Efficient electrocatalytic water oxidation at neutral and high pH by adventitious nickel at nanomolar concentrations

Electrolytic water oxidation using earth-abundant elements is a key challenge in the quest to develop cheap, large surface area arrays for solar-to-hydrogen conversion. There have been numerous studies in this area in recent years, but there remains an imperative to demonstrate that the current densities reported are indeed due to the species under consideration and not due to the presence of adventitious (yet possibly highly active) contaminants at low levels. Herein, we show that adventitious nickel at concentrations as low as 17 nM can act as a water oxidation catalyst in mildly basic aqueous solutions, achieving stable (tens of hours) current densities of 1 mA cm–2 at overpotentials as low as 540 mV at pH 9.2 and 400 mV at pH 13. This nickel was not added to the electrolysis baths deliberately, but it was found to be present in the electrolytes as an impurity by ICP-MS. The presence of nickel on anodes from extended-time bulk electrolysis experiments was confirmed by XPS. In showing that such low levels of nickel can perform water oxidation at overpotentials comparable to many recently reported water oxidation catalysts, this work serves to raise the burden of proof required of new materials in this field: contamination by adventitious metal ions at trace loadings must be excluded as a possible cause of any observed water oxidation activity

An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex

The copper-containing nitrite reductases (CuNIRs) are a class of enzymes that mediate the reduction of nitrite to nitric oxide in biological systems. Metal–ligand complexes that reproduce the salient features of the active site of CuNIRs are therefore of fundamental interest, both for elucidating the possible mode of action of the enzymes and for developing biomimetic catalysts for nitrite reduction. Herein, we describe the synthesis and characterization of a new tris(2-pyridyl) copper complex ([Cu1(NO2)2]) that binds two molecules of nitrite, and displays all three of the common binding modes for NO2−, with one nitrite bound in an asymmetric quasi-bidentate κ2-ONO manner and the other bound in a monodentate fashion with a linkage isomerism between the κ1-ONO and κ1-NO2 binding modes. We use density functional theory to help rationalize the presence of all three of these linkage isomers in one compound, before assessing the redox activity of [Cu1(NO2)2]. These latter studies show that the complex is not a competent nitrite reduction electrocatalyst in non-aqueous solvent, even in the presence of additional proton donors, a finding which may have implications for the design of biomimetic catalysts for nitrite reduction

Ultra-high brilliance multi-MeV γ\gamma-ray beam from non-linear Thomson scattering

We report on the generation of a narrow divergence ($\theta\approx 2.5$ mrad), multi-MeV ($E_\text{MAX} = 18$ MeV) and ultra-high brilliance ($\approx 2\times10^{19}$ photons s$^{-1}$ mm$^{-2}$ mrad $^{-2}$ 0.1\% BW) $\gamma$-ray beam from the scattering of an ultra-relativistic laser-wakefield accelerated electron beam in the field of a relativistically intense laser (dimensionless amplitude $a_0\approx2$). The spectrum of the generated $\gamma$-ray beam is measured, with MeV resolution, seamlessly from 6 MeV to 18 MeV, giving clear evidence of the onset of non-linear Thomson scattering. The photon source has the highest brilliance in the multi-MeV regime ever reported in the literature

Bright X-ray radiation from plasma bubbles in an evolving laser wakefield accelerator

We show that the properties of the electron beam and bright x-rays produced by a laser wakefield accelerator can be predicted if the distance over which the laser self-focuses and compresses prior to self-injection is taken into account. A model based on oscillations of the beam inside a plasma bubble shows that performance is optimised when the plasma length is matched to the laser depletion length. With a 200~TW laser pulse this results in an x-ray beam with median photon energy of \unit[20]{keV}, $> 6\times 10^{8}$ photons above \unit[1]{keV} per shot and a peak brightness of \unit[3 \times 10^{22}]{photons~s^{-1}mrad^{-2}mm^{-2} (0.1\% BW)^{-1}}.Comment: 5 pages, 4 figure

Polarization Dependence of Bulk Ion Acceleration from Ultrathin Foils Irradiated by High-Intensity Ultrashort Laser Pulses

The acceleration of ions from ultrathin (10-100 nm) carbon foils has been investigated using intense (∼ 6 x1020 Wcm-2), ultrashort (45 fs) laser pulses, highlighting a strong dependence of the ion beam parameters on the laser polarization, with circularly polarized (CP) pulses producing the highest energies for both protons and carbons (25-30 MeV/nucleon); carbon ion energies obtained employing CP pulses were signicantly higher (∼2.5 times) than for irradiations employing linearly polarized (LP) pulses. Particle-in-cell simulations indicate that Radiation Pressure Acceleration becomes the dominant mechanism for the thinnest targets and CP pulses