Applied Catalysis A: General 439–440 (2012) 111–124

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Hydrodeoxygenation of guaiacol over carbon-supported molybdenum nitride

catalysts: Effects of nitriding methods and support properties
I. Tyrone Ghampson a,b , Catherine Sepúlveda c , Rafael Garcia c , Ljubisa R. Radovic d,e , J.L. García Fierro f ,
William J. DeSisto a,g,∗ , Nestor Escalona c,∗∗
a
Department of Chemical and Biological Engineering, University of Maine, Orono, ME 04469, United States
b
Unidad de Desarrollo Tecnológico, Universidad de Concepcićn, Casilla 4051, Concepcićn, Chile
c
Universidad de Concepćion, Facultad de Ciencias Quimicas, Casilla 160c, Concepcićn, Chile
d
Penn State University, University Park, PA 16802, United States
e
Universidad de Concepcićn, Facultad de Ingenieria, Dept. Ing. Quimica, Concepcićn, Chile
f
Instituto de Catalisis y Petroquimica, CSIC, Cantoblanco, 28049 Madrid, Spain
g
Forest Bioproducts Research Institute, University of Maine, Orono, ME 04469, United States

a r t i c l e i n f o a b s t r a c t

Article history: Molybdenum nitride catalysts supported on activated carbon materials with different textural and chem-
Received 25 April 2012 ical properties were synthesized by nitriding supported Mo oxide precursors with gaseous NH3 or N2 /H2
Received in revised form 25 June 2012 mixtures using a temperature-programmed reaction. The supports and catalysts were characterized by
Accepted 28 June 2012
N2 physisorption, XRD, chemical analysis, TPD, FT-IR and XPS. Guaiacol (2-methoxyphenol) hydrodeoxy-
Available online 5 July 2012
genation (HDO) activities at 5 MPa and 300 ◦ C were evaluated in a batch autoclave reactor. Molybdenum
nitrides prepared using a N2 /H2 mixture resulted in more highly dispersed catalysts, and consequently
Keywords:
more active catalysts, relative to those prepared using ammonolysis. The HDO activity was also related to
Hydrodeoxygenation
Guaiacol
pore size distribution and the concentration of oxygen-containing surface groups of the different carbon
Activated carbon supports. Increased mesoporosity is argued to have facilitated the access to active sites while increased
Mo2 N catalysts surface acidity enhanced their catalytic activity through modification of their electronic properties. The
highest activity was thus attributed to the highest dispersion of the unsaturated catalyst species and the
highest support mesoporosity. Surprisingly, addition of Co did not improve the HDO activity.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction prevention of coke formation/catalyst deactivation and (ii) selec-

Due to long-term economic and environmental concerns, bio-oil
derived from pyrolysis of woody biomass has received consider-
able attention as an alternative renewable feedstock to crude oil
for the production of fuels and value-added chemicals [1]. Its uti-
lization as fuel is limited, however, by high viscosity, low heating
value, incomplete volatility and thermal instability, which stem
from the relative abundance of oxygenated organic compounds
[2]. Catalytic hydrodeoxygenation (HDO) reactions are typically
performed to refine bio-oil and increase its quality as transporta-
tion fuel. There are two significant challenges in this process: (i)
∗ Corresponding author at: Department of Chemical and Biological Engineering,
University of Maine, Orono, ME 04469, United States. Tel.: +1 207 581 2291;
fax: +1 207 581 2323.
∗∗ Corresponding author at: Tel.: +56 41 2207236; fax: +56 41 2245374.
E-mail addresses: WDeSisto@umche.maine.edu (W.J. DeSisto),
nescalona@udec.cl (N. Escalona).
tive removal of oxygen without excessive hydrogenation of
aromatic and olefinic compounds [2,3].
Model compounds have been used to mimic HDO studies of
bio-oil components in an effort to understand the role and fate of
different functional groups present in the feed, as well as provide
additional insight into the development of improved catalysts and
processes [3]. Guaiacol (2-methoxyphenol) is commonly used as a
model compound for HDO studies to represent the large number
of mono- and dimethoxy phenols present in bio-oil [4]; it is known
to be a precursor to catechol but it also subsequently forms coke
[5,6]. Also, guaiacol possesses two different oxygenated functional
groups ( OCH3 and OH) which make it challenging to achieve
complete deoxygenation [7].
Heterogeneous catalysts commonly studied for HDO of guaia-
col (and many other model compounds) are conventional sulfided
Co(Ni)Mo/␥-Al2 O3 [5,8] and supported noble metal catalysts such
as Ru, Rh and Pd [9,10]. The initial interest in the metal sulfides
was driven by high cost and lack of selective HDO activity of
the noble metal catalysts. Despite the high catalytic activity for

