Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics

Article abstract of DOI:10.1002/anie.201511558

Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and “real-world” biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity.

Full text of DOI:10.1002/anie.201511558

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201511558
German Edition: DOI: 10.1002/ange.201511558
Heterogeneous Catalysis Hot Paper
Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic
PtCo Nanoparticles for Upgrading of Biophenolics
Guang-Hui Wang, Zhengwen Cao, Dong Gu, Norbert Pfꢀnder, Ann-Christin Swertz,
Bernd Spliethoff, Hans-Josef Bongard, Claudia Weidenthaler, Wolfgang Schmidt,
Roberto Rinaldi, and Ferdi Schꢁth*
Abstract: Hydrodeoxygenation (HDO) is an attractive route
for the upgrading of bio-oils produced from lignocellulose.
Current catalysts require harsh conditions to effect HDO,
decreasing the process efficiency in terms of energy and carbon
balance. Herein we report a novel and facile method for
synthesizing bimetallic PtCo nanoparticle catalysts (ca.
phosphides (e.g., Ni P and Co P), metal carbides (e.g., W C
2 2 2
[
4]
and Mo C), or related compounds. Recently, we found that
2
bimetallic PtCo nanoparticles (ca. 3.6 nm) in hollow carbon
nanospheres show high activity for hydrogenolysis of 5-
hydroxymethylfurfural to 2,5-dimethylfuran with 98%
[
5]
yield. Such catalysts are capable of hydrodeoxygenating
1
.5 nm) highly dispersed in the framework of nitrogen-doped
C=O and CÀOH groups without the drawbacks associated
ordered mesoporous carbon (NOMC) for this reaction. We
demonstrate that NOMC with either 2D hexagonal (p6m) or
3
adjusting the polymerization temperature. We also demon-
strate that PtCo/NOMC (metal loading: Pt 9.90 wt%; Co
with the use of acidic supports (i.e. the promotion of side
reactions, e.g., dehydration, cracking, and polymerization; the
polymerization reaction contributes to catalyst deactivation
via formation of carbonaceous deposits on the metal parti-
¯
D cubic (Im3m) structure can be easily synthesized by simply
[
4a,b]
cles).
Therefore, we hypothesized that the bimetallic PtCo
3
.31 wt%) is a highly effective catalyst for HDO of phenolic
catalysts should also be conducive to efficient upgrading of
biomass-derived phenolic streams.
compounds and “real-world” biomass-derived phenolic
streams. In the presence of PtCo/NOMC, full deoxygenation
of phenolic compounds and a biomass-derived phenolic
stream is achieved under conditions of low severity.
To utilize the active PtCo components efficiently, one
approach is to downsize the bimetallic PtCo nanoparticles
and finely disperse them on supports. The supports should
allow efficient mass transfer, and suppress sintering and loss
of the active catalyst during the HDO process. Nitrogen-
doped ordered mesoporous carbon (NOMC) meets these
requirements as a result of a combination of properties, that
is, ordered mesoporosity of the carbon (with narrow pore size
distribution, interconnected mesopores, large pore volumes
and surface areas) and a nitrogen-doped carbon framework
B
io-oils are mixtures of highly functionalized oxygenates
[
1]
[2]
obtained by pyrolytic or non-pyrolytic processes per-
formed on lignocellulose. An essential step in the utilization
of bio-oils as a feedstock for the production of biofuels
constitutes the catalytic upgrading, that is, the removal of
oxygen-containing groups from the bio-oils (oxygen content:
[6]
3
0–50 wt%). This step improves the stability of the bio-oils,
(with improved basicity and enhanced p-donor capability).
and increases the energy density, so that properties similar to
those of conventional fossil, oil-based, transportation fuels
However, synthesis of PtCo/NOMC with small size of the
metal particles and high dispersion of the particles in a simple
way is very challenging. Firstly, it is hard to synthesize NOMC
via soft-templating with in situ nitrogen doping, which would
be the simplest method with respect to materials synthesis,
owing to the limited availability of suitable nitrogen-contain-
[
3]
are achieved. Hydrodeoxygenation (HDO), a highly attrac-
tive route for upgrading of bio-oils, involves reactions of the
[1]
bio-oil with hydrogen to produce hydrocarbons and water.
