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Carbon nanofiber-supported ReOx catalysts for

the hydrodeoxygenation of lignin-derived
Cite this: DOI: 10.1039/c5cy01992c
compounds†
I. Tyrone Ghampson,*a Catherine Sepúlveda,b Rafael García,b José L. G. Fierroc and
Néstor Escalona*ad

Received 19th November 2015,
Accepted 26th January 2016
DOI: 10.1039/c5cy01992c
www.rsc.org/catalysis
The effect of ReOx loading (2–13 wt%) and H2 pressure (0–5 MPa) for the hydrodeoxygenation of phenol
has been studied for carbon nanofiber-supported ReOx catalysts in a batch reactor at 573 K. Characteriza-
tion of the supports and catalysts has been obtained from N2 physisorption, TPD, FTIR, XRD, potentiometric
titration, TPR and XPS measurements, which revealed the presence of a crystalline and surface ReOx phase
whose particle size and surface coverage increased with loading. The reactivity of the catalysts was linked
to the in situ partial reduction of ReO3 to form Re4+ and Re6–7+ sites, whose presence and relative amounts
were determined by post-reaction XPS analysis. The reaction rate increased with ReOx loading up to 10
wt%, attributed to the increase in Re surface coverage; a decrease in reaction rate at higher loading was as-
cribed to the formation of aggregates. The study revealed a strong affinity for direct cleavage of the C–O
bond to form benzene. The similar relative abundance of the Re species is responsible for the similar trend
in product distribution of the catalysts. The dependence of activity and product distribution with respect to
H2 pressure has been related to kinetics and thermodynamics. The reactivity of the best catalyst for the
HDO of guaiacol (2-methoxyphenol), anisole (methoxybenzene), phenol and o-cresol (2-methylphenol)
further demonstrated the catalyst's preference for C–O bond scission.

1. Introduction
The need to reduce the overreliance on fossil fuels and reduce
greenhouse gas (GHG) emissions provides an impetus to the
development of renewable energy. The recent interest in lig-
nocellulosic biomass in the literature underscores how bio-
mass has emerged as a viable alternative to conventional
crude oil for the production of hydrocarbon fuels and value-
added chemicals. Among the choices of conversion technolo-
gies, the fast pyrolysis of woody biomass to produce bio-oil
has become an important strategy despite significant barriers
that limit its wide implementation, such as high viscosity, low
stability, corrosivity, low energy content, etc. These deleterious
a
Departamento de Ingeniería Química y Bioprocesos, Escuela de Ingeniería,
Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul,
Santiago, Chile. E-mail: isaactghampson@udec.cl; Fax: +56 41 2245374;
Tel: +56 41 2203353
b
Universidad de Concepción, Facultad de Ciencias Químicas, Casilla 160c,
Concepción, Chile
c
Instituto de Catálisis y Petroleoquímica, CSIC, Cantoblanco, 28049 Madrid,
Spain
d
Facultad de Ciencias Químicas, Pontificia Universidad Católica de Chile,
Santiago, Chile. E-mail: neescalona@ing.puc.cl; Fax: +56 2 3547962;
Tel: +56 2 3547962
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c5cy01992c
properties are associated with the high level of water and oxy-
genated compounds in the feed.1 Hence, it is important to re-
duce the high oxygen content.
Much of the research aimed at addressing this issue has
focused on catalytic hydrodeoxygenation (HDO). There has
been an upsurge in the research on catalyst development in
HDO over the past decade using model compounds, which
has led to several classes of materials being demonstrated to
be capable of catalytically removing oxygen in the liquid, va-
pour and aqueous phases.2 Lignin-derived monomers have
received the most attention in these studies because they
have been identified to be present in significant quantities,
and are among the most recalcitrant compounds, in bio-
oil.3–5 In particular, phenol and substituted phenols such as
guaiacol, anisole and cresol are commonly studied due to
their intransigence to selective deoxygenation and hence are
utilized to probe the reactivities of catalysts and their tenden-
cies in steering the reaction towards either ring hydrogena-
tion or direct deoxygenation.6
Studies on conventional hydrotreating sulfide catalysts were
the initial focus on HDO reactions of lignin-derived com-
pounds and were instrumental in laying the groundwork for
future studies.7–11 Since then, meaningful strides have been
made in several studies detailing the reactivity,5,12 mecha-
nism13 and kinetics.14 A common theme in these studies is

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the good selectivity of sulfide catalysts to aromatic hydrocar-
bons—including benzene, toluene, xylene, ethylbenzene—
which is at the heart of HDO reactions because of the ability
to cleave the carbon–oxygen bond and the prevention of com-
plete saturation of CC bonds. However, the use of sulfide
catalysts is complicated by the addition of a sulfiding agent to
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replenish stripped sulfur active sites, leading to the risk of
contamination of naturally sulfur-free liquid.
There has been significant interest in exploring non-
sulfide catalysts due to the deficiencies of sulfide catalysts.
Noble metals, often used in conjunction with solid acid cata-
lysts (such as HZSM-5, HBEA, SO42−/ZrO2, and Nafion etc.),
have proven extremely effective in HDO reactions of
phenolics.15–23 These studies reported complete conversion
and high deoxygenation of lignin monomers, whereby the no-
ble metals act as hydrogenation catalysts while the acid cata-
lysts are responsible for dehydration. However, although no-
ble metal catalysts boast high activity, several challenges
(their price, rarity, etc.) prevent their widespread use.
Transition metal carbide,24,25 nitride26 and phosphide cat-
alysts27,28 hold promise as a cheaper alternative to noble
metal catalysts. Recent studies have demonstrated their capa-
bilities for catalysing HDO of phenolics to aromatic hydrocar-
bons.29 Many challenges, however, stand in the way of this
less-expensive alternative, the most significant of which are
the severe preparation conditions and their poor stability
during regeneration.
Nickel-based catalysts have recently made inroads into HDO
reactions driven by their high hydrogenation activity and low
cost.30–37 Studies on guaiacol,32,34 phenol,30 anisole,35,36 etc.
have found these catalysts to be highly active and selective to hy-
drogenated products, including cyclohexane, methylcyclohexane,
etc. Recently, similar to bifunctional noble metal-based catalysts,
Ni catalysts have often been paired with acid catalysts such as
HZSM-5 to augment its activity towards saturated hydrocar-
bons.38,39 Nevertheless, the drawbacks of using Ni-based cata-
lysts are their hydrogen inefficiency as a result of their excessive
saturation ability and their questionable stability due to
sintering under HDO conditions.
The results of these studies exemplify the need to improve
the capabilities and performance of these catalysts still further
or explore other classes of catalysts. Reducible transition metal
oxides represent an attractive alternative to the other catalytic
systems. Their reactivity is essentially linked to the partial reduc-
tion of surface metal oxide species under reaction conditions.
Recent studies have demonstrated their adeptness at directly
cleaving C–O bonds in lignin derivatives, an important capabil-
ity due to its potential impact on hydrogen efficiency.40–42 In ad-
dition, metal oxide catalysts can be regenerated by calcination,40
and their emergence renders often costly pre-activation proce-
dures such as sulfidation, reduction, carburization and
phosphidation unnecessary.
