Professional Documents
Culture Documents
Q1 Journal
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
Downloaded by Cornell University on 08 May 2012
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.
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.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
Downloaded by Cornell University on 08 May 2012
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
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View 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
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
(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, still induce further edema and damage to the basal ganglia.34,35,39
alcohols, glycol ethers, and acetone) and only slightly soluble soluble
in These facts account for most clinical and pathological features
in non-polar solvents such as benzene, toluene, dichloroethane, tolueneof 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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
+
Downloaded by Cornell University on 08 May 2012
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.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
Downloaded by Cornell University on 08 May 2012
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.
Copyright 2010 Elsevier.
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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
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.
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.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
Downloaded by Cornell University on 08 May 2012
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.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
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
Downloaded by Cornell University on 08 May 2012
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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
Downloaded by Cornell University on 08 May 2012
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.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
Pt(HCOOH)ads - Pt(CO)ads + 2H2O (10) Fig. 4 Schematic of the AEM-DEGFC. Reproduced with permission
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
Downloaded by Cornell University on 08 May 2012
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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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
Downloaded by Cornell University on 08 May 2012
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
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
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
Table 8 Catalytic performance of ethylene glycol decomposition on Pt and M/Pt bimetallic surfaces
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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
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
Downloaded by Cornell University on 08 May 2012
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.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
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
Downloaded by Cornell University on 08 May 2012
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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
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
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
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.
Downloaded by Cornell University on 08 May 2012
Scheme 22 Chemical microstructures of synthesized aliphatic homopolyesters and copolyesters. Reproduced with permission from ref. 310.
Copyright 2008 Elsevier.
(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
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
Scheme 23 Two-step reaction schemes from formation of ESBO–EG complex to bio-based polyurethane. Reproduced with permission from
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
ref. 311. Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA.
Downloaded by Cornell University on 08 May 2012
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
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View 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
References
catalysts. Alternatively, synthesis of EG from syngas based on 1 E. Canada and H. Canada, Canadian Environmental Protection
the oxidative coupling of CO to form DMO with subsequent Act, 2000.
2 M. W. Forkner, J. H. Robson, W. M. Snelling, A. E. Martin,
hydrogenation is a promising process; however, integration of F. H. Murphy and T. E. Parsons, Glycols–Ethylene Glycols, 2004.
the two steps with high energy and reaction efficiency is the 3 D. Mackay, W. Y. Shiu and K. C. Ma, Illustrated handbook of
primary problem to be solved prior to possible industrialization. physical-chemical properties and environmental fate for organic
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
conversion rate as the cellulose has a highly crystalline structure. 7 G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006, 106,
This issue merits a systematic and comprehensive investigation, 4044–4098.
particularly regarding the single-step conversion of cellulose over 8 A. Y. Yin, X. Y. Guo, W. L. Dai and K. N. Fan, Chem.
Commun., 2010, 46, 4348–4350.
base-metal catalysts. 9 Z. He, H. Q. Lin, P. He and Y. Z. Yuan, J. Catal., 2011, 277,
Several other important issues related to exploring applica- 54–63.
tions of EG should also be taken adequately into considera- 10 A. Yin, C. Wen, X. Guo, W. L. Dai and K. Fan, J. Catal., 2011,
280, 77–88.
tion. Although EG is a promising fuel for DEGFCs, many 11 A. Y. Yin, X. Y. Guo, W. L. Dai and K. N. Fan, J. Phys. Chem.
issues prevent the commercialization, such as deactivation of C, 2009, 113, 11003–11013.
electrode catalysts poisoned by the COads intermediate, low 12 A. Fukuoka and P. L. Dhepe, Angew. Chem., 2006, 118,
Faradic efficiency, and low electrochemical stability. Signifi- 5285–5287.
13 N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H. Wang,
cant efforts may be applied to improve CO tolerance of X. D. Wang and J. G. G. Chen, Angew. Chem., Int. Ed., 2008,
electrode catalysts. One of the major challenges in reforming 47, 8510–8513.
of EG for hydrogen production is to optimize the formula of 14 G. Xu, Y. Li, Z. Li and H. Wang, Ind. Eng. Chem. Res., 1995, 34,
2371–2378.
catalysts with high activity for cleavage of the C–C and C–H
15 X. Liu, K. Shen, Y. Wang, Y. Wang, Y. Guo, Y. Guo, Z. Yong
bonds and the WGS reaction but low activity towards metha- and G. Lu, Catal. Commun., 2008, 9, 2316–2318.
nation. Additionally, more efforts, probably relying on surface 16 G. W. Huber, J. W. Shabaker, S. T. Evans and J. A. Dumesic,
science studies and theoretical calculations, are needed to Appl. Catal., B, 2006, 62, 226–235.
17 G. W. Huber, J. W. Shabaker and J. A. Dumesic, Science, 2003,
clarify the reaction mechanism and to draw a correlation 300, 2075–2077.
between the structure of catalysts and reactivity, which would 18 A. Serov and C. Kwak, Appl. Catal., B, 2010, 97, 1–12.
be helpful for improving oxidation/hydration resistance and 19 V. Bambagioni, M. Bevilacqua, C. Bianchini, J. Filippi,
coking resistance. We have also noted that toxicity generation A. Marchionni, F. Vizza, L. Q. Wang and P. K. Shen, Fuel Cells,
2010, 10, 582–590.
in production and usage of EG cannot be ignored. Safety 20 L. An, T. S. Zhao, S. Y. Shen, Q. X. Wu and R. Chen, Int. J.
production and targeted usage are perhaps the most efficient Hydrogen Energy, 2010, 35, 4329–4335.
options to prevent EG entering the environment through its 21 C. Bianchini and P. K. Shen, Chem. Rev., 2009, 109, 4183–4206.
