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Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 4932−4940 pubs.acs.org/journal/ascecg

Structure and Properties of “Type IV” Lanthanide Nitrate

Hydrate:Urea Deep Eutectic Solvents
Oliver S. Hammond,† Daniel T. Bowron,‡ and Karen J. Edler*,†
†
Department of Chemistry and Centre for Sustainable Chemical Technologies, University of Bath, Claverton Down, Bath BA2 7AY,
U.K.
‡
ISIS Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Didcot OX11 0QX,
U.K.
*
S Supporting Information
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ABSTRACT: A series of lanthanide nitrate hydrate:urea “Type IV”

deep eutectic solvents (DES; Ln = Ce, Pr, Nd) were prepared and
their physical properties measured, showing very high surface tension
and density, with low viscosity and glass transition temperatures.
Calculated Gordon parameters were similar to water, with lower
molecular volumes than “Type III” DES. The LnDES were used as
reaction media for efficient combustion synthesis of lanthanide oxides.
The nanostructure of the Ce(NO3)3·6H2O:urea DES was measured
using neutron and X-ray scattering and resolved with empirical
potential structure refinement (EPSR) atomistic modeling. The
models showed the existence of strongly bonded yet fluxional
oligomeric [-Ce-NO3-] polyanions and polycations. Because of the
excess of the molecular component in the mixture, an intercalating H-
bonded nanostructure containing mainly water and urea was observed,
which can be considered as a lubricating molecular pseudophase. This dichotomous structural observation helps to explain some
of the unusual physical properties such as low viscosity and high surface tension, while also challenging the fundamental
definitions of DES.
KEYWORDS: Deep eutectic solvents, Lanthanides, Neutron scattering, Ionic liquids, Nanostructure, Physical properties

■ INTRODUCTION
Deep eutectic solvents (DES) are gaining attention as
have been reported which fall outside these categories but still
form useful liquids, including hydrophobic DES8−10 and
inherently tunable and potentially more environmentally hydrated metal salts.11 Hence, many now describe these
friendly drop-in replacements for traditional organic solvents.1 systems using umbrella terminology such as “Low-Melting
DES are extensively H-bonding eutectic mixtures of molecular Mixtures” (LMMs) or “Low Transition Temperature Mix-
and ionic compounds, forming a partially ionic liquid phase at tures” (LTTMs),2,12−15 though the terminology DES will be
desirable temperatures, and they are very often based around used herein. In the initial framework of DES, all “Type I−IV”
choline chloride (ChCl) and/or urea.2 Being partially ionic, systems were said to contain some form of complex-ion, based
DES have been described as a “4th generation” ionic liquid on mass spectrometry data.7,16 However, this technique is now
(IL);3 the two categories share qualities such as reduced regarded as inappropriate for characterization of ionic liquids
flammability compared to molecular solvents.4 Furthermore, and speciation; MS destructively ionizes the bulk liquid, and
the judicious design of DES to meet specific requirements can analysis of the gas-phase products usually leads to spurious
allow optimization within the framework of green chemistry,5 conclusions.17 For example, understanding of “Type III” DES
leading toward reduced waste and hence improving the E- nanostructure has evolved from a complex-ion model (ie.
factor of processes.6 [(urea)2·Cl]− + [cholinium]+) as concluded from MS,18 to an
As defined above, the term “DES” covers a huge composi- “alphabet soup” model with multifaceted disorder,19,20 with H-
tional space. Abbott et al. initially proposed a classification bonding contributions from all the various species,21−23 and
system with 4 types of DES;7 “Type I” DES are mixtures of minimal evidence for the initially posited charge delocalization
metal salts and quaternary ammonium salts (ie. ChCl:ZnCl2), and complex-ion formation as the driver for eutectic
“Type II” DES are hydrated variants of the former (ie. formation.18,24,25 Studies have also investigated the effect of
ChCl:ZnCl2·3H2O), “Type III” DES are the most commonly
studied and are made of ionic-molecular eutectic mixtures (ie. Received: October 27, 2018
ChCl:urea), and “Type IV” DES are mixtures of metal salts Revised: December 28, 2018
with molecular components (ie. ZnCl2:urea). Other variants Published: January 28, 2019