Many catalysts for HDO processes have been studied, and
they include metals (e.g., Pt, Pd, Ru, Rh, Fe, Ni, Co), metal
sulfides (e.g., CoMo- and NiMo-based sulfides), metal
[
6e]
ing precursors. Therefore, it is desirable to find suitable
precursors for synthesis of the NOMC with high nitrogen
content and well-defined ordered structures. Secondly, intro-
ducing metal nanoparticles, especially bimetallic nanoparti-
cles, into the ordered mesoporous structures with high
dispersion and narrow particle size distribution has proven
[
*] Dr. G.-H. Wang, Dr. Z. Cao, Dr. D. Gu, N. Pfꢀnder, A.-C. Swertz,
B. Spliethoff, H.-J. Bongard, Dr. C. Weidenthaler, Dr. W. Schmidt,
Prof. Dr. F. Schꢁth
[7]
to be very challenging. Herein, we report a simple method
to synthesize bimetallic PtCo nanoparticles supported in the
framework of NOMC with ultrafine dispersion and uniform
particle size distribution (ca. 1.5 nm). We demonstrate that
PtCo/NOMC shows outstanding catalytic performance in the
upgrading of phenolic compounds and ꢀreal-world“ biomass-
derived phenolic stream. In both cases, the oxygen content is
nearly fully removed.
Max-Planck-Institut fꢁr Kohlenforschung
Kaiser-Wilhelm-Platz 1, 45470 Mꢁlheim an der Ruhr (Germany)
E-mail: schueth@kofo.mpg.de
N. Pfꢀnder
Max-Planck-Institut fꢁr Chemische Energiekonversion
Stiftstrasse 34–36, 45470 Mꢁlheim an der Ruhr (Germany)
Dr. R. Rinaldi
Imperial College London, Department of Chemical Engineering
South Kensington Campus, London, SW7 2AZ (UK)
Our strategy for preparing NOMC and PtCo/NOMC is
illustrated in Scheme 1. NOMC is synthesized by the soft-
templating method using 3-aminophenol as both nitrogen and
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201511558.
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H2 in argon), PtCo/NOMC with
ultrafine dispersion and uniform
particle size distribution is pro-
duced (Scheme 1b).
Low-angle powder X-ray dif-
fraction
(XRD)
pattern
of
NOMC-1-600 (Figure 1a) shows
an intense diffraction peak and
two weak peaks, which can be
indexed as (10), (11), and (20)
reflections associated with 2D hex-
[
11]
agonal p6m symmetry. The posi-
tion of the intense (10) peak indi-
cates a d-spacing of 11.1 nm, corre-
sponding to a unit cell parameter of
1
2.8 nm. Transmission electron mi-
croscopy (TEM) images of NOMC-
-600 (Figure 1b,c) viewed along
1
the [001] and [110] directions,
together with the scanning electron
microscope (SEM) image (Fig-
ure 1g), further confirm the hexag-
onal mesoporous structure. The cell
parameter calculated from the
TEM image is 12.4 nm, which is in
Scheme 1. Synthesis of a) NOMC and b) PtCo/NOMC.
carbon source. Theoretically, both the phenolic hydroxy
group and amino group of 3-aminophenol have a strong
interaction via hydrogen-bonding with the PEO moiety of
F127 (poly(ethylene oxide)-poly(propylene oxide)-poly(eth-
ylene oxide) triblock copolymer, EO106PO70EO106), which
can induce the ordered assembly between 3-aminophenol/
[8]
formaldehyde resin and F127. However, the main problem
using 3-aminophenol as the precursor is the too fast, uncon-
trolled polymerization of 3-aminophenol with formaldehyde,
which hinders the formation of ordered mesoporous struc-
tures. In fact, on adding formaldehyde into a 3-aminophenol
solution, the mixture turns opaque white (colloidal resin
spheres formed) within 10 seconds even at room temperature,
[
9]
indicating rapid polymerization. In the present system,
hexamethylenetetramine (HMT) is used which can decom-
pose into formaldehyde and ammonia (no polymerization
occurred at room temperature). As the decomposition of
HMT is temperature dependent, the polymerization rate can
be thus efficiently controlled by adjusting the reaction
temperature. Notably, depending on the reaction temper-
ature, the selective formation of ordered mesostructured
resin/F127 composites with either 2D hexagonal (p6m,
Figure 1. a) XRD patterns of NOMC-1-600 and NOMC-2-600. TEM
images of NOMC-1-600 viewed in the b) [001] and c) [110] directions.
