Lithium-Directed Transformation of Amorphous Iridium (Oxy)hydroxides To Produce Active Water Oxidation Catalysts.

The oxygen evolution reaction (OER) is crucial to future energy systems based on water electrolysis. Iridium oxides are promising catalysts due to their resistance to corrosion under acidic and oxidizing conditions. Highly active iridium (oxy)hydroxides prepared using alkali metal bases transform into low activity rutile IrO2 at elevated temperatures (>350 °C) during catalyst/electrode preparation. Depending on the residual amount of alkali metals, we now show that this transformation can result in either rutile IrO2 or nano-crystalline Li-intercalated IrOx. While the transition to rutile results in poor activity, the Li-intercalated IrOx has comparative activity and improved stability when compared to the highly active amorphous material despite being treated at 500 °C. This highly active nanocrystalline form of lithium iridate could be more resistant to industrial procedures to produce PEM membranes and provide a route to stabilize the high populations of redox active sites of amorphous iridium (oxy)hydroxides.

Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films.

Exploiting the full potential of layered materials for a broad range of applications requires delamination into functional nanosheets. Delamination via repulsive osmotic swelling is driven by thermodynamics and represents the most gentle route to obtain nematic liquid crystals consisting exclusively of single-layer nanosheets. This mechanism was, however, long limited to very few compounds, including 2:1-type clay minerals, layered titanates, or niobates. Despite the great potential of zeolites and their microporous layered counterparts, nanosheet production is challenging and troublesome, and published procedures implied the use of some shearing forces. Here, we present a scalable, eco-friendly, and utter delamination of the microporous layered silicate ilerite into single-layer nanosheets that extends repulsive delamination to the class of layered zeolites. As the sheet diameter is preserved, nematic suspensions with cofacial nanosheets of ≈9000 aspect ratio are obtained that can be cast into oriented films, e.g., for barrier applications.

Imaging electrochemically synthesized Cu2O cubes and their morphological evolution under conditions relevant to CO2 electroreduction.

Copper is a widely studied catalyst material for the electrochemical conversion of carbon dioxide to valuable hydrocarbons. In particular, copper-based nanostructures expressing predominantly {100} facets have shown high selectivity toward ethylene formation, a desired reaction product. However, the stability of such tailored nanostructures under reaction conditions remains poorly understood. Here, using liquid cell transmission electron microscopy, we show the formation of cubic copper oxide particles from copper sulfate solutions during direct electrochemical synthesis and their subsequent morphological evolution in a carbon dioxide-saturated 0.1 M potassium bicarbonate solution under a reductive potential. Shape-selected synthesis of copper oxide cubes was achieved through: (1) the addition of chloride ions and (2) alternating the potentials within a narrow window where the deposited non-cubic particles dissolve, but cubic ones do not. Our results indicate that copper oxide cubes change their morphology rapidly under carbon dioxide electroreduction-relevant conditions, leading to an extensive re-structuring of the working electrode surface.

Al2 Pt for Oxygen Evolution in Water Splitting: A Strategy for Creating Multifunctionality in Electrocatalysis.

The production of hydrogen via water electrolysis is feasible only if effective and stable catalysts for the oxygen evolution reaction (OER) are available. Intermetallic compounds with well-defined crystal and electronic structures as well as particular chemical bonding features are suggested here to act as precursors for new composite materials with attractive catalytic properties. Al2 Pt combines a characteristic inorganic crystal structure (anti-fluorite type) and a strongly polar chemical bonding with the advantage of elemental platinum in terms of stability against dissolution under OER conditions. We describe here the unforeseen performance of a surface nanocomposite architecture resulting from the self-organized transformation of the bulk intermetallic precursor Al2 Pt in OER.

Site specific and localized structural displacements in open structured multimetallic oxides.

The structures of solids can locally differ from the macroscopic picture obtained by structural averaging techniques. This difference significantly influences the performance of any functional material. Measurements of these local structures are challenging. Thus, the description of defects is often disregarded. However, in order to understand the functionality, such irregularities have to be investigated. Here, we present a high resolution scanning transmission electron microscopic (STEM) study revealing local structural irregularities in open structured oxides using catalytically active orthorhombic (Mo,V,Te,Nb)Ox as a complex example. Detailed analysis of annular dark field- and annular bright field-STEM images reveal site specific local structural displacements of individual framework and channel sites in the picometer range. These experimental observables can be considered as an important structural addendum for theoretical modelling and should be implemented into the existing data in order to quantify site specific potential energies and stresses. This information can further be used to describe the impact of the structure on the catalytic performance in greater detail.