0926-860X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2012.06.047
112 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
guaiacol conversion, there are some drawbacks associated with
these sulfide catalysts: (i) The alumina support can be unstable in
water at processing conditions. (ii) The sulfide catalyst can oxi-
dize under processing conditions, requiring in situ regeneration
with a sulfiding agent to prolong catalyst activity; this regenera-
tion can contaminate products [5,6,11,12]. (iii) The acidic nature
of the alumina support is known to be the cause of substantial
coke deposition and rapid catalyst deactivation [13]. These draw-
backs prompted interest in less acidic materials such as silica [14],
zirconia [9,15] and activated carbon [16,17] as catalyst supports.
Centeno et al. [14] reported that despite the lower activity of
metal sulfides supported on silica and carbon compared with con-
ventional alumina-supported counterparts, the use of alternative
supports led to negligible coke formation. Furthermore, studies
involving carbon- and zirconia-supported catalysts indicated direct
elimination of the methoxy group which favored direct production
of phenol from guaiacol [14,18]. Particularly, based on their supe-
rior performance in hydrodesulfurization processes, carbons are
known to be promising supports for the HDO of bio-oil [19–21].
Interest in carbon supports has increased mainly due to its
remarkable flexibility and the ability to recover active metal after
catalyst deactivation [20]. For HDO reactions, such deactivation in
the presence of water could be limited due to the hydrophobic char-
acter of the carbon surface [22]. On the other hand, the weaker
interaction between the support surface and the active metal may
result in a lower dispersion of the sulfide phase [14,20]. The car-
bon surface can be ‘decorated’ with oxygen functionalities; this
improves catalytic activity by facilitating a higher dispersion of the
active phase [23,24]. For example, oxidative treatments with HNO3
modified the carbon surface chemistry and promoted the formation
of small, well-dispersed crystals of the molybdenum precursor on
the support [21,25] although this led to lower phenol yields during
guaiacol HDO [23]. Additional studies further confirmed that HDO
chemistry can be controlled by modifying the surface chemistry of
the carbon support and consequently the dispersion of the catalyst
[16,22]. This adds to the potential use of carbon-supported systems
in rational catalyst design [17,19].
A wide variety of active phases – metals [4,9,10,26], transition
metal phosphides [7] and transition metal nitrides [27] – have been
employed for HDO reactions in order to obviate the need to add sul-
fur to the feed. In particular, transition metal nitrides show great
potential as catalysts due to their ceramic-like physical properties
coupled with chemical properties resembling platinum-group met-
als [28]. These materials are also responsible for unique catalytic
pathways, leading to desirable product selectivities [28,29]. Con-
sequently, they offer a cheaper and more selective alternative to
noble-metal catalysts such as Ru, Pd and Pt. Our previous study
showed high activities and a high phenol/catechol ratio for bulk
molybdenum nitride catalysts in the HDO of guaiacol [30]. How-
ever, supported catalysts are preferred in commercial applications
for mechanical and morphological stability. The addition of Co as a
promoter is known to improve the activity of bulk and supported
Mo2 N catalysts for HDS and HDN reactions [31,32]. Furthermore,
Co-promoted MoS2 catalysts have been reported to exhibit sig-
nificantly higher HDO activity compared to non-promoted MoS2
catalysts for HDO of guaiacol [8]. Although addition of Co improved
the yield of deoxygenated products, the overall activity was not
enhanced compared to the monometallic nitride [30]. This moti-
vated us to investigate also the effect of Co promoters on the
catalytic properties of supported nitrides in HDO reactions.
Here we report on the behavior of molybdenum nitrides
dispersed on four different activated carbon supports. The
supports were both microporous/mesoporous and meso-
porous/macroporous carbons. The catalysts were synthesized
by impregnation of an aqueous salt and its subsequent conver-
sion to the nitride; thermal conversion was achieved by either
ammonolysis or reduction/nitridation using a N2 /H2 mixture.
The effects of the synthesis procedure, support properties and the
addition of Co as a promoter on the HDO of guaiacol were examined
in terms of catalytic activity and phenol/catechol selectivity.
2. Experimental
2.1. Preparation of catalysts
Four commercial activated carbons (Norit Americas, Inc.) were
used as supports: NORIT GAC 1240 Plus (0.42–2.00 mm particle
size, SBET = 976 m2 g−1 , total pore volume = 0.56 cm3 g−1 ), NORIT
GCA 1240 Plus (0.42–1.70 mm, 1132 m2 g−1 , 0.51 cm3 g−1 ), Darco
MRX (0.60–2.00 mm, 613 m2 g−1 , 0.62 cm3 g−1 ), and NORIT CGran
(0.50–1.70 mm, 1402 m2 g−1 , 1.15 cm3 g−1 ). Prior to their use, the
activated carbon materials were treated with 1 M HNO3 at 90 ◦ C
for 6 h. The solution was then filtered and extensively washed with
distilled water to bring the pH to ca. 7. The samples were dried
overnight under vacuum at 120 ◦ C. The supported molybdenum
oxide precursors were prepared by incipient wetness impregnation
using aqueous solutions of ammonium heptamolybdate (Fischer,
AHM, (NH4 )6 Mo7 O24 ·4H2 O, A.C.S. grade). After the impregnation,
the samples were kept at room temperature for 24 h, followed
by drying overnight at 110 ◦ C. The bimetallic oxide precursors
were prepared by sequential impregnation: Mo-loaded samples
were first prepared using the same drying–calcination procedure
described above; these samples were then impregnated with aque-
ous solution of cobalt (II) nitrate hexahydrate (Acros Organics,
Co(NO3 )2 ·6H2 O, 99%) and kept overnight at room temperature fol-
lowed by drying overnight at 110 ◦ C. The supported oxides were
prepared to obtain a nominal loading of 10 wt% Mo for monometal-
lic samples and 10 wt% Mo plus 2.4 wt% Co for the bimetallic
samples. All oxide precursors were sieved to obtain 180–450 ␮m
particle size range.
Molybdenum nitrides were prepared by loading a 10 mm i.d.
quartz reactor tube with 2.5 g of the oxidic precursor, while pass-
ing ammonia (Matheson Tri-Gas, NH3 , 99.99%) or a N2 /H2 mixture
(N2 : BOC Gases, Grade 5; H2 : Matheson Tri-Gas, 99.99%) over the
sample [33,34]. The reactor was initially purged with nitrogen for
30 min and switched to NH3 (300 mL min−1 ) or a N2 /H2 mixture
(300 mL min−1 , N2 /H2 = 5/1 (v/v)). The temperature was linearly
increased from ambient temperature to 300 ◦ C within 30 min
(9.33 ◦ C min−1 ), then from 300 to 500 ◦ C at 0.6 ◦ C min−1 , and from
500 to 700 ◦ C at 2 ◦ C min−1 . The temperature was maintained at
700 ◦ C for 2 h. The nitrides prepared using NH3 were cooled to room
temperature using the same flow rate of NH3 while the nitrides
prepared using the N2 /H2 mixture were cooled in 300 mL min−1 of
N2 . The materials were then passivated in 1% O2 /N2 (BOC Gases,
UHP grade) for 12 h to avoid oxidation upon exposure to air. The
preparation condition was adopted after careful review of the lit-
erature in addition to previous results to ascertain the optimal
condition for unsupported molybdenum nitrides [30]. Preparation
of nitride catalysts using NH3 and N2 /H2 is referred to as method
1 and method 2, respectively. For notation, Mo nitrides prepared
using method 1 have suffix “A”, while suffix “NH” implies method 2:
e.g., MoN/Darco-A and MoN/Darco-NH are Darco activated carbon-
supported Mo nitride catalysts prepared using NH3 and N2 /H2 ,
respectively.
Molybdenum, cobalt and nitrogen contents in the catalysts were
performed by Galbraith Laboratories using ICP-AES for the metals
and a combustion method for nitrogen.
2.2. Nitrogen porosimetry
Nitrogen adsorption/desorption isotherms were obtained at
77 K using a Micromeritics ASAP-2020 instrument to evaluate the
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
porous structure of the support and catalyst samples. Prior to
the measurements, the samples were outgassed under vacuum
at 200 ◦ C for 12 h. The isotherms were collected within a broad
relative pressure range, 10−6 < P/P0 < 0.995, and using a low pres-
sure incremental dosing (3 cm3 g−1 STP) in order to obtain an
adequate characterization of the micropore region. The isotherms
were used to calculate the BET specific surface area (SBET ), total
pore volume (TPV), average pore diameter (dpore ), and micropore
volume (V ). SBET was obtained from the adsorption branch in
the range 0.04 ≤ P/P0 ≤ 0.14 and TPV was recorded at P/P0 = 0.995.
Average pore diameters were calculated from the equation dpore =
2 · TPV/SBET , assuming slit-shaped pores. The pore size distribu-
tions (PSD) for 0.4–100 nm were determined from the adsorption
branch of the isotherm using the nonlocal density functional theory
(NLDFT) method [35,36]. Micropore volume was calculated from
the NLDFT cumulative volume of pores whose size was below 2 nm.
2.3. X-ray diffraction
Wide-angle X-ray diffraction (XRD) patterns of powdered sam-
ples were obtained using a PANalytical X’Pert Pro diffractometer
equipped with a graphite monochromator and Cu K␣ radiation
(45 kV, 40 mA) in a parallel beam optical geometry. The standard
