Ultra-low loading of Ni in catalysts supported on mesoporous SiO2 and their performance in hydrodeoxygenation of palmitic acid

Article abstract of DOI:10.1039/c9nj05450b

We synthesized a series of new Ni catalysts supported on mesoporous silica KIT-5. The metal loading on this support was varied (0.9-7.0 wt% NiO). The catalysts were characterized by N₂ physisorption, powder XRD, XRF spectrometry, UV-vis DRS, H₂-TPR, HRTEM and FT-IR with CO. The mesoporous structure is maintained in all the catalytic materials. The increase in the Ni loading resulted in the formation of crystalline phases at the KIT-5 surface. The catalysts were tested in hydrodeoxygenation (HDO) of palmitic acid. The catalytic activity increased with the metal loading, reaching a maximum by using the catalyst with 1.8 wt% NiO. On the other hand, calculation of kinetic parameters indicated the effective utilization of catalytically active Ni particles in the HDO process. Formation of oxygen-free products was higher for the catalyst with higher metal loading in this series. These catalytic materials were compared with a series of Ni catalysts supported on carbon, finding that the Ni/KIT-5 catalysts were much more active in the HDO reaction. These new catalysts supported on the mesoporous silica KIT-5 exhibited high activity with low metal loadings. This feature makes them attractive for their application in the HDO of fatty acids.

Full text of DOI:10.1039/c9nj05450b

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: D. Valencia, C.
Zenteno, P. Morales-Gil, L. Diaz-Garcia, D. Gomora-Herrera, E. Palacios-Gonzalez and J. Aburto, New J.
Chem., 2020, DOI: 10.1039/C9NJ05450B.
Volume 42
Number
March 2018
Pages 3963-4776
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
6
21
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Page 1 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Ultra-Low Loading of Ni in Catalysts Supported on
Mesoporous SiO2 and their Performance in
Hydrodeoxygenation of Palmitic Acid
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
*
Diego Valencia , Citlalli Zenteno, Perla Morales-Gil, Leonardo Díaz-García, Diana Gómora-
Herrera, Eduardo Palacios-González, Jorge Aburto
Dirección de Investigación en Transformación de Hidrocarburos, Instituto Mexicano del Petróleo,
Eje Central Lázaro Cárdenas Norte 152, Col. San Bartolo Atepehuacan, C.P. 07730, Mexico City,
Mexico.
*
Corresponding author: dvalencia@imp.mx
1

New Journal of Chemistry
Page 2 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Abstract
We synthesized a series of new Ni catalysts supported on mesoporous silica KIT-5. The metal
loading on this support was varied (0.9 - 7.0 wt. % NiO). The catalysts were characterized
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
by N
2
physisorption, powder XRD, XRF spectrometry, UV-Vis DRS, H -TPR, HRTEM and
2
FT-IR with CO. Mesoporous structure is maintained in all the catalytic materials. The
increase in the Ni loading resulted in the formation of crystalline phases at the KIT-5 surface.
The catalysts were tested in the hydrodeoxygenation (HDO) of palmitic acid. The catalytic
activity increased with the metal loading reaching a maximum by using the catalyst with 1.8
wt. % NiO. On the other hand, the calculation of kinetic parameters pointed out the effective
utilization of catalytically active Ni particles in the HDO process. The formation of oxygen-
free products was higher for the catalyst with higher metal loading in this series. These
catalytic materials were compared with a series of Ni catalysts supported on carbon, finding
that the Ni/KIT-5 catalysts were much more active in the HDO reaction. These new catalysts
supported on the mesoporous silica KIT-5 exhibited high active with low metal loadings.
This feature makes them attractive for their application in the HDO of fatty acids.
KEYWORDS: KIT-5, Nickel, Hydrodeoxygenation, biomass
2

Page 3 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Introduction
Environmental protection and depletion of fossil reservoirs are key elements to the
development of sustainable processes and new energy carriers. Linear hydrocarbons such as
alkanes are important class of molecules with a variety of chemical applications based on
their structure. Typically, they are obtained from fossil resources and used as fuels, building
blocks for the synthesis of polymers as well as lubricants.[1] These hydrocarbon chains can
also be obtained from vegetable oils, an intended more sustainable source. The production of
linear hydrocarbons from renewable resources is a technological challenge in contemporary
times.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
In this sense, hydrodeoxygenation (HDO)[2] is the main catalytic process to produce linear
hydrocarbon by reacting vegetable oils with hydrogen in the presence of a heterogeneous
catalyst. The aforementioned belongs to a series of well-known hydrotreating processes
developed for processing fossil resources. For this reason, some catalytic materials have been
[3]
adapted from the existing ones and used in the petroleum industry. These catalysts consist
of active phases such as sulfides or metal species supported on oxide materials. On the other
hand, these catalytic materials also face several challenges such as the presence of water or
coke formation that leads to a rapid deactivation or poor catalytic activities.[4]
Early investigations have shown that Ni is a metallic active phase for the hydrodeoxygenation
of different biomass feedstocks.[5][6][7][8] Fatty acids are transformed into linear hydrocarbons
over Ni-based catalysts in the HDO process. The catalytic performance of the Ni catalysts
depends on the support used. For instance, ZrO has shown superior catalytic performance
2
compared to other metal oxide supports.[9][10]. The use of oxide supports with different
chemical composition is relevant for the new generation of heterogeneous catalysts in the
3

