Article https://doi.org/10.

1038/s41467-023-36842-0

Vibrational signature of hydrated protons

confined in MXene interlayers

Received: 9 September 2022 Mailis Lounasvuori 1, Yangyunli Sun2, Tyler S. Mathis3, Ljiljana Puskar1,
Ulrich Schade 1, De-En Jiang 2,4, Yury Gogotsi 3 & Tristan Petit 1
Accepted: 15 February 2023

The hydration structure of protons has been studied for decades in bulk water
Check for updates and protonated clusters due to its importance but has remained elusive in
planar confined environments. Two-dimensional (2D) transition metal car-
1234567890():,;
1234567890():,;

bides known as MXenes show extreme capacitance in protic electrolytes,

which has attracted attention in the energy storage field. We report here that
discrete vibrational modes related to protons intercalated in the 2D slits
between Ti3C2Tx MXene layers can be detected using operando infrared
spectroscopy. The origin of these modes, not observed for protons in bulk
water, is attributed to protons with reduced coordination number in con-
finement based on Density Functional Theory calculations. This study there-
fore demonstrates a useful tool for the characterization of chemical species
under 2D confinement.

The hydrated excess proton is of fundamental importance in diverse Water in 2D confinement presents bulk-like water in the planar
systems ranging from biological processes1 to catalysis and fuel dimension, while being limited to thicknesses of 1-3 layers of water,
cells2. The solvation structure of a proton is usually described as the thus constituting an ideal platform to bridge the knowledge gap
Eigen cation3, where a hydronium ion is solvated by three water between clusters and bulk water. 2D confinement affects the
molecules, or the Zundel cation4, where the excess proton is equally H-bonding structure of water, leading to anomalous properties such as
solvated by two flanking water molecules. Recent theoretical and low dielectric constant12, exotic phases13 and high proton conduction14.
experimental studies are increasingly pointing to a distorted struc- Few reports detailing the spectroscopic characterization of such con-
ture, or a structure in between these two limiting cases5. Due to the fined water layers are available to date and are limited to neutral
dynamic hydrogen-bonding (H-bonding) patterns of water leading to water15–18. The hydration structure of protons under confinement
rapidly interconverting proton hydration structures, protons in bulk requires further attention. Confined protons are indeed expected to
solution display a broad vibrational signature that spans from ca. play a major role in the pseudocapacitive electrochemical charging of
1000 cm−1 to beyond 3000 cm−1 6. This so-called acid continuum 2D materials such as MXenes in acidic environment19,20. MXenes are a
absorption makes it difficult to assign features to any particular large family of 2D transition metal carbides, nitrides and carbonitrides
structure. However, the infrared (IR) spectra of protonated water which are most commonly prepared by the selective etching and
clusters present sharper bands compared to the spectra of bulk removal of the A layer from MAX phases21. The resulting MXenes are
solutions, which let to breakthroughs in the understanding of proton conductive with hydrophilic surfaces terminated by -O, -OH, and other
hydration7–9. Recently, ultrafast two-dimensional (2D) IR spectro- functional groups represented by Tx in the chemical formula. Over the
scopy measurements have demonstrated that protons are mostly last years, Ti3C2Tx MXene has shown remarkable electrochemical
solvated as Zundel complexes in bulk solution10,11. In contrast to properties in acidic electrolytes, putting this material at the forefront
clusters, which are limited to ca. 21 water molecules6, and bulk water, of pseudocapacitive energy storage materials22. Nevertheless, experi-
the vibrational modes of hydrated protons in 2D confinement remain mental evidence of the proton intercalation mechanisms in MXene
largely unexplored. remains elusive so far. Confined water in Ti3C2Tx MXene, the most

1
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Berlin, Germany. 2Department of Chemistry, University of California, Riverside, Riverside, CA,
USA. 3Department of Materials Science and Engineering and A. J. Drexel Nanomaterials Institute, Drexel University, Philadelphia, PA, USA. 4Present address:
Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, TN, USA. e-mail: [email protected]

