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Zhang, W.; Xu, Y.; Mu, X.; Li, S.; Liu, X.; Lei, Z. Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels. Encyclopedia. Available online: https://encyclopedia.pub/entry/43354 (accessed on 03 May 2024).
Zhang W, Xu Y, Mu X, Li S, Liu X, Lei Z. Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels. Encyclopedia. Available at: https://encyclopedia.pub/entry/43354. Accessed May 03, 2024.
Zhang, Wenxu, Yan Xu, Xuyang Mu, Sijie Li, Xiaoming Liu, Ziqiang Lei. "Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels" Encyclopedia, https://encyclopedia.pub/entry/43354 (accessed May 03, 2024).
Zhang, W., Xu, Y., Mu, X., Li, S., Liu, X., & Lei, Z. (2023, April 24). Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels. In Encyclopedia. https://encyclopedia.pub/entry/43354
Zhang, Wenxu, et al. "Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels." Encyclopedia. Web. 24 April, 2023.
Adsorption Properties of Polysaccharide-Based Natural Polymer Hydrogels
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This entry is adapted from the peer-reviewed paper 10.3390/gels9030249

The pollution and scarcity of freshwater resources are global problems that have a significant influence on human life. It is very important to remove harmful substances in the water to realize the recycling of water resources. Hydrogels have recently attracted attention due to their special three-dimensional network structure, large surface area, and pores, which show great potential for the removal of pollutants in water. In their preparation, natural polymers are one of the preferred materials because of their wide availability, low cost, and easy thermal degradation. However, when it is directly used for adsorption, its performance is unsatisfactory, so it usually needs to be modified in the preparation process. 

hydrogel adsorption natural polymer

1. Adsorption Mechanism and Kinetics of Polysaccharide-Based Hydrogels

The adsorption of the hydrogel can be divided into chemisorption and physisorption. Chemisorption is an irreversible process, mainly because its adsorbent and adsorbent are chemically bonded in the interaction; the destruction of the bond is permanent and, once destroyed, will not be able to bond again. In contrast, physisorption is an irreversible process, usually controlled by physical forces, such as hydrogen bonding, ionic bonding, π–π stacking, hydrophobic interactions, etc., and can be restored after being disrupted. In the preparation of hydrogels, physical action is usually combined with chemical action to strengthen their adsorption properties and mechanical properties, such as in self-healing hydrogels, which usually disperse energy consumption by physical action to ensure that the integrity of internal chemical bonds and mechanical properties is improved; such hydrogels are widely used in bioengineering [1]. In the preparation of hydrogels in the field of adsorption, researchers have also chosen to combine the two modes of action. The specific adsorption mechanisms and their classification are as follows.

1.1. Adsorption Mechanism

In the adsorption process, different functional groups have different adsorption mechanisms and different modes of action, and functional groups determine the type and strength of intermolecular forces and the chemical reactivity of molecules. The main functional groups involved in the adsorption process of polysaccharide-based hydrogel materials can be divided into three main categories: oxygen-containing functional groups, nitrogen-containing functional groups, and sulfur-containing functional groups. N, O, and S class heteroatoms can contribute to one or more electrons and form coordination bonds with metal ions while also undergoing ion exchange or electrostatic attraction to achieve the adsorption of a wide range of contaminants. Among the various metal adsorption mechanisms reported for hydrogels, the three methods of electrostatic interactions, ion exchange, and surface complexation (including coordination and chelation) have been found to be closely related to surface functional groups [2]. As shown in Figure 1, the process of action when adsorption is carried out by these three modes of action is depicted, among which most adsorption mechanisms of the two electrostatic interactions and ion exchange are reversible, and the adsorbents can be reused and belong to physical adsorption.
Gels 09 00249 g005 550
Figure 1. Schematic diagram of the adsorption process in three modes.

1.2. Adsorption Kinetics

1.2.1. Pseudo-First-Order Kinetic

The pseudo-first-order kinetic model is based on the modal diffusion theory, which assumes that the arrival of the adsorbent from the solution to the adsorbent’s surface is controlled by the diffusion step and that the adsorbent’s surface has only one binding site [3]. The form of the equation is as follows:
ln q e − q t = lnq e − K 1 t
where qt is the adsorption capacity at time t (mg/g), qe is the adsorption capacity at the moment of adsorption equilibrium (mg/g), and K1 is the rate constant of the first-order kinetic.
Although the first-order kinetic model has been widely used for various adsorption processes, it has limitations. It is often only suitable for the kinetic description of the initial stage of adsorption and cannot accurately describe the entire process of adsorption [4].