New Journal of Chemistry
Page 4 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
HDO of fatty acids. For instance, Ni supported on γ-Al
2
O has been also tested in the HDO
3
of methyl laurate with high catalytic activity.[11] Carbon is also a promising support in the
development of new sulfur-free catalysts in HDO. In this line, Ni catalysts supported on
activated carbon have been tested in the HDO of fatty acids, where higher loadings of metal
particles (20-30 %) are necessary to obtain products for bio-jet fuel.[12] The Ni loading is
usually very high in the catalytic materials for efficient biomass transformation (10-
80%)[13][14][15][16], which makes this system very much expensive and environmental
unfriendly. Therefore, the optimization of this catalytic system by reducing the metal loading
might provide a promising alternative for its utilization in biomass conversion.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Mesoporous ordered materials have been developed and used for several applications,
including heterogeneous catalysis.[17][18][19]Their synthesis conditions produce desired
textural properties such as high surface areas and arranged pores, which can accommodate
bigger molecules such as fatty acids within their cavities. For instance, mesoporous silica
with high surface area has been used as a support of catalytically active species in
hydrodesulfurization[20], oxygen evolution[21][22], immobilization of enzymes[23][24]
,
Knoevenagel condensation[25], etc. Mesoporous SiO
supports have been also tested in
2
biomass transformation.[26] These materials might be used for the conversion of biomass to
fuel or in the following upgrading steps, also new applications might come up in this field.
Metals supported on mesoporous materials combine their catalytic functions with the ordered
mesoporous, providing active centers where biomass-derived molecules can be converted.[27]
For instance, the catalysts supported on SBA-15 have shown remarkable catalytic activity
and selectivity in the transformation of biomass derived molecules.[28][29] In this line, Ni
catalysts supported on Al-SBA-15 are very active and selective towards deoxygenated
4

Page 5 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
products in lignin conversion.[30] To the best of our knowledge, mesoporous silica KIT-5 has
not been extensively exploited in biomass transformation processes, but few studies have
highlighted its tremendous potential.[31][32] This highly well-ordered nanocage type silica
mesoporous material possesses a cubic Fm3m close packed symmetry.[33] Its textural
characteristics are attractive to be used as a support in the conversion of large molecules such
as fatty acids.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Strategies to use nanostructured supports for Ni active phase produce higher reaction rates
compared to commercial zeolites in the HDO of triacylglycerides and related products.[34]
Zeolites with larger cavities such as SAPO-11 have shown remarkable results in this
process.[35][36] In most cases, the best catalytic performances were obtained at 7 wt. % of Ni
or higher loadings. Ni catalytically active species with low loadings are necessary to be
effective materials in biomass conversion. New generation of Ni-based catalysts combining
active materials with ultra-low metal loading can be produced with the help of mesoporous
silica as support. Here, we synthesized a novel series of Ni catalysts supported on KIT-5 to
continue exploring the use of mesoporous supports in the HDO of fatty acids. We prepared
a series of Ni-based catalysts supported on KIT-5 by varying the metal loading, while taking
in mind the need to reduce Ni content and enhancing catalytic performance.
Experimental
Synthesis of materials
The mesoporous silica molecular sieve KIT-5 was synthesized according to a procedure
reported elsewhere.[33] This highly ordered three-dimensional close-packed cage-type
5

New Journal of Chemistry
Page 6 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
mesoporous silica with Fm3m symmetry was used as a support for the Ni-based catalysts.
®
The copolymer Pluronic F127 (Sigma-Aldrich) was used as a template. The hydrothermal
synthesis was carried out at 100 °C for 48 h. The template was removed by calcination under
air atmosphere at static conditions at 550 °C for 4 h. The catalysts were prepared by wet
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
impregnation, using an aqueous solution of Ni(NO
3
)
2●6H O (Fisher) to the calcined KIT-5
2
material. The catalytic materials were dried overnight at room temperature, and then they
were calcined at 500 °C for 4 h under air atmosphere. We varied the metal loading in the
support to get a final of 0.9, 1.8, 3.5 and 7.0 wt. % NiO in the materials. We denoted the
samples as KN1, KN2, KN3 and KN4, respectively. These materials were reduced under a
-1
continuous H flux of 15 mLmin at 400 °C for 3 h and then, the temperature was decreased
2
to room temperature. These reduced samples were tested as Ni/KIT-5 catalysts.
Characterization of materials
The catalysts were characterized by nitrogen physisorption, powder X-ray diffraction (XRD),
X-ray fluorescence (XRF) spectrometry, UV-vis diffuse reflectance spectroscopy (DRS),
temperature-programmed reduction (TPR), High Resolution Transmission Electron
Microscopy (HRTEM) and Fourier Transform Infrared (FTIR) spectroscopy with CO as a
probe molecule. N
2
adsorption–desorption isotherms were measured with a Micromeritics
temperature. Prior to the experiments, the
ASAP 2405 automatic analyzer at liquid N
2
−
1
samples were degassed (p < 10 Pa) at 473 K for 1 h. The composition was determined by
XRF with a Thermo Fisher Scientific spectrometer model ARL ADVANT X. XRD patterns
were recorded within the 4 – 80° 2θ range on a Siemens D500 diffractometer, using Cu Kα
−
1
radiation (λ = 1.5405 Å) and a goniometer speed of 0.02° (2θ) min . The crystalline size (D)
6

