Role OfTiO2 pillared bentonit and catalyst nickel for hydrogenation glucose to generate sorbitol

Article abstract of DOI:10.13005/ojc/340619

Glucose hydrogenation using water at solvent was happened trough two step. First, water was reduced to hydrogen and oxygen gases by TiO₂ pillared bentonite. Second, hydrogen that produced was used to reduce glucose into sorbitol. The reaction was prepared in transpaharan medium for 30 days along under UV from sunlight. The product of reaction was characterized using SEM, XRD, FTIR and DSC.

Full text of DOI:10.13005/ojc/340619

ISSN: 0970-020 X
CODEN: OJCHEG
2018, Vol. 34, No.(6):
Pg. 2819-2825
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Access, Peer Reviewed Research Journal
www.orientjchem.org
Role ofTiO2 Pillared Bentonit and Catalyst Nickel for Hydrogenation
Glucose to Generate Sorbitol
MINTO SUPENO1, NURHAIdAPASARIBU1 and RIkSON SIBURIAN1*
1Chemistry Department, Universitas Sumatera Utara, Medan, Indonesia.
*Corresponding author E-mail: riksonsiburian2000@yahoo.com
http://dx.doi.org/10.13005/ojc/340619
(Received: August 16, 2018; Accepted: November 01, 2018)
ABSTRACT
Glucose hydrogenation using water at solvent was happened trough two step.First, water was
reduced to hydrogen and oxygen gases by TiO2 pillared bentonite. Second, hydrogen that produced
was used to reduce glucose into sorbitol. The reaction was prepared in transpaharan medium for
30 days along under UV from sunlight.The product of reaction was characterized using SEM, XRD,
FTIR and DSC.
keywords: TiO2, Pillariedbentonit, Glucose, Sorbitol, Nickel.
INTROdUCTION
metal intercalated with metals of larger diameter
that make the pores expand, then calcined at a
temperature of 300-500oC, the metals will forming an
oxide layer bonded to produce bentoniteterpilar. In
North Sumatra there are two types natural bentonite,
Wyoming bentonite and non Wyoming bentonite,
and both have the main composition of SiO2/Al2O3
with (4-6: 1) ratio. Bentonite is the common name of
a type of clay that can be used to adsorb color, oils,
fats and waxes. Pale land is a silicate of a variety of
compositions, the main constituent of SiO2 and Al2O3
containing water and chemically bonded.In addition
to the above two compounds bentonite also contains
CaO, MgO, Fe2O3, Na2O and K2O. Based on the
theory of Davis and Masser, that differences in levels
of SiO2 and Al2O3 ratio will affect the active power.
Soil that has a big ratio of SiO2 and Al2O3 is best
soils adsorb.While land with a small ratio of SiO2 and
Clay mineral is one of Indonesia's abundant
natural resources and has not been used optimally.
Clays geologically is a natural mineral from the
family of crystalline silicates with a layered structure.
Bentonite is a type of clay that is widely available in
Indonesia which there are in most areas of Nusa
Tenggara, Sulawesi, West Java, Central Java,
Yogyakarata, East Java, South Sumatra, Jambi,
North Sumatra.1
Bentonite has a strong capability of colloids,
when mixed with water it can expand. Principle
alter the surface and pore bentonite is to convert
the metals contain in the pores become wider.
Another method to expand the pores is pillaring,
in this case pores bentonite containing Na and K
This is an
Open Access article licensed under a Creative Commons license: Attribution 4.0 International (CC- BY).
Published by Oriental Scientific Publishing Company © 2018

2820
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
Al2O3 have the small ability to adsorb.Comparison of
SiO2 and Al2O3 for a good bentonites 5-6 :1, which
is able to adsorb, and has a large surface area.
layer that is free from oxide and silicon is then etched
with a solution of HF/ HNO3/CH3COOH/I2 so that
the silicon will be dissolved. The amount of surface
area that is produced depends on the time used for
etching. If the time spent too long SiO2 or Si late at
all and thus it is not expected that the time used for
etching needs to be controlled.8,9
Bentonite has a strong capability of colloids,
when mixed with water, it can inflate (Wyoming).
