Qinfeng Xu

Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis

An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance.

Single-particle spectroscopic measurements of fluorescent graphene quantum dots.

We have performed the first single-particle spectroscopic measurements on individual graphene quantum dots (GQDs) and revealed several intriguing fluorescent phenomena that are otherwise hidden in the optical studies of ensemble GQDs. First, despite noticeable differences in the size and the number of layers from particle to particle, all of the GQDs studied possess almost the same spectral lineshapes and peak positions. Second, GQDs with more layers are normally brighter emitters but are associated with shorter fluorescent lifetimes. Third, the fluorescent spectrum of GQDs was red-shifted upon being aged in air, possibly due to the water desorption effect. Finally, the missing emission of single photons and stable fluorescence without any intermittent behavior were observed from individual GQDs.

Construction and Nanoscale Detection of Interfacial Charge Transfer of Elegant Z-Scheme WO3/Au/In2S3 Nanowire Arrays

Elegant Z-scheme WO3/Au/In2S3 nanowire arrays were precisely constructed through a facile step-by-step route. Surface potential change on pristine or In2S3-Au coated WO3 single nanowire under dark and illumination detected through a Kelvin probe force microscopy (KPFM) technique indicates that the vectorial holes transfer of In2S3 → Au → WO3 should occur upon the excitation of both WO3 and In2S3. In such charge transfer processes, the embedded Au nanoparticles in the heterojunction systems act as a charge mediator for electrons in the conduction band of WO3 and holes in the valence band of In2S3. The strong charge carrier separation ability of this structure will finally enhance the oxidation ability of WO3 with high concertation of photogenerated holes and, further, leave the free electrons in the In2S3 with long surviving time. Therefore, the unique Z-scheme WO3/Au/In2S3 heterostructure shows great visible-light activity toward photocatalytic reduction of CO2 in the presence of water vapor into renewable hydrocarbon fuel (methane: CH4).

Rational construction of a CdS/reduced graphene oxide/TiO2 core–shell nanostructure as an all-solid-state Z-scheme system for CO2 photoreduction into solar fuels

Mimicking natural photosynthesis in green plants, an all-solid-state Z-scheme was constructed for photocatalytic reduction of CO2 in the presence of water vapor, consisting of CdS nanospheres (CdS NSs) and TiO2 nanoparticles as photocatalysts, and reduced graphene oxide (rGO) as a solid electron mediator. In this Z-scheme system, the photogenerated electrons from the conduction band of TiO2 transfer to rGO, and then recombine with the existing holes of CdS NSs, allowing the photo-generated electrons to enrich on the CdS semiconductor and holes on the TiO2. The photocatalytic efficiency of the Z-scheme system exhibits remarkable enhancement relative to pure CdS, CdS/TiO2, and CdS/rGO.

Energy Transfer of Biexcitons in a Single Semiconductor Nanocrystal

Photoluminescence (PL) decay dynamics of multiexcitons in semiconductor nanocrystals (NCs) are dominated by the nonradiative Auger effect, making it difficult to explore their basic optical processes such as radiative recombination and energy transfer (ET). Here we constructed a single-particle ET system by attaching several acceptor dyes to the surface of a donor NC to study the ET of biexcitons at a single-NC level. By comparing the single-exciton and biexciton PL lifetimes of the same donor NC before and after the acceptor dyes were bleached, their respective ET lifetimes could be reliably extracted without the Auger influence. From statistical measurements on a large number of single ET particles, the average ET rate ratio between biexcitons and single excitons was estimated to be larger than four, and the same scaling rule could be naturally extended to their radiative rates.

Extended storage of multiple excitons in trap states of semiconductor nanocrystals

Owing to the Auger recombination effect, multiple excitons (MEs) in semiconductor nanocrystals (NCs) are dissipated nonradiatively at the sub-nanosecond time scale, which sets a stringent limit on the time window within which one can operate with them. Here, we show that this issue can be resolved by utilizing an intrinsic energy transfer system in CdSe NCs, where MEs created in the donor quantized states can be effectively extracted to the acceptor trap states. This was evidenced by the step-like increase in the intensity and the apparent decrease in the rise time of the trap-state photoluminescence with the elevated laser excitation power. With the radiative lifetime being tens of nanoseconds for the trap states, extended storage of MEs has been achieved and marks a crucial step towards flexible manipulations of their optoelectronic properties.

Giant Up-Conversion Efficiency of InGaAs Quantum Dots in a Planar Microcavity

Self-assembled InGaAs quantum dots (QDs) were fabricated inside a planar microcavity with two vertical cavity modes. This allowed us to excite the QDs coupled to one of the vertical cavity modes through two propagating cavity modes to study their down- and up-converted photoluminescence (PL). The up-converted PL increased continuously with the increasing temperature, reaching an intensity level comparable to that of the down-converted PL at ~120 K. This giant efficiency in the up-converted PL of InGaAs QDs was enhanced by about 2 orders of magnitude with respect to a similar structure without cavity. We tentatively explain the enhanced up-converted signal as a direct consequence of the modified spontaneous emission properties of the QDs in the microcavity, combined with the phonon absorption and emission effects.