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 H 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.

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.

Light-induced MOF synthesis enabling composite photothermal materials.

Metal-organic frameworks (MOFs) are a class of porous materials known for their large surface areas. Thus, over the past few decades the development of MOFs and their applications has been a major topic of interest throughout the scientific community. However, many current conventional syntheses of MOFs are lengthy solvothermal processes carried out at elevated temperatures.

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.

Charge Transport in Zirconium-Based Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu.

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.

Anisotropic Redox Conductivity within a Metal-Organic Framework Material.

Engendering electrical conductivity in otherwise insulating metal-organic framework (MOF) materials is key to rendering these materials fully functional for a range of potential applications, including electrochemical and photo-electrochemical catalysis. Here we report that the platform MOF, NU-1000, can be made electrically conductive via reversible electrochemical oxidation of a fraction of the framework's tetraphenylpyrene linkers, where the basis for conduction is redox hopping. At a microscopic level, redox hopping is akin to electron self-exchange and is describable by Marcus' well-known theory of electron transfer.

Simultaneous laser-induced synthesis and micro-patterning of a metal organic framework.

Micro-patterning of a metal organic framework (MOF) from a solution of precursors is achieved by local laser heating. Nano-sized MOFs are formed, followed by rapid assembly due to convective flows around a heat-induced micro-bubble. This laser-induced bottom-up technique is the first to suggest simultaneous synthesis and micro-patterning of MOFs, alleviating the need for pre-preparation and stabilization.

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.

Probing charge transfer characteristics in a donor-acceptor metal-organic framework by Raman spectroelectrochemistry and pressure-dependence studies.

The stimuli responsive behaviour of charge transfer donor-acceptor metal-organic frameworks (MOFs) remains an understudied phenomenon which may have applications in tuneable electronic materials. We now report the modification of donor-acceptor charge transfer characteristics in a semiconducting tetrathiafulvalene-naphthalene diimide-based MOF under applied electrochemical bias and pressure. We employ a facile solid state in situ Raman spectroelectrochemical technique, applied for the first time in the characterisation of electroactive MOFs, to monitor the formation of a new complex TTFTC˙+-DPNI from a largely neutral system, upon electrochemical oxidation of the framework.

Tunable Molecular-Scale Materials for Catalyzing the Low-Overpotential Electrochemical Conversion of CO.

Electrochemical CO reduction provides a clean and viable alternative for mitigating the environmental aspects of global greenhouse gas emissions. To date, the simultaneous goals of CO reduction at high selectivity and activity have yet to be achieved. Here, the importance of engineering both sides of the electrode-electrolyte interface as a rational strategy for achieving this milestone is highlighted.

Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66.

Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active.

Improved catalytic activity of MoWSe alloy nanoflowers promotes efficient hydrogen evolution reaction in both acidic and alkaline aqueous solutions.

Layered transition metal dichalcogenides are noble-metal free electrocatalysts for the hydrogen evolution reaction (HER). Instead of using the common hydrothermal synthesis, which requires high pressure and temperature, herein a relatively simple and controlled colloidal synthesis was used to produce an alloy of MoWSe with nanoflower morphology as a model system for the electrocatalysis of hydrogen evolution in both acidic and alkaline environments. The results show that MoWSe alloys exhibit better catalytic activity in both acidic and alkaline solutions with low overpotentials compared to pure MoSe and WSe.

Rendering High Surface Area, Mesoporous Metal-Organic Frameworks Electronically Conductive.

We report the design and synthesis of a metal-organic framework (MOF)-polythiophene composite that has comparable electronic conductivity to reported conductive 3-D MOFs, but with display and retention of high porosity, including mesoporosity. A robust zirconium MOF, NU-1000, was rendered electronically conductive by first incorporating, via solvent-assisted ligand incorporation (SALI), a carefully designed pentathiophene derivative at a density of one pentamer per hexa-zirconium node. Using a cast film of the intermediate composite (termed pentaSALI) on conductive glass, the incorporated oligothiophene was electrochemically polymerized to yield the conductive composite, Epoly.

A Redox-Active Bistable Molecular Switch Mounted inside a Metal-Organic Framework.

We describe the incorporation of a bistable mechanically interlocked molecule (MIM) into a robust Zr-based metal-organic framework (MOF), NU-1000, by employing a post-synthetic functionalization protocol. On average, close to two bistable [2]catenanes can be incorporated per repeating unit of the hexagonal channels of NU-1000. The reversible redox-switching of the bistable [2]catenanes is retained inside the MOF, as evidenced by solid-state UV-vis-NIR reflectance spectroscopy and cyclic voltammetry.

Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs.

Catalytic activity for acyl transfer from N-acetylimidazole (NAI) to different pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC) is demonstrated for a set of topologically diverse, zirconium-based (porphinato)zinc metal-organic frameworks (MOFs). The MOFs studied are PCN-222, MOF-525, and NU-902, which are based on the csq, ftw, and scu topologies, respectively. The experimentally obtained reaction kinetics are discussed in light of molecular modeling results.

Modulating the rate of charge transport in a metal-organic framework thin film using host:guest chemistry.

Herein we demonstrate the use of host-guest chemistry to modulate rates of charge transport in metal-organic framework (MOF) films. The kinetics of site-to-site of charge hopping and, in turn, the overall redox conductivity, of a ferrocene-modified MOF can be altered by up to 30-fold by coupling electron exchange to the oxidation-state-dependent formation of inclusion complexes between cyclodextrin and channel-tethered metallocenes.

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution.

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst.