Analyses of reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems using recently developed thermodynamic rate equations

This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems.     

Detailed experimental and kinetic modeling study of 3-carene pyrolysis

3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry.     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

Interfacial Engineering FeOOH/CoO Nanoneedle Array for Efficient Overall Water Splitting Driven by Solar Energy

Interface engineering has been applied as an effective strategy to boost the electrocatalytic performance because of the strong coupling and synergistic effects between individual components. Here, we engineered vertically aligned FeOOH/CoO nanoneedle array with a synergistic interface between FeOOH and CoO on Ni foam (NF) by a simple impregnation method. The synthesized FeOOH/CoO exhibits outstanding electrocatalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. For the overall water splitting, the bifunctional FeOOH/CoO nanoneedle catalyst requires only a cell voltage of 1.58 V to achieve a current density of 10 mA cm⁻², which is much lower than that required for IrO₂//Pt/C (1.68 V). The FeOOH/CoO catalyst has been successfully applied for solar cell-driven water electrolysis, revealing its great potential for commercial hydrogen production and solar energy storage.     

Photoinduced Betaine Generation for Efficient Photothermal Energy Conversion

The conversion of solar energy to thermal, chemical, or electrical energy attracts great attention in chemistry and physics. There has been a considerable effort for the efficient extraction of photons throughout the entire solar spectrum. In this work light energy was efficiently harvested by using a long-lived betaine photogenerated from an acridinium-based electron donor–acceptor dyad. The photothermal energy-conversion efficiency of the dyad is significantly enhanced by simultaneous illumination with blue (420–440 nm) and yellow (>480 nm) light in comparison with the sum of the conversion efficiencies for individual illumination with blue or yellow light. The enhanced photothermal effect is due to the photogenerated betaine, which absorbs longer-wavelength light than the dyad, and thus the dyad–betaine combination is promising for efficient photothermal energy conversion. The mechanisms of betaine generation and energy conversion are discussed on the basis of steady-state and transient spectral measurements.     

Irreversible Structural Changes of Copper Hexacyanoferrate Used as a Cathode in Zn-Ion Batteries

The structural changes of copper hexacyanoferrate (CuHCF), a Prussian blue analogue, which occur when used as a cathode in an aqueous Zn-ion battery, are investigated using electron microscopy techniques. The evolution of Zn_xCu_1−xHCF phases possessing wire and cubic morphologies from initial CuHCF nanoparticles are monitored after hundreds of cycles. Irreversible introduction of Zn ions to CuHCF is revealed locally using scanning transmission electron microscopy. A substitution mechanism is proposed to explain the increasing Zn content within the cathode material while simultaneously the Cu content is lowered during Zn-ion battery cycling. The present study demonstrates that the irreversible introduction of Zn ions is responsible for the decreasing Zn ion capacity of the CuHCF cathode in high electrolyte concentration.     

Molybdenum Disulfide Based Nanomaterials for Rechargeable Batteries

The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS₂) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS₂ are first introduced. Then, typical synthetic methods for MoS₂ and MoS₂-based composites are presented. Furthermore, the recent progress in the design of diverse MoS₂-based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS₂-based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems.     

Exfoliation of 2D Materials for Energy and Environmental Applications

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.     

Bromine-Functionalized Covalent Organic Frameworks for Efficient Triboelectric Nanogenerator

Covalent organic frameworks (COFs) enable precise integration of various organic building blocks into porous skeletons through topology predesign. Here, we report the first example of COFs by integrating electron withdrawing bromine group onto the skeletons for triboelectric nanogenerators (TENG). The resulting framework exhibits high surface area and good crystallinity. Thus, the bromine functionalized COF has more regular aligned π columns and arrays over the skeleton than bare COFs, which in turn significantly enhances charge transport ability. As a result, bromine functionalized COFs showed higher electrical output performance at 5 Hz with a peak value of short circuit current density of 43.6 μA and output voltage of 416 V, which is 2 and 1.3 times higher than those of bare COFs (21.6 μA and 318 V), respectively. These results demonstrated that this strategy for engineering electron withdrawing groups on the skeleton could open a new aspect of COFs for developing TENG devices.     

Building Polyoxometalate “Nano-Walls” on 3D Porous Carbon Paper: A Solar Steam Generation System for Water Purification

As promising fresh-water purification devices, solar steam generation systems have attracted significant attention recently. However, in practice, the approach often suffers from a poor solar energy conversion efficiency and a low water production rate due to poor material selection and inefficient microscopic structure design. Here, we fabricate an efficient solar steam generation system by “building” polyoxometalate “nano-walls” on rice paper-derived three-dimensional porous carbon paper. In this solar steam generation system, the height of the vertically aligned CoP₄Mo₆ “nano-walls” range from 100 to 150 nm with thicknesses about 15 to 25 nm. Under 1 sun irradiation (1 sun = 1 kW m⁻²), the surface temperature increases from 29 to 50 °C in a short time with a solar thermal conversion efficiency achieving 92.8 %. The stability and durability of this solar steam generation system, which withstands fifteen cycle continuous tests, also offer good prospects. Its attractive solar energy conversion performance originates from the intense sunlight absorption and high conversion ability of the CoP₄Mo₆ “nano-walls”, as well as extremely promising heat localization and water transportation properties of the three-dimensional porous carbon paper. This solar steam generation system, which has produced some inspiring results, is employed for seawater desalination and for purification of water polluted with organic dyes.