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Preparation of Cellulose/Chitin Blend Materials and Influence of Their sustainability Article Preparation of Cellulose/Chitin Blend Materials and Influence of Their Properties on Sorption of Heavy Metals Dao Zhou 1,*, Hongyu Wang 1 and Shenglian Guo 2 1 School of Civil Engineering, Wuhan University, Wuhan 430072, China; [email protected] 2 School of Hydraulic Engineering, Wuhan University, Wuhan 430072, China; [email protected] * Correspondence: [email protected] Abstract: A series of biodegradable cellulose/chitin materials (beads and membranes) were success- fully prepared by mixing cellulose with chitin in an NaOH/thiourea–water system and coagulation in a H2SO4 solution. The effects of chitin content on the materials’ mechanical properties, morphology, structure, and sorption ability for heavy metal ions (Pb2+, Cd2+, and Cu2+) were studied by tensile tests, scanning electron micrographs, Fourier transform infrared spectroscopy, and atomic absorption spectrophotometry. The results revealed that the cellulose/chitin blends exhibited relatively good mechanical properties, a homogeneous, microporous mesh structure, and the existence of strong hydrogen bonds between molecules of cellulose and chitin when the chitin content was less than 30 wt%, which indicated a good compatibility of the cellulose/chitin materials. Furthermore, in the same chitin content range, Pb2+, Cd2+, and Cu2+ can be adsorbed efficiently onto the cellulose/chitin beads at pH0 = 5, and the sorption capacity of the beads is more than that of chitin flakes. This shows that the hydrophilicity and microporous mesh structure of the blends are favorable for the kinetics of sorption. Preparation of environmentally friendly cellulose/chitin blend materials provides a simple and economical way to remove and recover heavy metals, showing a potential application of chitin Citation: Zhou, D.; Wang, H.; Guo, S. as a functional material. Preparation of Cellulose/Chitin Blend Materials and Influence of Keywords: cellulose; chitin; blend materials; sorption; heavy metal removal Their Properties on Sorption of Heavy Metals. Sustainability 2021, 13, 6460. https://doi.org/10.3390/su13116460 1. Introduction Academic Editors: Junfeng Su, Qian Zhang and Sicheng Shao Although the utilization of synthetic polymers extracted from petroleum resources has had a sizable influence on the world economy, the problem of petroleum resource Received: 30 April 2021 shortages and environmental pollution from the waste of non-biodegradable synthetic Accepted: 4 June 2021 polymers, which are mainly derived from petroleum resources, is becoming increasingly Published: 7 June 2021 serious [1]. Therefore, the importance of research and exploitation of new materials based on natural polymers has been recognized in many countries [2]. Abundant biodegradable Publisher’s Note: MDPI stays neutral polymers in nature such as cellulose, chitin, lignin, starch, and various animal and plant with regard to jurisdictional claims in proteins, which possess various functional groups and are available in large quantities, may published maps and institutional affil- have potential for the development of new materials by physical or chemical modification. iations. Polymer blending is an easy, simple, and convenient method to develop new materials with excellent properties for practical use. Furthermore, the cost could be greatly reduced when using polymer blending for research and exploitation of new materials [3]. Nowadays, polymer mixtures or blends are widely used materials in modern industry. They represent Copyright: © 2021 by the authors. one of the most rapidly growing areas in polymer material science [4]. Licensee MDPI, Basel, Switzerland. Today, the global environmental problem is becoming increasingly serious with rapid This article is an open access article population growth, the acceleration of industrialization, and the use of new toxic chemicals. distributed under the terms and The issue of heavy metal pollution has attracted great attention. Heavy metals are widely conditions of the Creative Commons used in many industries, such as electroplating, printing and dyeing, oil paints, electrolysis, Attribution (CC BY) license (https:// pesticides, and medicine. Most heavy metals are toxic, carcinogenic, and can be accumu- creativecommons.org/licenses/by/ lated and transferred in living organisms. Wastewater containing heavy metals, when 4.0/). Sustainability 2021, 13, 6460. https://doi.org/10.3390/su13116460 https://www.mdpi.com/journal/sustainability Sustainability 2021, 13, x FOR PEER REVIEW 2 of 13 Sustainability 2021, 13, 6460 electrolysis, pesticides, and medicine. Most heavy metals are toxic, carcinogenic, and2 of can 11 be accumulated and transferred in living organisms. Wastewater containing heavy metals, when discharged