Elsevier

Carbohydrate Polymers

Volume 310, 15 June 2023, 120726
Carbohydrate Polymers

Bimetallic (AuAg, AuPd and AgPd) nanoparticles supported on cellulose-based hydrogel for reusable catalysis

https://doi.org/10.1016/j.carbpol.2023.120726Get rights and content

Abstract

Biopolymer-derived hydrogels with low-cost and sustainable features have been considered as fascinating supported materials for metal nanoparticles. Cellulose, as the most abundant biopolymer, is a renewable raw material to prepare biopolymer-derived hydrogels for catalysis. Here, a cellulose-based hydrogel is designed to load bimetallic (AuAg, AuPd and AgPd) nanoparticles. 4-Nitrophenol reduction and Suzuki–Miyaura coupling reactions are selected to evaluate and compare the catalytic performance of the resulting bimetallic nanoparticle-loaded cellulose-based composite hydrogels. The bimetallic nanocomposite hydrogels are easy to be recycled over 10 times during the catalytic experiments and possess good applicability and generality for various substrates. The catalytic activity of bimetallic nanocomposite hydrogels was compared with recent literatures. In addition, the possible catalytic mechanism is also proposed. This work is expected to give a new insight for designing and preparing bimetallic nanoparticle-based cellulose hydrogels and proves its applicability and prospect in the catalytic field.

Introduction

Metal nanoparticles have received growing interest in the fields of catalysis, electronics, biosensors, optics, nanomedicine and bioimaging (Baran, 2018; Chatterjee, Lou, Liang, & Yang, 2022; Sankar et al., 2020; Wang & Astruc, 2020). Especially, metal nanoparticles have the advantage to serve as catalytically active nanomaterials owing to their good catalytic activity and selectivity (Baran, 2019; Baran & Mentes, 2016; Du, Sheng, Astruc, & Zhu, 2020; Favier, Pla, & Gomez, 2020; Ji et al., 2023; Liu et al., 2016; Liu, Liu, Astruc, & Gu, 2019; Liu, Liu, Chen, & Fu, 2021a). It is worth noting that bimetallic nanoparticles have been considered as superior nanocatalysts due to the potential synergistic effect of two different metal centers (Harika, Sadhanala, Perelshtein, & Gedanken, 2020; Rangasamy, Lakshmi, & Selvaraj, 2021; Sahoo, Mansingh, Subudhi, Mohapatra, & Parida, 2019; Silva, de Oliveira, Pal, & Domingos, 2019; Wei et al., 2022). The electronic effect of bimetallic nanoparticles can be changed by the interaction of two different centers, and the alloy effect can enhance catalytic activity via altering the metal compositions and charge distribution (Hakkeem et al., 2022; Loza, Heggen, & Epple, 2020; Niakan and Masteri-Farahani, 2022a, Niakan and Masteri-Farahani, 2022b; Yang et al., 2016). In recent years, great efforts have been made for the design and preparation of bimetallic nanoparticle catalysts (Li et al., 2020; Olekszyszen et al., 2020; Shen et al., 2020). Nevertheless, similar to monometallic nanoparticles, bimetallic nanoparticles also have a strong trend to aggregate in the catalytic process due to their high surface energy, leading to the decrease or loss of the catalytic efficiency. Furthermore, bimetallic nanoparticles face the challenges of separation and recovery during catalytic reactions owing to their small sizes.

