Article

pubs.acs.org/JPCC

Bimodal Acidity at the Amorphous Silica/Water Interface

Morgane Pfeiffer-Laplaud,† Dominique Costa,‡ Frederik Tielens,§ Marie-Pierre Gaigeot,†,⊥
and Marialore Sulpizi*,#
†
LAMBE CNRS UMR8587, Université d’Evry val d’Essonne, Blvd F. Mitterrand, Bât Maupertuis, 91025 Evry, France
‡
Chimie Paristech CNRS, UMR8247, Institut de Recherches de Chimie de Paris, 11 rue P et M Curie, 75005 Paris, France
§
Sorbonne Universités, UPMC Univ Paris 06, CNRS, Collège de France, Laboratoire de Chimie de la Matière Condensé de Paris, 11
place Marcelin Berthelot, 75005 Paris, France
⊥
Institut Universitaire de France, 103 Blvd St Michel, 75005 Paris, France
#
Department of Physics, Johannes Gutenberg Universitat, Staudingerweg 7, 55099 Mainz, Germany

ABSTRACT: Understanding the microscopic origin of the

acid−base behavior of mineral surfaces in contact with water is
still a challenging task, for both the experimental and the
theoretical communities. Even for a relatively simple material,
such as silica, the origin of the bimodal acidity behavior is still a
debated topic. In this contribution we calculate the acidity of
single sites on the humid silica surface represented by a model
for the hydroxylated amorphous surface. Using a thermo-
dynamic integration approach based on ab initio molecular
dynamics, we identify two different acidity values. In particular,
some convex geminals and some type of vicinals are very acidic
(pKa = 2.9 and 2.1, respectively) thanks to a special
stabilization of their deprotonated forms. This recalls the behavior of the out-of-plane silanols on the crystalline (0001) α-
quartz surface, although the acidity here is even stronger. On the contrary, the concave geminals and the isolated groups present a
quite high pKa (8.9 and 10.3, respectively), similar to the one of silicic acid in liquid water.

■ INTRODUCTION
Knowledge of the acid−base behavior of mineral surfaces is
crucial for the understanding of their chemistry, including not
only surface dissolution, surface interactions with ligands
(especially biomolecules), and heterogeneous catalysis but
also the building of charge at the interface with solvent and its
consequence on ion transport, and more generally in the
context of technological applications. Measuring the acid−base
character of insulating mineral oxides often relies on indirect
measurements, using pH-sensitive molecules with spectroscopic
signatures1−3 or potentiometric titration techniques4,5 that only
operate over a limited pH range. Certainly a big step forward
was made in 1992 when Eisenthal and co-workers demon-
strated that nonresonant second harmonic generation (SHG)
spectroscopy can provide a surface-sensitive and label-free
method for monitoring the acid−base behavior of fused silica.6
The planar silica/water interface has hence been shown by
SHG and other methods to exhibit surface sites with two
distinct acidities.1,3,6−9 In particular, the SHG experiments
showed that 19% of silanol groups on fused silica surfaces
exhibit a pKa of 4.5, whereas 81% exhibit a pKa of 8.5.6
Nonlinear SFG spectroscopy experiments on α-quartz also lead
to similar conclusions on a bimodal behavior of silanols on
crystalline silica.9
Very recent SHG results from Gibbs−Davis points to a
trimodal or bimodal behavior of silica depending on the starting
pH, where the trimodal behavior is only observed when
tritation is initiated at high pH.10
Other techniques such as evanescent wave cavity experi-
ments3 have also shown the bimodal character of fused silica,
measuring a ratio 4:1 of pKa, respectively for non acidic/acidic
sites. See ref 11 and references therein for more description of
experimental works showing the existence of two types of
silanols in terms of acid−base character at the fused silica/water
interface.
Beyond the existence of two types of silanols at the surface of
silica and their actual pKa values, one challenge is to unravel the
microscopic nature of these two populations, which is the goal
of the present paper using theoretical simulations. Beforehand,
one has to specify the silanols nomenclature that will be used
throughout our work. See Figure 1 for a schematic
representation and also refs 11 and 12 for more details.
Qn refers to a Si atom bonded to n other Si atoms through
bridging oxygens, forming Si−O−Si siloxane groups. Upon
dissociation of water on the surface, (hydroxylated) Si−OH
silanol sites are formed. In the present work we will concentrate
on hydroxylated surface sites. On the hydroxylated silica
surface, a Q3 Si has one single Si−OH silanol group called
Received: March 25, 2015
Revised: November 9, 2015

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcc.5b02854

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The Journal of Physical Chemistry C
Figure 1. Scheme of silanols encountered at the surface of silica:
isolated Q3, H-bonded Q3, vicinal Q3, geminal Q2. This scheme does
not take into account the presence of an aqueous interface.
“isolated” because it does not share H-bonds with any other
silanol. This occurs whenever the distance between this Si−OH
and the closest Si−OH neighbor (d[(Si−O)−H···O−(Si)]) is
larger than 3.3 Å.11 See Figure 1a for a graphical representation.
