Catalysis Communications 94 (2017) 18–22

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Catalysis Communications

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Short communication

Effect of Ti loading on structure-activity properties of Cu-Ni/Ti-MCM-41

catalysts in hydrodeoxygenation of guaiacol
S.B. Abd Hamid a,⁎, Murtala M. Ambursa a,b, Putla Sudarsanam c, Lee Hwei Voon a, Suresh K. Bhargava c
a
Nanotechnology and Catalysis Research Centre (NANOCAT), University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Chemistry, Kebbi State University of Science and Technology Aliero, Nigeria
c
Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Science, RMIT University, Melbourne, Victoria 3001, Australia

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

Article history: Various Cu-Ni/Ti-MCM-41 catalysts by varying Ti amount (Ti/Si = 10, 20 and 30%) were synthesized for
Received 8 November 2016 hydrodeoxygenation of guaiacol and characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR and
Received in revised form 5 February 2017 Raman spectroscopy. The Ti loading shows an adverse effect on the catalyst surface area. But, more number of
Accepted 6 February 2017
acidic sites (5173.55 μmol/g) were found for 20% Ti loaded Cu-Ni/Ti-MCM-41 catalyst. The 20% Ti loaded Cu-
Available online 8 February 2017
Ni/Ti-MCM-41 catalyst shows a high guaiacol conversion (74.2%) and cyclohexane selectivity (48.81%) which
Keywords:
is due to abundant acid and redox sites: acid sites initiate removal of oxygen via dehydration, while hydrogena-
Biomass valorisation tion of guaiacol to cyclohexane is promoted by redox sites.
Lignin model compound © 2017 Published by Elsevier B.V.
Guaiacol
Hydrodeoxygenation
Cu-Ni/Ti-MCM-41
Ti loading

1. Introduction
Currently, the transformation of renewable biomass feed stocks into
valuable chemicals and fuels have gained considerable attention due to
continuous depletion of non-renewable fuel sources. Lignocellulose is
the second most abundant biomass feedstock after the marine micro/
macro-algae biomass and does not compete with food supplies because
of its non-edible nature [1,2]. Lignocellulose is mainly composed of cel-
lulose, hemicellulose, and lignin. Compared to cellulose and hemicellu-
lose, lignin valorisation remains a major challenge because of its
complex polyaromatic structure [3]. Generally, lignin is directly con-
verted into bio-oils through pyrolysis and liquefaction methods but
the pyrolysis method tend to be more promising. However, this process
exhibit large fraction of lignin-derived compounds with high amounts
of oxygen and oxo-functionalized groups that lower their energy densi-
ty relative to conventional hydrocarbon fuels [4]. Catalytic
hydrodeoxygenation (HDO) of lignin using molecular hydrogen is
seemed to be more advantageous than other conversion processes
since, it produces oil with little amount of oxygen that can be easily
upgraded to hydrocarbon fuels [4]. Due to complex nature of lignin frag-
ment, the use of model compounds in hydrodeoxygenation processes
has been adopted [5].
⁎ Corresponding author.
E-mail address: sharifahbee.ahamid@nanoc.com.my (S.B. Abd Hamid).
Guaiacol molecule has been used as lignin model compound [6] be-
cause it contains two types of O-containing functional groups (Caryl-
OCH3 and Caryl-OH), which are characteristic of lignin fragment [7,8].
It has been demonstrated that catalysts having both redox and acid
sites play a key role in the removal of oxygen from lignin via HDO pro-
cess [9]. Consequently, various bi-functional catalysts composed of
noble metals (Ru, Pt, Pd, and Re) with different supports, namely TiO₂,
CeO₂, and SiO₂ have been developed for the HDO of lignin model com-
pounds [7,8,10–20]. However, the catalytic applications of noble metals
are limited due to their high cost and low abundance. Other studies
using non-noble metals, such as Ni, NiMo, Mo, Fe, Ni2P, Co2P, etc. sup-
ported on acidic supports such as Al2O3, SiO2, ZrO₂, [21–25] have been
also explored. As well, metal oxide supports show smaller surface
area, leading into aggregation of active phases, hence low catalytic
performance.
In this context, the combination of non-noble metals like Cu and Ni
with large surface area mesoporous silica materials seems to be best
choice of catalytic system for HDO reaction of guaiacol. Both Cu and Ni
are cheap, high abundant and exhibit superior redox properties. As
well, mesoporous silica materials, for example MCM-41 shows a high
surface area and adequate acidic sites. It has been demonstrated that
the properties of MCM-41 material can be improved by incorporating
heteroatoms such as Ti [26,27]. Moreover, Ti species play a key role in
deoxygenation reaction [28]. It is therefore expected that the dispersion
of bimetallic CuNi particles on the surface of Ti-MCM-41 may provide
adequate redox and acid properties for efficient HDO of guaiacol.

