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Due to their eco-friendly nature, polysaccharides are desirable supporting materials in organic transformations. Nevertheless, as is the case for other supports, polysaccharides have to face the issue of seeking more binding sites via multifunctional structures to capture metal species in the catalyst, which enhance stability and promote catalytic...
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... Recently, Li et al. [45] described the silylation of microcrystalline cellulose by treatment with 3-aminopropyltriethoxy silane, generating Cell-NH2. The reaction of the amino group with pyridinyl benzaldehyde produced a Schiff base ligand (Cell-Sb) which was used to bind palladium, forming Cell-Sb-Pd(II). ...
In recent years, the immobilization of palladium nanoparticles on solid supports to prepare active and stable catalytic systems has been deeply investigated. Compared to inorganic materials, naturally occurring organic solids are inexpensive, available and abundant. Moreover, the surface of these solids is fully covered by chelating groups which can stabilize the metal nanoparticles. In the present review, we have focused our attention on natural biomaterials-supported metal catalysts applied to the formation of C–C bonds by Mizoroki–Heck, Suzuki–Miyaura and Sonogashira reactions. A systematic approach based on the nature of the organic matrix will be followed: (i) metal catalysts supported on cellulose; (ii) metal catalysts supported on starch; (iii) metal catalysts supported on pectin; (iv) metal catalysts supported on agarose; (v) metal catalysts supported on chitosan; (vi) metal catalysts supported on proteins and enzymes. We will emphasize the effective heterogeneity and recyclability of each catalyst, specifying which studies were carried out to evaluate these aspects.
... The XRD pattern of Cell shows three diffraction peaks characteristic of the (110), (200), and (004) reection planes of cellulose. 40 Similar peaks were also observed for Cell-G3-SO 3 H, conrming that the crystallinity of cellulose was preserved during the catalyst preparation process. However, compared to Cell, the XRD pattern of Cell-G3-SO 3 H revealed a signicant decrease in peak intensities due to the presence of amorphous modier species, including MPTMS and dendrimer layers. ...
An efficient heterogeneous acid catalyst was prepared via the growth of a thiol-functionalized third-generation dendrimer on the surface of cellulose employing thiol-ene click chemistry, followed by the formation of sulfonic acid groups via the oxidation of thiol groups. X-ray photoelectron spectroscopy confirmed the complete oxidation of the thiol groups to sulfonic acid groups utilizing H2O2 as an oxidant. The synthesized catalyst was studied for its ability to catalyze the conversion of fructose to 5-hydroxymethylfurfural (5-HMF). The effects of different factors on the yield of 5-HMF production were investigated. Over 96% of 5-HMF was achieved from fructose at 110 °C for 45 min in a biphasic acetone:water (2 : 1) medium. The excellent activity of this catalyst could be ascribed to the existence of a dendritic structure, which makes acidic active sites easily accessible. This catalytic system can also be used for efficiently transforming other carbohydrates to 5-HMF. After a fifth cycle of the dehydration of fructose, the catalyst exhibited no remarkable change in its catalytic activity and structure, demonstrating its high stability and recyclability.
... Alumina was added in order to supposedly stabilize the hybrid since C-O-Si bonds were said to be easily hydrolyzed. Such instability was however not described by other teams who successfully used C-O-Si bonds in other nanocatalysts [27,28,30,31,66,67]. CMC has been loaded with cerium(IV) hydroxide by successive chelation and precipitation within the biopolymer [68]. ...
... Alumina was added in order to supposedly stabilize the hybrid since C-O-Si bonds were said to be easily hydrolyzed. Such instability was however not described by other teams who successfully used C-O-Si bonds in other nanocatalysts [27,28,30,31,66,67]. ...
Despite providing interesting solutions to reduce the number of synthetic steps, to decrease energy consumption or to generate less waste, therefore contributing to a more sustainable way of producing important chemicals, the expansion of the use of homogeneous catalysis in industrial processes is hampered by several drawbacks. One of the most important is the difficulty to recycle the noble metals generating potential high costs and pollution of the synthesized products by metal traces detrimental to their applications. Supporting the metals on abundant and cheap biosourced polymers has recently appeared as an almost ideal solution: They are much easier to recover from the reaction medium and usually maintain high catalytic activity. The present bibliographical review focuses on the development of catalysts based on group 10 transition metals (nickel, palladium, platinum) supported on biopolymers obtained from wood, such as cellulose, hemicellulose, lignin, and their derivatives. The applications of these catalysts in organic synthesis or depollution are also addressed in this review with examples of C-C couplings, oxidation, or hydrogenation reactions.
