Daniel Rossi

Photoinduced Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals

Cesium lead halide (CsPbX3) perovskite nanocrystals (NCs) possess the unique capability of post-synthesis anion exchange providing facile tunability of the optical properties, which is usually achieved by mixing NCs with reactive anion precursors. In this work, we show that the controllable anion exchange can be achieved in a dihalomethane solution of CsPbX3 NC in the absence of any spontaneously reacting anion source using photoexcitation of CsPbX3 NCs as the triggering mechanism for the halide ion exchange. The reaction begins with the photoinduced electron transfer from CsPbX3 NCs to dihalomethane solvent molecules producing halide ions via reductive dissociation, which is followed by anion exchange. The reaction proceeds only in the presence of excitation light and the rate and extent of reaction can be controlled by varying the light intensity. Furthermore, the asymptotic extent of reaction under continuous excitation can be controlled by varying the wavelength of light that self-limits the reaction when light becomes off-resonance with the absorption of NCs. The light-controlled anion exchange demonstrated here can be utilized to pattern the post-synthesis chemical transformation of CsPbX3 NCs, not readily achievable using typical methods of anion exchange.

Orientational Control of Colloidal 2D-Layered Transition Metal Dichalcogenide Nanodiscs via Unusual Electrokinetic Response

We report an unusual response of colloidal layered transition metal dichalcogenide (TMDC) nanodiscs to the electric field, where the orientational order is created transiently only during the time-varying period of the electric field while no orientational order is created by the DC field. This result is in stark contrast to the typical electrokinetic response of various other colloidal nanoparticles, where the permanent dipole or (and) anisotropic-induced dipole creates a sustaining orientational order under the DC field. This indicates the lack of a sizable permanent dipole or (and) anisotropic-induced dipole in colloidal TMDC nanodiscs, despite their highly anisotropic lattice structure. While the orientational order is created only transiently by the time-varying field, a near-steady-state orientational order can be obtained by using an AC electric field. We demonstrate the utility of this method for the controlled orientation of colloidal nanoparticles that cannot be controlled via the usual interaction of the electric field with the nanoparticle dipole.

[Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

Nonplasmonic Hot-Electron Photocurrents from Mn-Doped Quantum Dots in Photoelectrochemical Cells.

We report the measurement of the hot-electron current in a photoelectrochemical cell constructed from a glass/ITO/Al2 O3 (ITO=indium tin oxide) electrode coated with Mn-doped quantum dots, where hot electrons with a large excess kinetic energy were produced through upconversion of the excitons into hot electron hole pairs under photoexcitation at 3 eV. In our recent study (J. Am. Chem. Soc. 2015, 137, 5549), we demonstrated the generation of hot electrons in Mn-doped II-VI semiconductor quantum dots and their usefulness in photocatalytic H2 production reaction, taking advantage of the more efficient charge transfer of hot electrons compared with band-edge electrons. Here, we show that hot electrons produced in Mn-doped CdS/ZnS quantum dots possess sufficient kinetic energy to overcome the energy barrier from a 5.4-7.5 nm thick Al2 O3 layer producing a hot-electron current in photoelectrochemical cell. This work demonstrates the possibility of harvesting hot electrons not only at the interface of the doped quantum dot surface, but also far away from it, thus taking advantage of the capability of hot electrons for long-range electron transfer across a thick energy barrier.

Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium

Cesium lead halide (CsPbX3) nanocrystals have emerged as a new family of materials that can outperform the existing semiconductor nanocrystals due to their superb optical and charge-transport properties. However, the lack of a robust method for producing quantum dots with controlled size and high ensemble uniformity has been one of the major obstacles in exploring the useful properties of excitons in zero-dimensional nanostructures of CsPbX3. Here, we report a new synthesis approach that enables the precise control of the size based on the equilibrium rather than kinetics, producing CsPbX3 quantum dots nearly free of heterogeneous broadening in their exciton luminescence. The high level of size control and ensemble uniformity achieved here will open the door to harnessing the benefits of excitons in CsPbX3 quantum dots for photonic and energy-harvesting applications.