Journal of Catalysis 318 (2014) 151161

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Kinetic and FTIR studies of 2-methyltetrahydrofuran

hydrodeoxygenation on Ni2P/SiO2
Ara Cho a,b,1, Hosoo Kim b, Ayako Iino a, Atsushi Takagaki a, S. Ted Oyama a,c,
a
Department of Chemical Systems Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
b
Corporate R&D, LG Chem Research Park, 188, Munji-ro, Yuseong-gu, Daejeon 305-738, Republic of Korea
c
Department of Chemical Engineering, Virginia Tech, Blacksburg, VA 24061, USA

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

Article history: The hydrodeoxygenation of 2-methyltetrahydrofuran (2-MTHF) at a medium pressure of 0.5 MPa is
Received 10 June 2014 studied over a Ni2P/SiO2 catalyst. Contact time studies show the formation of n-pentanal, 1-pentanol,
Revised 24 July 2014 2-pentanone, 2-pentanol, and 2-pentene, as reaction intermediates and the production of pentane and
Accepted 26 July 2014
butane as major products. The results are consistent with adsorption of 2-MTHF followed by rate-
Available online 27 August 2014
determining ring-opening to form either 1-pentoxide or 2-pentoxide alkoxide intermediates. Subsequent
hydrogen-transfer steps produce the various intermediates, a decarbonylation step of the pentanal forms
Keywords:
n-butane and CO, and further hydrodeoxygenation steps result in n-pentane. Fitting of the results using a
Hydrodeoxygenation
2-Methyltetrahydrofuran
rake mechanism that considers adsorbed intermediates gives excellent agreement with experimental
Ni2P/SiO2 data, and agrees with a simulation with a simpler rst-order model. The more detailed rake analysis indi-
Rake mechanism cates that the surface species from the 1-pentoxide intermediate are ten-fold more plentiful than those
In situ FTIR produced from the 2-pentoxide intermediate. In situ infrared measurements support this reaction
mechanism.
2014 Elsevier Inc. All rights reserved.

1. Introduction
The utilization of biomass to replace fossil fuels is a topic of
current interest due to increasing concerns about global climate
change induced by the release of carbon dioxide and the desire
to develop renewable sources of energy [14]. Many methods for
the conversion of biomass to fuels have been considered [5,6],
including the production of bioethanol [7], biodiesel [8], Fischer
Tropsch liquids [9,10], and pyrolysis oil [11]. The route involving
pyrolysis oil is competitive for converting biomass to naphtha
and diesel [12,13].
A problem with pyrolysis oil is that it contains considerable
amounts of oxygen (40 wt%) [11], which reduces its heating value
and makes the oil unstable. For this reason there has been
signicant work in the hydrodeoxygenation (HDO) of the oil, either
as it is produced [14] or in separate units [15]. Many catalysts
have been tried, including suldes [16], zeolites [17], carbides/
nitrides [18], phosphides [1922], and phosphide alloys [23,24].
Corresponding author at: Department of Chemical Systems Engineering, The
University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
E-mail addresses: ted_oyama@chemsys.t.u-tokyo.ac.jp, oyama@vt.edu
(S. Ted Oyama).
1
Current address: Corporate R&D, LG Chem Research Park, 188, Munji-ro, Yuseong-
gu, Daejeon 305-738, Republic of Korea.
Phosphides are particularly promising and the subject has been
reviewed [25,26].
Previous work in our laboratory on the reaction of guaiacol [27]
and ethanol [28] showed that Ni2P is an effective catalyst for
deoxygenation and this has been conrmed in a number of HDO
studies such as with guaiacol [29], anisole [23,22], dibenzofuran
[30], and 4-methoxyphenol [31]. Recent work in our laboratory
[32,33] employed the model compound 2-methyltetrahydrofuran
(2-MTHF) as a substrate for deoxygenation because there are
substantial amounts of furans contained in pyrolysis oil. Also, the
presence of the methyl group gives the compound two routes for
ring-opening and this can give information about the nature of
the active site that is involved in the reaction. An initial study at
0.1 MPa [32] showed that the order of activity was Ni2P > WP >
MoP > CoP > FeP, and a contact time analysis for Ni2P showed that
small amounts of intermediate alkenes were formed rst, then
small amounts of 2-pentanone, and n-pentanal and nally large
amounts of butane and pentane products. A subsequent study at
0.5 MPa on Ni2P [33] showed slight differences in intermediates
such that small amounts of alcohols were formed rst instead of
alkenes, then 2-pentanone, and nally butane and pentane. That
study used a simple rst-order kinetic scheme to simulate the net-
work, and it was concluded that the initial steps of ring-opening
were the rate-determining steps in the sequence.