TEM images of NOMC-2-600 viewed in the d) [111], e) [100], and
f) [110] directions. SEM images of g) NOMC-1-600 and h) NOMC-2-
600.
¯
NOMC-1 precursor) or 3D cubic (Im3m, NOMC-2 precursor)
symmetry can be achieved (Scheme 1a). After carbonization
at temperatures of 600 to 10008C (argon atmosphere),
NOMC with high nitrogen content and well-defined ordered
¯
structures (p6m NOMC-1 and Im3m NOMC-2) can be
agreement with the value calculated from XRD data.
Increasing the carbonization temperatures to 8008C and
10008C, the XRD patterns (Supporting Information, Fig-
ure S1a) are similar to that of NOMC-1-600, demonstrating
the preservation of p6m symmetry and structure. As
expected, the peak positions are shifted to higher angles,
obtained (Scheme 1a), owing to the thermally highly stable
resin/F127 composite framework with 3D-connected benzene
[
10]
2À
3À
rings. Alternatively, both PtCl4 and Co(CN)6 ions can be
introduced simultaneously into the resin/F127 composite by
ion exchange. After pyrolysis under reductive condition (5%
2
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indicating shrinkage of the carbon framework with elevated
carbonization at temperatures between 600 to 10008C (Fig-
temperature (cell parameters decrease to 12.5 and 11.9 nm
based on XRD data, Table S1). The XRD pattern of NOMC-
ure S2d and Table S1).
The X-ray photoelectron spectrum (XPS) of NOMC-1-
600 (Figure S3a) shows intense signals of carbon, nitrogen,
and oxygen. In the N 1s region, the spectrum of NOMC-1-600
(Figure S3b) exhibits two peaks which can be attributed to
2
-600 (Figure 1a) also shows well-resolved reflections that
can be indexed as (110), (200), and (211) reflections
[12]
¯
associated with body-centered cubic Im3m symmetry. The
cell parameter is estimated at 15.3 nm based on XRD data.
TEM images (Figure 1d–f) show that NOMC-2-600 has a high
degree of periodicity viewed from [111], [100], and [110]
directions. The SEM image (Figure 1h) also shows a long-
range order and large domains of interconnected cage-type
pores in cubic 3D arrangement. This observation confirms the
[14]
pyridinic (398.4 eV) and pyrrolic nitrogen (400.5 eV).
Increasing the carbonization temperature to 800 and
10008C results in a N 1s spectra with five peaks, which can
be assigned to nitride (397.9 eV), amine (399.1 eV), pyridonic
nitrogen (400.8 eV), probably quaternary nitrogen
(401.9 eV), and pyridine-N-oxide (403.3 eV; Figure S3b).
According to the elemental analysis by sample combustion,
the amount of bulk nitrogen in NOMC-1-600 is 9.2 wt%.
However, the total nitrogen content decreases to 7.8 wt% for
NOMC-1-800 and 3.5 wt% for NOMC-1-1000, respectively
(Table S1).
[
15]
¯
formation of a cubic mesoporous structure (Im3m). The cell
parameter calculated from TEM is 14.7 nm, in agreement
with the value determined from XRD data. Also, the XRD
patterns (Figure S1b) confirm that the cubic mesoporous
structures are retained upon carbonization at 8008C and
1
0008C. Also for NOMC-2, a shrinkage of the structure was
To introduce PtCo metal nanoparticles into NOMC with
homogenous dispersion, the Pt and Co precursors were
adsorbed into the polymer matrix (NOMC-2 precursor) first.
