10 Search Results

Direct excitation of nickel photocatalysts has gained popularity over the last several years following the successful activation of nickel by Ir and Ru photosensitizers. The ability to pair these photosensitizers with Ni catalysts facilitates the formation of crucial chemical bonds under relatively mild conditions. However, there are still gaps in our understanding of what influences the performance of these Ni photocatalysts. Previous work from our group identified a nickel photocatalyst supported by a tridentate pyridinophane ligand that undergoes wavelength-dependent cross-coupling reactivity. Herein, we report detailed studies of the wavelength dependence of the C–O cross-coupling reactivity, illustrating that the catalytic activitymore » has an optimal wavelength, and excitation on both the blue and red sides of this optimal wavelength leads to a reduction in product yield. We also reveal a crucial catalyst-alcohol preirradiation interaction that drastically alters the catalyst’s optical properties. Furthermore, we investigate both wavelength dependency and alcohol dependency via optical transient absorption spectroscopy and reveal a substrate binding process responsible for the observed wavelength-dependent cross-coupling catalysis.« less

Oxidation of primary alcohols to carboxylic acids is a fundamental transformation in organic chemistry, yet despite its simplicity, extensive use, and relationship to pH, it remains a subject of active research for synthetic organic chemists. Since 2013, a great number of new methods have emerged that utilize transition-metal compounds as catalysts for acceptorless dehydrogenation of alcohols to carboxylates. The interest in this reaction is explained by its atom economy, which is in accord with the principles of sustainability and green chemistry. Furthermore, the methods for the direct synthesis of carboxylic acids from alcohols is ripe for a modern survey, whichmore » we provide in this review.« less

The mechanism for catalytic conversion of ethanol over La_0.7Sr_0.3MnO_3–x(100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does notmore » produce ethene, indicating that acetaldehyde is not an intermediate to ethene and that the hydrogen and oxygen abstraction from ethanol to ethene are decoupled steps. Further evidence for this mechanistic nuance was obtained using isotopically labeled ethanol (CD₃CH₂OH), which produces CD₃CHO and CD₂CH₂. Additionally, the ratio of aldehyde production to alkene production increases with reduction, suggesting that aldehyde is produced from a disproportionation reaction between ethoxy species in adjacent O-vacancies, while ethene is produced from a dehydrogenation reaction with ethoxy species in vacancies without requiring adjacent O-vacancies. Counterintuitively, this finding indicates that the more oxygenated product (aldehyde vs ethene) is favored with more vacancies and that the net alcohol conversion is autocatalytic. Density functional theory calculations were able to find the previously unknown disproportionation pathway between ethoxies in adjacent O-vacancies, and kinetic Monte Carlo simulations support this interpretation by reproducing experimental selectivities. The activation energies for these pathways are estimated as 132 ± 10 kJ/mol for the disproportionation reaction (when occurring between ethoxies in adjacent vacancies) and as 148 ± 11 kJ/mol for the direct dehydrogenation reaction of an ethoxy in a vacancy. Based on these results, a mechanism with operative pathways based on elementary steps in O-vacancies is reported.« less

Supplementing petroleum fuels with sustainable and renewable alternatives is a good option for increasing the sustainability of transportation fuels. Alcohols are particularly attractive blendstocks for spark ignition engines, mainly due to their desirable fuel properties including high octane, evaporative cooling, and reduced sooting propensity. Although the use of SI engines is widespread around the world, predominately for light duty vehicles, concerns about CO2 emissions and other sustainability issues necessitate increased engine efficiencies, reduced tailpipe pollutants, and lower lifecycle carbon emissions. The intelligent blending of C2-C4 alcohols into motor gasoline is a viable method for achieving these goals. There are amore » multitude of ways to produce renewable alcohols such as through fermentation from first-generation feedstocks (sugar and corn) and second-generation feedstocks (lignocellulosic biomass), or by gasification and mixed alcohol fuel synthesis routes from lignocellulosic biomass. Currently ethanol is extensively used in motor gasoline fuels worldwide and although many have proposed the use of C3 and C4 alcohols in motor gasoline as an improvement over ethanol, the higher cost of production and lack of clear definition as to their benefit over ethanol when blended into motor gasoline have led to slow acceptance into the market. In this review, special emphasis is placed on the effects of blending C3 and C4 alcohols into motor gasoline in terms of physicochemical properties, volatility behavior, and engine performance when compared to ethanol blends. Furthermore, the impact of blending C3 and C4 alcohols with gasoline on emission (particulate matter, nitrogen oxides, carbon monoxide, hydrocarbons, and unregulated oxygenates) and combustion (volumetric efficiency, thermal efficiency, fuel consumption, and cold performance) characteristics is discussed. Although there are some disagreements in the literature over the effect of alcohols predominately around the type of SI engine, i.e., port fuel injected versus direct fuel injected and engine operating mode, generally it is stated that alcohols can potentially reduce soot, unburned hydrocarbons and CO emissions while increasing thermal efficiency when proper engine configuration/calibration is used. Lastly, research that must be conducted to find the optimum combination of alcohol blends and engine configurations is highlighted and discussed.« less

