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In the chemical industry, formaldehyde is an important bulk chemical. The traditional synthesis of formaldehyde involves an energy intensive oxidation of methanol over a metal oxide catalyst. The selective electrochemical oxidation of methanol is challenging. Herein, we report a catalytic system with an immobilized TEMPO electrode that selectively oxidizes methanol to formaldehyde with high turnover numbers. Upon the addition of various organic and inorganic bases, the activity of the catalyst could be tuned. The highest Faradaic efficiency that was achieved was 97.5 %, the highest turnover number was 17100. Additionally, we found that the rate determining step changed from the step in which the carbonyl specie is created from the methanol‐TEMPO adduct to the oxidative regeneration of the TEMPO+ species. Finally, we showed that the system could be applied to the oxidation of other aliphatic alcohols. [ABSTRACT FROM AUTHOR]

Carbon capture and utilization (CCU) technologies present a promising solution for converting CO2 emissions into valuable products. Here we show how amines, such as monoethanolamine (MEA) and 2-amino-2-methyl-1-propanol (AMP), influence the electrochemical CO2 reduction process in an integrated CCU system. Using in situ spectroscopic techniques, we identify the key roles of carbamate bond strength, proton shuttling, and amine structure in dictating reaction pathways on copper (Cu) and lead (Pb) electrodes. Our findings demonstrate that on Cu electrodes, surface blockage by ammonium species impedes CO₂ reduction, whereas on Pb electrodes, proton shuttling enhances the production of hydrocarbon products. This study provides additional insights into optimizing CCU systems by tailoring the choice of amines and electrode materials, advancing the selective conversion of CO₂ into valuable chemicals. Integrated carbon capture and utilization (CCU) systems offer a sustainable approach to converting CO₂ emissions into valuable chemicals. Here, the authors report the choice of amine and electrode materials significantly impact the efficiency and selectivity of CO2 reduction in CCU processes. [ABSTRACT FROM AUTHOR]

MXenes are a new family of 2D carbides or nitrides that have attracted attention due to their layered structure, tunable surface groups and high electrical conductivity. Here, we report for the first time that the Ti2CTx MXene catalyses the selective oxidative dehydrogenation of n‐butane to butenes and 1,3‐butadiene. This catalyst showed higher intrinsic activity compared to a commercial TiC and TiO2 samples in terms of C4 olefin formation rate. We propose that the stabilisation of structural vacancies and the change in composition (from a carbide to a mixed phase oxide) in the MXene causes its higher catalytic activity. These vacancies can lead to a higher concentration of unpaired electrons in the MXene‐derived material, enhancing its nucleophilic properties and favouring the production of olefins. [ABSTRACT FROM AUTHOR]

The electrochemical CO 2 reduction reaction (CO 2 RR) is a promising technology for the utilization of captured CO 2 . Though systems using aqueous electrolytes is the state-of-the-art, CO 2 RR in aprotic solvents are a promising alternative that can avoid the parallel hydrogen evolution reaction (HER). While system parameters, such as electrolyte composition, electrode material, and applied potential are known to influence the reaction mechanism, there is a lack of intuitive understanding as to how. We show that by using multivariate data analysis on a large dataset collected from the literature, namely random forest modelling, the most important system parameters can be isolated for each possible product. We find that water content, current density, and applied potential are powerful determinants in the reaction pathway, and therefore in the Faradaic efficiency of CO 2 RR products., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Asymmetric hydrogenation of alkene moieties is important for the synthesis of chiral molecules, but achieving high stereoselectivity remains a challenge. Biocatalysis using ene-reductases (EReds) offers a viable solution. However, the need for NAD(P)H cofactors limits large-scale applications. Here, we explored an electrochemical alternative for recycling flavin-containing EReds using methyl viologen as a mediator. For this, we built a bio-electrocatalytic setup with an H-type glass reactor cell, proton exchange membrane, and carbon cloth electrode. Experimental results confirm the mediator's electrochemical reduction and enzymatic consumption. Optimization showed increased product concentration at longer reaction times with better reproducibility within 4-6 h. We tested two enzymes, Pentaerythritol Tetranitrate Reductase (PETNR) and the Thermostable Old Yellow Enzyme (TOYE), using different alkene substrates. TOYE showed higher productivity for the reduction of 2-cyclohexen-1-one (1.20 mM h -1 ), 2-methyl-2-cyclohexen-1-one (1.40 mM h -1 ) and 2-methyl-2-pentanal (0.40 mM h -1 ), with enantiomeric excesses ranging from 11 % to 99 %. PETNR outperformed TOYE in terms of enantioselectivity for the reduction of 2-methyl-2-pentanal (ee 59 % ± 7 % (S)). Notably, TOYE achieved promising results also in reducing ketoisophorone, a challenging substrate, with similar enantiomeric excess compared to published values using NADH., (© 2024 The Authors. ChemBioChem published by Wiley-VCH GmbH.)

