Plasma-Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO2

Article abstract of DOI:10.1002/cssc.201903384

The first plasma-assisted immobilization of an organocatalyst, namely a bifunctional phosphonium salt in an amorphous hydrogenated carbon coating, is reported. This method makes the requirement for prefunctionalized supports redundant. The immobilized catalyst was characterized by solid-state ¹³C and ³¹P NMR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy. The immobilized catalyst (1 mol %) was employed in the synthesis of cyclic carbonates from epoxides and CO₂. Notably, the efficiency of the plasma-treated catalyst on SiO₂ was higher than those of the SiO₂ support impregnated with the catalyst and even the homogeneous counterpart. After optimization of the reaction conditions, 13 terminal and four internal epoxides were converted with CO₂ to the respective cyclic carbonates in yields of up to 99 %. Furthermore, the possibility to recycle the immobilized catalyst was evaluated. Even though the catalyst could be reused, the yields gradually decreased from the third run. However, this is the first example of the recycling of a plasma-immobilized catalyst, which opens new possibilities in the recovery and reuse of catalysts.

Full text of DOI:10.1002/cssc.201903384

Accepted Article
Title: Plasma-assisted immobilization of a phosphonium salt and its
use as a catalyst in the valorization of CO2
Authors: Yuya Hu, Sandra Peglow, Lars Longwitz, Marcus Frank, Jan
Dirk Epping, Volker Brüser, and Thomas Werner
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ChemSusChem
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Plasma-assisted immobilization of a phosphonium salt and its
use as a catalyst in the valorization of CO2
[
a]
[b]
[a]
[c, d]
[e]
[b]
Yuya Hu, SandraPeglow, Lars Longwitz, Marcus Frank,
Thomas Werner*[a]
Jan Dirk Epping, Volker Brüser,
Dedication ((optional))
[
a]
Y. Hu, L. Longwitzand PD Dr. T. Werner
Leibniz-Institute for Catalysis
Albert-Einstein-Straße 29a, 18059, Rostock, Germany
E-mail: Thomas.Werner@catalysis.de
Dr. S. Peglow and Dr. V. Brüser
Leibniz-Institute for Plasma Science and Technology (INP)
Felix-Hausdorff-Straße2, 17489, Greifswald, Germany
PD Dr. M. Frank
[
[
b]
c]
Medical Biology and Electron Microscopy Center
UniversityMedicine Rostock
Stremelstraße 14, 18057, Rostock, Germany
[
[
d]
e]
PD Dr. M. Frank
Department Life, Light& Matter
Universityof Rostock
Albert-Einstein-Straße 25, 18059, Rostock, Germany
Dr. J. Epping
Institute ofChemistry
Technical Univers it yof Berlin
Straße des 17 Juni 135, 10623, Berlin, Germany
Supporting information for this articleis given via a link at theend of the document.((Please delete thistextif not appropriate))
Abstract: Herein, we report the first plasma-assisted immobilizat io n
of an organocatalyst namely a bifunctional phosphonium salt in an
amorphous hydrogenated carbon coating. This method makes the
requirement of prefunctionalized supports redundant. The
transformation can be catalyzed by organocatalysts which are
[
4]
typically readily available and nontoxic. A significant benefit of
organocatalysts is the carbon-based scaffold which allows facile
structural modification and catalyst tuning as well as catalyst
13
31
[5]
immobilized catalyst was characterized by solid state C and
P
immobilization.
NMR as well as SEM and EDX. The immobilized catalyst (1.0 mol%)
was employed in the synthesis ofcyclic carbonates from epox id es and
Amorphous hydrogenated carbon (a-C:H) thin films generated
with plasma techniques are promising materials due to their
chemical inertness and interesting physical properties such as
high density, thermal stability, low friction, high wear resistance,
CO
2
. Notably, the efficiency of the plasma treated catalyst on SiO
2
was higher compared to SiO
2
support impregnated with the cata ly st
[
6]
and even to the homogenous counterpart. After optimization of the
reaction conditions 13 terminal and 4 internal epoxides were
and hardness. These filmsare applied as protective coatings for
[
7]
optical windows , antireflective coatings for crystalline silicon
[
8]
[9]
converted with CO
2
to the respective cyclic carbonates in yields up to
solar cells , for biomedical applications and wear resistant
[
10]
9
9%. Furthermore, the possibility to recycle the immobilized cata ly st
coatings for tools . Due to their unique properties, amorphous
hydrogenated carbonthin films, are highlyattractive materialsfor
the immobilizationof catalysts. An additionaladvantagein the use
of plasma generated a-C:H films is the direct attachment of the
polymeric film to a desired surface without any pretreatment.
