PCDD/F adsorption enhancement over nitrogen-doped biochar: A DFT-D study.

Polychlorinated dibenzo-p-dioxin/furans (PCDD/F) have a great threat to the environment and human health, resulting in controlling PCDD/F emissions to regulation far important for emission source. Considering 2,3,4,7,8-pentachlorodibenzo-p-furan (PeCDF) identified as the most contributor to international toxic equivalent, 2,3,4,7,8-PeCDF can be considered as the target molecule for the adsorption of PCDD/F emission from industries. With the aim to in-depth elucidate how different types of nitrogen (N) species enhance 2,3,4,7,8-PeCDF on the biochar and guide the specific carbon materials design for industries, systematic computational investigations by density functional theory calculations were conducted. The results indicate pristine biochar intrinsically interacts with 2,3,4,7,8-PeCDF by π-π electron donor and acceptor (EDA) interaction, six-membered carbon rings of PeCDF parallel to the biochar surface as the strongest adsorption configuration. Moreover, by comparison of adsorption energy (-150.16 kJ mol-1) and interaction distance (3.593 Å) of pristine biochar, environment friendly N doping can enhance the adsorption of 2,3,4,7,8-PeCDF on biochar. Compared with graphitic N doping and pyridinic N doping, pyrrolic N doping biochar presents the strongest interaction toward 2,3,4,7,8-PeCDF molecule due to the highest adsorption energy (-155.56 kJ mol-1) and shortest interaction distance (3.532 Å). Specially, the enhancing adsorption of PeCDF over N doped biochar attributes to the enhancing π-π electron EDA interaction and electrostatic interaction. In addition, the effect of N doping species on PeCDF adsorbed on the biochar is more than that of N doping content. Specially, the adsorption capacity of N doping biochar for PCDD/F can be improved by adding pyrrolic N group most efficiently. Furthermore, pyrrolic N and pyridinic N doping result in the entropy increase, and electrons transform from pyrrolic N and pyridinic N doped biochar to 2,3,4,7,8-PeCDF molecule. A complete understanding of the research would supply crucial information for applying N-doped biochar to effectively remove PCDD/F for industries.