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Article https://doi.org/10.1038/s41467-023-36842-0

studied MXene so far, has been characterized by NMR23 and inelastic mode using microstructured Si substrates as the internal reflection
neutron scattering24; however, an effective method of directly char- element (IRE). All IR-active vibrational modes of Ti3C2Tx MXene itself,
acterizing the hydrated protons confined within the layers of MXenes except for the terminal O–H stretch, are calculated to appear below the
has yet to be demonstrated. wavenumber range accessible with this setup25. The ATR mode helps to
In this work, we utilized operando Fourier Transform Infrared remove much of the bulk electrolyte signal since the probing depth is
(FTIR) spectroscopy to probe the water molecules and hydrated pro- less than the thickness of the Ti3C2Tx film (Supplementary Note1,
tons confined within the interlayer spacing of Ti3C2Tx during potential- Supplementary Fig. 2). Therefore, the recorded water and hydrated
induced proton intercalation. FTIR spectroscopy is ideally suited for proton signatures only originate from confined water in the interlayer
the study of water due to the strong IR absorption of O–H bonds but spaces between the MXene sheets and potentially from any bulk-like
has not yet been utilized to probe intercalation and solvation phe- water present in macropores within the Ti3C2Tx film. For these mea-
nomena in MXenes. By combining FTIR spectroscopy and theoretical surements, Ti3C2Tx MXene was synthesized according to the method
modelling, we have been able to show that the H-bonding structure of described in26 (see Methods for details). Successful etching of the
hydrated protons electrochemically intercalated into 2D slits between parent MAX phase is demonstrated by the X-ray diffraction (XRD)
Ti3C2Tx MXene layers is fundamentally different from bulk solution. pattern, where only the (00 l) reflections are present (Fig. 1b). The
sharp (002) reflection at 7.29° corresponds to a d-spacing of 12.1 Å and
Results and discussion an interlayer distance of 2.7 Å due to residual Li+ and a monolayer of
FTIR spectroscopy analysis of intercalated species in Ti3C2Tx water confined between the layers27. The expanded 2D structure of the
MXene interlayer Ti3C2Tx film is evident from the SEM image on a freestanding film.
The experimental setup of the operando FTIR system is shown sche- We first measured the infrared spectrum of the Ti3C2Tx film under
matically in Fig. 1a (see Supplementary Fig. 1 for a top view of the vacuum before and after exposure to 0.5 M H2SO4 (Fig. 1c). The pre-
spectroelectrochemical cell). We use the term operando spectroscopy sence of water confined in the interlayer spaces of the Li-intercalated
to emphasize the fact that infrared spectroscopic characterization of Ti3C2Tx film is apparent from the absorption features at 1640 cm−1
the Ti3C2Tx MXene film was acquired during the CV measurement, (bending mode) and 3400 cm−1 (stretching mode). The sharp band at
without stopping the potential at any fixed value. Each spectrum is 3640 cm−1 is attributed to dangling O–H bonds of water molecules6,28.
averaged over a scanning range of 60 mV (see SI for details). The Exposing the dry Ti3C2Tx film to an acidic solution replaces the residual
measurements were made in the attenuated total reflectance (ATR) Li+ ions, which were present in the Ti3C2Tx interlayer spaces as a result

a b (002)
Intensity (arb. units)

CE
MXene
RE

Silicon

Graphene (004)
(006) (008) (010) (012)

10 20 30 40 50
2θ (degrees)

In vacuum In liquid
c 1.0 Li-intercalated Ti3C2T x d 1.0 Intercalated
0.5 M H2SO4
ΔAbsorbance (a. u.)

Proton-intercalated Ti3C2T x

0.8 0.8
Normalized absorbance

Normalized absorbance

0.6 0.6 Bulk 0.5 M H2SO4

2750 2250

0.4 0.4
Bulk H2O
Ti3C2T x + H2O

0.2 0.2 Ti3C2T x + 0.5 M H2SO4

0.0 0.0
3750 3250 2750 2250 1750 3750 3250 2750 2250 1750
Wavenumber (cm−1) Wavenumber (cm−1)

Fig. 1 | Probing confined water and protons within Ti3C2Tx MXene interlayers. spectra of Ti3C2Tx MXene film before (Li-intercalated) and after (proton-inter-
a Schematic of the operando ATR-FTIR spectroscopy cell with a thin Ti3C2Tx film calated) exposure to 0.5 M H2SO4, recorded in vacuum. d FTIR spectra of bulk
drop casted on a graphene-coated silicon wafer and used as a working electrode. water, confined water in MXene film, and 0.5 M H2SO4 solution confined in MXene
Platinum and silver wires were used as counter and reference electrodes, respec- film normalized to highest absorbance. Inset: IR difference of bulk and MXene-
tively (CE and RE). The inset represents the Ti3C2Tx MXene unit cell used for the confined 0.5 M H2SO4 solution after subtraction of the spectrum of pure water. The
density functional theory (DFT) calculations. b XRD pattern and scanning electron difference spectra are offset for clarity.
microscopy (SEM) image (inset) of a freestanding Ti3C2Tx film. c Normalized FTIR