http://dx.doi.org/10.1016/j.catcom.2017.02.006
1566-7367/© 2017 Published by Elsevier B.V.
 S.B. Abd Hamid et al. / Catalysis Communications 94 (2017) 18–22
Therefore, this work investigates the synthesis of Cu-Ni/Ti-MCM-41 cat-
alysts by varying the Ti amount (Ti/Si = 10, 20 and 30%) for HDO of
guaiacol. A systematic characterization has been undertaken to eluci-
date the influence of Ti on the acid, redox, and catalytic properties of
NiCu/Ti-MCM-41 catalysts.
2. Experimental
2.1. Catalysts synthesis
Various Ti-MCM-41 materials with different Ti/Si atomic ratios (10/
90, 20/80 and 30/70) were prepared by modifying the reported proce-
dure [29]. The detailed synthesis procedure was presented in Supple-
mentary information (ESI). The NiCu (10 wt% as 3:1 of Ni:Cu)
catalysts supported on Ti-MCM-41 samples were synthesized according
to the procedure reported elsewhere [7]. 1.06 g Ni(NO3)2·6H2O (99%,
Aldrich) and 0.48 g Cu(NO3)2·3H2O (99%, Aldrich) were dissolved in
deionised water. This solution was added to another solution containing
4.25 g of Ti-MCM-41 in deionised water and aged at 70 °C with stirring
for 6 h. The resulting viscous solution was dried at 90 °C for 18 h and
then calcined in air at 550 °C for 4 h.
2.2. Catalysts characterization
The small angle XRD analysis was carried out using small angle X-ray
scattering diffractometer (Bruker) with Cu Kα (λ = 0.1542 nm) in the
range of 0 to 10° with step size of 0.01° and step time of 5 s. The wide
angle XRD analysis was performed using X-ray diffractometer (Bruker
D8 advance) with Cu Kα (λ = 0.1542 nm) radiation run at 40 kV and
40 mA in the range of 2θ = 2 to 80° with the step size of 0.03° and
step time of 1 s. Then the N2 adsorption-desorption analysis was con-
ducted (Tristar II series; micrometric) to estimate the textural proper-
ties of the samples. Prior to analysis, 300 mg of the sample was
outgassed at 300 °C for 5 h in the analyser sample tube. The NH3-TPD
analysis was conducted on TPDRO 1100 instrument with Ser.
Fig. 1. NH3-TPD profiles of Ti-MCM-41 samples with different Ti loadings.
19
Nr.20022896 with a thermal conductivity detector (TCD). For each ex-
periment, 51.30 mg of the catalyst was first outgassed at 120 °C for
1 h in He gas, followed by cooling the system to 50 °C before following
10% NH3/Heat 20 ml/min for 1 h. The weakly physisorbed NH3 was re-
moved by purging with 100% helium gas for I hr. Then, thermal desorp-
tion of NH3 was carried out between the temperature of 100–900 °C at
10 °C/min in a He atmosphere flowing at 20 ml/min with a final holding
time of 30 min. Similarly, H2-TPR was conducted on the same instru-
ment. In a typical procedure, 50 mg of the sample was heated from 30
to 650 °C at a heating rate of 10 °C/min with 20% H2 in N2 at a flow
rate of 40 ml/min with a terminal holding time of 60 min. Raman anal-
ysis was conducted using Renishaw in via confocal Raman microscope
having charge coupled device with visible laser of 514 nm.
2.3. Catalysts performance test
Prior to the reaction, the catalysts were reduced in 20% H2 in He with
a flow rate of 40 ml/min at 550 °C for 5 h. Then, 0.1 g of the reduced cat-
alyst (inside glass bulb), 96 wt% heptane, and 4 wt% guaiacol were
transferred into the reactor. The reactions were performed at 10 MPa
H2 pressure, 260 °C, 1000 rpm and 6 h. The reaction products were
analysed qualitatively using GC–MS (Agilent GC-MS6890N) with HP-
5MS (30 m × 0.250 mm × 0.25 μm) capillary column and quantitatively
using GC-FID (Agilent GC-6890N) equipped with HP-5
(30 m × 0.53 mm).
3. Results and discussion
3.1. Physicochemical characterization
Small angle XRD patterns of Ti-MCM-41 samples show a high inten-
sity peak at (100) plane (Fig. S1, ESI), indicating the formation of or-
dered hexagonal cylindrical structures as a model for MCM-41 [30].
With the increase of Ti loading from 20 to 30%, there was a peak shifting
(from 2.85 to 2.70°) toward lower angle side. This is due to the
20 S.B. Abd Hamid et al. / Catalysis Communications 94 (2017) 18–22