The challenge of moving to a carbon-free energy economy is highlighted in the context of technology and materials restrictions. Many technologies needed for the so-called energy transition depend on critical metals such as platinum, lithium, iridium and cobalt. Here we focus on solid borohydride salts as hydrogen carriers, studying catalysts for hydrogen release. We combine metal 3D printing technology and a Raney-type leaching process to make structured macroscopic catalyst/reactor monoliths of cobalt, aluminium and stainless steel with well-defined micropores. Remarkably, the blank catalyst samples, which are made only from aluminium and stainless steel (Al-SS), show high activity and, importantly, high stability in borohydride hydrolysis, with no mass loss and no surface poisoning. The batch results are confirmed in a continuous setup running for 96 h. Catalyst performance is attributed to the stable porous structure, the mechanical stability of the stainless steel macrostructure, and the presence of accessible Al(OH)x sites. This research shows a clear contribution to sustainability based on multi-factor comparison: The Al-SS catalyst outperforms the state-of-the-art on mechanical and chemical durability, it is both PGM-free and CRM-free, and its preparation follows a simple, scalable and low-waste procedure., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The local coordination environment of single atom catalysts (SACs) often determines their catalytic performance. To understand these metal-support interactions, we prepared Pt SACs on cerium dioxide (CeO 2 ) cubes, octahedra and rods, with well-structured exposed crystal facets. The CeO 2 crystals were characterized by SEM, TEM, pXRD, and N 2 sorption, confirming the shape-selective synthesis, identical bulk structure, and variations in specific surface area, respectively. EPR, XPS, TEM and XANES measurements showed differences in the oxygen vacancy density following the trend rods > octahedra > cubes. AC-HAADF-STEM, XPS and CO-DRIFTS measurements confirmed the presence of only single Pt 2+ sites, with different surface platinum surface concentrations. We then compared the performance of the three catalysts in ammonia borane hydrolysis. Precise monitoring of reaction kinetics between 30-80 °C gave Arrhenius plots with hundreds of data points. All plots showed a clear inflection point, the temperature of which (rods > octahedra > cubes) correlates to the energy barrier of ammonia borane diffusion to the Pt sites. These activity differences reflect variations in the - facet dependent - degree of stabilization of intermediates by surface oxygen lone pairs and surface-metal binding strength. Our results show how choosing the right macroscopic support shape can give control over single atom catalysed reactions on the microscopic scale., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: Diabetic foot ulcers (DFU) are a costly complication of diabetes mellitus (DM), with significant implications for the patient and the healthcare professionals that treat them. The primary objective of this study was to evaluate if there were improved healing rates in patients with a DFU that were taking a statin medication compared to those patients with a DFU who were not taking a statin medication. Secondary outcomes assessed were correlations with wound healing or statin use on data obtained from retrospective chart review., Methods: A case-control series was performed to obtain appropriate demographic information, comorbid conditions, laboratory values, and physical examination findings. From the time of presentation with DFU, these patients were followed for 12 weeks to evaluate for healing. Healing was defined as full epithelialization of the DFU with no further drainage. Wound healing and statin use correlation testing was then done for collected variables and each cohort. Chi square and Pearson correlation were then performed to identify any significant correlations. All p-values were two-sided, and findings were considered statistically significant at p < 0.05., Results: Our study identified 109 patients, 75 patients with a DFU on statin medication and 34 patients with a DFU not on statin medication. The statin cohort was more likely to be older, less than 5-year duration of diabetes, have more comorbidities, decreased low-density lipoprotein (LDL) cholesterol, and decreased total cholesterol (p < 0.05). Among those patients taking a statin medication, 48.0% (36/75) healed their DFU within 12 weeks. Among those patients not taking a statin medication, 44.1% (15/34) healed their DFU within 12 weeks. No correlation was noted between wound healing and statin use (p = 0.7). For wound healing, a negative correlation was noted for prior minor amputations (p < 0.05). For statin use, correlations were noted for age, duration of DM, LDL cholesterol level, total cholesterol level, HTN, CAD, and HLD (p < 0.05)., Conclusions: Statin medication use did not influence DFU healing rates between cohorts. There was a correlation noted between wound healing and prior minor amputations and between statin use and age, duration of DM, LDL cholesterol, total cholesterol, HTN, CAD and HLD. Additionally, we observed no correlation between DFU healing rates and use of a statin medication., (© 2024. The Author(s).)

