Nanoscaled reusable palladium catalyst supported on chitosan hybrid composite microcapsules reinforced with ZnO nanoparticles for Heck coupling reactions

doi:10.21203/rs.3.rs-1594510/v1

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Nanoscaled reusable palladium catalyst supported on chitosan hybrid composite microcapsules reinforced with ZnO nanoparticles for Heck coupling reactions

https://doi.org/10.21203/rs.3.rs-1594510/v1

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In the present work, a novel nanocatalyst system (Pd@CS-ZnO) was developed by adorning palladium nanoparticles on the hybrid nanocomposite consisting of chitosan and ZnO nanoparticles which are prepared as a suitable stabilizer. Morphological/structural features of Pd@CS-ZnO were studied by FT-IR, TEM, SEM, XRD, and EDS analyses. The catalytic efficiency of Pd@CS-ZnO was then assessed as a heterogeneous nanocatalyst against Heck coupling reaction. The tests revealed that Pd@CS-ZnO was a useful nanocatalyst which can couple the reactions of various aryl halides (I, Br, Cl) with styrene. Additionally, Pd@CS-ZnO nanocatalyst proved to be easily separated with filtration and reapplied for six consecutive reaction runs. Moreover, it was found that Pd@CS-ZnO was one of the most effective catalysts against Heck reaction by protecting its chemical structure. Furthermore, the designed catalyst system offers other benefits such as (1) cost efficiency, (2) eco-friendly nature, (3) facile preparation, (4) moisture/air insensitivity, (5) easy work up, and (6) high yields.

Chitosan

ZnO

palladium

Heck reaction

Metal catalyzed C-C forming reactions such as Suzuki-Miyaura, Sonogashira, and Mizoroki-Heck reactions have an important place in synthetic chemistry as they are utilized in the production of various valuable compounds such as natural products, biologically active molecules, and pharmaceuticals (Ghorbani-Choghamarani et al., 2016; Zhang et al., 2018). Among these, Heck coupling reaction which is used to form Csp²-Csp² bonds between olefins and aryl halides is one of the most important methodologies (Marandi and Koukabi, 2021). Palladium is one of the most important transition metals which catalyzes carbon-carbon coupling reactions (Aryanasab et al., 2021; Veisi et al., 2016). Heck reactions are commonly carried out by using various homogeneous Pd salts as catalyst (palladium chloride, palladium acetate) or Pd complexes containing phosphine ligands. (Kantam et al., 2013; Luo et al., 2021; Marandi and Koukabi, 2021). However, most phosphine ligands are costly, toxic, air and moisture sensitive. Therefore, their use in large-scale industrial applications is limited (Khairul et al., 2020; Li and Hor, 2008). Another issue with the use of homogenous catalysts in Heck reactions is that they display some disadvantages in separation, recoverability, reusability, instability, and tedious work-up (Dohendou et al., 2021; Pei et al., 2021; Zhang et al., 2007). To solve these issues, a Heck reaction protocol that permits preparation and use of phosphine-free palladium-catalysts is needed. Additionally, the preparation of heterogeneous catalysts is highly desirable to solve problems associated with isolation and recyclability. Therefore, stabilization of metal species as heterogeneous catalysts onto a solid support can be considered a very important strategy (Zheng et al., 2020). In this context, researchers have recently made great efforts to synthesize heterogeneous catalysts, and numerous inorganic/organic supports such as polymers, zeolites, silica, metal oxides, and carbon nanotubes have been used (Hosseini-Sarvari et al., 2014; Lin et al., 2003; Nabid et al., 2011; Yang et al., 2009). However, the production of simple, eco-friendly, economic, and efficient heterogeneous catalyst systems is still an important topic from an environmental, sustainable, and economic stand points.

Chitosan (CS), which is one of the most promising biopolymers, has characteristics such as biocompatibility, biodegradability, chemical inertness and low cost (Naghipour and Fakhri, 2016; Sinha et al., 2004). Because of these unique properties, it has been widely used in a number of applications including drug delivery systems, biosensors, wastewater treatment, and food packaging (Bernkop-Schnürch and Dünnhaupt, 2012; Crini, 2006; Puttipipatkhachorn et al., 2001; Tsai et al., 2007). Additionally, CS has abundant -NH₂ and -OH chelating functional groups on its surface, which can provide strong coordination or affinity for transition metal species, which makes it an ideal support for catalytic systems (Bao et al., 2019; Hajipour and Tavangar-Rizi, 2017; Jadhav et al., 2015). Moreover, CS has a unique ability to form composites, microspheres, membranes, gel beads, fibers, and blends through incorporation of natural or synthetic valuable materials to its backbone to improve its physical or mechanical properties (Guibal, 2005; Leonhardt et al., 2010; Zheng et al., 2020). Among these forms, fabrication of micro-structured chitosan beads via crosslinking procedure is one of the most important methods due to it easy preparation (Gotoh et al., 2004). In particular, CS-based beads can provide good mechanical strength, high thermal durability, and low metal leaching, and thus they can serve as promising materials for different catalytic systems. Therefore, various micro-structured CS-based beads can be easily fabricated by incorporating various organic/inorganic valuable materials into CS to be used as catalysts or catalyst supports in different catalytic reactions.

