Valorization of Oceanic Waste Biomass: A Catalytic Perspective

Personal Account DOI: 10.1002/tcr.
201800195
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THE
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Valorization of Oceanic Waste Biomass:
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RECORD A Catalytic Perspective
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11 Nishita Lucas,[a] Anjali A. Athawale,*[a] and Chandrashekhar V. Rode*[b]
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Chem. Rec. 2019, 19, 1 – 28 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 1
Pe r s o n a l A c c o u n t THE CHEMICAL RECORD
1 Abstract: Efficacious waste utilization is vital in context of sustainability. The past decade has
2 witnessed attempts of usage of land biomass and wastes for various applications, contributing
3 towards a sustainable society. Exploitation of the marine biomass, which does not compete with
habitation and food production like land biomass has been largely unnoticed and therefore not
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being utilized judiciously. Researchers have mainly exploited these resources as functional
5 materials having significant potential applications. However, a catalytic perspective for the
6 valorisation of these polymers arising from oceanic waste widens their scope and ameliorates its
7 use. The objective of the present review is to demonstrate the effectiveness of chitin/chitosan as a
8 catalyst and as a feedstock for deriving important fuels and chemicals. It displays all the reactions
9 heterogeneously catalyzed by them along with the strategic methodology. Their important
10 catalytic organic transformations attempted so far, have also been discussed. The future
11 perspectives are also presented which if inculcated would improve the value addition of the waste,
paving a way for greener and imperishable world.
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13 Keywords: oceanic, waste, valorisation, catalytic, perspective
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16 shells/exoskeletons of crustaceans and molluscus, which can
1. Introduction
17 be used as a source of chemicals and materials.[16] Chitin, a
18 The genesis of the quest for sustainable alternatives can be natural amino-biopolymer is the basic building block which
19 ascribed to dwindling fossil reserves, the associated environ- gives strength to these exoskeletons. It is the second most
20 mental devastation and energy crisis. These alarming issues abundant polymer after cellulose (1011 tonnes produced
21 are indicative of an imperative transition from fossil based annually).[17] The rigid and unique structure of chitin makes
22 chemicals to bio-chemicals thus contributing towards a it different from other carbohydrate biopolymers as the key
23 sustainable society.[1] This has spurred the research in primary metabolite and structural component of the animal
24 industries and academia for deriving fuels and chemicals and plant kingdom. The estimated global market for chitin is
25 (bulk and speciality) from renewable feedstock. Consequently, around 118000 tonnes in terms of weight by 2020.[18]
26 waste from various sources such as crops and food Chitin is a polymer in which the monomer N-acetyl
27 industry,[2–4] wood and forest,[5–8] sludge and municipality,[9–12] glucosamine (NAG) is bound through b (1,4) glycosidic
28 bakery and other biological systems[13,14] have been utilized as linkage to give rise to long chains. Individual chains can be
29 feedstock to deliver wide array of fuels and chemicals. described as helices in which each sugar monomer is inverted
30 Visualizing this, it can be inferred that land biomass is fairly with respect to its neighbours.[16] The difference in arrange-
31 well explored justifying some of Green Chemistry principles. ment/number of these chains, unit cell size and degree of
32 On the other hand, oceanic biomass which is also an hydration yields the three different crystalline allomorphs of
33 abundant and easily accessible renewable resource is surpris- chitin (a, b and g).[19] In a-chitin, the unit cell is composed of
34 ingly largely overlooked. Oceans are the habitat to diverse dimer N,N’-diacetylchitobiose (dimer) forming two chains in
35 biota from which different products could be possible for anti-parallel direction held together strongly by intramolecu-
36 various applications.[15] The sagacious utilization of oceanic lar hydrogen bonding. These chains form sheets due to
37 biomass integrated with innovative approaches will lead to intermolecular hydrogen bonding of N H bonds.[20–22] This
38 successful paradigm shift towards bio-refinery and thus imparts it a highly rigid and crystalline structure. These
39 sustainability. In this context, the valorisation of oceanic waste polymer chains, if allowed to crystallize give rise to micro-
40 is more challenging rather than exploitation of algal plants. fibrils due to self assembly.[23] The b-chitin has same unit cell
41 Oceanic waste arises from shellfish processing and contains however, it has a parallel arrangement of polymeric chains
42 with no intramolecular hydrogen bonding but the intermo-
43 lecular hydrogen bonding exists yielding firm sheets. As a
44 [a] Dr. N. Lucas, Dr. A. A. Athawale result, it has less rigid structure than a-chitin. While the third
Department of Chemistry
45
S.P. Pune University
allomorph, g–chitin possesses mixed parallel and anti-parallel
46 Pune, Maharashtra, India orientations.[16]
47 E-mail: nishita.lucas@gmail.com The unique structure imparts interesting physico-chemical
48 agbed@chem.unipune.ac.in characteristics to chitin. The acetyl amino group on the
49 [b] Dr. C. V. Rode polymer backbone plays a crucial role in exhibiting these
Chemical Engineering and Process Development Division
50 National Chemical Laboratory properties. The presence of this moiety expands the
51 Pune, Maharashtra, India dimensions of chitin for various applications making it
52 E-mail: cv.rode@ncl.res.in superior to cellulose, its structural analogue. Chitin on
1 deacetylation gives chitosan which also possesses immense