© 2019 American Chemical Society 4932 DOI: 10.1021/acssuschemeng.8b05548

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water on “Type III” DES, showing that it contributes to the room temperature for a long time. The surface tension was measured
overall H-bonding network at low volume fractions without using a Sigma Attension instrument equipped with a platinum du
significant perturbation26 but overwhelms the interesting Nöuy ring. The ring was repeatedly flamed until red-hot using a
intermolecular structuring that defines DES above a threshold butane torch and washed with deionized water to ensure the full
removal of organic and inorganic impurities. Density was measured
water volume fraction of ca. 0.5.27 Overall, sophisticated using a pycnometer calibrated against water (Elga, 18.2 MΩ), and
studies into DES continue to unearth interesting results, with viscosity was measured using a TA Instruments HR-3 Discovery
potential impact on their applications, and are beginning to Hybrid Rheometer. Investigation of the response to shear rate (shown
challenge the basis of the current dividing lines between DES in the Supporting Information) revealed that the samples were
and IL mixtures,28,29 but they have been generally limited to Newtonian liquids.
the “Type III” systems. Radiation Total Scattering Measurements. Wide Q-range
Very few “Type IV” DES have been explored, and the neutron diffraction measurements were made of urea−cerium nitrate
understanding is limited to mass spectrometric interpretations mixtures using the NIMROD diffractometer,42 located at TS2 of the
of a few metal halide systems, such as ZnCl2:urea, AlCl3:urea, STFC Rutherford Appleton Laboratory, Harwell, Oxford, UK.
NIMROD uses time-of-flight neutrons of wavelength 0.05 ≤ λ ≤
and CrCl3·6H2O:urea, where it is suggested that complex 11 Å, with detector banks spanning the angular range of 0.6−37.5°,
cations and anions exist arising from disproportiona- yielding an effective Q-range of 0.01 ≤ Q ≤ 50 Å−1 or an approximate
tion.7,11,16,30−33 Halide-free metallic DES can be more real-space length scale of 0.1−300 Å.
sustainable and functional,34 and demonstrating new systems Two isotopic contrasts of the samples were used for measurements,
with different metal ions may offer new utility. For example, using either protonated or d4-urea with Ce(NO3)3·6H2O. The
lanthanide-containing DES could be designed as a greener samples were loaded into flat-plate sample cells of null-scattering
task-specific solvent or CVD precursor for lanthanide- TiZr alloy (0.68:0.32 Ti:Zr molar ratio). The cells are vacuum-sealed,
containing materials, which are useful in applications such as with a 1 mm path length and 1 mm wall thickness, accommodating
superconductors, lasers, magnets, catalysis, and elec- approximately 1.5 g of sample within the 30 × 30 mm square
NIMROD incident neutron beam footprint. Filled cells are mounted
tronics.35−37 Furthermore, lanthanide DES are intriguing as directly into a metal sample changer, throughout which a water/
low-temperature molten salt analogues in the processing, ethylene glycol mixture is recirculated using a Julabo heater/chiller
solvation, and separation of nuclear materials.38,39 In this unit to regulate the temperature to 303 ± 0.1 K at the sample
paper, we will therefore describe the first lanthanide “Type IV” positions.
DES based around urea mixtures with lanthanide nitrate Measurements were also made of empty cells, the empty
hydrates. Their structure will be resolved using neutron instrument, and a standard 3 mm thick sample of V for calibration
diffraction measurements with isotopic labeling, alongside X- and normalization of the instrument and data. Measurements were
ray diffraction, as constraints upon an atomistic model. Such made for a median of 2 h, with some variation in counting time
neutron scattering measurements have enabled significant depending on the deuteration state of the sample. Processing of the
raw data was accomplished using the GudrunN software package;43
advances in the understanding of IL structure1,17 and are corrections were made for the sample multiple scattering and the
beginning to extend to DES, but thus far only metal-free or inherent background of the sample environment, as well as for
dilute metal−ion systems have been reported.40 We will attenuation, normalization, and a final iterative hydrogen inelasticity
explore the formation of complex ions, the intercomponent subtraction. This produces data sets that can be modeled using
structuring and clustering, and the behavior of water, to assess Empirical Potential Structure Refinement modeling (EPSR). The
where they sit in the greater framework of liquids. In doing so, computed and measured scattering cross sections agreed strongly,
we aim to demonstrate the potential of DES as task-specific confirming that the atomic composition of the samples matched the
green solvents, as well as challenge the current perception of expected levels.
these systems. In addition to the neutron measurements, the protonated samples

