Article

Cite This: J. Phys. Chem. B XXXX, XXX, XXX−XXX pubs.acs.org/JPCB

Moving Water Droplets: The Role of Atmospheric CO2 and Incident

Radiant Energy in Charge Separation at the Air−Water Interface
Magdalena Kowacz* and Gerald H. Pollack
Department of Bioengineering, University of Washington, Box 355061, Seattle, Washington 98195, United States
*
S Supporting Information

ABSTRACT: One of the characteristics of aqueous interfaces is their

negative charge, whose origin is still a subject of scientific debate. In this work,
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we provide spectroscopic evidence that bicarbonate anions, from dissolution

of atmospheric CO2, can be a source of negative charge at the air−water and/
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or solid−water interface. Also, interfacial charge separation, with a negatively

charged droplet rim and positive charges gathering more toward the interior,
makes water droplets receptive systems. We found that these droplets move in
a controlled fashion because of electrostatic forces acting between droplets
and a solid support possessing a static electric charge. A trigger used to induce
droplets’ motion is IR emitted by different common objects. We interpret IR
action as resulting from its ability to enhance the negative charge of the interfacial water. Droplets that leave negatively charged
residues adsorbed to the solid, therefore acquiring a net positive charge, can defy the force of gravity and jump off the charged
surface instead of falling, as observed in our experiments. Insights obtained from infrared emission of water agree with the
possibility of excess protons residing in droplets after their contact with the solid. Our results show that (i) aqueous interfaces in
contact with CO2 gas from the atmosphere (or possibly from cellular respiration inside of the organisms) acquire a negative
surface charge, and (ii) infrared energy, abundant externally from the sun and internally from metabolic heat, can impact this
process.

■ INTRODUCTION
Aqueous interfaces are widespread in nature and in industrial
concentration at the interface would have to be unreasonably
high. Further, OH− surface enrichment is inconsistent with
applications. Their characteristics determine the chemistry and high solubility of bases in water, as highly soluble substances
physics of aerosols and that of the sea-surface microlayer. cannot be surface active at the same time. Therefore,
Processes at the solid−liquid, or liquid−liquid, interface are polarization of interfacial water molecules has been proposed
crucial for numerous areas, including rock weathering, to give rise to the negative charge of the air−water interface.12
emulsification, interaction of biomineral and soft biological Yet, computer simulations implying polarization could
structures (e.g., cell membranes) with their environments, reproduce only the sign, but not magnitude, of the charge.
water-based lubrication, design of materials with specific Also, in the case of water droplets in contact with nonpolar
wettability, etc. Yet, characteristics of the interface differ oils, both experiments and molecular simulations imply
from those of the bulk solution. This can be due to different anisotropic orientation of water molecules rather than selective
affinity and partitioning of selected solution components to the adsorption of ions to be responsible for surface charge, which
interfacial region or due to specific structural arrangements of was found to be positive at the water−oil boundary.13
the solvent molecules. Alternatively, the presence of organized liquid crystallinelike
Experimental evidence consistently implies that water− layer of water [exclusion zone (EZ)] has been suggested to
hydrophobic interfaces, of which air−water boundary is a give origin to interfacial charging.14
classical representation, are negatively charged.1,2 Also, water Recently, it has been proposed that not only intrinsic
droplets sliding on solid surfaces have been repeatedly shown components of water should be considered but also dissolved
to leave the surfaces negatively charged, while themselves air gases present in any water under environmental conditions.
acquiring a positive charge.3−8 Bubbles bursting over the ocean Thus, bicarbonate anions coming from the dissolution of
also release negatively charged droplets from their rims and atmospheric CO2 in water have been considered as a possible
positively charged jet droplets formed from the interior source of negative charges at the water−hydrophobic inter-
liquid.9,10 The nature of the charge bearing species is still face.15,16 Such a conclusion was supported by experimental
debated. Protons and hydroxides (from autolysis of water) are observations, strongly implying, but not explicitly showing, the
the most often invoked candidates.1,2,11 Yet, preferential
accumulation of OH− at the water surface, although consistent Received: September 27, 2019
with charge measurements, has been recently considered Revised: December 5, 2019
unlikely.12 To account for the registered zeta potential, OH− Published: December 6, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcb.9b09161