Page 7 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
was estimated from the full width at half maximum, using the Scherrer equation and the Jade
010 software. The UV-Vis DRS studies were carried out in a Thermo-Scientific Evolution
model 600 spectrometer. H -TPR experiments were performed using a ZETON Altamira
model AMI-200, with a reduction mixture of hydrogen/argon (10 vol. % of H ), equipped
2
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
with a standard thermal conductivity detector (TCD). The HRTEM measurements were
performed in a TITAN80-300 microscope with Schottky type field emission filament
operating with an acceleration voltage of 300 kV. The micrographs were obtained using a
CCD camera and Digital Micrograph Software from GATAN. FTIR experiments were
carried out in a Thermo-Nicolet model 8700 FTIR spectrometer equipped with a home-made
-1
flow quartz cell (CaF
In all the cases, samples were prepared like self-supported wafers. All the catalysts were
activated by in-situ reduction under H atmosphere at 673 K for 90 min before the addition
2
window) with a spectral resolution of 4 cm , 75 scans, DTGS detector.
2
of CO (13 inHg). After addition, the wafers were cooled with liquid nitrogen, followed by
the evacuation of CO excess before increasing the temperature from 73 K to room
temperature.
Catalytic test
The catalysts were tested in the HDO of palmitic acid (PA), Sigma Aldrich > 99%. This
model compound represents a range of linear fatty acids, which are present in biomass
feedstocks. 0.1 g of reduced catalyst was used for each test with 40 mL of a solution
containing PA (39 mM) in n-dodecane (Sigma Aldrich, anhydrous > 99%). The catalysts
were tested in a Parr reactor at 280 °C and 5.2 MPa of H pressure for 6 h. The course of the
2
reaction was followed by withdrawing aliquots every hour and analyzing them on a gas
7

New Journal of Chemistry
Page 8 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
chromatograph equipped with a FID. Product identification was analyzed on a Hewlett
Packard GC-MS instrument. A series of carbon supported materials was prepared for
comparison purposes, using the same synthesis method and catalytic testing conditions as the
®
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
catalysts supported on KIT-5. Commercial activated charcoal Norit PK 3-5 (Sigma-Aldrich)
was used as a support for Ni/C catalysts.
Results and Discussion
Characterization of materials
Description of labels for the samples is given in Table 1. Nitrogen adsorption-desorption
isotherm of KIT-5 is shown in Figure 1. Its shape is characteristic of type IV isotherms with
an H1 hysteresis loop of ordered mesoporous materials. This isotherm corresponds to the
reported one for KIT-5, which is in good agreement due to the synthetic conditions. The
preparation of the Ni-supported catalysts preserves the parent adsorption-desorption isotherm
provided by the mesoporous KIT-5. The shape of the isotherms and of the hysteresis loops
did not suffer important changes after the incorporation of the Ni species into the support.
The adsorbed volume decreased in all the catalytic materials with respect to the pure support.
This decrement is explained by the incorporation of metal particles onto the surface of KIT-
5, which produced a decrease in the N
2
adsorbed volume. The textural characteristics of the
support and catalysts are enlisted in Table 1. The KIT-5 support exhibited a specific surface
2
3
of 669 m /g, total pore volume of 0.613 cm /g and pore diameter of 34.2 Å. The BET specific
areas of the catalysts are smaller than that of pure KIT-5. These values decreased as a function
of the Ni loading within the catalysts. For instance, KN1 with 0.9 wt. % NiO showed a SBET
8

Page 9 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
2
=
565 m /g, while the catalysts with the highest Ni loading (KN4) showed the lowest SBET
2
(
545 m /g). These results are in good agreement with the surface occupied by the metal
species due to the amount incorporated in KIT-5. In other words, higher amounts of Ni
occupied larger surface of the support, decreasing the surface area of the materials.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
4
3
00
00
(A)
4
3
2
1
0
(B)
200
100
0
.0
0.2
0.4
0.6
0
0.8
1.0
2
3
4
5
6
7
8
9
10
p/p
Pore width (nm)
Figure 1. (A) N adsorption-desorption isotherms and (B) pore size distribution from
desorption data of (○) KIT-5, (▼) KN1, (●) KN2, (♦) KN3 and (■) KN4.
2
Table 1. NiO or Ni content for the materials supported on KIT-5 and their textural
characteristics of KIT-5 and its NiO supported catalysts.
Nia
Nib
c
NiO
S
BET
2
d
3
e
Sample
V
p
(cm /g)
D (nm)
p
(wt. %) (wt. %) (wt. %)
(m /g)
KIT-5
KN1
KN2
KN3
KN4
--
--
669
0.613
0.534
0.529
0.580
0.512
3.4
0.9
1.8
3.5
7.0
0.7
1.0
2.7
5.5
0.6
1.1
2.9
5.5
565
3.4
3.4
3.2
3.2
555
549
545
a
b
c
d
Ni content on the samples (calculated).
Experimental Ni content on the samples determined by XRF spectrometry.
Specific surface area determined by the BET method.
Total pore volume determined by N
2
adsorption at a relative pressure of 0.98.
9