Scalable Production of Nanographene and Doping via Nondestructive Covalent Functionalization.

A new method for top-down, one-pot, gram-scale production of high quality nanographene by incubating graphite in a dilute sodium hypochlorite solution at only 40 °C is reported here. The produced sheets have only 4 at% oxygen content, comparable with nanographene grown by chemical vapor deposition. The nanographene sheets are covalently functionalized using a nondestructive nitrene [2+1] cycloaddition reaction that preserves their π-conjugated system. Statistical analyses of Raman spectroscopy and X-ray photoelectron spectroscopy indicate a low number of sp3 carbon atoms on the order of 2% before and 4% after covalent functionalization. The nanographene sheets are significantly more conductive than conventionally prepared nanographene oxide, and conductivity further increases after covalent functionalization. The observed doping effects and theoretical studies suggest sp2 hybridization for the carbon atoms involved in the [2+1] cycloaddition reaction leading to preservation of the π-conjugated system and enhancing conductivity via n-type doping through the bridging N-atom. These methods are easily scalable, which opens the door to a mild and efficient process to produce high quality nanographenes and covalently functionalize them while retaining or improving their physicochemical properties.

Ni Single Atom Catalysts for CO2 Activation.

We report on the activation of CO2 on Ni single-atom catalysts. These catalysts were synthesized using a solid solution approach by controlled substitution of 1-10 atom % of Mg2+ by Ni2+ inside the MgO structure. The Ni atoms are preferentially located on the surface of the MgO and, as predicted by hybrid-functional calculations, favor low-coordinated sites. The isolated Ni atoms are active for CO2 conversion through the reverse water-gas shift (rWGS) but are unable to conduct its further hydrogenation to CH4 (or MeOH), for which Ni clusters are needed. The CO formation rates correlate linearly with the concentration of Ni on the surface evidenced by XPS and microcalorimetry. The calculations show that the substitution of Mg atoms by Ni atoms on the surface of the oxide structure reduces the strength of the CO2 binding at low-coordinated sites and also promotes H2 dissociation. Astonishingly, the single-atom catalysts stayed stable over 100 h on stream, after which no clusters or particle formation could be detected. Upon catalysis, a surface carbonate adsorbate-layer was formed, of which the decompositions appear to be directly linked to the aggregation of Ni. This study on atomically dispersed Ni species brings new fundamental understanding of Ni active sites for reactions involving CO2 and clearly evidence the limits of single-atom catalysis for complex reactions.

A quasi in situ TEM grid reactor for decoupling catalytic gas phase reactions and analysis.

We present a versatile grid reactor setup for transmission electron microscopy (TEM), which is able to track catalytic conversion on TEM amounts of sample. It is based on the concept of decoupling catalytic gas-phase reactions from the structural analysis of identical particles before and after reaction. The system has superior properties in terms of image resolution and long-term measurements compared to conventional in situ TEM analysis. Monitoring catalytic conversions on a TEM grid is enabled by proton-transfer reaction mass spectrometry. In addition, identical location imaging benefits from a secure transfer of the sample between TEM and the reactor system by vacuum transfer holders. Using Pt and Cu/ZnO/Al2O3 as an example we show that structural changes of identical particles or areas of a Pt foil before and after reactive experiments can be tracked. During catalytic testing the samples are exposed to homogeneous reaction conditions. The concept minimizes electron-sample and electron-atmosphere interactions and can prospectively be considered as complementary tool to in situ TEM analysis.

Reactive Electrophilic OI- Species Evidenced in High-Performance Iridium Oxohydroxide Water Oxidation Electrocatalysts.

Although quasi-amorphous iridium oxohydroxides have been identified repeatedly as superior electrocatalysts for the oxygen evolution reaction (OER), an exact description of the performance-relevant species has remained a challenge. In this context, we report the characterization of hydrothermally prepared iridium(III/IV) oxohydroxides that exhibit exceptional OER performances. Holes in the O 2p states of the iridium(III/IV) oxohydroxides result in reactive OI- species, which are identified by characteristic near-edge X-ray absorption fine structure (NEXAFS) features. A prototypical titration reaction with CO as a probe molecule shows that these OI- species are highly susceptible to nucleophilic attack at room temperature. Similarly to the preactivated oxygen involved in the biological OER in photosystem II, the electrophilic OI- species evidenced in the iridium(III/IV) oxohydroxides are suggested to be precursors to species involved in the O-O bond formation during the electrocatalytic OER. The CO titration also highlights a link between the OER performance and the surface/subsurface mobility of the OI- species. Thus, the superior electrocatalytic properties of the iridium (III/IV) oxohydroxides are explained by their ability to accommodate preactivated electrophilic OI- species that can migrate within the lattice.