A Q3 silanol can also form hydrogen bonds, as shown in Figure
1b. A Q3 Si with one single Si−OH is called “vicinal” whenever
this silanol shares a common oxygen vertex in its tetrahedra
with another silanol, as illustrated in Figure 1c. A Q2 Si has a
pair of geminal Si−OH, as illustrated in Figure 1d. All Si−OH
silanols of Q3 type are generally labeled as terminal silanols.
The key issue is to provide a microscopic interpretation of
the two silanol surface acidities measured in experiments in
relation with Q3 and Q2 types of Si silica sites, and in relation
with their local environment (i.e., interactions with the surface
and with water at the wet surface). This is far from being fully
understood from experiments alone. The main reason is that
the 4:1 ratio of nonacidic versus acidic sites measured
experimentally3 is concomitant with several microscopic
structural properties with (i) the average ratio between H-
bonded and isolated silanols (IR experiments13) but also with
(ii) the ratio of Q2 versus terminal silanols (NMR experi-
ments11). Whether the 4:1 ratio of nonacidic/acidic sites on
silica corresponds to one or the other population, or to another
one, is still unknown. Things are even more complicated, as
Chuang and Maciel showed that these populations overlap, as
terminal and Q2 silanols may/may not be H-bonded,
depending on the local surface topology14 and on these sites’
interactions with the solvent at the wet surface. Several
hypotheses for explaining the bimodal acidity character of
silica have been put forward. We list here some of them, with a
special emphasis on the most acidic character. This one has
been hypothesized to be due to Q3-isolated silanols15 (e.g., near
a strained cycle that forms upon dehydration) because they
become engaged in interactions with the solvent once the
surface is wetted; alternative hypotheses are that this more
acidic character could be due to any H-bonded site,11 or on the
contrary, to silanols lacking hydrogen bonds,1 or to silanoliums
(doubly protonated silanols).16 In a previous theoretical work17
we have provided an explanation for the bimodal character of
silanols at the (0001) α-quartz interface in terms of H-bond
strengths, showing that the more acidic silanols (pKa = 4.56)
form the stronger hydrogen bonds to interfacial water whereas
the less acidic silanols (pKa = 8.56) form the weaker H-bonds
with interfacial water.
B DOI: 10.1021/acs.jpcc.5b02854
Article
A consensus on the microscopic nature of the acidity
bimodal character of silanols at silica surfaces is clearly far from
achieved, showing the need for a theoretical molecular
methodology that would provide a robust way of calculating
pKa values of surface sites in the presence of the solvent and
simultaneously provide a microscopic rationalization of these
values. This can be achieved through ab initio molecular
dynamics (AIMD) simulations of the full silica−water interface,
as already shown in refs 15 and 17. One can indeed generate
controlled surface models on which the pKa of selected sites can
be calculated, taking into account the presence of the liquid at
the interface. Following such a method and using multiple
representative crystalline silica surfaces, Leung has calculated
the deprotonation free energies of silanol groups with different
structural motifs.15 He showed that a plausible candidate for the
most acidic silanols observed in the experiments (pKa = 4.5)6
could be located on locally strained or defected regions with
sparse silanol coverage.15 These AIMD simulations lend
support to the role of interfacial water, finding that silanol
groups on hydrophobically restructured quartz exhibited the
lowest pKa.15 In this study it was also observed that the pKa of
silanols increased as the number of water layers increased. The
less acidic sites were shown to exhibit a pKa ≈ 9, which is
similar to that of the monomeric form of silica, i.e., monosilicic
acid (pKa(Si(OH)4) = 9.9).18
In a recent work17 we have addressed the special case of the
α-quartz (0001)/water interface. The acidity of the surface
groups were calculated from AIMD simulations using our
developed proton insertion technique.19−22 The (0001) α-
quartz surface certainly represents a special case because the
surface exhibits a regular pattern of Q2 silanol distribution and
an associated regular hydrogen bond arrangement.17 Indeed,
when the (0001) α-quartz surface is in contact with water, we
showed that half of the silanols maintain an “in-plane”
orientation, donating hydrogen bonds to nearby silanols,
whereas the other half of the silanols adopt an out-of-plane
orientation, and act as H-bond donors to interfacial water
molecules in the first adsorbed layer.17 With our calculations we
could conclude that (0001) α-quartz exhibits a bimodal
behavior with two different acidity constants, namely calculated
at pKa= 5.6 and 8.5, respectively for the out-of-plane and in-
plane silanols, and relate these pKa values to the H-bond
strengths that the silanols make with the first adsorbed water
layer, i.e., strong (out-of-plane) and weak (in-plane) H-bonds.
From the experimental data it is clear that the bimodal acidity
character is also present at the fused silica/water interface,3 i.e.,
a noncrystalline surface. So the question is how do silanols
behave on an amorphous silica surface in terms of interactions
with their environment (amorphous silica being taken as a
model for fused silica)? Can we predict and explain silanol
acidities in terms of local environment?
