A metal-organic framework converted catalyst that boosts photo-electrochemical water splitting

Realization of photo-electrochemical water splitting to generate H2 alternative fuel requires the facilitation of the kinetically-sluggish oxygen evolution reaction (OER) occurring at the photoanode. To do so, there is a need to develop new methods to assemble suitable OER co-catalysts at the semiconductor–solution interface. Although Metal–Organic Frameworks (MOFs) are frequently used as precursor materials to synthesize high surface area, effective OER electrocatalysts, until now their utilization as co-catalysts in a working photo-electrochemical cell (PEC) has remained underexplored. As a proof-of-concept, here we provide a simple route for modification of BiVO4-based photoanodes with highly-active porous cobalt-oxide co-catalysts, converted from a cobalt–imidazolium MOF (ZIF-67). Photo-electrochemical and impedance spectroscopy analysis reveal that the co-catalyst significantly accelerates photoanodic OER (rather than serving as a surface passivation layer), and thus greatly improves the overall PEC performance. Hence, given the chemical flexibility of MOFs, this work provides a new tool-kit for designing efficient water splitting PECs

Local CO2 reservoir layer promotes rapid and selective electrochemical CO2 reduction

Abstract Electrochemical CO2 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 CO2 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 CO2-solvation layer that increases its local concentration by ~27-fold compared to bulk electrolyte, reaching 0.82 M. When mounted on a Bi catalyst in a Gas Diffusion Electrode, the MOF drastically improves CO2-to-HCOOH conversion, reaching above 90% selectivity and partial HCOOH currents of 166 mA/cm2 (at −0.9 V vs RHE). The MOF also facilitates catalysis through stabilization of reaction intermediates, as identified by operando infrared spectroscopy and Density Functional Theory. Hence, the presented strategy provides new molecular means to enhance heterogeneous electrochemical CO2 reduction reaction, leading it closer to the requirements for practical implementation