Then, the polymer matrix was converted into NOMC-2 at
observed at elevated temperature (cell parameters decrease
to 14.4 nm for NOMC-2-800 and 14.0 nm for NOMC-2-1000
based on XRD data, Table S1).
The N sorption isotherm of NOMC-1-600 (Figure S2a)
5008C in a flow of 5% H in Ar. During that treatment the
2
2
shows a type-IV curve with type-H1 hysteresis loop, indicat-
bimetallic PtCo nanoparticles were formed with ultrafine
dispersion and narrow particle size distribution. The majority
of metal nanoparticles with diameters of about 1.5 nm were
incorporated into the carbon frameworks (Figure 2a–c, Fig-
ure S4). Thus, they are firmly anchored to the carbon support
[
11]
ing a mesoporous structure with cylindrical channels. BET
surface area and the total pore volume are calculated to be
2
À1
3
À1
4
50 m g and 0.26 cm g , respectively. The pore diameter is
about 3.3 nm with a narrow pore size distribution (Fig-
ure S2b). Increasing the carbonization tempera-
tures to 8008C and 10008C, the isotherms (Fig-
ure S2a) still show typical type-IV curves, indicat-
ing the preservation of mesoporous structures.
However, the adsorption and desorption branches
are not closed, a phenomenon that is often
observed for porous polymers and sometimes for
porous carbons, and which is not yet fully under-
stood. BET surface areas and the total pore
2
À1
volumes are decreased to 364 m g
and
3
À1
2
À1
0
0
.22 cm g for NOMC-1-800, and 254 m g and
.15 cm g for NOMC-1-1000, respectively. The
3
À1
pore diameters for both NOMC-1-800 and
NOMC-1-1000 are about 3.2 nm, which are similar
to that of NOMC-1-600 (Figure S2b and Table S1).
The N sorption isotherm of NOMC-2-600 (Fig-
2
ure S2c) shows a type-IV curve with type-H2
hysteresis loop, which is typical for spherical
[
13]
pores with narrow pore windows. NOMC-2-600
2
À1
has a large BET surface area of 464 m g and
3
À1
a pore volume of 0.30 cm g . The pore diameter is
about 4.7 nm with a narrow pore size distribution
(
Figure S2d). The mesoporous structures are also
preserved after carbonization at 8008C and 10008C
Figure S2c). Similar as for NOMC-1, the desorp-
(
tion branches of NOMC-2-800 and NOMC-2-1000
do not meet the adsorption branches at low
pressures. BET surface areas and the total pore
Figure 2. Structural characterization of PtCo/NOMC-2: a) TEM image. Inset: the
particle size distribution of PtCo. b,c) STEM images. d) Elemental mappings (white
ovals indicate the same particle in each panel). e) XRD pattern (positions of
reflections for pure Pt marked by vertical lines). Inset: low-angle XRD pattern. f) N2
2
À1
3
À1
volumes are 433 m g
and 0.28 cm g
for
2
À1
3
À1
NOMC-2-800, and 400 m g and 0.27 cm g for
NOMC-2-1000, respectively. Notably, the pore
diameters remain at approximately 4.6 nm after sorption isotherm. Inset: pore size distribution.
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[
5]
which should improve their thermal stability during catalysis.
EDX data (Figure S4) show that the sample contains Pt and
Co with a molar ratio of Pt:Co of about 1:1.1. This is in
agreement with data from atomic absorption spectrometry
Co in the bimetallic PtCo nanoparticles. Notably, compared
with results reported in recent literature (Table S3), the HDO
activity of PtCo/NOMC-2 is higher than most acid-free or
acidic support-free catalysts, and comparable to catalysts
containing acids or acidic supports.
(
AAS; 9.90 wt% Pt, 3.31 wt% Co; the corresponding molar
ratio of Pt and Co is 1:1.1). Furthermore, according to the
elemental mappings of Pt and Co (Figure 2d), the distribu-
tions of Pt and Co in the NOMC almost overlap with each
other. In the XRD pattern (Figure 2e) the reflections are
shifted to higher angles compared with those of pure Pt. This
observation indicates that Co is very likely incorporated into
the Pt fcc structure to form an alloy phase. In addition, the
XRD reflections are very broad, further confirming the
formation of small bimetallic PtCo nanoparticles. The low-
angle XRD pattern (Figure 2e, inset) shows well-resolved
reflections, indicating the presence of a cubic mesoporous
structure after introduction of PtCo nanoparticles. The N2
sorption isotherm of PtCo/NOMC-2 (Figure 2 f) still shows
a type-IV curve with type-H2 hysteresis loop, which further
confirms the stability of the ordered mesoporous structure.