Bentonite in the dry state beige to green with a
specific gravity of 2.4 to 2.8 g/mm3 and a melting
point between 1330-1430°C. Natural bentonite
generally contain little calcite, carbonate, gypsum
and quartz. Surface and pores natural bentonite
can be enlarged with the activation of chemical and
physical techniques,2 or by using pillaring elements
Zr,Ti, Fe, Na, Ca through intercalation technique and
calcination at 450°C to produce pillared bentonite
called photocatalyst powder.3,4
If the etching technique is achieved then
the surface and pores become larger pillared
bentonite which allegedly producemacropores
pillared bentonite. Pemilaran by using TiO2 and
etching silicate bentonite can change the physical
and chemical properties, increase the basal spasing
(D001), specific surface area, total volume, surface
acidity and decrease the average pore spokes.
Semiconductor photocatalyst powder
has been widely studied, has been found that
the activity of the photocatalyst is getting better
with decreasing particle size causes increased
surface area. A decrease in particle size between
5-10 nm causes changes in energy band structure
of the semiconductor becomes known as a side
effect Quantum. Further research has been done
to produce photochemical of various sizes and
shapes, particles of semiconductor Cholocogenide
such as CdS, ZnS, CdSe, GeSe, ZnSe and oxide
semiconductors of the type ZnO, Fe2O3, TiO2 has
been widely used to photocatalysts for producing
hydrogen from water.5
TiO2 pillared bentonite can be used as
catalysts in the manufacture of hydrogen gas and
oxygen from the water, in this study the researchers
are interested in examining the provision of this
pillared bentonite as catalyst.
Natural bentonite has 60% of its silicon
content, to provide this material as a catalyst it is
necessary to increase the surface area and pore
volume by way of intercalation withTiO2 and be-TiO2
pillared bentonite. Titania metal oxide is a material
that is sensitive to light and either be a photochemical
catalyst. If TiO2 pillared bentonite do etching with
chemicals then etched pillared bentonite can be
co-catalyst. So that needs to be studied preparing a
catalyst sensitive to sunlight than natural bentonite
and bentonite pillared whether TiO2 that has
been etched can be as a co-catalyst manufacture
hydrogen and oxygen gases from water.
Principlealterthesurfaceandporebentonite
was dissolving the metals contained in the pores
of bentonite with an acid and metal is already late
because the pores become wider. Another method
to expand the pores by means pillaring, in this case
pores bentonite containing Na and K metal intercalated
with metal cations diameter is larger so that the pores
inflates, then calcined at a temperature of 300-500°C.6,7
The metals will form oxides bonded to inter-layers,
resulting pillared bentonite.4 Through this technique
would be great porosity bentonite, metal oxides as
pillaring agent can be used for the catalyst.
Aldehyde group of glucose may experience
a reduction in the presence of hydrogen and a
catalyst to form a metal hydride into polyalcohols
called alditol. Product of the reduction of d-glucose
called D-sorbitol or sorbitol.10 Past research has
made the hydrogenation of glucose to sorbitol with
different catalysts11, where it was made from the
hydrogenation of glucose 50% at a temperature
of 353 K, a pressure of 4 MPa using a Ni catalyst.
Clauss, 2006 using a catalyst Ni/SO2 with glucose
20% at temperature of 393 K with pressure 120 bar.
It also hydrogenated glucose with Nickel catalyst at
temperature 95-105oC and pressure 60 bar. From
In this research, intercalation bentonite
pores using TiO2 and calcination temperatures of
300-500°C to produce TiO2 - pillared bentonite. Its
isolator part i.e oxides can be etched to remove
oxides by using a mixture of HF/H2O/ NH4F or HF/
HNO3/H2O or by using CF4/H2 which produces silicon

2821
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
the past research’s result, that generated 0.5963 g
sorbitol (g sorbitol/g g sorbitol early).12
in an oven at 100°C.After dried crushed into powder
and then sieved using a 100 mesh sieve. Results
saturation of bentonite clay is called Na-bentonite.
Based on the description above, the
researchers are interested to hydrogenate glucose to
sorbitol without pressure and high temperature.With
the TiO2 pillared bentonite as producing hydrogen
gas from water using UV light from solar energy.