22 X. Jiang, Y. Wang, T. Herricks and Y. Xia, J. Mater. Chem.,
manufacture, use, handling, and disposal and thus avoid 2004, 14, 695–703.
undesirable risks to people. Additionally, economic and 23 Y. Sun and Y. Xia, Science, 2002, 298, 2176–2179.
management analyses regarding the safety aspects of production 24 C. Li, K. L. Shuford, M. Chen, E. J. Lee and S. O. Cho, ACS
and utilization of EG are fairly limited in the literature. Nano, 2008, 2, 1760–1769.
25 S. E. Skrabalak, B. J. Wiley, M. Kim, E. V. Formo and Y. Xia,
It is also noteworthy that the global market demand of EG Nano Lett., 2008, 8, 2077–2081.
always surpasses its production capacity. Therefore, optimiza- 26 C. Li, K. L. Shuford, Q. H. Park, W. Cai, Y. Li, E. J. Lee and
tion and improvement of existing conventional technologies S. O. Cho, Angew. Chem., 2007, 119, 3328–3332.
27 D. P. Davis, K. J. Bramwell, R. S. Hamilton and S. R. Williams,
(e.g., hydration of ethylene oxide) as well as explorations of
J. Emerg. Med., 1997, 15, 653–667.
alternative processes, particularly those that are renewable and 28 C. A. Staples, J. B. Williams, G. R. Craig and K. M. Roberts,
environmentally friendly, deserve substantial attention and Chemosphere, 2001, 43, 377–383.
input in the near future. 29 R. Mosser-Ruck, K. Devineau, D. Charpentier and
M. Cathelineau, Clays Clay Miner., 2005, 53, 631–638.
30 R. Gomes, R. Liteplo and M. E. Meek, World Health Organization,
Acknowledgements Geneva, 2002, CICADS 45.
31 MeGlobal, 2008.
We are grateful to the financial support from the National 32 P. H. Howard, R. S. Boethling, W. F. Jarvis, W. M. Meylan and
E. M. Michalenko, Handbook of environmental degradation rates,
Natural Science Foundation of China (21006068), the Pro- Lewis Publishers, Chelsea, Michigan, 1991.
gram for New Century Excellent Talents in University 33 P. Leth and M. Gregersen, Forensic Sci. Int., 2005, 155, 179–184.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
34 M. Lovric, P. Granic, M. Cubrilo-Turek, Z. Lalic and J. Sertic, 74 E. M. G. A. V. Kruchten, US Pat., 5874653, 1999.
Forensic Sci. Int., 2007, 170, 213–215. 75 Y. C. Li, S. R. Yan, B. Yue, W. M. Yang, Z. K. Xie, Q. L. Chen
35 M. M. Moore, S. G. Kanekar and R. Dhamija, Radiology Case and H. Y. He, Appl. Catal., A, 2004, 272, 305–310.
Reports, 2008, 3, 122. 76 Y. C. Li, S. R. Yan, W. M. Yang, Z. K. Xie, Q. L. Chen, B. Yue
36 A. D. Walder and C. K. G. Tyler, Anaesthesia, 1994, 49, 964–967. and H. Y. He, J. Mol. Catal. A: Chem., 2005, 226, 285–290.
37 C. G. Guo and K. E. McMartin, Toxicology, 2005, 208, 347–355. 77 F. P. Yu, H. Cai, W. J. He, W. M. Yang and Z. K. Me, J. Appl.
38 A. Luqman, J. Stanifer, O. M. Asif Siddiqui, A. Naseer and Polym. Sci., 2010, 115, 2946–2954.
B. M. Wall, Am. J. Med. Sci., 2011, 341, 338. 78 I. Yusuke, Catal. Today, 1997, 33, 371–409.
39 Y. Chen, H. Liu, H. Chen, F. Tsai, C. Chang, Y. Lee, W. Lin and 79 D. Zavelev, M. Tsodikov, G. Zhidomirov and R. Kozlovskii,
W. Chen, Kidney Int., 2011, 80, 369–377. Kinet. Catal., 2011, 52, 659–671.
40 K. Froberg, R. P. Dorion and K. E. McMartin, Clin. Toxicol., 80 M. R. Altıokka and A. Çıtak, Appl. Catal., A, 2003, 239, 141–148.
2006, 44, 315–318. 81 Y. C. Li, S. R. Yan, W. M. Yang, Z. K. Xie, Q. L. Chen, B. Yue
41 Y. C. Li, B. Yue, S. R. Yan, W. M. Yang, Z. K. Xie, Q. L. Chen and H. Y. He, Catal. Lett., 2008, 124, 85–90.
and H. Y. He, Catal. Lett., 2004, 95, 163–166. 82 B. T. K. J. H. Robson, US Pat., 4571440, 1986.
42 V. F. Shvets, R. A. Kozlovskiy, I. A. Kozlovskiy, 83 M. C. van Engelen, H. T. Teunissen, J. G. de Vries and
M. G. Makarov, J. P. Suchkov and A. V. Koustov, Org. Process C. J. Elsevier, J. Mol. Catal. A: Chem., 2003, 206, 185–192.
