Computational Exploration of the Mechanism of the Hydrogenation Step of the Anthraquinone Process for Hydrogen Peroxide Production
Computational Exploration of the Mechanism of the Hydrogenation Step of the Anthraquinone Process for Hydrogen Peroxide Production
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DOI：
10.1021/acs.jpcc.5b01325
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发表时间：
2015-04-23
影响因子：
3.7
通讯作者：
Yoshizawa, Kazunari
中科院分区：
文献类型：
--
作者：
Kamachi, Takashi;Ogata, Tatsunobu;Yoshizawa, Kazunari
过氧化氢在商业上是通过蒽醌（AQ）和四氢蒽醌（THAQ）的连续氢化和氧化来生产的。采用周期性密度泛函理论（DFT）研究了AQ和THAQ在Pd（111）表面的氢化反应。二氢优先吸附在Pd原子的顶部，并且产生的氢原子在两个相邻的3重中空fcc位置上。AQ的三个苯环位于Pd（111）表面的桥位上。蒽醌和四氢蒽醌的两个羰基氧原子依次夺取表面氢原子，分别生成蒽氢醌（AHQ）和四氢蒽氢醌（THAHQ）。还研究了AQ方法的氢化步骤中不需要的副产物蒽酮（AN）、四氢蒽酮（THAN）、恶蒽酮（OAN）和四氢恶蒽酮（THOAN）的形成，以考虑这些副产物的抑制。
Hydrogen peroxide is produced commercially by the sequential hydrogenation and oxidation of anthraquinone (AQ) and tetrahydroanthraquinone (THAQ). The hydrogenation of AQ and THAQ on the Pd(111) surface is investigated with periodic density functional theory (DFT) calculations in this work. Dihydrogen is preferentially adsorbed on the top of a Pd atom, and the produced hydrogen atoms are on two neighboring 3-fold hollow fcc positions. The three benzene rings of AQ are located at bridge sites on the Pd(111) surface. The two carbonyl oxygen atoms of AQ and THAQ successively abstract the surface hydrogen atoms to produce anthrahydroquinone (AHQ) and tetrahydroanthrahydroquinone (THAHQ), respectively. The formation of unwanted byproducts, anthrone (AN), tetrahydroanthrone (THAN), oxanthrone (OAN), and tetrahydro-oxanthrone (THOAN), in the hydrogenation step of the AQ process is also studied to consider the suppression of these byproducts.