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www.rsc.org/chemsocrev Volume 41 | Number 11 | 7 June 2012 | Pages 4089–4380
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CRITICAL REVIEW
Hairong Yue, Yujun Zhao, Xinbin Ma and Jinlong Gong
Ethylene glycol: properties, synthesis, and applications 0306-0012(2012)41:11;1-C
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Ethylene glycol: properties, synthesis, and applications
Hairong Yue, Yujun Zhao, Xinbin Ma and Jinlong Gong*
Received 30th December 2011
DOI: 10.1039/c2cs15359a
Ethylene glycol (EG) is an important organic compound and chemical intermediate used in a
large number of industrial processes (e.g. energy, plastics, automobiles, and chemicals). Indeed,
owing to its unique properties and versatile commercial applications, a variety of chemical
systems (e.g., catalytic and non-catalytic) have been explored for the synthesis of EG, particularly
via reaction processes derived from fossil fuels (e.g., petroleum, natural gas, and coal) and
biomass-based resources. This critical review describes a broad spectrum of properties of EG and
significant advances in the prevalent synthesis and applications of EG, with emphases on the
catalytic reactivity and reaction mechanisms of the main synthetic methodologies and applied
strategies. We also provide an overview regarding the challenges and opportunities for future
research associated with EG.
1. Introduction widespread since 1953.1,2 Currently, the global production and

consumption of ethylene glycol are about 20 million metric
Ethylene glycol (EG)—the simplest diol—was first developed
tons in 2010 with an estimated increase of 5–10% per year.4
in 1859 by a French chemist—Charles-Adolphe Wurtz—via
EG underpins almost every aspect of everyday life, particularly
saponification of ethylene glycol diacetate with potassium
associated with energy, chemicals, automotives, textiles, transpor-
hydroxide.1,2 In the early stages, though EG was produced
tation, and manufacturing technologies. Hence, it has attracted
on a very small scale, its development created a considerable
intense research interest across interdisciplinary fields.
revolution in coolant and explosives industries during World
In view of various synthetic methodologies of EG in conven-
War I.3 As the state-of-the-art invention by the Carbide
tional industries and modern technologies (Scheme 1), great efforts
Company of vapor-phase oxidation of ethylene to ethylene oxide
have been undertaken in order to improve synthetic processes,
(EO)—a precursor for EG synthesis via hydration—became
enhance catalytic performance, and reduce cost of investment. At
cheaply available, the industrial production of EG has been
present, the technology of hydration of ethylene oxidation accounts
for the major market share.5,6 Ethylene oxide is commercially
Key Laboratory for Green Chemical Technology of Ministry of produced from ethylene via hydrocarbons obtained from cracking
Education, School of Chemical Engineering and Technology,
Tianjin University, Tianjin 300072, China. E-mail: jlgong@tju.edu.cn; petroleum; however, with the depletion of fossil-fuel resources
Fax: +86 22 87401818 and increasing environmental concerns, it is imperative to
Hairong Yue obtained his B.S. Yujun Zhao earned his B.S.
(2006) and M.S. (2009) degree (1998) of industrial
degrees in chemical engineering catalysis from Dalian University
from Sichuan University. He is of Technology and his PhD
currently pursuing his PhD degree (2008) of chemical
under the supervision of engineering from Dalian
Professors Xinbin Ma and Institute of Chemical Physics.
Jinlong Gong. He is interested He has been an associate
in designing and synthesizing professor of Tianjin University
metal oxides for catalytic since 2010. His research
synthesis of ethylene glycol interests involve energy and
and ethanol from syngas. green chemical processes
including oxygenated com-
pounds synthesis via syngas or
Hairong Yue Yujun Zhao biomass, copper-based hydro-
genation catalyst preparation,
and structure catalyst reactors.
4218 Chem. Soc. Rev., 2012, 41, 4218–4244 This journal is c The Royal Society of Chemistry 2012
View Article Online
Scheme 1 Synthetic methodologies and applications of EG covered in this review.

develop alternative economical and energy-efficient processes.7 aspects regarding reforming of EG to hydrogen and chemicals15–17
Of particular interest is an indirect synthetic route from syngas.5,8–11 and electro-oxidation of EG in fuel cells.18–21 Remarkable
This process is a two-step reaction and conventionally uses noble developments have been also made in the ethylene glycol-
metals as catalysts in homogenous systems. The high operational assisted processes for synthesis of nanostructures with controlled
cost and problems of product–catalyst separation spur the particle sizes and morphologies on a large scale.22–26
development of atoxic base-metal heterogeneous catalysts. As EG is abundant in resources and has enormous potential
Additionally, technologies for conversion of biomass-derived applications, the research on constructing a series of new
materials (e.g., cellulose and glycerol) to EG have become synthetic and applied approaches concerned with environment,
significant, and have been regarded as promising and environ- energy, economies, and technologies has been flourishing for the
mental alternatives.12,13 past couple of decades. A large amount of publications, including
The prevalence of EG primarily originates from its wide several excellent reviews,7,18,21,27–29 have been dedicated to these
range of applications (Scheme 1). Importantly, considerable topics. However, these reviews primarily focused on a specific
interest has been generated from different scientific communities interest of subjects relevant to EG. For instance, Davis et al.
for applications in various fields, such as an antifreeze and provided an elegant review regarding the pathology and
coolant in automobiles, a deicing fluid for windshields and pathophysiology of the toxicity of ethylene glycol on each
aircraft, a desiccant for natural gas production, and a precursor organ system, along with information on diagnosis and current
for manufacture of polyester fibers and resins.5,8,14 In addition, treatment recommendations.27 Staples et al. reviewed the fate,
increasing efforts have been devoted to understand fundamental effects, and potential environmental risks of ethylene glycol.28
Xinbin Ma received B.S. and Jinlong Gong studied chemical

M.S. degrees in Chemical engineering and received his
Engineering from Tianjin B.S. and M.S. degrees from
University. He obtained his Tianjin University and his
PhD degree in Chemical PhD degree from the Univer-
Engineering from Tianjin sity of Texas at Austin under
University in 1996 under the the guidance of C. B. Mullins.
tutelage of Hongfang Chen He was a visiting scientist at
and Genhui Xu. He continued the Pacific Northwest
his academic career as an National Laboratory in 2007.
assistant professor in the same After a stint with Professor
department, and was promoted George M. Whitesides as a
to full professor in 2004. His research associate at Harvard
main scientific interests are University, he joined the
Xinbin Ma conversion of C1 molecules Jinlong Gong faculty of Tianjin University,
and synthesis of organic where he is currently a
carbonates and oxalates. professor in chemical engineering. He has served on the editorial
boards for several journals including Chemical Society Reviews,
Scientific Reports, Renewable Energy, and International
Journal of Hydrogen Energy. His research interests in surface
science and catalysis include catalytic conversions of green
energy, novel utilizations of carbon dioxide, and synthesis and
applications of nanostructured materials.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev., 2012, 41, 4218–4244 4219
View Article Online
Mosser-Ruck et al. overviewed effects of saturation protocols glycolaldehyde, glycolic acid (GA), and glyoxylic acid.34,35
of ethylene glycol on XRD patterns.29 Serov et al. highlighted Ultimately, glyoxylic acid can be converted to oxalic acid,
recent achievements in the development of direct ethylene which precipitates in the kidney and other tissues in the
glycol fuel cells (DEGFCs).18 Bianchini et al.21 and Huber presence of calcium forming calcium oxalate crystals (metabolic
et al.7 examined the status of applications of ethylene glycol pathway shown in Scheme 2).35
for direct alcohol fuel cells on palladium-based electrocatalysts
and synthesis of transportation fuels from biomass, respectively. 3.2 Pathogenesis
Taking into account striking developments of EG in a variety Ethylene glycol causes toxicity via several routes, such as
of fields including chemistry, physics, materials, biology and ingestion, absorption by skin, and inhalation exposure. The
medicine, this review attempts to provide current understanding toxic metabolites can affect multi-organs but predominately
regarding chemicophysical properties, synthetic methodologies, causes depression of the central nervous system as well as
and applications of EG, with an emphasis on chemistry and cardiopulmonary and renal failure.33,35,37 The damage to
catalysis. multi-organs is mainly due to the effects of various deleterious
metabolites including an electron transfer chain, oxidative

2. Physical properties phosphorylation, cellular respiration, glucose metabolism,
and deoxyribose nucleic acid (DNA) replication.27,35 Calcium
Ethylene glycol is the simplest diol and possesses several unique oxalate monohydrates, which are needle-shaped and relatively
properties owing to its characteristic structure (i.e., two hydroxyl benign crystals formed during high urinary calcium and
(OH) groups at adjacent positions along a hydrocarbon chain).1 oxalate concentration, have been detected by microscopic
Ethylene glycol is a colorless, odorless, relatively non-volatile, analysis of urine samples and demonstrate high pathogenic
and hygroscopic liquid with low viscosity (detailed physical potential to the renal system.34,37,38 Additionally, deposition of
properties are listed in Table 1).1,2 It tastes sweet and imparts calcium oxalate crystals within walls of cerebral blood vessels, and
a warming sensation to the tongue upon swallowing.1,28 It is the accompanying perivascular edema and inflammation, could
completely miscible with many polar solvents (e.g., water, induce further edema and damage to the basal ganglia.34,35,39
alcohols, glycol ethers, and acetone) and only slightly soluble These facts account for most clinical and pathological features
in non-polar solvents such as benzene, toluene, dichloroethane, of EG-poisoning.33,40
and chloroform.1,2,30,31 It is difficult to crystallize.1 When it is
cooled, it forms a highly viscous, super-cooled mass that
eventually solidifies to produce a glass-like substance.1,28,31 4 Synthesis of ethylene glycol
At present, the industrial approach to produce EG is hydration of
3 Toxicity ethylene oxidation.41–47 Owing to the constantly increasing demand
for EG, alternative routes for synthesis of EG from syngas have
3.1 Mechanism of chemistry
become very significant and attracted much interest.6,48–52
Ethylene glycol inherently has a low toxicity but produces A promising indirect synthetic process is an integrated technology
toxic metabolites.33,34 Even a small quantity of ingestion can based on oxidative carbonylation of methanol to dimethyl oxalate
be rapidly metabolized into intermediate metabolites in the liver (DMO) and subsequent hydrogenation to EG.53,54 In addition,
by alcohol dehydrogenase (ADH) or other hepatic enzymes to increased attention has been paid to the development of approaches
Table 1 Physical properties of ethylene glycol1–3,28,31,32
Auto-ignition temperature 427.0 1C

Boiling point at 101.3 kPa 197.6 1C
Critical temperature 446.9 1C
Critical specific volume 19.1 102 L g1 mol
Cubic expansion coefficient at 20 1C 6.2 104 K1
Density at 20 1C 1113.5 109 g m3
Flash point, closed cup (Pensky-Martens closed cup ASTM D93) 126.7 1C
Flash point, open cup (Cleveland Open Cup ASTM D92) 137.8 1C
Heat of combustion at 25 1C 1053.0 kJ g1 mol
Heat of vaporization at 1 atm 53.2 kJ g1 mol
Lower explosive limit 3.2 vol%
Molecular weight 62.1 g mol1
Normal freezing point 13.0 1C
Onset of initial decomposition 240.0 1C
Refractive index at 25 1C 143.0 102
Specific gravity (20/20 1C) 111.0 102
Solubility in water at 20 1C 100 wt%
Solubility of water in ethylene glycol at 20 1C 100 wt%
Surface tension at 25 1C 48.0 103 N m1
Upper explosive limit 53.0 vol%
Vapor density (air = 1) 2.1
Vapor pressure at 20 1C 7.5 Pa
Viscosity at 20 1C 19.8 103 Pa s
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Catalysts for the catalytic hydration of EO to EG primarily include

anions of salts (such as bicarbonate, bisulfate, and formate)
immobilized on an ion-exchange resins (IER),47,67,72,73 quaternary
phosphonium halides,68 polymeric organosilane ammonium
salts,68,74 supported metal oxides, and zeolites.41,45,46,71,75–79 A list
of representative catalytic systems for hydration of EO to EG is
shown in Table 2.
Both homogeneous and heterogeneous catalysts exhibited
excellent activity for EO hydration. Low-cost soluble salts were
reported active for this reaction. For instance, inorganic salts
and their acidic derivatives such as carboxylates, carbonates,
phosphates and sulfites were evaluated by Yang et al. for EO
hydration.70 The difference in selectivity of EG over these
catalysts (Table 2) can be ascribed to the different electron

