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Photochemical C-N coupling via adsorption modulation: Selective synthesis of glycine from waste
Zixuan Zhang1, Xue Zhang1, Xiaohui Tang2
1School of Chemical Engineering and Technology, Key Laboratory for Green Chemical Technology of the Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin 300350, China.
Abstract:
Photocatalytic C-N coupling from polyols and nitrogen-containing small molecules for glycine synthesis provides an attractive strategy for upgrading of plastic/biomass waste. However, the uncontrolled intermediates coupling challenges the efficient glycine production regarding yield or selectivity. Here we report an In2O3 photocatalyst that can achieve a glycine formation rate of 1.167 mmol g-1 h-1 with 89% selectivity from waste poly(ethylene terephthalate) (PET) plastic-derived ethylene glycol (EG) and nitrate. Mechanism research reveals that EG is photo-oxidized into glycolaldehyde as a key intermediate over In2O3 catalyst, which subsequently undergoes C-N coupling with NH4+ obtained from nitrate reduction to form glycine. Compared to TiO2 catalyst, In2O3 can significantly inhibit the over-oxidation process of key intermediates, thereby suppressing the formation of by-product formic acid. This process is also successfully extended to transform real-word PET plastic and biomass-derived polyols into high-value glycine or amide. Techno-economic analysis (TEA) and life cycle assessment (LCA) further confirm the economic viability and environmental benefits of this C-N coupling system. This work provides a sustainable catalytic system for selective glycine photosynthesis by precisely regulating the C-N coupling routes of key intermediates, which achieves synergistic value-added conversion of dual waste streams, effectively alleviating environmental pressures.
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