New Journal of Chemistry
Page 10 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
e
Pore diameter corresponding to the maximum of the pore size distribution calculated from
the desorption isotherm by the BJH method.
Powder XRD patterns of KIT-5 and supported catalysts are displayed in Figure 2. The
support shows a broad band between 15 and 35 °, which is attributed to amorphous silica.
The preparation of the catalysts produced diffraction peaks due to crystalline phases formed
in the materials. These peaks are detected since low loadings of Ni species in the materials,
while the highest loaded sample (KN4), showed very intense peaks. The formation of
crystalline structures on the KIT-5 surface is a consequence of the poor dispersion of these
metal species in the silica support. The compound formed on the support surface was
identified as NiO (JCPDS 47-1049) as oxide materials. This oxide is transformed into the
metallic Ni species (JCPDS 4-016-6268) after the reduction treatment and the particles are
still detectable by this technique. We calculated the crystal size for the metal particles
detected by XRD on the surface of KIT-5. Those values are shown in Table 2. The crystal
size for the NiO particles in the KN1 catalyst is the lowest in this series (64 Å). The increase
in the NiO loading within the catalytic materials also produced larger particles on the support
surface. This increment is proportional to the loading in the catalytic materials, as expected,
due to the dispersion of nickel particles on the KIT-5 surface. The largest crystalline size was
obtained for the KN4 catalyst (218 Å). The values of the size of the Ni particles are very
similar as the NiO particles, pointing out that the reduction reaction did not change the size
of the particles. Similar results were reported for Ni catalysts supported on KIT-6 at different
reduction temperatures.[37] This might indicate that the particles would not be sintered under
reduction conditions.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
10

Page 11 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
(a)
(A)
(B)
(
a)
(
b)
•
•
•
•
•
•
• •
(b)
∗
(
c)
•
•
∗
∗
(
c)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
d)
•
•
(
d)
•
•
•
•
•
•
•
•
∗
(e)
(e)
1
0
20
30
40
50
60
70
80 10
20
30
40
50
60
70
80
2
θ (ꢀ)
2θ (ꢀ)
Figure 2. Powder X-ray Diffraction (XRD) patterns for (a) KIT-5, (b) KN1, (c) KN2, (d)
KN3 and (e) KN4 materials. (A) NiO and (B) Ni materials. ● NiO bunsenite (JCPDS 47-
1
049), * Ni (JCPDS 04-016-6268).
UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) was used to characterize the
electronic transitions in the catalysts supported on KIT-5 (Figure 3). The strong and broad
UV band can be attributed to the NiO absorption originated from the free hole-electron pair
transition.[38] The intensity of this band in the UV regions increases with the metal loading in
the materials, where this main band is correlated directly with the NiO amount in the samples.
2
+
The absorption band at 390 nm is attributed to Ni with octahedral symmetry. This band is
larger for the KN4 catalyst due to the concentration of the metal species in the support. We
found a band located at 720 nm, which can be attributed to larger NiO crystals on the KIT-5
surface.[39] This band is more pronounced in the catalysts with higher Ni content, which is in
agreement with the largest crystalline particles detected by XRD.
11

New Journal of Chemistry
Page 12 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(d)
(
(
c)
b)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(a)
2
00 300 400 500 600 700 800
Wavelength (nm)
Figure 3. UV-Vis DRS for (a) KN1, (b) KN2, (c) KN3 and (d) KN4.
Temperature-programmed reduction profiles for the Ni catalysts supported on KIT-5 are
shown in Figure 4. Such profiles display differences due to the Ni loading on the samples;
likewise, the TPR profiles showed higher H consumption for the samples with larger Ni
2
amounts (KN4), as expected, due to the high amount of reducible species. The main reduction
peak for the KN1 and KN2 catalysts is located at 420 °C, and it shows a shift to lower
temperatures for the KN3 and KN4 catalysts (390 °C). The increment in the Ni loading seems
to produce differences in the metal-support interactions. The NiO particles with lower
loadings interact strongly with the support in comparison with those having higher loadings.
These results are in good agreement with the XRD results, where larger NiO particles were
detected on the KIT-5 surface for the higher loaded samples. Additionally, we calculated the
12

