Generating Strong Metal-Support Interaction and Oxygen Vacancies in Cu/MgAlO Catalysts by CO Treatment for Enhanced CO Hydrogenation to Methanol.

Strong metal-support interactions (SMSIs) are essential for optimizing the performance of supported metal catalysts by tuning the metal-oxide interface structures. This study explores the hydrogenation of CO to methanol over Cu-supported catalysts, focusing on the synergistic effects of strong metal-support interaction (SMSI) and oxygen vacancies introduced by the CO treatment to the catalysts on the catalytic performance. Cu nanoparticles were immobilized on Mg-Al layered double oxide (LDO) supports and modified with nitrate ions to promote oxygen vacancy generation.

Atmospheric-Pressure Conversion of CO to Cyclic Carbonates over Constrained Dinuclear Iron Catalysts.

The conversion of CO and epoxides to cyclic carbonates over a silica-supported di-iron(III) complex having a reduced Robson macrocycle ligand system is shown to proceed at 1 atm and 80 °C, exclusively producing the -cyclohexene carbonate from cyclohexene oxide. We examine the effect of immobilization configuration to show that the complex grafted in a semirigid configuration catalytically outperforms the rigid, flexible configurations and even the homogeneous counterparts. Using the semirigid catalyst, we are able to obtain a TON of up to 800 and a TOF of up to 37 h under 1 atm CO.

First-Principle Colloidal Gate for Controlling Liquid and Molecule Flow Using 2D Claylike Nanoparticles.

Herein, we exploit the natural tendency of two-dimensional (2D) clay nanoparticles to self-assemble and restrict water permeability in soils to fabricate a first of its kind synthetic, pH-activated, reversible, and tunable colloidal flow gate. To realize this, we studied the effect of the pH level of a suspension of claylike layered double hydroxide (LDH) nanoparticles on the LDH coagulation process. We then packed the LDH into a fixed-bed column and examined the effect of pH on mass transport through the column.

Fe-N-C electrocatalysts in the oxygen and nitrogen cycles in alkaline media: the role of iron carbide.

Fe-N-C electrocatalysts hold a great promise for Pt-free energy conversion, driving the electrocatalysis of oxygen reduction and evolution, oxidation of nitrogen fuels, and reduction of N, CO, and NO. Nevertheless, the catalytic role of iron carbide, a component of nearly every pyrolytic Fe-N-C material, is at the focus of a heated controversy. We now resolve the debate by examining a broad range of FeC sites, spanning across many typical size distributions and carbon environments.

A rare 4-fold interpenetrated metal-organic framework constructed from an anionic indium-based node and a cationic dicopper linker.

A unique 4-fold interpenetrated metal-organic framework, TIF-1, was synthesized by combining an anionic indium node with a cationic linker. This framework shows a rare type of 4-fold interpenetrated dia network, constructed from tessellation of biangular and tetragonal type metal-organic micropores. The porosity of TIF-1 is moderate due to four-fold interpenetration and charge-balancing anions.

Critical Surface Parameters for the Oxidative Coupling of Methane over the Mn-Na-W/SiO Catalyst.

The work here presents a thorough evaluation of the effect of Mn-Na-W/SiO catalyst surface parameters on its performance in the oxidative coupling of methane (OCM). To do so, we used microporous dealuminated β-zeolite (Zeo), or mesoporous SBA-15 (SBA), or macroporous fumed silica (Fum) as precursors for catalyst preparation, together with Mn nitrate, Mn acetate and NaWO. Characterizing the catalysts by inductively coupled plasma-optical emission spectroscopy, N physisorption, X-ray diffraction, high-resolution scanning electron microscopy-energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and catalytic testing enabled us to identify critical surface parameters that govern the activity and C selectivity of the Mn-Na-W/SiO catalyst.

Sensors: A Highly Sensitive Diketopyrrolopyrrole-Based Ambipolar Transistor for Selective Detection and Discrimination of Xylene Isomers (Adv. Mater. 21/2016).

An ambipolar organic field-effect transistor (OFET) based on poly(diketopyrrolopyrrole-terthiophene) (PDPPHD-T3) is shown by P. Sonar, H. Haick, and co-workers on page 4012 to sensitively detect xylene isomers at low to 40 ppm level in multiple sensing features.

A Highly Sensitive Diketopyrrolopyrrole-Based Ambipolar Transistor for Selective Detection and Discrimination of Xylene Isomers.

An ambipolar poly(diketopyrrolopyrrole-terthiophene)-based field-effect transistor (FET) sensitively detects xylene isomers at low ppm levels with multiple sensing features. Combined with pattern-recognition algorithms, a sole ambipolar FET sensor, rather than arrays of sensors, can discriminate highly similar xylene structural isomers from one another.

Understanding the role of defect sites in glucan hydrolysis on surfaces.

Though unfunctionalized mesoporous carbon consisting of weakly Brønsted acidic OH-defect sites depolymerizes cellulose under mild conditions, the nature of the active site and how this affects hydrolysis kinetics--the rate-limiting step of this process--has remained a puzzle. Here, in this manuscript, we quantify the effect of surface OH-defect site density during hydrolysis catalysis on the rate of reaction. Our comparative approach relies on synthesis and characterization of grafted poly(1→4-β-glucan) (β-glu) strands on alumina.

Dialkylimidazolium ionic liquids hydrolyze cellulose under mild conditions.

The average molecular weight of cellulose derived from filter paper, poplar, and Avicel decreases by up to two orders of magnitude during typical mild dissolution protocols using ionic liquids (ILs). About an order of magnitude greater cellulose depolymerization rate during ionic liquid dissolution occurs in 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-ethyl-3-methylimidazolium chloride (EmimCl) compared to 1-ethyl-3-methylimidazolium acetate (EmimOAc), and, unintuitively, greater IL purity results in greater cellulose depolymerization. The following data support the mechanism of cellulose hydrolysis to be acid-catalyzed: (i) increase in number of reducing ends following cellulose dissolution in IL; (ii) addition of N-methylimidazolium base suppresses cellulose depolymerization during dissolution in IL; (iii) small amounts of glucose and traces of hydroxymethyl furfural are present following cellulose dissolution in IL.

Grafted poly(1→4-β-glucan) strands on silica: a comparative study of surface reactivity as a function of grafting density.

Grafted poly(β-glucan) (β-glu) strands on the surface of silica are synthesized with varying degrees of grafting density, and display an amorphous-like environment via (13)C CP/MAS NMR spectroscopy. Thermal gravimetric analysis of these materials under oxidative conditions shows increased β-glu thermal stability with higher degrees of grafting density. The range of temperature stability between the most and least hydrogen-bound grafted β-glu strands spans 321 to 260 °C.

Grafted cellulose strands on the surface of silica: effect of environment on reactivity.

The design, synthesis and characterization of materials consisting of grafted poly(1 → 4-β-glucan) strands on silica is reported. The silanol-rich environment provided in these materials activates the glycosidic bond for hydrolysis under mild conditions.