Search

Electrified solid–liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy1–5, biology6and geochemistry7. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products1–3. Despite its importance, direct probing the atomic dynamics of solid–liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO2electroreduction reactions (CO2ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline–amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

We report an investigation of the pseudo-photocatalytic behavior of rutile TiO2nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a “light” source to initiate the catalytic reaction and a “water-in-salt” aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO2nanorod under a low electron dose rate (9.3–18.6 e-/Å2·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Å2·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO2nanorods is further validated using density functional theory (DFT) calculation. Our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces.

Nb3O7(OH) and Nb2O5nanostructures are promising alternative materials to conventionally used oxides, e.g. TiO2, in the field of photoelectrodes in dye-sensitized solar cells and photoelectrochemical cells. Despite this important future application, some of their central electronic properties such as the density of states, band gap, and dielectric function are not well understood. In this work, we present combined theoretical and experimental studies on Nb3O7(OH) and H–Nb2O5to elucidate their spectroscopic, electronic, and transport properties. The theoretical results were obtained within the framework of density functional theory based on the full potential linearized augmented plane wave method. In particular, we show that the position of the H atom in Nb3O7(OH) has an important effect on its electronic properties. To verify theoretical predictions, we measured electron energy-loss spectra (EELS) in the low loss region, as well as, the O–K and Nb–M3element-specific edges. These results are compared with corresponding theoretical EELS calculations and are discussed in detail. In addition, our calculations of thermoelectric conductivity show that Nb3O7(OH) has more suitable optoelectronic and transport properties for photochemical application than the calcined H–Nb2O5phase.

Coccolithophore algae produce elaborately structured skeletons composed of sub-micrometer-scale calcite crystals. In order to understand calcite crystallization and assembly in a coccosphere with nanoscale resolution, the crystal orientation and interdigitation of the structural units were investigated by transmission electron microscopy imaging, selected-area and nano-probe electron diffraction. Focused ion beam sectioning of coccoliths of the coccolithophore species Emiliania huxleyi is used to obtain target-prepared specimens in suitable orientation. We were able to detect and analyze the V-unit, which is overgrown by the R-unit. For the V-unit the [001] direction points perpendicular to the coccolith plane while the [110] axis is tangential to the coccolith ring. The R-unit c-axis is parallel and the b-axis is perpendicular to the coccolith plane, thus confirming the R- and V-model which was based on scanning electron microscopy and optical microscopy. Furthermore we show that the distal- and the proximal shield element of an individual R-unit of a single segment are tilted by 4° ± 1° with respect to each other. This orientation change is required to obtain the flat domed character of the coccoliths, which is necessary to form the coccosphere. The orientation change between the distal- and the proximal shield element appears continuous.