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
Res. Dev., 2005, 9, 768–773. 84 B. Boardman, M. J. Hanton, H. van Rensburg and R. P. Tooze,
43 J. W. van Hal, J. S. Ledford and X. K. Zhang, Catal. Today, Chem. Commun., 2006, 2289–2291.
2007, 123, 310–315. 85 U. Matteoli, M. Blanchi, G. Menchi, P. Prediani and F. Piacenti,
44 K. Kawabe, Catal. Surv. Asia, 2010, 14, 111–115. J. Mol. Catal., 1984, 22, 353–362.
45 Y. C. Li, S. R. Yan, L. P. Qian, W. M. Yang, Z. K. Xie, 86 U. Matteoli, G. Menchi, M. Bianchi and F. Piacenti, J. Mol.
Q. L. Chen, B. Yue and H. Y. He, J. Catal., 2006, 241, 173–179. Catal., 1991, 64, 257–267.
46 T. Maihom, S. Namuangruk, T. Nanok and J. Limtrakul, 87 U. Matteoli, G. Menchi, M. Bianchi and F. Piacenti,
Downloaded by Cornell University on 08 May 2012
J. Phys. Chem. C, 2008, 112, 12914–12920. J. Organomet. Chem., 1986, 299, 233–238.
47 M. R. Altiokka and S. Akyalcin, Ind. Eng. Chem. Res., 2009, 48, 88 H. T. Teunissen and C. J. Elsevier, Chem. Commun., 1997, 667–668.
10840–10844. 89 A. Yin, C. Wen, W. L. Dai and K. Fan, Appl. Catal., B, 2011,
48 A. B. Metzner and J. E. Ehrreich, AIChE J., 1959, 5, 496–501. 108–109, 90–99.
49 H. Miyazaki, T. Uda, K. Hirai, Y. Nakamura, H. Ikezawa and 90 A. Yin, C. Wen, W. L. Dai and K. Fan, J. Mater. Chem., 2011,
T. Tsuchie, US Pat., 4585890, 1986. 21, 8997–8999.
50 S. Tahara, K. Fujii, K. Nishihira, M. Matsuda and K. Mizutare, 91 A. Y. Yin, X. Y. Guo, W. L. Dai, H. X. Li and K. N. Fan, Appl.
US Pat., 4453026, 1984. Catal., A, 2008, 349, 91–99.
51 S. Tahara, K. Fujii, K. Nishihira, M. Matsuda and K. Mizutare, 92 X. Y. Guo, A. Y. Yin, W. L. Dai and K. N. Fan, Catal. Lett.,
US Pat., 4467109, 1984. 2009, 132, 22–27.
52 W. J. Bartley and W. V. Charleston, US Pat., 4677234, 1987. 93 A. Yin, X. Guo, W. L. Dai and K. Fan, J. Phys. Chem. C, 2010,
53 Z. H. Gao, Z. C. Liu, F. He and G. H. Xu, J. Mol. Catal. A: 114, 8523–8532.
Chem., 2005, 235, 143–149. 94 A. Y. Yin, X. Y. Guo, W. L. Dai and K. N. Fan, Acta Chim.
54 X. Z. Jiang, Y. H. Su, B. J. Lee and S. H. Chien, Appl. Catal., A, Sinica., 2010, 68, 1285–1290.
2001, 211, 47–51. 95 A. Y. Yin, X. Y. Guo, K. N. Fan and W. L. Dai, ChemCatChem,
55 N. Ueda, Y. Nakagawa and K. Tomishige, Chem. Lett., 2010, 39, 2010, 2, 206–213.
506–507. 96 A. Y. Yin, X. Y. Guo, K. N. Fan and W. L. Dai, Appl. Catal., A,
56 N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H. Wang, 2010, 377, 128–133.
X. D. Wang, Y. Y. Shu, A. L. Stottlemyer and J. G. G. Chen, 97 Y. Y. Zhu, S. R. Wang, L. J. Zhu, X. L. Ge, X. B. Li and
Catal. Today, 2009, 147, 77–85. Z. Y. Luo, Catal. Lett., 2010, 135, 275–281.
57 Y. H. Zhang, A. Q. Wang and T. Zhang, Chem. Commun., 2010, 98 S. Wang, X. Li, Q. Yin, L. Zhu and Z. Luo, Catal. Commun.,
46, 862–864. 2011, 12, 1246–1250.
58 G. H. Zhao, M. Y. Zheng, A. Q. Wang and T. Zhang, Chin. J. 99 A. Yin, J. Qu, X. Guo, W. L. Dai and K. Fan, Appl. Catal., A,
Catal., 2010, 31, 928–932. 2011, 400, 39–47.
59 M. Y. Zheng, A. Q. Wang, N. Ji, J. F. Pang, X. D. Wang and 100 A. Yin, C. Wen, W. L. Dai and K. Fan, Appl. Surf. Sci., 2011,
T. Zhang, ChemSusChem, 2010, 3, 63–66. 257, 5844–5849.
60 F. E. Celik, T. J. Kim and A. T. Bell, Angew. Chem., 2009, 121, 101 A. Y. Yin, X. Y. Guo, W. L. Dai and K. N. Fan, Catal. Commun.,
4907–4909. 2011, 12, 412–416.
