Prominent Structural Dependence of Quantum Capacitance Unraveled by Nitrogen-Doped Graphene Mesosponge.

Porous carbons are important electrode materials for supercapacitors. One of the challenges associated with supercapacitors is improving their energy density without relying on pseudocapacitance, which is based on fast redox reactions that often shorten device lifetimes. A possible solution involves achieving high total capacitance (Ctot ), which comprises Helmholtz capacitance (CH ) and possibly quantum capacitance (CQ ), in high-surface carbon materials comprising minimally stacked graphene walls. In this work, a templating method is used to synthesize 3D mesoporous graphenes with largely identical pore structures (≈2100 m2 g-1 with an average pore size of ≈7 nm) but different concentrations of oxygen-containing functional groups (0.3-6.7 wt.%) and nitrogen dopants (0.1-4.5 wt.%). Thus, the impact of the heteroatom functionalities on Ctot is systematically investigated in an organic electrolyte excluding the effect of pore structures. It is found that heteroatom functionalities determine Ctot , resulting in the cyclic voltammetry curves being rectangular or butterfly-shaped. The nitrogen functionalities are found to significantly enhance Ctot owing to increased CQ .

Edge-Site-Free and Topological-Defect-Rich Carbon Cathode for High-Performance Lithium-Oxygen Batteries.

The rational design of a stable and catalytic carbon cathode is crucial for the development of rechargeable lithium-oxygen (LiO2 ) batteries. An edge-site-free and topological-defect-rich graphene-based material is proposed as a pure carbon cathode that drastically improves LiO2 battery performance, even in the absence of extra catalysts and mediators. The proposed graphene-based material is synthesized using the advanced template technique coupled with high-temperature annealing at 1800 °C. The material possesses an edge-site-free framework and mesoporosity, which is crucial to achieve excellent electrochemical stability and an ultra-large capacity (>6700 mAh g-1 ). Moreover, both experimental and theoretical structural characterization demonstrates the presence of a significant number of topological defects, which are non-hexagonal carbon rings in the graphene framework. In situ isotopic electrochemical mass spectrometry and theoretical calculations reveal the unique catalysis of topological defects in the formation of amorphous Li2 O2 , which may be decomposed at low potential (∼ 3.6 V versus Li/Li+ ) and leads to improved cycle performance. Furthermore, a flexible electrode sheet that excludes organic binders exhibits an extremely long lifetime of up to 307 cycles (>1535 h), in the absence of solid or soluble catalysts. These findings may be used to design robust carbon cathodes for LiO2 batteries.

Surfactant-mediated morphology evolution and self-assembly of cerium oxide nanocrystals for catalytic and supercapacitor applications.

Surfactant plays a remarkable role in determining the growth process (facet exposition) of colloidal nanocrystals (NCs) and the formation of self-assembled NC superstructures, the underlying mechanism of which, however, still requires elucidation. In this work, the mechanism of surfactant-mediated morphology evolution and self-assembly of CeO2 nanocrystals is elucidated by exploring the effect that surfactant modification has on the shape, size, exposed facets, and arrangement of the CeO2 NCs. It is directly proved that surfactant molecules determine the morphologies of the CeO2 NCs by preferentially bonding onto Ce-terminated {100} facets, changing from large truncated octahedra (mostly {111} and {100} exposed), to cubes (mostly {100} exposed) and small cuboctahedra (mostly {100} and {111} exposed) by increasing the amount of surfactant. The exposure degree of the {100} facets largely affects the concentration of Ce3+ in the CeO2 NCs, thus the cubic CeO2 NCs exhibit superior oxygen storage capacity and excellent supercapacitor performance due to a high fraction of exposed active {100} facets with great superstructure stability.

Anataselike Grain Boundary Structure in Rutile Titanium Dioxide.

The formation of nanoscale phases at grain boundaries in polycrystalline materials has attracted much attention, since it offers a route toward targeted and controlled design of interface properties. However, understanding structure-property relationships at these complex interfacial defects is hampered by the great challenge of accurately determining their atomic structure. Here, we combine advanced electron microscopy together with ab initio random structure searching to determine the atomic structure of an experimentally fabricated Σ13 (221) [11̅0] grain boundary in rutile TiO2. Through careful analysis of the atomic structure and complementary electron energy-loss spectroscopy analysis we identify the existence of a unique nanoscale phase at the grain boundary with striking similarities to the bulk anatase crystal structure. Our results show a path to embed nanoscale anatase into rutile TiO2 and showcase how the atomic structure of even complex internal interfaces can be accurately determined using a combined theoretical and experimental approach.

