Enhancing NiS performance: Na-doping for advanced photocatalytic and electrocatalytic applications.

Alkali metal doping is a new and promising approach to enhance the photo/electrocatalytic activity of NiS-based catalyst systems. This work investigates the impact of sodium on the structural, electronic, and catalytic properties of NiS. Comprehensive characterization techniques demonstrate that Na-doping causes significant changes in the NiS lattice and surface chemistry translating into a larger bandgap than NiS.

Understanding the Wettability of CN (Sub)Nanopores: Implications for Porous Carbonaceous Electrodes.

Understanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte-solid interface area. Herein, we study the interaction of water with nanoporous CN materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area.

Revisiting the phosphonium salt chemistry for P-doped carbon synthesis: toward high phosphorus contents and beyond the phosphate environment.

The introduction of phosphorus and nitrogen atoms in carbo-catalysts is a common way to tune the electronic density, and thereby the reactivity, of the material, as well as to introduce surface reactive sites. Numerous environments are reported for the N atoms, but the P-doping chemistry is less explored and focuses on surface PO groups. A one-step synthesis of P/N-doped carbonaceous materials is presented here, using affordable and industrially available urea and tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the N and P sources, respectively.

Beyond Conventional Carbon Activation: Creating Porosity without Etching Using Cesium Effect.

Facile synthesis of porous carbon with high yield and high specific surface area (SSA) from low-cost molecular precursors offers promising opportunities for their industrial applications. However, conventional activation methods using potassium and sodium hydroxides or carbonates suffer from low yields (<20%) and poor control over porosity and composition especially when high SSAs are targeted (>2000 m g) because nanopores are typically created by etching. Herein, a non-etching activation strategy is demonstrated using cesium salts of low-cost carboxylic acids as the sole precursor in producing porous carbons with yields of up to 25% and SSAs reaching 3008 m g.

Oxygen-Rich Carbon Nitrides from an Eutectic Template Strategy Stabilize Ni, Fe Nanosites for Electrocatalytic Oxygen Evolution.

Functionalized porous carbons are central to various important applications such as energy storage and conversion. Here, a simple synthetic route to prepare oxygen-rich carbon nitrides (CNOs) decorated with stable Ni and Fe-nanosites is demonstrated. The CNOs are prepared via a salt templating method using ribose and adenine as precursors and CaCl ·2H O as a template.

When High-Temperature Cesium Chemistry Meets Self-Templating: Metal Acetates as Building Blocks of Unusual Highly Porous Carbons.

Self-templating is a facile strategy for synthesizing porous carbons by direct pyrolysis of organic metal salts. However, the method typically suffers from low yields (<4%) and limited specific surface areas (SSA<2000 m  g ) originating from low activity of metal cations (e.g.

Green Light Photoelectrocatalysis with Sulfur-Doped Carbon Nitride: Using Triazole-Purpald for Enhanced Benzylamine Oxidation and Oxygen Evolution Reactions.

Materials dictate carbon neutral industrial chemical processes. Visible-light photoelectrocatalysts from abundant resources will play a key role in exploiting solar irradiation. Anionic doping via pre-organization of precursors and further co-polymerization creates tuneable semiconductors.

Catalytic Properties of High Nitrogen Content Carbonaceous Materials.

The influence of structural modifications on the catalytic activity of carbon materials is poorly understood. A collection of carbonaceous materials with different pore networks and high nitrogen content was characterized and used to catalyze four reactions to deduce structure-activity relationships. The CO cycloaddition and Knoevenagel reaction depend on Lewis basic sites (electron-rich nitrogen species).

Real-Space Identification of Non-Noble Single Atomic Catalytic Sites within Metal-Coordinated Supramolecular Networks.

With regard to the development of single atom catalysts (SACs), non-noble metal-organic layers combine a large functional variability with cost efficiency. Here, we characterize reacted layers of melamine and melem molecules on a Cu(111) surface by noncontact atomic force microscopy (nc-AFM), X-ray photoelectron spectroscopy (XPS) and ab initio simulations. Upon deposition on the substrate and subsequent heat treatments in ultrahigh vacuum (UHV), these precursors undergo a stepwise dehydrogenation.