61 T. Morimoto and K. Kakiuchi, Angew. Chem., Int. Ed., 2004, 43, 102 H. Yue, Y. Zhao, L. Zhao, J. Lv, S. Wang, J. Gong and X. Ma,
5580–5588. AIChE J., 2012, DOI: 10.1002/aic.12785.
62 T. Li, Y. Souma and Q. Xu, Catal. Today, 2006, 111, 288–291. 103 D. S. Brands, E. K. Poels and A. Bliek, Appl. Catal., A, 1999, 184,
63 S. Y. Lee, J. C. Kim, J. S. Lee and Y. G. Kim, Ind. Eng. Chem. 279–289.
Res., 1993, 32, 253–259. 104 T. Sodesawa, M. Nagacho, A. Onodera and F. Nozaki, J. Catal.,
64 S. R. Jagtap, M. D. Bhor and B. M. Bhanage, Catal. Commun., 1986, 102, 460–463.
2008, 9, 1928–1931. 105 H. Kobayashi, N. Takezawa and C. Minochi, J. Catal., 1981, 69,
65 B. M. Bhanage, S. Fujita, Y. F. He, Y. Ikushima, M. Shirai, 487–494.
K. Torii and M. Arai, Catal. Lett., 2002, 83, 137–141. 106 C. Carlini, M. Di Girolamo, A. Macinai, M. Marchionna,
66 S. M. Dhuri and V. V. Mahajani, J. Chem. Technol. Biotechnol., M. Noviello, A. M. R. Galletti and G. Sbrana, J. Mol. Catal.
2006, 81, 62–69. A: Chem., 2003, 200, 137–146.
67 V. F. Shvets, R. A. Kozlovskiy, I. A. Kozlovskiy, M. G. Makarov, 107 Z. Li, East China University of Science and Technology, 2004.
J. P. Suchkov and A. V. Koustov, Chem. Eng. J., 2005, 107, 199–204. 108 L. R. Lynd, P. J. Weimer, W. H. van Zyl and I. S. Pretorius,
68 K. Kawabe, US Pat., 6080897, 2000. Microbiol. Mol. Biol. Rev., 2002, 66, 506–577.
69 I. A. Kozlovsky, R. A. Kozlovsky, A. V. Koustov, 109 Y. H. P. Zhang and L. R. Lynd, Biotechnol. Bioeng., 2004, 88,
M. G. Makarov, J. P. Suchkov and V. F. Shvets, Org. Process 797–824.
Res. Dev., 2002, 6, 660–664. 110 W. S. L. Mok, M. J. Antal Jr and G. Varhegyi, Ind. Eng. Chem.
70 Z. J. Yang, N. Ren, Y. H. Zhang and Y. Tang, Catal. Commun., Res., 1992, 31, 94–100.
2010, 11, 447–450. 111 M. Sasaki, Z. Fang, Y. Fukushima, T. Adschiri and K. Arai, Ind.
71 Z. J. Yang, Y. F. Li, Q. B. Wu, N. Ren, Y. H. Zhang, Z. P. Liu Eng. Chem. Res., 2000, 39, 2883–2890.
and Y. Tang, J. Catal., 2011, 280, 247–254. 112 C. Luo, S. Wang and H. Liu, Angew. Chem., 2007, 119,
72 D. Othmer and M. Thakar, Ind. Eng. Chem., 1958, 50, 1235–1244. 7780–7783.
73 L. M. Reed, L. A. Wenzel and J. B. O’Hara, Ind. Eng. Chem., 113 X. Chen, T. Zhang, P. Ying, M. Zheng, W. Wu, L. Xia, T. Li,
1956, 48, 205–208. X. Wang and C. Li, Chem. Commun., 2002, 288–289.
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
114 H. H. Hwu and J. G. Chen, Chem. Rev., 2005, 105, 185–212. 157 C. Coutanceau, L. Demarconnay, C. Lamy and J. M. Léger,
115 B. Frühberger and J. G. Chen, J. Am. Chem. Soc., 1996, 118, J. Power Sources, 2006, 156, 14–19.
11599–11609. 158 Z. P. Sun, X. G. Zhang, Y. Y. Liang and H. L. Li, J. Power
116 P. L. Dhepe and A. Fukuoka, ChemSusChem, 2008, 1, 969–975. Sources, 2009, 191, 366–370.
117 J. P. Lange, Biofuels, Bioprod. Biorefin., 2007, 1, 39–48. 159 P. K. Shen and C. Xu, Electrochem. Commun., 2006, 8, 184–188.
118 J. Pang, M. Zheng, A. Wang and T. Zhang, Ind. Eng. Chem. Res., 160 C. Xu, Z. Tian, P. Shen and S. P. Jiang, Electrochim. Acta, 2008,
2011, 50, 6601–6608. 53, 2610–2618.
119 C. Luo, S. Wang and H. Liu, Angew. Chem.,Int. Ed., 2007, 46, 161 F. L. Cheng, H. Wang, Z. H. Sun, M. X. Ning, Z. Q. Cai and
7636–7639. M. Zhang, Electrochem. Commun., 2008, 10, 798–801.
120 A. Villa, G. M. Veith and L. Prati, Angew. Chem., Int. Ed., 2010, 162 Z. Wang, F. Hu and P. K. Shen, Electrochem. Commun., 2006, 8,
49, 4499–4502. 1764–1768.
121 J. Wang, S. H. Shen, B. D. Li, H. Q. Lin and Y. Z. Yuan, Chem. 163 M. S. Ureta-Zanartu, A. Alarcon, G. Munoz and C. Gutierrez,
Lett., 2009, 38, 572–573. Electrochim. Acta, 2007, 52, 7857–7864.
