Interfacial band-edge energetics for solar fuels production

Photoelectrochemical (PEC) water splitting has received growing attention as a potential pathway to replace fossil fuels and produce a clean, renewable, and sustainable source of fuel. To achieve overall water splitting and the associated production of solar fuels, complex devices are needed to efficiently capture light from the sun, separate photogenerated charges, and catalyze reduction and oxidation reactions. To date, the highest performing solar fuels devices rely on multi-component systems, which introduce interfaces that can be associated with further performance loss due to thermodynamic and kinetic considerations. In this review, we identify several of the most important interfaces used in PEC water splitting, summarize methods to characterize them, and highlight approaches to mitigating associated loss mechanisms.The authors thank Dr Eric Miller for the inspiration to compile this review, and the members of the U.S. Department of Energy’s Photoelectrochemical Working Group and Task 35 (Renewable Hydrogen) of the International E nergy Agency’s Hydrogen Imple- menting Agreement for helpful comments, suggestions, and dis- cussions, specifically Prof. Shane Ardo, Dr John Turner, Prof. Dunwei Wang, and Prof. Shannon Boettcher. WAS greatly acknowl- edges funding support from the FOM/NWO/Shell Program on CO 2 - neutral Fuels (Project – APPEL). IDS was supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. NCS acknowledges start-up funds from Lehigh University. JB thanks financial support from GeneralitatValenciana (ISIC/ 2012/008). A summary version of this review paper (DOI: 10.2172/1209498), and associated summary tables that will be updated as the field progresses, will be available on the working group website (http://energy.gov/eere/fuelcells/ photoelectrochemical-working-group)

Experimental demonstrations of spontaneous, solar-driven photoelectrochemical water splitting

Laboratory demonstrations of spontaneous photoelectrochemical (PEC) solar water splitting cells are reviewed. Reported solar-to-hydrogen (STH) conversion efficiencies range from 10% STH efficiency using potentially less costly materials have been reported. Device stability is a major challenge for the field, as evidenced by lifetimes of less than 24 hours in all but a few reports. No globally accepted protocol for evaluating and certifying STH efficiencies and lifetimes exists. It is our recommendation that a protocol similar to that used by the photovoltaic community be adopted so that future demonstrations of solar PEC water splitting can be compared on equal grounds

High-Transconductance Graphene Solution-Gated Field Effect Transistors

In this work, we report on the electronic properties of solution-gated field effect transistors (SGFETs) fabricated using large-area graphene. Devices prepared both with epitaxially grown graphene on SiC as well as with chemical vapor deposition grown graphene on Cu exhibit high transconductances, which are a consequence of the high mobility of charge carriers in graphene and the large capacitance at the graphene/water interface. The performance of graphene SGFETs, in terms of gate sensitivity, is compared to other SGFET technologies and found to be clearly superior, confirming the potential of graphene SGFETs for sensing applications in electrolytic environments.Comment: The following article has been submitted to Applied Physics Letters. After it is published, it will be found at apl.aip.or

Nanostructured amorphous gallium phosphide on silica for nonlinear and ultrafast nanophotonics

Nanophotonics based on high refractive index dielectrics relies on appreciable contrast between the indices of designed nanostructures and their immediate surrounding, which can be achieved by the growth of thin films on low-index substrates. Here we propose the use of high index amorphous gallium phosphide (a-GaP), fabricated by radio-frequency sputter deposition, on top of a low refractive index glass substrate and thoroughly examine its nanophotonic properties. Spectral ellipsometry of the amorphous material demonstrates the optical properties to be considerably close to crystalline gallium phosphide (c-GaP), with low-loss transparency for wavelengths longer than 650 nm. When nanostructured into nanopatches, the second harmonic (SH) response of an individual a-GaP patch is characterized to be more than two orders of magnitude larger than the as-deposited unstructured film, with an anapole-like resonant behavior. Numerical simulations are in good agreement with the experimental results over a large spectral and geometrical range. Furthermore, by studying individual a-GaP nanopatches through non-degenerate pump-probe spectroscopy with sub-10 fs pulses, we find a more than 5% ultrafast modulation of the reflectivity that is accompanied by a slower decaying free carrier contribution, caused by absorption. Our investigations reveal a potential for a-GaP as an adequate inexpensive and CMOS-compatible material for nonlinear nanophotonic applications as well as for photocatalysis.Fil: Tilmann, Benjamin. Ludwig Maximilians Universitat; AlemaniaFil: Grinblat, Gustavo Sergio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; ArgentinaFil: Berté, Rodrigo. Ludwig Maximilians Universitat; AlemaniaFil: Özcan, Mehmet. Ludwig Maximilians Universitat; AlemaniaFil: Kunzelmann, Viktoria F.. Technische Universitat München; AlemaniaFil: Nickel, Bert. Ludwig Maximilians Universitat; AlemaniaFil: Sharp, Ian D.. Ludwig Maximilians Universitat; AlemaniaFil: Cortés, Emiliano. Ludwig Maximilians Universitat; AlemaniaFil: Maier, Stefan A.. Ludwig Maximilians Universitat; AlemaniaFil: Li, Yi. Southern University Of Science And Technology; Chin

