Michael F. Durstock

Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction

The large-scale practical application of fuel cells will be difficult to realize if the expensive platinum-based electrocatalysts for oxygen reduction reactions (ORRs) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, we report that vertically aligned nitrogen-containing carbon nanotubes (VA-NCNTs) can act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction in alkaline fuel cells. In air-saturated 0.1 molar potassium hydroxide, we observed a steady-state output potential of –80 millivolts and a current density of 4.1 milliamps per square centimeter at –0.22 volts, compared with –85 millivolts and 1.1 milliamps per square centimeter at –0.20 volts for a platinum-carbon electrode. The incorporation of electron-accepting nitrogen atoms in the conjugated nanotube carbon plane appears to impart a relatively high positive charge density on adjacent carbon atoms. This effect, coupled with aligning the NCNTs, provides a four-electron pathway for the ORR on VA-NCNTs with a superb performance.

Soluble P3HT-grafted graphene for efficient bilayer-heterojunction photovoltaic devices.

CH(2)OH-terminated regioregular poly(3-hexylthiophene) (P3HT) was chemically grafted onto carboxylic groups of graphene oxide (GO) via esterification reaction. The resultant P3HT-grafted GO sheets (G-P3HT) are soluble in common organic solvents, facilitating the structure/property characterization and the device fabrication by solution processing. The covalent linkage and the strong electronic interaction between the P3HT and graphene moieties in G-P3HT were confirmed by spectroscopic analyses and electrochemical measurements. A bilayer photovoltaic device based on the solution-cast G-P3HT/C(60) heterostructures showed a 200% increase of the power conversion efficiency (η = 0.61%) with respect to the P3HT/C(60) counterpart under AM 1.5 illumination (100 mW/cm(2)).

Fabrication of Highly-Ordered TiO2 Nanotube Arrays and Their Use in Dye-Sensitized Solar Cells

Highly ordered TiO(2) nanotubes were successfully fabricated using a nanoporous alumina templating method. A modified sol-gel route was used to infiltrate the alumina pores with Ti(OC(3)H(7))(4) which was subsequently converted into TiO(2) nanotubes. The average external diameter, tube lengths, and wall thickness achieved were 295 nm, 6-15 microm, and 21-42 nm, respectively. Diffraction data reveals that the nanotubes consist solely of the anatase phase. Dye-sensitized solar cells using TiO(2) nanotube arrays as the working electrode yielded power conversion efficiencies as high as 3.5% with a maximum incident photon-to-current conversion efficiency of 20% at 520 nm.

Hole and Electron Extraction Layers Based on Graphene Oxide Derivatives for High-Performance Bulk Heterojunction Solar Cells

By charge neutralization of carboxylic acid groups in graphene oxide (GO) with Cs(2)CO(3) to afford Cesium-neutralized GO (GO-Cs), GO derivatives with appropriate modification are used as both hole- and electron-extraction layers for bulk heterojunction (BHJ) solar cells. The normal and inverted devices based on GO hole- and GO-Cs electron-extraction layers both outperform the corresponding standard BHJ solar cells.

Fullerene-Grafted Graphene for Efficient Bulk Heterojunction Polymer Photovoltaic Devices

A simple lithiation reaction was developed to covalently attach monosubstituted C60 onto graphene nanosheets. Detailed spectroscopic (e.g., Fourier transform infrared, Raman) analyses indicated that C60 molecules were covalently attached onto the graphene surface through monosubstitution. Transmission electron microscopic (TEM) observation revealed that these monosubstituted C60 moieties acted as nucleation centers to promote the formation of C60 aggregates of ∼5 nm in diameter on the graphene surface. The resultant C60-grafted graphene nanosheets were used as electron acceptors in poly(3-hexylthiophene)-based bulk heterojunction solar cells to significantly improve the electron transport, and hence the overall device performance, yielding a power conversion efficiency of ∼1.22%.

Graphene oxide derivatives as hole- and electron-extraction layers for high-performance polymer solar cells

Owing to their solution processability, unique two-dimensional structure, and functionalization-induced tunable electronic structures, graphene oxide (GO) and its derivatives have been used as a new class of efficient hole- and electron-extraction materials in polymer solar cells (PSCs). Highly efficient and stable PSCs have been fabricated with GO and its derivatives as hole- and/or electron-extraction layers. In this review, we summarize recent progress in this emerging research field. We also present some rational concepts for the design and development of the GO-based hole- or electron-extraction layers for high-performance PSCs, along with challenges and perspectives.

