Accepted Manuscript

Low-temperature CO2 adsorption on titania nanotubes (TNTs)

Lakshminarayana Kudinalli Gopalakrishna Bhatta ,

Seetharamu Subramanyam , Madhusoodana D Chengala ,
Umananda Manjunatha Bhatta , Krishna Venkatesh

PII: S2468-0230(17)30065-2
DOI: 10.1016/j.surfin.2017.06.001
Reference: SURFIN 106

To appear in: Surfaces and Interfaces

Received date: 5 February 2017

Revised date: 11 May 2017
Accepted date: 9 June 2017

Please cite this article as: Lakshminarayana Kudinalli Gopalakrishna Bhatta ,

Seetharamu Subramanyam , Madhusoodana D Chengala , Umananda Manjunatha Bhatta ,
Krishna Venkatesh , Low-temperature CO2 adsorption on titania nanotubes (TNTs), Surfaces
and Interfaces (2017), doi: 10.1016/j.surfin.2017.06.001

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 ACCEPTED MANUSCRIPT

Low-temperature CO2 adsorption on titania nanotubes (TNTs)

Order of Authors: Lakshminarayana Kudinalli Gopalakrishna Bhatta a,*, Centre for Incubation, Innovation,
Research and Consultancy
; Seetharamu Subramanyam b, BMS College of Engineering; Madhusoodana D Chengala
c, Bharat Heavy Electricals Ltd
; Umananda Manjunatha Bhatta a, Centre for Incubation, Innovation, Research and Consultancy;
Krishna Venkatesh a, Centre for Incubation, Innovation, Research and Consultancy.
*
Corresponding Author: Lakshminarayana Kudinalli Gopalakrishna Bhatta; E-mail:

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kglbhat@gmail.com, lakshmi.nb@ciirc.jyothyit.ac.in

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Author names and affiliations
1. Lakshminarayana Kudinalli Gopalakrishna Bhatta a, *

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Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Jyothy Institute of
Technology Campus, Tataguni, Off Kanakapura Road, Bengaluru-560 082, Karnataka, India; E-
mail: kglbhat@gmail.com, lakshmi.nb@ciirc.jyothyit.ac.in
2. Seetharamu Subramanyam b US
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R&D Centre, BMS College of Engineering (BMSCE), P.O. Box No.: 1908, Bull Temple Road,
Bengaluru-560 019, Karnataka, India; E-mail: sub.ramu@gmail.com
3. Madhusoodana D Chengala c
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CTI, Bharat Heavy Electricals Ltd, Bengaluru-560 012, India. Fax: +91 80 2346 6714; Tel: +91
80 2218 2391; E-mail: madhu@bhelepd.com, madhusoodana@yahoo.com
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4. Umananda Manjunatha Bhatta a

Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Jyothy Institute of
Technology Campus, Tataguni, Off Kanakapura Road, Bengaluru-560 082, Karnataka, India; E-
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mail: umananda.b@ciirc.jyothyit.ac.in
5. Krishna Venkatesh a
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Centre for Incubation, Innovation, Research and Consultancy (CIIRC), Jyothy Institute of
Technology Campus, Tataguni, Off Kanakapura Road, Bengaluru-560 082, Karnataka, India; E-
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mail: kv@ciirc.jyothyit.ac.in

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Abstract

In Carbon dioxide capture and storage (CCS) technology, adsorption of CO2 on solid adsorbents

has been widely investigated as a means of an alternative to benchmark absorption technology,

which is having many formidable problems. The various classes of solid adsorbents that have

been investigated for CO2 capture include zeolites, carbon based adsorbents, metal organic

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frameworks (MOFs), metal oxides, and alkaline ceramics. Among several types of metal oxide

based adsorbents for CO2 capture, titanium-based materials exhibit exciting prospects for CO2

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adsorption owing to high specic surface area and ion-exchangeability. The present work

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investigates the CO2 adsorption on Titania nanotubes (TNTs) at low-temperature. To this end,

nano TiO2, synthesized using TiCl4 by acid-hydrolysis method is used as a starting material for
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the synthesis of TNTs via hydrothermal treatment. Both nano TiO2 and TNTs are characterized

using different techniques and subsequently investigated for CO2 adsorption. TNTs exhibited
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better saturation adsorption capacity (0.35 mmol g-1) compared with nano TiO2 (0.17 mmol g-1)

at 30 C, 1 bar. The adsorption kinetics of CO2 on both the adsorbents obeys the pseudo-second-
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order kinetics well.

