Dong Chunyang, Wang Yinghao, Deng Ziqi, Wang Wenchao, Marinova Maya, Ben Tayeb Karima, Morin Jean-Charles, Dubois Melanie, Trentesaux Martine, Kolyagin Yury G, Tran My Nghe, Martin-Diaconescu Vlad, Safonova Olga, Zaffran Jeremie, Khodakov Andrei Y, Ordomsky Vitaly V
UCCS-Unité de Catalyse et Chimie du Solide, Université de Lille, CNRS, Centrale Lille, ENSCL, Université d'Artois, UMR, 8181, Lille, France.
Department of Chemistry, The University of Hong Kong, Hong Kong, China.
Nat Commun. 2024 Sep 18;15(1):8210. doi: 10.1038/s41467-024-52461-9.
Aliphatic diols such as ethylene and propylene glycol are the key products in the chemical industry for manufacturing polymers. The synthesis of these molecules usually implies sequential processes, including epoxidation of olefins using hydrogen peroxide or oxygen with subsequent hydrolysis to glycols. Direct hydroxylation of olefins by cheap and green oxidants is an economically attractive and environmentally friendly route for the synthesis of diols. Here, we report a photocatalytic reaction for the dihydroxylation of ethylene and propylene to their glycols at room temperature using water as the oxidant. The photocatalyst contains Pd clusters stabilized by sub-nanometric polyoxometalate with TiO as the host material. Under light irradiation, it results in production rates of ethylene glycol and propylene glycols of 146.8 mmol·g·h and 28.6 mmol·g·h with liquid-phase selectivities of 63.3 % and 80.0 %, respectively. Meanwhile, green hydrogen derived from water is produced as another valuable product. Combined spectroscopy investigation suggests that the reaction proceeds via π-bonded adsorption of olefins over Pd clusters with hydroxylation by hydroxyl radicals formed by photocatalytic dissociation of water.
脂肪族二醇，如乙二醇和丙二醇，是化学工业中制造聚合物的关键产品。这些分子的合成通常需要一系列过程，包括用过氧化氢或氧气对烯烃进行环氧化，随后水解生成二醇。使用廉价且绿色的氧化剂对烯烃进行直接羟基化是一种经济上有吸引力且环境友好的二醇合成路线。在此，我们报道了一种光催化反应，该反应在室温下以水作为氧化剂，将乙烯和丙烯二羟基化为它们的二醇。光催化剂包含由亚纳米多金属氧酸盐稳定的钯簇，以二氧化钛作为主体材料。在光照下，乙二醇和丙二醇的产率分别为146.8 mmol·g·h和28.6 mmol·g·h，液相选择性分别为63.3%和80.0%。同时，由水衍生的绿色氢气作为另一种有价值的产物产生。联合光谱研究表明，该反应通过烯烃在钯簇上的π键吸附进行，随后通过水的光催化解离形成的羟基自由基进行羟基化反应。
