Controlled synthesis of concave cuboctahedral nitrogen-rich metal–organic framework nanoparticles showing enhanced catalytic activation of epoxides with carbon dioxide

Abstract

Nitrogen-rich metal-organic framework (N-MOF) nanoparticles with an unusual concave cuboctahedral morphology were prepared through a facile wet-chemical route using benzimidazole as the modulator. Benzimidazole plays an essential role in controlling the concave cuboctahedral morphology of the nanoparticles.By changing the benzimidazole dosage, the resultant morphology can be tuned from a concave octahedron to a concave cuboctahedron. The concave cuboctahedral nanoparticles exhibit high catalytic efficiency for the activation of epoxides with carbon dioxide.

Metal–Organic Gel Material Based on UiO‐66‐NH2 Nanoparticles for Improved Adsorption and Conversion of Carbon Dioxide

“…The catalystw as more activef or the cycloaddition of aliphatic epoxidesa nd the reactions were finished within as horter time (4 h). The present high activity towards both small and large substrates [37] should be attributed to efficient mass transfer of the gel catalysts.…”

Strategies for Enhancing the Catalytic Performance of Metal–Organic Frameworks in the Fixation of CO2 into Cyclic Carbonates

“…Although less common, heterogeneous catalysts have also been reported for this reaction, including zeolites, metal oxides, double‐metal cyanides, immobilised metal complexes, ionic liquids and ammonium or phosphonium salts supported on SiO 2 . There are several studies on MOFs as catalysts for the synthesis of cyclic carbonates from CO 2 and epoxides . Although very promising results have been achieved, each MOF catalyst reported so far still suffers from one or more limitations, either owing to i) low stability upon recycling, or ii) the use of extremely high loading of organic halide, iii) harsh reaction conditions (e.g.…”

The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials

“…One of the most common approaches to control the size and morphology of reticular nanoparticles is the addition of modulating agents (Figure 2) to the reaction mixture. [28,38] The influence of modulator concentration during solvothermal nanoparticle synthesis has two effects: in small amounts, the modulating agent increases the concentration of deprotonated ligands causing nucleation centers and decreases the particle size. Second, modulator molecules compete with the organic linkers for the coordination sites of the metal-centers, slowing the reaction kinetics which in turn regulates the size and shape of the nanoparticles.…”

“…Solvothermal synthesis is commonly used in bulk synthetic methods and can be applied to initiate spontaneous precipitation by introducing additional heating steps. Reaction times usually range from a few hours to a week 26b,28. Solvothermal nanoparticle usually requires the use of diluted bulk‐reaction conditions to slow down the reaction kinetics and enable homogenous nanoparticle growth 29.…”

“…One of the most common approaches to control the size and morphology of reticular nanoparticles is the addition of modulating agents (Figure 2) to the reaction mixture 28,38. The influence of modulator concentration during solvothermal nanoparticle synthesis has two effects: in small amounts, the modulating agent increases the concentration of deprotonated ligands causing nucleation centers and decreases the particle size.…”