In a recent study, ReOx/SiO2 catalyst has displayed high ac-
tivity in the conversion of guaiacol and a high selectivity into ar-
omatic hydrocarbons (benzene, toluene, and xylene, BTX), a
valuable feedstock for downstream petrochemical processing.41
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These intriguing findings provide an incentive and a template
to expand this investigation into evaluating a possible struc-
ture–function relationship which will add insight into the de-
sign of effective catalysts. In this study, a series of carbon nano-
fiber (CNF)-supported ReOx catalysts with different loadings was
synthesized, characterized by N2 physisorption, TPD, FTIR,
XRD, potentiometric titration, TPR and XPS, and tested with
phenol HDO in a batch reactor. CNF was utilized as a support
because it boasts properties not available to conventional
supports (Al2O3, SiO2, etc.), including minimizing the effect of
the support on the active phase which will provide an opportu-
nity to observe the structural effects on catalytic HDO behaviour.
In addition, using a technique such as XPS to assess the struc-
tural changes of metal oxide catalysts occurring during reactions
is significantly easier when supported on CNF than when oxidic
supports are used.43 Carbon nanofiber has received scant atten-
tion in the literature for HDO reaction of phenolics: recent stud-
ies by Jongerius et al.5 and Santillan-Jimenez et al.44 on the
HDO of guaiacol over CNF-supported metal carbides (Mo2C and
W2C) have demonstrated their viability.
The HDO studies of the best ReOx/CNF catalyst was ex-
tended by testing at different H2 pressures for the conversion
of phenol, as well as on a library of model compounds
(guaiacol, anisole, o-cresol and phenol) to further illustrate
the effectiveness of this catalyst for HDO of lignin-derived
compounds.
2. Experimental
2.1. Sample preparation
A pyrolytically-stripped carbon nanofiber (CNF, PR-24-XT-PS,
SBET = 43 m2 g−1, >98% carbon basis) was purchased from
Sigma-Aldrich and treated with HNO3 (65%, Merck) at 363 K
for 16 h under vigorous stirring (10 g of CNF to 500 mL of
acid). Then, the mixture was cooled down to room tempera-
ture, filtered and extensively rinsed with distilled water. The
sample was dried in air at 383 K for 24 h. The oxidized sup-
port is denoted CNFox.
The supported rhenium oxide catalysts were prepared by
wetness impregnation of an aqueous solution with requisite
amounts of ammonium perrhenate (≥99%, NH4ReO4, Sigma-
Aldrich) to obtain a range of ReOx loading (2–13 wt%). After
impregnation, the samples were kept at room temperature
for 24 h, dried at 383 K for 15 h, and then calcined in static
air at 573 K (ramp rate of 2 K min−1) for 0.5 h. The samples
are referred to as yReOx/CNFox, where y indicates the ReOx
loading in wt%.
2.2. Sample characterization
Temperature-programmed decomposition (TPD) analyses of
the as-received and HNO3-treated CNF were carried out in a
U-shaped quartz tube micro-reactor, placed inside a program-
mable electrical furnace. TPD profiles of CO, CO2 and H2O
were obtained from room temperature to 1313 K, at 10 K
min−1 and under a helium flow of 50 mL min−1 (99.995%,
Linde). Evolution of desorbed gases was monitored by using
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Catalysis Science & Technology
a thermal conductivity detector (TCD) coupled to a non-
dispersive infrared device.
Electrophoresis measurement (EM) of the support was car-
ried out using a Zeta-Meter 3.0+ apparatus using 20 mg of
sample suspended in 200 mL of a 1 × 10−3 mol L−1 KCl solu-
tion. The pH was adjusted with either 0.1 mol L−1 HCl or
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KOH solution. The IEP (isoelectric point) was obtained from
the plot of pH vs. zeta potential.
FT-IR analyses of the supports were performed using a Ni-
colet 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 CNF and KBr support.
Acid site concentration and acid strength measurements
of the support were determined using a potentiometric
method,45 whereby a suspension in acetonitrile (99.9%,
Merck) was titrated with n-butylamine (99%, Merck). The vari-
ation in electric potential was registered using a Denver In-
strument UltraBasic pH/mV meter.
The BET specific surface area (SBET) and total pore volume
(Vp) of the samples were obtained from nitrogen sorption iso-
therms at 77 K using a Micromeritics TriStar II 3020 instru-
ment. Prior to the measurements, the samples were degassed
under inert atmosphere at 473 K for 2 h. SBET was calculated
from the adsorption branch in the range 0.05 ≤ P/P 0 ≤ 0.25
and Vp was recorded at P/P 0 = 0.97.
X-ray diffraction (XRD) patterns of the samples were
obtained using a Rigaku diffractometer equipped with Ni-
filtered CuKα1 radiation (λ =1.5418 Å). The standard scan pa-
rameters were 10–90° 2θ with a step size of 0.02° and a
counting time of 0.4 s per step. Identification of the phases
was achieved by reference to the ICDD files using EVA analy-
sis software.
H2-temperature programmed reduction (TPR) of the cal-
cined catalysts was performed in a U-shaped quartz tube
micro-reactor, placed inside a programmable electrical fur-
nace and connected to a TCD detector. The effluent gas was
passed through a cold trap filled with a mixture of iso-
propanol and liquid nitrogen to remove the steam produced
during the reduction before entering the TCD detector. Be-
fore the measurements, the sample (ca. 25 mg) was dried
overnight to remove weakly-adsorbed water molecules. Then,
the sample was heated in flowing 5 vol% H2/Ar (Linde) from
ambient temperature to 1273 K at a heating rate of 10 K
min−1.
X-ray photoelectron spectra of calcined and spent catalysts
were recorded on a VG Escalab 200R electron spectrometer
using a Mg Kα (1253.6 eV) photon source. The spent catalysts
were removed from the reactor, stored in flasks containing
dodecane and 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 284.8
eV. An estimated error of ± 0.1 eV can be assumed for all
measurements. The intensities of the peaks were calculated
from the respective peak areas after background subtraction
and spectrum fitting by the standard computer based statisti-
cal analysis which included fitting the experimental spectra
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to a sum of Gaussian and Lorentzian lines (90G-10L) using a
least squares minimization procedure for χ 2 with the help of
the XPS peak program. Relative surface atomic ratios were de-
termined from the corresponding peak areas, corrected with
tabulated sensitivity factors,46 with a precision of 7%.
2.3. Catalyst testing
The yReOx/CNFox catalysts were evaluated for phenol hydro-
deoxygenation in a 300 mL stirred-batch autoclave set-up
(Parr Model 4841) at 573 K and under a hydrogen pressure of
3 MPa for 4 h. The liquid reactant consisted of 1.8 g of phe-
nol (99%, Merck) and 700 μL of hexadecane (as an internal
standard, 99%, Sigma-Aldrich) dissolved in 80 mL of
dodecane (as solvent, 99%, Merck). The catalysts were dried
in an oven at 383 K to remove physisorbed water prior to cat-
alyst testing. This mixture and 200 mg of catalyst were loaded
into the reactor, purged with a 100 mL min−1 flow of nitrogen
(99.995%, Linde) for 20 min to evacuate air from the system,
heated to 573 K while stirring at 645 rpm, and charged with
hydrogen (99.995%, Linde) to 3 MPa. The start of the reaction
was assumed to be the time when the reaction temperature
was reached and H2 was introduced into the reactor. The re-
action was punctuated by the addition of hydrogen to main-
tain the pressure for the entire duration of the experiment.