■
were measured using X-ray total scattering (aka. XPDF) using a
Panalytical X’Pert Pro II diffractometer with Ag radiation (λ = 0.5594
EXPERIMENTAL SECTION Å). Samples were sealed into quartz glass X-ray capillaries of 2 mm
Lanthanide DES. Lanthanide DES were prepared using urea diameter and 0.01 mm wall thickness and mounted on a capillary
(Sigma-Aldrich, ≥99.5%) and the respective lanthanide (III) hydrate; spinner for measurement. The data were reduced using the GudrunX
cerium(III) nitrate hexahydrate (Acros, ≥99.99%), neodymium(III) software package, which corrects for the geometry and composition of
nitrate hexahydrate (Alfa Aesar, 99.9%), or praseodymium(III) nitrate the sample, Compton and multiple scattering, absorption, fluores-
hexahydrate (Acros, 99.9%). The mixtures were found to form room cence, background, and the Bremsstrahlung radiation inherent to the
temperature liquids in a wide range from ≥3 urea: 1 Ln(NO3)3·6H2O incident beam. Data are normalized to the atomic self-scattering level
salt. The 3.5:1 urea:Ln ratio was chosen for further study due to the of the sample and finally used as a further experimental constraint
formation of a single homogeneous and transparent phase with no upon the subsequent atomistic model alongside neutron data.
apparent separation of a single component even when kept in cold Empirical Potential Structure Refinement Modeling. Empiri-
storage, and corresponding with the previously reported “Type IV” cal potential structure refinement (EPSR) is an atomistic model-based
3.5:1 urea:ZnCl2 eutectic.41 Samples were found to be unsuitable for fitting approach that is derived initially from the Reverse Monte Carlo
Karl Fischer titration due to inconsistent readings and the formation (RMC) method, which uses diffraction data as an experimental
of precipitate. Due to the significant fraction of molecular species, the constraint upon a classical simulation.44 Full details of the procedures
LnDES are expected to display reduced hygroscopicity relative to pure are given in the Supporting Information, as well as the para-
ILs, molten salts, and DES. As a result, solutions were used metrization of the molecules. The assigned names of each atom type
immediately after preparation to ensure compositional purity, as for each molecule that will be referred to throughout the text are
water content is thereafter difficult to control. We therefore anticipate presented in Figure 1.

■
that room-temperature liquids of this type can be prepared at various
mixing ratios, though full investigation of the solid−liquid equilibrium RESULTS AND DISCUSSION
for the various samples was not attempted due to the very low
transition temperatures. Heating was avoided because the thermal Lanthanide DES. Lanthanide DES (LnDES) were found
decomposition of urea is anticipated to cause precipitation of to form homogeneous room-temperature liquids over a wide
lanthanide carbonates, which was observed in samples stored at mixing range. Mixtures in a lanthanide nitrate hydrate:urea
4933 DOI: 10.1021/acssuschemeng.8b05548
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Table 1. Measured Physical Properties at Room