density of acidic anions. The pH value also plays a key role in
determining EG selectivity since it could control the formation
Scheme 2 Metabolic pathway regarding the toxicity of ethylene rate of EOH+ by changing the concentration of H3O+.70 The
glycol. Reprinted with permission from ref. 36. Copyright 1994 optimal pH value for high EG selectivity was reported ranging
Wiley-VCH Verlag GmbH & Co. KGaA. from weakly acidic (3.0–6.0) to weakly basic (7.5–10.0).43,47
This result was also confirmed by van Hal et al., who
based on the conversion of biomass-derived glycerol,55 and investigated the influence of acidity/basicity for the homogeneous
cellulose.13,56–59 Other synthetic methods include conversion catalytic hydration over three types of catalysts—amines,
of formaldehyde or its derivatives,6,60–63 transesterification of bi-functional (e.g., acidic and moderately basic EDTA), and
ethylene carbonate,64–66 etc. salen materials (Table 2).43 Although both strong acidic or
basic catalysts can accelerate the reaction rate of the hydration,
4.1 Hydration of ethylene oxide
a low EG selectivity was obtained.43,47 Specifically, strong
Hydration of ethylene oxide is a conventional thermal process for acidity may accelerate the rate of the EOH+ formation, but
industrial production of ethylene glycol, which was established in the un-ionized anion species predominantly exist in the solution
1937 by the Union Carbide Corporation (UCC).46 This process at low pH values, which results in low EG selectivity.70 On the
initially proceeded in the absence of any catalysts and catalytic other hand, if the basicity is too strong, the rate of EOH+
processes were developed later on in order to obtain a higher formation would be low owing to the low concentration of
selectivity of EG.46,47 H3O+; consequently a large amount of unprotonated EO
The non-catalytic hydration reaction is dominant in industry would favor the oligomerization to form by-products.70 Therefore,
and generally proceeds at elevated temperatures. The reaction catalysts with adjustable pH ranges and suitable esterification
follows a serial-to-parallel route with formation of homologues capability would be desirable to enhance EG selectivity in
of ethylene glycol (Scheme 3).42,67–69 A carbon atom in the homogeneous systems.
protonated EO (EOH+) can be attacked by H2O to produce We note that a significant amount of work on hydration of
EG with the release of a proton.70 The formed EOH+ can also EO was carried out in heterogeneous catalytic systems. This status
be attacked by an unprotonated EO resulting in the creation of is attributed to the inherent advantages of heterogeneous catalysts
di-ethylene glycol (DEG).35 Similarly, tri-ethylene glycol since they could effectively eliminate the corrosive environment
(TEG) and polymerized ethylene glycols can be generated as and be easily removed from the reaction mixture by decantation
by-products.44 Note that DEG and TEG are mainly used and filtration.47,80 A large fraction of investigations cover the
for unsaturated polyesters and solvents and demands for use of catalysts immobilized on ion exchange resins, such as
both compounds are fairly steady. In order to obtain high styrene-divinylbenzene polymer multi-walled carbon nanotubes
selectivity to EG (e.g., 88–89%), a large excess amount of (PS-DVB/MWCNTs), bicarbonate-, bisulfate-, and formate-
water (20–25 molar ratio of water/EO) must be used.44,45 based DELOXAN AMP I-1, Lewatit M 500 WS, and Amberjet
However, higher water to EO ratio lowers EG concentration 4200 (Table 2).42,47,67,68,73,77 However, intrinsic drawbacks such
in the reaction mass, thus increasing capital investment for as swelling and deactivation of IERs under reaction conditions
unit operations (e.g., remove excess water).71 restricts their further industrial applications.43,45 Approaches
such as increasing cross-linking density have been considered to
Catalysts for EO hydration. Usage of appropriate catalysts solve the swelling problem, but it is at the cost of reducing the
is an alternative and simple way to attain high selectivity of EG. exchange capacity and the number of active sites of resins.77
Yu et al. have reported a method to deal with the swelling of
resins using a PS-DVB/MWCNTs IER composite, which was
prepared via an in situ suspension polymerization reaction,
followed by chloromethylation and amination.77 The resultant
Scheme 3 Reaction paths of oxide hydration reaction for the formation resin incorporated with CNTs had improved anti-swelling
of homologues of ethylene glycol. Reproduced with permission from capability, leading to improved stability without a decline in
ref. 67. Copyright 2005 Elsevier. conversion and selectivity in a long-time run (2200 h).
View Article Online
Table 2 Catalytic systems for the synthesis of EG by hydration of EO
Catalyst Reaction temperature/1C H2O/EO (mol mol1) EO conversion/% EG selectivity/% Ref.

HZSM-5 (Si/Al = 61.2) 150 22 98 76 41
Nb2O5nH2O 150 22 100 83 41
Ethylenediamine (EDA) 100 4 100 92 43
Na4EDTAa 100 4 100 86 43
N,N 0 0 -Bis(salicylidene)ethylenediamine 100 4 100 66 43
R1R2R3R4P+X b 50 B2 n/a 499 44
Sn-10wt%Nb2O5/a-Al2O3c 150 22 99.7 94.0 45
Amberjet 4200/HCO3 85 5 n/a 94.0 47
Lewatit MonoPlus M500/HCO3 85 5 n/a 94.3 47
Tributylmethylphosphonium iodide 150 2 98.0 81.8 68
Carboxylated 120 10 B100 96 70
Phosphated 120 10 B100 86 70
Carbonated 120 10 B100 95 70
Sulfited 120 10 B100 67 70

HxK1xNb3O8 (x = 0–1) 110 8 499 495 71
NaHCO3/LEWATIT M 500 WS 60 5 72.2 95.3 74
NaHCO3/DELOXAN AMP I-1 60 5 64.8 95.0 74
HCOONa/DELOXAN AMP I-1 60 5 49.7 93.1 74
NaOH/DELOXAN AMP I-1 60 5 37.5 95.4 74

Na2MO4/DELOXAN AMP I-1 60 5 46.0 93.6 74
10%Nb2O5/a-Al2O3 150 22 99.8 89.0 75
10%Nb2O5/2.23%MgAl2O4/a-Al2O3 150 22 99.8 90.6 76
PS-DVB/MWNT IER 85–105 8 99.2 95.6 77
Amberlite IR 120 127–193 n/a n/a Yield = 70–90 78
Nafion XR (6%)/SiO2 50–110 10 94 94 78
AlPO4-Cu(NO3)2 266 n/a 90 57 78
H2SO4 50–70 n/a n/a 90 78
a
EDTA: ethylenediaminetetraacetic acid. b
Ri: alkyl group, allyl group; X: halide ion. c Ratio of Sn/Nb = 0.80. d
pH value = 4.8. n/a: not
available.
Transition metal oxides are also promising catalysts for EO construction costs. Indeed, several commercial plants based on
hydration. Niobic acid (Nb2O5nH2O) possesses high acidity this technology have been established globally.
and structural stability and has been utilized for the reaction.81
A Nb2O5/a-Al2O3 catalyst exhibited an EG yield of B89% and Mechanisms of EO hydration. From an industrial viewpoint,
excellent stability within a 1000 h test, which was comparable to understanding of the reaction mechanism at a molecular level
Amberlite IR and Nafion XR (6%)/SiO2 and better than could help optimize the formula of catalysts and thus increase
AlPO4-Cu(NO3)2 and HZSM-5.41,75 Nb2O5/a-Al2O3 modified reactivity.70 As for the homogeneous systems, it is generally
with MgAl2O4 demonstrates a 1.6% increment in EG yield accepted that the hydration proceeds as follows: EO first reacts
(Table 2).76 However, the above approaches could not lower the with a proton to form a protonated EO, which further reacts with
H2O/EO feeding ratio, which is still an issue from an industrial nucleophilic H2O to form a protonated glycol. The protonated
standpoint. To further reduce water feeding, the addition of glycol then transfers a proton to H2O to form glycol and a
hydrophilic species (e.g., SnO2) to Nb2O5/a-Al2O3 could hydronium ion. Kozlovsky et al. investigated the homogeneous
significantly improve the water adsorption capacity and nucleophilic catalysts—anions of sodium bicarbonate—for
thereby result in a significant increase in EG selectivity.45 In catalytic hydration.69 They accordingly proposed a reaction
addition, Yang et al. prepared cation-exchangeable layered mechanism, which suggests that the reaction proceeded via
niobic acid (HxK1xNb3O8, x = 0–1) catalysts with facile ionization of the solvated a-oxides by the addition of nucleophilic
adjustability of acidity and unique self-exfoliation/re-stacking anion (A) and subsequent hydrolysis of an intermediate ester for
properties within the interlayer space, which exhibited the high formation of EG and regeneration of catalysts (Scheme 4).69,82
selectivity for EG (495%) under a H2O/EO ratio of 8.71 The Li et al. proposed a similar reaction mechanism in acidic
low H2O/EO ratio and high EG selectivity were ascribed to an systems (Scheme 5).45 The formation of positively charged
in situ self-exfoliation behavior of the catalysts and suitable water species via adsorption of H2O on acidic sites leads to the
acid strength of the Nb3O8 nanosheets. formation of positively charged EO species, which is subsequently
Additionally, a modified technology for EG production has attacked by nucleophile H2O to form positively charged EG by
been developed by the Mitsubishi Chemical Corporation proton transfer (Scheme 5A). As for the side reactions, the
(MCC), which consists of two reactions—carbonation with positively charged EG could react with another EO to form
CO2 to form ethylene carbonate (EC) and subsequent hydrolysis diethylene glycol and other polyglycols (Scheme 5B).45
to EG.44 The first step is typically catalyzed by phosphonium The nature of the acidity and basicity of catalysts could
salts (R1R2R3R4P+X). Overall selectivity of EG in the determine the type of intermediates and lead to different
process can reach more than 99%, which is higher than others reaction mechanisms. Van Hal et al. investigated several
reported in low water ratios (Table 2). This approach could simplify acidic/basic catalysts such as moderate basic amines, amphoteric
purification processes and induce lower energy consumption and compounds (e.g., EDTA-based), and salen ligands modified with
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mechanism (Fig. 1a), the reaction proceeded via ring opening

of ethylene oxide to form an alkoxide intermediate, which was
consequently hydrated to ethylene glycol. For the concerted
mechanism (Fig. 1b), the reaction occurred in a single step of
simultaneous ring opening and hydration. Based on calculated
activation energies, the concerted mechanism was suggested to
be favorable for the hydration of ethylene oxide to ethylene
glycol over H-ZSM-5 zeolites.
Scheme 4 Proposed mechanism of the catalytic hydration of EO by 4.2 Hydrogenation of dimethyl oxalate
anions. Reproduced with permission from ref. 69. Copyright 2002
Hydrogenation of DMO is one of the key steps in the synthesis
American Chemical Society.
of EG from syngas (e.g., derived from coal, natural gas,
biomass).14,49 The reaction proceeds via two steps—formation
CO2 or acetic acid.43 They proposed a plausible reaction of methyl glycolate (MG) and hydrogenation of MG to EG
mechanism as shown in Scheme 6.43 For acid-catalyzed reaction, (Scheme 8).83,84 The reaction can be carried out in both
a proton first attacks the nucleophilic oxygen of an EO molecule homogeneous and heterogeneous systems based on base- and
to form an intermediate species, CH2(OH+)CH2, which was noble-metal catalysts, such as Ru, Ag, and Cu.5,8–11,83–90
subsequently converted to a more stable intermediate, For homogeneous systems, catalysts explored primarily focus on
+
CH2(OH)CH2. The latter reacts with H2O to form ethylene ruthenium-based compounds. For instance, H4Ru4(CO)8(PBu3)4,
glycol releasing a proton that maintains the constant acidity of the Ru(CO)2(CH3COO)2(PBu3)2, and Ru(CO)2(Ac)2(PBu)3 can
reaction solution. The base-catalyzed reaction follows a similar catalyze the hydrogenation of DMO with a maximum EG
trend and pH value of the solution determines selectivity of EG. yield of 82%, but a variety of by-products were produced from
In order to further clarify why EG selectivity increases with esterification, transesterification, and decarboxylation reactions.85–87
the increasing of the catalyst concentration when the pH value In addition, a high H2 pressure (e.g., 200 bar) is required for
of the solution keeps constant, Yang et al. evaluated the the efficient conversion of DMO.88 In order to further improve
reaction using inorganic salts and their acidic counterparts, selectivity and avoid using rigorous reaction conditions, interest
such as carboxylates, carbonates, phosphates and sulfites, and has been directed towards the use of ruthenium complexes with
proposed a more comprehensive mechanism (Scheme 7).70 an increased electron density on the ruthenium center, which
When the pH value is low, the strong acidity could accelerate would enhance the nucleophilicity of the intermediate hydride.
the formation rate of EOH+ so that Route 2 would be Elsevier and co-workers have employed Ru-based homogeneous
suppressed since the anion species predominantly exist in the catalysts obtained from Ru(acac)3 with the facially coordinating
un-ionized form in the solution. Alternatively, when the tridentate phosphine ligand CH3C(CH2PPh2)3 for the hydro-
formation rate of EOH+ is low, a large amount of unprotonated genation of DMO.83,88 Remarkably, this catalyst enabled
EO will favor the oligomerization through Route 3. complete conversion of DMO under relatively mild conditions
With respect to the heterogeneous systems, Maihom et al. (80–100 bar H2, 120 1C for 16 h) with an EG yield of 95%.
theoretically elucidated the reaction mechanism over H-ZSM-5 Considering that sulfur-based ligands have similar properties to
zeolites.46 Two different pathways—so called stepwise and the phosphine ligands, Boardman et al. reported on utilization of
concerted—have been considered (Fig. 1). For the stepwise facially-capping sulfur-based ligands [MeC(CH2SBu)3] coupled
Scheme 5 Proposed mechanism of the catalytic hydration of EO under acidic conditions. Reproduced with permission from ref. 45. Copyright
2006 Elsevier.
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Scheme 6 Schematic diagrams of reaction mechanisms in acidic and basic systems for hydration of EO. Reproduced with permission from ref. 43.
Copyright 2007 Elsevier.
Scheme 7 Modified schematic diagrams of reaction mechanisms in (a) acidic and (b) basic systems. Reproduced with permission from ref. 70.
with a ruthenium complex.84 However, the obtained results on neutral or weak acid/alkaline carriers. Representative copper-
indicated that the catalyst was not highly selective for EG, but based catalytic systems for hydrogenation of DMO to EG are
tended to form methyl glycolate. listed in Table 3.
Inexpensive heterogeneous catalysts for hydrogenation of Numerous efforts have been exerted to understand the
oxalates have attracted extensive attention for the past nature of active sites for the hydrogenation of DMO to EG.
years.5,9–11,91–102 Particularly, copper-based catalysts have Particularly, the valence state of active copper sites is still
been reported to be highly active for vapor-phase hydrogenation elusive. Li et al. prepared a number of Cu/SiO2 catalysts via
of DMO to EG.5,9,11,91,97,102 Cupreous sites account for selective several methods and found that Cu+ species could be the
hydrogenation of the carbon–oxygen bond and are relatively active site.107 Chen et al. investigated Cu/SiO2 catalysts with
inactive for hydrogenolysis of the carbon–carbon bond.103–105 various ratios of Cu+/Cu0 and copper surface areas prepared
We note that strong acidic sites induce the intermolecular at different temperatures of ammonia evaporation.5 On the
dehydration of EG to ethanol, whereas strong basic sites catalyze basis of a correlation between catalytic activity with Cu0 and
the Guerbet reaction leading to the formation of 1,2-butanediol Cu+ surface areas, they proposed that catalytic activity lay in the
(1,2-BDO).106 Both products diminish the selectivity of EG. cooperative effect between Cu0 and Cu+, which dissociated
Therefore, catalysts for this reaction are generally supported hydrogen and activates DMO, respectively. Yin et al. synthesized
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catalysts exhibited excellent performance owing to the highly

