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Chitosan-based zeolite-Y and ZSM-5 porous biocomposites for H2 and

CO2 storage

Santosh Kumar, Ranajit Bera, Neeladri Das, Joonseok Koh

PII: S0144-8617(19)31476-6
DOI: https://doi.org/10.1016/j.carbpol.2019.115808
Reference: CARP 115808

To appear in: Carbohydrate Polymers

Received Date: 19 October 2019

Revised Date: 19 December 2019
Accepted Date: 29 December 2019

Please cite this article as: Kumar S, Bera R, Das N, Koh J, Chitosan-based zeolite-Y and
ZSM-5 porous biocomposites for H2 and CO2 storage, Carbohydrate Polymers (2019),
doi: https://doi.org/10.1016/j.carbpol.2019.115808

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© 2019 Published by Elsevier.

Chitosan-based zeolite-Y and ZSM-5 porous biocomposites for H2 and CO2

storage

Santosh Kumar1, Ranajit Bera2, Neeladri Das2, Joonseok Koh1*

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Division of Chemical Engineering, Konkuk University, Seoul 05029, Republic of Korea
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Department of Chemistry, Indian Institute of Technology Patna, Patna 801106, Bihar, India

Email: santoshics@gmail.com; santoshics@konkuk.ac.kr (SK)

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Corresponding author*: Division of Chemical Engineering, Konkuk University, Seoul 05029,

Republic of Korea, Tel.: +82-2-3437-0238; Fax: +82-2-3437-0238. Email: ccdjko@konkuk.ac.kr

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(JK)

Graphical abstract
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Highlights

 New chitosan-based zeolite biocomposites (ZeY@CS and ZSM-5@CS) synthesized

using an inexpensive materials namely zeolite Y, ZSM-5 and chitosan

 Physicochemical properties of chitosan-based zeolite-Y and ZSM-5 porous

biocomposites studied in detail.

 Surface area of biocomposites higher than precursors such as pristine zeolites or

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chitosan

 Biocomposites show enhanced gas storage for small molecule like CO2 and hydrogen

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 Biocomposites are potential candidates for carbon capture and sequestration (CCS)

and energy storage applications.

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ABSTRACT

Sustainable energy is the most valuable clean and renewable energy for the future. A simple,
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robust, and inexpensive ecofriendly method has been developed here to prepare chitosan-based

zeolite porous biocomposites via solvent exchange followed by calcination. The resulting
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chitosan-based zeolite biocomposites were characterized using advanced technologies including

attenuated total reflection-infrared (ATR-IR) spectroscopy, X-ray powder diffraction (XRD)

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analysis, thermogravimetric analysis (TGA), high-resolution field-emission scanning electron

microscopy (HR-FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and

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nitrogen adsorption-desorption isotherms. The Brunauer-Emmett-Teller (BET) surface area of

the ZeY@CS composite (795 m2g−1) was greater than those of ZSM-5@CS (444 m2g−1), pure

chitosan, pure zeolite Y, and ZSM-5. The chitosan-based zeolite biocomposites show enhanced

gas storage for small molecule like CO2 and hydrogen. Therefore, chitosan-based zeolite

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biocomposites should be suitable for energy storage, carbon capture, and sequestration (CCS)

applications.

Keywords: Chitosan, zeolite, carbon dioxide, hydrogen, adsorption.

1. Introduction

Carbon dioxide (CO2) is a greenhouse gas whose increasing concentration in the atmosphere can

cause severe problems to both human health and wildlife (G. Bala, 2013). Environmental

pollution is a serious problem for our ecosystems due to the rapid pace of industrialization. In

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2015, the seriousness of reducing CO2 emissions from fossil fuel combustion was highlighted by

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the United Nations agreement at the Paris Climate Conference (Haszeldine, 2009). Zeolites are

natural aluminosilicate microporous minerals, which have good thermal stabilities and ion

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exchange abilities, and can be used in a variety of applications such as purification, separation,
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adsorbents, catalysis (Ding et al., 2015; Li et al., 2016; Martin et al., 2016; Ohlin et al., 2016;