2 potential for various applications.[24] The notable properties
3 of chitin and chitosan are depicted in Figure 1, which include
4 adsorption, chelation, coagulation, flocculation, fibre and
5 film forming properties, non-toxicity and distinctive bio-
6 logical properties. Chitin and chitosan adsorb dyes, proteins,
7 aromatic hydrocarbons, toxic metals and metal cations.[25,26]
8 Chitosan being a polycationic polymer has been used for
9 coagulation and flocculation in waste water treatment.[27]
10 Rinaudo has effectively displayed the ability of chitin and
11 chitosan to form hydrogels, films, fibres, blends and
12 composites.[28] Additionally, due to their biocompatibility,
13 biodegradability and non-toxicity they have pharmaceutical,
14 physiological and biological applications. They are used in
15 immunity enhancement, eliciting biological responses, hypo-
16 lipidemic and heamostatic activity, antimicrobial activity,
Figure 1. Potential Applications of N-containing biopolymers.
17 wound healing and mucoadhesion.[29] Chitosan acts as an
18 efficient polymer support for tissue engineering, cell culture
19 and gene delivery.[30]
20 Based on their unique properties, researchers have Kurita describes the fundamental aspects of these materials
21 reported the potential applications of chitin and chitosan. For such as preparation, extent of N-acetylation, crystallography
22 example, Sashiwa et al. studied the chemical modifications of and other properties. [29] This study also focuses on the
23 chitin and chitosan which had important biomedical elemental modification reactions like acylation, alkylation,
24 applications. Sugar modified chitosan was an excellent carboxyalkylation, silylation etc. Hamblin et al. surveyed the
25 candidate for drug delivery, chitosan-dendrimers hybrid were biosynthesis and isolation of chitin/chitosan and summarized
26 multifunctional macromolecules. Role of each functional their applications in nanotechnology ranging from wound
27 group in these applications was emphasized.[31] Review by dressings, antimicrobial agents, tissue engineering, vaccine
28
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30 Dr. Nishiita Lucas received her Ph. D. Dr. Chandrashekhar Rode received his
31 from National Chemical Laboratory, Pune Ph.D. from University of Pune in 1993.
32 in 2015. She worked as Post-doctoral Currently, he is an Emeritus Scientist at
33 fellow at Department of Chemical Engi- National Chemical Laboratory, Pune. He
34 neering, Technion from 2015–2016. She is a Fellow of Indian National Academy of
35 is presently availing the prestigious D.S. Engineering (FNAE). His research inter-
36 Kothari Post-doctoral fellowship of India. ests include Catalysis for Sustainable De-
37 Her research is mainly focussed on con- velopment which includes biomass utiliza-
38 version of biomass to value added chem- tion for value added products and catalysis
39 icals. in super critical carbon dioxide medium.
40 Dr. Anjali Athawale received her Ph.D.
41 from University of Pune in 1988. Presently
42 she is a Professor in Physical Chemistry at
43 Department of Chemistry, S.P. Pune Uni-
44 versity. She is a recipient of Bristish
45 Commonwealth Erasmus Mundus and
46 Fullbright teacher fellowships. Her current
47 research is focussed on conducting poly-
48 mers, biodegradable polymers and perov-
49 skites/oxides for antifouling/anticorrosion
50 coatings, food packaging and organic
51 catalytic applications.
52
1 adjutants and anti-aging cosmetics.[16] Important pharmaceut- support material for this transformation particularly, for C C
2 ical and biomedical applications were displayed by Zhang coupling. Zeng et al. directly cross linked Pd cation on
3 et al. The study also emphasized on the biological and chitosan membranes 1 which were highly active for Heck
4 chemical modifications of chitosan to enhance its solubility reaction (Scheme 1).[36] They achieved 98 % yield of the
5 and absorbability in-vivosystems to ameliorate its utiliza- product under the optimized conditions. Recyclability studies
6 tion.[32] The study pertaining to the solid state structure, revealed that the catalyst retained its activity for 12 cycles
7 solubility and application in medical and cosmetic field is which was attributed to well entrapped Pd nanoparticles
8 discussed by M. Rinaudo.[28] An excellent review by Kerton inside the chitosan matrix.
9 et al. highlights the achievements and potential opportunities
10 in the use of algae, shellfish waste and finfish processing. It
11 also includes efficient solvent for extraction of lipids, pig-
12 ments, oils and sugars systems. Potential chemicals which can
13 be obtained from chitin/chitosan have also been identified.[33]
14 Although these review articles summarize most of the
15 important applications of chitin/chitosan in diverse areas, the
16 full potential of these materials from the catalysis perspectives
17 for its valorisation has not been yet addressed. These nitrogen
18 containing biopolymers can render a wide array of platform
19 chemicals which could be accessed by novel catalyst systems.
20 Additionally, due to the inherent nitrogen moieties, they can
21 act as efficient catalysts or catalyst support. Thus, the present
22 review will focus on these two aspects and provide a holistic
23 evaluation of the chitinuous biomass waste. Scrutinizing the
24 oceanic biomass waste from a catalytic perspective is vital for
25 ‘greener’ process technologies and realization of bio-refinery Scheme 1. Heck coupling of iodobenzene and n-butylacrylate catalyzed by
26 concept. Pd on chitosan.
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29 2. N-containing Biopolymers as an Efficient Pd was also used as an active metal by Movassagh et al.[37]
30 They prepared a magnetic, porous and biodegradable catalyst
Catalyst
31 (chitosan thienyl-imine palladium, 2) for the coupling of aryl
32 The development of heterogeneous catalytic systems has halides and various terminal olefins in water (Scheme 2). The
33 gained considerable momentum as they are easy to separate, catalyst rendered the products in good to excellent yields. It
34 recover and reuse. Functionalized polymers have played a was easily recoverable by simple magnetic separation and
35 predominant role as heterogeneous catalysts. The use of worked truly as a heterogeneous catalyst as evidenced by its
36 functionalized polystyrenes and other monomers derived recyclability studies.
37 from petroleum feedstock, as catalysts have been well In a similar approach, Fe3O4 particles were embedded in
38 documented.[34,35] Replacing them with renewable polymers is Pd supported on chitosan Schiff base which were catalytically
39 important due to the dwindling fossil reserves. While there effective for Suzuki-Miyaura and Mizoroki-Heck reactions
40 are reports on functionalization of chitin hence, chitosan is a and also facilitated the separation from the reaction crude.
41 better candidate for catalysis as it is soluble in acidic Ideal yield (99 %) was obtained for the respective products
42 solutions. This solution can be cast into spherical particles, under the optimized conditions with a good catalyst
43 films and fibres thus forming catalyst particles, films and recyclability for both the coupling reactions.[38]
44 membranes which can be used for various organic trans- Researchers attempted the immobilization of Pd on
45 formations. The upcoming sections reveal the potential of modified/functionalized chitosan (Figure 2). Salicylaldehyde
46 chitosan for chemical catalysis. was grafted on chitosan to give chitosan Schiff base which
47 was treated with Li2PdCl4 in methanol to give imine
48 palladacycle complex (Figure 2A) which was tested for Heck
2.1. Coupling Reactions
49 reaction giving stereoselectivity for arylation of conjugated
50 The coupling reactions are very important which are used to alkenes with aryl halides (99 % yield).[39] Cui et al. prepared
51 synthesize intermediate products in the synthesis of fine two catalysts, in the first, Pd complexes were anchored
52 chemicals. Chitosan has been used extensively as a catalytic directly on the cross linked chitosan and in the second, it was
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23 Scheme 2. Heck coupling of aryl halides and terminal olefins catalyzed by Pd
24 on chitosan membranes.
25 Figure 2. Pd complexes supported on (A) salicaldehyde modified chitosan,
(B) salicaldehyde modified cross linked chitosan, (C) biguanidine modified
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chitosan, (D) 2-pyridine carboxaldehyde modified chitosan, (E) 2-(diphenyl-
27 anchored on salicylaldehyde modified chitosan (Figure 2B). phosphino)benzaldehyde modified chitosan, (F) methoxypolyethylene modi-
28 Both the catalysts were deployed for Heck reactions. fied chitosan, (G) thiourea modified chitosan.
29 Comparing the catalytic activity under the ideal conditions
30 for both, the salicylaldehyde modified catalyst gave superior
31 results, clearly revealing the efficacy of modifications of natural and green reducing agent in water. The catalyst
32 chitosan.[40] These results led to the development of numerous worked truly as heterogeneous catalyst for Suzuki cross
33 strategies for modifying the chitosan for better entrapment of coupling of various aryl iodide/bromides with substituted aryl
34 active sites. Pd nanoparticles entrapped on biguanidine boronic acids in water under mild conditions. Good to
35 functionalized chitosan (Figure 2C) was used for Suzuki excellent yields, ease of separation and absence of inert
36 Miyaura coupling reaction. Excellent yields of the product atmosphere were significant advantages of this protocol.[44]
37 were obtained (98 %) in EtOH H2O with K2CO3 as base at Conclusively, modification of chitosan resulted in superior
38 40 8C for 2 h, without any leaching of Pd.[41] In another entrapment and confinement of Pd active sites.
39 approach, 2-pyridine carboxaldehyde or 2-(diphenylphosphi- Considering the advantageous implications of chitin/
40 no) benzaldehyde was condensed with amine groups of chitosan modifications, researchers focused on this aspect for
41 chitosan to give modified Schiff ’s base which was followed by design of novel, efficient catalyst systems. The effect of
42 Pd entrapment (Figure 2D and E). This catalyst also worked modification on chitosan before complexation with Pd was
43 well for Suzuki-Miyaura and Heck cross coupling reactions. investigated for coupling reactions under microwave irradi-
44 Importantly, they performed better than the homogeneous ation.[45] Chitosan modified by 2-pyridinecarboxaldehyde
45 structural analogues.[42] Similarly, chitosan modified by rather than salicaldehyde followed by subsequent Pd deposi-
46 methoxy polyethylene glycol before Pd chelation (Figure 2F) tion resulted in highly active catalyst rendering 99 % yield of
47 worked well for Suzuki coupling retaining the characteristics the product. The catalyst prepared by co-precipitation and
48 of heterogeneous catalyst.[43] In another study, chitosan was adsorption gave inferior yields. Researchers then executed the
49 modified by thiourea on which Pd nanoparticles were coupling reactions in water as a green solvent.[46] Barren et al.
50 embedded (Figure 2G). Interestingly, spherical and cubical could improve the performance of Suzuki coupling reaction
51 shaped particles were obtained by intercalating Pd acetate on using a very small amount of novel chitosan Schiff base
52 modified chitosan followed by reduction using ellagic acid; a supported Pd catalyst, 3 in solvent free conditions under
1 microwave irradiation giving a very high turnover frequency morphologies of chitosan. Porous chitosan microspheres were
2 and excellent recyclability (Scheme 3).[47] Chitosan membrane prepared and Pd was immobilized through selective dissolu-
3 was used as a support for immobilizing oxadiazoline and tion. The catalyst was screened for Heck cross coupling of
4 ketoimine Pd complexes (4 and 5 respectively), used for aromatic halides with acrylates and Ullmann type reductive
5 Suzuki Miyaura cross coupling in water to give the product in homo coupling. Interestingly, the catalyst could be used in
6 quantitative yield (Scheme 4). Both the catalysts exhibited environmentally benign aqueous solution due to highly
7 good catalytic activity Although high turnover frequency was hydrophilic hydroxyl and amine group of chitosan. The high
8 obtained but the catalyst suffered loss in activity with each catalytic activity was a result of high surface area, higher
9 reuse.[48] porosity and a strong chelation between Pd and groups like
10 amine, hydroxyl and carbonyl on the surface. The large size
11 of the microspheres also facilitated easy separation and
12 recycling.[49] Silica-chitosan hybrid materials were synthesized
13 as a support for Pd[50] and very good yields (> 90 %) were
14 obtained for Suzuki-Miyaura and Mizoroki-Heck cross
15 coupling reaction products. Raston et al.[51] developed Pd-
16 chitosan composite nanofibres by fabricating nanofibres
17 (62 9 nm) of cross linked chitosan with high aspect ratio by
18 electrospinning, for Heck cross coupling reactions. When
19 iodobenzene, butyl acrylate, triethyl amine and dimethylfor-
20 mamide were mixed with the nanofibres at 80 8C for 16 h,
21 quantitative yield was obtained. Despite the low Pd loading
22 (0.17 mol%) excellent activity was achieved upto seven cycles.
23 Apart from Pd, other metals have been also supported on
24 chitosan and explored for C C or C X (X = heteroatom)
25 reactions. For example, chitosan bound silver nanoparticles
26 Scheme 3. Solvent free Suzuki cross-coupling using Pd supported on chitosan were used as catalyst for C C coupling of phenolic
27 under microwave irradiation. compounds in the presence of molecular iodine. The reaction
28 proceeded with the formation of p-iodophenol followed by o-
29 p coupling leading to the products in good yields (75–98 %).
30 Studies were not confined only to modifications of A plausible mechanism was postulated demonstrating the role
31 chitosan, but were expanded to the use of different of silver (Figure 3).[52] In the experimental conditions, the Ag
32 nanoparticles dissociated the molecular iodine into iodine
33 atoms which remained adsorbed on their surface. On
34 addition of phenol, these iodine atoms abstracted a hydrogen
35 from the phenol and the resultant phenoxy radical was
36 adsorbed on the surface. This was followed by iodination at
37 the para position and subsequent desorption of p-iodophenol.
38 The Ag nanoparticles play a crucial role in (i) chemisorption
39 of phenol by OH moiety in a geometry where the ring plane
40 is nearly parallel to the surface and (ii) in formation of Ag I
41 complex which is only formed when molecular iodine is used.
42 The addition of salt leads to the formation of molecular AgI
43 which was catalytically inactive for the reaction. For the
44 selective coupling of phenol (Figure 3B), the iodine atom
45 present on the surface facilitates the adsorption of phenoxy
46 and p-iodophenoxy radical on the surface of Ag nanoparticles.
47 They are adsorbed to give a sandwich type geometry because
48 of stability of the complex. A molecule of HI was eliminated
49 leading to o-p coupling. This was followed by iodination at
50 the ortho position that is nearest to the surface which results
51 Scheme 4. Solvent free Suzuki cross-coupling using Pd supported on chitosan into ortho-iodonated C C coupled products. The absorption
52 under microwave irradiation.
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Scheme 5. Sonogashira cross coupling and homo coupling reaction using Au
19 supported on chitosan fibers.
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28 Figure 3. Plausible mechanism for (A) formation of p-iodophenol, (B)
29 selective coupling of phenol by chitosan-Ag NPs.
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32 of radicals in the preferred orientation was the key for this
33 coupling over the Ag nanoparticles.
34 Primo et al. synthesized macroporous hybrid materials by
35 dispersing nanosized gold in the fibrils of the chitosan matrix,
36 followed by supercritical CO2 drying. This catalyst was used
37 for Sonogashira cross coupling and homocoupling reaction
38 (Scheme 5) without any leaching of Au. As compared to the
39 previous reports this methodology was superior due to mild
40 reaction conditions, low catalyst loading and high reactiv-
41 ity.[53]
42 Among non-noble metals, Cu was widely used (Scheme 6)
43 e.g. Cu(OAc)2 supported on chitosan was prepared by Shen
44 et al. for the synthesis of aryl sulphones in excellent yields.
45 The catalyst was prepared by a simple method in aqueous
46 medium, which also exhibited excellent recyclability.[54] A
47 highly efficient, economic, green and sustainable process was
48 developed for the C N cross coupling between aryl halides
49 and aliphatic diamines/amino alcohols using chitosan sup-
50 ported copper catalyst. Very high yield (94 %) was obtained Scheme 6. (1) C S coupling catalyzed by Cu(OAc)2 supported on chitosan,
51 in reduced reaction time (3 h) using acetonitrile as a solvent. (2) C N cross coupling catalyzed by Cu on chitosan, (3) Ullmann C N
52 Additionally, the work up procedure was convenient, the coupling catalyzed by Cu on functionalized chitosan.
1 catalyst was recyclable and contamination of the metal with hexanone and cyclohexanol (93 %) as compared to Mn-TPP-
2 the products was negligible.[55] Yang et al. attempted this cellulose (82 %). The differences in catalytic performance
3 coupling but in water medium using Cu supported on were attributed to the variation in the microenvironment of
4 functionalized chitosan (CSP). Various aromatic amines were the support.[58] After evaluating the superiority of chitosan,
5 prepared from substituted aryl halides (electron withdrawing Mn-TPP-chitosan was also used for toluene oxidation using
6 and electron donating), anilines, benzylamine, aliphatic molecular oxygen (Scheme 7.2). The conversion of toluene
7 amines and imidazole with good to excellent yields, even for was dependent on reaction parameters (temperature, air
8 the hindered o-substituted aryl halides. However, leaching of pressure and catalyst amount) but the selectivity for aldehyde
9 Cu was observed during recyclability tests.[56] Visualizing all and alcohol was independent. Toluene conversion of 5.9 %
10 these studies, the potential of chitosan for coupling reactions with 96 % selectivity for benzaldehyde and benzyl alcohol
11 can be inferred. were obtained.[59]
12 Sun et al. also covalently immobilized Mn(111) detuopor-
13 phyrin 8 on chitosan and used it for aerobic oxidation of
2.2. Oxidation Reactions
14 cyclohexane (Scheme 8.1).[60] Effect of various reaction
15 Oxidation is a powerful transformation which can render a parameters was studied and under the optimized conditions,
16 variety of important chemicals. The synthesis of heteroge- 16.9 % of cyclohexane conversion with a chemoselectivity of
17 neous catalysts based on chitosan is well attempted for 88.7 % (cyclohexanol and cyclohexanone) was achieved. The
18 oxidation of many substrates, predominantly for saturated supported catalyst exhibited superior performance over
19 and unsaturated hydrocarbons which is a challenging and unsupported Mn(111) detuoporphyrin and synthetic
20 vital reaction. Aerobic oxidation of cyclohexane in the absence Mn(111) tetraphenylporphyrin. The results were explained
21 of additives was attempted by Huang and coworkers using on the basis of intermolecular interaction between the amino
22 iron, cobalt and manganese tetraphenylporphyrins (TPP) 7, moieties on chitosan and dipropionic group in Mn(111)
23 supported on chitosan (Scheme 7.1). Under the optimum detuoporphyrin. Due to the capability of forming a covalent
24 conditions the catalytic activity of the three catalysts were linkage, other Mn complexes were also anchored on the
25 compared. Co-TPP-chitosan gave the highest activity but support. Salophen Mn complexes, 9 were supported on
26 lower ketone and alcohol selectivity while, Fe-TPP-chitosan chitosan and deployed for aerobic oxidation of cyclohexene
27 behaved in an opposite manner. The chitosan supported
28 complexes gave higher conversion/turnover frequency (TOF)
29 (6 times) as compared to unsupported complexes, clearly
30 revealing the important role of chitosan in cyclohexane
31 oxidation. The differences in activity were attributed to the
32 difference in the potential for O2 activation by bivalent metal
33 ions and chitosan assisted metal-TPP catalysis. The catalyst
34 (Co-TPP-chitosan) could be used upto 5 cycles without any
35 loss in activity.[57] Manganese tetraphenylporphyrin (Mn-
36 TPP) was supported on chitosan, chitin and cellulose. Mn-
37 TPP-chitosan/chitin resulted in higher selectivity of cyclo-
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51 Scheme 7. (1) Metal-TPP catalyzed oxidation of cyclohexane, (2) Toluene Scheme 8. Chitosan supported Mn complex catalyzed (1) cyclohexane
52 oxidation catalyzed by Mn-TPP. oxidation, (2) cyclohexene oxidation and (3) alkene oxidation.
1 (Scheme 8.2). The oxidation was achieved in absence of

