Elsevier

Journal of Catalysis

Volume 382, February 2020, Pages 305-319
Journal of Catalysis

Design and synthesis of a versatile cooperative catalytic aerobic oxidation system with co-immobilization of palladium nanoparticles and laccase into the cavities of MCF

https://doi.org/10.1016/j.jcat.2019.12.023Get rights and content

Highlights

  • Discovery of a novel reusable cooperative catalytic aerobic oxidation system.

  • Co-immobilization of the oxygen-activating catalyst and oxidizing catalyst onto same support.

  • The biohybrid catalyst was applied in aerobic dehydrogenation of Csingle bondO, Csingle bondC and Csingle bondN bonds.

  • The methods conform to several of the guiding principles of green chemistry.

Abstract

We have designed a versatile reusable cooperative catalyst oxidation system, consisting of palladium nanoparticles and laccase with unprecedented reactivity. This biohybrid catalyst was synthesized by the stepwise immobilization of laccase as an enzyme and Pd as a nanometallic component into the same cavity of siliceous mesocellular foams (MCF). MCF and nanobiohybrid catalyst were characterized by BET, SAXS, SEM, EDX elemental mapping, ICP-OES, TEM, TGA, FT-IR, and XPS techniques and the stepwise immobilization of laccase enzyme and Pd onto MCF was evaluated through several compelling electrochemical studies. The present catalytic system exhibits high activity toward (i) aerobic oxidation of alcohols to the corresponding carbonyl compounds, (ii) aerobic oxidation of cyclohexanol and cyclohexanone to phenol and (iii) aerobic dehydrogenation of important N-heteocyclic compounds (tetrahydro quinazolines, quinazolonones, pyrazolines and 1,4-diydropyridines) in the presence of catalytic amount of hydroquinone (HQ) as mediator in phosphate buffer (0.1 M, pH 4.5, 4 mL)/THF (4%, 1 mL) as solvent under mild conditions. The immobilization of both oxygen-activating catalyst (laccase) and oxidizing catalyst (Pd) onto the same support makes the present catalyst system superior to other currently available heterogeneous palladium based catalytic aerobic oxidation systems.

Graphical abstract

A new class of heterogeneous cooperative catalytic system is reported for the aerobic oxidative dehydrogenation of organic compounds.

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Introduction

The selective oxidation of organic compounds is an easy way to transform simple precursors into valuable products. Among the various reactions of organic chemistry, oxidation reactions have always been a challenge and have been discussed. Since most of these reactions have low selectivity and by-products are seen when oxidizing stoichiometric values are used. In this regard, the development of aerobic oxidation in a liquid phase with high chemoselectivity, regioselectivity and stereoselectivity can have a great impact on the synthesis of drugs, agrochemicals, and fine chemicals [1]. Also, the industry's need for environmentally friendly processes has increased demand for eco-friendly oxidants today, with H2O2 and O2 meeting this need [2]. Aerobic oxidation in the presence of palladium dates back to the late 1950s when Wacker process was discovered. In the decades following the discovery of the Wacker process, these reactions have been considered and developed often in the direction of oxidative alkene functionalization, but over the past two decades, the oxidation reactions in the presence of homogeneous palladium catalysts have led to many other reactions, including oxidation of alcohols, dehydrogenation of C-C bonds and oxidative C-H functionalization’s [1]. Although these reactions proceed in good to high yields, in most of aerobic oxidation reactions catalyzed by palladium, organic solvents, high pressure and/or temperature [3], [3]a), [3]b), expensive ligands [1] and strongly basic pH are required. As well, because of the unfavorable electron transfer between Pd0 and O2, palladium-catalyzed oxidation reactions with direct reoxidation of Pd0 by molecular oxygen sometimes fail. Thus, the use of Electron Transfers Mediators (ETMs) for many Pd-catalyzed aerobic oxidation reactions are required to obtain high selectivity and high efficiency [2], [4].