BET surface area, pore volume and pore size of PtCo/
Recycling tests of PtCo/NOMC-2 for HDO of guaiacol
were carried out at 573 K under 10 MPa H2 for 1 h. The
guaiacol conversion slightly decreased from 100% in cycle 1
to 94% in cycle 5 (Figure S7). However, the HDO activity
gradually decreased after three runs, as indicated by the
increased cyclohexanol formation in conjunction with the
decrease in the cyclohexane selectivity (Figure S7, run 4 and
5). This result may be associated with the leaching of Co from
the surface of the bimetallic PtCo nanoparticles during the
recycling tests (Figure S8). Accordingly, a hot filtration test
was also performed. After removal of the solid catalyst, the
reaction in the filtrate did not proceed (Table S2, entries 8–
10), indicating that no catalytically active species are present
in the filtrate. However, trace amounts of Pt (8.3 ppm) and Co
(0.8 ppm) were still detected (AAS) in the filtrate. These
results indicate that the catalytic effect in this system results
from the PtCo nanoparticles on the support and not from
leached metal species.
2
À1
3
À1
NOMC-2 are 507 m g , 0.41 cm g and 6.5 nm, respectively,
which are larger than those for NOMC-2–600 without metal
loading. This result can be attributed to the decomposition of
carbon in the presence of Co or the lower pyrolysis temper-
ature (5008C). This finding has also been observed in a related
synthesis for the generation of bimetallic PtCo nanoparticles
We further applied the PtCo/NOMC-2 catalyst for HDO
of a lignin-derived non-pyrolytic bio-oil, which had been
obtained from early-stage catalytic conversion of lignin
[
16]
(ECCL) through hydrogen transfer reaction in the pres-
[
5]
[2]
encapsulated in hollow carbon spheres.
ence of Raney Ni and 2-propanol. Through this approach,
The catalytic performance of PtCo/NOMC-2 was evalu-
ated for HDO of phenolic compounds. First a blank reaction
without added catalyst was carried out. In this test, the
conversion of guaiacol was lower than 3% even after reaction
for 24 h (Table S2, entry 1). Next, a commercial Pt/C catalyst,
Pt/NOMC-2 and Co/NOMC-2 (Figure S5) were compared in
the HDO of guaiacol under the same conditions. In the
presence of commercial Pt/C, full conversion of guaiacol was
achieved, but rendering an HDO degree of only 27%
lignin is depolymerized directly after its extraction from plant
biomass in a one-pot process. Advantageously, in its compo-
sition, the lignin oil stream mostly comprises monocyclic
phenols and, to a lesser extent, alcohols and phenolic
oligomers. Moreover, as ECCL directly reduces carbonyl
functionalities (associated with ketones and aldehydes), the
lignin oil stream is obtained as a thermally stable stream.
Therefore, the “new” lignin stream clearly exhibits properties
that are conducive to downstream using highly active, tailor-
made nanocatalysts as these reported herein.
(
Table S2, entry 2); the main products were methoxycyclo-
hexanol (57%), cyclohexanol (33%), and cyclohexane
10%), indicating that the main reaction channel is the
The main components in the as-obtained non-pyrolytic
bio-oil (elemental analysis: C 57.1%; H 7.9%; O 35.0% by
difference) are phenolics derived from lignin (Figure 3a).
After HDO of the lignin-oil over PtCo/NOMC-2, the main
products are cycloalkanes (Figure 3b). Remarkably, almost
no oxygen-containing compounds were detected by GC ꢁ
GC-MS analysis. The HSQC spectrum of the product after
HDO (isolated at 313 K under 50 mbar) clearly shows only
(
aromatic ring saturation. For Pt/NOMC-2, a 96% conversion
of guaiacol was obtained, affording a 50% HDO degree
(
Table S2, entry 3); the main products were methoxycyclo-
hexanol (4%), cyclohexanol (79%) and cyclohexane (4%).
