Volume 24

Number 28
28 July 2022
Pages 16925–17364

PCCP
Physical Chemistry Chemical Physics
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ISSN 1463-9076

PAPER
Tiancheng Mu et al.
Acidity scales of deep eutectic solvents based on
IR and NMR
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Acidity scales of deep eutectic solvents based on

IR and NMR†
Cite this: Phys. Chem. Chem. Phys.,
2022, 24, 16973
Fengyi Zhou,a Ruifen Shi,a Yingxiong Wang, b
Zhimin Xue, *c Baolong Zhanga
and Tiancheng Mu *a

Received 20th April 2022,
Accepted 27th May 2022
DOI: 10.1039/d2cp01816k
rsc.li/pccp
Acidic deep eutectic solvents (ADESs) have been utilized in various applications. Clearly, it is crucial to
obtain acidity information that could reveal the relationship with performance. However, appropriate
methods for measuring acidity are limited. Herein, we developed two promising approaches (without
additional solvents) to identify and characterize both Lewis and Brønsted acidities by applying
acetonitrile as an infrared probe and trimethylphosphine oxide (TMPO) as a nuclear magnetic resonance
(NMR) probe. The acetonitrile IR approach is suitable for measuring the acidity of Lewis ADESs by
monitoring the peak of n(CRN) around 2300 cm 1, and the 31
P-TMPO NMR approach could identify and
scale both Lewis and Brønsted acidities precisely. Moreover, a perfect linear relationship between the IR
shift of n(CRN) and the effective charge density of metal cations was established, which provides a better
understanding of Lewis acidity. In short, this study not only offers two efficient acidity measurement
methods but also provides a molecular basis for optimizing the performance of ADESs in applications.

Introduction Developing a robust acidity measurement method is chal-

Acidic deep eutectic solvents1 (ADESs) have exceptional proper-
ties that make them popular in catalysis, dissolution, and
extraction.2,3 They are cheaper and more environmentally
friendly than mineral acids (such as H2SO4 and HF). More
importantly, their acidic strength and type could be adjusted
easily according to specific reaction demands. It is well known
that acid types (Lewis/Brønsted) and acid strength have effects
on the activity and selectivity of catalytic reactions.4,5 According
to the acid type, ADESs could be divided into Brønsted acidic
deep eutectic solvents (BADES) and Lewis acidic deep eutectic
solvents (LADES).3 The acidity of BADES and LADES depends
on the activity of protons and the electron deficiency of the
metal ions, respectively. However, the acidity measurement of
ADESs with general applicability is limited.6,7 In this regard, it
is of great theoretical interest and industrial significance to
explore acidity measurement techniques and study the acid
rules of ADES.
a
Key Laboratory of Advanced Light Conversion Materials and Biophotonics,
Department of Chemistry, Renmin University of China, Beijing, 100872, China.
E-mail: tcmu@ruc.edu.cn; Tel: +86-10-62514925
b
Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan, 030001, China
c
Beijing Key Laboratory of Lignocellulosic Chemistry, College of Materials Science
and Technology, Beijing Forestry University, Beijing, 100083, China.
E-mail: zmxue@bjfu.edu.cn
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
10.1039/d2cp01816k
lenging because most methods require specific measurement
conditions. So far, several spectroscopy methods have been
proposed.8–10 As a basic molecule, pyridine could be used to
probe Lewis and Brønsted acid types simultaneously. In infra-
red (IR) spectroscopy, its absorption band at 1437 cm 1 has a
blue shift when pyridine interacts with Lewis acid sites, and a
new band around 1540 cm 1 appears when Brønsted acid sites
exist. Compared with pyridine, acetonitrile is a weaker base and
thus more sensitive.11,12 The n(CRN) stretching vibration of neat
acetonitrile appears at 2253 cm 1, and it shifts to a higher
frequency when interacting with acid sites. In addition to IR
probes, NMR probes have been applied for measuring acidity as
well.13,14 Due to the 100% natural abundance of 31P isotope and
a broad chemical shift range, the 31P-NMR technique has
relatively high sensitivity and good resolution. Thus, some
organic phosphorus compounds such as trimethylphosphine
(TMP) and trialkylphosphine oxides (R3PO) have been used as
probes for solid acids.15 It is worth noting that trimethylpho-
sphine oxide (TMPO) is more stable than TMP because TMP
could be oxidized to TMPO under ambient conditions.
Pyridine and acetonitrile have been employed to determine
the Lewis acidity of ionic liquids.10 However, the mechanism
for the appearance of multiple IR peaks upon the formation of
acetonitrile-acid complexes is still not very clear, and further
investigation into it is required. Coffie et al.16 used triethylpho-
sphine oxide (TEPO) as a probe to measure the Lewis super-
acidic ionic liquids with tricoordinate borenium cations, and
they found that the acidity was weakened by solvation when the

