Kristine Liao

Colloidal Synthesis of 1T-WS2 and 2H-WS2 Nanosheets: Applications for Photocatalytic Hydrogen Evolution

In recent years, a lot of attention has been devoted to monolayer materials, in particular to transition-metal dichalcogenides (TMDCs). While their growth on a substrate and their exfoliation are well developed, the colloidal synthesis of monolayers in solution remains challenging. This paper describes the development of synthetic protocols for producing colloidal WS2 monolayers, presenting not only the usual semiconducting prismatic 2H-WS2 structure but also the less common distorted octahedral 1T-WS2 structure, which exhibits metallic behavior. Modifications of the synthesis method allow for control over the crystal phase, enabling the formation of either 1T-WS2 or 2H-WS2 nanostructures. We study the factors influencing the formation of the two WS2 nanostructures, using X-ray diffraction, microscopy, and spectroscopy analytical tools to characterize them. Finally, we investigate the integration of these two WS2 nanostructured polymorphs into an efficient photocatalytic hydrogen evolution system to compare their behavior.

The Rational Design of a Single-Component Photocatalyst for Gas-Phase CO2 Reduction Using Both UV and Visible Light

The solar‐to‐chemical energy conversion of greenhouse gas CO2 into carbon‐based fuels is a very important research challenge, with implications for both climate change and energy security. Herein, the key attributes of hydroxides and oxygen vacancies are experimentally identified in non‐stoichiometric indium oxide nanoparticles, In2O3‐x(OH)y, that function in concert to reduce CO2 to CO under simulated solar irradiation.

Spatial Separation of Charge Carriers in In2O3–x(OH)y Nanocrystal Superstructures for Enhanced Gas-Phase Photocatalytic Activity

The development of strategies for increasing the lifetime of photoexcited charge carriers in nanostructured metal oxide semiconductors is important for enhancing their photocatalytic activity. Intensive efforts have been made in tailoring the properties of the nanostructured photocatalysts through different ways, mainly including band-structure engineering, doping, catalyst-support interaction, and loading cocatalysts. In liquid-phase photocatalytic dye degradation and water splitting, it was recently found that nanocrystal superstructure based semiconductors exhibited improved spatial separation of photoexcited charge carriers and enhanced photocatalytic performance. Nevertheless, it remains unknown whether this strategy is applicable in gas-phase photocatalysis. Using porous indium oxide nanorods in catalyzing the reverse water-gas shift reaction as a model system, we demonstrate here that assembling semiconductor nanocrystals into superstructures can also promote gas-phase photocatalytic processes. Transient absorption studies prove that the improved activity is a result of prolonged photoexcited charge carrier lifetimes due to the charge transfer within the nanocrystal network comprising the nanorods. Our study reveals that the spatial charge separation within the nanocrystal networks could also benefit gas-phase photocatalysis and sheds light on the design principles of efficient nanocrystal superstructure based photocatalysts.

Non-wettable, oxidation-stable, brightly luminescent, perfluorodecyl-capped silicon nanocrystal film.

Here we describe for the first time the synthesis of colloidally stable, brightly luminescent perfluorodecyl-capped silicon nanocrystals and compare the properties of solutions and films made from them with those of their perhydrodecyl-capped relatives. The perfluorodecyl capping group compared to the perhydrodecyl capping group yields superior hydrophobicity and much greater resistance to air oxidation, the enhanced electron-withdrawing character induces blue shifts in the wavelength of photoluminescence, and the lower-frequency carbon-fluorine stretching modes disfavor non-radiative relaxation pathways and boost the absolute photoluminescence quantum yield. Together these attributes bode well for advanced materials and biomedical applications founded upon perfluorodecyl-protected silicon nanocrystals.

Activation of Ultrathin Films of Hematite for Photoelectrochemical Water Splitting via H2 Treatment

Thermal treatment of ultrathin films of hematite (α-Fe2 O3 ) under an atmosphere of 5 % H2 in Ar is presented as a means of activating α-Fe2 O3 towards the photoelectrochemical splitting of water. Spin-coated films annealed in air exhibited no photoactivity, whereas films treated in hydrogen exhibited a photocurrent response. X-ray photoelectron spectroscopy and UV/Vis absorption spectroscopy results showed that the H2 -treated films contain oxygen vacancies, which suggests improved charge transport. However, Tafel slopes, scan-rate dependent measurements, and kinetic analyses performed by using H2 O2 as a hole scavenger suggested that surface modification may also contribute to their induced photoactivity. Electrochemical impedance spectroscopy results revealed the buildup of a surface trap capacitance at the point of photocurrent onset for the hydrogen-treated films under illumination. A decrease in charge trapping resistance was also observed, which suggests improved transport of charges away from the surface.

