DOI: 10.1002/cctc.
201200117
Influence of Support and Linker Parameters on the
Activity of Silica-Supported Catalysts for Cyclic Carbonate
Synthesis
Michael North* and Pedro Villuendas[a]
Silica-supported, bimetallic aluminium(salen) complexes bear-
ing pendant quaternary ammonium groups catalyse the syn-
thesis of cyclic carbonates from epoxides and carbon dioxide
in both batch and gas-phase flow reactors. The influence of
particle and pore size of the silica support on catalyst activity
was investigated with smaller particle sizes (< 80 mm) being
advantageous to catalyst activity, whereas the silica pore size
had little effect on catalyst activity. The nature of the silica sup-
Introduction
There is currently a renaissance of interest in carbon dioxide
chemistry[1] driven by the realisation that carbon dioxide can
provide a sustainable C1-building block for a future chemicals
industry and that carbon capture and utilisation can be cost ef-
fective and has the potential to offset some of the costs associ-
ated with carbon capture and storage.[2] The most effective re-
actions of carbon dioxide are those that are exothermic and
can be performed at a reasonable rate close to ambient tem-
perature and pressure to avoid the need for energy consump-
tion during the chemical transformation. A perceived limitation
in this respect is the thermodynamic stability of carbon dioxide
(DHf = 394 kJ mol 1).[3] However, despite this highly negative
heat of formation, there are reactions of carbon dioxide that
are exothermic and some of these have been commercialised.
Thus, the synthesis of urea from carbon dioxide and ammonia
(DHr = 119 kJ mol 1)[4] has been a commercial process since
1922 and the synthesis of salicyclic acid from phenol and
carbon dioxide (DHr = 31 kJ mol 1)[5] was first commercialised
in 1890. Another important reaction of carbon dioxide is its re-
action with epoxides to form either cyclic[6] or polycarbonates[7]
(Scheme 1). The synthesis of cyclic carbonates in this way has
been a commercial process for over 50 years and is again
a highly exothermic reaction (DHr = 140 kJ mol 1 for ethylene
carbonate)[8] and the production of polycarbonates has also re-
cently become a commercial process.[9]
Cyclic carbonates have numerous applications.[10] They are
important chemical intermediates for the synthesis of dimethyl
Scheme 1. Synthesis of cyclic and polycarbonates from epoxides and CO2.
ChemCatChem 2012, 4, 789 – 794  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
port also affected catalyst stability and the Fluorochem LC301
silica gave a catalyst with both the highest intrinsic activity
and the lowest rate of deactivation. The catalysts are attached
to the silica through a linker containing three or eleven carbon
atoms. The longer linker was found give a catalyst loading
three times higher than the shorter linker, but this was offset
by a three times lower activity for the catalyst with the longer
linker.
carbonate[11] and ethylene glycol,[12] electrolytes for lithium-ion
batteries[13] and polar aprotic solvents.[14] However, the current
commercial production of cyclic carbonates employs quaterna-
ry ammonium or phosphonium salts as catalysts,[11, 12, 15] requir-
ing the use of temperatures above 100 8C and pressures above
twenty bar. Under these conditions, more carbon dioxide is
generated owing to the energy required to operate the pro-
cess than is consumed by the chemical reaction.
In 2007,[16] we first reported bimetallic aluminium(salen)
complex 1 (Figure 1) as an exceptionally active and recycla-
ble[17] homogeneous catalyst for cyclic carbonate synthesis at
room temperature and 1 bar carbon dioxide pressure. If used
with tetrabutylammonium bromide as a cocatalyst, 2.5 mol %
of complex 1 was capable of converting a wide range of termi-
nal epoxides into the corresponding cyclic carbonates. Mecha-
nistic studies revealed that both metal ions of catalyst 1 had
catalytic roles: activation of the epoxide and preorganisation
of the reagents for carbonate synthesis, respectively, and that
the tetrabutylammonium bromide had two catalytic roles: pro-
viding bromide to ring-open the epoxide and acting as an
in situ source of tributylamine to activate the carbon diox-
ide.[17, 18] Complex 1 has been shown to be compatible with
waste carbon dioxide produced by methane combustion,[19] its
cost of production has been minimised[20] and its structure sim-
plified to acen complex 2,[21] which is also an active catalyst for
cyclic carbonate synthesis, but which can be prepared for one
sixth the cost of complex 1.[20]
[a] Prof. M. North, Dr. P. Villuendas
School of Chemistry and University Research Centre in
Catalysis and Intensified Processing
Newcastle University
Bedson building, Newcastle upon Tyne, NE1 7RU (UK)
Fax: (+ 44) 191-2226929
E-mail: Michael.north@ncl.ac.uk
789
 M. North and P. Villuendas

nates. Catalyst 4 was also shown to be unaffected by simulat-

ed power station flue-gas[25] and its activity for cyclic carbonate
synthesis in the flow reactor was also unaffected when it had
been exposed to real flue-gas (20 mL min 1 for 16 h) from
a 160 kW emissions reduction test facility.[27]
Previous work[25, 26] has shown that silica is the optimal sup-
port for catalyst 4. However, the influence of the physical prop-
erties of the support and the linker on the activity and lifetime
of the catalyst had not been investigated. Therefore, in this
paper we report the results of a study examining the effect of
silica particle size and porosity, as well as linker length on the
activity and lifetime of supported catalyst 4.