dispersed silver particles that are active in chemo-selective
hydrogenation of both CQC and CQO bonds.8,89 Moreover,
the selectivity of MG and EG can be tuned efficiently over this
catalyst by regulating the reaction temperature. Copper based
alloys (e.g., CuxNiy/HMS and CuAu alloys) were also examined
to understand the origin of ensemble and ligand effects for the
reaction.10,90
4.3 From biomass

Conversion of cellulose. Cellulose is the most abundant
source of biomass.7 Since it comes mainly from grass and
agricultural and wood wastes, direct conversion into useful organic

compounds, including sugars and alcohols, is one of the most
attractive routes for industrial utilizations of cellulose.13,56,57,59
Fig. 1 Energetic profiles for (a) stepwise and (b) concerted mecha- This process can be generally divided into two steps, including
nisms of the ethylene oxide hydration calculated at the ONIOM level
selective hydrolysis into glucose and further transformation

of theory (energies are in kcal mol1). Reproduced with permission
into fuels and chemicals.13,56 However, unlike other water
from ref. 46. Copyright 2008 American Chemical Society.
soluble polysaccharides, cellulose has a highly crystalline structure
composed of b-1,4-glycosidic bonds of D-glucose and is therefore
difficult to hydrolyze.56,108 Up to now, the hydrolysis of cellulose
with enzymes, mineral acids and bases, and supercritical water
still suffers from a series of problems such as separation of
products and catalysts and corrosion hazards.56,109–111
Scheme 8 Schematic diagrams of reaction mechanisms for hydro- Suitable catalysts for a single-step conversion of cellulose to
genation of DMO. Reproduced with permission from ref. 84. Copyright fuels or chemicals are desirable, which could promote several
2006 Royal Society of Chemistry. types of reactions including hydrolysis, hydrogenolysis, and
hydrogenation.56 Fukuoka et al. developed a one-step catalytic
Cu/HMS catalysts with different copper loadings to study the process of converting cellulose into polyols using a Pt/Al2O3
nature of active copper species.11 In addition to the synergetic catalyst with a 31% yield (25% sorbitol and 6% mannitol).12
effect between Cu0 and Cu+, they proposed that Cu+ could Based on this work, Luo et al. have greatly increased the
function as electrophilic or Lewis acidic sites to polarize the cellulose conversion (83.1%) and selectivity of sugar alcohols
CQO bond via the electron lone pair on oxygen, and thus (i.e. hexitol, 61.1%) using a Ru/AC catalyst at elevated reaction
improve the reactivity of the ester group in DMO. However, temperature (513 K).112
all of these investigations failed to unravel the precise role of However, the use of noble metals limits wide applications of
Cu0 or Cu+, and the synergetic effect of Cu0 and Cu+ was this process. Therefore, many efforts have been made towards
largely speculative. the development of less expensive but efficient catalytic systems.
Several other transition metals have also been reported Since the transition-metal carbides have similar electronic structures
active for the synthesis of EG from DMO. For example, Ag-, compared to Pt-group metals, Ji et al. reported Ni-promoted W2C
Ni- and Au-based catalysts could offer decent activity. Ag/SiO2 catalysts for direct catalytic conversion of cellulose to polyols
Table 3 Copper-based catalytic systems for hydrogenation of DMO to EG
Selectivity (%)
a 1 1
Catalyst Preparation method LHSV/h H2/DMO (mol mol ) T/K Conversion (%) DMO EG MG EtOH Ref.
20%Cu/SiO2-363 AE 0.5 50 473 79 57 43 1.8 5
1B-Cu/SiO2b UAG 0.7 80 463 99.7 93.0 3.3 1.8 9
5%Cu/HMS IWI 0.2 120 473 100 92 n/a n/a 91
50%Cu/SBA-15 ADP 0.6 100 473 100 99 n/a n/a 92
25%Cu/Al-HMS DP 1.8 50 473 100 98 n/a n/a 93
20%Cu/HMS-333 IE 0.7 100 473 100 98 n/a n/a 95
20%Cu/SiO2 IM 0.8 60 516 100 62.5 9.8 25.6 97
20%Cu/SiO2 DP 0.8 60 516 100 94.1 1.2 2.0 97
15.6%Cu/SiO2 UH 0.8 200 473 100 90 n/a n/a 98
CuB/HMS(2/1)c EVI 2.5 120 473 100 98 n/a n/a 99
Cu/H1S1d MIM 1.5 100 473 100 98 n/a n/a 100
20%Cu/SiO2e AE 2.7 80 473 95.4 92.8 5.1 1.1 102
a
AE: ammonia evaporation, IWI: incipient wet impregnation, ADP: ammonia-driving deposition–precipitation, DP: deposition–precipitation,
IE: ion-exchange, UAG: urea-assisted gelation, UH: urea hydrolysis, EVI: ammonia evaporation-induced, MIM: modified impregnation.
b
1B-Cu: 1%B and 27% Cu. c Cu/B = 2/1. d H1S1:HMS/silica sol mass ratio of 1/1. e LHSV = 2.75 h1. n/a: not available.
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Zheng et al. have also prepared a series of W-based bimetallic

catalysts including Ni-W, Pd-W, Pt-W, Ru-W, and Ir-W and
obtained the maximum yield of EG (75.4%) on a Ni-W/SBA-15
catalyst.59
Lignocellulosic materials are another attractive feedstock
for EG production. As lignocelluloses are agriculturally available
in large quantities, conversion of lignocelluloses into energy
compounds and fine chemicals is of great significance for building
a sustainable world.116,117 Pang et al. used corn stalks as a
lignocellulosic feedstock instead of the commercial pure
microcrystalline cellulose over nickel-promoted tungsten carbide
catalysts for generation of EG and 1,2-propylene glycol.118 This
process can readily convert the lignocelluloses into EG with a
yield of B48% upon the corn stalk pretreatment with butanediol,

NaOH, H2O2, and ammonia.
Hydrogenolysis of polyols. Biomass-derived polyols have

Scheme 9 Catalytic conversion of cellulose into polyols. Reproduced emerged as promising building blocks for liquid fuels and
with permission from ref. 13. Copyright 2008 Wiley-VCH Verlag value-added chemicals.119,120 Among them, transformation of
GmbH & Co. KGaA. glycerol (a large surplus of glycerol is formed as a by-product
from production of biodiesel) to valuable commodity chemicals
(Scheme 9).13,56,113–115 In particular, Zhang et al. prepared would be of great interest.121,122 Catalytic hydrogenolysis
mesoporous carbon (MC) with three-dimensional (3D) inter- of glycerol to produce glycols such as ethylene glycol and
connected mesopores via a nanocasting approach to enhance propanediols (1,2-PDO and 1,3-PDO) is particularly attractive
dispersion and accessibility of the tungsten carbides.57 Compared (Scheme 10).55,121,123
to ordered mesoporous carbon (CMK-3) with 1D ordered Catalysts used for liquid-phase hydrogenolysis of glycerol
mesochannels or activated carbon with microporous structure, primarily focus on Cu-, Ni- and Ru-based compounds.55,121,123–127
MC-supported tungsten carbide catalyst exhibited a higher Representative catalytic systems for aqueous hydrogenolysis of
selectivity towards EG (up to 72.9%) in an aqueous solution. glycerol are listed in Table 4.
Scheme 10 Overall reaction of converting glycerol to propylene and ethylene glycols. Reproduced with permission from ref. 123. Copyright 2005 Elsevier.
Table 4 Catalytic systems for hydrogenolysis of aqueous glycerola
Selectivity
Catalyst P/MPa T/K Time/h Conversion/% EG EtOH CH3OH CH4 PDO Ref.
10%Ni/g-Al2O3 8 453 24 11.0 20.0 1.0 0 10.0 69.0 55
Ru+5%Ni/g-Al2O3b 8 453 24 12.0 12.0 3.0 1.0 8.0 76.0 55
Rh+5%Ni/g-Al2O3b 8 453 24 11.0 32.0 2.0 1.0 26.0 38.0 55
Ir+5%Ni/g-Al2O3b 8 453 24 9.0 35.0 2.0 1.0 26.0 35.0 55
0.5%Pt+5%Ni/g-Al2O3 8 453 24 64.0 42.0 3.0 2.0 37 15.0 55
Ru/CNTs-EG 4 473 12 82.9 23.0 3.3 n/a 20 30.0 121
Ru/AC 4 473 12 51.6 23.2 6.9 n/a 31.7 24.4 121
Ru/TiO2 4 473 12 81.7 12.7 8.3 n/a 25.3 35.2 121
Ru/Al2O3 4 473 12 80.8 11.5 7.1 n/a 36.1 26.7 121
Ru/graphite 4 473 12 16.0 18.3 4.7 n/a 36.1 53.0 121
Cu-ZnO (0.6)c 4.2 473 12 22.5 1.3 n/a n/a n/a 20.4 124
Ru/C+Amberlyst 8 473 10 6.5 1.9 0.8 0 1.3 75.6 126
Ru/C 8 473 10 29.1 40.0 0.9 4.7 24.4 29.4 126
a b
Reaction temperature: 473 K. Noble metal/Ni molar ratio 0.03. c Cu/Zn atomic ratio 0.6. n/a: not available.
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As shown in Table 4, Ru-based catalysts are highly reactive Ru particles.131 In addition, BASF used Pd/C and Pd/g-Al2O3
for glycerol hydrogenolysis. Specifically, bifunctional (i.e., catalysts to convert sorbitol to lower polyhydric alcohols
dehydration and hydrogenation) Ru/C catalysts combined (e.g., EG, 1,2-PG, ethanol and 1-propanol) with a overall
with an ion-exchange resin (Amberlyst) offered a selectivity conversion of 100% and 88%, respectively.137 For hydrogenolysis
of EG of B12% under 8.0 MPa.126 However, heat resistance of the of xylitol, DuPont achieved high yields of EG (B45%) and
ion-exchange resin could be of serious concern and excessive C–C PG (B33%) on Ni/Al2O3 and Ni/SiO2 catalysts by using
cleavage would be facilitated under hydrogenolysis conditions. more basic NaOCH3.135,138 The modification of Ni catalysts
Wang et al. developed CNTs-supported Ru catalysts for glycerol (e.g., 2.5%Ni-2.5%Re/C) resulted in improved performances
hydrogenolysis to produce 1,2-PDO and EG as major products.121 (a combined selectivity of 89% to EG, PG and glycerol, and a
Ni-based catalysts are another interesting material since Ni conversion of 50%) in the presence of KOH.136 Recently, Sun
is inexpensive and has the capability to break the C–C bond et al. systematically investigated the effects of acid-basicity and
efficiently. Ni/g-Al2O3 promoted by a small amount of Pt showed dehydrogenation/hydrogenation properties of supported Ru
a high selectivity of ethylene glycol from hydrogenolysis of catalysts to elucidate the reaction mechanism for xylitol
glycerol, which was attributed to promotion of the retro-aldol hydrogenolysis.129 The results reflected that the reaction
reaction of glyceraldehydes and dissociation of the C–C bond by involves a bimodal reaction pathway, i.e. dehydrogenation
the Pt atoms on the Ni-rich PtNi alloy surface.55 Recently, an of xylitol to glycolaldehyde and glyceraldehyde, followed by
efficient catalytic route based on coupling of catalytic aqueous direct glycolaldehyde hydrogenation to EG and by sequential
reforming and hydrogenation of glycerol has been developed glyceraldehyde dehydration and hydrogenation to PG.
using RANEYs Ni for production of EG (Scheme 11).127 It is
noteworthy that no hydrogen was needed and the diluted
aqueous glycerol can be directly used as the feedstock under 4.4 Transesterification of ethylene carbonate and methanol
milder reaction conditions (0.1 MPa nitrogen atmosphere). In Ethylene glycol can also be synthesized concurrently with
addition, diol products can be easily separated because glycerol is dimethyl carbonate (DMC) by a transesterification reaction
fully converted and the catalyst can be easily removed by filtration between ethylene carbonate and methanol (Scheme 12).65,66,139
or magnetic separation (RANEYs Ni is paramagnetic).127 As EC is generally synthesized via the reaction of carbon
Higher polyols (e.g., xylitol and sorbitol) are also noticeable dioxide (an abundantly available green house gas) and ethylene
because they can be converted to different products such as oxide, the transesterification for EG synthesis is useful from the
EG and PG and are readily available from abundant ligno- viewpoint of green chemistry and sustainable development.64
cellulose.128 Hydrogenolysis of xylitol and sorbitol to EG and Efforts focused on this process were made primarily on
PG requires cleavage of specific C–C and C–O bonds, which developing highly efficient catalysts. Strong or moderate basic
generally involves the use of Ni, Ru and Pd-based catalysts sites were found to be catalytic active for this reaction.140
and basic promoters.129–138 For hydrogenolysis of sorbitol, Nippon Shokubai Co., Ltd. reported 59% conversion of EC
Clark explored kieselguhr supported Ni catalysts with Ca(OH)2 as with a 30% yield of EG using rare earth oxides such as yttrium
a promoter, leading to an EG yield of 16% in water.132 The Ethyl oxide and cerium oxide.141 Smectites containing magnesium
Corporation reported sulfur-modified Ru/C catalysts for the and/or nickel species exhibited excellent reactivity for the
reaction with a combined selectivity of EG, PG and glycerol as concurrent synthesis of DMC and EG (conversion of EC is
high as 96% in the presence of Ca(OH)2.134 Zhou et al. employed B55–75% and the overall selectivity is B89–92%).65 Smectite
mesoporous carbon nanofibers instead of the commercial is a layered clay mineral consisting of one octahedral sheet
activated carbons to support Ru nanoparticles and obtained an sandwiched by two tetrahedral sheets.142 Since the octahedral
increase in the selectivity of EG (26.1%), which was attributed to sheet and the interlayer were introduced with transition metal
the facilitated mass transfer and electronic modification of the cations and the alkali metal cations, the acidic and basic properties
of smectite could be tuned accordingly.142,143 Interestingly, the
weakly basic catalyst—macro-reticular anion-exchange resin
(Amberlyst A-21)—was also active for this reaction with a
B35% conversion of EC, while the selectivity towards EG and
DMC was more than 95%.66 As a homogeneous system, poly-4-
vinyl pyridine was reported to have high catalytic activity with an
EG yield of 75%.64
Scheme 11 Proposed reaction pathway for glycerol reforming to Scheme 12 Synthesis of ethylene glycol by transesterification of EC
propylene glycol (PG) and ethylene glycol. Reproduced with permission with methanol. Reproduced with permission from ref. 65. Copyright
from ref. 127. Copyright 2009 Royal Society of Chemistry. 2002 Springer.
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4.5 From formaldehyde (DMM), a dimethyl acetal of formaldehyde (route (3) of