Nature Communications | (2023)14:1322 2

Article https://doi.org/10.1038/s41467-023-36842-0

Potential (V vs. Ag/AgCl)

0.1 M H2SO4 0.5 M H2SO4 -0.6 -0.4 -0.2 0.0
−1 −1
Wavenumber (cm ) Wavenumber (cm ) e
a 3750 3250 2750 2250 1750 b 3750 3250 2750 2250 1750
0.2 7
0V 0.1

0.0
-0.5 6
-1.0
-1.5
-2.0
7.5
5
5.0
2.5
Absorbance (arb. units)

0.0
8
4

ΔArea (arb. units)

4

0
1.0 3

0.5

2 2
1
0
1.5
1
1.0
0.5
0V 0.0
3750 3250 2750 2250 1750 3750 3250 2750 2250 1750 -0.6 -0.4 -0.2 0.0
Wavenumber (cm−1) Wavenumber (cm−1) Potential (V vs. Ag/AgCl)
0.02
c 0.1 M H2SO4 @ 0.6 V d 0.5 M H2SO4 @ 0.6 V f
0.4
ΔAbsorbance (arb. units)

Current density (A/g)

0.01 0.2

0.0

0.00 -0.2
0.1 M H2SO4
-0.4
7 6 5 4 3 2 1 7 6 5 4 2 1 0.5 M H2SO4
-0.01
3750 3250 2750 2250 1750 3750 3250 2750 2250 1750 -0.6 -0.4 -0.2 0.0
Wavenumber (cm−1) Wavenumber (cm−1) Potential (V vs. Ag/AgCl)

Fig. 2 | Operando electrochemical IR spectroscopy on Ti3C2Tx electrodes. numbered from one to seven and the numbers are displayed below the compo-
a, b FTIR difference spectra measured during electrochemical cycling in 0.1 M nents. Each component was labelled with a different colour for clarity. e Integrated
H2SO4 (a) and 0.5 M H2SO4 (b). The spectrum recorded at 0 V is subtracted from peak areas from the fit as a function of potential, with peak numbers corresponding
subsequent spectra. Spectra are offset for clarity. c, d Peak fit of difference spec- to the numbering in c, d. f CVs recorded during operando FTIR measurements.
trum at −600 mV in 0.1 M H2SO4 (c) and 0.5 M H2SO4 (d). The fit components are

of the MXene synthesis and delamination process, with protons, subtracted. The so-called acid continuum between 1700-3000 cm−1 in
leading to a significant decrease in the water bands and the appearance the bulk case is featureless, apart from the bands at 1760 cm−1 and
of new bands at 1820 cm−1, 2040 cm−1, 2560 cm−1 and 3090 cm−1, which 3000 cm−1, which are attributed to stronger H-bonding occurring in
are attributed to confined hydrated protons (see Supplementary Fig. 3 the presence of hydrated protons11. In the MXene-confined acid solu-
and Supplementary Table 1 for peak fits). The strong reduction of the tion, distinct bands are discernible at 1830 cm−1, 2000 cm−1, 2260 cm−1
band at 3640 cm−1 indicates that the dangling O–H bonds are to a large and 2520 cm−1 as opposed to the bulk water which appears as a con-
extent related to water molecules in the hydration shells of Li+ initially tinuum. These bands correspond well with the proton features recor-
present in the Ti3C2Tx film. The remaining water molecules are most ded on the dry Ti3C2Tx film (Fig. 1c).
likely bonded in small clusters, as observed in supercritical water29.
The FTIR spectra for bulk water, water in the initial Ti3C2Tx film Operando FTIR spectroscopy of protons intercalated in Ti3C2Tx
and 0.5 M H2SO4 solution intercalated in the Ti3C2Tx film normalized to MXenes
the highest absorbance are presented in Fig. 1d. The bulk 0.5 M H2SO4 Operando FTIR spectra were then recorded during electrochemical
spectrum is nearly identical to the pure water spectrum and therefore cycling in 0.1 M and 0.5 M H2SO4 at a scan rate of 2 mV/s (Fig. 2a, b).
not shown here. The O–H stretching band shifts strongly toward Multiple successive CVs were recorded (Supplementary Fig. 4) show-
higher wavenumbers going from bulk to confined water in the pre- ing minor hysteresis, but overall the response is very stable, and the
sence of Li+ and further in the confined acid solution after the removal spectroscopic data recorded during different cycles is very repro-
of the intercalated Li+. The water present in the proton-intercalated ducible. When negative polarization occurs, dramatic changes in the
MXene appears to be more weakly H-bonded compared to the water spectra are observed which are decomposed into 7 main peaks (Fig. 2c,
present before the removal of Li, which may be related to the smaller d). Difference spectra are shown here for clarity but the full spectra are
interlayer spacing found in proton-intercalated Ti3C2Tx MXene30. The also available in Supplementary Fig. 5 and show that potential-
inset in Fig. 1d shows spectra for the acidic solutions with pure water dependent changes are observable even without subtractions. First,