Page 13 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
reducibility factor (α
H
) for the NiO/KIT-5 catalysts from the integration of H
2
consumption
from the TPR profiles. It was calculated with the experimental volume consumed in the
samples divided by the theoretical volume (α = V/V ) to reduce completely NiO species.
Therefore, this value is a consequence of the reduction capacity of the supported NiO
particles under H atmosphere to form Ni catalytic species. We enlisted the values in Table
. We found that α is 1 for the KN1 and KN2 catalysts, which means that the chemical
reaction NiO + H → Ni + H O is almost complete under TPR conditions. These materials
have the lowest Ni loadings and it seems that their transformation into Ni particles was fully
achieved. However, the catalysts with higher Ni content showed lower α values. The
H
t
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
2
H
2
2
H
differences in the reducibility factors due to the Ni loading in KIT-5 is a consequence of the
metal-support interactions and the particle sizes. The larger particles detected by XRD
measurements are more difficult to be reduced than the smaller ones.
(
a)
(
b)
(
c)
(d)
200
400
600
800
Temperature (°C)
Figure 4. H
2
-TPR profiles for (a) KN1, (b) KN2, (c) KN3 and (d) KN4.
13

New Journal of Chemistry
Page 14 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
HRTEM measurements were performed on selected samples to obtain the changes in the NiO
and Ni particles supported on KIT-5. Figure 5 shows representative micrographs for the KN4
catalyst before and after reduction under H atmosphere. We can clearly see that both NiO
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
and Ni particles are well dispersed inside the KIT-5 pores. The reduction reaction for these
materials to form the catalytically active species presents homogeneously dispersion,
indicating that the active particles possess thermal stability inside the pores of KIT-5.
HRTEM images confirmed the crystallinity of the NiO and Ni particles, in good agreement
with XRD results.
14

Page 15 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 5. HRTEM micrographs of KN4 catalysts as oxide and metal species. (A) and (B)
NiO; (C) and (D) Ni.
The CO uptake was estimated for the Ni/KIT-5 catalysts in order to get insights into the
exposure of the catalytically active sites in the materials (Table 2). This characterization
technique was used with the reduced samples of Ni particles. This information is useful in
terms of the catalytic active sites, since these sites will be used in the HDO of palmitic acid.
-1
We found that the irreversible CO uptake of KN1 catalyst is 6.7 μmolg and it increased for
15

New Journal of Chemistry
Page 16 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
the higher loadings of Ni in the materials. A maximum value was obtained between the KN3
and KN4 catalysts. However, these materials have different loadings of Ni species on KIT-
5
. This fact indicates that the catalytically active sites optimally increased up to 3.5 wt. %.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
However, higher loadings did not increase significantly the exposed Ni atoms with catalytic
sites to bind CO. We also calculated the CO/Ni atomic ratio to establish a comparison
between the exposed Ni atoms in the materials. We found that the utilization of these particles
is successful in terms of metal loading and exposed active sites in the KN3 catalyst. This
value is the lowest for KN4 catalyst, which indicates that half percent of Ni is not used
catalytically compared to KN3.
Table 2. Selected parameters of reduction properties, crystal size and CO uptake for the
Ni/KIT-5 catalysts.
b
c
D (Å)
D (Å)
Irreversible
CO
CO/Ni
atomic
a
Catalyst
α
H
uptaked
-
1
(µmol g )
6
4
69
6.7
0.058
0.063
0.067
0.032
KN1
KN2
KN3
KN4
1.00
1.00
0.90
0.85
121
14.8
31.6
31.5
109
161
163
218
222
a
b
c
d
Reducibility factor calculated from TPR.
Crystalline size of NiO calculated from the XRD data from the (200) plane.
Crystalline size of Ni calculated from the XRD data from the (111) plane.
CO uptake calculated from FT-IR experiments for the Ni catalysts.
16

Page 17 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Catalytic test
The PA conversion over the Ni catalysts supported on KIT-5 is plotted in Figure 6. The
conversion over KN1 catalyst is very low compared to the catalysts with higher Ni amounts.
The KN2 catalyst showed significant PA conversion in this series due to its Ni loading. The
best catalytic performance was achieved with either the KN3 or KN4 catalysts. Both catalysts
showed very similar PA conversions throughout the time tested. These catalysts reached PA
conversions of 93 and 95 % at 6h, respectively. It is important to note that KN4 catalyst
contains twice the Ni amount compared to KN3 catalyst, and both exhibited very similar PA
conversion.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
00
80
60
4
2
0
0
0
0
1
2
3
time (h)
4
5
6
Figure 6. Conversion of palmitic acid over the catalysts ( ) KN1, (●) KN2, (♦) KN3 and (■)
KN4.
▼
17

