Proton exchange membrane electrolysis sustained by water vapor

The current–voltage characteristics of a proton exchange membrane (PEM) electrolyzer constructed with an IrRuOx water oxidation catalyst and a Pt black water reduction catalyst, under operation with water vapor from a humidified carrier gas, have been investigated as a function of the gas flow rate, the relative humidity, and the presence of oxygen. The performance of the system with water vapor was also compared to the performance when the device was immersed in liquid water. With a humidified Ar(g) input stream at 20 °C, an electrolysis current density of 10 mA cm^(−2) was sustained at an applied voltage of ~ 1.6 V, with a current density of 20 mA cm^(−2) observed at ~ 1.7 V. In the system evaluated, at current densities >40 mA cm^(−2) the electrolysis of water vapor was limited by the mass flux of water to the PEM. At <40 mA cm^(−2), the electrolysis of water vapor supported a given current density at a lower applied bias than did the electrolysis of liquid water. The relative humidity of the input carrier gas strongly affected the current–voltage behavior, with lower electrolysis current density attributed to dehydration of the PEM at reduced humidity values. The results provide a proof-of-concept that, with sufficiently active catalysts, an efficient solar photoelectrolyzer could be operated only with water vapor as the feedstock, even at the low operating temperatures that may result in the absence of active heating. This approach therefore offers a route to avoid the light attenuation and mass transport limitations that are associated with bubble formation in these systems

Repeated epitaxial growth and transfer of arrays of patterned, vertically aligned, crystalline Si wires from a single Si(111) substrate

Multiple arrays of Si wires were sequentially grown and transferred into a flexible polymer film from a single Si(111) wafer. After growth from a patterned, oxide-coated substrate, the wires were embedded in a polymer and then mechanically separated from the substrate, preserving the array structure in the film. The wire stubs that remained were selectively etched from the Si(111) surface to regenerate the patterned substrate. Then the growth catalyst was electrodeposited into the holes in the patterned oxide. Cycling through this set of steps allowed regrowth and polymer film transfer of several wire arrays from a single Si wafer

Silicon and tungsten oxide nanostructures for water splitting

Inorganic semiconductors are promising materials for driving photoelectrochemical water-splitting reactions. However, there is not a single semiconductor material that can sustain the unassisted splitting of water into H_2 and O_2. Instead, we are developing a three part cell design where individual catalysts for water reduction and oxidation will be attached to the ends of a membrane. The job of splitting water is therefore divided into separate reduction and oxidation reactions, and each catalyst can be optimized independently for a single reaction. Silicon might be suitable to drive the water reduction. Inexpensive highly ordered Si wire arrays were grown on a single crystal wafer and transferred into a transparent, flexible polymer matrix. In this array, light would be absorbed along the longer axial dimension while the resulting electrons or holes would be collected along the much shorter radial dimension in a massively parallel array resembling carpet fibers on a microscale, hence the term "solar carpet". Tungsten oxide is a good candidate to drive the water oxidation. Self-organized porous tungsten oxide was successfully synthesized on the tungsten foil by anodization. This sponge-like structure absorbs light efficiently due to its high surface area; hence we called it "solar sponge"

Synthesis and Characterization of Silicon Nanorod Arrays for Solar Cell Applications

Silicon nanorods have been grown by chemical vapor deposition of silane, using both gold and indium as catalysts for the vapor liquid solid (VLS) process. Conditions for optimal rod morphology for each catalyst were identified by varying silane partial pressure and temperature in the range P = 0.05-1 Torr and T = 300-600 C, respectively. In most cases, catalyst particles were formed by partial de-wetting of evaporated films of the catalytic material to form droplets with diameters of tens to hundreds of nanometers. Also, periodic arrays of catalyst particles with controlled size and spacing were achieved both by the use of porous alumina membranes and also by electron-beam lithography. Using these techniques, silicon nanorods were grown with diameters of 100 nm to microns and lengths of microns to tens of microns. Four-point and gate-bias-dependent resistance measurements were made on single wires, and these indicate that rods we have grown with gold catalysts and phosphine doping have metal-like conductivity

Electrical conductivity, ionic conductivity, optical absorption, and gas separation properties of ionically conductive polymer membranes embedded with Si microwire arrays

The optical absorption, ionic conductivity, electronic conductivity, and gas separation properties have been evaluated for flexible composite films of ionically conductive polymers that contain partially embedded arrays of ordered, crystalline, p-type Si microwires. The cation exchange ionomer Nafion, and a recently developed anion exchange ionomer, poly(arylene ether sulfone) that contains quaternary ammonium groups (QAPSF), produced composite microwire array/ionomer membrane films that were suitable for operation in acidic or alkaline media, respectively. The ionic conductivity of the Si wire array/Nafion composite films in 2.0 M H_(2)SO_4(aq) was 71 mS cm^(−1), and the conductivity of the Si wire array/QAPSF composite films in 2.0 M KOH(aq) was 6.4 mS cm^(−1). Both values were comparable to the conductivities observed for films of these ionomers that did not contain embedded Si wire arrays. Two Si wire array/Nafion membranes were electrically connected in series, using a conducting polymer, to produce a trilayer, multifunctional membrane that exhibited an ionic conductivity in 2.0 M H_(2)SO)4(aq) of 57 mS cm^(−1) and an ohmic electrical contact, with an areal resistance of ~0.30 Ω cm^2, between the two physically separate embedded Si wire arrays. All of the wire array/ionomer composite membranes showed low rates of hydrogen crossover. Optical measurements indicated very low absorption (<3%) in the ion-exchange polymers but high light absorption (up to 80%) by the wire arrays even at normal incidence, attesting to the suitability of such multifunctional membranes for application in solar fuels production

