Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions
The (eco)design and synthesis of durable heterogeneous catalysts starting from renewable sources derived from biomass waste represents an important step for reducing environmental impacts of organic transformations. Herein, we report the efficient loading of Pd(II) ions on an eco-safe cellulose-base...
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MDPI AG
2022-12-01
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| Online Access: | https://www.mdpi.com/2310-2861/8/12/789 |
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| author | Laura Riva Gloria Nicastro Mingchong Liu Chiara Battocchio Carlo Punta Alessandro Sacchetti |
| author_facet | Laura Riva Gloria Nicastro Mingchong Liu Chiara Battocchio Carlo Punta Alessandro Sacchetti |
| author_sort | Laura Riva |
| collection | DOAJ |
| description | The (eco)design and synthesis of durable heterogeneous catalysts starting from renewable sources derived from biomass waste represents an important step for reducing environmental impacts of organic transformations. Herein, we report the efficient loading of Pd(II) ions on an eco-safe cellulose-based organic support (CNS), obtained by thermal cross-linking between TEMPO-oxidized cellulose nanofibers and branched polyethyleneimine in the presence of citric acid. A 22.7% <i>w</i>/<i>w</i> Pd-loading on CNS was determined by the ICP-OES technique, while the metal distribution on the xerogel was evidenced by SEM–EDS analysis. XPS analysis confirmed the direct chelation of Pd(II) ions by means of the high number of amino groups present in the network, so that further functionalization of the support with specific ligands was not necessary. The new composite turned to be an efficient heterogeneous pre-catalyst for promoting Suzuki–Miyaura coupling reactions between aryl halides and phenyl boronic acid in water, obtaining yields higher than 90% in 30 min, by operating in a microwave reactor at 100 °C and with just 2% <i>w</i>/<i>w</i> of CNS-Pd catalyst with respect to aryl halides (4.5‰ for Pd). At the end of first reaction cycle, Pd(II) ions on the support resulted in being reduced to Pd(0) while maintaining the same catalytic efficiency. In fact, no leaching was observed at the end of reactions, and five cycles of recycling and reusing of CNS-Pd catalyst provided excellent results in terms of yields and selectivity in the desired products. |
| first_indexed | 2024-03-09T16:31:34Z |
| format | Article |
| id | doaj.art-95edddf65e8e4e8c8b986d04d6177c44 |
| institution | Directory Open Access Journal |
| issn | 2310-2861 |
| language | English |
| last_indexed | 2024-03-09T16:31:34Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Gels |
| spelling | doaj.art-95edddf65e8e4e8c8b986d04d6177c442023-11-24T15:01:04ZengMDPI AGGels2310-28612022-12-0181278910.3390/gels8120789Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling ReactionsLaura Riva0Gloria Nicastro1Mingchong Liu2Chiara Battocchio3Carlo Punta4Alessandro Sacchetti5Department of Chemistry, Materials, and Chemical Engineering “G. Natta” and INSTM Local Unit, Politecnico di Milano, 20131 Milan, ItalyDepartment of Chemistry, Materials, and Chemical Engineering “G. Natta” and INSTM Local Unit, Politecnico di Milano, 20131 Milan, ItalyDepartment of Chemistry, Materials, and Chemical Engineering “G. Natta” and INSTM Local Unit, Politecnico di Milano, 20131 Milan, ItalyDepartment of Science, Roma Tre University, Via della Vasca Navale 79, 00146 Rome, ItalyDepartment of Chemistry, Materials, and Chemical Engineering “G. Natta” and INSTM Local Unit, Politecnico di Milano, 20131 Milan, ItalyDepartment of Chemistry, Materials, and Chemical Engineering “G. Natta” and INSTM Local Unit, Politecnico di Milano, 20131 Milan, ItalyThe (eco)design and synthesis of durable heterogeneous catalysts starting from renewable sources derived from biomass waste represents an important step for reducing environmental impacts of organic transformations. Herein, we report the efficient loading of Pd(II) ions on an eco-safe cellulose-based organic support (CNS), obtained by thermal cross-linking between TEMPO-oxidized cellulose nanofibers and branched polyethyleneimine in the presence of citric acid. A 22.7% <i>w</i>/<i>w</i> Pd-loading on CNS was determined by the ICP-OES technique, while the metal distribution on the xerogel was evidenced by SEM–EDS analysis. XPS analysis confirmed the direct chelation of Pd(II) ions by means of the high number of amino groups present in the network, so that further functionalization of the support with specific ligands was not necessary. The new composite turned to be an efficient heterogeneous pre-catalyst for promoting Suzuki–Miyaura coupling reactions between aryl halides and phenyl boronic acid in water, obtaining yields higher than 90% in 30 min, by operating in a microwave reactor at 100 °C and with just 2% <i>w</i>/<i>w</i> of CNS-Pd catalyst with respect to aryl halides (4.5‰ for Pd). At the end of first reaction cycle, Pd(II) ions on the support resulted in being reduced to Pd(0) while maintaining the same catalytic efficiency. In fact, no leaching was observed at the end of reactions, and five cycles of recycling and reusing of CNS-Pd catalyst provided excellent results in terms of yields and selectivity in the desired products.https://www.mdpi.com/2310-2861/8/12/789nanocelluloseSuzuki–Miyaura couplingheterogeneous catalysissustainable catalystnanocellulose-based xerogelsgreen chemistry |
| spellingShingle | Laura Riva Gloria Nicastro Mingchong Liu Chiara Battocchio Carlo Punta Alessandro Sacchetti Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions Gels nanocellulose Suzuki–Miyaura coupling heterogeneous catalysis sustainable catalyst nanocellulose-based xerogels green chemistry |
| title | Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions |
| title_full | Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions |
| title_fullStr | Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions |
| title_full_unstemmed | Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions |
| title_short | Pd-Loaded Cellulose NanoSponge as a Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reactions |
| title_sort | pd loaded cellulose nanosponge as a heterogeneous catalyst for suzuki miyaura coupling reactions |
| topic | nanocellulose Suzuki–Miyaura coupling heterogeneous catalysis sustainable catalyst nanocellulose-based xerogels green chemistry |
| url | https://www.mdpi.com/2310-2861/8/12/789 |
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