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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.)

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.)

The Hansen solubility parameter approach is revisited by implementing the thermodynamics of dissolution and mixing. Hansen's pragmatic approach has earned its spurs in predicting solvents for polymer solutions, but for molecular solutes improvements are needed. By going into the details of entropy and enthalpy, several corrections are suggested that make the methodology thermodynamically sound without losing its ease of use. The most important corrections include accounting for the solvent molecules' size, the destruction of the solid's crystal structure, and the specificity of hydrogen-bonding interactions, as well as opportunities to predict the solubility at extrapolated temperatures. Testing the original and the improved methods on a large industrial dataset including solvent blends, fit qualities improved from 0.89 to 0.97 and the percentage of correct predictions rose from 54 % to 78 %. Full Matlab scripts are included in the Supporting Information, allowing readers to implement these improvements on their own datasets., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Perovskite-type oxides, ABO(3), can be successfully applied as solid "oxygen reservoirs" in redox reactions such as selective hydrogen combustion. This reaction is part of a novel process for propane oxidative dehydrogenation, wherein the lattice oxygen of the perovskite is used to combust hydrogen selectively from the dehydrogenation mixture at 550 degrees C. This gives three key advantages: it shifts the dehydrogenation equilibrium to the side of the desired products, heat is generated, thus aiding the endothermic dehydrogenation, and it simplifies product separation (H(2)O vs H(2)). Furthermore, the process is safer since it uses the catalysts' lattice oxygen instead of gaseous O(2). We screened fourteen perovskites for activity, selectivity and stability in selective hydrogen combustion. The catalytic properties depend strongly on the composition. Changing the B atom in a series of LaBO(3) perovskites shows that Mn and Co give a higher selectivity than Fe and Cr. Replacing some of the La atoms with Sr or Ca also affects the catalytic properties. Doping with Sr increases the selectivity of the LaFeO(3) perovskite, but yields a catalyst with low selectivity in the case of LaCrO(3). Conversely, doping LaCrO(3) with Ca increases the selectivity. The best results are achieved with Sr-doped LaMnO(3), with selectivities of up to 93 % and activities of around 150 mumol O m(-2). This catalyst, La(0.9)Sr(0.1)MnO(3), shows excellent stability, even after 125 redox cycles at 550 degrees C (70 h on stream). Notably, the activity per unit surface area of the perovskite catalysts is higher than that of doped cerias, the current benchmark of solid oxygen reservoirs.

Ceria-based mixed oxides, in which about 10 mol % of the cerium is replaced by another metal, catalyze the selective combustion of hydrogen from a mixture of hydrogen, propane, and propene at 550 degrees C. This makes them attractive catalysts for the oxidative dehydrogenation of propane. Hydrogen combustion shifts the equilibrium to the products side, supplies energy for the endothermic dehydrogenation, and simplifies product separation. The type of metal added has an important effect on the catalytic properties. To gain insight into the process, a set consisting of six mixed oxides was synthesized and the catalytic properties and redox behavior were tested. The mixed oxides generally release more oxygen than plain ceria. Mixed oxides containing Bi, Cu, Fe, Pd or Ca release between 1.6 and 2.0 mg of oxygen per 100 mg sample (compared to only 1.2 mg for plain ceria). This result is important for reactions in which the catalyst acts as an oxygen reservoir, such as selective hydrogen combustion. The temperature at which oxygen is released is generally lower for the mixed oxides, and varies from 110 degrees C (for Cu-CeO2) to 550 degrees C (for Ca-CeO2), which enables catalytic applications over a wide temperature range. The reduction rate at 550 degrees C is related to the reduction onset of the catalysts. Those catalysts with a relatively low reduction temperature, such as Cu-, Mn-, Bi-, and Pb-CeO2, show a high reduction rate, whereas those with a high reduction temperature, such as Ca-CeO2, Fe-CeO2, and plain ceria, reduce at a slower rate. The latter catalysts also have a low selectivity towards hydrogen combustion. The influence of the catalyst composition and crystallite size on the activity and selectivity is discussed.

The challenge of predicting the melting point of ionic liquids is outlined. A descriptor modelling approach for two separate sets of ionic liquids is presented. In each case, the cations and the anions are modelled separately, using quantitative structure-property relationships. Both models include constitutional, topological and geometric descriptors as well as quantum mechanical ones. This approach gives access to (nxm) ionic liquids using only (n+m) calculations. The protocol is tested and validated for predicting the melting points of two sets, comprised of 22 and 62 imidazolium-based ionic liquids, respectively. Good correlations and predictions are obtained in both cases. Within the data set selected (only monopositive and mononegative ions are studied, and so total charge was not a factor), the degree of sphericity is the most important variable for the anion, while for the cation the main descriptors pertained to three radial distribution functions that describe three different sections in the cation. These characterise the ionic interactions, the symmetry-breaking region, and the length of the side chains.

The problem of soot emissions from diesel engines is introduced and the possible solution of combining doped perovskites and microwave (mw) irradiation to "clean up" diesel soot filters is outlined. Eighteen doped perovskite catalysts are synthesized and tested for propane and CO oxidation, which are taken as model components for soot. The activity, selectivity, and SO2 tolerance are compared under conventional heating and mw irradiation. By combining mw irradiation and doped perovskites, one can create "hot spots" on the catalyst, resulting in efficient and selective heating of the active site, as well as less poisoning. Sr-doped and Ce-doped manganese perovskites show the highest activity. These catalysts are also the most selective, and have a high mw susceptibility. Optimal SO2 tolerance is displayed by Cr perovskites, from which the La0.8Ca0.2CrO3 combination uniquely converts propane before CO, and therefore can be used to remove >C2 hydrocarbons from a mix with CO. Possible mechanistic scenarios are presented and discussed.

The importance of small metal clusters in catalysis and the problems in understanding the clustering process in solution are outlined. A new analysis method for UV/Vis spectra is presented and applied to monitor the kinetics of ion reduction and cluster formation in situ. This method, which is based on a combination of two chemometric techniques, takes into account the entire UV/Vis spectrum and offers better interpretation possibilities than the traditional "band-assignment" approach. This is particularly true for nanoclusters because these have significant spectral contributions also outside the broad plasmon band that is usually associated with them. The reduction of palladium, gold, and silver ions and the formation of the corresponding clusters is monitored in the presence of two different reducing agents, sodium borohydride and tetraoctylammonium acetate. While Pd2+ is found to reduce and cluster directly, the spectral decomposition of the Au3+ reduction profiles shows two species corresponding to the Au+ intermediate and the Au0 clusters. The rates of reduction and clustering for Pd, Au, and Ag are compared and the possibilities of synthesising multimetallic clusters of these metals by coreduction are discussed.