Rational design of an acceptor-chromophore-relay-catalyst tetrad assembly for water oxidation.

We report the step-by-step synthesis of a precious metal-free acceptor-chromophore-relay-catalyst tetrad assembly that exhibits a turnover frequency (TOF) of 7.5 × 10-3 s-1 under neutral conditions. Transient absorption spectroscopic studies indicate that upon fullerenol incorporation into the investigated complexes, charge separation efficiency increases considerably.

Production of demineralised high quality hierarchical activated carbon from lignite and determination of adsorption performance using methylene blue and p-nitrophenol: The role of surface functionality, accessible pore size and surface area.

In the adsorption process, the surface area, pore and particle size distribution and the chemical structure of the solid and the type of adsorbent are of vital importance. Activated carbon (AC) is a very good adsorbent material and its cost is highly dependent on the starting material and production method. The pore size and functional structure of the surface depend on the amount of activation chemical used. Hierarchical ACs were produced from lignite by loading two different amounts of KOH. The impregnation ratio (KOH/lignite) was chosen as 1/1 and 3/1 and the produced ACs were labelled as AC1 and AC3. The surface areas of AC1 and AC3 were determined as 1321.3 and 2421.3 m2/g, and the total pore volumes were 1.079 and 1.425 cm3/g. Methylene blue (MB) and p-nitrophenol (p-NP) were used to determine the adsorption performance of the produced ACs. The adsorption data were evaluated in terms of the Langmuir and Freundlich models. The amounts of MB and p-NP adsorbed on the surface were calculated in mg/g, total and accessible surface area in mg/m2. It was determined that the MB and p-NP adsorbed to the AC1 sample were higher than the AC3 sample per m2 of population. Molecular orientation is possible depending on the solid surface functionality and chemical structure of the molecule to be adsorbed. It was concluded that in addition to the large surface area, the pore width that can be entered and the functional structure of the surface are very significant factors in the adsorption processes.

Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis.

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co-Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm-2 ), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.

A Dormant Reagent Reaction-Diffusion Method for the Generation of Co-Fe Prussian Blue Analogue Periodic Precipitate Particle Libraries.

Liesegang patterns that develop as a result of reaction-diffusion can simultaneously form products with slightly different sizes spatially separated in a single medium. We show here a reaction-diffusion method using a dormant reagent (citrate) for developing Liesegang patterns of cobalt hexacyanoferrate Prussian Blue analog (PBA) particle libraries. This method slows the precipitation reaction and produces different-sized particles in a gel medium at different locations. The gel-embedded particles are still catalytically active. Finally, the applicability of the new method to other PBAs and 2D systems is presented. The method proves promising for obtaining similar inorganic framework libraries with catalytic abilities.

"Plug and Play" Photosensitizer-Catalyst Dyads for Water Oxidation.

We present a simple and easy-to-scale synthetic method to plug common organic photosensitizers into a cyanide-based network structure for the development of photosensitizer-water oxidation catalyst (PS-WOC) dyad assemblies for the photocatalytic water oxidation process. Three photosensitizers, one of which absorbs red light similar to P680 in photosystem II, were utilized to harvest different regions of the solar spectrum. Photosensitizers are covalently coordinated to CoFe Prussian blue structures to prepare PS-WOC dyads. All dyads exhibit steady water oxidation catalytic activities throughout a 6 h photocatalytic experiment. Our results demonstrate that the covalent coordination between the PS and WOC group not only enhances the photocatalytic activity but also improves the robustness of the organic PS group. The photocatalytic activity of "plug and play" dyads relies on several structural and electronic parameters, including the position of the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the PS with respect to the HOMO level of the catalytic site, the intensity and wavelength of the absorption band of the PS, and the number of catalytic sites.

Electrodeposited cobalt hexacyanoferrate electrode as a non-enzymatic glucose sensor under neutral conditions.

A CoFe Prussian blue analogue (CoFe PB) modified FTO electrode, prepared via a facile electrodeposition method, is investigated as a non-enzymatic glucose sensor under neutral conditions. The electrode exhibits a linear detection of glucose in the 0.1-8.2 mmol/L range with a detection limit of 67 µM, a sensitivity of 18.69 µA/mM.cm2, and a fast response time of less than 7 s under neutral conditions. Its stability is confirmed with both electrochemical experiments and characterization studies performed on the pristine and post-mortem electrode. We also conducted a comprehensive electrochemical analysis to elucidate the identity of the active site and the glucose oxidation mechanism on the Prussian blue surface.