1.2.2. Pseudo-Second-Order Kinetic

The pseudo-second-order kinetic model is based on the adsorption rate-limiting step and contains the adsorption mechanism, such as chemisorption, which involves electron sharing or electron transfers between the adsorbate and the adsorbent [5]. The conformity to the pseudo-second-order kinetic model indicates that adsorption kinetics are mainly controlled by chemical interactions rather than by the material transport steps. The form of the equation is as follows:
t q t = 1 K 2 q e 2 + t q e
where qt is the adsorption capacity at time t (mg/g), qe is the adsorption capacity at the moment of adsorption equilibrium (mg/g), and K2 (g/mg·h) is the pseudo-second-order rate constant.

1.3. Adsorption Isotherms

1.3.1. Langmuir Isotherm Equation

The Langmuir adsorption isotherm model is the most widely used molecular adsorption model, which can predict the maximum adsorption capacity of adsorbents by considering the influence of the adsorbent’s surface and temperature [6]. This theory is a single molecular layer adsorption theory, which requires a homogeneous solid surface with the same adsorption capacity and no interaction between the adsorbed molecules, but the assumptions of the model are far from the actual conditions, and the information obtained is sometimes highly inaccurate [7]. The form of the equation is as follows:
C e q e = C e q m + 1 q m K L
where Ce is the equilibrium concentration of the solution, mg/L, Qe is the adsorption capacity at the moment of adsorption equilibrium (mg/g), Qm is the maximum adsorption capacity (saturation), mg/g, and KL is the Langmuir constant related to the affinity and adsorption energy of the bonding site, L/g.

1.3.2. Freundlich Isotherm Equation

The Freundlich isothermal adsorption equation is an empirical equation with no assumptions. The form of the equation is as follows:
lnq e = lnK F + 1 n lnC e
where Qe is the adsorption amount, mg/g, when adsorption reaches equilibrium, Ce is the concentration of adsorbate in solution at adsorption equilibrium, mg/L, KF is the constant related to adsorption capacity and adsorption strength under the Freundlich model, and 1/n is the Freundlich constant. A large value of KF is a sign of a better adsorption performance of the adsorbent. Freundlich adsorption isotherms can be obtained by plotting lnqe against lnCe at different temperatures [8].

