Qu Wenjia, Wei Pengpeng, Li Jingfang, Liang Liye, Ma Liqiang, Li Guangming
Key Laboratory of Functional Inorganic Material Chemistry (MOE), School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, Heilongjiang, China.
Dalton Trans. 2024 Jul 30;53(30):12610-12619. doi: 10.1039/d4dt01568a.
Because global sulfur emission has escalated, the development of high-efficiency deep desulfurization techniques has become imperative. Herein, to design a high-activity heterogeneous catalyst for the aerobic oxidation desulfurization (AODS) of fuel, Dawson-type polyoxometalate (HPWO abbreviated as D-PW), characterized by its high activity and strong oxidative capacity, was applied to react with CuCl·2HO and HTZI a one-pot hydrothermal method. Consequently, blue crystalline HPWO[CuO(TZI)(HO)] (abbreviated as D-PW@-MOF-1; -MOF-1 = [CuO(TZI)(HO)]·HO) was afforded. X-ray diffraction analysis indicated that D-PW was successfully encapsulated in two different cages of -MOF-1, which is distinct from the crystal structure of Keggin-type POMs@-MOF-1. It represents the first crystal structure of Dawson-type POMs@-MOF-1. When D-PW@-MOF-1 was employed as a catalyst for AODS under ambient oxygen pressure with the assistance of surfactant dioctadecyl dimethyl ammonium chloride (DODMAC), it demonstrated remarkable catalytic capability and recyclability for both model fuel and commercial diesel. Further, the AODS reaction mechanism, identified as a free radical oxidation-reduction process, was verified by way of radical quenching experiments, EPR and XPS analysis. This approach offers a feasible route for the synthesis of new Dawson-type POMs@MOFs of heterogeneous catalysts for highly active AODS of fuel.
由于全球硫排放不断增加，高效深度脱硫技术的开发变得势在必行。在此，为了设计一种用于燃料有氧氧化脱硫（AODS）的高活性多相催化剂，将具有高活性和强氧化能力的道森型多金属氧酸盐（HPWO，简称为D-PW）通过一锅水热法与CuCl·2H₂O和HTZI反应。结果，得到了蓝色晶体HPWO[Cu₂O(TZI)(H₂O)]（简称为D-PW@β-MOF-1；β-MOF-1 = [Cu₂O(TZI)(H₂O)]·H₂O）。X射线衍射分析表明，D-PW成功封装在β-MOF-1的两个不同笼中，这与Keggin型POMs@β-MOF-1的晶体结构不同。它代表了道森型POMs@β-MOF-1的首个晶体结构。当D-PW@β-MOF-1在表面活性剂二辛基二甲基氯化铵（DODMAC）的辅助下，在环境氧气压力下用作AODS的催化剂时，它对模型燃料和商业柴油都表现出显著的催化能力和可回收性。此外，通过自由基猝灭实验、电子顺磁共振（EPR）和X射线光电子能谱（XPS）分析验证了AODS反应机理为自由基氧化还原过程。该方法为合成用于燃料高活性AODS的新型道森型POMs@MOFs多相催化剂提供了一条可行的途径。