Van de Vyver & Román-Leshkov, 2015; C. Wang et al., 2019; N. Wang, Qian, & Wei, 2016;
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Zhang, Liu, Lei, & Chen, 2016), and drug delivery (Derakhshankhah et al., 2016; He et al.,

2015). Zeolites are usually used as catalysts to refine crude petroleum into hydrocarbon fuels and
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to convert carbohydrate-derived compounds from biomass to aromatic hydrocarbons during

pyrolysis (Cheng, Jae, Shi, Fan, & Huber, 2012; Thilakaratne, Tessonnier, & Brown, 2016; K.
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Wang, Zhang, H. Shanks, & Brown, 2015). ZSM-5 has been reported to be the best zeolite in

achieving high conversions to aromatic hydrocarbons, mainly due to its unique structure and acid
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sites (Ivanova et al., 2007). Zeolites have high stability and can be modified with small targeting

molecules toward controlled release in drug therapy applications because of their non-toxicity,

microporous structure, and exceptional biocompatibility. Wen et al. have synthesized hollow

mesoporous ZSM-5 chitosan ellipsoids loaded with doxorubicin as a pH-responsive drug

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delivery system against osteosarcoma (Wen, Yang, Ke, Xie, & Guo, 2017). Zeolites have tunable

channels with a very rigid framework. This imparts zeolites with excellent shape selectivity

capabilities towards guest molecules and high thermal stabilities, making them ideal industrial

adsorbent materials (Ennaert et al., 2016). Zeolites are generally characterized by a relatively

high CO2 capture capacity and demonstrate selectivity over other small-molecular gases at low

pressure, which makes them promising candidates for CO2 separation from flue gases (Boot-

Handford et al., 2014; Chue, Kim, Yoo, Cho, & Yang, 1995). In yet another application of

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zeolites, Faisal et al. demonstrated the recovery of L-arginine from both a real fermentation broth

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and aqueous model solutions using a zeolite-Y adsorbent (Faisal et al., 2019).

Chitosan (CS) is an abundant natural polysaccharide, which contains reactive amino and

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hydroxyl groups on its backbone due the presence of numerous acetamido groups (Jayakumar,
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Menon, Manzoor, Nair, & Tamura, 2010; Kumar, Deepak, Kumari, & Dutta, 2016; Muzzarelli,

1977). It possesses several interesting properties including but not limited to hydrophilicity,
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biocompatibility, biodegradability, antibacterial activity and low cytotoxicity (Dang & Leong,

2006; Fan, Zhang, Zhang, Shu, & Shi, 2013; Garg et al., 2013; Kumar, Dutta, & Dutta, 2009;
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Kumar et al., 2015; Kumar & Koh, 2013; Murali et al., 2019; Wan Ngah, Teong, & Hanafiah,

2011). In addition, chitosan attracted attention in the fields of agriculture as soil conditioner
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(Iftime, Ailiesei, Ungureanu, & Marin, 2019), biosensors (Zhai et al., 2019), wastewater

treatment (Kumar, Krishnakumar, Sobral, & Koh, 2019), textiles (Lv, Hu, Guan, Tang, & Chen,
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2019), pharmaceutical (Dokhaee, Maghsoudi, Ghiaci, & Ghiaci, 2019), tissue engineering (Pok

et al., 2014) and lithium-ion transportation (Xu, Jin, Chen, & Wen, 2018). Porous chitosan

microspheres with high specific surface area were developed using agarose for application in bio

separations such as protein (Qiao, Zhao, Liang, & Du, 2019). Huang et al. developed chitosan

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based hierarchical porous carbons for application in super-capacitors (Huang et al., 2017). In

another application of chitosan based materials, Kumar et al. have synthesized a triphenylamine

chitosan derivative (Kumar, de A. e Silva, Wani, Dias, & Sobral, 2016) and chitosan-based

meso-tetrakis (4-sulfonatophenyl) porphyrin porous materials (Kumar, de A. e Silva, Wani, Gil,

& Sobral, 2017) for CO2 capture studies. Recently, Kumar et al. demonstrated that a ZY-CS

composite may be used to carry out the CO2 catalytic conversion of epichlorohydrin in excellent

yield (99.5%) (Kumar, Prasad, Gil, Sobral, & Koh, 2018).