These results indicate that monometallic Pt nanoparticles
possess high hydrogenation activity but low deoxygenation
activity. In turn, Co/NOMC-2 led to a 21% conversion of
guaiacol and 31% HDO degree (Table S2, entry 4). However,
when using PtCo/NOMC-2 as the catalyst, full conversion of
guaiacol into cyclohexane (selectivity > 99%) was achieved
3
the characteristic signals of aliphatic C(sp )-H; the oxygen
functionalities in the non-pyrolytic bio-oil were almost fully
removed (Figure S9). The elemental analysis shows that the
sum of C and H in the isolated product is up to 99% (C
84.9%; H 14.1%). Therefore, PtCo/NOMC-2 is indeed an
effective catalyst for HDO of complex phenolic streams
derived from native lignin without added acid co-catalysts or
acidic supports. The deoxygenated product mixture can
potentially be processed in conventional oil refineries, and
therefore, valorizing residual lignin streams obtained from
cellulosic bio-ethanol.
(
Table S2, entry 5). Guaiacol thus seems to undergo a hydro-
genation-deoxygenation process under the reaction condi-
tions over PtCo/NOMC-2 (Figure S6). The high HDO activity
of PtCo/NOMC-2 was further confirmed by experiments
using other phenolic compounds (Table S2, entries 6 and 7).
The selectivity for the alkanes was always > 99%, which gave
an overall HDO degree of > 99% at full conversion.
Altogether, these results demonstrate a synergism between
Pt and Co caused by the electronic interaction between Pt and
In summary, we have developed a soft-templating path-
way for the synthesis of NOMC using 3-aminophenol as both
4
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performance-enhancer of synthetic fuels produced by the
Fischer–Tropsch process.
Acknowledgements
This work was conducted in the framework of the ERC
Advanced Grant project “POLYCAT” and the CASCAT-
BEL project funded by the European Commission (Grant
Agreement No. 604307). R.R. is grateful to the funding
provided by Alexander von Humboldt Foundation (Sofja
Kovalevskaja Award 2010). This work was performed as part
of the Cluster of Excellence “Tailor-Made Fuels from
Biomass”, which is funded by the Excellence Initiative by
the German federal and state governments to promote
science and research at German universities. We thank Mr.
Markus Kochius for NMR tests.
Keywords: bimetallic nanoparticles · biomass ·
hydrodeoxygenation · mesoporous materials · phenols
[
[
1] G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006, 106, 4044.
2] P. Ferrini, R. Rinaldi, Angew. Chem. Int. Ed. 2014, 53, 8634;
Angew. Chem. 2014, 126, 8778.
[
3] a) J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius, B. M. Weck-
huysen, Chem. Rev. 2010, 110, 3552; b) R. K. Sharma, N. N.
Bakhshi, Energy Fuels 1993, 7, 306; c) E. Furimsky, Appl. Catal.
A 2000, 199, 147.
[
4] a) P. M. Mortensen, J. D. Grunwaldt, P. A. Jensen, K. G. Knud-
sen, A. D. Jensen, Appl. Catal. A 2011, 407, 1; b) M. Saidi, F.
Samimi, D. Karimipourfard, T. Nimmanwudipong, B. C. Gates,
M. R. Rahimpour, Energy Environ. Sci. 2014, 7, 103; c) D. A.
Ruddy, J. A. Schaidle, J. R. Ferrell, J. Wang, L. Moens, J. E.
Hensley, Green Chem. 2014, 16, 454; d) H. M. Wang, J. Male, Y.
Wang, ACS Catal. 2013, 3, 1047; e) K. L. Li, R. J. Wang, J. X.
Chen, Energy Fuels 2011, 25, 854; f) N. Ji, M. Y. Zheng, A. Q.
Wang, T. Zhang, J. G. G. Chen, ChemSusChem 2012, 5, 939; g) C.
