Romy Ettlinger

Here we present the electrochemical hydrogenation (ECH) of 1-octene to n -octane using the homogeneous complex [( ^iPr PNP)CoCl] [CoCl] and water as the source of hydrogen atoms. We showcase how tuning only electrode surface area, as well as supporting electrolyte type and concentration can drastically increase the reaction selectivity for ECH over parasitic H ₂ evolution from initially 9% to eventually 82% faradaic efficiency, without traditional chemical reaction optimization or catalyst tuning. The ECH process runs via a single electron path of hydrogen atom transfer (HAT) rather than hydride transfer according to quantum chemical calculations. Two consecutive HAT cycles must be completed to hydrogenate one substrate molecule, which renders the process more sensitive to mass transport effects and reaction design than hydride transfer mediated ECH with two electrons transferred in one step. Mechanistically, upon an initial one-electron reduction of [CoCl] , the complex undergoes HAT at one of its benzylic C–H positions to afford a dearomatized ligand structure. A key step of the active ECH cycle is then the oxidative addition of H ₂ O to a Co(I) intermediate, affording a fleeting Co(III)-hydroxy-hydride, which immediately undergoes HAT to the substrate, forming a more stable Co(II)–OH species. A proton coupled electron transfer regenerates Co(I) for the next cycle. Using Bu ₄ NOH in water as hydrogen atom source proved the resilience towards high pH values and suggests that the process does not rely on high proton activity in the electrolyte.

Modulator-assisted aqueous synthesis enables phase-selective formation of ZIF polymorphs with improved sustainability and enhanced enzyme entrapment.

The rapid growth of research on metal–organic frameworks (MOFs) and related porous materials has highlighted a critical need for standardized reporting of synthetic procedures and material properties. Synthesis consistency is often compromised by incomplete protocols and inconsistent nomenclature, with even well‐established MOFs exhibiting substantial variability depending on subtle and frequently unreported factors. To address this critical challenge, we introduce the Material Preparation Information File (MPIF), a modular, machine‐ and human‐readable format for documenting synthesis protocols alongside key characterization data. Built on the Self‐defining Text Archive and Retrieval (STAR) file architecture, MPIF consolidates essential information, including reagents, conditions, equipment, and handling procedures—into a structured format that supports both digital processing and practical laboratory use. To streamline MPIF creation and editing, a web‐based interface has been developed (mpif.jackdevans.com). By aligning with existing standards such as CIF and AIF, MPIF enables integration with databases, promotes FAIR data principles, and provides a foundation for data‐driven materials discovery, informatics, and automation. We envision MPIF becoming a community‐wide standard for transparent and consistent reporting of MOF and related material syntheses.

Despite extensive investigation of metal-organic framework (MOF) derived materials over the last 20 years, no systematic approach to predict the structural properties of the derived metal oxides is available. We present an integrated machine learning (ML) approach leveraging Smooth Overlap of Atomic Positions (SOAP) and multiple ML models, including Kernel Ridge Regression (KRR), to predict thermally derived zirconium dioxide (ZrO2) polymorph from diverse Zr-based precursors. By a systematic experimental dataset of calcination parameters, we train the ML model to quantitatively forecast material properties and the weight fraction of crystalline phases of the resulting ZrO2. Experimental validation of model predictions confirms that the chemical composition of precursors and calcination parameters have a profound influence on the crystallinity of MOF-derived ZrO2 polymorph. Our findings demonstrate the utility of small-data-driven predictive ML modeling and transfer learning for guiding the synthesis of advanced oxide materials providing a blueprint for accelerated discovery of MOF-derived nanomaterials.

β-Cyclodextrin (β-CD) is a cyclic heptasaccharide, part of the family of molecules which are widely used in several biological applications. The unique cone-shape of cyclodextrins with multiple binding sites make them a well-suited building block for constructing porous crystalline solids, such as metal-organic frameworks (MOFs). However, owing to the symmetry constraints, progress in the coordination chemistry of β-CD with alkali and alkaline earth metal cations has been limited and there is less understanding of this chemistry compared to its analogues of α-CD and γ-CD. In this work, synthetic conditions were optimised to obtain two MOF structures with β-CD as the organic linker, one each with Na ⁺ and K ⁺ cations. As well as structural determination, detailed solid-state characterization is reported for both the MOFs. The structure analysis helps shed light on the binding tendencies of β-CD and these structures will further facilitate the deployment of biocompatible building blocks for the development of reticular solid materials.