Nature Communications | (2023)14:1322 3

Article https://doi.org/10.1038/s41467-023-36842-0

the loss of neutral water within the Ti3C2Tx film during proton inter- frequencies in both concentrations. Peaks 1, 2, 6 and 7 do not shift at all
calation is concluded from the decrease of the water bending mode at during potential cycling, whereas peaks 3, 4 and 5 shift to lower
1645 cm−1. The increasing peaks 1 (~1920 cm−1), 2 (~2080 cm−1), 3 wavenumber with more negative potential. From the cyclic voltam-
(~2380 cm−1) and 4 (~2840 cm−1) are attributed to hydrated protons mograms (CVs) shown in Fig. 2f, we estimate that ~2.3 and 2.6 protons
and are not observed when the same measurement is performed per 12 MXene formula units are intercalated at the most negative
using a neutral electrolyte (0.1 M Li2SO4, Supplementary Note 2 and potential in 0.1 M and 0.5 M H2SO4, respectively (see Supplementary
Supplementary Fig. 6). In D2SO4, a clear isotopic shift of features 1-4 Note 4 for details).
is observed (Supplementary Note 3 and Supplementary Fig. 7), con-
firming that these bands are associated with intercalated protons. Vibrational modes of intercalated protons
Significant changes in the O–H stretching mode region (ca. 3000- Density Functional Theory (DFT) calculations were performed to
3700 cm−1) are also detected, assigned primarily to vibrations from clarify the vibrational structure of the new bands in the region 1800-
water molecules located beyond the first excess proton hydration 2400 cm−1 associated with hydrated protons confined in the MXene
shell. A positive band that shifts from 3300 cm−1 to 3220 cm−1 (peak 5) interlayers. The absorbance spectra were calculated for two layers of
is accompanied by a distinct negative band at 3530 cm−1 (peak 6). water in the MXene interlayer space of ~5.1 Å and the number of pro-
These two bands together show that neutral water is eliminated tons was varied from zero to three protons per 12 MXene formula units
within the Ti3C2Tx interlayer spacing due to proton intercalation, and (Fig. 3a). The calculated spectra were compared to experimental
that the remaining water molecules experience stronger H-bonding. spectra recorded operando at 0 V and −0.6 V, the potentials that cor-
This observation, also performed on water trapped in graphene respond to the lowest and highest number of protons, respectively,
nanobubbles at high temperature31, has previously been assigned to within the Ti3C2Tx film. In the case of confined protons, three peaks
an increase of the water density in the confined environment32. The were found in the calculated spectra that closely agree with peaks 1-3 in
increase of the band at 3630 cm−1 (peak 7) from dangling O–H bonds the experimental spectra in 0.1 M H2SO4 (Fig. 3b). The normal modes
is also observed in a neutral electrolyte and therefore not specific to corresponding to these peaks all exhibit stretching and bending
proton intercalation (Supplementary Fig. 6). As the scan direction is characteristics of the central hydronium ion mixed with bending and/
reversed and the potential cycled back towards 0 V, all absorbance or stretching of three water molecules in the first hydration shell. The
bands decrease in area until no features are seen in the spectrum at most representative normal modes are shown in Fig. 3c and further
0 V showing a good reversibility of the proton intercalation process. details on the other ones are available in Supplementary Tables 2–4.
The spectral evolution is similar in both concentrations, with some Peaks 1–2 do not appear in the calculated spectrum of one proton in
notable exceptions (Fig. 2). Peaks 1 and 2 are significantly more pro- bulk water (Supplementary Fig. 10b), confirming that the specific
minent in the 0.5 M solution, whereas peak 3 is only observed in 0.1 M vibrational modes are only present when the hydrated protons are
H2SO4, because it does not evolve with potential in 0.5 M H2SO4 (it is confined within the Ti3C2Tx interlayers.
clearly present at this concentration before electrochemical cycling as The classification of proton hydration structures as Eigen or
seen in the inset of Fig. 1d). The larger negative area of peak 6, together Zundel is often based on the proton-sharing parameter, δ, which
