Selective ligand removal to improve accessibility of active sites in hierarchical MOFs for heterogeneous photocatalysis

Metal-organic frameworks (MOFs) are commended as photocatalysts for H2 evolution and CO2 reduction as they combine light-harvesting and catalytic functions with excellent reactant adsorption capabilities. For dynamic processes in liquid phase, the accessibility of active sites becomes a critical parameter as reactant diffusion is limited by the inherently small micropores. Our strategy is to introduce additional mesopores by selectively removing one ligand in mixed-ligand MOFs via thermolysis. Here we report photoactive MOFs of the MIL-125-Ti family with two distinct mesopore architectures resembling either large cavities or branching fractures. The ligand removal is highly selective and follows a 2-step process tunable by temperature and time. The introduction of mesopores and the associated formation of new active sites have improved the HER rates of the MOFs by up to 500%. We envision that this strategy will allow the purposeful engineering of hierarchical MOFs and advance their applicability in environmental and energy technologies.

Ultrasensitive fluorescence detection of norfloxacin in aqueous medium employment a 2D Zn(II)-based coordination polymer

A mixed-ligand ternary Zn(II) coordination polymer (CP), {[Zn(L)0.5(mip)] 1.75H2O}n (1) (L = 1,4-bis(thiabendazol-1-ylmethyl)benzene, H2mip = 5-methylisophthalic acid), was prepared and characterized. 1 features a 2D hcb layer, which can further...

Multivariate sodalite Zeolitic Imidazolate frameworks: a direct solvent-free synthesis

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology. In particular, the versatility of...