title: Immobilized methyltrioxo rhenium (MTO)/H2O2 systems for the oxidation of lignin and lignin model compounds.
abstract: A convenient and efficient application of heterogeneous methylrhenium trioxide (MTO) systems for the selective oxidation of lignin model compounds and lignins is reported. Environmental friendly and low-cost H2O2 was used as the oxygen atom donor. Overall, the data presented and discussed in this paper point toward the conclusion that the immobilized heterogeneous catalytic systems based on H2O2/and MTO catalysts are able to extensively oxidize both phenolic and non-phenolic, monomeric, and dimeric, lignin model compounds. Condensed diphenylmethane models were found also extensively oxidized. Technical lignins, such as hydrolytic sugar cane lignin (SCL) and red spruce kraft lignin (RSL), displayed oxidative activity with immobilized MTO catalytic systems. After oxidation, these lignins displayed the formation of more soluble lignin fragments with a high degree of degradation as indicated by the lower contents of aliphatic and condensed OH groups, and the higher amounts of carboxylic acid moieties. Our data indicate that immobilized MTO catalytic systems are significant potential candidates for the development of alternative totally chlorine-free delignification processes and environmental sustainable lignin selective modification reactions.
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche Università di Tor Vergata, Via della ricerca Scientifica, 00133, Roma, Italy. crestini@uniroma2.it
authors.forename: Claudia
authors.initials: C
authors.lastname: Crestini
authors.forename: Maria Chiara
authors.initials: MC
authors.lastname: Caponi
authors.forename: Dimitris S
authors.initials: DS
authors.lastname: Argyropoulos
authors.forename: Raffaele
authors.initials: R
authors.lastname: Saladino
mesh_terms: D002384:Catalysis; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008031:Lignin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction
chemical_list: D009942:Organometallic Compounds; D016877:Oxidants; C411866:methyltrioxorhenium VII; D008031:Lignin; D006861:Hydrogen Peroxide