2. Adsorption Applications of Polysaccharide-Based Hydrogels

2.1. Heavy Metal Ion Adsorption

Heavy metal ions are highly toxic, non-degradable, and bioaccumulative in the environment and circulate through the food chain in water and biological systems, seriously affecting the organisms at the top of the food chain [9][10]. Heavy metals are metals with a density greater than 4.5 g/cm3, mainly including Au, Ag, Cu, Pb, Zn, Ni, Co, Cd, Hg, Cd, and more than 40 other kinds of metals [11]. The five most toxic to humans are lead, mercury, chromium, arsenic, and cadmium. These heavy metals cannot be decomposed in water, and their toxicity is amplified when they enter the human body; therefore, efficient and special methods are needed to remove heavy metal contaminants from water systems [12]. The adsorption process of heavy metal ions is directly related to the functional groups of the adsorbent materials themselves, and most current studies mainly revolve around the adsorption of divalent heavy metal ions, of which Cu2+, Pd2+, and Cd2+ are predominant. Table 1 summarizes the polysaccharide-based adsorbent materials in the last two years for this application of heavy metal ion adsorption.
Table 1. Adsorption of heavy metal ions by different polysaccharide-based composite hydrogels.
Polysaccharide
Hydrogel
Adsorption		 Adsorbates Adsorption Capacity (mg/g) Adsorption
Isotherm		 Adsorption
Kinetics		 Ref.
AM/AA Cu2+ 157.51 Langmuir PSO [13]
Pd2+ 393.28 Langmuir PSO
Cd2+ 289.97 Langmuir PSO
Nanocellulose/Carbon dot Cr6+ 599.9 Freundlich PSO [14]
Straw cellulose Cd2+ 95.62 Langmuir PSO [15]
Nanocellulose/SA Pb2+ 318.47 Langmuir PSO [16]
GO-PVA-CS Cd2+ 172.11 Langmuir PSO [17]
Ni2+ 70.37 Langmuir PSO
CYCS/CNC Pb2+ 334.92 Langmuir PSO [18]
Chitosan oligosaccharide Cr6+ 148.1 Langmuir PSO [19]
α-ketoglutaric acid–PAM-CS Cu2+ 72.39 Langmuir PSO [20]
Pd2+ 61.41 Langmuir PSO
Zn2+ 51.89 Langmuir PSO
CPCS-PAM-PVA Cr6+ 95.31 Langmuir PFO [21]
Millettia speciosa Champ cellulose-CS Cu2+ 23.37 Freundlich PFO [22]
All-lignocellulose Cu2+ 350 Langmuir PSO [23]
Caffeic acid starch Cr6+ 96.45 Langmuir PSO [24]
Starch-FMBO As3+ 161.29 Langmuir PSO [25]
Starch nanoparticle Pb2+ 40.52 Langmuir PSO [26]
Cu2+ 32.88 Langmuir PSO
dibenzo-18-crown-6 starch Cd2+ 368.5 Freundlich PSO [27]
Ni2+ 182.5 Freundlich PSO
Zn2+ 377.5 Freundlich PSO
Cu2+ 385 Freundlich PSO
Succinic anhydride-SNCs Cu2+ 84.07 Freundlich PSO [28]
PVA-SA Pb2+ 784.97 Langmuir PSO [29]
ZIF-67-SA Cu2+ 153.63 Langmuir PSO [30]
AM-GO-SA Cu2+ 68.76 Langmuir PSO [31]
Pb2+ 240.69 Langmuir PSO
Zeolite-PVA-SA Pb2+ 99.5 Langmuir PFO [32]
Cd2+ 99.2 Langmuir PFO
Sr2+ 98.8 Langmuir PFO
Cu2+ 97.2 Langmuir PFO
Zn2+ 95.6 Langmuir PFO
Ni2+ 93.1 Langmuir PFO
Mn2+ 92.4 Langmuir PFO
Starch ether-SA Cu2+ 25.81 Langmuir PSO [33]
Reptilite-Starch Pb2+ 180.8 Langmuir PSO [34]
NCDs-CNF/CS Cu2+ 148.3 Langmuir PSO [35]
Cr6+ 294.46 Langmuir PSO
CTS/CA/BT Pb2+ 434.89 Freundlich PSO [36]
Cu2+ 115.30 Freundlich PSO
Cd2+ 102.38 Freundlich PSO
GO-SA As5+ 277.39 Langmuir PSO [37]
PAN-PPY-SA-GO Cu2+ 133.7 Redlich–Peterson PFO [38]
Cr6+ 87.2 Redlich–Peterson PFO

