encapsulation of molybdenum carbide nanoclusters inside
TRANSCRIPT
1
Supporting Information
Encapsulation of molybdenum carbide nanoclusters inside zeolite micropores
enables synergistic bifunctional catalysis for anisole hydrodeoxygenation
Takayuki Iida1,2
, Manish Shetty2, Karthick Murugappan
2, Zhenshu Wang
2, Koji Ohara
3,
Toru Wakihara1*
, and Yuriy Román-Leshkov2*
1) Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan
2) Department of Chemical Engineering, Massachusetts Institute of Technology, 25
Ames Street, Cambridge, Massachusetts 02139, United States of America
3) Japan Synchrotron Radiation Research Institute/SPring-8, Kouto 1-1-1, Sayo-gun,
Hyogo 679-5198, Japan
*Corresponding Author: [email protected], [email protected];
Phone: Prof. Yuriy Román-Leshkov (+1) 617-253-7090, Prof. Toru Wakihara (+81)
3-5841-7368
2
Contents
1. Experimental methods
2. Evaluation of the effect of external and internal mass transfer
Table S1 Values of parameters relevant to the calculation of Mears' criterion for
estimating the external mass-transfer limitation for MoCx/FAU catalysts
Table S2 Values of parameters relevant to the calculation of Weisz-Prater criterion
for estimating the internal mass-transfer limitation for MoCx/FAU catalysts
Table S3 Textural properties of various catalysts
Table S4 Acid and metal site concentration calculated by NH3-TPD and CO
chemisorption
Figure S1 Powder XRD patterns of zeolite and carbide catalysts used in this work
Figure S2 Ziman-Faber Total Structure Factor, S(Q), used for the calculation of pair
distribution functions, G(r)
Figure S3 Assignment of the correlation peaks in Mo2C made using the PDFgui
software.
Figure S4 d-PDF results and the theoretical pair distribution functions, G(r), of
various molybdenum compounds
3
Figure S5 Mo3d XPS results for Mo6+
/FAU, MoCx/FAU and Mo2C
Figure S6 Comparison of the theoretical PDF results for α-MoC1-x and Mo2C (hcp
and orthorhombic) phases calculated using the PDFgui software.
Figure S7 N2 adsorption desorption isotherms of various catalysts
Figure S8 Selectivity time profile of MoCx/FAU catalyst
Figure S9 Selectivity time profile of Mo2C catalyst
Figure S10 Selectivity time profile of FAU catalyst
Figure S11 Selectivity time profile of Mo2C+FAU catalyst
Figure S12 TEM image of MoCx/FAU catalyst after reaction
Figure S13 Conversion time profile of MoCx/FAU catalyst at reduced loading and
regeneration of the deactivated catalyst by hydrogen treatment
References
4
1. Experimental methods
1.1 Reagents
The feed, anisole (99%, Sigma–Aldrich), was used without further purification. H2
(99.999%), CH4 (99.999%), CH4/H2 mixed gas (15% CH4/H2 balance), Ar/He mixed
gas (1% Ar/He balance), NH3 (anhydrous), and air (dry grade) were purchased from
Airgas. Ammonium heptamolybdate tetrahydrate ((NH4)6Mo7O24∙4H2O, 99.5 wt%) was
purchased from Alfa Aesar. Silicon carbide, (SiC 46 grit, Sigma–Aldrich) was used as
an inert diluent for all reactions. FAU zeolites (CBV720, Zeolyst) was used as
purchased.
1.2 Synthesis of the catalysts
The synthesis of MoCx/FAU was performed as follows. Solid state ion exchange of
Mo6+
into zeolite framework was performed by impregnation, first dissolving
(NH4)6Mo7O24∙4H2O into deionized water, adding the zeolite into the transparent
solution, and drying the slurry at 100˚C in an oven. After physical mixing in the mortar,
the dried solid was calcined at 600˚C for 10 h under dry air flow (100 mL/min) to
facilitate the solid-state ion-exchange. The Mo/Al ratio was fixed to 0.5. For
carburization to prepare the samples for structure characterizations, the ion-exchanged
5
zeolite was treated at 700˚C for 3 h under 25 ml/min CH4 and 140 ml/min H2 after
ramping to the designated temperature at 2 K/min heating rates in a quartz tube furnace.