Scheme 13).60 They used H-Faujasite (H-FAU, an acidic zeolite)
Carbonylation of formaldehyde or its derivatives has been
as a catalyst and achieved the maximum selectivity of MMAc of
investigated for producing glycolic acid and its esters/ethers,
79% at relatively low pressure (3 atm of CO).60 It is noteworthy
which can be converted readily into ethylene glycol. Overall
that disproportionation of DMM to dimethyl ether (DME) and
reaction pathways are shown in Scheme 13.6,62,63
MF can be minimized by keeping the ratio of PCO to PDMM high,
Route (1) occurs via the Koch mechanism over acidic
which could improve the selectivity of MMAc and subsequent
catalysts in the liquid phase, which starts with protonation of
yield of EG.
formaldehyde to yield a carbocation that undergoes CO addition
to produce a resonance-stabilized acyl carbocation.62,63 Addition 4.6 From ethylene and hydrogen peroxide
of water and subsequent deprotonation form glycolic acid. MG
is formed by esterification of glycolic acid with methanol, which Direct synthesis of ethylene glycol from ethylene and hydrogen
can be hydrogenated to produce EG.6 peroxide is a green technology consisting of a coupling process,
DuPont practised this process commercially with a yield of namely, epoxidation of ethylene and sequential hydrolysis of
EG higher than 96% using H2SO4 as a catalyst. However, the ethylene oxide. Due to its bifunctional properties (e.g., oxidation
reaction was carried out under reaction conditions of 900 atm and hydrolysis), an Al-TS-1 catalyst was introduced for ethylene
of CO and temperatures between 130 and 200 1C.144 The epoxidation and the ring-opening process for ethylene glycol
resultant high corrosion rates led to discontinuation of production (reaction model shown in Fig. 2).145 The catalyst
the technology in 1968.63 Thereafter, renewed interest arose with (with a SiO2/Al2O3 molar ratio of 504) offered a conversion of
the use of solid acids for this reaction. Lee et al. have investigated a H2O2 of 95% and a total yield of EG and MME of 10% under
number of strong acidic exchange resins (e.g., sulfonic acidic resins mild conditions (0.7 MPa, 333 K).
and heteropolyacids such as H3PW12O40 (PW12) and H3PMo12O40
(PMo12)) as catalysts for carbonylation of HCHO.63 Among 5 Chemistry and applications of ethylene glycol
them, the Amberlyst-based catalytic systems, consisting of a
sulfonic acid resin catalyst and 1,4-dioxane as a solvent, achieved 5.1 Electrooxidation of ethylene glycol for alcohol fuel cells
complete HCHO conversion and MG yields higher than 80%.63 EG is a new type of liquid feed in the development of fuel
Requirement of high CO pressure for carbonylation of cells.146–150 Electrooxidation of ethylene glycol (namely, direct
formaldehyde is due to low solubility of CO in the liquid phase, ethylene glycol fuel cells) has attracted considerable interest
and thus development of carbonylation chemistry without CO is for mobile, stationary, and portable applications owing to its
an interesting research direction.6 Methyl formate (MF) can be high theoretical energy capacity (4.8 A h ml1), high boiling
catalytically decarbonylated to CO (eqn (1)),61 which can act as point, and high efficiency of electric power conversion.18,151 In
the CO source to react with formaldehyde for MG (eqn (2)) principle, complete oxidation of ethylene glycol to CO2 produces
production directly instead of GA (route (2) of Scheme 13).6,62 The 10 electrons per glycol molecule.18
release of methanol from MF decarbonylation leads to methyl
methoxyacetate (MMAc) (eqn (3)) and which is subsequently (CH2OH)2 + 2H2O - 2CO2 + 10H+ + 10e (4)
hydrolyzed and hydrogenated to EG.6
However, further development of this process is still a challenge
HCOOCH3 - CO + CH3OH DG1 = +0.4 kJ mol1 because partial oxidation of glycol can produce several C2
(1) intermediates and products such as glycolaldehyde, glyoxal,
glycolic acid, glyoxylic acid, and oxalic acid (Scheme 14), which
HCOOCH3 + HCHO - HOCH2COOCH3 decrease current efficiency significantly.18,21,150 This issue makes
DG1 = 70.4 kJ mol1 (2) the development of efficient catalysts for complete oxidation of
ethylene glycol highly important.
HCOOCH3 + HCHO + CH3OH
- CH3OCH2COOCH3 + H2O Catalysts for EG electrooxidation. Notable efforts have
1 been devoted to design catalytic materials for electrochemical
DG1 = 96.4 kJ mol (3)
oxidation of EG, such as Pt,152–156 Pd,19,157–162 Au,163 alloys of
For vapor-phase systems, Celik et al. have recently demon- Pt-Ru,152,154,155 Pt-Pd,164,165 Pt-Sn155 electrodes and thin films.163
strated an example of the carbonylation of dimethoxymethane
Fig. 2 Proposed model of Al-TS-1 as a bifunctional catalyst for

Scheme 13 Reaction pathways for ethylene glycol synthesis from ethylene epoxidation and ring-opening process. Reproduced with
formaldehyde. permission from ref. 145. Copyright 2009 Elsevier.
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on a platinized electrode was only about 5%, whereas that for

glycolaldehyde formation varied with potential from 85%
(0.6 V) to 60% (0.7 V).153 The carboxyl groups of ethylene
glycol weakly interact with the platinum surface, and thus
the dissociation rate is low.18,153 Moreover, formation of the
COads intermediate via an indirect pathway (Scheme 14) on Pt
surfaces causes serious poisoning and drastically impairs
catalytic activity.170,178 An increase in the amount of platinum
supported on carbon materials (Vulcan XC-72) can enhance the
binding of intermediates, thus leading to improved complete
oxidation.18,150 However, high cost of Pt-based catalysts makes
Scheme 14 Reaction scheme for electrooxidation of ethylene glycol. their utilization less attractive.21
Reproduced with permission from ref. 150. Copyright 2009 Elsevier.
Notable attempts have therefore been made to design alternative
catalytic materials for DEGFC anodes that could improve

In addition, a large number of studies have been concerned with electro-oxidation activity of ethylene glycol and eliminate
operating media (e.g., basic (alkaline) and acidic) and supporting undesirable products,19,153,165,179 particularly, the capability
materials, such as CNTs, Ti mesh, and carbonized porous to oxidize EG with fast kinetics and tolerable deactivation.21
alumina.148,154,157,162,166–168 Table 5 summarizes representative Within this context, addition of a second element to Pt is the
electrocatalytic systems for oxidation of ethylene glycol. simplest strategy.170 For example, Pt-M alloy (M = Pd, Au,
Platinum or platinum-alloys electrodes have been extensively Ru, Ni, Pb, Bi, etc.) or modified electrodes (Table 5) could be
investigated and are probably the most popular electrocatalysts very efficient for enhancing the conversion of ethylene glycol,
for DEGFCs in acidic media,18,153,165,177,178 while monometallic and were widely used for promoting the catalytic performance
and bimetallic palladium-based materials have emerged as anode in direct methanol fuel cells (DMFCs).18,153,165,177 The
catalysts generally operated in alkaline solutions.19,157–162 It has presence of a secondary metal promotes activation of water
been unambiguously established that the type of supporting molecules at lower potentials and oxidation of COads to CO2
materials and co-presence of metals or metal oxides can remarkably and thus leads to an enhanced catalytic activity.18,180–183
affect catalytic performance in terms of activity and stability.21 Selvaraj et al. found enhanced stability of Pt-Ru/CNTs
Platinum-based catalysts represent the major group of towards ethylene glycol oxidation, which can be ascribed to
anodic materials for DEGFCs in electrochemical adsorption the formation of Ru–OH species that is active for the oxidation
and oxidation of EG. But using Pt anodes would result in low of COads.154 Kim et al. compared catalytic activities of Pt/C,
efficiencies of fuel utilization and massive emission of undesired PtRu/C, and PtRuSn/C catalysts for electrocatalytic oxidation
incomplete oxidation.18,150 Current efficiency for CO2 production of EG.170 The ternary PtRuSn/C catalyst showed the best
Table 5 Representative electrocatalysts for ethylene glycol oxidation
Metal Oxide/support Acid/base reagent Ref.