Compared to other coating procedures it reduces preparative
steps and allows in principle the direct incorporation of a
functionalized catalyst.
was evaluated. Even though the catalyst could be re-used the yie ld s
gradually decreased from the third run. However, this is the first
example of the recycling of a plasma immobilized catalyst which
opens new possibilities in the recovery and reuse of catalysts.
Introduction
So far, there are only a very limited number of reports regarding
the immobilization of catalysts using plasma techniques. For
A crucial point in the development of sustainable catalytic
[11]
[12]
example, Kruth et al. encapsulated Ru-, as well as Ir-dyes
with plasma polyallylamine (PPAAm) onto TiO . The prepared
stable TiO /N (Ru dye complex)/PPAAm catalyst assembliesand
encapsulated Ru sensitizer at theTiO surface, showed improved
[1]
processes is the separation and recycling of the catalysts. In
2
[
2]
contrast to many other separation techniques,
the
2
3
immobilization of catalysts allow the facile separations from the
product avoiding tedious purification and isolation steps as well
2
catalytic performance in the visible-light-driven hydrogen
evolution. Additionally, significant enhancement of photo
[
3]
as easy recovery and reuse of the catalyst. Numerous
1
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ChemSusChem
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efficiency was observed with the PPAAm encapsulated Ir
dye/titania catalyst assemblies. There are also some examples
concerning plasma immobilization techniques in biology, for
instance, the entrapment of enzymes. In thisrespect, the groups
Bifunctionalphosphonium salts bearing a hydroxyl group in the 2-
position proved to be a superior structural motif in the
cycloaddition of CO and epoxides to form cyclic carbonates.
2
[23]
We envisioned that an allyl substituent might allow the
subsequent immobilization in an amorphous hydrogenated
carbon thin film generated with plasma techniques. Thus,
bifunctional phosphonium salts 5a and 5b were synthesized by
allylation of 2-(diphenylphosphanyl)phenol (3) with allyl bromide
(4a) or allyl iodide (4b) (scheme 1a).The incorporation of 5a and
5b into the a-C:H filmswillmostprobably lead to saturated linkage
in the immobilized catalyst 6 (scheme 1b). Hence, we additionally
prepared salts 5c and 5d bearing a saturated side chain for
[
13]
[14]
of Belhacene and Elagli reported the polymerization of
tetramethyldisiloxane to immobilize β-galactosidase via plasma
enhanced chemical vapor deposition. Furthermore, Heyse et
[
15]
al. described the simultaneous injection of an enzyme solution
and acetylene or pyrrole to an atmosphericplasma to immobilize
enzymes while preserving their bioactivity.
The atom economic addition of carbon dioxide to epoxides
yielding cycliccarbonatesis an interestingand frequently studied
[
16]
reaction (figure 1a). Lately, highlyactive systemsbased on OH- comparison of theactivity.
functionalized organocatalysts were reported forthe synthesis of
[
17]
cyclic carbonates. The superior activity of these catalysts is
attributed to the epoxide activation and the stabilization of
[
18]
intermediates by hydrogen bonding. We are interested in
development of bifunctional onium salt catalysts for synthesis of
cycliccarbonatesas well as theirrecoveryand reuse.
[
17a, 17b,19]
In
this respect one strategy is the immobilization of the onium salt
catalyst on organic or inorganic supports. The immobilization of
monofunctional phosphonium salt catalysts was studied
[
20]
previously.
Pioneering work on the immobilization of
bifunctional structural motifs has been reported by the groups of
[
21]
[22]
Dai.
and Liu.
Recently, we reported the successful
immobilization of a bifunctional phosphonium bromide bearing a
phenol moiety utilizing functionalized polystyrene and silica
[
19b]
supports (figure 1b).
Herein, we report the use of plasma
techniques as strategy for the direct immobilization of P-based
organocatalysts on unfunctionalized titanium dioxide, iron oxide
and silica (figure 1c). Furthermore, the efficiencyand recyclability
of the immobilized catalystswere studied in the synthesisof cyclic
carbonates.
Scheme 1. a) Synthesis of phosphoniumsalts 5. b) Putativestructure 6 of the
immobilized phosphoniumsalts 5a and 5b.
Subsequently, we tested catalysts 5 (1 mol%) in the model
reaction of 1,2-butylene oxide (1a)with CO
carbonate 2a (table 1). At 90 °C and a CO
2
to generate the cyclic
pressure of 1.0 MPa
2
the bromide 5a and iodide 5b showed similar activity, giving the
desired carbonate 2a after 2 h in 68% and 67%, respectively
(
table 1, entries 1 and 2). The propyl substituted phosphonium
bromide 5c gave 2a only in 40% yield (entry3). Notably, the iodide
d gave the best result under these reaction conditionsand 1,2-
5
butylene carbonate (2a) was obtained in 83% yield (entry 4).
