Interpretability of high-resolution transmission electron microscopy images.

High-resolution electron microscopy is a well-suited tool for characterizing the nanoscale structure of materials. However, the interaction of the sample and the high-energy electrons of the beam can often have a detrimental impact on the sample structure. This effect can only be alleviated by decreasing the number of electrons to which the sample is exposed but will come at the cost of a decreased signal-to-noise ratio in the resulting image. Images with low signal to noise ratios are often challenging to interpret as parts of the sample with a low interaction with the electron beam are reproduced with very low contrast. Here we suggest simple measures as alternatives to the conventional signal-to-noise ratio and investigate how these can be used to predict the interpretability of the electron microscopy images. We test the models on a sample consisting of gold nanoparticles supported on a cerium dioxide substrate. The models are evaluated based on series of images acquired at varying electron dose.

Breaking the Axis-Symmetry of a Single-Wall Carbon Nanotube During Its Growth.

The asymmetrical growth of a single-wall carbon nanotube (SWCNT) by introducing a change of a local atomic structure, is usually inevitable and supposed to have a profound effect on the chirality control and property tailor. However, the breaking of the symmetry during SWCNT growth remains unexplored and its origins at the atomic-scale are elusive. Here, environmental transmission electron microscopy is used to capture the process of breaking the symmetry of a growing SWCNT from a sub-2-nm platinum catalyst nanoparticle in real-time, demonstrating that topological defects formed on the side of a SWCNT can serve as a buffer for stress release and inherently break its axis-symmetrical growth. Atomic-level details reveal the importance of the tube-catalyst interface and how the atom rearrangement of the solid-state platinum catalyst around the interface influences the final tubular structure. The active sites responsible for trapping carbon dimers and providing enough driving force for carbon incorporation and asymmetric growth are shown to be low-coordination step edges, as confirmed by theoretical simulations.

Stereolithography-Derived Three-Dimensional Pyrolytic Carbon/Mn3O4 Nanostructures for Free-Standing Hybrid Supercapacitor Electrodes.

The development of permeable three-dimensional (3D) macroporous carbon architectures loaded with active pseudocapacitive nanomaterials offers hybrid supercapacitor (SC) materials with higher energy density, shortened diffusion length for ions, and higher charge-discharge rate capability and thereby is highly relevant for electrical energy storage (EES). Herein, structurally complex and tailorable 3D pyrolytic carbon/Mn3O4 hybrid SC electrode materials are synthesized through the self-assembly of MnO2 nanoflakes and nanoflowers onto the surface of stereolithography 3D-printed architectures via a facile wet chemical deposition route, followed by a single thermal treatment. Thermal annealing of the MnO2 nanostructures concurrent with carbonization of the polymer precursor leads to the formation of a 3D hybrid SC electrode material with unique structural integrity and uniformity. The microstructural and chemical characterization of the hybrid electrode reveals the predominant formation of crystalline hausmannite-Mn3O4 after the pyrolysis/annealing process, which is a favorable pseudocapacitive material for EES. With the combination of the 3D free-standing carbon architecture and self-assembled binder-free Mn3O4 nanostructures, electrochemical capacitive charge storage with very good rate capability, gravimetric and areal capacitances (186 F g-1 and 968 mF cm-2, respectively), and a long lifespan (>92% after 5000 cycles) is demonstrated. It is worth noting that the gravimetric capacitance value is obtained by considering the full mass of the electrode including the carbon current collector. When only the mass of the pseudocapacitive nanomaterial is considered, a capacitance value of 457 F g-1 is achieved, which is comparable to state-of-the-art Mn3O4-based SC electrode materials.

Transformations of supported gold nanoparticles observed by in situ electron microscopy.

Oxide supported metal nanoparticles play an important role in heterogeneous catalysis. However, understanding the metal/oxide interface and their evolution under reaction conditions remains challenging. Herein, we investigate the interface between Au nanoparticles and a CeO2 substrate by environmental transmission electron microscopy with atomic resolution. We find that the Au nanoparticles have two preferential epitaxial relationships with the substrate, i.e. Type I (111)[-110]CeO2//(111)[-110]Au and Type II (111)[-110]CeO2//(111)[1-10]Au orientation relationships, where Type I is preferred. In situ observations in the presence of O2 show that the gas can stimulate the supported Au nanoparticles to transform between these two orientations even at room temperature. Moreover, when increasing the temperature to 973 K, the transformation of an Au nanoparticle between the two orientation states and a non-crystalline state in the presence of O2 is also observed. DFT calculations of the binding between Au and CeO2 in the two relationships are strongly influenced by the presence of oxygen vacancies. For a given position of a vacancy, there is a significant energy difference between the energy of the two types. However, for some positions, Type I is preferred, and for others, Type II, but the most favourable position of the vacancy for the two types has a very similar energy. This is consistent with the observation of both types of adhesion.

Modeling of temperature profiles in an environmental transmission electron microscope using computational fluid dynamics.

The temperature and velocity field, pressure distribution, and the temperature variation across the sample region inside an environmental transmission electron microscope (ETEM) have been modeled by means of computational fluid dynamics (CFD). Heating the sample area by a furnace type TEM holder gives rise to temperature gradients over the sample area. Three major mechanisms have been identified with respect to heat transfer in the sample area: radiation from the grid, conduction in the grid, and conduction in the gas. A parameter sensitivity analysis showed that the sample temperature was affected by the conductivity of the gas, the emissivity of the sample grid, and the conductivity of the grid. Ideally the grid should be polished and made from a material with good conductivity, e.g. copper. With hydrogen gas, which has the highest conductivity of the gases studied, the temperature difference over the TEM grid is less than 5 °C, at what must be considered typical conditions, and it is concluded that the conditions on the sample grid in the ETEM can be considered as isothermal during general use.