摘要
有机过氧化物在大气氧化过程中占据核心地位,其反应路径与速率直接影响自由基循环、臭氧生成、气溶胶形成及区域复合污染的演化过程。作为对流层中最丰富的物种之一,水在气相与气-液界面均可能参与有机过氧化物大气反应,并通过氢键网络、溶剂化效应及质子迁移的促进作用,显著改变有机过氧化物的反应机理。基于量子化学计算、反应动力学及第一性原理分子动力学(BOMD)模拟,系统梳理了水分子在HO_(2)+OH、CH_(2)OO+H_(2)O、HO_(2)+HO_(2)等典型气相反应中的催化效应,结果表明水分子的参与可形成稳定水合物、降低关键成键和氢转移能垒,并使反应速率提高数个数量级。在气-液界面上,以CH_(2)OO+HCHO、CH_(2)OO+HCl、CH_(3)CHOO+H_(2)SO_(4)为代表的体系进一步表明,界面水分子通过构建定向氢键网络并促进质子迁移,从而加速反应,使原本受限的转化在皮秒尺度内迅速发生。总而言之,水分子在有机过氧化物的大气关键反应中不仅是反应介质,更是调控反应路径、速率及产物选择性的关键催化因子,对深入理解大气氧化性演变与二次污染形成具有重要意义。
Organic peroxides are central to atmospheric oxidation processes,directly influencing radical cycling,ozone formation,aerosol growth,and regional complex pollution through their reaction pathways and rates.As one of the most abundant species in the troposphere,water participates in these key reactions both in the gas phase and at the air-water interface,significantly modifying the mechanisms of organic peroxide reactions via hydrogen-bond networks,solvation effects,and the promotion of proton transfer.This review employs quantum chemical calculations,reaction kinetics,and first-principles molecular dynamics simulations to systematically examine the catalytic role of water in representative gas-phase reactions such as HO_(2)+OH,CH_(2)OO+H_(2)O,and HO_(2)+HO_(2).Results indicate that water facilitates the formation of stable hydrates,lowers energy barriers for key bond forming and hydrogen-transfer steps,and increases reaction rates by several orders of magnitude.At the air-water interface,systems including CH_(2)OO+HCHO,CH_(2)OO+HCl,and CH_(3)CHOO+H_(2)SO_(4)further demonstrate that interfacial water molecules accelerate multiple reaction pathways by enhancing local concentrations,organizing oriented hydrogen-bond networks,and promoting proton migration,enabling otherwise hindered transformations to occur on picosecond timescales.In summary,water acts not merely as a reaction medium but as a decisive catalytic factor that steers the pathways,rates,and product selectivity of key atmospheric reactions involving organic peroxides,providing critical insight into the evolution of atmospheric oxidative capacity and secondary pollution formation.
作者
王冠华
李炫烨
郭晓凯
崔鹤然
李垚庚
王睿
张田雷
WANG Guanhua;LI Xuanye;GUO Xiaokai;CUI Heran;LI Yaogeng;WANG Rui;ZHANG Tianlei(Shaanxi Key Laboratory of Catalysis Fundamentals and Applications,School of Chemical and Environmental Science,Shaanxi University of Technology,Hanzhong 723000,China)
出处
《陕西理工大学学报(自然科学版)》
2026年第1期1-10,共10页
Journal of Shaanxi University of Technology:Natural Science Edition
基金
国家自然科学基金项目(22073059)。
关键词
水分子
有机过氧化物
气相反应
气-液界面
催化机制
water
organic peroxide
gas phase reaction
air-water interface
catalytic mechanism