In this paper we provide an explanation for the bimodal
acidity behavior for the amorphous silica/liquid water interface,
considering an extended model of the amorphous silica surface.
In particular, our model is based on an original structure
developed by Garofalini23 and subsequently relaxed via ab initio
simulations.24 This surface has been characterized in both dry
and microsolvated conditions,24,25 and more recently in contact
with bulk water.26 The model presents a distribution of
tetrahedral (SiO4) rings in the bulk solid mainly composed of
four-, five-, and six-membered rings, in good agreement with
the experimental data.24 It is important to note that besides the
flexible Si−O−Si bond,27 no strained 3R-rings are present, by
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construction. The bulk slab is about 10 Å thick (vertical
spacing), with an in-plane cell size of 13 Å × 17.5 Å, which
resulted in Si27O67H26 composition (120 atoms as a whole).
The slab is about three-layers thick, with thickness locally
varying between 5 and 8 Å, reflecting the surface rugosity, see
Figure 2. The OH density of 5.8 OH/nm2 mimics the behavior
of an hydroxylated amorphous silica surface (4.5/4.9 OH/
nm2).
Figure 2. Amorphous silica slab used for calculations. Color code:
yellow, Si; red, O; white, H atoms. The five studied silanol sites are
highlighted in blue and use a larger size.
The acidity of the silanols at the dry surface has been
characterized in ref 24. The terminal Q3 hydroxyl groups were
found to have a deprotonation energy of ∼650 kJ/mol and the
Q2 ones of ∼600 kJ/mol, with geminal silanols thus slightly
more acidic. The small 50 kJ/mol difference in the
deprotonation energies may, however, not be enough to
confidently predict the order of acidity in the presence of an
aqueous phase. Vacuum DFT calculations of the adsorption of
lutidine (2,6-dimethylpyridine) on Q2- and Q3-isolated silanols
of this surface furthermore confirm the slightly higher acidity of
Q2 sites.28 In the same spirit, we identified that the convex
silanol nest formed around the Q2 site exhibits a higher
chemical reactivity than Q3-isolated silanols, being typically an
attracting site for the adsorption of glycine, and stabilizing basic
adsorbates.25
Is the higher chemical reactivity of Q2 silanols maintained at
the aqueous interface?
■ METHODS
Calculation of the Acidity Constants. The acidity
constants of surface groups are computed using the reversible
proton insertion/deletion method.19−22 The method was
initially developed and tested on a series of aqueous
compounds,19−22 and then applied to the calculation of the
acidity of surface groups of several oxides in contact with
water.17,26,33−35 The advantage of this approach is that the solid
(mineral) surface and the solvent (water) are treated at the
same level of theory, and therefore the approach is particularly
suitable for heterogeneous environments such as interfaces.
The acidity constants are calculated from the free energy for
transferring a proton from a group on the surface (in our case
the silanol OH) to a water molecule in the bulk solution. The
following reaction is considered:
C DOI: 10.1021/acs.jpcc.5b02854
Article
−SiOH + H 2O(aq) → −SiO− + H3O+(aq) (1)
The transfer process is implemented using the thermodynamic
integration. The charge of the acidic proton of a surface OH
group is gradually switched off, transforming the proton into a
neutral “dummy” particle. Simultaneously, a similar dummy
proton attached to a water molecule is charged up, creating a
hydronium in the Eigen form. The fractional charges on the
two groups always add up to unity. Following the approach that
we have discussed in detail in ref 22, the discharge integral is
calculated according to
1
ΔdpA = ∫0 dη⟨ΔdpE⟩r η
(2)
where ΔdpE is the vertical energy gap, defined as the potential
energy difference between product P (MO−+H3O+(aq) in eq
1) and reactant R (−MOH + H2O(aq)) for instantaneous
configurations of a molecular dynamics trajectory. The
subscript rη indicates that the averages are evaluated over the
restrained mapping Hamiltonian
/η = (1 − η)/R + η /P (3)
where η is a coupling parameter that is gradually increased from
0 (−MOH + H2O(aq)) to 1 (−MO− + H3O+(aq)). This
Hamiltonian also contains a harmonic restraining potential
Vrestr keeping the dummy atom close to the equilibrium
position of the H+ nucleus in the protonated system. The
Simpson rule (three-point approximation) is used to evaluate
the integral in eq 2:
1 2
ΔA TP = (⟨ΔE⟩0 + ⟨ΔE⟩1) + ⟨ΔE⟩0.5
6 3 (4)
This requires generation of three trajectories corresponding to
values of η = 0, 0.5, 1. This formula is often a good compromise
between computational cost and accuracy of the free energy
change.19,36 The pKa value of a surface group is obtained from
the proton transfer integral of eq 2 by adding a thermochemical
correction. The leading term in this correction adds in the
translational entropy generated by the acid dissociation. This
term is missing in reaction 1, which is formally a proton transfer
reaction conserving the number of translational degrees of
freedom. Indeed, this translational entropy term is related to
the definition of our solvated proton, which is assumed to be in
the Eigen form, namely, as H3O+(aq), where instead the proton
is actually free to diffuse around and should be instead
represented as H+(aq). The simplification is motivated by the
necessity to have a well-defined position for the proton
insertion. A detailed explanation about this issue can be found
in ref 22. The overall formula used for the pKa calculation
becomes
1
2.30kBTpK a = ∫0 dη ΔdpE η + kBT ln[c o Λ 3H+]
(5)
where co = 1 mol dm−3 is the unit molar concentration and ΛH+
is the thermal wavelength of the proton. We refer the reader to
ref 22 for a detailed derivation of such a formula. The logarithm
of the product coΛ3H+ accounts for the liberation entropy of the
proton and is responsible for a correction of −3.2 pK units to
the thermodynamic integral.