Liquid samples were periodically withdrawn during the
course of the reaction and identified by using a Perkin Elmer
GCMS-SQ8T (Clarus 680) gas chromatograph equipped with
an Elite-1 column (Perkin Elmer, 30 m × 0.32 mm, film thick-
ness of 0.25 μm). The liquid samples were also quantified by
using a Perkin Elmer (Clarus 400) gas chromatograph
equipped with a CP-Sil 5 column (Agilent, 30 m × 0.53 mm,
film thickness of 1.0 μm) and a FID. The products were also
identified by their column retention time in comparison with
available standards.
Phenol conversion as a function of H2 pressure of the best
yReOx/CNFox catalyst was also carried out at 573 K and at a
pressure ranging from 0 to 5 MPa following the aforemen-
tioned procedure. The reaction at 0 MPa was conducted in
the absence of hydrogen and under 0.5 MPa of nitrogen.
Finally, the HDO studies of the best yReOx/CNFox catalyst
were extended by testing on lignin model compounds
(guaiacol, anisole, phenol and o-cresol) at 573 K and 5 MPa
H2 pressure for 4 h. The substrates were guaiacol (98%,
Merck), anisole (99%, Merck), and o-cresol (99%, Merck).
About 200 mg of the catalyst was added to the reactor
charged with 0.232 mol L−1 of the substrate dissolved in 80
mL of dodecane and 700 μL of hexadecane.
The conversion of the substrate (XSUB) was calculated from
(eqn (1)):
(1)
where n0substrate is the initial moles of the substrate (typically
phenol) in the solution (mol) and nisubstrate is the moles of the
substrate at time i (mol). The initial reaction rate rs (mol g−1
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s−1) was calculated from the initial slope of the conversion vs.
time plot b (s−1) according to (eqn (2)):
(2)
where m (g) is the mass of the catalyst. The intrinsic rate
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(molecPHEconverted at Re−1 s−1) was calculated using (eqn (3)):
(3)
where MWC is the molar mass of carbon (12 g mol−1); XReO3
is the ReO3 loading (wt%) and (Re/C)XPS is the XPS surface
atomic Re/C ratio (at./at.). The yield of product (Y) was calcu-
lated from (eqn (4)):
(4)
where niproduct j is the moles of product j formed at time i
(mol). The product selectivity was calculated using eqn (5):
(5)
where nproduct j is the moles of product j formed (mol) and
nsubstrate converted is the moles of substrate converted (mol). A
number of repeated runs under the same conditions were
performed to ensure satisfactory reproducibility of the data.
3. Results and discussion
3.1. Support characterization
The carbon nanofiber support was oxidized with concen-
trated HNO3 to decorate the inner and outer areas of the sup-
port with oxygen-containing functional groups.47 In a recent
study, Ni catalysts supported on an as-received carbon nano-
tube (CNT) and an oxidized CNT (CNTox) have been com-
pared, and it was found that the presence of surface oxygen
groups enhanced the hydrogenolysis capacities of the Ni/
CNTox catalyst.48 Since CNT and CNF possess similar physi-
cal and chemical properties,49 we decided to pre-oxidize the
CNF support prior to ReOx impregnation. The methodology
used for the oxidation of CNF has already been reported to
be effective by Tessonnier et al.47
The chemical nature of the oxygen functional groups of
the support was determined by means of TPD profiles shown
in Fig. 1. The untreated CNF displayed a broad peak and a
shoulder at high temperatures (1080–1180 K), while the oxi-
dized CNF displayed broad (1000–1170 K) shoulders. These
peaks typically arise from the decomposition of carbonyl and
quinone groups, which leads to the desorption of CO, indi-
cating the presence of weakly acidic, neutral and basic
groups whose carbon atom is bonded to one oxygen
atom.50–52 In addition to these peaks, the oxidized CNF sup-
port also exhibited a broad 545–670 K peak, which is indica-
tive of the presence of lactonic and carboxylic groups.52,53
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Fig. 1 (a) TPD profiles and (b) FTIR of as-received CNF and nitric acid-
treated CNF.
Decomposition of these groups releases CO2 and is consis-
tent with the presence of strong acid sites.51
The presence of these groups on CNF was supported by
FT-IR analysis of the samples (Fig. 1b). Both the pristine and
the oxidized CNF displayed bands in the 1600–1500 cm−1 re-
gion which correspond to a graphite structure,54 in addition
to bands in the 1500–1000 cm−1 region which can be attrib-
uted to the weak oxidation of CNF as a result of exposure to
ambient conditions.55 The oxidized CNF support also
displayed bands at 1754 and 1042 cm−1, attributed to the
CO and C–O stretching vibration modes, respectively, in
the carboxylic groups. These additional bands confirm that
oxidation introduced oxygen surface groups on the support,
in agreement with deductions from TPD results.
Isoelectric point (IEP) results obtained from electrophore-
sis measurements showed an IEP at pH = 4.2 and 2.5 for the
as-received CNF and the oxidized CNF, respectively, indicative
of surface modification of CNF after oxidative treatment in
accordance with FTIR and TPD results. The lower IEP value
of CNFox can be attributed to an increase in surface acidity
due to the oxidation of the functional groups on the
support.56
The BET surface area and pore volume (Table 1) remained
essentially unchanged after oxidation, implying that textural
properties were not altered after oxidative treatment and that
the oxygen-containing surface groups were mostly introduced
on the surface and not on the pore walls and entrances.
The surface acidity of the supports was estimated from po-
tentiometric 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 acid site density (total number of acid sites nor-
malized by the surface area). The pristine CNF and oxidized
CNF presented weak acid sites (−82 mV) and very strong acid
Table 1 Textural and structural properties of materials under study
Sample ReOx loading (wt%) BET (m2 g−1) Vp (cm3 g−1)
CNF — 42 0.06
CNFox — 45 0.06
2ReOx/CNFox 2 42 0.06
4ReOx/CNFox 4 39 0.06
6ReOx/CNFox 6 39 0.06
8ReOx/CNFox 8 39 0.06
10ReOx/CNFox 10 39 0.06
13ReOx/CNFox 13 39 0.06
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sites (147 mV), respectively, according to the criterion pro- Table 2 XPS data of the calcined catalysts
posed by Cid and Pecchi.57 Additionally, the oxidized CNF Binding energy (eV) Surface atomic
had a higher amount of surface acid (37%). This acidity dif- (distribution/%) ratio (at%)
ference is due to the introduction of surface oxygen groups, Sample C1s Re 4f5/2 O1s O/C Re/C
in line with the findings of Tessonnier et al.47
CNF 284.8 (76)
XRD patterns of the pristine CNF (not shown) and the oxi- 286.3 (18) — 531.8 (37) 0.032 —
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dized CNF (Fig. 2) show no observable differences, indicating 288.1 (6) 533.2 (63)
that the crystalline structure of the carbon material remained CNFox 284.8 (65)
286.3 (23) — 531.6 (41) 0.161 —
unchanged after oxidative treatment. This is not surprising
288.3 (12) 533.1 (59)
considering the similarities of the textural parameters of the 2ReOx/CNFox 284.8 (66)
two samples. The supports showed peaks indexed as 286.3 (25) 45.5 531.6 (38) 0.145 0.0022
graphite-like carbon (ICDD file no. 01-075-0444) and carbon 288.4 (8) 533.1 (62)
4ReOx/CNFox 284.8 (67) 531.1 (26)
(ICDD file no. 01-080-0017). There were some unidentified
286.3 (23) 45.7 532.2 (32) 0.144 0.0042
peaks which are possibly associated with the metal catalyst 288.4 (10) 533.3 (42)
used for the growth of the fibres. 6ReOx/CNFox 284.8 (61) 531.1 (38)
XPS analysis was used to further assess the effect of the 286.3 (26) 45.6 532.3 (23) 0.159 0.0051
288.4 (13) 533.4 (39)
oxidative treatment on the surface of the CNF support. It can 8ReOx/CNFox 284.8 (62) 531.1 (36)
be seen in Table 2 that the C 1s binding energies (BE) of the 286.3 (29) 45.7 532.3 (22) 0.151 0.0061
parent CNF and oxidized CNF consisted of three peaks with 288.5 (9) 533.3 (42)
BEs at 284.8 eV, 286.3 eV and 288.2 eV ± 0.1 eV, and the O 1s 10ReOx/CNFox 284.8 (56) 531.2 (39)
286.3 (29) 45.7 532.4 (24) 0.166 0.0077
peak consisted of two peaks at 531.7 eV ± 0.1 eV and 533.2 eV 288.2 (15) 533.5 (37)
which are all close to the binding energies previously 13ReOx/CNFox 284.8 (57) 531.1 (40)
reported for this type of material:58 the C 1s BE at 284.8 eV 286.3 (30) 45.7 532.3 (24) 0.159 0.0098
represents graphitic carbon, consistent with the XRD data; 288.3 (13) 533.5 (36)
the C 1s peak at 286.3 eV and the O 1s signal at 531.7 eV cor-
respond to the C–O bonds in the phenolic or ether groups;
the C 1s BE at 288.2 eV and the O 1s BE at 533.2 eV are con- IEP and FTIR results that the surface of CNF become
sistent with carboxyl and/or ester groups. The relative peak O-enriched after nitric acid oxidation.
