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.

Nickel-Iron-Modified 2D Metal-Organic Framework as a Tunable Precatalyst for Electrochemical Water Oxidation.

Mixed-metal metal-organic framework (MOF)-based water oxidation precatalysts have aroused a great deal of attention due to their remarkable catalytic performance. Yet, despite significant advancement in this field, there is still a need to design new MOF platforms that allow simple and systematic control over the final catalyst's metal composition. Here, we show that a Zr-BTB 2D-MOF could be used to construct a series of Ni-Fe-based oxide hydroxide water oxidation precatalysts with diverse Ni-Fe compositions.

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.

Electrochemically Driven Cation Exchange Enables the Rational Design of Active CO Reduction Electrocatalysts.

Metal oxides or sulfides are considered to be one of the most promising CO reduction reaction (CO RR) precatalysts, owing to their electrochemical conversion in situ into highly active electrocatalytic species. However, further improvement of the performance requires new tools to gain fine control over the composition of the active species and its structural features [e.g.

Spatially confined electrochemical conversion of metal-organic frameworks into metal-sulfides and their electrocatalytic investigation scanning electrochemical microscopy.

There is an on-going search for new earth-abundant electrocatalytic materials, suitable for replacing noble-metals as efficient accelerators of energy-conversion reactions. In this regard, over the last few years, metal-organic framework (MOF)-converted materials have demonstrated promising electrocatalytic properties. Nevertheless, the discovery of new catalytic materials requires development of methods combining high-throughput synthesis and electrochemical-activity screening.

Active-Site Modulation in an Fe-Porphyrin-Based Metal-Organic Framework through Ligand Axial Coordination: Accelerating Electrocatalysis and Charge-Transport Kinetics.

The construction of artificial solar fuel generating systems requires the heterogenization of large quantities of catalytically active sites on electrodes. In that sense, metal-organic frameworks (MOFs) have been utilized to assemble unpreceded concentration of electrochemically active molecular catalysts to drive energy-conversion electrocatalytic reactions. However, despite recent advances in MOF-based electrocatalysis, so far no attempt has been made to exploit their unique chemical modularity in order to tailor the electrocatalytic function of MOF-anchored active sites at the molecular level.

Pristine versus Pyrolyzed Metal-Organic Framework-based Oxygen Evolution Electrocatalysts: Evaluation of Intrinsic Activity Using Electrochemical Impedance Spectroscopy.

Metal-organic frameworks (MOFs) have emerged as outstanding electrocatalysts for water oxidation. Commonly, MOFs are utilized for electrocatalytic water oxidation either in pristine or pyrolyzed form. Yet, despite significant advancements in their catalytic performance, further improvement requires new insights on the parameters influencing MOF-based catalysts activity.