Organic light-emitting diode microcavities from transparent conducting metal oxide photonic crystals.

We report herein on the integration of novel transparent and conducting one-dimensional photonic crystals that consist of periodically alternating layers of spin-coated antimony-doped tin oxide nanoparticles and sputtered tin-doped indium oxide into organic light emitting diode (OLED) microcavities. The large refractive index contrast between the layers due the porosity of the nanoparticle layer led to facile fabrication of dielectric mirrors with intense and broadband reflectivity from structures consisting of only five bilayers. Because our photonic crystals are easily amenable to large scale OLED fabrication and simultaneously selectively reflective as well as electronically conductive, such materials are ideally suited for integration into OLED microcavities. In such a device, the photonic crystal, which represents a direct drop-in replacement for typical ITO anodes, is capable of serving two necessary functions: (i) as one partially reflecting mirror of the optical microcavity; and (ii) as the anode of the diode.

Cross-linking Bi2S3 ultrathin nanowires: a platform for nanostructure formation and biomolecule detection.

This paper describes the use of chemical cross-linking of ultrathin inorganic nanowires as a bottom-up strategy for nanostructure fabrication as well as a chemical detection platform. Nanowire microfibers are produced by spinning a nanowire dispersion into a cross-linker solution at room temperature. Nanomembranes with thicknesses down to 50 nm were obtained by injecting the nanowire dispersion at the cross-linker-solution/air interface. Furthermore, the sensitivity of the nanowire to amine cross-linkers allowed development of a novel sensing platform for small molecules, like the neurotransmitter serotonin, with detection limits in the picomolar regime.

Photothermal Catalyst Engineering: Hydrogenation of Gaseous CO2 with High Activity and Tailored Selectivity.

This study has designed and implemented a library of hetero-nanostructured catalysts, denoted as Pd@Nb2O5, comprised of size-controlled Pd nanocrystals interfaced with Nb2O5 nanorods. This study also demonstrates that the catalytic activity and selectivity of CO2 reduction to CO and CH4 products can be systematically tailored by varying the size of the Pd nanocrystals supported on the Nb2O5 nanorods. Using large Pd nanocrystals, this study achieves CO and CH4 production rates as high as 0.75 and 0.11 mol h-1 gPd-1, respectively. By contrast, using small Pd nanocrystals, a CO production rate surpassing 18.8 mol h-1 gPd-1 is observed with 99.5% CO selectivity. These performance metrics establish a new milestone in the champion league of catalytic nanomaterials that can enable solar-powered gas-phase heterogeneous CO2 reduction. The remarkable control over the catalytic performance of Pd@Nb2O5 is demonstrated to stem from a combination of photothermal, electronic and size effects, which is rationally tunable through nanochemistry.

Nanostructured Indium Oxide Coated Silicon Nanowire Arrays: A Hybrid Photothermal/Photochemical Approach to Solar Fuels.

The field of solar fuels seeks to harness abundant solar energy by driving useful molecular transformations. Of particular interest is the photodriven conversion of greenhouse gas CO2 into carbon-based fuels and chemical feedstocks, with the ultimate goal of providing a sustainable alternative to traditional fossil fuels. Nonstoichiometric, hydroxylated indium oxide nanoparticles, denoted In2O3-x(OH)y, have been shown to function as active photocatalysts for CO2 reduction to CO via the reverse water gas shift reaction under simulated solar irradiation. However, the relatively wide band gap (2.9 eV) of indium oxide restricts the portion of the solar irradiance that can be utilized to ∼9%, and the elevated reaction temperatures required (150-190 °C) reduce the overall energy efficiency of the process. Herein we report a hybrid catalyst consisting of a vertically aligned silicon nanowire (SiNW) support evenly coated by In2O3-x(OH)y nanoparticles that utilizes the vast majority of the solar irradiance to simultaneously produce both the photogenerated charge carriers and heat required to reduce CO2 to CO at a rate of 22.0 µmol·gcat(-1)·h(-1). Further, improved light harvesting efficiency of the In2O3-x(OH)y/SiNW films due to minimized reflection losses and enhanced light trapping within the SiNW support results in a ∼6-fold increase in photocatalytic conversion rates over identical In2O3-x(OH)y films prepared on roughened glass substrates. The ability of this In2O3-x(OH)y/SiNW hybrid catalyst to perform the dual function of utilizing both light and heat energy provided by the broad-band solar irradiance to drive CO2 reduction reactions represents a general advance that is applicable to a wide range of catalysts in the field of solar fuels.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Spatial Separation of Charge Carriers in In2O3-x(OH)y Nanocrystal Superstructures for Enhanced Gas-Phase Photocatalytic Activity.