distortion of hexagonal structure of MCM-41, an evidence for the incor-

poration of titanium species within the silica matrix [31]. Owing to
higher ionic radius of titanium (Ti4+ = 0.072 nm) [32] compared to sil-
icon (Si4+ = 0.041 nm) [33], the bond length in Ti-O-Si of Ti-MCM-41
could be larger than in Si-O-Si of pure MCM-41, resulting in the distor-
tion of hexagonal structure of MCM-41.
N2 adsorption-desorption isotherms of Ti-MCM-41 samples show a
type IV with H3 hysteresis loop, indicating mesoporous nature of the
materials (Fig. S2, ESI) [34]. The BET surface area of Ti-MCM-41 sample
is decreased from ~833, 731, and 496 m2/g with the Ti loading from 10,
20 and 30%, respectively (Table S1, ESI). Similarly, the pore volume of Ti-
MCM-41 sample is decreased from ~0.5, ~0.4, and ~0.3 cm3/g with the
Ti loading from 10, 20 and 30%, respectively. The decrease of BET surface
area and pore volume at higher Ti loadings could be due to collapsed of
other part within the MCM-41 structure as evidenced by XRD studies
(Fig. S1, ESI) as Ti is heavier than Si. On the contrary, the pore size of Fig. 2. Guaiacol conversion over Cu-Ni/Ti-MCM-41 catalysts at 260 °C, 10 MPa H2 pressure
and 6 h.
Ti-MCM-41 increases from ~2.6, ~2.7, and ~3.0 nm with the Ti loading
from 10, 20, and 30%, respectively which is due to more Ti coordination
in the silicate structures.
The NH3-TPD profiles of Ti-MCM-41 samples are presented in Fig. 1. ~24° is a manifestation of amorphous structures in the synthesized ma-
The peak at low temperature (394 °C) indicates desorption of NH3 from terials [47].
the weak acid sites [35–37] which is shifted to lower temperatures with All the Cu-Ni/Ti-MCM-41 catalysts exhibit type IV isotherm with H3
the increase of Ti loading. This could be affiliated to poor distribution of hysteresis loop (Fig. S6, ESI). The BET surface area of Ti-MCM-41 sam-
coordinated titanium species in MCM-41 frame work. On the contrary, ples were found to decrease from ~833, ~731, and ~497 m2/g to ~512,
the high temperature peak at 555 °C (desorption of NH3 from strong ~497, and ~205 m2/g after the addition of Cu and Ni to 10, 20 and 30%
acidic sites) is shifted to high temperatures with the increase of Ti load- Ti-MCM-41 samples, respectively (Tables S1 and S2). Also, the pore vol-
ing. These observations indicate that the strength of strong acidic sites ume and average pore size were found to decrease to ~0.3–~0.19 cm3/g
increases as the titanium loading increases from 10, 20 and 30%. The and ~ 2.5–~2.3 nm after the addition of Cu and Ni to Ti-MCM-41 sam-
data presented in Table S1, ESI reveal that the 20% Ti loaded MCM-41 ples, respectively. The decreased textural properties in supported cata-
sample has high concentration of acidic sites, which could play a lysts could be due to the occupation of dispersed CuO and NiO species
favourable role in HDO of guaiacol as discussed in the later paragraphs. within the internal and external surface of Ti-MCM-41 supports.
The H2-TPR profiles of Cu-Ni/Ti-MCM-41 samples are shown in
(Fig. S3, ESI). The position of reduction peaks of both copper and nickel
oxides is shifted to higher temperatures with the increase of Ti loading. 3.2. Hydrodeoxygenation of guaiacol over CuNi/Ti-MCM-41 catalysts
This indicates an enhancement in the interactions of copper and nickel
oxides with Ti-MCM-41 as Ti loading increases. The observed peaks at The obtained results in hydrodeoxygenation of guaiacol over CuNi/
240 and 280 °C for 10 and 20% Ti loaded samples, respectively, could Ti-MCM-41 catalysts are shown in Fig. 2. It was found that, the conver-
be assigned to reduction of CuO to Cu, while the peaks noticed at 330 sion of guaiacol increases from 51.5 to 74.2%, when the Ti loading in-
and 353 °C are associated with the reduction of NiO to Ni [38,39]. The creases from 10 to 20% and then decreases to 55.9% for 30% Ti loaded
