead to liquid-like nutation behavior for all
39K spins.
Taken together, our 39K NMR results at room temperature
are largely consistent with a two-site exchange model for
interlayer and surface K+ above the melting transition originally
reported for interlayer K+ in Wyoming-type montmorillonite
(which bears some tetrahedral charge) from the molecular
dynamics (MD) simulations of Chang et al.37 Their results show
that at a basal spacing of 12.5 Å comparable to a majority of
the hectorite particles in our paste sample, K+ hops between
partially hydrated inner-sphere sites coordinated by basal
oxygens and located near tetrahedral charge sites and outer-
sphere sites coordinated by eight H2O molecules and centered
at the mid-plane of the interlayer. The hopping rate is >5000
MHz at 300 K, substantially larger than the range of room
temperature rates revealed by our 39K NMR results. The
discrepancy in jump rate is likely related to the reduced
tetrahedral charge in San Bernardino hectorite, although dynamic
behavior in MD calculations are model-dependent,80,81 and the
behavior of simulated montmorillonite at 300 K may not
quantitatively reflect the behavior of San Bernardino hectorite
at the same temperature. However, the suggested hopping
between inner- and outer-sphere sites in the interlayer or on
the external surface would generate the nonzero time-averaged
quadrupolar interaction suggested by our nutation, T1, and PQ
data because the motion involves at least one asymmetric
binding site.
If two-site exchange is responsible for the observed 39K EFG
modulation, NMR experiments at temperatures low enough to
freeze out motion at frequencies greater than or equal to the
approximate static peak width could result in multiple observable
resonances, analogous to the results of Weiss et al. for
Cs-exchanged smectites.75,76 The presence of only a single broad
resonance at -50 and -30 °C indicates that if multiple sites
are present, their NMR resonances are not resolvable under our
experimental conditions. This may be because the two peaks
overlap sufficiently to be indistinguishable. As noted earlier,
however, the increase in sensitivity associated with the tem-
perature increase from -50 to -30 °C is opposite the behavior
predicted by the Curie magnetization law and suggests that
dynamic line narrowing occurs via motion at a rate close to the
static peak width. Thus, we cannot rule out the possibility of
multiple K+ sites on the basis of NMR results from -50 °C
and must obtain lower temperature NMR experiments to truly
test this possibility. Unfortunately, signal-to-noise and equipment
limitations prevented such experiments under static or MAS
conditions at this time. MD simulations of K-hectorite are
planned within our group to verify the two-site exchange model
F J. Phys. Chem. C
Figure 5. 2H VT NMR spectra from 14.1 T of the 1/1.5 wt K-hectorite/
2 deuteron bond.18,84 This has been used by other authors to justify
H2O paste. The thin lines represent dynamic simulations incorporating
both tetrahedral jump motion for the free H2O and fast rotation for
confined H2O at an angle between the principal axis of the 2H electric
field gradient and the rotation axis of θ ) 127.5 ( 0.5°.
TABLE 2: 2H Jump Rates (in kHz) for the Bulk Water
Phase in the Hectorite Paste Compared with Those of
Wittebort et al.82
temp (°C) K-hectorite paste water-ice 1h82
-50 1.5 <1.2
-30 6.0 12
-10 54 52
0 isotropic
or propose other potential motional mechanisms for K+ and will
be published as part of a separate work.
H2O Structure and Dynamics in the 1/1.5 K-Hectorite/
Water Paste. The 2H NMR data for the 1/1.5 wt K-hectorite/
D2O paste (Figure 5) are fully consistent with the structural and
dynamical picture shown by the 39K data and show a direct
connection between the H2O and K+ dynamical behavior. At
-30 and -50 °C, the 2H data show the presence of two H2O
environments. The broader resonance is roughly 310 kHz in
basal width at -50 °C, and the “rigid-limit” best-fit quadrupolar
parameters (CQ ) 213 kHz, η ) 0.09) are similar to those
reported by Wittebort et al. for ice-1h at -53 °C.82 The
temperature-dependent changes in the resonance shape and
intensity are well modeled using tetrahedral jump motion, which
is known to occur via Bjerrum defects in ice-1h between -50
and 0 °C,51,83 with jump rates very close to those reported by
Wittebort et al. at similar temperatures (Table 2).82 These ice-
1h dynamics also accurately reproduce the intensity decrease
with increasing echo delay due to irreversible dephasing via
molecular motion (Figure 6).52 Therefore, we assign this
resonance to H2O in a water-like phase external to the hectorite
particles. This water cannot be in the interlayer because all
interlayer H2O in clays with basal spacings e19.4 Å are within
two molecular radii of a surface, a location where surface effects
Bowers et al.