2 solvents. The catalyst resulted in high turnover numbers
3 (based on the manganese atom), which was about 44 times
4 higher than the unsupported one.[61] In a very interesting
5 approach, Jacobsen catalyst, 10 was immobilized on chitosan
6 membranes as interface catalyst in organic/aqueous system for
7 alkene oxidation (Scheme 8.3) wherein the membranes acted
8 as catalytic barriers between the two different phases: aqueous
9 phase containing the oxidising agent and organic phase
10 containing the substrate, dismissing the need for phase
11 transfer agents and leading to better product yields compared
12 to the catalyst in homogeneous medium. Under the
13 optimized reaction conditions, a TOF of 160 was obtained
14 for cyclooctene oxide and TOF of 65 for styrene oxide.
15 For styrene epoxidation, the formation of phenylaceta-
16 lyene suggested the rearrangement of intermediate species
17 within the chitosan membranes. On using t-BuOOH,
18 benzaldehyde was also obtained which was due to the
19 homolytic cleavage (Figure 4), thus explaining the role of
20 solvent. The catalyst did not leach from the support and was
21 used several times.[62]
22 Apart from manganese, iron complexes also displayed
23 good catalysis. The chitosan supported m-oxo dimeric iron
24 tetraphenyl porphyrin catalyzed the aerobic oxidation of
25 cyclohexane to corresponding alcohol in the absence of co
26 reductants and solvents. Yield of 13 % for both the products
27 was obtained at 125 8C, 0.6 MPa pressure. The support plays
28 a crucial role as the catalyst was found to be more robust
29 towards the destruction of oxygen.[63] Additionally, iron based
30 novel magnetic chitosan supported catalysts were prepared
31 and used for various oxidation reactions.
32 Zhu et al. prepared a magnetic catalyst in which the
33 protonated peroxotungstate was immobilized on a network of
34 cross linked chitosan protonated peroxotungstate with a super
35 magnetic Fe3O4 core (Figure 5A). It was used for oxidizing
36 variety of substrates including olefins, amines, sulphides and
37 allylic alcohol using H2O2. Yields of different products were
38 obtained in the range of 75–99 %. The presence of
39 peroxotungstate improved the catalytic performance and the Figure 4. Mechanism of oxidation activation for t-BuOOH over chitosan
40 magnetic core facilitated the separation.[64] Researchers also immobilized Jacobsen catalyst.
41 demonstrated the use of such magnetic catalyst for alkene
42 oxidation. Magnetic core shell type Fe3O4@chitosan-Schiff
43 bases of (Figure 5B) Cu(II), Mn (II), Co (II) were prepared complexes modified by salicyldehydes, o- and m-nitro-
44 by a simple method and tested for aerobic oxidation of benzaldehydes were also prepared (Figure 5C–E). Highest
45 cyclohexene. Best results were obtained for Schiff base Co cyclohexene conversion (80.2 %), high selectivity to the
46 complex derived from 5-nitrosalicyaldehyde which gave alcohol and ketone (39.2 %) was attained by copper chelated
47 46.8 % conversion of cyclohexene, 77.2 % selectivity to 2- on m-nitrobenzaldehyde modified chitosan. The researchers
48 cyclohexene-1-one under ambient pressure at 70 8C for 12 h also studied the effect of additives (acidic and basic). There
49 of reaction. The catalyst was easily separated by a magnet and was no advantage of additives on conversion but it altered the
50 used several times without loss in activity.[65] Cyclohexene product distribution. The addition of acid resulted in the
51 oxidation was also attempted by cross linked chitosan bound formation of 2-cyclohexene-ol while the base gave 2-cyclo-
52 Schiff base copper complexes. Chitosan and their copper hexene-one. Reduction in conversion was attributed to the
1 ranked as [Cu(SC)SA] > [Cu(SC)ST] > [Cu(SC)VA]. 34 %

2 conversion of cyclohexane and 100 % selectivity to cyclo-
3 hexanol and cyclohexanone was obtained at 70 8C with
4 5 mmol of substrate, 10 mmol of H2O2, 0.5 g of catalyst for
5 8 h. From this study, the researchers concluded that the
6 textural properties of the catalyst can be tailored using
7 appropriate synthesis strategy which improves the catalytic
8 performance.[68] Effect of metal on oxidation has also been
9 investigated. Three novel quadridentate metal-Schiff base
10 complexes [Cu(OIAc)Cl2], [Co(OIAc)Cl2] and [Ni(OIAc)
11 Cl2] were prepared (Figure 5G). The different metals
12 imparted different textural features which originated from the
13 difference between the complexation behaviour of the metal
14 ions. Complexes with rough surfaces ([Cu(OIAc)Cl2]) have
15 shown higher catalytic activity in comparison to others.
16 However, the performance of the catalyst deteriorated with
17 number of reuses which was due to poor chemical resistance
18 and mechanical strength of chitosan biopolymeric back-
19 bone.[69] The inferences of this study were proven by another
20 study in which the same metal (Cu, Co, Ni) complexes were
21 synthesized with a bidentate Schiff base ligand derived from
22 functional polymer chitosan and 1,2- diphenylethane-dione
23 (Figure 5H).[70] The basic sites on chitosan form stable
24 covalent bonds with the metal complexes rendering excellent
25 catalytic activity for oxidation of various substrates.
26 To unleash the full potential of chitosan, researchers
27 attempted interesting synthesis strategy using different
Figure 5. (A) Magnetic cross linked chitosan Protonated peroxotungstate, (B)
28
Magnetic chitosan Shciff base Cu complex, (C) Salicaldehyde modified
morphologies, composites of different organic-inorganic
29 chitosan Cu complex, (D) o-nitrobenzaldehyde modified chitosan Cu hybrid materials, introducing multiple functionality, applica-
30 complex, (E) m-nitrobenzaldehyde modified chitosan Cu complex, (F) tions extending beyond the liquid phase oxidations i. e.
Salicyldenechitosan modified chitosan Cu complex, (G) Quadridentate
31 metal-Schiff base complex, (H) Bidentate Schiff base modified metal
photo-oxidation and electro oxidation etc. These results are
32 complexes. presented here. In an excellent study undertaken by Mansur
33 et al., nanophotocatalysts based on ZnS quantum dots
34 functionalized with chitosan were prepared using a green
35 formation of salt with chitosan on adding acid and the colloidal chemical method in water at room temperature. The
36 preference of Cu caused chelation with pyridine rather on catalysts exhibited potential for photodegradation of hazard-
37 chitosan on adding the base.[66] They then extended the ous organic pollutants present in waste water. Methylene blue
38 application of this catalyst and tested it for oxidation of n- and methyl orange dyes were oxidized by ZnS/chitosan
39 propyl benzene (PB), isopropyl benzene (IPB) and ethyl nanocrystals (3.8 nm) under UV irradiation. Degradation
40 benzene (EB) using Ni complexes. It gave good selectivity efficiency of 87 % and 68 % was obtained for methylene blue
41 towards a-one and a-ol products for PB and IPB oxidation. and methyl orange, respectively, after 2 h.
42 However, for all these reactions the recyclability studies were Additionally, these nanoconjugates showed blue photo-
43 not undertaken.[67] Cu complexes supported on modified luminiscent behaviour upon UV excitation.[71] A new bifunc-
44 chitosan were also used for oxidation of cyclohexane. Here, tional catalyst comprising of metalphthalocyanine complexes
45 the effect of chitosan modification on the reaction was anchored on chitosan aerogels microspheres,11 was used for
46 studied. Salicyldenechitosan (Figure 5F) was used as the aerobic oxidation of b-isophorone (Scheme 9). Chitosan
47 ligand from which Cu(II) mixed ligand complexes [Cu(SC) serves as an organic base and a support for chelation. With
48 SA], [Cu(SC)ST] and [Cu(SC)VA] were prepared, where Co-Phthalocyanine complex on chitosan as catalyst, 90 %
49 SA = salicyledeneaniline, ST = salicyledenethioures, VA = va- conversion and 31 % yield of ketoisophorone is achieved.
50 nillideneaniline. The three complexes differed in geometry, Combination of oxidation and basic sites in one solid
51 thermal stability and surface morphology which altogether material facilitated efficient heterogenous clean oxidation.[72]
52 had a marked effect on the catalytic activity. The activity was
1 their integrity and electronic conductivity. The methodology