J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

presence of bicarbonate ions at the interface and calling for by the negatively charged Petri dish and repelled by the
further evidence for the latter. Yet, calculations based on positively charged one.
surface tension measurements imply that neither selective After the Petri dish acquired a static charge, water droplets
adsorption of ions coming from autoprotolysis of water nor were released either from the tip of an automatic pipette
those from dissolved air gasses can account for water surface (Rainin, Bioclean), or from a syringe through a stainless-steel
characteristics.17,18 Presence of charged surface-active impur- needle, and placed on the surface of a Petri dish that was not in
ities is then suggested to explain the measured zeta potential previous contact with any other material (triboelectric charging
and other properties of the water interface.17,18 was achieved by rubbing the other side of the dish with the
Water droplets undergoing phase transition (evaporation or respective material). Different solid objects were subsequently
condensation) have been shown to acquire net charge because positioned underneath the dish. They included a finger (with
of nonequilibrium partitioning of OH− and H+ charge carriers or without a glove), a circular polished aluminum reflector (7
between vapor and water phases.19−21 Generally, water mm in diameter), stainless steel tweezers, the rubber end of a
droplets that are out of equilibrium, and exchange materials small stainless steel spatula, folded paper wiping tissue
or energy with the environment, can become responsive (Kimwipes Kimtech by Kimberly-Clark), a wine cork, glass
systems, able to perform different functions, such as controlled (5 mm thick, cut), and Teflon (cuboidal) or Styrofoam
movement.22 Nonequilibrium systems include many kinds of (cuboidal). Movement of water droplets induced by the
water droplets in nature, such as those in the process of presence of these objects could then be observed. Positioning
evaporation, freshly deposited and interacting with the solid of the objects next to the droplets, on the same side of the Petri
surface, or absorbing/emitting particular optical wavelengths. dish, was verified to have the same effect.
Electric fields have been used to achieve controlled Droplet Movement in the Presence of Nafion.
responses of pure water droplets, expressed by inducing their Additional experiments were performed, in which a piece of
motion on a solid surface. Attraction of water droplets to the a hydrated Nafion tube (TT-030 purchased from Perma Pure)
source of charge or their self-propulsion due to droplet- was placed on a Petri dish, and water droplets were
generated nonuniformity of the field have been explained by subsequently deposited next to the tube, without contacting
water−dipole polarization, without accounting for the presence it. Spontaneous directional movement of droplets, in response
of charges at the water interface.23,24 In another study, droplet to the presence of Nafion material, was then observed.
motion in response to an electric field was suggested to result Droplets under Inert Gas. Control experiments were also
from the acquired charge on water droplets contacting a performed under an Argon atmosphere. In this case, a water
hydrophobic support.25 Predeposited water droplets, charged volume of 100 mL was bubbled with argon gas for 35 min in
by contact with ionized air, could also jump off from order to remove dissolved air gasses. A negatively charged Petri
superhydrophobic surfaces in response to a strong electrostatic dish was then placed under the stream of Ar, and droplets of
field.26 Therefore, water droplets can move in an electric field water previously bubbled with Ar were deposited onto it. The
either thanks to polarization of water dipoles or due to response of water droplets to the presence of remote objects
(acquired) net charge. was then verified under the argon atmosphere.
In this work, we address the still-debated question of Attenuated Total Reflection−Fourier Transform In-
characteristics of charges at the air−water and solid−water frared Spectroscopy. Attenuated total reflection−Fourier
interfaces. Related to the presence of charges, we analyze transform infrared spectroscopy (ATR−FTIR) was used in
induced movement of water droplets in response to previously order to get insight into the character of the air−water and
unexplored external stimuli in the form of IR. solid−water interface. A Nicolet Nexus 670 spectrophotometer

