Semiconductor photoelectrodes for solar hydrogen production by water photoelectrolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers. Iron oxide (α-Fe(2)O(3)) is one ...of few materials meeting these requirements, but its poor transport properties present challenges for efficient charge-carrier generation, separation, collection and injection. Here we show that these challenges can be addressed by means of resonant light trapping in ultrathin films designed as optical cavities. Interference between forward- and backward-propagating waves enhances the light absorption in quarter-wave or, in some cases, deeper subwavelength films, amplifying the intensity close to the surface wherein photogenerated minority charge carriers (holes) can reach the surface and oxidize water before recombination takes place. Combining this effect with photon retrapping schemes, such as using V-shaped cells, provides efficient light harvesting in ultrathin films of high internal quantum efficiency, overcoming the trade-off between light absorption and charge collection. A water photo-oxidation current density of 4 mA cm(-2) was achieved using a V-shaped cell comprising ~26-nm-thick Ti-doped α-Fe(2)O(3) films on back-reflector substrates coated with silver-gold alloy.
In recent years, hematite's potential as a photoanode material for solar hydrogen production has ignited a renewed interest in its physical and interfacial properties, which continues to be an active ...field of research. Research on hematite photoanodes provides new insights on the correlations between electronic structure, transport properties, excited state dynamics, and charge transfer phenomena, and expands our knowledge on solar cell materials into correlated electron systems. This research news article presents a snapshot of selected theoretical and experimental developments linking the electronic structure to the photoelectrochemical performance, with particular focus on optoelectronic properties and charge carrier dynamics.
Hematite is a promising photoanode material for photoelectrochemical water splitting. The main challenges toward achieving efficient hematite photoanodes are reviewed. Particular focus is placed on linking the electronic structure to the processes of light absorption, charge transport, and the surface electrochemical reaction. The main losses are identified and discussed, while promising avenues for future research are highlighted.
A 2‐nm thick Nb2O5 underlayer deposited by atomic layer deposition increases the charge separation efficiency and the photovoltage of ultrathin hematite films by suppressing electron back injection. ...Absorbed photon‐to‐current efficiencies (APCE) as high as 40%, which are one of the highest ever reported with hematite photoanodes, are obtained at 400 nm at +1.43 V vs. RHE.
This work presents a new route to suppress grain growth and tune the sensitivity and selectivity of nanocrystalline SnO2 fibers. Unloaded and Pd‐loaded SnO2 nanofiber mats are synthesized by ...electrospinning followed by hot‐pressing at 80 °C and calcination at 450 or 600 °C. The chemical composition and microstructure evolution as a function of Pd‐loading and calcination temperature are examined using EDS, XPS, XRD, SEM, and HRTEM. Highly porous fibrillar morphology with nanocrystalline fibers comprising SnO2 crystallites decorated with tiny PdO crystallites is observed. The grain size of the SnO2 crystallites in the layers that are calcined at 600 °C decreases with increasing Pd concentration from about 15 nm in the unloaded specimen to about 7 nm in the 40 mol% Pd‐loaded specimen, indicating that Pd‐loading could effectively suppress the SnO2 grain growth during the calcination step. The Pd‐loaded SnO2 sensors have 4 orders of magnitude higher resistivity and exhibit significantly enhanced sensitivity to H2 and lower sensitivity to NO2 compared to their unloaded counterparts. These observations are attributed to enhanced electron depletion at the surface of the PdO‐decorated SnO2 crystallites and catalytic effect of PdO in promoting the oxidation of H2 into H2O. These phenomena appear to have a much larger effect on the sensitivity of the Pd‐loaded sensors than the reduction in grain size.
Nanocrystalline SnO2 fibers are fabricated by electrospinning using Pd as a grain growth inhibitor and a catalyst for enhancing oxidation reactions. Pd‐loaded or unloaded (pristine) SnO2 fibers can be used as gas sensors capable of detecting trace concentrations as low as several parts per billion (ppb) of H2 and NO2, respectively.
Oxygenic photosynthetic organisms perform solar energy conversion of water and CO
to O
and sugar at a broad range of wavelengths and light intensities. These cells also metabolize sugars using a ...respiratory system that functionally overlaps the photosynthetic apparatus. In this study, we describe the harvesting of photocurrent used for hydrogen production from live cyanobacteria. A non-harmful gentle physical treatment of the cyanobacterial cells enables light-driven electron transfer by an endogenous mediator to a graphite electrode in a bio-photoelectrochemical cell, without the addition of sacrificial electron donors or acceptors. We show that the photocurrent is derived from photosystem I and that the electrons originate from carbohydrates digested by the respiratory system. Finally, the current is utilized for hydrogen evolution on the cathode at a bias of 0.65 V. Taken together, we present a bio-photoelectrochemical system where live cyanobacteria produce stable photocurrent that can generate hydrogen.
The compensated magnetic order and characteristic terahertz frequencies of antiferromagnetic materials make them promising candidates to develop a new class of robust, ultrafast spintronic devices. ...The manipulation of antiferromagnetic spin-waves in thin films is anticipated to lead to new exotic phenomena such as spin-superfluidity, requiring an efficient propagation of spin-waves in thin films. However, the reported decay length in thin films has so far been limited to a few nanometers. In this work, we achieve efficient spin-wave propagation over micrometer distances in thin films of the insulating antiferromagnet hematite with large magnetic domains while evidencing much shorter attenuation lengths in multidomain thin films. Through transport and magnetic imaging, we determine the role of the magnetic domain structure and spin-wave scattering at domain walls to govern the transport. We manipulate the spin transport by tailoring the domain configuration through field cycle training. For the appropriate crystalline orientation, zero-field spin transport is achieved across micrometers, as required for device integration.
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