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DFT Insights into the Effect of Metal Substitution on the Catalytic Activity of Molybdenum-Based Heteropoly Acid in the Oxidation of Methacrolein to Methacrylic Acid
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2024-03-10 , DOI: 10.1021/acs.iecr.3c04269 Yuan Tian 1 , Hanwen Yan 2 , Jie Li 2 , Yiqian Yang 1 , Tianyu Guo 2 , Xiangping Zhang 2 , Shuguang Xiang 1 , Chunshan Li 2, 3
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2024-03-10 , DOI: 10.1021/acs.iecr.3c04269 Yuan Tian 1 , Hanwen Yan 2 , Jie Li 2 , Yiqian Yang 1 , Tianyu Guo 2 , Xiangping Zhang 2 , Shuguang Xiang 1 , Chunshan Li 2, 3
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The selective oxidation of methacrolein (MAL) to methacrylic acid (MAA) over heteropolyacid has received great attention, while the “structure–activity” descriptor for catalyst development and improvement needs intensive exploration. Herein, the selective oxidation of MAL to MAA on phosphorus molybdenum heteropolyanion PMo12O403– (HPA) with different substitutions of coordinated metal atoms (M = W, V, Nb, and Ta) was calculated using density functional theory (DFT). The effect of substituted metal atoms on the electronic properties of HPA, adsorption and oxidation of MAL to MAA on HPA and PMo11MO40n– (M-HPA; n = 3 or 4), and activation of oxygen by vacancy were revealed as well as the catalytically active sites. The differences in the energy barriers of the rate-determining step were compared and explained. The accessible electronegativity was used as the descriptor associated with the energy barrier of the rate-determining step, and an inverted volcano relationship was unraveled. To further understand the break and the formation of crucial bond during the reaction, a formula defined as matched-degree was proposed. These studies would be beneficial for the efficient screening and design of heteropoly acid catalysts.
中文翻译：
DFT 洞察金属取代对钼基杂多酸异丁烯醛氧化成甲基丙烯酸催化活性的影响
异丁烯醛（MAL）在杂多酸上选择性氧化为甲基丙烯酸（MAA）受到了广泛关注，而催化剂开发和改进的“结构-活性”描述符需要深入探索。在此，使用密度泛函理论（DFT）计算了MAL在具有不同配位金属原子取代（M = W、V、Nb和Ta）的磷钼杂多阴离子PMo 12 O 40 3–（HPA）上选择性氧化为MAA的情况。取代金属原子对 HPA 电子性质、MAL 在 HPA 和 PMo 11 MO 40 n– (M-HPA; n = 3 或 4) 上吸附和氧化为 MAA 以及空位对氧的活化的影响如下：以及催化活性位点。比较并解释了速率决定步骤的能垒的差异。可达到的电负性被用作与速率决定步骤的能垒相关的描述符，并且解开了倒火山关系。为了进一步了解反应过程中关键键的断裂和形成，提出了一个定义为匹配度的公式。这些研究将有利于杂多酸催化剂的有效筛选和设计。
更新日期：2024-03-10
中文翻译：
DFT 洞察金属取代对钼基杂多酸异丁烯醛氧化成甲基丙烯酸催化活性的影响
异丁烯醛（MAL）在杂多酸上选择性氧化为甲基丙烯酸（MAA）受到了广泛关注，而催化剂开发和改进的“结构-活性”描述符需要深入探索。在此，使用密度泛函理论（DFT）计算了MAL在具有不同配位金属原子取代（M = W、V、Nb和Ta）的磷钼杂多阴离子PMo 12 O 40 3–（HPA）上选择性氧化为MAA的情况。取代金属原子对 HPA 电子性质、MAL 在 HPA 和 PMo 11 MO 40 n– (M-HPA; n = 3 或 4) 上吸附和氧化为 MAA 以及空位对氧的活化的影响如下：以及催化活性位点。比较并解释了速率决定步骤的能垒的差异。可达到的电负性被用作与速率决定步骤的能垒相关的描述符，并且解开了倒火山关系。为了进一步了解反应过程中关键键的断裂和形成，提出了一个定义为匹配度的公式。这些研究将有利于杂多酸催化剂的有效筛选和设计。
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