Figure 6. Variable τ delay 2H solid echo spectra (thick lines) and
simulations (thin, red lines) using tetrahedral jump motion for the 1/1.5
wt K-hectorite/2H2O paste at -50 °C (a) and -30 °C (b). The
corresponding τ delays from top to bottom are 40, 70, and 100 µs,
respectively.
lead to structural and dynamical behavior that differs from bulk
water (as noted in the Introduction). The narrow 39K resonance
at -10 °C is strongly correlated with increasingly rapid motion
of these water-like H2O molecules as the ice melts, visible in
the 2H NMR spectra as the loss of the broad resonance at
-10 °C and decreased depth of the dip near 0 ppm in the 0 °C
spectrum.
We assign the narrower, quadrupole-dominated resonance
observed from -50 to 0 °C to H2O confined in the two-
dimensional interlayer space. It is well-known that the 2H
quadrupolar interaction is dominated by intramolecular contribu-
tions due to the alignment of the EFG principal axis along the
using the quadrupolar parameters of ice-1h in calculations of
2H dynamics for 2H O at a variety of temperatures and
2
heterogeneous environments.18,20,51 If we also assume that the
2H quadrupolar parameters of 2H O do not vary significantly
2
with temperature, the observed spectral narrowing in our 2H
NMR must be due to nonisotropic 2H2O motion. Interactions
with the basal silicate surfaces and K+ ions are likely to cause
such restricted motion. The narrow 2H resonance cannot be
modeled using tetrahedral jump motion at frequencies up to the
fast-motion limit and must be associated with a different
anisotropic dynamic process than that occurring in ice-1h. A
number of authors have reported spectroscopic evidence of fast
rotation about the molecular dipole moment of H2O (co-incident
with the C2 symmetry axis) in clay interlayers.22,24,85,86 The
relationship between the principal axes of the two 2H electric
field gradient tensors and the molecular dipole axis for this type
of motion is characterized by the angles θ ) 128° and φ ) 0°
and 180° (where θ and φ are defined as in Figure 7). Rotation
about an axis with θ ) 127.5 ( 0.5° at a rate 1/τc g 2 MHz
(where τc is the motional correlation time) provides an excellent
fit to the narrower of the two 2H resonances observed at and
below 0 °C, consistent with C2 rotation (Figure 5). However,
there are a number of potential interlayer H2O environments
that may give rise to this type of motion. These include H2O
coordinating the interlayer cation along the dipole moment and
rotating about the electrostatic bond24,39,86 and H2O accepting
hydrogen bonds along the dipole moment from hydroxyl groups
at defect sites in the interlayer (Figure 8).87 Non-C2-type
motions may also exhibit rotation in the fast-motion limit about
an axis where θ ) 128°. One example is H2O donating at least
one hydrogen bond to the hexagonal silicate rings with both
hydrogen atoms oriented toward the surface and rapidly rotating
about an axis perpendicular to the clay layer.88,89 NMR line-
shape analysis of the 2H NMR spectra cannot distinguish
between these possibilities, and molecular modeling is the best
approach to resolve this uncertainty. We also note that the fast
2H and 39K NMR Investigations of Hectorite
Figure 7. Definition of θ (a) and φ (b) for an H2O molecule rotating
around the axis Zmol. θ reflects the orientation between the rotation
axis and the Vzz principal axis of the deuterium electric field gradient
tensor. φ reflects the position of the deuterium electric field gradient
principal axis projected in a plane perpendicular to the rotation axis.
Figure 8. Three potential confined H2O environments where rotation
at θ ) 128° may occur. Schematic (a) represents H2O coordinating an
interlayer K+ ion along the molecular C2 axis and rotating about this
axis, where we expect H2O to donate a hydrogen bond to oxygen atoms
at the clay surface. Schematic (b) shows an H2O molecule accepting a
hydrogen bond along the molecular C2 axis from a surface hydroxyl
at a defect site and rotating about this hydrogen bond. Schematic (c)
reflects a confined H2O molecule with both hydrogen atoms directed
toward oxygen atoms at the clay surface and hopping about an axis
perpendicular to the surface such that the angle between the two 2H
electric field gradients and the rotation axis is θ ) 128°.
restricted rotation in the interlayer must not induce significant
modulation of the 39K EFG because evidence of dynamic
averaging at a rate >2 MHz is absent in the 39K NMR spectra
below -10 °C.
