Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO₂ reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO₂ reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO₂ reduction over hydrogen evolution in aqueous electrolytes. Specifically, we observed that plasmon-driven CO₂ reduction increased the production of carbon monoxide and formate, while simultaneously reducing the evolution of hydrogen. Our results demonstrate an optical route toward steering the selectivity of artificial photosynthetic systems with plasmon-driven photocathodes for photoelectrochemical CO₂ reduction in aqueous media

Impact of hydrothermalism on the ocean iron cycle

As the iron supplied from hydrothermalism is ultimately ventilated in the iron-limited Southern Ocean, it plays an important role in the ocean biological carbon pump. We deploy a set of focused sensitivity experiments with a state of the art global model of the ocean to examine the processes that regulate the lifetime of hydrothermal iron and the role of different ridge systems in governing the hydrothermal impact on the Southern Ocean biological carbon pump. Using GEOTRACES section data, we find that stabilization of hydrothermal iron is important in some, but not all regions. The impact on the Southern Ocean biological carbon pump is dominated by poorly explored southern ridge systems, highlighting the need for future exploration in this region. We find inter-basin differences in the isopycnal layer onto which hydrothermal Fe is supplied between the Atlantic and Pacific basins, which when combined with the inter-basin contrasts in oxidation kinetics suggests a muted influence of Atlantic ridges on the Southern Ocean biological carbon pump. Ultimately, we present a range of processes, operating at distinct scales, that must be better constrained to improve our understanding of how hydrothermalism affects the ocean cycling of iron and carbon

Hot Hole Collection and Photoelectrochemical CO_2 Reduction with Plasmonic Au/p-GaN Photocathodes

Harvesting nonequilibrium hot carriers from plasmonic-metal nanostructures offers unique opportunities for driving photochemical reactions at the nanoscale. Despite numerous examples of hot electron-driven processes, the realization of plasmonic systems capable of harvesting hot holes from metal nanostructures has eluded the nascent field of plasmonic photocatalysis. Here, we fabricate gold/p-type gallium nitride (Au/p-GaN) Schottky junctions tailored for photoelectrochemical studies of plasmon-induced hot-hole capture and conversion. Despite the presence of an interfacial Schottky barrier to hot-hole injection of more than 1 eV across the Au/p-GaN heterojunction, plasmonic Au/p-GaN photocathodes exhibit photoelectrochemical properties consistent with the injection of hot holes from Au nanoparticles into p-GaN upon plasmon excitation. The photocurrent action spectrum of the plasmonic photocathodes faithfully follows the surface plasmon resonance absorption spectrum of the Au nanoparticles and open-circuit voltage studies demonstrate a sustained photovoltage during plasmon excitation. Comparison with Ohmic Au/p-NiO heterojunctions confirms that the vast majority of hot holes generated via interband transitions in Au are sufficiently hot to inject above the 1.1 eV interfacial Schottky barrier at the Au/p-GaN heterojunction. We further investigated plasmon-driven photoelectrochemical CO_2 reduction with the Au/p-GaN photocathodes and observed improved selectivity for CO production over H_2 evolution in aqueous electrolytes. Taken together, our results offer experimental validation of photoexcited hot holes more than 1 eV below the Au Fermi level and demonstrate a photoelectrochemical platform for harvesting hot carriers to drive solar-to-fuel energy conversion

The CFT dual of AdS gravity with torsion

We consider the Mielke-Baekler model of three-dimensional AdS gravity with torsion, which has gravitational and translational Chern-Simons terms in addition to the usual Einstein-Hilbert action with cosmological constant. It is shown that the topological nature of the model leads to a finite Fefferman-Graham expansion. We derive the holographic stress tensor and the associated Ward identities and show that, due to the asymmetry of the left- and right-moving central charges, a Lorentz anomaly appears in the dual conformal field theory. Both the consistent and the covariant Weyl and Lorentz anomaly are determined, and the Wess-Zumino consistency conditions for the former are verified. Moreover we consider the most general solution with flat boundary geometry, which describes left-and right-moving gravitational waves on AdS_3 with torsion, and shew that in this case the holographic energy-momentum tensor is given by the wave profiles. The anomalous transformation laws of the wave profiles under diffeomorphisms preserving the asymptotic form of the bulk solution yield the central charges of the dual CFT and confirm the results that appeared earlier on in the literature. We finally comment on some points concerning the microstate counting for the Riemann-Cartan black hole.Comment: 17 pages, uses JHEP3.cls. References added, minor errors correcte