The development of strategies for increasing the lifetime of photoexcited charge carriers in nanostructured metal oxide semiconductors is important for enhancing their photocatalytic activity. Intensive efforts have been made in tailoring the properties of the nanostructured photocatalysts through different ways, mainly including band-structure engineering, doping, catalyst-support interaction, and loading cocatalysts. In liquid-phase photocatalytic dye degradation and water splitting, it was recently found that nanocrystal superstructure based semiconductors exhibited improved spatial separation of photoexcited charge carriers and enhanced photocatalytic performance. Nevertheless, it remains unknown whether this strategy is applicable in gas-phase photocatalysis. Using porous indium oxide nanorods in catalyzing the reverse water-gas shift reaction as a model system, we demonstrate here that assembling semiconductor nanocrystals into superstructures can also promote gas-phase photocatalytic processes. Transient absorption studies prove that the improved activity is a result of prolonged photoexcited charge carrier lifetimes due to the charge transfer within the nanocrystal network comprising the nanorods. Our study reveals that the spatial charge separation within the nanocrystal networks could also benefit gas-phase photocatalysis and sheds light on the design principles of efficient nanocrystal superstructure based photocatalysts.

Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals.

Silicon constitutes 28% of the earth's mass. Its high abundance, lack of toxicity and low cost coupled with its electrical and optical properties, make silicon unique among the semiconductors for converting sunlight into electricity. In the quest for semiconductors that can make chemicals and fuels from sunlight and carbon dioxide, unfortunately the best performers are invariably made from rare and expensive elements. Here we report the observation that hydride-terminated silicon nanocrystals with average diameter 3.5 nm, denoted ncSi:H, can function as a single component heterogeneous reducing agent for converting gaseous carbon dioxide selectively to carbon monoxide, at a rate of hundreds of µmol h(-1) g(-1). The large surface area, broadband visible to near infrared light harvesting and reducing power of SiH surface sites of ncSi:H, together play key roles in this conversion. Making use of the reducing power of nanostructured hydrides towards gaseous carbon dioxide is a conceptually distinct and commercially interesting strategy for making fuels directly from sunlight.

Photomethanation of Gaseous CO2 over Ru/Silicon Nanowire Catalysts with Visible and Near-Infrared Photons.

Gaseous CO2 is transformed photochemically and thermochemically in the presence of H2 to CH4 at millimole per hour per gram of catalyst conversion rates, using visible and near-infrared photons. The catalyst used to drive this reaction comprises black silicon nanowire supported ruthenium. These results represent a step towards engineering broadband solar fuels tandem photothermal reactors that enable a three-step process involving i) CO2 capture, ii) gaseous water splitting into H2, and iii) reduction of gaseous CO2 by H2.

The Rational Design of a Single-Component Photocatalyst for Gas-Phase CO2 Reduction Using Both UV and Visible Light.

The solar-to-chemical energy conversion of greenhouse gas CO2 into carbon-based fuels is a very important research challenge, with implications for both climate change and energy security. Herein, the key attributes of hydroxides and oxygen vacancies are experimentally identified in non-stoichiometric indium oxide nanoparticles, In2O3-x(OH)y, that function in concert to reduce CO2 to CO under simulated solar irradiation.

See-through dye-sensitized solar cells: photonic reflectors for tandem and building integrated photovoltaics.

See-through dye-sensitized solar cells with 1D photonic crystal Bragg reflector photoanodes show an increase in peak external quantum efficiency of 47% while still maintaining high fill factors, resulting in an almost 40% increase in power conversion efficiency. These photoanodes are ideally suited for tandem and building integrated photovoltaics.