We present here the synthesis and performance of dual-atom catalysts (DACs), analogous to well-known single-atom catalysts (SACs). DACs feature sites containing pairs of metal atoms and can outperform SACs due to their additional binding possibilities. Yet quantifying the improved catalytic activity in terms of proximity effects remains difficult, as it requires both high-resolution kinetic data and an understanding of the reaction pathways. Here, we use an automated bubble counter setup for comparing the catalytic performance of ceria-supported platinum SACs and DACs in ammonia borane hydrolysis. The catalysts were synthesized by wet impregnation and characterized using SEM, HAADF-STEM, XRD, XPS, and CO-DRIFTS. High-precision kinetic studies of ammonia borane hydrolysis in the presence of SACs show two temperature-dependent regions, with a transition point at 43 °C. Conversely, the DACs show only one regime. We show that this is because DACs preorganize both ammonia borane and water at the dual-atom active site. The additional proximal Pt atom improves the reaction rate 3-fold and enables faster reactions at lower temperatures. We suggest that the DACs enable the activation of the water-O-H bond as well as increase the hydrogen spillover effect due to the adjacent Pt site. Interestingly, using ammonia borane hydrolysis as a benchmark reaction gives further insight into hydrogen spillover mechanisms, above what is known from the CO oxidation studies., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Grafting molecular complexes on solid supports is a facile strategy to synthesize advanced materials. Here, we present a general and simple method for noncovalent grafting on charge-neutral surfaces. Our method is based on the generic principle of counterion confinement in surface micropores. We demonstrate the power of this approach using a set of three platinum complexes: Pt 1 (Pt 1 L 4 (BF 4 ) 2 , L = p -picoline), Pt 2 (Pt 2 L 4 (BF 4 ) 4 , L = 2,6-bis(pyridine-3-ylethynyl)pyridine), and Pt 12 (Pt 12 L 24 (BF 4 ) 24 , L = 4,4'-(5-methoxy-1,3-phenylene)dipyridine). These complexes share the same counterion (BF 4 - ) but differ vastly in their size, charge, and structure. Imaging of the grafted materials by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and energy-dispersive X-ray (EDX) showed that our method results in a homogeneous distribution of both complexes and counterions. Nitrogen sorption studies indicated a decrease in the available surface area and micropore volume, providing evidence for counterion confinement in the surface micropores. Following the adsorption of the complexes over time showed that this is a two-step process: fast surface adsorption by van der Waals forces was followed by migration over the surface and surface binding by counterion confinement. Regarding the binding of the complexes to the support, we found that the surface-adsorbate binding constant ( K S ) increases quadratically with the number of anions per complex up to K S = 1.6 × 10 6 M -1 equaling Δ G ° ads = -35 kJ mol -1 for the surface binding of Pt 12 . Overall, our method has two important advantages: first, it is general, as you can anchor different complexes (with different charges, counterions, and/or sizes); second, it promotes the distribution of the complexes on the support surface, creating well-distributed sites that can be used in various applications across several areas of chemistry., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a powerful strategy for fine-tuning their catalytic properties but is fairly difficult to achieve. To address this problem, we immobilized supramolecular cages where the primary- and secondary coordination sphere are controlled by ligand design. The kinetics of these catalysts were studied in a model reaction, the hydrolysis of ammonia borane, over a temperature range using fast and precise online measurements generating high-precision Arrhenius plots. The results show how catalytic properties can be enhanced by placing a well-defined reaction pocket around the active site. Our fine-tuning yielded a catalyst with such performance that the reaction kinetics are diffusion-controlled rather than chemically controlled., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Immobilizing molecular catalysts on electrodes is vital for electrochemical applications. However, creating robust electrode-catalyst interactions while maintaining good catalytic performance and rapid electron transfer is challenging. Here, without introducing any foreign elements, we show a bottom-up synthetic approach of constructing the conjugated C-C bond between the commercial Vulcan carbon electrode and an organometallic catalyst. Characterization results from FTIR, XPS, aberration-corrected TEM and EPR confirmed the successful and uniform heterogenization of the complex. The synthesized Vulcan-LN 4 -Co catalyst is highly active and selective in the oxygen reduction reaction in neutral media, showing an 80 % hydrogen peroxide selectivity and a 0.72 V (vs. RHE) onset potential which significantly outperformed the homogenous counterpart. Based on single-crystal XRD and NMR data, we built a model for density functional theory calculations which showed a nearly optimal binding energy for the *OOH intermediate. Our results show that the direct conjugated C-C bonding is an effective approach for heterogenizing molecular catalysts on carbon, opening new opportunities for employing molecular catalysts in electrochemical applications., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

We constructed a high-performance biosensor for detecting uric acid by immobilizing an engineered urate oxidase on gold nanoparticles deposited on a carbon-glass electrode. This biosensor showed a low limit-of-detection (9.16 nM), a high sensitivity (14 μA/μM), a wide range of linearity (50 nM-1 mM), and more than 28 days lifetime.