with the decrease of the water bending mode at 1645 cm−1 for the 0.5 M describes the difference in the distance of the shared excess proton
acid compared to the 0.1 M acid, suggests that a larger amount of from the O atoms of the two nearest water molecules (for more details
neutral water is lost upon cycling with increasing acid concentration. see Methods). δ = 0 Å for an ideal Zundel cation, whereas configura-
Overall, a concentration dependence is observed for peaks 1–3, whereas tions with δ > 0.1 Å are classified as Eigen states. The simulated snap-
the other peak areas are remarkably consistent in both concentrations. shots show practically no Zundel character for any normal modes
Comparing the peak fit results for 0.1 and 0.5 M acid concentrations, we contributing to peaks 1 and 2; instead, these peaks arise predominantly
interpret the evolution of the IR features with potential in terms of two from Eigen modes. For peaks 1-3, both δ and peak frequency decrease
parallel processes: (i) water reordering toward stronger H-bonding due in the order 3 > 2 > 1 (Table 1). Smaller δ has previously been shown to
to polarization at the MXene-electrolyte interface and (ii) proton result in lower vibrational frequency33. Asymmetrically hydrated Eigen
intercalation and/or surface redox reactions. Process (i) is independent cations (one water molecule removed from or one water molecule
of proton concentration and is related to changes in water stretching added to H9O4+) exhibit redshifts in the Eigen core frequency and
modes as evidenced by peaks 4 and 5, the areas of which are nearly present bands close to peaks 1 and 2 observed here7. Similarly,
identical at both acid concentrations. Also, peak 7, attributed to water hydrated protons confined inside reverse micelles were found to exist
molecules with a dangling OH bond6,28 appears at almost the same predominantly in asymmetric Eigen-like hydration structures, with one
frequency and intensity in both, acidic and neutral electrolytes (Sup- weaker H-bond and two stronger H-bonds formed by the central
plementary Fig. 6c, d). Peak 5, related to more coordinated water hydronium ion5. Moreover, vibrational sum frequency spectroscopy
molecules, is more intense in 0.1 M Li2SO4 and is split into two com- measurements that are sensitive to interfacial modes show that
ponents, reflecting an additional process of water co-intercalation with hydrated protons at a charged liquid-vapour interface have a preferred
Li+. Process (ii) is dependent on the proton concentration and gives rise orientation and strongly favour an Eigen-like configuration34. We do
to peaks 1-3 and loss of peak 6. Peaks 1-3 are associated with the diffu- not observe a peak at 1750 cm−1, which is prominent in difference
sion of protons within the MXene interlayers, which replaces the weakly spectra of bulk acid solutions and widely attributed to the bending
bonded neutral water (peak 5). mode of a Zundel cation5,11,35, further supporting our DFT results and
Some peaks exhibit considerable hysteresis in their integrated the assignment of peaks 1-3 to Eigen modes. The assignment of the
areas, which may be related to the state of protonation of the Ti3C2 experimental features based on these DFT calculations is summarized
surface and how that affects the way protons are hydrated in the in Table 1.
interlayer space. As can be observed by visual inspection of the CV A surface redox reaction is also expected to occur according to
curve in Fig. 2f, the surface redox reaction that takes place at the Ti3C2 the equation:
electrode deviates from the ideal, where the anodic and the cathodic
peak potentials would be symmetric. The Ti3C2 film was optimized for Ti3 C 2 O2 + nH + + ne
"Ti3 C 2 O2
n ðOH Þn ð1Þ
IR study and the dropcasting method produced a film with a higher
resistance compared to conventional supercapacitor electrode films. However, we are currently unable to definitively assign a parti-
The peak frequencies are summarized in Supplementary Fig. 8 for cular absorption band to the surface hydroxyl groups. DFT calcula-
both concentrations. All peaks appear at identical or near-identical tions predict the stretching mode of the surface -OH to appear at ca.