In the recent years, nano-structured materials have attracted much interest in both scientific and technological areas due to their large surface area and outstanding physicochemical characteristics. Therefore, different natural or engineered nanomaterials have been designed for various applications (Das et al., 2013; Talebian et al., 2013). Nanoscaled inorganic metal oxides (CaO, MgO, TiO₂, and ZnO) play a very important function in the science of materials because of their distinctive catalytic, optical, magnetic, electronic, and antimicrobial properties (Ingle et al., 2008; Janaki et al., 2015). Among these oxides, Zinc oxide (ZnO) which is non-toxic, biodegradable, low-cost, and abundant is one of the most useful metal oxide materials (Kalpana and Devi Rajeswari, 2018; Tsay et al., 2010). Thanks to these properties, ZnO nanoparticles have found use in different applications such as semiconductors, electrical/ optical devices, catalysts, and biomedical sciences (Chakrabarti and Dutta, 2004; Gopikrishnan et al., 2010; Khan et al., 2010; Tsay et al., 2010). Taking advantage of such superior properties of CS and ZnO particles, incorporating chitosan with ZnO particles can constitute an important approach to prepare CS-ZnO based microspheres as support material, and different metallic nanoparticles can be immobilized on the prepared support. Catalytic features and reusability of resulting nano-sized metallic catalyst can be tested in various organic reactions.

In light of our interest in the fabrication of sustainable and eco-friendly catalyst systems, we designed a new heterogeneous catalyst in this study by anchoring palladium nanoparticles on a new developed immobilizer agent consisting chitosan and ZnO nanoparticles. Nano-sized structure of Pd@CS-ZnO catalyst was identified fully using different analytical techniques including FT-IR, TEM, EDS, SEM, and XRD. Pd@CS-ZnO was then applied for Heck reaction under phosphine-free conditions, and the tests indicated that it confirmed to be an effective catalyst for Heck reactions by producing good reaction yields in the range of 70–98%. Additionally, the reusability experiments showed that Pd@CS-ZnO nanocatalyst could be reapplied up to six successive runs with no significant decrease in yield (91% yield). Moreover, it was found that the chemical structure of Pd@CS-ZnO was maintained during recycling tests, showing that it has high chemical stability.

2.1. Material and devices

Chitosan, Zn(NO₃)₂. 6H₂O, (NH₄)₂CO₃, PdCl₂, aryl halides, styrene, glyoxal, K₂CO₃, Na₂CO₃, Cs₂CO₃, DMF, toluene, and ethanol (EtOH) were purchased from Sigma Aldrich Chemical Co. FT-IR spectra of CS-ZnO and Pd@CS-ZnO nanocatalyst were obtained by a Perkin Elmer Spectrum 100 F T-IR spectrophotometer. FE-SEM/EDS images of ZnO nanoparticles, CS-ZnO, and Pd@CS-ZnO nanocatalyst were recorded using a QUANTA-FEG 250ESEM/EDAX-Metek. XRD spectra of ZnO nanoparticles, CS-ZnO, and Pd@CS-ZnO nanocatalyst were obtained by using a Rigaku smart lab system. TEM images of ZnO nanoparticles and Pd@CS-ZnO nanocatalyst were acquired with Zeiss Sigma 300.

2.2. Synthesis of ZnO nanoparticles

5.94 g of Zn(NO₃)₂. 6H₂O and 3.61 g of (NH₄)₂CO₃ were dissolved in 20 mL of water and denoted as solution A and solution B, respectively. Then, solution A was slowly dropped into solution B, and the resulting mixture was stirred at room temperature for 3 h to obtain ZnO precursors. The precipitates were collected from the reaction media with filtration, washed with water and ethanol, and dried at 100°C for 6h. Finally, the dried ZnO precursors were calcinated at 550°C for 4 h to form ZnO nanoparticles.

