Editorial
pubs.acs.org/CR
Introduction: Ionic Liquids
I onic liquids (ILs) are normally dened as compounds
completely composed of ions with melting point below 100
C. The rst IL (ethylammonium nitrate) was reported by Paul
Walden in 1914, who at that time never realized that ILs would
become a major scientic area after almost one century.
Actually, ILs as innovative uids have received wide attention
only during the past two decades. The number of SCI papers
published on ILs has exponentially increased from a few in
1996 to >5000 in 2016, exceeding the annual growth rates of
other popular scientic areas. This indicates that more and
more researchers are engaged in studying this exciting area,
with the outcomes being plentiful. A multidisciplinary study on
ILs is emerging, including chemistry, materials science,
chemical engineering, and environmental science. More
specically, some important fundamental viewpoints are now
dierent from the original concepts, as insights into the nature
of ILs become deeper. For example, the physicochemical
properties of ILs are now recognized as ranging broadly from
the oft quoted nonvolatile, non-ammable, and air and water
stable to those that are distinctly volatile, ammable, and
unstable. This is attributed to numerous combinations of
cations and anions that meet the denition of ILs, leading to a
diverse suite of behaviors. Regardless, ILs remain more
desirable than conventional volatile solvents and/or catalysts
in many physical and chemical processes, often exhibiting
green and designer properties to a useful degree.
As their chemical variety has grown, ILs have been further
divided into many types, e.g., room-temperature ILs
(RTILs),16 task-specic ILs (TSILs),7,8 polyionic liquids
(PILs),9,10 and supported IL membranes (SILMs)11,12 that
include composites of ILs supported on metalorganic
frameworks (MOFs).13,14 The hybrid organicionic nature of
ILs and the resulting intermolecular interactions give rise to a
complex set of phenomena, creating an area of study that is
both fascinating and challenging. Scientists and engineers are
often required to screen for suitable ILs quickly for a specic
process. For this purpose, the identication of structure
performance relationships disclosing the interplay among ILs,
solutes, supports, and the components in mixtures becomes
vital, requiring a close integration of experimental, theoretical,
and computational methods. Thus, it is necessary to collect our
recent ndings in this area and summarize the governing rules
behind these complex phenomena. This compelled us to invite
a number of prestigious scientists to contribute to this thematic
issue on ILs for Chemical Reviews. We should mention that
deep eutectic solvents (DESs) are not highlighted in this
thematic issue because DESs and ILs form two quite dierent
solvent families. For more detail on DESs, please see the
excellent review written by Smith, Abbott, and Ryder.15
This issue covers a range of dierent aspects of ILs,
beginning with the multiscale science of ILs. It is evident that a
better understanding of IL behavior at the microscopic scale
will help to elucidate macroscopic uid phenomena, and thus
promote the industrial application of ILs. Dong, Liu, Dong,
Zhang, and Zhang16 discuss the multiscale aspects of ILs,
2017 American Chemical Society
ranging from the molecular level to the industrial level. The
popular multiscale method originating from other disciplines
was extended to IL systems. Furthermore, Izgorodina, Seeger,
Scarborough, and Tan17 give an overview on how to predict the
energetic, physical, and spectroscopic properties of ILs by
means of quantum chemical methods and empirical ap-
proaches. Among others, the COSMO-RS (conductor-like
screening model for real solvents) model, which is an a priori
predictive model, is the most widely used in the IL community,
enabling theoretical calculations to decrease the amount of
required experimental work. Zhang, Zhang, Zhang, and Deng18
focus on the nanoconned scale in ILs and the interactions
between ILs and the pore walls inside porous materials; this
brings to the ILs distinctly modied physicochemical properties
when compared to the corresponding bulk liquid. The potential
applications of nanoconned ILs in catalysis, separation,
ionogels, supercapacitors, carbonization, and lubrication are
thoroughly reviewed.