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Article https://doi.org/10.1038/s41467-023-36842-0

a b

Experiment
−0.6 V
0V

Absorbance (arb. units)

1
2
3

Theory
High [H+]
0 [H+]

3 2 1

2400 2200 2000 1800 1600

Wavenumber (cm −1)

c
3 2 1

2252 cm−1 1994 cm−1 1912 cm−1

Fig. 3 | Vibrational signature of hydrated protons in the interlayer space of with 0 protons (blue) and 1–3 protons (black). The dashed green, purple and red
Ti3C2Tx MXene. a The structure of three protons confined within the MXene lines show the peak components. c The main vibrational normal modes con-
interlayer space. Two unit cells are shown. b Top: Operando FTIR spectra at 0 V tributing to the peaks are highlighted in corresponding colours, indicating the
(blue) and −0.6 V (black) in 0.1 M H2SO4 referenced to the bare graphene-covered Si important contribution from the special pair (the hydronium ion with its closest
IRE represent low and high proton content, respectively. The dotted green, purple neighbouring water) in the Eigen state (the proton-sharing parameter, δ, >0.1 Å, see
and red lines show peak components 1, 2 and 3 superimposed onto the spectrum at Methods).
0 V. Bottom: Calculated spectra of two layers of water in the MXene interlayer space

3730 cm−1 in vacuum25; however, in the presence of hydrogen- modes are likely buried in the background. NMR36 and Raman25
bonding to water, this mode is expected to redshift. Surface -OH spectroscopies, which can access other Ti-OH vibrational modes at
groups may contribute to peak 6 at 3630 cm−1 but this assignment is low wavenumbers (200-600 cm−1), may be more appropriate to
not straightforward since this peak is also seen to increase in size in resolve the Ti-OH contribution. X-ray absorption spectroscopy has
neutral electrolyte under a more negative potential. In our DFT proved useful in revealing the change in the Ti chemical bonding
molecular dynamics simulations, we can see that the surface OH environment induced by hydroxylation and redox reaction of tita-
groups are highly dynamic, with fast and reversible deprotonation- nium carbide MXenes19,37,38.
protonation in the local environment including the hydrogen bond
network in confinement. We have taken about 10 instantaneous 2D confinement of protons in Ti3C2Tx MXene interlayer
snapshots and analysed the normal models of the surface OH groups To find out the structural origin responsible for the vibrational modes
and found that they vary from 1700 to 3300 cm−1 and are sensitive to of hydrated protons in confinement, we compared the H-bonding
the O–H distance. Hence, we think that the surface O–H vibration network of the hydrated proton in confinement with that of a hydrated
proton in bulk water. For a fully solvated hydronium ion, the three
hydrogen atoms each donate a H-bond to a water molecule (labelled
Table 1 | Peak assignments for operando FTIR spectra of
Ti3C2Tx MXene in dilute H2SO4 electrolyte HD), and the oxygen in the hydronium accepts one H-bond from a
neighbouring water molecule (labelled OA). These interactions are
Peak # Mean frequency Assignment Ref. highlighted in the inset of Fig. 4a with blue and orange dashed lines,
(cm−1) respectively. The donated H-bonds of the hydronium ion all have a
1 1923 νO-H, Eigen core (δ = 0.25 Å) This work length of ~1.6 Å and involve three water molecules for both the bulk
2 2078 νO-H, Eigen core (δ = 0.32 Å) This work and the confined systems. On the other hand, the accepted H-bond of
3 2385 νO-H, Eigen core (δ = 0.37 Å) This work the confined hydronium ion is significantly influenced by confinement.
4 2839 νO-H, Eigen core (2500-2650 cm−1) and 7,11,50 At the H-bond cutoff distance of 2.5 Å32,39, the proton coordination
Zundel flanking water (3185 cm−1) number drops from 3.5 in the bulk to 3.0 in the confined interlayer
5 3262 νO-H, strongly H-bonded water 11,51
space at both concentrations. This decrease of the hydronium coor-
6 3533 νO-H, weakly H-bonded water 51 dination number matches well with the main normal modes of the
7 3621 νO-H, dangling OH of interfacial water 3,4 confined protons, which all involved three water molecules. Recent
theoretical and experimental studies have found that the protonated