2.3. Preparation of CS-ZnO beads

0.8 g of ZnO nanoparticles was added into 100 mL of chitosan solution (2% w:w, dissolved in acetic acid solution) and stirred at room temperature for 2h. Then, the solution was mixed by ultrasonic bath for 30 min to make a good homogenous mixture. Subsequently, this homogenous mixture was dropped into alkaline solution which consisted of water (60mL)-methanol (40 mL)-NaOH (12g) to form gelatinous beads. The gelatinous beads were cross-linked with glyoxal in ethanol solution at 60^⸰C for 5h. Finally, CS-ZnO beads were formed by cross-linking gelatinous beads with glyoxal in ethanol solution at 60°C for 5h.

2.4. Synthesis of Pd@CS-ZnO nanocatalyst

Glyoxal cross-linked CS-ZnO beads (0.5 g) and PdCl₂ (0.1g) were stirred at 70^⸰C in ethanol (25 mL) for 4 h. After the reaction, it was observed that the color of solution was turned dark. Finally, Pd@CS-ZnO was collected by filtration, rinsed with ethanol, and dried.

2.5. General protocol for Heck coupling reactions

A mixture of Pd@CS-ZnO nanocatalyst (30 mg), aryl halides (1.0 mmol), K₂CO₃ (2.0 mmol), styrene (1.5 mmol), and toluene (3 mL) was heated at 120 ^oC for 6 h. Upon the completion of Heck reaction which was followed by TLC, Pd@CS-ZnO was retrieved from the reaction media by filtration, and the mixture was extracted with CH₂Cl₂:water. Organic phase was dried on MgSO4, and Heck products were obtained with column-chromatography. All synthesized Heck products were known compounds, and their structure were illuminated by ¹H NMR and ¹³C NMR analyses.

3.1. Pd@CS-ZnO nanocatalyst characterization

FT-IR spectra of CS-ZnO (a) and Pd@CS-ZnO nanocatalyst (b) are shown in Fig. 1. The spectrum of CS-ZnO exhibits some important peaks at 3259, 2913 − 2881, 1549, 1374, and 1020cm^− 1 corresponding to N–H/O–H stretching, C-H stretching, amide II band stretching, C–N stretching (Amide III), and C-O-C stretching, respectively (Kamel et al., 2017). The stretching of imine bonds (-C = N) which formed among CS, ZnO nanoparticles, and glyoxal is observed at 1646 cm^− 1, confirming the formation of CS-ZnO beads. The characteristic Zn-O stretching peaks appear at 571 and 418 cm^− 1 (Wasly et al., 2018). However, we could not detect Zn-O stretching because of the range of ATR/FT-IR. Thus, the presence of ZnO nanoparticles in CS-ZnO or Pd@CS-ZnO nanocatalyst was confirmed by TEM, XRD, EDS, and FE-SEM analyses. After the immobilization of Pd NPs onto the surface of CS-ZnO, it was observed that the chemical structure of Pd@CS-ZnO did not change significantly compared to its support, except the shifts of imine vibration (1637 cm^− 1) due to the strong interaction of Pd NPs.

Crystal structure and purity of the prepared ZnO (a), CS-ZnO (b), and Pd@CS-ZnO nanocatalyst (c) were studied using XRD (Fig. 2). XRD pattern of ZnO nanoparticles show specific peaks at diffraction angles 2θ = 31.89°, 34.54°, 36.38°, 47.62°, 56.68°, 62.91°, 66.40°, 68.03°, and 68.13°. These peaks correspond to (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2), and (2 0 1) planes of hexagonal zincite phase of ZnO particles, confirming that it was synthesized with high purity (Nath et al., 2018; Rana et al., 2014). The spectrum of CS-ZnO indicate that the peaks of ZnO remain unchanged, and a new diffraction peak appears at 19.84° which belongs to chitosan. XRD spectrum of Pd@CS-ZnO nanocatalyst displays four-diffraction peaks at 40.16°, 46.65°, 68.10°, and 82.05° along with the peaks of chitosan and ZnO nanoparticles. These peaks are due to face-centered cubic Pd (111), (200), (220), and (311) phases (Dusane et al., 2021; Tang et al., 2021), affirming that palladium nanoparticles were successfully immobilized on the surface of CS-ZnO.

