Ren Zhuoyi, Yuan Qibin, Dai Chunyan, Zhu Linhua
College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou571158, China.
Key Laboratory of Water Pollution Treatment and Resource Reuse of Hainan Province, Haikou571158, China.
ACS Omega. 2023 Feb 2;8(6):5593-5606. doi: 10.1021/acsomega.2c06893. eCollection 2023 Feb 14.
Oxidative desulfurization (ODS) has been proved to be an efficient strategy for the removal of aromatic sulfur compounds from diesel oils, which are one of the main sources of air pollution. Heteropolyacid catalysts are highly active species for ODS, but the promotion of their catalytic activity and clarification of their catalytic mechanism remain an important issue. Herein, a series of novel imidazole-based heteropolyacid catalysts are prepared by a one-pot method for multiphase deep ODS of fuel with hydrogen peroxide as an oxidant. The experimental results show that the desulfurization performance of the prepared imidazole-based heteropolyacid catalysts is high up to 99.9% under mild conditions. The catalyst also possesses excellent recovery performance, and the desulfurization activity remains at 97.7% after being recycled seven times. Furthermore, density functional theory calculation is first employed to clarify the origin of the high desulfurization activity, and the results show that with the imidazole-based heteropolyacid (HPW-VIM) as the catalyst, the energy barrier is much lower than that with phosphotungstic acid (HPW) as the catalyst.
氧化脱硫（ODS）已被证明是从柴油中去除芳烃硫化合物的有效策略，柴油是空气污染的主要来源之一。杂多酸催化剂是ODS的高活性物种，但提高其催化活性并阐明其催化机理仍然是一个重要问题。在此，通过一锅法制备了一系列新型咪唑基杂多酸催化剂，以过氧化氢为氧化剂用于燃料的多相深度ODS。实验结果表明，所制备的咪唑基杂多酸催化剂在温和条件下脱硫性能高达99.9%。该催化剂还具有优异的回收性能，循环使用七次后脱硫活性仍保持在97.7%。此外，首次采用密度泛函理论计算来阐明高脱硫活性的来源，结果表明，以咪唑基杂多酸（HPW-VIM）为催化剂时，能垒远低于以磷钨酸（HPW）为催化剂时的能垒。