Activation of Na-Bentonite with Acid
Each 35 g of Na-bentonite dispersed
into 150 ml solution of sulfuric acid 0,5; 1; 1.5; and
2.0 M while stirring with a magnetic stirrer for 6 hours.
Then allowed to stand for 24 h, and then filtered
by vacuum filtration and washed with hot distilled
water until free of sulfate ions. This is indicated
by a negative test against BaCl2. Activated acid
Na-bentonite is then dried in an oven at 100°C.After
dried crushed into powder sieved using a 100 mesh
sieve size.This product was called the Na-bentonite,
the product was tested by X-ray diffraction.
MATERIALS ANd METHOdS
The materials used in this study include
1.
The bentonite clay was taken from the District
Padang Tualang, Langkat, North Sumatera,
which have passed the 100 mesh sieve.
Chemical reagents with quality p.a was made
by E.Merck as follows: TiCl4, concentrated
HCl, H2SO4, AgNO3, BaCl2, NaCl, ethanol,
HF, NH4F, CH3COOH, I2.
2.
Intercalation and pillarization Na-bentonite
Weighting each 30 g of Na-bentonite
clay and dispersed into 1.5 l of deionized water
(aquabidest) and stirred with a magnetic stirrer
for 6 hours. Then into each Na-bentonite poured
piecemeal solution of 0.82 M TiCl4 while stirring
with a magnetic stirrer for 10 hours. Results of
intercalation separated by vacuum filtration and
then washed several times with deionized water until
free of chloride ions. Washing stopped if the filtrate
was tested with silver nitrate does not form a white
precipitate.Bentonite clay that has been intercalated
with TiCl4 dried in an oven at 100°C. Once dried
crushed into powder and sieved with a 100 mesh
sieve then calcined at 350°C. This product is called
TiO2-bentonite.6,7
3.
Distilled water and demineralized water.
Bentonite clay with a composition of 61.0 2
% SiO2; 15.21% Al2O3; 4.89% Fe2O3; 0.62%
TiO2; 2.08% CaO; 1.94% MgO; 0.46% K2O;
3.45% Na2O; 10.31% incandescent lost.
Based on this, the composition of bentonite
District of Padang Tualang, Langkat, types of
Na-bentonite.Bentonite is sieved to 100 mesh
sieve passes are then washed with distilled
water several times and filtered by vacuum
filtration and dried in an oven at 100°C for
5 hours. After that bentonite clay is dried and
crushed into powder and sieved using a 100
mesh sieve.
Etching TiO2 pillared Bentonite
Provision of Na-bentonite
One hundred grams of bentonite clay
TiO2 pillared bentonite was calcined at a
temperature of 400°C, taken 20 g, and then put in
a plastic container. Etcher solution is then added (a
mixture of: 3 ml HF (p)+5ml HNO3 (p)+3 ml CH3COOH
(glacial)/I2 of 0.3 g/250 ml H2O). Then stirred using
a plastic stirrer for 10 min. then the precipitate is
separated from the solution by decantation using
a plastic pipette. The precipitate was dispersed in
aqua bidestilate then neutralized pH, decanted using
a plastic pipette. Etching products are divided into
3parts,eachfurnacedat400,450,500°Cfor1hour.Then
the lower heated products were analyzed by SEM.
(3.3) was dispersed into the 1.5 l NaCl 1 M and
submergeded for 1 week in which every two days
NaCl solution was replaced with a new one. At every
replacement of NaCl stirring for 24 h, by heating to
60-70°C for 4 h, then after its precipitate was filtered
and then washed with demineralized water until free
of chloride ions, evidenced by negative silver nitrate
test. Filtering was done using vacuum filters and
bentonite obtained dried in an oven of 100°C until dry,
then crushed and sieved using a 100 mesh sieve.
Furthermore, bentonite is saturated using 6
M NaCl while stirring for 24 h, then filtered by vacuum
filtration and washed with distilled water until free of
chloride ions with negative AgNO3 test. Then dried
The results of SEM images indicate that the
product is heated at a temperature of 450°C has the
most extensive surface area and will be used to test
the catalyst/co-catalyst in water.