2 also resulted in higher dispersion of the nanoparticles. The
3 superior catalytic performance of the chitosan nanohybrids
4 than the pristine CNTs originated from the higher electro-
5 chemical surface area, good proton conductivity of chitosan
6 and stability towards electrocatalytic oxidation.[73] A slight
7 modification was done by Cui et al. in which they function-
8 alized the CNTs with chitosan and heteropoly acids
9 (phosphomolybdic acid and phosphotungstic acid). This was
10 followed by encapsulation of PtRu nanoparticles. The Mo-
11 containing heteropoly acid was better than W-containing acid
12 in terms of electrocatalytic activity and high tolerance towards
13 CO poisoning. Since Mo-containing heteropoly acids have
14 more labile terminal oxygen to provide additional active
15 oxygen sites it accelerates the CO and methanol oxidation.
16 The nature of the peripheral metal atoms in heteropoly acids
17 may play an important role in promoting/facilitating the
18 electrochemical reactions.[74]
19 Chitosan matrix was also very effective in stabilizing
20 Scheme 9. Oxidation of b-isophorone using Co-phthalocyanine. different metals which worked well for various oxidation
21 reactions (Scheme 10). Au, AuPt, AuPd nanoclusters were
22 synthesized by using this approach. The strategy yielded very
23 In another interesting study, chitosan functionalized small particles (2.3 nm) which could catalyze the oxidation of
24 carbon nanotubes (CNTs) were deployed as support for PtRu various aromatic primary alcohols under ambient conditions.
25 nanoparticles. The synthesis procedure is shown in Figure 6. High yields (> 90 %) of aldehyde/acids were obtained
26 They were screened for electrocatalytic oxidation of methanol. depending on the para-substituent present on the ring.
27 Since the functionalization was carried out in the absence of Entrapment of the Au nanoclusters in the chitosan matrix
28 corrosive acids and at room temperature, CNTs preserved facilitated easy recovery and reuse.[75] Similarly, chitosan was
29 used as a stabilizing polymer for Au colloids by PruBe et al.
30 They used this catalyst for glucose oxidation using molecular
31 oxygen in which conversion of 5.9 % of glucose and 99 %
32 selectivity towards gluconic acid was obtained. During the
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51 Figure 6. Schematic diagram for the preparation of PtRu NP/CNT-chitosan Scheme 10. Metal nanoparticles (NPs) supported on chitosan as catalyst for
52 nanohybrids. oxidation reactions.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24 Figure 7. Catalyst structures for Pd supported on chitosan.
25
26
27 recyclability studies, the catalyst showed marginal loss in catalyst reduced the by-product formation enhancing the
28 activity which was due to handling issues and not due to yields of benzoquinone. They proposed that the use of these
29 leaching.[76] Copper was also stabilized on chitosan to give hollow fibres as supports benefitted the reaction. The
30 isolated Cu + 2 ions in square planar coordination. Hetero- controlled diffusion of dioxygen through the fibres and its
31 genized copper-chitosan samples exhibited high catalytic reaction at the surface of the catalytic metal provides the
32 activity and stability for the oxidation of dihydroxybenzenes controlled oxidizing conditions that appear to be favourable
33 into quinines. It worked better than the homogenous reaction for the selective formation of benzoquinone.[79] In addition to
34 which was characterized by irreversible poisoning due to the the synthesis methodology the applications were also
35 formation of copper-hydroquinone complexes. Thin films of diversified. Cu-chitosan complexes were used for degradation
36 copper-chitosan supported on macroporous silica were also of azo textile dyes in aqueous solution with hydrogen
37 prepared which drastically enhanced the catalytic activity. peroxide. Under the optimal conditions (pH = 7, H2O2 =
38 Role of water was also elucidated. Swelling in water provided 50 mM) with 3.6 % Cu + 2, 91.5 % decolourization was
39 elasticity to the polymer matrix which resulted in better obtained in 20 min. Other dyes required higher time 9 ~
40 interaction of Cu centres and reactive groups of chitosan.[77] 180 min. The rate of decomposition was dependent on the
41 The researchers then heterogenized copper complexes on concentrations of the dye and the oxidant.[80] It can be seen
42 composite supports (egg shell type chitosan/SiO2, chitosan that for oxidation reactions, all the scientific dimensions were
43 MCM-41) where they could retain the Cu + 2 sites in the same explored to maximize the use of chitosan.
44 coordination. The binary composite system demonstrated
45 higher activity than bulk Cu/chitosan samples. These studies
2.3. Hydrogenation Reactions
46 opened up a promising way of synthesis of supported
47 chitosan catalyst with non-noble metals.[78] Guibal et al. Apart from other transformations, chitosan based catalysts
48 attempted the use of chitosan with different morphologies. have also been extensively screened for hydrogenation
49 They supported Cu on chitosan flakes and tested its ability to reactions. Noble and non-noble metal complexes, magnetic,
50 catalyze the oxidation of hydroquinone. The effect of the metallic nanoparticle etc. on chitosan/functionalized chitosan
51 reaction conditions was investigated. At pH = 5.8, short have been prepared and used for a variety of substrates
52 contact time, low H2O2 concentration, small amount of (Tables 1 and 2). Chiral catalyst for asymmetric hydro-
1 Table 1. Hydrogenation reaction catalyzed by chitosan supported Pd complexes.

2
Entry Catalyst Reaction Scheme TOF Ref.
3
4
5
6
7 1. 12 3–30 3 104 [81]
8
9
10
11
12
13
14
15
16
17 2. 13 n.d. [82]
18
19
20
21
22
23
24
25
26
27 3. 14 n.d. [83]
28
29
30
31
32
33 4. 14 2500 [85]
34
35
36
37
38 5. 15 53 3 102 [87]
39
40
41
42 6. 16 n.d. [88]
43
44
45
46 10 3 104
7. 17 [89]
47 2.053 3 103
48
49
50
51
52
1 Table 1. continued
2
3 Entry Catalyst Reaction Scheme TOF Ref.
4
5
6 8. 18 1.258 3 104 [90]
7
8
9
10
11 9. 19 12–14 3 103 [91]
12
13
14
15
16
17
10. 20 11.6 3 103 [92]
18
19
20
21 11. 19 n.d. [93]
22
23
24
25
26
27
28
29
30 12. 21 n.d. [94]
31
32
33
34
35
36
37
TOF – Turn over frequency, Ref. = reference, n.d. = not determined.
38
39
40
41 genation are an added asset. Among the noble metals, Pd was reversible in the cycle of pH = 11 to pH = 2 and vice versa.[81]
42 screened to the utmost (Table 1, Figure 7). Pd complexes of In other approaches, chitosan was first modified before
43 chitin and chitosan were prepared by Wang et al. to study immobilization. Chitosan was cross linked with hexamethy-
44 their catalytic behaviours for hydrogenation rections. The lendiisocynate, loaded with Pd followed by reduction with
45 catalyst was efficacious as it could not only catalyze the sodium borohydride. The catalyst was used for hydrogenation
46 reaction at room temperature and atmospheric pressure but of several substrates (benzalacetone phenone, 1,2 diphenyl
47 also a variety of substrates like olefins, aromatic nitro acetylene, N-benzylidinenaniline, cyclohex-2-enone) under
48 compounds and acrylic acid were hydrogenated giving 100 % mild conditions under microwave irradiation using alcohol
49 yield of the product (Entry 1). The catalyst was very active, (Entry 2). Good yields of the product (85–99 %) were
50 stable and selective but displayed different activities at varying obtained. Reduction of catalyst was the crucial parameter
51 pH. The most interesting finding was that the catalytic which affected the catalytic activity. The catalyst was recycled
52 activity of the two polymer supported metal complexes were upto ten times without loss in activity. The ability of the
1 Table 2. Hydrogenation reactions catalyzed by other metal supported on chitosan.

