Prediction of reaction mechanism for OH radical-mediated phenol oxidation using quantum chemical calculation

化学 反应速率常数 对苯二酚 过渡态理论 苯酚 反应机理 电泳剂 计算化学 羟基自由基 基本反应 反应速率 物理化学 动力学 激进的 有机化学 催化作用 物理 量子力学
作者
Dhimas Dwinandha,Bei Zhang,Manabu Fujii
出处
期刊:Chemosphere [Elsevier]
卷期号:291: 132763-132763 被引量:15
标识
DOI:10.1016/j.chemosphere.2021.132763
摘要

Understanding the reaction mechanism of OH•-mediated oxidation of organic micropollutants (OMPs) contributes to the assessment and development of advanced oxidation processes (AOPs) for removal of OMPs in water environment. In this study, a theoretical approach using quantum chemical calculation (QCC) was employed to investigate the prediction accuracy of the reaction mechanism (i.e., reaction site and rate) for OH•-mediated oxidation of phenol, where the hydroquinone and catechol are generated as transformation products (TPs) via radical and electrophilic reactions. We compared three different levels of theory (Hartree-Fock, B3LYP, and M06-2X) with 6-311 + G (2d,2p)/SMD, and the reaction site and rate constants were predicted by the Fukui function and transition state theory, respectively. Overall, the prediction accuracy of the TPs formation mechanism was the highest in the calculations using M06-2X. For example, the initial OH• addition to phenol was predicted to occur with a probability of 77% for the ortho position and 23% for the para position, which was consistent with the experimental observation. By applying the transition state theory, the rate constants toward TPs formation pathway can be reasonably reproduced, suggesting that M06-2X has an effective function for polycyclic reactions. However, the observed discrepancies in rate constants are inferred from dispersion effects and the multi-reference property in the computational system or derived from mismatch of target reactions between theoretical calculations and experiments. Overall, this study provides an insight into QCC application for investigating the formation mechanism of TPs in AOPs for removal of OMPs in water environment.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
大幅提高文件上传限制,最高150M (2024-4-1)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
cctv18应助hoozhwen采纳,获得10
刚刚
刚刚
刚刚
1秒前
1秒前
1秒前
Tong完成签到,获得积分10
1秒前
1秒前
漂流平平完成签到,获得积分10
1秒前
1秒前
兴奋小林发布了新的文献求助10
1秒前
shiqiang mu应助尧九采纳,获得10
2秒前
2秒前
3秒前
4秒前
大狒狒发布了新的文献求助10
4秒前
4秒前
4秒前
mo发布了新的文献求助10
4秒前
4秒前
cnbhhhhh完成签到,获得积分10
5秒前
对苏完成签到,获得积分10
5秒前
张琦完成签到 ,获得积分10
5秒前
英勇的小强完成签到 ,获得积分10
6秒前
nini发布了新的文献求助10
6秒前
JamesPei应助冷傲迎梦采纳,获得10
7秒前
独特笙发布了新的文献求助10
7秒前
8秒前
8秒前
Seven完成签到,获得积分10
8秒前
8秒前
依梦完成签到,获得积分10
9秒前
兴奋小林完成签到,获得积分10
9秒前
跳跃绮菱完成签到,获得积分10
9秒前
luni360完成签到,获得积分10
10秒前
10秒前
临泉发布了新的文献求助10
10秒前
新青年完成签到,获得积分0
10秒前
10秒前
11秒前
高分求助中
The late Devonian Standard Conodont Zonation 2000
Nickel superalloy market size, share, growth, trends, and forecast 2023-2030 2000
The Lali Section: An Excellent Reference Section for Upper - Devonian in South China 1500
Smart but Scattered: The Revolutionary Executive Skills Approach to Helping Kids Reach Their Potential (第二版) 1000
Very-high-order BVD Schemes Using β-variable THINC Method 850
Mantiden: Faszinierende Lauerjäger Faszinierende Lauerjäger 800
PraxisRatgeber: Mantiden: Faszinierende Lauerjäger 800
热门求助领域 (近24小时)
化学 医学 生物 材料科学 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 基因 遗传学 催化作用 物理化学 免疫学 量子力学 细胞生物学
热门帖子
关注 科研通微信公众号,转发送积分 3249276
求助须知:如何正确求助?哪些是违规求助? 2892624
关于积分的说明 8272826
捐赠科研通 2560904
什么是DOI,文献DOI怎么找? 1389300
科研通“疑难数据库(出版商)”最低求助积分说明 651144
邀请新用户注册赠送积分活动 627946