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Photocatalytic CO 2 reduction is a means of alleviating energy crisis and environmental deterioration. In this work, a rising two-dimensional (2D) material rarely reported in the field of photocatalytic CO 2 reduction, black phosphorus (BP) nanosheets, is synthesized, on which Co 2 P is in situ grown by solvothermal treatment using BP itself as a P source. Co 2 P on the BP nanosheets (BPs) surface can prevent the destruction of BPs in ambient air and, in the meantime, favor charge separation and CO 2 adsorption and activation during the catalytic process. Upon light irradiation, Co 2 P can extract the photogenerated electrons effectively across the intimate interface and lower the CO 2 activation energy barrier, supported by both experimental characterizations and theoretical calculations. Benefitting from integrated advantages of BPs and Co 2 P, the optimal Co 2 P/BPs exhibit photocatalytic reduction of CO 2 to CO at a rate of 25.5 μmol g −1 h −1 with a selectivity of 91.4%, both of which are higher than those of pristine BPs. This work presents ideas for stabilizing BPs and improving their CO 2 reduction performance simultaneously.

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