Results and Discussion

Seven different silicas were selected for this study and their rel-
evant physical properties are given in Table 1. Fluorochem
LC301 is the ‘standard’ amorphous flash silica that we have
used in all previous work.[25–27] The other six silicas were
Figure 1. Bimetallic catalysts 1–4 and 9 for cyclic carbonate synthesis.
chosen to provide particle sizes of 15–500 mm and pore sizes
of 60 or 150 . Images of the seven silicas taken at magnifica-
tions of  32 and  128 revealed that they all consisted of irreg-
Although catalysts 1 and 2 are highly active homogeneous ular particles that differed only in the particle size. Each silica
catalysts for cyclic carbonate synthesis, the optimal utilisation was functionalised with (3-chloropropyl)-triethoxysilane and
of waste carbon dioxide for cyclic carbonate synthesis would then treated with salen complex 5[25, 26] to give supported com-
be in a gas-phase flow reactor, especially in view of the com- plex 6 and finally quaternised by treatment with benzyl bro-
mercial demand being largely focused on ethylene and propyl- mide, whilst simultaneously undergoing anion exchange using
ene carbonates, which are derived from ethylene and propyl- tetrabutylammonium bromide to give silica-supported cata-
ene oxides with boiling points of 11 and 34 8C respectively. In lysts 4, as shown in Scheme 2. The aluminium content of each
addition the potential demand for cyclic carbonates is as high
as 40 Mtonnes per annum should dimethyl carbonate be
adopted as an oxygenating agent for petrol[22] or other fuels[23]
and this scale of production would necessitate the use of
a continuous flow reactor. Therefore, the immobilisation of cat-
alyst 1 was undertaken. Initially, one-component catalyst 3 was
developed to avoid the need for a cocatalyst,[24, 25] then one of
the ammonium groups was used as a convenient functional
group to attach the catalyst to an insoluble support through
a linker, giving immobilised catalyst 4.[25, 26] When used in
a packed-bed, gas-phase flow reactor at 100 8C and 1 bar pres-
sure, immobilised catalyst 4 was shown to convert both ethyl-
Scheme 2. Synthesis of silica-supported catalysts.
ene and propylene oxides into the corresponding cyclic carbo-

Table 1. Physical data and activities of the silicas used in this work.

Entry Name Particle size [mm] Pore size [] Catalyst loading[a] Conv. [%][b] TOF [h 1][c]
1 Fluorochem LC301 43–60 60 0.43 60 1.38
2 Davisil 636 250–500 60 0.39 9 0.15
3 Davisil 646 250–500 150 0.26 6 0.12
4 Davisil 635 150–250 60 0.56 11 0.33
5 Davisil 633 38–75 60 1.00 37 0.99
6 Davisil 643 38–75 150 0.77 23 1.22
7 Merck 1.15111 15–40 60 0.58 64 1.32
8[d] Fluorochem LC301 43–60 60 1.21 20 0.41

[a] Determined by ICP-OES analysis and given in mmol of catalyst per gram of support. [b] conversion of styrene oxide to styrene carbonate after a reaction
time of 24 h in a batch reactor at 26 8C. [c] TOF = turn over frequency for ethylene carbonate production in a flow reactor at 100 8C. [d] Using an eleven
carbon linker rather than a three carbon linker.

790 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 789 – 794
Supported Catalysts for Cyclic Carbonate Synthesis
supported catalyst 4 was determined by ICP-OES and used to
calculate the catalyst loadings given in Table 1.