scan parameters were 15–85◦ 2 with a step size of 0.02◦ and a
counting time of 10 s per step. Identification of the phases was
achieved by reference to the JCPDS data files.
2.4. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectra of reduced catalysts were obtained
on a VG Escalab 200R electron spectrometer using a Mg K␣
(1253.6 eV) photon source. The samples were pre-reduced ex situ
with H2 at 450 ◦ C for 6 h. After reduction, the samples were cooled
to room temperature, flushed with nitrogen and stored in flasks
containing isooctane (Merck, 99.8%), then transferred to the pre-
treatment chamber of the spectrometer. The binding energies (BE)
were referenced to the C 1s level of the carbon support at 284.9 eV.
An estimated error of ±0.1 eV can be assumed for all measurements.
Intensities of the peaks were calculated from the respective peak
areas after background subtraction and spectrum fitting by a com-
bination of Gaussian/Lorentzian functions. Relative surface atomic
ratios were calculated from
(SMo 3d /fMo 3d )
(Mo/C)atomic ratio = ; (Co/C)atomic ratio
(SC 1s /fC 1s )
(SCo 2p /fCo 2p ) (SN 1s /fN 1s )
= ; (N/C)atomic ratio =
(SC 1s /fC 1s ) (SC 1s /fC 1s )
where S is the corresponding peak areas and f is the respective
tabulated sensitivity factor [37] and the factor for the device. The
atomic ratios were calculated at a precision of 7%.
2.5. Temperature-programmed decomposition–mass
spectroscopy (TPD–MS)
TPD analyses of the carbon supports were carried out in an
in-house apparatus which consisted of a U-shaped quartz tube
micro-reactor, placed inside a programmable electrical furnace.
The TPD profiles of CO, CO2 and H2 O were obtained from room
temperature to 1040 ◦ C, at 10 ◦ C min−1 under helium (AGA Chile,
99.995%) flow of 50 mL min−1 . Evolution of desorbed gases was
monitored by a thermal conductivity detector (TCD). In addition,
to quantify the gases produced during thermal decomposition of
the surface functionalities, TPD was coupled with mass spectrom-
etry (Altamira AMI-200 R-HP instrument equipped with a SRS
RGA-300 mass spectrometer). About 0.2 g of the activated carbon
113
sample was first pretreated at 100 ◦ C for 4 h in He (50 mL min−1 ) to
remove most of the weakly adsorbed water, and cooled to room
temperature in He. The pretreated sample was then heated in
a flow of He (50 mL min−1 ) from room temperature to 800 ◦ C at
10 ◦ C min−1 .
2.6. Fourier transform-infrared transmission (FT-IR) spectroscopy
FT-IR analyses of the supports were performed on a Nicolet
Nexus FTIR in the wavenumber range (4000–400 cm−1 ) and with a
scan of 64. The samples were prepared using a 1:100 mg of activated
carbon and KBr support.
2.7. Acidity measurements
Acid site concentrations and acid strength measurements of the
supports and selected catalysts were determined using a potentio-
metric method [38], whereby a suspension in acetonitrile (Merck,
99.9%) was titrated with n-butylamine (Merck, 99%). The varia-
tion in electric potential was registered on a Denver Instrument
UltraBasic pH/mV meter.
2.8. Reaction characterization
Reactivity studies were performed in a 300 mL stirred-batch
autoclave set-up (Parr Model 4841) at 300 ◦ C and under a hydrogen
pressure of 5 MPa. Prior to catalyst testing, the passivated samples
were activated ex situ under H2 (AGA Chile, 99.99%) at a flow rate
of 60 mL min−1 and 450 ◦ C for 6 h, conditions that were shown in
previous studies to maximize HDO conversion [27]. Approximately
0.25 g of freshly pre-treated catalyst was added to the reactor
charged with 80 mL of decalin (Merck, 99%), 2.53 mL of guaiacol
(0.232 mol L−1 , Merck, 99.5%), and 700 ␮L of hexadecane (Merck,
99%). Hexadecane was used as an internal standard for quanti-
tative GC analysis. The sealed reactor was flushed with nitrogen
(AGA Chile, Grade 5) for 30 min to evacuate air from the system.
While continuously stirring the mixture, the reactor was heated to
300 ◦ C under N2 . Once the reaction temperature was attained, N2
was replaced with H2 and then pressurized to 5 MPa. This pressure
was maintained for the entire duration of the experiment by adding
H2 to the reactor whenever necessary. Liquid samples were peri-
odically withdrawn during the course of the reaction after purging
the sampling line by withdrawing a small amount of the reactant
mixture. The samples were analyzed by a Perkin Elmer (Clarus
400) gas chromatograph equipped with a flame ionization detector
(FID) and a CP-Sil 5 CB column (Agilent, 30 m × 0.53 mm × 1.0 ␮m
film thickness). The injector and FID were held at 275 and 180 ◦ C,
respectively. (The GC oven program consisted of an initial isother-
mal operation at 30 ◦ C for 6 min, followed by heating to 70 ◦ C at
30 ◦ C min−1 with an isotherm of 22 min, and a subsequent ramp
to 275 ◦ C at 30 ◦ C min−1 .) The product distributions were identified
by their column retention time in comparison with available stan-
dards. The initial concentration of guaiacol was taken as 100% in
order to ignore slight conversion before isothermal condition was
achieved. The catalytic activity was expressed as the initial reaction
rate, calculated from the slope of the conversion vs. time plot, as
well as by the intrinsic activity (in moles of guaiacol consumed per
mole of Mo per second). A number of repeated runs under the same
conditions were performed to ensure satisfactory reproducibility of
the data. The uncertainty in the calculation of reaction rates from
the GC peaks is 3%. The phenol/catechol ratios were determined at
10% conversion of guaiacol.
The stability of selected nitride catalysts during the HDO reac-
tion was compared to that of a commercial reference catalyst
in a stainless steel continuous-flow micro-reactor. In a typi-
cal experiment, approximately 0.2 g of catalyst was diluted 1:1
114 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
Fig. 1. Pore size distribution of HNO3 treated activated carbon supports.
with SiC (Soviquim, Chile) and loaded into the reactor tube,
while the remaining reactor space was packed with SiC. Prior to
the reaction, the nitride catalyst was reduced in situ using the
same pretreatment conditions employed for the batch reaction,
while the commercial Ni–Mo/Al2 O3 catalyst (Procatalyse, HR 346,
SBET = 256 m2 g−1 ) was sulfided in situ using a 10 vol.% H2 S (AGA
Chile, 99.99%) in H2 , at a flow rate of 67.5 mL min−1 and 350 ◦ C for
3 h. The liquid reactant mixture and hydrogen were connected to
the reactor inlet where they flowed downward through the cata-
lyst bed. The conditions for HDO reactions were as follows: 300 ◦ C,
3 MPa, 5.4 g/h of liquid feed corresponding to liquid hourly space
velocity (LHSV) of 27 h−1 , H2 gas hourly space velocity (GHSV)
of 3600 h−1 , H2 /guaiacol molar ratio of 23. Fresh samples were
collected at an hourly interval for 8–9 h with regular flushing pre-
ceding each collection. The liquid products were then analyzed by
GC–FID.
3. Results and discussion
3.1. Textural properties
The pore size distributions (PSD) for the activated carbons, cal-
culated from the adsorption branch of the isotherm using the NLDFT
method, are shown in Fig. 1. All the support materials have a wide
range of pore sizes, including micropores in the range 0.4–2.0 nm.
However, the results for CGran and Darco supports reveal a pre-
dominance of larger mesopores (up to 100 nm). In contrast, the GCA
and GAC supports are more microporous; the latter also possesses
an appreciable amount of larger mesopores (3–100 nm).
The BET surface areas, total and micropore volumes of supports
and nitride catalysts are presented in Table 1. Significant differ-
ences in these textural parameters among the four supports are
obvious. The CGran and GCA carbons both have higher surface areas
but the latter has a larger fraction of micropores (76 vs. 32%). The
lowest SBET displayed by the Darco support is consistent with this
material having the lowest microporosity (19%) of all the supports.
The porosity of the GAC support is more evenly distributed: 57%
mesoporosity and 43% microporosity.
Oxidation pretreatment of the supports with HNO3 produced
varying changes in the textural properties of the original samples.
In particular, a significant loss of surface area (28%), total pore vol-
ume (25%) and micropore volume (24%) was found for the CGran
activated carbon; this is attributed to an increase in the quantity of
oxygen-containing surface groups on the pore walls and entrances,
making them inaccessible to N2 molecules at 77 K [39]. The pre-
treatment resulted in significantly less micropore volume decrease
in the GAC carbon (5%), corresponding to a 4% loss of surface area; in
contrast, there was an increase in surface area and pore volume for
the Darco and GCA activated carbons, possibly due to the removal
of impurities from the pores. The pore size distributions of the car-
bons were not significantly modified after the treatment, however.
Results summarized in Table 1 also show that impregnation of the
supports with Mo and Mo/Co, followed by thermal conversion to
the nitrides, led to a general decrease in surface area, as well as total
and micropore volume, especially in the case of the CGran support.
These results suggest that nitride formation occurred inside the
porous structure. For the Darco support in particular, they suggest
preferential nitride formation inside the mesopores; conversely, for
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124 115

