C_xN_y : new carbon nitride organic photocatalysts

The search for metal-free and visible light-responsive materials for photocatalytic applications has attracted the interest of not only academics but also the industry in the last decades. Since graphitic carbon nitride (g-C3N4) was first reported as a metal-free photocatalyst, this has been widely investigated in different light-driven reactions. However, the high recombination rate, low electrical conductivity, and lack of photoresponse in most of the visible range have elicited the search for alternatives. In this regard, a broad family of carbon nitride (CxNy) materials was anticipated several decades ago. However, the attention of the researchers in these materials has just been awakened in the last years due to the recent success in the syntheses of some of these materials (i.e., C3N3, C2N, C3N, and C3N5, among others), together with theoretical simulations pointing at the excellent physico-chemical properties (i.e., crystalline structure and chemical morphology, electronic configuration and semiconducting nature, or high refractive index and hardness, among others) and optoelectronic applications of these materials. The performance of CxNy, beyond C3N4, has been barely evaluated in real applications, including energy conversion, storage, and adsorption technologies, and further work must be carried out, especially experimentally, in order to confirm the high expectations raised by simulations and theoretical calculations. Herein, we have summarized the scarce literature related to recent results reporting the synthetic routes, structures, and performance of these materials as photocatalysts. Moreover, the challenges and perspectives at the forefront of this field using CxNy materials are disclosed. We aim to stimulate the research of this new generation of CxNy-based photocatalysts, beyond C3N4, with improved photocatalytic efficiencies by harnessing the striking structural, electronic, and optical properties of this new family of materials

Carbonaceous materials : the beauty of simplicity

The current mandates of a sustainable society and circular economy lead to the request that materials chemistry, but also chemistry as such, has to become significantly redesigned. Changes include commonplaces as the glassware we use, the minimization of wastes and side products or replacement strategies in the materials choice, among others. In this context, “carbons” are very versatile and already have found their place in a myriad of applications for a “carbon-neutral” society. They already take key enabling positions for sensors and biomaterials preparation, as energy conversion and storage electrode, or as effluent remediation sorbents. Herein, we describe how carbon chemistry can be again re-designed to outperform benchmark materials in a number of fields, especially in energy storage, (electro)catalysis, as sorbent, but also in a new chemistry of the confined state

“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.e., many carbon precursors contain oxygen functionalities), its participation in carbon materials performance is often overlooked on behalf of other heteroatoms (mainly nitrogen). In this Mini-review, we summarize recent and relevant publications on the effect that oxygen functionalization has on carbonaceous materials performance in different electrochemical applications and some strategies to introduce such functionalization purposely. Our aim is to revert the current tendency to overlook it and raise the attention of the materials science community on the benefits of using oxygen functionalization in many state-of-the-art applications

Guanine derived porous carbonaceous materials : towards C₁N₁

Herein, we study 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. At temperatures below 700 °C stable and more basic addition products with at C:N ratio of 1 (C1N1 adducts) and with rather uniform micropore sizes are formed. Carbonization at higher temperatures breaks the structural motif, and N-doped carbons with 11 wt% and surface areas of 1900 m g-1 are obtained. The capability for CO2 sorption and catalytic activity of the materials depend of both their basicity and their pore morphology. The optimization of the synthetic parameters lead to very active (100% conversion) and highly selective (99% selectivity) heterogeneous base catalysts, as exemplified with the model Knoevenagel condensation of benzaldehyde with malononitrile. The high stability upon oxidation of these covalent materials and their basicity open new perspectives in heterogeneous organocatalysis

Overcoming electron transfer efficiency bottlenecks for hydrogen production in highly crystalline carbon nitride-based materials

The hydrogen evolution reaction (HER) is a complex reaction involving many interdependent physicochemical steps. Highly ordered carbon nitride-based materials, such as Na-PHI and K-PHI, display some of the highest activities for H2 evolution among the carbon nitride-based materials, due to their electronic properties, but also the presence of cyanimide terminations, which favors the charge transfer for the Pt cocatalyst nanoparticles (NPs). For such highly optimized semiconductor structures, the necessity to control and improve other steps of the photocatalytic process becomes essential, in particular the poor electron transfer from the Pt NPs to the protons in solution over the Helmholtz or Stern layer. Taking highly ordered Na-PHI as a test material, the influence of water-dissolved alkali cations on the HER is systematically studied and it is experimentally verified that the electron transfer from the Pt NPs to the protons in solution limits the efficiency of heterogeneous carbon nitride-based catalysts. This paper explains how hydrated alkali cations influence electron transfer and are able to boost the H2 evolution rate of the same Na-PHI from 2401 up to 5330 µmol h-1 g-1 with an apparent quantum yield of 13% at 420 nm

Following carbon condensation by in-situ TEM : towards a rational understanding of the processes in the synthesis of nitrogen-doped carbonaceous materials.