2
Entry Catalyst Reaction Scheme TOF Ref.
3
4
5
6 1. n.d. [95]
7
8
9
10
11 2. n.d. [96]
12
13
14
15
16
17
3. 6.66 3 102 [98]
18
19
20
21
22 4. n.d. [99]
23
24
25 TOF – Turn over frequency, Ref. = reference, n.d. = not determined.
26
27
28 catalyst to hydrogenate a variety of substrates was the most reduction. The inferior performance of other catalysts for
29 striking feature of the study.[82] Vincent et al. first functional- chromate reduction was attributed to lower Pd concentration
30 ized chitosan by glutaraldehyde and then immobilized Pd and incomplete reduction.[84] They further extended their
31 onto it followed by insitu chemical reduction. Tested on work by anchoring the Pd complexes on polymer with
32 nitroaniline degradation; an organic pollutant, the catalyst different morphology (functionalized hollow chitosan fibres).
33 was very efficient in the presence of sodium formate as a They designed a new continuous catalytic reactor. Hydrogen
34 hydrogen donor (Entry 3). Optimum degradation occurred at gas was fed at constant pressure and the substrate (nitro-
35 pH close to 3. To ensure complete degradation, formate must toluene) was circulated inside the lumen of the fibre. The
36 be in excess and for kinetic study of degradation the effects of parameters like substrate concentration, flow rate,
37 formate:nitroaniline ratio must be greater than 13. Particle metal content in the fibre were evaluated using surface
38 size of the catalyst and its dosage are important experimental response methodology to optimize the process (Entry 4).
39 parameters. Since the reaction appears to be limited to Accordingly, 45.4 % conversion of nitrotoluene and 77 %
40 external layers, increasing the catalyst dosage and decreasing yield of o-nitrotoluidine were obtained at the ideal con-
41 the particle size significantly improved the degradation ditions.[85] Later, they also studied the effect of mesoporosity,
42 kinetics.[83] The researchers then investigated the effect of diffusion, fibre drying, solvent and temperature.[86] Research-
43 chitosan modification and the effect of reduction on the ers also attempted other modifications. Pd complexes were
44 catalyst performance. Chitosan was modified by glutaralde- immobilized on silica supported chitosan and used for
45 hyde and sulphate crosslinking. After modification, Pd was hydrogenation of chloronitrobenzenes (Entry 5). It gave
46 immobilized and reduced using three reducing agents-sodium 100 % yield of the products under mild conditions. Support-
47 borohydride, sodium formate and insitu hydrogen produced ing chitosan on silica imparted higher stability under the
48 by the reaction of sulphuric acid and Zn. The reduction of reaction conditions enabling the catalyst to work effectively
49 Pd loaded on glutaraldehyde crosslinked chitosan reduced by for many recycles.[87] Further, nanosized Pd catalyst on
50 insitu generation of hydrogen yielded the optimum catalyst. chitosan/silica was prepared through a complex transition
51 The addition of Zn in the reactions, improves the perform- method. Optimum activity (H2 uptake capacity) was achieved
52 ance as it generates more insitu hydrogen leading to complete with monolayer coverage of the polymer coil adsorbed on the
1 silica (Entry 6). The Pd:chitosan molar ratio appeared to be a catalytic activity. They carried the reaction in one pot process
2 decisive parameter for the synthesis of nanoparticles and for combining the catalyst synthesis and hydrogenation reaction,
3 highest activity.[88] Adlim et al. undertook a comparative study which was equally good. Thus, a one pot process was
4 in which they synthesized Pt and Pd colloidal nanoparticles developed which assures fast reaction rates under milder
5 stabilized on chitosan for hydrogenation of octene (Entry 7). conditions, avoiding catalyst’s isolation and purification
6 The important conclusions were that chitosan could control easing the reaction scale up.[92] Recently, Rode et al. reported
7 the particle size of Pt and Pd within 1.9–2.2 nm when the Pd decorated chitosan catalyst prepared by simple
8 NaBH4 or CH3OH were used as reducing agent, Pt gave impregnation method and evaluated for the regioselective
9 superior performance to Pd as it was selective towards octane hydrogenation of styrene oxide (Entry 11). Complete con-
10 whereas Pd gave 2-octene and 3-ocetene in addition to octane version of reactant and 65 % selectivity to 2-phenyl ethanol
11 thereby lowering its selectivity.[89] and 33 % selectivity to 1-phenyl ethanol was obtained under
12 From various studies, it was clear that highly dispersed the optimized conditions. The performance of the catalyst
13 metal nanoparticles were crucial for effective catalysis. There- was dependent on the nature of the support. The basicity of
14 fore, research was oriented towards improving the catalyst the catalyst plays a crucial role in dissociative adsorption of
15 synthesis which could render stable, dispersed and active hydrogen which leads to the ring opening of styrene oxide.
16 metal nanoparticles. In this context, Xue et al. prepared Thus, chitosan not only rendered good chelation and
17 highly dispersed Pd on chitosan using ionic liquid, 1-butyl-3- dispersion of Pd but also facilitated the reaction. Excellent
18 methylimidazolium acetate, by using compressed CO2 as anti recyclability up to ten cycles was established without any loss
19 solvent and regulator. They tested the catalyst for styrene in activity.[93] Magnetic Pd-chitosan catalyst was also used for
20 hydrogenation (Entry 8); the activity could be changed by hydrogenation of various aromatic nitro and unsaturated
21 tuning the CO2 pressure. There were two key roles played by compounds (Entry 12). Excellent yields of the product (>
22 CO2 for higher dispersion of Pd. Firstly, charging CO2 in 99 %) were obtained at the optimized conditions. The catalyst
23 ionic liquid decreased its viscosity, density, surface tension showed outstanding recyclability and easy recovery.[94] Con-
24 and solvation power of ionic liquid which favoured the clusively, the Pd catalyst was very efficient for hydrogenation
25 adsorption of Pd nanoparticles on chitosan from the CO2 reactions as observed from the high TOF values.
26 expanded ionic liquid solution. Secondly, the interaction Other metal complexes integrated with modified systems
27 between chitosan and ionic liquid was suppressed and were used (Table 2). In a different approach, parahydrogen-
28 decreasing the solubility of chitosan in ionic liquid facilitated induced polarization (PHIP) technique was used for hydro-
29 its regeneration. . Highest pressure of CO2 (14.2 MPa) gave genation of 1,3-butadiene and 1-butyene over Rh/chitosan
30 the best catalyst which rendered 99 % yield of ethyl benzene. catalyst in gaseous and liquid phase (Entry 1). Notably, the
31 In addition to excellent catalytic performance, it exhibited catalyst demonstrated high activity in the hydrogenation of 1-
32 very good recyclability.[90] Jin et al. adopted a method in butyne after its activation in the hydrogenation of 1,3-
33 which the polymer matrix was a mixture of two polymers i. e. butadiene. Therefore, it was used for the removal of these
34 chitosan-polyacrylic acid, chitosan-polymethacrylic acid. On reactants from gaseous butane streams. In the gas phase, the
35 the polymer matrix, Pd was anchored and the resulting syn and anti-addition of the hydrogen molecule to both the
36 complexes were supported on silica. The catalyst could substrates proceeded in a pair-wise manner while in liquid
37 hydrogenate nitrobenzene to aniline and acrylic acid to phase both the hydrogen atoms from the same molecule were
38 propionic acid at room temperature under atmospheric added to 1-butyne only through the syn addition route.[95]
39 pressure (Entry 9). 100 % yields of the products were Metal nanoparticle-chitosan biconjugates were prepared by
40 obtained with very high turnover number (> 14000). The use simple methods and used as effective catalyst for the
41 of biopolymer matrix increases the activity, selectivity and reduction of 4-nitrophenol (Entry 2). Ag nanoparticle bicon-
42 stability for hydrogenation.[91] Galletti et al. adopted a very jugates exhibited superior catalytic performance than Au
43 interesting approach in which microwave irradiation was used nanoparticle conjugates. 100 % reduction was achieved at
44 for synthesizing the catalyst as well as for the reaction. Pd- 95 8C in 5 min. The polymer acts as a scaffold for nano-
45 chitosan was prepared using microwaves which was superior particles thereby leading to improved catalysis.[96] This quality
46 to conventional heating method in terms of milder conditions was exploited by Qui et al. for the same reaction in which
47 and short reaction times. The catalyst was deployed for they incorporated Fe3O4 in chitosan and prepared an environ-
48 hydrogenation of ethyl cinnamate (Entry 10) in both the mentally benign magnetic composites which acted as reduc-
49 modes: thermal heating and microwave irradiation using tant and stabilizer for Au nanoparticles. The magnetic catalyst
50 ethanol as a solvent and reducing agent. 75 % conversion of displayed superior catalytic performance as compared to Au-
51 reactant and 100 % selectivity of the product was obtained. chitosan. 81 % of the compound underwent degradation in
52 The reactions carried out by thermal heating were inferior in presence of NaBH4 and chemical kinetics was also analyzed.
1 The superior advantages of this system were easy recovery by

2 application of external magnetic field, eco-friendly synthesis
3 procedure which was in accordance with stringent require-
4 ment of Green chemistry and biodegradability/biocompati-
5 bility of the composite that promotes the potential applica-
6 tions in biochemical catalysis.[97]
7 Researchers were also inclined towards the use of non-
8 noble metal complexes from the economical point of view.
9 Silica supported monometallic (Cu, Ni) and bimetallic (Cu/
10 Zn, Cu/Cr) complexes of chitosan were prepared and used
11 for hydrogenation of aromatic nitro compounds (Entry 3).
12 Yield of the products ranged from 86–100 % The type of
13 metal, reaction temperature and pressure, solvent, nitrogen/
14 metal molar ratio have a profound effect on yields. Replacing
15 the noble metals was the key achievement, however no
16 recyclability studies were undertaken to understand the
17 heterogeneity of the catalyst.[98] CuO ZnO nanocomposites
18 were prepared by chitosan assisted co precipitation method
19 and tested for CO2 hydrogenation to methanol (Entry 4).
20 Chitosan acted not only as a coordination compound to
21 produce a homogeneous combination of nanocomposites but
22 also as a soft template for hollow nanospheres. Very small
23 crystallite sizes of CuO (11.5 nm) and ZnO (18.8 nm) were
24 obtained for these nanospheres. The change in the chitosan
25 concentration induced significant textural changes. With
26 higher concentration, the hollow structure collapsed and
27 aggregates of CuO ZnO were obtained, which inturn
28 detoriated the catalytic activity. The catalyst prepared by
29 using chitosan as a precipitating agent exhibited higher space
30 time yield of methanol (140 g/kgcath) than the unmodified Scheme 11. Chitosan supported asymmetric (1) hydrogenation of diketone,
31 catalyst. Thus, a low and optimum concentration of chitosan (2) hydrogenation of propiophenone and acetophenone, (3) hydrogenation
32 was favourable for the reaction.[99] of 2-hexanone and methyl acetoacetate, (4) hydrogenation of substituted
ketones, (5) hydrogenation of acetophenone and (6) hydration of 1-octene.
33 Asymmetric hydrogenation was also studied by many
34 researchers (Scheme 11). Chitosan Rh complex was supported
35 on MgO which was a stereoselective catalyst for asymmetric
36 hydrogenation of some diketones to corresponding chiral the reactions at low temperature (Scheme 11.3).[102] However
37 alcohols. The optical yields of (2S,3S)-(+)-2,3-butanediol, for the bimetallic complexes the role of individual metals
38 (3S,4S)-(+)-2,4-pentanediol were 87 % and 81.2 % respec- were not explained clearly. Babdin et al. attempted a different
39 tively (Scheme 11.1), The catalyst preparation was simple and strategy. They functionalized chitosan with pivaloyl and used
40 it was effectively used for 5 cycles.[100] The researchers then it as a polyligand for [Ru(p-cymene)Cl2] moiety (Figure 8).
41 extended the study to synthesize bimetallic chitosan-iron- The catalyst was deployed for asymmetric hydrogenation of
42 nickel complex supported on silica and tested them for ketones (including functionalized ones) giving yields up to
43 asymmetric hydrogenation of propiophenone and acetophe- 80 % and enantiomeric excess upto 72 % (Scheme 11.4) with
44 none. Good optical yields of the products (R)-(+)-1-phenyl- the intrinsic chirality of chitosan, being the only source of
45 1-propanol (91.7 %) and (R)-(+)-1-phenyl-ethanol (77.7 %) enantioselection.[103] Pd based complexes have also been used
46 were obtained in the optimized conditions (Scheme 11.2). for asymmetric hydrogenation. Silica supported Pd-chitosan
47 The catalyst retained its heterogeneous nature as witnessed by complexes were prepared by Sun et al. and used to catalyze
48 the recyclability study.[101] Similar bimetallic complex of asymmetric transfer hydrogenation of prochiral acetophenone
49 Pt Fe-chitosan was prepared and supported on silica which to alcohol with formate salts as hydrogen donor
50 were screened for asymmetric hydrogenation of 2-hexanone (Scheme 11.5). The conditions like reaction temperature,
51 and methyl acetoacetate giving good yields of respective solvent and hydrogen donor affects the catalysis. For this
52 products (85 % and 75 %).The presence of Pt could catalyze reaction, ethanol was the best solvent and ammonium or
1 catalysis for hydrolysis/esterification reaction was also studied