Implantation and atomic-scale investigation of self-interstitials in graphene.

Crystallographic defects play a key role in determining the properties of crystalline materials. The new class of two-dimensional materials, foremost graphene, have enabled atomically resolved studies of defects, such as vacancies,1-4 grain boundaries,(5-7) dislocations,(8,9) and foreign atom substitutions.(10-14) However, atomic resolution imaging of implanted self-interstitials has so far been reported neither in any three-dimensional nor in any two-dimensional material. Here, we deposit extra carbon into single-layer graphene at soft landing energies of ∼ 1 eV using a standard carbon coater. We identify all the self-interstitial dimer structures theoretically predicted earlier,(15-17) employing 80 kV aberration-corrected high-resolution transmission electron microscopy. We demonstrate accumulation of the interstitials into larger aggregates and dislocation dipoles, which we predict to have strong local curvature by atomistic modeling, and to be energetically favorable configurations as compared to isolated interstitial dimers. Our results contribute to the basic knowledge on crystallographic defects and lay out a pathway into engineering the properties of graphene by pushing the crystal into a state of metastable supersaturation.

Experimental observation of boron nitride chains.

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions.

Triazine-based graphitic carbon nitride: a two-dimensional semiconductor.

Graphitic carbon nitride has been predicted to be structurally analogous to carbon-only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine-based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two-dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long-range, in-plane order, while optical spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field-effect transistors and light-emitting diodes.

A quantum dot photoswitch for DNA detection, gene transfection, and live-cell imaging.

Quantum dots (QDs) coated with an albumin-derived copolymer shell exhibit significant photoresponsiveness to DNA loading and have great potential for investigating gene delivery processes. The QDs reported herein are positively charged, have attractive optical properties, and are noncytotoxic and notably stable in live cells. Their complex formation with plasmid DNA leads to proportionally decreased photoluminescence and efficient gene transfection is observed. Therefore, they are suitable for live-cell bioimaging and mechanistic studies of nonviral gene delivery. Fluorescence correlation spectroscopy is applied for the first time to investigate individual QDs diffusing in large endosomes inside living cells, and serves as a valuable tool to study the physical properties of QDs inside live cells. The data obtained in this study strongly support the notable stability of these QDs, even in cell endosomes.

Experimental analysis of charge redistribution due to chemical bonding by high-resolution transmission electron microscopy.

The electronic charge density distribution or the electrostatic atomic potential of a solid or molecule contains information not only on the atomic structure, but also on the electronic properties, such as the nature of the chemical bonds or the degree of ionization of atoms. However, the redistribution of charge due to chemical bonding is small compared with the total charge density, and therefore difficult to measure. Here, we demonstrate an experimental analysis of charge redistribution due to chemical bonding by means of high-resolution transmission electron microscopy (HRTEM). We analyse charge transfer on the single-atom level for nitrogen-substitution point defects in graphene, and confirm the ionicity of single-layer hexagonal boron nitride. Our combination of HRTEM experiments and first-principles electronic structure calculations opens a new way to investigate electronic configurations of point defects, other non-periodic arrangements or nanoscale objects that cannot be studied by an electron or X-ray diffraction analysis.

Selective sputtering and atomic resolution imaging of atomically thin boron nitride membranes.

We report on the preparation, atomic resolution imaging, and element selective damage mechanism in atomically thin boron nitride membranes. Flakes of less than 10 layers are prepared by mechanical cleavage and are thinned down to single layers in a high-energy electron beam. At our beam energies, we observe a highly selective sputtering of only one of the elements and predominantly at the exit surface of the specimen, and then subsequent removal of atoms next to a defect. Triangle-shaped holes appear in accordance with the crystallographic orientation of each layer. Defects are compared to those observed in graphene membranes. The observation of clean single-layer membranes shows that hexagonal boron nitride is a further material (in addition to graphene) that can exist in a quasi-two-dimensional allotrope without the need for a substrate.