James R. McKone

Solar Water Splitting Cells

Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction

Nanoparticles of nickel phosphide (Ni2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni2P nanoparticles were hollow and faceted to expose a high density of the Ni2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media.

Photoelectrochemical Hydrogen Evolution Using Si Microwire Arrays

Arrays of B-doped p-Si microwires, diffusion-doped with P to form a radial n(+) emitter and subsequently coated with a 1.5-nm-thick discontinuous film of evaporated Pt, were used as photocathodes for H(2) evolution from water. These electrodes yielded thermodynamically based energy-conversion efficiencies >5% under 1 sun solar simulation, despite absorbing less than 50% of the above-band-gap incident photons. Analogous p-Si wire-array electrodes yielded efficiencies <0.2%, largely limited by the low photovoltage generated at the p-Si/H(2)O junction.

Earth-abundant hydrogen evolution electrocatalysts

Splitting water to hydrogen and oxygen is a promising approach for storing energy from intermittent renewables, such as solar power. Efficient, scalable solar-driven electrolysis devices require active electrocatalysts made from earth-abundant elements. In this mini-review, we discuss recent investigations of homogeneous and heterogeneous hydrogen evolution electrocatalysts, with emphasis on our own work on cobalt and iron complexes and nickel-molybdenum alloys.

Evaluation of Pt, Ni, and Ni–Mo electrocatalysts for hydrogen evolution on crystalline Si electrodes

The dark electrocatalytic and light photocathodic hydrogen evolution properties of Ni, Ni–Mo alloys, and Pt on Si electrodes have been measured, to assess the viability of earth-abundant electrocatalysts for integrated, semiconductor coupled fuel formation. In the dark, the activities of these catalysts deposited on degenerately doped p+-Si electrodes increased in the order Ni < Ni–Mo ≤ Pt. Ni–Mo deposited on degenerately doped Si microwires exhibited activity that was very similar to that of Pt deposited by metal evaporation on planar Si electrodes. Under 100 mW cm−2 of Air Mass 1.5 solar simulation, the energy conversion efficiencies of p-type Si/catalyst photoelectrodes ranged from 0.2–1%, and increased in the order Ni ≈ Ni–Mo < Pt, due to somewhat lower photovoltages and photocurrents for p-Si/Ni–Mo relative to p-Si/Ni and p-Si/Pt photoelectrodes. Deposition of the catalysts onto microwire arrays resulted in higher apparent catalytic activities and similar photoelectrode efficiencies than were observed on planar p-Si photocathodes, despite lower light absorption by p-Si in the microwire structures.

Hydrogen-evolution characteristics of Ni-Mo-coated, radial junction, n + p-silicon microwire array photocathodes†

The photocathodic H2-evolution performance of Ni–Mo-coated radial n+p junction Si microwire (Si MW) arrays has been evaluated on the basis of thermodynamic energy-conversion efficiency as well as solar cell figures of merit. The Ni–Mo-coated n+p-Si MW electrodes yielded open-circuit photovoltages (Voc) of 0.46 V, short-circuit photocurrent densities (Jsc) of 9.1 mA cm−2, and thermodynamically based energy-conversion efficiencies (η) of 1.9% under simulated 1 Sun illumination. Under nominally the same conditions, the efficiency of the Ni–Mo-coated system was comparable to that of Pt-coated n+p-Si MW array photocathodes (Voc = 0.44 V, Jsc = 13.2 mA cm−2, η = 2.7%). This demonstrates that, at 1 Sun light intensity on high surface area microwire arrays, earth-abundant electrocatalysts can provide performance comparable to noble-metal catalysts for photoelectrochemical hydrogen evolution. The formation of an emitter layer on the microwires yielded significant improvements in the open-circuit voltage of the microwire-array-based photocathodes relative to Si MW arrays that did not have a buried n+p junction. Analysis of the spectral response and light-intensity dependence of these devices allowed for optimization of the catalyst loading and photocurrent density. The microwire arrays were also removed from the substrate to create flexible, hydrogen-evolving membranes that have potential for use in a solar water-splitting device.

