Gold-Sensitized Silicon/ZnO Core/Shell Nanowire Array for Solar Water Splitting.
ABSTRACT: Solar water splitting represents one of the most promising strategies in the quest for clean and renewable energy. However, low conversion efficiency, use of sacrificial agents, and external bias for current water splitting system limit its practical application. Here, a gold-sensitized Si/ZnOcore/shell nanowire photoelectrochemical (PEC) cell is reported for efficient solar water oxidation. We demonstrated gold-sensitized n-Si/n-ZnO nanowire arrays exhibited higher energy conversion efficiency than gold-sensitized p-Si/n-ZnO nanowire arrays due to the favorable energy-band alignment characteristics. Without any assistance from an external electrical source and sacrificial reagents, gold-sensitized n-Si/n-ZnO core/shell nanowire array photoanode achieved unbiased water splitting under simulated solar light illumination. This method opens a promising venue to cost-efficient production of solar fuels.
Project description:Hydrogen production from water splitting using solar energy based on photoelectrochemical (PEC) cells has attracted increasing attention because it leaves less of a carbon footprint and has economic superiority of solar and hydrogen energy. Oxide semiconductors such as ZnO possessing high stability against photocorrosion in hole scavenger systems have been widely used to build photoanodes of PEC cells but under visible light their conversion efficiencies with respect to incident-photon-to-current conversion efficiency (IPCE) measured without external bias are still not satisfied. An innovative way is presented here to significantly improve the conversion efficiency of PEC cells by constructing a core-shell structure-based photoanode comprising Au@CdS core-shell nanoparticles on ZnO nanowires (Au@CdS-ZnO). The Au core offers strong electronic interactions with both CdS and ZnO resulting in a unique nanojunction to facilitate charge transfer. The Au@CdS-ZnO PEC cell under 400 nm light irradiation without any applied bias provides an IPCE of 14.8%. Under AM1.5 light illumination with a bias of 0.4 V, the Au@CdS-ZnO PEC cell produces H2 at a constant rate of 11.5 ?mol h-1 as long as 10 h. This work provides a fundamental insight to improve the conversion efficiency for visible light in water splitting.
Project description:Artificial photosynthesis and the production of solar fuels could be a key element in a future renewable energy economy providing a solution to the energy storage problem in solar energy conversion. We describe a hybrid strategy for solar water splitting based on a dye sensitized photoelectrosynthesis cell. It uses a derivatized, core-shell nanostructured photoanode with the core a high surface area conductive metal oxide film--indium tin oxide or antimony tin oxide--coated with a thin outer shell of TiO2 formed by atomic layer deposition. A "chromophore-catalyst assembly" 1, [(PO3H2)2bpy)2Ru(4-Mebpy-4-bimpy)Rub(tpy)(OH2)](4+), which combines both light absorber and water oxidation catalyst in a single molecule, was attached to the TiO2 shell. Visible photolysis of the resulting core-shell assembly structure with a Pt cathode resulted in water splitting into hydrogen and oxygen with an absorbed photon conversion efficiency of 4.4% at peak photocurrent.
Project description:Development of renewable fuels from solar light appears as one of the main current challenges in energy science. A plethora of photocatalysts have been investigated to obtain hydrogen and oxygen from water and solar light in the last decades. However, the photon-to-hydrogen molecule conversion is still far from allowing real implementation of solar fuels. Here we show that 111 facet-oriented gold nanoplatelets on multilayer graphene films deposited on quartz is a highly active photocatalyst for simulated sunlight overall water splitting into hydrogen and oxygen in the absence of sacrificial electron donors, achieving hydrogen production rate of 1.2?molH2 per gcomposite per h. This photocatalytic activity arises from the gold preferential orientation and the strong gold-graphene interaction occurring in the composite system.
Project description:Branched nanostructures of semiconductors based on one-dimensional heterostructures have many promising applications in optoelectronics, supercapacitors, photocatalysts, etc. Here, we report a novel branched core/shell CdO/ZnO hetero-nanostructure that resembles a Crimson bottlebrush (<i>Callistemon Citrinus</i>) but with intriguing hexagonal symmetry. The nanomaterials were fabricated via an improved one-step chemical vapor deposition method and consist of a CdO wire as the core and ZnO as the shell. With cadmium acting as a catalyst, ZnO nanowires grow as perpendicular branches from the CdO/ZnO one-dimensional core/shell structure. The nanostructures were characterized with X-ray diffraction scanning and transmission electron microscopy. A homogeneous epitaxial growth mechanism has been postulated for the formation of the nanostructure. The materials show a broad and strong absorption ranging from visible to ultraviolet and a better photoelectrocatalytic properties in comparison to pure ZnO or CdO. Our synthetic strategy may open up a new way for controlled preparation of one-dimensional nanomaterials with core/shell heterostructure, which could find potential applications in solar cells and opto-electrochemical water-splitting devices.
