Thomas Pedersen

Bioinspired molecular co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

The production of fuels from sunlight represents one of the main challenges in the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and although platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth-abundant alternatives are needed for large-scale use. We show that bioinspired molecular clusters based on molybdenum and sulphur evolve hydrogen at rates comparable to that of platinum. The incomplete cubane-like clusters (Mo(3)S(4)) efficiently catalyse the evolution of hydrogen when coupled to a p-type Si semiconductor that harvests red photons in the solar spectrum. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by density functional theory calculations of the Mo(3)S(4) clusters adsorbed on the hydrogen-terminated Si(100) surface, providing insights into the nature of the active site.

Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n+p-Silicon Photocathode†

A low-cost substitute: A titanium protection layer on silicon made it possible to use silicon under highly oxidizing conditions without oxidation of the silicon. Molybdenum sulfide was electrodeposited on the Ti-protected n(+)p-silicon electrode. This electrode was applied as a photocathode for water splitting and showed a greatly enhanced efficiency.

MoS2—an integrated protective and active layer on n+p-Si for solar H2 evolution

A new MoS2 protected n(+)p-junction Si photocathode for the renewable H2 evolution is presented here. MoS2 acts as both a protective and an electrocatalytic layer, allowing H2 evolution at 0 V vs. RHE for more than 5 days. Using a MoSx surface layer decreases the overpotential for H2 evolution by 200 mV.

Integrating a dual-silicon photoelectrochemical cell into a redox flow battery for unassisted photocharging

Solar rechargeable flow cells (SRFCs) provide an attractive approach for in situ capture and storage of intermittent solar energy via photoelectrochemical regeneration of discharged redox species for electricity generation. However, overall SFRC performance is restricted by inefficient photoelectrochemical reactions. Here we report an efficient SRFC based on a dual-silicon photoelectrochemical cell and a quinone/bromine redox flow battery for in situ solar energy conversion and storage. Using narrow bandgap silicon for efficient photon collection and fast redox couples for rapid interface charge injection, our device shows an optimal solar-to-chemical conversion efficiency of ∼5.9% and an overall photon–chemical–electricity energy conversion efficiency of ∼3.2%, which, to our knowledge, outperforms previously reported SRFCs. The proposed SRFC can be self-photocharged to 0.8 V and delivers a discharge capacity of 730 mAh l−1. Our work may guide future designs for highly efficient solar rechargeable devices.

Back-illuminated Si photocathode: a combined experimental and theoretical study for photocatalytic hydrogen evolution

Si is an excellent absorber material for use in 2-photon photoelectrochemical hydrogen production. So far nearly all studies of silicon photoelectrodes have employed frontal illumination despite the fact that in most water-splitting 2-photon device concepts the silicon is the “bottom” cell in the tandem stack and therefore illuminated from the back with respect to the electrolyte. In the present work, we investigate back-illuminated Si photoelectrodes experimentally, as well as by modelling, the dependence of induced photocurrent on various parameters, such as carrier diffusion length (Le) and surface recombination velocity (vs) to quantify their relative importance. A bifacial light absorbing structure (p+pn+ Si) is tested under back-illumination conditions which mimic the actual working environment in a tandem water splitting device. The thickness of the absorbing Si layer is varied from 30 to 350 μm to assess the impact of the diffusion length/thickness ratio (Le/L) on photocatalytic performance. It is shown how the induced photocurrent (JL) of a back-illuminated sample increases as wafer thickness decreases. Compared to the 350 μm thick sample, a thinned 50 μm thick sample shows a 2.7-fold increase in JL, and consequently also a higher open circuit voltage. An analytical model is developed to quantify how the relative Le/L-ratio affects the maximum JL under back-illumination, and the result agrees well with experimental results. JL increases with the Le/L-ratio only up to a certain point, beyond which the surface recombination velocity becomes the dominant loss mechanism. This implies that further efforts should to be focused on reduction of surface recombination. The present study is the first experimental demonstration of a Si wafer based photocathode under back-illumination. Moreover, the comparative experimental and theoretical treatment also highlights which photoabsorber properties merit the most attention in the further development towards full tandem water splitting devices.

Gas phase photocatalytic water splitting with Rh2−yCryO3/GaN:ZnO in μ-reactors

Rh2−yCryO3/GaN:ZnO has been tested for gas phase overall photocatalytic water splitting by dosing water vapor. The sample has been deposited in a μ-reactor and evolves hydrogen and oxygen under illumination of solar light. This experiment proves the possibility to study solar active materials and the mechanism of the water splitting reaction with gas phase experiments. The high impact of the relative humidity on the activity has been shown by changing the water partial pressure and the reactor temperature.