2822
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
Making Hydrogen and Oxygen Gas from Water
Using the catalyst/co-catalyst TiO2 pillared
Bentonite by UV irradiation
Na-bentonite subsequently dispersed into
several solution of sulfuric acid 0,5;1;1.5;2 M stirred
with a magnetic stirrer, activation carried out for 24 h,
filtered by vacuum filtration and then dried in an oven.
Activation is aimed to increase the distance between
Na-bentonite layer so that it becomes larger.
Bentonite was weighed as much as 4
g, then put in a pumpkin that has been filled in
10 ml of distilled water and stirred for 10-15 min.
then measured the pH. Pumpkin is connected
with a thermometer and three branch pipes are
connected to a manometer.Subsequently irradiated
with ultraviolet as irradiation was carried out for
1-5 days and observed no changes in the manometer.
Manometer result of changes in total gas pressure
can be calculated total gas (%).
Once the distance between the layer of
Na-bentonite new enlarged carried intercalation
and pillarization where activated Na-bentonite
dispersed 0.82 MTiCl4 complex solution while stirring
with a magnetic stirrer for 18 hours. The results of
this intercalation separated by a vacuum pump,
intekalasion purpose to enter into the complex Ti
distancesbetweenthebentonitelayer, thencalcinated
at 350°C to form a more solid oxide pillars.
Sorbitol Hydrogenation
We inserted into a transparent bottle
containing 2.5 glucose, 0.1 g of nickel powder, 1 g
ofTiO2 pillared bentonite and 20 ml of distilled water
and then sealed. Stirred with a magnetic stirrer and
placed under a UV sun rays for 30 days.Then filtered,
pH measured and tested with Tollens reagent and
Fehling reagents. After that, the filtrate evaporated
and sucked up a vacuum to form crystals. Tested
melting point and were characterized by FTIR.
AnalysiswasdonebyX-raydiffraction, using
Cu powder radiated by Ka, each 2 g of TiO2 pillared
bentonite and activated clay filled into a sample and
then made diffractogram with l = 1.5425 Å.
Based on the results of measurement
of basal spacing (D001) there was an increase in
basal spacing on the TiO2-pillared bentonite using
acid activation of 0.5 and 1.5 M while those using
TiO2 pillared bentonite activation damaged.It can be
seen from the X-ray diffraction data. The increase
in basal spacing will be followed by an increase in
surface area, increased porosity, and total volume.
RESULTS
Bentonite of Padang Tualang district,
Langkat composition show in Table 1.
Table 1: Composition of Bentonit of Padang
Tulang district
SiO2
Al2O3
Fe2O3
TiO2
61,02%
15,21%
4,89%
MgO
K2O
Na2O
1,94%
0,46%
3,45%
0,62% missing incandescent 10,31%
2,08% Water content 7,07%
Based on the analysis of the composition of
CaO
bentonite Kabupatan langkat then bentonite above
include Na-bentonite type or swelling, bentonite was
dried in an oven at 100°C and crushed and sieved to
100 mesh sieve. Bentonite was soaked in 1 M NaCl
for 1 week, so going enrichment of Na-bentonite
after forming sodium bentonite then put into a 100°C
oven until dry and after dry sieved to 100 mesh sieve.
The last step enrichment sodium bentonite made
by dispersing the Na-bentonite 6 M NaCl solution
or saturated NaCl for 24 h, then washed and dried
100°C, this material is called Na-bentonite.
Fig. 1. XRd diffractogram of Pillaried Bentonite
Based on Fig. 1, pillaried bentonite was
characterized by peaks at 2-theta ie: 5.92; 6.36;
18.84; 29.28 with basal spacing d (A) respectively:
14.91; 13.88; 4.70; 3.04 and other peaks are
kaolinite, quartz, mica means bentonite has not been
enriched so there are still impurities.

2823
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
From this diffractogram Fig. 1 can be
given information about changes in the angle theta
6 changes the distance between layers of
Na-bentonite into a pillared bentonite-TiO2 for
observation or pillared bentonite changes in the
angle theta 0-5. From Fig. 1 and 2 have been
changes in peak intensity and changing the distance
between layers D001.From the X-ray diffraction data
above Fig. 1 and 2 can be determined the distance
between layers, as well as identification in identifying
the types of clay mineral, to calculate the distance
between layers (d) mineral bentonite can be used
formula Bragg.
