Role of Fe decoration on the oxygen evolving state of Co3O4 nanocatalysts.

The production of green hydrogen through alkaline water electrolysis is the key technology for the future carbon-neutral industry. Nanocrystalline Co3O4 catalysts are highly promising electrocatalysts for the oxygen evolution reaction and their activity strongly benefits from Fe surface decoration. However, limited knowledge of decisive catalyst motifs at the atomic level during oxygen evolution prevents their knowledge-driven optimization. Here, we employ a variety of operando spectroscopic methods to unveil how Fe decoration increases the catalytic activity of Co3O4 nanocatalysts as well as steer the (near-surface) active state formation. Our study shows a link of the termination-dependent Fe decoration to the activity enhancement and a significantly stronger Co3O4 near-surface (structural) adaptation under the reaction conditions. The near-surface Fe- and Co-O species accumulate an oxidative charge and undergo a reversible bond contraction during the catalytic process. Moreover, our work demonstrates the importance of low coordination surface sites on the Co3O4 host to ensure an efficient Fe-induced activity enhancement, providing another puzzle piece to facilitate optimized catalyst design.

Highly loaded bimetallic iron-cobalt catalysts for hydrogen release from ammonia.

Ammonia is a storage molecule for hydrogen, which can be released by catalytic decomposition. Inexpensive iron catalysts suffer from a low activity due to a too strong iron-nitrogen binding energy compared to more active metals such as ruthenium. Here, we show that this limitation can be overcome by combining iron with cobalt resulting in a Fe-Co bimetallic catalyst. Theoretical calculations confirm a lower metal-nitrogen binding energy for the bimetallic catalyst resulting in higher activity. Operando spectroscopy reveals that the role of cobalt in the bimetallic catalyst is to suppress the bulk-nitridation of iron and to stabilize this active state. Such catalysts are obtained from Mg(Fe,Co)2O4 spinel pre-catalysts with variable Fe:Co ratios by facile co-precipitation, calcination and reduction. The resulting Fe-Co/MgO catalysts, characterized by an extraordinary high metal loading reaching 74 wt.%, combine the advantages of a ruthenium-like electronic structure with a bulk catalyst-like microstructure typical for base metal catalysts.

Role of Nanoscale Inhomogeneities in Co2FeO4 Catalysts during the Oxygen Evolution Reaction.

Spinel-type catalysts are promising anode materials for the alkaline oxygen evolution reaction (OER), exhibiting low overpotentials and providing long-term stability. In this study, we compared two structurally equal Co2FeO4 spinels with nominally identical stoichiometry and substantially different OER activities. In particular, one of the samples, characterized by a metastable precatalyst state, was found to quickly achieve its steady-state optimum operation, while the other, which was initially closer to the ideal crystallographic spinel structure, never reached such a state and required 168 mV higher potential to achieve 1 mA/cm2. In addition, the enhanced OER activity was accompanied by a larger resistance to corrosion. More specifically, using various ex situ, quasi in situ, and operando methods, we could identify a correlation between the catalytic activity and compositional inhomogeneities resulting in an X-ray amorphous Co2+-rich minority phase linking the crystalline spinel domains in the as-prepared state. Operando X-ray absorption spectroscopy revealed that these Co2+-rich domains transform during OER to structurally different Co3+-rich domains. These domains appear to be crucial for enhancing OER kinetics while exhibiting distinctly different redox properties. Our work emphasizes the necessity of the operando methodology to gain fundamental insight into the activity-determining properties of OER catalysts and presents a promising catalyst concept in which a stable, crystalline structure hosts the disordered and active catalyst phase.

Isolated Pd atoms in a silver matrix: Spectroscopic and chemical properties.

Over the past decade, single-atom alloys (SAAs) have been a lively topic of research due to their potential for achieving novel catalytic properties and circumventing some known limitations of heterogeneous catalysts, such as scaling relationships. In researching SAAs, it is important to recognize experimental evidence of peculiarities in their electronic structure. When an isolated atom is embedded in a matrix of foreign atoms, it exhibits spectroscopic signatures that reflect its surrounding chemical environment. In the present work, using photoemission spectroscopy and computational chemistry, we discuss the experimental evidence from Ag0.98Pd0.02 SAAs that show free-atom-like characteristics in their electronic structure. In particular, the broad Pd4d valence band states of the bulk Pd metal become a narrow band in the alloy. The measured photoemission spectra were compared with the calculated photoemission signal of a free Pd atom in the gas phase with very good agreement, suggesting that the Pd4d states in the alloy exhibit very weak hybridization with their surroundings and are therefore electronically isolated. Since AgPd alloys are known for their superior performance in the industrially relevant semi-hydrogenation of acetylene, we considered whether it is worthwhile to drive the dilution of Pd in the inert Ag host to the single-atom level. We conclude that although site-isolation provides beneficial electronic structure changes to the Pd centers due to the difficulty in activating H2 on Ag, utilizing such SAAs in acetylene semi-hydrogenation would require either a higher Pd concentration to bring isolated sites sufficiently close together or an H2-activating support.