Zhao, J. A. Lercher, ChemCatChem 2012, 4, 64; h) C. R. Lee,
J. S. Yoon, Y. W. Suh, J. W. Choi, J. M. Ha, D. J. Suh, Y. K. Park,
Catal. Commun. 2012, 17, 54; i) D. Y. Hong, S. J. Miller, P. K.
Agrawal, C. W. Jones, Chem. Commun. 2010, 46, 1038; j) T.
Nimmanwudipong, R. C. Runnebaum, D. E. Block, B. C. Gates,
Energy Fuels 2011, 25, 3417; k) X. Wang, R. Rinaldi, Catal.
Today 2016, 269, 48.
Figure 3. GCꢂGC-MS analysis of lignin-derived non-pyrolytic bio-oil
before (a) and after (b) HDO over PtCo/NOMC-2. Reaction conditions:
bio-oil (200 mg), n-hexadecane (GC internal standard, 0.4 mmol),
catalyst (200 mg), and n-hexane (solvent, 5 mL), 10 MPa (573 K,
constant), 573 K for 12 h.
¯
carbon and nitrogen source. NOMC with p6m and Im3m
mesostructured symmetries were successfully synthesized by
simply changing the polymerization temperature. The nitro-
gen content of NOMC can be adjusted from approximately
[5] G. H. Wang, J. Hilgert, F. H. Richter, F. Wang, H. J. Bongard, B.
9
.2 wt% to approximately 3.5 wt% by increasing the carbon-
Spliethoff, C. Weidenthaler, F. Schꢂth, Nat. Mater. 2014, 13, 294.
6] a) X. Jin, V. V. Balasubramanian, S. T. Selvan, D. P. Sawant,
[
ization temperature from 6008C to 10008C. Moreover, the
structures of NOMC are stable even upon carbonization at
1
ters of around 1.5 nm were successfully introduced into the
NOMC framework with ultrafine dispersion and uniform
particle size distribution. The loadings of Pt and Co are
M. A. Chari, G. Q. Lu, A. Vinu, Angew. Chem. Int. Ed. 2009, 48,
7884; Angew. Chem. 2009, 121, 8024; b) L. Liu, Q. F. Deng, T. Y.
0008C. Notably, bimetallic PtCo nanoparticles with diame-
Ma, X. Z. Lin, X. X. Hou, Y. P. Liu, Z. Y. Yuan, J. Mater. Chem.
2
2
011, 21, 16001; c) T. Y. Ma, L. Liu, Z. Y. Yuan, Chem. Soc. Rev.
013, 42, 3977; d) W. Z. Shen, W. B. Fan, J. Mater. Chem. A 2013,
1, 999; e) X. Q. Wang, C. G. Liu, D. Neff, P. F. Fulvio, R. T.
Mayes, A. Zhamu, Q. Fang, G. R. Chen, H. M. Meyer, B. Z. Jang,
S. Dai, J. Mater. Chem. A 2013, 1, 7920; f) J. Wei, D. D. Zhou,
Z. K. Sun, Y. H. Deng, Y. Y. Xia, D. Y. Zhao, Adv. Funct. Mater.
9
.90 wt% and 3.31 wt%, respectively. The PtCo/NOMC
shows outstanding catalytic performance in the HDO of
phenolic compounds and complex “real-world” phenolic
mixtures. The conversion of lignin oil obtained by ECCL
produced cycloalkanes; the oxygen content was nearly fully
removed. Such a lignin product mixture comprising cyclo-
alkanes could already find uses as drop-in fuels or as
2013, 23, 2322; g) P. F. Zhang, Y. T. Gong, H. R. Li, Z. R. Chen,
Y. Wang, Nat. Commun. 2013, 4, 1593; h) D. D. Zhou, W. Y. Li,
X. L. Dong, Y. G. Wang, C. X. Wang, Y. Y. Xia, J. Mater. Chem.
A 2013, 1, 8488; i) X. Q. Wang, J. S. Lee, Q. Zhu, J. Liu, Y. Wang,
S. Dai, Chem. Mater. 2010, 22, 2178; j) J. H. Yu, M. Y. Guo, F.
Angew. Chem. Int. Ed. 2016, 55, 1 – 7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Muhammad, A. F. Wang, G. L. Yu, H. P. Ma, G. S. Zhu, Micro-
porous Mesoporous Mater. 2014, 190, 117; k) J. Y. Yu, M. Y. Guo,
F. Muhammad, A. F. Wang, F. Zhang, Q. Li, G. S. Zhu, Carbon
[12] D. Y. Zhao, Q. S. Huo, J. L. Feng, B. F. Chmelka, G. D. Stucky, J.
