Ruthenium-rhenium and ruthenium-palladium supramolecular photocatalysts for photoelectrocatalytic CO2 and H+ reduction.

Photoelectrocatalysis offers the opportunity to close the carbon loop and convert captured CO2 back into useful fuels and feedstocks, mitigating against anthropogenic climate change. However, since CO2 is inherently stable and sunlight is a diffuse and intermittent energy source, there are considerable scientific challenges to overcome. In this paper we present the integration of two new metal–organic photocatalysts into photocathodes for the reduction of CO2 using ambient light. The two molecular dyads contained a rhenium carbonyl or palladium-based catalytic centre bridged to a ruthenium bipyridyl photosensitizer functionalised with carboxylic acid groups to enable adsorption onto the surface of mesoporous NiO cathodes. The photocathodes were evaluated for photoelectrochemical reduction of CO2 to CO or H+ to H2 and the performances were compared directly with a control compound lacking the catalytic site. A suite of electrochemical, UV-visible steady-state/time-resolved spectroscopy, X-ray photoelectron spectroscopy and gas chromatography measurements were employed to gain kinetic and mechanistic insight to primary electron transfer processes and relate the structure to the photoelectrocatalytic performance under various conditions in aqueous media. A change in behaviour when the photocatalysts were immobilized on NiO was observed. Importantly, the transfer of electron density towards the Re–CO catalytic centre was observed, using time resolved infrared spectroscopy, only when the photocatalyst was immobilized on NiO and not in MeCN solution. We observed that photocurrent and gaseous photoproduct yields are limited by a relatively low yield of the required charge-separated state across the NiO|Photocatalyst interface. Nonetheless, the high faradaic efficiency (94%) and selectivity (99%) of the Re system towards CO evolution are very promising

Ultrafast electronic, infrared, and X-ray absorption spectroscopy study of Cu(i) phosphine diimine complexes

The study aims to understand the role of the transient bonding in the interplay between the structural and electronic changes in heteroleptic Cu(I) diimine diphosphine complexes. This is an emerging class of photosensitisers which absorb in the red region of the spectrum, whilst retaining a sufficiently long excited state lifetime. Here, the dynamics of these complexes are explored by transient absorption (TA) and time-resolved infrared (TRIR) spectroscopy, which reveal ultrafast intersystem crossing and structural distortion occurring. Two potential mechanisms affecting excited state decay in these complexes involve a transient formation of a solvent adduct, made possible by the opening up of the Cu coordination centre in the excited state due to structural distortion, and by a transient coordination of the O-atom of the phosphine ligand to the copper center. X-ray absorption studies of the ground electronic state have been conducted as a prerequisite for the upcoming X-ray spectroscopy studies which will directly determine structural dynamics. The potential for these complexes to be used in bimolecular applications is confirmed by a significant yield of singlet oxygen production

Model-independent measurement of mixing parameters in D0^{0} → KS0_{S}^{0} π+^{+}π−^{−} decays

The first model-independent measurement of the charm mixing parameters in the decay $D^0 \to K_S \pi^+ \pi^-$ is reported, using a sample of $pp$ collision data recorded by the LHCb experiment, corresponding to an integrated luminosity of 1.0 fb$^{-1}$ at a centre-of-mass energy of 7 TeV. The measured values are \begin{eqnarray*} x &=& (-0.86 \pm 0.53 \pm 0.17) \times 10^{-2}, \\ y &=& (+0.03 \pm 0.46 \pm 0.13) \times 10^{-2}, \end{eqnarray*} where the first uncertainties are statistical and include small contributions due to the external input for the strong phase measured by the CLEO collaboration, and the second uncertainties are systematic.Comment: 25 pages, 3 figures. Sign error in x fixed as of v2. All figures and tables, along with any supplementary material and additional information, are available at https://lhcbproject.web.cern.ch/lhcbproject/Publications/LHCbProjectPublic/LHCb-PAPER-2015-042.htm