The catalyst loadings given in Table 1 only vary by a factor
of four (entries 3 and 5) even though the particle sizes vary by
over an order of magnitude (entries 3 and 7) and the particle
surface area varies by over two orders of magnitude. There is
also no clear correlation between particle size and catalyst
loading. Thus, although Davisil 633 and 643 give the highest
catalyst loadings (entries 5 and 6), Fluorochem LC301 with
a similar particle size gives a much lower catalyst loading
(entry 1). In both cases for which silicas had identical particle
sizes, but different pore volumes, the silica with the smaller
pore volume was found to give the higher catalyst loading (en-
tries 2,3 and 5,6). This suggests that the attachment of the cat-
alyst to the silica is entirely a surface effect as the larger pore
volumes do not facilitate the attachment of catalyst to the
voids within the silica.
Each silica-supported catalyst was first tested in the conver-
sion of styrene oxide 7 a into styrene carbonate 8 a in a batch
reactor at 26 8C, under 1 bar carbon dioxide pressure and in
the absence of any solvent (Scheme 3). These reactions were
Scheme 3. Synthesis of styrene carbonate.
performed using the same number of moles of active sites in
the supported catalyst, so that the results would reflect the in-
trinsic activity of the supported catalyst, not the catalyst load-
ing and the results are included in Table 1. It is apparent from
the results that the catalysts supported on silica with large par-
ticle sizes (150–500 mm, entries 2–4) had very low activity. The
highest catalytic activity was obtained with catalysts supported
on the Fluorochem and Merck silicas with particle sizes of (15–
60 mm, entries 1–7). However, particle size appears not to be
the only relevant factor as two other catalysts supported on
Davisil silicas with similar particle sizes (38–75 mm, entries 5
and 6) displayed much more modest levels of catalytic activity
in this reaction.
The influence of silica particle size and pore volume was ex-
pected to be most pronounced on reactions performed in the
gas-phase flow reactor. Therefore, all seven silica supported
catalysts were used to convert ethylene oxide 7 b into ethylene
carbonate 8 b in the gas-phase flow reactor that we have pre-
viously described.[25, 26] These reactions were all performed for
24 h with the silica-supported catalyst packed into a 3 cm by
1 cm tubular reactor and held at 100 8C (Scheme 4). The ethyl-
ene carbonate produced was collected and used to calculate
Scheme 4. Synthesis of ethylene carbonate.
ChemCatChem 2012, 4, 789 – 794  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
the turn over frequency (TOF) for each silica-supported cata-
lyst, the data being given in Table 1.
The results obtained in the flow reactor are more readily ex-
plained on the basis of particle size. Thus, catalysts supported
on Fluorochem and Merck silicas with small particle sizes (15–
60 mm), which had given the best results in the production of
styrene carbonate in the batch reactor also gave the best re-
sults in the flow reactor (entries 1 and 7). However, catalysts
supported on the Davisil silicas with similarly small particle
sizes (38–75 mm), which had performed poorly in the batch re-
actor, performed much better in the flow reactor (entries 5 and
6). In contrast, catalysts supported on silicas with particle sizes
of (150–500 mm) gave very poor results in the flow reactor (en-
tries 2–4). The only comparison between silicas with different
pore sizes that can be made is entries 5 and 6 and this sug-
gests that the larger pore size may be beneficial for reactions
performed in the gas-phase flow reactor. The TOF obtained
with each catalyst in the flow reactor was found to show an in-
verse exponential relationship with the silica particle surface
area after the catalyst loadings were normalised (Figure 2).
Figure 2. Relationship between turn over frequency (TOF) and silica particle
surface area normalised for catalyst loading. The calculation of the surface
area assumes the silica particles are spherical.
Under the reaction conditions, although the ethylene oxide
and carbon dioxide are gases, the ethylene carbonate is
formed as a liquid, which coats the silica particles. Carbon di-
oxide is known to be soluble in cyclic carbonates[ 14a] and this
provides an explanation for the results as the smaller particles
give a higher total surface area within the reactor. As the ethyl-
ene carbonate is formed it can act as a solvent, dissolving
both the ethylene oxide and carbon dioxide and concentrating
them on the surface of the silica where they can react in the
presence of aluminium(salen) units.