■ EXPERIMENTAL SECTION
Deionized water from a Barnstead D3750 Nanopure Diamond
(Thermo Scientific) was employed. Spectra were recorded
with 256 number of scans and 4 cm−1 resolution. OMIC
software was used to perform the analysis.
purification system and Petri dishes (35 × 10 mm, Falcon) In the ATR−FTIR technique, typical penetration depth of
were used in this work. Aqueous solutions containing either an infrared beam ranges from 0.5 to 5 μm. This is too thick to
HCl (0.01, 0.1, or 1 M), NaOH (0.01 or 0.1 M), or 0.01 M provide information about the very interfacial layer of water in
solutions of neutral salts (BaCl2 or NaCl) were also employed. contact with the crystal, whose characteristics would be
Petri dishes of different sizes and produced by different averaged over bulk liquid. On the other hand, the beam
manufacturers were tested, and the same phenomena could be penetration depth is not sufficient to reach to and scan air−
observed. water interface through the film of water. Therefore, in order
Droplet Motion on Charged Surfaces in Response To to access the air−water−solid contact line (Figure 1, upper
Remote Objects. Before depositing water droplets, Petri scheme), instead of depositing a layer of liquid onto the ATR
dishes were either negatively or positively charged. For that crystal, we deposited an array of discrete water droplets. Then,
purpose, Petri dishes were gently rubbed with different we analyzed the difference in the spectra of the droplets that
materials, usually a lab coat or filter paper, to obtain static were air-exposed or placed in a closed chamber (by covering
negative charges, or a laboratory glove taken freshly from the the ATR crystal with deposited droplets with a dedicated lid in
box to acquire positive charges. The magnitude and sign of the the latter case), termed “open” and “closed” configuration,
acquired static charge was measured with the use of a surface respectively (Figure 1a,b). When changing the configuration
dc voltmeter (AlphaLab Inc.). The sign of the charge was from closed to open, air flow increases and encourages
additionally verified by approaching the respective Petri-dish enhanced droplet evaporation. This allows us to register
surface with a cellulose acetate sheet, which is at the positive minute changes at the air−water−solid contact line on
end of the triboelectric series, as opposed to polystyrene evaporation.
(material of which a Petri dish is made), which charges ATR−FTIR of Evaporating Droplets. In order to verify
predominantly negative. The sheet was then strongly attracted that observed changes in the infrared spectra of water droplets
B DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

Figure 1. ATR crystal with deposited water droplets in open (a) and
closed (b) configuration.

are due to evaporation, control experiments were performed, in

which droplets were left on the ATR crystal and allowed to
completely evaporate. Spectra of the remaining residue were
measured and compared with the spectral characteristics
developing in droplets exposed to enhanced air flow in open-
chamber configuration. An additional factor that could
potentially contribute to the differences observed between
open and closed configuration was ambient light. Hence, its
potential impact was excluded by performing control experi-
ments in a completely light-shielded environment.
Effect of a Remote Object on ATR−FTIR Spectra of
Water. To investigate spectral features developing in water
droplets exposed to a remote object, an aluminum plate was
positioned 2.5 cm above the droplets deposited on the ATR
crystal, and the spectrum was registered. The experimental
configuration allowed for unrestricted air flow. Therefore, the
only variable in these experiments was the presence of the
aluminum plate.
Emission in the Infrared. The infrared radiation emitted
by the water droplets was observed with the use of an infrared
sensing camera (ThermoVision SC-6000, FLIR Systems) with
a spectral sensitivity range between 3 and 5 μm in wavelength.
Software used for visualization of the data was ExaminIR
1.2.0.1076 (FLIR Systems). ExaminIR generates a false-color
image, with different colors or shades representing the
intensities of the infrared radiation emitted by the object and
received by the InSb detector.

■ RESULTS AND DISCUSSION

We found that remote stimuli, in the form of different solid
objects, can induce movement of water droplets on the surface
of a Petri dish possessing a static electric charge. The behavior
of the droplets depended upon the sign of the charge of the
solid support (here a Petri dish).
Droplet Movement on a Negatively Charged Sup-
port. On negatively charged surfaces, water droplets were Figure 2. Water droplets lying on a negatively charged Petri dish
always repelled by the remote solid objects placed underneath sliding away from the finger approaching the surface from the
the Petri dish containing the droplets (Figure 2, Movie S1). underneath. Red (greenish) dotted lines and red (greenish) arrow
For inducing droplet motion, the most effective objects were designate changes in the position of a large (small) droplet in
the human finger and aluminum, followed by stainless steel, response to the stimuli (a fingertip). Consult the Movie S1

C DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

Figure 2. continued Droplets responded to the stimulus only if the object placed
underneath touched the positively charged surface of the Petri
(Supporting Information) to see droplets in motion. Note larger dish (contact mode). Failure to touch elicited no motion.
droplet repelling the smaller one when approaching it. Furthermore, water droplets moving on a positively charged
support attracted each other, easily coalescing. They were also
paper tissue, cork, rubber, and glass. Yet, materials that were attracted to the edges of the Petri dish.
absolutely ineffective for this purpose were Styrofoam and Droplets Jumping off the Solid. We also observed a
Teflon. On a negatively charged surface, droplet motion could frequent event, when droplets released from the pipette tip,
be easily induced without physical contact between the support positioned above the Petri dish, never touched the dish, but,
and the object (termed contactless mode). Droplets also overcoming the force of gravity, jumped away from the surface
responded to remote stimuli (solid objects placed at some instead of falling (Figure 5, Movie S4). We were able to
distance from the Petri dish) and moved easily against the identify spots on the surface of the Petri dish that were
force of gravity, sliding upward on a vertically positioned solid effective in rejecting water droplets.
support (motion path perpendicular to earth’s surface).
Therefore, a droplet (that would otherwise slide down, pulled
by gravity) could climb upward along the surface of a Petri dish
when repelled by a remote object (e.g., a fingertip).
Furthermore, moving water droplets repelled each other and
were repelled from the edges of a Petri dish. They were also
repelled from a hydrated Nafion tube, with larger droplets
spontaneously sliding away from the Nafion (Figure 3, Movie
S2).