30% Ti loaded sample shows various peaks; the initial tail at 250 °C rep- catalyst. Fig. 3 shows selectivity of cyclohexane obtained in HDO of
resents the reduction of highly exposed and less interacted CuO to Cu guaiacol over NiCu/Ti-MCM-41 catalysts. The selectivity of cyclohexane
metal. The bands at 310 and 390 °C could be attributed to the reduction was found to increase from 37.7 to 48.8% when the Ti loading increases
of bulk CuO to Cu and NiO to Ni, respectively [40]. from 10 to 20% in NiCu/Ti-MCM-41 catalyst. In contrast, the cyclohex-
Two major Raman bands are noticed for 10 and 20% Ti loaded sam- ane selectivity decreases from 48.8 to 39.0% with the increase of Ti load-
ples (Fig. S4, ESI): the first peak located at 580 cm− 1 is assigned to ing from 20 to 30%, respectively. The observed high conversion of
Ni\\O symmetric stretching vibration while the second peak at guaiacol and high yield of cyclohexane in the case of 20% Ti loaded
1077 cm− 1 indicates the asymmetric stretching vibration mode of NiCu/Ti-MCM-41 catalyst is due to well-balanced acid and redox sites.
Ni\\O [41,42]. No Raman peaks of CuO were found for 10 and 20% Ti
loaded samples, which could be attributed to low Cu loading. The no-
ticed peaks at ~576 and 1060 cm−1 for 30% Ti loaded catalyst is ascribed
to symmetric and asymmetric stretching modes of Ni\\O, respectively
[43]. The peak at ~690 cm−1 is assigned to vibrational mode of Cu\\O.
A red shifting from 580 and 1077 cm−1 to 576 and 1060 cm−1 is noticed
for 30% Ti loaded sample, respectively, which could be related to high
degree of interaction between NiO and the support, in line with H2-
TPR results (Fig. S3, ESI).
The XRD patterns (Fig. S5, ESI) of Ni-Cu/Ti-MCM-41 samples show
various peaks at ~38°, 43° and 63°, corresponding to (111), (200) and
(220) planes of cubic phase NiO, respectively [44,45]. The 30% Ti loaded
Cu-Ni/Ti-MCM-41 catalyst shows two peaks at ~ 36 and ~ 39°, corre-
sponding to (002) and (111) planes of CuO, respectively [46]. But,
only (002) plane of CuO was noticed for 20% Ti containing Cu-Ni/Ti-
MCM-41, while no CuO XRD peaks were observed for 10% Ti containing
Cu-Ni/Ti-MCM-41. The observed small surface area in 30% Ti containing
MCM-41 sample (Table S1, ESI) could be attributed to larger particles Fig. 3. Selectivity of cyclohexane in HDO of guaiacol over NiCu/Ti-MCM-41 catalysts at
which could be detected by XRD analysis. The noticed broad peak at 260 °C, 10 MPa H2 pressure and 6 h.
 S.B. Abd Hamid et al. / Catalysis Communications 94 (2017) 18–22
Table 1
Products distribution from HDO of guaiacol over Ni-Cu/Ti-MCM-41 catalysts with different
Ti loading from 10, 20 and 30%.
Products Products distributions (%)
10% 20%
Cyclohexane 37.7 48.8
Cyclohexene 15.5 11.2
Cyclohexanol 12.8 15.2
Cyclohexanone 7.1 4.2
Phenol 20.8 – 15.4
Methyl cyclohexane 4.1 19.0
Bicyclohexyl 2.0 1.1
Anisole – –
Methoxycyclohexane – –
The number of metal sites is expected to be the same due to similar
metal loading of Cu and Ni in all the Cu-Ni/Ti-MCM-41 catalysts. But,
the number of acids sites varied with a high concentration of these
acids sites over 20% Ti loaded NiCu/Ti-MCM-41 catalyst (Fig. 1 and
Table S1, ESI). Acids sites play a major role in the oxygen removal
through dehydration, whereas the hydrogenation of guaiacol to yield
cyclohexane is promoted by the redox sites [47].
Table 1 shows products distribution in HDO of guaiacol over NiCu/Ti-
MCM-41 catalysts. In addition to cyclohexane as a major product, eight
other different products including cyclohexene, cyclohexanol, cyclohex-
anone, methyl-cyclohexane, bicyclohexyl, anisole, methoxy-
cyclohexane and phenol were found over NiCu/Ti-MCM-41 catalysts.
Anisole and methoxycyclohexane were not observed over 10% Ti loaded
CuNi catalyst (Table 1). In addition to these two products, phenol was
also absent over 20% Ti loaded NiCu/Ti-MCM-41 catalyst. There are
four pure hydrocarbons found including cyclohexane, cyclohexene,