The NiOOH electrode is commonly used in electrochemical alcohol oxidations. Yet understanding the reaction mechanism is far from trivial. In many cases, the difficulty lies in the decoupling of the overlapping influence of chemical and electrochemical factors that not only govern the reaction pathway but also the crystal structure of the in situ formed oxyhydroxide. Here, we use a different approach to understand this system: we start with synthesizing pure forms of the two oxyhydroxides, β-NiOOH and γ-NiOOH. Then, using the oxidative dehydrogenation of three typical alcohols as the model reactions, we examine the reactivity and selectivity of each oxyhydroxide. While solvent has a clear effect on the reaction rate of β-NiOOH, the observed selectivity was found to be unaffected and remained over 95% for the dehydrogenation of both primary and secondary alcohols to aldehydes and ketones, respectively. Yet, high concentration of OH - in aqueous solvent promoted the preferential conversion of benzyl alcohol to benzoic acid. Thus, the formation of carboxylic compounds in the electrochemical oxidation without alkaline electrolyte is more likely to follow the direct electrochemical oxidation pathway. Overoxidation of NiOOH from the β- to γ-phase will affect the selectivity but not the reactivity with a sustained >95% conversion. The mechanistic examinations comprising kinetic isotope effects, Hammett analysis, and spin trapping studies reveal that benzyl alcohol is oxidatively dehydrogenated to benzaldehyde via two consecutive hydrogen atom transfer steps. This work offers the unique oxidative and catalytic properties of NiOOH in alcohol oxidation reactions, shedding light on the mechanistic understanding of the electrochemical alcohol conversion using NiOOH-based electrodes., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Single-atom catalysts often show exceptionally high performance per metal loading. However, the isolated atom sites tend to agglomerate during preparation and/or high-temperature reaction. Here we show that in the case of Rh/Al 2 O 3 this deactivation can be prevented by dissolution/exsolution of metal atoms into/from the support. We design and synthesise a series of single-atom catalysts, characterise them and study the impact of exsolution in the dry reforming of methane at 700-900 °C. The catalysts' performance increases with increasing reaction time, as the rhodium atoms migrate from the subsurface to the surface. Although the oxidation state of rhodium changes from Rh(iii) to Rh(ii) or Rh(0) during catalysis, atom migration is the main factor affecting catalyst performance. The implications of these results for preparing real-life catalysts are discussed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Alkaline water electrolysis (AWE) is among the most developed technologies for green hydrogen generation. Despite the tremendous achievements in boosting the catalytic activity of the electrode, the operating current density of modern water electrolyzers is yet much lower than the emerging approaches such as the proton-exchange membrane water electrolysis (PEMWE). One of the dominant hindering factors is the high overpotentials induced by the gas bubbles. Herein, the bubble dynamics via creating the superaerophobic electrode assembly is optimized. The patterned Co-Ni phosphide/spinel oxide heterostructure shows complete wetting of water droplet with fast spreading time (≈300 ms) whereas complete underwater bubble repelling with 180° contact angle is achieved. Besides, the current collector/electrode interface is also modified by coating with aerophobic hydroxide on Ti current collector. Thus, in the zero-gap water electrolyzer test, a current density of 3.5 A cm -2 is obtained at 2.25 V and 85 °C in 6 m KOH, which is comparable with the state-of-the-art PEMWE using Pt-group metal catalyst. No major performance degradation or materials deterioration is observed after 330 h test. This approach reveals the importance of bubble management in modern AWE, offering a promising solution toward high-rate water electrolysis., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Alkali metal borohydrides are promising candidates for large-scale hydrogen storage. They react spontaneously with water, generating dihydrogen and metaborate salts. While sodium borohydride is the most studied, potassium has the best chance of commercial application. Here we examine the physical and chemical properties of such self-hydrolysis solutions. We do this by following the hydrogen evolution, the pH changes, and monitoring the reaction intermediates using NMR. Most studies on such systems are done using dilute solutions, but real-life applications require high concentrations. We show that increasing the borohydride concentration radically changes the system's microstructure and rheology. The changes are seen already at concentrations as low as 5 w/w%, and are critical above 10 w/w%. While dilute solutions are Newtonian, concentrated reaction solutions display non-Newtonian behaviour, that we attribute to the formation and (dis)entanglement of metaborate oligomers. The implications of these findings towards using borohydride salts for hydrogen storage are discussed., (© 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)