Assembly and photocarrier dynamics of heterostructured nanocomposite photoanodes from multicomponent colloidal nanocrystals

Multicomponent oxides and their heterostructures are rapidly emerging as promising light absorbers to drive oxidative chem. To fully exploit their functionality, precise tuning of their compn. and structure is crucial. Here, we report a novel soln.-based route to nanostructured bismuth vanadate (BiVO4) that facilitates the assembly of BiVO4/metal oxide (TiO2, WO3, and Al2O3) nanocomposites in which the morphol. of the metal oxide building blocks is finely tailored. The combination of transient absorption spectroscopy-spanning from picoseconds to second time scales-and photoelectrochem. measurements reveals that the achieved structural tunability is key to understanding and directing charge sepn., transport, and efficiency in these complex oxide heterostructured films

Discovery of Fe–Ce Oxide/BiVO_4 Photoanodes through Combinatorial Exploration of Ni–Fe–Co–Ce Oxide Coatings

An efficient photoanode is a prerequisite for a viable solar fuels technology. The challenges to realizing an efficient photoanode include the integration of a semiconductor light absorber and a metal oxide electrocatalyst to optimize corrosion protection, light trapping, hole transport, and photocarrier recombination sites. To efficiently explore metal oxide coatings, we employ a high-throughput methodology wherein a uniform BiVO_4 film is coated with 858 unique metal oxide coatings covering a range of metal oxide loadings and the full (Ni–Fe–Co–Ce)O_x pseudoquaternary composition space. Photoelectrochemical characterization of the photoanodes reveals that specific combinations of metal oxide composition and loading provide up to a 13-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Through mining of the high-throughput data we identify composition regions that form improved interfaces with BiVO_4. Of particular note, integrated photoanodes with catalyst compositions in the range Fe_((0.4–0.6))Ce_((0.6–0.4))O_x exhibit high interface quality and excellent photoelectrochemical power conversion. Scaled-up inkjet-printed electrodes and photoanodic electrodeposition of this composition on BiVO_4 confirms the discovery and the synthesis-independent interface improvement of (Fe–Ce)O_x coatings on BiVO_4

Two new Wolf-Rayet stars in the LMC

We report the discovery of two previously unknown WN3 stars in the Large Magellanic Cloud. Both are bright (15th magnitude), isolated, and located in regions covered in earlier surveys, although both are relatively weak-lined. We suggest that there may be $\mathcal{O}(10)$ remaining undiscovered WNE stars in the LMC

Developing an award program for children's settings to support healthy eating and physical activity and reduce the risk of overweight and obesity

<p>Abstract</p> <p>Background</p> <p>This paper aimed to identify the best way to engage, motivate and support early childhood services (ECS) and primary schools (PS) to create policy and practise changes to promote healthy eating and physical activity. This information would be used to develop a suitable program to implement within these children's settings to reduce the risk of childhood overweight and obesity.</p> <p>Methods</p> <p>The Medical Research Council's (UK) framework for the design and evaluation of complex interventions was used to guide the development of the healthy eating and physical activity program suitable for ECS and PS. Within this framework a range of evaluation methods, including stakeholder planning, in-depth interviews with ECS and PS staff and acceptability and feasibility trials in one local government area, were used to ascertain the best way to engage and support positive changes in these children's settings.</p> <p>Results</p> <p>Both ECS and PS identified that they had a role to play to improve children's healthy eating and physical activity. ECS identified their role in promoting healthy eating and physical activity as important for children's health, and instilling healthy habits for life. PS felt that these were health issues, rather than educational issues; however, schools saw the link between healthy eating and physical activity and student learning outcomes. These settings identified that a program that provides a simple guide that recognises good practise in these settings, such as an award scheme using a health promoting schools approach, as a feasible and acceptable way for them to support children's healthy eating and physical activity.</p> <p>Conclusion</p> <p>Through the process of design and evaluation a program - <it>Kids - 'Go for your life'</it>, was developed to promote and support children's healthy eating and physical activity and reduce the risk of childhood overweight and obesity. <it>Kids - 'Go for your life' </it>used an award program, based on a health promoting schools approach, which was demonstrated to be a suitable model to engage ECS and PS and was acceptable and feasible to create policy and practise changes to support healthy eating and physical activity for children.</p