Tang Chun, Su Meiling, Lu Taige, Zheng Jueting, Wang Juejun, Zhou Yu, Zou Yu-Ling, Liu Wenqing, Huang Ruiyun, Xu Wei, Chen Lijue, Zhang Yanxi, Bai Jie, Yang Yang, Shi Jia, Liu Junyang, Hong Wenjing
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University Xiamen China
Chem Sci. 2024 Jul 25;15(33):13486-13494. doi: 10.1039/d4sc03759f. eCollection 2024 Aug 22.
Nucleophilic substitution is one of the most fundamental chemical reactions, and the pursuit of high reaction rates of the reaction is one of the ultimate goals in catalytic and organic chemistry. The reaction barrier of the nucleophilic substitution originates from the highly polar nature of the transition state that can be stabilized under the electric field created by the solvent environment. However, the intensity of the induced solvent-electric field is relatively small due to the random orientation of solvent molecules, which hinders the catalytic effects and restricts the reaction rates. This work shows that oriented external electric fields applied within a confined nanogap between two nanoscopic tips could accelerate the Menshutkin reaction by more than four orders of magnitude (over 39 000 times). The theoretical calculations reveal that the electric field inside the nanogap reduces the energy barrier to increase the reaction rate. Our work suggests the great potential of electrostatic catalysis for green synthesis in the future.
亲核取代是最基本的化学反应之一，追求该反应的高反应速率是催化化学和有机化学的终极目标之一。亲核取代反应的势垒源于过渡态的高极性，这种极性可以在溶剂环境产生的电场下得到稳定。然而，由于溶剂分子的随机取向，诱导溶剂电场的强度相对较小，这阻碍了催化作用并限制了反应速率。这项工作表明，在两个纳米尖端之间的受限纳米间隙内施加定向外部电场，可以使门舒特金反应加速四个数量级以上（超过39000倍）。理论计算表明，纳米间隙内的电场降低了能垒，从而提高了反应速率。我们的工作表明了静电催化在未来绿色合成方面的巨大潜力。