http://dx.doi.org/10.1016/j.jcat.2014.07.021
0021-9517/ 2014 Elsevier Inc. All rights reserved.
152 A. Cho et al. / Journal of Catalysis 318 (2014) 151161
Nomenclature
Symbol description units
ni total number of measurements over all experiments for
measured variable i ()
NE number of experiments ()
NM number of measurements ()
The objective of the present study is to provide a more in-depth
kinetic analysis of the reaction network at the intermediate
pressure of 0.5 MPa that takes into consideration adsorbed species.
In the previous work, [33] measurements were carried out to a
contact time of just under 0.1 s and conversions of 1%. In the
present paper, the contact time was reduced to about 0.01 s and
conversions of 0.1% were studied. A further goal is to monitor the
adsorbed species using in situ infrared spectroscopy also at
0.5 MPa to provide independent evidence for the reaction
sequence. Selectivity measurements are carried out with attention
placed on the low contact time region to check on previous results,
and to determine the formation of n-pentanal, a key reaction
intermediate.
2. Experimental
2.1. Catalyst synthesis and characterization
The nickel phosphide catalyst was synthesized by incipient wet-
ness impregnation followed by temperature programmed reduc-
tion (TPR) as described elsewhere [34]. Briey, a silica Cabosil
support was impregnated with aqueous solutions of Ni(NO3)26H2O
and (NH4)2HPO4, which was followed by drying at 383 K for 12 h
and calcination at 773 K for 6 h in static air. The initial Ni/P ratio
in the impregnating solution was kept at 1/2. The calcined precur-
sors were pelletized and sieved to particles of 6501180 lm diam-
eter, and the resulting particles were reduced to phosphide by a TPR
method in 1 l/min of hydrogen. The temperature was increased at a
rate of 3 K/min from room temperature to the nal temperature of
863 K, which was determined by TPR of samples and the tempera-
ture was maintained at the nal state for 2 h. After cooling to room
temperature in He ow, reduced samples were passivated in 0.5%
O2/He mixture at room temperature for 3 h before being taken
out from the TPR reactor. The levels of Ni loading in the Ni2P/SiO2
catalyst were 1.16 mmol (g support)1.
Carbon monoxide (CO) uptakes on the samples were measured
by a pulse injection method using a catalyst analyzer (CHEMBET-
3000, Quantachrome Instruments) equipped with a thermal con-
ductivity detector to estimate the dispersion of active sites on
the catalysts. Prior to adsorption, 0.3 g of passivated samples were
placed in a quartz reactor and were re-reduced with hydrogen at
723 K for 1 h and then cooled to room temperature in helium ow.
Pulses of volume 25 ll of 10% CO/He were injected using a helium
carrier owing at 100 ml min1 to a reactor containing the catalyst
at room temperature until saturation of the sample surface with
CO was achieved.
Transmission electron microscopy (TEM) images of Ni2P/SiO2
were taken with a JEOL JEM 2000EXII operated at 200 kV. The
Ni2P/SiO2 catalysts were ground to ne particles and dispersed into
ethanol and put on a carbon-coated copper grid.
In situ extended X-ray absorption ne-structure (EXAFS) mea-
surements were made at the BL9C, beam line of the Photon Factory
in the Institute of Materials Structure Science, High-Energy Accel-
erator Research Organization (KEK-IMSS-PF). The EXAFS spectra
were obtained in transmittance mode, and were calibrated using
NV number of measured variables ()
Wj weight of experiment j ()
z predicted model response ()
~z measured response ()
ki heteroscedasticity parameter for measured variable i ()
a Ni foil. The storage ring was operated at 2.5 GeV with a beam
current of 300 mA. For the EXAFS measurements, the samples were
prepared in the form of pellets (/ = 1 cm) with 60 mg of calcined
Ni2P/SiO2 precursor and, for the reference, a mixture of bulk Ni2P
(6 mg) and BN (36 mg) was used. The pellet of the Ni2P/SiO2
sample was reduced in a quartz reactor in the same manner as
the catalyst sample at 723 K (450 C). After reduction, the reactor
containing sample was carefully moved into a glove box without
exposing it to air and the sample was taken out and taped on both
sides of the pellet with polyamide tape. The measurements were
done at room temperature in transmission mode. The EXAFS spec-
tra were analyzed using WinXAS3.1. Theoretical scattering ampli-
tudes and phase shifts for the Ni2P were calculated by FEFF8
code [35]. Curve tting was conducted using the three dominant
shells (2 NiP, 4 NiP and 4-NiNi) [36], and the reducing factor
(So2) was xed as 0.8.
2.2. Contact time analysis
The effect of contact time on the conversion and selectivity for
the HDO of 2-MTHF was studied in a xed-bed ow reactor in the
gas phase at 573 K and 0.5 MPa over the Ni2P/SiO2 catalyst. Prior to
the reaction, passivated catalysts were re-reduced with hydrogen
at 723 K for 2 h at atmospheric pressure. The reactant, 2-MTHF,
containing 5 vol% of n-heptane as an internal standard, was fed
using a liquid pump to a vaporizer before delivery to the reactor.
During the reaction, products were sampled every 1 h and were
analyzed on-line using a Shimadzu 10A gas chromatograph (GC)
equipped with a silicone capillary column and ame ionization
detector (FID). The analytical method was improved compared to
past work by increasing the integrator sensitivity. Contact time
was changed in the range of 0.010.31 s while keeping the inlet
molar ratio of H2 to 2-MTHF constant at 19. Contact time (s) was
dened as s (s) = V/v, where V is the volume of the catalyst bed
and v is the ow rate of hydrogen. Total conversion was kept below
11% for every measurement except one point.
2.3. Fourier transform infrared spectroscopy
Temperature programmed desorption (TPD) of 2-MTHF
adsorbed on the Ni2P/SiO2 catalyst was studied using infrared
spectroscopy under nitrogen or hydrogen ow. For the in situ
