ABSTRACT
The hybrid composite of cesium phosphomolybdate (CsPM) encapsulated in hierarchical porous UiO-66 (HP-UiO-66) was synthesized using a modulated solvothermal method. A variety of characterization results demonstrated that the pore size distribution of CsPM@HP-UiO-66 is broader than traditional microporous CsPM@UiO-66 and cesium phosphomolybdate clusters are uniformly distributed in the octahedral cages of HP-UiO-66. The catalytic properties of the hybrid composite were investigated in alkene epoxidation reaction with tert-butyl hydroperoxide (t-BuOOH) as an oxidant. CsPM@HP-UiO-66 showed much higher catalytic activity for the alkene epoxidation reaction in comparison with the reference catalysts and could be easily reused by centrifugation and recycled for at least ten runs without significant loss in catalytic activity. The superior catalytic activity and stability of the hybrid composite CsPM@HP-UiO-66 should be mainly attributed to the hierarchical pores in the support HP-UiO-66 promoting the diffusion of alkene molecules, the uniform distribution of highly active CsPM clusters in the octahedral cages of HP-UiO-66, the introduction of cesium cations to form the insoluble cesium phosphomolybdate and the strong metal-support interactions (SMSI) between the CsPM clusters and the HP-UiO-66 framework.
ABSTRACT
The chemical microenvironment of polyoxometalates (POMs) encapsulated in metal-organic frameworks (MOFs) presents a significant influence on their catalytic performance, which can be easily regulated by the linker functional group alteration or metal substitution in MOFs. Herein, a series of cesium phosphomolybdate (CsPM) encapsulated in hierarchical porous UiO-66-X composites (CsPM@HP-UiO-66-X, X = H, 2CH3, or 2OH, where X represents the alterable group grafted onto the linker benzene ring) were successfully synthesized through a one pot modulated solvothermal method. The catalytic performances of the obtained materials were explored in alkene epoxidation reaction with tert-butyl hydroperoxide (t-BuOOH). CsPM@HP-UiO-66-2CH3 showed relatively high catalytic activity, stability, and epoxidation selectivity in cyclooctene epoxidation among the CsPM@HP-UiO-66-X composites. Moreover, CsPM@HP-UiO-66-2CH3 was effective in the epoxidation of numerous alkenes, especially cyclic alkenes. The superior catalytic activity of CsPM@HP-UiO-66-2CH3 is mainly attributed to the modulation of the microenvironment surrounding CsPM active sites by introducing a hydrophobic methyl group. Meanwhile, the size-matched effect, the introduction of cesium cations, and the strong metal-support interactions (SMSIs) between CsPM and HP-UiO-66-2CH3 play a crucial role in the stability of CsPM@HP-UiO-66-2CH3.
ABSTRACT
Nitrogen-doped carbon material (NCM) supported ZnO catalysts were prepared by wet impregnation method, following a high-temperature thermal treatment process. The resultant ZnO/NCM catalysts calcined at different temperatures were characterized by X-ray diffraction (XRD), Raman spectroscopy, N2 adsorption-desorption, elemental analysis, X-ray photoelectron spectroscopy (XPS) to investigate their physicochemical properties and the interaction between ZnO and NCM support. Their catalytic properties were studied by liquid phase transesterification of dimethyl carbonate (DMC) with diethyl carbonate (DEC). Of these the catalyst calcined at 800 °C, named ZnO/NCM-800 exhibits the highest catalytic activity, as well as excellent stability and recyclability for the synthesis of ethyl methyl carbonate (EMC). The NCM support possesses abundant mesopores, rich surface oxygen-containing and nitrogen-containing functional groups, which are beneficial to build relatively strong interaction between ZnO nanoparticles and the NCM support, resulting in the generation of a highly active and stable acidic-basic bifunctional catalyst for the transesterification of DMC with DEC.
