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首页> 外文期刊>ACS catalysis >Theoretical Study of 4-(Hydroxymethyl)benzoic Acid Synthesis from Ethylene and 5-(Hydroxymethyl)furoic Acid Catalyzed by Sn-BEA
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Theoretical Study of 4-(Hydroxymethyl)benzoic Acid Synthesis from Ethylene and 5-(Hydroxymethyl)furoic Acid Catalyzed by Sn-BEA

机译：Sn-BEA催化乙烯与5-（羟甲基）糠酸合成4-（羟甲基）苯甲酸的理论研究

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摘要

A sustainable route has been reported for the production of terephthalic acid (PTA) from 5-(hydroxymethyl)furoic acid (HMFA) and ethylene, both of which can be derived from biomass. This process starts with the production of 4-(hydroxymethyl)benzoic acid (HMBA) from HMFA and ethylene catalyzed by Sn-BEA. The subsequent oxidation of HMBA leads to PTA. The present study reports the results of a detailed computational investigation of the mechanism of HMBA synthesis from ethylene and HMFA mediated by Sn-BEA. Density functional theory calculations show that the formation of HMBA proceeds via Diels-Alder cycloaddition of HMFA and ethylene, which is rate-limiting, followed by Lewis acid-catalyzed dehydration. The solution-phase reaction and six different pathways in Sn-BEA, including one pathway on the Si site and five different pathways on the Sn site, are investigated for the Diels Alder cycloaddition of HMFA and ethylene. Energy decomposition analysis (EDA) shows that the Sn site stabilizes the transition state of the Diels Alder reaction electrostatically instead of facilitating charge transfer between HMFA and ethylene. Therefore, the preferred pathway for the Diels Alder reaction starts with binding HMFA to the Sn site by the carbonyl oxygen, which is the configuration that maximizes electrostatic interactions between substrates and the catalyst in the transition state. The effect of substituting Sn in the active site by Zr and Ti was examined and the highest reaction barriers were for the Ti sites. Using EDA, we found that though the barriers of the Sn and Zr site are comparable, the individual contributing effects are different: lower energy penalty associated with distortion of the geometry of the Zr site overcomes less favorable electrostatic and charge transfer effects compared to the Sn site.
机译：已经报道了由5-（羟甲基）糠酸（HMFA）和乙烯生产对苯二甲酸（PTA）的可持续路线，两者都可以来源于生物质。该过程开始于由HMFA和由Sn-BEA催化的乙烯生产4-（羟甲基）苯甲酸（HMBA）。随后的HMBA氧化导致生成PTA。本研究报告的详细计算研究结果的乙烯和HMFA由Sn-BEA介导HMBA合成机理的详细计算研究。密度泛函理论计算表明，HMBA的形成是通过限速的HMFA和乙烯的Diels-Alder环加成反应进行的，随后是路易斯酸催化的脱水反应。研究了HMFA和乙烯的Diels Alder环加成反应，研究了固溶相反应和Sn-BEA中的6种不同途径，包括在Si位点上的一条途径和在Sn位点上的5条不同途径。能量分解分析（EDA）表明，Sn位置在静电作用下稳定了Diels Alder反应的过渡态，而不是促进HMFA和乙烯之间的电荷转移。因此，Diels Alder反应的优选途径始于通过羰基氧使HMFA与Sn位点结合，这是在过渡态下使底物与催化剂之间的静电相互作用最大化的构型。研究了用Zr和Ti替代活性位中的Sn的效果，最高的反应势垒是Ti位。使用EDA，我们发现尽管Sn和Zr站点的势垒是可比的，但各自的影响是不同的：与Sn相比，与Zr站点的几何形状变形相关的较低能量损失克服了不利的静电和电荷转移效应现场。

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