Sergey Pronkin

Merging Single-Atom-Dispersed Silver and Carbon Nitride to a Joint Electronic System via Copolymerization with Silver Tricyanomethanide

Herein, we present an approach to create a hybrid between single-atom-dispersed silver and a carbon nitride polymer. Silver tricyanomethanide (AgTCM) is used as a reactive comonomer during templated carbon nitride synthesis to introduce both negative charges and silver atoms/ions to the system. The successful introduction of the extra electron density under the formation of a delocalized joint electronic system is proven by photoluminescence measurements, X-ray photoelectron spectroscopy investigations, and measurements of surface ζ-potential. At the same time, the principal structure of the carbon nitride network is not disturbed, as shown by solid-state nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy analysis. The synthesis also results in an improvement of the visible light absorption and the development of higher surface area in the final products. The atom-dispersed AgTCM-doped carbon nitride shows an enhanced performance in the selective hydrogenation of alkynes in comparison with the performance of other conventional Ag-based materials prepared by spray deposition and impregnation-reduction methods, here exemplified with 1-hexyne.

One step synthesis of niobium doped titania nanotube arrays to form (N,Nb) co-doped TiO2 with high visible light photoelectrochemical activity

The chemical modification of aligned titanium dioxide nanotube (TiO2-NT) arrays provides new doping possibilities to improve their photoelectrochemical activity under visible light. Niobium doped TiO2-NTs containing up to 15% of Nb in the near-surface region are prepared by a flexible single step procedure using a fluoroniobate complex simultaneously acting as a source of the doping element and fluoride anions required for nanotube formation. This negatively charged complex allows an efficient insertion of Nb in the forming TiO2-NT structure during the anodization process. These nanotube arrays are further modified with nitrogen to achieve (Nb,N) co-doped nanotubes with noticeable visible light photoelectrochemical activity.

Hybrid layer-by-layer composites based on a conducting polyelectrolyte and Fe3O4 nanostructures grafted onto graphene for supercapacitor application

Using the layer-by-layer process, we developed a new and original ternary hybrid material based on magnetite iron oxide raspberry nanostructures, 250–300 nm in size, synthesized directly on few layer graphene (Fe3O4@FLG) alternated with conducting poly(3,4-ethylenedioxy thiophene):poly(styrene sulfonate) (PEDOT:PSS) as the electrode material for supercapacitors. Magnetite based nanostructures were used as electroactive materials. Graphene and PEDOT:PSS ensured the electrical conductivity. PEDOT:PSS also plays the role of a binder conferring cohesion to the hybrid material. Using spin-coating, the step-by-step buildup leads to very regular and well controlled film properties such as the film thickness and the content of iron oxide. The electrochemical properties of the so-obtained hybrid material were investigated in 0.5 M Na2SO3 aqueous electrolyte by cyclic voltammetry, electrochemical impedance spectroscopy and chronopotentiometry. In contradiction with the reported poor capacitance and poor cycling stability of iron oxide based supercapacitors, hybrid Fe3O4@FLG/PEDOT:PSS multilayers provide a high specific capacitance (153 F g−1 at 0.1 A g−1) and a high structural and cycling stability (114% retention after 3500 cycles). This hybrid developed system opens the route for even higher specific capacitance using other types of metal oxides.

Potassium Poly(heptazine imides) from Aminotetrazoles: Shifting Band Gaps of Carbon Nitride‐like Materials by 0.7 V for More Efficient Solar Hydrogen and Oxygen Evolution

Potassium poly(heptazine imide) (PHI) is a photocatalytically active carbon nitride material that was recently prepared from substituted 1,2,4‐triazoles. Here, we show that the more acidic precursors, such as commercially available 5‐aminotetrazole, upon pyrolysis in LiCl/KCl salt melt yield PHI with the greatly improved structural order and thermodynamic stability. Tetrazole‐derived PHIs feature long‐range crystallinities and unconventionally small layer stacking distances, leading to the altered electronic band structures as shown by Mott–Schottky analyses. Under the optimized synthesis conditions, visible‐light driven hydrogen evolution rates reach twice the rate provided by the previous gold standard, mesoporous graphitic carbon nitride, which has a much higher surface area. More interestingly, the up to 0.7 V higher valence band potential of crystalline PHI compared with ordinary carbon nitrides makes it an efficient water oxidation photocatalyst, which works even in the absence of any metal‐based co‐catalysts under visible light. To our knowledge, this is the first case of metal‐free oxygen liberation from water.

“The Easier the Better” Preparation of Efficient Photocatalysts—Metastable Poly(heptazine imide) Salts

Cost-efficient, visible-light-driven hydrogen production from water is an attractive potential source of clean, sustainable fuel. Here, it is shown that thermal solid state reactions of traditional carbon nitride precursors (cyanamide, melamine) with NaCl, KCl, or CsCl are a cheap and straightforward way to prepare poly(heptazine imide) alkali metal salts, whose thermodynamic stability decreases upon the increase of the metal atom size. The chemical structure of the prepared salts is confirmed by the results of X-ray photoelectron and infrared spectroscopies, powder X-ray diffraction and electron microscopy studies, and, in the case of sodium poly(heptazine imide), additionally by atomic pair distribution function analysis and 2D powder X-ray diffraction pattern simulations. In contrast, reactions with LiCl yield thermodynamically stable poly(triazine imides). Owing to the metastability and high structural order, the obtained heptazine imide salts are found to be highly active photocatalysts in Rhodamine B and 4-chlorophenol degradation, and Pt-assisted sacrificial water reduction reactions under visible light irradiation. The measured hydrogen evolution rates are up to four times higher than those provided by a benchmark photocatalyst, mesoporous graphitic carbon nitride. Moreover, the products are able to photocatalytically reduce water with considerable reaction rates, even when glycerol is used as a sacrificial hole scavenger.

