A series of thorium(IV) (3, 4, 9, 10) and uranium(IV) (5, 6, 11, 12) complexes decorated with the unsymmetrical imidazolin-2-iminato ligands L₁ and L₂ were synthesized and found to be effective as catalysts in the transfer hydrogenation of aldehydes and ketones with 2-propanol to form the corresponding alcohols with good yields, representing a rare example for actinides as transfer hydrogenation catalysts with alcohols. The transfer hydrogenation of aldehydes and ketones was found to be selective, tolerating a wide range of other functional groups, including those prone to reduction, such as nitro, alkynes, and nitriles. The neutral imine ligand was found to be coordinated in the active catalyst along with the alkoxo group.

Coal fly ash (CFA) disposal is controversial because constituents of potential concern such as heavy metals in the ash can be released to the ground and reach aquifers, which poses risks to communities and the environment. Whereas thoughtful utilization of CFA may result in economic and environmental benefits. Geotechnical use of CFA as fill material in embankments could be economically competitive while reducing environmental impact. However, CFA must compete with low-cost alternatives like sand, which do not need to adhere to stringent environmental regulations and have not been evaluated against CFA previously in life cycle assessment (LCA) studies. Therefore, this work aims to evaluate the environmental effects of using CFA versus sand through LCA. Leaching experiments were carried out to create mass balance emission profiles of heavy metals from the embankment. Those emissions were integrated into a complete life cycle inventory for use of the material. Results show a net reduction in the impact categories for CFA re-used in embankments compared to landfilled. The effects of sand impacts were mostly attributed to the sand mining process. The ultimate environmental impacts from utilizing CFA as fill material in an embankment were a result of truck emissions from transporting CFA from power stations to point of utilization, diesel production and its consumption during truck transport, and leachate emissions. The breakeven distance for transporting CFA as opposed to sand was evaluated as 115km.

Creating atomically coherent interfaces can sharpen the physiochemical properties and functionalities of nanomaterials for efficient energy conversion via manipulating the charge flow. While coherent interfaces can be built between transition metal dichalcogenides with structural similarities and weak interlayer van der Waals interactions, it remains challenging to realize interfacial coherency with more generic transition metal chalcogenides via cost-effective wet chemical routes. Here we establish a coherent CdS(010)|CoS(010) interface via in-situ heteroepitaxial growth of CoS nanoflakes onto CdS nanowires. The uniform and oriented distribution of CoS nanoflakes on the CdS nanowires features an interesting “leaves-on-a-branch” nano-architecture with coherent interface and well-aligned energy levels, allowing efficient separation of photoexcited charge carriers. Combined with the outstanding proton reduction kinetics of the CoS “nanoleaves”, striking photochemical solar-to-hydrogen conversion performance can be obtained. Our findings provide a viable design strategy of nanojunctions with atomic level coherency and great application prospect in catalysis, nanoelectronics and many others.

This paper studies the impact of electric vehicle charging on congestion in low-voltage networks and the economic feasibility of energy storage as an alternative to conventional network upgrades. To this end, we propose a computationally efficient graph-based methodology and employ it on a GIS data set of over 6,500 low-voltage networks. We provide insights regarding the types of networks that are most congested due to electric vehicle charging, the typical location of overloaded network components, and the types of networks in which a storage-based upgrade is profitable. A main result is that the number of networks in which it is profitable to use energy storage grows exponentially as the cost of energy storage decreases, regardless of the electric vehicle penetration level and charging power. Our findings also show that using energy storage to alleviate congestion can incur substantial savings, conditioned with a cost reduction of stationary energy storage to 200 US$/kWh and below.

Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [H₃tpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [Fe^IIItpfc(py)]₂COT and 6-coordinate [Fe^IIItpfc(py)₂]₂COT, with one and two axial pyridine ligands per metal, respectively. X-Ray crystallography reveals a dome-shaped structure for [Fe^IIItpfc(py)]₂COT and a perfectly planar geometry which (surprisingly at first) is also characterized by shorter Fe–N (corrole) and Fe–N (pyridine) distances. Computational investigations clarify that the structural phenomena are due to a change in the iron(III) spin state from intermediate (S = 3/2) to low (S = 1/2), and that both the 5- and 6-coordinated complexes are enthalpically favored. Yet, in contrast to iron(III) porphyrins, the formation enthalpy for the coordination of the first pyridine to Fe(III) corrole is more negative than that of the second pyridine coordination. Possible interactions between the two corrole subunits and the chelated iron ions were examined by UV–Vis spectroscopy, electrochemical techniques, and density functional theory (DFT). The large differences in the electronic spectra of the dimer relative to the monomer are concluded to be due to a reduced electronic gap, owing to the extensive electron delocalization through the fusing bridge. A cathodic sweep for the dimer discloses two redox processes, separated by 230 mV. The DFT self-consistent charge density for the neutral and cationic states (1- and 2-electron oxidized) reveals that the holes are localized on the macrocycle. A different picture emerges from the reduction process, where both the electrochemistry and the calculated charge density point toward two consecutive electron transfers with similar energetics, indicative of very weak electron communication between the two redox active iron(III) sites. The binuclear complex was determined to be a much better catalyst for the electrochemical hydrogen evolution reaction (HER) than the analogous mononuclear corrole.