After cooling to room temperature, the carburized product was passivated with 1 vol%
O2/N2 for 2 h. For preparing the MoCx/FAU in-situ inside the reactor for catalytic test
runs, the catalysts were treated at 700˚C for 3 h under 15 ml/min CH4 and 85 ml/min H2,
and were subjected to 85 ml/min H2 flow for an extra hour under at 700˚C to scavenge
the residual coke. The reactor was cooled to the reaction temperature (250˚C; 523 K)
after 165 min, and the catalysts were used directly for reactions without any exposure to
air.
Mo2C catalyst was prepared by carburization of (NH4)6Mo7O24 4H2O at 650˚C for 3 h
under identical gas flow conditions and passivation treatment procedures. Mo2C+FAU,
the control catalyst containing identical metal and Brønsted acid content with
MoCx/FAU, was obtained by physical mixing of the thus obtained Mo2C and parent
FAU zeolite in a mortar. Before the reaction, the catalysts were also treated at 700◦C
following the identical conditions that is used for the carburization pretreatment of
MoCx/FAU.
6
1.3 Catalyst characterization
Powder X-ray diffraction (XRD) patterns were collected using Bruker D8
diffractometer with Nickel-filtered Cu Ka radiation (λ = 1.5418 Å) for a 2θ range of 5°–
70°. N2 physisorption and CO chemisorption measurements were carried out on
Quantachrome Autosorb iQ automated gas sorption system. For physisorption analysis,
all samples were degassed under vacuum prior to use (350°C, 12 h) and the
measurement was conducted at liquid nitrogen temperature (-196°C). For CO
chemisorption, ex-situ carburization of the ion-exchanged zeolite or Mo2C nanoparticle
was performed at 700°C under 15% CH4/ 85% H2 mixed gas flow inside the 9 mm flow
chemisorption cell for 3 h, and an extra hour under H2 flow at 700°C, following the
carburization conditions used for pretreatment before running catalytic reactions. The
pretreated catalysts were further treated at 400°C under H2 flow for 2 h inside the gas
sorption system before the CO chemisorption measurement, which was performed at
40°C. Ammonia temperature programmed desorption (NH3-TPD) measurement was
conducted in a quartz U-tube setup connected to a mass spectrometer (MS, Hiden
Analytical HPR-20/QIC). Before NH3 dosing, an ex-situ carburization pretreatment was
performed under identical conditions. NH3 was dosed at 100°C until the breakthrough
curve was confirmed in the MS. NH3 desorption was performed at 10 K/min heat ramp
7
ratio under 1% Ar/99% He mixed gas flow. The signal at M/Z = 40, assigned to Ar, was
used as reference to account for the possible background shifts in the MS. Acid site
quantification was performed by calculating the area of the h-line peak. The
transmission electron microscopy images were acquired using JEOL 2010 FEG
Analytical Electron Microscope. The X-ray photoelectron spectroscopy (XPS)
measurements were carried out on JEOL JPS-9000 instrument by using MgKα radiation,
and calibration was performed using C1s binding energy = 284.8 eV (assigned to
adventitious carbon). Coke quantification of the spent catalyst was performed with a
thermogravimetric analysis (TGA; Instruments Q500 analyzer).
The high-energy X-ray Total Scattering (HEXTS) measurements were performed on
powder sample in a quartz capillary at room temperature using a horizontal two-axis
diffractometer at the BL04B2 high-energy X-ray diffraction beamline (SPring-8, Japan).
The energy of incident X-rays was 61.43 keV (λ = 0.2018 Å). The maximum Q (Q = 4π
sin θ / λ), Qmax, collected in this study was 20 Å−1
. The obtained data were subjected to
well-established analysis procedures, such as absorption, background, and Compton
scattering corrections, and subsequently normalized to give a Faber–Ziman total
structure factor S(Q)1,2. These collected data were used to calculate the pair distribution
function, G(r), using the following function:
8
𝐺(𝑟) = 4π𝑟[𝜌(𝑟) − 𝜌0] =2
π∫ 𝑄[𝑆(𝑄) − 1] sin(𝑄𝑟) d𝑄,
𝑄max
𝑄min
where ρ is the atomic number density.
For the calculation of differential pair distribution functions (d-PDFs), pair
distribution function, G(r), of the parent zeolite was normalized based on that of the
molybdenum carbide encapsulated zeolite by the height at the T-O (T = Si, Al)
correlation at (r = 1.61 Å), and the calculation was performed using the following
equations.
