This work mechanistically investigated the influence of CO2 in the thermo-chemical process of microalgal biomass (Chlorella vulgaris and Microcystis aeruginosa) to achieve a fast virtuous cycle of carbon via recovering energy. This work experimentally justified that the influence of CO2 in pyrolysis of microalgal biomass could be initiated at temperatures higher than 530 degrees C, which directly led to the enhanced generation of syngas. For example, the concentration of CO from pyrolysis of M. aeruginosa increased up to similar to 3000% at 670 degrees C in the presence of CO2. The identified universal influence of CO2 could be summarized by the expedited thermal cracking of VOCs evolved from microalgal biomass and by the unknown reaction between VOCs and CO2. This identified effectiveness of CO2 was different from the Boudouard reaction, which was independently occurred with dehydrogenation. Thus, microalgal biomass could be a candidate for the thermo-chemical process (pyrolysis and gasification). (C) 2015 Elsevier Ltd. All rights reserved.