Robustly supported rhodium nanoclusters: Synthesis and application in selective hydrogenation of lignin derived phenolic compounds

Article abstract of DOI:10.1039/c6nj01974a

The stabilization of small rhodium nanoclusters (NCs) in a polymer derived silicon carbonitride (SiCN) matrix has been reported to generate highly robust and active solid catalysts for the selective hydrogenation of phenolic compounds. An aminopyridinato Rh complex was used to modify a preceramic polymer (HTT 1800) followed by its pyrolysis at 1100 °C to afford small Rh NCs nicely dispersed over dense SiCN ceramic. For the synthesis of porous catalysts containing Rh NCs, microphase separation (followed by pyrolysis) of a diblock copolymer of HTT 1800 with hydroxy-polyethylene (PE-OH) was used. Both catalysts exhibit high activity in the hydrogenation of substituted phenols at room temperature and under low hydrogen pressure. The catalysts remained highly active and selective for six consecutive catalytic runs.

Full text of DOI:10.1039/c6nj01974a

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Journal Name
ARTICLE
Robustly supported rhodium nanoclusters: Synthesis and
applications in selective hydrogenation of lignin derived phenolic
compounds
Received 00th January 20xx,
Accepted 00th January 20xx
Sonja Fehn [a], Muhammad Zaheer [b*], Christine E. Denner [a], Martin Friedrich [a]
Rhett Kempe [a*]
,
DOI: 10.1039/x0xx00000x
www.rsc.org/
The stabilization of small rhodium nanoclusters (NCs) in polymer derived silicon carbonitride (SiCN) matrix is reported to
generate highly robust and active solid catalysts for the selective hydrogenation of phenolic compounds. An aminopyridinato
Rh complex was used to modify preceramic polymer (HTT1800) followed by its pyrolysis at 1100°C to afford small Rh NCs
nicely dispersed over dense SiCN ceramic. For the synthesis of porous catalysts containing Rh NCs, microphase separation
(followed by pyrolysis) of a diblock copolymer of HTT 1800 with hydroxy-polyethylene (PE-OH) was used. Both catalysts
exhibit high activity for the hydrogenation of substituted phenols at room temperature and under low hydrogen pressure.
The catalysts remained highly active and selective for consecutive six catalytic runs.
is the work of Antonietti et.al.;16 who achieved high selectivity
with Pd@C3N4 using water as a green solvent. In polar solvents
like water stability and reuse of the catalyst becomes an
important consideration along with the possible leaching of
catalytically active metal particles. Therefore, fabrication of
highly active, selective and stable (reusable) catalysts for the
hydrogenation of lignin derived phenolic compounds under
mild and environmentally benign conditions are still
demanding.
Introduction
Lignin constitutes 20-30% of the lignocellulose biomass and is
considered as a potential source of phenolic compounds, for
instance substituted guaicols which could be obtained from
lignin via catalytic depolymerization.1, These substituted
2
phenols are important raw materials for the production of
important chemicals and materials (polymers).3 Catalytic
hydrogenation in this regard provides an efficient route towards
the synthesis of these key chemicals. For instance, amination of
cyclohexanol obtained by the selective hydrogenation of phenol
could provide important organic compounds via C-N bond
formation.4 On the other, hydrogenation of phenol to
cyclohexanone is important in the sense that the latter is an
intermediate for the production of Nylon-6 polymer.5 Industrial
production of cyclohexanone from phenol is a two-step process
where the second step, i.e., the dehydrogenation of
cyclohexanol to cyclohexanone demands temperature above
400°C.6 In the last few years many heterogeneous liquid phase
catalysts have been developed for the selective hydrogenation
of phenol under mild conditions.7-14 One of the most
outstanding examples is the dual-supported palladium catalyst
of Han et.al.; showing high selectivity towards cyclohexanone
within a high phenol conversion at 50°C.15 However, the use of
Lewis acids and non-green solvents narrows the applicability of
the catalysts under experimental conditions. Worth mentioning
Rh seems to be an interesting metal for phenol hydrogenation
since it provides high activity in arene hydrogenation17, 18 and
there are only few published examples for the selective
hydrogenation of phenol to cyclohexanone with usable
21, 22
catalysts19, 20 not requiring supercritical CO2.