Fundamental Limit of Plasmonic Cathodoluminescence.

We use cathodoluminescence (CL) spectroscopy in a transmission electron microscope to probe the radial breathing mode of plasmonic silver nanodisks. A two-mirror detection system sandwiching the sample collects the CL emission in both directions, that is, backward and forward with respect to the electron beam trajectory. We unambiguously identify a spectral shift of about 8 nm in the CL spectra acquired from both sides and show that this asymmetry is induced by the electron beam itself. By numerical simulations, we confirm the observations and identify the underlying physical effect due to the interference of the CL emission patterns of an electron-beam-induced dipole and the breathing mode. This effect can ultimately limit the achievable fidelity in CL measurements on any system involving multiple excitations and should therefore be considered with care in high-precision experiments.

Tailored Nanoscale Plasmon-Enhanced Vibrational Electron Spectroscopy.

Atomic vibrations and phonons are an excellent source of information on nanomaterials that we can access through a variety of methods including Raman scattering, infrared spectroscopy, and electron energy-loss spectroscopy (EELS). In the presence of a plasmon local field, vibrations are strongly modified and, in particular, their dipolar strengths are highly enhanced, thus rendering Raman scattering and infrared spectroscopy extremely sensitive techniques. Here, we experimentally demonstrate that the interaction between a relativistic electron and vibrational modes in nanostructures is fundamentally modified in the presence of plasmons. We finely tune the energy of surface plasmons in metallic nanowires in the vicinity of hexagonal boron nitride, making it possible to monitor and disentangle both strong phonon-plasmon coupling and plasmon-driven phonon enhancement at the nanometer scale. Because of the near-field character of the electron beam-phonon interaction, optically inactive phonon modes are also observed. Besides increasing our understanding of phonon physics, our results hold great potential for investigating sensing mechanisms and chemistry in complex nanomaterials down to the molecular level.

How Dark Are Radial Breathing Modes in Plasmonic Nanodisks?

Due to a vanishing dipole moment, radial breathing modes in small flat plasmonic nanoparticles do not couple to light and have to be probed with a near-field source, as in electron energy loss spectroscopy (EELS). With increasing particle size, retardation gives rise to light coupling, enabling probing breathing modes optically or by cathodoluminescence (CL). Here, we investigate single silver nanodisks with diameters of 150-500 nm by EELS and CL in an electron microscope and quantify the EELS/CL ratio, which corresponds to the ratio of full to radiative damping of the breathing mode. For the investigated diameter range, we find the CL signal to increase by about 1 order of magnitude, in agreement with numerical simulations. Due to reciprocity, our findings corroborate former optical experiments and enable a quantitative understanding of the light coupling of dark plasmonic modes.

3D Imaging of Gap Plasmons in Vertically Coupled Nanoparticles by EELS Tomography.

Plasmonic gap modes provide the ultimate confinement of optical fields. Demanding high spatial resolution, the direct imaging of these modes was only recently achieved by electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). However, conventional 2D STEM-EELS is only sensitive to components of the photonic local density of states (LDOS) parallel to the electron trajectory. It is thus insensitive to specific gap modes, a restriction that was lifted with the introduction of tomographic 3D EELS imaging. Here, we show that by 3D EELS tomography the gap mode LDOS of a vertically stacked nanotriangle dimer can be fully imaged. Besides probing the complete mode spectrum, we demonstrate that the tomographic approach allows disentangling the signal contributions from the two nanotriangles that superimpose in a single measurement with a fixed electron trajectory. Generally, vertically coupled nanoparticles enable the tailoring of 3D plasmonic fields, and their full characterization will thus aid the development of complex nanophotonic devices.

Tomographic imaging of the photonic environment of plasmonic nanoparticles.

