1

Controlled oxidation state of

Ti in Mgo-TiO2 composite for
CO2 capture

UTHKAR SAILU (16CH60R25)

DEPARTMENT OF CHEMICAL ENGINEERING
IIT kharagpur

content
2.Different molar ratios of mg/Ti in composite
formation
3.Synthesis of xMgo-Tio2 composite
4.Thermo Gravimetric study of 3.0 mgo-TiO2
5.FTIR spectrum and EPR spectrum
6.N2 adsorption desorption studies
7.CO2 adsorption study
8.Conclusion
9.references

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1.introduction

Carbon dioxide in atmosphere

Carbon capture and

storage(CCS) technology
has recognized as
reduction of carbon
dioxide in atmosphere to
overcome green house
effect.

many process available to

capturing co2

Absorption by aqueous
amines and

adsorption by solid media

Zeolite

Act carbon

Hydrotalcites

Metal oxides etc.

4
Among this mesoporous xMgo-Tio2 composite shows the
good co2 capture.

Where x is molar ratio of mg/Ti, different molar ratios of

mesoporous mgo-tio2 are synthesized and co2 adsorption is
investigated.

Insertion of Mgo in Tio2 leads to formation of phase

MgTio3,MgTi2o4,mg2Tio4

Ti posses the different oxidation staaes thats is +4(MgTiO3),

+3(MgTi2O4),+4(Mg2tio4).

Ti oxidation state is important in co2 capture because of

create stong Mg-O-Ti ion pair,

MgTi2O4(Ti3+-O-Mg2+) could create highly basic sites

compared to MgTio3 and Mg2Tio4.

This basic site is responsible for the adsorption of co 32carbonates ions.

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2.synthesis

5
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2.3gm of tryblock co-polymer(pluronic P123) is dissolved in ethanol under

constant stirring for 4hrs

5gm of titanium propoxyde dissolved and 5ml of nitric acid added for the
complete hydrolysis.

Then required amount of magnesium nitrate hexahydrate(Mg(No 3)26H2o) .

Solution stirred for 5hr and then metal precursor is induced via evaporation of
the solution at 600C for 48 hrs.

Resulted solid is calcinated at 5500C for 5 hr.

3.thermo Gravimetric of 3Mgo-TiO2

100

Weight loss at 25-1500C due to

the surface adsorbed water and
volatile compounds

150-2000C due to the selfassemble of surfactant p-123

with the metal precursor which
leads to well ordered
mesoporous structure.

No other impuritys observed

above the 5000C.

90

Weight loss (%)

80

70

60

50

40

30

100

200

300

400

500

600

700

800

temperature

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XRD pattern for xMgo-Tio2 adsorbent

The phase transformation with the

introduction of MgO in the TiO2 lattice,
has occurred in the sequence of
MgTiO3 (Mg/Ti = 1.0 and 2.0) , MgOMgTi2O4 (Mg/Ti = 3.0 and 4.0) , MgOMg2TiO4 (Mg/Ti P 5.0)

The number of sharp peaks in the

range 2b = 2080 degree, describe
the higher crystallinity of MgTiO3
phase.

Decrease in Intensity at molar

ratio>2

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2-theta(degree)

Signify the mg0 is present at higher

amout.

FTIR spectrum for xMgo-Tio2

90

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80

70

1435.1

1512.2

60

O-H bond.

50
Transmittance (%)

Peak at 3425.2 is
stretching vibration of

Peak at 1636.2 is due

to adsorbed water mol.

Peak at 1435-1512.2
are due to adsorbed
co32-

1636.2
40

TiO2
2

1.0MgO-TiO2
2

30

2.0MgO-TiO2
2

3.0MgO-TiO2
2

20

3425.2

40MgO-TiO2
2

5.0MgO-TiO2
2

636.6

10
4000

3500
-1

number(cm )

3000

Wave

2500

2000

1500

1000

432.5

500

5.EPR spectrum

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Magnetic field

In order to ensure the presence

of Ti3+ species, EPR analysis was
carried out. Because electron
paramagnetic resonance (EPR),

which is highly sensitive to

paramagnetic species containing
unpaired electrons.

Signal at g=1.98 indicate less

amount of Ti3+

signal at g=2.355 indicates the

presence of Ti3+in bulk.

