摘要：Metal-N_(4)(M-N_(4))macrocyclic complexes are interesting electrocatalysts due to their well-defined structures and rich molecular *** them,metal phthalocyanines have been widely studied for the carbon dioxide reduction reaction(CO_(2)RR)in heterogeneous systems and demonstrated good electrocatalytic ***,other complexes like metal corroles and metal porphyrins are much less explored,and often show inferior *** this study,three cobalt macrocyclic complexes,cobalt phthalocyanine,cobalt meso-tetraphenylporphyrin,and cobalt meso-triphenylcorrole(CoPc,CoTPP and CoTPC)are investigated in heterogeneous electrocatalysis of CO_(2)*** CoPc/carbon nanotube(CNT)hybrid exhibits high electrocatalytic activity,CNT hybridization does not work for CoTPC and CoTPP that hold weak interactions with *** the drop-dry method with a high molecular loading of 5.4×10^(–7) mol cm^(–2),CoTPC and CoTPP could deliver appreciable electrode ***(4-vinylpyridine)(PVP)introduction is further demonstrated as a facile method to afford enhanced activities for CoTPP at low molecular loadings through enhancing molecule-substrate *** partial current density of carbon monoxide for CoTPP+CNT/PVP is around 8 times higher than the sample without PVP at–0.67 V versus reversible hydrogen *** work provides solutions to enhance the electrode activities of molecular electrocatalysts with weak substrate interactions in heterogeneous systems.