Overcoming solubility and separation barriers: A scalable biphasic electrocatalytic strategy for sterols oxidation

Abstract Electrocatalytic oxidation of sterols presents a sustainable method for steroid synthesis, yet industrial adoption is impeded by challenges including poor solubility, limited efficiency, and complex product separation. Here, we report a biphasic electrocatalytic system integrating Ni 3 S 2 ‐NH 2 ‐bdc/Ni@GF composite electrocatalyst with 2,2,6,6‐tetramethyl‐1‐piperidine‐ N ‐oxyl, enabling highly efficient sterols electrooxidation. The electrocatalyst design incorporates a nickel interlayer to enhance structural robustness and Ni 3 S 2 ‐embedded metal–organic framework to optimize electrocatalytic activity, achieving excellent performance with 96% conversion and 99% selectivity in a flow electrolyzer. This strategy effectively overcomes solubility limitations and exhibits broad applicability, as validated with 12 distinct sterols. Scalability was successfully validated at the 120‐g scale, attaining a space–time yield of 25.4 kg/(m 3 h) following electrolyzer optimization. Mechanism studies revealed reconstruction of the electrocatalyst and synergistic interactions with aminoxyl radicals. This work establishes an efficient, scalable, and readily separable electrocatalytic method for sterols electrooxidation, highlighting its significant potential for industrial steroid synthesis.