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Keywords: Titania nanotubes, nano TiO2, CO2 adsorption, breakthrough curve, kinetics
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1. Introduction
The growing concern over climate change due to anthropogenic emission of greenhouse gases

(GHGs) has compelled the humankind to explore various GHG mitigation strategies. Among

various strategies explored hitherto carbon dioxide capture and storage (CCS) offers mid-term

commercially viable technological solution to reduce GHG emissions. Capturing CO2 form large

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point sources such as including fossil fuel power plants, fuel processing plants, and industrial

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plants can be achieved through different techniques including absorption, membranes, and

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adsorption. Among these, solid adsorbents have been most commonly investigated for post

combustion CO2 capture in recent years [1,2]. There have been many classes of CO2 solid

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adsorbents, including zeolites, carbon based adsorbents, metal organic frameworks (MOFs),

metal oxides, and alkaline ceramics. Among several types of metal oxide based adsorbents for
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CO2 capture (CaO, MgO, NiO, CuO, Fe3O4, etc), titanium-based materials exhibit exciting

prospects for CO2 adsorption owing to high specic surface area and ion-exchangeability [3].
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Several studies have shown that nanoporous TiO2 and titania nanotubes (TNTs) with or without
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amine impregnation can be used for effective CO2 capture [49]. A variety of TiO2

nanostructures, such as nanoparticles, nanotubes, nanorods, nanofibers, and nanoflowers, can be

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developed through various synthesis methods, including the solgel method, hydrothermal
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method, microwave method, and reverse micelle method [10]. The intriguing physic-chemical

properties of titanium-based materials have been mainly attributed to variation in synthesis

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methods and conditions. Evidently, these variations signicantly influence the feasibility of

applications of titanium-based materials for intended purposes [11]. The TNTs are attractive

materials due to their hydrothermally stable tubular structure and large pore systems allowing

good accessibility for functionalization and adsorption [3]. These aspects imply that there is still

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a huge scope for research and development of TNTs with desired properties and for specific

applications.

In the present work, nano TiO2 was synthesized using TiCl4 by acid-hydrolysis method. The

nano TiO2 thus synthesized was used as a starting material for the synthesis of TNTs via

hydrothermal treatment. Both nano TiO2 and TNTs were characterized using different techniques

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and subsequently investigated for CO2 capture application.

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2. Materials and Methods

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Titanium tetrachloride (assay > 98.5%) and sodium hydroxide (AR) were purchased from

Sigma-Aldrich. All other chemicals (AR grade) were purchased from S D Fine-Chem Ltd

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(India). The double distilled water was used throughout the study. In order to obtain nano TiO2,

titanium tetrachloride (50 ml) was added in drops to 5 dm3 of ice-cold water carefully, followed
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by the addition of 1 ml of 18 M H2SO4. The pH of gel thus obtained was maintained at 7 8 by

adding ammonia solution and aged for a day. The gel was then filtered and washed with water
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several times till it becomes free of chloride and ammonium ions. The gel was dried at 110 C
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and finally calcined at 600 C for 6 h in air [12]. Synthesis of TNTs involves the following steps

[4]. Nano TiO2 (5 g) was dispersed in 100 ml of 10 M NaOH using ultrasonic liquid processor
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(Johson Plastosonic Pvt. Ltd). The dispersion was transferred into a Teflon-lined sealed
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autoclave and kept at 140 C for 24 h followed by natural cooling. Then the sample was washed

with water several times, dispersed in 0.1 M HCl, and left as such for a day. The sample was
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washed with water to pH = 7. Finally, the white product was dried at 110 C and calcined at 350

C for 2 h in air.

The textural properties of samples were determined by N2 adsorption/desorption at liquid-

nitrogen temperature, using a NOVA 1000 Quanta Chrome high-speed gas sorption analyzer.

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While the specic surface areas (SSA) were obtained using BET relation, the pore volume and

pore size distribution were evaluated using Bopp-Jancso-Heinzinger method from the desorption

isotherms. Powder X-ray diffraction (PXRD) patterns were obtained using a Bruker D8

ADVANCE ECO X-ray diffractometer equipped with a Cu K radiation source (0.154 nm). The

samples were also characterized by a Fourier transform infrared ray (FTIR) analysis (Perkin

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Elmer FTIR spectrum 2). The samples were dried prior to be mixed with KBr powder, and the

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spectra were recorded in the range of 400 4000 cm-1, with a resolution of 4 cm-1. The surface

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morphology of samples were studied using scanning electron microscope (SEM) images, which

were obtained from Carl Zeiss, Neon 40 FESEM instrument coupled with an energy dispersive