Polymer derived siliconcarbonitride (SiCN) ceramics offer high
temperature stability, corrosion resistance, long-term durability
and the low processing temperatures.23-26 Via a molecular
approach
using
amido-metal
complexes27-35
metal
nanoparticles (NPs) had been generated in the SiCN matrix
(M@SiCN) and used as robust catalysts for various reactions of
industrial importance.36-39 The unique feature of SiCN support is
its ability to stabilize very small metal clusters and show an
excellent reusability which may be attributed to the availability
of nitrogen functions in the SiCN network.40 Due to the fact that
M@SiCN catalysts possess small surface areas and low metal
dispersion, the catalytic activity of such catalysts is rather low.
Until now different methods have been introduced to create a
porous SiCN material utilizing both hard and soft templates.41-48
Our group has previously reported the formation of SiCN
nanofibers via the microphase separation and pyrolysis of the
block polymer of commercial polycarbosilazane (HTT 1800) with
a.Inorganic Chemistry II, University of Bayreuth, 95440 Bayreuth (Germany)
b.Department of Chemistry, SBA School of Science and Engineering, Lahore
University of Management Sciences (LUMS), 54792 Lahore Pakistan
*Corresponding authors email: muhammad.zaheer@lums.edu.pk, kempe@uni-
bayreuth.de
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/C6NJ01974A
.
Scheme 1: Synthetic approaches for the fabrication of dense (route a) and porous (route
b) Rh@SiCN catalysts. The first step in route (a) describes the chemical modification of
polysilazane while route (b) involves the formation of a diblock copolymer and its
modification with Rh ions. Second step in both routes corresponds to the pyrolysis under
nitrogen leading to either dense (Rh@SiCN) or porous (P-Rh@SiCN) materials.
Fig. 1: (a), (b) TEM micrograph of a dense Rh@SiCN ceramic (Rh-20), (c) Particle size
distribution with an average particle size of 1.6 nm, (d) PXRD pattern with rhodium
reflexes and corresponding reference pattern (red).
hydroxy-polyethylene (PEOH).49 PEOH is cheap, can be
eliminated under pyrolysis conditions and its block copolymer
with HTT 1800 could provide different nanostructures upon
microphase separation.50 Here we report the fabrication of
porous and non-porous rhodium NCs supported SiCN ceramics
as active and selective catalysts for the hydrogenation of
phenolic compounds.
So far we were successful in obtaining very small rhodium NPs
nicely distributed in SiCN matrix. These materials possess very
small surface area which could lead to severe mass transport
constraints when used as catalysts. In order to introduce
porosity within the materials a block copolymer of PE-OH with
HTT 1800 was synthesized. PEOH was dissolved in toluene and
mixed with the silazane precursor. Afterwards the rhodium
complex, which catalyses the cross-linking reaction, was added.
After 20 h reaction time the solvent was removed and a
Results and Discussion
The synthesis of the Rh@SiCN catalysts was carried out by the
pyrolysis of chemically modified polycarbosilazane (HTT 1800). In the
first step a rhodium complex (1 in scheme 1) reacts with HTT 1800 by structured green body was obtained. During pyrolysis (at
the elimination of the ApTMAH ligand and leads to the cross-linking of
preceramic polymer. The “green body” upon pyrolysis at 1100°C
provided the Rh@SiCN catalyst (Scheme 1, pathway-a) as confirmed
by FT-IR studies (figure S1 in supporting information: SI) and solid
state NMR (figure S2 in SI). The metal loading in the final materials is
described in terms of Si/Rh ratio.
1000°C under nitrogen) PEOH decomposes leaving behind the
porous Rh@SiCN (p-Rh@SiCN) materials (Scheme 1, pathway
2). Again the very small particle size as was observed in dense
ceramics previously prepared, was not compromised in this
approach and homogeneously distributed rhodium NPs in a size
range of 1.0 – 2.8 nm were obtained (figure 2a-b).