Based on the data of three X-RD, a
concentration of 1.5 M sulfuric acid good for
intercalation in pillarization produce physical
changes in basal spacing, surface area and total
pore volume increases.
Furthermore TiO2 pillared bentonite
activated in best H2SO4 etched using a mixture
(28 ml HF + 170 ml H2O + 113 g NH4F) for 2-10
minutes for etching the oxide on silica and make a
lot of holes (H+) on silica, then etched using solution
(1 ml 5 ml HF + HNO3 + 2 ml CH3COOH + 0.3 g I2
/250 ml H2O) for 5-10 min. for etching silicon further
heated to 400, 450, and 500°C for 1 hour. With such
technique will produce pillared bentonite macropore
and reproduce (H+).
nl = 2 d Sin q
Where, d = the distance between the fields of
atomic crystals.
Based on this data Table 2 then etching
increases the surface area of the surface area of
Na-bentonite 89.0563 m2/g increased to 92.0123
m2/g so that the average increase surface area of
2.956 m2/g, this result has been satisfactory. These
results were further tested using analysis of surface
area (BET), the result is as follows.
l = wavelength (1 Å = 10-10 m)
q = angle of diffraction
n = order of diffraction
(a) The distance between layers (d) for the Na-
bentonite.
Table 2: Surface AreaTiO2 pillared Bentonite which
has been etched on the differentTemperatures
n = 1
l = wavelength (1 Å = 10-10 m)
2 q = 5.920; q = 2.960
Temperature Surface Area Totat Pores Volume
(oC )
(m2.g-1)
(cc.g-1)
400
450
500
902,387
920,123
911,255
0,0446
0,0444
0,0444
d = 14.917 Å
(b) TiO2 pillared Bentonite using 1.5 M sulfuric acid
can be calculated as follows.
Furthermore TiO2 pillared bentonite
photographed SEM showed that the surface be great.
n = 1
l = 1.54 x 10-10 m
2 q = 5.920; q = 2.960
d = 16.9807 Å
Further changes in the distance between layers
(Dd) are.
(Dd) = d (b) - d (a)
= 16.980 to 14.916
= 2.063 Å
Based on X-ray diffraction analysis then
by intercalation and pillarization add, increase the
porosity of the basal spacing = 2.06 Å.
Fig. 2. SEM image of etched TiO2 pillared bentonite and
heated 450°C

2824
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
Figure 2 shows the number of holes on the
Intercalation and pillarization
surface of the silicate almost entirely on TiO2 pillared
bentonite that has been etched. This surface could
imply that the TiO2 pillared bentonite has a lot of holes
etched then occurs in the silicate external and internal
possibilities.Forsorbitolandglucoee, wecharacterized
by using FTIR and DSC Figure 3 and 4.
Na-bentonite subsequently soaked with
sulfuric acid of 0.5-2 M and intercalated using Ti2+
then pillared at 350°C. The calcination is useful to
form the pillars of oxide on bentonite. Thus forming
a TiO2 pillared bentonite. For the identification
of pillared bentonite have seen from the X-ray
diffraction data at an angle 0-5 theta, which turned
into a basal spacing is 16.9807 Å.
It means, the manufacture of the pillared
bentonite has been successful in increasing the basal
spacing, surface area and pore volume. The study
of literature obtained basal spacing of 28.3 Å. This
could occur because of the purity of the bentonite is
used, meaning that bentonite material is different then
produced basal spacing on different pillars.
EtchingTiO2 pillared Bentonite
TiO2 pillared bentonite subsequently etched
using a chemical etcher to reproduce hole (H+).Holein
silicate form marked changes in surface area and pore
volume of the original.Also, based on the SEM image
surface becomes more rugged than ever before.
Fig. 3. FTIR of Sorbitol and Glucose
As a result of ultraviolet radiation l = 180
nm, the hydrogen bonding of water will be released
and oxygen from water interacting with metal oxides
TiO2 and hydrogen from the water molecule will
interact with silica.These interactions can lower the
activation energy of water molecules.Ultraviolet light
enter the pores of bentonite by SiO2 ultraviolet light
is converted to shortwave resulting hydrogen and
oxygen molecules to break up.