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X-ray (EDX) spectroscope (INCA, Oxford). High-resolution transmission electron microscopy
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(HRTEM) images were obtained on a JEOL 2010, operating at 200 kV. The temperature

programmed desorption (TPD) of CO2 was carried out at atmospheric pressure using BELCAT II
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(Japan) TPD analyzer. A known amount of sample (~100 mg) was pretreated under 100%

helium ow (50 ml min-1) at 250 C for 30 min. After cooling to 40 C, the sample was saturated
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with CO2 using 10% CO2/90% He premixed gas for 60 min. The system was purged with helium

for 30 min to remove trapped CO2. The temperature of system was raised to 500 C at a ramping
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rate of 5 C min-1 under helium flow (50 ml min-1). Thermal conductivity detector (TCD) was
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used to monitor the effluent CO2 concentration.

The CO2 adsorption capacity of adsorbents was determined using dynamic column breakthrough
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method as described in our earlier papers [13,14]. In brief, a known quantity of sample ( 2 g)

was pre-treated at 250 C for 1 h under helium flow (30 ml min-1) at 1 bar and cooled to

laboratory temperature. A gas mixture of 10% CO2 balanced by helium was passed through the

bed at a flow rate of 20 ml min-1. Then, a portion of column efuent gas was fed to gas

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chromatograph. The breakthrough capacity (qBT) and saturation adsorption capacity (qSA) of

sample were evaluated using the data of CO2 concentration at exit, obtained from integrating the

gas chromatograph peak area with necessary corrections for blank experiment. In order to test

the cyclic stability of TNTs, the sorbent regeneration was carried out by passing He (20 ml min-
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) through the bed at 250 C for 1 h. The same adsorption desorption procedure was conducted

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for 8 cycles.

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3. Results and discussion

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Fig. 1. shows N2 adsorption-desorption isotherms of synthesized materials, which correspond to

type IV isotherms, exhibiting H3 hysteresis according to the IUPAC classication. Type IV

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isotherms are typical for mesoporous materials. The most characteristic feature of the type IV

isotherm is the hysteresis loop, which is associated with the occurrence of pore condensation
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[15]. The Type H3 loop, which does not exhibit any limiting adsorption at high P/P0, is observed
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with aggregates of plate-like particles giving rise to slit-shaped pores. While nano TiO2 exhibited

a narrow pore size distribution with maxima at 14 nm, TNTs showed a wide pore size
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distribution in the mesopore range (Fig. 2). The textural properties are presented in Table 1.

TNTs exhibited higher surface area and total pore volume compared with TiO2.
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Fig. 1. N2 adsorption-desorption isotherms showing type IV according to the IUPAC

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classification
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Fig. 2. Pore size distributions of adsorbents

Table 1 Surface area and pore characteristics of samples

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Sample Surface area (m2 g-1) Total pore volume (cm3 g-1) Average pore diameter (nm)
TiO2 26.9 0.154 22.9
TNTs 57.3 0.203 14.2

Fig. 3 shows the XRD patterns of TiO2 and TNTs. All the peaks indicate the presence of anatase
phase as indexed (JCPDS No. 01-086-1157). In the case of TNTs, the peaks became sharper,

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indicating the higher degree of crystallinity. In particular, (101) peak becomes stronger which is
also corroborated by Selected area electron diffraction (SAED) analysis. Several suppressed
peaks due to lesser crystallinity in TiO2 are more clearly visible as shown by the appearance of
(103), (112) and (112) peaks.

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Fig. 3. XRD patterns of TiO2 and TNTS
The FTIR spectra of both samples (Fig. 4) show three apparent peaks at 3400, 1630 and 500 cm -
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, which can be assigned to the stretching vibration of OH, the bending vibration of HO bond

and the vibration of TiOTi bond, respectively. These results are in good agreement with
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literature [16].
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Fig. 4. FTIR spectra of TiO2 and TNTs

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Fig. 5. presents the electronic microscope images of adsorbents. The surface of TiO2 appears to

be porous with loosely bound, random shaped particles (10-80 nm) with tens of nanometers of

interparticle gap (Fig. 5a,c). TNTs exhibited variable length (50-250 nm) with external diameter

of 10-30 nm and inner dia less than 10 nm. SAED shows polycrystalline nature with reflections

corresponding to anatase (Fig. 5b,d). The EDAX analysis shows the presence of Ti and oxygen

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in samples.