Surface properties of ZnO, CS-ZnO, and Pd@CS-ZnO were investigated by FE-SEM analyses. SEM images of ZnO nanoparticles (Fig. 3a-e) indicate that they are predominantly spherical in shape and mostly aggregated into particles. After the crosslinking of chitosan with ZnO nanoparticles, FE-SEM results revealed that ZnO nanoparticles are dispersed on the surface of CS which is flat (Fig. 3f-j). Additionally, it can be clearly seen from the images that CS-ZnO and Pd@CS-ZnO nanocatalyst were prepared as microspheres (Fig. 3g and l). With the immobilization of palladium nanoparticles on the prepared support, it was found that surface of CS-ZnO was covered with particles (Fig. 3m-o). For further characterization, the elemental distributions on the surface of ZnO, CS-ZnO, and Pd@CS-ZnO nanocatalyst were investigated by EDS. As seen in Fig. 4a, the existence of Zn and O elements confirm the synthesis of ZnO nanoparticles. Figure 4b clearly indicates the presence of C, N, Zn, and O species on the surface of CS-ZnO. While Zn and O peaks exist due to ZnO nanoparticles, the presence of C and N peaks can be explained with chitosan. EDS spectrum Pd@CS-ZnO nanocatalyst shows that it is formed from C, N, Zn, O, and Pd elements, and this result confirms the effective stabilization of Pd NPs on its support (Fig. 4c).

The morphologies and sizes of ZnO nanoparticles and Pd@CS-ZnO were examined by TEM, and their micrographs are depicted in Fig. 5. As seen from TEM micrographs, ZnO nanoparticles were slightly agglomerated and formed as partially spherical in shape. Figure 5c-3 represents TEM images of Pd@CS-ZnO nanocatalyst, and it can be concluded that the black colored particles with larger particle size are due to ZnO. Additionally, the small spherical dark dots represent Pd NPs, and it can be observed that they are homogenously dispersed on the support. Moreover, their average dimension is 8 nm (Fig. 6).

3.2. Catalytic behavior of Pd@CS-ZnO nanocatalyst in Heck coupling reactions

Following the detailed structural/morphological characterization of Pd@CS-ZnO nanocatalyst, its efficiency was assessed towards phosphine-free Heck coupling of aryl halides. Initially, the coupling reaction between 1-bromo-4-nitrobenzene and styrene was chosen as model reagents to investigate optimal experimental parameters such as solvent, base system, time, and amount of Pd@CS-ZnO nanocatalyst (Fig. 7). The model coupling reaction was assessed by using K₂CO₃, KOH, Na₂CO₃, and Cs₂CO₃ as the base. Although the corresponding Heck product was obtained with good yields by using Cs₂CO₃ and Na₂CO₃ as the base, the highest yield was reached with K₂CO₃ which was selected as the appropriate base system for further tests. Varieties of solvents such as DMF, toluene, and EtOH and were evaluated, and DMF was found to be the most favorable medium. Different catalyst dosages (5mg, 10mg, 20 mg, 30mg and 35 mg) were surveyed in the model experiment, and the most appropriate catalyst dosage was determined to be 30mg. Various reaction times were screened, and the results displayed that 6 h was the best choice for further catalytic tests. Based on these results, the optimal experimental parameters for Pd@CS-ZnO catalyzed Heck reactions are determined to be toluene as solvent, 30 mg as catalyst dosage, DMF as solvent, K₂CO₃ as the base, and 6h as reaction time.

Having determined the optimal reaction conditions, the applicability of Pd@CS-ZnO nanocatalyst was investigated against Heck coupling reactions of different aryl halides, and the results are presented in Table 1. Entries 1–5 display the coupling of aryl iodides, and all reactions were coupled with excellent reaction yields by Pd@CS-ZnO nanocatalyst (> 90%). Heck reaction of 4-Iodoanisole resulted in 96% yield. 4-Iodotoluene and 3-iodotoluene were successfully converted into the corresponded products with 93 and 90% yields, respectively. As seen in Table 1, Pd@CS-ZnO nanocatalyst also worked well in the coupling reactions of aryl bromides. For example, 4-bromobenzonitrile was reacted smoothly by Pd@CS-ZnO nanocatalyst, and the target product was reached with 97% yield. Desired Heck product was formed with 92% yield with 1-bromo-3-nitrobenzene as substrate. The reactions of bromobenzene, 4-bromoanisole, and 1-bromonaphthalene were afforded with high efficiencies (90%, 94%, and 91%, respectively). The catalytic behavior of Pd@CS-ZnO was also investigated against coupling reactions of some aryl chlorides, and the desired products were acquired with moderate to good yields (Table 1, entry 14–16). Additionally, the model Heck reaction was carried out in the absence of Pd@CS-ZnO nanocatalyst under optimal experimental parameters, and it was observed that the reaction failed. This control experiment confirmed that Pd@CS-ZnO has favorable catalytic activity for Heck coupling reaction. Furthermore, the comparison of catalytic performance of Pd@CS-ZnO with other reported catalysts in the literature for Heck reaction of 4-bromotoluene is illustrated in Table 2. It may be seen that Pd@CS-ZnO provides better reaction yield with shorter reaction time than those of other catalysts.

