Menny Shalom

Quantum-Dot-Sensitized Solar Cells

Quantum-dot-sensitized solar cells (QDSCs) are a promising low-cost alternative to existing photovoltaic technologies such as crystalline silicon and thin inorganic films. The absorption spectrum of quantum dots (QDs) can be tailored by controlling their size, and QDs can be produced by low-cost methods. Nanostructures such as mesoporous films, nanorods, nanowires, nanotubes and nanosheets with high microscopic surface area, redox electrolytes and solid-state hole conductors are borrowed from standard dye-sensitized solar cells (DSCs) to fabricate electron conductor/QD monolayer/hole conductor junctions with high optical absorbance. Herein we focus on recent developments in the field of mono- and polydisperse QDSCs. Stability issues are adressed, coating methods are presented, performance is reviewed and special emphasis is given to the importance of energy-level alignment to increase the light to electric power conversion efficiency.

Improving Carbon Nitride Photocatalysis by Supramolecular Preorganization of Monomers

Here we report a new and simple synthetic pathway to form ordered, hollow carbon nitride structures, using a cyanuric acid-melamine (CM) complex in ethanol as a starting product. A detailed analysis of the optical and photocatalytic properties shows that optimum hollow carbon nitride structures are formed after 8 h of condensation. For this condensation time, we find a significantly reduced fluorescence intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes. Enhanced charge transfer is seen as well from a drastic increase of the photocatalytic activity in the degradation of rhodamine B dye, which is shown to proceed via photoinduced hole transfer. Moreover, we show that various CM morphologies can be obtained using different solvents, which leads to diverse ordered carbon nitride architectures. In all cases, the CM-C3N4 structures exhibited superior photocatalytic activity compared to the bulk material. The utilization of CM hydrogen-bonded complexes opens new opportunities for the significant improvement of carbon nitride synthesis, structure, and optical properties toward an efficient photoactive material for catalysis.

Quantum Dot Sensitized Solar Cells with Improved Efficiency Prepared Using Electrophoretic Deposition

Quantum dot sensitized solar cells (QDSSC) may benefit from the ability to tune the quantum dot optical properties and band gap through the manipulation of their size and composition. Moreover, the inorganic nanocrystals may provide increased stability compared to organic sensitizers. We report the facile fabrication of QDSSC by electrophoretic deposition of CdSe QDs onto conducting electrodes coated with mesoporous TiO(2). Unlike prior chemical linker-based methods, no pretreatment of the TiO(2) was needed, and deposition times as short as 2 h were sufficient for effective coating. Cross-sectional chemical analysis shows that the Cd content is nearly constant across the entire TiO(2) layer. The dependence of the deposition on size was studied and successfully applied to CdSe dots with diameters between 2.5 and 5.5 nm as well as larger CdSe quantum rods. The photovoltaic characteristics of the devices are greatly improved compared with those achieved for cells prepared with a linker approach, reaching efficiencies as high as 1.7%, under 1 sun illumination conditions, after treating the coated electrodes with ZnS. Notably, the absorbed photon to electron conversion efficiencies did not show a clear size-dependence indicating efficient electron injection even for the larger QD sizes. The electrophoretic deposition method can be easily expanded and applied for preparations of QDSSCs using diverse colloidal quantum dot and quantum rod materials for sensitization.

Built-in Quantum Dot Antennas in Dye-Sensitized Solar Cells

A new design of dye-sensitized solar cells involves colloidal semiconductor quantum dots that serve as antennas, funneling absorbed light to the charge separating dye molecules via nonradiative energy transfer. The colloidal quantum dot donors are incorporated into the solid titania electrode resulting in high energy transfer efficiency and significant improvement of the cell stability. This design practically separates the processes of light absorption and charge carrier injection, enabling us to optimize each of these separately. Incident photon-to-current efficiency measurements show a full coverage of the visible spectrum despite the use of a red absorbing dye, limited only by the efficiency of charge injection from the dye to the titania electrode. Time resolved luminescence measurements clearly relate this to Forster resonance energy transfer from the quantum dots to the dye. The presented design introduces new degrees of freedom in the utilization of quantum dot sensitizers for photovoltaic cells. In particular, it opens the way toward the utilization of new materials whose band offsets do not allow direct charge injection.

