Thermodynamically Stable Mesoporous C3 N7 and C3 N6 with Ordered Structure and Their Excellent Performance for Oxygen Reduction Reaction.

Carbon nitrides with a high N/C atomic ratio (>2) are expected to offer superior basicity and unique electronic properties. However, the synthesis of these nanostructures is highly challenging since many parts of the CN frameworks in the carbon nitride should be replaced with thermodynamically less stable NN frameworks as the nitrogen content increases. Thermodynamically stable C3 N7 and C3 N6 with an ordered mesoporous structure are synthesized at 250 and 300 °C respectively via a pyrolysis process of 5-amino-1H-tetrazole (5-ATTZ). Polymerization of the precursor to the ordered mesoporous C3 N7 and C3 N6 is clearly proved by X-ray and electron diffraction analyses. A combined analysis including diverse spectroscopy and FDMNES and density functional theory (DFT) calculations demonstrates that the NN bonds are stabilized in the form of tetrazine and/or triazole moieties in the C3 N7 and C3 N6 . The ordered mesoporous C3 N7 represents the better oxygen reduction reaction (ORR) performances (onset potential: 0.81 V vs reversible hydrogen electrode (RHE), electron transfer number: 3.9 at 0.5 V vs RHE) than graphitic carbon nitride (g-C3 N4 ) and the ordered mesoporous C3 N6 . The study on the mechanism of ORR suggests that nitrogen atoms in the tetrazine moiety of the ordered mesoporous C3 N7 act as active sites for its improved ORR activity.

Ordered Mesoporous C3 N5 with a Combined Triazole and Triazine Framework and Its Graphene Hybrids for the Oxygen Reduction Reaction (ORR).

Mesoporous carbon nitrides (MCN) with C3 N4 stoichiometry could find applications in fields ranging from catalysis, sensing, and adsorption-separation to biotechnology. The extension of the synthesis of MCN with different nitrogen contents and chemical structures promises access to a wider range of applications. Herein we prepare mesoporous C3 N5 with a combined triazole and triazine framework via a simple self-assembly of 5-amino-1H-tetrazole (5-ATTZ). We are able to hybridize these nanostructures with graphene by using graphene-mesoporous-silica hybrids as a template to tune the electronic properties. DFT calculations and spectroscopic analyses clearly demonstrate that the C3 N5 consists of 1 triazole and 2 triazine moieties. The triazole-based mesoporous C3 N5 and its graphene hybrids are found to be highly active for oxygen reduction reaction (ORR) with a higher diffusion-limiting current density and a decreased overpotential than those of bulk g-C3 N4 .

A Data-Driven Approach to Molten Salt Synthesis of N-Rich Carbon Adsorbents for Selective CO2 Capture.

Applying a design of experiments methodology to the molten salt synthesis of nanoporous carbons enables inverse design and optimization of nitrogen (N)-rich carbon adsorbents with excellent CO2 /N2 selectivity and appreciable CO2 capacity for carbon capture via swing adsorption from dilute gas mixtures such as natural gas combined cycle flue gas. This data-driven study reveals fundamental structure-function relationships between the synthesis conditions, physicochemical properties, and achievable selective adsorption performance of N-rich nanoporous carbons derived from molten salt synthesis for CO2 capture. Taking advantage of size-sieving separation of CO2 (3.30 Å) from N2 (3.64 Å) within the turbostratic nanostructure of these N-rich carbons, while limiting deleterious N2 adsorption in a weaker adsorption site that harms selectivity, enables a large CO2 capacity (0.73 mmol g-1 at 30.4 Torr and 30 °C) with noteworthy concurrent CO2 /N2 selectivity as predicted by the ideal adsorbed solution theory (SIAST = 246) with an adsorbed phase purity of 91% from a simulated gas stream containing only 4% CO2 . Optimized N-rich porous carbons, with good physicochemical stability, low cost, and moderate regeneration energy, can achieve performance for selective CO2 adsorption that competes with other classes of advanced porous materials such as chemisorbing zeolites and functionalized metal-organic frameworks.

Pyridinic-N-rich carbon dots in IFE-based Turn-off Fluorometric detection of nerve agent Mimic- Diethyl chlorophosphate and multicolor cell imaging.

Fluorometric sensors for the detection of nerve agent mimics have received a lot of interest nowadays due to their high sensitivity and selectivity, ease of operation, and real-time monitoring. Pyridinic-N-rich carbon dots (NCDs) prepared through microwave-assisted pyrolysis of l-Malic acid and urea have been explored first time in this work as a novel turn-off fluorescent probe for the sensitive and selective detection of diethyl chlorophosphate (DCP), a nerve agent mimic. The as-prepared carbon dots contained a large amount of pyridinic nitrogen on their surface, which can modulate the photoluminescence properties of the NCDs. The blue emissive NCDs possessed both excitation wavelength-dependent and independent emission behavior. The detection of DCP was premised on quenching of the fluorescence emission intensity of NCDs in the presence of similar chemical reagents (e.g., trimethyl phosphate, triethyl phosphate, triethyl phosphonoacetate, triphenyl phosphate, diphenyl phosphate, tributyl phosphate). Fluorescence quenching of the NCDs in the presence of DCP has been attributed to the inner filter effect (IFE). From the linear Stern-Volmer plot (R2 = 0.9992), the limit of detection (LOD) was found to be 84 µM for sensing DCP for the concentration ranging between 3 and 15 mM. The biocompatibility of NCDs was assessed through cytotoxicity assay on MDA-MB-231 breast cancer cells. Fluorescence imaging demonstrated that NCDs have low cytotoxicity and can be employed successfully in cell imaging.

