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Surfaces, Interfaces, and Catalysis; Physical Properties of Nanomaterials and Materials

Increased Acid Dissociation at the Quartz/Water Interface
Shivam Parashar, Dominika Lesnicki, and Marialore Sulpizi
J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.8b00686 • Publication Date (Web): 10 Apr 2018
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8 Increased Acid Dissociation at the
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Quartz/Water Interface
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15 Shivam Parashar,† Dominika Lesnicki,‡ and Marialore Sulpizi∗,‡
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18 †Department of Chemical Engineering, Indian Institute of Technology Roorkee, India.
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20 ‡Institute of Physics, Johannes Gutenberg University Mainz, Staudingerweg 7, 55099
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22 Mainz, Germany
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25 E-mail: sulpizi@uni-mainz.de
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27 Phone: +49 6131 39 23641. Fax: +49 6131 39 25441
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Abstract
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6 As shown by a quite significant amount of literature, acids at the water surface tends
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8 to be "less" acid, meaning that their associated form is favored over the conjugated base.
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10 What happens at the solid/liquid interface? In the case of the silica/water interface
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we show how the acidity of adsorbed molecules can instead increase. Using a free
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13 energy perturbation approach in combination with electronic structure -based molecular
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15 dynamics simulations, we show how the acidity of pyruvic acid at the quartz/water
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17 interface is increased of almost two units. Such increased acidity is the result of the
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19 specific microsolvation at the interface and in particular of the stabilization of the
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21 deprotonated form by the silanols, on the quartz surface, and the special interfacial
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23 water layer.
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27 Graphical TOC Entry
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30 Pyruvic acid
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33 pKa = -1.85
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36 Quartz 0001

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Introduction
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6 The acid dissociation constants of molecules in bulk aqueous solution are routinely deter-
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8 mined using techniques like potentiometric titration, voltammetry, and electrophoresis. 1 A
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10 more complicated task is to measure dissociation constants at interfaces since the signal orig-
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12 inating from bulk molecules typically overwhelms that from surface molecules. The advent
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14 of interface selective vibrational spectroscopy techniques, capable to probe the molecular
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16 structure of the nanometric layer of a liquid interface, has recently permitted to selectively
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18 address properties of molecules at interfaces, also providing information on the degree of
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20 proton dissociation.
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22 Pioneering interface selective spectroscopic studies of acid/base pairs have shown that
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24 the surface favors the neutral form of the acid/base pair in comparison to the bulk. 2 For in-
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26 stance, using second harmonic generation (SHG) and vibrational Sum Frequency Generation
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28 (VSFG), it has been shown for phenol and carboxylic acids that the neutral acid species is
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30 favored over the anionic conjugate base. 3–5 Similarly, it was found for molecules containing
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32 an acid ammonium group that the neutral amine base species was favored over the cationic
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34 quaternary ammonium acid. 6,7 Nitric acid, known as a strong acid in bulk aqueous solution
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36 was also investigated at the water/air surface. Its dissociation does not occurs at the water
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38 surface while generally occurs in the first and second surface layers depending on the acid’s
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40 orientation and its solvation. 8–11 Amino acids, such as L-alanine and L-proline studied by
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42 VSFG present a reduced acid dissociation at the water surface. Higher pH values are re-
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44 quired to induce the dissociation of carboxylic acid groups of molecule at surface. 12 Tahara
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46 and coworkers have evaluated the pH at model biological membranes (lipid/water interfaces),
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48 which substantially deviates from the bulk pH. The pH at the lipid/water interface is higher
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50 than that in the bulk when the head group of the lipid is positively charged, whereas the pH
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52 at the lipid/water interface is lower when the lipid has a negatively charged head group. 13
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54 Now the question is what happens instead at the solid/liquid interface? The solid surface
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56 may contain hydrophilic groups (such as silanols in the case of quartz and silica), as well as
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ions, which can influence the dissociation constant. Can the situation effectively be reversed?