At present, supported bimetallic nanoparticle catalysts with high dispersion, large surface area and recyclability have become an increasing trend. All kinds of supported materials (such as metal-organic frameworks, polymers, dendrimers, metal oxides, zeolites, porous organic cages, graphene, carbon nanotubes, etc.) are applied to enhance the catalytic efficiency and recyclability of bimetallic nanoparticles (Gao, Lyu, & Yin, 2021; Loza et al., 2020; Wei et al., 2022). Hydrogels that are composed of three-dimensional hydrophilic polymer networks have been considered as a kind of promising supported materials for bimetallic nanoparticle catalysts (Gancheva & Virgilio, 2018; Li et al., 2019; Liu et al., 2021; Liu, Liu, Liu, & Gu, 2021; Liu, Zhao, Liu, Astruc, & Gu, 2020). Hydrogels with easy designability possess unique physical and chemical properties, which are able to prevent the aggregation of bimetallic nanoparticles and enhance their dispersibility (Hao, Gao, Liu, Hu, & Ju, 2020; Ilgin, Ozay, & Ozay, 2019). Hydrogels also offer a suitable microenvironment for catalysis. In addition, bimetallic nanoparticles are easily separated and recycled when being supported on hydrogels. Biopolymers widely exist in various plants and animals, which are highlighted for the preparation of hydrogels because of their renewability, biocompatibility, biodegradability, low toxicity, and so on (Liu, Jamal, Abdiryim, & Liu, 2022; Liu, Liu, Chen, & Fu, 2021b). Biopolymer-based hydrogels have emerged as fascinating supported materials for metal nanoparticle catalysts (Ramirez et al., 2022; Slavik, Kurka, & Smith, 2018; Zhu et al., 2021). Cellulose is the most abundant biopolymer on our planet, which possesses attractive properties, such as biodegradability, renewability, extensive resources, low price, hydrophilicity, etc. (Li, Wu, Moon, Hubbe, & Bortner, 2021; Nasrollahzadeh, Sajjadi, Iravani, & Varma, 2021). Cellulose and its derived materials (including bacterial cellulose, cellulose nanofibrils and cellulose nanocrystals) have been used to prepare functional hydrogels for supporting metal nanoparticles in catalysis (Niakan, Masteri-Farahani, Shekaari, & Karimi, 2021; Xie, Asoh, & Uyama, 2019; Zhang et al., 2020; Zhang, Li, Yu, Su, & Zhang, 2021). For instance, Li’s group used wheat straw cellulose and feather protein to fabricate magnetic hydrogel that served as a carrier for Cu nanoparticles, and the resulting magnetic composite hydrogel was utilized for the catalytic reduction of 2-nitrobenzoic acid to 2-aminobenzoic acid (Su et al., 2019). Ni and co-workers found that cationic nanocellulose–alginate hydrogel supported Pd nanoparticles for degrading methylene blue and catalyzing Suzuki–Miyaura reactions (Wang et al., 2020). Indeed, cellulose-based hydrogels are promising carriers for metal nanoparticle catalysts (Niakan et al., 2021; Xie et al., 2019; Zhang et al., 2020). However, most of studies focus on monometallic nanoparticles (Kamel & Khattab, 2021). The use of cellulose-based hydrogels to support bimetallic nanoparticle catalysts is investigated little.

Hence, we proposed that a cellulose-based hydrogel was designed to support bimetallic nanoparticles for catalysis. On one hand, natural cellulose is the most abundant biopolymer, which is a favorable supporting material for various catalysts. On the other hand, β-cyclodextrin is introduced into the hydrogel, which would create a unique advantage of enhancing catalytic efficiency and activity (Souza et al., 2023). In addition, hydrogels make a contribution to the exchange and transportation of substrates during catalysis, and also prevent the aggregation of bimetallic nanoparticles. Thus, it is hypothesized that the cellulose-based hydrogel gives a cheap and simple way to support bimetallic nanoparticles and improve their catalytic efficiency, activity, as well as recyclability. In this study, we describe a facile strategy to prepare bimetallic (AuAg, AuPd and AgPd) nanoparticle-loaded cellulose-based hydrogels, whose catalytic activity was evaluated and compared in 4-nitrophenol reduction and Suzuki–Miyaura reactions (Fig. 1). The applicability and recyclability of composite hydrogels were also investigated. This study gives a simple method to design biomass-based hydrogels for supporting bimetallic nanoparticles in catalysis.

Section snippets

Materials

NaBH4, NaOH, KCl, HAuCl4, PdCl2, AgNO3, K2CO3, epichlorohydrin, cellulose (>95 %, DP ∼ 750), β-cyclodextrin, urea, 4-nitrophenol and other chemical products were obtained from Energy Chemical.

Instruments

TEM was employed to characterize the sizes and morphologies of bimetallic nanoparticles. TEM images were obtained from a JEOL JEM 2100F at 200 kV. The morphology of the freeze-dried hydrogels was analyzed via SEM (JSM-7500F). Bruker AV II-400 MHz (1H NMR) was applied to determine the chemical structures of

Results and discussion

To prepare bimetallic nanoparticles, tannic acid was selected as a stabilizer and NaBH4 was used as a reductant. Tannic acid (a kind of polyphenol) features abundant phenolic hydroxyl groups, which is a good stabilizer for metal nanoparticles (Xu, Neoh, & Kang, 2018). Three kinds of metal salt precursors (HAuCl4, AgNO3 and PdCl2) were combined in pairs to synthesize bimetallic (AuAg, AuPd and AgPd) nanoparticles. The morphologies and size distributions of bimetallic (AuAg, AuPd and AgPd)

Conclusions

In summary, a series of bimetallic alloy (AuAg, AuPd and AgPd) nanoparticles were synthesized and loaded into cellulose-based hydrogel for catalysis. EDS mapping analysis confirmed that these bimetallic nanoparticles were in the form of alloys. TEM and XRD measurements showed that the size of these bimetallic nanoparticles was smaller than 10 nm. XPS results demonstrated that all metal species exhibited zero valent state in composite hydrogels. The catalytic performance of bimetallic

CRediT authorship contribution statement

Xiong Liu: Conceptualization, Methodology, Formal analysis, Validation, Investigation, Data curation, Writing – original draft, Supervision. Fangfei Liu: Conceptualization, Data curation, Writing – review & editing, Supervision.

Declaration of competing interest

There are no conflicts to declare.

Acknowledgements

The helpful discussion with Dr. Jinwei Zhang (College of Biomass Science and Engineering, Sichuan University) is gratefully acknowledged.

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