intensities (shown in parentheses) indicate the predomi-
nance of graphitic carbon on the surface of all the samples.
Furthermore, the relative concentration of the C 1s BE corre- 3.2. Characterization of the metal oxide
sponding to carboxyl and/or ester groups doubled after nitric Textural characterization results of the catalysts are summa-
acid oxidation which is consistent with the characterization rized in Table 1. The BET specific surface areas of the cata-
data discussed earlier. The clearest evidence, however, of the lysts ranged from 39 to 42 m2 g−1. The decrease in BET sur-
effect of the oxidation treatment can be found in the XPS O/C face area after impregnation and subsequent calcination was
atomic ratio in Table 2: the oxidized CNF support showed a minimal, indicating that pore blockage was not significant
marked 5-fold increase in O/C atomic ratio compared with and that most of the ReOx nanoparticles are located on the
the pristine CNF, supporting the interpretation from TPD, outer surface of the support.
The XRD patterns of the support and calcined catalysts
are shown in Fig. 2. The patterns of all the catalysts showed
peaks indexed as graphite-like carbon (ICDD file no. 01-075-
0444) and carbon (ICDD file no. 01-080-0017), indicating that
the structural integrity of the CNFox support remained intact
after impregnation of NH4ReO4 and calcination. All the cata-
lysts except the lowest loaded 2ReOx/CNFox catalyst exhibited
diffraction lines corresponding to hexagonal ReO3 crystals
(ICDD card no. 00-040-1155). The absence of ReO3 diffraction
peaks in the 2ReOx/CNFox catalyst suggests that it contains
small crystallites of Re oxide below the detection limit or that
the reflections of CNF may have masked the low-intensity Re
oxide peaks. The catalysts with low Re loading—4ReOx/CNFox
and 6eOx/CNFox—displayed a barely discernible characteristic
peak for ReO3 at 2θ = 16.5°, 30.1° and 34.7°. These peaks be-
came more well defined with increasing loading due to the
formation of an increased amount of ReO3. At high loadings,
Fig. 2 X-ray diffraction patterns of calcined ReOx/CNFox catalysts. new reflections of ReO3 emerged with the most prominent at

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2θ = 25.3°, 34.7°, 40.0°, 50.8° and 52.1°; the appearance of
the reflection at 2θ = 25.3° confirms that the support peak at
2θ = 26.1° masked some of the ReO3 peak at lower loadings.
The average ReOx crystallite size (nm) of the three high-
loaded catalysts was calculated from the Scherrer equation
using the ReOx reflection at 2θ = 16.5°; the crystallite size for
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the catalysts with lower loadings was not calculated because
the peak could not be satisfactorily resolved from the back-
ground. Instrumental contribution to line broadening was
accounted for by measuring a silicon standard (NIST SRM
640e) using an identical optical configuration. The particle
size increased in the order 8ReOx/CNFox (20.5 nm) < 10ReOx/
CNFox (21.7 nm) < 13ReOx/CNFox (24.1 nm), in line with the
well-documented increase in particle size with loading.
The reduction behaviour as a function of ReOx content
was examined by TPR as shown in Fig. 3. The TPR profiles of
CNF-supported ReOx catalysts show mainly two H2 consump-
tion peaks: a peak (I) observed in the 550–590 K temperature
range for all catalysts, except 2ReOx/CNFox, may be assigned
to the reduction of an isolated ReOx crystallite; and a broad
peak (II) observed over the temperature range of 660–830 K
may be attributed to the deep reduction of Re species
Fig. 3 TPR profiles of the calcined ReOx/CNFox catalysts.
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interacting with the CNF support surface. This suggests the
presence of two types of Re species on the catalysts. A frac-
tion of the higher temperature peak could be due to pyrolysis
or gasification of the carbon support to produce CO.59 The
TPR profile of the bare CNFox support show no H2 consump-
tion peak in the temperature range of 550–590 K, suggesting
that peak I observed for the catalysts is associated with the
reduction of ReOx species. However, the CNFox TPR profile
did reveal a broad peak centred at 1060 K attributed to gasifi-
cation of the CNFox support. There are some other notable
observations in the TPR profiles. The relative intensity of
peak I to peak II changed with Re loadings. In fact, the
2ReOx/CNFox catalyst only presented the higher temperature
peak which implies that the majority of the ReOx species
were in close contact with the CNFox support, consistent with
the XRD data in Fig. 2 which indicated that ReOx species in
that catalyst were well dispersed on the support. At higher
ReOx content (≥4 wt%), peak I developed with increasing Re
loading and the reduction maximum slightly shifted to a
higher temperature, indicative of a decrease in reducibility of
rhenium oxide species with increasing Re surface coverage.
This trend is in agreement with BET surface area results
which suggested that the Re species were not confined in the
pore of the support but rather deposited on the surface.
Thus, as the ReOx loading increased, the amount of surface
Re oxide species increased and formed several surface layers
of ReOx clusters,60 which may have limited H2 diffusion to
the ReOx species in the innermost layer and decreased the
reducibility.
The catalysts were analysed by XPS to characterize the sur-
face by monitoring the Re 4f, C 1s and O 1s regions before
and after (phenol HDO at 573 K and 3 MPa H2) reaction. The
binding energies (BE) and atomic ratios for all the calcined
catalysts are listed in Table 2. Fig. 4a shows the Re 4f XPS
spectra of the selected calcined catalysts. The rest of the XPS
spectra can be found in the ESI (Fig. S1†). The C 1s binding
Fig. 4 XPS spectra of selected catalysts in the Re 4f spectral region of
the (a) calcined and (b) spent ReOx/CNFox catalysts.