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superacidic ionic liquids are employed in solutions. More 1 : 10, and pyridine is 2 : 5), and then spreading into liquid films
importantly, according to Oliver’s work,17 low levels (o1 w%) on KBr windows or IR glasses. The FTIR spectra were recorded
of water could alter DES’s structure enough. Both studies on an FTIR spectrometer (Tensor27, Bruker) with a resolution
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suggest the demand for characterizing ADES without additional of 1 cm 1. All processes were performed at room temperature.
solvents. However, most studies of BADES indicate their acidity
in terms of pH and pKa values.7,18 In this case, it is desired to 31P-NMR characterization
characterize the acidity of ADESs under solvent-free conditions. All NMR samples were prepared by mixing TMPO and DESs in a
In this work, we describe two promising spectroscopic molar ratio of 1 : 10 and then taken and transferred to NMR
techniques to characterize the acidity of ADESs. The first tubes. Solution-state31P NMR spectra were recorded by using a
method uses acetonitrile as a probe to study the shift of the Bruker Avance 400 MHz NMR spectrometer. Because the deut-
IR absorption band, i.e., n(CRN). The second one is monitoring erated reagents may alter the DESs’ structure and affect its
the 31P chemical shift in NMR by using TMPO as the probe. acidity, we performed the NMR experiment by selecting D2O as
These two methods were investigated under solvent-free con- an external lock (D2O loaded in an inserted capillary tube). 85%
ditions to avoid the interference of solvent molecules on DESs’ H3PO4 aq. was used as the external reference at 0 ppm. And the
structures. The commonly used ADESs of four types were NMR data were later processed using the MestReNova program.
investigated to explore the universality of these methods, and
further results improve the understanding of Lewis acidity.
Results and discussion
Experimental The essence of spectroscopic probe methods lies in the inter-
action of probes with acid sites, which is illustrated in
Materials
Scheme 1. For the acetonitrile IR approach, the electron density
Malonic acid (99.5%), 1,3-butanediol (99%), and trimethylpho- of the CRN group decreases with interactions with acid sites,
sphine oxide (TMPO, 97%) were purchased from Aladdin which results in a blue shift of CRN stretching vibaration.19
Biochemical Technology Co., Ltd (Shanghai, China). Choline Similarly, variations of the 31P NMR chemical shifts are induced
chloride (ChCl, 98%), oxalic acid (99%) and 1,6-hexanediol by the change of P electron density when the acid sites interact
(97%) were acquired from J&K Scientific Ltd. Formic acid with the O atom of TMPO.15 These shifts resulting from the
(98%), acetic acid (99.8%), 1,2-propanediol (99%), 1,3- interactions are prerequisites for the following work.
propanediol (99%), 1,2-butanediol (98%), copper (II) chloride
dihydrate (AR) and 1,4-butanediol (99%) were purchased from IR probe
Macklin Biochemical Technology Co., Ltd (Shanghai, China).
Acetonitrile was chosen as the IR probe because the CRN
Propionic acid (99.5%), zinc chloride (98%), ferric chloride
stretching vibration absorption is sensitive and its region in IR
(97%), magnesium dichloride hexahydrate (98%), chromium
spectra is uncluttered.19 Compared with pyridine, acetonitrile
trichloride hexahydrate (99%), acetonitrile, and pyridine were
could probe the acidity with a smaller molar ratio. To explore
purchased from Sinopharm Chemical Reagent Co., Ltd. Gly-
the applicability of the acetonitrile IR approach in both Lewis
cerol (99.5%) ethylene glycol (99%) copper (II) chloride (98%),
and Brønsted acidic DESs, four type I DESs based on ChCl and
tin(II) chloride (99%), cobalt dichloride hexahydrate (98%),
metal chlorides, five type II DESs based on ChCl and metal
acetonitrile-d3 (99.5 atom% D), ferric (II) chloride tetrachloride
chloride hydrates, seven type III DESs formed by ChCl and
(98%), aluminum chloride hexahydrate (98%) and manganese
organic alcohols and acids, and sixteen type IV DESs composed
dichloride tetrahydrate (98%) were acquired form Innochem.
by metal chlorides and polyols were chosen (Table S1, ESI†).
Calcium dichloride hexahydrate (98%) was acquired from Acros
Fig. 1A–C show that type I DESs were explored by using CH3CN,
Organics. All chemicals were used as received without further
CD3CN, and pyridine as probes, respectively. For pure CH3CN,
purification.
the peak at 2293 cm 1 is formed by the Fermi resonance
Synthesis
All DESs were prepared by simply mixing components at fixed
ratios and heating at the given temperatures until a homoge-
neous, transparent phase had formed. The components, molar
ratios, and heating temperatures of the prepared DESs are
shown in Table S1 (ESI†). The water content of the prepared
DESs was determined to be below 300 ppm by Karl Fischer
titration.