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a Bulk: H2O·0.05H+ b c
5
Low confined [H+]
High confined [H+]
4
3.5

confinement
g (rOA-HD)
3

CN

2D
3.0
3.0 HD OA

2
OA HD
HD
HD
1
OA
OA
0
1 1.5 2 2.5 3 3.5 Bulk water
R (Å)

Ti3C2TX MXene interlayer

Fig. 4 | Hydrogen bonding in 2D confinement. a Radial distribution function of dotted line represents the hydrogen bond length cutoff at 2.5 Å. The coordination
non-covalently bonded OA-HD distances between a hydronium ion and its four numbers at this O–H distance are marked in the figure. Inset: Hydronium ion with 4
nearest-neighbour water molecules (solid lines) and the resulting coordination nearest water molecules; the H-bonds are marked by dashed lines. b Fully
numbers of the hydronium ion (dashed lines) in bulk water with 0.05 H+ per H2O H-bonded hydronium ion in bulk water. c Schematic representation of the effect of
(black), MXene-confined water at low [H+] (Ti3C2O2·1.42H2O·0.08H, red), and 2D confinement on proton hydration.
MXene confined water at high [H+] (Ti3C2O2·1.42H2O·0.25H, blue). The vertical

water cluster H+(H2O)21, referred to as a magic number cluster due to obtain single- and few-layer Ti3C2Tx MXene. A stock aqueous suspen-
its stability, exhibits IR bands in the 1800-2400 cm−1 region6,40. In the sion at a concentration of 5.9 mg/ml was stored under argon in a sealed
most stable conformer of the H+(H2O)21 cluster, the excess proton is bottle and fresh aliquots were drawn on the day of the experiments.
found in an Eigen configuration with three donated H-bonds but no
accepted H-bond, similar to the H-bonding structure found in our DFT MXene film preparation
calculations. The loss of the accepted H-bond is therefore the main All electrolytes and Ti3C2Tx suspensions were made with doubly
change in the hydration of the protons which is observed when the deionized water (Millipore, resistivity 18.2 MΩ ∙ cm). Li2SO4 and H2SO4
protons are confined within a two-dimensional environment in MXene, (Sigma-Aldrich) were used as received. All electrolytes were deox-
as represented schematically in Fig. 4b, c. ygenated by bubbling with nitrogen for 30 min prior to experiments. A
In summary, we have found that there are discrete vibrational Ti3C2Tx stock suspension was diluted to 1 mg/ml, 125 µl was pipetted
modes of protons that are confined within the interlayer spaces Ti3C2Tx onto a graphene-covered Si wafer (vide infra) and the droplet was
using operando ATR-FTIR. These vibrational modes differ significantly allowed to dry at room temperature. Some manual manipulation of the
from the continuum band that is observed for protons in bulk water. drying droplet was necessary to ensure that the infrared beam probed
The major increase of these bands at negative potentials provides an area fully covered by MXene. The resulting film was ca. 600 nm
spectroscopic evidence of the intercalation of protons within Ti3C2Tx thick. Measurements were also made with thinner films by reducing
layers during electrochemical cycling. At this stage, the associated the amount of Ti3C2Tx MXene suspension pipetted onto the wafer.
vibrational modes are interpreted as a consequence of the reduction of
the coordination number of hydronium ions resulting from 2D con- Electrochemical measurements
finement between the layers of Ti3C2Tx and possess an Eigen-like Electrochemical measurements were performed in a three-electrode
character. A strengthening of the overall water H-bonding is also spectroelectrochemical cell designed and built in-house (Supplemen-
observable for high proton concentrations. The peculiar proton tary Fig. 1). Electrical contact to the Ti3C2Tx working electrode was
hydration occurring under 2D confinement may correlate with the high made through the graphene film, although measurements were also
pseudocapacitive electrochemical energy storage performance that has performed without the graphene layer with very similar electro-
been reported not only for MXenes19,20 but also for other 2D and layered chemical results. A coiled Pt wire and an Ag wire were used as the
materials41. Going forward, this experimental method can be applied to counter and quasi-reference electrodes, respectively. Prior to use, the
probe the intercalation of any type of ion, molecule or electrolyte within Ag wire was anodized at 50 mV vs. OCP in 0.1 M HCl. The potential was
the interlayer spacing of MXenes, thereby offering new opportunities controlled with a Bio-Logic SP-200 potentiostat running EC-Lab soft-
for the characterization of chemical species under 2D confinement. ware. With all electrodes mounted, the cell was filled with electrolyte,
sealed, mounted into the infrared spectrometer and the spectrometer
Methods was evacuated until the pressure in the sample chamber reached 0.8
MXene synthesis mbar (typically ca. 1 h). After this equilibration time, the open-circuit
Ti3C2Tx MXene was synthesized according to the procedure described potential (OCP) of the system was recorded and used as the starting
in26. By including excess aluminium during synthesis of the Ti3AlC2 potential for the CV. Each CV was recorded between 0 V and −0.6 V
MAX phase precursor, single- and few-layer Ti3C2Tx MXene was with a scan rate of 2 mV/s. Several cycles were performed to verify the
obtained with improved stoichiometry, resistance to oxidation and stability of the MXene electrode.
increased electrical conductivity. Briefly, the MAX phase was synthe-
sized from TiC, Ti, and Al powders at 1380 °C under a constant argon FTIR measurements
flow. The washed, dried, and sieved Ti3AlC2 precursor was etched in a The measurements were carried out at the IRIS beamline at the BESSY
mixture of HCl and HF to produce multilayered MXene, which was then II electron storage ring operated by the Helmholtz-Zentrum Berlin für
delaminated by dispersing the multilayer MXene in a LiCl solution to Materialen und Energie42. A conventional internal broadband IR source

