Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and am...Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.展开更多
It remains as a challenge for realizing efficient photo-responsive catalysts towards largescale degradation of organic pollutants under natural sunlight.This work reports a new pore engineering strategy for creating u...It remains as a challenge for realizing efficient photo-responsive catalysts towards largescale degradation of organic pollutants under natural sunlight.This work reports a new pore engineering strategy for creating ultra-porous g-C_(3)N_(4) micro-tubes with an unprecedentedly high specific surface area of 152.96 m^(2)/g.This is mainly associated with releasing internal vapor pressure in the autoclave where the hydrothermal treatment of the urea/melamine mixture is processed.Supported by microscopic observation,porosity measurement and spectroscopic characterization,it is found that releasing the pressure at halfway of hydrothermal process is vital for forming exfoliated rod-like precursors and the de-aggregation of these rods presents substantial benefits on the production of mesopores on g-C_(3)N_(4) microtubes during the calcination of precursors.This offers a large number of reactive sites required by photocatalytic reaction.Coupling these micro-tubes with Ti_(3)C_(2)T_(X) nanosheets via electrostatic interaction yields a 1D/2D heterojunction with a close interfacial contact.The addition of metallically conductive Ti_(3)C_(2)T_(X) nanosheets accelerates the separation between electrons and holes,and also enhances the light absorption.All these merits of structural design lead to forming a group of highly efficient catalysts demonstrating an excellent photocatalytic degradation rate of k=0.0560 min^(-1)for RhB dyes under 100 mW/cm~2 visible light radiation that micks sunlight outdoors.This laboratory valuation is further supported by an outdoor test that shows a fast degradation rate of 0.0744 min^(-1)under natural sunlight.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22572141,22178266)Talent Program Fund of Tianjin University(Nos.0701321039,0903074107)supported by a grant from the Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province(No.2024HZYB02)。
文摘Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.
基金supported by the National Natural Science Foundation of China (No.21503110)the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘It remains as a challenge for realizing efficient photo-responsive catalysts towards largescale degradation of organic pollutants under natural sunlight.This work reports a new pore engineering strategy for creating ultra-porous g-C_(3)N_(4) micro-tubes with an unprecedentedly high specific surface area of 152.96 m^(2)/g.This is mainly associated with releasing internal vapor pressure in the autoclave where the hydrothermal treatment of the urea/melamine mixture is processed.Supported by microscopic observation,porosity measurement and spectroscopic characterization,it is found that releasing the pressure at halfway of hydrothermal process is vital for forming exfoliated rod-like precursors and the de-aggregation of these rods presents substantial benefits on the production of mesopores on g-C_(3)N_(4) microtubes during the calcination of precursors.This offers a large number of reactive sites required by photocatalytic reaction.Coupling these micro-tubes with Ti_(3)C_(2)T_(X) nanosheets via electrostatic interaction yields a 1D/2D heterojunction with a close interfacial contact.The addition of metallically conductive Ti_(3)C_(2)T_(X) nanosheets accelerates the separation between electrons and holes,and also enhances the light absorption.All these merits of structural design lead to forming a group of highly efficient catalysts demonstrating an excellent photocatalytic degradation rate of k=0.0560 min^(-1)for RhB dyes under 100 mW/cm~2 visible light radiation that micks sunlight outdoors.This laboratory valuation is further supported by an outdoor test that shows a fast degradation rate of 0.0744 min^(-1)under natural sunlight.