Another factor that will affect the effectiveness of a support-
ed catalyst is its lifetime. We have previously studied this for
the Fluorochem LC301 supported catalyst[25, 26] and shown that
in the flow reactor, at 100 8C, partial catalyst deactivation
occurs over a period of eight days. This deactivation is due to
dequaternisation of the ammonium groups within the support-
ed catalyst (Figure 3, cleavage of bonds of type a) and can be
reversed by treatment of the partially deactivated catalyst with
an alkylating agent (benzyl bromide) to requaternise the
amines. In contrast, cleavage of bonds of type b would result
in irreversible loss of catalyst activity and cleavage of bonds of
www.chemcatchem.org 791

Figure 3. Origin of supported catalyst deactivation.
type c would result in irreversible loss of catalyst activity ac-
companied by loss of the whole aluminium(salen) unit from
the solid support. Since the Merck and Davisil 633 and 643 sili-
cas had been shown to be effective when used in the gas-
phase flow reactor, the deactivation of these catalysts was also
investigated. Thus, each supported catalyst was used to in the
gas-phase flow reactor for nine days and the results are shown
in Figure 4 along with those for the Fluorochem LC301 sup-
ported catalyst for comparison.
Figure 4. Lifetime of supported catalysts for cyclic carbonate synthesis. Fluo-
rochem LC301 (&, reactivated after day 7); Merck 1.15111 (~, reactivated
after day 6); Davisil 643 (^, reactivated after day 7); Davisil 633 (*, reactivat-
ed after day 7).
It is apparent from Figure 4 that all of the silica-supported
catalysts display the same trend in catalyst deactivation and re-
activation. Thus, the Fluorochem supported catalyst loses 42 %
of its activity over seven days, the Merck silica-supported cata-
lyst loses 68 % of its activity over six days, the Davisil 643 sup-
ported catalyst loses 50 % of its activity over seven days and
the Davisil 633 supported catalyst loses 64 % of its activity over
seven days. In all cases however, the catalyst could be reacti-
vated by treatment with benzyl bromide. Overall, it is apparent
from analysis of the results in Table 1 and Figure 4 that Fluoro-
chem LC301 provides the optimal support amongst those in-
vestigated, giving both the highest TOF and the lowest rate of
catalyst deactivation.
Having optimised the silica used as the support, the effect
of changing the length of the linker between the silica and
aluminium(salen) unit was also investigated by the synthesis of
792 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
M. North and P. Villuendas
Fluorochem LC301 supported catalyst 9 with an eleven carbon
linker between the support and catalyst, rather than the three
carbon linker used for catalysts 4. Catalyst 9 was prepared by
the same route used to prepare catalysts 4 (Scheme 2) and
was tested for the synthesis of both styrene carbonate 8 a in
batch mode (Scheme 3) and ethylene carbonate 8 b in the
flow reactor (Scheme 4). The results are included in Table 1.
Comparing the data in entries 1 and 8 of Table 1, it is apparent
that the longer linker in catalyst 9 enabled the catalyst loading
to be increased by a factor of three, but that catalyst 9 was in-
trinsically three times less active than Fluorochem LC301-sup-
ported catalyst 4 in both batch and flow reactions. The lifetime
of catalyst 9 in the gas-phase flow reactor was also investigat-
ed. Compared in Figure 5 is the activity of Fluorochem LC301
Figure 5. Lifetime of Fluorochem LC301 supported catalysts for cyclic car-
bonate synthesis. Three carbon linker (&); eleven carbon linker (^, reactivat-
ed after day 5).
supported catalysts 4 and 9 over a seven day period. During
this time, catalyst 4 loses 42 % of its initial activity. In contrast,
catalyst 9 with the longer linker loses 49 % of its initial activity
over the first five days. The catalyst was then reactivated by
treatment with benzyl bromide, but this only restored the cat-
alyst activity to 73 % of its original activity. The failure of cata-
lyst 9 to fully reactivate may be attributed to dealkylation oc-
curring at type c sites (Figure 3), which would be facilitated by
the less hindered environment around the catalyst with the
longer linker and which results in irreversible loss of catalyst
from the silica support. This was supported by ICPOES analysis
of a sample of catalyst 9 after reactivation, which showed that
the aluminium content (and hence catalyst loading) was only
75 % of its original value.