Transmission electron microscopy (TEM) provided the detailed
microstructure of synthesized materials. In the case of Rh-10
(Si/Rh=10), as expected, agglomeration of NPs took place due the
high metal content leading to broad distribution of particle size
(figure S3, SI). The material with lower Rh metal content (Rh-20:
Rh/Si ratio = 20) provided very small NPs with an average size of 1.6
nm (see figure 1a-c).
X-Ray powder diffraction (PXRD) measurement (figure 1d) showed
the typical reflection pattern of the cubic phase of the rhodium at 2θ
of 41.1°, 47.7° and 69.9° (reference code: 00-005-0685). The
presence of elemental metal within the materials could be attributed
to the reduction of Rh(II) ion under the reductive atmosphere of
furnace due to the generation of hydrogen, ammonia and methane.
Fig. 2: (a) TEM micrograph of a porous Rh@SiCN ceramic, (b) Particle size distribution
with an average particle size of 1.4 nm, (c) N2 sorption isotherm showing a surface area
of 205 m²/g, (d) Pore size distribution with a pore size in meso scale between 3 and 12
nm.
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The existence of Rh(0) nanoparticles was confirmed by PXRD In ethanol (EtOH) and ethyl acetate (EtOAc) a high VcieownvAretircsleioOnnlionef
DOI: 10.1039/C6NJ01974A
measurements which showed the reflection pattern of the cubic phenol but a low selectivity to cyclohexanone (CHN) was obtained
phase of the rhodium (see S4 in SI).
(entries 1 and 2). In tetrahydrofuran (THF) and toluene (TOL) the
catalyst showed almost the same activity but toluene was more
selective towards CHN (entries 3 and 4). In solvent screening, water
provided the highest selectivity to CHN (entry 5) and as it is an
environment friendly solvent it was selected for further studies. In
pure water almost quantitative conversion of phenol to cyclohexanol
(CHL) was observed after four hours (entry 6). Notably, with the
addition of chlorobenzene, ZnCl2*4H2O, acetone or y-valerolactone
(GVL) as co-solvents to water, the selectivity to CHN was greatly
enhanced (entries 8 to 16). The consumption of acetone or GVL
during the course of the reaction was not observed which shows
their sole role as solvent or promoter, probably due to their binding
with the CHN. As GVL is a renewable chemical accessible from
biomass51, was selected as a co-solvent for additional studies. The
addition of a Lewis acid ZnCl2.4H2O led to the deactivation of the
catalyst (entry 9). Compared to dense material the porous catalysts
has a higher activity (entry 14) since more metal is accessible due to
increase in porosity of the materials.
The success of the synthesis route and the generation of the porosity
was established by N2-adsorption. Adsorption-desorption isotherm
of p-Rh@SiCN (figure 2c) is close to type-IV isotherm known to be
shown by mesoporous materials, though high adsorption of nitrogen
at P/P0 <0.1 also suggests the existence of micropores. The specific
surface area of a p-Rh@SiCN material was found to be 205 m²/g.
NLDFT was applied to adsorption branch of the isotherm which
provided a pore size distribution (figure 2d) in the range 3 to 12 nm.
The porous Rh@SiCN (p-Rh-20) was investigated in the selective
hydrogenation of phenol at room temperature. The results of the
first screening with different solvents (entry 1-6) are shown in table
1.
Table 1. Hydrogenation of phenol over Rh@SiCN catalysts[a]
.
The substrate scope was investigated in order to find out the effect
of various substituents on phenol hydrogenation and results are
presented in table 2. The dihydroxy arenes were selectively
converted to hydroxyl-cyclohexanones with the highest selectivity
observed in the case of catechol (entry 3) as compared to resorcinol
(entry 2) and hydroquinone (entry 1) for which C-O bond cleavage
was also observed providing CHN and CHL in low yield (< 20%). For
lignin derived guaiacols almost similar selectivity to ketonic product
was observed for ortho, para and meta-isomers (entry 4-6). However
introduction of an electron donating alkyl group para to -OH resulted
in an increased selectivity of 85-91% (entry 7-8). Recycling studies of
the catalysts up to six consecutive runs are presented in Figure 3b.
entry pH2 time solvent
(bar) (h)
additive
Conv.
