Photocatalytic Selective Organic Transformation And Surface Regulation Of The Non-noble Metals Driven By Visible Light

As a key step in chemical production and other industrial production,organic transformation reaction is a critical chemical reaction in improving the quality of life and contributing to social development.And in the future,finding the environmentally friendly and sustainable organic conversion methods is the development trend of chemical production,and photocatalytic technology shows great potential and application prospect in selective organic conversion.In this paper,two types of organic transformation reactions were discussed in detail.On the one hand,the influence of visible light on the organic transformation reaction was discussed.On the other hand,non-noble metal was used as photocatalyst to discuss the applicability of non-noble metal catalyst for organic transformation reaction and the surface regulation mechanism.In this thesis,cheap metal photocatalysts were designed and synthesized in a simple way,and the application of non-noble metal to typical organic transformation reactions and surface regulation under visible light was fully discussed.1.In the first study,we develop a visible-light-driven procedure for the direct α-alkylation of ketones with alcohols using oxidized TiN photocatalysts under mild conditions.The product selectivity can be well-tuned by switching the surface N/O ratio of the synthesized photocatalysts through a facile and flexible thermal oxidation method.The proof-of-concept study was conducted for the α-alkylation of acetophenone with benzyl alcohol to form chalcone and dihydrochalcone and almost complete conversion was achieved at 100℃ under visible light.The selectivity toward chalcone increased gradually with increasing the surface N/O ratio,which meant that the proportion of the two products can be well-tuned using the oxidized TiN photocatalysts.2.In the second study,we developed a novel plasmon-driven catalysis method on Ni nanoparticles for the selective hydrogenolysis of aryl ethers in lignin under visible light.This novel photocatalytic hydrogenolysis procedure holds great potential in the valorization of various lignin samples.Using this novel photocatalysis procedure,we successfully cleaved the three aryl ether bonds at very mild conditions with excellent conversion and good to excellent selectivity under visible light.Especially,for the α-O-4 model,BPE and two β-O-4 models,PP-of and PP-one,excellent conversion and selectivity can be obtained at room temperature.Finally,photocatalytic depolymerization of dealkaline lignin at 80℃ gave 14 aromatic monomer products with a total yield of 9.84wt%.In conclusion,the two parts of this paper successfully realized the study of visible light driven selective organic transformation of non-noble metal photocatalysis,and discussed the relevant surface regulation mechanism through selective regulation,which laid a good foundation for the subsequent related research.