We comment that all the pKa values have been calculated on
a neutral surface, so at the point of zero charge condition. It is
expected that if the overall charge of the surface varies, in
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Figure 3. Representative snapshots of the local structures around the SiOH groups at the water/amorphous silica interface. Hydrogen bonds appear
in white dashed lines.

Table 1. Energies (eV) Obtained in the pKa Calculations of the Geminal, Isolated, and Vicinal Silanols on Amorphous Silicaa
system traj ΔE0 ΔE0.5 ΔE1 ΔA pKa ΔpKa
Q2-Gem. 1 Whole −7.18 ± 1.62 0.35 ± 0.54 7.09 ± 1.03 0.28 2.9 1.6
Half1 −7.45 ± 1.59 0.51 ± 0.53 7.16 ± 0.98 0.36 4.1
Half2 −6.91 ± 1.60 0.19 ± 0.51 7.01 ± 1.06 0.15 0.9
Q2-Gem. 2 Whole −6.34 ± 1.45 0.77 ± 0.52 7.30 ± 1.09 0.67 8.9 0.2
Half1 −6.23 ± 1.49 0.75 ± 0.53 7.30 ± 1.08 0.68 9.0
Half2 −6.45 ± 1.40 0.78 ± 0.50 7.33 ± 1.10 0.66 8.7
Q3-Iso. Whole −5.49 ± 0.67 0.75 ± 0.54 7.24 ± 1.28 0.79 10.3 1.5
Half1 −5.62 ± 0.63 0.66 ± 0.48 7.04 ± 1.31 0.67 8.4
Half2 −5.36 ± 0.69 0.76 ± 0.54 7.45 ± 1.23 0.86 11.3
Q3-Vic. 1 Whole −8.30 ± 2.82 0.63 ± 0.53 7.40 ± 1.53 0.23 2.1 0.7
Half1 −8.62 ± 3.31 0.70 ± 0.57 7.66 ± 1.59 0.31 3.4
Half2 −7.99 ± 2.18 0.56 ± 0.47 7.14 ± 1.43 0.23 2.1
Q3-Vic. 2 Whole −5.24 ± 0.64 1.42 ± 0.50 6.43 ± 1.06 1.15 16.2 0.5
Half1 −5.31 ± 0.72 1.39 ± 0.52 6.56 ± 1.03 1.13 15.9
Half2 −5.18 ± 0.55 1.46 ± 0.49 6.49 ± 1.06 1.19 16.9
a
ΔE represents vertical energy gaps and ΔA is the difference in free energy. Uncertainties on the final values are qualitatively evaluated via an
estimation on the pKa in the first half (Half1) and in the second half (Half2) of the trajectories. This last part confirms the convergence of the
calculations.

particular when a nearby group gets deprotonated, this can have
a strong impact on the site pKa.
Model Systems. Our AIMD simulations follow the same
general setups used in our previous investigations of solid−
liquid interfaces.17,26,33−35 DFT-based Born−Oppenheimer
molecular dynamics (BOMD) simulations have been per-
formed with the CP2K/Quickstep package,37 using the hybrid
Gaussian and plane wave method. The Perdew−Burke−
Ernzerhof (PBE) exchange−correlation density functional was
used. Goedecker−Teter−Hutter pseudopotentials,38,39 a dou-
ble-ζ DZVP plus polarization Gaussian basis set for the orbitals
and a density cutoff of 400 Ry were used. Only the Γ point was
considered in a supercell approach. The box dimensions are
12.77 × 17.64 × 25.17 Å3. Periodic boundary conditions are
applied in all directions of space. Dynamics were conducted in
the canonical NVT ensemble (after 9 ps of equilibration for
geminal 1, 5 ps for geminal 2 and vicinal 2, 10 ps for vicinal 1
D DOI: 10.1021/acs.jpcc.5b02854
and 2 ps for the isolated SiOH) with a time step of 0.5 fs. On
average, the lengths of the trajectories (true data collection) are
10 ps for geminal 1 and vicinal 1, 15 ps for the isolated site, and
20 ps for geminal 2 and vicinal 2. These sites are described in
the next section.
■ RESULTS AND DISCUSSION
In our recent work26 we have shown that this amorphous silica/
water interface is characterized by a strongly adsorbed layer of
water at the interface. In particular, three zones were identified,
with increasing “local ordering” of the interfacial water, namely,
Q3-isolated silanols and concave and convex geminal Q2
silanols.
