In-situ DRIFTS insights into the evolution of surface functionality of biochar upon thermal air oxidation

Biochar surface functionality is crucial for its application. Herein, the evolution of biochar surface functionality upon thermal air oxidation (TAO) was investigated in-situ by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and thermogravimetric analysis (TGA). The results show that, although the surface functionality of biochar is remarkably changed during TAO at the initial low temperature range, the biochar weight is still stable in the initial low temperature range, suggesting the chemisorption of O₂ as intermediate oxygenated functional groups (OFGs) on biochar surface. Moreover, the evolution of biochar surface functionality upon TAO is highly affected on its preparation temperature and intrinsic minerals. Specifically, biochar produced at a high temperature is more resistant to TAO, and more favorable for the formation of ketone groups during TAO. While the biochars prepared at low or medium temperatures show a remarkable formation of carboxyl/lactone groups upon TAO, and the maximum temperature for the formation of carboxyl/lactone groups can be achieved at 400 °C. It's worth noting that the intrinsic minerals in biochar catalyze the TAO reaction, resulting in a much higher mass loss of biochar upon TAO. Furthermore, with the catalysis of intrinsic minerals, TAO is more suitable for enhancing the performance of biochar with intrinsic minerals. These results facilitate the design of engineered biochar via TAO for enhanced applications.