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energies of the calcined catalysts were identical to those ob-
served for the oxidized CNF support discussed earlier (the
same holds true for the O 1s signals). The Re 4f XPS spectra
of the calcined catalysts display the characteristic 4f doublet
whose spin–orbit splitting (Re 4f7/2 and 4f5/2) is 2.4 eV. Nota-
bly, the Re 4f7/2 component for the calcined catalysts with dif-
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other hand, the binding energies of the second doublet
showed small negative shifts of −0.2 eV to −0.5 eV relative to
the BE of Re6–7+ species in the calcined samples. This de-
crease in positive Re6–7+ charge could be attributed to partial
replacement of oxygen with a less electronegative carbon
from the support to form a Re oxycarbide species. It has been

ferent loadings are nearly identical, which could be attributed previously reported that defective carbon atoms from the
to the weak Re–carbon support interaction in comparison to CNFox support are capable of dissolving into metal and metal
other supports.41 The observed BE at 45.6 eV ± 0.1 eV corre- oxide lattices during reduction.66,67
sponds to Re6–7+ species because it is 0.7 eV higher than the The distribution of rhenium oxidation states derived from
BE normally observed for ReO3 (Re6+) but 1.1 eV less than the XPS spectra of fresh and spent catalysts is shown in pa-
that for Re2O7 (Re7+).61–63 This value was slightly less than rentheses in Tables 2 and 3 and illustrated in Fig. 5. The data
the Re 4f7/2 BE value observed for reference bulk ReOx (46.0 reveal similar relative abundance of Re species, suggesting
eV) which is assigned to ReO4− species.64 On the other hand, that the ReOx/CNFox catalytic sites were not significantly mod-
the same Re6–7+ species was present on the ReOx/SiO2 catalyst ified by an increase in Re loading. A corollary of this observa-
reported by Leiva et al.;41 however, unlike the ReOx/SiO2 cata- tion is that product distribution from phenol conversion is
lyst, only one Re oxide species was present on the surface of anticipated to be similar.
the ReOx/CNFox samples, suggesting that surface oxygen func- The coverage of the support by Re species in the catalyst
tional groups on the CNFox support may have stabilized the was estimated from the measurements of the Re/C intensity
ReOx structure during calcination. ratio in the XPS spectra. The results in Fig. 5 show that Re
The O1s BE of the bulk ReOx sample (not shown) surface coverage increases linearly with ReOx loading for the
appeared at 531.2 eV for lattice Re-O which is close to the BE calcined catalysts, indicating homogeneous distribution of
of 531.7 assigned to phenolic or ether groups of the CNFox rhenium oxide on the CNFox support within the range of
support. Thus, a part of the O 1s BE at 531.1 eV observed for loading used. Fig. 5 also shows that the Re/C atomic ratio of
the ReOx/CNFox catalysts is certainly related to the presence the spent catalyst decreased relative to the corresponding cal-
of Re6–7+ species. The absence of surface and crystalline cined catalyst and the difference became more pronounced
Re2O7 nanoparticles from XRD and XPS analyses is due to the at high loadings, leading to a slight deviation from linearity
volatility of dimeric and polymeric Re2O7 species65 of Re dispersion above 10 wt% ReOx attributed to the forma-
The XPS results of the spent catalysts are summarized in tion of ReOx agglomerates. Thus, in summary, the above re-
Table 3. Similarly, the data show that the observed Re 4f7/2 sults show that although the nature of the active sites on
and 4f5/2 signals are similar in all the catalysts. The most ReOx/CNFox is independent on loading, the amount increases
intense 4f7/2 component of the 4f doublet is located at 42.5 ± almost linearly with loading.
0.1 eV and 45.4 eV ± 0.3 eV: the Re 4f7/2 signal observed at
42.5 eV is assigned to ReIJIV) species of ReO2 (ref. 61 and 62),
indicating partial H2 reduction during the reaction. On the 3.3. Catalytic activity
The reactivity of the ReOx/CNFox catalysts is tested in the
hydrodeoxygenation of lignin-derived phenolic compounds.
Table 3 XPS data of the spent catalysts We firstly delved into the effect of rhenium oxide loading to
determine the possible structure–reactivity relationship for
Binding energy (eV) Surface atomic
(distribution/%) ratio (at%)
Sample C 1s Re 4f5/2 O1s O/C Re/C
2ReOx/CNFox 284.8 (63)
286.2 (28) 42.4 (37) 531.6 (38) 0.121 0.0017
288.5 (9) 45.1 (63) 533.1 (62)
4ReOx/CNFox 284.8 (61) 531.1 (26)
286.2 (26) 42.4 (25) 532.2 (32) 0.133 0.0029
288.6 (13) 45.2 (75) 533.3 (42)
6ReOx/CNFox 284.8 (55) 531.1 (38)
286.2 (33) 42.6 (27) 532.3 (23) 0.156 0.0038
288.5 (12) 45.2 (73) 533.4 (39)
8ReOx/CNFox 284.2 (63) 531.1 (36)
286.3 (26) 42.6 (26) 532.3 (22) 0.109 0.0054
288.5 (11) 45.2 (74) 533.3 (42)
10ReOx/CNFox 284.8 (63) 531.2 (39)
286.2 (26) 42.3 (27) 532.4 (24) 0.114 0.0063
288.4 (11) 45.5 (73) 533.5 (37)
13ReOx/CNFox 284.8 (65) 531.1 (40) Fig. 5 Distribution of rhenium oxidation states and Re/C surface
286.2 (27) 42.6 (22) 532.3 (24) 0.136 0.0073 atomic ratio of fresh and spent ReOx/CNFox catalysts as a function of
288.3 (8) 45.7 (78) 533.5 (36) ReOx loading.

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the conversion of phenol, investigated the impact of hydro-
gen pressure, and compared the reactivity of other phenolic
model compounds.
3.3.1. Effect of ReOx loading. The conversion of phenol
and the evolution of reaction products are shown in Fig. 6.
The concentration of the reactants and the product yields
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were determined relative to the hexadecane standard. The
ReOx/CNFox catalysts displayed similar concentration profiles:
benzene and cyclohexane were the major products, while
cyclohexanol and cyclohexene were the minor products.
These compounds and the undetected cyclohexanone consti-
tute the product stream from phenol conversion over other
catalytic systems as well.30 The reaction pathway during the
conversion of phenol is depicted in Fig. 7,14,31 whereby phe-
nol proceeds through either direct deoxygenation (DDO) of
the C–O σ bond to form benzene or hydrogenation (HYD) of
the aromatic ring to form cyclohexanol. Benzene can then be
saturated to form cyclohexane. On the other hand, cyclo-
hexanol can be dehydrated to form cyclohexene and then a fi-
nal hydrogenation step to form cyclohexane.
The catalytic active sites on reducible metal oxides are
coordinatively unsaturated metal sites (i.e. oxygen vacancies)
and Brønsted acid sites of surface hydroxyls formed during in
situ partial reduction of the surface lattice oxygen of the
metal oxide.42,68,69 The oxygen vacancies are created through
the loss of water via dehydroxylation on terminal sites when
H2 adsorbs on the surface oxygens forming hydroxyl groups.
In effect, the surface hydroxyls are instrumental in the forma-
tion of both the oxygen vacancies and Brønsted acid sites.68
Fig. 6 Conversion of phenol and the yield of products with time over
(a) 2ReOx/CNFox, (b) 4ReOx/CNFox, (c) 6ReOx/CNFox, (d) 8ReOx/CNFox,
(e) 10ReOx/CNFox, and (f) 13ReOx/CNFox catalysts. Reaction conditions:
phenol (1.783 g), yReOx/CNFox (200 mg), dodecane (80 mL), 573 K, 3
MPa H2.