A picture showing the local environment for a few selected
groups can be found in Figure 3. For our pKa analysis we have
chosen different types of sites that are representative of
different Qn sites (namely silanols with different number of
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bridging oxygens) and different types of local environment and
solvation. In particular, we chose two different types of
geminals, namely Geminal 1 (panel a in Figure 3), which is a
convex Q2 silanol, and Geminal 2, which is a concave Q2 silanol
(panel b in Figure 3). From our detailed analysis of the
solvation structure at the interface with the amorphous silica,
we could already suggest that the convex Q2 silanol represents
possibly low acidity sites.26 Additional investigated sites include
two Q3 vicinals with very diffferent environments and a Q3-
isolated site. The two vicinals are reported in Figure 3, panels c
and d, and are characterized by two distinct exposures to
solvent. Vicinal 1 (panel c) corresponds to a hydroxyl group
fully immersed into liquid water. It is H-bonded to a
neighboring silanol through a bridging water molecule and is
part of a four-membered H-bond ring. In particular, it receives
and donates 2 H-bonds with two water molecules. Conversely,
Vicinal 2 (panel d) is a completely buried site, almost
inaccessible to solvent. It only shares its proton directly with
a nearby silanol. Finally, the isolated site is depicted in panel e
of Figure 3 and is H-bonded with one water molecule.
We provide here a quantitative estimate of these site acidities,
applying our proton insertion approach19−22 as in ref 17. pKa
values will be compared to those calculated for the in-plane and
out-of-plane Q2 silanols of the crystalline quartz−water
interface.
The pKa values found are 2.9 for the convex Q2 silanol and
8.9 for the concave Q2 silanol. This first result suggests that the
acidity is not depending on the type of site only (Q2 for both
cases) but is strongly influenced by the local environment,
namely, by the solvent accessibility and H-bond network
around the OH site. A similar conclusion also holds for the Q3
sites. Indeed, vicinals with different local environments can have
very different acidities. The Q3 vicinal 1, which is characterized
by steady hydrogen bonds with interfacial water, has a pKa value
of 2.1, whereas another vicinal with its hydrophobic environ-
ment, namely, our Q3 vicinal 2, has a much higher pKa value of
16.2. Finally, the Q3-isolated silanol has a pKa of 10.3. (A
summary of the pKa analysis is reported in Table 1).
The (convex) geminal 1 and the vicinal 1 are thus very acidic,
even more acidic than the Q2 out-of-plane silanols at the α-
quartz/water interface (pKa = 5.6),17 whereas the geminal 2 and
the isolated sites have a relatively high pKa that is similar to the
one of the silanols in silicic acid (pKa ≈ 9.9 from our previous
AIMD simulations17). Finally, the pKa of vicinal 2 is outside the
water window and would possibly not be probed in titration
experiments. Overall, we recover a bimodal behavior at the
water/amorphous silica with a first acidity around 2−3 pKa
units and a second one around 9−10.
Now the key question is where does the strong/weak acidity
come from? To provide an answer to such a question, we have
analyzed in detail the solvation structure of both the protonated
and the deprotonated forms of the silanols. To guide the
structural analysis, a scheme is reported in Figure 4, which
shows a silanol in the protonated form (left panel) and a silanol
in the deprotonated form (right panel) and their hydrogen
bond networks obtained from our AIMD simulations. In the
scheme, the average hydrogen bond distances for the Q2- and
Q3-isolated silanols at the amorphous silica/water interface, and
for the Q2 aqueous quartz out-of-plane silanols,17 are reported
for discussion. Note that for clarity, we do not report here all
the sites.
On the basis of the average distances reported in Table 2 for
the neutral form of the amorphous silica sites, the convex Q2
E DOI: 10.1021/acs.jpcc.5b02854
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Figure 4. Schematic view of the solvation of the different surface sites
of silica (amorphous and crystalline quartz) obtained from our AIMD
simulations: amorphous Q2 convex geminal (red); amorphous Q3-
isolated (black); quartz Q2 out-of-plane (OP) (green). Left: neutral
Si−OH form of the silanol site. Right: deprotonated Si−O− form of
the silanol site (conjugated base, silanolate). Labels show the average
number of hydrogen bonds formed between the Si−OH (left)/Si−O−
(right) and their surrounding (silanols and water molecules).
Si−OH (geminal 1) donates a strong hydrogen bond to water
(1.57 Å, (Si)O−H···Ow intermolecular distance), stronger than
the one formed by the concave Q2 Si−OH (1.69 Å) and slighly
stronger than that formed by the Q2 out-of-plane silanol from
the (0001) quartz crystalline surface (1.60 Å).