... Within the recent years, several researchers have reported the use of cellulose supporting palladium as active site. Mainly, hydrogenation and cross-coupling reactions in liquid phase were studied (Nishikata et al. 2014;Zheng et al. 2015;Li et al. 2017bLi et al. , 2018Gopiraman et al. 2018;Lu et al. 2018;Xiang et al. 2018;Islam et al. 2019;Seyednejhad et al. 2019;Dong et al. 2019;Kempasiddaiah et al. 2020;Yamada et al. 2020). However, and to the best of our knowledge, this is the first report where cellulose is employed as an effective catalytic support for the gas-phase reduction of NO, reaction of environmental concern. ...
... For the fibers containing palladium, it can be clearly observed a sharp and exothermic peak at 317°C. This could be related to the presence of the metallic entities that catalyzes the combustion of the fibers, as it was reported for similar palladium -cellulose based materials (Cai et al. 2009;Ruan et al. 2016;Shi et al. 2019;Dong et al. 2019). However, all fibers are stable up to 300°C. ...
Palladium was incorporated into carboxymethylated cellulose fibers as a support, thereby becoming an efficient and stable catalyst for low temperature gas phase reaction. Thus, NO was used as test molecule of Greenhouse Gas to be catalytically reduced with hydrogen on an eco-friendly sustainable material containing palladium as the active site. Prior to the catalytic test, the catalysts were reduced with glucose as an eco-friendly reagent. The material characterization was performed by SEM–EDS, XRD, LRS, TGA and FTIR. The catalytic results showed that at 170 °C, NO conversion was 100% with a selectivity of 70% to nitrogen. While NOX species were completely converted into N2 at temperatures higher than 180 °C. The starting commercial dissolving pulp was also studied, but its performance resulted lower than the ones of functionalized fibers. The use of this strategy, i.e., the functionalization of cellulose fibers followed by in-situ formation of metallic nanoparticles, can be further applied for the design of a wide range of materials with interesting applications for gas and liquid phase reactions under mild conditions.
Graphic abstract
... 8,9 Currently, most researchers have focused on utilization of eco-friendly, renewable resources and sustainable solid supports and processes that apply to tangible assistance. 10 The solid-supported catalysts, namely, metal-organic framework/covalent organic framework (MOF/COF)-supported, 11,12 polystyrene-supported, 13 nonmagnetic-and magnetic-supported, 14 carbon-based, 15 MCM-supported, 16 metaldecorated hyper-cross-linked network, 17 and salen-based hyper-cross-linked polymer catalysts, 18,19 showed an extraordinary catalytic ability toward the organic reaction. Nevertheless, they are out of the viewpoint of sustainable protocols in green chemistry principles. ...
... By considering sustainable protocols, natural polymers are more suitable as solid supports in the synthesis of heterogeneous catalysts. The natural polymers including alginate, 20 gelatin, 21 starch, 22 chitosan, 23 and cellulose 10,24,25 have been utilized as solid support for catalytic reactions. In recent years, cellulose-supported adsorbents utilized as a catalyst have gained significant interest due to their biodegradability, abundance in nature, eco-friendly characteristics, water insolubility, and cost-effectiveness. ...
... 27−32 In addition, most researchers have been focusing on exploring a new type of ligand to functionalize the cellulose surface, which has a profound impact on the catalytic ability with low leaching of metal species. 10 Recently, several studies reported, such as functionalized waste corn-cob cellulose-supported copper nanoparticles for N-alkylation reaction of amines; 33 a cellulose-supported palladium catalyst for the Heck, Ullmann, and Sonogashira coupling reaction; 34−37 a cellulose-supported copper catalyst for aza-Michael addition and click reactions; 38−40 functionalized cellulose with several binding sites; 10 and 2-aminopyridine functionalized-, 41 N-methylimidazole functionalized-, 25 N-heterocyclic carbene functionalized hydroxyethyl, 9 and amine functionalized 42 cellulose-supported palladium complex catalysts, have been used for the Suzuki reaction. However, only a few studies have been found where cellulose-supported copper catalysts were used for the Ullmann crosscoupling reaction. ...
