Theory of hot-carrier generation in bimetallic plasmonic catalysts

Bimetallic nanoreactors in which a plasmonic metal is used to funnel solar energy toward a catalytic metal have recently been studied experimentally, but a detailed theoretical understanding of these systems is lacking. Here, we present theoretical results of hot-carrier generation rates of different Au-Pd nanoarchitectures. In particular, we study spherical core-shell nanoparticles with a Au core and a Pd shell as well as antenna-reactor systems consisting of a large Au nanoparticle that acts as an antenna and a smaller Pd satellite nanoparticle separated by a gap. In addition, we investigate an antenna-reactor system in which the satellite is a core-shell nanoparticle. Hot-carrier generation rates are obtained from an atomistic quantum-mechanical modeling technique which combines a solution of Maxwell's equation with a tight-binding description of the nanoparticle electronic structure. We find that antenna-reactor systems exhibit significantly higher hot-carrier generation rates in the catalytic material than the core-shell system as a result of strong electric field enhancements associated with the gap between the antenna and the satellite. For these systems, we also study the dependence of the hot-carrier generation rate on the size of the gap, the radius of the antenna nanoparticle, and the direction of light polarization. Overall, we find a strong correlation between the calculated hot-carrier generation rates and the experimentally measured chemical activity for the different Au-Pd photocatalysts. Our insights pave the way toward a microscopic understanding of hot-carrier generation in heterogeneous nanostructures for photocatalysis and other energy-conversion applications

Magnetic and magnetocaloric properties of Co2-xFexVGa Heusler alloys

The magnetic and magnetocaloric properties of iron-substituted Co2VGa alloys, Co2-xFexVGa (x = 0, 0.1, 0.15, 0.2, 0.3), were investigated. The Fe-substituted samples, prepared by arc melting, melt spinning, and annealing, crystallized in the L21 Heusler structure, without any secondary phases. The Curie temperature and highfield magnetization at 50 K decreased from 345 K and 44 emu/g (1.90 μB/f.u.) for Co2VGa to 275 K and 39 emu/g (1.66 μB/f.u.) for Co1.7Fe0.3VGa, respectively, but the maximum entropy change remained almost insensitive to Fe concentration for x ≤ 0.2, the highest value being 3.3 J/kgK at 7 T for Co1.85Fe0.15VGa. First-principle calculations show that Co2VGa retains its half-metallic band structure until at least 30% of the cobalt atoms are replaced by Fe atoms. The wide operating temperature window near room temperature and the lack of thermal and magnetic hysteresis are the interesting features of these materials for application in room-temperature magnetic refrigeration

Effect of disorder on the magnetic and electronic structure of a prospective spin-gapless semiconductor MnCrVAl

Recent discovery of a new class of materials, spin-gapless semiconductors (SGS), has attracted considerable attention in the last few years, primarily due to potential applications in the emerging field of spin-based electronics (spintronics). Here, we investigate structural, electronic, and magnetic properties of one potential SGS compound, MnCr-VAl, using various experimental and theoretical techniques. Our calculations show that this material exhibits ≈ 0.5 eV band gap for the majority-spin states, while for the minority-spin it is nearly gapless. The calculated magnetic moment for the com- pletely ordered structure is 2.9 μB/f.u., which is different from our experimentally measured value of almost zero. This discrepancy is explained by the structural disorder. In particular, A2 type disorder, where Mn or Cr atoms exchange their positions with Al atoms, results in induced antiferromagnetic exchange coupling, which, at a certain level of disorder, effectively reduces the total magnetic moment to zero. This is consistent with our x-ray diffraction measurements which indicate the presence of A2 disorder in all of our samples. In addition, we also show that B2 disorder does not result in antiferromagnetic exchange coupling and therefore does not significantly reduce the total magnetic moment

Plasmonic bimetallic two-dimensional supercrystals for H2 generation

Sunlight-driven H-2 generation is a central technology to tackle our impending carbon-based energy collapse. Colloidal photocatalysts consisting of plasmonic and catalytic nanoparticles are promising for H-2 production at solar irradiances, but their performance is hindered by absorption and multiscattering events. Here we present a two-dimensional bimetallic catalyst by incorporating platinum nanoparticles into a well-defined supercrystal of gold nanoparticles. The bimetallic supercrystal exhibited an H-2 generation rate of 139mmolg(cat)(-1)h(-1) via formic acid dehydrogenation under visible light illumination and solar irradiance. This configuration makes it possible to study the interaction between the two metallic materials and the influence of this in catalysis. We observe a correlation between the intensity of the electric field in the hotspots and the boosted catalytic activity of platinum nanoparticles, while identifying a minor role of heat and gold-to-platinum charge transfer in the enhancement. Our results demonstrate the benefits of two-dimensional configurations with optimized architecture for liquid-phase photocatalysis

Effect of Fe substitution on the structural, magnetic and electron-transport properties of half-metallic Co2TiSi

