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MOLCAA-8868; No. of Pages10
ARTICLE IN PRESS
A. Tathod et al. / Journal of Molecular Catalysis A: Chemical xxx (2013) xxx–xxx
3
Tetraamine platinum nitrate (99.99%) was purchased from Alfa
Aesar, UK. Sodium carbonate (Na2CO3) (99.5%), sodium hydroxide
(NaOH) (98%) and xylose were purchased from Loba Chemicals,
India. Sorbitol and levulinic acid were purchased from Aldrich
Chemicals, USA. Glucose, arabitol, arabinose, xylitol, mannitol,
gluconic acid, glycerol, ethylene glycol, 1,2-propanediol were pur-
chased from S.D. Fine Chemicals Limited, India. All the chemicals
were used as received.
2.5. Catalytic reactions and analysis
2.5.1. Glucose and xylose oxidation reactions and analysis
Glucose and xylose oxidation reactions were carried out in a
batch mode reactor (Parr autoclave, USA) with a teflon beaker. The
reactor was charged with 3.9 mmol of glucose or 4.7 mmol of xylose
in 30 mL water. Subsequently supported metal catalyst was added.
While reactions were conducted using Pt/␥-Al2O3 catalyst, either
0.2 g of Na2CO3 or 0.3 g HT was added in the reaction mixture. In
this work during the course of reaction (intermediate addition) to
maintain the pH of the solution, no base was added. The reactor
was flushed 3 times with oxygen and then environment of oxygen
was maintained (atmospheric oxygen pressure). The autoclave was
then heated to desired temperature under slow stirring (100 rpm).
After attaining the reaction temperature, stirring was increased to
700 rpm Reaction mixture was analyzed using HPLC (Shimadzu,
Japan) equipped with HC-75 H+ (9 m, 7.8 mm × 305 mm) column
while succinic acid (0.5 mmol) is used as an eluent (0.5 mL/min).
The refractive index detector (model no. RID-6A) was used for the
detection and calibration of compounds. The calibration of com-
pounds was done using commercially available standards.
2.2. Synthesis of hydrotalcite
Hydrotalcite was synthesized by co-precipitation method.
NaOH was used to maintain the pH, while Na2CO3 was used as a
carbonate source. For the synthesis of catalyst by co-precipitation
method, an aqueous solution ‘A’ (37.5 mL) of Mg(NO3)·6H2O
(0.279 mol) and Al(NO3)3·9H2O (0.093 mol) were slowly added into
aqueous solution ‘B’ (37.5 mL) of NaOH (0.4375 mol) and Na2CO3
(0.1125 mol) under vigorous stirring over a period of 2 h. Solution
pH was maintained between 8 and 10. The white precipitate thus
obtained was kept in autoclave at 60 ◦C for 16 h. Precipitate was
then washed with deionised water until pH becomes neutral. Solid
thus obtained was then dried at 80 ◦C for 18 h. Sample was calcined
at 550 ◦C in the presence of air for 8 h. Mg/Al ratio in hydrotalcite
obtained was 3.
2.5.2. Glucose and xylose hydrogenation reactions and analysis
Glucose and xylose hydrogenation reactions were carried out in
a batch reactor (Amar equipments, India). The reactor was charged
with 0.83 mmol of glucose or 1.00 mmol of xylose in 35 mL water.
During reactions catalyst/substrate ratio was kept constant at 1:2
(wt/wt). When reactions were conducted using HT, 0.075 g of HT
was added. Experiments were conducted at temperatures ranging
between 60 ◦C and 190 ◦C under 8–24 bar of hydrogen pressure.
The reactions were conducted for 2–6 h. Reaction mixture was ana-
lyzed using HPLC (Agilent, USA) equipped with HC-75 Pb++ (9 m,
7.8 mm × 300 mm) column. Water was used as an eluent, at the flow
rate of 0.6 mL/min, and RID (model no. 1260 infinity) was used to
detect the compounds. The products which are poorly separable by
using HC-75 Pb++ column, were analyzed using HPLC (Shimadzu,
Japan) equipped with HC-75 H+ (9 m, 7.8 mm × 305 mm) col-
umn. Succinic acid (0.5 mmol) is used as an eluent (0.5 mL/min).