transmission infrared measurement of the Ni2P/SiO2 catalyst sur-
face, the sample was prepared in the form of self-supporting disk
of diameter 1 cm (15 mg) and was placed in the center of an IR
cell equipped with KBr windows (Fig. 1). To reduce the dead vol-
ume of the IR cell, stainless-steel rods with a hole (/ = 0.8 cm) were
inserted in both sides of the IR cell and KBr rods were inserted into
those holes to minimize absorption by gas-phase species in the IR
spectra. Before dosing the reactants, the sample was reduced at
623 K for 3 h in a ow of 100 ml (NTP)/min of hydrogen. After cool-
ing to 423 K in a N2 or H2 ow, background spectra were obtained
at 423, 448, 473, 498, 523, 548, 573, and 598 K, respectively. After
cooling again to 423 K, 2-MTHF was injected to the sample with N2
or H2 as the carrier and then the sample was purged with the same
 A. Cho et al. / Journal of Catalysis 318 (2014) 151161
Fig. 1. Schematic diagram of in situ IR cell.
gas for 0.5 h to remove gas-phase species. IR spectra were collected
in situ at increasing temperature from 423 to 598 K under N2 or H2
ow with a JASCO FT/IR-6100 equipped with a MCT detector with a
resolution of 1 cm1 in the region of 40001000 cm1.
Transient spectra for desorption of 2-MTHF adsorbed on the
Ni2P/SiO2 catalyst were obtained at constant temperature, 523 K
under nitrogen or hydrogen ow using the same reactor as used
for the other IR measurements (Fig. 1). After pretreatment at
623 K the samples were cooled to 523 K in a N2 or H2 ow and
background spectra were obtained in the absence of 2-MTHF. Then
2-MTHF was injected to the sample with N2 or H2 as the carrier
until saturation was achieved. After saturation, IR spectra were col-
lected under N2 or H2 ow without 2-MTHF injection keeping the
temperature constant at 523 K. Measurement was made every
60 s with a resolution of 4 cm1 in the region of 4000500 cm1
using 100 scans spectrum1. (For the TPD experiments, measure-
ments were made with a resolution of 4 cm1 in the region of
40001000 cm1 using 200 scans spectrum1).
2.4. Parameter estimation
The proposed mechanism was modeled with Aspen Custom
Modeler (ACM), a commercially available software package devel-
oped by AspenTech, and then the kinetic parameters were esti-
mated by a mathematical routine that optimizes the t of model
results to measured values from the experiment data by varying
the kinetic parameters. The following maximum likelihood log
function was used for the objective function, which denes an opti-
mal t.
8 2 !2 3
<1 XNV XNE NM
Xij 2 ~zijk  zijk
min n ln2p 1 ni ln 4ni Wj 5
:2 i1 i j1 k1
~zkijki
) catalyst. The rst and the second shells correspond to two different
NE NM
X Xij   NiP bonds and the third shell corresponds to a NiNi bond. For the
ki ln W j ~zijk
j1 k1
For solving this optimization problem, FEASOPT and Nelder
Mead solvers were used in sequence. The experiment data did
not contain sufcient information to provide good initial guesses
to accurately determine the 16 kinetic parameters. Therefore, ini-
tial guesses for the kinetic parameters of the mechanism were rst
obtained using FEASOPT solver, a feasible path successive qua-
dratic programming which can rapidly move the model parame-
ters in a correct direction based on gradient information. Next, a
NelderMead solver was used to get a better solution from the
initial guesses by minimizing the objective function based on the
153
simplex algorithm that is computationally cheap since it only
involves function evaluations and no gradient or Hessian informa-
tion [37]. It can require many more iterations to converge than gra-
dient based methods; however, it may be able to solve complex
problems which fail to converge using FEASOPT.
3. Results and discussion
A transmission electron microscopy (TEM) image of a freshly
reduced and passivated Ni2P/SiO2 catalyst (Fig. 1a) shows highly
dispersed particles with narrow size distribution. The particle size
distribution for 100 particles (Fig. 1b) shows that the average par-
ticle diameter was 3.7 nm.
Structural characterization of a freshly reduced sample placed
in a cell with Kapton windows was carried out with extended
X-ray absorption ne-structure (EXAFS) at room temperature.
The EXAFS spectrum shows two peaks (Fig. 2) due to NiP and
NiNi bonds (Table 2) at 0.225 nm and 0.26 nm, respectively,
which agree well with previously reported values of 0.23 and
0.26 nm [34]. The low coordination numbers are consistent with
particle sizes in the vicinity of 4 nm, in agreement with the TEM
results [38] (see Fig. 3).
Earlier, we had estimated particle sizes from the CO uptake and
this gave a particle size of 22 nm [33]. We suspect that the CO
uptake was low because of site blockage by phosphorus, and this
gave the large value. Low values of chemisorptions were found ear-
lier [39]. The present TEM results are more reliable because they
are a direct determination.
Table 2 summarizes the selected crystallographic Ni2P standard
data which was used in the curve tting and the tting parameters
(bond distance, coordination number, and DebyeWaller factor) of
the EXAFS spectra for the bulk Ni2P reference and the Ni2P/SiO2
Ni2P/SiO2 catalyst in the rst shell, the coordination number was
almost same as that of bulk Ni2P, whereas coordination numbers
in the second and the third shells appeared larger and smaller,
respectively, than those of bulk Ni2P. It was reported that smaller
Ni2P crystallites have stronger NiP interaction and are decorated
with phosphorus on the surface resulting in larger coordination
number in the second shell (NiP) [34,40]. It was also suggested
that the decrease in the coordination number in the third shell
(NiNi) may due to extra phosphorus inducing reduction of the
NiNi coordination [37]. The EXAFS analysis results conrm that
the highly dispersed Ni2P was formed on the SiO2 support, which
is consistent with the TEM results.
154 A. Cho et al. / Journal of Catalysis 318 (2014) 151161