The structural, magnetic and electron-transport properties of Co2Ti1-xFexSi (x = 0, 0.25, 0.5) ribbons prepared by arc-melting and melt-spinning were investigated. The rapidly quenched Co2Ti0.5Fe0.5Si crystallized in the cubic L21 structure whereas Co2Ti0.75Fe0.25Si and Co2TiFe0Si showed various degrees of B2-type disorder. At room temperature, all the samples are ferromagnetic, and the Curie temperature increased from 360 K for Co2TiSi to about 800 K for Co2Ti0.5Fe0.5Si. The measured magnetization also increased due to partial substitution of Fe for Ti atoms. The ribbons are moderately conducting and show positive temperature coefficient of resistivity with the room temperature resistivity being between 360 µΩcm and 440 µΩcm. The experimentally observed structural and magnetic properties are consistent with the results of first-principle calculations. Our calculations also indicate that the Co2Ti1-xFexSi compound remains nearly half-metallic for x ≤ 0.5. The predicted large band gaps and high Curie temperatures much above room temperature make these materials promising for room temperature spintronic and magnetic applications

Magnetic and magnetocaloric properties of Co2-xFexVGa Heusler alloys

The magnetic and magnetocaloric properties of iron-substituted Co2VGa alloys, Co2-xFexVGa (x = 0, 0.1, 0.15, 0.2, 0.3), were investigated. The Fe-substituted samples, prepared by arc melting, melt spinning, and annealing, crystallized in the L2(1) Heusler structure, without any secondary phases. The Curie temperature and high-field magnetization at 50 K decreased from 345 K and 44 emu/g (1.90 mu(B)/f.u.) for Co2VGa to 275 K and 39 emu/g (1.66 mu(B)/f.u.) for Co1.7Fe0.3VGa, respectively, but the maximum entropy change remained almost insensitive to Fe concentration for x 1.85Fe0.15VGa. First-principle calculations show that Co2VGa retains its half-metallic band structure until at least 30% of the cobalt atoms are replaced by Fe atoms. The wide operating temperature window near room temperature and the lack of thermal and magnetic hysteresis are the interesting features of these materials for application in room-temperature magnetic refrigeration. (c) 2018 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/1.500664

Effect of disorder on the magnetic and electronic structure of a prospective spin-gapless semiconductor MnCrVAl

Recent discovery of a new class of materials, spin-gapless semiconductors (SGS), has attracted considerable attention in the last few years, primarily due to potential applications in the emerging field of spin-based electronics (spintronics). Here, we investigate structural, electronic, and magnetic properties of one potential SGS compound, MnCrVAl, using various experimental and theoretical techniques. Our calculations show that this material exhibits ≈ 0.5 eV band gap for the majority-spin states, while for the minority-spin it is nearly gapless. The calculated magnetic moment for the completely ordered structure is 2.9 µB/f.u., which is different from our experimentally measured value of almost zero. This discrepancy is explained by the structural disorder. In particular, A2 type disorder, where Mn or Cr atoms exchange their positions with Al atoms, results in induced antiferromagnetic exchange coupling, which, at a certain level of disorder, effectively reduces the total magnetic moment to zero. This is consistent with our x-ray diffraction measurements which indicate the presence of A2 disorder in all of our samples. In addition, we also show that B2 disorder does not result in antiferromagnetic exchange coupling and therefore does not significantly reduce the total magnetic moment

Easy-To-Synthesize Spirocyclic Compounds Possess Remarkable in Vivo Activity against Mycobacterium tuberculosis

Society urgently needs new, effective medicines for the treatment of tuberculosis. To kick-start the required hit-to-lead campaigns, the libraries of pharmaceutical companies have recently been evaluated for starting points. The GlaxoSmithKline (GSK) library yielded many high-quality hits, and the associated data were placed in the public domain to stimulate engagement by the wider community. One such series, the spiro compounds, are described here. The compounds were explored by a combination of traditional in-house research and open source methods. The series benefits from a particularly simple structure and a short associated synthetic chemistry route. Many members of the series displayed striking potency and low toxicity, and highly promising in vivo activity in a mouse model was confirmed with one of the analogues. Ultimately the series was discontinued due to concerns over safety, but the associated data remain public domain, empowering others to resume the series if the perceived deficiencies can be overcome

On the security of consumer wearable devices in the Internet of Things

Miniaturization of computer hardware and the demand for network capable devices has resulted in the emergence of a new class of technology called wearable computing. Wearable devices have many purposes like lifestyle support, health monitoring, fitness monitoring, entertainment, industrial uses, and gaming. Wearable devices are hurriedly being marketed in an attempt to capture an emerging market. Owing to this, some devices do not adequately address the need for security. To enable virtualization and connectivity wearable devices sense and transmit data, therefore it is essential that the device, its data and the user are protected. In this paper the use of novel Integrated Circuit Metric (ICMetric) technology for the provision of security in wearable devices has been suggested. ICMetric technology uses the features of a device to generate an identification which is then used for the provision of cryptographic services. This paper explores how a device ICMetric can be generated by using the accelerometer and gyroscope sensor. Since wearable devices often operate in a group setting the work also focuses on generating a group identification which is then used to deliver services like authentication, confidentiality, secure admission and symmetric key generation. Experiment and simulation results prove that the scheme offers high levels of security without compromising on resource demands