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Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.
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Rate constants and temperature dependences for the reactions of OH with CF3OCH3 (HFOC-.
Relative rate experimental data are used to derive rate constants and temperature dependencies of the reactions of OH with several halocarbons. Rate constants for additional similar compounds are estimated. The experimental data, estimated data, and previously reported data are used to illustrate the effects of F, CL and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes, as well as some higher HFCs.
Shape-memory resists capable of high-resolution curing into arbitrarily designed structures are increasingly demanded for soft robotics, optical sensors, microscale manufacturing, and biomedicine. Amorphous, shape-memory thiol-vinyl networks were printed using two-photon polymerization (2PP) curing of a simple resin formulated with commercially available reagents. The ability to print high-resolution feature sizes down to 200 nm is attributed to the use of radicalmediated, thiol-vinyl step-growth polymerization that quickly crosslinks the resin, limiting diffusive transport. The thermomechanical behavior of the 2PP-cured material analyzed in compression, tension and three-point bending is similar to the behavior of the UV-polymerized samples. To demonstrate the ability to design, field, and test 4D responsive microstructures, an array of nine springs with coil diameters of 330 μm was printed. Following compressive shapefixing, printed arrays can release 11 μJ of stored elastic strain energy when reheated. Further, a new concept of dichroic-memory of a metamaterial device is demonstrated by printing a twisted woodpile structure with circular dichroism as characterized by Mueller Matrix ellipsometry. Furthermore, our results demonstrate how combining high-resolution 2PP curing with stimuli-responsive molecular architectures can further the engineering of responsive microstructures and metamaterials.
Abstract Faced with the contradictory results of two recent experimental studies [Jara‐Toro et al., Angew. Chem. Int. Ed . 2017 , 56 , 2166 and Chao et al., Angew. Chem. Int. Ed . 2019 , 58 , 5013] of the possible catalytic effect of water vapor on CH 3 OH + OH reaction, we report calculations that corroborate the conclusion made by Chao et al. and extend the rate constant evaluation down to 200 K. The rate constants of the CH 3 OH + OH reaction catalyzed by a water molecule are computed as functions of temperature and relative humidity using high‐level electronic structure and kinetics calculations. The Wuhan–Minnesota Scaling (WMS) method is used to provide accurate energetics to benchmark a density functional for direct dynamics. Both high‐frequency and low‐frequency anharmonicities are included. Variational and tunneling effects are treated by canonical variational transition state theory with multidimensional small‐curvature tunneling. And, most significantly, we include multistructural effects in the rate constant calculations. Our calculations show that the catalytic effect of water vapor is not observable at 200–400 K.
Dianionic hyponitrite (N 2 O 2 2- ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme-copper oxidases and nitric oxide reductases. In this work, we examine the gas-solid reaction of nitric oxide with the metal–organic framework Cu I -ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .- intermediate. These results highlight the advantage provided by site-isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one-electron couple in these enzymes.
Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li0, with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. Using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.
Abstract Dianionic hyponitrite (N 2 O 2 2− ) is often proposed, based on model complexes, as the key intermediate in reductive coupling of nitric oxide to nitrous oxide at the bimetallic active sites of heme‐copper oxidases and nitric oxide reductases. In this work, we examine the gas‐solid reaction of nitric oxide with the metal–organic framework Cu I ‐ZrTpmC* with a suite of in situ spectroscopies and density functional theory simulations, and identify an unusual chelating N 2 O 2 .− intermediate. These results highlight the advantage provided by site‐isolation in metal–organic frameworks (MOFs) for studying important reaction intermediates, and provide a mechanistic scenario compatible with the proposed one‐electron couple in these enzymes.
Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li 0 , with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. In conclusion, using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.
Increasing population and resource-intensive lifestyles are driving enhanced demands for clean water, food, and energy. In parallel, land-use change, climate change, and perturbations—including drought, floods, fires, and early snowmelt—are significantly reshaping interactions within watersheds throughout the world. While watersheds are the Earth's key functional unit for assessing and managing water resources, hydrological processes in watersheds also mediate biogeochemical interactions that support terrestrial life on Earth (Kaushal, Gold, Bernal, & Tank, 2018; National Research Council, 2012). Although society is dependent upon clean water availability, tractable prediction of watershed hydrobiogeochemical behavior, including watershed response to perturbations, remains a challenge. Central to the challenge are complex, multiscale interactions between plants, microorganisms, organic matter, minerals, dissolved constituents, and migrating fluids, which occur within and across bedrock-to-canopy compartments and along extensive lateral gradients of a watershed. Several recent community reports have synthesized formidable challenges associated with watershed science and technology (AGU, 2018; Blöschl et al., 2019). Here, we discuss emerging technologies and collaboration modes that are critical for developing generalizable insights about and predictive understanding of complex watershed hydrobiogeochemical behavior, which are important for underpinning optimized natural resource management.
Abstract This study used experimental and computational analysis to investigate the advanced oxidation of bisphenol A (BPA) and 2,4‐dinitroanisole (DNAN). The pseudo first‐order reaction rate constants depended on the molar peroxide ratio and were between 0.13 and 0.28 min −1 for BPA and between 0.018 and 0.032 min −1 for DNAN. The kinetic differences appear to be due in part to the energy requirements for oxidation, which depended on the reaction mechanism but were typically lower for BPA than they were for DNAN. Density functional theory (DFT) was used to develop transformation pathways that included experimentally‐detected byproducts. The most energetically favored pathway for BPA oxidation begins with the formation of hydroxylated derivatives, while for DNAN, the most energetically favorable degradation pathway begins with the substitution of the methoxy group. Overall, these findings demonstrate the power of combining experimental and computational tools to reveal transformation mechanisms during water treatment. Practitioner Points Advanced oxidation transformations for two emerging water pollutants, bisphenol A and dinitroanisole, was investigated. The observed reaction kinetics depended on molar peroxide ratio in a manner that is in keeping with previous findings. Density functional theory‐based analysis revealed reaction energy requirements and degradation pathways.
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