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In a continuation of our previous study on novel materials for energy storage and carbon capture

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(Hsan, Dutta, Kumar, Bera, & Das, 2019; Krishnakumar et al., 2019; Kumar, Kumar Mishra,

Sobral, & Koh, 2019; Kumar, Prasad, et al., 2018; Kumar, Wani, Koh, Gil, & Sobral, 2018), we

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have selected naturally occurring chitosan biopolymer and zeolites (zeolite Y and ZSM-5) to
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synthesize their hybrid biocomposites using a simple green synthetic strategy. The biocomposites

were investigated in terms of their structural composition, surface morphology, thermal

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properties, and CO2 and H2 capture properties.

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2. Materials and methods

2.1. Materials
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High-molecular-weight chitosan (degree of deacetylation 75-85%; 50-190 kDa) and glacial

acetic acid were purchased from Sigma-Aldrich. Acetone was purchased from DaeJung chemical,
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Korea. Zeolite-Y and ZSM-5 were purchased from Alfa Aesar (Product of United States).

2.2. Characterization

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Attenuated total reflection-infrared (ATR-IR) spectra were recorded over the wavenumber range

4000-500 cm-1 on a JASCO, FT-IR-4100 spectrometer. A Rigaku Smart Lab X-ray

diffractometer was used to record the X-ray powder diffraction (XRD) patterns.

Thermogravimetric analysis (TGA) was carried out on a Q50 TA instrument. Samples were

heated in alumina crucibles from 25 to 700 ºC at a heating rate of 10 ºC min-1. The surface

morphology of the materials was analyzed using high-resolution field emission scanning electron

microscopy (HR-FE-SEM) on a Hitachi SU8010 instrument and high-resolution transmission

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electron microscopy (HR-TEM) on a JEM-3010 JEOL instrument. The porosity, surface area,

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and gas adsorption data were measured on a Quantachrome Autosorb iQ2 analyzer.

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2.3. Preparation of the chitosan-based zeolite biocomposites
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Chitosan-based zeolite biocomposites was prepared by dissolving natural biopolymer chitosan (2

g) in 1 wt% of acetic acid solution (80 mL) with stirring for 12 h. Zeolite Y (1 g) was dispersed
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into 20 mL of distilled water and subjected to mild ultrasonication for 30 min to form a

homogeneous dispersion. The zeolite dispersion was added to the chitosan solution with stirring,
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which was continued for 6 h to ensure the homogeneous dispersion of zeolite in the chitosan

solution. The hydrogel solution thus obtained was subjected to solvent exchange with acetone to
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remove water. The resulting powder was filtered, dried at 60 °C for 10 h, and placed in muffle

furnace for calcination at 450 °C for 5 h to yield a fine powder (Scheme 1). Similarly, ZSM-
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5@chitosan was also prepared following the procedure described above.

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Scheme 1. A schematic representation of the preparation of the chitosan-based zeolite

biocomposites.
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2.4. Porous property and gas adsorption (CO2 and H2) study
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Porosity, surface area and gas adsorption data were collected using Quantachrome

autosorb iQ2 analyzer. In a typical gas sorption experimental setup, the biocomposite (100 - 125
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mg) sample was taken in a 9 mm large cell and attached to the degasser unit. The contents inside

the cell were degassed at 150 °C by adjusting the delta pressure 25 micron for 5-7 h. Later, the
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cell was refilled with helium gas and detached from the degasser unit. Subsequently, the cell was

weighed carefully and then it was reattached to the analysis unit of the instrument for performing
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the adsorption-desorption isotherms experiments. Various temperatures of the analysis unit

sample cell were attained by either using a KGW isotherm bath (filled with liquid N2 to maintain

77K), or a temperature-controlled bath (to maintain 298K).

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3. Results and discussion

3.1. Physicochemical characterization of the chitosan-based zeolite biocomposites

The ATR-IR spectra recorded for zeolite Y, ZSM-5, chitosan and ZeY@CS and ZSM-5@CS

biocomposites are presented in Fig. 1. The spectra recorded for pure zeolite Y and ZSM-5 (Fig.