Temperature (298 K) of LnDES and the Computed Gordon
Parameter, alongside Literature Data for H2O and the
“Type III” ChCl:Urea DES
Surface Gordon
Densitya Viscosity/ Tension/ Parameterb
Ln / g cm−3 mPa·s mN m−1 (G)/J m−3
Ce 1.789 168 ± 1 83.33 ± 0.32 2.79
Pr 1.795 181 ± 3 81.41 ± 0.47 2.73
Nd 1.801 168 ± 1 82.82 ± 0.26 2.77
H2O 0.997c 0.889c 71.99d 2.74−2.75e
Figure 1. Cartoons showing the atom type labels that were used in ChCl:U 1.2f 750g 66.0 ± 1.0h 1.57h
a
EPSR simulations and will be used throughout the text. Uncertainties in density values, derived from pycnometry measure-
ments, calibrated against water are 0.001 g cm−3. bG is calculated
mixing ratio of 1:3.5, commensurate with the previously using the equation G = γ/(3√Vm), where γ is the air−solvent
reported “Type IV” ZnCl2:urea DES,41 were chosen for further interfacial tension, and Vm is the molar volume. The molar volume,
study, as these were not found to crystallize on cooling. The Tg though varying subtly due to the different counterion mass, was
calculated to be around 26.67 cm3 mol−1, as determined from the
was determined using extrapolation of the viscosity/temper-
densities and mean molar mass (47.73 g mol−1) of the multi-
ature relationship with the Vogel−Fulcher−Tammann (VFT) component solvents. cDerived from Kestin et al.48 dTaken from
equation and differential scanning calorimetry (DSC), shown Vargaftik et al.49 eAs published by Greaves and Drummond.50
in the Supporting Information.45,46 Both techniques suggest a f
Derived from data collected by Yadav et al.51 gData reported by
Tg of 215 K, which is a significant eutectic depression when D’Agostino et al.52 hAs reported by Arnold et al.53
compared with the melting points of the urea (406 K) and
lanthanide precursors i.e. Ce(NO3)3·6H2O (369 K), and
relatable to the more extreme eutectic depressions such as that components and higher viscosities, such as choline chlor-
of ChCl:urea.47 Refrigerated samples were stable, though the ide:urea (average Mr = 86.6 g mol−1).54 The LnDES also have
urea-Ce(NO3)3·6H2O system formed trace pale precipitate, remarkably high surface tensions, higher than the majority of
likely a cerium carbonate or oxide, when kept for long times typical ILs (ca. 40−50 mN m−1),55 higher than “Type III”
(>1 year) at RT. The solvents adopted the native Ln3+ cation DES, (ca. 60−70 mN m−1),53 and even higher than water (72
coloration, colorless for cerium, bright green for praseody- mN m−1), implying strong H-bonding associations. From these
mium, while the neodymium sample displays the Alexandrite properties, the solvent cohesive energy density (Gordon
effect where the color of the sample ranges from lilac to blue parameter, G) was calculated.50 “Type III” DES such as
depending on the lighting. These colors are shown in Figure 2. ChCl:urea have Gordon parameters of around 1.5 J m−3, which
is within the range of typical molecular solvents (1−2 J m−3),
above most ILs (generally 0.5−1.5 J m−3) but far below that of
water (2.743 J m−3).50 The computed G of the LnDES is
≥2.73 J m−3, making their cohesive energy density comparable
to, and in some cases slightly higher than, water. A similar set
of properties were observed for a “Type IV” CrCl3·6H2O:urea
DES,16 where it was highlighted that the low viscosity was due
to Cl− being the main mobile species, and hole theory
suggested a void radius of 1.16 Å. However, when considering
the viscosity, density, surface tension, calculated G, and lack of
Cl− in our samples, it seems that the viscosity is adequately
explained by the much lower average Mr and hence molar
volume (26.7 cm3 mol−1) when compared to ChCl:urea (75.3
Figure 2. Photographs of (a) the 3.5 urea:1 Ce(NO3)3·6H2O, (b) 3.5 cm3 mol−1).53 This points toward a structural model where the
urea:1 Pr(NO3)3·6H2O, and (c) 3.5 urea:1 Nd(NO3)3·6H2O LnDES, viscosity and associated physical properties simply arise from
taken under Hg-vapor fluorescent strip lighting. the dynamics of local bond-making and bond-breaking, cf.
Egami et al.’s universal framework for the molecular origin of
Furthermore, the DES were investigated as reaction media for viscosity,56,57 rather than from the population of vacant liquid
the formation of lanthanide oxides; an efficient self-solvated “holes”,16,58−60 which were not observed in previous structural
direct combustion synthesis method was developed, which is studies.19 The importance of understanding the fundamental
detailed in the Supporting Information. nanostructure, as well as the dynamics, of such systems is
An interesting combination of physical properties were therefore highlighted.
measured, as shown in Table 1. They are very dense liquids of Neutron and X-ray Diffraction Fits and Data. Neutron
ca. 1.8 g cm−3, which partially derives from the relatively high diffraction data for the two isotopic contrasts of the 3.5:1
concentration of heavy lanthanide ions; the Ce-based LnDES urea:Ce(NO3)3·6H2O DES are shown in Figure 3 alongside
is composed of 21.74 wt % lanthanide, 32.62 wt % urea, 16.77 corresponding X-ray data and fits using empirical potential
wt % water, and 28.87 wt % nitrate. Despite the presence of structure refinement (EPSR) modeling, in both Q and r space.
very heavy ions, the large proportion of small molecules gives a The DES based on the cerium salt is considered an adequate
low average computed Mr (Ce LnDES = 47.73 g mol−1), when proxy for the solution structure of the other systems due to the
compared to “Type III” DES which have much bulkier chemical similarities, and measurement of the Pr(NO3)3·6H2O
4934 DOI: 10.1021/acssuschemeng.8b05548
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(1.45 Å−1),19 and ChCl:malic acid (1.15 Å−1)26 but at longer

distances than in D2O (2 Å−1),62 proving that the major
correlation lengths of the systems are distinct. Shorter average
length scales of interaction in the “Type IV” DES reflect the
higher charge density and hence stronger Coulombic
attractions arising from the high concentration of highly
charged ions in the mixture, as well as a smaller average
molecular radius.
Coordination Network of Ce3+. As “Type IV” DES have
been related to complex-ionic liquids such as the well-known
halometallates, the speciation of the metal centers was
investigated first. Figure 4 shows the cerium-centered partial