Beside high catalytic role, recyclability of an ideal catalyst is another particularly important parameter which makes it industrially/academically valuable. Therefore, we investigated the reusability of Pd@CS-ZnO in catalyzing the selected model reagents. Upon the completion of the first cycle, Pd@CS-ZnO nanocatalyst was easily separated with filtration from the reaction mixture due to its microspheres and heterogeneous form, rinsed with ethanol, dried, and reapplied in the next run. The same regeneration process was used for each run. The tests indicate that Pd@CS-ZnO could be re-applicable up to six consecutive cycles by producing 91% yield. Additionally, TEM and FE-SEM analyses were done after the 6th cycle of Pd@CS-ZnO and are shown in Fig. 8. These analyses revealed that the structure and morphology of Pd@CS-ZnO nanocatalyst persisted unchanged after the recycling tests. Based on the evidence above, it may be concluded that Pd@CS-ZnO is a highly stable and robust nanocatalyst.

In conclusion, a novel Pd nanocatalyst supported on the microspheres consisting chitosan and ZnO nanoparticles was developed and characterized with various analytic techniques. Then the developed Pd@CS-ZnO was utilized as a heterogeneous catalyst for Heck coupling reactions. The performed catalytic experiments indicate that Pd@CS-ZnO efficiently catalyzed Heck reactions of aryl halides bearing different groups (such as -CH₃, −OCH₃, −NO₂, and -CN) and styrene by exhibiting wide substrate scope and good functional group tolerance (up to 98%). Due to the spherical form of Pd@CS-ZnO nanocatalyst, it could be effectively recovered from the reaction media and successfully used in the reusability tests, and the yield of desired product was as high as 91% after recycling 6 times. Considering the obtained results, it can be concluded that the prepared Pd@CS-ZnO nanocatalyst can be used not only for Heck coupling reactions but other coupling reactions in future studies, and this catalyst system can be a competitive candidate for different catalytic reactions.

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Table 1 is available in the Supplementary Files section.

Table 2

Comparison of catalytic behavior of Pd@CS-ZnO nanocatalyst with other reported catalysts against Heck reaction of 4-bromotoluene and styrene.
Entry	Catalyst	Time	Yield (%)	Ref.
1	Fe₃O₄@OA–Pd	12h	88	(Rafiee and Kahrizi, 2016)
2	Complex 1	10 h	76	(Muthumari et al., 2015)
3	catalyst 5	12h	83	(Shen et al., 2015)
4	Ni-Co/ZnO	16h	72	(Bankar et al., 2020)
5	complex	9h	82	(Song et al., 2017)
6	cross-linked poly (ITC-HPTPy)-Pd	7h	92	(Targhan et al., 2020)
7	NHC-Pd (II)-Py complex	12h	93	(Li et al., 2021)
8	GO-Fe₃O₄-Cellulose-Pd	7h	90	(Niakan et al., 2021)
9	Cell–OPPh₂-Pd⁰	13h	61	(Du and Li, 2012)
10	Pd@CS-ZnO nanocatalyst	6h	92	Present study

Table1.jpg

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Editor assigned by journal
26 Apr, 2022
First submitted to journal
25 Apr, 2022

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Nanoscaled reusable palladium catalyst supported on chitosan hybrid composite microcapsules reinforced with ZnO nanoparticles for Heck coupling reactions

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Abstract

Figures

1. Introduction

2. Experimental

2.1. Material and devices

2.2. Synthesis of ZnO nanoparticles

2.3. Preparation of CS-ZnO beads

2.4. Synthesis of Pd@CS-ZnO nanocatalyst

2.5. General protocol for Heck coupling reactions

3. Results And Discussions

3.1. Pd@CS-ZnO nanocatalyst characterization

3.2. Catalytic behavior of Pd@CS-ZnO nanocatalyst in Heck coupling reactions

4. Conclusion

References

Tables

Supplementary Files

Status:

Version 1