122 M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi and C. Della 164 K. Matsuoka, Y. Iriyama, T. Abe, M. Matsuoka and Z. Ogumi,
Pina, Angew. Chem., Int. Ed., 2007, 46, 4434–4440. J. Electrochem. Soc., 2005, 152, A729–A731.
123 M. A. Dasari, P. P. Kiatsimkul, W. R. Sutterlin and G. J. Suppes, 165 Y. Y. Feng, W. P. Yin, Z. Li, C. D. Huang and Y. X. Wang,
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
Appl. Catal., A, 2005, 281, 225–231. Electrochim. Acta, 2010, 55, 6991–6999.
124 S. Wang and H. Liu, Catal. Lett., 2007, 117, 62–67. 166 Y. J. Fan, Z. Y. Zhou, C. H. Zhen, S. P. Chen and S. G. Sun,
125 J. Chaminand, L. Djakovitch, P. Gallezot, P. Marion, C. Pinel Electrochem. Commun., 2011, 13, 506–508.
and C. Rosier, Green Chem., 2004, 6, 359–361. 167 C. Jin, Y. Song and Z. Chen, Electrochim. Acta, 2009, 54,
126 T. Miyazawa, Y. Kusunoki, K. Kunimori and K. Tomishige, 4136–4140.
J. Catal., 2006, 240, 213–221. 168 D. M. Zeng and M. Schell, Electrochim. Acta, 2011, 56,
127 A. Yin, X. Guo, W. Dai and K. Fan, Green Chem., 2009, 11, 4703–4710.
Downloaded by Cornell University on 08 May 2012
1514–1516. 169 E. Sitta, B. C. Batista and H. Varela, Chem. Commun., 2011, 47,
128 J. J. Bozell and G. R. Petersen, Green Chem., 2010, 12, 539–554. 3775–3777.
129 J. Sun and H. Liu, Green Chem., 2011, 13, 135–142. 170 H. J. Kim, S. M. Choi, S. Green, G. A. Tompsett, S. H. Lee,
130 C. Montassier, J. C. Ménézo, L. C. Hoang, C. Renaud and G. W. Huber and W. B. Kim, Appl. Catal., B, 2011, 101, 366–375.
J. Barbier, J. Mol. Catal., 1991, 70, 99–110. 171 D. Morales-Acosta, D. L. de la Fuente, L. G. Arriaga,
131 J. H. Zhou, M. G. Zhang, L. Zhao, P. Li, X. G. Zhou and G. V. Gutierrez and F. J. R. Varela, Int. J. Electrochem. Sci.,
W. K. Yuan, Catal. Today, 2009, 147, 225–229. 2011, 6, 1835–1853.
132 I. Clark, Ind. Eng. Chem., 1958, 50, 1125–1126. 172 N. W. Maxakato, C. J. Arendse and K. I. Ozoemena, Electro-
133 L. Zhao, J. H. Zhou, Z. J. Sui and X. G. Zhou, Chem. Eng. Sci., chem. Commun., 2009, 11, 534–537.
2010, 65, 30–35. 173 J. P. Wang, R. M. Asmussen, B. Adams, D. F. Thomas and
134 M. Dubeck and G. G. Knapp, US Pat., 4430253, 1984. A. C. Chen, Chem. Mater., 2009, 21, 1716–1724.
135 M. S. S. R. Tanikella, US Pat., 4404411, 1983. 174 I. Basumallick, M. Chatterjee, A. Chatterjee and S. Ghosh,
136 T. A. Werpy, J. G. Frye Jr., A. H. Zacher and D. J. Miller, US Electrochim. Acta, 2009, 54, 7299–7304.
Pat., 7038094, 2006. 175 R. B. de Lima, V. Paganin, T. Iwasita and W. Vielstich, Electro-
137 B. W. Hoffer and R. Prochazka, US Pat., 0019191, 2010. chim. Acta, 2003, 49, 85–91.
138 M. S. S. R. Tanikella, EP, 0072629, 1982. 176 V. Selvaraj and M. Alagar, Nanotechnology, 2008, 19, 045504.
139 Y. Watanabe and T. Tatsumi, Microporous Mesoporous Mater., 177 L. Demarconnay, S. Brimaud, C. Coutanceau and J. M. Leger,
1998, 22, 399–407. J. Electroanal. Chem., 2007, 601, 169–180.
140 B. M. Bhanage, S.-i. Fujita, Y. Ikushima and M. Arai, Appl. 178 B. Wieland, J. P. Lancaster, C. S. Hoaglund, P. Holota and
Catal., A, 2001, 219, 259–266. W. J. Tornquist, Langmuir, 1996, 12, 2594–2601.
141 Y. Urano, M. Kirishiki, Y. Onda and H. Tsuneki, US Pat., 179 B. Wu, Y. Gao, G. C. Li, W. L. Qu and Z. H. Jiang, Catal. Lett.,
5430170, 1995. 2006, 106, 167–170.
142 Y. Nishiyama, M. Arai, S. L. Guo, N. Sonehara, T. Naito and 180 T. Ghosh, B. M. Leonard, Q. Zhou and F. J. DiSalvo, Chem.
