Balancing the Hydrogen Evolution Reaction, Surface Energetics, and Stability of Metallic MoS2 Nanosheets via Covalent Functionalization.

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS2) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS2 nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS2 functionalized with the most electron donating functional group (p-(CH3CH2)2NPh-MoS2) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS2. The p-(CH3CH2)2NPh-MoS2 is more stable than unfunctionalized metallic MoS2 and outperforms unfunctionalized metallic MoS2 for continuous H2 evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS2 nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS2 nanosheet. The functional groups preserve the metallic nature of the MoS2 nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS2 nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS2 and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.

Nanocrystalline TiO2 solar cells sensitized with InAs quantum dots.

We report nanocrystalline TiO2 solar cells sensitized with InAs quantum dots. InAs quantum dots of different sizes were synthesized and incorporated in solar cell devices. Efficient charge transfer from InAs quantum dots to TiO2 particles was achieved without deliberate modification of the quantum dot capping layer. A power conversion efficiency of about 1.7% under 5 mW/cm2 was achieved; this is relatively high for a nanocrystalline metal oxide solar cell sensitized with presynthesized quantum dots, but this efficiency could only be achieved at low light intensity. At one sun, the efficiency decreased to 0.3%. The devices are stable for at least weeks under room light in air.

Absorption cross-section and related optical properties of colloidal InAs quantum dots.

We report the absorption cross-section of colloidal InAs quantum dots of mean radii from 1.6 to 3.45 nm. We find excellent agreement between the measured results and calculated values based on a model of small-particle light absorption. The absorption cross-section per dot is 6.2 x 10(-16)R(3) cm(2) at 2.76 eV and 3.15 x 10(-16)R(1.28) cm(2) at the first-exciton absorption peak, with the dot radius R in nm. We find that the per-quantum-dot particle oscillator strength of the first-exciton transition is constant for all sizes studied. The radiative lifetime of the first exciton calculated from the oscillator strength increases with dot size and ranges from 4 ns for the smallest dots to 14 ns for the largest ones.