Recently, cooperative catalyst systems have been developed as highly promising sustainable alternatives to traditional catalysts. In these catalysts, two or more catalytic centers cooperate to reduce the energy of chemical transformations. In nature, such systems are abundantly seen in metalloenzymes that use a metal and an organic cofactor [5], [5]a), [5]b). Several research groups designed bioinspired oxidation cooperative catalytic systems to carry out reactions under mild conditions [4], [6], [6]a), [6]b), [6]c), [6]d), [6]e), [6]f), [6]g), [6]h). Although these protocols represent considerable advances, there are still other drawbacks, such as homogeneity of the catalyst systems, and the use of transition metal complexes and expensive ligands (Scheme 1A). Therefore, the development of intramolecular heterogeneous cooperative catalytic systems with simple separation and recycling in the ligand-free and benzoquinone-free aerobic oxidation of organic compounds under mild conditions is highly desirable.

Recently, several one-pot tandem catalytic systems have been developed, which combine the reactivity of transition metal catalysis and the selectivity of enzymatic catalysis [7]. Despite these developments, there has been no report on the design of heterogeneous cooperative catalyst systems that make use of both biocatalysis and transition metals being employed in the oxidation of organic compounds.

Laccases, multi-copper-containing oxidoreductase enzymes, are highly attractive biocatalysts in modern organic synthesis. They catalyze the oxidation of various compounds such as benzenediols, aminophenols, polyphenols, polyamines, and lignin-related molecules using oxygen as an electron acceptor and producing water as by-product. The most efficient strategy to extend the range of laccase substrates is the simultaneous use of the enzyme and redox mediators [8]a), [8]b), [8]c), [8]d), [8]e), [8]f), [8]g), [8]h).

Recently, Bäckvall and co-workers reported Pd@MCF as an efficient nanocatalyst for aerobic oxidation of alcohols [9] and bifunctional biomimetic catalyst in which Pd nanoparticles and lipase are co-immobilized on MCF for dynamic kinetic resolution of an amine [10]. These works and our previously published results on the application of laccase and laccase-mediated catalytic system in organic reactions [11]a), [11]b), [11]c), [11]d), [11]e), [11]f) prompted us to design a heterogenous cooperative catalyst system, consisting of palladium nanoparticles and laccase enzyme for biomimetic oxidation of organic compounds (Scheme 1B). In this work, we used mesocellular foams (MCF) as a support because of features such as simple preparation, large channel size, high surface areas, and the presence of a large number of silanol groups that contribute to high catalyst loading. Also, it is important to keep in mind that we use catalytic amount of hydroquinone [12] instead of stoichiometric amount of benzoquinone, a toxic mediator (Scheme 1B).

Section snippets

Material and instrumentation

All substances, reagents and solvents except N-heterocyclic compounds were bought from the Merck and Aldrich Chemical Companies and used without further purification. The N-heterocyclic compounds were synthesized using previous methods in our research lab [13], [13]a), [13]b), [13]c), [13]d). FT-IR and 1H, 13CNMR spectra were recorded on Thermo Nicolet Nexus 670 and BrukerAvance spectrometers (300 MHz). The physical properties of mesoporous materials were determined from N2

Catalyst preparation

In order to prepare the Pd-Laccase@MCF, firstly palladium nanoparticles were immobilized in aminopropyl-functionalized MCF. Then, further functionalization of the aminopropyl groups that are uncoordinated to Pd was carried out with glutaraldehyde. Finally, laccase was covalently linked to the support by the bond formation between the remaining single bondCHO group of glutaraldehyde and single bondNH2 group situated on the enzyme surface. The synthetic route was depicted in Scheme 6. The Pd-Laccase@MCF was

Conclusions

In conclusion, we have successfully synthesized a heterogeneous reusable artificial metalloenzyme by co-immobilization of palladium nanoparticles and laccase into the cavities of the mesocellular foams. This hybrid catalyst was applied in aerobic oxidative dehydrogenation of Csingle bondO, Csingle bondC and Csingle bondN bonds. The major advantages of these procedures are as follows: (1) this is the first report of Co-immobilization of laccase and palladium for use as a robust and highly efficient heterogeneous cooperative

Declaration of Competing Interest

We declar that we have no competing interest.

Acknowledgements

We gratefully acknowledge financial support of this research by University of Kurdistan and the Iranian National Science Foundation (INSF, Grant Number: 96016233). We are also thankful to Prof. T. Hudlicky, Brock University, for editing the paper.

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