LAUSR

Photocatalytic conversion of CO2 into renewable fuels with high efficiency and selectivity is desirable for solar energy utilization, but remains a great challenge. Herein, cobalt(II)-porphyrin functionalized conjugated polymers with acetylene bridging units, which are assembled via the Sonogashira cross coupling reaction, as heterogeneous catalysts for CO2 photoreduction are presented. Experimental investigations and density functional theory calculations demonstrated the crucial roles of Co centers in porphyrin units for CO2 activation and conversion, while excessive acetylene group would prompt the competing hydrogen evolution reaction and reduce the selectivity. Thus, the CoPor-DBBP affords superior activity for the CO generation with a rate of 286.7 μ mol g-1 h-1 and high selectivity up to 90.4%. This work presents a new insight for rationally designing of porphyrin-based conjugated polymers as energetic photocatalyst in CO2 reduction.