Local CO reservoir layer promotes rapid and selective electrochemical CO reduction.

Electrochemical CO reduction reaction in aqueous electrolytes is a promising route to produce added-value chemicals and decrease carbon emissions. However, even in Gas-Diffusion Electrode devices, low aqueous CO solubility limits catalysis rate and selectivity. Here, we demonstrate that when assembled over a heterogeneous electrocatalyst, a film of nitrile-modified Metal-Organic Framework (MOF) acts as a remarkable CO-solvation layer that increases its local concentration by ~27-fold compared to bulk electrolyte, reaching 0.

Electrostatic Secondary-Sphere Interactions That Facilitate Rapid and Selective Electrocatalytic CO Reduction in a Fe-Porphyrin-Based Metal-Organic Framework.

Metal-organic frameworks (MOFs) are promising platforms for heterogeneous tethering of molecular CO reduction electrocatalysts. Yet, to further understand electrocatalytic MOF systems, one also needs to consider their capability to fine-tune the immediate chemical environment of the active site, and thus affect its overall catalytic operation. Here, we show that electrostatic secondary-sphere functionalities enable substantial improvement of CO -to-CO conversion activity and selectivity.

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO Reduction.

Electrochemically active Metal-Organic Frameworks (MOFs) have been progressively recognized for their use in solar fuel production schemes. Typically, they are utilized as platforms for heterogeneous tethering of exceptionally large concentration of molecular electrocatalysts onto electrodes. Yet so far, the potential influence of their extraordinary chemical modularity on electrocatalysis has been overlooked.

Evolution of metal organic frameworks as electrocatalysts for water oxidation.

In the last two decades, metal organic frameworks (MOFs) have been extensively investigated to develop heterogeneous electrocatalysts for water oxidation (WO). The scope of reticular synthesis, enormous surface area and accessible internal volume of MOFs make them promising candidates for catalysis. However, low electrical conductivity, slow mass transport and lack of stability restrict the scope of MOF-based WO.

Efficient Electrocatalytic Water Oxidation by Fe(salen)-MOF Composite: Effect of Modified Microenvironment.

An efficient and robust heterogeneous electrocatalyst, ((Fe-(salen)(OH) + H[SiWO]·HCl)@ZIF-8) for oxygen evolution reaction (OER) at the neutral pH, was developed by coencapsulation of Fe-salen (i.e., Fe(salen)Cl) and SiW (i.

Designing UiO-66-Based Superprotonic Conductor with the Highest Metal-Organic Framework Based Proton Conductivity.

Metal-organic framework (MOF) based proton conductors have received immense importance recently. The present study endeavors to design two post synthetically modified UiO-66-based MOFs and examines the effects of their structural differences on their proton conductivity. UiO-66-NH is modified by reaction with sultones to prepare two homologous compounds, that is, PSM 1 and PSM 2, with SOH functionalization in comparable extent (Zr:S = 2:1) in both.

Polyoxometalate-Supported Bis(2,2'-bipyridine)mono(aqua)nickel(II) Coordination Complex: an Efficient Electrocatalyst for Water Oxidation.

A polyoxometalate (POM)-supported nickel(II) coordination complex, [Ni(2,2'-bpy)][{Ni(2,2'-bpy)(HO)}{HCoWO}]·3HO (1; 2,2'-bpy = 2,2'-bipyridine), has been synthesized and structurally characterized. We could obtain a relatively better resolved structure from dried crystals of 1, Ni(2,2'-bpy)][{Ni(2,2'-bpy)(HO)}{HCoWO}]·HO (D1). Because the title compound has been characterized with a {Ni(2,2'-bpy)(HO)} fragment coordinated to the surface of the Keggin anion ([H(CoWO]) via a terminal oxo group of tungsten and the [Ni(2,2'-bpy)] coordination complex cation sitting as the lattice component in the concerned crystals, the electronic spectroscopy of compound 1 has been described by comparing its electronic spectral features with those of [Ni(2,2'-bpy)(HO)Cl]Cl, [Ni(2,2'-bpy)]Cl, and K[CoWO]·6HO.

A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF-8, an Efficient and Robust Electrocatalyst.

Keggin-type polyoxometalate anions [XM O ] are versatile, as their applications in interdisciplinary areas show. The Keggin anion [CoW O ] turns into an efficient and robust electrocatalyst upon its confinement in the well-defined void space of ZIF-8, a metal-organic framework (MOF). [H CoW O ]@ZIF-8 is so stable to water oxidation that it retains its initial activity even after 1000 catalytic cycles.