LAUSR

Abstract An efficient metal‐free photocatalyst composed of black phosphorus (BP) and graphitic carbon nitride (CN) is prepared on a large scale by ball milling. Using economical urea and red phosphorus (RP) as the raw materials, the estimated materials cost of BP/CN is 0.235 Euro per gram. The BP/CN heterostructure shows efficient charge separation and possesses abundant active sites, giving rise to excellent photocatalytic H2 evolution and rhodamine B (RhB) degradation efficiency. Without using a co‐catalyst, the metal‐free BP/CN emits H2 consistently at a rate as large as 786 µmol h−1 g−1 and RhB is decomposed in merely 25 min during visible‐light irradiation. The corresponding electron/hole transfer and catalytic mechanisms are analyzed and described. The efficient metal‐free catalyst is promising in visible‐light photocatalysis and the simple ball‐milling synthetic method can be readily scaled up.