1b and 1c) show bands in the region 1000-1050 cm−1 due to the stretching vibrations of the

zeolite structural framework. The Si−OH group on the surface of the zeolite framework appears

in the region of 3400−3500 cm−1 (Kumar, Prasad, et al., 2018). The band observed in the region

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of 1600-1650 cm−1 was attributed to the bending vibration of the H−O−H bond (Teimouri et al.,

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2016). The ATR-IR spectrum of CS, as shown in Fig. 1a, reveals typical bands in the region of

3300−3500 cm−1 due to stretching vibrations of the OH and N−H bonds, 1600−1650 cm−1 due to

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the N−H bond of the acetyl group and 1000−1100 cm−1 due to C−O−C group. The spectra
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recorded for the chitosan-based zeolite biocomposites (Fig. 1d and 1e) are similar to a

combination of the zeolite (zeolite Y and ZSM-5) and CS spectra and contain bands due to both
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the zeolite and chitosan. In the chitosan-based zeolite biocomposites, the zeolites peaks are

dominant when compared with chitosan, which can be attributed to the electrostatic interaction
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observed between the negatively charged sites of the zeolite (Si−O−) and positively charged

amino (NH3+) groups of chitosan (Kumar, Prasad, et al., 2018).

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Fig. 1. FT-IR of chitosan (CS) (a), zeolite Y (b), ZSM-5 (c), ZeY@CS (d) and ZSM-5@CS (e).
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3.2. X-ray diffraction analysis

Fig. 2 shows the powder XRD patterns recorded for zeolite Y, ZSM-5, and the chitosan-based
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zeolite biocomposite materials (ZeY@CS and ZSM-5@CS). CS shows a broad peak at 2θ = 20º

(not incorporated in Fig. 2), (Kumar, Deepak, et al., 2016) whereas zeolite Y shows diffraction
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peaks at 6.28, 10.26, 12.00, 15.87, 18.98, 20.47, 23.96, 27.31, 30.05, 31.17, 31.91 and 34.65º

(Fig. 2a). Pure ZSM-5 display diffraction peaks at 7.90, 8.89, 13.14, 13.76, 14.75, 15.75, 17.86,

20.23, 20.72, 23.21, 23.83, 24.33, 26.94, 30.05 and 45.34º (Fig. 2b). The XRD patterns observed

for the chitosan-based zeolite biocomposites mainly display the zeolite peaks (Fig. 2c and d),

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whereas the chitosan related XRD peaks were not detected due to decomposition of chitosan

during calcination at 500 oC. Decomposition of chitosan biopolymer is also proved by TGA

analysis.

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Fig. 2. XRD patterns of zeolite Y (a), ZSM-5 (b), ZeY@CS (c), and ZSM-5@CS (d).
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3.3. Thermogravimetric analysis

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The thermograms recorded for zeolite Y, ZSM-5, ZeY@CS, ZSM-5@CS and CS are shown in

Fig. 3. TGA of high molecular weight CS indicated that two-weight loss steps occurred in the

temperature range from 30 to 128 °C due to the evaporation of water molecules and between

248−377 °C due to the degradation of the saccharide rings (Fig. 3). TGA of zeolite Y and ZSM-5

indicated a weight loss step between 32−188 °C due to loss of chemically and physically

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absorbed water present in channels, or the loss of the peripheral –OH groups. However, TGA of

ZeY@CS and ZSM-5@CS showed a weight loss step at 34−193 °C due to loss of chemically

and physically absorbed water, or loss of the peripheral −OH groups. The mass loss detected for

ZeY@CS and ZSM-5@CS indicates that the biocomposites have high thermal stability when

compared to chitosan and the pure zeolites.

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Fig. 3. TGA of CS (a), zeolite Y (b), ZSM-5 (c) ZeY@CS (KU22) (d), and ZSM-5@CS (KU23)
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(e).

3.4. Surface morphology

The morphologies of the as prepared materials were investigated using HR-FE-SEM. Fig. 4

shows the HR-FE-SEM images recorded for the chitosan-based zeolite biocomposites. The
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surface morphology of zeolite Y is octahedral, whereas the HR-FE-SEM image of the ZeY@CS

biocomposite indicated it has a hexagonal prismatic and rose flower structured (Fig. 4 a, and b).