Ultrafast Studies of Hot-Hole Dynamics in Au/p-GaN Heterostructures

Harvesting non-equilibrium hot carriers from photo-excited metal nanoparticles has enabled plasmon-driven photochemical transformations and tunable photodetection with resonant nanoantennas. Despite numerous studies on the ultrafast dynamics of hot electrons, to date, the temporal evolution of hot holes in metal-semiconductor heterostructures remains unknown. An improved understanding of the carrier dynamics in hot-hole-driven systems is needed to help expand the scope of hot-carrier optoelectronics beyond hot-electron-based devices. Here, using ultrafast transient absorption spectroscopy, we show that plasmon-induced hot-hole injection from gold (Au) nanoparticles into the valence band of p-type gallium nitride (p-GaN) occurs within 200 fs, placing hot-hole transfer on a similar timescale as hot-electron transfer. We further observed that the removal of hot holes from below the Au Fermi level exerts a discernible influence on the thermalization of hot electrons above it, reducing the peak electronic temperature and decreasing the electron-phonon coupling time relative to Au samples without a pathway for hot-hole collection. First principles calculations corroborate these experimental observations, suggesting that hot-hole injection modifies the relaxation dynamics of hot electrons in Au nanoparticles through ultrafast modulation of the d-band electronic structure. Taken together, these ultrafast studies substantially advance our understanding of the temporal evolution of hot holes in metal-semiconductor heterostructures and suggest new strategies for manipulating and controlling the energy distributions of hot carriers on ultrafast timescales.Comment: 12 pages, 4 figure

Mutual heavy ion dissociation in peripheral collisions at ultrarelativistic energies

We study mutual dissociation of heavy nuclei in peripheral collisions at ultrarelativistic energies. Earlier this process was proposed for beam luminosity monitoring via simultaneous registration of forward and backward neutrons in zero degree calorimeters at Relativistic Heavy Ion Collider. Electromagnetic dissociation of heavy ions is considered in the framework of the Weizsacker-Williams method and simulated by the RELDIS code. Photoneutron cross sections measured in different experiments and calculated by the GNASH code are used as input for the calculations of dissociation cross sections. The difference in results obtained with different inputs provides a realistic estimation for the systematic uncertainty of the luminosity monitoring method. Contribution to simultaneous neutron emission due to grazing nuclear interactions is calculated within the abrasion model. Good description of CERN SPS experimental data on Au and Pb dissociation gives confidence in predictive power of the model for AuAu and PbPb collisions at RHIC and LHC.Comment: 46 pages with 7 tables and 13 figures, numerical integration accuracy improved, next-to-leading-order corrections include

Particle emission following Coulomb excitation in ultrarelativistic heavy-ion collisions

We study nuclear reactions induced by virtual photons associated with Lorentz-boosted Coulomb fields of ultrarelativistic heavy ions. Evaporation, fission and multifragmentation mechanisms are included in a new RELDIS code, which describes the deexcitation of residual nuclei formed after single and double photon absorption in peripheral heavy-ion collisions. Partial cross sections for different dissociation channels, including the multiple neutron emission ones, are calculated and compared with data when available. Rapidity and transverse momentum distributions of nucleons, nuclear fragments and pions, produced electromagnetically, are also calculated. These results provide important information for designing large-rapidity detectors and zero-degree calorimeters at RHIC and LHC. The electromagnetic dissociation of nuclei imposes some constrains on the investigation of exotic particle production in gamma-gamma fusion reactions.Comment: 26 LaTeX pages including 8 figures, uses epsf.st

ER and HER2 expression are positively correlated in HER2 non-overexpressing breast cancer

PMCID: PMC3446380This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited

Quantifying the roles of ocean circulation and biogeochemistry in governing ocean carbon-13 and atmospheric carbon dioxide at the last glacial maximum

We use a state-of-the-art ocean general circulation and biogeochemistry model to examine the impact of changes in ocean circulation and biogeochemistry in governing the change in ocean carbon-13 and atmospheric CO2 at the last glacial maximum (LGM). We examine 5 different realisations of the ocean's overturning circulation produced by a fully coupled atmosphere-ocean model under LGM forcing and suggested changes in the atmospheric deposition of iron and phytoplankton physiology at the LGM. Measured changes in carbon-13 and carbon-14, as well as a qualitative reconstruction of the change in ocean carbon export are used to evaluate the results. Overall, we find that while a reduction in ocean ventilation at the LGM is necessary to reproduce carbon-13 and carbon-14 observations, this circulation results in a low net sink for atmospheric CO2. In contrast, while biogeochemical processes contribute little to carbon isotopes, we propose that most of the change in atmospheric CO2 was due to such factors. However, the lesser role for circulation means that when all plausible factors are accounted for, most of the necessary CO2 change remains to be explained. This presents a serious challenge to our understanding of the mechanisms behind changes in the global carbon cycle during the geologic past