Energy Level Alignment in CdS Quantum Dot Sensitized Solar Cells Using Molecular Dipoles

The energy levels of CdS quantum dots (QDs) can be shifted in a systematic fashion with respect to the TiO(2) bands using molecular dipoles. Dipole moments pointing toward the QD surface shift the energy levels toward the vacuum level (a), thus enabling electron injection from excited QD states into the TiO(2) conduction band at lower photon energies compared to QDs with adsorbed molecular dipoles which are pointing away from the QD surface (b). In CdS QD sensitized solar cells this leads to a dipole dependent shift of the photovoltage onset and the photocurrent.

A general salt-templating method to fabricate vertically aligned graphitic carbon nanosheets and their metal carbide hybrids for superior lithium ion batteries and water splitting

The synthesis of vertically aligned functional graphitic carbon nanosheets (CNS) is challenging. Herein, we demonstrate a general approach for the fabrication of vertically aligned CNS and metal carbide@CNS composites via a facile salt templating induced self-assembly. The resulting vertically aligned CNS and metal carbide@CNS structures possess ultrathin walls, good electrical conductivity, strong adhesion, excellent structural robustness, and small particle size. In electrochemical energy conversion and storage such unique features are favorable for providing efficient mass transport as well as a large and accessible electroactive surface. The materials were tested as electrodes in a lithium ion battery and in electrochemical water splitting. The vertically aligned nanosheets exhibit remarkable lithium ion storage properties and, concurrently, excellent properties as electrocatalysts for hydrogen evolution.

Quantum Dot-Dye Bilayer-Sensitized Solar Cells: Breaking the Limits Imposed by the Low Absorbance of Dye Monolayers

Here, we present a new DSSC design, consisting of sequential QDs and dye sensitization layers, that opens the path toward high optical density DSSCs that cover a significant part of the solar spectrum. The new configuration is enabled by the application of an amorphous TiO2 layer between the two sensitizers, allowing both electron injection from the outer absorber and fast hole extraction from the inner sensitizing layer. Utilizing two sensitizing layers, we obtain a 250% increase in cell efficiency compared to a QD monolayer cell.

Controlled carbon nitride growth on surfaces for hydrogen evolution electrodes.

Efficient and low-cost electrocatalysts for the hydrogen evolution reaction are highly desired for future renewable energy systems. Described herein is the reduction of water to hydrogen using a metal-free carbon nitride electrocatalyst which operates in neutral and alkaline environments. An efficient, easy, and general method for growing ordered carbon nitride on different electrodes was developed. The metal-free catalyst demonstrates low overpotential values, which are comparable to those of non-noble metals, with reasonable current densities. The facile deposition method enables the fabrication of many electronic and photoelectronic devices based on carbon nitride for renewable energy applications.

Quantum rod-sensitized solar cell: nanocrystal shape effect on the photovoltaic properties.

The effect of the shape of nanocrystal sensitizers in photoelectrochemical cells is reported. CdSe quantum rods of different dimensions were effectively deposited rapidly by electrophoresis onto mesoporous TiO(2) electrodes and compared with quantum dots. Photovoltaic efficiency values of up to 2.7% were measured for the QRSSC, notably high values for TiO(2) solar cells with ex situ synthesized nanoparticle sensitizers. The quantum rod-based solar cells exhibit a red shift of the electron injection onset and charge recombination is significantly suppressed compared to dot sensitizers. The improved photoelectrochemical characteristics of the quantum rods over the dots as sensitizers is assigned to the elongated shape, allowing the build-up of a dipole moment along the rod that leads to a downward shift of the TiO(2) energy bands relative to the quantum rods, leading to improved charge injection.

Silver Phosphate/Graphitic Carbon Nitride as an Efficient Photocatalytic Tandem System for Oxygen Evolution

Herein, we show the facile synthesis of an efficient silver phosphate/graphitic carbon nitride (Ag3 PO4 /g-C3 N4 ) photocatalyst for oxygen production and pollutant degradation by using electrostatically driven assembly and ion-exchange processes. The composite materials demonstrate a sheet-like C3 N4 structure, decorated with different Ag3 PO4 particles sizes. Detailed analysis of the reactions mechanism by electron-spin resonance and radical-capture agents strongly imply the formation of an in situ Z-scheme by the evolution of small silver nanoparticles in the interface of the materials under illumination. The Ag nanoparticles improve charge separation within the composite material by acting as a storage and recombination center for electrons and holes from Ag3 PO4 and C3 N4 , respectively. In addition, the photostability of Ag3 PO4 is enhanced relative to that of the bulk materials, which results in a stabilized heterojunction. We believe that this work provides new insight into the operation mechanism of composite photocatalysts for water splitting and opens the possibility for advanced photocatalysis based on the higher oxidation power of Ag3 PO4 .