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Fig. 7 Reaction scheme for the conversion of phenol. The figure is
drawn on the basis of the information from ref. 14 and 31.
For the ReOx/CNFox catalysts, XRD and XPS data showed the
presence of Re6–7+ species in the calcined catalysts. On the
other hand, XPS analysis of the spent catalyst showed the
presence of incompletely reduced Re4+ and Re oxycarbide
species. Taken together, it is plausible to deduce the presence
of oxygen vacancies and surface hydroxyls on these catalysts
during the reaction.
Analogous to sulfur vacancies on sulfide catalysts,14 the
oxygen vacancy sites on the ReOx/CNFox catalyst serve as se-
lective sites for the adsorption of phenol. A possible sche-
matic representation adapted from the studies by Romero
et al.,13 Mortensen et al.,30 Moberg et al.68 and Prasomsri
et al.40 is shown in Fig. 8. After the creation of an oxygen va-
cancy and surface hydroxyls, selective deoxygenation of phe-
nol on reducible ReOx takes place in a stepwise fashion
according to this schematic: (1) the coordinatively unsatu-
rated Re4+ acts as a Lewis acid and interacts with the oxygen
lone pair on phenol; (2) then, the C-1 of phenol becomes
Fig. 8 Possible mechanism of direct deoxygenation of phenol to
benzene on the partially reduced ReOx phase. The figure is drawn on
the basis of the information from ref. 13, 30, 40, and 68.
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Catalysis Science & Technology
highly nucleophilic and accepts a proton (H+) from surface
hydroxyl groups, leading to the formation of an adsorbed
phenoxide ion;70 (3) C–O bond cleavage of the phenoxide and
desorption; and (4) the recovery of the oxygen vacancy by the
elimination of water. For the less preferred hydrogenation
pathway, a flat adsorption through the aromatic π bonding
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involving at least two neighbouring vacancies as active sites
is typically proposed.13,14 The product selectivity calculated at
10% conversion of phenol shown in Fig. 9a better illustrates
the preferred route for the ReOx/CNFox catalyst. All the cata-
lysts demonstrated a strong preference for the DDO pathway
as evidenced by benzene being the most dominant product
(51–59%). Cyclohexanol (3–8%) and cyclohexene (2–11%),
products of the HYD pathway, were produced in significantly
less quantities. The products also included cyclohexane (26–
35%) which can be formed via either route according to the
reaction scheme shown in Fig. 7. These results indicate that
despite the DDO pathway being preferred by a significant
margin, the HYD pathway cannot be ignored due to the ap-
preciable quantities of ring hydrogenated products. However,
based on these results, the ReOx/CNFox catalysts likely
followed the possible schematic representation shown in
Fig. 8. Our results agree well with the observation of Prasomsri
et al.40 who reported that MoO3 was selective for C–O bond
cleavage of anisole. A recent kinetic study by Leiva et al.71
has proposed the presence of only one active site on ReOx/
SiO2, likely coordinative unsaturated sites, which converts
Fig. 9 (a) Product selectivity calculated at 10% phenol conversion and
(b) reaction and intrinsic rates as a function of ReOx loading. The
product selectivity did not include the 2ReOx/CNFox catalyst due to its
very low conversion value. Reaction conditions: phenol (1.783 g),
yReOx/CNFox (200 mg), dodecane (80 mL), 573 K, 3 MPa H2.
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guaiacol to phenol. In addition, the creation of vacancies by
H2 as a reductant and the coordination of the OH group of
the substrate to the low-valent Re species mimic the mecha-
nism proposed by Ota et al.72 in the HDO of 1,4-
anhydroerythritol over the ReOx–Pd/CeO2 catalyst. The forma-
tion of cyclohexanol and the significant amount of cyclohexane
demonstrate the bi-functionality of the reducible ReOx catalysts
possessing both hydrogenolysis (metal oxide) and hydrogenating
(metal-like) sites. It is unclear which of the Re species deter-
mined from XPS measurements of post-reaction catalysts (ReO2
or ReOxCy) is responsible for the hydrogenating capabilities of
these catalysts. Computational calculations and surface science
experiments are warranted to provide insight into the respective
reactivities of these Re species. Another noteworthy observation
is the similarity in the selectivity pattern of all the ReOx/CNFox
catalysts. This can be explained by the relative abundance of Re
active sites derived from XPS analysis (shown in Fig. 5). The ref-
erence bulk ReOx catalyst produced a higher selectivity to ben-
zene (73%) in comparison to the CNT-supported catalysts. The
results further demonstrate the propensity of the ReOx phase
for C–O bond scission.
The influence of acid sites on the oxidized CNF support
on the selectivity cannot be completely discounted. In fact,
the 10ReOx/CNFox catalyst displayed higher benzene selectiv-
ity (59%) compared to a reference ReOx/SiO2 catalyst (45%)
with similar Re surface density which can be attributed to en-
hanced hydrogenolysis capability of the former due to the
presence of acidic surface oxygen groups on the CNFox
support.
The catalytic activity of the ReOx/CNFox catalyst, expressed
as the initial reaction rate (μmolPHE converted gcat−1 s−1), is
given in Table 4 and illustrated in Fig. 9b. The unsupported
ReOx catalyst is included as reference. The activity increased
continuously with an increase in the ReOx loading, reaching
a maximum at 10 wt%, and then declined. A look at Fig. 5
shows that the trend of the initial reaction rates follows the
XPS Re/C atomic ratio of the spent catalyst and not the cal-
cined catalysts. It can thus be inferred that changes to the
catalyst surface induced by the reactive H2 at 573 K and 3 MPa
occurred within the first 40 min of the reaction and remained
stable afterwards. Thus, although the true nature of the active
Table 4 Initial reaction rates of ReOx/CNFox catalysts as a function of
ReOx loading and H2 pressure for the HDO of phenol at 573 K
Reaction rates
Catalyst (μmolPHE converted gcat−1 s−1)
2ReOx/CNFox 0.2
4ReOx/CNFox 1.2
6ReOx/CNFox 2.9
8ReOx/CNFox 4.7
10ReOx/CNFox 9.0
13ReOx/CNFox 4.8
Unsupported ReOx 5
10ReOx/CNFox (0 MPa) 0
10ReOx/CNFox (2 MPa) 4.7
10ReOx/CNFox (3 MPa) 9.0
10ReOx/CNFox (5 MPa) 14.6
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phase during the reaction is unknown, post-reaction surface
characterization of reducible metal oxide catalysts is more re-
flective of the catalyst behaviour than the pre-reaction character-
ization. Hence, the activity of ReOx/CNFox catalyst is assigned to
the presence of Re4+ and Re6–7+ species derived from XPS mea-
surements of the spent catalysts. This is in agreement with the
study by Ota et al.72 who attributed the high catalytic perfor-
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mance of ReOx-Pd/CeO2 catalyst in the HDO of 1,4-
anhydroerythritol to rhenium species with the +4 valence state.
In relation to the trend, the low activity at low loadings reflects
the paucity of Re active sites, while the increase in the number
of catalytically active sites with Re loading enhanced the rate of
phenol conversion. However, a further increase in loading be-
yond an optimum value (10 wt% ReOx loading) led to loss of ac-
tive sites from crystallite agglomeration and, as a consequence,
a drop in activity. Fig. 9b also shows the intrinsic activity (reac-
tion rates normalized with exposed Re atoms derived from XPS
Re/C surface atomic ratios). The trend obtained for the intrinsic
rate was similar to the reaction rates, indicating a clear depen-
dency of the activity on the dispersion of the ReOx sites.
Based on the results discussed here, the 10ReOx/CNFox cat-
alyst was selected for further study.
3.3.2. Effect of hydrogen pressure. It is well known that
low H2 pressure favours the direct production of aromatics,
while high H2 pressure tends to steer the reaction towards
the HYD route.4 Thus, to elucidate whether the ReOx/CNFox
catalyst affinity for cleaving C–O bond was due to their inher-
ent properties or the favourable reaction conditions
employed, the impact of hydrogen pressure was investigated
at 2, 3 and 5 MPa H2 and at 300 °C. A reaction was also
conducted in the absence of hydrogen (under 0.5 MPa N2) and
would be referred to here as 0 MPa H2. There was no detect-
able conversion after 4 h in the absence of H2 (at 0 MPa H2),
indicative of the indispensability of H2 in catalytic HDO. The
time course of the HDO of phenol at varying pressure is shown
in the ESI (Fig. S2†). Fig. 10a shows the sensitivity of the HDO
of phenol to hydrogen pressure. Similar hydrogen pressure ef-
fects on lignin-derived compounds have been reported for
other catalytic systems.8,35 The initial reaction rates increased
almost linearly with H2 pressure, suggesting a pseudo first-
order dependence on the rate of phenol conversion with hy-
drogen pressure within the range studied. This observation
mirrors the findings of Odebunmi and Ollis8 with sulfided
CoO–MoO3/Al2O3 catalysts for the conversion of cresols.
Fig. 10 Product selectivity from conversion of phenol as a function of
H2 pressure: (a) at 20% conversion and (b) after 4 h reaction time.
Phenol (1.783 g), 10ReOx/CNFox (200 mg), dodecane (80 mL), 573 K.
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Product selectivity was calculated at 20% phenol conversion
and shown in Fig. 10a, which reveals clear distinction of prod-
uct distribution with H2 pressure. An increase in hydrogen
pressure decreased the yield of benzene and enhanced the se-
lectivity of cyclohexanol and cyclohexane. This trend indicates
enhanced hydrogenation activity at the expense of direct deox-
ygenation activity, consistent with the recent findings by Jin
et al.35 for the HDO of anisole. The selectivity to cyclohexene
was low and insensitive to hydrogen pressure, possibly because
the hydrogenation of cyclohexene is a significantly faster reac-
tion than the other steps.30 It thus appears that changes in re-
action rates and product distribution as a function of H2 pres-
sure are kinetically controlled. However, we cannot discount
the effect of the increase in H2 pressure on the nature of the
catalytically active surface during the reaction. An increase in
H2 pressure is expected to increase H2 dilution which might
induce significant changes to the catalyst's surface properties
and, thus, modify the mechanism of the reaction.
The dependence of phenol HDO on H2 pressure is even
more evident at 4 h reaction time, as shown in Fig. 10b. Total
conversion increased to 100 mol% at 3 MPa and above. Addi-
tionally, a more pronounced increase in cyclohexane selectiv-
ity, with a concomitant decrease in benzene production, with
hydrogen pressure was observed. There were also loss of
cyclohexanol and cyclohexene. This profound effect suggests
possible thermodynamic effects. Furimsky4 showed, through
equilibrium calculations, that phenol conversion increases
with H2 pressure due to enhanced oxygen elimination and in-
creased aromatic ring hydrogenation. In a nutshell, although
high H2 pressure hampered direct deoxygenation, benzene
was still formed in a significant amount over the ReOx/CNFox
catalyst. The desirability of the DDO route has implications
on their potential as a hydrogen efficient HDO catalyst.
3.3.3. Conversion of lignin model compounds. To demon-
strate the efficacy of the reducible Re oxide catalysts for the
conversion of other lignin monomers, the 10ReOx/CNFox cata-
lyst was tested for the conversion of guaiacol, anisole,
o-cresol and phenol under conditions comparable to the
studies reported by Jongerius et al.5 Fig. 11 illustrates the
evolution of the reaction products from the conversion of
guaiacol (Fig. 11[a]), phenol (Fig. 11[b]), anisole (Fig. 11[c])
and o-cresol (Fig. 11[d]). Guaiacol yielded mainly phenol,
benzene and cyclohexane, while toluene and anisole were
detected in minor amounts. In addition, trace amounts of
cyclohexanol, xylene and cyclohexane were also detected. Phe-
nol and anisole were intermediate products judging by their
concentration profiles. In the conversion of phenol (Fig. 11[b]),
cyclohexane and benzene were the dominant products, while
cyclohexanol and cyclohexene were detected in significantly
less quantities. Fig. 11(c) shows that anisole was converted to
benzene and methoxycyclohexane and subsequently to cyclo-
hexane; a trace amount of methanol was also detected. The
conversion of o-cresol yielded toluene and methylcyclohexane
in almost equal quantities. Methylcyclohexanol was an inter-
mediate product; in addition, benzene, cyclohexene and cyclo-
hexane were detected in trace amounts.
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Fig. 12 Reaction scheme of the conversion of guaiacol including the

Fig. 11 Conversion of lignin-derived substrates and the yield of prod-
ucts as a function of time over the 10ReOx/CNFox catalyst. Substrate:
(a) guaiacol, (b) anisole, (c) phenol and (d) o-cresol. Reaction condi-
tions: substrate (0.232 mol L−1), 10ReOx/CNFox (200 mg), dodecane (80
mL), 573 K, 5 MPa H2.
Table 5 shows that complete conversion of guaiacol and
phenol was achieved after 4 h of reaction, while conversions
of 88% and 44% were observed for anisole and cresol, respec-
tively. The significantly lower reactivity of o-cresol could be
due to the catalyst's relative inertness towards C–C bond scis-
sion which would be discussed later on. However, steric and
electronic effects associated with the methyl group cannot be
discounted.73
The product yields calculated at 1 h and 4 h reaction times
are also presented in Table 5. The data at 1 h depict the com-
mencement of the reaction after the initial induction period of
the catalyst and, hence, are used to elucidate the routes of pri-
mary conversion of the substrate. A generalized reaction scheme
of the conversion of guaiacol—encompassing the conversions of
phenol, anisole and o-cresol—adapted from Bui et al.74 and
Nimmanwudipong et al.75 is shown in Fig. 12 to illustrate the
pathways taken by the catalyst. On the basis of the results,
conversions of anisole, phenol and cresol. The figure is drawn on the
basis of the information from ref. 74 and 75.
guaiacol (Gua) underwent either demethoxylation (DMO) to
form phenol (Phe) or dehydroxylation (DDO) to form anisole
(Ani). The non-detection of catechol cannot be unequivocally at-
tributed to the reaction bypassing the catechol intermediate; it
could be due to its rapid conversion to phenol since this reac-
tion is facile.27 The DMO pathway was more prevalent than the
DDO pathway (22.1 vs. 1.2 mol%) which is likely due to the
lower bond dissociation energy (BDE) of Caromatic–OCH3 than
Caromatic–OH (91.5 vs. 109.2 kcal mol−1);76 consequently, it is eas-
ier to remove methoxyl than hydroxyl from guaiacol. The second
stage conversion such as the DDO of phenol to form benzene
(Ben) also occurred, which attests to the high reactivity of
guaiacol with the ReOx/CNFox catalyst. On the other hand,
anisole conversion was initiated by demethoxylation to produce
benzene (8.6 mol%) or hydrogenation to form methoxy-
cyclohexane (0.9%), followed by ring hydrogenation to form
cyclohexane (CyH, 5.7 mol%).
