Electrocatalysis offers a sustainable route for producing value-added chemicals, yet its widespread adoption is limited by low turnover frequency (TOF) and electron efficiency (EE). Here, we unveil a promotion effect in molecular phthalocyanine catalysts, enabling synergistic oxygen reduction reaction (ORR) and cyclohexanone oxidation (CyO). This mechanism bypasses the kinetic limitations of ORR steps and the overpotential penalties of CyO, achieving a record TOF of 1711 h–1 with superior EE (∼100% at 0.5 VRHE) for adipic acid production. Near-ambient pressure X-ray photoelectron spectroscopy reveals that this remarkable activity arises from interactions between *OOH intermediates at metal centers and substrates on neighboring nitrogen atoms. Integrating this design into microbial fuel cell reactors enables self-driven adipic acid synthesis alongside spontaneous bioelectricity generation, i.e., the system operates without any external power input. Life cycle assessment shows a 43% reduction in CO2 emissions, surpassing conventional adipic acid production methods. This self-driven strategy establishes a new paradigm for coupling energy generation with chemical synthesis, offering highly efficient and environmentally sustainable models for industrial processes.
Bu et al. (Thu,) studied this question.