Tuning structures and catalysis performance of two-dimensional covalent organic frameworks based on copper phthalocyanine building block and phenyl connector

Based on the experimentally reported stable and conductive two-dimensional covalent organic frameworks with copper phthalocyanine (CuPc) as building block and cyan substituted phenyl as connector (CuCOF-CN) as an electrocatalyst for CO₂ reduction reaction (RR), first principle calculations were performed on CuCOF-CN and its analog with the CN being replaced by H (CuCOF). Comparatively studied on the crystal structures, electronic properties, and CO₂RR performance of the two catalysts found that CuCOF has reduced crystal unit size, more positive charge on Cu and CuPc segments, smaller band gap, and lower reaction barrier for CO₂ RR than CuCOF-CN. CuCOF is proposed to be good potential electrocatalyst with good environment friendliness. The substituent effect and structure-property-performance relationship would help for designing and fabricating new electrocatalysts.