(a)

k -weighted FT / a.u.
Bulk Ni2P

3
Ni2P/SiO2

50 nm
0 2 4 6
R (10 nm)

Fig. 3. Fourier transform Ni K-edge EXAFS oscillations of Ni2P/SiO2 reduced in H2 at

(b) 40
723 K (450 C) for 8 h and bulk Ni2P.
Average 3.7 nm
35

30 of the 20-fold difference in scales (70% vs. 3.5%). One set of mea-
surements was made for the entire data, but the points were taken
25
Counts

at increasing and decreasing contact times to establish that the

20
catalyst was stable during the experiment. The selectivity to
n-pentane increases monotonically as expected for a nal product
15 in a sequence. The selectivity to n-butane also increases but much
more gradually, because it is a product of an intermediate,
10
n-pentanal, that can react to form both n-butane by decarbonyla-
5 tion and n-pentane by sequential hydrogenation.
The data in Fig. 4 are largely in agreement with previous results
0
1 2 3 4 5 6 7 8 9 10 [33], except that an improved analytical method was used here
Particle size / nm that enabled the observation of n-pentanal, an intermediate that
appears at the lowest concentration (Fig. 4b). Based on the present
Fig. 2. (a) TEM image of Ni2P/SiO2 and (b) particle distributions of Ni2P/SiO2 100 contact time results, the overall reaction pathway for the 2-MTHF
particles.
HDO over Ni2P/SiO2 is modied so that n-pentanal is shown explic-
itly (Fig. 5). The pathway has two branches, with ring-opening by
CO bond breaking occurring at either the more hindered (k1) or
Reactivity results in the form of selectivity vs. contact time were the more open (k5) position. Previous work carried out also at
used to determine the reaction network (Fig. 4). The top panel 0.5 MPa showed that these rate constants were small compared
(Fig. 4a) shows the selectivity to the main products, and the bot- to the rest of the rate constants and, thus, that the ring-opening
tom panel to the minor products (Fig. 4b). Note should be made step was rate-determining [31].

Table 1
Textural properties of Ni2P catalyst.

Catalyst BET area CO uptake Crystallite size from CO uptake Crystallite size from TEM
Ni2P/SiO2 214 m2/g 55 lmol/g 22 nm 3.7 nm

Table 2
EXAFS parameters for the bulk Ni2P and Ni2P/SiO2.

NiP (I) NiP (II) NiNi (I and II)

Reference R-factor (%)
CN 2 2 1 4 2 2 4
R (nm) 0.2209 0.2266 0.2369 0.2457 0.2605 0.2613 0.2678
Bulk Ni2P 0.74
CN 1.8 1.2 3.9
R (nm) 0.2240 0.2348 0.2611
r2 (105 nm2) 1.89 0.26 7.52
Ni2P/SiO2 0.78
CN 1.7 2.2 2.9
R (nm) 0.2219 0.2349 0.2626
r2 (105 nm2) 0.17 1.24 6.71

CN: coordination number, R: bond distance, r2: DebyeWaller factor.

R-factor: residual-factor.
 A. Cho et al. / Journal of Catalysis 318 (2014) 151161 155

70 sequence that considers adsorption steps is developed here based

(a) on a rake mechanism. A rake mechanism considers a sequence of
60 steps on a surface with each intermediate being capable of desorb-
ing [41]. The term rake is used because the written out mechanism
50 n-Pentane with the vertical adsorption/reaction steps and the horizontal sur-
Selectivity / %

n-Butane face steps resembles the prongs of the device used to gather leaves
40 (Fig. 6). In the present case, the simplest possible description of a
2-Pentanone
realistic reaction network was targeted, with each major observed
30 species assigned a corresponding surface intermediate. The two
species produced with the lowest selectivity (<0.5%), n-pentanal
20 and 2-pentene, were omitted in order to minimize the number of
tting variables and keep the simulation within proper statistical
10 bounds. Actually, a simulation with those two species was
attempted (Supplementary information), and although good ts
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
to the data were obtained, a unique set of rate constants could
Contact time / s not be produced. The errors produced by omitting the two species
3.5 are likely to be small because of their very low levels.
(b) 2-Pentanol The treated sequence (Fig. 6) follows that considered before
3.0 1-Pentanol (Fig. 5) and begins with the adsorption of the reactant 2-MTHF.
Adsorption occurs via the oxygen atom, which activates the
2-Pentene
2.5 adjacent bonds, and makes them susceptible to reaction. This
Selectivity / %