Donor-π-Acceptor Conjugated Copolymers for Photovoltaic Applications: Tuning the Open-Circuit Voltage by Adjusting the Donor/Acceptor Ratio

A class of new conjugated copolymers containing a donor (thiophene)-acceptor (2-pyran-4-ylidene-malononitrile) was synthesized via Stille coupling polymerization. The resulting copolymers were characterized by 1H NMR, elemental analysis, GPC, TGA, and DSC. UV-vis spectra indicated that the increase in the content of the thiophene units increased the interaction between the polymer main chains to cause a red-shift in the optical absorbance. Cyclic voltammetry was used to estimate the energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) and the band gap (Eg) of the copolymers. The basic electronic structures of the copolymers were also studied by DFT calculations with the GGA/B3LYP function. Both the experimental and the calculated results indicated an increase in the HOMO energy level with increasing the content of thiophene units, whereas the corresponding change in the LUMO energy level was much smaller. Polymer photovoltaic cells of a bulk heterojunction were fabricated with the structure of ITO/PEDOT/PSS (30 nm)/copolymer-PCBM blend (70 nm)/Ca (8 nm)/Al (140 nm). It was found that the open-circuit voltage (Voc) increased (up to 0.93 V) with a decrease in the content of thiophene units. Although the observed power convention efficiency is still relatively low (up to 0.9%), the corresponding low fill factor (0.29) indicates considerable room for further improvement in the device performance. These results provided a novel concept for developing high Voc photovoltaic cells based on donor-pi-acceptor conjugated copolymers by adjusting the donor/acceptor ratio.

Nanolaminates: increasing dielectric breakdown strength of composites.

Processable, low-cost, high-performance hybrid dielectrics are enablers for a vast array of green technologies, including high-temperature electrical insulation and pulsed power capacitors for all-electric transportation vehicles. Maximizing the dielectric breakdown field (E(BD)), in conjunction with minimization of leakage current, directly impacts system performance because of the fields quadratic relationship with electrostatic energy storage density. On the basis of the extreme internal interfacial area and ultrafine morphology, polymer-inorganic nanocomposites (PNCs) have demonstrated modest increases in E(BD) at very low inorganic loadings, but because of insufficient control of the hierarchal morphology of the blend, have yielded a precipitous decline in E(BD) at intermediate and high inorganic volume fractions. Here in, we demonstrate that E(BD) can be increased up to these intermediate inorganic volume fractions by creating uniform one-dimensional nanocomposites (nanolaminates) rather than blends of spherical inorganic nanoparticles and polymers. Free standing nanolaminates of highly aligned and dispersed montmorillonite in polyvinyl butyral exhibited enhancements in E(BD) up to 30 vol % inorganic (70 wt % organically modified montmorillonite). These relative enhancements extend up to five times the inorganic fraction observed for random nanoparticle dispersions, and are anywhere from two to four times greater than observed at comparable volume fraction of nanoparticles. The breakdown characteristics of this model system suggested a trade-off between increased path tortuosity and polymer-deficient structural defects. This implies that an idealized PNC morphology to retard the breakdown cascade perpendicular to the electrodes will occur at intermediate volume fractions and resemble a discotic nematic phase where highly aligned, high-aspect ratio nanometer thick plates are uniformly surrounded by nanoscopic regions of polymer.

Graphene Oxide Nanoribbon as Hole Extraction Layer to Enhance Efficiency and Stability of Polymer Solar Cells

Graphene oxide nanoribbons for efficient and stable polymer solar cells are discussed. With controllable bandgap, good solubility and film forming property, graphene oxide nanoribbons serve as a new class of excellent hole extraction materials for efficient and stable polymer solar cells outperforming their counterparts based on conventional hole extraction materials, including PEDOT:PSS.

Nanostructured 3D Electrode Architectures for High-Rate Li-Ion Batteries

By initially depositing a sub-10 nm-thick SnO2 film, the microstructural evolution that is often considered problematic can be utilized to form Sn nanoparticles on the surface of a 3D current collector for enhanced cycling stability. The work described here highlights a novel approach for the uniform deposition of Sn nanoparticles, which can be used to design electrodes with high capacities and high-rate capabilities.