In many chemical reaction processes, ILs are suggested as
solvents, catalysts, reagents, or combinations of these. Zhang,
Song, and Han19 provide a comprehensive review on the
catalytic conversion of cellulose, hemicellulose, lignin, and
lignocellulosic biomass into value-added chemicals and fuel
products, in which ILs act as the solvents or as IL-based
catalysts. Various useful products can be obtained through
lignocellulose valorization using ILs. Qiao, Ma, Theyssen,
Chen, and Hou20 discuss an interesting family of ILs, i.e.
temperature-responsive ILs, which are used for the thermo-
regulated catalytic systems, such as hydroformylation, reduction
with H2 or CO, and coupling reactions. The working principle
is that this type of IL can form a homogeneous mixture with the
reactants and products, but be separated from them readily
when the reaction conditions are changed. From the viewpoint
of chemical engineering, the most important advantage is that
the gas/liquidsolid mass transfer limitations, which may be
the rate-determining step in many catalytic transformations, can
be overcome. Dai, Zhang, Huang, and Lei21 provide a detailed
review of ILs in several important and typical selective
oxidation reactions. ILs are preferable in this context as highly
ecient catalysts and innovative green solvents due to their
unique physical properties, including their nonvolatility,
reaction rate acceleration eects, and high thermal stability.
In particular, their use as biphasic catalysts, or immobilized
catalysts obtained by immobilizing metal- or nonmetal-
containing ILs onto mineral or polymer supports, is highlighted
in detail.
In separation processes, the selection of suitable solvents (or
separating agents) is a key for targeted process intensication.
Ventura, e Silva, Quental, Mondal, Freire, and Coutinho22 oer
a detailed review on the use of ILs as solvents in the extraction
and/or purication of bioactive compounds, ranging from small
organic compounds to more complex molecules. Dierent IL-
Special Issue: Ionic Liquids
Published: May 24, 2017
6633 DOI: 10.1021/acs.chemrev.7b00246
Chem. Rev. 2017, 117, 66336635
Chemical Reviews
based extraction processes are addressed, including liquid
liquid extraction, solidliquid extraction, solid-phase extraction,
and induced-precipitation techniques. The use of ILs can bring
about higher extraction yields and purication factors when
compared to conventional solvents and materials.
The progress in IL science is closely related to the
development of characterization techniques. Infrared (IR) and
Raman spectroscopies have proven to provide exceptional
fundamental insight into ionic interactions and the resulting
liquid structure in ILs. Paschoal, Faria, and Ribeiro23 discuss the
application of IR and Raman spectroscopies in the mid- and
low-frequency range in the bulk liquid, as well as in
understanding the structural modications of ILs accompanying
phase transitions induced by variable temperature or pressure.
To the best of our knowledge, it is the rst review on this topic,
and we expect that many scientists and engineers will nd it to
be a useful resource.
Are ILs chemically stable? This topic is very important to
ensure that potential industrial application of ILs becomes a
reality. The review by Wang, Qin, Mu, Xue, and Gao24 covers
the chemical stability and reactivity of popular imidazolium-
based ILs, including thermal decomposition, hydrolysis, and
nucleophilic reactions of anions under actual operating
conditions (e.g., high temperature, and the presence of water,
air, or other gases). Thus, this review will provide a guide for
further industrial application of ILs.
Two reviews in this issue deal with innovative applications of
ILs in emerging areas. Egorova, Gordeev, and Ananikov25
discuss the biological activity of ILs and their applications in
drug synthesis and drug delivery systems, with a particular
emphasis on a novel active pharmaceutical ingredientionic
liquid (APIL-IL) concept. In these cases, ILs are utilized as
components of drug or drug delivery systems, and in the dual
roles of reaction media and catalysts in drug synthesis. In an
entirely dierent area, Watanabe, Thomas, Zhang, Ueno,
Yasuda, and Dokko26 discuss the application of ILs in energy
storage and conversion materials and devices. They review the
use of ILs as electrolyte materials for Li/Na ion, Li/S, and Li/
O2 batteries, fuel cell electrolytes, and electrode materials,
especially those including ionic-liquid-derived N-doped car-
bons. Some ILs can meet the stringent criteria imposed by
various energy applications due to their unique properties,
including nonammability, high electrochemical stability, and
high ionic conductivity.
Finally, we would like to thank all the authors for their
excellent contributions to this thematic issue. We also thank the
editorial sta of Chemical Reviews for their valuable suggestions
in initiating the thematic issue, as well as their hard work in
handling the manuscripts. We hope that young scientists and
students who are engaged in studying this exciting area can
benet signicantly from the publication of this collection of
reviews and thereby make further important progress in the
eld.