Pentanal
occurs by ring-opening, and as before, there are two branches (this
2.0 time left and right), which, respectively, produce 2-pentoxide or
1-pentoxide intermediates. Further reactions are hydrogen-
1.5
transfer steps that produce alcohol precursors or bond-shift steps
that produce alkyl groups.
1.0
The experimental data used in the parameter estimation were
obtained under excess of hydrogen. So, hydrogen adsorption on
0.5
the surface was not considered.
0.0 In the diagram above, [A], [B], [D], [E], [G], and [I] (lmol cm3)
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 are concentrations of 2-methyltetrahydrofuran, 2-pentanone, 2-
Contact time / s pentanol, n-pentane, 1-pentanol, and n-butane, respectively, in
the gaseous phase. [A*], [B*], [D*], [E*], [G*], and [H*] (lmol cm2)
Fig. 4. Effect of contact time on the product selectivity over the Ni2P/SiO2 catalyst:
are concentrations of the surface intermediates. The symbol [*] rep-
Contact time vs. selectivity at 573 K (300 C) and 0.5 MPa. (a) Majority products and
(b) minority products. resents the concentration of the empty adsorption sites on the cat-
alyst. The rate constants for the adsorption of each component are
denoted as kA, kB, kD, and kG (cm3 lmol1 s1). The rate constants
The 2-pentene selectivity shows a uniform rise with decreasing for desorption are denoted as k-A, k-B, k-D, k-E, k-G, k-H, and k-I
contact time, which would normally indicate that it is a primary (s1). The constants k1, k2, k4, k5, and k7 (s1) are the rate constants
intermediate. However, its very low level suggests that it is a prod- of the surface reactions. The kinetic rate law equations for the
uct of 2-pentanol dehydration, and that the lack of a maximum in major species are given below (Table 3).
selectivity is probably due to lack of data at very low contact time. The rates of reaction for the formation of the surface intermedi-
A limitation of the prior analysis is that the reaction network ates are given below (Table 4). These equations are solved simulta-
was modeled by a series of rst-order steps, without consideration neously with those of the gaseous species.
of adsorbed intermediates or the chemistry of each step. Although The rate constants obtained from the tting are summarized
such treatments are common, they can miss essential steps in the below (Table 5), and the calculated concentration curves are plot-
reaction pathway by not considering surface species [25]. To ted (Fig. 7). The points are the actual data presented earlier (Fig. 4).
improve the kinetic analysis, a more realistic description of the The kinetic ts for the observable gas-phase species show excellent

Fig. 5. Proposed reaction pathway for the 2-MTHF HDO at 0.5 MPa over Ni2P/SiO2 (rate constants are reported in previous work [33]).
156 A. Cho et al. / Journal of Catalysis 318 (2014) 151161

Fig. 6. Rake mechanism for the 2-MTHF HDO over the Ni2P/SiO2 and simplied nomenclature.

Table 3
Rate expressions for observable gaseous species.

dA dB
V
S ds
kA A kA A  V
S ds
kB B kB B 
dD  dE
V
S ds
kD D kD D  V
S ds
kE E  kH H 
dG dI
V
S ds
kG G kG G  V
S ds
kI G 
S
V 1:0  104 cm, where S is the total surface area of Ni2P and V is the volume of the catalyst bed

Table 4
Rate expressions for the surface intermediates.

dA  dB 
ds
kA A  kA k1 k2 A  ds
kB B k1 A   kB k4 B 
dD    dE 
ds
kB D k4 B   kD k5 D  ds
k5 D   kE E 
dG  dH 
ds
kG G k2 A   kG kI k7 G  ds
k7 G   kH H 
The total concentration of the adsorption sites, L is given as follows:
 
mol g1 104 cm2
CO uptake
L Effectiv e surface area of Ni2 P
5542lm 2 g1 m2
1:3  104 lmol cm2
Effectiv e surface area of Ni2 P q6Dc q = 7.09 g cm3 Dc = average crystallite size
L = [*] + [A*] + [B*] + [D*] + [E*] + [G*] + [H*]

agreement with the experimental data. The conversion of 2-MTHF
can be calculated from the decrease in 2-MTHF concentration. It is
linear with contact time and is 3.1% at s = 0.32 s. This also indicates
that product inhibition is not occurring, as if this were the case the
conversion would be proportionally lower at higher contact time.
The standard error estimates for each species (Table 6) indicate
low values. These are consistent with the good ts of the data.
However, it should be noted that the tting method used here
involving the optimization and solution of differential algebraic
equations performed in a two tier approach cannot guarantee that
the obtained solution is a global minimum, though it should be
close.
The reaction scheme together with the rate constants is sum-
marized below (Fig. 8) in order to ease visualization of the results.
 A. Cho et al. / Journal of Catalysis 318 (2014) 151161 157

Table 5
Estimated kinetic parameters from experimental data.