New Journal of Chemistry
Page 18 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Kinetic parameters are enlisted in Table 3. The initial rate (r
) for KN1 catalyst is 3.0 x 10-2
o
molL h gcat-1, this r
value for the catalysts with larger loadings of Ni is about 7 x 10 molL
-
1
-1
-2
-
o
1h-1gcat-1. The KN2 to KN4 catalysts showed very similar initial rates of HDO. The rate
constants in the HDO of PA are also shown in Table 2. These constants showed differences
with the lowest value for KN1 (0.6 h-1gcat-1), while the values for this parameter for KN3 and
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
KN4 catalysts are very similar, 4.2 and 4.7 h gcat-1, respectively. In general, the kinetic
parameters for the KN3 and KN4 catalysts are also very similar. We calculated the
normalized rate constant per mmol of Ni to get a better overview of the effectiveness of these
materials due the increasing Ni loadings. The best utilization of Ni is found in the KN2
-1
catalyst, where we get a k = 11.6 h mmolNi-1. The KN3 catalyst also showed an optimal
-1
compromise in its Ni content with a k = 8.9 h mmolNi-1. We can state that the KN3 catalyst
is highly active due to its kinetic parameters and it contains half Ni content with respect to
KN4 catalyst, therefore this is a very promising catalytic material for HDO. The calculation
of turnover frequency (TOF) of these catalysts is also shown in Table 3. We obtained the
highest TOF values for the KN1 and KN2 catalysts. On the other hand, the KN3 and KN4
catalysts exhibited lower values. These TOF values pointed out the catalytic activity obtained
from the dispersion of the catalytic active species in the HDO of palmitic acid.
-1
18

Page 19 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Table 3. Kinetic parameters in the hydrodeoxygenation of palmitic acid over the Ni/KIT-5
catalysts.
a, 102
k (h gcat-1)
b
-1
c
TOFd
Conversion at
6 h (%)
r
o
k
n
Catalyst
(molL h gcat-1)
-1
-1
(h mmolNi
-1
-1)
(s )
-1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3.0
0.6
2.7
4.2
4.7
5.2
16.1
17.5
8.5
KN1
KN2
KN3
KN4
32
79
93
95
7.2
11.6
8.9
7
7
.5
.7
4.9
8.8
a
Initial rate of reaction.
Pseudo-first order rate constant.
Normalized pseudo-first order rate constant by mmol of Ni.
Turnover frequency calculated with the dispersion of exposed atoms of Ni obtained from
b
c
d
CO uptake and the initial rate of reaction.
We analyzed the products formed in the HDO of PA over the Ni/KIT-5 catalysts in this study.
The main products identified were n-pentadecane, n-hexadecane, 1-hexadecanol and cetyl
palmitate. These products were obtained by decarboxylation or decarbonylation reactions,
total HDO and condensation reactions, respectively. The mixture of products obtained at 6 h
of HDO of PA over all the catalysts is depicted in Figure 7. The catalysts with lower Ni
loadings, KN1 and KN2, showed very little amounts of n-pentadecane and n-hexadecane, the
main O-free products. We found that the main product for both catalysts is 1-hexadecanol,
which means that both catalysts did not complete the HDO of PA. The catalysts with higher
Ni loadings, KN3 and KN4, showed major production of n-pentadecane and less than the
alcohol product. Therefore, the KN3 and KN4 catalysts with very similar rate constants have
different selectivity. The catalyst with the highest Ni amount is active and selective towards
19

New Journal of Chemistry
Page 20 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
HDO, while the catalysts with lower Ni concentration are also active, but less selective
towards the production of O-free molecules.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
100
80
60
40
20
0
1
8
2
5
6
16
38
54
72
60
60
40
19
19
KN1
KN2
KN3
KN4
Figure 7. Relative distribution of products in the HDO of palmitic acid over the Ni/KIT-5
catalysts. Color coding: orange = n-pentadecane, grey = 1-hexadecanol, yellow = n-
hexadecane and blue = cetyl palmitate.
This series of catalysts showed differences in their performance due to several reasons that
were analyzed by their physical and chemical characteristics. On the other hand, any of these
catalysts can be chosen depending on specific purpose. The KN3 and KN4 catalysts showed
very similar PA conversion, which is desired to be converted in a specific period; the case of
KN1 catalyst, the conversion was very poor. The KN2 catalyst showed a conversion of
palmitic acid of 79 % at 6h, but its normalized rate constant and TOF are the highest. These
20

Page 21 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
kinetic data indicate that the utilization of Ni catalytically active species, in these materials
supported on KIT-5, is the best. The mixture of products obtained from the HDO of palmitic
acid is another important factor in the performance of these materials. The KN1 and KN2
catalysts showed the less amount of n-pentadecane (19 %), and produced higher amounts of
O-containing products. The KN3 catalyst increased twice the production of n-pentadecane
and KN4 produced 60 % of n-pentadecane. Therefore, the amount of Ni is important to
achieve higher yields of O-free hydrocarbons. The performance of the Ni/KIT-5 catalysts
showed that it is a promising system for its application in the production of green fuels. The
Ni loading needed is lower than other catalytic systems and these new materials can be
modified to get desired properties.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Finally, we compared the performance of Ni/KIT-5 catalysts with other Ni supported
materials. Carbon has been proposed as a support of Ni catalysts in the HDO of biomass. [12]
[
40][41]
We synthesized a series of Ni/C catalysts with the same metal loadings and preparation
method for comparison. These materials were tested in the HDO of palmitic acid to be
compared with the Ni/KIT-5 catalysts. Figure 8 shows the PA conversion over both Ni
supported catalysts. For all the loadings, the Ni catalysts supported on KIT-5 showed superior
catalytic performance compared to their counterparts supported on carbon. For instance, the
PA conversion over the catalyst with a loading of 0.9 wt. % supported on KIT-5 is 32 %,
while on carbon it is 8 %. The PA conversion over the Ni-based catalysts showed the
outstanding activity of KIT-5 as a support for all the loadings under study. It is important to
note that the catalytic performance of Ni supported on carbon increased with the metal
loading, while the conversion of palmitic acid reached a maximum at 3.5 wt. % using KIT-5
as support. We can immediately note that the metal loading is successfully utilized with KIT-
21

