Electrocatalytic water oxidation from a mixed linker MOF based on NU-1000 with an integrated ruthenium-based metallo-linker.

A novel tetratopic metallo-linker, [Ru(tda)(py(PhCOOH))], 1, (tda = 2,2':6',2''-terpyridine-6,6''-dicarboxylate; py(PhCOOH) = (4,4'-(pyridine-3,5-diyl)dibenzoic acid), that is structurally based on one of the most active molecular water oxidation catalysts has been prepared and fully characterized, including single crystal X-ray diffraction. 1 bears geometric similarities to HTBAPy (HTBAPy = 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetrabenzoic acid), the native linker in NU-1000, which offers the possibility to synthesize NU-1000-Ru mixed linker MOFs solvothermally. Mixed linker MOF formation was demonstrated by powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM), and Ru linker incorporation confirmed by FT-IR, energy-dispersive X-ray (EDX) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES).

Elemental Depth Profiling of Intact Metal-Organic Framework Single Crystals by Scanning Nuclear Microprobe.

The growing field of MOF-catalyst composites often relies on postsynthetic modifications for the installation of active sites. In the resulting MOFs, the spatial distribution of the inserted catalysts has far-reaching ramifications for the performance of the system and thus needs to be precisely determined. Herein, we report the application of a scanning nuclear microprobe for accurate and nondestructive depth profiling of individual UiO-66 and UiO-67 (UiO = Universitetet i Oslo) single crystals.

Analysis of Electrocatalytic Metal-Organic Frameworks.

The electrochemical analysis of molecular catalysts for the conversion of bulk feedstocks into energy-rich clean fuels has seen dramatic advances in the last decade. More recently, increased attention has focused on the characterization of metal-organic frameworks (MOFs) containing well-defined redox and catalytically active sites, with the overall goal to develop structurally stable materials that are industrially relevant for large-scale solar fuel syntheses. Successful electrochemical analysis of such materials draws heavily on well-established homogeneous techniques, yet the nature of solid materials presents additional challenges.

Facile Orientational Control of MLP SURMOFs on ⟨100⟩ Silicon Substrates and Growth Mechanism Insights for Defective MOFs.

Layer-by-layer growth of Cu(bdc)(dabco) surface-mounted metal-organic frameworks (SURMOFs) was investigated on silicon wafers treated with different surface anchoring molecules. Well-oriented growth along the [100] and [001] directions could be achieved with simple protocols: growth along the [100] direction was achieved by substrate pretreatment with 80 °C piranha, while growth along the [001] direction was enabled by only rinsing silicon with absolute ethanol. Growth along the [001] direction produced more homogeneous SURMOF films.