Rate constant (s1) Rate constant (s1) Rate constant (cm3 lmol1 s1)
k-A 0.04 k1 46 kA 1.4
k-B 11,491 k2 82 kB 10
k-D 2810 k4 11,564 kD 15
k-E 12,111 k5 11,067 kG 16
k-G 88 k7 1157
k-H 814
k-I 452

10 metallic sites. The desorption rate constants are shown to the right
2-MTHF of the vertical arrows and show an interesting trend. The constants
Concentration (mol/cm3)

n-Pentane
1 intermediates on the right are formed from secondary carbons
0.1
0.01
0.0 0.1
Contact time, (s)
Fig. 7. Comparison of experimental and estimated concentrations of 2-MTHF, n-
pentane, n-butane, 2-pentanone, 2-pentanol, and 1-pentanol at 573 K (300 C) and
0.5 MPa.
Table 6
Estimation result: standard error estimates.
Measured variable
[A]
[B]
[D]
[E]
[G]
[I]
The vertical reactions represent adsorption and desorption steps,
while the horizontal reactions represent surface transformation
steps. The sequence begins with the adsorption of the reactant
2-MTHF (indicated). Once adsorbed the 2-MTHF can undergo ring
opening in two manners, on the unsubstituted side (left sequence)
or on the methyl side (right sequence). These are indicated in the
horizontal direction (Fig. 8). The ratio of rate constants for ring
opening on the unsubstituted side to the methyl substituted side
is 82 s1/46 s1 = 1.8. This agrees with a previous determination
using a simple rst-order sequence of steps [33] of 2.2. It should
be noted that the higher value of the rate constant for the forma-
tion of adsorbed 1-pentoxide (82 s1) compared to the lower value
of the rate constant for the formation of adsorbed 2-pentoxide
(46 s1) is not inconsistent with the observation of 2-pentanone
as a major gas-phase intermediate, since the rate constant for its
desorption (11,491 s1) is extremely high compared to those of
the products from the left branch.
The adsorption rate constants are shown in the vertical direc-
tion in red to the left of the arrows. These constants follow the
order: alcohols > ketone > ether, which is in the order of electron
donating ability of the functional groups, and probably indicates
that there are interactions of these groups with electron-accepting
are substantially larger for the three intermediates to the right of
n-Butane
adsorbed 2-MTHF than for the two intermediates to the left. The
and those on the left from terminal primary carbons, and differ-
2-Pentanone ences in reactivity are expected, perhaps by stabilization of transi-
2-Pentanol tion states with partial carbonium ion character on the carbons.
The analysis also allows calculation of concentrations of the
suggested surface intermediates. Plots of these surface concentra-
1-Pentanol tions show that they do not depend greatly on contact time
(Fig. 9). The most abundant intermediate is adsorbed 2-MTHF,
the reactant. This is reasonable, as its further reaction by ring open-
0.2 0.3 ing is rate-determining for both branches.
Quantitative comparisons with experimental quantities are
possible. From Fig. 9, the average concentration of adsorbed
2-MTHF (A*), which is the major surface species, can be calculated
to be 1.3  105 lmol/cm2 for s = 0.21 s. To put this value in per-
spective, recall that the total surface area of the sample was
214 m2/g and the CO uptake of the supported Ni2P phase was
55 lmol/g (Table 1). This gives a site density of n = (55 lmol/g)/
(214 m2/g)(104 cm2/m2) = 2.6  105 lmol/cm2, which, as should
be, is higher than the concentration of A* calculated above. In terms
Standard error of estimates
of coverages this is the equivalent of h = 0.50. In a previous study
6.85E02 [31] of the kinetics of the reaction at the same temperature
9.62E03
(573 K) and pressure (0.5 MPa), a LangmuirHinshelwood equation
2.28E04
2.19E02 was obtained which allowed calculation of the adsorbed 2-MTHF
9.13E04 coverage. The calculated value at s = 0.21 s was h = 0.40, which
5.27E03 agrees well with the h = 0.50 determination here by a completely
independent method. Since the sites are based on the chemisorp-
tion of CO, these calculated coverages are on the Ni2P surface
and do not count the support.
The second most abundant species are the two species with pri-
mary carbons, G* and H* (protonated 1-alkoxide and 1-alkyl), in the
left branch of the reaction scheme, whose concentrations are about
a tenth of that of the adsorbed 2-MTHF. The least abundant species
are the three species with secondary carbons, D*, B*, and E* (proton-
ated 2-alkoxide, 2-alkoxide, and 2-alkyl), in the right branch of the
reaction scheme, whose concentration are about one hundredth of
that of the adsorbed 2-MTHF. These results are completely consis-
tent with the magnitude of the rate constants discussed earlier
(Fig. 8), with the species with the smallest desorption constants
on the left branch having the larger coverages. The species on the
right branch are more reactive as they desorb more rapidly, and
their coverages are smaller. This lower surface concentration is in
accord with expectations for highly reactive species.
An important consideration is whether the adsorbed species
can be observed and distinguished by a technique such as infrared
spectroscopy. At rst glance, all the suggested adsorbed intermedi-
ates appear to be similar. They all are alkyl or alkoxide species with
similar structural units, so look impossible to differentiate. How-
ever, close examination of the structures reveals a distinguishing
feature, which is the number of methylene groups (CH2). The
adsorbed reactant A* has three CH2 groups, the two species to the
158 A. Cho et al. / Journal of Catalysis 318 (2014) 151161

Fig. 8. Summary of the rake mechanism and kinetic parameter estimations. The units of the rate constants kA, kB, kD, and kG are cm3 lmol1 s1 and those for the surface
reactions k-A, k-B, k-D, k-E, k-G, k-H, k-I, k1, k2, k4, k5, and k7 are s1.