Conclusions
The influence of silica particle size and pore size, as well as
linker length, on the activity of silica-supported aluminium-
(salen) complexes as catalysts for cyclic carbonate synthesis
has been investigated. Pore size was found not to be a major
factor, but the silica particle size was important with the most
active catalysts being formed from silicas with particle sizes of
15–75 mm. For large scale application in a gas-phase flow reac-
tor however, the very small particle size silicas are likely to
result in high back pressures, so the optimal silica size will be
around 75 mm. Catalyst lifetime was also affected by the silica
ChemCatChem 2012, 4, 789 – 794
Supported Catalysts for Cyclic Carbonate Synthesis
support, with the Fluorochem LC301 supported catalyst being
the most resilient. Extending the linker length from three to
eleven carbon atoms resulted in a three-fold increase in cata-
lyst loading, but this was offset by a three-fold reduction in
catalyst activity and a decrease in catalyst stability.
Experimental Section
Infrared spectra were recorded at room temperature by using
a Varian 800 FT-IR Scimitar series spectrometer fitted with an ATR
sample holder. 1H NMR spectra were recorded by using a Bruker
Avance 300 spectrometer at 300 MHz. All spectra were recorded at
room temperature. Chemical shifts are reported in ppm and are
relative to TMS internally referenced to the residual solvent peak.
The multiplicity of signals is reported as singlet (s), doublet (d),
triplet (t), quartet (q), multiplet (m), broad (br) or a combination of
any of these. GC–MS were recorded by using a Varian CP-800-
SATURN 2200 GC–MS ion-trap mass spectrometer using a Factor-
Four (VF-5ms) capillary column (30 m  0.25 mm) with helium as
the carrier gas. Spectra were obtained by electron ionisation (EI).
The conditions used were: initial temperature 60 8C, hold at initial
temperature for 3 min then ramp rate 15 8C min 1 to 270 8C; hold
at final temperature for 5 min. For the first 3.50 min, the eluent
was routed away from the mass detector. Subsequently, the detec-
tor was operated in full EI scan mode. The detector response was
calibrated using known mixtures of styrene oxide and styrene car-
bonate. ICPOES data was obtained by using a UNICAM 701 emis-
sion spectrometer. Digital photographs were taken by using
a Leica Z16 APO microscope.
Silicas were obtained from Merck, Fluorochem, or Aldrich (Davisil)
and used without further purification. Ethylene oxide, CO2 and N2
cylinders were supplied by BOC. Other chemicals and solvents
were obtained from Aldrich and used as provided.
3-Chloropropyl silicas: (3-Chloropropyl)-triethoxysilane (0.5 g,
2.0 mmol) was added to a mixture of a silica (20.0 g) in dry toluene
(125 mL) and the reaction was refluxed under N2 for 24 h. Then,
the mixture was filtered and washed with EtOAc (4  150 mL) to
give the 3-chloropropyl silica (20.7 g, 95 %) as a yellow powder.
ñmax = 2505, 2160, and 1975 cm 1.
11-Chloropropyl silica: (11-Chloroundecyl)-triethoxysilane (0.7 g,
2.0 mmol) was added to a mixture of Fluorochem LC301 silica
(20 g) in dry toluene (125 mL) and the reaction was refluxed under
N2 for 24 h. Then, the mixture was filtered and washed with EtOAc
(4  150 mL) to give the 11-chloropropyl silica (20.65 g, 95 %) as
a white powder. ñmax = 3480 and 1062 cm 1.
Silica-supported complexes 6: 3-Chloropropyl- or 11-chloroundec-
yl-functionalised silica (4.3 g) was added to a solution of aluminium
complex 5[25, 26] (7.5 g, 6.4 mmol) in CH3CN (40 mL) and the mixture
was refluxed overnight. Then, the mixture was filtered and washed
with EtOAc (4  50 mL) to give silica-supported complexes 6 (49–
60 %) as a yellow powder, which were immediately used in the
next step.