Project description:ZnO has long been considered as a model UV-driven photoanode for photoelectrochemical water splitting, but its performance has been limited by fast charge-carrier recombination, extremely poor stability in aqueous solution, and slow kinetics of water oxidation. These issues were addressed by applying a strategy of optimization and passivation of hydrothermally grown 1D ZnO nanowire arrays. The length and diameter of bare ZnO nanowires were optimized by varying the growth time and precursor concentration to achieve optimal photoelectrochemical performance. The addition of earth-abundant cobalt phosphate (Co-Pi) and nickel borate (Ni-B) oxygen evolution catalysts onto ZnO nanowires resulted in substantial cathodic shifts in onset potential to as low as about 0.3?V versus the reversible hydrogen electrode (RHE) for Ni-B/ZnO, for which a maximum photocurrent density of 1.1?mA?cm(-2) at 0.9?V (vs. RHE) with applied bias photon-to-current efficiency of 0.4?% and an unprecedented near-unity incident photon-to-current efficiency at 370?nm. In addition the potential required for saturated photocurrent was dramatically reduced from 1.6 to 0.9?V versus RHE. Furthermore, the stability of these ZnO nanowires was significantly enhanced by using Ni-B compared to Co-Pi due to its superior chemical robustness, and it thus has additional functionality as a stable protecting layer on the ZnO surface. These remarkable enhancements in both photocatalytic activity and stability directly address the current severe limitations in the use of ZnO-based photoelectrodes for water-splitting applications, and can be applied to other photoanodes for efficient solar-driven fuel synthesis.
Project description:Silver nanowires in conjunction with sputter-coated Al-doped ZnO (AZO) thin films were used as a composite transparent top electrode for hybrid radial-junction ZnO nanowire/a-Si:H p-i-n thin-film solar cells. Solar cells with the composite nanowire top contacts attained a short-circuit current density (Jsc) of 13.9 mA/cm2 and a fill factor (FF) of 62% on glass substrates while a Jsc of 13.0 mA/cm2 and FF of 62% was achieved on plastic substrates. The power conversion efficiency (PCE) of the 3-dimensional solar cells improved by up to 60% compared to using AZO electrodes alone due to enhanced coverage of the top electrode over the 3-D structures, decreasing the series resistance of the device by 5×. The composite layer also showed a 10× reduction in sheet resistance compared to the AZO thin-film contact under applied mechanical strain.
Project description:Dye-sensitized solar cells with an energy storage function are demonstrated by modifying its counter electrode with a poly (vinylidene fluoride)/ZnO nanowire array composite. This simplex device could still function as an ordinary solar cell with a steady photocurrent output even after being fully charged. An energy storage density of 2.14 C g(-1) is achieved, while simultaneously a 3.70% photo-to-electric conversion efficiency is maintained.
Project description:The piezo-phototronic effect is about the enhanced separation, transport, and recombination of the photogenerated carriers using the piezoelectric polarization charges present in piezoelectric-semiconductor materials. Here, it is presented that the piezo-phototronic effect can be effectively applied to improve the relative conversion efficiency of a flexible solar cell based on n-ZnO/p-SnS core-shell nanowire array for 37.3% under a moderate vertical pressure. The performance of the solar cell can be effectively enhanced by a gentle bending of the device, showing its potential for application in curly geometries. This study not only adds further understanding about the concept of increasing solar energy conversion efficiency via piezo-phototronic effect, but also demonstrates the great potential of piezo-phototronic effect in the application of large-scale, flexible, and lightweight nanowire array solar cells.
Project description:Developing highly efficient and stable photoelectrochemical (PEC) water-splitting electrodes via inexpensive, liquid phase processing is one of the key challenges for the conversion of solar energy into hydrogen for sustainable energy production. ZnO represents one the most suitable semiconductor metal oxide alternatives because of its high electron mobility, abundance, and low cost, although its performance is limited by its lack of absorption in the visible spectrum and reduced charge separation and charge transfer efficiency. Here, we present a solution-processed water-splitting photoanode based on Co-doped ZnO nanorods (NRs) coated with a transparent functionalizing metal-organic framework (MOF). The light absorption of the ZnO NRs is engineered toward the visible region by Co-doping, while the MOF significantly improves the stability and charge separation and transfer properties of the NRs. This synergetic combination of doping and nanoscale surface functionalization boosts the current density and functional lifetime of the photoanodes while achieving an unprecedented incident photon to current efficiency (IPCE) of 75% at 350 nm, which is over 2 times that of pristine ZnO. A theoretical model and band structure for the core-shell nanostructure is provided, highlighting how this nanomaterial combination provides an attractive pathway for the design of robust and highly efficient semiconductor-based photoanodes that can be translated to other semiconducting oxide systems.
Project description:To date, solar energy generation devices have been widely studied to meet a clean and sustainable energy source. Among them, water splitting photoelectrochemical cell is regarded as a promising energy generation way for splitting water molecules and generating hydrogen by sunlight. While many nanostructured metal oxides are considered as a candidate, most of them have an improper bandgap structure lowering energy transition efficiency. Herein, we introduce a novel wet-based, successive photoreduction process that can improve charge transfer efficiency by surface plasmon effect for a solar-driven water splitting device. The proposed process enables to fabricate ZnO/CuO/Ag or ZnO/CuO/Au hierarchical nanostructure, having an enhanced electrical, optical, photoelectrochemical property. The fabricated hierarchical nanostructures are demonstrated as a photocathode in the photoelectrochemical cell and characterized by using various analytic tools.