This is also clear from the (Si−O)H···Ow distances reported
in Table 2 taken from the position of the first peak in the radial
distribution functions between silanol H atoms and Ow
oxygens of water (curves reported in Figure 5). Maybe, more
importantly, from these curves one can obtain the information
concerning the position of the second peaks in the H···Ow
radial distribution functions and their microscopic interpreta-
tion. The second peak of H···Ow for the amorphous Q2 silanol
(Figure 5, red line) corresponds to the interaction of this site
with three nearby silanols and four water molecules from the
liquid. A very similar strong coordination from the environment
was also found for the Q2 out-of-plane silanol of the crystalline
(0001) quartz, as it is also surrounded by two to three
neighboring SiOH groups and by two to three water molecules.
The high computational cost of our AIMD proton-insertion
method for pKa calculations prevents us from determining the
intrinsic acidity of each surface site. However, we could
envisage estimating acidic heterogeneities within the same type
of silanol group by looking at the local environment around the
protonated and deprotonated forms. The rdfs of all the convex
geminals are reported in Figure 6. The red lines (continuous
and dashed) refer to a pair sharing the same Si, and the blue
lines (continuous and dashed) refer to another pair sharing the
same Si. We only have two concave geminals at the surface,
which is clearly a very limited statistics. A comparison of the
rdfs is nonetheless reported in Figure 7. Note that the color
code in Figures 6 and 7 to the same code chosen in the
previous figures; namely, the continuous red line corresponds
to the convex geminal 1 and the continuous orange line is for
the concave geminal 2.
The position of the first peaks in the H/O rdfs (Figures 6
and 7), corresponding to proton sharing with a nearby hydroxyl
(from silanol or water), are all shifted to larger distances with
respect to the continuous red line of convex geminal 1. From
considering only the H/O rdfs, the weaker H-bond donor
character could reflect lower acidity. Considering that for more
acidic sites, the OH bond is more polarized implying a greater
negative charge on the oxygen, its H-bond acceptor character
should be enhanced. Indeed, from the O/H rdfs, the more
acidic convex geminal 1 and the less acidic concave geminal 2
correspond to the extreme H-bond acceptor behaviors, the
more acidic site being a very strong acceptor and the less acidic
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Table 2. Positions and Heights of the First Two Peaks from the Radial Distributions Functions (rdf) around the Q2-Geminal 1
(Gem. 1), Q2-Geminal 2 (Gem. 2), Q3-Isolated (Iso.), Q3-Vicinal 1 (Vic. 1), Q3-Vicinal 2 (Vic. 2), and Out-of-Plane (OP)
Silanols
first peak second peak
rmax(Å) Imax rmin(Å) Imin rmax(Å) Imax rmin(Å) Imin
H−O Gem. 1 1.57 3.65 2.14 0 3.14 1.40
3.42 2.18 4.10 0.57
H−O Gem. 2 1.69 2.78 2.24 0 3.42 1.76 3.66 0.75
H−O Iso. 1.60 3.83 2.19 0 3.25 1.30 3.47 0.96
H−O Vic. 1 1.74 2.73 2.28 0 3.23 1.44 3.76 0.73
H−O Vic. 2 1.65 3.44 2.16 0 4.03 0.97 4.35 0.44
H−O OP 1.55 4.10 2.03 0 2.82 2.67 3.22 0.66
O−H Gem. 1 1.69 1.42 2.56 0.11 3.10 1.54 3.60 0.31
1.89 1.49
O−H Gem. 2 1.87 0.61 2.46 0.12 2.99 1.08 3.52 0.42
O−H Iso. 1.78 1.34 2.39 0.10 3.22 1.70 3.66 0.76
O−H Vic. 1 2.21 0.40 2.42 0.31 3.07 1.60 4.40 0.53
O−H Vic. 2 3.41 0.69 4.27 0.19
O−H OP 1.58 2.34 2.16 0 3.08 0.93 3.31 0.74
3.53 1.30 3.77 0.64
O−−H Gem. 1 1.57 4.08 2.23 0.06 3.06 1.16 3.79 0.36
O−−H Gem. 2 1.63 3.85 2.11 0.00 3.02 1.41 3.40 0.67
O−−H Iso. 1.70 3.66 2.48 0.23 3.13 1.36 3.34 0.87
O−−H Vic. 1 1.58 3.39 2.36 0.15 3.11 1.47 4.34 0.39
O−−H Vic. 2 1.50 3.36 2.14 0.04 3.90 0.65 4.74 0.35
O−−H OP 1.53 4.77 2.28 0.08 3.54 1.81 4.17 0.49

Figure 5. Radial distribution functions (rdf) around SiOH and SiO−
on amorphous silica or on α-quartz. The black line correspond to the
Q3-isolated sites, the red and orange ones to the Q2-convex (geminal
1) and concave (geminal 2) geminals, respectively. Blue lines represent
the Q3-vicinals, dark blue for vicinal 1 and light blue for the buried
vicinal 2. The green line is used for the out-of-plane silanol on quartz.