𝐺A+B(𝑟) ≅ 𝑥A𝐺A(𝑟) + 𝑥B𝐺B(𝑟) ⋯ (𝑆1)
𝑥A𝐺A(𝑟) ≅ 𝐺A+B(𝑟) − 𝑥B𝐺B(𝑟) ⋯ (𝑆2)′
In the strict sense, the coefficients 𝑥A and 𝑥B in equation (S1) is a function of 𝑟 since
the scattering factor is a function of 𝑟 in case of X-ray experiments, and thereby,
subtraction error can occur in the d-PDF because of this effect. In this work, after
approximating the error size at larger 𝑟 values where no signal should be present (r ~10
Å), only the qualitative discussion of the observable peaks in the d-PDF was argued.
The theoretical PDFs were calculated using PDFgui software3, and information
regarding the crystal structures of the Mo compounds were taken from the following
literatures; Mo(bcc) 4, Mo2C(hcp)
5, Mo2C(orthorhombic)
6, MoO2
7, and MoO3
8. The
crystal structure of α-MoC1-x (fcc) was made using the lattice parameter (4.28 Å)
9
reported in a previous literature9.
1.4 Catalyst activity measurement and product analysis
Catalytic activity and stability experiments were carried out in a vapor-phase
packed-bed down-flow reactor. The reactor consisted of a stainless-steel tube (0.95 cm
OD) with wall thickness (0.089 cm) mounted in a single-zone furnace (Applied Test
Systems, Series 3210, 850W/115V). The temperature was controlled by a temperature
controller (Digi-Sense, model 68900-10) connected to a K-type thermocouple (Omega,
model TJ36-CAXL-116u) mounted downstream in direct contact with the catalyst bed.
The catalyst (pellet size between 250 ~ 500 μm) was mixed with SiC (total 2 g) and
packed between two inert layers of SiC (1 g each) and kept in the middle of the furnace.
Before the reaction, in-situ carburization treatment was performed for all of the
catalysts to ensure a direct comparison between the catalysts. The furnace temperature
was then reduced to the reaction temperature (250ºC; 523 K) by 3 K min-1
.
Next, anisole was delivered into the reactor via a capillary tube connected to a syringe
pump (Harvard Apparatus, model 703005) at an injection rate of 150 μl/ h, and mixed
with H2 gas (70 ml/min) at the inlet of the reactor. The reactor effluent lines were heated
to 523 K to prevent any condensation of effluents. The effluents were analyzed and
10
quantified via an online gas chromatographer (GC) equipped with a mass selective
detector for identification (MSD, Agilent Technologies, model 5975 C) and a flame
ionization detector for quantification (FID, Agilent Technologies, model 7890 A). The
GC was fitted with a DB-5 column (Agilent, 30 m 0.25 mm ID 0.25 lm). The GC
parameters used for analysis are as follows: detector temperature 573 K, injector
temperature 548 K, split ratio 1:20. The initial oven temperatures was 308 K, increased
to 523 K at a ramping rate of 15 K/min, and finally increased to 543 K at a ramping rate
of 20 K/min.
For the analysis of the light gas C5- products, sampling of the effluent was performed
with a gas bag, and the sampled gas was injected into GC-FID (GC: GC-2014,
Shimadzu, Column: Aglient HP-plot Al2O3 S(19091P-S33)) for quantification. The GC
parameters used for analysis are as follows: detector temperature 453 K, injector
temperature 453 K, split ratio 1:20. After 2 min of hold time at 308 K (initial oven
temperature), the oven was heated to 433 K with a ramp rate of 10 K min-1
.
The following definitions were used to quantify experimental data:
Conversion [%] = moles of carbon of reactant consumed
moles of carbon of reactant fed × 100
Selectivity to hydrocarbons [%] = moles of carbon of hydrocarbons in product
moles of carbon of reactant consumed × 100
11
For all of the catalytic runs used in this work, the mass balances were near 100%. The
data points during the transient period (i.e., TOS before 92 min) where the mass balance
does not close (mass balance below 90%) were not used for the calculation of
conversion and selectivity.
12
2. Evaluation of the effect of external and internal mass transfer
2.1 Calculation of Mears’ Criterion
Mears’ criterion10
, as shown in Eq. (S1), was estimated to confirm the absence of
any external mass-transfer limitations10
.