Pd/Pd-Ni–Zn P/Carbon Vulcan XC-72 NaOH, KOH 19
Pt-Sn-Ni Carbon Vulcan XC-72 H2SO4 146
Pt-Sn-Ru Carbon Vulcan XC-72 H2SO4 146
Pt40-Pd60 MWCNTs H2SO4, C2H6O2 147
Pt/Pt-Ru/Pt-Ru-W Plain Ti mesh H2SO4 148
Pt Carbon Vulcan XC-72 H2SO4 150, 153
Pt-Ru BPPGE-fMWCNTs H2SO4 152
Pt/Pt-Ru CNTs H2SO4 154
Pd Carbon Vulcan XC-72 NaOH 157
Pd S-MWNTs KOH 158
Pd CeO2/C, Co3O4/C, Mn3O4/C, NiO/C KOH 159
Pd CeO2/C, NiO/C, Co3O4/C, Mn3O4/C KOH 160
Pd (Pd nanowire arrays) KOH 161
Pd Carbonized porous anodic alumina KOH 162
Au polyNiTSPc/Q NaOH 163
Au/Pt a-Fe2O3/C KOH 164
Pt/Pt-Pb/Pt-Ru Carbon Vulcan XC-72 KOH 165
Pt (Pt single crystal) H2SO4, HClO4 166
Pt-Au Carbon Vulcan XC-72 NaOH 167
Pt (Pt disk/foil) Perchloric acid 168
Pt (Polycrystalline Pt) LiOH, NaOH, KOH 169
Pt-Ru-Sn Carbon Vulcan XC-72R H2SO4 170
Pt-Co MWCNTs H2SO4 171
Pt-Ru MWCNTs H2SO4 172
Pt-Pb (Nanodendrites) H2SO4 173
Pt/Pt-Ru Carbon black H2SO4 174, 175
Pt/Pt-Ru PTh–CNTs NaOH 176
Pt/Pt-Pd/Pt-Bi/Pt-Pd-Bi Carbon Vulcan XC-72 NaOH 177
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Fig. 3 Schematic illustration of catalytic surface reactions over the ternary PtRuSn/C catalyst for electrooxidation of ethylene glycol.
Reproduced with permission from ref. 170. Copyright 2011 Elsevier.
performance with its current density (14.6 mA cm2) about 8Had + 8OH - 8H2O + 8e (6)
twice as high compared to Pt/C. This enhancement was

attributed to the alteration in lattice parameters and partial Other metallic electrodes have also been considered for the
filling of the d-band vacancies over the ternary catalyst, which electro-oxidation of ethylene glycol in alkaline media.19,163
facilitates scission of the C–C bond and increases the poisoning For example, Ureta-Zanartu et al. examined Au and poly-
tolerance over CO (Fig. 3a).170 Additionally, synergistic interaction nickel-tetra-sulfophthalo cyanine-modified (polyNiTSPc/Au/Q)
of Ru and Sn facilitates the complete oxidation of CO and electrodes for this reaction, employing electrochemical quartz
adsorption ability of EG on the Pt sites (Fig. 3b). crystal microbalance (EQCM) in conjunction with cyclic
Another strategy for enhancing electrocatalytic performance is voltammetry (CV).163 Interestingly, the reaction over poly-
the substitution of platinum with palladium-based anodes for NiTSPc/Au/Q electrodes proceeded at a higher rate (50%
DEGFCs. Palladium disfavors the breaking of the C–C bond, increase compared with Au/Q), probably due to the enhanced
which leads to an increase in production of oxalate and alleviation hydrophobicity of electrode surfaces.
of electrode poisoning by COads, thus enhancing the catalytic
stability.21 In addition, palladium is more abundant in nature and Mechanistic aspects of EG oxidation. A generally accepted
less expensive than Pt.19,157–162 Pd/C showed a higher stability as mechanism of ethylene glycol oxidation consists of two distinct
compared to Pt/C.160 Addition of oxides (e.g., CeO2, NiO, Co3O4 reaction paths: a path involving the COads intermediate and a
and Mn3O4) to Pd/C can further improve activity and path not breaking the C–C bond. Specifically, a series of
stability.159,160 The promotional effect was attributed to the parallel, two-electron oxidation steps has been proposed for
formation of OHad species, which can transform COads or oxidation of ethylene glycol to CO2 on a platinum surface and is
other carbonaceous species on the surface of Pd to CO2.160 depicted in Scheme 15.178
The combination of Pd with other metals has also been studied Production of a number of C2 intermediates has been
over the past years in order to increase activity and stability of observed in EG oxidation, including glycolaldehyde, glyoxal,
catalysts. This approach could further reduce the cost of glycolic acid, glyoxylic acid, and oxalic acid.18,178,185 Halseid
catalysts by diluting Pd with base metals.21 Bambagioni et al. reported in details on model studies of adsorption
et al. examined the reaction on nanostructured Pd-(Ni–Zn)/ and electro-oxidation of ethylene glycol by employing online
C and Pd-(Ni–Zn–P)/C, which were found more reactive than differential electrochemical mass spectrometry (DEMS) via
Pd/C catalysts.19 continuous electrolyte flow.150,153 The authors identified C2
The attraction of Pd-based electrocatalysts originates in the products from incomplete oxidation on platinum surfaces and
fact that they are more active than Pt-based electrocatalysts in
alkaline media for the oxidation of a variety of substrates.21
The alkaline environment offers a number of advantages over the
acidic one for the reaction:21,184 (i) a wide selection of possible
electrode materials for both cathode and anode, (ii) a high efficiency
for oxygen reduction, (iii) a lack of sensitivity of the anodic reaction
to the surface structure, (iv) easy water management, and (v)
sufficient stability for non-noble metals.19,21,155,161,164,165,177,184
Additionally, it could prevent flooding and the risk of corrosion of
the materials, while the electro-osmotic drag transports water away
from the cathode.19,21,184 Most of all, the alkaline environment
facilitates oxidation of ethylene glycol to oxalate, not COads
(eqn (5) and (6)).175
Scheme 15 Pathway of ethylene glycol oxidation to CO2 on plati-
num. Reproduced with permission from ref. 178. Copyright 1996
(CH2OH)2 + 2OH -
C2O42 + 8Had (5) American Chemical Society.
View Article Online
concluded that electro-oxidation of EG proceeds via two different

pathways for CO2 production as shown in Scheme 14.153,155,156
As mentioned earlier, the presence of a second metal alters
the electronic structure of Pt, weakens CO adsorption on the
Pt surface, and thus alleviates catalyst poisoning.18 A possible
mechanism of such a catalytic enhancement can be expressed
as follows:18
(CH2–OH)2 - (CH2–OH)2(ads) (7)
(CH2–OH)2(ads) - (:COH)2 (8)
(:COH)2 + 2H2O - (HCOOH)ads + 2H+ + 2e (9)
Pt(HCOOH)ads - Pt(CO)ads + 2H2O (10) Fig. 4 Schematic of the AEM-DEGFC. Reproduced with permission
from ref. 20. Copyright 2010 Elsevier.

Pt + H2O - Pt(OH)ads (11)
to the enhanced kinetics of EG oxidation and oxygen
Pt(OH)ads + Pt(CO)ads - Pt + CO2 + H +
(12)
reduction reaction (ORR) in alkaline media.188,189 The
M + H2O - M(OH)ads + H+ + e (13) membrane electrode assembly (MEA) comprised of an AEM

sandwiched between an anode and a cathode is shown in
M(OH)ads + Pt(CO)ads - Pt + M + CO2 + H + e (14) +
Fig. 4. A fuel solution containing EG is fed into the anode flow
Electrooxidation of EG on Pd in alkaline media does not channel, while pure oxygen is fed to the cathode without
diverge substantially from Pt.21 In particular, the oxidation humidification. Ogumi et al. investigated the performance of
mechanism has been studied both on a smooth Pd electrode by EG using AEM and Pt as an anode at 50 1C.190 Cell performance
in situ FTIR spectroscopy and on nanostructured Pd-based with EG (9.2 mW cm2) was higher than that with methanol
catalysts by a cyclic voltammetry.19 It has been shown that (5.5 mW cm2) due to smaller polarization for electro-oxidation
formation of carbonate and oxalate is favored in high pH of EG compared to methanol. Recently, An et al. developed a
values (e.g., above 12) on the smooth Pd surface, whereas high performance AEM-DEGFC with non-platinum electro-
carboxylates are readily produced at relatively lower pH catalysts and obtained a maximum yield of power density of
values.19,21 Detailed CV investigations on Pd-(Ni-Zn)/C, 67 mW cm2 and a current density of 225 mA cm2 at 60 1C.20
Pd-(Ni-Zn-P)/C, and Pd/C electrocatalysts yielded the distribution
of products.19,186 Pd/C was the most selective catalyst for producing 5.2 Hydrogen production from ethylene glycol
glycolate, while mixtures of glycolate, oxalate, and carbonate were Production of H2 from biomass, which in principle leads to net zero
obtained on Pd-(Ni-Zn)/C or Pd-(Ni-Zn-P)/C, indicating that the CO2 emissions, has been paid much attention.191 Among various
oxidation of EG proceeds via parallel routes with path c prevailing endeavors, aqueous-phase reforming (APR) and steam reforming
over a–b for oxalate production (Scheme 16).19 (SR) of ethylene glycol are thermodynamically and kinetically
feasible in generating H2-rich fuel gases.192–194 In addition, super-
Membranes for DEGFCs. Membranes for DEGFCs are
critical water gasification (SCWG) and decomposition of EG are
typically divided into two types: proton-exchange-membranes
emerging processes for H2 production.195–197
(PEM) typically based on Nafion, and anion-exchange-
membranes (AEM).20,148,149,175,187 Although PEM-DEGFCs
can achieve decent reactivity at high temperatures (4110 1C), APR process. The APR process is promising owing to its
their performance at room temperatures is rather poor because of advantages of high energy efficiency and low CO concen-
the sluggish kinetics associated with acidic membranes and the tration in the product gas.16 Since ethylene glycol contains
mixed potential caused by EG crossover.187 AEM-DEGFCs offer functional groups including C–C, C–O, C–H, and O–H, it has
substantially improved cell performance, primarily attributed been considered as an ideal model molecule for studying
aqueous-phase reforming reactions.198,199
Mechanism of H2 production from APR of EG has been
elegantly described by the Dumesic group over Pt-based
catalysts.200 The process includes the following stoichiometric
reactions:17,192,193,200,201
C–C cleavage leading to CO and H2,
C2H6O2 2 2CO + 3H2 (15)
Water–gas shift (WGS),
CO + H2O 2 CO2 + H2 (16)

