The development of one-pot photocatalytic systems for the production of tunable syngas ratios has thus far been a challenge. Herein, carbon nitride loaded with Co2+ active sites (Co@C3N4) forms a heterojunction with black phosphorus (BP) capable of simultaneous proton and CO2 reduction under simulated solar irradiation. H2/CO syngas ratios ranging from 1-5 were achieved by varying the BP % weight with a constant 2 mg Co@C3N4. 20 wt % BP achieved the maximum total gas evolution of 70 μmol g-1 h-1 with an H2/CO ratio of 2. Increasing CoCl2 additions resulted in increased H2 evolution coupled with decreased CO evolution. The formed hybrid material has a higher total gas evolution than each of the materials independently, indicative of the formation of a heterojunction. We propose the heterojunction formed in situ constitutes a Type I heterojunction due to the thickness of the exfoliated BP flakes. Efforts to create thinner BP flakes and create a Type II heterojunction will also be discussed.

Highly tunable photocatalytic syngas production from a black phosphorus/carbon nitride heterojunction with Co2+ ion co-catalyst sites

ACS Fall 2021

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