into aquatic bodies, poses a serious threat to human health and dischargedthe survival into of animals aquatic and bodies, plants, poses even a seriousif the heavy threat metals to human are presen healtht in and trace the quantities survival of[5]. animals To remove and heavy plants, metals even iffrom the heavywastewater, metals various are present conventional in trace treatment quantities methods [5]. To removehave been heavy employed, metals from including wastewater, chemical various precipitation conventional [6], treatmentdistillation methods [7], ion have exchange been employed,[8], adsorption including [9], reverse chemical osmosis precipitation [10], elec [trolysis6], distillation [11], etc. [7 ],However, ion exchange these [ 8techniques], adsorp- tionhave [9 ],certain reverse deficiencies osmosis [10 such], electrolysis as high [cost11],, etc.low However, efficiency, these high techniques energy requirements, have certain deficienciesoperational suchcomplexity, as high cost,and lowlarge-scale efficiency, genera hightion energy of sludge requirements, or toxic operationalwaste materials, com- plexity,which may and large-scalerequire special generation treatment of sludge[12]. Henc or toxice, environmentally waste materials, friendly which methods may require with speciallow cost treatment and high [12 efficiency]. Hence, are environmentally necessary for friendlyremoving methods toxic metals with low from cost wastewater. and high efficiencyBiosorption are of necessary heavy metal for removingions has been toxic regarded metals from as one wastewater. of the most Biosorption reliable and of efficient heavy metalmethods. ions Natural has been polymer regarded materials as one ofthat the are most obtained reliable in great and efficient quantities, methods. or certain Natural kinds polymerof waste materialsproducts thatfrom are industrial obtained or in agricu greatltural quantities, processes, or certain including kinds various of waste bacteria prod- ucts[13], from yeast industrial [14], fungi or [15], agricultural algae [16], processes, etc., may includinghave potential various as inexpensive bacteria [13 ],biosorbents. yeast [14], fungiCellulose [15], algae is [ 16the], etc.,most may abundant have potential natural aspolymer inexpensive material biosorbents. in nature and is mainly foundCellulose in trees, is cotton, the most hemp, abundant cereal plants, natural and polymer other materialhigher plants. in nature As a andbiocompatible is mainly foundcarrier, in cellulose trees, cotton, has special hemp, cerealproperties, plants, such and as other being higher non-toxic, plants. safe, As ahydrophilic, biocompatible and carrier,biodegradable cellulose and has possessing special properties, high chemical such stability, as being good non-toxic, mechanical safe, hydrophilic,strength, and and low biodegradablecost [17]. It is andwidely possessing used in highfood, chemicalmedicine, stability, construction, good mechanicalpapermaking, strength, wastewater and lowtreatment, cost [17 ].printing, It is widely electronics, used in food,and medicine,other fields construction, [18,19]. Chitin papermaking, is the second wastewater most treatment,abundant printing,resource electronics,(after cellulose) and otherin nature, fields has [18 ,a19 similar]. Chitin chemical is the second structure most to abundant cellulose, resourceand may (after be considered cellulose) incellulose nature, haswith a C-2 similar hydroxyl chemical replaced structure by toan cellulose, acetamido. and Chitin may bemainly considered comes cellulose from the with exoskeletons C-2 hydroxyl of arthro replacedpods by (shrimp, an acetamido. crabs, Chitinand insects) mainly and comes the fromcell walls the exoskeletons of some fungi, of arthropodsalgae, etc. Figure (shrimp, 1 shows crabs, the and chemical insects) andstructures the cell of walls cellulose of some and fungi,chitin. algae, etc. Figure1 shows the chemical structures of cellulose and chitin. FigureFigure 1.1.Chemical Chemical structuresstructuresof ofcellulose celluloseand and chitin. chitin. ChitinChitin and and chitosan chitosan (deacetylation (deacetylation of chitin)of chitin) are regardedare regarded as good as good metal metal ligands. ligands. They canThey form can coordination form coordination complexes complexes with heavy with metalheavy ions.metal It ions. has beenIt has reported been reported that stable that complexesstable complexes are formed are formed between between the N-acetyl the N-ac groupetyl in group chitin andin chitin the heavy and the metal heavy ions metal [20]. However,ions [20]. thereHowever, are some there problems are some with problems directly with applying directly chitin applying in flake chitin shape, in flake such asshape, the separationsuch as the of separation chitin after of sorption,
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