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Are hydrophilic surface enhancing the acid dissociation? Experimental investigation of acid/
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base equilibrium at "buried" solid/liquid interface are more difficult. The group, e.g. of V.
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9 Grassian has been extensively studying adsorption and dissociation of strong and weak acids
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11 on silica particles, 14,15 however it is challenging for such experiments to quantify a change in
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13 the acidity upon adsorption at the solid/liquid interface. Some recent computational studies
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15 in the group of R.B. Gerber have evidenciated fast deprotonation of HCl and H2 SO4 on quartz
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17 surface covered by a water monolayer, 16,17 although, again, a quantitative measument of the
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19 acidity on such surface (and in comparison to liquid bulk conditions) was not provided.
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21 The group of D. Marx has recently addressed with accurate free energy calculations, also
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23 including nuclear quantum effects, the issue of acid dissociation in HCl-water clusters, and
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25 has shown that, a minimum of four water molecules is needed to stabilize the fully dissociated
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27 solvent-shared ion pair at low-temperature and thus to create the smallest droplet of acid. 18
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29 In order to answer the question if adsorption at the solid/liquid interface can enhance acid
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31 dissociation, we will discuss in details the dissociation of pyruvic acid, the simplest α-keto
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33 acid, at silica/water interface. Pyruvic acid plays a key role in the intricate chemistry of the
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35 atmosphere as intermediate in the oxidative channels of isopropene and of secondary organic
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37 aerosols. 19 Silica is the main component of mineral dust particles in the atmosphere, and
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39 reactions on its surface, in presence of variable levels of humidity, and also including proton
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41 dissociation, have a direct impact on radical concentration and the ability of dust particles
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43 to serve as cloud condensation nuclei or ice nuclei. 20 Noticeably, the dissociation constant
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45 of pyruvic acid (bulk pKa 2.5) is close to the point of zero charge of α-quartz surface, 21,22
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47 therefore pyruvic acid and silanols may compete for protons at the quartz surface. For
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49 example, we have shown that on the quartz 0001 surface two species of silanols exists, with
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51 the most acidic one, represented by the out-of-plane silanols presenting a pKa of 5.6. 21
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53 Similarly at the amorphous silica/ water interface we also found that some convex geminals
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55 groups, as well as some type of vicinals are very acid with pKa of 2.9 and 2.1, respectively, 23
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therefore very close to the pKa of bulk pyruvic acid of 2.5.
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Anticipating our results, we find that pyruvic acid acidity is enhanced at the quartz/water
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interface, of almost two units. This result is quite interesting, since it goes in the opposite
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9 direction of what normally found for acids at the water/vapor interface. As we will explain
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11 in details in this Letter, such increased acidity is the results of the specific micro-solvation
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13 around the acid/abase groups and, in particular, of the stabilization of the conjugated base
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15 by the silanols groups on the quartz surface.
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17 In order to obtain a detailed microscopic understanding of the interface pKa variations,
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19 molecular modeling at the atomistic level is required. In particular, using ab initio molecular
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21 dynamics simulations, the acidity constants will be computed using the reversible proton
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23 insertion/deletion method 24,25 that we already applied to a wide range of chemical groups,
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25 also at solid/liquid interface. 21,23,26,27 Since our approach permits to explicitly take into
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27 account the solvent and its specific interaction with the molecule as well as with the surface,
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29 we will be able to pin down the origin of the pKa changes in terms of molecular orientation
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31 and local hydrogen bond strength. The inclusion of the full electronic structure will permit
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33 to address anharmonicity and polarization effects, which cannot be easily incorporated in a
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35 simpler empirical force field approach.