Figure 4. Calculated partial radial distribution functions (pRDFs)

showing the coordination of species around cerium ions. These
pRDFs are an ensemble average of >5000 iterations of the EPSR
model.
Figure 3. Corrected neutron and X-ray diffraction data (colored
markers) and EPSR fits to the models (dashed black lines) are shown
as a function of Q-space (a), and r-space (b). Discrepancies in the r- radial distribution functions (pRDFs), computed by accumu-
space data below approximately 1 Å are spurious features carried
lating the EPSR model of the experimental neutron and X-ray
forward from the Fourier transform of high-Q noise, especially for the
X-ray measurement. data shown in Figure 3. From these, the coordination numbers
were calculated and are shown in Table 2. Full convergence of
the pRDFs is generally seen at 1 nm, with no long-range bulk
and Nd(NO3)3·6H2O-based DES using this method on the order, and most of the pRDFs show a very strong nearest-
utilized pulsed neutron source instrument (NIMROD) would neighbor interaction and insignificant higher-order solvation.
be complicated by neutron resonances, particularly for the The most dominant bonds are close range Ce−O ligation with
neodymium containing sample. The model refines well to both nitrate, water, and urea, displayed in Figure 4a. The Ce−O1
neutron and X-ray data despite the difficulties of corefinement, and Ce−OU ordering are distributed normally around 2.5 Å−1,
with only minor discrepancies in the neutron data at Q ≤ 2 Å whereas the Ce−NN and Ce−ON associations show a clear
due to residual proton inelasticity, which is challenging to bimodal distribution with two different coordination environ-
subtract from the data.61 No small-angle scattering was ments and different interaction lengths. Contrasting these
observed. The X-ray contrast proved essential because X-rays pRDFs with their corresponding coordination numbers (Table
are sensitive to electron density and hence highlight the 2) reveals that each cerium center is solvated by 3 water and
lanthanide coordination, shown by the prominent peak in the 1.5 urea molecules, and two shells of nitrate, approximately
X-ray data at Q = 2.8 Å−1. Simultaneously, the X-ray data and distributed as 1 close-range and 4 more distant anions, where
fits also match well with the major “solvent structure” peak the proximal ON is centered at 2.5 Å, and the distal ON is
seen at Q = 1.85 Å−1 in the two neutron contrasts, which are found at 4.5 Å. This would therefore suggest a range of cerium
more sensitive to proton positions. This peak occurs at slightly species, which are on average anionic, with cerium centers
higher-Q, and therefore shorter real-space distances, than the relatively overcoordinated by nitrate, but which also feature
same peak in the previously studied “Type III” DES ChCl:urea water and urea.16
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Table 2. Calculated Coordination Numbers (Ncoord) around

Cerium Ionsa
A B Rmax Ncoord
Ce Ce 7.6 3.25 ± 1.60
Ce O1 3.2 2.90 ± 1.56
Ce H1 3.7 5.91 ± 3.11
Ce NN 3.3 0.77 ± 0.81
Ce NN 4.2b 3.72 ± 1.36
Ce NN 4.2 4.49 ± 1.20
Ce ON 3.3 5.29 ± 1.55 Figure 5. Example oligomeric [-Ce-NO3-] complex taken from a
Ce ON 5.2b 10.25 ± 2.56 snapshot of the EPSR model. Nitrates that are not within bonding
Ce ON 5.2 15.54 ± 3.47 distance have been omitted for clarity, alongside urea and water,
Ce CU 4.3 1.49 ± 1.20 though these are also present as ligands. Here, Ce atoms are yellow, O
Ce OU 3.4 1.47 ± 1.19 atoms are red, and N atoms are blue.
Ce NU 5.4 5.62 ± 2.52
Ce HU2 5.4 6.33 ± 2.46 particularly “Type III” DES.28,29 Therefore, despite the
Ce HU1 6.4 10.96 ± 3.50 profound eutectic observed for these systems, the space they
Ce HU1 5.4 4.06 ± 2.09 occupy in the landscape remains an open question.65 It is
a
The presented numbers are the mean, calculated from >5000
noteworthy that this polyconjugated Ce-network structure is
iterations of the EPSR average, and the displayed errors represent one the maximum-entropy solution to the measured structure, with
standard deviation in coordination number as the system rearranges EPSR being an RMC-derived technique.66,67
about equilibrium. Rmax displays the maximum radius of integration Intercalating Nanostructure. Considering the SDF plots
for coordination numbers (ie. the first minima in respective pRDFs) in Figure 6 (orange surfaces, bottom row) supports the
accurate to 1 data bin, where the minimum radius of integration is set
to an arbitrary value before the onset of the peak. bRmin = 3.3 Å.