Table 1
Nitrogen porosimetry results for supports and catalysts.

Sample SBET (m2 g−1 ) dpore (nm) Pore volume (cm3 g−1 )

TPV V

Darcoas-received 612 2.0 0.62 0.12

Darcopretreated 664 2.0 0.68 0.14
MoN/Darco-A 561 2.1 0.58 0.13
MoN/Darco-NH 560 2.1 0.60 0.14
CoMoN/Darco-A 475 2.3 0.54 0.10
CGranas-received 1402 1.6 1.15 0.37
CGranpretreated 1014 1.7 0.86 0.28
MoN/CGran-A 566 1.6 0.46 0.15
MoN/CGran-NH 571 1.6 0.47 0.15
CoMoN/CGran-A 461 1.9 0.44 0.11
GACas-received 976 1.1 0.56 0.32
GACpretreated 942 1.2 0.55 0.31
MoN/GAC-A 775 1.2 0.46 0.25
MoN/GAC-NH 752 1.2 0.45 0.24
CoMoN/GAC-A 706 1.5 0.52 0.21
GCAas-received 1132 0.9 0.51 0.39
GCApretreated 1202 0.9 0.55 0.42
MoN/GCA-A 995 0.9 0.45 0.35
MoN/GCA-NH 1066 0.9 0.49 0.35
CoMoN/GCA-A 950 0.9 0.44 0.33

the CGran support they suggest preferential deposition in microp-
ores or at the entrances to such pores.
3.2. Surface chemical properties of the support
The chemical nature of oxygen functionalities present on the
activated carbon surface after HNO3 treatment was determined
from TPD/MS measurements, as shown in Fig. 2 and summarized
in Table 2: lactonic (190–650 ◦ C) [40–42], carboxylic (200–300 ◦ C)
[41,42], phenolic (600–700 ◦ C) [40,42], carbonyl (800–980 ◦ C)
[40,42], and quinone groups (700–1000 ◦ C) [42,43]. Decomposi-
tion of groups whose carbon atom is bonded to two oxygen atoms
(carboxylic acids, lactones, and carboxylic anhydrides) releases
CO2 , indicative of the presence of strong acidic sites [21,24]. All
the supports exhibited pronounced peaks at low temperatures
(250–400 ◦ C) and thus possessed large amount of acidic CO2 -
desorbing groups, as expected [24]. In the high temperature region,
the GCA, GAC and Darco supports presented broader 515–1000 ◦ C
shoulders, which is indicative of the prevalence of phenolic and
quinone groups. The CGran support exhibited a 415–730 ◦ C peak
which is suggestive of the presence of mostly phenolic groups;
decomposition of these groups, which leads to desorption of CO,
indicates the presence of weakly acidic, neutral and basic groups
whose carbon atom is bonded to one oxygen atom [21,24]. In addi-
tion, integration of the evolved gas TPD profiles shows that CGran
contained the greatest amount of CO2 - and CO-desorbing groups
among the activated carbon supports. Table 2 also shows that the
GCA and Darco carbons had similar quantities of CO2 - and CO-
releasing functional groups. (The H2 O profiles at low temperature,
indicating weakly bound desorbed molecules, were not quantified.)
Furthermore, comparison of TPD/MS results of pretreated and as-
received activated carbon supports (not shown) indicates greater
amounts of CO2 - and CO-desorbing groups in the former. This is
consistent with the well documented effectiveness of oxidative
HNO3 treatment [21]. It should be clarified, however, that if advan-
tage is not taken of the surface oxygen anchoring sites – by making
sure, during catalyst preparation, that there is attraction between
the positively charged support surface and the negatively charged
catalyst precursor, or vice versa – then the only benefit of surface
oxidation can be to render the support more hydrophilic (unless
textural properties are significantly modified).
Fig. 3 shows the FT-IR spectra of the activated carbon sup-
ports. The supports displayed bands in the 3500–3300 cm−1 ,
1600–1500 cm−1 and 1500–1000 cm−1 regions which can be
assigned to anhydrides, quinonic, carboxylic or ether groups,
respectively [44]. There is no apparent difference between the
GCA, GAC and Darco spectra, indicating, in agreement with TPD
results, that they have similar surface oxygenated species. For the

