LAUSR

Cooperative coupling of photocatalytic H2O2 production with organic synthesis has an expansive perspective in converting solar energy into storable chemical energy. However, traditional powder photocatalysts suffer from severe agglomeration, limited light absorption, poor gas reactant accessibility, and reusable difficulty, which greatly hinders their large‐scale application. Herein, floatable composite photocatalysts are synthesized by immobilizing hydrophobic TiO2 and Bi2O3 on lightweight polystyrene (PS) spheres via hydrothermal and photodeposition methods. The floatable photocatalysts are not only solar transparent, but also upgrade the contact between reactants and photocatalysts. Thus, the floatable step‐scheme (S‐scheme) TiO2/Bi2O3 photocatalyst exhibits a drastically enhanced H2O2 yield of 1.15 mm h−1 and decent furfuryl alcohol conversion to furoic acid synchronously. Furthermore, the S‐scheme mechanism and dynamics are systematically investigated by in situ irradiated X‐ray photoelectron spectroscopy and femtosecond transient absorption spectrum analyses. In situ Fourier transform infrared spectroscopy and density functional theory calculations reveal the mechanism of furoic acid evolution. The ingenious design of floatable photocatalysts not only furnishes insight into maximizing photocatalytic reaction kinetics but also provides a new route for highly efficient heterogeneous catalysis.