Based on these results, phosphonium salt 5b was chosen for the
immobilization in a-C:Hfilmson TiO , FeOand SiO .
2 2
Table 1. Comparison of phosphonium sa lt s 5 as catalysts in the synthes is of
carbonate 2a.
[
a]
2
Figure 1. a) Synthesis of cyclic carbonates 2 from CO and epoxides 1. b)
Entry
Catalyst
5a
Loading / mol%
Yield 2a / %
Previous strategyfor the immobilization of bifunct io nal phosphon iu m salts us in g
functionalized supports. c) Conceptfor the immobilizat io n of phosphoniumsa lt
catalysts in an amorphous hydrogenated carbon thin film using plasma
polymerization techniques.
1
2
3
4
1
1
1
1
68
67
40
83
5b
5c
5d
Reaction conditions: Epoxide 1a (13.9 mmol, 1.0 equiv), cata ly st 5 (1 mo l% ),
1
Results and Discussion
90 °C, 2 h, p(CO
mesitylene asinternal standard.
2
)= 1.0 MPa solvent-free. [a] Yie ld s determinedby H NMR w it h
2
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Initially, the supports were tested in the model reaction and
homogeneously coated while the deposition on particles takes
place non-uniformlyand partially. Profilometricmeasurements of
the nominal layer thickness of a-C:H films obtained after 6.5, 25
proved not facilitate the conversion of 1a with CO
2
(table 2, entries
1–3). Subsequently, these supports were treated with low
[
24]
pressure plasma techniques, generating an a-C:H coating. Also, and 39 min of plasma treatment gave layer thicknesses of 53.3,
in the presence of the plasma treated supports, the formation of
a was not observed (entries 4–6). Furthermore, the supports
136.8 and 190 nm,respectively. We studied theimpact of different
plasma treating times(6.5, 25 and 39 min) on the catalytic activity
2
were impregnated with catalyst 5b and tested in the model
reaction (entries 7–9). The catalyst retained its catalytic activity
and all three samples 5b@TiO , 5b@FeO as well as 5b@SiO
2 2
2 2
of 5b on TiO , FeO and SiO and the effect of the catalyst
recyclability in our model reaction. To reveal the effect of the
plasma treatment, the recycling of the non-plasma treated
gave 1,2-butylene carbonate (2a) in excellent yieldsof 87%, 78%
and 88%, respectively (entries 7–9). Subsequently, the
2 2
impregnated catalysts 5b@TiO , 5b@FeO and 5b@SiO were
initially investigated (figure 2). In the model reaction all three
catalyst samples gave good yields up to 88% after 6 h at 90 °C
impregnated supports 5b@TiO
treated with a low pressure plasma. The obtained catalyst
samples 5bb℗TiO , 5bb℗FeOas well as 5bb℗SiO were tested
in the model reaction (entries 10–12). Notably, with 1 mol%
catalyst loading, TiO and SiO supported catalystsconverted the
,2-butylene oxide (1a) into the 1,2-butylene carbonate (2a) with
3% and 99% yields(table 2, entries10 and 12), while with FeO
2 2
, 5b@FeO and 5b@SiO were
2
and 1.0 MPa CO pressure in the first run. The product was
2
2
obtained after simple filtration and the recovered catalyst was
reused in a second run under the same reaction conditions.
Notably, the yieldsdropped significantly. The best yield achieved
in the second run wasonly31% with 5b@SiO . We assumed that
2
the low yieldscan be explained by the leachingof catalyst 5b into
2
2
1
9
supported catalyst, a moderate yield of 72% was obtained (table
, entry 11). These yields were comparable to the results obtained
with the impregnated samples(entries 7–9 vs. 10–12).
the liquid phase. This is easily possible since the catalyst is not
3
1
2
covalentlybonding to the supports.The PNMR spectrum of the
product mixture showed a signal at = 20.2 ppm which was
assigned to the homogenous catalyst 5b. This consequently
confirmsthe proposed leaching.
Table 2. Screeningof supportsand immobilized catalysts.
[
a]
[b]
Entry
Support
TiO
FeO
SiO
TiO
FeO
SiO
TiO
FeO
SiO
TiO
FeO
SiO
5b/ mol%
Cat.
t / min
Yield 2a/ %
1
2
3
4
5
6
7
8
9
2
-
-
0
-
-
0
2
-
-
0
2
-
25
25
25
-
0
-
0
2
-
0
2
1
1
1
1
1
1
5b@TiO
2
87
78
5b@FeO
5b@SiO
5bb℗TiO
5bb℗FeO
5bb℗SiO
-
[C]
2
2
-
88 (65)
93
10
11
12
2
2
25
25
25
Figure 2. Recyclability evaluation of impregnated catalyst samples 5b@TiO
b@FeO and 5b@SiO . Reaction conditions: Epoxide 1a (13.9 mmol, 1.0
equiv), immobilized catalyst (500 mg, 1 mol% catalystloading in respect to 1a),
2
,
72
5
2
[
C]
2
2
99(77)
st
9
0 °C, 6 h, p(CO )= 1.0MPa, solvent-free. For the 1 runs isolated yields are
2
n
d
1
given. For the 2 runs the y ie ld wasdetermined by H NMR with mesity le ne as
internal standard.
