Alkynes Electrooxidation to α,α-Dichloroketones in Seawater with Natural Chlorine Participation via Competitive Reaction Inhibition and Tip-Enhanced Reagent Concentration

被引：11

作者：

Yao, Junwei ^{[1
]}

Yang, Rong ^{[1
]}

Liu, Cuibo ^{[1
]}

Zhao, Bo-Hang ^{[1
]}

Zhang, Bin ^{[1
]}

Wu, Yongmeng ^{[1
]}

机构：

[1] Tianjin Univ, Sch Sci, Dept Chem, Tianjin 300072, Peoples R China

来源：

ACS CENTRAL SCIENCE | 2023年 / 10卷 / 01期

基金：

中国国家自然科学基金;

关键词：

NICO2O4;

D O I：

10.1021/acscentsci.3c01277

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The traditional synthesis of a,a-dichloroketones usually requires corrosive chlorine, harsh reaction conditions, or excessive electrolytes. Here, we report an electrooxidation strategy of ethynylbenzenes to a,a-dichloroketones by directly utilizing seawater as the chlorine source and electrolyte solution without an additional supporting electrolyte. High-curvature NiCo2O4 nanocones are designed to inhibit competitive O-2 and Cl-2 evolution reactions and concentrate Cl- and OH- ions, accelerating a, a-dichloroketone electrosynthesis. NiCo2O4 nanocones produce 81% yield, 61% Faradaic efficiency, and 44.2 mmol gcat.-1 h-1 yield rate of a,a-dichloroketones, outperforming NiCo2O4 nanosheets. A Cl- radical triggered Cl- and OH- radical addition mechanism is revealed by a variety of radicaltrapping and control experiments. The feasibility of a solar-powered electrosynthesis system, methodological universality, and extended synthesis of a,a-dichloroketone-drug blocks confirm its practical potential. This work may provide a sustainable solution to the electrocatalytic synthesis of a,a-dichloroketones via the utilization of seawater resources.

引用

页码：155 / 162

页数：8