New Journal of Chemistry
Page 22 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
5
. For instance, Ni/KIT (0.9 wt.%) showed a similar conversion to that of Ni/C (3.5 wt. %),
but the amount of Ni is ultra-low in KIT-5. The textural characteristics and topology of KIT-
exhibited a tremendous potential as a support to be exploited in the HDO of biomass
5
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
feedstocks. It possess a convenient pore arrangement where the fatty acids can fit and be
converted over the Ni catalytic species. Therefore, we can suggest that KIT-5 is a very
promising support for the development of new catalysts in HDO of fatty acids.
100
8
0
60
40
20
0
0.9%
1.8%
3.5%
7.0%
KIT-5
Carbon
Figure 8. Comparison between Ni catalysts supported on KIT-5 and activated carbon.
Conversion of palmitic acid at 6 h of HDO over the catalysts varying the metal loading.
22

Page 23 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Conclusions
We have synthesized a series of new Ni catalysts supported on KIT-5 by varying the metal
loading. The textural properties of this support were preserved after the preparation of the
catalytic materials. We found the formation of crystalline structures at the surface of KIT-5.
The size of these crystalline particles is related to the metal loading. These catalysts are
highly active in the HDO of palmitic acid since very low loadings of Ni in the KIT-5 support.
The kinetic parameters confirmed the effective utilization of the catalytically Ni active sites
in the conversion of palmitic acid since 1.8 wt. %. The increase in the Ni loading exerts a
small effect on the rate constants, but these catalysts can produce major proportion of O-free
hydrocarbons in the HDO of palmitic acid. The use of mesoporous materials to support
catalysts aimed at performing the HDO of fatty acids is very promising, since highly active
materials need low metal loadings compared with commercial supports.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
The authors wish to thank Project Y.61023 CEMIE-BIO Clúster bioturbosina (Instituto
Mexicano del Petróleo) and Fondos SENER-CONACYT Sustentabilidad Energética
(248090) for financial support. R. I. Conde is gratefully acknowledged for her help in
catalytic testing. J. Navarrete-Bolaños, T. Gómez, L.F. Ramírez-Verduzco and A. Vázquez
are also acknowledged for FT-IR, GC-MS, managing and N physisorption, respectively.
2
23

New Journal of Chemistry
Page 24 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
References
[
1]
A. Deneyer, T. Renders, J. Van Aelst, S. Van den Bosch, D. Gabriëls, B. F. Sels,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Curr. Opin. Chem. Biol. 2015, 29, 40.
[
[
[
[
2]
3]
4]
5]
E. Furimsky, Appl. Catal. A Gen. 2000, 199, 147.
D. Kubička, L. Kaluža, Appl. Catal. A Gen. 2010, 372, 199.
E. Furimsky, Catal. Today 2013, 217, 13.
T. Miyazawa, T. Kimura, J. Nishikawa, S. Kado, K. Kunimori, K. Tomishige, Catal.
Today 2006, 115, 254.
[
[
6]
7]
P. Ferrini, R. Rinaldi, Angew. Chemie Int. Ed. 2014, 53, 8634.
C. Zhao, Y. Kou, A. A. Lemonidou, X. Li, J. A. Lercher, Chem. Commun. 2010, 46,
412.
[
8]
Q. Bu, H. Lei, A. H. Zacher, L. Wang, S. Ren, J. Liang, Y. Wei, Y. Liu, J. Tang, Q.
Zhang, R. Ruan, Bioresour. Technol. 2012, 124, 470.
[9]
B. Peng, C. Zhao, S. Kasakov, S. Foraita, J. A. Lercher, Chem. – A Eur. J. 2013, 19,
4
732.
[
[
[
[
10] H. Chen, Y. Wu, S. Qi, Y. Chen, M. Yang, Appl. Catal. A Gen. 2017, 529, 79.
11] S. Chen, G. Zhou, H. Xie, Z. Jiao, X. Zhang, Appl. Catal. A Gen. 2019, 569, 35.
12] J. Wu, J. Shi, J. Fu, J. A. Leidl, Z. Hou, X. Lu, Sci. Rep. 2016, 6, 27820.
13] M. Artetxe, M. A. Nahil, M. Olazar, P. T. Williams, Fuel 2016, 184, 629.
24