Silicon protected with atomic layer deposited TiO2: conducting versus tunnelling through TiO2

The present work demonstrates that tuning the donor density of protective TiO2 layers on a photocathode has dramatic consequences for electronic conduction through TiO2 with implications for the stabilization of oxidation-sensitive catalysts on the surface. Vacuum annealing at 400 °C for 1 hour of atomic layer deposited TiO2 increased the donor density from an as-deposited value of 1.3 × 1019 cm−3 to 2.2 × 1020 cm−3 following the annealing step. Using an Fe(II)/Fe(III) redox couple it was shown that the lower dopant density only allows electron transfer through TiO2 under conditions of weak band bending. However it was shown that increasing the dopant density to 2.2 × 1020 cm−3 allows tunneling through the surface region of TiO2 to occur at significant band bending. An important implication of this result is that the less doped material is unsuitable for electron transfer across the TiO2/electrolyte interface if the potential is significantly more anodic than the TiO2 conduction band due to moderate to large band bending. This means that the lesser doped TiO2 can be used to prevent the inadvertent oxidation of sensitive species on the surface (e.g. H2 evolution catalysts) as long as the redox potential of the material is significantly more anodic than the TiO2 conduction band. Conversely, for situations where an oxidative process on the surface is desired, highly doped TiO2 may be used to enable current flow via tunneling.

Ebolavirus comparative genomics

The 2014 Ebola outbreak in West Africa is the largest documented for this virus. To examine the dynamics of this genome, we compare more than 100 currently available ebolavirus genomes to each other and to other viral genomes. Based on oligomer frequency analysis, the family Filoviridae forms a distinct group from all other sequenced viral genomes. All filovirus genomes sequenced to date encode proteins with similar functions and gene order, although there is considerable divergence in sequences between the three genera Ebolavirus, Cuevavirus and Marburgvirus within the family Filoviridae. Whereas all ebolavirus genomes are quite similar (multiple sequences of the same strain are often identical), variation is most common in the intergenic regions and within specific areas of the genes encoding the glycoprotein (GP), nucleoprotein (NP) and polymerase (L). We predict regions that could contain epitope-binding sites, which might be good vaccine targets. This information, combined with glycosylation sites and experimentally determined epitopes, can identify the most promising regions for the development of therapeutic strategies. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

Selective production of hydrogen peroxide and oxidation of hydrogen sulfide in an unbiased solar photoelectrochemical cell

A solar-to-chemical conversion process is demonstrated using a photoelectrochemical cell without external bias for selective oxidation of hydrogen sulfide (H2S) to produce hydrogen peroxide (H2O2) and sulfur (S). The process integrates two redox couples anthraquinone/anthrahydroquinone and I−/I3−, and conceptually illustrates the remediation of a waste product for producing valuable chemicals.

Photoelectrocatalysis and electrocatalysis on silicon electrodes decorated with cubane-like clusters

The influence of the cluster-core unit in cluster-decorated p-Si on photo-electrochemical (PEC) hydrogen evolution has been investigated using a homologous series of cubane-like heterobimetallic sulfide compounds. These compounds stem from the generic cluster structure A3S4 or A3B?startSend?4 (A = W, Mo; B = Co, Cu). We find that the Mo-based (A = Mo) cluster-decorated Si photoelectrodes show higher PEC performance than otherwise equivalent W-based (A = W) cluster-decorated ones. This is consistent with higher electrocatalytic activity of the Mo-based clusters supported on n-Si when measured in the dark. The result of stability tests is that photoelectrodes decorated with clusters without Co (B ≠ Co) can exhibit promising stability, whereas clusters of the structure A3CoS4  (A = W, Mo) yield photoelectrodes that are highly unstable upon illumination. X-ray photoelectron spectroscopy (XPS) results suggest that both oxidation and material loss play a role in deactivation of the A3CoS4 materials. Additionally, we observe that the photocurrent depends linearly on the light intensity in the limiting current region, and the corresponding incident photon to current efficiency (IPCE) may reach approximately 80%. Density functional theory (DFT) calculations of the clusters adsorbed on the hydrogen-terminated Si surface are used to estimate and compare cluster adsorption energies on the surface as well as the H-binding energies, which is a descriptor for electrocatalytic activity.