Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry.

Correlative methods to characterize single entities by electrochemistry and microscopy/spectroscopy are increasingly needed to elucidate structure-function relationships of nanomaterials. However, the technical constraints often differ depending on the characterization techniques to be applied in combination. One of the cornerstones of correlative single-entity electrochemistry (SEE) is the substrate, which needs to achieve a high conductivity, low roughness, and electrochemical inertness. This work shows that graphitized sputtered carbon thin films constitute excellent electrodes for SEE while enabling characterization with scanning probe, optical, electron, and X-ray microscopies. Three different correlative SEE experiments using nanoparticles, nanocubes, and 2D Ti3C2Tx MXene materials are reported to illustrate the potential of using carbon thin film substrates for SEE characterization. The advantages and unique capabilities of SEE correlative strategies are further demonstrated by showing that electrochemically oxidized Ti3C2Tx MXene display changes in chemical bonding and electrolyte ion distribution.

Porous N-doped carbon-encapsulated iron as a novel catalyst architecture for the electrocatalytic hydrogenation of benzaldehyde.

Carbon porous materials containing nitrogen functionalities and encapsulated iron-based active sites have been suggested as electrocatalysts for energy conversion, however their applications to the hydrogenation of organic substrates via electrocatalytic hydrogenation (ECH) remain unexplored. Herein, we report on a Fe@C:N material synthesized with an adapted annealing procedure and tested as electrocatalyst for the hydrogenation of benzaldehyde. Using different concentrations of the organic, and electrolysis coupled to gas chromatography experiments, we demonstrate that it is possible to use such architectures for the ECH of unsaturated organics. Potential control experiments show that ECH faradaic efficiencies >70% are possible in acid electrolytes, while maintaining selectivity for the alcohol over the pinacol dimerization product. Estimates of product formation rates and turnover frequency (TOF) values suggest that these carbon-encapsulated architectures can achieve competitive performance in acid electrolytes relative to both base and precious metal electrodes.

Enhanced photoinduced mass migration in supramolecular azopolymers by H-bond driven positional constraint.

Here we investigated the role of hydrogen bonding in the design of supramolecular azopolymers with a highly directional and constrained azobenzene-chain interaction involving the aromatic ring of the photoactive molecule, by exploiting the 2-aminopyrimidine/carboxylic acid supramolecular synthon as the tool for molecular recognition. We have shown that this approach is advantageous for producing affordable and versatile photopatternable azomaterials by complexation with polyacrylic acid (PAA). Molecular model complexes were successfully prepared and characterized by X-ray diffraction analysis and FTIR spectroscopy to reveal the multiple, non-ionic interaction occurring between the azobenzene units and the polymer chains. Surface photopatterning of thin films, driven by the typical mass migration phenomenon occurring in azopolymers, resulted strongly enhanced with increasing azobenzene content until equimolar composition. Results show that polymers with synthon-based azobenzenes markedly outperform single H-bonded systems bearing azomolecules with similar structure and electronic properties. We finally demonstrated that the azobenzene units can be easily extracted from a photopatterned film by a simple solvent rinse and without any chemical pre-treatment, leaving the periodicity of the inscribed surface relief gratings unaltered. This result was enabled by the orthogonal solubility of the components in the supramolecular system.