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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
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,
Walden in 1914, who at that time never realized that ILs would Scarborough, and Tan17 give an overview on how to predict the
become a major scientic area after almost one century. energetic, physical, and spectroscopic properties of ILs by
Actually, ILs as innovative uids have received wide attention means of quantum chemical methods and empirical ap-
only during the past two decades. The number of SCI papers proaches. Among others, the COSMO-RS (conductor-like
published on ILs has exponentially increased from a few in screening model for real solvents) model, which is an a priori
1996 to >5000 in 2016, exceeding the annual growth rates of predictive model, is the most widely used in the IL community,
other popular scientic areas. This indicates that more and enabling theoretical calculations to decrease the amount of
more researchers are engaged in studying this exciting area, required experimental work. Zhang, Zhang, Zhang, and Deng18
with the outcomes being plentiful. A multidisciplinary study on focus on the nanoconned scale in ILs and the interactions
ILs is emerging, including chemistry, materials science, between ILs and the pore walls inside porous materials; this
chemical engineering, and environmental science. More brings to the ILs distinctly modied physicochemical properties
specically, some important fundamental viewpoints are now when compared to the corresponding bulk liquid. The potential
dierent from the original concepts, as insights into the nature applications of nanoconned ILs in catalysis, separation,
of ILs become deeper. For example, the physicochemical ionogels, supercapacitors, carbonization, and lubrication are
properties of ILs are now recognized as ranging broadly from thoroughly reviewed.
the oft quoted nonvolatile, non-ammable, and air and water In many chemical reaction processes, ILs are suggested as
stable to those that are distinctly volatile, ammable, and solvents, catalysts, reagents, or combinations of these. Zhang,
unstable. This is attributed to numerous combinations of Song, and Han19 provide a comprehensive review on the
cations and anions that meet the denition of ILs, leading to a catalytic conversion of cellulose, hemicellulose, lignin, and
diverse suite of behaviors. Regardless, ILs remain more lignocellulosic biomass into value-added chemicals and fuel
desirable than conventional volatile solvents and/or catalysts products, in which ILs act as the solvents or as IL-based
in many physical and chemical processes, often exhibiting catalysts. Various useful products can be obtained through
green and designer properties to a useful degree. lignocellulose valorization using ILs. Qiao, Ma, Theyssen,
As their chemical variety has grown, ILs have been further Chen, and Hou20 discuss an interesting family of ILs, i.e.
divided into many types, e.g., room-temperature ILs temperature-responsive ILs, which are used for the thermo-
(RTILs),16 task-specic ILs (TSILs),7,8 polyionic liquids regulated catalytic systems, such as hydroformylation, reduction
with H2 or CO, and coupling reactions. The working principle
(PILs),9,10 and supported IL membranes (SILMs)11,12 that
is that this type of IL can form a homogeneous mixture with the
include composites of ILs supported on metalorganic
reactants and products, but be separated from them readily
frameworks (MOFs).13,14 The hybrid organicionic nature of
when the reaction conditions are changed. From the viewpoint
ILs and the resulting intermolecular interactions give rise to a
of chemical engineering, the most important advantage is that
complex set of phenomena, creating an area of study that is
the gas/liquidsolid mass transfer limitations, which may be
both fascinating and challenging. Scientists and engineers are the rate-determining step in many catalytic transformations, can
often required to screen for suitable ILs quickly for a specic be overcome. Dai, Zhang, Huang, and Lei21 provide a detailed
process. For this purpose, the identication of structure review of ILs in several important and typical selective
performance relationships disclosing the interplay among ILs, oxidation reactions. ILs are preferable in this context as highly
solutes, supports, and the components in mixtures becomes ecient catalysts and innovative green solvents due to their
vital, requiring a close integration of experimental, theoretical, unique physical properties, including their nonvolatility,
and computational methods. Thus, it is necessary to collect our reaction rate acceleration eects, and high thermal stability.
recent ndings in this area and summarize the governing rules In particular, their use as biphasic catalysts, or immobilized
behind these complex phenomena. This compelled us to invite catalysts obtained by immobilizing metal- or nonmetal-
a number of prestigious scientists to contribute to this thematic containing ILs onto mineral or polymer supports, is highlighted
issue on ILs for Chemical Reviews. We should mention that in detail.
deep eutectic solvents (DESs) are not highlighted in this In separation processes, the selection of suitable solvents (or
thematic issue because DESs and ILs form two quite dierent separating agents) is a key for targeted process intensication.
solvent families. For more detail on DESs, please see the Ventura, e Silva, Quental, Mondal, Freire, and Coutinho22 oer
excellent review written by Smith, Abbott, and Ryder.15 a detailed review on the use of ILs as solvents in the extraction
This issue covers a range of dierent aspects of ILs, and/or purication of bioactive compounds, ranging from small
beginning with the multiscale science of ILs. It is evident that a organic compounds to more complex molecules. Dierent IL-
better understanding of IL behavior at the microscopic scale
will help to elucidate macroscopic uid phenomena, and thus
Special Issue: Ionic Liquids
promote the industrial application of ILs. Dong, Liu, Dong,
Zhang, and Zhang16 discuss the multiscale aspects of ILs, Published: May 24, 2017