2 (Entry 3). Effect of chitosan morphology on immobilization
3 was investigated which showed that the beads resulted in
4 better anchoring than flakes e. g. in case of olive oil
5 hydrolysis. The source of chitosan also has a profound effect
6 on the catalytic activity. For esterification, higher C-contain-
7 ing acids/alcohols were used and moderate yield of the ester
8 was achieved. The inherent amine moieties were also used as
9 active basic catalyst. Due to rigid and compact structure,
10 these moieties are not easily exposed to the reactants.
11 Therefore, chitosan hydrogels are prepared and used as basic
12 catalyst (Entry 4). An efficient heterogeneous basic organo
13 catalyst was prepared by simple methods. A variety of
14 products with high yields and high chemo selectivity were
15 rendered under mild conditions.
16 In context of CO2 mitigation, cyclic carbonates have been
17 synthesized using chitosan based catalysts (Entries 5–7).
18 Figure 8. Synthesis of [Ru(p-cymene)Cl2] supported on chitosan. Quaternary ammonium salts were functionalized as catalysts
19 (Entry 5). The most striking feature of this study is a solvent
20 free process for the synthesis of cyclic carbonates. It finds a
21 sodium formate was the best hydrogen donor. At 80 8C, an potential application in industry due to simplicity, easy
22 enantiomeric excess of R-1-phenylethanol reaches 68 % in the product separation, recyclability and use of biopolymer as
23 optimized conditions. The simple preparation, easy handling support. Several other cyclic carbonates have been prepared
24 and usage in atmosphere are the striking features of the by this strategy. Tharun et al. has quaternized chitosan itself
25 catalyst.[104] Even the non-noble metal complexes were used and used for synthesising the carbonates (Entry 7). The
26 for such hydrogenations. Silica supported chitosan-cobalt reaction conditions were mild giving higher yields of the
27 complexes were found to be a high stereo selective catalyst for product with an easy, economically viable methodology. Sun
28 asymmetric hydration of 1-octene (Scheme 11.6). The prod- et al. used Ionic liquid functionalized chitosan (Entry 6)
29 uct, (S)-(+)-2-octanol amounted to 97.8 % enantiomeric without a metal catalyst and co-solvent. They furnished
30 excess. The catalyst was economic, effective, stable and insights into the role of support. Chitosan plays a bifunc-
31 recyclable.[105] Thus, it can be inferred that chitosan supported tional role in which hydrogen bond assisted ring opening and
32 catalysts can effectively catalyze hydrogenation reactions of the nucleophilic tertiary nitrogen induced CO2 activation.
33 different moieties giving important and useful products. Another interesting reaction was cycloaddition reactions
34 (Entry 8 and 9). Cu was anchored on chitosan directly or
35 after modification. Direct anchoring rendered cost effective,
2.4. Other Transformations
36 highly active and reusable catalyst. In addition, it was a green
37 The scope of chitosan utilization for catalysis has been further and benign process as reactions were carried out in water
38 widened in which many other transformations were also (Entry 9). For the other catalyst, the synthesis in water under
39 explored. Table 3 summarizes all the transformations at- sonochemical conditions was extremely fast and efficient.
40 tempted so far, using chitosan based catalyst. These have been However, excellent yields of the products are obtained for a
41 mostly used as solid acid catalysts (Entries 1 and 2). Acidic variety of substrates, for both the catalysts.
42 moieties were anchored onto chitosan which catalyzed the Chitosan based catalysts also find applications in allylic
43 reaction. For acetalization reactions (Entry 1) the catalyst was reactions (Entries 10–12). An effective and simple strategy for
44 highly active for acetal production under mild conditions. the N-allylation of amines was developed by Baig et al.
45 Through this study, a simple method of preparation of highly (Entry 10). The unprecedented general strategy deploys
46 acidic catalyst possessing nanosized magnetic cores which also chitosan directly (without modification) and is applicable to
47 eases the separation of catalyst was achieved. For esterification aliphatic, benzyl amines, substituted/unsubstituted allyl ace-
48 reaction (Entry 2) the researchers attempted pervaporation tates. Pd on chitosan was also used for allylic substitution of
49 assisted esterification which effectively enhances the yield of (E)-cinnamyl ethyl carbonate (Entry 11). Apart from the ideal
50 the product. Higher yields could be achieved with lower yields obtained, the finding that the addition of CTAB in the
51 TEOS content in the membrane and initial E : L molar ratio, reaction mixture increases the activity and ideal yield in lesser
52 higher reaction temperature and catalyst loading. Enzymatic time was beneficial. This was attributed to the increase in the
52
51
50
49
48
47
46
45
44
43
42
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
Table 3. Potential transformations catalyed by chitosan based catalyst.
Entry Reaction Catalyst Reaction conditions Result Recyclability Ref.
1. Acetalization reaction Silico-tungstic acid/chi- EG:BZ = 10 : 1, cyclohexane = 190 mmol, BZ Conv. = 100 %, Acetal 5 times without [106]
of benzaldehyde (BZ) tosan/Fe3O4 cat. = 6 mg, RT, 2 h. Sel. = 98 % loss in activity
with ethylene glycol
(EG)
2. Esterification of Lac- Chitosan-tetraethyloxisi- E : L = 3 : 1, cat. = 2 wt% of L, 80 8C, 9 h. Yield of ethyl lactate = 80 wt% – [107]
Chem. Rec. 2019, 19, 1 – 28

tic acid (L)and lanehybrid membranes
Pe r s o n a l A c c o u n t
ethanol (E)
3. Hydrolysis and ester- Lipase immobilized on Hydrolysis: FFA = 1 mmol, pH = 7, Hydrolysis: Conv. = 70 %, – [108]
ification reaction chitosan 37 8C,RPM = 150 Sel. = 100 %,
Esterification:nBuOH = 250 mM, Esterification: Conv. = 40–
BA = 300 mM, cat. = 1 g, pH = 7,RPM = 150, 45 mol%, Ester Sel. = 100 %, Alco-
37 8C, 24 h. hol(C2–C10) conv. = 26–45 mol %,
Ester Sel. = 100 %
4. Aldol and Knoevena- Chitosan hydrogels Aldol condensation: Ald. = 1 mmol, ac = 1 mL, Conv. = 23–100 %, Yield = 21– Several times [109]
gel condensation DMSO = 4 mL, CGB = 20 units, RT, 18 h 100 % without loss in
Knoevenagel reaction: Ald. = 1 mmol, do- Conv. = 72–100 %, Yield = 100 % activity
nor = 1.1 mmol, DMSO = 3 mL, CGB = 20 u-
nits, RT, 3–10 min
5. Synthesis of cyclic Quaternary NH4 + salt PO = 57.2 mmol, cat. PO Conv. = 100 %, PC 5 times without [110]
carbonates from ep- functionalized chitosan (CS N + Me3I ) = 1.7 mmol % of PO, P CO2 = 4 Sel. = 100 % loss in activity
oxides and CO2 Mpa, 160 8C, 6 h, 4 MPa
6. Synthesis of cyclic Chitosan functionalized PO = 1 mL, cat. = 50 mg, PCO2 = 4 Mpa, 120 8C, PO Conv. = 3–96 % (for various 5 times without [111]
carbonates from ep- IL (EMIM halides) 4 h, halides), PC Sel. = 100 % loss in activity
oxides and CO2
7. Synthesis of cyclic Quaternized chitosan AGE = 18.6 mmol, cat. = 0.1 g, PCO2 = 1.17 Conv. = 81–91 %, Yield = 80–90 % 5 times with [112]
carbonates from ep- (QS) Mpa,120 8C, 6 h. slight loss in ac-
oxides and CO2 tivity.
8. [3 + 2] cycloaddition Cu anchored on chitosan Alkyne azide = 10 mol%, cat. = 10 mol%, Yield = 86–95 % – [113]
of azide/Alkyne modified by HMD H2O:dioxane = 8 : 2, temp. = 70 8C, time = 30 -
min.
9. Azide/Alkyne [3 + 2] CuSO4-chitosan Al. A. = 1.2 mmol, alkyne = 1.0 mmol, Yield = 93–99 % 10 times with- [114]
cycloaddition cat. = 5 mg, H2O, RT, 4–12 h. out loss in activ-
ity
10. N-allylation of Pd-chitosan Amine = 1.2 mmol, AA = 1 mmol, Yield of the products = 81–92 % 5 times without [115]
© 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
amines with allyl ace- K2CO3 = 2 mmol, cat. = 30 mg, DMF = 4 mL, loss in activity
tates 120 8C, 24 h.
11. Allylic substitution Pd-chitosan CEC = 0.32 mmol, Mr. = 0.30 mmol, Yield = 100 % – [116]
reaction BeZ. = 8 mL, cat. = 0.013 mmol Pd, 50 8C, 2 h.
12. Allylic substitution Pd-IL supported on chi- DPAP = 0.42 mmol, Mr. = 1.3 eqv., Pd = 0.05 Yield = 95 %, 10 cycles with- [117]
reaction tosan eqv., ligand = 0.2 eqv., RT, 1 h. other substrates = 72–97 % out loss in activ-
ity
13. Ring opening poly- Chitosan supported RE- Al/RE = 50 (molar), Acac/Al = 50, [PO]/ Conv. of PO = 74–87 %, – [118]
merization of PO complex, TBA and acac [RE] = 3600, Toluene, 708 C, 8 h. Yield (kg of PO/mol RE) = 155–
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52
51
50
49
48
47
46
45
44
43
42
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
Table 3. continued
Entry Reaction Catalyst Reaction conditions Result Recyclability Ref.
3
14. Hydroformylation of Cyclohexylimino Oct. = 6.37 mmol, cat. = 2.8X10 mmol of Rh, Conv. of Oct = 81 %. Ald. Sel. 4-times without [119]
1-octene (Oct) phosphine Rh complex xylene = 10 mL, Psyngas = 30 bar, 75 8C = 95 %, IsoOct Sel. = 5 % loss of activity
supported on chitosan and selectivity
15. Reductive decholrina- Pd Fe nanoparticles TCB = 170 mM, cat. = 0.11 g, 90 min, shaking at TCB decomposition = 100 %, – [120]
tion of TCB supported on chitosan 250 RPM Benzene conc. = 88 %, others
Chem. Rec. 2019, 19, 1 – 28

