Show Abstract ▼

Abstract: Fuel cells are a key new green technology that have applications in both transport and portable power generation. Carbon supported platinum (Pt) is used as an anode and cathode electrocatalyst in low-temperature fuel cells fuelled with hydrogen or low molecular weight alcohols. The cost of Pt and the limited world supply are significant barriers to the widespread use of these types of fuel cells. Compara-tively palladium has a three times higher abundance in the Earth’s crust. Here a facile, low temperature and scalable synthetic route to-wards 3D nanostructured palladium (Pd) employing electrochemical templating from inverse lyotropic lipid phases is presented. The obtained single diamond morphology Pd nanostructures exhibited excellent catalytic activity and stability towards methanol, ethanol and glycerol oxidation compared to commercial Pd black and the nanostructure was verified by small-angle X-ray scattering (SAXS), scanning tunneling electron microscopy (STEM) as well as by cyclic voltammetry (CV).

Open Access

Show Abstract ▼

Abstract: The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix. The coordinative bonding and chemical structure of a MIL-53 crystalline phase are preserved within the ZIF-62 glass matrix. Whilst separated phases, the interfacial interactions between the closely contacted microdomains improve the mechanical properties of the composite glass. More significantly, the high temperature open pore phase of MIL-53, which spontaneously transforms to a narrow pore upon cooling in the presence of water, is stabilised at room temperature in the crystal-glass composite. This leads to a significant improvement of CO2 adsorption capacity.

Show Abstract ▼

Abstract: Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices. This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects. Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance, perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance. The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions and with local strain, both of which make devices less stable. Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process, we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices.

Show Abstract ▼

Abstract: Dopants in two-dimensional dichalcogenides have a significant role in affecting electronic, mechanical, and interfacial properties. Controllable doping is desired for the intentional modification of such properties to enhance performance; however, unwanted defects and impurity dopants also have a detrimental impact, as often found for chemical vapor deposition (CVD) grown films. The reliable identification, and subsequent characterization, of dopants is therefore of significant importance. Here, we show that Cr and V impurity atoms are found in CVD grown MoS2 monolayer 2D crystals as single atom substitutional dopants in place of Mo. We attribute these impurities to trace elements present in the MoO3 CVD precursor. Simultaneous annular dark field scanning transmission electron microscopy (ADF-STEM) and electron energy loss spectroscopy (EELS) is used to map the location of metal atom substitutions of Cr and V in MoS2 monolayers with single atom precision. The Cr and V are stable under electron irradiation at 60 to 80 kV, when incorporated into line defects, and when heated to elevated temperatures. The combined ADF-STEM and EELS differentiates these Cr and V dopants from other similar contrast defect structures, such as 2S self-interstitials at the Mo site, preventing misidentification. Density functional theory calculations reveal that the presence of Cr or V causes changes to the density of states, indicating doping of the MoS2 material. These transferred impurities could help explain the presence of trapped charges in CVD prepared MoS2.

Show Abstract ▼

Abstract: AbstractWe use electron-beam nanofabrication to create sub-nanometer (sub-nm) pores in 2D monolayer MoS2 with fine control over the pore size down to 0.6 nm, corresponding to the loss of a single Mo atom and surrounding S atoms. The sub-nm pores are created in situ with 1 nm spatial precision in the MoS2 lattice by control of the angstrom sized probe in an aberration corrected scanning transmission electron microscope with real time tracking of the pore creation. Dynamics of the sub-nm pore creation are captured at the atomic scale and reveal the mechanism of nanopore formation at accelerating voltages of 60 and 80 kV to be due to displacing a Mo atom from the lattice site onto the surface of the MoS2. This process is enabled by the destabilization of the Mo bonding from localized electron beam induced S atom loss. DFT calculations confirm the energetic advantage of having the ejected Mo atom attach on the sheet surface rather than being expelled into vacuum, and indicate sensitivity of the nanopore potential as a function of the adsorption position of the ejected Mo atom. These results provide detailed atomic level insights into the initial process of single Mo loss that underpins the nucleation of a nanopore and explains the formation mechanism of sub-nm pores in MoS2.