Am. Chem. Soc. 1998, 120, 6024.
[13] J. R. Matos, M. Kruk, L. P. Mercuri, M. Jaroniec, L. Zhao, T.
Kamiyama, O. Terasaki, T. J. Pinnavaia, Y. Liu, J. Am. Chem.
Soc. 2003, 125, 821.
2014, 69, 502; l) Y. D. Xia, R. Mokaya, Adv. Mater. 2004, 16,
1553; m) M. Kruk, B. Dufour, E. B. Celer, T. Kowalewski, M.
Jaroniec, K. Matyjaszewski, J. Phys. Chem. B 2005, 109, 9216;
n) P. F. Fulvio, M. Jaroniec, C. D. Liang, S. Dai, J. Phys. Chem. C
[14] J. R. Pels, F. Kapteijn, J. A. Moulijn, Q. Zhu, K. M. Thomas,
Carbon 1995, 33, 1641.
2
008, 112, 13126.
[15] K. Artyushkova, B. Kiefer, B. Halevi, A. Knop-Gericke, R.
Schlçgl, P. Atanassov, Chem. Commun. 2013, 49, 2539.
[16] R. Rinaldi, R. Jastrzebski, M. T. Clough, J. Ralph, M. Kennema,
P. C. A. Bruijnincx, B. M. Weckhuysen, Angew. Chem. Int. Ed.
2016, 55, DOI: 10.1002/anie.201510351; Angew. Chem. 2016, 128,
DOI: 10.1002/ange.201510351.
[
[
[
7] X. L. Ji, K. T. Lee, R. Holden, L. Zhang, J. J. Zhang, G. A.
Botton, M. Couillard, L. F. Nazar, Nat. Chem. 2010, 2, 286.
8] J. Wang, H. Y. Liu, X. M. Gu, H. H. Wang, D. S. Su, Chem.
Commun. 2014, 50, 9182.
9] J. M. Zhao, W. X. Niu, L. Zhang, H. R. Cai, M. Y. Han, Y. L.
Yuan, S. Majeed, S. Anjum, G. B. Xu, Macromolecules 2013, 46,
140.
[
[
10] Y. Meng, D. Gu, F. Q. Zhang, Y. F. Shi, H. F. Yang, Z. Li, C. Z.
Yu, B. Tu, D. Y. Zhao, Angew. Chem. Int. Ed. 2005, 44, 7053;
Angew. Chem. 2005, 117, 7215.
11] D. Y. Zhao, J. L. Feng, Q. S. Huo, N. Melosh, G. H. Fredrickson,
B. F. Chmelka, G. D. Stucky, Science 1998, 279, 548.
Received: December 12, 2015
Revised: February 28, 2016
Published online: && &&, &&&&
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 7
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Heterogeneous Catalysis
The phenol cut: A novel method allows
the synthesis of bimetallic PtCo nano-
particles (ca.1.5 nm) which are highly
dispersed in the framework of nitrogen-
doped ordered mesoporous carbon
(NOMC). The resulting PtCo-NOMC
shows high catalytic activity for hydro-
deoxygenation of phenolic compounds
and “real-world” biomass-derived phe-
nolic streams.
G.-H. Wang, Z. Cao, D. Gu, N. Pfꢁnder,
A.-C. Swertz, B. Spliethoff, H.-J. Bongard,
C. Weidenthaler, W. Schmidt, R. Rinaldi,
F. Schꢂth*
&&&& — &&&&
Nitrogen-Doped Ordered Mesoporous
Carbon Supported Bimetallic PtCo
Nanoparticles for Upgrading of
Biophenolics
Angew. Chem. Int. Ed. 2016, 55, 1 – 7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7
These are not the final page numbers!