- Hydrogen on Cobalt Phosphide
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Cobalt phosphide (CoP) is one of the most promising earth-abundant replacements for noble metal catalysts for the hydrogen evolution reaction (HER). Critical to HER is the binding of H atoms. While theoretical studies have computed preferred sites and energetics of hydrogen bound to transition metal phosphide surfaces, direct experimental studies are scarce. Herein, we describe measurements of stoichiometry and thermochemistry for hydrogen bound to CoP. We studied both mesoscale CoP particles, exhibiting phosphide surfaces after an acidic pretreatment, and colloidal CoP nanoparticles. Treatment with H2 introduced large amounts of reactive hydrogen to CoP, ca. 0.2 H per CoP unit, and on the order of one H per Co or P surface atom. This was quantified using alkyne hydrogenation and H-atom transfer reactions with phenoxy radicals. Reactive H atoms were even present on the as-prepared materials. On the basis of the reactivity of CoP with various molecular hydrogen donating and accepting reagents, the distribution of binding free energies for H atoms on CoP was estimated to be roughly 51-66 kcal mol-1 (δG°H 0 to -0.7 eV vs H2). Operando X-ray absorption spectroscopy gave preliminary indications about the structure of hydrogenated CoP, showing a slight lattice expansion and no significant change of the effective nuclear charge of Co under H2-flow. These results provide a new picture of catalytically active CoP, with a substantial amount of reactive H atoms. This is likely of fundamental relevance for its catalytic and electrocatalytic properties. Additionally, the approach developed here provides a roadmap to examine hydrogen on other materials.
- Delley, Murielle F.,Wu, Zishan,Mundy, M. Elizabeth,Ung, David,Cossairt, Brandi M.,Wang, Hailiang,Mayer, James M.
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p. 15390 - 15402
(2019/11/02)
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- Process for concentrating halogenoanthraquinones
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A process for concentrating at least one of (a) individual halogenoanthraquinones (b) binary mixtures of di-halogenoanthraquinones and (c) binary mixtures of trihalogenoanthraquinones, from a mixture containing at least two halogenoanthraquinones, comprising subjecting said mixture containing at least two halogenoanthraquinones to fractional vacuum distillation in a heated rectification column having an efficiency corresponding to about 20 to 50 theoretical stages with an absolute pressure at the top of about 0.5 to 50 mm Hg and a reflux to take-off ratio of about 5/1 to 50/1. Advantageously, distillation is carried out continuously in a cascade of columns, the products withdrawn from the top of the first column being 2-chloroanthraquinone in the first stage, 1-chloroanthraquinone in the second stage, 1,6- and 1,7-dichloroanthraquinone in the third stage and 1,5- and 1,8-dichloroanthraquinone in the fourth stage, 1,4,5- and 1,4,6-trichloroanthraquinone being obtained in the sump of the 4th stage and being separated therefrom by film evaporation. The mixture of halogenoanthraquinones is advantageously a mixture of chloroanthraquinones such as is obtained by the action of chlorine, chloric acid or a chlorate on various industrial mixtures of nitro- or sulfo-anthraquinones.
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- Triazinyl dyes
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Vat dyestuffs of the formula EQU1 wherein R represents alkyl with 1 to 4 carbon atoms, R1 and R2 represent hydrogen or alkyl with 1 to 4 carbon atoms and each of A1 and A2 represents a vattable radical with 3 to 7 condensed rings are characterized by improved resistance to alkali and are suitable for dyeing and printing the most diverse materials, in particular fibers made from natural or regenerated cellulose.
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