IR characterization
Scheme 1 Interactions of probes, (a) acetonitrile and (b) trimethylpho-
All IR samples were prepared by mixing probe molecules with sphine (TMPO), with Brønsted acid sites (H+) and Lewis acid sites (Mn+),
DESs at given molar ratios (the ratio of CH3CN and CD3CN is respectively.

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Fig. 1 FT-IR spectra of (A and D) CH3CN, (B and E) CD3CN and (C and F)
pyridine as probes mixed with LADESs at fixed molar ratios of 1 : 10
(CH3CN/CD3CN : DES) and 2 : 5 (pyridine : DES). (A–C) Type I DESs
(a) ChCl:2SnCl2, (b) ChCl:2FeCl3, (c) ChCl:2ZnCl2, (d) ChCl:2CuCl2. Gray
lines on the top are FT-IR spectra of pure probes: (A) CH3CN, (B) CD3CN,
and (C) pyridine. (D–F) Type II DESs (a) ChCl:2CaCl2
6H2O, (b) ChCl:MgCl2

6H2O, (c) ChCl:CoCl2
6H2O, (d) ChCl:CuCl2
2H2O, (e) ChCl:CrCl3
6H2O.
between n(CRN) and the combination of d(CH3) and n(C–C).19,20 In
this study, CD3CN was used to avoid the interference of Fermi
resonance, and pyridine was used as a control to verify the
results given by acetonitrile.12 As shown in Fig. 1A(b and c), a
new band appears at 2310 cm 1 for ChCl:2FeCl3, 2318 cm 1 for
ChCl:2ZnCl2, and 2321 cm 1 for ChCl:2CuCl2, indicating that
Lewis acidity increases in the order ChCl:2FeCl3 o ChCl:2ZnCl2 o
ChCl:2CuCl2. While ChCl:2SnCl2 has no new band occurred, it
is probably because the new band overlaps with the other peak.
After removing the Fermi resonance by using deuterated acet-
onitrile, as shown in Fig. 1B(a), there is a shoulder and the
fitting result shows its position is 2277 cm 1 (Fig. S2, ESI†).
Thus, the results are consistent (Fig. 1A–C). Following are the
results of type II DESs, as shown in Fig. 1D and E, the acidity
order is ChCl:2CaCl2
6H2O o ChCl:MgCl2
6H2O o ChCl:CoCl2

