Elsevier

Carbohydrate Polymers

Volume 295, 1 November 2022, 119765
Carbohydrate Polymers

Comprehensive preparation and catalytic activities of Co/TEMPO-cellulose nanocomposites: A promising green catalyst

https://doi.org/10.1016/j.carbpol.2022.119765Get rights and content

Highlights

  • “Cobalt(0)/TEMPO oxidized cellulose” heterogeneous catalyst was prepared.

  • The characterizations have shown nanometric size and good dispersion of Co0 particles.

  • A screening effect of TEMP-Cell, which prevent Cosingle bondB components formation, was highlighted.

  • High catalytic performances have been shown for the reduction of nitro to amine groups.

  • The catalyst retains catalytic activity even after 11 cycles without significant loss of its catalytic activity.

Abstract

A green method for the production of cobalt/(TEMPO-Cellulose) aerogel heterogeneous catalyst was developed. The preparation implied the reduction of CoSO4 by NaBH4 in TEMPO-Cellulose water dispersion in ambient conditions. The formation of Cobalt nanoparticles is due to the presence of “TEMPO-Cell” which screens the Co2+ ions and prevents their combination with boron. SEM, XRD, EDX, FTIR, TEM and XPS were used to analyze the structure of the catalyst and showed that metallic cobalt particles have nanometric size and are well dispersed in the aerogel. The catalyst showed excellent activity for model reactions such as the reduction of 4-nitroaniline, 4-nitrophenol and 2-nitrophenol in water, in the presence of NaBH4. The reaction kinetic was studied by UV–visible spectroscopy, which showed that this catalyst is efficient to achieve 100 % reduction with high reaction rate and turnover frequency. The aerogel catalyst was reused more than ten times without significant loss of its catalytic activity.

Introduction

The development of green, economic and highly active catalysts is at the heart of the research in catalysis. Heterogeneous catalysis is one of the most promising technology used in chemical reactions and environmental remediation (Munnik et al., 2015; A. Mondal et al., 2017). Metal and metal oxide nanoparticles (NPs) are emerging to be promising candidates due to their excellent catalytic activities for different organic chemical reactions (Choo et al., 2015). However, their applications are limited because of their self-agglomeration in solution, which reduces their catalytic performances. In addition, they are difficult to recover from the reaction medium. This is a supplementary challenge that limits their application in heterogeneous catalysis in non-supported structure.(Cao et al., 2002; García-Álvarez et al., 2013; M. Hu et al., 2012; Kaushik & Moores, 2016; P. Mondal et al., 2013).

The effective approach to overcome these problems is the immobilization of metal nanoparticles on different materials (Kaushik & Moores, 2016). In fact, supported heterogeneous catalysts is one of the major focuses of research in catalysis. The supports can be Metal oxides, Silica, Zeolites, Fibers, Ceramic materials, Pillared clays, and polymers notably (Cao et al., 2002; Choo et al., 2015; Eisa et al., 2018; García-Álvarez et al., 2013; M. Hu et al., 2012; Kaushik & Moores, 2016; A. Mondal et al., 2017; P. Mondal et al., 2013; Munnik et al., 2015). More recently, many research investigations have been directed towards the exploration of sustainable bio resources to be used as support of metallic particles catalysts. Being the most abundant, renewable, ecofriendly, biocompatible and biodegradable natural polymer, cellulose is widely used as a biomaterial support for catalytic systems due to its properties such as high specific area and strength promising good metallic nanoparticles integration (Gopiraman et al., 2018; Gu et al., 2018; Jeremic et al., 2019; Nasrollahzadeh et al., 2020; Q. Zhang et al., 2020).

On the other hand, important research attention has been paid towards the utilization of the first row transition metals, especially Ni, Co and Fe, as catalyst in organic synthesis (A. Mondal et al., 2017; Rajesh et al., 2018; Singh & Spiccia, 2013). These metals represent advantageous alternative in organic synthesis compared to their equivalent noble metals of the second and third rows, which are less abundant and more expensive. More specifically, the catalytic performances of cobalt ions (either Co2+ or Co3+) as well as the less frequently used Co0, have been widely and extensively studied for, oxidations, Csingle bondH amination, Allylation, Alkenylation, etc. reactions (Chirila & Whiteoak, 2017; Dey & Dhal, 2019; P. Hu & Long, 2016; Jiang et al., 2017; Kommagalla & Chatani, 2017; Y. Park et al., 2017; Prakash et al., 2018; Sakata et al., 2017; Sun et al., 2014). Apart from the organic synthesis, various cobalt oxides based supported catalysts have been explored and extensively studied in high temperatures process, such as in catalytic decomposition of methane (CDM) for the production carbon nanomaterials, for example. This enabled to reduce the CDM temperature to the range of 450–800 °C (Majewska & Michalkiewicz, 2013; Pudukudy & Yaakob, 2015). On the other hand, this family of catalysts has been recently tested for water splitting and oxygen evolution or generation (Dou et al., 2016; Y. C. Liu et al., 2014; J. Wang et al., 2017; Yang et al., 2016; Zhu et al., 2017).

