Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution: Applications in flow chemistry

Synthetic carbons with hierarchical mesopores are promising for developing new catalysts for intensified continuous-flow catalysis in structured reactors.Financial support from the Engineering and Physical Sciences Research Council (Engineering Functional Materials, EP/C519736/1), the Overseas Research Students Awards Scheme and the University of Bath Research Studentship is gratefully acknowledged. The assistance of Dr Martin Jennings Dr. Chris Muryn (School of Chemistry, The University of Manchester) on ICP-OES and XPS analyses is acknowledged. KW acknowledges the Royal Society for the award of an Industry Fellowship.This is the author accepted manuscript. The final version is available from RSC via http://dx.doi.org/10.1039/C5CY01401

Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution: applications in flow chemistry

Two new types of phenolic resin-derived synthetic carbons with bi-modal and tri-modal pore-size distributions were used as supports for Pd catalysts. The catalysts were tested in chemoselective hydrogenation and hydrodehalogenation reactions in a compact multichannel flow reactor. Bi-modal and tri-modal micro-mesoporous structures of the synthetic carbons were characterised by N2 adsorption. HR-TEM, PXRD and XPS analyses were performed for characterising the synthesised catalysts. N2 adsorption revealed that tri-modal synthetic carbon possesses a well-developed hierarchical mesoporous structure (with 6.5 nm and 42 nm pores), contributing to a larger mesopore volume than the bi-modal carbon (1.57 cm3 g–1 versus 1.23 cm3 g–1). It was found that the tri-modal carbon promotes a better size distribution of Pd nanoparticles than the bi-modal carbon due to presence of hierarchical mesopore limitting the growth of Pd nanoparticles. For all the model reactions investigated, the Pd catalyst based on tri-modal synthetic carbon (Pd/triC) show high activity as well as high stability and reproducibility. The trend in reactivities of different functional groups over the Pd/triC catalyst follows a general order alkyne >> nitro > bromo >> aldehyde.Financial support from the Engineering and Physical Sciences Research Council (Engineering Functional Materials, EP/C519736/1), the Overseas Research Students Awards Scheme and the University of Bath Research Studentship is gratefully acknowledged. The assistance of Dr Martin Jennings Dr. Chris Muryn (School of Chemistry, The University of Manchester) on ICP-OES and XPS analyses is acknowledged. KW acknowledges the Royal Society for the award of an Industry Fellowship.This is the author accepted manuscript. The final version is available from RSC via http://dx.doi.org/10.1039/C5CY01401

Porous Nanocrystalline Silicon Supported Bimetallic Pd-Au Catalysts: Preparation, Characterization, and Direct Hydrogen Peroxide Synthesis.

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterized by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt (DCS) single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 [Formula: see text] at selectivity of 50% and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10°C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability, and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process

Wideband 67-116 GHz cryogenic receiver development for ALMA Band 2

The Atacama Large Millimeter/sub-millimeter Array (ALMA) is already revolutionising our understanding of the Universe. However, ALMA is not yet equipped with all of its originally planned receiver bands, which will allow it to observe over the full range of frequencies from 35-950 GHz accessible through the Earth's atmosphere. In particular Band 2 (67-90 GHz) has not yet been approved for construction. Recent technological developments in cryogenic monolithic microwave integrated circuit (MMIC) high electron mobility transistor (HEMT) amplifier and orthomode transducer (OMT) design provide an opportunity to extend the originally planned on-sky bandwidth, combining ALMA Bands 2 and 3 into one receiver cartridge covering 67-116 GHz. The IF band definition for the ALMA project took place two decades ago, when 8 GHz of on-sky bandwidth per polarisation channel was an ambitious goal. The new receiver design we present here allows the opportunity to expand ALMA's wideband capabilities, anticipating future upgrades across the entire observatory. Expanding ALMA's instantaneous bandwidth is a high priority, and provides a number of observational advantages, including lower noise in continuum observations, the ability to probe larger portions of an astronomical spectrum for, e.g., widely spaced molecular transitions, and the ability to scan efficiently in frequency space to perform surveys where the redshift or chemical complexity of the object is not known a priori. Wider IF bandwidth also reduces uncertainties in calibration and continuum subtraction that might otherwise compromise science objectives. Here we provide an overview of the component development and overall design for this wideband 67-116 GHz cryogenic receiver cartridge, designed to operate from the Band 2 receiver cartridge slot in the current ALMA front end receiver cryostat.Comment: 8 pages, proceedings from the 8th ESA Workshop on Millimetre-Wave Technology and Applications (https://atpi.eventsair.com/QuickEventWebsitePortal/millimetre-wave/mm-wave

ALMA Band 5 receiver cartridge. Design, performance, and commissioning

We describe the design, performance, and commissioning results for the new ALMA Band 5 receiver channel, 163–211 GHz, which is in the final stage of full deployment and expected to be available for observations in 2018. This manuscript provides the description of the new ALMA Band 5 receiver cartridge and serves as a reference for observers using the ALMA Band 5 receiver for observations. At the time of writing this paper, the ALMA Band 5 Production Consortium consisting of NOVA Instrumentation group, based in Groningen, NL, and GARD in Sweden have produced and delivered to ALMA Observatory over 60 receiver cartridges. All 60 cartridges fulfil the new more stringent specifications for Band 5 and demonstrate excellent noise temperatures, typically below 45 K single sideband (SSB) at 4 K detector physical temperature and below 35 K SSB at 3.5 K (typical for operation at the ALMA Frontend), providing the average sideband rejection better than 15 dB, and the integrated cross-polarization level better than –25 dB. The 70 warm cartridge assemblies, hosting Band 5 local oscillator and DC bias electronics, have been produced and delivered to ALMA by NRAO. The commissioning results confirm the excellent performance of the receivers