high wavenumbers, 3737 and 3661 cm1, which are due to SiOH
and POH, respectively [34,42]. They appear negative because the
10
-5
[A*] hydroxyl groups are consumed by interaction with the 2-MTHF.
1.3 x 10 -5 Both sets of spectra also show aliphatic CH stretching bands,
Concentration (mol/cm2)

29702870 cm1 [43], and CH bending and scissoring bands,

-6
10
-7
10
-8
10
0.0 0.1 0.2
Contact time, (s)
Fig. 9. Estimated concentrations of the reaction intermediates.
left have four CH2 groups, while the three species to the right each
have two CH2 groups (Table 7). Thus, it should be possible to dis-
tinguish between the species by focusing on the CH2 vibration in
the infrared spectrum. This was duly found to be the case.
Infrared spectra of the adsorbed species were obtained in an in
situ cell (Fig. 1) at two sets of conditions, in a N2 ow stream and in
a H2 ow stream. First, results for adsorption of 2-MTHF as temper-
ature was progressively raised are reported (Fig. 10).
The spectra at the adsorbed 2-MTHF in the inert N2 and reactive
H2 atmospheres display similar features, but also important differ-
ences which will be discussed momentarily. First, covering similar-
ities, the spectra at the two conditions show two negative peaks at
14601380 cm1 [44], that are due to adsorbed 2-MTHF and/or
[H*] CH3
O
some reaction intermediates. A peak at around 1700 cm1 can be
[G*] +
* assigned to adsorbed 2-MTHF and/or 2-methylfuran. A very small
feature at 2483 cm1 is due to PH vibrations. A doublet band at
[D*] 2365/2330 cm1 is due to atmospheric CO2 outside the in situ cell.
[B*] A band at 2035 cm1 is due to linearly adsorbed CO on Ni2P, which
[E*] appears at slightly lower wavenumber than in other reports
[45,46], possibly because of the high dispersion of the present sam-
ple. In the IR spectra in N2 of 2-MTHF adsorbed on the Ni2P/SiO2
0.3
(Fig. 10a), all of signals decrease and negative peaks are recovered
as temperature increases. This is noteworthy for the case for the
OH stretches at high wavenumber, which go to the baseline level
already at 453 K, and indicate that desorption from the support
is complete at that temperature. Thus, the overall decrease in peak
intensity is due to desorption of 2-MTHF from rst the support and
then the Ni2P.
The IR bands in H2 of 2-MTHF adsorbed on the Ni2P/SiO2
(Fig. 10b) show a similar tendency to decrease with increasing
temperature as those taken in N2. However, it can be readily seen
that although the intensities begin at a comparable level, in H2 the
adsorbate signals do not decrease as rapidly with rising tempera-
ture as in N2, but rather tend to persist. The retention of the band
intensities in the presence of H2 can be explained by the transfor-
mation of adsorbed 2-MTHF to adsorbed ring-opened products
(Fig. 8) by hydrogen-transfer steps. Thus, instead of desorbing,
the adsorbed 2-MTHF reacts with hydrogen to form other adsorbed

Table 7
Differences between adsorbed species.

Left branch products Reactant Right branch products

H* G* A* D* B* E*
4 CH2 4 CH2 3 CH2 2 CH2 2 CH2 2 CH2
 A. Cho et al. / Journal of Catalysis 318 (2014) 151161 159

2970
(a)Under N2 flow
2934 0.05
2876
1385
3737 3661 1420
2365/2330 1461
Absorbance

448 K 2483 2035

473 K
498 K
523 K
548 K
573 K
598 K

4000 3500 3000 2500 2000 1500

Wavenumbers (cm-1)

2964
(b) Under H 2 flow 2936 0.05
2878
1384
3738 2365/2327 1419
1460
Absorbance

3666
2483 2041 1570 Fig. 11. In situ FTIR spectra of 2-MTHF adsorbed on the Ni2P/SiO2 catalyst at various
448 K 1695 temperatures: 33002750 cm1 (a) under N2 ow and (b) under H2 ow.
473 K
498 K
523 K There is another signicant change observed when the carrier
548 K gas is changed from inert N2 to reactive H2. A sharp strong feature
573 K 2060 scarcely present under N2 appears at 2035 cm1, which is due to
598 K linearly adsorbed CO on Ni2P. There are also smaller intensity
bands in the range 18201920 cm1 due to bridging CO species.
4000 3500 3000 2500 2000 1500 The formation of CO is due to a decarbonylation reaction of a ter-
Wavenumbers (cm-1) minal aldehyde. At steady state this results in equal amounts of
CO and n-butane, which is observed experimentally [31]. The rea-
Fig. 10. In situ FTIR spectra of 2-MTHF adsorbed on the Ni2P/SiO2 catalyst at various
son the decarbonylation occurs in the presence of H2 is that the
temperatures. (a) Under N2 ow and (b) under H2 ow.