"Red Carbon": A Rediscovered Covalent Crystalline Semiconductor.

Carbon suboxide (C O ) is a unique molecule able to polymerize spontaneously into highly conjugated light-absorbing structures at temperatures as low as 0 °C. Despite obvious advantages, little is known about the nature and the functional properties of this carbonaceous material. In this work, the aim is to bring "red carbon," a forgotten polymeric semiconductor, back to the community's attention.

Constructing Interfacial Boron-Nitrogen Moieties in Turbostratic Carbon for Electrochemical Hydrogen Peroxide Production.

The electrochemical oxygen reduction reaction (ORR) provides a green route for decentralized H O synthesis, where a structure-selectivity relationship is pivotal for the control of a highly selective and active two-electron pathway. Here, we report the fabrication of a boron and nitrogen co-doped turbostratic carbon catalyst with tunable B-N-C configurations (CNB-ZIL) by the assistance of a zwitterionic liquid (ZIL) for electrochemical hydrogen peroxide production. Combined spectroscopic analysis reveals a fine tailored B-N moiety in CNB-ZIL, where interfacial B-N species in a homogeneous distribution tend to segregate into hexagonal boron nitride domains at higher pyrolysis temperatures.

"We Are Here!" Oxygen Functional Groups in Carbons for Electrochemical Applications.

Heteroatom doping of carbon networks may introduce active functional groups on the surface of the material, induce electron density changes that alter the polarity of the carbon surface, promote the formation of binding sites for molecules or ions, or make the surface catalytically active for different reactions, among many other alterations. Thus, it is no surprise that heteroatom doping has become a well-established strategy to enhance the performance of carbon-based materials for applications ranging from water remediation and gas sorption to energy storage and conversion. Although oxygen functionalization is sometimes inevitable (i.

Mn(II) sub-nanometric site stabilization in noble, N-doped carbonaceous materials for electrochemical CO reduction.

The preparation of stable and efficient electrocatalysts comprising abundant and non-critical row-materials is of paramount importance for their industrial implementation. Herein, we present a simple synthetic route to prepare Mn(II) sub-nanometric active sites over a highly N-doped noble carbonaceous support. This support not only promotes a strong stabilization of the Mn(II) sites, improving its stability against oxidation, but also provides a convenient coordination environment in the Mn(II) sites able to produce CO, HCOOH and CHCOOH from electrochemical CO reduction.

Ultrahigh water sorption on highly nitrogen doped carbonaceous materials derived from uric acid.

Hypothesis: Developing materials for thermally driven adsorption chillers and adsorption heat pumps is a growing research field due to the potential of these technologies to address up to 50% of the world's total energy demand. These materials must be abundant, easy to synthesize, hydrophilic, and low in cost. Bare carbon materials are hydrophobic and therefore usually not considered for these applications.

Caffeine-Derived Noble Carbons as Ball Milling-Resistant Cathode Materials for Lithium-Ion Capacitors.

Energy consumption is a growing phenomenon in our society causing many negative effects such as global warming. There is a need for the development of new sustainable materials for energy storage. Carbons are materials derivable from biowaste that can rather easily store energy due to their high conductivity and surface area.

CN: A Class of Covalent Frameworks with Unique Properties.

CN is a unique member of the CN family (carbon nitrides), i.e., having a covalent structure that is ideally composed of carbon and nitrogen with only 33 mol% of nitrogen.

Guanine-Derived Porous Carbonaceous Materials: Towards C N.

Herein, the basic nature of noble covalent, sp2-conjugated materials prepared via direct condensation of guanine in the presence of an inorganic salt melt as structure directing agent was studied. At temperatures below 700 °C stable and more basic addition products with at C/N ratio of 1 (C N adducts) and with rather uniform micropore sizes were formed. Carbonization at higher temperatures broke the structural motif, and N-doped carbons with 11 wt % and surface areas of 1900 m  g were obtained.