Fig. 2. TPD profiles of the activated carbon supports. Fig. 3. FT-IR spectra of the activated carbon supports.
116 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
Table 2
Surface chemical and acidic properties of oxidized supports.
Support TPD (arbitrary units)
CO2 CO
Darco 12 8 127
CGran 26 29
GAC 16 16
GCA 12 8 61
CGran support, a strong band appears at 1691 cm−1 which can
be assigned to lactonic groups [44], in agreement with the cor-
responding TPD profile; another two bands were detected in the
3124–3037 cm−1 and 2904–2844 cm−1 regions, assigned to aro-
matic and aliphatic groups [44]. By comparing the spectra in Fig. 3,
CGran support displayed the greatest intensity of carboxylic or
ether groups suggesting that it contains the greatest quantity of
surface acidic oxygen groups. This result is consistent with the
interpretation from TPD profiles.
The surface acidity of the supports was estimated from poten-
tiometric titration curves with n-butylamine as the probe molecule.
The results include the maximum acid strength of the surface
sites (derived from the initial electrode potential, E0 ) and the total
number of acid sites normalized by the surface area (acid site
density). The acid strength can be determined according to the cri-
terion proposed by Cid and Pecchi [38]: E0 > 100 mV, very strong
sites; 0 < E0 < 100 mV, strong sites; −100 < E0 < 0 mV, weak sites;
E0 < −100 mV, very weak sites. Accordingly, the results confirm that
the HNO3 -treatment produced strong acid sites on the activated
carbon supports. Table 2 shows that the CGran, Darco and GAC sup-
ports displayed very strong acid sites with E0 > 100 mV, whereas
the GCA carbon displayed strong acid sites with 0 < E0 < 100 mV.
As mentioned, the Darco carbon had the highest acid site density,
while the GAC and CGran carbons had similar densities. The lowest
density of acid sites was measured for the GCA carbon.
3.3. Bulk and surface composition of nitrided catalysts
Bulk molybdenum, cobalt and nitrogen contents of passivated
supported catalysts are listed in Table 3. The nitrogen content is
due to nitride formation and the creation of pyridine- and pyrrole-
like functions during ammonolysis and N2 /H2 treatment [43]. To
distinguish the nitrogen content due to the molybdenum nitride
from those associated with the carbon support, we nitrided blank
support in a manner similar to that used to prepare the sup-
ported Mo and CoMo nitride catalysts, and performed chemical
nitrogen analysis: the results indicate that between 52 and 73% of
the total nitrogen content of the monometallic method 1 samples
were due to contributions from the support’s nitrogen-functional
groups; by comparison, the nitrogen species of the carbon support
accounted for between 27 and 45% of the total nitrogen content
of the monometallic method 2 catalyst; the corresponding sup-
port nitrogen groups for the bimetallic samples ranged 42–90%.
This clearly shows that for the same support the nitrogen contents
were consistently higher for samples prepared via method 1 (A-
series). Ammonolysis was thus more effective than with N2 /H2 . The
measured metal content values, in most part, correspond to theo-
retical values (10 wt% for Mo and 2.4 wt% for Co). However, some
of the catalysts had metal contents lower than the nominal values
which could be attributed to the possible loss of volatile molyb-
dates and cobaltates during the decomposition steps of catalyst
preparation such as drying and nitridation, a phenomenon which
has also been observed by other authors [22,45]. The bulk N/Mo
atomic ratios (due to the nitrogen structure of the molybdenum
nitride and denoted (N/Mo)nitride in Table 3) for the catalysts were
generally higher than the stoichiometric N/Mo ratio for ␥-Mo2 N
Acidity measurements
Acid strength (mV) Total acidity (mequiv. m−2 )
2.3
290 1.5
119 1.6
1.2
(i.e. 0.5) and ␤-Mo2 N0.78 (i.e. 0.39) which suggests nitrogen enrich-
ment, possibly residing in interstitial sites. Table 3 also shows that
the N/Mo ratio was higher for the method 1 samples than method 2
samples; this suggests a higher degree of nitridation of the former.
The surface composition of the reduced and passivated nitride
catalysts was determined by XPS and the results are summarized in
Table 4. The C 1s binding energies consisted of four peaks between
284.8 and 289.2 eV. The peak at 284.8 eV was assigned to C C
and/or C C bonds of aromatic (and aliphatic) carbon [42,46], while
at 286.3 eV it is indicative of C O bonds in phenolic or ether groups
[47,48], or may be due to the presence of C N bonds [49]. The peak
at 287.7 eV is consistent with quinone-type groups or C N species
[49,50], and at 289.3 eV with carboxyl groups and esters [48]. The
relative peak intensities (shown in parentheses) indicate the pre-
dominance of aromatic carbon on the surface of all the catalysts.
The XRD patterns of the GAC-, GCA- and Darco-supported metal
nitrides (see Supplementary data) revealed only peaks due to the
original carbon supports. The absence of Mo nitride diffraction
peaks suggests that the catalysts contained small crystallites of
Mo nitride below the detection limit, or that the broad 0 0 2 and
1 0 bands from the support may have masked the low-intensity
Mo nitride peaks. The XRD results of CGran supported nitrides are
summarized in Fig. 4. The MoN/CGran-NH catalyst displayed the
characteristic peaks for ␤-Mo2 N0.78 (2 = 37.61◦ , 62.53◦ , 75.53◦ )
together with broad features (2 = 26◦ and 43◦ ) associated with the
carbon supports; a barely discernible peak at 2 = 37.41, consistent
with the ␥-Mo2 N (1 1 1) phase, was observed in the MoN/CGran-
A catalyst. Also shown in Fig. 4 is the diffraction pattern for
CoMoN/CGran-A, which indicated the presence of Co3 Mo3 N crys-
tallites (2 = 40.09◦ , 42.59◦ , 46.59◦ ).
XPS results of Mo 3d5/2 , N 1s and Co 2p3/2 species are summa-
rized in Table 4. The binding energies of Mo 3d and N 1s of some
selected catalysts are shown in Fig. 5. The Mo 3d spectra, shown in
Fig. 5(a), presented two spectral lines centered at 232.6 ± 0.3 eV
and 235.7 ± 0.3 eV corresponding to the Mo 3d5/2 and Mo 3d3/2
spin orbits respectively, assigned to Mo(VI) species [51]. This indi-
cates that after the reduction treatment only Mo oxynitrides was
present on the catalyst surface. In the CoMo nitride catalysts the
Fig. 4. XRD patterns of CGran carbon-supported nitrides.
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124 117

Table 3
Chemical analysis of metal nitride catalysts.

Catalyst Elemental composition (wt%) Atomic ratio

Mo Co N (N/Mo)total (N/Mo)nitride

MoN/Darco-A 10.20 – 3.70 2.5 0.8

MoN/Darco-NH 9.57 – 1.59 1.1 0.7
CoMoN/Darco-A 8.53 2.05 4.10 3.3 1.2
MoN/CGran-A 9.62 - 5.58 4.0 1.1
MoN/CGran-NH 10.3 – 1.26 0.8 0.5
CoMoN/CGran-A 10.1 2.87 4.55 3.1 0.3
MoN/GAC-A 7.6 – 2.14 1.9 0.9
MoN/GAC-NH 9.97 – 1.58 1.1 0.8
CoMoN/GAC-A 9.48 1.97 2.35 1.7 0.9
MoN/GCA-A 9.93 – 2.09 1.4 0.7
MoN/GCA-NH 8.79 – 1.16 0.9 0.6
CoMoN/GCA-A 8.44 2.03 2.54 2.1 1.2

Fig. 5. The XPS spectra of the (a) Mo 3d doublet and (b) N 1s in selected catalysts.
118 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124

Table 4
XPS results of reduced-passivated nitride catalysts.

Catalyst Binding energy (eV) (distribution/%) Surface atomic ratio (at.%)

C 1s Mo 3d5/2 N 1s Co 2p3/2 Mo/C Co/C (N/C)T (N/C)nitride a N/Mob

284.8 (72)
286.2 (16) 396.5 (19)
MoN/Darco-A 232.7 – 0.0140 – 0.0506 0.0096 0.7
287.7 (6) 398.4 (55)
289.3 (6) 400.1 (26)

284.8 (73)
286.2 (16) 396.9 (21)
MoN/Darco-NH 232.7 – 0.0159 – 0.0400 0.0084 0.5
287.7 (6) 398.5 (59)
289.3 (5) 400.1 (20)

284.8 (72)
286.2 (16) 396.5 (19)
CoMoN/Darco-A 232.6 781.4 0.0102 0.0061 0.0468 0.0089 0.9
287.7 (6) 398.4 (54)
289.3 (6) 400.1 (27)

284.8 (77)
286.3 (14) 396.8 (7)
MoN/CGran-A 232.8 – 0.0088 – 0.0531 0.0037 0.4
287.7 (5) 398.4 (63)
289.3 (4) 400.1 (30)

284.8 (79)
286.3 (13) 396.9 (12)
MoN/CGran-NH 233.0 – 0.0176 – 0.0529 0.0064 0.4
287.7 (4) 398.6 (55)
289.3 (4) 400.1 (33)

284.8 (80)
286.3 (12) 396.6 (17)
CoMoN/CGran-A 232.7 781.5 0.0182 0.0095 0.0088 0.0015 0.8
287.7 (4) 398.5 (57)
289.2 (4) 400.2 (26)

284.8 (76)
286.3 (16) 396.3 (15)
MoN/GAC-A 232.5 – 0.0128 – 0.0380 0.0057 0.5
287.7 (5) 398.3 (56)
289.2 (3) 399.6 (29)

284.8 (76)
286.3 (15) 396.8 (19)
MoN/GAC-NH 232.5 – 0.0157 – 0.0410 0.0078 0.5
287.7 (5) 398.4 (62)
289.2 (4) 400.1 (19)

284.8 (73)
286.2 (16) 396.3 (38)
CoMoN/GAC-A 232.5 781.3 0.0143 0.0075 0.0485 0.0184 1.3
287.7 (6) 398.3 (40)
289.3 (5) 399.6 (22)

284.8 (77)
286.2 (15) 396.3 (15)
MoN/GCA-A 232.4 – 0.0139 – 0.0436 0.0065 0.5
287.7 (5) 398.3 (56)
289.2 (3) 399.6 (29)

284.8 (76)
286.3 (15) 396.8 (19)
MoN/GCA-NH 232.5 – 0.0146 – 0.0379 0.0072 0.5
287.7 (5) 398.4 (62)
289.2 (4) 400.1 (19)

284.8 (72)
286.2 (17) 396.3 (38)
CoMoN/GCA-A 232.5 781.5 0.0104 0.0045 0.0421 0.0160 1.5
287.7 (6) 398.3 (40)
289.2 (5) 399.6 (22)
a
Calculated by multiplying the distribution of N 1s in the region of 396.3–396.9 eV to the total N/C atomic ratios.
b
N/Mo = (N/C)nitride /(Mo/C).

Co 2p3/2 binding energy was 781.4 eV; BE characteristic of Co(II)
species is normally observed at 781.8 eV [52], showing a decrease
in positive Co2+ charge, indicating partial replacement of oxygen
with a less electronegative nitrogen forming oxynitrides [53]. The
result confirms that despite reduction of the passivated catalyst at
450 ◦ C, its surface is mainly an oxynitride rather than a nitride. The
absence of nitride species on the external surface is attributed to a
higher concentration of oxygenated functionalities on the support
surface (as a result of the HNO3 -pretreatment): negatively charged
heptamolybdate units interact more strongly with the positively
charged carbon surfaces which may have inhibited the formation
of fully nitrided groups during nitridation. In contrast to these
results, XRD analyses showed detectable nitride amounts on the
CGran support, suggesting that nitride forms inside the pores of
the support rather than on the external surface of the supported
catalyst particles. This could be related to the heterogeneity in the
distribution of oxygenated functionalities of the carbon support
during HNO3 -treatment. Due to diffusional effects the amount of
oxygen groups inside the pores is expected to be less than those
at the exterior [25]; consequently, the inner pores of the sup-
port are less positively charged and thus adsorbed less strongly to
the heptamolybdate anion, leading to relatively easier decomposi-
tion and transformation of the precursor to nitride. This proposal
goes further by demonstrating that the decrease in support textu-
ral parameters after impregnation and thermal conversion shows
that the XRD-detected Mo2 N, Mo2 N0.78 and Co3 Mo3 N species were
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
present on internal surfaces of the particles. Thus, the results imply
difference in composition between internal and external surfaces
of the carbon support.
The XPS peaks in the N 1s region shown in Fig. 5(b) and pre-
sented in Table 4, 398.3 ± 0.1, 399.6 and 400.1 eV, are ascribed to
pyridine, amide and pyrrolic groups created at the edges of the
graphene layers by nitridation [47,54]. The component at ∼396.5 eV
is attributed to N 1s in the Mo N bond [55], confirming the presence
of molybdenum oxynitrides. The relative abundance of each nitro-
gen species of the catalysts indicates that monometallic catalysts
prepared via method 2 contained more N species associated with
the Mo N bonds than catalysts prepared via method 1; the result
suggests that the effectiveness of surface molybdenum oxynitride
formation was related to the nitridation method. At the same time
higher total abundance of nitrogen-functional groups of the carbon
support was obtained for the method 1 samples, compared to the
method 2 samples. This result qualitatively agrees with the bulk
nitrogen content analysis in Table 3, confirming that ammonia is
more effective at nitriding the carbon support.
The atomic Mo/C, N/C and Co/C ratios are also listed in Table 4.
The XPS atomic ratios, estimated from intensity ratios of particle
related peaks and support related peaks, have a strong dependence
on catalyst dispersion, and can qualitatively be used to compare
the dispersion of supported catalysts [56]. The differences in Mo/C
ratios are indicative of dispersion differences when the catalysts are
prepared under different conditions. Thus, for example, the cata-
lysts prepared via method 2 (NH series) displayed higher Mo/C ratio
than those prepared via method 1 (A-series). It can be concluded
from Table 4 that the thermal conversion of the oxide catalyst
precursor using N2 /H2 mixture led to more highly dispersed Mo
oxynitride particles. We can make a hypothesis on the basis of the
information from the bulk and surface concentration of nitrogen
moieties on the carbon support. Nitridation reduces the quantity of
surface oxygen groups and simultaneously increases the nitrogen
functional groups; it has been confirmed that ammonolysis is more
effective than N2 /H2 mixture for the nitridation of carbon supports.
Consequently, the greater quantity of negatively charged surface
nitrogen species in the method 1 samples would induce a greater
degree of partial distribution of molybdenum oxynitrides towards
the interior of the catalyst. The N/C atomic ratio, which expresses
the dispersion of the total nitrogen species (including nitrogen from
oxynitride and nitrogen from organic species) on the carbon sup-
port surface, did not follow any observable trend; these results are
less informative in relation to the degree of dispersion of the molyb-
denum oxynitride phase due to contributions from surface nitrogen
species on the carbon support. However, the N/C atomic ratio per-
taining to the molybdenum oxynitride species can be elucidated
by multiplying the total N/C atomic ratio by the percent distribu-
tion, denoted as (N/C)nitride and shown in Table 4. Except for the
samples supported on Darco carbon, (N/C)nitride atomic ratios for
monometallic samples are higher for method 2 samples than for
method 1 samples. This result indicates the nitridation method is
an essential factor in the control of the relative dispersion of molyb-
denum oxynitride species for carbon supported nitrides. The Co/C
ratio did not follow any observable trend.
The surface N/Mo atomic ratio was evaluated from the XPS Mo/C
and (N/C)nitride atomic ratios and is summarized in Table 4. The
calculated values were close to the stoichiometric N/Mo value of ␥-
Mo2 N and ␤-Mo2 N0.78 . However, because XPS results indicated the
presence of only molybdenum oxynitride, this observation is prob-
ably due to excess nitrogen residing in defect sites like irregular
grain boundary surfaces. Moreover, the N/Mo atomic ratio was sim-
ilar to each other suggesting that the method of nitridation and the
surface chemistry of the support had no observable control on the
surface Mo oxynitride species formed. This infers that the nature
of the nitrogen deficient sites was the same for all the catalysts.
119
Fig. 6. Surface N/Mo atomic ratio (from XPS) vs. bulk N/Mo atomic ratio (from
chemical analysis) of the carbon-supported catalysts.
A plot of the surface N/Mo atomic ratio (calculated from XPS) vs.
bulk N/Mo atomic ratio (calculated from chemical analysis) after
subtracting nitrogen content on the carbon support is shown in
Fig. 6, and clearly indicates that for monometallic catalysts the bulk
remained enriched with nitrogen relative to the surface compo-
sition. This result suggests that molybdenum nitrides/oxynitrides
with higher nitrogen deficiencies were located in the interior of the
catalysts, in line with the interpretation derived from XRD and XPS.
In contrast, the CoMo nitride catalysts, except for CoMoN/CGran-A
catalyst, had higher nitrogen concentration on the external surface
than in the bulk; this result is not yet clear.
The textural and chemical surface properties of the support
could also influence Mo dispersion as demonstrated abundantly in
the literature [24]. Indeed, the highest dispersion displayed by the
MoN/CGran-NH catalyst is attributed to the fact that this support
has the most abundant oxygen surface groups (most hydrophilic
character) and the highest mesoporosity; this facilitates access of
the aqueous solution to the internal pore structure and allows a
homogenous radial distribution of the metal precursor within the
particles of the support [23]. Conversely, the lowest dispersion of
the MoN/GCA-NH catalyst is attributed to the lowest concentra-
tion of oxygen surface groups (most hydrophobic character) as well
as the predominance of micropores in the support. Furthermore,
the intermediate dispersion of the MoN/GAC-NH catalyst corre-
lates with this solid possessing intermediate surface chemical and
textural property. It is important to remark that the presence of
oxygen functional groups can render the support surface negatively
charged over a wide range of pH condition, causing electrostatic
repulsions between the support and the heptamolybdate anion
[25]. This can result in metal particles aggregation, leading to less
surface Mo atoms as evident by the low Mo/C atomic ratio of the
MoN/CGran-A catalyst.
3.4. Catalytic activity
The conversion of guaiacol and the evolution of reaction prod-
ucts are illustrated in Figs. 7 and 8. Periodic samplings of the
liquid mixture in the reactor were analyzed by GC, from which the
concentration of the reactant and the product yields were deter-
mined relative to the hexadecane standard. The observed products
were similar for all the catalysts and include phenol, catechol,
120 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124

Fig. 7. Variation of the transformation of guaiacol and the yield of products with time with (a) MoN/GCA-A, (b) MoN/GCA-NH, (c) CoMoN/GCA-A, (d) MoN/GAC-A (e)
MoN/GAC-NH, and (f) CoMoN/GAC-A catalysts.

deoxygenated compounds (such as cyclohexene, cyclohexane and
benzene), and heavy compounds (such as mono- to tetra-methyl
phenols and dimethyl catechols). Other possible products, such as
anisole, m- and o-cresol were not observed. Furthermore, CGran-
and GAC-supported catalysts produced very small quantities of
methylcatechol which were attributed to the higher total acidi-
ties of these catalysts. Fig. 7 illustrates similarities in the product
distribution for the GCA-supported Mo nitride catalysts (Fig. 7(a)
and (b)) and the GAC-supported Mo nitride catalysts (Fig. 7(d)
and (e)): guaiacol was mainly converted to phenol, while cate-
chol and the deoxygenated compounds were observed in smaller
quantities. Heavy compounds were formed in significant amount
and are attributed to the methylation of the aromatic ring [57].
The production of heavy compounds was even more prominent in
the CoMo nitride catalysts supported on GCA and GCA, as seen in
Fig. 7(c) and (d), respectively. By comparison, the CGran-supported
catalysts exhibited some slight differences in the products distri-
bution at higher conversion, as shown in Fig. 8(a)–(c): phenol was
found to be the dominant product over the MoN/CGran-NH cata-
lyst while heavy products and phenol were the main competing
products formed in almost equal amounts with the MoN/CGran-A
and CoMoN/CGran-A catalysts. As seen in Fig. 8(d)–(f), the Darco-
supported catalysts showed similar behavior in the evolution of
products. The product evolution observed indicates that guaiacol
HDO followed the reaction scheme proposed by Bui et al. [57]
shown in Fig. 9. The two general pathways are: (i) initial demethy-
lation (DME) to form catechol, followed by dehydroxylation to form
phenol; or (ii) direct demethoxylation (DMO) to form phenol. (Light
products such as methane and methanol could not be separated
by the column used under batch conditions, but they are expected
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124 121

Fig. 8. Variation of the transformation of guaiacol and the yield of products with time with (a) MoN/CGran-A, (b) MoN/CGran-NH, (c) CoMoN/CGran-A, (d) MoN/Darco-A, (e)
MoN/Darco-NH, and (f) CoMoN/Darco-A catalysts.

byproducts of DME and DMO, respectively.) Further deoxygenation Table 5

Catalytic activities of carbon-supported Mo nitride catalysts.
of phenol produces benzene, cyclohexene and cyclohexane, while
methyl-substitution of catechol forms methylcatechol. Continuous Catalyst Activity Intrinsic activity
production of catechol at longer reaction times indicated that the (×106 mol g−1
catalyst
s−1 ) (×104 molec. Mo at−1 s−1 )
conversion of catechol to phenol was not prominent although both MoN/Darco-A 6.4 60.5
demethylation and direct demethoxylation occurred over these MoN/Darco-NH 6.5 65.1
catalysts. The same tendency was observed for bulk metal nitrides CoMoN/Darco-A 6.2 69.6
MoN/CGran-A 4.6 46.3
[30].
MoN/CGran-NH 9.0 83.6
Table 5 summarizes the catalytic activities. The initial reaction CoMoN/CGran-A 5.3 49.9
rates calculated from the slopes of the guaiacol conversion curves MoN/GAC-A 5.9 74.1
are given in Fig. 10. Negligible conversions were obtained using MoN/GAC-NH 7.9 75.6
the bare supports (not shown), indicating that the activities were CoMoN/GAC-A 2.9 33.1
MoN/GCA-A 6.8 65.8
associated with the Mo oxynitride and not the support. Thus, the
MoN/GCA-NH 7.5 81.8
surface oxygen functional groups of the activated carbon did not CoMoN/GCA-A 5.4 61.2
participate in the conversion of guaiacol; however, the interaction
122 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124
Fig. 9. Hydrodeoxygenation pathway of guaiacol.
Adapted from Bui et al. [57].
between the metal precursor compound and the surface groups of
the support promotes good dispersion, leading to enhanced activ-
ities. This is supported by the observed higher activities compared
to our previous results for non-modified carbon supported Mo2 N
catalysts [27]. The reaction rate was not related to the surface N/Mo
atomic ratio, as a consequence of the catalysts possessing the same
nature of surface nitrogen deficient sites discussed previously in
regard to the reported XPS N/Mo ratio data. However, the reported
activities were affected by the method of nitridation: the cata-
lysts prepared by method 2 (NH series) had consistently higher
activities. This is related to their higher Mo oxynitride dispersion
(illustrated in Fig. 11), confirmed by the Mo/C and (N/C)nitride atomic
ratio in Table 4. The method 2 catalysts contained a greater number
of active sites associated with molybdenum oxynitride, leading to
higher activities. Correlation of HDO activity with dispersion has
similarly been reported for sulfided Co–Mo/carbon and reduced
Fig. 10. Reaction rates of carbon-supported Mo nitride catalysts.
Ni–W/carbon catalysts [22,23]. The higher HDO activity for method
2 catalysts coupled with the reported advantages in the large-scale
synthesis of Mo nitride using a N2 /H2 mixture as a reactant over the
NH3 synthesis makes method 2 attractive for potential industrial
application [34]; thus, for example, the N2 and H2 reactants can be
economically recycled by drying, and their use simplifies handling
procedures as well as eliminate heat transfer problems associated
with endothermic decomposition of NH3 [34].
Other trends can be observed in Fig. 10 when the catalysts
prepared using the same method but dispersed on different sup-
ports are considered. The specific activity of the method 2 catalysts
(NH series) decreased in the order: MoN/CGran-NH > MoN/GAC-
NH > MoN/GCA-NH > MoN/Darco-NH. Thus HDO activity appears
to be favored by a combination of higher Mo dispersion and
higher support mesoporosity (MoN/Darco-NH being the excep-
tion): the highest Mo oxynitride dispersion and the easiest
reactant accessibility to the support’s mesoporous structure led
Fig. 11. Reaction rates vs. XPS Mo/C atomic ratio.
 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124 123