Figure 5. Sequence of images showing the water droplet released

from a pipette tip and jumping off the tip instead of falling toward the
surface of a charged Petri dish. (The droplet and its motion path have
been color edited for better visualization.) Consult Movie S4
(Supporting Information) to see the process.
Figure 3. Water droplets sliding away from the hydrated Nafion tube.
All droplets had been deposited at the same distance from the tube.
Droplets of larger volume spontaneously moved farther away. For In summary, water droplets could be repelled by different
details, consult Movie S2 (Supporting Information). solid objects or by other droplets when residing on a negatively
charged solid support. On the contrary, if deposited on a
positively charged surface, droplets were attracted by solid
objects and by each other.
The ease of movement (repulsion) in response to the stimuli Electrostatic Repulsion of Water Droplets and the
generally increased with the increasing droplet volume. Nature of Charges. The most common explanation for the
Droplet Movement on a Positively Charged Support. behavior of water in response to nearby charged objects/
On a positively charged surface, on the other hand, water surfaces takes into consideration the possibility of the
droplets were attracted by remote objects, in this case mainly orientation of water dipoles at the liquid interface by an
the human finger, and followed its movements (Figure 4, externally imposed electric field.27,28 Such an approach implies
Movie S3). attraction between polarized water molecules and the source of

Figure 4. Water droplet on a positively charged Petri dish following movement of a finger along a curved path. Red dotted lines designate the
reference (start and end) position of the droplet. Consult Movie S3 (Supporting Information) to see droplets in motion.

D DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

charge (e.g., bending of water stream by the static electricity, or

electrowetting phenomena). Nevertheless, observed events of
droplet repulsion (by other droplets, container edge, Nafion,
remote objects, or the surface of a Petri dish) cannot be
explained by realignment of water molecules. The latter always
assumes attraction. Repulsion would require that (i) dipoles
are fixed and cannot reorient in response to electric field or
that (ii) a droplet and the other body (e.g., solid surface or
water droplet) possess net charge of the same sign.
Negative Charge of Air−Water and Solid−Water
Interface. In order to explain water-repulsion phenomena
and to gain insight into the nature of charges at the air−water
interface, we performed ATR−FTIR analysis of water droplets.
On changing droplet’s environmental conditions from closed
to open chamber configuration (enhanced evaporation), we Figure 7. ATR−FTIR spectra of residue left after water−droplet
could obtain information about the interfacial species at the evaporation (a and b) and difference spectra showing absorption
air−water−solid contact line. This is because exchange of peaks developing in the process of droplet evaporation (c). Note, on
energy and matter takes place across this three-phase contact progressive dehydration (from partialc to complete droplet
evaporationa and b), splitting of the peak ascribed to the hydrated
line, and consequent changes are expressed in the IR difference bicarbonate anion (highlighted in yellow) into three new peaks (stars,
spectra. Evolution of the absorption peak at 1638 cm−1, a and b) and increased intensity of the carbonate anion peak (dotted
generally ascribed to surface-adsorbed hydrated bicarbonate oval, a and b).
anions (HCO3−), could be clearly identified in evaporating
droplets. Also, the appearance of surface-bound carbonate
for surface deposition of (bi)carbonate ions. Rather, our
anions (CO32−) could be detected as indicated by an
experimental approach enabled us to gain insight into the
absorption peak at 1541 cm−1 (Figure 6).29,30
intrinsic character of the water interface by analyzing its
changes on evaporation.
It is instructive to consider at this point that the 1638 cm−1
absorption band, ascribed to HCO3− anions, can in fact be a
combination of spectral features coming from the bicarbonate
anion and from water hydroxy groups. This is because
absorption at 1638 cm−1 originates from OH vibrations that
can belong to either water or bicarbonate ions. Therefore,
negative charge at the solid−water interface could result from
the presence of ions not only from CO2 dissolution but also
from water’s intrinsic components. It has been recently argued
that interfacial accumulation of OH− is unlikely.12 Yet, specific
alignment of water molecules was proposed in this computer
simulation study to account for the experimentally observed
negative charge.12 Experimental studies have shown the
possibility of development of an extensive negatively charged
Figure 6. ATR−FTIR difference spectra between water droplets in
closed and open chamber configuration. Spectra show absorption
hydration layer (termed EZ water) due to water’s internal
peaks generally ascribed to surface-adsorbed bicarbonate (highlighted structuring near interfaces.31 Thus, surface-induced specific
area) and carbonate (dotted oval) anions developing as the droplets orientation of water molecules giving rise to the negative
evaporate. charge should also be considered a likely scenario on the basis
of our spectroscopic data.
Charge Separation at the Air−Water Interface. The
The residue left after complete droplet evaporation (Figure source of HCO3−/CO32− ions is of course atmospheric CO2.
7) confirms the presence of adsorbed CO32−, whose The calculation of Uematsu et al.17,18 predicts an equilibrium
contribution greatly increases on dry surfaces (as evidenced concentration (c) of species in water in contact with
by relative increase in peak height) and might suggest a
atmospheric air as cH3O+ = 10−5.6 M, cOH− = 10−8.4 M, and
HCO3− to CO32− transition on dehydration. The band
corresponding to hydrated HCO3− splits into three peaks cHCO 3− = 10−5.6 M. Yet, for out of equilibrium (e.g.,
(1736, 1598, and 1376 cm−1), which can be attributed to evaporating) water droplets exchanging energy and matter
different surface speciation of (bi)carbonate ions or very labile across the interface with the environment, the actual
surface-bound CO2.29 The splitting is in agreement with concentration of species can vary from the interface to the
different band positions of surface-adsorbed HCO3−/CO32− bulk. Regarding the mechanism, recent findings show that CO2
recognized in dry and wet systems.29 dissolves in water by first forming HCO3− and H3O+ that
Therefore, on droplet evaporation, negatively charged remain water separated and cannot easily recombine to yield
(bi)bicarbonate species appear to partition onto the solid H2CO3.32 This agrees with other results, indicating that
surface. To the best of authors’ knowledge, this is the first H2CO3 is preferentially dissociated at the air−water inter-
spectroscopic evidence for (bi)carbonate ions contributing to a face.33 Furthermore, hydrogen bonding to the hydroxyl group
negative charge at the air−water and/or solid−water interface. of the bicarbonate anion was found to be particularly
It is reasonable to assume that evaporation is not a prerequisite unfavorable,34 giving it a certain propensity to reside at the
E DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