Highly active natural pandanus-extracted cellulose-supported poly(hydroxamic acid)–Cu(II) complex 4 was synthesized. The surface of pandanus cellulose was modified through graft copolymerization using purified methyl acrylate as a monomer. Then, copolymer methyl acrylate was converted into a bidentate chelating ligand poly(hydroxamic acid) via a Loosen rearrangement in the presence of an aqueous solution of hydroxylamine. Finally, copper species were incorporated into poly(hydroxamic acid) via the adsorption process. Cu(II) complex 4 was fully characterized by Fourier transform infrared (FTIR), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses. The cellulose-supported Cu(II) complex 4 was successfully applied (0.005 mol %) to the Ullmann etherification of aryl, benzyl halides, and phenacyl bromide with a number of aromatic phenols to provide the corresponding ethers with excellent yield [benzyl halide (70–99%); aryl halide (20–90%)]. Cu(II) complex 4 showed high stability and was easily recovered from the reaction mixture. It could be reused up to seven times without loss of its original catalytic activity. Therefore, Cu(II) complex 4 can be commercially utilized for the preparation of various ethers, and this synthetic technique could be a part in the synthesis of natural products and medicinal compounds.
... The high-functionalised surface of these lignocellulosic materials is very appropriate for different purposes. For example, cellulose derivatives have a great potential to prepare materials for multiple applications (Thomas et al. 2018) such as bio-based hybrid materials for photocatalysis (Colmenares and Kuna 2017), bio-polymer support for metal catalysts (Dong et al. 2019) or as catalysts for carbon dioxide fixation (Liu et al. 2019). ...
Lignocellulosic wastes obtained from vegetal residues in combination with nucleophiles were used as catalysts for carbon dioxide fixation in epoxides to form cyclic carbonates. An adequate combination of the residue and the nucleophile was essential to obtain active catalytic systems. The best binary systems were formed by olive bones, grape waste, date pit and corn leaves husk residues with tetrabutylammonium bromide (TBAB). High conversions in the cycloaddition of CO2 to propylene oxide (76–84%) and 1,2-epoxyhexane (68–79%) were achieved at very low nucleophile loading (0.47 mol % respect to the substrate) under mild conditions (95 °C and 10 atm of CO2). The vegetal wastes were stable under catalytic conditions and could be recycled after adequately supporting the nucleophile TBAB in silica gel. The mechanistic computational study carried out with Density Functional Theory calculations on model catalysts describes the contribution of individual lignin and cellulosic components to the experimental substrate conversion into cyclic carbonate. The energy barriers obtained and the experimental data suggest that the contribution of lignin to the total catalytic activity (barrier energy of 9.9 kcal/mol) may be more important than the contribution of cellulose (energy barrier 11.9 kcal/mol).
Graphic abstract
... In this regard, the homogeneous Pd catalysts have been immobilized on various solid supports making them heterogeneous in nature [6][7][8]. Recently, cellulose has received significant attention as support for developing heterogeneous Pd catalyst systems owing to its outstanding properties such as abundant availability, non-toxicity, biodegradability, environmental friendly, and low cost [9][10][11][12][13][14][15]. Also, abundant hydroxyl groups in cellulose backbone can act as both reducing and stabilizing agents for many metal nanoparticles and therefore eliminate the requirement of a reducing agent or stabilizer [16,17]. ...
... Consequently, the reactions were first screened with various hydrophilic and hydrophobic DESs at 90°C using 0.3 mol % of the catalyst. The catalyst showed higher efficiency in hydrophilic DESs ( Table 2, entries 1-8) than hydrophobic one ( Table 2, entries [8][9][10][11][12]. This might be attributed to the hydrophilic nature of the catalyst that offered more dispersion in hydrophilic DESs and thus improved its catalytic activity. ...