The conversion of phenol proceeded via two routes: (i) direct
deoxygenation to benzene (19.0%) or (ii) ring hydrogenation to
form cyclohexanol (CyHnol, 6.8 mol%). The DDO and HYD
pathways have already been discussed in the earlier sections.

Table 5 HDO of lignin model compounds over the 10ReOx/CNFox catalyst in a batch reactor at 573 K and 5 MPa H2 for 1 and 4 h

Time Conv. HDO Selectivity (mol%)

(h) (mol%) % CyH Ben Phe CyHnol Ani Tol MetCyH MetCyHnol
Gua 1 27.7 10.4 1.3 1.3 22.1 1.3 1.2 0 0 0
4 100 88.6 66.1 19.0 7.9 1.2 1.8 3.3 0 0
Ani 1 14.8 98.5 5.7 8.6 0 0 — 0 0 0
4 88.1 99.5 52.7 30.2 0 0 — 0 0 0
Phe 1 50.6 86.6 24.1 19.0 — 6.8 0 0 0 0
4 100 100 82.4 17.6 0 0 0 0 0
Cre 1 7.2 77.9 0.1 0.1 0 0 0 3.2 2.2 1.6
4 43.9 96.6 1.1 0.5 0 0 0 19.3 21.4 1.5

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A notable observation is the difference in benzene selectiv-
ity from the conversion of phenol and anisole: the latter
yielded more benzene than the former (53.0 vs. 37.5%). This
is consistent with the higher bond strength of the Caromatic–
OH bond (106.1 kcal mol−1) compared with the Caromatic–
OCH3 bond (91.1 kcal mol−1), in a similar fashion as the de-
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methoxylation vs. dehydroxylation selectivity difference from
guaiacol conversion.76 However, it should be noted that the
relative bond strength alone cannot explain the observed se-
lectivity differences. The ReOx/CNFox catalyst preferentially
cleaved the much stronger Caromatic–OCH3 bond over the O–
CH3 bond (51.2 kcal mol−1) in guaiacol and anisole, in line
with the findings of Prasomsri et al.76 over reducible MoO3
catalysts. Furthermore, unlike phenol conversion which pro-
duced cyclohexanol in appreciable amounts, the ring hydro-
genated counterpart from anisole conversion (i.e. methoxy-
cyclohexane) was only produced in trace amounts; this
demonstrates the affinity of the ReOx/CNFox catalyst to DMO.
Hence, it can be inferred that the –OCH3 on guaiacol and
anisole bonds with surface reducible metal oxide (ReO2 and
ReOxCy) species, in agreement with the recent findings by
Prasomsri et al.40 who demonstrated from the DFT model
that reduced MoO3 (Mo3O9) bonded with the methoxy group
on anisole. In addition, Chang et al.77 reported that partially
reduced MoOx (Mo4+) species were responsible for the direct
demethoxylation of guaiacol and anisole to form phenol and
benzene, respectively.
The o-cresol reaction proceeded solely via DDO to produce
toluene (Tol), part of which was subsequently hydrogenated
to form methylcyclohexane (MetCyH).
The selectivity at 4 h shed insight into the products
formed at the tail end of the reaction. A very high to com-
plete degree of hydrodeoxygenation was obtained for all the
compounds (83.4–100%). The conversion of the lignin mono-
mers over the ReOx/CNFox catalyst resulted in the predomi-
nant formation of ring saturated products such as cyclohex-
ane and methylcyclohexane: guaiacol, phenol and anisole
generated 59.5–82.4% cyclohexane, formed mainly from the
hydrogenation of benzene; o-cresol produced 48.7% of
methylcyclohexane. However, a significant fraction of aroma-
ticity was retained as evidenced by the 17.6–34.0% selectivity
towards benzene, toluene and xylene (BTX). The selectivity to-
wards other products such as cyclohexanol and methyl-
cyclohexanol (MetCyHnol) did not exceed 3%. Some other
noteworthy observations from Table 5 are as follows: (1) no
cresols (methylphenols) were detected from the conversion of
guaiacol. Typically, methylation (ME) of phenol to produce
cresols could occur as a result of CH4 produced from demeth-
ylation (DME) of guaiacol to form catechol. However, there
was no evidence of DME which explains the absence of cre-
sols in the product stream. (2) The catalyst's relative inert-
ness towards C–C bond cleavage is evident in Table 5, where
demethylated products account for a measly 3.9% of the
product selectivity from the conversion of o-cresol. It was pre-
viously noted by Ausavasukhi et al.78 in the study of the HDO
of m-cresol over Ga-modified beta zeolite catalysts that strong
Catal. Sci. Technol.
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Catalysis Science & Technology
support acidity is required for dealkylation. A Ga/HBEA cata-
lyst was substantially more active than a Ga/SiO2 catalyst,
and the authors suggested that the disparity associates with
the fact that SiO2 does not contain any significant acidity.
However, the CNFox support contains significant acidity but
was nonetheless unable to cleave the C–C bond on o-cresol.
Therefore, we can conclude that the very low degree of
dealkylation cannot be associated with the acidity of the
ReOx/CNFox catalyst but rather by the intrinsic preference of
ReOx species for C–O bond scission.
Direct comparison of these results with the studies
reported by Jongerius et al.5 with the sulfided CoMo/Al2O3
catalyst under comparable conditions underscores the poten-
tial of the ReOx/CNFox catalyst for the conversion of lignin-
derived compounds. The authors reported guaiacol, phenol,
anisole and o-cresol conversions of 50, 30, 40 and 27%, re-
spectively, which lagged far behind the ReOx/CNFox catalyst
which exhibited corresponding conversions of 100, 100, 88
and 44%. Additionally, there was no evidence of demethyla-
tion and transalkylation with this catalyst, in contrast to the
sulfided catalyst. However, the ReOx/CNFox catalyst also
exhibited an inherent hydrogenation character and, thus, was
more prone to over-saturation of the aromatic ring. Addi-
tional studies are required to suppress its hydrogenation ac-
tivity without sacrificing its high activity.
4. Conclusions
Phenol was used as a lignin model compound to determine
the reactivity of carbon nanofiber-supported rhenium oxide
catalysts as a function of ReOx loading and revealed a direct
correlation between the initial reaction rate and relative Re
dispersion derived from XPS measurements of spent cata-
lysts. The reaction was catalysed in situ generated oxygen va-
cancies and exhibited a preference for direct deoxygenation
of phenol to benzene. In addition, the product distribution
was largely congruent, indicative that the nature of the active
sites was not modified by an increase in loading. The activity
and product distribution were also strong functions of H2
pressure: a higher pressure enhanced the activity and the hy-
drogenation capability but diminished the benzene selectiv-
ity. The best ReOx/CNFox catalyst was also applied to other
lignin-derived substrates such as guaiacol, anisole and
o-cresol and demonstrated an ability to selectively cleave the
C–O bond without C–C bond cleavage, thereby retaining all
carbon atoms. This demonstrates that the ReOx phase is
hydrogen-efficient and carbon-atom economical.
Acknowledgements
The authors gratefully acknowledge the financial support
from CONICYT-Chile for FONDECYT Project No. 3150033 and
1140528 and Project Basal PFB-27. We thank Dr. Freddy Celis
and Dr. Marcelo Campos for helpful discussion on Raman
spectra measurements.
This journal is © The Royal Society of Chemistry 2016

Catalysis Science & Technology
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