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37 We compute the pKa difference between the acid at the interface and the acid in the bulk,
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39 using a thermodynamics integration which transforms the acid into its conjugated base. We
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41 consider the α-quartz 0001 surface in contact with water in the neutral, fully hydroxilated
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43 form. As schematically shown in Fig.1 we actually transform a model system which contains
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45 the acid (AH) at the interface and the conjugated base (A-) in the bulk (left panel in Fig.1)
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47 into a system which contains the base (A-) at the interface and the acid (AH) in the bulk
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49 (right panel in Fig.1).
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51 The difference in pKa ’s between interface and bulk (∆pKa = pKaI − pKaB ) is then given
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3 AH =
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AH A-
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14 (a) E0 (b) E1
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16 Figure 1: The model used for the calculation of ∆pKa value. On the left side the protonated
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18 form of pyruvic acid (AH) and the deprotonated form (A− ) are shown. Schematic view of
19 the simulation setup (a) the initial state with protonated acid (AH) at the interface and
20 deprotonated acid (A-) in the bulk. (b) the final state with the acid in the bulk (AH) and
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25 by the following equation:
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28 (∆dp AAH )I − (∆dp AAH )B
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33 where (∆dp AAH )I,B is the deprotonation free energy for interface (I) and bulk (B), respec-
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35 tively, and can be calculated with the thermodynamic integration approach. We remand the
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reader to the Supplementary Information for all the details of the method implementation.
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DFT based Born-Oppenheimer molecular dynamics (DFTMD) simulations were per-
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formed using Becke exchange 28 and Lee, Yang and Parr 29 correlation functionals. All calcu-
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lations have been carried out with the freely available DFT package CP2K/Quickstep which
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is based on the hybrid Gaussian and plane wave method. 30 Analytic Goedecker-Tecter-Hutter
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pseudopotentials, 31,32 a TZV2P level basis set for the orbitals and a density cutoff of 280
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Ry were used. Dynamics were conducted in the canonical NVT ensemble with a timestep
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of 0.5 fs using the CSVR thermostat with the target temperature of 330 K to avoid the
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glassy behavior of BLYP water and a time constant of 1 ps. A periodic orthorhombic box
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of dimensions 19.64×17.008×43.5 Å is considered (see Supplementary Material for details
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of the system preparation). For each simulation, an equilibrium trajectory of 5 ps and an
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additional production run of 20 ps was used for the ∆pKa calculation.
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For both bulk and interface the most stable Tce isomer was considered. At the interface
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9 the acid is stabilized in a configuration with the heavy atoms plane parallel to the quartz
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11 surface. The acid remains localized within the first adsorbed layer of water, as shown by
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13 the position of the center of mass in Fig. 3 of the SI. In the protonated form the binding
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15 between pyruvic acid and the surface silanols is not direct, but mediated by a water bridge
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17 (see for example a snapshot from the simulation in Fig. 4 (b)). Additionally the methyl
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19 group of pyruvic acid also accommodates on the hydrophobic patch on the quartz surface
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21 (see Fig. 2 for a top view perspective). Such binding configuration is quite stable along the
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23 simulation trajectory as shown by the time traces reported in Fig. 2. Essentially pyruvic
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25 acid acid cannot freely diffuse at the interface, but remains quite strongly localized.
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48 Figure 2: Top view of the (0001) α-quartz interface where the pyruvic acid is located (position
49 in Å). Dots represent the average position of the Si (yellow), O (red) and H (black) atoms
50 from the quartz interface. The lines represent the time traces (position as function of time)
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of the center of mass (cyan), the methyl group (magenta), the oxygen (red) and hydrogen
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53 (black) atoms from the pyruvic acid and the oxygen atom (blue) from the water bridge.
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56 From our calculation we find that the interfacial pyruvic acid is more acidic than the one
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in the bulk by 1.84 pKa units. The easier deprotonation at the quartz/water interface can
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be understood through an analysis of the solvation structure around both protonated and
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deprotonated species. In particular we will discuss the solvation structure in terms of radial
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9 distribution functions and coordination numbers, specifically defined for the solid/liquid
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11 interface as described in the Supplementary Material.