Silica-supported catalysts 4 and 9: BnBr (3.0 g, 17.5 mmol) and
Bu4NBr (4.1 g, 11.64 mmol) were added to a suspension of silica
supported complex 6 (6.7 g, 2.9 mmol) in CH3CN (150 mL) and the
resulting mixture was refluxed overnight. Then, the mixture was fil-
tered and washed with EtOAc (4  50 mL) to give silica-supported
catalysts 4 or 9 (7.4 g, 67 %) as a yellow powder. To determine the
ChemCatChem 2012, 4, 789 – 794  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
catalyst loading, supported catalyst (10.0 mg) was digested with
1 m HCl (5 mL) for 24 h and the resulting solution analysed by
ICPOES to determine the aluminium concentration in ppm from
which the catalyst loading in mmol per gram of support could be
determined. 4-Fluorochem LC301: ICPOES 48.48 ppm aluminium
corresponding to a catalyst loading of 0.43 mmol g 1; ñmax = 3410,
1633, and 1078 cm 1. 4-Davisil 636: ICPOES 28.69 ppm aluminium
corresponding to a catalyst loading of 0.39 mmol g 1; ñmax = 3421,
1715, and 1048 cm 1. 4-Davisil 646: ICPOES 44.16 ppm aluminium
corresponding to a catalyst loading of 0.26 mmol g 1; ñmax = 3472,
1716, and 1053 cm 1. 4-Davisil 635: ICPOES 62.83 ppm aluminium
corresponding to a catalyst loading of 0.56 mmol g 1; ñmax = 3500,
1635, and 1063 cm 1. 4-Davisil 633: ICPOES 113.00 ppm aluminium
corresponding to a catalyst loading of 1.00 mmol g 1; ñmax = 3378,
1630, and 1066 cm 1. 4-Davisil 643: ICPOES 86.36 ppm aluminium
corresponding to a catalyst loading of 0.77 mmol g 1; ñmax = 3376,
1630, and 1065 cm 1. 4-Merck 1.15111: ICPOES 65.48 ppm alumini-
um corresponding to a catalyst loading of 0.58 mmol g 1; ñmax =
3500, 1633, and 1062 cm 1. 9-Fluorochem LC301: ICPOES
135.1 ppm aluminium corresponding to a catalyst loading of
1.21 mmol g 1; ñmax = 3491, 1627, and 1071 cm 1.
Styrene carbonate 8 a: Styrene oxide 7 a (0.2 g, 1.7 mmol) and
a silica-supported catalyst (0.04 mmol of active sites) were placed
in a sample vial fitted with a magnetic stirrer bar and placed in
a large conical flask. The conical flask was placed in a thermostatted
oil bath at 26 8C. Cardice pellets were added to the conical flask,
which was fitted with a rubber stopper pierced by a deflated bal-
loon. The contents of the reaction vial were stirred for 24 h during
which time the balloon inflated as the cardice pellets evaporated.
Then, the reaction mixture was filtered to remove the supported
catalyst, washing the flask and solid with EtOAc (3  50 mL) and the
solution evaporated in vacuo. The residue was analysed by GC–MS
and 1H NMR spectroscopy to determine the conversion of styrene
oxide to styrene carbonate and to confirm that no by-products
were formed. GC: TR 7.33 min (styrene oxide), TR 12.09 min (styrene
carbonate); (CDCl3): dH = 4.28 (1 H, t J 8.0 Hz), 4.74 (1 H, t J 8.4 Hz),
5.61 (1 H, t J 8.0 Hz), 7.2–7.5 ppm (5 H, m); peaks corresponding to
unreacted styrene oxide 7 a were also present: 2.74 (1 H, dd J 5.5,
2.6 Hz), 3.08 (1 H, dd J 5.5, 4.1 Hz), 3.79 (1 H, dd J 4.0, 2.6 Hz), 7.2–
7.5 ppm (5 H, m).
Ethylene carbonate 8 b: Ethylene oxide 7 b was collected from a cyl-
inder into a cooled beaker at 78 8C and placed, with a magnetic
stirrer bar, inside a 360 mL stainless steel pressure vessel pre-
cooled to 30 8C. The vessel was then sealed. All tubing used in
the system was composed of stainless steel with an internal diame-
ter of 1.6 mm. N2 (2.5 mL min 1) and CO2 (0.8 mL min 1) were sup-
plied from cylinders via mass flow controller units and their respec-
tive lines merged to the inlet of the pressure vessel. The tempera-
ture of the pressure vessel was controlled by a cryostatically
cooled bath ( 30 8C) to provide an ethylene oxide evaporation
rate of 1.2 mL h 1. The vessel outlet line was then connected to
a stainless steel tubular reactor (3 cm  1 cm internal diameter)
packed with a silica-supported catalyst and plugged at both ends
with a small amount of cotton wool. The tubular reactor was kept
at 100 8C in a Kugelrohr oven. The mixture of CO2, ethylene oxide,
and N2 was passed through the reactor column at a steady flow
rate. The outlet from the reactor was passed into a glass tube at
ambient temperature, where the ethylene carbonate 8 b collected.
The reactor as run for 1–9 days to provide information on TOF and
catalyst lifetime. The ethylene carbonate was collected at 24 hour
intervals, recrystallised from Et2O/hexane and analysed by GC–MS
www.chemcatchem.org 793
 M. North and P. Villuendas

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