The development of an efficient and sustainable catalytic system for the preparation of biphenyls through the Suzuki-Miyaura coupling reaction is still a great challenge to green chemistry. Encouraging the prevailing challenge, in the present work, a heterogeneous Pd catalyst was synthesized through a green method and used for the production of biphenyls in deep eutectic solvents (DESs) as green reaction media. In order to prepare the catalyst, magnetite-graphene oxide nanocomposite was modified with cellulose via the click reaction and applied as support for Pd nanoparticles. Cellulose acted as both reducing and stabilizing agent for Pd nanoparticles and eliminated the requirement of a reducing agent. The prepared catalyst was characterized by different methods such as FT-IR, EDX, EDX-mapping, XPS, SEM, TEM, XRD, VSM, and ICP-OES analyses. Catalytic properties of the obtained catalyst was explored in the coupling reaction of aryl halides with aryl boronic acids in different hydrophilic and hydrophobic DESs. The presence of cellulose with hydrophilic character on the structure of catalyst offered well dispersion of the catalyst in hydrophilic DESs, which led to enhancement of its catalytic activity. Among various hydrophilic DESs, the DES composed of dimethylammonium chloride and glycerol was verified as the most effective solvent for the preparation of biphenyls. The catalyst was compatible with a variety of substrates, with which all the Suzuki coupling products were achieved in high to excellent yields. Thanks to the low solubility of catalyst and DES in organic solvents, the separated aqueous phase containing both of the catalyst and DES could be readily recovered by evaporating water and reused up to five successive runs with a stable activity. This simple and new separation strategy provided a clean and highly efficient synthetic methodology for the synthesis of various biphenyls. Moreover, hot filtration test efficiently confirmed that the catalyst is heterogeneous and completely stable under reaction conditions.
... In 1839 this raw material was first segregated from plants by Anselme Payen [2]. Since then, the cellulose extraction has been developed, and now it can be extracted from different sources (plants, wood, tunicates, algae, bacteria etc. [3]). The global cellulose market size was 191.74 billion Euro in 2018 ( Figure 1) and is projected to reach 266.47 billion Euro by 2026 [1]. Figure 1. ...
Since the beginning, Mobile Bed Biofilm Reactor (MBBR) technology has been extensively used, both at the level of small on-site treatment units and at industrial scale. Moreover, this technology represents a starting point for many researches aimed at improving performance, such as the use of microorganisms, enrichment with anammox bacteria to accelerate nitrogen removal and more. Within the present paper, a new generation of carriers (consisting of a mix of high-density polyethylene + talcum + cellulose) was bio-augmented with a WRF (White Rot Fungi) strain, namely Cerioporus squamosus , in static conditions (data not shown in this paper). The wastewater, targeted for treatment, originated from National R&D Institute for Textile and Leather, INCDTP Bucharest, leather subsidiary, Leather and Footwear Research Institute, technological flux, characterized by high tannins concentration, and cellulosic content. Wastewater treatment aimed the reduction of COD value, as a water quality parameter, with satisfactory results, obtaining a percentage reduction rate of 48.53%. Also, GC-MS chromatography analysis was carried out on five vegetal tannins, used in leather treatment, highlighting main compounds for Mimosa, Chestnut, Gambier, Myrobalan and Quebracho natural tannins.
... Dong et al. [109] reported on the synthesis of new heterogeneous palladium catalyst in three steps: (1) cellulose was reacted with 3-aminopropyltriethoxysilane to yield Cell-NH2; (2) synthesis of Schiff-base functionalized cellulose; (3) addition of Na2PdCl4 to yield the final catalyst [109]. Both 13 C-NMR and FTIR analyses corroborate that cellulose has successfully been modified for the metalligand interaction. ...
... Dong et al. [109] reported on the synthesis of new heterogeneous palladium catalyst in three steps: (1) cellulose was reacted with 3-aminopropyltriethoxysilane to yield Cell-NH2; (2) synthesis of Schiff-base functionalized cellulose; (3) addition of Na2PdCl4 to yield the final catalyst [109]. Both 13 C-NMR and FTIR analyses corroborate that cellulose has successfully been modified for the metalligand interaction. ...
... The performance of the catalyst in Suzuki cross-coupling, using chlorobenzene, idobenzene and different bromobenzenes with phenylboronic acid derivatives in EtOH/H2O (1:1) at 70 °C , yielded TOFs from 53 to 341 h −1 [109]. The catalyst was also tested for reusability for five runs, during which the yield of 4-methoxybiphenyl decreased from 96% to 77%. ...
Polysaccharides derived from natural sources exhibit unique structures and functional groups, which have recently garnered them increased attention for their potential applicability as supports for metal catalysts. Renewable polysaccharide matrices were employed as supports for palladium complexes, with or without previous modification of the support, and were used in Suzuki cross-coupling of halobenzenes and phenylboronic acid derivatives. In this review, recent developments in the immobilization of palladium-based complexes are reported, including descriptions of the preparation procedures and catalytic activity of each system. In addition, the effects of the nature of the polymeric support and of the reaction conditions on catalytic performance are discussed.
