Potassium-Assisted Fabrication of Intrinsic Defects in Porous Carbons for Electrocatalytic CO₂ Reduction.

Abstract

The fabrication of intrinsic carbon defects is usually tangled with doping effects, and the identification of their unique roles in catalysis remains a tough task. Herein, a K⁺ -assisted synthetic strategy is developed to afford porous carbon (K-defect-C) with abundant intrinsic defects and complete elimination of heteroatom via direct pyrolysis of K⁺ -confined metal-organic frameworks (MOFs). Positron-annihilation lifetime spectroscopy, X-ray absorption fine structure measurement, and scanning transmission electron microscopy jointly illustrate the existence of abundant 12-vacancy-type carbon defects (V₁₂ ) in K-defect-C. Remarkably, the K-defect-C achieves ultrahigh CO Faradaic efficiency (99%) at -0.45 V in CO₂ electroreduction, far surpassing MOF-derived carbon without K⁺ etching. Theoretical calculations reveal that the V₁₂ defects in K-defect-C favor CO₂ adsorption and significantly accelerate the formation of the rate-determining COOH* intermediate, thereby promoting CO₂ reduction. This work develops a novel strategy to generate intrinsic carbon defects and provides new insights into their critical role in catalysis.