6H2O o ChCl:CuCl2
2H2O o ChCl:CrCl3
6H2O. However, the
results are not completely aligned with the results of pyridine.
The shift of n(CRN) in ChCl:CrCl3
6H2O is the highest, while
for pyridine, ChCl:CrCl3
6H2O is less acidic than ChCl:CoCl2

6H2O as shown in Fig. 1F. The discrepancies identified between
the results obtained using the two probes have little relation-
ship with the use of different molar ratios (Fig. S3, ESI†), and
we think the main reason is the different structures and
properties of probes. Previous studies about acetonitrile found
it correlates with the radius and charge of the cation,21,22 and
further verification is provided in detail below. Type IV DESs
are Lewis acids comprised of metal chlorides and polyols. As
shown in Fig. 2A–C, CuCl2:4EG, ZnCl2:4EG, and FeCl3:4EG were
measured by using different probes, and the results are con-
sistent with each other, CuCl2:4EG 4 ZnCl2:4EG 4 FeCl3:4EG.
Likewise, as shown in Fig. 2A and B, the peak of the Fermi
resonance overlaps with the highest peak of FeCl3:4EG. In
addition, the acidity of BADESs was investigated by the
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Fig. 2 FT-IR spectra of (A, E) CH3CN, (B, D) CD3CN, and (C) pyridine as
probes mixed with different DESs at fixed molar ratios of 1 : 10 (CH3CN/
CD3CN : DES) and 2 : 5 (pyridine : DES). (A–C) From top to bottom, green,
red, and blue lines are systems CuCl2:4EG, ZnCl2:4EG, and FeCl3:4EG,
respectively. (D) The system of CuCl2:nEG at different molar ratios, from
top to the bottom, n = 2.5, 3, 4, 5. (E) ChCl:nHCOOH as Brønsted DESs
with decreasing acid content from top to the bottom, n = 9, 5, 2. (F) The
correlation between n(CRN) of CD3CN as the probe in type II DESs and the
effective charge density Z* of metal cation equal to the charge and radius
cubed ratio, Z* = z/r3.
acetonitrile IR approach as well (Fig. S4, ESI†). The results
show that different DESs appeared in spectra without distinc-
tions, even though the pKa values of constituent acids in DESs
are quite different. From the point that the higher content of
probe could show a clearer peak signal, we also explored the
effect of acetonitrile content in BADES, but the results (Fig. S5,
ESI†) show it has little impact in improving performance. In
other words, in comparison with BADES, the acetonitrile IR
approach is more suitable for LADES.
Common metal salts can be hydrolyzed easily so it is
difficult to measure their Lewis acidity, therefore little informa-
tion is available regarding their Lewis acidity. In this context,
the interaction mechanism between acetonitrile and metal ions
of DESs is important. First, CuCl2 and ethylene glycol were used
to prepare DESs at different molar ratios, as shown in Fig. 2D,
the area of peaks at 2315 cm 1 increases with the increasing
content of CuCl2, which confirms that the interaction between
Lewis acid and acetonitrile results in the formation of the high
peak, while the low peak around 2263 cm 1 (CD3CN) or
2253 cm 1 (CH3CN) has no intuitional relationship in deter-
mining Lewis acidity. As mentioned above, it was found that
shifts of the high peaks in spectra are highly linear-correlated
with the effective charge density Z* of the metal cation (Fig. 2F).
This supported the theory that the decrease of ionic radius and
the increase of charge density could increase the effective
charge density,23,24 and thus the Lewis acidity increases. It
should be mentioned that FeCl3 absorbs water easily so that
two FeCl3-containing DESs as shown in Fig. 1C(b) and 2C have
peaks at 1540 cm 1, indicating the existence of Brønsted acidic
sites. And this may explain why these two DESs have higher
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peaks around 2255 cm 1 than the other DESs’ peaks (Fig. 1A