−𝑟𝑜𝑏𝑠 × 𝜌𝑏 × 𝑅 × 𝑛
𝑘𝑐 × 𝐶𝑏< 0.15 (S1)
In this equation, −𝑟𝑜𝑏𝑠 represents the observed reaction rate for anisole conversion in
mol kg cat-1
s-1
¸ 𝜌𝑏 represents the catalyst bed density in kg m-3
, 𝑅 represents the
catalyst pellet size in m, 𝑛 represents the reaction order, 𝑘𝑐 represents the
mass-transfer coefficient in m s-1
, and 𝐶𝑏 represents the bulk concentration of anisole
at the reaction temperature (250°C; 523 K), in mol m-3
. The Reynold’s number for the
flow around the catalyst pellet is given by 𝑅𝑒 = 2U × R × ρ/µ, where U represents the
superficial velocity in m s-1
, R represents the catalyst pellet radius in m, ρ represents
the density in kg m-3
, and µ represents the viscosity in kg m-1
s-1
, of the reactant
mixture. Sherwood number ( 𝑆ℎ = 𝑘𝑐 ×2R
D= 2 ) was used to extrapolate the
mass-transfer coefficient since the Reynold’s number << 1, where D represents the
diffusivity of the reactant (anisole) mixture in m2 s
-1. Table S1 tabulates all the relevant
parameters for the calculation of MoCx/FAU catalyst. The reaction is a mixture of
(trans)alkylation and hydrogenation, and thereby the reaction order is expected to be
13
between zero and one with respect to the substrate (anisole)11-12
. Thus, the satisfaction
of the criterion for 𝑛 = 1 was made, to over-estimate the left-side of the inequality in
Eq. S1. If the criterion is satisfied for 𝑛 = 1 , it should be satisfied for any
fractional-order reaction.
The absence of external mass-transfer limitations is confirmed from Mears’ criterion
shown in Table S1 (8.6 × 10-4
<< 0.15).
14
2.2 Calculation of Weisz-Prater Criterion
Weisz-Prater criterion10
, as shown in Eq. (S2), was estimated to confirm the
absence of any internal mass-transfer limitations.
𝐶𝑊𝑃 =−𝑟𝑜𝑏𝑠 × 𝜌𝑐 × 𝑅2
𝐷𝑒 × 𝐶𝑠 ≪ 1 (S2)
In this equation, −𝑟𝑜𝑏𝑠 represents the observed reaction rate for anisole conversion in
mol kg cat-1
s-1
¸ 𝜌𝑐 represents the catalyst density in kg m-3
, 𝑅 represents the catalyst
particle radius in m, 𝐷𝑒 represents the effective diffusivity (inside the zeolite
micropores) in m2 s
-1, and 𝐶𝑠 represents the surface anisole concentration at the
reaction temperature (250°C; 523 K), in mol m-3
. The calculated 𝐶𝑊𝑃 is found to be
1.7 × 10-2
for MoCx/FAU. Since 𝐶𝑊𝑃 ≪ 1, the reaction is not internal mass-transfer
limiting10
. The effective diffusivity of anisole inside the zeolite frameworks was
estimated based on the reported effective diffusivity value of p-xylene inside FAU
zeolite13
, a molecule having similar molecular dimensions with anisole. The effect of
MoCx encapsulation on the diffusivity was calculated based on the previously reported
theory that can account for micropore connectivity blockage14
. Table S2 tabulates all the
relevant parameters for the calculation of MoCx/FAU catalyst.
15
Table S2: Values of parameters relevant to the calculation of Mears' criterion for
estimating the external mass-transfer limitation for MoCx/FAU catalysts.
Parameters relevant for estimation of Mears’
criterion Values
Observed reaction rate: −𝑟𝑜𝑏𝑠(mol kg cat-1
s-1
) 5.0 × 10-4
Catalyst bed density: 𝜌𝑏 (kg m-3
)a 5.1 × 10
2
Pellet radius: 𝑅 (m) 2.1 × 10-4
Reaction order: nb 1
Bulk concentration: 𝐶𝑏(mol m-3
)c 1.8 × 10
-1
Superficial velocity: U (m s-1
) 2.0 × 10-2
Viscosity: µ (kg m-1
s-1
)d 1.3 × 10
-5
Fluid density: ρ (kg m-3
)d 4.7 × 10
-2
Reynold’s number: Re 3.1 × 10-2
Diffusion coefficient: D (m2 s
-1)
e 7.1 × 10
-5
Mass-transfer coefficient: kc (m s-1
)f 3.4 × 10
-1
Mears’ criterion 8.6× 10-4
a: Catalyst bed density estimated by measuring mass of catalyst pellets packed into a known
cylindrical volume.
b: Reaction order considered as 1 for the purpose of this calculation to obtain an upper limit on
the Mears’ criterion.
c: Bulk concentration calculated from ideal gas law.
d: Viscosity taken for H2 gas15, and fluid density calculated from ideal gas law, at 523 K.
e: Diffusion coefficient calculated for anisole-H2 mixture at 523 K using Chapman-Enskog
Theory.15
f: kc calculated from the relation 𝑆ℎ = 𝑘𝑐 ×2R
D= 2. 𝑘𝑐 =
𝐷
𝑅
Table S2: Values of parameters relevant to the calculation of Weisz-Prater criterion for
16
estimating the internal mass-transfer limitation for MoCx/FAU catalyst.