Thin films of poly(vinylidene fluoride-co-hexafluoropropylene)-ionic liquid mixtures as amperometric gas sensing materials for oxygen and ammonia.

Gas sensors are important devices used to monitor the type and amount of gas present. Amperometric gas sensors - based on measuring the current upon an applied potential - have been progressing towards miniaturised designs that are smaller, lower cost, faster responding and more robust compared to commercially available sensors. In this work, a planar thin-film electrode device is employed for gas sensing with a thin layer of gel polymer electrolyte (GPE).

Encoding Metal-Cation Arrangements in Metal-Organic Frameworks for Programming the Composition of Electrocatalytically Active Multimetal Oxides.

In the present contribution, we report how through the use of metal-organic frameworks (MOFs) composed of addressable combinations of up to four different metal elements it is possible to program the composition of multimetal oxides, which are not attainable by other synthetic methodologies. Thus, due to the ability to distribute multiple metal cations at specific locations in the MOF secondary building units it is possible to code and transfer selected metal ratios to multimetal oxides with novel, desired compositions through a simple calcination process. The demonstration of an enhancement in the electrocatalytic activity of new oxides by preadjusting the metal ratios is here reported for the oxygen reduction reaction, for which activity values comparable to commercial Pt/C catalysts are reached, while showing long stability and methanol tolerance.

Adjusting the Structure and Electronic Properties of Carbons for Metal-Free Carbocatalysis of Organic Transformations.

Carbon nanomaterials doped with some other lightweight elements were recently described as powerful, heterogeneous, metal-free organocatalysts, adding to their high performance in electrocatalysis. Here, recent observations in traditional catalysis are reviewed, and the underlying reaction mechanisms of the catalyzed organic transformations are explored. In some cases, these are due to specific active functional sites, but more generally the catalytic activity relates to collective properties of the conjugated nanocarbon frameworks and the electron transfer from and to the catalytic centers and substrates.

Reline aqueous solutions behaving as liquid mixtures of H-bonded co-solvents: microphase segregation and formation of co-continuous structures as indicated by Brillouin and H NMR spectroscopies.

Deep eutectic solvents (DESs) offer a suitable alternative to conventional solvents in terms of both performance and cost-effectiveness. Some DESs also offer certain green features, the greenness of which is notoriously enhanced when combined with water. Aqueous DES dilutions are therefore attracting great attention as a novel green medium for biotechnological processes, with the aqueous dilutions of reline - a DES composed of urea and choline chloride - being one of the most studied systems.

Sulfur-doped carbons prepared from eutectic mixtures containing hydroxymethylthiophene as metal-free oxygen reduction catalysts.

A template-free approach based on the use of eutectic mixtures composed of 2-hydroxymethylthiophene and furfuryl alcohol has been designed for the preparation of hierarchical sulfur-doped carbons (SPCs) in monolithic form. The temperature used for carbonization, for example, 600, 800, or 900 °C, determined most of the physicochemical properties of the resulting SPCs. Thus, the surface area increased from below 400 to up 775 m(2)  g(-1) , along with the carbonization temperature, whereas the sulfur content decreased from approximately 15 to 5 wt %.

Use of eutectic mixtures for preparation of monolithic carbons with CO₂-adsorption and gas-separation capabilities.

With global warming becoming one of the main problems our society is facing nowadays, there is an urgent demand to develop materials suitable for CO2 storage as well as for gas separation. Within this context, hierarchical porous structures are of great interest for in-flow applications because of the desirable combination of an extensive internal reactive surface along narrow nanopores with facile molecular transport through broad "highways" leading to and from these pores. Deep eutectic solvents (DESs) have been recently used in the synthesis of carbon monoliths exhibiting a bicontinuous porous structure composed of continuous macroporous channels and a continuous carbon network that contains a certain microporosity and provides considerable surface area.