and 2A). Therefore, when acetonitrile is used as the IR probe to
determine Lewis acidity, three peaks generally appear and we
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classify them into i, ii, and iii (Table 1). The peak i around
2253 cm 1 (CH3CN) and 2263 cm 1 (CD3CN) could be affected
by protons and free acetonitrile. The peak ii around 2293 cm 1
is the Fermi resonance (CH3CN) which is not directly affected
by the Lewis acid. The peak iii around 2300 cm 1 is the main
evidence of Lewis acidity. To corroborate the effectiveness of
this approach in practical applications, we made a correlation
between the Lewis acidity of metal ions and performance in
different applications (Fig. S6, ESI†) and found a certain
relevance, which means that this approach could offer gui-
dance in designing ADESs for specific reactions.
To better understand the peak i when acetonitrile interacts
with DESs, similar experiments were performed in BADESs
(ChCl:nHCOOH). As shown in Fig. 3E, a new band appears at
2263 cm 1 under conditions of a high content of HCOOH, and
the new band completely overlaps with the peak at 2253 cm 1
when the acid content is low. What contributes to the overlap is Fig. 3 31P NMR spectra of TMPO as the probe in ADESs. (A) TMPO mixed
with ChCl:2EG in different molar ratios. (B) 31P NMR spectra of TMPO
the key question to answer. Firstly, the peak is formed by the
mixed with BADESs in a fixed molar ratio of 1 : 10. (i) ChCl:2Oxalic acid,
overlap of multi-peaks. According to previous studies,20,25 (ii) ChCl:2malonic acid, (iii) ChCl:2formic acid, (iv) ChCl:2acetic acid, and
different ionic species exist in DES, and acetonitrile molecules (v) ChCl:2propanoic acid. (C) 31P NMR spectra of TMPO in LADESs.
interact with these ionic species by hydrogen bonding.19 Sec- (i) ZnCl2:4(1,2-butanediol), (ii) ZnCl2:4(1,2-propanediol), (iii) ZnCl2:4ethy-
ondly, the magnitude of the blue shift is affected by the acidity lene glycol, (iv) ZnCl2:4(1,3-propanediol), (v) ZnCl2:4(1,3-butanediol),
(vi) ZnCl2:4(1,6-hexanediol), and (vii) ZnCl2:4(1,4-butanediol). (D) Blue
(Fig. 2E), which means that the increasing proton content
pentagons show the correlation between the 31P NMR chemical shift of
strengthens the hydrogen bonding with the CRN group. TMPO in BADES and pKa of organic acids used in BADES; orange rhombi
Consequently, the CRN group could form hydrogen bonds show the correlation between the 31P chemical shift of TMPO in organic
with both protons and other ionic species, and their formed IR acid and pKa of organic acids. pKa: 1.27 (oxalic acid), 2.82 (malonic acid),
peaks would overlap since the hydrogen bond strength is 3.74 (formic acid), 4.74 (acetic acid), and 4.87 (propanoic acid).

similar.

NMR probe
TMPO could interact with both Lewis and Brønsted acids, and
the electron density on the 31P atom decreases with increasing
acid strength thus the dP values increase.15 As shown in Fig. 3A,
the appropriate molar ratio of TMPO to DES is 1 : 10,26,27 which
shows a clear 31P signal. As shown in Fig. 3B, the acidity of
BADES could be differentiated clearly, and the acidity order of
BADES corresponds to the pKa of organic acids: ChCl:2propa-
noic acid o ChCl:2acetic acid o ChCl:2formic acid o
ChCl:2propanedioic acid o ChCl:2oxalic acid. The results
indicate that HBDs have a significant effect on Brønsted acidity,
and their linear correlation provides an additional validation
(Fig. 3D). To better understand the meaning of intervals of dP
values, we measured the dP values of organic acids (Fig. S10,
ESI†), and a good linear correlation between the 31P NMR
chemical shift and pKa was found (Fig. 3D). We also compared
the dP values of BADESs with their Kamlet–Taft hydrogen
bonding acidity (a), as shown in Table S2 (ESI†), they also have
the same sequence and similar intervals. This means that the
intervals of dP values might be the actual difference in acidity
and the dP values could provide a scale for BADES.
Next, LADESs comprised of ZnCl2 and different polyols were
measured. As shown in Fig. 3C, 31P NMR has a better resolution
than the acetonitrile IR approach (Fig. S4, ESI†). The dP values
revealed the subtle impact of different polyols on acidity.
Notably, there are no Brønsted acid sites in ZnCl2 and polyols,