Scheme 16 Proposed electrooxidation mechanism of EG to glycolic Dehydrogenation,
acid or oxalic acid on Pd. Reproduced with permission from ref. 19.
Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA. C2H6O2 2 C2H6xO2 + x/2H2 (17)
View Article Online
Scheme 17 Reaction pathways for production of H2 by reactions of Fig. 5 Comparison of catalytic performance of metals for APR
oxygenated hydrocarbons with water. (Asterisk represents a surface of EG at 483 K and 22 bar. White bar: CO2 TOF 103 (min1);
metal site.) Reprinted with permission from ref. 193. Copyright 2002 grey bar: percentage alkane selectivity; black bar: percentage H2
Nature Publishing Group. selectivity. Reproduced with permission from ref. 192. Copyright
2003 Elsevier.
Dehydration/hydrogenation,
and selective for this reaction.193 Although Pd/SiO2 is also
C2H6O2 + H2 2 C2H5OH + H2O (18) highly selective to H2, its reactivity in terms of production rate
of CO2 is about one order of magnitude lower than that of the
Methanation,
Pt/SiO2 catalyst.192 This could be due to the lower reaction
CO + 3H2 2 CH4 + H2O (19) rate of the water–gas shift reaction over Pd catalysts. Huber
et al. deduced that the rate determining step for APR of EG on
Reaction pathways (Scheme 17) have been considered to be Pd could be the WGS reaction.16,199 Therefore, a possible
involved in the formation of H2 and alkanes from oxygenated approach to obtain better catalysts could be optimization of
hydrocarbons.193,200 The reactant undergoes dehydrogenation the formulation of metal alloys such as Pt-Pd.16
steps on metal surfaces to produce surface-bonded intermedi- Ni has excellent capacity for C–C bond scission and is much
ates.17,192,193,198,202,203 Subsequent cleavage of the C–C bond less expensive than Pt; thus, several types of Ni-based catalysts
leads to the formation of CO and H2.51,52 Adsorbed CO have been prepared and evaluated in the APR of EG.194,211–217
species must be removed from the surface via the water–gas The status of the utilization of Ni catalysts for the reaction is
shift reaction since high surface coverage of CO leads to summarized in Table 6.
deactivation of catalysts.192,193,200 The desired catalytic path- However, supported Ni nanoparticles suffer from severe
way involves cleavage of the C–C bond as well as C–H and/or deactivation during APR of EG. For instance, Ni and Ni9Sn
O–H bonds to form adsorbed species, while undesired reactions catalysts lost B90% of their initial activities after 48 h
proceed via cleavage of C–O bonds followed by hydrogenation to on stream at 498 K.194,217 Skeletal Ni catalysts, such as
form alcohols, by rearrangement reactions to form organic acids, RANEYs-Ni, showed better stability but lose their initial
or by hydrogenation of adsorbed CO and CO2 to form alkanes.17 activity over a similar period.194 Addition of Sn could improve
Therefore, an ideal catalyst for the reforming reaction in aqueous the stability of RANEYs-Ni due to enhanced coking resistance
phase must facilitate the cleavage of the C–C bond and the upon the formation of NiSn alloys;194 nevertheless, Sn is
removal of adsorbed CO species.204 Moreover, the catalyst adverse to the APR activity. The initial activity of RANEYs
should be inert to parallel and series competing reactions such Ni14Sn drastically dropped to only about one half of that of
as the cleavage of the C–O bond and methanation, which greatly RANEYs Ni.217,218 Recently, Petró et al. prepared a novel
deteriorate productivity of H2.199 non-pyrophoric Ni catalyst (NP Ni) from the Ni-Al alloys,
Since the group VIII metals are active for cleavage of which consists of metallic Ni, gibbsite, and bayerite.219,220 The
C–C bonds, they are highly effective for reforming of oxyge- NP Ni catalyst offered higher APR activity compared to the
nates.16,192,198–200,202,205–210 Davda et al. prepared silica-sup- conventional RANEYs Ni.213
ported group VIII noble metal (Pt, Ru, Rh, Pd, etc.) Other metallic catalysts have also been used for APR of
nanoparticles for APR of EG (Fig. 5).192 They found that ethylene glycol. As Co exhibits appreciable activities for steam
Pt- and Pd-based catalysts exhibited higher selectivity for reforming of alcohols,221 the WGS reaction, and the
production of H2 with lower rates of alkane production, Fischer–Tropsch (F-T) synthesis,192,222 it has been explored
whereas Rh, Ru, and Ni showed an inverse trend.192 There- by Chu et al. for the APR process.223 Co/ZnO catalysts
fore, both types of catalysts were considered to be promising prepared by a co-precipitation method exhibited high activity
materials for the selective production of hydrogen by APR and H2 selectivity, and the highest TOF and selectivity of H2
of EG.192,198,200,202,204 Moreover, it has been verified that reach up to 101.4 h1 and 89%, respectively, which are higher
Pt/Al2O3 could meet the criteria mentioned above and is active than those of RANEYs Ni catalysts. Moreover, these catalysts
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Table 6 Ni-based catalysts for APR of ethylene glycol
TOF/min1
Catalyst Preparationa T/K H2 CO CO2 CH4 Ref.
30%Ni/Al2O3 IWI 483 0.29 n/a 0.21 0.08 16
Pt1Ni1/Al2O3 IM 498 3.53 n/a 8.06 0 16
RANEYs Ni IWI 498 1.12 0.02 0.61 0.28 217
RANEYs Ni270Sn IWI 498 1.40 0.30 0.69 0.23 218
19%Ni/SiO2 ED 483 0.05 n/a 0.01 n/a 192
498 0.04 n/a 9.0 103 n/a
NP Nib n/a 498 0.22 8.0 103 0.10 0.04 213
RQ Nic n/a 498 0.22 n/a 0.16 0.16 215
RQ Ni80Sn20 SROC 498 0.77 n/a 0.27 0 215
a b
ED: evaporative deposition; SROC: surface reaction of organotin compounds; IM: impregnation. NP: non-pyrophoric Ni. c RQ: rapidly
quenched. n/a: not available.
produced negligible amounts of CO, which is particularly the maximum on the catalyst with a Cr/Fe molar ratio of 1 : 9
desirable for fuel cell applications.223 Bimetallics offer unique (Table 7), on which a high BET surface area of mixed oxides
catalytic properties not seen for either of the parent metals.207 and large amount of magnetite phase are present.15
Skoplyak et al. prepared Ni-Pt-Pt(111) catalysts by deposition
of a monolayer of Ni on Pt(111), which displayed a significantly SR process. Steam reforming is a classical and well-established
higher reforming activity compared to Pt(111).207 Based on process for hydrogen production.224 It is also one of the primary
density functional theory (DFT) calculations, they concluded methods for conversion of biomass-derived oxygenates for
that the reforming activity was correlated with the d-band production of hydrogen-rich gas with high efficiency and full use
center of the bimetallic surface.207 of water in the feed.225,226 EG is highly oxygenated with a
Understanding of the nature of supports is crucial to tune the hydroxyl group on each carbon atom and an internal carbon-
activity and selectivity of APR of ethylene glycol.15,198,199,204,212,214 to-oxygen ratio (C/O) equal to 1. This renders a challenge for gas-
Representative Pt and Pd catalysts supported on a number of phase EG reforming and a significant thermodynamic limitation
supporting materials (e.g., TiO2, SiO2, Al2O3) are summarized for production of synthesis gas relative to the reforming of
in Table 7. High TOFs for hydrogen, gaseous alkanes, and alkanes.227 A desirable catalyst for hydrogen production from this
liquid-phase compounds were attained over Pt-black and process should be highly active in C–C and C–H bond scission and
Pt nanoclusters supported on TiO2, carbon, and Al2O3.198 the WGSR but have low activity towards the methanation.
Enlightened by the discovery of Huber et al. that the production However, the correlation between the nature of the catalyst and
rates of CO2 and H2 were surprisingly elevated over Pd/Fe2O3, Liu reactivity of steam reforming of ethylene glycol has been poorly
et al. prepared an iron oxide-supporting Pd catalyst employing a established.
co-precipitation method.199 Pd/Fe3O4 is superior to Pd/Fe2O3 for Nickel-based catalysts have also been introduced to the SR
APR of EG, which is attributed to the boosted WGS reaction by of ethylene glycol.228 Hu et al. investigated the influence of
the synergistic effect of Pd nanoparticles and magnetite (Fe3O4).16 reaction parameters including reaction temperature, steam to
Additionally, as chromium compounds are usually employed carbon ratios (S/C), and reaction time over a Ni/Al2O3
to improve stability and the surface area, Pt supported on Fe-Cr catalyst.229 The results showed that ethylene glycol could be
mixed oxides were prepared by solid thermal decomposition for efficiently reformed to hydrogen below 500 1C and high
enhancing catalytic performance.15 Catalytic activity reached temperature and S/C facilitate the elimination of by-products,
such as ethylene, CO, and acetone, which are the main sources
Table 7 Various supported catalysts for reforming of ethylene glycol of coking formation. Li et al. examined several representative
to H2 at 498 K oxides (e.g., Al2O3, CeO2, MgO, and ZrO2) supporting nickel
TOF/min1 catalysts for the process.226 High dispersion of nickel metal
could increase the catalytic activity towards C–C bond rupture
Catalyst H2 CO CO2 CH4 Ref.
and the methanation reaction at low temperature. Oxides with
a
Pt/1Cr-9Fe 63 0.11 n/a 0.06 15 strong acidic sites could lead to the production of alkanes,
Pt/ZrO2 4.87 4.1 103 2.27 0.03 198
while the carriers with high oxygen storage capacity favor the
Pt/C 7.52 1.1 102 4.30 0.51 198
Pt/TiO2 11.1 7.8 103 4.90 0.05 204 water gas shift reaction.
Pt/SiO2-Al2O3 4.60 3.9 103 2.06 0.05 204 The Schmidt group has creatively developed an autothermal
Pt/CeO2 1.20 5.5 103 0.52 0.00 204 steam reforming (ATSR) process based on a simple concept. That
Pt/Al2O3 7.04 8.0 104 3.07 0.00 204
Pt/ZnO 1.55 6.0 104 0.19 0.00 204 is, catalytic partial oxidation of EG is an exothermic reaction
Pt/SiO2 0.70 6.3 104 0.33 0.00 198, 204 (eqn (20)), while steam reforming of EG is a highly endothermic
Pt-black 8.54 7.5 103 3.95 0.00 198, 204 reaction (eqn (21)).227 Thus, EG conversion readily occurs with-
Pd/Fe2O3 48.8 0.43 18.0 1.9 102 199 out the need of an external heat source (eqn (22)).227,230
Pd/Fe3O4 109 0.12 32.6 9.8 103 199
a
Indicates the rate of H2, CO, CO2, and CH4 production (mmol min1 HOCH2CH2OH + O2 - 2CO2 + 3H2
1
g ). n/a: not available.
DH1 = 393 kJ mol1 (20)
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HOCH2CH2OH + 2H2O - 2CO2 + 5H2 Pt surfaces covered with a single monolayer of other metal
DH1 = 123 kJ mol 1
(21) (e.g., Ni-Pt-Pt(111), Fe-Pt-Pt(111), Ti-Pt-Pt(111)) exhibit higher
activities for the decomposition reaction compared to monome-
HOCH2CH2OH + H2O + 0.5O2- 2CO2 + 4H2 tallic Pt catalysts. To gain further insight into the reaction
DH1 = 160 kJ mol1 (22) pathway and mechanism of EG decomposition and the origin
of the enhanced activity on bimetallic surfaces, Salciccioli et al.
Monolithic noble catalysts, such as rhodium and platinum examined the transition states of dehydrogenation intermediates
nanoparticles supported on ceramics, were used for auto-thermal, of EG via DFT and isotopic labeling experiments on Pt and
fast (B10 ms) steam reforming, due to their excellent properties Ni/Pt catalysts.197 The results confirmed that decomposition of
of heat transfer.227 Rh/CeO2 loaded on a g-Al2O3 washcoat layer EG on Pt started with O–H bond cleavage and followed by C–H
exhibited excellent catalytic performance with the maximum and the second O–H bond cleavages, whereas both O–H bonds
selectivity of H2 of 92% at optimized conditions.227 were cleaved simultaneously on the Ni/Pt(111) bimetallic surface
to form 1,2-dioxyethylene (OCH2CH2O). The favorable energetic
SCWG process. Supercritical water gasification of EG is an
pathway to OCH2CH2O leads to increased activity on the

intensified process for hydrogen production.196,231,232 Properties
Ni/Pt(111) surface. Recently, upon examination of two catalytic
of water (e.g. density, dielectric constant, and viscosity) under
kinetic models for the decomposition, the same group showed
supercritical conditions (T: 375 1C, P: 220 bar) are greatly
that the initial cleavages of O–H bond and dehydrogenation
different from those in the gas or liquid phase.231 Comparing
reactions (specifically HOCH2CH2O* - HOCH2CHO* + H*)

to other reforming processes, the SCWG process has many
were kinetically important reactions.195
advantages such as higher reaction rate, lower interphase mass
transfer resistance, and better heat transfer, and longer lifetime of
5.3 Selective oxidation of ethylene glycol
catalysts.196,231
Similar to the APR process, catalysts for SCWG of EG Selective/partial oxidation of EG leads to the production of
should be active for breaking the C–C bond and favor the glyoxal, glycolic acid, and methyl glycolate.156,237–243
water gas shift reaction, whereas the reactions of methanation
and Fischer–Tropsch should be suppressed.192,196 de Vlieger Glyoxal. Glyoxal is widely used in wood-processing,
et al. studied monometallic Pt, Ir, and Ni and bimetallic Pt-Ni tanning, pharmaceutical, textile and many other industrial
catalysts supported on alumina for reforming of EG under applications.237–240,244,245 Glyoxal can be commercially
supercritical conditions.196 The Pt-Ni bimetallic catalyst was produced via partial oxidation of EG on Ag or double-layer
more reactive than the monometallic Pt catalyst, owing to the Cu-Ag catalysts.238,240,243,246 Interaction of EG and oxygen
lower CO coverage and the enhanced accessibility to Pt sites in was examined on both clean and oxidized surfaces of silver
the presence of Ni. single crystals and films.247,248 On the clean surface, EG was
Decomposition of EG. Due to the high oxygen content, reversibly adsorbed with the formation of a multilayer cover-
decomposition of EG (i.e., no need for addition of water or age, while EG on oxygen pre-covered Ag surfaces underwent
oxygen) to syngas is highly endothermic and occurs stoichio- decomposition to form water and surface intermediates.247
metrically (eqn (23)); the complete decomposition (eqn (24)) The intermediates further reacted via two parallel routes:
leads to production of H2, and adsorbed Cad and Oad on the oxidation and dehydrogenation.247 The dissociative EG could
surface.197,227,233,234 be easily oxidized to glyoxal, while the C–C bond is broken
leading to the formation of formaldehyde and CO2.247,248
C2H6O2 - 2CO + 3H2 DH1 = 173 kJ mol1 (23) Performance of Ag-based catalytic systems can be enhanced
by adding promoters. Volatile compounds such as iodine,
C2H6O2 - 2Cad + 2Oad + 3H2 (24)
alkyl phosphates, and alkylhalogenides have been mixed with
Several catalysts, primarily Pt-based, have been investigated in the reactants to promote glyoxal selectivity.246 Magaev et al.
the decomposition reaction.233–236 The catalytic performance reported that P-containing electrolytic Ag catalysts yielded
for decomposition of EG on Pt and M/Pt bimetallic surfaces enhanced activity and selectivity as well as thermal stability.249
are summarized in Table 8. The promotional effect can be attributed to the active oxygen
Table 8 Catalytic performance of ethylene glycol decomposition on Pt and M/Pt bimetallic surfaces
Activity (ML)a Selectivity (%)