Reaction conditions: Epoxide 1a (13.9mmol, 1.0 equiv), 500 mg ofthe support
or catalyst, 90 °C, 6 h, p(CO )= 1.0 MPa, solvent-free. [a]Plasma treatingt im e.
b] Yield determined by H NMR with mes it ylene as internal standard. [c] 2 h
reaction time.
2
1
[
We studied the immobilized catalyst 5b on different supports
The nominallayerthickness ofthe a-C:H coating is related to the
plasma treating time. Longer treating time will result in a thicker
film and better coverage of the particle. This might lead to a
stronger catalyst binding to the surface, reducing catalyst
leaching and enhancing its recyclability. The nominal layer
thickness is determined by profilometry of an a-C:H coating
(
TiO
same conditions. Catalysts 5ba℗TiO
gave the desired carbonate 2a in good to excellent yields up to
2
, FeO and SiO
2
) after 6.5 min plasma treating timeunderthe
2
, 5ba℗FeO and 5ba℗SiO
2
9
5
8% (figure 3a). Even though with catalysts 5ba℗TiO
ba℗FeO the yieldsdropped significantlyin the second run, in the
carbonate 2a was obtained in >80%.
2
and
presence of 5ba℗SiO
2
[
24]
deposited on planar glassplate. Thisis only an approximation
for films on particles because the planar glass plate is
These resultsmight be explained by an insufficient immobilization
due to the short plasma treating time. Nevertheless, compared to
3
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the impregnated catalysts the plasma treatment led to a
significant improvement of the yield (Figure 2 vs. Figure 3a).
to an improved catalyst binding to the a-C:Hcoatings. Finally, the
plasma treating time was extended to 39 min and the prepared
catalystswere tested underthe standard conditions(figure 3c). In
2
the case of 5bc℗TiO the yields dropped in the first and second
runs compared to the results with shortertreating times(figure 3a
and 3b). In contrast5bc℗FeO showed increased yieldscompared
to the previous experiments. Again, the best result was obtained
with 5bc℗SiO
2
giving yields of 99% for2a in the first and second
runs.
As observed for 5bc℗TiO
2
longer plasma treating times might
lead to a better recyclability most probably due to an improved
immobilization (figure 3a and 3b). However, if theplasmatreating
2
time is too long, e.g. 39 min for 5bc℗TiO , this might lead to partial
coverage of the catalyst and thus lower yields (figure 3c vs. 3a
and 3b). In the case of 5bb℗FeOthe yield and recyclability were
enhanced by a plasma treating time of 39 min indicating a better
immobilization of 5b on the support. This suggests that not only
the plasma treating time but also the nature of the support
material is of crucial importance for the efficiencyand recyclability
of the catalyst.
Based on these results, 5bb℗SiO
promising catalyst. Thus, 5bb℗SiO
various analytical methods and compared to the homogenous
catalyst 5b as well as 5b impregnated on SiO , 5b@SiO . As
expected, the elementalanalysis of both the impregnated catalyst
b@SiO and the plasma treated catalyst 5bb℗SiO showed the
presence of phosphorus and iodine. The solid state PNMR
spectrum of the plasma treated catalyst 5bb℗SiO showed a
broad signal at =16.9 ppmwhich isin the similar range assignal
2
was identified to be the most
2
was characterized with
2
2
5
2
2
3
1
2
3
1
in the PNMR spectrum of homogenous catalyst 5b (= 20.2
ppm), indicating the presence of the phosphonium motif. The solid
1
3
state C NMR spectra of the impregnated 5b@SiO
plasma treated sample 5bb℗SiO showed the expected signals
compared to the C NMR spectrumof the homogeneouscatalyst
b (figure 4a–c). Notably, thecharacteristicsignal forthe phenolic
carbon at =161 ppm for 5b can clearly be identified in the solid
state NMR of 5b@SiO and 5bb℗SiO . This is of particular
2
and the
2
1
3
5
2
2
importance since it indicates that the bifunctional nature of the
immobilized catalyst stays intact, which is crucial for its superior
catalyticactivity.