Ceramic phases with one-dimensional long-range order.

Solids are generally classified into three categories based on their atomic arrangement: crystalline, quasicrystalline and amorphous1-4. Here we report MgO and Nd2O3 ceramic phases with special atomic arrangements that should belong to a category of solids different from these three well known categories by combining state-of-the-art atomic-resolution scanning transmission electron microscopy and first-principles calculations. The reported solid structure exhibits a one-dimensional (1D) long-range order with a translational periodicity and is composed of structural units that individually have atomic arrangements similar to those observed in coincidence-site lattice configurations present at grain boundaries. Regardless of the insulating nature of the bulk MgO, the bandgap of which is measured to be 7.4 eV, the MgO 1D ordered structure is a wide-bandgap semiconductor with a bandgap of 3.2 eV owing to this special atomic arrangement. The discovery of 1D ordered structures suggests that the structural categories of solids could be more abundant, with physical properties distinct from their regular counterparts.

Atomic-Scale Valence State Distribution inside Ultrafine CeO2 Nanocubes and Its Size Dependence.

Atomic-scale analysis of the cation valence state distribution will help to understand intrinsic features of oxygen vacancies (VO ) inside metal oxide nanocrystals, which, however, remains a great challenge. In this work, the distribution of cerium valence states across the ultrafine CeO2 nanocubes (NCs) perpendicular to the {100} exposed facet is investigated layer-by-layer using state-of-the-art scanning transmission electron microscopy-electron energy loss spectroscopy. The effect of size on the distribution of Ce valence states inside CeO2 NCs is demonstrated as the size changed from 11.8 to 5.4 nm, showing that a large number of Ce3+ cations exist not only in the surface layers, but also in the center layers of smaller CeO2 NCs, which is in contrast to those in larger NCs. Combining with the atomic-scale analysis of the local structure inside the CeO2 NCs and theoretical calculation on the VO forming energy, the mechanism of size effect on the Ce valence states distribution and lattice expansion are elaborated: nano-size effect induces the overall lattice expansion as the size decreased to ≈5 nm; the expanded lattice facilitates the formation of VO due to the lower formation energy required for the smaller size, which, in principle, provides a fundamental understanding of the formation and distribution of Ce3+ inside ultrafine CeO2 NCs.

Direct Imaging for Single Molecular Chain of Surfactant on CeO2 Nanocrystals.

Organic surfactant controls the synthesis of nanocrystals (NCs) with uniform size and morphology by attaching on the surface of NCs and further facilitates their assembly into ordered superstructure, which produces versatile functional nanomaterials for practical applications. It is essential to directly resolve the surfactant molecules on the surface of NCs to improve the understanding of surface chemistry of NCs. However, the imaging resolution and contrast are insufficient for a single molecule of organic surfactant on NCs. In this work, direct characterization of organic surfactant on CeO2 NCs is conducted by using the state-of-the-art aberration corrected scanning transmission electron microscopy (STEM) imaging and electron energy loss spectra (EELS) techniques. The explicit evidence for the existence and distribution of organic surfactant on CeO2 NCs are obtained on the atomic scale by EELS elemental mapping. Besides, STEM imaging parameters are systematically adjusted and optimized for the direct imaging of a single molecular chain of organic surfactant on CeO2 NCs. Such direct visualization of organic surfactant molecule on the surface of NCs can be a significant step forward in the fields of nanomaterials surface chemistry and materials characterization.

Single-Crystal Growth of Cl-Doped n-Type SnS Using SnCl2 Self-Flux.

