A study on free radical behaviors and reactions in supercritical water using quantum chemical simulation

Supercritical water (SCW) gasification is one of clean and efficient utilization way of biomass, other organic matters or coal for hydrogen production, in which radical reactions studies in SCW are limited but crucial. Density-functional tight-binding (DFTB) molecular simulation is one of efficient and convenient approaches to investigate these microscopic processes. Therefore, free radical reactions in severe SCW environment were investigated via DFTB calculations in this work. The results showed that the order of the free radicals containing bond cleavages reacted in SCW environment was ·OH, ·CH, ·CH₂, ·HO₂, ·CH₃ and ·C₆H₅ under the same conditions. The reaction processes of different radicals in SCW were obtained. ·H was the most active free radical of reactions. This work is expected to understand the properties of free radicals in SCW better and explore intrinsic reaction mechanisms, which may provide a theoretical support for accomplishing efficient and low-carbon complete SCW gasification for hydrogen production.