K. Torii, Appl. Catal., A, 1993, 95, 171–181. Mater., 2010, 22, 2190–2202.
143 M. Shirai, K. Aoki, K. Torii and M. Arai, Appl. Catal., A, 1999, 181 J. C. Bauer, X. Chen, Q. S. Liu, T. H. Phan and R. E. Schaak,
187, 141–146. J. Mater. Chem., 2008, 18, 275–282.
144 A. T. Larson, U.S. Pat., 2153064, 1939. 182 S. Maksimuk, S. C. Yang, Z. M. Peng and H. Yang, J. Am. Chem.
145 H. Li, Q. Lei, X. M. Zhang and J. S. Suo, Catal. Commun., 2009, Soc., 2007, 129, 8684.
10, 1936–1939. 183 J. Y. Wang, Y. Y. Kang, H. Yang and W. B. Cai, J. Phys. Chem.
146 A. O. Neto, T. R. R. Vasconcelos, R. W. R. V. D. Silva, M. Linardi C, 2009, 113, 8366–8372.
and E. V. Spinacé, J. Appl. Electrochem., 2005, 35, 193–198. 184 J. S. Spendelow and A. Wieckowski, Phys. Chem. Chem. Phys.,
147 D. Morales-Acosta, L. G. Arriaga, L. Alvarez-Contreras, 2007, 9, 2654–2675.
S. F. Luna and F. J. R. Varela, Electrochem. Commun., 2009, 185 C. Lamy, E. M. Belgsir and J. M. Léger, J. Appl. Electrochem.,
11, 1414–1417. 2001, 31, 799–809.
148 R. Chetty and K. Scott, J. Appl. Electrochem., 2007, 37, 186 V. Bambagioni, C. Bianchini, J. Filippi, W. Oberhauser,
1077–1084. A. Marchionni, F. Vizza, R. Psaro, L. Sordelli, M. L. Foresti
149 V. Livshits, M. Philosoph and E. Peled, J. Power Sources, 2008, and M. Innocenti, ChemSusChem, 2009, 2, 99–112.
178, 687–691. 187 V. Livshits and E. Peled, J. Power Sources, 2006, 161, 1187–1191.
150 H. Wang, Z. Jusys and R. J. Behm, Electrochim. Acta, 2009, 54, 188 E. H. Yu and K. Scott, J. Power Sources, 2004, 137, 248–256.
6484–6498. 189 K. Matsuoka, M. Inaba, Y. Iriyama, T. Abe, Z. Ogumi and
151 D. Kaplan, L. Burstein, Y. Rosenberg and E. Peled, J. Power M. Matsuoka, Fuel Cells, 2002, 2, 35–39.
Sources, 2011, 196, 8286–8292. 190 Z. Ogumi, K. Matsuoka, S. Chiba, M. Matsuoka, Y. Iriyama,
152 N. W. Maxakato, K. I. Ozoemena and C. J. Arendse, Electro- A. B. E. Takeshi and M. Inaba, Electrochemistry, 2002, 70, 980–983.
analysis, 2010, 22, 519–529. 191 J. Turner, G. Sverdrup, M. K. Mann, P. C. Maness, B. Kroposki,
153 M. C. Halseid, Z. Jusys and R. J. Behm, J. Electroanal. Chem., M. Ghirardi, R. J. Evans and D. Blake, Int. J. Energy Res., 2008,
2010, 644, 103–109. 32, 379–407.
154 V. Selvaraj, M. Vinoba and M. Alagar, J. Colloid Interface Sci., 192 R. R. Davda, J. W. Shabaker, G. W. Huber, R. D. Cortright and
2008, 322, 537–544. J. A. Dumesic, Appl. Catal., B, 2003, 43, 13–26.
155 H. Wang, Y. Zhao, Z. Jusys and R. J. Behm, J. Power Sources, 193 R. D. Cortright, R. R. Davda and J. A. Dumesic, Nature, 2002,
2006, 155, 33–46. 418, 964–967.
156 H. Wang, Z. Jusys and R. J. Behm, J. Electroanal. Chem., 2006, 194 J. W. Shabaker, D. A. Simonetti, R. D. Cortright and
595, 23–36. J. A. Dumesic, J. Catal., 2005, 231, 67–76.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.
View Online
195 M. Salciccioli and D. G. Vlachos, ACS Catal., 2011, 1, 232 A. Yamaguchi, N. Hiyoshi, O. Sato, K. K. Bando, M. Osada and
1246–1256. M. Shirai, Catal. Today, 2009, 146, 192–195.
196 D. J. M. de Vlieger, A. G. Chakinala, L. Lefferts, S. R. 233 O. Skoplyak, M. A. Barteau and J. G. Chen, J. Phys. Chem. B,
A. Kersten, K. Seshan and D. W. F. Brilman, Appl. Catal., B, 2006, 110, 1686–1694.
2012, 111–112, 536–544. 234 O. Skoplyak, M. A. Barteau and J. G. Chen, Catal. Today, 2009,
197 M. Salciccioli, W. Yu, M. A. Barteau, J. G. Chen and 147, 150–157.
D. G. Vlachos, J. Am. Chem. Soc., 2011, 133, 7996–8004. 235 O. Skoplyak, C. Menning, M. Barteau and J. Chen, Top. Catal.,
