Density functional theory calculation of two-dimensional transition metal-hexaiminotriphenylene (TM-HITP) electrocatalytic CO2 reduction

Carbon dioxide reduction technology can solve the shortage of resources and climate issues like warming of the planet. Metal-organic frameworks (MOFs) contain well-defined active sites, a huge specific surface, and a robust porous structure, making them a good candidate for use in CO2 electrocatalytic reduction. Using the principles of spin-polarization density functional theory, the two-dimensional MOF constructed from transition metal-hexaiminotriphenylene was calculated to reduce CO2 electrocatalytically. The results show that for ten transition metal (TM-HITP) two-dimensional network structures spanning Sc through Zn, the formation energies E-f are all negative, and they can theoretically be synthesised experimentally, and the metal atoms can be disseminated in the HITP framework steadily because their binding energies to HITP are highly sufficient. Considering the competition with the HER, all catalysts showed CO2RR selectivity except Co-HITP. Co-HITP catalysts required pH >7.22 to show CO2RR selectivity. The main products and overpotentials of both Fe and Co catalysts were in agreement with the available literature values, indicating that the calculations were reliable. HCOOH is the primary product for Sc, Ni, and Cu. The principal product of Ti and V is CH4. CH3OH is the primary product for Cr, Fe, and Co. The product selectivity of Mn was poor and three products, CH4, HCHO and HCOOH, were obtained simultaneously at the same limiting potential. The limiting potentials of these ten catalysts for electrocatalytic CO2 reduction ranged from 0.296 to 0.738 volts and the overpotentials between 0.027 V and 0.754 V, all of which were rather little. Consequently, we forecast that the two-dimensional MOFs constructed with transition metals with hexaiminotriphenylene are potential electrocatalysts for CO2 reduction because they demonstrate excellent catalytic activity in the electrocatalytic reduction of CO2.

Automated summary

Metal-organic frameworks (MOFs) have excellent performance in electrocatalytic reduction of CO2 and can address resource scarcity and climate issues. The two-dimensional MOF constructed from transition metal-hexaiminotriphenylene was found to be an ideal electrocatalyst based on theoretical calculations and reliable data. Various metal catalysts showed promising catalytic activity and can be used for CO2 reduction.