At 10, 25, and 40 °C, there are two narrow 2H resonances
(Figure 9) reflecting melting of the bulk water and the interlayer
melting transition observed in the 39K NMR data. At 10 °C
and above, the intense and very narrow resonance arises from
isotropic motion in the free water phase. This strong, narrow
peak is not observed for free water at -10 °C due to motion-
related signal dephasing by fast tetrahedral jumps (see Figure
5 and ref 81) but does appear in the 2H NMR spectrum at 0 °C
as a decrease in the depth of the central dip near 0 ppm. This
is because melting of bulk water/ice produces intensity in a
narrow band near the reference frequency. The second, some-
what broader resonance is due to interlayer H2O and possibly
H2O undergoing exchange with the bulk exterior water phase.
This assignment is justified because confinement introduces a
residual time-averaged quadrupolar interaction that leads to line
broadening relative to the free water case. We know that a
fraction of H2O remains confined on the experimental time scale
based on the average H2O interlayer residence time. The average
H2O interlayer residence time calculated using the MD-
computed diffusion coefficient for interlayer H2O in 12.5 Å
J. Phys. Chem. C G
Figure 9. A zoomed view of the 2H peaks above 0 °C in the 1/1.5 wt
K-hectorite/2H2O paste. Note the presence of two narrow peaks, a
broader component likely associated with H2O that is confined during
part or all of the experiment and a narrow peak reflecting isotropic
motion of free water. Also note that the relative intensity of the confined
H2O phase increases with increasing temperature and time.
K-montmorillonite (D ) 1.3 × 10-10 m2/s)37 and assuming that
this value corresponds to predominantly lateral diffusion and
that the hectorite particles are plate-like and 1 µm in diameter
is greater than 6 ms. This value is longer than the observed 2H
T2* values (0.8 and 4.1 ms for the broad and narrow resonances,
respectively), where T2* is determined from the line width and
represents an upper limit on the true T2. Thus, most of the
interlayer water remains confined on the experimental time scale.
This residence time also suggests that a small fraction of
confined H2O near particle edges exchanges with bulk H2O, in
agreement with VT 2H NMR experiments of K-hectorite
equilibrated in a 100% relative humidity 2H2O environment
(Figure S3). This sample contains significantly less bulk H2O
and complete narrowing of the confined H2O fraction is not
observed above 0 °C, suggesting that exchange between
interlayer and free states is an important contributor to motional
narrowing of interlayer H2O above melting. Once again,
molecular dynamics simulations will be needed to identify
specific mechanisms of motion for H2O between -50 and 40 °C.
The increase in relative intensity of the broader 2H peak from
10 to 40 °C (Figure 9) should be interpreted with caution given
the extent of left shifting and back-prediction used in processing
the data (see Experimental Section and Supporting Information).
It may, however, reflect an increase in the fraction of water
molecules that spend part of their time in the interlayer, a loss
of water from the sample, or temperature-dependent variations
in T2 relaxation that affect the relative intensity. The epoxy seal
remained intact, and the sample’s physical appearance did not
change over the course of the NMR experiments, suggesting
that water was not lost. If exchange of water molecules between
the interlayer and bulk fluid is important, an increasing H2O
diffusion coefficient with increasing temperature would cause
a greater fraction of H2O molecules to experience confinement
during the acquisition period, increasing the intensity of the
broader peak. Likewise, an increase in the T2 relaxation rate
H J. Phys. Chem. C
for the free water phase with respect to the confined fraction(s)
may also affect the relative intensity in a solid-echo NMR
experiment in the fashion observed in the 2H NMR spectra. A
thorough evaluation of these and other potential origins for the
relative intensity changes requires a substantial number of NMR
and computational investigations of multiple clays and clay/
H2O ratios and is beyond the scope of this paper.
Dynamic Coupling of K+ and H2O. The NMR data
presented here demonstrate a close relationship between the
dynamic behavior of K+ and H2O in the hectorite paste. As
noted earlier, the absence of 39K dynamic averaging in the 10
Å powder at room temperature is clear evidence that dynamic
averaging in the paste is associated with the presence of H2O.
The melting transition observed for bulk H2O by 2H NMR
between -10 and 0 °C is directly associated with the onset of
39K line narrowing for a small spin population, possibly
associated with the external hectorite surface (Figures 3 and
5). Assuming the 39K signal does come from the surface spins,
this relationship likely reflects increased mobility of surface K+
that depends directly on the dynamics of bulk interparticle H2O.