From these various interactions, it can be inferred that in the

absence of halides, the Ce-‘X’ correlations occur generally
through a strong Ce−O bond, and binding with nitrate is
electrostatically favored. The weaker close-range interactions
such as those shown in Figure 4b, i.e. the Ce−H1 and Ce−HU1
interactions, are merely a consequence of Ce−O ligation and
interactions between molecules, such as urea−water H-
bonding. Interestingly, most interaction distances are short,
and the Ce−Ce distance is the only prominent longer-range
interaction in the mixture, which peaks at 6.4 Å, with each Ce
surrounded by 3.25 other Ce centers. This is a remarkably
short separation for charge-dense cations, implying effective
short-range screening by the solvation corona of NO3−.
Coincidentally the Ce−Ce separation is almost exactly twice Figure 6. Spatial density function (SDF) plots showing the most
that of the Ce−NN (the nitrate center-of-mass), which may likely 3D configuration of each molecule with respect to one another,
help to explain the unusually large second-shell coordination of computed from >5000 iterations of the model. The top row shows
nitrate, if nitrate is acting as a bridging ligand to form urea (purple isosurfaces) and water (dark blue isosurfaces), whereas
the bottom row shows cerium (orange isosurfaces) and nitrate (cyan
concatenated chains of Ce3+. Simply viewing the EPSR box
isosurfaces), respectively around water (first column), nitrate (second
shows that many oligomeric [-Ce-NO3-] species can be found column), and urea (third column). The probability level of each
in the LnDES, an example of which is shown in a snapshot in isosurface is variable to facilitate viewing.
Figure 5. The variety of interactions throughout the box
supports the idea that “Type IV” DES contain both positive
and negative complex ions but do not necessarily support expected Ce−O bonding modes described above. However,
disproportionation.16 Having hidden the other neutral ligands, when these are considered alongside the neutral species, and
which are of course still present and tightly bound in reality, their calculated pRDFs (Figure 7) and associated coordination
the species in Figure 5 would be [Ce3(NO3)7]2+, and if only numbers (given in Supporting Information), a secondary
considering the nearest-neighbor of each lanthanide center, the picture of the solvent nanostructure becomes apparent, as
mean Ce formal charge is canceled without undergoing redox. these pRDFs give site-specific structural information for all
The dominance of the Ce−O structuring and the transient atom types.
formation of oligomeric cerium species is reminiscent of the The unbound neutral species appear to form an independent
polymeric chains found in network glasses, and indeed, the hydrogen-bonded network. There is significant self-structuring
formation of oligomeric chains is a well-known structural of each component; as shown in the water-centric pRDFs in
characteristic for trivalent metal ions in halide molten salts.63,64 Figure 7a, each water molecule is directly bound to 1 other
In this context, the ionic structuring in LnDES is more water at close-range with 6.3 waters in the second solvation
structurally relatable to molten salts and halometallate ILs17 shell (O1−O1 and O1−H1). Meanwhile, urea−urea interactions
than the structure of most organic molecular liquids, ILs,1 and (Figure 7b) are predominantly through HU12−OU H-bonds,
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Figure 7. Calculated pRDFs showing site−site correlations; (a) describes water−‘x’ interactions centered around the water O atom, (b) shows
urea−‘x’ interactions based around either the urea C or O, (c) shows nitrate−‘x’ interactions for both nitrate O and N, and (d) shows proton-based
interactions. The displayed pRDFs represent a statistical average of >5000 model iterations.