Parameters relevant for Weisz-Prater
criterion
Values
Observed reaction rate: −𝑟𝑜𝑏𝑠(mol kg cat-1
s-1
)
5.0 × 10-4
Catalyst density: 𝜌𝑀𝑜𝐶𝑥/𝐹𝐴𝑈 (kg m-3
)a 1.4 × 10
3
Particle radius: 𝑅 (m) 2.5 × 10-7
Effective diffusivity: 𝐷𝑒 (m2 s
-1)
b 1.3 × 10
-11
Surface concentration: 𝐶𝑠(mol m-3
)c 1.8 × 10
-1
𝐶𝑊𝑃 1.7 × 10-2
a: Density of FAU zeolite calculated based on the framework density (13.3 T atoms/u.c.) and
the density of Mo2C (8900 kg m-3 ) were taken for calculation of the catalyst density.
b: Diffusivity inside the micropore of FAU-type zeolite was estimated using experimental
model provided by Masuda et al. 13, using values for p-xylene, an aromatic having similar
molecular size with anisole.
c: In absence of external mass-transfer limitation, surface concentration is the same as bulk
concentration.
17
Table S3. Textural properties of various catalysts
*Calculated using the t-plot method
Table S4. Acid and metal site concentration calculated by NH3-TPD and CO
chemisorption
All measurements were performed after an ex-situ carburization pretreatment at 700°C
18
Figure S1. Powder XRD patterns of zeolite and carbide catalysts used in this work
19
Figure S2. Ziman-Faber Total Structure Factor, S(Q), used for the calculation of pair
distribution functions, G(r). The total structure factors are offset for clarity.
20
Figure S3. A) Comparison of d-PDF results with the simulated pair distribution function,
G(r), of Mo2C (hcp phase) using PDFgui software3 (identical with Figure 1 C of the
maintext). Correlations corresponding to the Mo2C phase were observed up to r ~7 Å
for MoCx/FAU (shown with black dotted lines), but were not observed at longer
distances (shown with red dotted lines). Correlations that do not match with those of
Mo2C phase assigned to MoOx species are marked with an asterisk (*). B) Assignment
of the correlation peaks in the theoretical PDFs of Mo2C (hcp phase) made using the
PDFgui software. For example, Mo-Mo shows the probability of finding Mo-Mo
distance at a given distance, r. Most correlations visible were found to originate from
Mo-Mo or Mo-C correlations (at 2.0 Å) due to the relatively large X-ray scattering
factor by Mo compared to C.
108642
G(r
)
r [Å]
d-PDF (MoCx/FAU)
d-PDF (Physical mixture,
Mo2C 5 wt%)
Mo2C (Theoretical; hcp)
Mo-CMo-Mo
*
* *
All-All
Mo-Mo
Mo-C
C-C
G(r
)
r [Å]108642
B)
A)
21
Figure S4. d-PDF results and comparison with the theoretical pair distribution functions,
G(r), of various molybdenum compounds. Dotted line corresponds to the correlation
peaks assignable to MoOx (either MoO2 or MoO3). The shaded area in light blue
corresponds to the correlation region to distinguish Mo2C and metallic Mo phase (bcc).
22
Figure S5. Mo3d XPS results for MoCx/FAU, Mo6+
/FAU, and Mo2C
23
Figure S6. Comparison of the theoretical PDF results for α-MoC1-x and Mo2C (hcp and
orthorhombic) phases calculated using the PDFgui software3. The shaded area at r = 5.8
~ 6.2 Å corresponds to the region to compare the presence of α-MoC1-x and Mo2C (hcp
and orthorhombic) phases. Correlations corresponding to Mo2C are shown with dotted
lines, and the correlations assigned to MoOx species are marked with an asterisk(*).