There is also a close relationship between the dynamics of the
remaining K+ population and H2O confined in the interlayer.
At 0 °C, we observe 39K dynamic averaging via EFG modula-
tions at a rate g200 kHz and narrowing of the confined H2O
2H NMR spectrum by motion at a rate that is insufficient to
fully average the 2H quadrupolar interaction (rate <300 kHz).
At 10 °C, the 2H NMR results show that dynamic averaging of
confined H2O occurs via 2H EFG fluctuations at a rate sufficient
to significantly reduce the residual quadrupolar interaction of
the 2H2O and 39K (g300 kHz). These rate/temperature relation-
ships show that both confined K+ and H2O experience an
increase in the motional degrees of freedom in the interlayer (a
melting-type process) near -10 °C and that coupled motion
leads to the dynamic averaging observed above this temperature.
The mechanism of motion is likely site exchange between inner-
and outer-sphere K+ sites (observed in MD simulations of
K-montmorillonite37) or diffusion of K+ that in either case is
enabled by the onset of diffusional mobility for H2O. MD
simulations of the K-hectorite system on the multi-nanosecond
time scale represent the best means for testing this hypothesis
by investigating the particular types of dynamic processes
responsible for the observed dynamic behavior of K+ and H2O
(exchange, diffusion, etc.).
Conclusions
Combined 39K and 2H VT NMR spectroscopic data examining
H2O and K+ structure and dynamics in hectorite and a hectorite/
H2O paste offer unique insight into the fundamental dynamic
processes that occur in phyllosilicates and phyllosilicate-water
systems as well as highlighting the ability of NMR to provide
simultaneous structural and dynamical information in disordered
K-bearing systems. K+ is rigidly bound as an inner-sphere
complex in 10 Å hectorite and as a mixture of interlayer and
external surface sites that are indistinguishable by 39K NMR in
a 1/1.5 by weight K-hectorite/H2O paste. All K+ in the paste
sample associated with the hectorite undergoes a transition
between -10 and 0 °C from a static structural environment or
one undergoing relatively slow motion (∼20 kHz) to environ-
ments affected by motion at a rate in excess of 200 kHz. This
transition occurs over a very narrow temperature range, as
expected for a melting-type process, and it appears that this
melting-type transition occurs at slightly different temperatures
for surface and confined K+. Both melting transitions are
associated with the freeing of the local H2O environment.
Bowers et al.
Evidence of 39K line narrowing in the paste between -50 and
-30 °C suggests that other dynamic processes may be active
at these temperatures, and additional 39K and 2H NMR experi-
ments at lower temperatures will be necessary to clarify the
low-temperature behavior. There are two H2O environments in
the paste, H2O external to the clay particles that is structurally
and dynamically similar to bulk water, and H2O confined in
the hectorite interlayers. The bulk-like water undergoes a melting
transition near 0 °C, leading to the very narrow, liquid-like
resonance observed at 10 °C and above. Between -50 and 0 °C,
the confined H2O experiences rotation at frequencies in excess
of 2 MHz at an angle between the principal axis of the 2H
electric field gradient and the rotation axis of 127.5 ( 0.5°.
This geometry is consistent with rotation about the molecular
C2 symmetry axis that does not modulate the 39K EFG
significantly, though other types of motion can yield the same
line shape. Above 0 °C, the interlayer H2O experiences motion
with a rate of the order of 300 kHz that leads to a narrowed
peak that is slightly broader than the one for bulk-like water.
The small residual quadrupolar broadening is due to unaveraged
electric field gradients experience by 2H in the interlayer. The
correlations between the melting transitions of H2O and 39K
observed in the VT NMR spectra and the trends in the rates of
2H and 39K motion demonstrate a clear relationship between
the dynamics of H2O and K+ in the confining interlayer and at
the external surface.
Acknowledgment. This research was supported by the
United States Department of Energy Office of Basic Energy
Science, Grant DE-FG01-05ER05-010201. A portion of the
research described in this paper was performed in the Environ-
mental Molecular Sciences Laboratory, a national scientific user
facility sponsored by the Department of Energy’s Office of
Biological and Environmental Research and located at Pacific
Northwest National Laboratory. The authors thank Liming Zhu
for help communicating the controlled RH XRD results.
Supporting Information Available: Details of sample
preparation, XRD experiments, and NMR experiments; Figures
S1-S3. This material is available free of charge via the Internet
at http://pubs.acs.org.
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