Table 1 Assignments of the FT-IR peaks in the n(CRN) region

Position Assignment
Classify n (cm 1) Pure CH3CN CH3CN in DES
i 2253 n(CRN) —
B2253 — CRN


HDES (OH, CH3, and H+, e.g. CRN


HOCh+)a
ii 2293 Fermi resonance: ns,deform.(CH3) + n(C–C) —
B2293 — Fermi resonance with ns,deform.(CH3)


ODES (e.g. C–HCH3CN


O–HCh+)a
iii B2300 (2253 + Dn) — CRN


Mn+
a
Referenced to this work.25

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hence it could be simply explained that polyols could affect the
electron deficiency of Zn2+. Results show that ZnCl2:4(1,4-
butanediol) is more acidic than ZnCl2:4glycerol and
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ZnCl2:4ethylene glycol. Previous work has demonstrated the
existence of cationic species [ZnCl(ethylene glycol)]+ and
[ZnCl(ethylene glycol)2]+ by employing mass spectroscopy,28
and the formation of Zn ’ O bond has been verified as
well.29 Therefore, it suggests the steric effect of 1,4-butanediol
hinders the second OH group from complexing with Zn2+.
Compared to ZnCl2:4ethylene glycol, the ZnCl2:4(1,6-
hexanediol) has a similar chemical shift, which is further
evidence of the steric effect. To weaken the steric effect, we
changed the relative position of OH groups by choosing the
systems containing 1,2-butanediol and1,3-butanediol. As
shown in Fig. 3C(ii and iv), their lower Lewis acidity confirmed
our theory. Therefore, the 31P-TMPO NMR approach is such a
powerful tool that it could measure both Lewis and Brønsted
acid precisely and reliably.
Conclusions
In conclusion, we proposed acidity scales for Lewis and
Brønsted acidic DESs using the IR and NMR technique without
the addition of water or organic solvents (except for probes).
Accordingly, the acetonitrile IR approach is more suitable for
LADES, and the peak around 2300 cm 1 represents the inter-
action between the Lewis site and the CRN group. By examin-
ing different types of LADESs in this approach, the Lewis acidity
sequences of the metal cation are given as: Cu2+ 4 Zn2+ 4 Fe3+
(type IV), Cr3+ 4 Cu2+ 4 Co2+ 4Mg2+ 4 Ca2+ (type II), Cu2+ 4
Zn2+ 4 Fe3+ 4 Sn2+ (type I), and they are set apart because of
the different coordination environments. By validating the
linear correlation between Lewis acidity (Dn) and the effective
charge density Z*, we demonstrated for the first time that
decreasing the ionic radius and increasing the charge number
could enhance Lewis acidity. We also proved that the IR
acetonitrile method is versatile for practical application. The
subsequent results revealed that the 31P-TMPO NMR approach
could measure acidity accurately but fail to distinguish between
Lewis and Brønsted acidity because different acid types appear
in the same range. Furthermore, a good linear relationship
between the pKa and the chemical shift of organic acids was
found, which verifies that the NMR probe method could
provide an acidity scale for ADESs. Overall, by the combination
of IR and NMR techniques, the acidity of all types of DES can be
scaled. This work not only provides a tool for acidity determi-
nation but also deepens the understanding of ADESs.
Author contributions
Fengyi Zhou: investigation, writing – original draft, and writing –
review & editing. Ruifen Shi, Baolong Zhang and Yingxiong
Wang: investigation. Zhimin Xue: conceptualization, and writ-
ing – review & editing. Tiancheng Mu: conceptualization, writ-
ing – review & editing, and supervision.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (22073112, 21873012) for financial support and
Dr Chuanyu Yan at the National University of Singapore for
valuable discussions and suggestions.
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