108642
108642
G(r
)
r [Å]
d-PDF (MoCx/FAU)
d-PDF (Physical mixture,
Mo2C 5 wt%)
Mo2C (Theoretical; hcp)
Mo-CMo-Mo
*
* *
Mo2C (Theoretical; hcp)
Mo2C (Theoretical; orthorhombic)
α-MoC1-x (fcc)
G(r
)
r [Å]
B)
A)
24
Figure S7. N2 adsorption desorption isotherms of various catalysts
25
Figure S8. Selectivity time profile of MoCx/FAU catalyst. Reaction conditions: Reaction
temperature: 523 K, anisole feed: 150 μl/h, catalyst loading: 750 mg, pTotal = 1.013 bar,
panisole = 0.0079 bar and balance H2.
0 200 400 600 800 1000 1200
0
20
40
60
80
100
Sel
ectivi
ty [
C-m
ol%
]
TOS [min]
Light Gas C5- Cycloalkanes Alkylated Anisoles Alkylated Phenols Phenol Aromatics C8+ Toluene Benzene
0
20
40
60
80
100
Sele
ctivity [
C-m
ol%
]
MoCx/FAU Mo2C FAU Mo2C+FAU
Light Gas C5-
CycloalkanesAlkylated AnisolesAlkylated Phenols
Phenol
Aromatic C8+
TolueneBenzene
26
Figure S9. Selectivity time profile of Mo2C catalyst. Reaction conditions: Reaction
temperature: 523 K, anisole feed: 150 μl/h, catalyst loading: 322 mg, pTotal = 1.013 bar,
panisole = 0.0079 bar and balance H2.
0 200 400 600 800 1000 1200
0
20
40
60
80
100
Sel
ectivi
ty [
C-m
ol%
]
TOS [min]
Methane Toluene Benzene
27
Figure S10. Selectivity time profile of FAU catalyst. Reaction conditions: Reaction
temperature: 523 K, anisole feed: 150 μl/h, catalyst loading: 600 mg, pTotal = 1.013 bar,
panisole = 0.0079 bar and balance H2.
0 200 400 600 800 1000 1200
0
20
40
60
80
100
Sel
ectivi
ty [
C-m
ol%
]
TOS [min]
Light Gas C5- Cycloalkanes Alkylated anisoles Alkylated Phenols Phenol Aromatics C8+ Toluene Benzene
0
20
40
60
80
100
Sele
ctivity [
C-m
ol%
]
MoCx/FAU Mo2C FAU Mo2C+FAU
Light Gas C5-
CycloalkanesAlkylated AnisolesAlkylated Phenols
Phenol
Aromatic C8+
TolueneBenzene
0
20
40
60
80
100
Sele
ctivity [
C-m
ol%
]
MoCx/FAU Mo2C FAU Mo2C+FAU
Light Gas C5-
CycloalkanesAlkylated AnisolesAlkylated Phenols
Phenol
Aromatic C8+
TolueneBenzene
28
Figure S11. Selectivity time profile of Mo2C+FAU catalyst. Reaction conditions:
Reaction temperature: 523 K, anisole feed: 150 μl/h, catalyst loading: 922 mg, pTotal =
1.013 bar, panisole = 0.0079 bar and balance H2.
0 200 400 600 800 1000 1200
0
20
40
60
80
100
Sel
ectivi
ty [
C-m
ol%
]
TOS [min]
Light Gas C5- Cycloalkanes Alkylated Anisoles Alkylated Phenols Phenol Aromatics C8+ Toluene Benzene
0
20
40
60
80
100
Sele
ctivity [
C-m
ol%
]
MoCx/FAU Mo2C FAU Mo2C+FAU
Light Gas C5-
CycloalkanesAlkylated AnisolesAlkylated Phenols
Phenol
Aromatic C8+
TolueneBenzene
0
20
40
60
80
100
Sele
ctivity [
C-m
ol%
]
MoCx/FAU Mo2C FAU Mo2C+FAU
Light Gas C5-
CycloalkanesAlkylated AnisolesAlkylated Phenols
Phenol
Aromatic C8+
TolueneBenzene
29
Figure S12. TEM image of MoCx/FAU catalyst after reaction.
30
Figure S13. Conversion time profile of MoCx/FAU catalyst at reduced loading and
regeneration of the deactivated catalyst by hydrogen treatment at 773 K for 4 h.
Reaction conditions: Reaction temperature: 523 K, anisole feed: 150 μl/h, catalyst
loading: 250 mg, pTotal = 1.013 bar, panisole = 0.0079 bar and balance H2.
31
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