198 J. W. Shabaker, G. W. Huber, R. R. Davda, R. D. Cortright and 2008, 51, 49–59.
J. A. Dumesic, Catal. Lett., 2003, 88, 1–8. 236 A. L. Stottlemyer, H. Ren and J. G. Chen, Surf. Sci., 2009, 603,
199 J. Liu, B. Sun, J. Y. Hu, Y. Pei, H. X. Li and M. H. Qiao, 2630–2638.
J. Catal., 2010, 274, 287–295. 237 M. A. Salaev, A. A. Krejker, O. V. Magaev, V. S. Malkov,
200 J. W. Shabaker, R. R. Davda, G. W. Huber, R. D. Cortright and A. S. Knyazev, E. S. Borisova, V. M. Khanaev, O. V. Vodyankina
J. A. Dumesic, J. Catal., 2003, 215, 344–352. and L. N. Kurina, Chem. Eng. J., 2011, 172, 399–409.
201 N. Wang, N. Perret and A. Foster, Int. J. Hydrogen Energy, 2011, 238 A. N. Pestryakov, V. V. Lunin, A. N. Devochkin, L. A. Petrov,
36, 5932–5940. N. E. Bogdanchikova and V. P. Petranovskii, Appl. Catal., A,
202 R. R. Davda, R. Alcala, J. Shabaker, G. Huber, R. D. Cortright, 2002, 227, 125–130.
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
M. Mavrikakis and J. A. Dumesic, Science and Technology in 239 V. R. Chumbhale and P. A. Awasarkar, Appl. Catal., A, 2001,
Catalysis 2002, 2003, 145, 79–84. 205, 109–115.
203 J. Greeley and M. Mavrikakis, J. Am. Chem. Soc., 2002, 124, 240 O. V. Magaev, A. S. Knyazev, O. V. Vodyankina,
7193–7201. N. V. Dorofeeva, A. N. Salanov and A. I. Boronin, Appl. Catal.,
204 R. R. Davda, J. W. Shabaker, G. W. Huber, R. D. Cortright and A, 2008, 344, 142–149.
J. A. Dumesic, Appl. Catal., B, 2005, 56, 171–186. 241 T. Hayashi, T. Inagaki, N. Itayama and H. Baba, Catal. Today,
205 R. R. Davda and J. A. Dumesic, Angew. Chem., 2003, 115, 2006, 117, 210–213.
Downloaded by Cornell University on 08 May 2012
Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2012
View Online
266 S. P. Chopade and M. M. Sharma, React. Funct. Polym., 1997, 34, 292 B. F. Blin, D. Beaupere and M. Figlarz, New J. Chem., 1989, 13,
37–45. 67–72.
267 B. R. Jermy and A. Pandurangan, J. Mol. Catal. A: Chem., 2006, 293 K. E. Korte, S. E. Skrabalak and Y. Xia, J. Mater. Chem., 2008,
256, 184–192. 18, 437–441.
268 Y. J. Gong, Y. Li, D. Wu and Y. H. Sun, Catal. Lett., 2001, 74, 294 C. C. Li, W. P. Cai, B. Q. Cao, F. Q. Sun, Y. Li, C. X. Kan and
213–216. L. D. Zhang, Adv. Funct. Mater., 2006, 16, 83–90.
269 S. Shylesh, S. Sharma, S. P. Mirajkar and A. P. Singh, J. Mol. 295 A. Miyazaki, I. Balint, K.-i. Aika and Y. Nakano, J. Catal., 2001,
Catal. A: Chem., 2004, 212, 219–228. 204, 364–371.
270 J. Song, V. Zello, A. L. Boehman and F. J. Waller, Energy Fuels, 296 V. G. Komvokis, M. Marti, A. Delimitis, I. A. Vasalos and
2004, 18, 1282–1290. K. S. Triantafyllidis, Appl. Catal., B, 2011, 103, 62–71.
271 E. Garcia, M. Laca, E. Perez, A. Garrido and J. n. Peinado, 297 J. Zhang, H. Xu, Q. Ge and W. Li, Catal. Commun., 2006, 7,
Energy Fuels, 2008, 22, 4274–4280. 148–152.
272 G. Li, B. Wang, J. Wang, Y. Ding, L. Yan and J. Suo, J. Mol. 298 Q. Zhang, C. Cobley, L. Au, M. McKiernan, A. Schwartz,
Catal. A: Chem., 2005, 236, 72–76. L. Wen, J. Chen and Y. Xia, ACS Appl. Mater. Interfaces,
273 E. Nieddu, M. Cataldo, F. Pinna and G. Strukul, Tetrahedron 2009, 1, 2044–2048.
Lett., 1999, 40, 6987–6990. 299 P. Setua, R. Pramanik, S. Sarkar, C. Ghatak, S. K. Das and
Published on 10 April 2012 on http://pubs.rsc.org | doi:10.1039/C2CS15359A
274 E. Lebègue, S. Baranton and C. Coutanceau, J. Power Sources, N. Sarkar, J. Phys. Chem. B, 2010, 114, 7557–7564.
2011, 196, 920–927. 300 B. J. Hwang, S. M. S. Kumar, C. H. Chen, R. W. Chang,
275 Y. Zhang, M. E. Grass, W. Huang and G. A. Somorjai, Lang- D. G. Liu and J. F. Lee, J. Phys. Chem. C, 2008, 112, 2370–2377.
muir, 2010, 26, 16463–16468. 301 C. K. Tsung, J. N. Kuhn, W. Huang, C. Aliaga, L. I. Hung,
276 M. H. Kim, B. Lim, E. P. Lee and Y. Xia, J. Mater. Chem., 2008, G. A. Somorjai and P. Yang, J. Am. Chem. Soc., 2009, 131,
18, 4069–4073. 5816–5822.
