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A strategy based on grafting organocatalytic units as side-chain on the organic linkers, a TEMPO radical decorated terphenyl-dicarboxylic acid linker was synthesized. By employing acetic acid as modulator, TEMPO radical decorated UiO-68-TEMPO nanocrystals were synthesized by using H2tpdc-TEMPO as organic linker and ZrOCl2 as metal source under solvothermal conditions. UiO-68-TEMPO are monodispersed nanocrystals with side in the range of 800-1200 nm, with high BET areas (up to 1320 m2/g), and contain a large number of TEMPO radicals as evidenced by solid-state EPR spectrum. UiO-68-TEMPO nanocrystals enable selective oxidation of a broad range of alcohols, including primary aromatic alcohols, secondary aromatic alcohols, and heterogeneous atomic alcohols, with high efficiency and selectivity. The catalytic activity of UiO-68-TEMPO nanocrystals remains 75% after catalysis for four cycles. Finally, a plausible catalytic mechanism for the oxidation of benzyl alcohol by UiO-68-TEMPO was proposed, that is the TBN co-catalyst produces NO2/NO redox mediator, which enables the oxidation of TEMPO radicals to oxoammonium cations by O2, and finally oxidize benzyl alcohol to benzaldehyde.

The iron salts (ferric and ferrous salts) play a critical role for the synthesis of morphology and size controllable, and highly crystalline MIL-100(Fe). The use of ferrous salt results in octahedral, highly crystalline MIL-100(Fe) with high surface areas. In contrast, the use of ferric salt only results in smaller Fe-BTC metal-organic polymers with low crystallinity. The crystal structure, morphology, photo-absorption property, absorption and photocatalytic-degradation properties of MIL-100(Fe) and Fe-BTC toward RhB, were fully characterized by XRD, SEM, FT-IR, UV-Vis DRS, and UV-Vis spectroscopy. The results indicate that the slow oxidation of Fe2+ to Fe3+ is key to the synthesis of highly crystalline MIL-100(Fe) since this process facilitates the formation of μ3-OFe(Ⅲ)O6, which is inorganic secondary building unit (SBU) of MIL-100(Fe). When FeCl3 used as iron source, the fast dynamic reaction of Fe3+ with BTC3- is not beneficial to the formation of μ3-OFe(Ⅲ)O6 SBU; therefore, Fe-BTC nanoparticle polymer is obtained. The smaller size of Fe-BTC nanoparticless, and meso-/macroporous structure in the aggregated nanoparticle surface, which facilitates the diffusion of RhB as well as the photodegradated forms. Fe-BTC shows better absorption capacity and photocatalytic activity toward RhB compared to MIL-100(Fe).

In order to prepare highly crystalline and stable metal-organic frameworks (MOFs) nanoparticles in a straightforward and low cost method, trimesic acid was depronated by three equivalent NaOH in water, and mixed with ferrous salts (e.g. FeCl2 and Fe(OAc)) solution under vigorous stirring for 24h at room temperature. The morphology and photocatalytic activity of the obtained MIL-100(Fe) nanoparticles were fully characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and UV-Vis spectroscopy. The results demonstrate that the MIL-100(Fe) nanoparticles exhibit excellent photocatalytic performance toward high concentrated Rhodamine B (RhB) and methyl orange (MO) organic dyes in the presence of H2O2 as a co-catalyst under UV light irradiation.