conc. = 12 %
Pe r s o n a l A c c o u n t
16. Multicomponent syn- Chitosan in acetic acid For PBD:Et.A = 5 mmol, Ald. = 5 mmol, Yield = 84–93 % 10 times where [121]
thesis of heterocycles AB = 5 mmol, chitosan = 0.08 g, 60 65 8C, Yield = 72–96 % activity reduced
80 100 min. slightly after 5th
For TOTD:DD = 5 mmol, aromatic Ald = 5 m- cycle
mol, AB or urea or thiourea or ATZ = 5 mmol,
chitosan = 0.08 g in 2 % AcA. in H2O,
60 65 8C, 55 100 min
17. Synthesis of Spiropi- Ce-chitosan Amine = 4 mmol, AMC = 8 mmol, cat. = 0.8 g, Yield = 81–94 % 5 times with [122]
peridine derivatives PEG200 = 15 mL, RT, 32–48 min marginal loss
18. Enantioselective Mi- Chitosan supported cin- DCC = 0.2 mmol, toluene = 1.5 mL, Yield = 91 %, ee = 93 %, For other 5 times with [123]
chael reaction chona alkaloids NBM = 0.24 mmol, cat. = 10 mol%, RT, sunstrates Yields = 72–93 %, marginal loss in
Time = unless the disappearance of reactant ee = 80–90 % activity.
Legend: Ref. = reference, cat. = catalyst, FFA = free fatty acid, Conv. = conversion, Sel. = selectivity, nBuOH = n-butanol, BA = butyric acid, ac = acetone, DMSO = dimethyl
sulphoxide, CGB = chitosan gel beads, Ald = Aldehyde, RT = room temperature, PO=Propylene oxide, PC=Propylene carbonate, IL = ionic liquid, AGE=Allyglycidyl ether,
HMD = hexamethylene diisocyanate, Al.A. = Alkyl azide, AA = allyl acetate, DMF = dimethyl formamide, CEC = (E)-cinnamyl ethyl carbonate, Mr. = morpholine, BeZ. =
benzonitrile, DPAP = (E) 1,3-diphenyl-3-acetoxyprop-1-ene, RE = rare earth, TBA = triisobutyl aluminium, acac = acetyl acetone, TCB = 1,2,4-trichloro benzene,
conc. = concentration, PBD = 4H-Pyrimido[2,1-b]benzothiazole Derivatives: EtA=Ethyl acetoacetate, AB = 2-aminobenzothiole, TOTD = 1,2,4-Triazoloquinazoline, Octahy-
droquinazolinone and and Fused Thiazolo [2,3,–b]quinazolinone derivative, DD=Dimedone„ ATZ = 3-amino-1,2,4-Triazole, AcA. = acetic acid, AMC = active methylene
compound, PEG = polyethylene glycol, DCC = 1,3-dicarbonyl compound, NBM=N-benzylmaleimide
© 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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1 dispersion of the solid in solvent on addition of CTAB.

2 Baudoux et al. extended the study and used ionic liquid with
3 Pd and chitosan (Entry 12). A high level of activity,
4 recyclability and reusability were obtained in animation
5 reaction. No organic solvent was used. The application was
6 extended to a variety of substrates.
7 Among several other reactions, ring opening polymer-
8 ization was studied by Zeng et al. using chitosan supported
9 rare earth complex (Entry 13). The effect of polymerization
10 temperature, acac/Al molar ratio, polymerization time,
11 catalyst content has been investigated. Kinetic studies showed
12 that polymerization rate is first order w.r.t. monomer and
13 catalyst concentration. Activation energy of polymerization
14 reaction is 37.1 kJ/mol. Makhubela et al. studied the hydro-
15 formylation reaction (Entry 14). Under the optimized con-
16 ditions, the catalyst shows high chemoselectivity towards the
17 aldehyde which is in line with green chemistry principle of
18 atom economy. The heterogenized catalyst worked better
19 than the homogeneous counterpart [Rh(CO)2(acac)] and
20 exhibited good recyclability. Bimetallic chitosan catalyst was
21 also active for reductive dechlorination of TCB (Entry 15).
22 The catalyst was very active for the dechlorination, the rate
23 increased with increase in Pd loading. As compared to
24 Pd Fe-silica, the chitosan supported catalyst displayed better
25 performance as it does not lead to agglomerization of
26 particles. The reaction appeared to follow pseudo-first-order
27 kinetics w.r.t. the transformation of parent compound. The Figure 9. Transformation of oceanic waste to value added chemicals.
28 reaction model derived, predicted that reductive dechlorina-
29 tion of TCB followed parallel pathway: complete reduction
30 to benzene and reductive hydrogenolysis to dichlorobenzenes. section highlights the potential of these nitrogen containing
31 Unique, one pot-three component reaction system for the polymers as feedstock and furnishes insights into their
32 synthesis of libraries of nitrogen compounds was established catalytic transformations rendering important products.
33 by Sahu et al. using acidic chitosan (Entry 16). The method- The transformation of chitin to chemicals is very
34 ology adopted has various advantages like freedom from challenging due to its poor solubility in common solvents. It
35 organic solvents, eco-friendly catalyst system, recyclability and is soluble only in some ionic liquids, environment unfriendly
36 easy work up procedure. Similar multicomponent system was solvents like hexafluoro isopropanol, hexafluoroacetone and
37 deployed for synthesis of spiropiperidine derivatives (En- chloroalcohols. This poses a problem in developing a green
38 try 17) which had all the advantages of such systems stated protocol for chitin transformation to value added chemicals.
39 before. Enantioselective Michael reaction was also feasible To ameliorate its utilization, researchers tried to derive
40 over chitosan supported cinchona alkaloid catalyst (Entry 18). important chemicals from chitin either by improvising the
41 Highly congested products (with adjacent quaternary and methodology, reaction medium, process technology or
42 tertiary stereocentres) were synthesized in high yields with catalysis. A very fine example is presented by the study
43 high stereoselectivity. The high catalytic activity displayed the undertaken by Chen et al. in which they derived low
44 potential of the catalyst for other asymmetric transformations molecular weight chitosan mechano-chemically (ball milling)
45 also. from chitin and shrimp shells by using a simple base catalyst.
46 Chitin was deacylated and depolymerized simultaneously
47 giving good yields of chitosan, whose molecular weight was
48 3. N-containing Biopolymers as a Source of much more narrowly distributed, with a polydispersity of 1.1.
49 The advantages of this system were (i) compared to the
Platform Chemicals
50 traditional method, the usage of base was reduced to about
51 Chitin and chitosan are not only excellent catalyst supports 1/10 (ii) chitosan with improved quality was obtained (iii)
52 but also are a source of variety of chemicals (Figure 9). This solvent free, economic and environmental friendly method
1 was developed. The efficiency of the process depended on the