SnS is a promising photovoltaic semiconductor owing to its suitable band gap energy and high optical absorption coefficient for highly efficient thin film solar cells. The most significant carnage is demonstration of n-type SnS. In this study, Cl-doped n-type single crystals were grown using SnCl2 self-flux method. The obtained crystal was lamellar, with length and width of a few millimeters and thickness ranging between 28 and 39 µm. X-ray diffraction measurements revealed the single crystals had an orthorhombic unit cell. Since the ionic radii of S2- and Cl- are similar, Cl doping did not result in substantial change in lattice parameter. All the elements were homogeneously distributed on a cleaved surface; the Sn/(S + Cl) ratio was 1.00. The crystal was an n-type degenerate semiconductor with a carrier concentration of ∼3 × 1017 cm-3. Hall mobility at 300 K was 252 cm2 V-1 s-1 and reached 363 cm2 V-1 s-1 at 142 K.

Direct Determination of Atomic Structure and Magnetic Coupling of Magnetite Twin Boundaries.

Clarifying how the atomic structure of interfaces/boundaries in materials affects the magnetic coupling nature across them is of significant academic value and will facilitate the development of state-of-the-art magnetic devices. Here, by combining atomic-resolution transmission electron microscopy, atomistic spin-polarized first-principles calculations, and differential phase contrast imaging, we conduct a systematic investigation of the atomic and electronic structures of individual Fe3O4 twin boundaries (TBs) and determine their concomitant magnetic couplings. We demonstrate that the magnetic coupling across the Fe3O4 TBs can be either antiferromagnetic or ferromagnetic, which directly depends on the TB atomic core structures and resultant electronic structures within a few atomic layers. Revealing the one-to-one correspondence between local atomic structures and magnetic properties of individual grain boundaries will shed light on in-depth understanding of many interesting magnetic behaviors of widely used polycrystalline magnetic materials, which will surely promote the development of advanced magnetic materials and devices.

Atomic-Scale Origin of the Quasi-One-Dimensional Metallic Conductivity in Strontium Niobates with Perovskite-Related Layered Structures.

The quasi-one-dimensional (1D) metallic conductivity of the perovskite-related SrnNbnO3n+2 compounds is of continuing fundamental physical interest as well as being important for developing advanced electronic devices. The SrnNbnO3n+2 compounds can be derived by introducing additional oxygen into the SrNbO3 perovskite. However, the physical origin for the transition of electrical properties from the three-dimensional (3D) isotropic conductivity in SrNbO3 to the quasi-1D metallic conductivity in SrnNbnO3n+2 requires more in-depth clarification. Here we combine advanced transmission electron microscopy with atomistic first-principles calculations to unambiguously determine the atomic and electronic structures of the SrnNbnO3n+2 compounds and reveal the underlying mechanism for their quasi-1D metallic conductivity. We demonstrate that the local electrical conductivity in the SrnNbnO3n+2 compounds directly depends on the configuration of the NbO6 octahedra in local regions. These findings will shed light on the realization of two-dimensional (2D) electrical conductivity from a bulk material, namely by segmenting a 3D conductor into a stack of 2D conducting thin layers.

Mathematical analysis and STEM observations of arrangement of structural units in 〈001〉 symmetrical tilt grain boundaries.

A collaborative work between mathematics and atom-resolved scanning transmission electron microscopy (STEM) has been conducted. The grain boundary in a bicrystal of a simple rock-salt oxide can show a complicated arrangement of structural units, which can be well predicted by an algorithm utilizing the Farey sequence. The estimated arrangements had a nice agreement with those observed by STEM in atomic-scale up to several tens of nanometers.

Interfacial Atomic Structure of Twisted Few-Layer Graphene.

A twist in bi- or few-layer graphene breaks the local symmetry, introducing a number of intriguing physical properties such as opening new bandgaps. Therefore, determining the twisted atomic structure is critical to understanding and controlling the functional properties of graphene. Combining low-angle annular dark-field electron microscopy with image simulations, we directly determine the atomic structure of twisted few-layer graphene in terms of a moiré superstructure which is parameterized by a single twist angle and lattice constant. This method is shown to be a powerful tool for accurately determining the atomic structure of two-dimensional materials such as graphene, even in the presence of experimental errors. Using coincidence-site-lattice and displacement-shift-complete theories, we show that the in-plane translation state between layers is not a significant structure parameter, explaining why the present method is adequate not only for bilayer graphene but also a few-layered twisted graphene.