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Fig. 5. SEM images of (a) nano TiO2, (b) TNTs; TEM images of (c) nano TiO2, (d) TNTs
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The CO2 breakthrough curves of adsorbents are shown in Fig. 6. TNTs exhibited better

saturation adsorption capacity (0.35 mmol g-1) compared with nano TiO2 (0.17 mmol g-1) at 30
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C, 1 bar. The rate of adsorption is a useful metric for adsorber design and operation. The most
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common approach to describe the kinetic behavior is to t experimental data with a series of

popular models and nd the most suitable one which provides the best t. In the present work,
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Lagergrens pseudo-rst-order (PFO) and Hos pseudo-second-order (PSO) models have been

applied to experimental data. The non-linear forms of pseudo-rst-order and pseudo-second-

order adsorptions are given by equations (1) and (2), respectively [17].

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qt qe ( 1 exp k1t ) (1)

k2 qe2 t
qt (2)
1 k2 qe t

where qe and qt are the amounts of CO2 adsorbed (mmol g-1) at equilibrium and at time t (min),

respectively. While k1 (min-1) is the rate constant of pseudo-rst-order adsorption, k2 (g mmol-1

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min-1) is the rate constant of pseudo-second-order adsorption. The model parameters were

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obtained by non-linear regression analysis of experimental data (q vs. t) and are tabulated in

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Table 2 along with the values of error functions. The pseudo-second-order model has the same

inflection points as the experimental data for both the adsorbents, indicating that the adsorption

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kinetics of CO2 on both the adsorbents followed the pseudo-second-order kinetics well (Fig. 7).
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This suggests that the chemisorption is the rate controlling step [18]. The chemisorption is

confirmed by TPD-CO2 analysis (Fig. 8). The desorption peak for TiO2 occurred at 133 C while
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TNTs showed a desorption peak at 158 C. Additionally, the area under the peak for TNTs is

larger (58795 a.u) than that of TiO2 (54139 a.u), indicating TNTs possess better adsorption
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capacity than TiO2.

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Fig. 6. The CO2 breakthrough curves of adsorbents at 30 C, 1 bar

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Table 2 Kinetic rate model parameters with results of error functions

TiO2 TNTs
PFO PSO PFO PSO
Rate constanta 0.1593 3.5437 0.1677 1.2354
qe (mmol g-1) 0.1760 0.1826 0.3737 0.3958
R2 0.9999 0.9999 0.9999 0.9995

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S.E 0.0019 0.0001 0.0041 0.0030

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2 0.0001 0.0001 0.0001 0.0001
a
k1 in min-1; k2 in g mmol-1 g-1.

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Fig. 7. Adsorption capacity vs. time plots for TiO2 and TNTs (Symbols: Experimental data, Solid

lines: model predictions)

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Fig. 8. TPD profiles of TiO2 and TNTs

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Fig. 9 shows the normalized cyclic adsorption capacities of TNTs in 8 consecutive runs. Starting

from the first cycle the adsorbent showed almost stable adsorption/desorption performance
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during the remaining consecutive runs. Thus, the adsorbent shows a fair stability and

regenerability under the tested conditions for multiple-cycle operation. Further, the values of
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adsorption capacities of tested adsorbents fall in the region of those reported values in literature
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[4,19]. The reason could be the lower surface area due to variation in synthesis protocol as

mentioned in the introduction.

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Fig.9. Normalized CO2 adsorption capacity on TNTs over 8 adsorption-desorption cycles

(adsorption 30 C; desorption 250 C)
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4. Conclusion
Titanium-based materials exhibit exciting prospects for CO2 adsorption owing to high specic

surface area. In the present work, nano TiO2 and TNTs were synthesized following the

procedures reported in literature and tested for CO2 adsorption capacity. The samples were also

characterized using different techniques. The TNTs exhibited better saturation adsorption

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capacity (0.35 mmol g-1) compared with nano TiO2 (0.17 mmol g-1) at 30 C, 1 bar. The

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adsorption kinetics of CO2 on both the adsorbents obeys the pseudo-second-order kinetics well.

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The TNTs showed a fair stability and regenerability under the tested conditions for multiple-

cycle operation. Further, the values of adsorption capacities of tested adsorbents fall in the region

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of those reported values in literature. The relatively lower values could be due to lower specific

surface area. However, the characterization of synthesized TNTs indicated the potentiality of
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material for modification with amine impregnation for further enhancement in sorption capacity.
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Acknowledgements

The authors would like to thank Prof P. V. Satyam (IOP, Bhubaneswar) and Mr. Kiran N
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(CIIRC, JIT, Bengaluru) for helping in electron microscopy measurements. The authors also
thank the authorities of Bengaluru Institute of Technology, Bengaluru for N2
adsorption/desorption analysis and PPISR, Bengaluru for TPD-CO2 analysis.
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