2 ball milling parameters and the type of base.[124] The
3 researchers then extended the study and aimed for further
4 hydrolysis of chitosan to its monomer glucosamine (GLA).
5 Tandem synthesis of GLA was achieved from ball milled
6 chitin with acids in aprotic solvents. Under the optimized
7 conditions (Diethylenediethyl ether = 4 mL, water = 1 mL,
8 BM chitin = 50 mg, H2SO4 = 100 mM, 175 8C, 1 h)
9 80 mol% yield of GLA was obtained.[125] Interestingly, under
10 these conditions chitin did not undergo hydrolysis to give its
11 monomer (NAG). However, when sulphuric acid was added
12 during ball milling and the reaction was carried out at high
13 temperatures it could facilitate hydrolysis of chitin giving
14 NAG. 53 mol% yield of NAG was obtained at 170 8C, Scheme 12. Reaction pathway for hydrogenation of NAG (intermediates in
15 substrate:catalyst = 2 : 1 with 206 mg of chitin in 1 h. When boxes and final products in red).
16 methanol was used as a solvent and reaction conditions were
17 altered slightly, the yield of the product increased to
18 70 mol%. This increase was attributed to enhanced reactivity
19 of the substrate and stability of the product. Mechanical
20 forces were found to be essential for selective catalytic
21 depolymerization of chitin.[126] After optimizing the reaction
22 conditions for depolymerization they tested the hydrogena-
23 tion of NAG. Addition of Ru/TiO2 (5 wt% of chitin) to the
24 depolymerized reaction mixture yielded Acetamido-2-deoxy-
25 sorbitol in good yields (52 mol%) under 4 MPa H2 pressure
26 and pH = 5. This was an excellent approach to facilitate one
27 pot cascade catalysis for such rigid reactants, contributing
28 significantly towards waste valorisation.[127] When NAG was
29 used as a reactant over transition metal catalyst in water still
30 higher yields of polyols were achieved. Under 180 8C, 40 bar
31 H2 with 1 mol% loading of Ru/C, 71.9 % of C6 N-
32 containing polyols, 6.1 % C4 polyols and 8.7 % N-acetylmo-
33 noethanolamine (NMEA) were produced. Through the
34 kinetic studies, the mechanistic pathway was proposed which
35 confirmed the formation of NMEA through retro aldol
36 condensation (Scheme 12).[128]
37 Another complex reaction is the synthesis of N-containing
38 furans from chitin since it involves hydrolysis to its
39 monomers followed by dehydration. Kerton et al. were
40 pioneers in this area, the product, 3-acetamido-5-acetyl furan Scheme 13. Potential transformations of 3 A5AF.
41 (3 A5AF) was an important platform chemical for various
42 chemicals with useful applications (Scheme 13). 3 A5AF was
43 directly derived from chitin using boric acid and alkaline used various ionic liquids in which chloride containing ones
44 chlorides as additives and N-methyl pyrrolidone as solvent. lead to complete dissolution of chitin. Under the optimized
45 Good conversion of chitin (50 mol%) but very low yields of conditions (chitin = 80 mg, [BMIm]Cl = 1 g, HCl =
46 furan (7.5 mol%) was obtained. Mechanistic investigations 100 mol%, boric acid = 400 mol%, 180 8C, 1 h) upto 6 %
47 revealed that boron forms a complex intermediate during the yield was obtained. When NAG was used as a reactant along
48 reaction shedding light on the promotional effects of boric with extraction with organic solvents under microwave
49 acid. Depolymerization was the rate determining step, so irradiation 3 A5AF yields increased upto 34 %. From this
50 disruption of hydrogen bonds either before or during the study, it was concluded that advanced strategies like extrac-
51 reaction was the key to further improving the reaction tion/distillation were effective for monomers and improved
52 yield.[129] Therefore, for disrupting the H-bonds they then methods for in-situ chitin hydrolysis are needed as key step in
1 one pot transformation into N-chemicals.[130] Visualizing this, of chitosan was used, the LA yields increased to 32 wt%.[140]
2 a systematic study on the pre-treatment methods of chitin Researchers also demonstrated the use of strong acids for the
3 was pursued by them. Methods like ball milling, grinding, hydrolysis. Lee et al. used H2SO4 (2.2 %) and at 174 8C in
4 steam explosion, alkaline treatment, and ionic liquid/ 37 min they achieved 12 wt% of HMF.[141] Other solvents
5 phosphoric acid dissolution-precipitation were used and their e. g. dimethyl sulphoxide (DMSO) and ionic liquids which
6 effect on the catalytic activity was evaluated. The study are known to give very high yields of HMF from
7 enabled direct comparison of these methods and helped in lignocellulosic biomass were also tested with chitosan.[142] In
8 understanding the structure activity relationship. Ball milling DMSO-H2O solvent mixture, metal salts were screened.
9 in dry mode was the most effective pre-treatment method as FeCl2 exhibited the best performance achieving 26.6 % and
10 it remarkably increased the yield of 3 A5AF to 28.5 %.[131] 37.9 % HMF yield from chitosan and GLA respectively at
11 After deducing this, they carried out formic acid assisted ball 180 8C under hydrothermal conditions. These were the
12 milling for liquefaction of chitin. Formic acid displayed highest yields reported. When chitosan with higher molecular
13 remarkable ability in depolymerization (giving 60 %yield of weight and chitin was used the yields decreased. Reaction
14 monomers at 100 8C in 12 h) and in the ability to function- conditions were optimized during which it was deduced that
15 alize giving an increased yield of the furanic compound (35 % THF-H2O systems also performed at par to DMSO-H2O
16 of 5-formyloxymethyl furfural) after a longer reaction time. system. The Lewis acid i. e. FeCl2 forms a complex with the
17 Raw shrimp shells could also be used effectively.[132] Following amine functionality thereby weakening the adjacent C O
18 this was the acid catalyzed liquefaction of chitin in ethylene bond facilitating hydrolysis. A plausible mechanism was also
19 glycol. Under the optimized conditions (EG = 2 g, sulfuric postulated in which the nitrogen of the chitosan is lost as
20 acid = 0.16 g, 8 % w/w EG, and chitin = 0.3 g, 15 % w/w ammonia to give HMF.[143]
21 EG, 165 8C, 90 min) good yield of hydroxyethyl-2-amino-2- They then tested ionic liquid (IL) as a reaction medium
22 deoxyhexopyranoside and hydroxyethyl-2-acetamido-2-deox- and catalyst. In presence of acidic ionic liquid, N-methyl
23 yhexopyranoside (30 %) was obtained.[133] Such method- imidazolium hydrogen sulphate (NMIM-HSO4), best results
24 ologies with proper catalysis paved the way for suitable were obtained. Under the optimal reaction conditions (4 wt
25 exploitation of oceanic waste. Microwave irradiation a green % of IL, chitosan = 100 mg, 180 8C, 5 h) 29.5 mol% of
26 tool was also deployed but for the monomers. Using NAG, HMF was obtained. With this system, chitosan with variable
27 Kerton et al.[134] achieved very good yields of 3 A5AF. With higher molecular weight could also be converted to HMF.[144]
28 boric acid and NaCl using dimethyl aceamide as solvent In their next study they used Bronsted Lewis acidic ionic
29 under microwave irradiation at 220 8C in 15 min 62 % yield liquid ([Hmim][HSO4]-0.5FeCl2). Addition of Lewis acidity
30 of the product was obtained. The yields they obtained were was beneficial and it increased the yield to 44.1 %. Moreover,
31 30 times more than the yields obtained by pyrolysis of IL could be recycled effectively by simple separation.[145] Since
32 NAG[135,136] clearly demonstrating the superiority of catalytic IL’s are costly their use as reaction medium becomes
33 conversion. When they used ionic liquids as a reaction uneconomical so Zhang et al. used NMIM-HSO4 only as
34 medium, reaction time decreased to only 3 min rendering the catalyst in DMSO-H2O medium and dehydrated NAG to
35 same yields. Amongst all the ionic liquids studied, the Cl̄ give HMF. This was the first study in which NAG rather than
36 containing ones were efficient.[137] Using HCl as catalyst GLA was screened for producing HMF. Highest yield of
37 which furnished protons and Cl̄ effective depolymerization/ HMF (64.6 %) was achieved at 180 8C for 6 h without the
38 dehydration took place and chloromethyl furfural was addition of other catalyst. Thus, an efficient and economical
39 achieved in good yields (45 %) from chitin.[138] method was developed for using N-containing monomers for
40 Chitosan was also explored to derive crucial platform HMF production.[146] Another interesting system was de-
41 molecules like 5-Hydroxymethyl furfural (HMF) and Levu- ployed by Wang et al. ZnCl2 aqueous solution was used as
42 linic acid (LA) which have identified as “Top 10 bio-based reaction medium and metal salts as catalyst. With AlCl3 and
43 chemicals” by US-Department of energy. These compounds B(OH) 3 as catalyst at 120 8C for 90 min using 1 g of GLA,
44 have a wide range of applications.[139] Hydrolysis of chitosan 21.9 wt% yield of HMF was achieved. Thus, the focus on the
45 was performed in the presence of Lewis acids with effective reaction medium is another logical way of deriving
46 SnCl4.5H2O providing best results. Under microwave irradi- chemicals from waste in good yields.[147]
47 ation at 200 8C for 30 min using 100 mg of chitosan and There are reports on the synthesis of levulinic acid from
48 0.24 mmol of catalyst and 4 mL of water, LA yield of GLA based glycans. Mostly, strong homogeneous inorganic
49 23.9 wt% was obtained. For HMF (10 % yield) the catalyst acids were used for the one pot conversion of NAG, GA, and
50 amount was decreased (0.12 mmol) and amount of water was chitosan to LA at higher temperature. Using 2 M sulphuric
51 increased (15 mL). Thus, by tuning the reaction conditions acid at 190 8C under microwave irradiation, LA yield of
52 both the products could be produced. When GLA, monomer 20.6–32 % was obtained in 30 min. In this system, large
1 molecular weight chitin was also degraded to give 37.8 % of ling studies in addition to optimization and kinetic studies
2 LA which is the best yield reported so far.[148] Lower yield of will provide more insights into deep understanding. Lastly,
3 LA was achieved (29.3 %) from GLA in the absence of this naturally occurring polymer based catalyst should be
4 microwave irradiation.[149] This shows the superiority of MW deployed in the transformations of biomass origin which will
5 methods in transforming waste to chemicals. a-Amino acids maximize the use of renewable resources for sustainability.
6 are another class of important chemicals which can be derived Deriving important chemicals from oceanic waste is an
7 from these biopolymers.[150] Through the aqueous oxidation area of ultimate potential that has been triggered recently.
8 of amino sugars catalyzed by gold nanoparticles dispersed on Most of the reports on the catalytic conversion of polymers
9 basic support, corresponding acids were obtained in excellent and monomers are with homogeneous catalysis. There is only
10 yields (87–99 %). MgO was the best support amongst all the a single report on oxidation and reduction using heteroge-
11 others. The aqueous aerobic oxidation operating under mild neous catalyst. Since the homogeneous catalysts are always
12 conditions offering good yields for a variety of substrates with associated with drawbacks like environmental hazards,
13 retention of heterogeneity were the striking features of the corrosion, handling issue etc. there is an urgency to replace
14 study.[151] Thus, many chemicals which are currently pro- them with greener heterogeneous catalyst. Thus, bridging the
15 duced from conventional downstream processing of petro- gap in the synthesis of platform chemicals from marine
16 leum can be derived from renewable marine polymers also. polymers by heterogeneous catalysis is the ideal approach and
17 the need of the hour. Nevertheless, economic catalyst and
18 potent reaction systems should be adopted which facilitates
4. Summary and Outlook
19 the commercial production of these chemicals. Infusion of
20 The present review has addressed the potency of abundantly these approaches will result into a paradigm shift towards
21 available marine polymers (chitin/chitosan) in a catalytic greener future.
22 scenario encompassing its efficiency as a renewable feedstock
23 to deliver value added chemicals and as a promising catalyst
Acknowledgements
24 material. As a catalyst or catalyst support, it has been used in
25 several types of reactions such as carbon-carbon, carbon- Nishita Lucas acknowledges University Grant Commission,
26 heteroatom coupling reactions, oxidation, hydrogenation, India for providing D.S. Kothari Post-doctoral fellowship.
27 base and acid catalyzed reactions. Researchers have used novel
28 synthesis methodology, green protocols, effective reaction
29 systems and advanced strategies which have been discussed
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1 PERSONAL ACCOUNT
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In context of waste valorization for sus- Dr. N. Lucas, Dr. A. A. Athawale*,
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tainability, this review presents a Dr. C. V. Rode*
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catalytic perspective for the efficient con-
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version of oceanic waste such as chitin
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and chitosan to N-containing products. Valorization of Oceanic Waste
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These feedstocks being marine biopoly- Biomass: A Catalytic Perspective
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mers can be also used as efficient catalyst
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supports
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Valorization of Oceanic Waste Biomass: A Catalytic Perspective

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Personal Account DOI: 10.1002/tcr.

1 deacetylation gives chitosan which also possesses immense

1 (Scheme 8.2). The oxidation was achieved in absence of

1 ranked as [Cu(SC)SA] > [Cu(SC)ST] > [Cu(SC)VA]. 34 %

1 their integrity and electronic conductivity. The methodology

1 Table 1. Hydrogenation reaction catalyzed by chitosan supported Pd complexes.

1 Table 2. Hydrogenation reactions catalyzed by other metal supported on chitosan.

1 The superior advantages of this system were easy recovery by

1 catalysis for hydrolysis/esterification reaction was also studied

Chem. Rec. 2019, 19, 1 – 28

Wiley Online Library

Chem. Rec. 2019, 19, 1 – 28

1 dispersion of the solid in solvent on addition of CTAB.

1 was developed. The efficiency of the process depended on the

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