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The solution-processing of metal chalcogenides offers a promising route to improve the manufacturing of semiconductor devices. The amine–thiol solvent system has been deemed an “alkahest” for its ability to dissolve a wide range of metals and metal chalcogenides. Therefore, it enables convenient synthesis of metal sulfides. However, in the literature there are limited reports of analogous selenium-based “alkahest” chemistry. Here we show that solutions containing n-alkylammonium polyselenides can dissolve a wide range of metals and metal compounds through the formation of soluble metal polyselenides. These metal polyselenides can subsequently be utilized as precursors for the synthesis of a wide range of binary and multinary metal selenide thin films and nanoparticles, including Cu(In,Ga)Se2, Cu2ZnSnSe4, and Ag2ZnSnSe4.more » « less
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Strong metal–support interaction catalysts have been shown to improve desired product selectivity at the cost of fractional rates due to active site coverage. The goal of this study was to determine if the active site coverage of metallic nanoparticles could be controlled to lower levels than have been previously reported in SMSI catalysts with the aim of improving the rate while maintaining high selectivity. 2Pd– X Ti/SiO 2 (2 wt% Pd, X wt% Ti) strong metal–support interaction (SMSI) catalysts with Ti loadings between 0–1.0 wt% were synthesized to control Pd nanoparticle coverage. Calcination at 450 °C and reduction at 550 °C were sufficient for forming ∼2 nm sized Pd particles in all catalysts. Increasing the Ti loading from 0.1 to 1.0 wt% increased the surface coverage from 40 to 85% at a fixed reduction temperature of 550 °C. The IR spectra of the SMSI catalysts were similar with a high fraction of linear bonded CO which was much higher than that of Pd nanoparticles of similar size. The SMSI overlayer could be removed by oxidation at 350 °C and re-reduction at 200 °C. EXAFS of the oxidized catalysts indicates that nearly full oxidation of the metallic nanoparticle was required to remove the SMSI overlayer. Oxidation temperatures from 30 to 300 °C partially oxidized the Pd nanoparticles and subsequent re-reduction at 200 °C partially decreases the SMSI coverage. The fractional surface coverage was determined by measuring the rate of propylene hydrogenation with and without the SMSI overlayer. Increasing the reduction temperature from 200 to 550 °C increased the SMSI coverage from 0 to 85% depending on the Ti loading and temperature. After reduction at 550 °C and oxidation at 350 °C, the range of coverages varied between ∼10% with 0.1 wt% Ti after re-reduction at 300 °C and ∼85% with 1 wt% Ti after reduction at 550 °C.more » « less
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Abstract Olefin oligomerization by γ‐Al2O3has recently been reported, and it was suggested that Lewis acid sites are catalytic. The goal of this study is to determine the number of active sites per gram of alumina to confirm that Lewis acid sites are indeed catalytic. Addition of an inorganic Sr oxide base resulted in a linear decrease in the propylene oligomerization conversion at loadings up to 0.3 wt %; while, there is a >95 % loss in conversion above 1 wt % Sr. Additionally, there was a linear decrease in the intensity of the Lewis acid peaks of absorbed pyridine in the IR spectra with an increase in Sr loading, which correlates with the loss in propylene conversion, suggesting that Lewis acid sites are catalytic. Characterization of the Sr structure by XAS and STEM indicates that single Sr2+ions are bound to the γ‐Al2O3surface and poison one catalytic site per Sr ion. The maximum loading needed to poison all catalytic sites, assuming uniform surface coverage, was ∼0.4 wt % Sr, giving an acid site density of ∼0.2 sites per nm2of γ‐Al2O3, or approximately 3 % of the alumina surface.more » « less