1
0
2+

Mg

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Mg

Mg

2+

2+

Ti

ABO

4+

Ti

AB

MgTiO3

2.0)

3mgo-tio2

50nm 3.Mgo-Ti02

Ti

A BO

MgTi2O4

( Mg/Ti=1.0 and

3+

( Mg/Ti=3.0

and 4.0)

5nm 3.Mgo-Ti02

Mg

Mg2TiO4
4

( Mg/Ti=5.0)

4+

6.Nitrogen adsorption and desorption study

1
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Relative pressure
ratio

dp(mm)

mg/ti molar

Table.1 The detailes of texture properties of xMgo-Tio2

Specific surface area
(m2/g)a

Pore diameter
(nm)b

0MgO-TiO2

41.0

17.16

0.17

1.0MgO-TiO2
2.0MgO-TiO2
3.0MgO-TiO2
4.0MgO-TiO2
5.0MgO-TiO2

80.6
113.3
111.4
100.6
79.9

26.52
21.98
16.44
14.52
13.63

0.53
0.62
0.45
0.36
0.27

(cm3/g)c

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xMgO-yTiO2

1
2
Pore volume

The surface area initially increases up to Mg/Ti = 2.0 then starts to

decrease. The BJH pore volume also follows the same trend.

This illustrates that the Mg2+ and Ti2+ ions undergo complexation with
the hydrophilic EO groups in surfactant (P123) and this results in
better dispersion of the active metal species but this are not stable .

Formation of stable species could be beneficial.

CO2 adsorption study at 250C

From the graph sample with

lower amount of Mgo in TiO2
have poorer attraction to the
acidic co2.

Thre is no appreciable change

in adsorption performance of
1Mgo-TiO2 and 2.0 Mgo-TiO2.
because they posses similar
phase structure .has proved
from XRD pattern.

3Mgo-TiO2 shows the higher

co2 adsorption value due to
high basic site of Mg2+-O-Ti3+
ion.

1
3

Time(min)

B) Effect of Mg/Ti molar ratio on co2 adsorption

Co2 uptake is maximum at

3.Mgo-Tio2 this is representation
of high formation of high basic
site of Mg-O-Ti ion.

Further increase in molar ration

co2 uptake decreases this due to
the increasing in Mgo
incorporation.

Mg/Ti molar ratio

1
4

C) Co2 adsorption study of 3.0 Mgo-TiO2with

effect of temperature.

Weight uptake is folling

from 250C to 2000C.

Nature of adsorption curve

constant its implies that no
change in kinetics of co2
adsorption.

The developed xMgo-TiO2 is

feasible for co2 adsorption
at lower temperature.

Time(min)

1
5

CO2 adsorption graph with composition

1
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MgTio3(

mg/ti=1.0 and 2), MgTi2o4(Mg/ti=3.0 and

4.0),Mg2Tio4(mg/ti=5.0)

MgTi2o4(Mg/ti=3.0

and 4.0) Magnesium titanate having more

attraction towards the co2.

conclusion

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Series of ordered mesoporous MgO-TiO2 adsorbents

synthesized to evaluate CO2 adsorption.

XRD pattern and EPR spectra revealed that phase changes

occurred in the sequence of MgTio3(Mg/Ti=1.0 and 2.0)
MgTi2O4 (Mg/Ti=3.0 and 4.0)Mg2TiO4(Mg/Ti=5).

Titanium oxidation state key factor in determining the co2

adsorption capacity.

3.Mg0-Tio2 has more adsorption capacity due to its highly

basic site of (Mg+2-O-Ti+3) ions .

Co2 adsorption in order of

Mg+2-O-Ti+3(MgTi2o4)>Mg+2-O-Ti+4(Mg2Tio4)>Mg+2-OTi+4(MgTio3)

References

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8

K.K. Han, Y. Zhou, Y. Chun, J.H. Zhu, Efficient MgO-based mesoporous

Co2 trapper and its performance at high temperature, J. Hazard. Mater.
203204 (2012) 341347.

C.Y. Lu, H.L. Bai, B.L. Wu, F.S. Su, J. Fen-Hwang, Comparative study of
CO2 capture by carbon nanotubes, activated carbons, and zeolites,
Energy Fuels 22 (2008) 30503056.

A. Zukal, J. Pastva, J. Cejka, MgO-modified mesoporous silica

impregnated by potassium carbonate for carbon dioxide adsorption,
Micro porous Mesoporous Mater. 167 (2013) 4450.

S.J. Han, Y. Bang, H.J. Kwon, H.C. Lee, V. Hiremath, I.K. Song, J.G. Seo,
Elevated temperature CO2capture on nano-structured MgOAl2O3
aerogel: effect of Mg/Al molar ratio, Chem. Eng. J. 242 (2014) 357363.