Furthermore, EDX measurements were performed on the
impregnated 5b@SiO
well as on the SiO support. The EDX spectrum of the SiO
support showed no signal in the range between 1.90 and 4.10 keV
figure 5a). In contrast the impregnated and plasma treated
samples show signals at 2.04 keV (P K ) which indicates the
presence of phosphorous (figure 5b and 5c). Notably, the
impregnated sample 5b@SiO does not show an iodine signal
figure 5b) while the plasma treated sample has a low intensity
2 2
and plasma treated sample 5bb℗SiO as
[
24]
2
2
(

2 2
Figure 3. Recyclability evaluation of cata ly sts 5b on TiO , FeO and SiO w it h
different plasma treating time (a) 6.5 min, b) 25 min c) 39 min plasma treat in g
time). Reaction conditions: Epoxide 1a (13.9 mmol, 1.0 equiv), immobil iz ed
2
(
catalyst (500mg, 1 mol% catalyst loading in respectto 1a), 90 °C, 6 h, p(CO
2
)=
st
nd
signal at 4.07 keV(I Lα1 and L ) which ischaracteristicforiodine
β1
1
.0 MPa, solvent-free. For the 1 runsisolated yieldsare given. For the 2 runs
1
the yield was determined by H NMR with mesitylene as internal standard.
(figure 5c). The absence of the signal for I Lα1 and Lβ1 in figure 5b
and the low intensityof the signal in figure 5c can be explained by
problems of detecting surface associated iodine, which isresulted
from the high energy required for the excitation of the iodine L
transitions. This can be overcome by changing the sample
pretreatment, e.g., the EDX spectra of the impregnated sample
Hence, the same set of experimentswas repeated with catalysts
(
5bb℗TiO2, 5bb℗FeO and 5bb℗SiO
plasma treating time(figure 3b). In the first run, allthree catalysts
gave results comparable to 5ba℗TiO2, 5ba℗FeO and 5ba℗SiO
2
) obtained after 25 min
2
2
5b@SiO which was copper sputtered clearly showed the
st
(
figure 3a vs. 3b, 1 run). The yields for 2a were significantly
increased in the case of the TiO and SiO supported catalysts
5bb℗TiO and 5bb℗SiO ) in the second run (figure 3a vs. 3b, 2
run). This indicates that the prolonged plasma treatingtime leads
presence of iodide (figure 5d). The copper layer (z= 29, 10 nm)
altered penetration and spreading of the electron beam within the
sample surface compared to the rather electron transparent
carbon coating(z=6, 10–15 nm). Notably, a comparable peak for
2
2
nd
(
2
2
4
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FULL PAPER
phosphorus is obtained under both pretreatment conditions
(
figure 5b and 5d).
Figure 6. SEM images of the silica support (Ia) and catalyst 5bb℗SiO
EDX mapping with color coded intensity range of carbon (Ib) and phosphorus
Ic) for the silica support. EDX mapping with colour coded intensity range of
2
(IIa).
(
[
24]
2
carbon (IIb) and phosphorus(IIc)for the immobilized catalyst 5bb℗SiO .
Subsequently we studied the performance of catalyst 5bb℗SiO
2
under different reaction parameters (table 3). Under the
conditions of the catalyst screening the desired product 2a was
obtained in 99% yield (entry1). Adecrease of the reactiontime to
1
3
Figure 4. a) C NMR spectrum of homogeneouscatalyst 5b in CDCl
3
. b) Solid
13
state C NMR spectrum of impregnated catalyst 5b@SiO
C NMR spectrum of plasma immobilized catalyst 5bb℗SiO .
2
2
and c) Sol id state
13
3
2
h gave 1,2-butylene carbonate (2a) in 99% isolated yield (entry
) and even after 1 h a yield of 57% was obtained (entry 3). The
influence of the CO
reduction of the CO pressure to 0.5 MPa led to a lower yield of
8% compared to the standard conditions (entry 1 vs. entry 4).
Next, the reaction temperature was decreased to 45 °C. Even at
5 °C the immobilized catalyst 5bb℗SiO led to full conversion
2
pressure was also investigated. The
2
8
4
2
and 99% yield after 6 h (entry 5). Notably, 21% yield of 2a was
still obtained after 3 h at this temperature (entry 6).
Table 3. Catalytic reaction conditions optimization for the conversion of 1,2-
butylene oxide 1a.
[
a]
Figure 5. Section of EDX spectra between 1.90 and 4.10 keV for a) the SiO
support (black, carbon coated), b) the impregnated catalyst 5b@SiO (grey,
carbon coated), c) the plasma treatedcatalyst 5bb℗SiO (blue, carbon coated)
and d) the impregnated catalyst 5b@SiO (red, Cu-sputtered).