(%)
Sel.
to (a) in
%
1
2
6
6
6
6
6
6
6
6
6
6
6
6
10
6
6
6
1
1
1
1
1
4
2
2
2
2
2
4
3
4
6
5
EtOH
EtOAc
THF
-
46
72
38
38
27
100
54
26
0
44
33
38
68
70
0
-
3
-
4
toluene
H2O
-
5
-
6
H2O
-
-
7
H2O
67
77
0
8
H2O
chlorbenzene
ZnCl2*4H2O
acetone
GVL
9
H2O
10
11
12
13
14 [b]
15 [b]
16
H2O
37
29
67
74
23
73
99
82
86
72
73
80
68
73
H2O
H2O
GVL
H2O
GVL
H2O
GVL
H2O
GVL
Fig. 3: Time conversion plot (a) and recycling studies (b) using p-Rh@SiCN catalysts. (c)
Comparison of the p-Rh-20 with commercial available Rh/C and Rh/Al2O3 Conditions:
Reaction conditions: 2 mol% catalyst, 6 bar, 25°C.
H2O
GVL
[a] Reaction conditions: 2 mol% p-Rh-20 catalyst, 25°C, 3 ml solvent, 10 mmol
additive; [b] 2 mol% Rh-20 catalyst. GVL=γ-valerolactone.
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Table 2. Hydrogenation of hydroxylaromatic derivatives with porous Rh@SiCN. [a]
the introduction of porosity and increasing surface area of the
View Article Online
DOI: 10.1039/C6NJ01974A
materials. This was achieved by synthesis of a block copolymer of a
time
[h]
conv.
[%]
sel.[1]
[%]
sel.[2]
[%]
Ent.
1
substrate
product
commercial polysilazane with hydroxyl- polyethylene and its
subsequent pyrolysis that afforded porous Rh@SiCN catalysts. The
size of the metal particles can be altered by adjusting the amount of
added rhodium complex. These novel catalysts exhibit a high activity
in the selective hydrogenation of phenol at room temperature and
under low hydrogen pressure. Porous catalysts were found more
reactive as compared to their dense counterparts. The catalysts offer
reusability and offer broad substrate scope.
7 h
95
67
0*
2
8h
94
66
0**
3
4 h
99
95
83
40
14
50
Experimental
Synthesis of the ligand: ApTMAH (4-Methyl-pyridin-2-yl)-(2,4,6-
tri-methyl-phenyl)-amin] was carried out using a reported
method. Details of a typical synthesis are given in SI.
Synthesis of the [Rh(ApTMA)(cod) complex (1): A modified
literature method was followed. 435 mg (1.92 mmol) ApTMAH in
35 ml diethyl ether was cooled down to 0°C and 1.25 ml of butyl
lithium (BuLi) were added. Afterwards a suspension of 473.5
mg (0.96 mmol) [RhCl(cod)]2 and 20 ml diethyl ether were
added at 0°C to the lithiated ligand and stirred overnight.
Lithium chloride was filtered off from the complex solution and
washed three times with 20 ml diethylether. The solution was
concentrated and the complex crystalized at -20°C. Yield: 699
mg (83.5%).
4
11 h
5
6
11 h
15 h
95
90
33
40
55
52
7
8
16 h
16 h
99
99
2
5
91
85
1H NMR (500 MHz, CDCl3, 296 K): δ = 7.87 (d, 1H, NCH), 6.90 (d,
2H, arom. H), 6.79 (d, 1H, arom. H), 6.74 (s, 1H, arom. H), 5.27
(s, 4H, cod), 3.96 (bs, 6H, cod), 2.56 (s, 3H, ar-CH3), 2.20 (bs, 9H,
ar. CH3), 1.57 (bs, 8H, cod) ppm.