The refractive index detector (Model no. RID-6A) was used for the
detection and calibration of compounds. The calibration of all the
compounds was done using commercially available standards.
Calculations of selectivity and yield (%),
2.3. Preparation of supported platinum catalysts
Before the synthesis of supported metal catalysts, supports were
evacuated at 150 ◦C for 6 h. An aqueous solution of platinum precur-
sor, tetrammine platinum nitrate (quantity used corresponding to
3.5 wt% loading on support) was added to the support suspended in
water. The solution was stirred for 16 h at room temperature. Next,
water was removed by rotary evaporator and powder obtained was
dried in oven at 60 ◦C for 16 h. The powder was later dried under
vacuum at 150 ◦C for 6 h. This dry powder was subjected for calci-
nation in air flow (20 mL/min) and was reduced in hydrogen flow
(20 mL/min) at 400 ◦C for 2 h each.
2.4. Characterization of catalysts
The powder X-ray diffraction (XRD) patterns of all samples were
ꢀ
ꢁ
mole of gluconic acid formed (HPLC)
mole of glucose converted (HPLC)
recorded on a Philips Powder XRD, operated at Cu K␣ radiation
Selectivity (%) =
× 100
˚
(ꢀ = 1.540598 A) as a primary beam. The patterns were recorded
with a scanning rate of 2◦/min. Nitrogen sorption analysis at
low temperature was performed using Dona Quantachrome Nova
4200e instrument. The surface areas of catalysts were calculated by
the BET method. The temperature programmed desorption (TPD) of
CO2 was done using the Micromeritics AutoChem 2910 instrument.
Prior to measurement, samples were activated at 350 ◦C for 15 min
The adsorption of CO2 was done at 50 ◦C and then the sample was
kept at 100 ◦C under He flow. Next, sample was heated from 100 ◦C
to 600 ◦C with a ramping rate of 4 ◦C/min. The TPD-NH3 analysis
was done using Micrometrics Autochem-2910 model, instrument;
USA. Catalyst was activated at a temperature of 500 ◦C in He gas
flow (25 mL/min). NH3 adsorption (30 mL/min) was done at 100 ◦C
and desorption was started from 100 ◦C to 823 ◦C at the rate of
10 ◦C/min. Metal contents in the prepared catalysts were ana-
lyzed by inductive coupled plasma atomic emission spectroscopy
(ICP-AES) using SPECTRO ARCOS Germany, FHS 12 instrument.
Transmission electron microscopy (TEM) was done using FEI Tec-
nai TF-30 instrument. UV absorbance spectras were recorded using
PerkinElmer spectrophotometer (model-Lambda 650). Tempera-
ture programmed reduction (TPR) was done using Micromeritics
AutoChem chemisorptions analyzer.
ꢀ
ꢁ
mole of product formed (HPLC)
theoretical mole of product
Yield (%) =
× 100
3. Results and discussion
3.1. Catalysis
3.1.1. Results
3.1.1.1. Oxidation reactions. Oxidation of glucose was carried out
over Pt supported on ␥-Al2O3 and HT catalysts in water medium
at 50 ◦C under atmospheric oxygen pressure (Table 1). The Pt/HT
and Pt/␥-Al2O3 + Na2CO3 catalysts gave similar oxidation results
(entry 1 and 2). Pt/HT catalytic system without addition of any
homogeneous base gave good performance for the oxidation of
glucose showing 83% gluconic acid yield after 12 h reaction time
(entry 1). Along with gluconic acid ca. 8% fructose formation was
also observed. Whereas in conventional system in which homoge-
neous base, Na2CO3 was used along with the Pt/␥-Al2O3 catalyst
82% gluconic acid yield was observed (entry 2). In this reaction ca.