Surface Reforming Complete decomposition Total Reforming Complete decomposition Ref.
Pt(111) 0.030 0.004 0.034 88 12 233
Pt-Ni-Pt(111) 0.025 0 0.025 100 0 233
Ni-Pt-Pt(111) 0.144 0.023 0.167 86 14 233
Thick Ni/Pt(111) 0.122 0.016 0.138 88 12 233
Pt-Fe-Pt(111) 0.080 0 0.080 100 0 234
Fe-Pt-Pt(111) 0.107 0.015 0.122 88 12 234
Pt-Ti-Pt(111) 0.011 0.018 0.029 38 62 234
Ti-Pt-Pt(111) 0.128 0.029 0.157 82 18 234
a
ML: the saturation coverage of H2 on surfaces.
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species produced from decomposition of surface oxide-like 5.4 For synthesis of acetals and fructone
species (Ag2O) for deep oxidation of EG.250,251
Acetalization is one of the most widely used methods for
Coke formation leads to a decrease in activity and lifetime
protection of aldehydes and ketones in synthetic organic
of catalysts. Vodyankina et al. explored the nature of coke via
chemistry.262 The reaction is typically carried out by treatment
examination of reaction parameters of EG oxidation on
of carbonyl compounds with alcohols, diols, or the corres-
Ag and Cu-Ag catalysts and found two types of deposited
ponding orthoformates in the presence of protic or Lewis
carbon.243 Graphite-like structures were formed on Cu surfaces
acidic catalysts. The acetalization of carbonyl compounds is
at lean contents of oxygen, while the oxycarbon structure grew
performed with ethylene glycol for synthesis of acetals262–268
as filaments in the reaction mixture.243,252
and fructone.269
For synthesis of acetals. Acetals such as 1,3-dioxolane

Glycolic acid. Glycolic acid has versatile applications in derivatives and 2-alkyl-dioxolanes are commonly used as additives
adhesives, metal cleaning, textiles, leather processing, biodegradable in gasoline and diesel, which are promising replacements for
polymers, and health-care products.253,254 Partial oxidation of both ethanol and methyl tert-butyl ether (MTBE).270,271 The
ethylene glycol to glycolic acid was conventionally performed on acid-catalyzed reaction of ethylene glycol is one of major
gold-based catalysts in aqueous solutions.242 Oxygen adsorption on manufacturing methods for synthesis of 1,3-dioxolanes.265,272
Au/Al2O3 catalysts with different gold contents and dispersion Shimizu et al. reported on sulfonic acid-functionalized
determines activity of catalysts. Surprisingly, a negligible effect of FSM-16 mesoporous silica (SO3H-FSM) as a highly effective
particle size was reported, implying the process on Au/Al2O3 (90–98% yield) and reusable catalyst for the acetalization of
catalysts could be structural insensitive.242 various carbonyl compounds with ethylene glycol.264 Leonard
Bioconversion of ethylene glycol is an attractive and alternative et al. employed bismuth triflate as a versatile and robust
method for producing glycolic acid.255 To increase the selectivity catalyst for acetals formation by treatment of aldehydes and
of glycolic acid, an integrated approach was introduced with ketones.265 A good yield (76%) was obtained for the acetalization
simultaneous separation of product by using anion ion-exchange of trialkyl orthoformate and ethylene glycol in the presence of
resins, which could eliminate the effect of end-product inhibition bismuth compounds (Bi(OTf)34H2O). Nieddu et al. used
by keeping the product concentration below the inhibitory diphosphine cationic complexes of palladium as catalysts for
value.256,257 the acetalization of a,b-unsaturated carbonyl compounds
with ethylene glycol, which demonstrated excellent selectivity
towards acetal formation under mild conditions.273 Interestingly,
Methyl glycolate. MG is a chemical intermediate and monomer Fan et al. reported a viable one-step synthesis of 1,3-dioxolanes
for various materials, such as medicines, cosmetics, food, and from EG and syngas using iron nanoparticles under mild
fragrances. Hayashi et al. developed a liquid-phase aerobic conditions.263 This approach was inspired by the aqueous
oxidation process for a one-step production of methyl glyco- Fischer–Tropsch synthesis through simply changing the reaction
late from ethylene glycol, methanol, and oxygen using gold medium from water to EG, which resulted in the formation of a
nanoparticles supported on metal oxides (e.g., Al2O3, TiO2, series of 2-alkyl-1,3-dioxolane derivatives (Scheme 19).
and ZrO2).241,258 Four types of esters were produced as
illustrated in Scheme 18. A speculative reaction path follows Formation of fructone. Acetalization of ethylene glycol with
EG - aldehyde - hemi-acetal - carboxylic ester (glycolate) ethylacetoacetate (EAA) to produce fructone proceeds over silica
and the rate-determining step could be the first reaction.259 functionalized with Brønsted sulfonic acid (SiO2-SO3H40) with a
The Au/Al2O3 catalyst was more active and selective (83% maximum conversion of 88% and selectivity greater than 90%
selectivity to methyl glycolate with 63% conversion) compared after reaction for 3 h at 373 K (Scheme 20).269
to supported Pd and Ru nanoparticles.260 The origin of
5.5 Ethylene glycol-mediated synthesis of nanomaterials
enhanced selectivity is from the difference in adsorption
properties between MeOH (monodentate) and EG (bidentate) The ethylene glycol-mediated synthetic process (frequently called
on catalyst surfaces. Additionally, Nippon Shokubai Co. Ltd the polyol process) is a convenient, versatile, and low-cost method
built up a pilot plant in 2004 for the production of methyl for synthesis of nanostructures on a large scale.22–26,274–281
glycolate using a continuous process, which consisted of Ethylene glycol acts both as a solvent for precursors and as a
aerobic oxidation, separation, and purification, and MG was reducing reagent for reactions.26 Through this process, it is
obtained with a high purity over 98%.261 possible to synthesize monodispersed metallic nanocrystals
Scheme 18 Direct esterification of primary alcohols to methyl esters. Reproduced with permission from ref. 259. Copyright 2011 American
Chemical Society.
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Subsequently, a metal species with zero-valence is nucleated to

form nanoparticles that are surrounded with lone pair electrons
of oxygen of 2,3-butanedione derived from ethylene glycol.291
The presence of a lone pair of electrons keeps these metal
particles separated leading to controllable particle sizes.286,292
Scheme 19 One-step synthesis of 2-alkyl-dioxolanes from ethylene
A number of anisotropic metal nanostructures have been
glycol and syngas. Reproduced with permission from ref. 263. Copyright
successfully synthesized based on this synthetic technique,
2009 Wiley-VCH Verlag GmbH & Co. KGaA.
such as single-crystal silver nanocubes/nanowires,278,293 CuO
nanocubes/spheres,276 CdSe nanoballs,280 single-crystal Au
nanosheets,294 and nano-catalysts.279,290,295–297 We summarize
a number of these nanostructures as listed in Table 9.
The morphology of the nanostructures can be tuned by
changing the reaction conditions such as reaction temperature
Scheme 20 Acetalization of ethylene glycol with ethylacetoacetate. and reducing medium.278,282,283 For example, silver nanocubes
Reproduced with permission from ref. 269. Copyright 2004 Elsevier. were obtained by reducing AgNO3 with ethylene glycol
through redox reactions. Once the concentration of silver
with a manipulated morphology and a controlled particle size atoms has reached the saturation value, they start to nucleate
at a nanometre scale.278,282–285 Moreover, it is an energy- and grow into nanocubes.278 Silver nanowires were synthesized
efficient and environmentally friendly process as the reaction through the EG-mediated process by addition of CuCl or CuCl2
is carried out under closed system conditions compared to (Fig. 6).293 In this system, the adsorbed and dissociated O2 on
those based on thermal decomposition using toxic organic silver surfaces could contribute to some degree of oxidative
solvents.286 etching and block the reactive sites from adding Ag atoms. The
Ethylene glycol-mediated synthesis starts with reducing Cu(I), generated from the reduction of Cu(II) by EG, effectively
metallic precursors to their zero-valence state by oxidation scavenged any adsorbed atomic oxygen from the surface of
of ethylene glycol (eqn (25) and (26)).25,286–289 The reduction seeds, and Cl reduced the level of free Ag+ present initially,
reaction is activated at temperatures around the boiling point thus facilitating the growth of Ag nanowires.
of EG (i.e., 197.6 1C).274,290 Cu2O nanostructures could also be synthesized by the
EG-mediated method with well-defined shapes (spheres/nano-
HOCH2CH2OH - CH3CHO + H2O (25) cubes) (Fig. 7).276 Anionic species play an interesting role in
the synthetic process. When chloride anions are absent in the
system, nucleation and growth of Cu2O take place instantaneously
2/nMn+ + 2CH3CHO - CH3COCOCH3 + 2/nM + 2H+ forming nanoparticles with small sizes that further agglomerate to
(26) colloidal spheres with large sizes in order to reduce their free
Table 9 Representative nanostructures obtained via the ethylene glycol-mediated synthesis
Metal/catalyst Reaction systema Structures Particle size (nm) Ref.

TiO2, SnO2, In2O3, PbO Ti(OR)4, In(OOCC7H15)(OC3H7)2, Pb(CH3COO)2, SnC2O4-EG Nanowires d = 50, L = 30 000 22
Ag AgNO3-EG-PVP (100), (110), (111) facets n/a 23
Au HAuCl4-EG-PVP (100), (111) facets n/a 23
Au HAuCl4-EG-PDDA Nanooctahedra 20–320 24
Pt/C H2PtCl6-EG-XC 72 Nanoparticles 2.5 274
Rh RhAc2-EG-PVP (111)-Oriented nanocrystal 6.5 275
Rh RhAc2-EG-TMAB-PVP (100)-Oriented nanocrystal 6.2 275
Cu2O CuNO3-EG-PVP Cubic/spheres 151–412 276
Ag AgNO3-EG-PVP-HCl Nanocubes 5.0–20.0 278
CdSe Cadmium acetate-EG-Se Nanoballs 330 280
Cu CuCl2-EG-H2O Nanocubes 2.3 282
Fe3O4 FeCl3-succinic acid-EG-urea Clusters B300 283
CuS CuNO3-EG-NaS Powders 10 284
Ni NiCl2-EG-PVP-NaBH4 Nanoparticles 3.4–3.8 285
Co Co(CH3CO2)2-EG-OC-SH Nanoparticle 10 286
Co Co(CH3CO2)2-EG-NaOH Nanoparticles 75 291
Ag AgNO3-EG-PVP-CuCl2 Nanowires d = 100, L = 50 000 293
Au HAuCl4-EG Nanosheets 70–100 thick 294
Ru/g-Al2O3 RuCl3-EG-g-Al2O3 Nanoparticles 1–3 296
Ru/MgO RuCl3-EG-Mg(NO3)2 Nanoparticles 2.0 297
Ag AgNO3-EG-TMAB-PVP Nanocubes 5.0–9.0 298
Ag AgNO3-EG-NaHs-PVP Nanocubes 25–45 298
Ag AgNO3-EG-AOT Nanoparticles 3.6 299
Pt-Ag/C H2Pt(OH)6-EG-AgNO3-XC 72 Nanoparticles 1.2–3.1 300
Pt H2PtCl6-EG-TMAB-PVP Nanocubes 5.0–9.0 301
a
AOT: sodium bis-2-ethylhexyl sulfosuccinate; PVP: poly(vinylpyrrolidone); TMAB: tetramethylammonium bromide; SH: sodium hydroxide;
PDDA: poly(diallyldimethylammonium); RM: reverse micellar; OC: oleic acid. n/a: not available.
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on mesoporous TiO2 prepared by a one-step ultrasound-

assisted EG-mediated method.302 In both cases, the catalysts
were highly active and selective towards the formation of H2
and CO. Additionally, Zhang et al. showed that Ru nano-
particles supported on MgO prepared by the EG-mediated
method (Ru B1.2–2.3 nm) were more active for catalytic
decomposition of NH3 to H2 compared to those synthesized
Fig. 6 (A) Schematic illustration depicting the role of Cu-containing by incipient wetness-impregnation.297 More recently, Komvokis
salts and (B) SEM image of the Ag nanowires obtained in the presence et al. investigated the behavior of Ru/g-Al2O3 catalysts prepared
of both CuCl and NaCl. Reproduced from ref. 293. Copyright 2008 by the EG-mediated method in a deNOx process.296 The catalysts
Royal Society of Chemistry. with smaller Ru nanoparticles (1–3 nm) exhibited higher TOF
values (90% conversion of N2O) and lower apparent activa-
surface energy.276 Upon introduction of sodium chloride, chloride tion energy (Eapp) than impregnated-calcined catalysts.296
ions could prevent rapid aggregation of the formed Cu2O seeds by