13C NMR (125 MHz, CDCl3, 296 K): δ = 19.31, 21.38, 21.84,
31.67, 105.06, 107.99, 129.63, 133.29, 134.01, 141.90, 143.91,
151.03, 176.15 ppm.
[a] Reaction conditions: 2 mol% Rh@SiCN-b-PE catalyst, 25°C, 3 ml H2O, 10 mmol
γ-valerolactone. [1] selectivity to alcohol; [2] selectivity to ketone; *10%
cylclohexanone and 18% cyclohexanol was observed. **7% cyclohexanone, 19%
cyclohexanol.
Synthesis of a Rh@SiCN ceramic:
For the synthesis of Rh-10 (Si/Rh = 10) ceramic 338.84 mg and
analogous for Rh-20 (Si/Rh = 20) ceramic 169.42 mg (0.389
mmol) [Rh(ApTMA)(cod)] was solved in 3 ml hexane. After
addition of 0.5 ml (7.77 mmol) HTT 1800 the solution changed
its colour from yellow to dark red. After 10 min at room
temperature viscous material was generated. The greenbodies
were put in a quartz boat and pyrolysed with the following
program at 1100°C:
No loss in activity was observed so the NCs are firmly embedded in
the SiCN matrix and no metal was found in the solution. Time
conversion plot of phenol hydrogenation in water at 25°C is
presented in Figure 3a. A full conversion was achieved in 5 hours. In
contrast to the p-Rh-20 catalyst commercially available Rh catalysts
showed similar a selectivity but were found less active (figure 3c).
After 5 hours with the same catalyst loading of 2 mol% the p-Rh-20
catalyst achieved 99% conversion while Rh/Al2O3 and Rh/C showed
49% and 36% conversion respectively.
The following ceramic yields were obtained: for Rh-10: 65.9%
and 80.8% for Rh-20. The ceramics were pulverized using a ball
miller for 20 minutes.
Conclusions
The generation and stabilization of small-sized rhodium
nanoparticles in thermally robust silicon carbonitride matrix has
Synthesis of the porous Rh@SiCN ceramics:
been achieved by the pyrolysis (1100°C/nitrogen) of a chemically The metal loading in the final material was adjusted in terms of
modified commercial polysilazane. An amido rhodium complex used silicon to Rh ratio (Si:Rh) and catalysts with a Si:Rh=10 (Rh-10) and
for chemical modification also serves as a catalyst for the cross Si/Rh=20 (Rh-20) were prepared. For a Rh-20, [PEOH:HTT 1800
linking of polysilazane at room temperature via hydrosilylation weight ratio = 70:30], 233 mg of PEOH (Mn= 2110, Mw= 4053, PDI =
reaction. The accessibility of rhodium nanoparticles was improved by 1.9) were solved in 5 ml toluene at 130°C. Afterwards 100 μl (1.554
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mmol) HTT 1800 were added without stirring the solution. After 1 15.
hour 33.88 mg (for Rh-20) Rh-complex solved in 1 ml toluene were
added. On the next day the solvent was removed and greenbodies
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were put in a quartz boat and pyrolyzed at 1000°C. The Rh-10 catalyst
contains 13.0 wt% Rh and the Rh-20 contains 8.1 wt% Rh.
17.
18.
Catalytic studies:
The catalyst was pre-treated with 1.6 M NaOH solution and
methanol for 16 hours at 80°C.
19.
For the hydrogenation reactions a vial with 0.5 mmol substrate,
3 ml solvent and additive were placed in a steel autoclave. The
20.
autoclave was purged with hydrogen. After a certain reaction
time EtOAc and 0.5 mmol n-dodecan as international standard
were placed in the vial. After separation of the catalyst the
solution was analyzed with GC.
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centrifugation at 2000 rpm and used again under the same
conditions.
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Graphical abstract text
Rh@SiCN catalysts synthesized by a one-pot process afford selective hydrogenation of phenolic
compounds.