Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2024-11-12 DOI:10.1016/j.comptc.2024.114987

Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang

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Abstract

In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the OH bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H₂O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H₂O.

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氧化钙催化四溴双酚 A 的热解机理：密度泛函理论研究

本文通过密度泛函理论方法研究了氧化钙（CaO）催化热解四溴双酚 A（TBBPA）的机理。结果表明，四溴双酚 A 的酚羟基是 CaO 提取质子的首选位点，生成的阴离子通过脱甲基和氢转移反应进一步转化为 2,6-二溴苯酚。CaO 与溴化氢的反应活性相对较高，能垒为 133.2 kJ/mol。CaO 生成钙离子，钙离子与溴离子结合生成溴化钙，从而达到固定溴的目的。此外，钙离子的参与使 OH 键更容易裂开，从而进一步降低了酮烯醇同分异构反应的反应能垒。催化热解过程中产生的 H2O 也具有明显的催化作用，在 H2O 的参与下，酮烯醇同分异构反应的能垒从 309.1 kJ/mol 降至 150.6 kJ/mol。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.