Hydrogen evolution from Pt/Ru-coated p-type WSe2 photocathodes.

Crystalline p-type WSe(2) has been grown by a chemical vapor transport method. After deposition of noble metal catalysts, p-WSe(2) photocathodes exhibited thermodynamically based photoelectrode energy-conversion efficiencies of >7% for the hydrogen evolution reaction under mildly acidic conditions, and were stable under cathodic conditions for at least 2 h in acidic as well as in alkaline electrolytes. The open circuit potentials of the photoelectrodes in contact with the H(+)/H(2) redox couple were very close to the bulk recombination/diffusion limit predicted from the Shockley diode equation. Only crystals with a prevalence of surface step edges exhibited a shift in flat-band potential as the pH was varied. Spectral response data indicated effective minority-carrier diffusion lengths of ∼1 μm, which limited the attainable photocurrent densities in the samples to ∼15 mA cm(-2) under 100 mW cm(-2) of Air Mass 1.5G illumination.

Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

An n+p-Si microwire array coupled with a two-layer catalyst film consisting of Ni–Mo nanopowder and TiO2 light-scattering nanoparticles has been used to simultaneously achieve high fill factors and light-limited photocurrent densities from photocathodes that produce H2(g) directly from sunlight and water. The TiO2 layer scattered light back into the Si microwire array, while optically obscuring the underlying Ni–Mo catalyst film. In turn, the Ni–Mo film had a mass loading sufficient to produce high catalytic activity, on a geometric area basis, for the hydrogen-evolution reaction. The best-performing microwire array devices prepared in this work exhibited short-circuit photocurrent densities of −14.3 mA cm−2, photovoltages of 420 mV, and a fill factor of 0.48 under 1 Sun of simulated solar illumination, whereas the equivalent planar Ni–Mo-coated Si device, without TiO2 scatterers, exhibited negligible photocurrent due to complete light blocking by the Ni–Mo catalyst layer.

Photoelectrochemical water splitting: silicon photocathodes for hydrogen evolution

The development of low cost, scalable, renewable energy technologies is one of todays most pressing scientific challenges. We report on progress towards the development of a photoelectrochemical water-splitting system that will use sunlight and water as the inputs to produce renewable hydrogen with oxygen as a by-product. This system is based on the design principle of incorporating two separate, photosensitive inorganic semiconductor/liquid junctions to collectively generate the 1.7-1.9 V at open circuit needed to support both the oxidation of H2O (or OH-) and the reduction of H+ (or H2O). Si microwire arrays are a promising photocathode material because the high aspect-ratio electrode architecture allows for the use of low cost, earth-abundant materials without sacrificing energy-conversion efficiency, due to the orthogonalization of light absorption and charge-carrier collection. Additionally, the high surfacearea design of the rod-based semiconductor array inherently lowers the flux of charge carriers over the rod array surface relative to the projected geometric surface of the photoelectrode, thus lowering the photocurrent density at the solid/liquid junction and thereby relaxing the demands on the activity (and cost) of any electrocatalysts. Arrays of Si microwires grown using the Vapor Liquid Solid (VLS) mechanism have been shown to have desirable electronic light absorption properties. We have demonstrated that these arrays can be coated with earth-abundant metallic catalysts and used for photoelectrochemical production of hydrogen. This development is a step towards the demonstration of a complete artificial photosynthetic system, composed of only inexpensive, earth-abundant materials, that is simultaneously efficient, durable, and scalable.

CHAPTER 3:Structured Materials for Photoelectrochemical Water Splitting

Structured materials possess several benefits and drawbacks when used in photoelectrochemical water splitting systems. The first section of this chapter introduces the relevant parameters of semiconductor/catalyst photoelectrochemical systems including light absorption, charge separation, photovoltage, mass transport, and catalytic turnover. This section further presents the interplay and tradeoffs that exist when optimizing these parameters together into a practical device that utilizes structured materials. The second section of this chapter reviews recent developments of photoelectrochemical water splitting components with control over structure at the micro and nano scales and concludes with some perspectives on future developments for the realization of functional solar water splitting systems.