Nature Communications | (2023)14:1322 6

Article https://doi.org/10.1038/s41467-023-36842-0

was used for the measurements. FTIR spectra were collected with referred to as the special pair, and OD (OA) refers to the oxygen from
Bruker 70 v spectrometer equipped with a liquid nitrogen cooled MCT the H-bond donor (acceptor) molecule. The classification of hydration
detector. The internal reflection element (IRE) was a microstructured structures is defined through the proton-sharing parameter δ:
Si wafer (Irubis) covered by a monolayer film of graphene (Graphenea)
transferred as per instructions. A fresh graphene-covered wafer was δ = ∣r OD H
r OA H ∣ ð3Þ
prepared for each measurement. The graphene layer improved adhe-
sion between the MXene film and the IRE, leading to a higher sensitivity where r is the distance between Oi and H. Special pair configurations
to interlayered water layers and more reversible spectra during elec- where δ < 0.1 Å are classified as Zundel and δ > 0.1 Å as Eigen33. It is
trochemical cycling. The optical accessory was designed and built in- important to note that this cutoff value is arbitrary; other classification
house to accommodate the microstructured Si wafer as the IRE and methods can be found in the literature49. A perfectly symmetric Zundel
provides an angle of incidence of 28.74°. Each spectrum consisted of cation would have δ = 0 Å and a perfectly symmetric Eigen cation
128 scans and took ~30 s to record, with a 20-s waiting time between would have δ = 0.53 Å41.
spectra resulting in one spectrum every 50 s. With a cyclic voltam-
metry scan rate of 2 mV/s, this equates to one spectrum per 0.1 V. The Data availability
timing was manually synchronized with the cyclic voltammetry such The FTIR data generated in this study has been deposited in the
that the midpoint of each spectrum collection coincided with poten- Zenodo database under accession code https://doi.org/10.5281/
tial = 0.1n V, where n = integer. For example, an FTIR spectrum, the zenodo.7600123. Further data is available upon request to the authors.
collection of which started when the potential was −0.17 V and finished
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23455–23462 (2017). Künsting for the illustration in Fig. 1a.
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IR spectral assignments for the hydrated excess proton in liquid Author contributions
water. J. Chem. Phys. 146, 154507 (2017). M.L., Y.G. and T.P. formulated the idea and conceived the experiments.
34. Tyrode, E., Sengupta, S. & Sthoer, A. Identifying Eigen-like hydrated D.J. conceived the DFT calculations. M.L. performed the FTIR measure-
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493 (2020). M.L., U.S., L.P. and T.P. designed custom equipment for the experiments.
35. Dahms, F., Fingerhut, B. P., Nibbering, E. T. J., Pines, E. & Elsaesser, T. T.S.M. synthesized and characterized the Ti3C2Tx MXene under the
Large-amplitude transfer motion of hydrated excess protons map- supervision of Y.G., M.L. and Y.S. analysed the data. All authors con-
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tance after urea intercalation studied by Soft X-ray absorption Funding
spectroscopy. J. Phys. Chem. C 124, 5079–5086 (2020). Open Access funding enabled and organized by Projekt DEAL.
38. Prenger, K. et al. Metal cation pre-intercalated Ti3C2Tx MXene as
ultra-high areal capacitance electrodes for aqueous super- Competing interests
capacitors. ACS Appl. Energy Mater. 5, 9373–9382 (2020). The authors declare no competing interests.

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