Regarding the preparation of cobalt oxides (CoxOy), it is worthy to emphasis that these different oxides are often synthesized by high temperature processes (T > 400 °C) involving oxidative/calcination of Co(OH)2, formerly prepared by alkaline treatment of Co2+ salts (CoCl2, Co(NO3)2 or CoSO4, etc.). Other investigations have been conducted on the preparation of cobalt oxides by heating CO3Co in vacuum or in CO2, or by reduction of Co2O3 by NH3 or of Co3O4, by carbon. Vice versa, Co3O4 can be obtained by the oxidation of CoO (Dou et al., 2016; Y. C. Liu et al., 2014; Majewska & Michalkiewicz, 2013; Pudukudy & Yaakob, 2015; J. Wang et al., 2017; Yang et al., 2016; Zhu et al., 2017). On the other hand the preparation of metallic Co0 from Co2+ ions based salts, such as CoSO4, can be achieved at room temperature by reduction reaction in presence of reducing agent such as hydrazine (Zhao et al., 2019), sodium borohydrid (D. Wang et al., 2019), etc.

In this work, we developed a novel, simple and eco-friendly biohybrid aerogels based on cellulose derivative (TEMPO oxidized cellulose) as support and cobalt metallic (Co0) particles as catalyst. The preparation of this biohybrid catalyst passes through the dispersion of Co2+ ion salt (CoSO4) in the TEMPO-cellulose aerogel and its reduction in mild condition using NaBH4 as reducing agent. To the best of the authors knowledge, few studies are dedicated to the catalytic properties of cobalt supported on cellulose and the use of TEMPO-Cellulose as catalyst support for metal nanoparticles has never been reported. In comparison to TEMPO-NFC, which production is energy demanding due to the mechanical defibrillation, the use of TEMPO-cellulose is a simple and novel way to endow cellulose with carboxylic groups that enhance the screen of Co2+ cation to permit its reduction to Co0 in presence of borate anions. Compared to other nanocelluloses, this TEMPO-cellulose can be effective to produce stable, efficient Co0 supported catalyst. The morphology of this composite aerogel is characterized and its catalytic performances for the reduction of nitro-functionalized molecules to amino-functionalized ones were tested.

Section snippets

Chemicals and starting materials

The rachis of date palm tree (Phoenix dactylifera L.) was used in this work as the original source of cellulose. Cellulose was extracted from the rachis following the procedure well described in our previous work (A. Bendahou et al., 2009).

TEMPO (1-oxo-2,2,6,6-tétraméthylpipyridine1-oxyle), sodium bromide, sodium hypochlorite solution (15 %), HCl, NaOH, Cobalt (II) sulphate heptahydrate [CoSO4.7H2O], Sodium borohydride NaBH4, 4-nitroaniline (4-NA), 4-nitrophenol (4-NP) and 2-nitrophenol (2-NP)

Aerogels characterization

The morphology of Co/TEMPO-Cell was characterized by mean of scanning electron microscopy (SEM-EDX), FTIR spectroscopy, X-ray diffraction (XRD) and XPS.

Fig. 1 shows the SEM pictures of pure TEMPO-Cell aerogel taken as reference and those of the Co/TEMPO-Cell aerogel composite with different magnifications. The optical photos of the aerogels are also presented to show their macroscopic aspect (Fig. 1-A and B). The SEM micrograph of cross section of the aerogel made of pure TEMPO-Cell aerogel

Conclusion

In this study, Co/TEMPO-Cellulose aerogel composite was prepared by simple in situ reduction of Co2+ (CoSO4) in water dispersion of TEMPO oxidized-Cellulose using sodium borohydride NaBH4 as reducing agent. The in situ NaBH4 reduction process in the presence of TEMPO oxidized-cellulose very selectively orients the reduction reaction for the metallic Co0 nanoparticles. With this reduction process, the formation of CoB and Co2B is not observed, and Co metal nanoparticles were formed exclusively.

CRediT authorship contribution statement

NE: Investigations, Formal analysis, original draft writing.

LB: Conceptualization, Supervision HK, LB, NM and PZ gratefully acknowledge the French Ministry of Foreign Affairs for funding NE stay in Lille through the Toubkal PHC program. Chevreul Institute (FR 2638), Ministère de l'Enseignement Supérieur de la Recherche et de l'Innovation, Région Hauts de France and CNRS are also acknowledged for supporting and funding partially this work.

PZ: Funding acquisition, Supervision, review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Hamid Kaddami, Larbi Belachemi, Nicolas Merle and Philippe Zinck gratefully acknowledge the French Ministry of Foreign Affairs for funding Nouaamane El Idrissi stay in Lille through the Toubkal PHC program. Chevreul Institute (FR 2638), Ministère de l'Enseignement Supérieur de la Recherche et de l'Innovation, Région Hauts de France and CNRS are also acknowledged for supporting and funding partially this work.