Page 25 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
[
[
[
14] F. Chen, C. Wu, L. Dong, A. Vassallo, P. T. Williams, J. Huang, Appl. Catal. B
Environ. 2016, 183, 168.
15] S. A. Selishcheva, M. Y. Lebedev, S. I. Reshetnikov, L. I. Trusov, V. A. Yakovlev,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Catal. Ind. 2014, 6, 60.
16] G. Zafeiropoulos, N. Nikolopoulos, E. Kordouli, L. Sygellou, K. Bourikas, C.
Kordulis, A. Lycourghiotis, Catalysts 2019, 9, DOI 10.3390/catal9030210.
[17] M. E. Davis, Nature 2002, 417, 813.
[18] M. Vallet-Regí, L. Ruiz-González, I. Izquierdo-Barba, J. M. González-Calbet, J.
Mater. Chem. 2006, 16, 26.
[
[
[
[
[
19] B. J. Scott, G. Wirnsberger, G. D. Stucky, Chem. Mater. 2001, 13, 3140.
20] D. Valencia, T. Klimova, Appl. Catal. B Environ. 2013, 129, 137.
21] F. Jiao, H. Frei, Angew. Chemie Int. Ed. 2009, 48, 1841.
22] F. Jiao, H. Frei, Chem. Commun. 2010, 46, 2920.
23] H. Takahashi, B. Li, T. Sasaki, C. Miyazaki, T. Kajino, S. Inagaki, Chem. Mater.
2
000, 12, 3301.
[
24] J. Aburto, M. Ayala, I. Bustos-Jaimes, C. Montiel, E. Terrés, J. M. Domínguez, E.
Torres, Microporous Mesoporous Mater. 2005, 83, 193.
[
[
[
25] S. L. Hruby, B. H. Shanks, J. Catal. 2009, 263, 181.
26] S. Miao, B. H. Shanks, Appl. Catal. A Gen. 2009, 359, 113.
27] C. Perego, A. Bosetti, Microporous Mesoporous Mater. 2011, 144, 28.
25

New Journal of Chemistry
Page 26 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
[
[
28] W. Trisunaryanti, E. Suarsih, Triyono, I. I. Falah, RSC Adv. 2019, 9, 1230.
29] K. B. Baharudin, Y. H. Taufiq-Yap, J. Hunns, M. Isaacs, K. Wilson, D. Derawi,
Microporous Mesoporous Mater. 2019, 276, 13.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
[
[
30] X. Wang, R. Rinaldi, Catal. Today 2016, 269, 48.
31] A. Najafi Chermahini, H. Hafizi, N. Andisheh, M. Saraji, A. Shahvar, Res. Chem.
Intermed. 2017, 43, 5507.
[
32] S. Budhi, C. Mukarakate, K. Iisa, S. Pylypenko, P. N. Ciesielski, M. M. Yung, B. S.
Donohoe, R. Katahira, M. R. Nimlos, B. G. Trewyn, Green Chem. 2015, 17, 3035.
[33] F. Kleitz, D. Liu, G. M. Anilkumar, I.-S. Park, L. A. Solovyov, A. N. Shmakov, R.
Ryoo, J. Phys. Chem. B 2003, 107, 14296.
[
[
34] M. W. Schreiber, D. Rodriguez-Niño, O. Y. Gutiérrez, J. A. Lercher, Catal. Sci.
Technol. 2016, 6, 7976.
35] H. Zuo, Q. Liu, T. Wang, L. Ma, Q. Zhang, Q. Zhang, Energy & Fuels 2012, 26,
3
747.
[
[
36] Q. Liu, H. Zuo, Q. Zhang, T. Wang, L. Ma, Chinese J. Catal. 2014, 35, 748.
37] Y. Lv, Z. Xin, X. Meng, M. Tao, Z. Bian, Microporous Mesoporous Mater. 2018,
262, 89.
[38] R. Suresh, V. Ponnuswamy, C. Sankar, M. Manickam, S. Venkatesan, S. Perumal, J.
Magn. Magn. Mater. 2017, 441, 787.
[
39] R. E. N. Shibiao, Q. I. U. Jinheng, W. Chunyan, X. U. Bolian, F. A. N. Yining, C.
26

Page 27 of 28
New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
Yi, 2007, 28, 651.
40] A. B. Dongil, I. T. Ghampson, R. García, J. L. G. Fierro, N. Escalona, RSC Adv.
016, 6, 2611.
41] E. Santillan-Jimenez, T. Morgan, J. Lacny, S. Mohapatra, M. Crocker, Fuel 2013,
03, 1010.
[
[
2
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
27

New Journal of Chemistry
Page 28 of 28
View Article Online
DOI: 10.1039/C9NJ05450B
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Ni/KIT-5 = L O W M E T A L L O A D I N G
H I G H C A T A L Y T I C A C T I V I T Y
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
00
Supports
HDO
80
60
40
20
0
KIT-5
Ni
Ni
Ni
Carbon
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
0.9%
1.8%
3.5%
7.0%
TEXT:
Ni catalysts supported on KIT-5 are attractive heterogeneous catalysts for
hydrodeoxygenation of biomass feedstocks.