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In this work, we prepared flexible carbon-fiber/semimetal Bi nanosheet arrays from solvothermal-synthesized carbon-fiber/Bi2O2CO3 nanosheet arrays via a reductive calcination process. The flexible carbon-fiber/semimetal Bi nanosheet arrays can function as photocatalysts and photoelectrocatalysts for 2,4-dinitorphenol oxidation. Comparing with carbon-fiber/Bi2O2CO3 nanosheet arrays, the newly designed flexible carbon-fiber/semimetal Bi nanosheet arrays show enhanced ultraviolet-visible (UV-vis) light absorption efficiency, photocurrent, p