Accurate and fast classification of FDEs is crucial to power systems situation awareness and stability control. However, various database used in recent studies makes it hard to directly compare different classification methods. To relieve the lack of a standardized database that can be used as a benchmark, this work proposes an open-source package which generates frequency events based on PowerFactory named PF-FEDG. PF-FEDG can produce various labeled FDEs with random parameters such as generator trips, load disconnections, line outages, frequency ramp ups, frequency ramp downs, and frequency oscillations. Furthermore, the package includes three reference FDEs classifiers based on deep learning techniques. These models are tested on the IEEE 39-bus system and IEEE 118-bus system and achieve high performance. The package generating capability and the reference classifiers can be used by the community as benchmarks for comparison and development of new algorithms for FDEs detection. The code of PF-FEDG is available on GitLab.

Superhydrophobicity is a well-known wetting phenomenon found in numerous plants and insects. It is achieved by the combination of the surface's chemical properties and its surface roughness. Inspired by nature, numerous synthetic superhydrophobic surfaces have been developed for various applications. Designated surface coating is one of the fabrication routes to achieve the superhydrophobicity. Yet, many of these coatings, such as fluorine-based formulations, may pose severe health and environmental risks, limiting their applicability. Herein, we present a new family of superhydrophobic coatings comprised of natural saturated fatty acids, which are not only a part of our daily diet, but can be produced from renewable feedstock, providing a safe and sustainable alternative to the existing state-of-the-art. These crystalline coatings are readily fabricated via single-step deposition routes, namely thermal deposition or spray-coating. The fatty acids self-assemble into highly hierarchical crystalline structures exhibiting a water contact angle of ∼165° and contact angle hysteresis lower than 6°, while their properties and morphology depend on the specific fatty acid used as well as on the deposition technique. Moreover, the fatty acid coatings demonstrate excellent thermal stability. Importantly, this new family of coatings displays excellent anti-biofouling and antimicrobial properties against Escherichia coli and Listeria innocua, used as relevant model Gram-negative and Gram-positive bacteria, respectively. These multifunctional coatings hold immense potential for application in numerous fields, ranging from food safety to biomedicine, offering sustainable and safe solutions.

Manual chemical kinetic model construction often requires modelists to at least implicitly guess all possible decay pathways and their relative fluxes for all important species. We present a workflow and associated tool for automatic generation and refinement of pressure-dependent networks (multiwell potential energy surfaces) that should enable modelists to efficiently and comprehensively identify decay pathways and estimate respective parameters for chemical species. This tool within the Arkane software combines the capabilities of the Reaction Mechanism Generator (RMG) software to generate possible reaction paths, determine thermochemistry, approximate rate coefficients and estimate frequencies with the capabilities of Arkane to use quantum chemical parameters to compute thermochemistry and pressure-dependent rate coefficients. A flux-based algorithm is used to decide which isomers to add to the network. Isomers added to the network are reacted to form other channels. When enough of the flux is accounted for by the isomers and bimolecular product channels, the generation process terminates to yield a comprehensive network. Network sensitivity analysis is applied to identify the most important wells and barriers that can be refined using quantum chemistry calculations. Iterative refinement can then be used to achieve accuracy. The comprehensive network can be easily reduced using energy and flux-based algorithms to the most important channels and isomers.

Harvesting an electrical current from biological photosynthetic systems (live cells or isolated complexes) is typically achieved by immersion of the system into an electrolyte solution. In this study, we show that the aqueous solution found in the tissues of succulent plants can be used directly as a natural bio-photo electrochemical cell. Here, the thick water-preserving outer cuticle of the succulent Corpuscularia lehmannii serves as the electrochemical container, the inner water content as the electrolyte into which an iron anode and platinum cathode are introduced. We produce up to 20 μA/cm² bias-free photocurrent. When 0.5 V bias is added to the iron anode, the current density increases ∼10-fold, and evolved hydrogen gas can be collected with a Faradaic efficiency of 2.1 and 3.5% in dark or light, respectively. The addition of the photosystem II inhibitor 3-(3,4-dichlorophenyl)-1,1-dimethylurea inhibits the photocurrent, indicating that water oxidation is the primary source of electrons in the light. Two-dimensional fluorescence measurements show that NADH and NADPH serve as the major mediating electron transfer molecules, functionally connecting photosynthesis to metal electrodes. This work presents a method to simultaneously absorb CO₂ while producing an electrical current with minimal engineering requirements.