(a) Under N2 flow

species which populate the surface before themselves desorbing.
The question is which species are on the surface? 2970-2876

Absorbance
0.1
The answer can be obtained by examining an expanded region of
the CH stretching region (Fig. 11). There are three bands which
under H2 appear at 2964, 2936, and 2878 cm1 (Fig. 11b). Similar
2035
bands appear under N2 (Fig. 11a). These can be assigned predomi-
nantly to the stretching frequencies of the CH bonds in CH3, CH2,
and CH groups [47,48]. In actuality some overlap occurs, e.g. due
to symmetric and asymmetric band contributions. The notable 2
4
in
aspect of the spectra under H2 is that the central band at
/m

6
2936 cm1 due mainly to CH2 vibrations is visibly stronger than 8
e
m

10
Ti

under N2. Its intensity is almost equal to that of the rst band at 4000 3500 3000 2500 2000 1500
-1
2964 cm1 due to CH3 vibrations. This is a clear indication that Wavenumbers / cm
the species formed by hydrogenation of the adsorbed 2-MTHF have
more CH2 bonds than in N2 and points to the majority surface spe- (b)Under H2 flow
cies after 2-MTHF being those on the left branch (Table 6). This is 2041
Absorbance

exactly as predicted in the tting calculations (Fig. 9) which indi- 2964-2878 0.1
cated that the terminal alkoxy and alkyl species on the left branch
are more numerous than the secondary species on the right branch.
The spectra under N2 can be integrated to give an estimate of
the heat of adsorption of 2-MTHF. A linear vant Hoff plot was
obtained (Supplementary information), which gave a heat of
adsorption of 12.0 kJ/mol. 2
The main ndings obtained by raising the temperature are 4
in

6
/m

duplicated in transient spectra at constant temperature (Fig. 12). 8

e
m

The peaks close to the high 2900 cm1 range are due to the CH 10
Ti

4000 3500 3000 2500 2000 1500

stretches of adsorbed species, and it can be seen that in N2 the high -1
Wavenumbers / cm
wavenumber band due to CH3 groups is dominant, while in H2, a
double peak caused by CH3 and CH2 contributions is the main Fig. 12. Transient spectra of 2-MTHF on Ni2P at 523 K (250 C). (a) Desorption in N2
feature. and (b) reaction in H2.
160 A. Cho et al. / Journal of Catalysis 318 (2014) 151161
Fig. 13. Possible steps in the transformation of 2-MTHF. (a) Ring-opening and (b) decarbonylation.
precursor aldehyde needs to be formed by a ring-opening reaction
(Fig. 13a). A possible mechanism of reaction for this portion of the
network indicates that a hydride is also necessary for the decarb-
onylation (Fig. 13b).
To summarize, this work investigated the hydrodeoxygenation
(HDO) pathway of the biomass model compound 2-meth-
yltetrahydrofuran (2-MTHF) over a Ni2P/SiO2 catalyst at 0.5 MPa
and 573 K (300 C). The results were analyzed using a rake mech-
anism where a sequence of reactions occur on the surface of the
catalyst and each intermediate species can desorb. The 2-MTHF
reactant is interesting because in the course of reaction it can
undergo ring-opening in two manners, by cleavage of the ring
CO bond on the more hindered side to give intermediates with
oxygen on a primary carbon or cleavage of the ring CO bond on
the more open side to give intermediates with oxygen on a second-
ary carbon.
The studies here conrm previous work that showed that both
pathways are possible. However, the present studies go consider-
ably further, by considering surface intermediates and providing
evidence for the rst time that the ring-opening pathway that
results in bonding through a primary carbon results in intermedi-
ates at high levels of concentration. This is conrmed by in situ FTIR
measurements that show that the intermediates bonded through
primary carbons are more plentiful than those bonded through sec-
ondary carbons. This gives a complete and consistent picture of the
reaction pathways in the HDO of 2-methyltetrahydrofuran.
4. Conclusions
The main ndings of this study are the following:
1. The hydrodeoxygenation of 2-methyl tetrahydrofuran, a
cyclic saturated ether compound, over a Ni2P/SiO2 catalyst
at 0.5 MPa proceeds through a reaction network in which
ring-opening can occur on either the side with the methyl
group or on the unfunctionalized side.
2. Ring-opening on the side with the methyl group is slightly
less favored and produces intermediates with secondary
carbon substitution such as 2-pentanone and 2-pentanol
before formation of the nal product n-pentane.
3. Ring-opening on the unsubstituted side is more favored
and produces intermediates with primary carbon substitu-
tion such as n-pentanal and 1-pentanol before formation of
the same nal product n-pentane.
4. The n-pentanal can undergo a decarbonylation step to pro-
duce CO which adsorbs on the surface.
5. Kinetic modeling of the reaction network with a rake mech-
anism that considers plausible adsorbed intermediates
gives excellent ts to contact time data, and predicts that
the species formed with primary carbon substitution are
ten-fold more abundant than those with secondary carbon
substitution.
6. Measurements of adsorbed species at reaction conditions
with Fourier transform infrared spectroscopy conrm that
the species with primary carbon substitution are more
plentiful on the surface.
Acknowledgments
This work was supported by the US Department of Energy, Ofce
of Basic Energy Sciences, through Grant DE-FG02-963414669,
the National Science Foundation through Grant CBET-144316,
and the Japan Ministry of Agriculture, Forestry, and Fisheries
(Norinsuisansho).
The TEM pictures in this work were taken in Research Hub for
Advanced Nano Characterization, The University of Tokyo,
supported by the Ministry of Education, Culture, Sports, Science
and Technology (MEXT), Japan.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcat.2014.07.021.
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