A new metal-organic framework (MOF) comprising copper and 2,3-dihydroxyterephthalate (2,3-dhtp) has been prepared using solvothermal synthesis. The solid (chemical formula of the as-made material: Cu₁₂(dhtp)₄(H₂dhtp)₃(CH₃CO₂)₂.2DMF.10H₂O is flexible in that its pore size adapts to match the size of guest molecules that are adsorbed. Carboxylate-containing molecules of different sizes (acetate, benzoic acid and ibuprofen) can be accommodated within the pores of the material and are coordinated to a dimeric copper unit. The localisation of the adsorbate guest molecule, the mode of binding and relatively low symmetry of the MOF allows the system to be used as a crystalline sponge. The crystal structure determination of the as-synthesised acetate-bound MOF was accomplished using single-crystal X-ray diffraction using a synchrotron source, while the benzoate- and ibuprofen-bound structures were solved using electron diffraction. A more practical adsorbent can be formulated by growing the MOF on a cotton fabric substrate, and this is shown to adsorb ibuprofen in a similar manner to the powdered MOF.

The significant impact of the SARS‐CoV‐2 (COVID‐19) pandemic outbreak on people's lives has highlighted the urgent need for effective personal protective equipment. To improve the limited protection of existing surgical face masks, the fabrication of face masks containing porous metal–organic framework (MOF) nanoparticles is proposed. Utilizing low toxicity MOFs, such as Al‐Fumarate and HKUST‐1(Cu), allows i) the modification of their external surface with active moieties to specifically bind on proteins or virus surfaces, such as the spike protein of the SARS‐CoV‐2 virus; ii) the adsorption of large amounts of water in their pores, enabling them to dehydrate virus aerosols; and iii) the preparation of MOF‐based composites, providing good breathability. To ensure optimal binding, the MOFs are grown in situ on the fabric and then functionalized with test antiviral agents. Carefully evaluating their protein binding performance with bovine albumin serum (BSA) shows a ten‐fold higher binding of proteins than surgical face masks. Further plaque assays with a SARS‐CoV‐2 virus with an incubation period of 30 min verifies the great potential of MOF‐composites to effectively reduce the recovered viable SARS‐CoV‐2 particles up to 99%. Consequently, the smart MOF‐composites represent an elegant and innovative approach to effectively combat airborne viruses and reduce their spread.

The rapid growth of research on metal–organic frameworks (MOFs) and related porous materials has highlighted a critical need for standardized reporting of synthetic procedures and material properties. Reproducibility is often compromised by incomplete protocols and inconsistent nomenclature, with even well-established MOFs exhibiting substantial variability depending on subtle and frequently unreported factors. To address this critical challenge, we introduce the Material Preparation Information File (MPIF), a modular, machine- and human-readable format for documenting synthesis protocols alongside key characterization data. Built on the (Self-defining Text Archive and Retrieval (STAR) file architecture, MPIF consolidates essential informations—including reagents, conditions, equipment, and handling procedures—into a structured format that supports both digital processing and practical laboratory use. To streamline MPIF creation and editing a web-based interface has been developed (mpif.jackdevans.com). By aligning with existing standards such as CIF and AIF, MPIF enables integration with databases, promotes FAIR data principles, and provides a foundation for data-driven materials discovery, informatics, and automation. We envision MPIF becoming a community-wide standard for transparent and reproducible reporting of MOF and related material syntheses.

Metal-organic frameworks (MOFs), with their high porosities and surface areas, show great utility in the field of gas adsorption. To unlock this porosity, MOFs are generally fully activated by removing all adsorbed guests using high temperatures and low pressures. However, this is energy intensive and can be unfeasible if the MOF is part of a composite, where the maximum temperature of the composite is below the activation temperature. To investigate the effect of activation temperature on adsorption, a series of in situ single-crystal X-ray diffraction (scXRD) studies were performed on Ni-MOF-74 loaded with the gas nitric oxide (NO) under different conditions. These experiments uncovered anomalous adsorption results where partially activated samples adsorb ∼14% more NO per framework material than did the fully activated sample. The scXRD experiments revealed a new NO binding site that is only present if the open metal sites are partially occupied by water molecules. To shed more light on the respective binding of the two different NO sites in Ni-MOF-74, these were studied in situ under different treatment conditions, such as the exposure to vacuum at different temperatures. This study yields insights into the nature of binding sites in MOFs, how these are affected by activation, and helps to pave the way for the improved design of processing conditions.