2
Entry
T/ °C
90
p/ MPa
1.0
t/ h
6
Yield 2a/ %
2
2
1
2
3
4
5
6
99
99
57
88
99
21
[24]
2
90
1.0
3
90
1.0
1
2
Moreover, we studied the plasma treated sample 5bb℗SiO by
scanning electron microscopy (SEM) and EDX mapping in
comparison to the neat support (figure 6). TheSEM imagesof the
90
0.5
6
45
1.0
6
2
silica support and 5bb℗SiO areshown in figure 6, Ia and IIa. The
carbon EDXmapping on these particlesshow clearlyan increase
of carbon surface coating due to the plasma treatment (figure 6,
Ib vs. IIb). The mappingforphosphorus indicatesthat the catalyst
is evenly distributed over the support as well as the absence of
phosphorouson the neat support (figure 6, Ic and IIc).
45
1.0
3
Reaction conditions: Epoxide 1a (13.9 mmol, 1.0 equ iv ), immobilized cata ly st
5bb℗SiO (500 mg, 1 mol% catalystloading in respect to 1a), T, t, p, solvent-
2
free. [a] Isolated y ie lds are given.
Based on these results we determined reaction conditions
(
2 2
1 mol% catalyst 5bb℗SiO , 45 °C, 6 h, p(CO )=1.0 MPa,
solvent-free)suitable forthe evaluation of the substrate scope. As
shown in scheme 2, terminal aliphatic epoxides 1a–d were
converted into the respective carbonates 2a–d in yields up to
>99% under these conditions. In contrast styrene oxide (1e)
showed onlymoderateconversion and 2e was obtained in a yield
of 61%. However, with a prolonged reaction time of 24 h, full
conversion was achieved and the desired productwas isolated in
5
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9
2% yield. In this reaction acetophenone from a Meinwald
2l and siloxane 2m which both were isolated in 95% yield and are
used as monomersand adhesion promotors.
[
25]
[34]
rearrangement was observed as a by-product.
We turned our attention to the conversion of internal epoxides with
CO which is in general more challenging. Under the standard
2
conditions2n was obtained onlyin 13% yield. At higher reaction
temperatures of 90 °C carbonate 2n was obtained in 61% yield
after 24 h, which is a good result for an internal epoxide
considering that a heterogeneousorganocatalyst with low loading
(
1 mol%) was used. Full conversion wasachieved forthe reaction
between 3,4-epoxytetrahedrofuran (1o) and CO . However, due
2
to partial polymerization only31% of the desired product 2o were
isolated. The conversion of cis-stilbene oxide (cis-1p) and
epoxidized methyl oleate (cis-1q) gave the desired cyclic
carbonates in yields of 13% and 30%, respectively. For the
reaction of cis-1pa solvent was required since both the substrate
and product are solid. In respect to the stereochemistry it hasto
be mentioned that, in the case of cis-1p the onlyproduct observed
was the thermodynamicallymore stable trans-2p, which indicates
that in thiscase the reaction proceedsvia an cationicintermediate
[
35]
N
and an S 1-type mechanism. Similarly, the conversion of bio-
based cis-1q led to 2q as a mixture of cis/transisomers(28:72).
Finally, we studied the recyclabilityof theplasma treated catalyst
on SiO
parameters on the outcome of the model reaction over five runs
using 5bb℗SiO as the catalyst was evaluated. Under the
2
in more detail. At first the impact of the different reaction
2
standard conditions of the substrate screening the recycling
experiments revealed that at 45 °C the yield decreased from
st
nd
th
>
99% in the 1 run, 81% in the 2 down to below 10% in the 5
Scheme 2. Evaluation of the substrate scope using catalyst 5bb℗SiO
Reaction conditions: Epoxide 1 (13.9 mmol, 1.0 equiv), 5bb℗SiO (500 mg,
mol% catalystloading in respect to 1), 45 °C, 6 h, p(CO )= 1.0 MPa, solvent-
2
.
run (figure7).
2
1
2
free. Isolated yields are given. [a] 24 h. [b] 90 °C. [c] 90 °C, 24h. d 1.0 mL 1-
BuOH was used as thesolvent.
Glycerol has become widely available since it is the major by-
[
26]
product in the manufacturing of biodiesel.
The so-called
“
biodiesel” isa popular term forthe fatty acid methylestersformed
[
27]
by transesterification of vegetable oils with methanol. It has
been investigated that the use of glycerolas the feedstockforthe
synthesis of carbonates can lead to a significant reduction in the
carbon footprint of their production compared to the use of fossil
resources. Glycidol (1f), epichlorohydrin (1g) as well as their
derivatives 1h–1m can be obtained from glycerol as renewable
[
28]
[
29]
feedstock.
The respective carbonates often show unique
properties and are used as synthetic building blocks, monomers
[
30]
and solvents. Hence, we were particularly interested in the
preparation of carbonates 2f–2m. Despite notable progress that
2
Figure 7. Recyclabilityinvestigat io n for catalyst 5bb℗SiO at different react io n
temperatures and times. Reaction conditions: Epoxide 1a (13.9 mmol, 1.0
equiv), immobilized catalyst (500 mg, 1 mol% catalystloading in respect to 1a),
2
was recently reported in the reaction of glycidol (1f) with CO to
[
31]
carbonate 2f the conversion of 1f is challenging. Especiallyfor
the use of heterogeneous catalysts in this reaction, it typically
requires drastic reaction conditions such as high reaction
2
T, t, p(CO )= 1.0 MPa, solvent-free. Isolated yields are given for the 1strun. For
1
run 2–5 the yields were determined by H NMR with mesitylene as internal
standard. [a] 2 mo l% catalystloading in respectto 1a.
[
32]
2
temperatures (≥ 110 °C) and high CO pressure (≥ 1 MPa).
Under the standard reaction conditions 2f was obtained in a yield
of 58% and in 85% when extending the reaction time. In contrast,
epichlorohydrin (1g)and glycidylether 1h were isolated in 84 and
Improved yields were achieved at a higher reaction temperature
of 90 °C. At this temperature 2a was obtained in a yield of >99%
99% yield after 6 h. However, to achieve full conversion of the
st
nd
in the 1 and 2 run. In the subsequent runs the yield gradually
decreased to 20%. We envisioned that catalyst leaching is
responsible for yield decrease and postulated that the leaching
might correlates to the reaction time. Thus, we reduced the
reaction time to 3 h and repeated catalyst recycling (figure 7).
other glycidol derivatives 1i–1m, the reaction condition were
adjusted and high yieldsup to 96% on the respective carbonates
2i–2m were achieved. Of particular interest are the products 2k
which was obtained in 89% yield and is used as electrolyte in
[
33]
lithium ion batteries, aswellas glycerol carbonatemethacrylate
st
nd
Even though similar results were obtained in the 1 and 2 run,
6
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ChemSusChem
10.1002/cssc.201903384
FULL PAPER
the yields in the following runs could not be improved. As
expected with a higher catalyst loading of 2 mol%, the yields of
surface. However, considering that the sample still showed
catalytic activity, the concentration of the catalyst on the surface
might be below the detection limit of these methods. In contrast
the EDX mapping shows the presence of low amount evenly
dispersed phosphoruscompared to neat support (figure 9a vs. 9b).
2a were significantly improved in runs 3–5, though in this set of
rd
experimentsthe yield graduallydecreased from 90%in the 3 run
to 41% in the last run.
Due to these resultswe were especially interested on the impact
th
However, the concentration of phosphorusafter the 5 run is still
of different plasma treating times (6.5 min for 5ba℗SiO
2
, 25 min
significantlylower compared to the fresh catalyst (figure9a vs. 9c).
for 5bb℗SiO and 39 min for 5bc℗SiO , figure 8) on the
2
2
recyclability of the respective catalysts. Full conversions and
st
yields >99% were achieved in the 1 run for all three catalysts.
The same results were achieved with catalyst 5bb℗SiO
2
and
nd
5bc℗SiO
2
in the 2 run while 5ba℗SiO
2
gave a lower yield of
8
2% which might be addressed to an insufficient immobilization
rd
due to the short treating time. In the 3 run the yields in the
presence of all three catalysts were decreased. 5bb℗SiO led to
the best result yielding 2a in 81% while 5ba℗SiO and 5bc℗SiO
2
Figure 9. EDX mapping with color coded in tensity range of phosphorus a) for
2
2
5
bb℗SiO
2
after 5 reaction cycles b) of the neat SiO support and c) of
2
[24]
gave 2a in similar yields of 70 and 74% respectively. This trend
further continued forallthree catalysts wherebyyields 20%were
immobilized catalyst 5bb℗SiO .
2
th
observed in the 5 run. Apparently, a plasma treating time of 25
min for 5bb℗SiO
the a-C:H coating (compared to 5ba℗SiO
avoiding the coverage of the catalytically active species
compared to 5bc℗SiO ).
2
led to a good balance between the binding to
Conclusion
2
) and its thickness,
In summary, we designed and synthesized a functionalized
phosphonium salt suitable for plasma immobilization. The
obtained catalysts were tested in the synthesis of 1,2-butylene
(
2
carbonate from CO
Among the three tested potential supports (TiO
SiO proved to be the most suitable. In initial recycling
2
and 1,2-butylene oxide as the modelreaction.
2
, FeO and SiO
2
)
2
experiments the support impregnated with the catalyst was
compared to its plasma treated counterpart. These experiments
revealed the clear advantage of the plasma treatment.
