Direct growth of copper(I) oxide nanocubes on graphitic carbon nitrides enhancing aqueous carbon dioxide photoreduction

Semiconductor hybrid structures containing multiple components have been considered an ideal photocatalyst design to generate long-lived charge-separated states. Particularly for the reactions requiring high activation energies, such as a CO2 reduction reaction (CO2RR), the reaction activity is highly susceptible to the catalyst component and morphology. In this study, we selected g-C3N4 and Cu2O as photocatalytic components having bandgaps suitable for CO2RR. Then, we tried to form good electric junctions between two domains by direct growth of Cu on g-C3N4 using a polyol process. The resulting g-C3N4/Cu2O hybrid was employed as photocatalysts in an aqueous medium without hole acceptors. The catalyst exhibited a noticeable activity (5.4 mmol gcat-1h-1) and quantum yield (3.7%) with a nearly quantitative selectivity for CH4 production, superior to any other photocatalysts for CO2RR. The strong coordination of g-C3N4 to the Cu2O surface could form a conductive junction and induce effective electron transfer enforcing the Z-scheme process for CO2RR in high activity and selectivity. This result ensured the importance of junctions and interfaces in the hybrid catalyst structure to exhibit excellent photocatalytic CO2RR performances.

Glycosyl Exchange of Unactivated Glycosidic Bonds: Suppressing or Embracing Side Reactivity in Catalytic Glycosylations

While developing boron-catalyzed glycosylations using glycosyl fluoride donors and trialkylsilyl ether acceptors, competing pathways involving productive glycosylation or glycosyl exchange were observed. Experimental and computational mechanistic studies suggest a novel mode of reactivity where a dioxolenium ion is a key intermediate that promotes both pathways through addition to either a silyl ether or to the acetal of an existing glycosidic linkage. Modifications in catalyst structure enable either pathway to be favored, and with this understanding, improved multicomponent iterative couplings and glycosyl exchange processes were demonstrated.

Stroboscopic operando spectroscopy of the dynamics in heterogeneous catalysis by event-averaging

Heterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. A key finding is that at 3.2 mbar total pressure a metallic, predominantly CO-covered metallic surface turns highly active for a few seconds once the O2:CO ratio becomes high enough to lift the CO poisoning effect before mass transport limitations triggers formation of a √5 oxide.

One-Pot Synthesis of Al-P-O Catalysts and Their Catalytic Properties for O-Methylation of Catechol and Methanol

A series of Al-P-O catalysts (Al-xP-O) were prepared using a P123-assisted one-pot method at different P/Al molar ratios and used for O-methylation of catechol and methanol. The influences of the P/Al molar ratio and P123 addition on catalyst structure and surface acid-base characteristics were investigated in detail. Increasing the P/Al molar ratio more favored crystalline aluminophosphate. The P123-assisted Al3+ and PO43− are known to be stabilized through weak steric force so that the formation of crystalline aluminophosphate could be inhibited at higher P/Al molar ratios. The results showed that the prepared Al-P-O catalysts possessed appropriate weak acid and weak base sites, which was beneficial to the reaction of catechol and methanol. The Al-1.1P-O catalyst synthesized with the assistance of P123 exhibited superior catalytic performances, with 52.5% catechol conversion and higher guaiacol selectivity of 97.6%.

Enantioenriched α-substituted glutamates/pyroglutamates via enantioselective cyclopropenimine-catalyzed Michael addition of amino ester imines

A procedure for the enantioselective synthesis of α-substituted glutamates and pyroglutamates via a cyclopropenimine-catalyzed Michael addition of amino ester imines is described. Enantioselectivities of up to 94% have been achieved, and a variety of functional groups were found to be compatible. The impact of the catalyst structure and imine substitution is discussed. Compared to other methods, this protocol allows for a broader and more enantioselective access to pyroglutamate derivatives.

A simple model for desulphurisation of flue gas using reactive filters

Desulphurisation of flue gas is essential before it can be released safely into the atmosphere. One way of removing sulphur dioxide is to use a purification device incorporating a reactive filter, in which the flue gas stream passes in front of a porous-catalyst-filled structure which converts the gaseous sulphur dioxide into liquid sulphuric acid. In this paper, we build and solve a simple mathematical model to describe the operation of a paradigm reactive filter. Our model captures the transport of sulphur dioxide through the device via advection in the main “outer” flow and diffusion through the catalyst structure along with the production of sulphuric acid. This sulphuric acid gradually accumulates in the filter rendering it less efficient. We determine the clogging time for an individual channel (that is, the time at which the entrance to the channel becomes completely filled with liquid) and explore how the concentrations of sulphur dioxide and oxygen and the thickness of the sulphuric acid layer change as the key dimensionless parameters are varied, comparing numerical and asymptotic results where appropriate. We then turn our attention to the device scale and solve our model numerically to determine the overall lifetime of the device. We vary the key dimensionless parameters and explore how they affect the efficiency of the device. In the physically relevant parameter regime, we find an explicit solution to the outer flow problem which agrees well with numerical solutions and provides a formula for the lifetime of the device. Finally, we propose a formula for determining the catalyst reaction rate, given data on the concentration of sulphur dioxide exiting the device.