Synthesis of an electronically modified carbon nitride from a processable semiconductor, 3-amino-1,2,4-triazole oligomer, via a topotactic-like phase transition

A thermally induced topotactic transformation of organic polymeric semiconductors is achieved using similarity of the chemical structures of two C,N,H-containing materials. Namely, the oligomer of 3-amino-1,2,4-triazole (OATA) is transformed into an electronically modified graphitic carbon nitride (OATA-CN) upon heating at 550 °C. During the transition, the flat band potential of the organic semiconductor is only slightly shifted from −0.11 eV to −0.06 eV, while the optical band gap is significantly expanded from 1.8 eV to 2.2 eV. The advantage of the suggested approach is the processability of the starting semiconductor combined with minor morphology changes during the heat-treatment that enable preservation of the original oligomer micro- and macrostructures in the resulting carbon nitrides. As an illustration, different OATA morphologies, including spherical nanoparticles, nanobarrels, nanowires and self-assembled macrospheres and composite sheets are synthesized and then transformed into OATA-CN with the retention of morphology. The surface area of the final carbon nitrides reaches 66 m2 g−1, without using any template, auxiliary reagent or post treatment. As a consequence, the photocatalytic activity of the obtained carbon nitrides in visible light driven hydrogen evolution is up to 5 times higher than that measured for the reference bulk carbon nitride prepared by pyrolysis of melamine.

Exploring the Influence of the Nickel Oxide Species on the Kinetics of Hydrogen Electrode Reactions in Alkaline Media

The influence of the oxidation of Ni electrodes on the kinetics of the hydrogen oxidation (HOR) and evolution reactions (HER) has been explored by combining an experimental cyclic voltammetry study, microkinetic modeling and X-ray photoelectron spectroscopic analysis. Almost 10 times enhancement of the activity of Ni in the HOR/HER has been observed after its oxidation under the contact with air at ambient conditions and assigned to the presence of NiO species on the surface of metallic Ni. The experimental cyclic voltammetry curves have been analyzed with the help of kinetic model in order to shed light on the mechanism of the HOR/HER for two types of Ni electrodes and its dependence on the presence of NiO on the surface of the electrode. The main features of the experimental current-potential curves can be reproduced with a kinetic model assuming that the free energy of the adsorbed hydrogen intermediate is increased and that the kinetics of the Volmer step is enhanced in the presence of nickel oxide species. The kinetic model provides evidence for the switching from the Heyrovsky–Volmer mechanism on metallic Ni to Tafel–Volmer mechanism on the activated electrode, where surface oxide species co-exist with metal Ni sites.Graphical Abstract

Towards Organic Zeolites and Inclusion Catalysts: Heptazine Imide Salts Can Exchange Metal Cations in the Solid State

Highly crystalline potassium (heptazine imides) were prepared by the thermal condensation of substituted 1,2,4-triazoles in eutectic salt melts. These semiconducting salts are already known to be highly active photocatalysts, for example, for the visible-light-driven generation of hydrogen from water. Herein, we show that within the solid-state structure, potassium ions can be exchanged to other metal ions while the crystal habitus is essentially preserved.

Electrochemistry on Stretchable Nanocomposite Electrodes: Dependence on Strain

Stretchable nanocomposite conductors are essential for engineering of bio-inspired deformable electronics, human-machine interfaces, and energy storage devices. While the effect of strain on conductivity for stretchable conductors has been thoroughly investigated, the strain dependence of multiple other electrical-transport processes and parameters that determine the functionalities and biocompatibility of deformable electrodes has received virtually no attention. The constancy of electrochemical parameters at electrode-fluid interfaces such as redox potentials, impedances, and charge-transfer rate constants on strain is often tacitly assumed. However, it remains unknown whether these foundational assumptions actually hold true for deformable electrodes. Furthermore, it is also unknown whether the previously used charge-transport circuits describing electrochemical processes on rigid electrodes are applicable to deformable electrodes. Here, we investigate the validity of the strain invariability assumptions for an elastic composite electrode based on gold nanoparticles (AuNPs). A comprehensive model of electrode reactions that accurately describes electrochemical processes taking place on nanocomposite electrodes for ferro-/ferricyanide electrochemicals pair at different strains is developed. Unlike rigid gold electrodes, the model circuit for stretchable electrodes is comprised of two parallel impedance segments describing (a) diffusion and redox processes taking place on the open surface of the composite electrode and (b) redox processes that occur in nanopores. AuNPs forming the open-surface circuit support the redox process, whereas those forming the nanopores only increase the double-layer capacitance. The redox potential was found to be strain-independent for tensile deformations as high as 40%. Other parameters, however, display strong strain dependence, exemplified by the 2-2.5 and 27 times increases of active area of the open and nanopore surface area, respectively, after application of 40% strain. Gaining better understanding of the strain-dependent and -independent electrochemical parameters enables both fundamental and practical advances in technologies based on deformable electrodes.