277 L. S. Sarma, C. H. Chen, S. M. S. Kumar, G. R. Wang, S. C. Yen, 302 N. Perkas, Z. Y. Zhong, L. W. Chen, M. Besson and
Downloaded by Cornell University on 08 May 2012
D. G. Liu, H. S. Sheu, K. L. Yu, M. T. Tang, J. F. Lee, C. Bock, A. Gedanken, Catal. Lett., 2005, 103, 9–14.
K. H. Chen and B. J. Hwang, Langmuir, 2007, 23, 5802–5809. 303 M. Gollin and D. Bjork, SAE Technical Paper Series SP-1175,
278 S. H. Im, Y. T. Lee, B. Wiley and Y. Xia, Angew. Chem., 2005, 1996, pp. 115–123.
117, 2192–2195. 304 J. J. JuGer and R. F. Crook, SAE Technical Paper Series SP-
279 J. Chen, T. Herricks and Y. Xia, Angew. Chem., 2005, 117, 1456, 1999, pp. 23–33.
2645–2648. 305 C. Oliet, A. Oliva, J. Castro and C. D. Pérez-Segarra, Appl.
280 O. Palchik, R. Kerner, A. Gedanken, A. M. Weiss, M. A. Slifkin Therm. Eng., 2007, 27, 2033–2043.
and V. Palchik, J. Mater. Chem., 2001, 11, 874–878. 306 M. Dehghandokht, M. G. Khan, A. Fartaj and S. Sanaye, Int. J.
281 K. J. Carroll, J. U. Reveles, M. D. Shultz, S. N. Khanna and
Therm. Sci., 2011, 50, 1615–1627.
E. E. Carpenter, J. Phys. Chem. C, 2011, 115, 2656–2664.
307 J. M. Hollis, F. J. Lovas, P. R. Jewell and L. H. Coudert,
282 H. Kawasaki, Y. Kosaka, Y. Myoujin, T. Narushima,
Astrophys. J. Lett., 2002, 571, L59.
T. Yonezawa and R. Arakawa, Chem. Commun., 2011, 47,
308 ASHRAE Handbook - Fundamentals, American Society of Heat-
7740–7742.
ing, 2009.
283 C. Cheng, F. Xu and H. Gu, New J. Chem., 2011, 35, 1072–1079.
309 A. Nishio, A. Mochizuki, J. I. Sugiyama, K. Takeuchi, M. Asai,
284 F. F. Castillón-Barraza, M. H. Farı́as, J. H. Coronado-López,
M. A. Encinas-Romero, M. Pérez-Tello, R. Herrera-Urbina and K. Yonetake and M. Ueda, J. Polym. Sci., Part A: Polym. Chem.,
A. Posada-Amarillas, Adv. Sci. Lett., 2011, 4, 596–601. 2001, 39, 416–429.
285 G. G. Couto, J. J. Klein, W. H. Schreiner, D. H. Mosca, A. J. 310 C. Tsai, W. Chang, C. Chen, H. Lu and M. Chen, Eur. Polym. J.,
A. de Oliveira and A. J. G. Zarbin, J. Colloid Interface Sci., 2007, 2008, 44, 2339–2347.
311, 461–468. 311 A. A. Lubguban, Y. C. Tu, Z. R. Lozada, F. H. Hsieh and
286 C. W. Kim, H. G. Cha, Y. H. Kim, A. P. Jadhav, E. S. Ji, G. J. Suppes, J. Appl. Polym. Sci., 2009, 112, 2185–2194.
D. I. Kang and Y. S. Kang, J. Phys. Chem. C, 2009, 113, 5081–5086. 312 U. Meyer and W. F. Hoelderich, Appl. Catal., A, 1999, 178,
287 B. Jeyadevan, K. Shinoda, R. J. Justin, T. Matsumoto, K. Sato, 159–166.
H. Takahashi, Y. Sato and K. Tohji, IEEE Trans. Magn., 2006, 313 F. Ning, L. Zhang, G. Jiang, Y. Tu, X. Wu and Y. Yu, J. Nat.
42, 3030–3035. Gas Chem., 2011, 20, 25–33.
288 C. Cheng, Y. Wen, X. Xu and H. Gu, J. Mater. Chem., 2009, 19, 314 S. B. Kaasa, K. Sandengen and T. Østvold, NTNU in SPE
8782–8788. International Symposium on Oilfield Scale, Society of Petroleum
289 D. Larcher and R. Patrice, J. Solid State Chem., 2000, 154, Engineers Aberdeen, United Kingdom, 2005, p. 13.
405–411. 315 E. M. Flaten, M. Seiersten and J. P. Andreassen, J. Cryst.
290 I. Balint, A. Miyazaki and K.-i. Aika, J. Catal., 2003, 220, 74–83. Growth, 2009, 311, 3533–3538.
291 R. J. Joseyphus, T. Matsumoto, H. Takahashi, D. Kodama, 316 M. W. Forkner, J. H. Robson, W. M. Snellings, A. E. Martin,
K. Tohji and B. Jeyadevan, J. Solid State Chem., 2007, 180, F. H. Murphy and T. E. Parsons, in Kirk-Othmer Encyclopedia of
3008–3018. Chemical Technology, John Wiley & Sons, Inc., 2000.
This journal is c The Royal Society of Chemistry 2012 Chem. Soc. Rev.