Evan C. Wegener

Pd–In intermetallic alloy nanoparticles: highly selective ethane dehydrogenation catalysts

Silica supported Pd and Pd–In catalysts with different In:Pd atomic ratios and similar particle size (∼2 nm) were tested for ethane dehydrogenation at 600 °C. For a monometallic Pd catalyst, at 15% conversion, the dehydrogenation selectivity and initial turnover rate (TOR, per surface Pd site) were 53% and 0.03 s−1, respectively. Addition of In to Pd increased the dehydrogenation selectivity to near 100% and the initial TOR to 0.26 s−1. Carbon monoxide IR, in situ synchrotron XAS and XRD analysis showed that for Pd–In catalysts with increasing In loading, different bimetallic structures were formed: at low In loading a fraction of the nanoparticle surface was transformed into PdIn intermetallic compound (IMC, also known as intermetallic alloy) with a cubic CsCl structure; at higher In loading, a Pd-core/PdIn-shell structure was formed and at high In loading the nanoparticles were pure PdIn IMC. While a Pd metal surface binds CO predominantly in a bridge fashion, the PdIn IMC predominantly binds CO linearly. Formation of the PdIn IMC structure on the catalyst surface geometrically isolates the Pd catalytic sites by non-catalytic, metallic In neighbors, which is suggested to be responsible for the high olefin selectivity. Concomitant electronic effect due to Pd–In bond formation likely leads to the increase in TOR. Though multiple IMC structures with different atomic ratios are possible for the Pd–In binary system, only a cubic PdIn IMC with CsCl structure was observed, implying a kinetically controlled solid state IMC formation mechanism.

High-Performance Transition Metal Phosphide Alloy Catalyst for Oxygen Evolution Reaction

Oxygen evolution reaction (OER) is a pivotal process in many energy conversion and storage techniques, such as water splitting, regenerative fuel cells, and rechargeable metal-air batteries. The synthesis of stable, efficient, non-noble metal-based electrocatalysts for OER has been a long-standing challenge. In this work, a facile and scalable method to synthesize hollow and conductive iron-cobalt phosphide (Fe-Co-P) alloy nanostructures using an Fe-Co metal organic complex as a precursor is described. The Fe-Co-P alloy exhibits excellent OER activity with a specific current density of 10 mA/cm2 being achieved at an overpotential as low as 252 mV. The current density at 1.5 V (vs reversible hydrogen electrode) of the Fe-Co-P catalyst is 30.7 mA/cm2, which is more than 3 orders of magnitude greater than that obtained with state-of-the-art Fe-Co oxide catalysts. Our mechanistic experiments and theoretical analysis suggest that the electrochemical-induced high-valent iron stabilizes the cobalt in a low-valent state, leading to the simultaneous enhancement of activity and stability of the OER catalyst.

A molecular cross-linking approach for hybrid metal oxides

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as ‘molecular cross-linking’, whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2–. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.TiO2 and other metal oxides were interfaced with molecular boron clusters to form a hybrid material. This modifies the electrochemical and photocatalytic properties, enabling fast electron transfer and dye degradation under red light.

Speciation of CuCl and CuCl2 Thiol-Amine Solutions and Characterization of Resulting Films: Implications for Semiconductor Device Fabrication