Remarkably, the immobilized catalyst even showed similar (or
higher) efficiency than its homogenous analogue. Furthermore,
the impact ofdifferent plasma treating timeson the efficiencyand
recyclability was investigated. The best catalytic material was
characterized by solid state NMR, elemental analysis, SEM and
EDX. The analysis revealed the formation of an amorphous
hydrogenated carbon coating as well as the presence of the
catalytically active species. After the optimization of the reaction
conditions 13 terminal and 4 internal epoxides were converted
Figure 8. Recyclability invest ig ation of SiO
different plasma treating times 5ba℗SiO
bc℗SiO (39 min). React io n conditions: Epoxide 1a (13.9 mmol, 1.0 equ iv ),
immobilized catalyst(500 mg, 1 mol% catalystloading in respectto 1a), 90 °C,
2
supported catalyst 5b with cata ly sts
2
with CO to the respective cyclic carbonates in yieldsup to 99%.
2
(6.5 min), 5bb℗SiO (25 min) and
2
Special attention was paid to the conversion of 8 glycerol
derivatives which can be obtained from the biodiesel production
waste glycerol. Considering that a heterogeneous catalyst was
used, it is noteworthy that most of the terminal substrates could
be efficiently converted to the desired products under mild
5
2
st
6
2
h, p(CO )= 1.0 MPa, solvent-free. Isolated yie ld s are given for the 1 run. For
1
runs 2–5 the yields were determined by H NMR with mesitylene as internal
standard.
2
reaction conditions (45 °C, 6 h, p(CO )= 1.0 MPa) with low
catalyst loading of 1 mol%. Subsequently, we studied the
recyclability of the catalyst for the model reaction in detail. Even
though the catalyst was used in 5 consecutive runs, the yields
graduallydecreased from the second to the fifth run. The analysis
of the produced cyclic carbonate as well as the characterization
of catalyst after the fifth run revealed catalyst leaching into the
product phase. The optimization of the coating process might
allow the reduction of the catalyst leaching and is currently under
investigation. To the best of our knowledge this is the first
example on the successful recycling of a plasma immobilized
catalyst. This prove of concept opens the opportunity for further
studies on the applicationof plasma polymerizationtechniques in
catalyst recycling.
2
To get a better insight in the catalyst deactivation, 5bb℗SiO was
th
isolated after the 5 run and analyzed by solid state NMR, SEM,
EDX and elemental analysis. Notably, the elemental analysis
indicatesthat the phosphonium salt is detached from the surface
3
1
of the SiO
2
support. This is supported by the PNMR spectrum
which do not display any phosphorussignal as wellas solid state
1
3
C NMR spectrum which does not show the expected signals
from the aryl substituents at the phosphorusin the aromaticregion.
3
1
st
In contrast the PNMR spectra of theproduct obtained in the1
and 2 run clearly indicate leaching of the catalyst into the
nd
product. Notably, the elemental analysis of the used catalyst
showed a higher carbon and hydrogen content while solid state
1
3
C NMR spectrum displayed several new multiplets between 0
and 80 ppm which indicates product deposition on the catalyst
7
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201903384
FULL PAPER
Experimental Section
Acknowledgements ((optional))
Preparation of bifunctional catalysts 5 (GP1)
This research was funded by the Leibniz Association within the
scope of the Leibniz ScienceCampus Phosphorus Research
Rostock(www.sciencecampus-rostock.de). We thankDr. Armin
Springer (Electron Microscopy Centre) for support during EDX
analyses. ThomasFrankenberger(Dept. of Physics, Universityof
Rostock) is acknowledged for helping with sample sputtering.
A mixture of 1.0 equiv phosphane 3 and 5.0 equiv alkyl halides 4 were
stirred 24 h at 23–102 °C under argon atmosphere. The crude product was
washed with diethyl ether and dried in vacuo.
Procedure for the screening of homogeneous catalyst (Table 1)
3
Keywords: CO fixation • Plasma • Immobilization • Cyclic
2
A 45 cm stainless-steel autoclave was charged with catalyst 5 (1.0 mol%).
Subsequently, 1,2-butylene oxide (1a, 1.00 g, 13.9 mmol, 1.0 equiv) was
carbonates • Organocatalysts
added. The autoclave was purged with CO
while p(CO , 90 °C) was kept constant at 1.0 MPa. The reactor was cooled
with an ice bath below 20 °C and CO was released slowly. The conversion
of the epoxide 1a and yield of the carbonate 2a were determined by
2
and heated to 90 °C for 2 h,
2
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Entry for the Table of Contents
Insert graphicfor Table of Contents here. ((Please ensure yourgraphicis in one of following formats))
Plasma polymerization hasbeen employed as a strategyfor theimmobilization of an organocatalyst on unfunctionalized supports
SiO , TiO and FeO). The catalyticmaterialwas used in synthesizing cycliccarbonatesfrom epoxides and CO . Under the optimized
(
2
2
2
conditions17 cyclic carbonateswere synthesized in up to 99% yield undermild conditions. Furthermore, the unprecedented recycling
of a catalyst immobilized by plasma techniqueswas investigated.
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