References (72)

  • P. Finocchiaro et al.

    Synthesis and characterization of novel polyamides from new aromatic phosphonate diamine monomer

    European Polymer Journal

    (2008)
  • M. Goswami et al.

    Synthesis of cellulose impregnated copper nanoparticles as an efficient heterogeneous catalyst for C-N coupling reactions under mild conditions

    Carbohydrate Polymers

    (2018)
  • J. Gu et al.

    Reagentless preparation of shape memory cellulose nanofibril aerogels decorated with pd nanoparticles and their application in dye discoloration

    Applied Catalysis B: Environmental

    (2018)
  • S. Gupta et al.

    Cobalt-boride: An efficient and robust electrocatalyst for hydrogen evolution reaction

    Journal of Power Sources

    (2015)
  • Y. He et al.

    Carboxymethyl cellulose/cellulose nanocrystals immobilized silver nanoparticles as an effective coating to improve barrier and antibacterial properties of paper for food packaging applications

    Carbohydrate Polymers

    (2021)
  • P. Hu et al.

    Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications

    Applied Catalysis B: Environmental

    (2016)
  • S. Jeremic et al.

    Production of bacterial nanocellulose (BNC) and its application as a solid support in transition metal catalysed cross-coupling reactions

    International Journal of Biological Macromolecules

    (2019)
  • X. Jiang et al.

    Cobalt(III)-catalyzed fast and solvent-free C-H allylation of indoles using mechanochemistry

    Journal of Organic Chemistry

    (2017)
  • Y. Kommagalla et al.

    Cobalt(II)-catalyzed CH functionalization using an N, N′-bidentate directing group

    Coordination Chemistry Reviews

    (2017)
  • K. Kuroda et al.

    Reduction of 4-nitrophenol to 4-aminophenol over Au nanoparticles deposited on PMMA

    Journal of Molecular Catalysis A: Chemical

    (2009)
  • J. Liu et al.

    A thermosensitive hydrogel carrier for nickel nanoparticles

    Colloids and Interface Science Communications

    (2015)
  • Y.C. Liu et al.

    Conversion of electrodeposited Co(OH)2 to CoOOH and Co3O4, and comparison of their catalytic activity for the oxygen evolution reaction

    Electrochimica Acta

    (2014)
  • J. Lu et al.

    Cobalt precipitation by reduction with sodium borohydride

    Hydrometallurgy

    (1997)
  • D. Musino et al.

    Hydroxyl groups on cellulose nanocrystal surfaces form nucleation points for silver nanoparticles of varying shapes and sizes

    Journal of Colloid and Interface Science

    (2021)
  • B. Naik et al.

    Short communication

    Catalysis Communications

    (2011)
  • M. Nasrollahzadeh et al.

    Recent progresses in the application of cellulose, starch, alginate, gum, pectin, chitin and chitosan based (nano)catalysts in sustainable and selective oxidation reactions: A review

    Carbohydrate Polymers

    (2020)
  • H. Park et al.

    Skin irritation and sensitization potential of oxidative hair dye substances evaluated with in vitro, in chemico and in silico test methods

    Food and Chemical Toxicology

    (2018)
  • M. Pudukudy et al.

    Methane decomposition over Ni, Co and Fe based monometallic catalysts supported on sol gel derived SiO2 microflakes

    Chemical Engineering Journal

    (2015)
  • N. Rajesh et al.

    Recent advances in C(sp3)H bond carbonylation by first row transition metals

    Tetrahedron Letters

    (2018)
  • M.Z. Rong et al.

    Surface modification of magnetic metal nanoparticles through irradiation graft polymerization

    Applied Surface Science

    (2002)
  • N. Sahiner

    Soft and flexible hydrogel templates of different sizes and various functionalities for metal nanoparticle preparation and their use in catalysis

    Progress in Polymer Science

    (2013)
  • N. Sahiner et al.

    New catalytic route: Hydrogels as templates and reactors for in situ Ni nanoparticle synthesis and usage in the reduction of 2- and 4-nitrophenols

    Applied Catalysis A: General

    (2010)
  • K. Sakata et al.

    Cp∗CoIII-catalyzed C-H alkenylation/annulation reactions of indoles with alkynes: A DFT study

    Journal of Organic Chemistry

    (2017)
  • A. Sbiai et al.

    TEMPO-mediated oxidation of lignocellulosic fibers from date palm leaves

    Carbohydrate Polymers

    (2011)
  • H. Sehaqui et al.

    High-porosity aerogels of high specific surface area prepared from nanofibrillated cellulose (NFC)

    Composites Science and Technology

    (2011)
  • A. Singh et al.

    Water oxidation catalysts based on abundant 1st row transition metals

    Coordination Chemistry Reviews

    (2013)
  • Cited by (4)

    View full text