Photo-oxidative desulfurization (PODS) properties of MoO₃–metal–organic framework composite photocatalysts were investigated by introducing the proper weight percent of MoO₃ into a Zn(II)-based MOF, [Zn(oba)(4-bpdh)_0.5]_n·1.5DMF (TMU-5), for the mineralization of dibenzothiophene from model oil. The addition of 3 wt % of MoO₃ into a TMU-5 host acting as a crystal growth inhibitor was confirmed by PXRD and BET results. For the first time, under mild and green reaction conditions, 5 wt % MoO₃–TMU-5 composite (MT-5) exhibited good photocatalytic activity in the model oil PODS reaction, which has no limitations in the current oxidative desulfurization catalytic systems. Only 3% of the total amount of MoO₃ content in the MT catalyst is leached during the reaction. In addition, the rate of PODS of MT-5 obeys a pseudo-first-order equation with an apparent rate constant of 0.0305 min^–1 and half-life t_1/2 of 22.7 min. Radical scavenger experiments and terephthalic acid fluorescence techniques confirmed that OH^• and O₂^•– are the main reactive species in the dibenzothiophene photocatalytic degradation. The synergic effects of the active surface of TMU-5 (organic linkers as antennas) together with the active sites of MoO₃ may lead to the further enhancement of the PODS activity of the MT-5 photocatalyst. Moreover, a possible photocatalytic desulfurization mechanism was proposed in the presence of MoO₃–TMU-5 composites.

中文翻译：

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MoO _3-金属有机骨架复合材料在轻油PODS工艺中作为同时的光催化剂和催化剂

通过将适当重量百分比的MoO ₃引入到基于Zn（II）的MOF [Zn（oba）（4-bpdh）_0.5）中，研究了MoO _3-金属-有机骨架复合光催化剂的光氧化脱硫（PODS）性能。] _n ·1.5DMF（TMU-5），用于从模型油中矿化二苯并噻吩。通过PXRD和BET结果证实了向作为晶体生长抑制剂的TMU-5主体中添加3wt％的MoO ₃。第一次，在温和和绿色的反应条件下，5 wt％MoO ₃–TMU-5复合材料（MT-5）在模型油PODS反应中表现出良好的光催化活性，在当前的氧化脱硫催化体系中没有任何限制。在反应期间，仅MT催化剂中的MoO ₃含量的总量的3％被浸出。此外，MT-5的PODS速率服从拟一级方程式，其表观速率常数为0.0305 min ^–1，半衰期t _1/2为22.7 min。自由基清除剂实验和对苯二甲酸荧光技术证实OH ^•和O ₂ ^•–是二苯并噻吩光催化降解中的主要反应物种。TMU-5的活性表面（有机连接物作为天线）与MoO ₃的活性位点的协同作用可能导致MT-5光催化剂的PODS活性进一步增强。此外，在MoO ₃ –TMU-5复合材料的存在下，提出了一种可能的光催化脱硫机理。