ZSM-5@CS has a coffin-shaped nail structure arranged in a regular manner (Fig. 4c and d). The

HR-FE-SEM results also showed that the chitosan-based zeolite biocomposites have a sharp and

clear crystallinity.

Fig. 5 shows the HR-TEM images recorded for the chitosan-based zeolite biocomposites. The

HR-TEM images of ZSM-5@CS display a coffin-shaped nail structure (Fig. 5c and d).

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Fig. 4. SEM images recorded for ZeY@CS (a and b) and ZSM-5@CS (c and d).

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Fig. 5. HR-TEM images recorded for ZeY@CS (a and b) and ZSM-5@CS (c and d).
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3.5. BET surface area analysis

The BET surface areas of the chitosan-based zeolite biocomposites were analyzed using a

nitrogen gas adsorption method. The N2 adsorption-desorption isotherms at 77K recorded for

ZeY@CS and ZSM-5@CS are presented in Fig. 6. The isotherms with a small hysteresis loop

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confirm a type IV adsorption behavior. This is attributed to the presence of mesopores present in

these biocomposites. The pore size distributions obtained for the ZeY@CS and ZSM-5@CS

biocomposites are depicted in Fig. 7. The BET surface area of the ZeY@CS composite (795

m2g−1) is higher than the pure zeolite Y (730 m2g−1). Similarly, the BET surface area of ZSM-

5@CS (444 m2g−1) is relatively more than that of pristine ZSM-5 (425 m2g−1). These data clearly

suggests that there is an improvement in BET surface area of zeolites when it is present as a

hybrid biocomposite with CS. The larger pore size distribution and relatively higher pore volume

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observed in case of ZeY@CS composite in comparison with ZSM-5@CS may be due to the

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presence of super cages in ZeY. This may also be the cause of the higher volume of micropores

in the ZeY@CS composite when compared with ZSM-5@CS. Garshasbi et al. have prepared

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zeolite 13X from natural kaolin clay, which showed a BET surface area of 591 m2g−1 (Garshasbi,
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Jahangiri, & Anbia, 2017).
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Fig. 6. N2 Adsorption-desorption isotherms recorded for the ZeY@CS (a) and ZSM-5@CS (b)

biocomposites at 77 K.

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Fig. 7. Pore size distributions recorded for the ZeY@CS (a) and ZSM-5@CS (b) biocomposites.

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3.6. Carbon dioxide adsorption study

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CO2 is a greenhouse gas, which is the emitted in large quantities from industries such as cement
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production, power plants etc. A simple ecofriendly procedure using non-toxic CS at room

temperature was developed to prepare chitosan-based zeolite biocomposites using a solvent

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exchange method followed by calcination to enhance CO2 capture. The CO2 adsorption capacity

at 1 bar was obtained for the ZeY@CS and ZSM-5@CS biocomposite was 36.712 and 53.610
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ccg−1 at 298K (Fig. 8). The CO2 adsorption ability of chitosan based biocomposites (ZeY@CS:

36.712 cc g-1 and ZSM-5@CS: 53.610 cc g−1 at 298 K and 1 bar pressure, reported in this work,
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is better than that of another previously reported chitosan based biocomposite namely CS grafted

graphene oxide aerogels (Hsan et al., 2019). The isotherms are almost reversible with negligible
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hysteresis suggesting easy desorption of CO2. Presence of considerable narrow micropores in

biocomposites ZeY@CS and ZSM-5@CS are also responsible for their efficient CO2 uptake

ability in the low pressure region and this feature is related to the kinetic diameter of CO 2 (0.33

nm) (Liu, Wang, Shen, Ju, & Yuan, 2015). The ZSM-5@CS biocomposite displays enhanced

CO2 adsorption when compared to ZeY@CS. The results show that the higher basicity of the
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amino chitosan-based zeolite biocomposites increases the adsorption of CO2 when compared to

zeolite due to their large surface areas. The zeolites basicity occurs from the number of charges

and oxygen atom in the zeolite lattice, which depends on balancing the cations properties and the

Si/Al ratio (Weitkamp & Puppe, 2013). CO2 capture studies have been carried out on

immobilized zeolite 13X with monoethanolamine, ethylenediamine, and isopropanolamine