The photonic local density of states (LDOS) governs the enhancement of light-matter interaction at the nanoscale, but despite its importance for nanophotonics and plasmonics experimental local density of states imaging remains extremely challenging. Here we introduce a tomography scheme based on electron microscopy that allows retrieval of the three-dimensional local density of states of plasmonic nanoparticles with nanometre spatial and sub-eV energy resolution. From conventional electron tomography experiments we obtain the three-dimensional morphology of the nanostructure, and use this information to compute an expansion basis for the photonic environment. The expansion coefficients are obtained through solution of an inverse problem using as input electron-energy loss spectroscopy images. We demonstrate the applicability of our scheme for silver nanocuboids and coupled nanodisks, and resolve local density of states enhancements with extreme sub-wavelength dimensions in hot spots located at roughness features or in gaps of coupled nanoparticles.Imaging the photonic local density of states of plasmonic nanoparticles remains extremely challenging. Here, the authors introduce a tomography scheme based on electron microscopy that allows retrieval of the three-dimensional local density of states with nanometre spatial and sub-eV energy resolution.

Direct-Write 3D Nanoprinting of Plasmonic Structures.

During the past decade, significant progress has been made in the field of resonant optics ranging from fundamental aspects to concrete applications. While several techniques have been introduced for the fabrication of highly defined metallic nanostructures, the synthesis of complex, free-standing three-dimensional (3D) structures is still an intriguing, but so far intractable, challenge. In this study, we demonstrate a 3D direct-write synthesis approach that addresses this challenge. Specifically, we succeeded in the direct-write fabrication of 3D nanoarchitectures via electron-stimulated reactions, which are applicable on virtually any material and surface morphology. By that, complex 3D nanostructures composed of highly compact, pure gold can be fabricated, which reveal strong plasmonic activity and pave the way for a new generation of 3D nanoplasmonic architectures that can be printed on-demand.

Spectrum image analysis tool - A flexible MATLAB solution to analyze EEL and CL spectrum images.

Spectrum imaging techniques, gaining simultaneously structural (image) and spectroscopic data, require appropriate and careful processing to extract information of the dataset. In this article we introduce a MATLAB based software that uses three dimensional data (EEL/CL spectrum image in dm3 format (Gatan Inc.'s DigitalMicrograph®)) as input. A graphical user interface enables a fast and easy mapping of spectral dependent images and position dependent spectra. First, data processing such as background subtraction, deconvolution and denoising, second, multiple display options including an EEL/CL moviemaker and, third, the applicability on a large amount of data sets with a small work load makes this program an interesting tool to visualize otherwise hidden details.

Edge Mode Coupling within a Plasmonic Nanoparticle.

The coupling of plasmonic nanoparticles can strongly modify their optical properties. Here, we show that the coupling of the edges within a single rectangular particle leads to mode splitting and the formation of bonding and antibonding edge modes. We are able to unambiguously designate the modes due to the high spatial resolution of electron microscopy-based electron energy loss spectroscopy and the comparison with numerical simulations. Our results provide simple guidelines for the interpretation and the design of plasmonic mode spectra.

Plasmon modes of a silver thin film taper probed with STEM-EELS.

By focusing propagating surface plasmons, electromagnetic energy can be delivered to nanoscale volumes. In this context, we employ electron energy loss spectroscopy in a scanning transmission electron microscope to characterize the full plasmonic mode spectrum of a silver thin film tapered to a sharp tip. We show that the plasmon modes can be ordered in film and edge modes and corroborate our assignment through supplementary numerical simulations. In particular, we find that the focused plasmon field at the taper tip is fueled by edge modes.

Universal dispersion of surface plasmons in flat nanostructures.

Dimensionality has a significant impact on the optical properties of solid-state nanostructures. For example, dimensionality-dependent carrier confinement in semiconductors leads to the formation of quantum wells, quantum wires and quantum dots. While semiconductor properties are governed by excitonic effects, the optical response of metal nanostructures is dominated by surface plasmons. Here we find that, in contrast to excitonic systems, the mode dispersions in plasmonic structures of different dimensionality are related by simple scaling rules. Employing electron energy loss spectroscopy, we show that the modes of silver nanodisks can be scaled to the surface and edge modes of extended silver thin films. We thereby introduce a general and intuitive ordering scheme for plasmonic excitations with edge and surface modes as the elementary building blocks.

Dark plasmonic breathing modes in silver nanodisks.

We map the complete plasmonic spectrum of silver nanodisks by electron energy loss spectroscopy and show that the mode which couples strongest to the electron beam has radial symmetry with no net dipole moment. Therefore, this mode does not couple to light and has escaped from observation in optical experiments. This radial breathing mode has the character of an extended two-dimensional surface plasmon with a wavenumber determined by the circular disk confinement. Its strong near fields can impact the hybridization in coupled plasmonic nanoparticles as well as couplings with nearby quantum emitters.