Figure 8. EPSR model snapshots showing the position and distribution of (a) water, (b) urea, and (c) nitrate molecules, represented as shaded
isosurfaces to aid with the visualization of the clustering phenomena. For scale, the box side length is 4.93 nm in every case. Arbitrary colors are
used except in the case of urea (b), where the color represents the distribution of nitrogen-rich (blue), hydrogen-rich (white), and oxygen-rich
(red) subdomains.

where each urea carbonyl group may be bound to either the The contribution of the nitrate must also be considered
proximal or distal urea protons, with no significant preference (Figure 7c). As with the neutral species, much of the nitrate is
for either. The primary solvation shell of urea, determined tightly bound to cerium centers via Ce−O bonding, and
from each molecular center (the CU carbon atom) is at probably more so due to the Coulombic attractions and
relatively long-range (Rmax = 5.9 Å), and 4.9 neighboring ureas effective close-range charge screening that is inferred.
are found within this sphere. The urea−urea and water−water However, nitrate−nitrate, nitrate−urea, and nitrate−water
interactions are shown in the SDF plots in Figure 6 (blue and interactions are still clearly observed. 2.43 nitrates are
purple surfaces, top row), which also highlights the interspecies associated with each water molecule (O1−NN), while 4.15
interactions. Water is generally found close to the water O1, nitrates are associated with each urea (NN-CU), and each
and the urea−water SDF also demonstrates how water is nitrate center sees 3.61 neighboring nitrates in its first solvation
capable of donating H-bonds to the urea OU or accepting them shell (NN−NN). Such high coordination, especially the
from the urea HU2 protons. The strong H-bonds between urea nitrate−nitrate interaction, is likely to be a secondary effect
and water are reflected in the O1−OU and O1−HU12 pRDFs from neighbors in the oligomeric [-Ce-NO3-] chains, when
and Ncoords. On average, each water has 1.5 urea molecules in considering the like-charge repulsions between anions and the
its primary solvation shell as determined from the O1−OU dominance of the cerium-centered interaction strength.
pRDF, though considering the low Ncoords for the O1−HU12 Similarly, the high urea-nitrate and water-nitrate Ncoords are
interactions, it appears that water is a more capable donor of likely to be a secondary feature, from nearest-neighbor and
H-bonds to urea than the reverse. The combination of urea− second-neighbor interactions within these species. The nitrate-
urea, water−water, and urea−water H-bonding interactions in based interactions can be visualized in Figure 5 (bottom row,
the LnDES is evocative of the nanostructure of concentrated cyan surfaces), helping to describe this effect. For example,
urea−water aqueous solutions.68 water is seen to form a strong and directional Ce−O bond, and
4937 DOI: 10.1021/acssuschemeng.8b05548
ACS Sustainable Chem. Eng. 2019, 7, 4932−4940
ACS Sustainable Chemistry & Engineering Research Article

while water−nitrate interactions are also seen in terms of X-ray scattering and atomistic modeling, and have correlated
strong H-bonds between protons and ON atoms, further this with their physical properties.
water−nitrate structuring can be seen extending in the same The LnDES have unusual physical properties, including low
plane as the Ce−O bond. Nitrates occupy the spaces between viscosity and high surface tension, and Gordon parameters
the linear ON-Ce bonding axes, while strong H-bonds are also higher than water. Analysis of neutron and X-ray diffraction
seen between the HU12−ON atom types, with relatively small data shows that their structure does not align closely with
Ncoords of 0.35 and 0.38 with significant standard deviations. “Type III” DES and is more relatable to chlorometallate ILs. In
Overall, considering the cerium-centered and molecular- the cerium-based DES that we have studied in detail, the
centered pRDF analysis as well as the SDFs gives a picture of nanostructure is dominated by Ce−O interactions, which are
two separate but interacting nanostructures in the liquid bulk, sufficiently strong that transient, network-like oligomeric
which is demonstrated by comparing snapshots of water and species of [-Ce-NO3-] are seen, forming a variety of polyanions
urea clusters (Figure 8a,b) and nitrate clusters (Figure 8c). and polycations, which were previously hypothesized of “Type
First there is a charge-dense pseudophase, containing IV” DES. Neutral species participate in this bonding, but
predominantly cerium centers and tightly bound ligands, stoichiometrically the cerium centers are overcrowded, and the
which include all the species present in the mixture but are remnants form a H-bond-rich pseudophase that is more closely
mostly nitrate, forming a network which contains fluxional related to the “Type III” DES structure but is even more like
oligomeric [-Ce-NO3-] polycations and polyanions. This concentrated mixtures of urea and water. Our findings contrast
region can be thought of as a networked molten salt-like with previous descriptions of metallic DES structures which
domain.69 Second, there is a mostly uncharged pseudophase, were considered as true ILs with perhalogenated metal
which is an H-bonded network predominantly of urea and of complex ions or disproportionated complexes. Our findings
water, though some nitrate is present. This region can be are therefore in line with previous studies of “Type IV” DES
thought of as a networked molecular solvent-like domain. This which suggested the formation of complex ions, but diffraction
pseudophase is less metal-rich and still appears to be associated techniques offer a more nuanced view of the structure, which
with the cerium centers and their complexes, likely leading to can be considered as a molecular-rich H-bonded pseudophase
fluxional behavior and constant ligand exchange. However, the which is “lubricating” an ionic pseudophase. Ongoing
reason behind the secondary pseudophase is evident when fundamental studies into DES therefore continue to show
considering the system stoichiometry: for each metal ion, there unexpected structures and outcomes and are challenging the
are 3 anions and 9.5 uncharged molecules. Hence, despite the fundamental definition of what constitutes a DES. The
strong Ce−O ligation, only so many species can coordinate considerations shown here are potentially of broad interest
each cation at a time due to steric crowding. Despite the usage to groups working with DES and attempting to apply these
of the term “pseudophase”, we stress that the system is fully neoteric solvents in any discipline; we have demonstrated this
miscible and hence there is no true phase separation, and these by showing the viability of LnDES for the direct combustion
are only transient structures which do not give any synthesis of lanthanide oxides for the first time. Clearly, there is
experimental small-angle signal and hence are not genuine a vast scope for further structural studies of DES in general
including the LnDES presented here.