Improving O_2 production of WO_3 photoanodes with IrO_2 in acidic aqueous electrolyte

WO_3 is a promising candidate for a photoanode material in an acidic electrolyte, in which it is more stable than most metal oxides, but kinetic limitations combined with the large driving force available in the WO_3 valence band for water oxidation make competing reactions such as the oxidation of the acid counterion a more favorable reaction. The incorporation of an oxygen evolving catalyst (OEC) on the WO_3 surface can improve the kinetics for water oxidation and increase the branching ratio for O_2 production. Ir-based OECs were attached to WO_3 photoanodes by a variety of methods including sintering from metal salts, sputtering, drop-casting of particles, and electrodeposition to analyze how attachment strategies can affect photoelectrochemical oxygen production at WO_3 photoanodes in 1 M H_2SO_4. High surface coverage of catalyst on the semiconductor was necessary to ensure that most minority-carrier holes contributed to water oxidation through an active catalyst site rather than a side-reaction through the WO_3/electrolyte interface. Sputtering of IrO_2 layers on WO_3 did not detrimentally affect the energy-conversion behavior of the photoanode and improved the O_2 yield at 1.2 V vs. RHE from ~0% for bare WO_3 to 50–70% for a thin, optically transparent catalyst layer to nearly 100% for thick, opaque catalyst layers. Measurements with a fast one-electron redox couple indicated ohmic behavior at the IrO_2/WO_3 junction, which provided a shunt pathway for electrocatalytic IrO_2 behavior with the WO_3 photoanode under reverse bias. Although other OECs were tested, only IrO_2 displayed extended stability under the anodic operating conditions in acid as determined by XPS

Modeling, simulation, and design criteria for photoelectrochemical water-splitting systems

A validated multi-physics numerical model that accounts for charge and species conservation, fluid flow, and electrochemical processes has been used to analyze the performance of solar-driven photoelectrochemical water-splitting systems. The modeling has provided an in-depth analysis of conceptual designs, proof-of-concepts, feasibility investigations, and quantification of performance. The modeling has led to the formulation of design guidelines at the system and component levels, and has identified quantifiable gaps that warrant further research effort at the component level. The two characteristic generic types of photoelectrochemical systems that were analyzed utilized: (i) side-by-side photoelectrodes and (ii) back-to-back photoelectrodes. In these designs, small electrode dimensions (mm to cm range) and large electrolyte heights were required to produce small overall resistive losses in the system. Additionally, thick, non-permeable separators were required to achieve acceptably low rates of product crossover

Si microwire-array solar cells

Si microwire-array solar cells with Air Mass 1.5 Global conversion efficiencies of up to 7.9% have been fabricated using an active volume of Si equivalent to a 4 μm thick Si wafer. These solar cells exhibited open-circuit voltages of 500 mV, short-circuit current densities (J_(sc)) of up to 24 mA cm^(-2), and fill factors >65% and employed Al_2O_3 dielectric particles that scattered light incident in the space between the wires, a Ag back reflector that prevented the escape of incident illumination from the back surface of the solar cell, and an a-SiN_x:H passivation/anti-reflection layer. Wire-array solar cells without some or all of these design features were also fabricated to demonstrate the importance of the light-trapping elements in achieving a high J_(sc). Scanning photocurrent microscopy images of the microwire-array solar cells revealed that the higher J_(sc) of the most advanced cell design resulted from an increased absorption of light incident in the space between the wires. Spectral response measurements further revealed that solar cells with light-trapping elements exhibited improved red and infrared response, as compared to solar cells without light-trapping elements

Silicon and tungsten oxide nanostructures for water splitting

Inorganic semiconductors are promising materials for driving photoelectrochemical water-splitting reactions. However, there is not a single semiconductor material that can sustain the unassisted splitting of water into H_2 and O_2. Instead, we are developing a three part cell design where individual catalysts for water reduction and oxidation will be attached to the ends of a membrane. The job of splitting water is therefore divided into separate reduction and oxidation reactions, and each catalyst can be optimized independently for a single reaction. Silicon might be suitable to drive the water reduction. Inexpensive highly ordered Si wire arrays were grown on a single crystal wafer and transferred into a transparent, flexible polymer matrix. In this array, light would be absorbed along the longer axial dimension while the resulting electrons or holes would be collected along the much shorter radial dimension in a massively parallel array resembling carpet fibers on a microscale, hence the term "solar carpet". Tungsten oxide is a good candidate to drive the water oxidation. Self-organized porous tungsten oxide was successfully synthesized on the tungsten foil by anodization. This sponge-like structure absorbs light efficiently due to its high surface area; hence we called it "solar sponge"

Energy-Conversion Properties of Vapor-Liquid-Solid–Grown Silicon Wire-Array Photocathodes

Silicon wire arrays, though attractive materials for use in photovoltaics and as photocathodes for hydrogen generation, have to date exhibited poor performance. Using a copper-catalyzed, vapor-liquid-solid–growth process, SiCl_4 and BCl_3 were used to grow ordered arrays of crystalline p-type silicon (p-Si) microwires on p^+-Si(111) substrates. When these wire arrays were used as photocathodes in contact with an aqueous methyl viologen^(2+/+) electrolyte, energy-conversion efficiencies of up to 3% were observed for monochromatic 808-nanometer light at fluxes comparable to solar illumination, despite an external quantum yield at short circuit of only 0.2. Internal quantum yields were at least 0.7, demonstrating that the measured photocurrents were limited by light absorption in the wire arrays, which filled only 4% of the incident optical plane in our test devices. The inherent performance of these wires thus conceptually allows the development of efficient photovoltaic and photoelectrochemical energy-conversion devices based on a radial junction platform