methyl-cyclohexane and bicyclohexyl over 10% and 20% Ti loaded
NiCu/Ti-MCM-41 catalysts. On the other hand, methyl-cyclohexane
and bicyclohexyl were not found over 30% Ti loaded NiCu/Ti-MCM-41
catalysts. This explains that, as Ti loading increases, products selectivity
changes toward oxygenated products. The possible reason is that, the
number of acid sites generated by coordinated Ti species beyond 20%
Ti loading is decreased and poorly dispersed due to decrease in the sur-
face area of the catalysts. The decrease in surface area could result to
poor distribution of coordinated species leading to strength loss of
acids sites to weak ones. This type of behaviour could reduce deoxygen-
ation performance of the catalysts leading to more oxygenated products
as observed from 20% to 30% Ti loaded catalysts. Similar to this observa-
tion in which textural properties and acidity of the catalysts strongly in-
fluenced HDO performance has been reported elsewhere; the catalysts
with higher acidity and better textural properties show better perfor-
mance in HDO reactions [17] similar observation to 20% Ti loaded
NiCu/Ti-MCM-41 catalysts. The cooperative role of metal functions on
deoxygenated compounds converts unsaturated to saturated
Scheme 1. Possible reactions pathways for Guaiacol HDO over Cu\
21
hydrocarbons products. The total distribution of pure hydrocarbons
were found to increase in the following order 20% (80.2%) N 10%
(59.3) N 30% (43.3%) Ti loaded NiCu/Ti-MCM-41 catalysts. Based on
this distribution, along with the reported literature articles [48–50],
30% the possible reaction pathways were proposed (Scheme 1). According
to Scheme 1, HDO of guaiacol proceeds via dihydroxylation and
39.0
4.3 demethoxylation pathways over acid sites to yield phenol and anisole
14.6 and then metal sites promote the hydrogenation of aryl ring to yield cy-
16.2 clohexanone and methyl-cyclohexane. Subsequent hydrogenation, de-
hydration and further hydrogenation convert cyclohexanone into
–
–
cyclohexanol, cyclohexene and cyclohexane, respectively. On the other
1.8 hand, methoxy-cyclohexane can either totally be deoxygenated and in-
8.7 stantly methylated by methyl transfer to form methyl cyclohexane or
can produce cyclohexane which transform into bicyclohexyl through
ring coupling reactions. Further studies are underway to optimise the
reaction conditions for achieving maximum yield of cyclohexane over
20% Ti loaded NiCu/Ti-MCM-41 catalyst.
4. Conclusions
In summary, a series of Ti-MCM-41 supports with various Ti loadings
(Ti/Si ratio = 10, 20 and 30%) and the corresponding supported Cu\\Ni
catalysts were prepared and fully characterized their structural, acidic,
and redox properties. The investigated characterization results showed
that the increase of Ti loading decrease the surface area of the catalyst.
But, the concentration of acid sites increases and decreases with Ti load-
ing having the highest concentration of acidic sites on 20% Ti loaded
CuNi/Ti-MCM-41 catalyst.
The performance of Cu-Ni/Ti-MCM-41 catalysts for HDO of guaiacol
shows that, guaiacol conversion and selectivity of cyclohexane were ob-
served to increase and decrease with increased of Ti loading. The 20% Ti
loaded NiCu/Ti-MCM-41 shows a best performance in terms of guaiacol
conversion (74.2%) and cyclohexane selectivity (48.8%). The presence of
ample amount of acidic and redox sites are found to be key factors for
high performance of 20% Ti loaded NiCu/Ti-MCM-41 catalyst in
hydrodeoxygenation of guaiacol.
Acknowledgement
The authors are grateful for scholarship from Kebbi State University
of Science and Technology Aliero, Nigeria and funding from University
of Malaya, Malaysia (Grand challenge: GC grant no: GC001A-14AET).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.catcom.2017.02.006.
\Ni supported on Ti-MCM-41.
22 S.B. Abd Hamid et al. / Catalysis Communications 94 (2017) 18–22

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