A Z‐Scheme Heterojunctional Photocatalyst Engineered with Spatially Separated Dual Redox Sites for Selective CO2 Reduction with Water: Insight by In Situ µs‐Transient Absorption Spectra

Abstract Solar‐driven CO 2 reduction by water with a Z‐scheme heterojunction affords an avenue to access energy storage and to alleviate greenhouse gas (GHG) emissions, yet the separation of charge carriers and the integrative regulation of water oxidation and CO 2 activation sites remain challenging. Here, a BiVO 4 /g‐C 3 N 4 (BVO/CN) Z‐scheme heterojunction as such a prototype is constructed by spatially separated dual sites with CoO x clusters and imidazolium ionic liquids (IL) toward CO 2 photoreduction. The optimized CoO x ‐BVO/CN‐IL delivers an ≈80‐fold CO production rate without H 2 evolution compared with urea‐C 3 N 4 counterpart, together with nearly stoichiometric O 2 gas produced. Experimental results and DFT calculations unveil the cascade Z‐scheme charge transfer and subsequently the prominent redox co‐catalysis by CoO x and IL for holes‐H 2 O oxidation and electrons‐CO 2 reduction, respectively. Moreover, in situ µs‐transient absorption spectra clearly show the function of each cocatalyst and quantitatively reveal that the resulting CoO x ‐BVO/CN‐IL reaches up to the electron transfer efficiency of 36.4% for CO 2 reduction, far beyond those for BVO/CN (4.0%) and urea‐CN (0.8%), underlining an exceptional synergy of dual reaction sites engineering. This work provides deep insights and guidelines for the rational design of highly efficient Z‐scheme heterojunctions with precise redox catalytic sites toward solar fuel production.