Active sites on hydrogen evolution photocatalyst

Solar hydrogen production assisted with semiconductor materials is a promising way to provide alternative energy sources in the future. Such a photocatalytic reaction normally takes place on the active sites of the catalysts surface, and the identification of the active sites is crucial for understanding the photocatalytic reaction mechanism and further improving the photocatalytic efficiency. However, the active sites of model catalysts are still largely disputed because of their structural complexity. Conventionally, H-2 evolution from solar water splitting over Pt/TiO2 is widely deemed to take place on metallic Pt nanoparticles. Oppositely, we report through a combined experimental and theoretical approach, that metallic Pt nanoparticles have little contribution to the activity of photocatalytic H-2 evolution; the oxidized Pt species embedded on the TiO2 surface are the key active sites and primarily responsible for the activity of the hydrogen evolution Pt/TiO2 photocatalyst.

A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

Physical origin of the high reactivity of subsurface hydrogen in catalytic hydrogenation

In the catalytic hydrogenation of hydrocarbons, subsurface hydrogen is known experimentally to be much more reactive than surface hydrogen. We use density functional theory to identify low-energy pathways for the hydrogenation of methyl adsorbed on Ni(111) by surface and subsurface hydrogen. The metastability of subsurface hydrogen with respect to chemisorbed hydrogen is mainly responsible for the low activation barrier for subsurface reactions. (C) 1999 American Institute of Physics.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Hydrogen-Poor Superluminous Supernovae and Long-Duration Gamma-Ray Bursts Have Similar Host Galaxies

We present optical spectroscopy and optical/near-IR photometry of 31 host galaxies of hydrogen-poor superluminous supernovae (SLSNe), including 15 events from the Pan-STARRS1 Medium Deep Survey. Our sample spans the redshift range 0.1 ≲ z ≲ 1.6, and is the first comprehensive host galaxy study of this specific subclass of cosmic explosions. Combining the multi-band photometry and emission-line measurements, we determine the luminosities, stellar masses, star formation rates, and metallicities. We find that, as a whole, the hosts of SLSNe are a low-luminosity (〈M_B 〉 ≈ -17.3 mag), low stellar mass (〈M〉 ≈ 2 × 10⁸ M_⊙) population, with a high median specific star formation rate (〈sSFR〉 ≈ 2 Gyr^-1). The median metallicity of our spectroscopic sample is low, 12 + log (O/H) ≈ 8.35 ≈ 0.45 Z_⊙, although at least one host galaxy has solar metallicity. The host galaxies of H-poor SLSNe are statistically distinct from the hosts of GOODS core-collapse SNe (which cover a similar redshift range), but resemble the host galaxies of long-duration gamma-ray bursts (LGRBs) in terms of stellar mass, SFR, sSFR, and metallicity. This result indicates that the environmental causes leading to massive stars forming either SLSNe or LGRBs are similar, and in particular that SLSNe are more effectively formed in low metallicity environments. We speculate that the key ingredient is large core angular momentum, leading to a rapidly spinning magnetar in SLSNe and an accreting black hole in LGRBs.

PS1-10bzj: A Fast, Hydrogen-poor Superluminous Supernova in a Metal-poor Host Galaxy

We present observations and analysis of PS1-10bzj, a superluminous supernova (SLSN) discovered in the Pan-STARRS Medium Deep Survey at a redshift z = 0.650. Spectroscopically, PS1-10bzj is similar to the hydrogen-poor SLSNe 2005ap and SCP 06F6, though with a steeper rise and lower peak luminosity (M bol ~= -21.4 mag) than previous events. We construct a bolometric light curve, and show that while PS1-10bzj's energetics were less extreme than previous events, its luminosity still cannot be explained by radioactive nickel decay alone. We explore both a magnetar spin-down and circumstellar interaction scenario and find that either can fit the data. PS1-10bzj is located in the Extended Chandra Deep Field South and the host galaxy is imaged in a number of surveys, including with the Hubble Space Telescope. The host is a compact dwarf galaxy (MB ≈ -18 mag, diameter

Hydrogen-permeation characteristics of a SrCeO3-based ceramic separation membrane:Thermal, ageing and surface-modification effects

Dense ceramics with mixed protonic-electronic conductivity are of considerable interest for the separation and purification of hydrogen and as electrochemical reactors. In this work, the hydrogen permeability of a Sr_0.97Ce_0.9Yb_0.1O_{3 - δ} (SCYb) membrane with a porous Pt catalytic layer on the hydrogen feed-exposed side has been studied over the temperature range 500-804 °C employing Ar as the permeate sweep gas. A SiO₂-B₂O₃-BaO-MgO-ZnO-based glass-ceramic sealant was successfully employed to seal the membrane to the dual-chamber reactor. After 14 h of exposure to 10% H₂:90% N₂ at 804 °C, the H₂ flux reached a maximum of 33 nmol cm^{- 2} s^{- 1}, over an order of magnitude higher than that obtained on membranes of similar thickness without surface modification. The permeation rate then decreased slowly and moderately on annealing at 804 °C over a further 130 h. Thereafter, the flux was both reproducible and stable on thermal cycling in the range 600-804 °C. The results indicate an important role of superficial activation processes in the flux rate and suggest that hydrogen fluxes can be further optimised in cerate-based perovskites. © 2009 Elsevier B.V. All rights reserved.

Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water

Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry.

Production of ultracold hydrogen and deuterium via Doppler-cooled Feshbach molecules

A counterintuitive scheme to produce ultracold hydrogen via fragmentation of laser cooled diatomic hydrides is presented where the final atomic H temperature is inversely proportional to the mass of the molecular parent. In addition, the critical density for formation of a Bose-Einstein condensate (BEC) at a fixed temperature is reduced by a factor (mH/mMH)3/2 over directly cooled hydrogen atoms. The narrow Feshbach resonances between a S01 atom and hydrogen are well suited to a tiny center of mass energy release necessary during fragmentation. With the support of ab initio quantum chemistry, it is demonstrated that BaH is an ideal diatomic precursor that can be laser cooled to a Doppler temperature of ∼26μK with just two rovibronic transitions, the simplest molecular cooling scheme identified to date. Preparation of a hydrogen atom gas below the critical BEC temperature Tc is feasible with present cooling technology, with optical pulse control of the condensation process.

Combining Bio- and Chemo-Catalysis for the Conversion of Bio-Renewable Alcohols: Homogeneous Iridium Catalysed Hydrogen Transfer Initiated Dehydration of 1,3-Propanediol to Aldehydes

Combining whole cell biocatalysis and chemocatalysis in a single reaction sequence avoids unnecessary separations, and the associated waste and energy consumption. Bacterial fermentation has been employed to convert waste glycerol from biodiesel production into 1,3-propanediol. This 1,3-propanediol can be extracted selectively from the aqueous fermentation broth using ionic liquids. 1,3-propanediol in ionic liquid solution was converted to propanal by hydrogen transfer initiated dehydration (HTID) catalysed by a Cp*IrCl2(NHC) (Cp* = pentamethylcyclopentadienyl; NHC = carbene ligand) complex. The use of an ionic liquid solvent enabled the reaction to be performed under reduced pressure, facilitating the isolation of the product, and improving the reaction selectivity. The Ir(III) catalyst in ionic liquid was found to be highly recyclable.

The application of a novel fluidised photo reactor under UV-Visible and natural solar irradiation in the photocatalytic generation of hydrogen

With advancements in the development of visible light responsive catalysts for H2 production frequently being reported, photocatalytic water splitting has become an attractive method as a potential ‘solar fuel generator’. The development of novel photo reactors which can enhance the potential of such catalyst, however, is rarely reported. This is particularly important as many reactor configurations are mass transport limited, which in term limits the efficiency of more effective photocatalysts in larger scale applications. This paper describes the performance of a novel fluidised photo reactor for the production of H2 over two catalysts under UV-Visible light and natural solar illumination. Catalysts Pt-C3N4 and NaTaO3.La were dispersed in the reactor and the rate of H2 was determined by GC-TCD analysis of the gas headspace. The unit was an annular reactor constructed from stainless steel 316 and quartz glass with a propeller located in the base to control fluidisation of powder catalysts. Reactor properties such as propeller rotational speed were found to enhance the photo activity of the system through the elimination of mass transport limitations and increasing light penetration. The optimum conditions for H2 evolution were found to be a propeller rotational speed of 1035 rpm and 144 W of UV-Visible irradiation, which produced a rate of 89 µmol h-1 g-1 over Pt-C3N4. Solar irradiation was provided by the George Ellery Hale Solar Telescope, located at the California Institute of Technology.

Simultaneous cellulose conversion and hydrogen production assisted by cellulose decomposition under UV-light photocatalysis

Photocatalytic conversion of cellulose to sugars and carbon dioxide with simultaneous production of hydrogen assisted by cellulose decomposition under UV or solar light irradiation was achieved upon immobilization of cellulose onto a TiO2 photocatalyst. This approach enables production of hydrogen from water without using valuable sacrificial agents, and provides the possibility for recovering sugars as liquid fuels.

Time-dependent electron interference prior to ionization in the hydrogen atom and hydrogen molecular ion

We investigate electron dynamics in the hydrogen atom and the hydrogen molecular ion when exposed to long wavelength laser pulses yet having intensity insufficient to ionize the system. We find that the field is still able to drive the electron, leading to time-dependent interference effects.