interface and separate from the bulk solution. Our charge of water, conflicts with the results of many studies (ref
experimental observations agree with computational predic- 12 and references therein). Therefore, other species or
tions, inferring the presence of HCO3− at the water interface.35 mechanisms contributing to the negative charge of the water
Strongly hydrated CO32−, on the other hand, prefers bulk surface have to be considered. In our case, dissolution of CO2
hydration35 and appears at the solid surface rather as a result of seems indispensable, as no motion can be induced without its
surface transformation of bicarbonate anions (as inferred from presence.
our spectroscopic observations). Then, diffusivity of hydro- Charge-Separation and Droplets on a Charged
nium is much faster than that of the bicarbonate.36 Therefore, Support. At a negatively charged surface, water droplets,
when HCO3− and H3O+ are generated at the interface because with the negative charge of their outermost layer, are repelled
of CO2 dissolution, H3O+ ions diffuse quickly into the bulk from each other and from the negatively charged edges of the
solution leaving bicarbonate anions at the interface. This container. They are also pushed away from a hydrated Nafion
creates effective charge separation with the negatively charged tube, a material with negatively charged functional groups
interface and positively charged interior (of a droplet e.g.). In generating negative potential in its interfacial water.40
fact, charge separation induced by CO2 dissolution has recently On a positively charged surface, droplets are attracted to the
been employed to propose a membraneless filtration system.36 positively charged edge of the container and to each other. The
In that system, negatively charged particles are repelled from latter behavior can be explained by the presence of unlike
the negative charge of the water interface, induced by (positive) charges residing at the solid support and mediating
dissolution of CO2. Particles are then concentrated at some mutual attraction of negatively charged droplets.41−43 Also,
distance from the interface where protons, which diffuse creating a larger droplet (by coalescence) increases the surface
rapidly to the bulk, accumulate. area of the contact of a negatively charged droplet with a
Recent calculations predict a rather low affinity of positively charged support. As consequence, droplet coales-
bicarbonate ions to the air−water interface, thus suggesting cence enhances favorable interactions between the droplet and
that dissolved air gases cannot account for the negative surface the support.
charge of the interface and that surface-active impurities should Charge Splitting at the Solid−Liquid Interface and
be considered.17,18 In order to verify that CO2 dissolution in the Net Droplet Charge. Interfacial charge separation,
water is a prerequisite to the droplet behavior observed in our meaning H3O+ diffusing to the bulk and HCO3− residing at the
experiments, we deposited water droplets on a charged Petri air−water interface, together with the propensity of bicar-
dish under an Ar atmosphere. In this case, no motion could be bonate ions to the solid surface, may explain why droplets
induced. Therefore, the presence of charged impurities alone sliding off the solid leave its surface negatively charged. HCO3−
cannot explain droplets’ responsivity, as impurities should not ions are being adsorbed, while droplets themselves gain
be affected by the changing gas atmosphere. It seems positive charges as excess protons (coming from CO 2
reasonable that the role of dissolving CO2 in providing charge dissolution) are left in the water. Adsorption of the bicarbonate
separation is especially important for out of equilibrium anion could happen in addition to the intrinsic water charge
droplets. Droplets in contact with atmospheric air of low carriers, protons, and hydroxide ions, that can also partition
relative humidity (as in the lab environment) evaporate between the solid and liquid.39
throughout their large surface areas. Because of evaporative The net positive charge of water droplets that develops after
cooling, CO2 gas, whose solubility in water depends strongly their contact with the solid surface (e.g., a pipette tip) enables
on temperature, is constantly dissolving.37,38 CO2 dissolution us to explain the apparent droplet rejection by charged
gives rise to HCO3− and H3O+ that can migrate toward droplet surfaces. If a like-charge spot of high charge density resides on
interior with different velocities (as shown, e.g., in experiments the surface, a strong enough repulsive force can be generated
on membraneless filtration.36 to counteract the force of gravity and prevent the droplet from
Our experiments on droplet motion under different pH and falling. It has been recognized that the static charge developing
varying solution compositions point toward the important role on a surface on contact electrification (as in a process of
of protons. Droplets were observed to remain mobile under rubbing a Petri dish against another material) has a mosaiclike
highly acidic conditions of 0.1 M HCl but became immobile character.44 Discrete positively and negatively charged patches
when the aqueous phase contained 0.01 M NaOH. At basic bear substantially a higher charge than that measured as a net
pH, protons generated from CO2 dissolution combine with surface charge.44 We were able to identify spots that were most
OH− to give a water molecule. Droplets containing solutions of likely to reject falling droplets in our experiments. As identified
neutral salts exhibited similar mobility as pure water droplets. with the use of a polarizing filter, these were places of increased
Therefore, protons seem a prerequisite for assuring interfacial strain in the plastic (Figure 8).
charge separation. This could be due to their faster migration It has been shown previously that strained areas are charged
toward bulk solution in comparison to HCO3−.36 differently (usually positively) than the rest of the surface, with
It is important to mention that charge splitting at the solid− the possibility of the charge of the strained area being opposite
water interface takes place also in pure water droplets without to that of the surrounding.45 Therefore, interaction between a
dissolved atmospheric CO2 gas (as demonstrated in previous droplet possessing a net positive charge and positive charges at
experiments under N2 atmosphere).39 Therefore, intrinsic the Petri dish can result in mutual repulsion. It seems that the
water components, H+ and OH−, definitely contribute to repulsive interaction can be strong enough to make the droplet
charge separation, as inferred also from experimental results on jump off the surface against the force of gravity.
the splitting of charges within interfacial water (termed EZ Splitting off the charges between the surface and the droplet,
water with its characteristic negative charge).31 Yet, this and leaving the latter with net positive charge, provides
mechanism itself may not suffice for making the droplets understanding for droplet repulsion from a like-charged
responsive to the stimuli applied in our work. The excess of surface. Yet, our experimental observations made with the
interfacial OH−, that could result in the measured surface use of an infrared camera imply that such positive charging has
F DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