retarding the reaction and enhancing the stability of the
5.6 Antifreeze, coolant and heat transfer fluids
particles. In addition, chloride ions stabilize the (100) planes
of the Cu2O nanocrystals and thus induce the formation of Ethylene glycol is ubiquitously used as a major component of
single-crystal nanocubes, antifreeze, coolant and heat transfer fluids in automobiles, aircraft
As for preparation of nano-catalysts with tunable dispersion anti-icing/deicing materials, chilled water air conditioning systems,
and particle sizes of metallic species, we take ruthenium (Ru) and heat transport through geothermal heat pumps.28 Pure
nanoparticles as an example. Miyazaki et al. obtained Ru ethylene glycol should not be used as an engine coolant or
nanoparticles (Ru B5 nm) in a colloidal solution by reducing antifreeze in most cases due to the low specific heat capacity and
RuCl3 in ethylene glycol.295 The supported nano-Ru/g-Al2O3 heat transfer efficiency. Nevertheless, physical properties of
catalyst showed an unusually high activity for ammonia ethylene glycol–water mixtures vary significantly. For instance,
synthesis with its formation rate more than ten times higher the depressed freezing points as well as elevated boiling points were
compared to that prepared by conventional methods. The attained with increasing the percentage of ethylene glycol in a
promotional effect was attributed to the uniform shape and water solution, which makes mixtures with high antifreeze
size of the Ru nanoparticles. Balint et al. prepared a Ru/Al2O3 capabilities.303–306 The minimum freezing point was ca. 55 1C
catalyst (Ru B5.8 nm) via the same method for partial when the percentage of ethylene glycol is about 70%, as shown in
oxidation of methane.290 Perkas et al. studied the same Table 10. Indeed, percentage of EG in water solution determines
reaction with Ru nanoparticles (Ru B1.5–3 nm) supported cooling capacity and the overall heat transfer coefficient
Fig. 7 A schematic illustration of the reaction pathways that lead to the formation of Cu2O colloidal spheres and nanocubes. Reproduced from
ref. 276. Copyright 2008 Royal Society of Chemistry.
Table 10 Influence of EG to water ratios of coolant fluids on thermal, fluid-dynamic performance and heat transfer rate
Freezing Boiling Specific heata/ Cooling Heat transfer Heat transfer

Fluids point/1C point/1C kJ kg1 K1 capacity/kW coefficient/W m2 K1 rate/Wb Ref.
Pure EG 13 197 2.5 n/a n/a n/a 3, 32
70%EG/water 55 118 3.0 n/a n/a n/a 3, 32
50%EG/water 34 107 3.4 7.2 152 18.4 305–308
30%EG/water 15 104 3.8 8.5 189 n/a 305–308
Pure water 0 100 4.2 9.8 228 17.5 305–308
a
At 26.7 1C. b Total mass flux is 1244 kg m2 s1 for measuring heat transfer rate. Coolant fluid flow is 1000 kg h1 for measuring cooling
capacity, pressure drop and overall heat transfer coefficient. n/a: not available.
View Article Online
Scheme 21 The formation of HT polyurethane from EG with alkyl tin catalysts. Reproduced with permission from ref. 309. Copyright 2001 John
Wiley & Sons, Inc.
Scheme 22 Chemical microstructures of synthesized aliphatic homopolyesters and copolyesters. Reproduced with permission from ref. 310.
(Table 10), and thus influences thermal and fluid-dynamic This bis(2-hydroxyethyl) terephthalate can be formed by trans-
performance of coolant and heat transfer fluids.306,307 esterification of dimethyl terephthalate with ethylene glycol over
basic catalysts (e.g., amines, alkali metal oxides, and basic
zeolites).312
5.7 Precursor to polymers
Methyl benzoate (MB) reacts with ethylene glycol over NaX
Ethylene glycol is an important precursor to produce polyesters, zeolites under the reaction conditions (150 1C, EG/MB = 2,
such as polyurethane, poly(ethylene succinate) (PES), and poly- and ambient pressure) to yield 2-hydroxyethyl benzoate
ethylene terephthalate (PET). (HEB) with a conversion of 53.4% and a selectivity
Head-to-tail (HT) polyurethane has been successfully prepared of 94.5%, which subsequently reacts with MB to form
by the poly-addition reaction of p-isocyanatobenzyl isocyanate with 1,2-ethanediol dibenzoate (EDB) (Scheme 24).312
ethylene glycol using alkyl tin catalysts.309 The regularity of HT Additionally, monomer bis(2-hydroxyethyl) terephthalate
polyurethane was improved to B83% in the presence of 1,1,3,3- (BHET) can be synthesized by transesterification of dimethyl
tetraphenyl-1,3-dichlorodistannoxane (shown in Scheme 21). terephthalate (DMT) with ethylene glycol (Scheme 25) over
Biodegradable polymers—poly(ethylene succinate), poly(tri- basic Cs2O/CsX with a conversion of 94% and a selectivity of
methylene succinate) (PTS)—can be synthesized through a 59% to BHET at 180 1C.312
polycondensation reaction from ethylene glycol, 1,3-propanediol
(PD), and succinic acid with titanium tetraisopropoxide as a
5.8 As a hydrate inhibitor
catalyst (Scheme 22).310
Bio-based polyurethane has been prepared by noncatalytic As the oil and gas industries continue to increase their activity
polymerization of epoxidized soybean oil (ESBO) and ethylene in deep water, the production and transportation of natural
glycol. This approach incorporates epoxidized soy-based gas in long subsea pipelines are challenges when it comes
polyols as replacements for petroleum-based polyether polyols, to hydrate prevention, corrosion, and mineral scaling.313,314
and substantially reduces the isocyanate loading in the rigid Calcium carbonate could precipitate in pipelines when carbon
foam formulation (Scheme 23).311 dioxide from the gas is absorbed in the calcium-containing
Polyethylene terephthalate is usually produced by poly- water originating from the reservoir, which reduces heat
condensation of bis(2-hydroxyethyl) terephthalate and its oligomers. transfer coefficiency.315 Ethylene glycol is commonly used in
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Scheme 23 Two-step reaction schemes from formation of ESBO–EG complex to bio-based polyurethane. Reproduced with permission from
ref. 311. Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
Scheme 24 Reaction of MB with EG to form HEB and EDB. Reproduced with permission from ref. 312. Copyright 1999 Elsevier.
Scheme 25 Reaction of DMT with EG to form HET and BHET. Reproduced with permission from ref. 312. Copyright 1999 Elsevier.
dehydration and hydrate inhibition of natural gas as it could 6. Summaries, challenges and opportunities
remove water and inhibit the formation of natural gas clathrates
(hydrates) and be reused after purification treatment.315 Ning The past decades have witnessed remarkable progress in the
et al. estimated the hydrate inhibition effect of aqueous organic synthetic approaches and applications of EG; significant
and electrolyte solutions using ethylene glycol as a hydrate efforts have been made towards improving synthetic processes,
inhibitor.313 Results showed that the composition of oil-based promoting the catalytic performance, and reducing the energy
drilling fluids (OBDFs) at a safety margin is 1.6 L vaporizing oil, consumption and environmental pollution. Renewable biomass,
2 wt% emulsifying agent, 1 wt% organobentonite, 0.5 wt% such as cellulose and other polyols, has been explored as raw
SP-1, 1 wt% LP-1, 10 wt% water, and 40 wt% EG, which can be materials for EG production, which could be a burgeoning area
used at a water depth of up to 1900 m. for future research due to its environmental friendliness and
long-term economical advantages. It should be noticed that it
is substantially different from conversion of corn and starch;
5.9 Other applications
the latter would cause potential competition with the food
Ethylene glycol is an excellent solvent and has been used in supply. On the other hand, broad applications of EG are not
numerous applications, such as humectants for tobacco, media limited to the production of polyesters, coolants, and anti-
for suspending conductive salts in electrolytic capacitors, freezes and new utilizations have been immensely boosted in
stabilizers for soy bean foam used in fire extinguishers and facilitating the development of technologies for H2 energy, fuel
in the manufacture of explosives, plasticizers, elastomers, and cells, and synthesis of fine chemicals. In this context, it is
synthetic waxes, separations for aromatic and paraffinic anticipated that research in this field will become even more
hydrocarbons, detergents for equipment cleaning, and inks widespread in the near future, particularly in the fields of
for ball-point pens.2,31 exploitation of renewable energy resources and production of
In addition, EG can be used as binders for foundry sand high-value chemicals.
molding and lubricants for glass- and cement-grinding.31 EG However, there are still a number of grand challenges that
can also be used as an ingredient in hydraulic brake fluids, must be faced and addressed; tremendous potential exists for
as a component of deicing fluids for aircraft, runways, and breakthroughs in the development of more efficient technology
taxiways, as an intermediate in the synthesis of esters, ethers, and optimal catalytic systems that allow the rational production
polyester fibers and resins, etc.316 and consumption of EG. Although the hydration of ethylene oxide
View Article Online
is a mature technology for EG production at the present time, only (NCET-10-0611), China Postdoctoral Science Foundation
a few catalytic systems have been carefully examined and applied in (20090450090), the Scientific Research Foundation for the
commercial applications. The nature of catalysts and their reaction Returned Overseas Chinese Scholars (MoE), Seed Foundation
mechanisms are not well understood, particularly for the properties of Tianjin University (60303002), and the Program of Intro-
of active species and origin of poor thermal stability. There- ducing Talents of Discipline to Universities (B06006).
fore, rational designs of catalytic processes need to be invoked
to overcome issues regarding high cost, high water and energy
consumption, and poor thermal stability and regenerability of
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ChemInform Abstract: Ethylene Glycol: Properties, Synthesis, and

Article in Chemical Society Reviews · April 2012

Hairong Yue Yujun Zhao

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Chemical Society Reviews

Cite this: Chem. Soc. Rev., 2012, 41, 4218–4244

www.rsc.org/csr CRITICAL REVIEW

1. Introduction widespread since 1953.1,2 Currently, the global production and

Scheme 1 Synthetic methodologies and applications of EG covered in this review.

Xinbin Ma received B.S. and Jinlong Gong studied chemical

metabolites including an electron transfer chain, oxidative

Table 1 Physical properties of ethylene glycol1–3,28,31,32

Auto-ignition temperature 427.0 1C

Catalysts for the catalytic hydration of EO to EG primarily include

catalysts (Table 2) can be ascribed to the diﬀerent electron

Table 2 Catalytic systems for the synthesis of EG by hydration of EO

Catalyst Reaction temperature/1C H2O/EO (mol mol1) EO conversion/% EG selectivity/% Ref.

Sulﬁted 120 10 B100 67 70

NaOH/DELOXAN AMP I-1 60 5 37.5 95.4 74

mechanism (Fig. 1a), the reaction proceeded via ring opening

catalysts exhibited excellent performance owing to the highly

4.3 From biomass

agricultural and wood wastes, direct conversion into useful organic

selective hydrolysis into glucose and further transformation

Table 3 Copper-based catalytic systems for hydrogenation of DMO to EG

Zheng et al. have also prepared a series of W-based bimetallic

yield of B48% upon the corn stalk pretreatment with butanediol,

Hydrogenolysis of polyols. Biomass-derived polyols have

Table 4 Catalytic systems for hydrogenolysis of aqueous glycerola

4.5 From formaldehyde (DMM), a dimethyl acetal of formaldehyde (route (3) of

Fig. 2 Proposed model of Al-TS-1 as a bifunctional catalyst for

on a platinized electrode was only about 5%, whereas that for

catalytic materials for DEGFC anodes that could improve

Table 5 Representative electrocatalysts for ethylene glycol oxidation

Metal Oxide/support Acid/base reagent Ref.

twice as high compared to Pt/C. This enhancement was

concluded that electro-oxidation of EG proceeds via two diﬀerent

(CH2–OH)2(ads) - (:COH)2 (8)

(:COH)2 + 2H2O - (HCOOH)ads + 2H+ + 2e (9)

from ref. 20. Copyright 2010 Elsevier.

M + H2O - M(OH)ads + H+ + e (13) membrane electrode assembly (MEA) comprised of an AEM

C2H6O2 2 2CO + 3H2 (15)

Water–gas shift (WGS),

CO + H2O 2 CO2 + H2 (16)

Table 6 Ni-based catalysts for APR of ethylene glycol

quenched. n/a: not available.

pathway to OCH2CH2O leads to increased activity on the

reactions (speciﬁcally HOCH2CH2O* - HOCH2CHO* + H*)

Activity (ML)a Selectivity (%)

For synthesis of acetals. Acetals such as 1,3-dioxolane

Subsequently, a metal species with zero-valence is nucleated to

Table 9 Representative nanostructures obtained via the ethylene glycol-mediated synthesis

Metal/catalyst Reaction systema Structures Particle size (nm) Ref.

on mesoporous TiO2 prepared by a one-step ultrasound-

ions could prevent rapid aggregation of the formed Cu2O seeds by

Freezing Boiling Speciﬁc heata/ Cooling Heat transfer Heat transfer

chemicals, CRC Press, Boca Raton, Florida, 1995.

241 T. Hayashi, T. Inagaki, N. Itayama and H. Baba, Catal. Today,

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