Photocatalytic Cleavage of β-<i>O</i>-4 Ether Bonds in Lignin over Ni/TiO<sub>2</sub>
Changzhou Chen,
Peng Liu,
Haihong Xia,
Minghao Zhou,
Jiaping Zhao,
Brajendra K. Sharma,
Jianchun Jiang
Affiliations
Changzhou Chen
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
Peng Liu
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
Haihong Xia
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
Minghao Zhou
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
Jiaping Zhao
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
Brajendra K. Sharma
Illinois Sustainable Technology Center, Prairie Research Institute, one Hazelwood Dr., Champaign, University of Illinois at Urbana-Champaign, Champaign, IL 61820, USA
Jianchun Jiang
Key Lab. of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization; Key and Open Lab. on Forest Chemical Engineering, Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, SFA, Nanjing 210042, China
It is of great importance to explore the selective hydrogenolysis of β-O-4 linkages, which account for 45–60% of all linkages in native lignin, to produce valued-added chemicals and fuels from biomass employing UV light as catalyst. TiO2 exhibited satisfactory catalytic performances in various photochemical reactions, due to its versatile advantages involving high catalytic activity, low cost and non-toxicity. In this work, 20 wt.% Ni/TiO2 and oxidant PCC (Pyridinium chlorochromate) were employed to promote the cleavage of β-O-4 alcohol to obtain high value chemicals under UV irradiation at room temperature. The Ni/TiO2 photocatalyst can be magnetically recovered and efficiently reused in the following four consecutive recycling tests in the cleavage of β-O-4 ether bond in lignin. Mechanism studies suggested that the oxidation of β-O-4 alcohol to β-O-4 ketone by oxidant PCC first occurred during the reaction, and was followed by the photocatalysis of the obtained β-O-4 ketone to corresponding acetophenone and phenol derivates. Furthermore, the system was tested on a variety of lignin model substrates containing β-O-4 linkage for the generation of fragmentation products in good to excellent results.
