Probing the role of O-containing groups in CO2 adsorption of N-doped porous activated carbon.

ABSTRACT

Porous activated carbons (PACs) are promising candidates to capture CO2 through physical adsorption because of their chemical stability, easy-synthesis, cost-effectiveness and good recyclability. However, their low CO2 adsorption capacity, especially low CO2/N2 selectivity, has limited their practical applications. In this work, an optimized PAC with a large specific surface area, a small micropore size, and a large micropore volume has been synthesized by one-step carbonization/activation of casein using K2CO3 as a mild activation agent. It showed a remarkably enhanced CO2 adsorption capacity as high as 5.78 mmol g-1 and an excellent CO2/N2 selectivity of 144 (25 °C, 1 bar). Based on DFT calculations and experimental results, the coexistence of adjacent pyridinic N and -OH/-NH2 species was proposed for the first time to make an important contribution to the ultra-high CO2 adsorption performance, especially CO2/N2 selectivity. This work provides effective guidance to design PAC adsorbents with high CO2 adsorption performance. The content of pyridine N combined with -OH/-NH2 was further elevated by additional nitrogen introduction, resulting in a further enhanced CO2 adsorption capacity up to 5.96 mmol g-1 (25 °C, 1 bar). All these results suggest that, in addition to the well-defined pore structure, pyridinic N with neighboring OH or NH2 species played an important role in enhancing the CO2 adsorption performance of PACs, thus providing effective guidance for the rational design of CO2 adsorbents.