2.2. Dye Adsorption

There are many methods for removing dyes from wastewater: biological dye removal, acoustic chemical degradation, electrocatalytic degradation, cation exchange membrane technology, etc. However, these processes produce toxic residues that cause secondary pollution and are costly to implement. In contrast, the gel’s adsorption method is simple, efficient, and inexpensive to operate. Hydrogels have a strong dye removal capability, and dyes are more easily diffused in the dissolved hydrogel, which enhances the adsorption capacity via electrostatic interactions with oppositely charged dyes [39].
There is a wide range of adsorbed dyes, among which methylene blue (MB), malachite green (MG), and methyl orange (MO) fuels are more widely adsorbed. MB is a phenothiazine cationic dye, an alkali, that is used to treat methemoglobinemia in histology and microscopy to identify and detect bacteria, to treat fungal infections by staining tissues [40], and to stain cotton and wood. The waste dye discharged into the environment after use can be harmful, causing dizziness, headaches, tremors, and mental confusion, among other symptoms [41]. Malachite green (MG) is a toxic trityl methane chemical, both as a dye and as a bactericidal and parasiticidal chemical, is an alkali, and is prohibited for use in aquaculture. In industries, it is used to color leather, paper, cotton, and silk. However, it is potentially carcinogenic, teratogenic, and mutagenic and is difficult to remove from water [42]. Table 2 summarizes polysaccharide-based adsorbent materials used in the past two years for this application of dye adsorption.
Table 2. Adsorption of dyes by different polysaccharide-based composite hydrogels.
Polysaccharide
Hydrogels
Adsorption		 Adsorbates Adsorption Capacity (mg/g) Adsorption
Isotherm		 Adsorption
Kinetics		 Ref.
C/SA/Fe MB 105.93 Langmuir PSO [43]
Carboxymethylcellulose MB 756 Freundlich PSO [44]
Pineapple peel
cellulose/diatomite		 MB 101.94 Langmuir PSO [45]
PCMC-PVA MB 172.14 Langmuir PSO [46]
All-lignocellulose MB 145 Langmuir PSO [23]
Millettia speciosa Champ cellulose-CS CR 221.43 Freundlich PSO [22]
PAM-Fe3O4-CS MB 1603 Langmuir PFO [47]
Montmorillonite-CS MB 530 Langmuir PSO [48]
GO-CS-Fe3O4 MB 289 Langmuir PSO [49]
EBT 292 Langmuir PSO [50]
Jute cellulose nanocrystal MB 131.58 Langmuir PSO
Succinic anhydride-SNCs MB 84.00 Freundlich PSO [28]
Reptilite-Starch MB 277.0 Langmuir PSO [34]
PAM-cassava starch MB 2000 Langmuir PSO [51]
MXene-SA MB 92.17 Langmuir PSO [52]
AA-GO-SA MG 628.93 Langmuir PSO [53]
Flax seed ash-SA MB 333.3 Langmuir PSO [54]
PEI-SA MB 400 Langmuir PSO [55]
AM-HEMA-Starch MG 164 Langmuir PFO [22]
MV 156 Freundlich PFO

2.3. Drug Antibiotics Adsorption

In the treatment of contaminants in water, attention has been focused mainly on the adsorption of textile dyes and heavy metals. However, the harmful effects of these emerging contaminants, such as pesticides, herbicides, fungicides, pharmaceutical compounds, and personal care products, on the water environment cannot be ignored. Once the toxic substances of pharmaceutical and medical waste enter the soil, they will be adsorbed by the soil, pollute the soil, kill microorganisms and protozoa in the soil, and destroy the microecology in the soil, which in turn will reduce the soil’s ability to degrade pollutants. Furthermore, the acid, alkali, and salts in the substances will change the nature and structure of the soil, leading to the acidification, alkalization, and hardening of the soil, affecting the development and growth of plant roots, and damaging the ecological environment; meanwhile, many harmful drug pollutants can cause serious damage to the liver and nervous systems. Table 3 summarizes the polysaccharide-based adsorption materials used for antibiotic adsorption in the past two years.
Table 3. Adsorption of drug antibiotics by different polysaccharide-based composite hydrogels.
Polysaccharide
Hydrogels
Adsorption		 Adsorbates Adsorption Capacity (mg/g) Adsorption
Isotherm		 Adsorption
Kinetics		 Ref.
Fe3O4-Starch Naphthalene 24.752 Langmuir PSO [56]
CS-Chitosan film Cefotaxime Sodium 1003.64 Freundlich PSO [57]
GO-SA Tetracycline 477.9 Freundlich PSO [37]
Amino/GO-SA Ciprofloxacin 301.36 Langmuir PSO [58]
Humicacid-CS-Biochar Ciprofloxacin 154.89 Langmuir PSO [59]
Biochar-CS Ciprofloxacin 106.038 Langmuir PSO [60]
Enrofloxacin 100.433 Langmuir PSO
GO-SA Fluoxacin 4.11 Langmuir PSO [61]
Moxifloxacin 3.43 Langmuir PSO
Fe3O4-SA Tetracycline 454.54 Langmuir PSO [62]
Amoxicillin 400 Langmuir PSO
Trimethylammonium chloride-CS Tetracycline 22.42 Langmuir PFO [63]
PVA-SA-Cu2+ Tetracycline 231.431 Langmuir PSO [64]

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Subjects: Polymer Science
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Wenxu Zhang
,
Yan Xu
,
Xuyang Mu
,
Sijie Li
,
Xiaoming Liu
,
Ziqiang Lei
View Times: 405
Revisions: 5 times (View History)
Update Date: 24 Apr 2023
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