■
large-scale structures with long lifetimes. Even oligomeric [-Ce-
NO3-] species are too small and transient to cause small-angle
scattering; these structures are simply manifestations of the ASSOCIATED CONTENT
differing degrees of short-range order. The term “micro- *
S Supporting Information

emulsion” is not appropriate for such phases, which are more The Supporting Information is available free of charge on the
adequately described by a bicontinuous, constantly interchang- ACS Publications website at DOI: 10.1021/acssusche-
ing, and fluxional structure. This is consistent with the overall meng.8b05548.
picture of protic ionic liquids presented by Hayes et al., where Glass transition temperature determination, combustion
all PILs were found to have a nanoscale structure that could be synthesis of lanthanide oxides, EPSR modeling, partial
described by a bicontinuous, spongelike model.70,71 The RDFs for noncerium species, and viscosity measure-
nanostructure described here also aligns with the “plasticized ments. (PDF)

■
Coulombic” region described by MacFarlane et al. for mixtures
of ILs with molecular solvents.3 Such systems could also be
AUTHOR INFORMATION
considered as an extended subclass of “poor” solvate ionic
liquids where the molecular species is a good donor but Corresponding Author
present in excess.72−74 Overall, the existence of these *E-mail: [email protected].
pseudophases can help to explain the unusual physical ORCID
properties of “Type IV” DES; the abnormally low viscosity Oliver S. Hammond: 0000-0002-5612-9343
and high calculated Gordon parameters are a result of strongly Daniel T. Bowron: 0000-0002-4557-1929
bound transient oligomers in flux with an interpenetrating H- Karen J. Edler: 0000-0001-5822-0127
bond network of small species. This can be understood as a Notes
pseudophase rich in H2O and urea which effectively lubricates
The authors declare no competing financial interest.

■
the system and mitigates the stronger Coulombic interactions
between cations and anions. ACKNOWLEDGMENTS

■ CONCLUSIONS
We have reported here the first lanthanide-based DES
O.S.H. thanks the STFC and EPSRC for cofunding a PhD
studentship via the EPSRC Centre for Doctoral Training in
Sustainable Chemical Technologies (EP/L016354/1; STFC
(LnDES), have investigated their structure using neutron and Studentship Agreement no. 3578). We thank the ISIS Pulsed
4938 DOI: 10.1021/acssuschemeng.8b05548
ACS Sustainable Chem. Eng. 2019, 7, 4932−4940
ACS Sustainable Chemistry & Engineering Research Article

Neutron and Muon Source for allocation of experimental Neutron Diffraction and Atomistic Modelling. Green Chem. 2016, 18,
beamtime on NIMROD, and for access to the X-ray diffraction 2736−2744.
instrument, under beamtime allocation RB1610312 (DOI: (20) Ashworth, C. R.; Matthews, R. P.; Welton, T.; Hunt, P. A.
10.5286/ISIS.E.73944558). Corrected neutron and X-ray Doubly Ionic Hydrogen Bond Interactions within the Choline
Chloride−urea Deep Eutectic Solvent. Phys. Chem. Chem. Phys.
scattering data is freely accessible in the Bath research data
2016, 18, 18145−18160.
archive system.75 (21) Araujo, C. F.; Coutinho, J. A. P.; Nolasco, M. M.; Parker, S. F.;

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