(Chatti et al., 2009). CO2 absorption has been analyzed on a zeolite ZSM5 filled polyvinylidene

fluoride hollow fiber mixed matrix membrane (Rezaei-DashtArzhandi et al., 2016). CO2 capture

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in the presence of water has been reported in zeolite@zeolitic imidazolate framework composites

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(Gao, Li, Bian, Hu, & Liu, 2015). Recently, Kumar et al. have also reported a zeolite-chitosan

for CO2 adsorption and catalytic activity in CO2 fixation (Kumar, Prasad, et al., 2018). Thakkar

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et al. have demonstrated zeolite 13X and 5A monoliths fabricated using a 3D printing technique
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for CO2 adsorption (Thakkar et al., 2016). Very recently, merlinoite zeolite has been synthesized

for CO2 adsorption using single-component isotherms, which demonstrated various cation-
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controlled molecule behavior, including breathing and opening of CO2 trigger pores (Georgieva

et al., 2019).
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Fig. 8. CO2 adsorption-desorption isotherms recorded for ZeY@CS (a) and ZSM-5@CS (b)

biocomposites at 298 K.

3.7. Hydrogen adsorption study

Hydrogen is one of the most valuable futuristic clean and renewable energy resources for

sustainable energy. Thus there is a lot of research effort towards design and development of

novel materials for storage of hydrogen. Hydrogen physisorption using porous materials has

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been considered as an excellent storage method because adsorption and desorption occur upon

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changing pressure and temperature. However, many efforts are still needed to make this solution

viable. The most common adsorbents studied today for hydrogen storage are micro- and

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mesoporous carbon materials, metal organic frameworks (MOFs), and covalent organic
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frameworks (COFs). We were interested to explore the potential of zeolite based biocomposites

as materials for hydrogen storage. Thus, the H2 uptake at 77 K was measured at 1 bar for the
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ZeY@CS and ZSM-5@CS biocomposites and these were found to be 113.61 and 110.75 ccg−1

respectively (Fig. 9). In comparison to chemisorption, physisorption processes are easy to handle,
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reversible due to the low interaction energy, and possess fast adsorption-desorption kinetics.

Efficient H2 uptake at low pressure (1 bar) recorded for biocomposites ZeY@CS and ZSM-
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5@CS is due to the presence of narrow micro pores in these biocomposites. This is related to the

kinetic diameter of H2 is 0.29 nm (Liu et al., 2015). In porous materials, such as zeolites, porous
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carbon structures, and metal organic frameworks (MOFs), hydrogen is physisorbed on the

surface of the pores and the capacity of the sorbent is mainly dependent on the surface area, pore

volume, working pressure, and working temperature. Typically, many of the physisorption-based

materials have acceptable hydrogen storage capacities at cryogenic temperatures (77 K) and high

pressure, but their capacities drop to below 1 wt.% at ambient temperature and pressure in the
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range of 50−100 bar (Broom et al., 2016). Recently Al-Naddaf et al. reported the synthesis and

development of zeolite-5A@MOF-74 composite adsorbents with core-shell structures, and

evaluated their use in the purification of H2 from simulated steam methane reforming off-gas

streams (Al-Naddaf, Thakkar, & Rezaei, 2018).

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Fig. 9. H2 adsorption-desorption isotherms recorded for the ZeY@CS (a) and ZSM-5@CS (b)
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biocomposites at 77 K.
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4. Conclusions

Crystalline and microporous chitosan-based zeolite biocomposites were synthesized via a facile
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solvent exchange and calcination method. The biocomposites were characterized using ATR-IR,

BET, HR-FE-SEM, HR-TEM, and powder X-ray diffraction. The zeolites are uniformly
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dispersed in the biopolymer matrix as confirmed by our morphological study. BET studies show

the biocomposites are nanoporous materials. The chitosan-based zeolite biocomposites exhibited

enhanced CO2 and H2 adsorption relative to both CS or their parent zeolites due to the high

surface area and pore volume observed in the biocomposite materials. These results suggest that

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chitosan-based zeolite biocomposites have potential applications in industry as CO2 and H2

storage materials.

Acknowledgements

This paper was supported by Konkuk University in 2018.

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