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(a) HAH - Ow (b) OA_ - Hw
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rdf

rdf
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0 2 4 6 8 0 2 4 6 8
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Figure 3: Radial distribution functions between (a) the hydrogen atom of the protonated
32 pyruvic acid (HAH ) and the oxygen atoms of the water solvent (Ow ) (acid in bulk in black,
33 acid at the interface in red), (b) the oxygen atom of the deprotonated pyruvic acid (OA− )
34 and the hydrogen atoms of the water solvent (Hw ) (conjugated base in bulk in black, at the
35 interface in red. The rdf between OA− and the silanol proton (HSi ) is also reported (red
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dashed line, y axis values readable on the right).
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40 In the protonated form the solvation structure around the OH group is similar when
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42 comparing bulk and interface. In both cases the OH group donates a relatively strong
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44 hydrogen bond, which however is slightly shorter at the interface (red line in Fig. 3, position
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46 of the first peak at 1.61 Å) than in the bulk (black line in Fig. 3, position of the first peak
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48 at 1.71 Å). This first observation would suggest that at the interface the proton is more
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50 keen to leave its oxygen. Such a difference in the local solvation is the result of the different
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52 water behavior in the bulk and at the interface. At the interface the interaction with the
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54 hydrophilic surface renders the water molecules in the first adsorbed monolayer quite special.
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56 Such waters have indeed much slower orientational and diffusion dynamics than those in bulk
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39 Figure 4: The H-bonds formed between the protonated/deprotonated pyruvic acid and the
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surrounding atoms: (a) protonated acid in the bulk water, (b) protonated acid at the in-
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42 terface, (c) deprotonated acid in the bulk water and (d) deprotonated acid at the interface.
43 Color code: Si, yellow; C, blue; O, red, H, white.
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water. As a result the hydrogen bond established between the interfacial water molecule and
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the OH group of pyruvic acid has a life time, larger than 20 ps, which even exceeds the
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simulation length.
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9 When we compare the behavior of the conjugated base (at the interface and in the
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11 bulk) we also notice interesting differences. Indeed while in the bulk the conjugated base is
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13 stabilized accepting hydrogen bonds from water (with an average number of Hbonds in the
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15 first shell of 2.64), at the interface it is stabilized by hydrogen Hbonds from water (on average
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17 1.87), but additionally also by accepting hydrogen bonds from a surface silanol (on average
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19 0.58). The hydrogen bond established with the silanol (dashed red line in Fig.3) is shorter
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21 (1.69 Å) than that accepted by water (continuous red line in Fig.3(b), position of the first
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23 peak at 1.85 Å). The shorter hydrogen bond is due to specific properties of the OH group in
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25 the silanols. As we have already shown in our previous work, 21,23 silanols may have acidity
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27 constants as low as 5, substantially lower than water, in turn establishing stronger hydrogen
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29 bonds than water. The silanols have therefore a special role in stabilizing the conjugated
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31 base and therefore in favoring the deprotonated form of pyruvic acid at the interface.
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33 The solvation behavior observed for pyruvic acid at the quartz/water interface is certainly
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35 not unique, and indeed a similar mechanism for the conjugated base stabilization could be
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37 in place also for other acids at hydroxilated interfaces. Of course the propensity to localize
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39 at the interface is strongly depending on the degree of hydrophilicity and hydrophobiticity
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41 of the acid as well as that of the solid surface.
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46 Acknowledgement
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49 This work was supported by the Deutsche Forschungsgemeinschaft (DFG) TRR146, project
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51 A4. All the calculation were performed on the supercomputer of the High Performance
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53 Computing Center (HLRS) of Stuttgart (grant 2DSFG).
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Supporting Information Available
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6 • Theory on the pKa calculation using thermodynamics integration
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9 • Simulation details
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12 • Vertical energy gaps
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15 • Radial distribution function in presence of an interface
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