New Hydrogen‐Evolution Heteronanostructured Photocatalysts: Pt‐Nb3O7(OH) and Cu‐Nb3O7(OH)

Nanorods of triniobium hydroxide heptaoxide, Nb3 O7 (OH), were synthesized by means of a hydrothermal method. Subsequently, Pt and CuO nanoparticles were introduced on the surface of Nb3 O7 (OH) nanorods by a microwave-assisted solvothermal nucleation and growth technique. The resulting Pt- and CuO-decorated Nb3 O7 (OH) nanorods demonstrated uniform particle dispersion and were fully characterized by X-ray diffraction, electron microscopy, and spectroscopic analysis. Furthermore, the solar-powered photocatalytic hydrogen production properties of these heteronanostructures were studied. The solar-driven H2 formation rate over Pt-Nb3 O7 (OH) was determined to be 710.4 ± 1.7 μmol g(-1) h(-1) with a quantum efficiency of ϕ=5.40% at λ=380 nm. Interestingly, the as-prepared CuO-Nb3 O7 (OH) heteronanostructure was found to be inactive under solar irradiation during an induction phase, whereupon it undergoes an in situ photoreduction process to form the photocatalytically active Cu-Nb3 O7 (OH). This restructuring process was monitored by an in situ measurement of the time-evolution of the optical absorption spectra. The solar-powered H2 production for the restructured compound was determined to be 290.3 ± 5.1 μmol g(-1) h(-1) .

Fe2O3/Cu2O heterostructured nanocrystals

We report the synthesis of colloidal γ-Fe2O3/Cu2O hetero-nanocrystals (HNCs) using a solution-phase seeded-growth approach. γ-Fe2O3 nanocrystals were used as seeds for the nucleation of metallic Cu followed by oxidation of the Cu domain to Cu2O upon exposure to air. The resulting dimer, trimer, and oligomer HNCs were characterized by high resolution electron microscopy, energy dispersive X-ray spectroscopy, and powder X-ray diffraction. The iron oxide component was found to be mainly γ-Fe2O3 using a combination of Raman and X-ray photoelectron spectroscopy. A maximal HNC yield of 72% was achieved by reducing particle growth time to a lower growth temperature with respect to the individual component particles. Size-selective precipitation was used to enrich the nanoparticle mixture in γ-Fe2O3/Cu2O dimers by removing the larger aggregates. Ultraviolet photoelectron spectroscopy was used to determine that γ-Fe2O3 and Cu2O are n-doped and p-doped respectively and form a staggered, type II band alignment. As such, γ-Fe2O3/Cu2O HNCs may be attractive candidates for applications in solar energy conversion and represent a valuable addition to the growing library of oxide–oxide hetero-nanocrystals.

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO2 reduction

Significance In this work, we investigate the role of defects on the electronic and photocatalytic properties of In2O3-x(OH)y nanoparticles that have been shown to effectively reduce CO2 to CO via the reverse water–gas shift reaction under light. To understand how such defects affect photogenerated electrons and holes in these materials, we studied the relaxation dynamics of these nanoparticles with varying concentration of defects. This analysis showed that higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation and correlate well with the observed trends in the photocatalytic activity. In2O3-x(OH)y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO2 to CO via the reverse water–gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In2O3-x(OH)y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play a significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO2 reduction.

Cationic Silicon Nanocrystals with Colloidal Stability, pH-Independent Positive Surface Charge and Size Tunable Photoluminescence in the Near-Infrared to Red Spectral Range.

In this report, the synthesis of a novel class of cationic quaternary ammonium‐surface‐functionalized silicon nanocrystals (ncSi) using a novel and highly versatile terminal alkyl halide‐surface‐functionalized ncSi synthon is described. The distinctive features of these cationic ncSi include colloidal stability, pH‐independent positive surface charge, and size‐tunable photoluminescence (PL) in the biologically relevant near‐infrared‐to‐red spectral region. These cationic ncSi are characterized via a combination of high‐resolution scanning transmission electron microscopy with energy‐dispersive X‐ray analysis, Fourier transform infrared, X‐ray photoelectron, and photoluminescence spectroscopies, and zeta potential measurements.