Porous carbonaceous materials obtained from biomass have been an important class of CO2 sorbents since ancient times. Recent progress in carbon-based adsorbent technology is based on the implication of the concept of heteroatom doping. In this respect, the synthesis of carbonaceous materials through one-step condensation of cheap nitrogen-containing molecular precursors is an attractive strategy for obtaining such N-doped carbons. The design of the adsorbents obtained by this route relies on the careful adjustment of synthesis parameters, such as the temperature, the heating rate, and the atmosphere. However, in most cases, the latter's choice remains rather empirical due to the lack of a fundamental understanding of the condensation mechanism of molecular precursors. In this work, we followed the structural, morphological, and chemical evolution of a molecular precursor (uric acid) at the nanoscale using a combination of in-situ condensation inside a scanning transmission electron microscope with ex-situ analysis of the products of condensation at different temperatures, atmospheres, and heating rates, and correlate our findings with the CO2 sorption properties of the obtained materials. We showed that varying pressures and reaction rates result in particles with different porosity. The porosity of the surface of the particles during the early stages of condensation governs the subsequent release of volatiles and the development of a hierarchical pore structure. We found that synthesis in vacuum enables effective condensation at considerably low temperatures (500 °C). Using a higher heating rate (10 °C/min) suppresses structural ripening and preserves the optimal size of micropores, thus giving a CO2 uptake twice as high compared to samples synthesized in nitrogen atmosphere, which is commonly used, preserving the same selectivity.ER

Cu^II/Cu^I decorated N-doped carbonaceous electrocatalysts for the oxygen reduction reaction

The oxygen reduction reaction (ORR) that for instance takes place at the cathode of fuel cells is one of the most examined model reactions of energy conversion. The ORR presents sluggish reaction kinetics, thus limiting the overall efficiency of these cells. Pt-based catalysts are still the widest choice though they exhibit important drawbacks such as long-term instability and intolerance to methanol crossover. In this context, engineering transition metals in the form of nano- and subnano-sites on carbonaceous supports has the potential of becoming an alternative to scarce noble metal-based catalysts. Herein, we describe a simple synthetic route towards CuII/CuI decorated N-doped carbonaceous ORR electrocatalysts. CuII/CuI nanosites are obtained by calcination in air of an ionic liquid derived noble carbonaceous support impregnated with copper(ii) acetate. The strong interaction between the copper and the noble support foster the co-formation of CuII/CuI nanosites. Larger amounts of copper(ii) acetate translate into larger amounts of CuI and lower Tafel slopes. The material with 4 wt% of copper catalyzes the selective reduction of oxygen through a 4-electron transfer pathway and exhibits a lower Tafel slope than commercial platinum, a minimal overpotential, and a higher limiting current density. Moreover, all materials show promising durability and high methanol stability, which makes them promising to replace noble metals for the ORR

Mn (II) sub-nanometric sites stabilization in noble, N-doped carbonaceous materials for electrochemical CO₂ reduction

The preparation of stable and efficient electrocatalysts comprising abundant and non-critical row-materials is of paramount importance for its 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 CH3COOH from the electrochemically CO2 reduction

PtRu nanoparticles supported on noble carbons for ethanol electrooxidation

In this work, three cytosine derived nitrogen doped carbonaceous materials (noble carbons, NCs) with different atomic C/N ratios and porous networks have been synthesized and used as supports for PtRu electrocatalysts in the ethanol oxidation reaction (EOR) for clean hydrogen production. Both, the metal phase and the carbon support play critical roles in the electrocatalysts final performance. Lower NPs size distribution was obtained over supports with low atomic C/N ratios (i.e., 4 and 6) and defined porosity (i.e., 1701 m2 g−1 for PtRu/CNZ and 1834 m2 g−1 for PtRu/CLZ, respectively). In contrast, a lower C/N ratio and poor porous network (i.e., 65 m2 g−1, PtRu/CLK) led to the largest particle size and fostered an increase of the alloying degree between Pt and Ru NPs (i.e., 3 for C/N ~ 6 and 28 for C/N ~ 3). Electrochemical active surface area was found to increase with decreasing NPs size and the alloy extent, due to a higher availability of Pt active sites. Accelerated degradation tests showed that PtRu/NCs outperform similar to PtRu NPs on commercial carbon pointing at the stabilizing effect of NCs. PtRu/CNZ exhibited the best electrochemical performance (i.e., 69.1 mA mgPt−1), outperforming PtRu/CLZ and PtRu/CLK by 3- and 9-fold, respectively, due to a suitable compromise between particle sizes, degree of alloy, textural properties and elemental composition. Best anodes were scaled-up to a proton exchange membrane cell and PtRu/CNZ was proved to provide the best electrocatalytic activity (262 mA cm−2 and low energy requirements), matching the values obtained by the state of the art of EOR electrocatalysts

New records of recently described chemosymbiotic bivalves for mud volcanoes within the European waters (Gulf of Cádiz)

Chemosymbiotic bivalves are important members of cold seep communities and information on their distribution in theEuropean waters is still quite scarce. This study reports the presence of living populations and shell remains of some recently described bivalves such as Lucinoma asapheus, Solemya elarraichensis and Acharax gadirae as well as Bathymodiolus sp. in the mud volcanoes of the Spanish Atlantic waters. Living populations of these species were thus far only found in Anastasya, Aveiro and Almazán mud volcanoes, together with other chemosymbiotic metazoa (Siboglinum spp.), suggesting the presence of moderate seepage activity. In other mud volcanoes (Albolote, Gazul), the benthic communities are dominated by sessile filter feeders on authigenic carbonates (chimneys, slabs) and only the shell remains of some chemosymbiotic bivalves were found, indicating earlier or very low seepage conditions. The present study elaborates on the known distribution of L. asapheus and S. elarraichensis to the European waters of the Gulf of Cádiz