Mesoporous spinel cobalt oxide (Co₃O₄) with fine-tuned pore size distributions (9.6–17.6 nm) and different surface areas (33–85 m²/g) were synthesized using a series of nonionic surfactants. A direct influence of the chemical composition of the surfactants and calcination temperature on crystallite size, morphology, pore size/volume, surface area, valance band edge, and Co²⁺/Co³⁺ ratio was recognized. Correlation between the aforementioned factors, transition metal ion incorporation and benzylamine homocoupling reaction was discussed. Shape-specific binding of amine on the cobalt oxide active sites was proposed based on substrate scope study. Tandem synthesis strategy to selectively synthesize amine (aliphatic/aromatic) homo-coupled imines and amine-alcohol cross-coupledmore » imines was introduced. Low-intensity light-induced singlet oxygen and hydroxyl radical-mediated reaction mechanism was proposed based on the EPR, XPS, photoreactor, and reactive oxygen species scavenger tests. Selective and switchable synthesis of homo-coupled (yield 85%) and cross-coupled (yield 87%) products was achieved with sodium azide and mannitol additives.« less

The kinetics for surface-catalyzed alcohol dehydration reactions often depend on the structure of the alcohol. Studies of structure–activity relations across primary, secondary, and tertiary alcohols can provide fundamental information on the nature of active sites on the surface. Here in this paper, we investigated the dehydration of 1-butanol, 2-butanol, and tert-butanol over TiO₂ anatase catalysts modified with various phosphonic acid (PA) self-assembled monolayers (SAMs). As a response to the presence of PAs, the three C4 alcohol isomers showed different dehydration rates, with 1-butanol dehydration being enhanced to the greatest extent by PA modification. Furthermore, the fluorinated, more polar 4-fluorobenzylphosphonic acidmore » outperformed alkyl PAs across all alcohols. Steady-state kinetic measurements and temperature-programmed desorption studies indicated that PA SAMs significantly lowered the dehydration activation barrier; the extent of reduction in the barrier was sensitive to both the substitution of the alcohol and the charge distribution on the PA in a way that was consistent with stabilization of a carbenium-like transition state. Overall, the effect of PA modifiers on alcohol dehydration rates was found to be determined from a balance between transition state stabilization and active site blocking effects, with the potential to tune activity and selectivity based on the structure and coverage of the SAM.« less

Next generation biofuels including longer-chain alcohols such as butanol are attractive as renewable, high-energy fuels. A barrier to microbial production of butanols is the increased toxicity compared to ethanol; however, the cellular targets and microbial defense mechanisms remain poorly understood, especially under anaerobic conditions used frequently in industry. Here we took a comparative approach to understand the response of Saccharomyces cerevisiae to 1-butanol, isobutanol, or ethanol, across three genetic backgrounds of varying tolerance in aerobic and anaerobic conditions. We find that strains have different growth properties and alcohol tolerances with and without oxygen availability, as well as unique and commonmore » responses to each of the three alcohols. Our results provide evidence for strain-by-alcohol-by-oxygen interactions that moderate how cells respond to alcohol stress.« less

Data from the National Health and Nutrition Examination Survey (NHANES) indicate 89% of Americans regularly consume caffeine, but these data do not include military personnel. This cross-sectional study examined caffeine use in Navy and Marine Corps personnel, including prevalence, amount of daily consumption, and factors associated with use. A random sample of Navy and Marine Corps personnel was contacted and asked to complete a detailed questionnaire describing their use of caffeine-containing substances, in addition to their demographic, military, and lifestyle characteristics. A total of 1708 service members (SMs) completed the questionnaire. Overall, 87% reported using caffeinated beverages ≥1 time/week, withmore » caffeine users consuming a mean ± standard error of 226 ± 5 mg/day (242 ± 7 mg/day for men, 183 ± 8 mg/day for women). The most commonly consumed caffeinated beverages (% users) were coffee (65%), colas (54%), teas (40%), and energy drinks (28%). Multivariable logistic regression modeling indicated that characteristics independently associated with caffeine use (≥1 time/week) included older age, white race/ethnicity, higher alcohol consumption, and participating in less resistance training. Prevalence of caffeine use in these SMs was similar to that reported in civilian investigations, but daily consumption (mg/day) was higher.« less

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH₃CN)₆²⁺. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH₃CN)₆²⁺-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH₃CN)₆²⁺] and [O₃] and independent of [substrate] at concentrations greater thanmore » ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k_cat = (8 ± 1) × 10⁴ M^–1 s^–1, and that for (C₂H₅)₂O is (5 ± 0.5) × 10⁴ M^–1 s^–1. In the absence of substrate, Fe(CH₃CN)₆²⁺ reacts with O₃ with k_Fe = (9.3 ± 0.3) × 10⁴ M^–1 s^–1. The similarity between the rate constants k_Fe and k_cat strongly argues for Fe(CH₃CN)₆²⁺/O₃ reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH₃CN)₆²⁺/O₃ reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less