Zhigang Lei*
State Key Laboratory of Chemical Resource Engineering,
Beijing University of Chemical Technology, China
Biaohua Chen
State Key Laboratory of Chemical Resource Engineering,
Beijing University of Chemical Technology, China
Yoon-Mo Koo
Department of Biological Engineering, Inha University,
Korea
6634
Editorial
Douglas R. MacFarlane
School of Chemistry, Monash University, Australia
AUTHOR INFORMATION
Corresponding Author
*E-mail: leizhg@mail.buct.edu.cn.
ORCID
Zhigang Lei: 0000-0001-7838-7207
Notes
Views expressed in this editorial are those of the authors and
not necessarily the views of the ACS.
Biographies
Zhigang Lei is a professor at the State Key Laboratory of Chemical
Resource Engineering at Beijing University of Chemical Technology,
China. He received his B.S. degree in 1995 from Wuhan Institute of
Technology, and his Ph.D. degree in 2000 from Tsinghua University.
Then, he became a postdoctoral researcher at Beijing University of
Chemical Technology, working with Professor Chengyue Li. In 2003
2005, he worked as a researcher at the Research Center of Supercritical
Fluid Technology (Tohoku University, Sendai, Japan). In 20052006,
he received the world-famous Humboldt Fellowship and carried out
his research as Chair of Separation Science and Technology
(Universitat Erlange-Nurnberg, Erlangen, Germany). In 2006, he
came back to Beijing University of Chemical Technology. His current
research interests include chemical process intensication and
predictive molecular thermodynamics. He has contributed to about
120 papers in international journals and one book entitled Special
Distillation Processes, published by Elsevier B.V. (2005).
Biaohua Chen is a professor at the State Key Laboratory of Chemical
Resource Engineering at Beijing University of Chemical Technology,
China. He received his Ph.D. degree in 1996 from China University of
Petroleum (Beijing). In 2000, he was a visiting scholar at Washington
University in St. Louis and the University of Washington. He has
received two National Science and Technology Progress Prizes
(second class), two provincial or ministerial level Science and
Technology Progress Prizes (rst class), and one Natural Science
Progress Prize. Now he is a member of the Standing Committee of the
Beijing Chemical Industry Association and a member of the Editorial
Board of the Journal of Petrochemical Universities (China). His main
research interests are green chemistry and environmental catalysis. He
has contributed to more than 150 papers in international journals.
Yoon-Mo Koo is a Professor at the Department of Biological
Engineering at Inha University, Korea. He received a B.S. degree
(Seoul National University, Korea), an M.S. degree (KAIST, Korea)
and a Ph.D. degree (Purdue University, USA), all in Chemical
Engineering. He served as the Dean of College of Engineering, Inha
University, and as the President of Korean Society of Biotechnology
and Bioengineering, and he is currently a Member of the National
Academy of Engineering, Korea. His research interests include
biological separation and purication, microbial mixed culture, and
ionic liquids. He has contributed to more than 140 papers in
international journals. He was the organizing committee chairman of
the 6th International Congress on Ionic Liquids (COIL-6), held on
June 1620, 2015, in Jeju, Korea.
Douglas R. MacFarlane is an Australian Laureate Fellow at Monash
University. He is also the program leader of the Energy Program at the
Australian Centre for Electromaterials Science. His research interests
focus on a broad range of ionic liquid properties and applications. He
was a Ph.D. graduate from Austen Angells group at Purdue and after
DOI: 10.1021/acs.chemrev.7b00246
Chem. Rev. 2017, 117, 66336635
Chemical Reviews Editorial

postdoctoral fellowships in France and New Zealand took up an (20) Qiao, Y.; Ma, W.; Theyssen, N.; Chen, C.; Hou, Z.
academic position at Monash in 1983. He has published more than Temperature-Responsive Ionic Liquids: Fundamental Behaviors and
600 papers and 30 patents. He was elected to the Australian Academy Catalytic Applications. Chem. Rev. 2017, DOI: 10.1021/acs.chem-
rev.6b00652.
of Sciences in 2007 and to the Australian Academy of Technological
(21) Dai, C.; Zhang, J.; Huang, C.; Lei, Z. Ionic Liquids in Selective
Sciences and Engineering in 2009. Oxidation: Catalysts and Solvents. Chem. Rev. 2017, DOI: 10.1021/
acs.chemrev.7b00030.
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Chem. Rev. 2017, 117, 66336635