Thiol-amine mixtures are an attractive medium for the solution processing of semiconducting thin films because of their remarkable ability to dissolve a variety of metals, metal chalcogenides, metal salts, and chalcogens. However, very little is known about their dissolution chemistry. Electrospray ionization high-resolution tandem mass spectrometry and X-ray absorption spectroscopy were employed to identify the species formed upon dissolution of CuCl and CuCl2 in 1-propanethiol and n-butylamine. Copper was found to be present exclusively in the 1+ oxidation state for both solutions. The copper complexes detected include copper chlorides, copper thiolates, and copper thiolate chlorides. No complexes of copper with amines were observed. Additionally, alkylammonium ions and alkylammonium chloride adducts were observed. These findings suggest that the dissolution is initiated by proton transfer from the thiol to the amine, followed by coordination of the thiolate anions with copper cations. Interestingly, the mass and X-ray absorption spectra of the solutions of CuCl and CuCl2 in thiol-amine were essentially identical. However, dialkyl disulfides were identified by Raman spectroscopy as an oxidation product only for the copper(II) solution, wherein copper(II) had been reduced to copper(I). Analysis of several thiol-amine pairs suggested that the dissolution mechanism is quite general. Finally, analysis of thin films prepared from these solutions revealed persistent chlorine impurities, in agreement with previous studies. These impurities are explained by the mass spectrometric finding that chloride ligands are not completely displaced by thiolates upon dissolution. These results suggest that precursors other than chlorides will likely be preferred for the generation of high-efficiency copper chalcogenide films, despite the reasonable efficiencies that have been obtained for films generated from chloride precursors in the past.

Publisher Correction: A molecular cross-linking approach for hybrid metal oxides

In the version of this Article originally published, Liban M. A. Saleh was incorrectly listed as Liban A. M. Saleh due to a technical error. This has now been amended in all online versions of the Article.

Identification of active sites on supported metal catalysts with carbon nanotube hydrogen highways

Catalysts consisting of metal particles supported on reducible oxides exhibit promising activity and selectivity for a variety of current and emerging industrial processes. Enhanced catalytic activity can arise from direct contact between the support and the metal or from metal-induced promoter effects on the oxide. Discovering the source of enhanced catalytic activity and selectivity is challenging, with conflicting arguments often presented based on indirect evidence. Here, we separate the metal from the support by a controlled distance while maintaining the ability to promote defects via the use of carbon nanotube hydrogen highways. As illustrative cases, we use this approach to show that the selective transformation of furfural to methylfuran over Pd/TiO2 occurs at the Pd-TiO2 interface while anisole conversion to phenol and cresol over Cu/TiO2 is facilitated by exposed Ti3+ cations on the support. This approach can be used to clarify many conflicting arguments in the literature.Understanding the location and nature of the catalytic active site is critical for controlling a catalyst’s activity and selectivity. Here, the authors separate the metal from the support by a controlled distance while maintaining the ability to promote defects via the use of carbon nanotube hydrogen highways.

Dominant Role of Entropy in Stabilizing Sugar Isomerization Transition States within Hydrophobic Zeolite Pores

Lewis acid sites in zeolites catalyze aqueous-phase sugar isomerization at higher turnover rates when confined within hydrophobic rather than within hydrophilic micropores; however, relative contributions of competitive water adsorption at active sites and preferential stabilization of isomerization transition states have remained unclear. Here, we employ a suite of experimental and theoretical techniques to elucidate the effects of coadsorbed water on glucose isomerization reaction coordinate free energy landscapes. Transmission IR spectra provide evidence that water forms extended hydrogen-bonding networks within hydrophilic but not hydrophobic micropores of Beta zeolites. Aqueous-phase glucose isomerization turnover rates measured on Ti-Beta zeolites transition from first-order to zero-order dependence on glucose thermodynamic activity, as Lewis acidic Ti sites transition from water-covered to glucose-covered, consistent with intermediates identified from modulation excitation spectroscopy during in situ attenuated total reflectance IR experiments. First-order and zero-order isomerization rate constants are systematically higher (by 3-12×, 368-383 K) when Ti sites are confined within hydrophobic micropores. Apparent activation enthalpies and entropies reveal that glucose and water competitive adsorption at Ti sites depend weakly on confining environment polarity, while Gibbs free energies of hydride-shift isomerization transition states are lower when confined within hydrophobic micropores. DFT calculations suggest that interactions between intraporous water and isomerization transition states increase effective transition state sizes through second-shell solvation spheres, reducing primary solvation sphere flexibility. These findings clarify the effects of hydrophobic pockets on the stability of coadsorbed water and isomerization transition states and suggest design strategies that modify micropore polarity to influence turnover rates in liquid water.