Fig. 4. dSC of Sorbitol and Glucose
Testing of gas generated a total of 78.5%
using pillared bentonite etched, while those usingTiO2-
pillared bentonite gas generated as much as 60.4%.
dISCUSSION
Preparation of Na-Bentonite
Bentonite samples from the District Padang
Sorbitol FTIR and dSC Spectrum
Tualang, Langkat that have not done enrichment
bentonite, made into Na-bentonite produce basal
spacing D001 is 14.917 Å, whereas in theory
Na-bentonite its basal spacing is 9.8 Å.This means
Na-bentonite absorbs water from the humidity so that
the measurement time X-ray diffraction to be great.
From the X-ray diffraction data Fig. 1 clearly show
Na-bentonite which still contains koilinit, quartz and
mica. Na-bentonite can be observed a peak at an
angle of 0-5 theta, at the height of this is the identity
of the Na-bentonite.
FTIR spectrum of the product (KBr) showed
an absorption band at 3391.2 cm-1, 2935 cm-1,
1646.02 cm-1, 1047.39 cm-1. Absorption at 3391.2
cm-1 region indicates streching stretching vibration
absorption OH OH group that stretched from
primary and secondary alcohols. Which supported
an absorption band 1418.07 cm-1 as buckling OH.
Absorption at 2915.7 cm-1 region showed the
presence of CH and CH2. While the C-O in alcohol
produced ribbons region in 1416 and 1047.39 cm-1.
Base on DSC, sorbitol has melting point = 61oC and

2825
SIBURIAN et al., Orient. J. Chem., Vol. 34(6), 2819-2825 (2018)
glucose = 81oC. It means we succeed to synthesize
sorbitol base on glucose as a raw material.
sunlight for 30 days and produced sorbitol as much
as 66.8%
CONCLUSION
ACkNOWLEdGEMENT
In this research, we concluded that
hydrogen gas produced byTiO2 bentonite in aqueous
solvent can be used for the hydrogenation of glucose
to sorbitol. Nickel catalysts and irradiation with UV
We would like to thankful for DRPM-Dikti,
Ministry of Research, Technology and Higher
Education, Republic of Indonesia who supported
the funding for this research.
REFERENCES
1.
Al-Qunaibit, M.H.; Mekhemer, W.K.; .The
Adsorption of Cu (II) Ion on Bentonite–a
Kinetic Study. J., 2004, 1-6.
Burch, R.; Pillared Clay., 1997, 283 – 297.
Barrer, R. M.; Zeolites and Clay Minerals as
Sorbent and Molecular Sieves., 2002.
Bradley, S.M.; Kydd, R.A.; Yamdagni R.;
Fyfe, C.A.; .Expanded Clays and Other
Microporous Materials: Synthesis of
Microporous Materials., 1992, 2.
Lapekina, C.I,; .Water Vapour Adsorption by
Soil Aggregate Fractions., 2004, 19, 47 – 52.
Klinowski, J.; Activation of Alumina-Silica.
1982, 525.
Ishisaki, K.; Komarmeni, S.;Nanko, M.;
Porous Material Process Technology and
Application., 1998, 6–11.
Darby, D.;TitaniumDioxidePigment, inModern
Inorganic Chemical Industry., 1997, 31.
Clauss, P,; Ni/SO2 Catalyst Prepared With
Ethylendiamine Nickel Precursor : Influence
of Pretreatment on The Catalytic Properties
in Glucose Hydrogenation., 2006, 45-53.
Cool,P.;Vansant,E.F.;PillaredClays:Preparation,
Characterization, and Application., 2002.
8.
9.
2.
3.
4.
10.
11.
5.
6.
7.
Darby,D.;.TitaniumDioxidePigment,inModern
Inorganic Chemical Industry., 1997, 31.
Bask., Introduction to Colloid Chemistry
Interscience., 1992, 15.
12.
Kharitonova, G.V,; Shein, E.V.;Vityazev, V.G.;