2017 American Chemical Society 6633 DOI: 10.1021/acs.chemrev.7b00246

Chem. Rev. 2017, 117, 66336635
Chemical Reviews Editorial

based extraction processes are addressed, including liquid Douglas R. MacFarlane

liquid extraction, solidliquid extraction, solid-phase extraction, School of Chemistry, Monash University, Australia
and induced-precipitation techniques. The use of ILs can bring
about higher extraction yields and purication factors when AUTHOR INFORMATION
compared to conventional solvents and materials.
Corresponding Author
The progress in IL science is closely related to the
development of characterization techniques. Infrared (IR) and *E-mail:
Raman spectroscopies have proven to provide exceptional ORCID
fundamental insight into ionic interactions and the resulting
Zhigang Lei: 0000-0001-7838-7207
liquid structure in ILs. Paschoal, Faria, and Ribeiro23 discuss the
application of IR and Raman spectroscopies in the mid- and Notes
low-frequency range in the bulk liquid, as well as in Views expressed in this editorial are those of the authors and
understanding the structural modications of ILs accompanying not necessarily the views of the ACS.
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 Zhigang Lei is a professor at the State Key Laboratory of Chemical
be a useful resource. Resource Engineering at Beijing University of Chemical Technology,
Are ILs chemically stable? This topic is very important to China. He received his B.S. degree in 1995 from Wuhan Institute of
ensure that potential industrial application of ILs becomes a Technology, and his Ph.D. degree in 2000 from Tsinghua University.
reality. The review by Wang, Qin, Mu, Xue, and Gao24 covers Then, he became a postdoctoral researcher at Beijing University of
the chemical stability and reactivity of popular imidazolium- Chemical Technology, working with Professor Chengyue Li. In 2003
based ILs, including thermal decomposition, hydrolysis, and 2005, he worked as a researcher at the Research Center of Supercritical
nucleophilic reactions of anions under actual operating Fluid Technology (Tohoku University, Sendai, Japan). In 20052006,
conditions (e.g., high temperature, and the presence of water, he received the world-famous Humboldt Fellowship and carried out
air, or other gases). Thus, this review will provide a guide for his research as Chair of Separation Science and Technology
further industrial application of ILs. (Universitat Erlange-Nurnberg, Erlangen, Germany). In 2006, he
Two reviews in this issue deal with innovative applications of came back to Beijing University of Chemical Technology. His current
ILs in emerging areas. Egorova, Gordeev, and Ananikov25 research interests include chemical process intensication and
discuss the biological activity of ILs and their applications in predictive molecular thermodynamics. He has contributed to about
drug synthesis and drug delivery systems, with a particular 120 papers in international journals and one book entitled Special
emphasis on a novel active pharmaceutical ingredientionic Distillation Processes, published by Elsevier B.V. (2005).
liquid (APIL-IL) concept. In these cases, ILs are utilized as Biaohua Chen is a professor at the State Key Laboratory of Chemical
components of drug or drug delivery systems, and in the dual Resource Engineering at Beijing University of Chemical Technology,
roles of reaction media and catalysts in drug synthesis. In an China. He received his Ph.D. degree in 1996 from China University of
entirely dierent area, Watanabe, Thomas, Zhang, Ueno, Petroleum (Beijing). In 2000, he was a visiting scholar at Washington
Yasuda, and Dokko26 discuss the application of ILs in energy University in St. Louis and the University of Washington. He has
storage and conversion materials and devices. They review the received two National Science and Technology Progress Prizes
use of ILs as electrolyte materials for Li/Na ion, Li/S, and Li/ (second class), two provincial or ministerial level Science and
O2 batteries, fuel cell electrolytes, and electrode materials, Technology Progress Prizes (rst class), and one Natural Science
especially those including ionic-liquid-derived N-doped car- Progress Prize. Now he is a member of the Standing Committee of the
bons. Some ILs can meet the stringent criteria imposed by Beijing Chemical Industry Association and a member of the Editorial
various energy applications due to their unique properties, Board of the Journal of Petrochemical Universities (China). His main
including nonammability, high electrochemical stability, and research interests are green chemistry and environmental catalysis. He
high ionic conductivity. has contributed to more than 150 papers in international journals.
Finally, we would like to thank all the authors for their
Yoon-Mo Koo is a Professor at the Department of Biological
excellent contributions to this thematic issue. We also thank the
Engineering at Inha University, Korea. He received a B.S. degree
editorial sta of Chemical Reviews for their valuable suggestions
(Seoul National University, Korea), an M.S. degree (KAIST, Korea)
in initiating the thematic issue, as well as their hard work in
and a Ph.D. degree (Purdue University, USA), all in Chemical
handling the manuscripts. We hope that young scientists and
Engineering. He served as the Dean of College of Engineering, Inha
students who are engaged in studying this exciting area can
University, and as the President of Korean Society of Biotechnology
benet signicantly from the publication of this collection of
and Bioengineering, and he is currently a Member of the National
reviews and thereby make further important progress in the
Academy of Engineering, Korea. His research interests include
eld. biological separation and purication, microbial mixed culture, and
Zhigang Lei* ionic liquids. He has contributed to more than 140 papers in
State Key Laboratory of Chemical Resource Engineering, international journals. He was the organizing committee chairman of
Beijing University of Chemical Technology, China the 6th International Congress on Ionic Liquids (COIL-6), held on
Biaohua Chen June 1620, 2015, in Jeju, Korea.
State Key Laboratory of Chemical Resource Engineering, Douglas R. MacFarlane is an Australian Laureate Fellow at Monash
Beijing University of Chemical Technology, China University. He is also the program leader of the Energy Program at the
Yoon-Mo Koo Australian Centre for Electromaterials Science. His research interests
Department of Biological Engineering, Inha University, focus on a broad range of ionic liquid properties and applications. He
Korea was a Ph.D. graduate from Austen Angells group at Purdue and after

6634 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-
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/
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6635 DOI: 10.1021/acs.chemrev.7b00246

Chem. Rev. 2017, 117, 66336635