Top panel: rdfs. Lower panel: integrated densities.
site being a poor one. All the remaining geminals lie in
between. Conclusions on their relative acidities are thus not
straightforward. Nonetheless, because the two concave sites are
not as good H-bond acceptors as the convex ones (maximum 1-
H-bond is accepted, Figure 7, right panels) we expect both
concave silanols to exhibit the similar less acidic pKa. Note that
the higher acidity correlated to a stronger H-bond acceptor
character also holds for acidic Q3 vicinal 1 vs basic Q3 vicinal 2
on one side and for acidic Q2 out-of-plane geminal vs less acidic
Q2 in-plane geminal on quartz on the other side.
F DOI: 10.1021/acs.jpcc.5b02854
Figure 6. Comparison of the local environment for convex geminal
silanols: (left) donated hydrogen bonds from silanol H atoms; (right)
accepted hydrogen bonds from water H atoms. The red lines
(continuous and dashed) refer to a pair sharing the same Si, and the
blue lines (continuous and dashed) refer to another pair sharing the
same Si.
If we now turn to the conjugated silanolate bases (Figure 4,
right), we observe that they are strongly and equally stabilized
for the convex Q2 Si−O− of amorphous silica and the Q2 out-
of-plane site of crystalline (0001) α-quartz. Note, e.g., that for
the amorphous convex Q2 SiO−, one H-bond is accepted by
one water (distance 1.64 Å) and two H-bonds are accepted by a
nearby silanol (1.64 Å). A pictorial view of the local
environment for the deprotonated convex geminal Q2 can be
found in Figure 8, panel a.
Similarly for the out-of-plane Q2 SiO− on the quartz
crystalline surface: two H-bonds are accepted from water
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Figure 7. Comparison of the local environment for concave geminal
silanols: (left) donated hydrogen bonds from silanol H; (right)
accepted hydrogen bonds from water H. Two OH groups sharing the
same Si are investigated. The continuous line refers to an OH group
that donates an H-bond to water (similar to convex silanols), and the
dashed line, to an OH group which donates an H-bond to a nearby
silanol.
(1.69 Å) and one H-bond is accepted from a nearby silanol
(1.53 Å). Both the amorphous Q2 SiO− and the quartz out-of-
plane Q2 SiO− are strongly stabilized by the environment and
exhibit an overall 3-fold coordination of the deprotonated
oxygen.
On the contrary, the concave Q2 SiO− site is not so strongly
stabilized. It only accepts two hydrogen bonds, which are also
weaker than those stabilizing the deprotonated convex site. A
pictorial view of the local environment for the deprotonated
concave geminal Q2 can be found in Figure 8, panel b.
Let us now turn to the vicinals and the isolated sites. Here we
investigated different types of environments on the Q3 sites.
For the vicinals a key element to interpret the acidity can be
again found in the conjugated base stabilization. Indeed, also
here the acidic site (vicinal 1) has a conjugated base that is
strongly stabilized by three hydrogen bonds. Instead, for vicinal
2 (higher pKa) the conjugated base is only stabilized by two
Figure 8. Representative snapshots of the local structures around the deprotonated SiO− silanols at the water/amorphous silica interface. Hydrogen
bonds appear in white dashed lines.
G DOI: 10.1021/acs.jpcc.5b02854
Article
hydrogen bonds. The isolated site seems not to fit within this
scheme. Indeed, its conjugated base has a coordination of 3.5;
however, it forms on average the weakest H-bonds with these
water molecules (1.82 Å), the weakest among all the H-bonds
stabilizing the other deprotonated silanols (also true when
looking for the strongest H-bond among the 3.5 possible). This
type of stabilization of the isolated silanolate may resemble that
of a silicic acid molecule where the base stabilization can only
come from solvent molecules, but not from other silanol
groups. A pictorial view of the local environment for the
deprotonated Q3 site can be found in Figure 8, panels c, d, and
e.
In addition to the radial distribution functions we have also
investigated the orientational distribution of the water around
the deprotonated silanols. We find that the orientational
distribution is very similar for all the cases (geminal, vicinal,
isolated) and the maxima are only displaced by a few degrees.
We can conclude that water orientation around the
deprotonated oxygen is not a discriminating element character-
izing the conjugated base.
In some recent analysis of a model of amorphous silica
surface the presence of hydrophobic−hydrophilic patches has
been suggested in connection to the siloxane density.29,30 It
thus may be interesting to comment on the eventual correlation
between the density of siloxane groups in vicinity of the silanol
groups and their pKa’s. Our analysis shows that low pKa is
possible for both Q2 (geminal 1) and Q3 (vicinal 1) sites, which
means it is independent of the number of siloxane bridges.
Convex and concave geminals have the same number of
siloxane bridging groups; however, they exhibit a quite large
difference in the pKa. This would suggest that the environment,
namely, the local topology and solvent accessibility are the key
element to determine silanols acidity. To quantify the local
hydrophobicity, we have calculated the rdf of the siloxane O
around the silanols with the solvent H, or the nearby silanol H.
These are reported in Figure 9. We find that the siloxanes are
quite hydrophobic, and no hydrogen bond is formed between
the siloxane oxygens and protons from the environment
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Figure 9. Local environment for siloxane groups. Upper panel: rdf
between the siloxane oxygen and the water hydrogens. Bottom panel:
integrated numbers. Black curve: siloxane oxygens around the isolated.
