A novel inverse CeO(2)/CuO catalyst for preferential oxidation of CO in H(2)-rich stream (CO-PROX) has been developed on the basis of a hypothesis extracted from previous work of the group (JACS 2007, 129, 12064). Possible separation of the two competing oxidation reactions involved in the process (of CO and H(2), respectively) is the key to modulation of overall CO-PROX activity and is based on involvement of different sites as most active ones for each of the two reactions. Achievement of large size CuO particles and adequate CeO(2)-CuO interfacial configurations in the inverse catalyst apparently allows appreciable enhancement of the catalytic properties of this kind of system for CO-PROX, constituting an interesting alternative to classic direct configurations so far explored for this process. Reasons for such behavior are analyzed on the basis of operando-XRD, -XAFS, and -DRIFTS studies.

P-type transparent conducting films of nanocrystalline (CuS)x:(ZnS)1-x were synthesized by facile and low-cost chemical bath deposition. Wide angle X-ray scattering (WAXS) and high resolution transmission electron microscopy (HRTEM) were used to evaluate the nanocomposite structure, which consists of sub-5 nm crystallites of sphalerite ZnS and covellite CuS. Film transparency can be controlled by tuning the size of the nanocrystallites, which is achieved by adjusting the concentration of the complexing agent during growth; optimal films have optical transmission above 70% in the visible range of the spectrum. The hole conductivity increases with the fraction of the covellite phase and can be as high as 1000 S cm(-1), which is higher than most reported p-type transparent materials and approaches that of n-type transparent materials such as indium tin oxide (ITO) and aluminum doped zinc oxide (AZO) synthesized at a similar temperature. Heterojunction p-(CuS)x:(ZnS)1-x/n-Si solar cells were fabricated with the nanocomposite film serving as a hole-selective contact. Under 1 sun illumination, an open circuit voltage of 535 mV was observed. This value compares favorably to other emerging heterojunction Si solar cells which use a low temperature process to fabricate the contact, such as single-walled carbon nanotube/Si (370-530 mV) and graphene/Si (360-552 mV).

A giant bandgap reduction in layered GaTe is demonstrated. Chemisorption of oxygen to the Te-terminated surfaces produces significant restructuring of the conduction band resulting in a bandgap below 0.8 eV, compared to 1.65 eV for pristine GaTe. Localized partial recovery of the pristine gap is achieved by thermal annealing, demonstrating that reversible band engineering in layered semiconductors is accessible through their surfaces.

Nonlinear frequency mixing (e.g. harmonic generation) and polarization rotation of electromagnetic waves are the foundation of many important and emergent applications, including laser technologies, optical switches, and frequency combs, among others. 1 The current state-ofthe-art for second-order harmonic generation is achieved using a sequence of multiple quantum wells that are designed to enhance transitions resonantly at both fundamental and harmonic frequencies. 2 However, these systems are intrinsically limited to the mid infrared, precluding their operation at frequencies relevant for optical imaging and telecommunications. Therefore, new materials that can achieve large nonlinear optical responses over a broader range of frequencies are needed. Here, we describe near-infrared-to-visible second harmonic generation for two-

Two-dimensional (2D) materials offer unique opportunities in engineering the ultrafast spatiotemporal response of composite nanomechanical structures. In this work, we report on high frequency, high quality factor (Q) 2D acoustic cavities operating in the 50–600 GHz frequency (f) range with f × Q up to 1 × 1014. Monolayer steps and material interfaces expand cavity functionality, as demonstrated by building adjacent cavities that are isolated or strongly-coupled, as well as a frequency comb generator in MoS2/h-BN systems. Energy dissipation measurements in 2D cavities are compared with attenuation derived from phonon-phonon scattering rates calculated using a fully microscopic ab initio approach. Phonon lifetime calculations extended to low frequencies (<1 THz) and combined with sound propagation analysis in ultrathin plates provide a framework for designing acoustic cavities that approach their fundamental performance limit. These results provide a pathway for developing platforms employing phonon-based signal processing and for exploring the quantum nature of phonons.

Recent studies have shown that MoS2 can undergo a structural phase transition from the 2H to 1T′ phase on Au substrates at moderate temperatures. Here, we use ultraviolet and x-ray photoelectron spectroscopy, Raman and photoluminescence spectroscopy, and scanning tunneling microscopy/spectroscopy to probe the impact of annealing exfoliated, monolayer MoS2 on Au. Our results across multiple length scales indicate that 2H-MoS2 becomes hybridized with Au upon thermal annealing without inducing the 1T′ structural phase and the bandgap can be modulated to zero width depending on the degree of hybridization. These results can be used to control the resistance of metal-MoS2 contacts at the atomic scale without introduction of defects or structural phase transitions and are important for devices such as memristors.

We report the growth of layered GaSe x Te 1−x mesostructures across the whole composition range. For compositions up to x = 0.32 (the Te-rich region), mesocrystals form predominantly in the monoclinic structure, similar to naturally occurring GaTe. However, the hexagonal crystal structure, similar to naturally occurring GaSe, begins growing at the x = 0.28 composition and grows almost exclusively in the range of x = 0.32 to pure GaSe, establishing a region of composition where both monoclinic and hexagonal crystals exist. While the optical bandgap of the monoclinic phase increases linearly from 1.65 to 1.77 eV with increasing Se content, the incorporation of Te in the hexagonal phase reduces the optical gap from 2.01 (pure GaSe) to 1.38 eV (x = 0.28). Specifically, a bandgap difference of ∼0.35 eV between monoclinic and hexagonal crystals is observed in the composition range where both crystal structures can be grown. These observations are in good agreement with direct-gap trends calculated by density functional theory, which show a linear dependence on composition for the direct gap of the monoclinic phase and a considerable bowing of the direct gap of the hexagonal phase for Te-rich compositions. Our results show that layered semiconductor alloys are remarkably versatile systems in which electronic properties can be controlled by not only thickness but also structural phase and composition.

The interaction between two-dimensional crystals (2DCs) and metals is ubiquitous in 2D material research. Here we report how 2DC overlayers influence the recrystallization of relatively thick metal films and the subsequent synergetic benefits this provides for coupling surface plasmon-polaritons (SPPs) to photon emission in 2D semiconductors. We show that annealing 2DC/Au films on SiO2 results in a 'reverse epitaxial' process where initially nanocrystalline Au films become highly textured and in close crystallographic registry to the 2D crystal overlayer.With continued annealing, the metal underlayer dewets to form an oriented pore enabled network (OPEN) film in which the 2DC overlayer remains suspended above or coats the inside of the metal pores. This OPEN film geometry supports SPPs launched by either direct laser excitation or by light emitted from the TMD semiconductor itself, where energy in-coupling and out-coupling occurs at the metal pore sites such that dielectric spacers between the metal and 2DC layer are unnecessary. At low temperatures a high density of single-photon emitters (SPEs) is present across an OPEN-WSe2 film, and we demonstrate non-local excitation of SPEs at a distance of 17 m with minimal loss of photon purity. Our results suggest the OPEN film geometry is a versatile platform that could facilitate the use of layered materials in quantum optics systems.