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: yroman@mit.edu, wakihara@chemsys.t.u-tokyo.ac.jp;

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

References

1. Faber, T. E.; Ziman, J. M., Philosophical Magazine 1965, 11, 153-173.

2. Kohara, S.; Itou, M.; Suzuya, K.; Inamura, Y.; Sakurai, Y.; Ohishi, Y.; Takata,

M., J. Phys.: Condens. Matter 2007, 19, 506101.

3. Farrow, C. L.; Juhas, P.; Liu, J. W.; Bryndin, D.; Bozin, E. S.; Bloch, J.;

Proffen, T.; Billinge, S. J., J. Phys.: Condens. Matter 2007, 19, 335219.

4. Bernuy-Lopez, C.; Allix, M.; Bridges, C. A.; Claridge, J. B.; Rosseinsky, M. J.,

Chem. Mater. 2007, 19, 1035-1043.

5. Wyckoff, R. W. G. In The Structure of Crystals, Reinhold Publishing

Corporation: Camden, N. J., 1935; Vol. 1935.

6. Khaenko, B. V.; Gnitetskii, O. A.; Kublii, V. Z., Dopovidi Akademii Nauk

Ukrains'koi RSR, Seriya A: Fiziko-Tekhnichni ta Matematichni Nauki 1991, 78-82.

7. Seisenbaeva, G. A.; Sundberg, M.; Nygren, M.; Dubrovinsky, L.; Kessler, V.

G., Mater. Chem. Phys. 2004, 87, 142-148.

8. Braekken, H., Zeitschrift fuer Kristallographie, Kristallgeometrie,

Kristallphysik, Kristallchemie (-144,1977) 1931, 78, 484-489.

9. Bouchy, C.; Derouane-Abd Hamid, S.; Derouane, E., Chem. Commun. 2000, 2,

125-126.

10. Fogler, H. S., Essentials of Chemical Reaction Engineering. Prentice Hall:

2011.

11. Zhu, X. L.; Mallinson, R. G.; Resasco, D. E., Appl. Catal. A Gen. 2010, 379,

172-181.

12. Lee, W. S.; Wang, Z. S.; Wu, R. J.; Bhan, A., J. Catal. 2014, 319, 44-53.

13. Masuda, T.; Fukuda, K.; Fujikata, Y.; Ikeda, H.; Hashimoto, K., Chem. Eng.

Sci. 1996, 51, 1879-1888.

14. Mo, T. W.; Wei, J., Chem. Eng. Sci. 1986, 41, 703-710.

15. Bird, R. B.; Stewart, W. E.; Lightfoot, E. N., Transport phenomena. John

Wiley & Sons: 2007.