Local CO2 reservoir layer promotes rapid and selective electrochemical CO2 reduction.

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.

Regulation of Catalyst Immediate Environment Enables Acidic Electrochemical Benzyl Alcohol Oxidation to Benzaldehyde.

Electrocatalytic alcohol oxidation in acid offers a promising alternative to the kinetically sluggish water oxidation reaction toward low-energy H2 generation. However, electrocatalysts driving active and selective acidic alcohol electrochemical transformation are still scarce. In this work, we demonstrate efficient alcohol-to-aldehyde conversion achieved by reticular chemistry-based modification of the catalyst's immediate environment. Specifically, coating a Bi-based electrocatalyst with a thin layer of metal-organic framework (MOF) substantially improves its performance toward benzyl alcohol electro-oxidation to benzaldehyde in a 0.1 M H2SO4 electrolyte. Detailed analysis reveals that the MOF adlayer influences catalysis by increasing the reactivity of surface hydroxides as well as weakening the catalyst-benzaldehyde binding strength. In turn, low-potential (0.65 V) cathodic H2 evolution was obtained through coupling it with anodic benzyl alcohol electro-oxidation. Consequently, the presented approach could be implemented in a wide range of electrocatalytic oxidation reactions for energy-conversion application.

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. In situ Raman spectroscopy characterization revealed that the MOF precatalysts could be electrochemically converted to the active catalysts (NiFeOOH). In turn, it was found that the highest water oxidation activity was obtained with a catalyst containing a 47:53 Ni:Fe molar ratio. Additionally, the obtained catalyst is also active toward electrochemical methanol oxidation, exhibiting high selectivity toward the formation of formic acid. Hence, these results could pave the way for the development of efficient electrocatalytic materials for a variety of oxidative reactions.

Electrostatic Secondary-Sphere Interactions That Facilitate Rapid and Selective Electrocatalytic CO2 Reduction in a Fe-Porphyrin-Based Metal-Organic Framework.

Metal-organic frameworks (MOFs) are promising platforms for heterogeneous tethering of molecular CO2 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 CO2 -to-CO conversion activity and selectivity. In situ Raman analysis reveal that immobilization of pendent positively-charged groups adjacent to MOF-residing Fe-porphyrin catalysts, stabilize weakly-bound CO intermediates, allowing their rapid release as catalytic products. Also, by varying the electrolyte's ionic strength, systematic regulation of electrostatic field magnitude was achieved, resulting in essentially 100 % CO selectivity. Thus, this concept provides a sensitive molecular-handle that adjust heterogeneous electrocatalysis on demand.

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO2 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. Herein, we demonstrate that, when assembled on a solid Ag CO2 reduction electrocatalyst, a non-catalytic UiO-66 MOF acts as a porous membrane that systematically tunes the active site's immediate chemical environment, leading to a drastic enhancement of electrocatalytic activity and selectivity. Electrochemical analysis shows that the MOF membrane improves catalytic performance through physical and electrostatic regulation of reactants delivery towards the catalytic sites. The MOF also stabilizes catalytic intermediates via modulation of active site's secondary coordination sphere. This concept can be expanded to a wide range of proton-coupled electrochemical reactions, providing new means for precise, molecular-level manipulation of heterogeneous solar fuels systems.

Electrochemically Driven Cation Exchange Enables the Rational Design of Active CO2 Reduction Electrocatalysts.

Metal oxides or sulfides are considered to be one of the most promising CO2 reduction reaction (CO2 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., grain boundaries (GBs) and undercoordinated sites (USs)], directly from a predesigned template material. Herein, we describe a novel electrochemically driven cation exchange (ED-CE) method that enables the conversion of a predesigned CoS2 template into a CO2 RR catalyst, Cu2 S. By means of ED-CE, the final Cu2 S catalyst inherits the original 3 D morphology of CoS2 , and preserves its high density of GBs. Additionally, the catalyst's phase structure, composition, and density of USs were precisely tuned, thus enabling rational design of active CO2 RR sites. The obtained Cu2 S catalyst achieved a CO2 -to-formate Faradaic efficiency of over 87 % and a record high activity (among reported Cu-based catalysts). Hence, this study opens the way for utilization of ED-CE reactions to design advanced electrocatalysts.

Spatially confined electrochemical conversion of metal-organic frameworks into metal-sulfides and their in situ electrocatalytic investigation via 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. To do so, here we couple the synthetical and the analytical virtues of scanning electrochemical microscopy (SECM). Namely, we first utilized an SECM tip electrode to induce spatially confined (µm-scale) electrochemical conversion of cobalt-based ZIF-67 MOFs into patterns of cobalt sulfide with a tuned chemical composition. In turn, the same SECM setup was used to map the H2 evolution activity of the as-formed cobalt sulfide. Hence, the presented method should have great implications for future screening of new electrocatalytic materials for a variety of energy-related applications.

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. Here, we show that the axial coordination of electron-donating ligands to active MOF-installed Fe-porphyrins dramatically alters their electronic properties, accelerating the rates of both redox-based MOF conductivity and the electrocatalytic oxygen reduction reaction (ORR). Additionally, electrochemical characterizations show that in multiple proton-coupled electron transfer reactions MOF-based redox hopping is not the only factor that limits the overall electrocatalytic rate. Hence, future efforts to enhance the efficiency of electrocatalytic MOFs should also consider other important kinetic parameters such as the rate of proton-associated chemical steps as well as mass-transport rates of counterions, protons, and reactants toward catalytically active sites.

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. Here, we have conducted a detailed comparison between the intrinsic electrocatalytic properties of pristine and pyrolyzed Ni-Fe-based MOFs. Interestingly, although pristine MOF exhibits the maximum overall electrocatalytic performance, apparent turnover frequency (TOF) values (intrinsic activity) of all pyrolyzed MOFs exceeded the one of pristine MOF. Moreover, an upper-limit estimation of TOF was extracted using electrochemical impedance spectroscopy (EIS), by excluding IR-drops linked with the electrochemical cell. By doing so, EIS-extracted TOF values were 10-times higher compared to the apparent TOFs. Accordingly, a great leap in performance should still be expected for these catalysts, by designing conductive MOF-platforms having larger pore-diameters to reduce mass-transport limitations.