Enzymes are characteristic of catalytic efficiency and specificity by maneuvering multiple components in concert at a confined nanoscale space. However, achieving such a configuration in artificial catalysts remains challenging. Herein, we report a microenvironment regulation strategy by modifying carbon paper with hexadecyltrimethylammonium cations, delivering electrochemical carbon–carbon coupling of benzaldehyde with enhanced activity and racemate stereoselectivity. The modified electrode–electrolyte interface creates an optimal microenvironment for electrocatalysis—it engenders dipolar interaction with the reaction intermediate, giving a 2.2-fold higher reaction rate (from 0.13 to 0.28 mmol h⁻¹ cm⁻²); Moreover, it repels interfacial water and modulates the conformational specificity of reaction intermediate by facilitating intermolecular hydrogen bonding, affording 2.5-fold higher diastereomeric ratio of racemate to mesomer (from 0.73 to 1.82). We expect that the microenvironment regulation strategy will lead to the advanced design of electrode–electrolyte interface for enhanced activity and (stereo)selectivity that mimics enzymes.

酶通过在有限的纳米级空间内协同操纵多个组分而具有催化效率和特异性的特征。然而，在人工催化剂中实现这种配置仍然具有挑战性。在此，我们报告了一种微环境调节策略，通过用十六烷基三甲基铵阳离子改性碳纸，提供具有增强活性和外消旋体立体选择性的苯甲醛电化学碳-碳偶联。修饰的电极-电解质界面为电催化创造了最佳的微环境——它与反应中间体产生偶极相互作用，使反应速率提高了2.2倍（从0.13到0.28 mmol h ^-1 cm ^-2 ）；此外，它排斥界面水，并通过促进分子间氢键调节反应中间体的构象特异性，使外消旋体与内消旋体的非对映体比率提高2.5倍（从0.73到1.82）。我们预计微环境调节策略将导致电极-电解质界面的先进设计，以增强模拟酶的活性和（立体）选择性。