Green curve: siloxane oxygens around the quartz geminal. Red curve:
siloxane oxygens around the convex Q2-Geminal 1. Orange curve:
siloxane oxygens around the concave Q2-Geminal 2. Black: Q3-Iso.
Dark blue: Q3-Vicinal 1. Light blue. Q3-Vicinal 2. All are at the water/
amorphous silica interface. Green: siloxane oxygens around the Q2-
out-of-plane site at the (0001) α quartz surface.
(namely protons from other silanols or from water). In all the
cases (geminal, isolated, vicinal, crystalline quartz) the first peak
in the radial distribution function appears around 3 Å. For the
convex geminal (red curve in Figure 9) the broad band around
3.0−3.5 Å is due to protons from the surrounding silanols,
whereas for the isolated (black line) the peak originates from
water molecules.
Leung et al.15 have also explored the influence of H-bonding
between Q2 silanols at the (100) β-cristobalite surface, where
the surface is composed of Q2 silanols sharing intramolecular
H-bonds with bond lengths of 1.70 Å in vacuum.31 pKa = 7.6
was calculated. The possibility of forming an H bond was then
eliminated by replacing the OH group by a H atom, so creating
an isolated Q2 silanol. The pKa was consequently found to
increase to 8.9, so that Leung et al. concluded that H-bonding
was responsible only for a small decrease of the pKa. In
particular, the simple removal of a hydrogen bond around the
Q2 silanols at the (100) β-cristobalite surface could not produce
a difference of 4 units between different Q2 sites and therefore
could not explain a bimodal character of that surface. However,
in comparing our result to the cristobalite, one should also take
into account the role of the surface flexibility. Indeed, Musso et
al.32 pointed out that for (100) cristobalite, the formation of H-
bonds between surface OH groups induces a large variation in
the flexible Si−O−Si angles with a sizable rearrangement of the
structure across the whole layer thickness. It was also found
that the layer thickness strongly influences the number of H-
bonds formed by the silanols on the surface.32 So one could
speculate that H-bond formation on cristobalite (100) is
energetically more expensive than on quartz (0001) and
amorphous silica, leading to a poorer associated base
stabilization. Certainly, the amorphous surface is more flexible
than crystalline surfaces, so that relaxation to maximize H-bond
formation should be easier.
H DOI: 10.1021/acs.jpcc.5b02854
Article
■ CONCLUSIONS
The first conclusion from our structural study is that the silanol
acidity does not depend on the actual n value of the Qn site, at
least not solely. We find pKa values of 2.9 and 8.9 for a convex,
respectively, concave Q2 geminal silanol and pKa of 2.1 and
16.2 for Q3 vicinal silanols with more hydrophilic or
hydrophobic environments, respectively. Finally, we find pKa
value of 10.3 for the isolated Q3 site. The local environment has
a strong impact on the silanols acidity and the geminals are a
good example where different environments (local topology
(nano-roughness) and hydrophobicity/philicity) can lead to
very different pKa. Some convex Q2 silanol at the amorphous/
water interface can form strong hydrogen bonds with water, so
exhibiting a major tendency of the proton to be shared with
water, thus pointing to a higher acidity (pKa value 2.9). On the
contrary, the SiO− deprotonated form of this convex geminal
can be more easily stabilized by the presence of nearby OH
groups from other surface silanols, which in this nested
configuration are particularly prone to solvate the silanolate
base. Overall, the convex conjugated base is 3-fold coordinated,
whereas the concave conjugated base is only 2-fold
coordinated. The same conclusion seems to hold for the
vicinals, where the acidic site has a 3-fold coordinated
conjugated base, whereas the more basic site has a 2-fold
coordinated base. We believe this special anion solvation is the
key element to explain the higher acidity of some of the Q2
geminal and some of the Q3 vicinal silanols at the amorphous
aqueous silica surface. The corollary is that both Q2-geminal 2
and the Q3-isolated silanols form weaker H-bonds with the
solvent, and more importantly their conjugated bases are not
stabilized by a substantial H-bond network. This is the key
element for the basic character of the Q3-isolated silanol at the
silica amorphous aqueous interface, and the intrinsic flexibility
of the silica framework that stabilizes the overall H-bond
network on the surface.
Our analysis supports and explains the acidity bimodal
character of amorphous (this work) and crystalline silica
silanols (this work and ref 17), as the result of local H-bond
organization and strength, that can lead to a strong stabilization
of the silanolate base. We have indeed shown that the essential
element resides in the stabilization of the conjugated base of the
silanol site, by local interactions with the surface and water. The
H-bond network that can be formed around the conjugated
base is the key factor to understand the ranking in acidity of
silica silanol sites.
■
AUTHOR INFORMATION
Corresponding Author
*M. Sulpizi. E-mail: sulpizi@uni-mainz.de.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Johannes Luetzenkirchen and Alvaro Cimas for
useful discussions and careful reading of the manuscript.
Computer time from HRLS (Hermit) is greatly acknowledged
(project number 2DSFG).
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