to the highest HDO activity of the MoN/CGran-NH catalyst.

The reaction rates of the method 1 catalysts (A-series) corre-
late with Mo oxynitride dispersion and decrease in the order:
MoN/GCA-A > MoN/GAC-A > MoN/Darco > MoN/CGran-A. Some of
the Darco-supported catalysts exhibited inferior activity, compared
to GCA-supported catalysts, despite their higher dispersion and
higher mesoporosity. This surprising behavior could be due to an
overestimation of the Mo signal obtained by XPS. Considering that
the Darco support possessed the lowest surface area of all the sup-
ports, and that all the catalysts were impregnated with a similar Mo
content, this catalyst should contain the largest Mo nitride particle
sizes. However, their measured Mo/C atomic surface ratios were
higher probably due to the inability of X-ray photons to penetrate
larger Mo nitride particles, leading to a higher intensity of the Mo
3d XPS signal and thus an overestimation of the Mo/C atomic sur- Fig. 12. Phenol/catechol ratio calculated at 10% guaiacol conversion.
face ratios. Similar behavior was previously observed by Lagos et al.
[58]. Therefore, the low activity of Mo nitride catalysts supported
nature of reduced passivated supported catalysts is inevitably
on Darco carbon was probably due to the loss of active sites through
different due to the elimination of the weakly adsorbed NHx species
the formation of agglomerates.
by passivation; thus, we infer that the surface of the carbon-
The intrinsic activities based on the Mo content are also given
supported Mo nitride catalysts expose coordinately unsaturated
in Table 5. The trends were similar to the total reaction rates.
Mo atoms and 4-fold type nitrogen deficient sites. Hypothesis can
Figs. 10 and 11 also show that the addition of Co did not increase the
be made that coordinately unsaturated Mo atoms are responsible
activity of the catalysts. In fact, GCA- and GAC-supported CoMoN
for demethoxylation (Caromatic OCH3 bond cleavage) and dehy-
catalysts were not nearly as active as their MoN counterparts. In
droxylation while demethylation (Cmethyl O bond cleavage) occurs
our previous, it was shown that addition of Co did not enhance the
at nitrogen deficient sites. This hypothesis is analogous to the
activity of unsupported Mo nitride catalyst [30]. This was attributed
distinction between sites for sulfide catalysts reported by Fer-
to incomplete formation of the bimetallic nitride, Co3 Mo3 N, phase.
rari et al. [60]. All the catalysts displayed high phenol production
The same interpretation applies to supported catalysts as well.
and this cannot be related directly to the surface acidic proper-
Unlike bimetallic sulfides and oxides, the formation of single-phase
ties of the carbon supports; recently, Sepulveda et al. [61] showed
bimetallic nitride is not trivial and often exists in multiple phases.
that strong acid sites favor catechol formation. The preference
Synthesis of pure-phase bimetallic nitride catalysts (Co3 Mo3 N and
for the demethoxylation pathway (Caromatic OCH3 bond cleavage)
Ni2 Mo3 N) and its HDO catalysis are warranted. Moreover, the sur-
suggests that unsaturated Mo sites were predominant in the cata-
face Mo/Co atomic ratio (from XPS analysis) is higher than the bulk
lyst. However, these high phenol/catechol ratios were significantly
Mo/Co atomic ratio (from metal content analysis), indicating that
lower than those observed for unsupported nitride catalysts [30],
cobalt is preferentially deposited in the interior of the support and
suggesting that the active sites on nitrides and/or oxynitrides were
are possibly trapped underneath molybdenum. This can be taken to
modified by the support, rendering them less selective for the
suggest that during impregnation cobalt migrated into the interior
demethoxylation route compared to the unsupported catalysts.
of the catalyst and caused the partial migration of molybdenum
This confirms that the generation of oxygen groups on the carbon
towards the exterior, in good agreement with the results obtained
surface has an indirect contribution on phenol/catechol selectivity
by Ferrari et al. [17]. This inhomogeneity in the distribution of cobalt
through the precursor/support interaction, modifying the nature of
could explain the diminishing influence on activity after Co incor-
the active sites and their selectivity. For example, N atoms present
poration: a higher concentration of surface Co species could create
on the surface of bulk Mo nitride catalysts may not be there on sup-
new (or modify) active sites which could enhance activity; con-
ported catalysts due to the metal nitride–support interaction and
versely, a large proportion of Co in the pores will not only hinder
this can have an overall effect on the phenol/catechol ratio and the
their accessibility but may also limit reactant diffusion into other
amount of deoxygenated products. Fig. 12 does not reveal any clear
catalytic active sites located in the internal surfaces of the support
tendencies in the phenol/catechol ratio, suggesting that the extent
which will negatively affect reaction rates. However, a more exten-
and manner of the effect of the surface chemistry of the support,
sive analysis of promoter effect (utilizing different Co precursors
dictated by the surface oxygen groups, is unclear. Therefore, this
and preparative methods such as sequential vs. co-impregnation)
warrants additional research.
on activity requires further investigation.
The selectivity results are summarized in Fig. 12. In con-
trast to metal hydrogenation catalysts like Ru [4], metal sulfide
and metal nitride hydrotreating catalysts have a higher selectiv-
ity for HDO reactions relative to hydrogenation of aromatic and
olefinic compounds [8,30]. During conversion of guaiacol over
Mo nitride/carbon catalysts, both demethylation and demethoxy-
lation reactions take place only at the active sites situated on
the metal nitrides due to the inertness of the carbon support.
Blank experiments with all the supports resulted in negligi-
ble conversion, suggesting that the physicochemical differences
of the carbon supports had no direct influence on the product
selectivity. The dual-pathway behavior of the Mo2 N/carbon cat-
alytic system provides evidence that two kinds of active sites
are present on these catalysts. Theoretical studies reveal that the
surface of fresh bulk Mo2 N consists of coordinately unsaturated Fig. 13. Time-on-stream behavior of the MoN/GAC-NH catalysts in terms of total
Mo and N atoms, and 4-fold type vacancies [59]. The surface conversion for HDO of guaiacol at 300 ◦ C, 3 MPa H2 pressure, H2 /guaiacol ratio of 23.
124 I.T. Ghampson et al. / Applied Catalysis A: General 439–440 (2012) 111–124

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