IR Supporting Interfacial Charge Separation. Inter-

facial charge separationnegative species residing at the
interface and hydrated protons more toward the bulkallows
us to explain the behavior in droplet−droplet and droplet-
charged surface scenarios, alike. The interactions appear to be
governed by electrostatic forces. Yet, the response of water
droplets to remote noncharged objects requires identification
of a stimulus that provokes the movement. Dissolution of CO2,
giving rise to HCO3− and H3O+, fuels directional ion-specific
distribution of charges near the air−water interface.36
Furthermore, water molecules themselves can align or split
near the interfaces and contribute to charge separation and the
negative surface charge.12,31 Our experimental observations
Figure 8. Surface of a Petri dish seen through a polarizing filter. imply that different objects may stimulate droplet movement
Colorful rings in the upper right indicate an area of increased plastic by means of emitted incident radiant energy that affects charge
strain. separation. ATR−FTIR measurements confirm that droplet
exposure to a remote object in the form of an aluminum plate
only a transient character. When water droplets move on a (material found very effective in inducing droplet’ motion)
solid support, the amount of radiant energy emitted from the promotes evolution of surface-adsorbed (bi)carbonate ions
droplets increases. Shortly after the movement, induced by and/or water OH groups (Figure 10). The same species are
remote solid objects, ceases, droplet emission equilibrates to observed on water evaporation (Figure 6). The only manner in
the level of the resting droplets (Figure 9). which an object can affect evaporation in a contactless mode is
This can be understood by considering charge splitting by emitting IR energy, a feature recognized to support
during droplet movement, that is, adsorption of negatively evaporation.48 We should emphasize at this point that water
charged species onto the solid surface, leaving their H3O+ droplets in our experiments are out of equilibrium systems,
counter-ions in the droplet interior. Those unbalanced protons exchanging with their environment mass and energy in an
residing in the droplet and stripped of their counter-ions (left evaporation process. This phase transition brings about
on the solid) should be highly mobile. When they are evaporative cooling. Also water, whose surface is cooler than
transferred along hydrogen-bonded water molecules, fluctua- the surrounding, can absorb incident radiant energy coming
tions of dipole moments are induced, giving rise to enhanced from the latter, such as the energy emitted by common objects
infrared emission.46 Yet, as shown by both experiments and used to induce droplets’ motion in our study.
theory,19−21,47 upon evaporation, protons preferentially escape IR radiation has been shown to be far more effective in
from the air−water interface, leaving the latter negatively promoting water evaporation than conductive heating.49,50
charged. Water vapor, at the same time, acquires a positive This is because IR of particular wavelengths resonates with
charge.19−21,47 Therefore, excess protons from a droplet can be specific vibrations of water molecules (libration motions) that
transferred to the vapor phase. The emission of droplet radiant are prerequisite for water molecules to be liberated to the
energy should then be reduced, as the motion of protons vapor phase.51−53 Upon evaporation, water droplets gain
stimulated by mutual repulsion will be attenuated on lowering negative charges because of nonuniform partitioning between
proton concentration inside the drop. water and vapor of intrinsic water charge carriers OH− and

Figure 9. Sequence of IR images showing changes in the droplet temperature (emitted IR energy) as the droplets move on the charged solid
support. Droplet “a” (upper row) appears hotter during motion (middle panel) and equilibrates to the temperature of resting droplets after
cessation of a movement (right panel). Droplet “b” (lower row) appears hotter when moving on a solid support (middle and right panel).

G DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

On a negatively charged solid support, water droplets are

repelled by the remote objects (e.g., fingertip or aluminum)
inducing, by means of emitted IR, development of more
negative charges at the air−water and solid−water interface
(Figure 2, Movie S1). On the contrary, on a positively charged
surface, water droplets cling to and follow the objects
enhancing the negative charge, as this supports attractive
interaction between the droplet and the surface (Figure 4,
Movie S3). Because of this mutual attraction, anchoring the
droplets to the support, on a positively charged solid, droplet
movement can be induced only in a contact mode (the object
touching the surface). This contrasts with a negatively charged
surface on which droplets slide with ease when responding to
objects in a contactless mode (motion-inducing object not
touching a Petri dish). Our results then imply that IR is able to
Figure 10. ATR−FTIR difference spectra between control droplets enhance negative charge density on water−droplet interfaces.
(deposited onto ATR crystal in an open configuration) and droplets These induced variations in the charge make droplets
exposed to an aluminum plate. Evolution of spectral features ascribed responsive systems.
to adsorbed hydrated bicarbonate (highlighted in yellow) and
Characteristics of the materials that are able to induce
carbonate (dotted oval) ions can be observed.
droplet movement further support the hypothesis that infrared
radiation is the stimulus acting on water droplets and
H+.19−21 Furthermore, when dissolved ions are present, and promoting their movement. All materials effective for that
water molecules leave the droplet surface, the concentration of purpose have polar bonds, which make them hydrophilic and
ions such as bicarbonates contributing to the negative surface emitting in the infrared range, as infrared radiation takes its
charge, increases. Then, evaporative cooling promotes further origin from fluctuations of dipole moments. Noneffective
dissolution of atmospheric CO2 and subsequent charge materials (Styrofoam and Teflon) are nonpolar, hydrophobic,
separation.38 Therefore IR-induced evaporation should in- and are thermal insulators blocking rather that emitting IR.
crease the negative charge of the droplet interface. Water evaporation (which can support development of
It is instructive to remember that negative species that negative charge) has been shown to depend primarily on the
absorb to the solid surface on evaporation are the ones present librational motions of water molecules resulting from
at the air−water interface. Therefore, the spectral features intermolecular interactions and particularly water rotations
ascribed to them, that appear after exposure to a remote object, within the hydrogen-bonded network.51−53 Librational mo-
indicate increased concentration of these negatively charged tions can be induced by infrared radiation at wavelengths
species in the interfacial region of the water droplet. In this centered around 4.65 μm (weak broad absorption) and 15 μm
context, it should be considered that, apart from promoting (strong absorption).60 In the same spectral regions lies the
evaporation, IR radiation can support directional proton absorption of different configurations of hydrated protons that
transfer.54,55 IR action can be related to collective rotations are constantly being transferred along chains of hydrogen-
of water molecules within a H-bonded network (libration bonded water molecules.46,54,61 Apparently, human skin (with
motions).56 In our case, proton transfer would be from the the human finger being very effective in inducing droplet
interface (where protons can be generated by CO2 dissolution movement) emits IR mainly in the wavelength range from 2 to
or by splitting of water molecules) to the bulk. Facilitated 20 μm with 90% of radiation at 8−15 μm.62 Cellulose-based
proton transfer further aids interfacial charge separation materials, such as paper tissue and cork, emit radiation mostly
(effectively increasing the negative surface charge). This is in in the long wavelength infrared from 7 to 20 μm and above.63
agreement with experimental results showing that IR promotes Aluminum and stainless steel act as mirrors reflecting the most
formation of an interfacial region of water, referred to as the IR radiation from the environment.64 Furthermore, all
EZ, that bears negative charge.57 The effect of IR promoting hydrophilic materials can emit around 4.65 μm because of
water vibrations and proton transfer can be related to the adsorbed moisture as this is the region at which water emits
thermophoresis phenomena if we consider that enhanced most in the infrared.65 Thus, all materials in this study found to
molecular vibrations are what manifests itself in measurements be effective at inducing droplet movement can be considered
as higher temperature. Motion of protons away from the capable of promoting water librational motions, and of
source of heat is 10−20 times faster than that of any salt ions supporting evaporation and directional proton transfer.
(such as bicarbonates);58 thus, charge separation can be Materials nonactive in the specific infrared range were also
expected in response to IR. Indeed, generation of a stable ineffective at inducing droplet movement.
proton gradient in solution was shown to be induced by a Dependence of droplet responsivity on the ability of
thermal gradient.59 materials to emit IR radiation highlights the importance of
In either scenario: evaporation, or promotion of proton this abundant form of energy in water-based processes. IR at
transfer and charge separation within a structured hydration wavelengths resonant with specific vibrations of water
layer in response to the presence of a remote object emitting molecules affects mutual alignment of water dipoles and can
IR, the interfacial negative charge density of a water droplet support directional proton transfer. The latter phenomenon
should be enhanced. Because droplet motion induced in our encourages separation of charges provided either by species
experiments results from electrostatic interactions between from dissolving air gases and/or originating from water itself.
droplets and the surface, IR-mediated increase in the negative In the latter context, IR has been previously shown to enhance
charge should affect the motion. the negatively charged layer of interfacial water (EZ water).31
H DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry B Article

■ CONCLUSIONS
In this work, we show the first spectroscopic evidence that
Notes
The authors declare no competing financial interest.
bicarbonate ions could contribute to the development of
negative charges at the air−water and solid−water interface.
Dissolution of atmospheric CO2, generating HCO3− and
■ ACKNOWLEDGMENTS
We thank the Software AG foundation (SAGST) for the
H3O+, results in interfacial charge separation, with negatively support of this work.
charged ions accumulating at the interface and hydronium
cations diffusing to the bulk. On contact with the solid surface,
bicarbonate ions can get adsorbed onto that surface, thus
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K DOI: 10.1021/acs.jpcb.9b09161
J. Phys. Chem. B XXXX, XXX, XXX−XXX