Effective enhancement of electron migration and photocatalytic performance of nitrogen-rich carbon nitride by constructing fungal carbon dot/molybdenum disulfide cocatalytic system.

To find a cocatalyst that can replace noble metals, fungal carbon dot (CD) modified molybdenum disulfide (MoS2) cocatalyst system was designed. The composites were prepared by hydrothermal and calcination methods with different ratios of CDs, MoS2 and nitrogen-rich carbon nitride (p-C3N5). p-C3N5 has excellent electronic properties, and MoS2 modified by CDs (D-MoS2) can significantly enhance the photocatalytic performance of p-C3N5 by improving the photogenerated electron migration efficiency. The experiments showed that the developed CDs/MoS2/C3N5 composites exhibited excellent performance in both photocatalytic hydrogen (H2) evolution and methylene blue (MB) degradation, with CMSCN5 (D-MoS2 with 5% mass fraction) showing the best photocatalytic activity. The corresponding H2 evolution rate of CMSCN5 was 444 µmol g-1h-1 and 1.45 times higher than that of unmodified p-C3N5, by 120 min, the removal rate of MB was up to 93.51%. The 5 cycle tests showed that CMSCN5 had great stability. The high charge mobility and high density of H2 evolution active sites of MoS2 nanosheets, together with the electron storage and transfer properties of CDs can obviously improve electron migration and reduce the photogenerated carrier recombination on the p-C3N5 surface. The design and preparation of such composites offer broad prospects for the development of photocatalytic systems with noble metal-free cocatalysts.

Nanofibrous Cathode Catalysts with MoC Nanoparticles Embedded in N-Rich Carbon Shells for Low-Overpotential Li-CO2 Batteries.

Li-CO2 batteries with high theoretical energy densities are recognized as next-generation energy storage devices for addressing the range anxiety and environmental issues encountered in the field of electric transportation. However, cathode catalysts with unsatisfactory activity toward CO2 absorption and reduction/evolution reactions hinder the development of Li-CO2 batteries with desired specific capacities and sufficient cycle numbers. In this work, a multifunctional nanofibrous cathode catalyst that integrates N-rich carbon shells embedded with molybdenum carbide nanoparticles and multiwalled carbon nanotube cores was designed and prepared. The N-rich carbon shell could strengthen the absorption capacity of CO2 and Li2CO3. The molybdenum carbide nanoparticles would improve the catalytic activity of both CO2 reduction and evolution reactions. The carbon nanotube cores would provide an efficient network for electron transportation. The synergistic effect of the cathode catalysts enhances the electrochemical performance of Li-CO2 batteries. A high cycling stability of more than 150 cycles at a current density of 250 mA g-1 with a cutoff capacity of 1000 mAh g-1 and a charge/discharge overpotential of less than 1.5 V is achieved. This work provides a feasible strategy for the design of a high-performance cathode catalyst for lithium-air batteries.

Magnetic N-rich carbon nitride framework material for the high selectivity extraction and determination of La(III).

A novel magnetic C3N5 framework material (Fe3O4/C3N5) was developed as a high selectivity extractant for La(III) determination in food samples. The Fe3O4/C3N5 material was synthesized by thermal deammoniation method and has larger surface area (100.3 m2 g-1) and more effective adsorption sites compared with that of individual C3N5 material (19.4 m2 g-1). It was proved that Fe3O4/C3N5 material displayed excellent selectivity and adsorption capacity for La(III). In addition, adsorption isotherm and kinetic data indicated that La(III) adsorption based on Fe3O4/C3N5 material is a monolayer adsorption which is compatible with Langmuir model and follows a pseudo-second-order kinetic equation. By using Fe3O4/C3N5 material as extractant, an analytical method was established with low limits of detection (3σ, n = 6) of 10.4 µg L-1, reasonable recoveries ranged from 86% to 106% and good precision with the RSD less than 10.7%. The analytical method was further applied to the determination of trace La(III) in food sample. It evinced that the concentration of La(III) in sea fish is 13.2 µg kg-1 and the content of 138La is 0.138 µg kg-1, which is 1.03% of total La(III).

Hierarchical ZnO@Hybrid Carbon Core-Shell Nanowire Array on a Graphene Fiber Microelectrode for Ultrasensitive Detection of 2,4,6-Trinitrotoluene.

A hierarchical architecture composed of nitrogen (N)-rich carbon@graphitic carbon-coated ZnO nanowire arrays on a graphene fiber (ZnO@C/GF) was fabricated by direct growth of a ZnO@zeolitic imidazolate framework-8 (ZIF-8) core-shell nanowire array on a GF followed by annealing and used as a microelectrode for detection of 2,4,6-trinitrotoluene (TNT). In such a design, ZnO accumulated TNT through a strong nitroxide-zinc interaction and ZIF-8 served as the precursor of the N-rich carbon@graphitic carbon layer that seamlessly connected ZnO with the GF to improve the poor conductivity of ZnO, thus enhancing the sensitivity of the ZnO@C/GF microelectrode. The constructed hierarchical hybrid fiber microsensor exhibited a wide linear response to TNT in a concentration range of 0.1-32.2 µM with a low detection limit of 3.3 nM. This ZnO@C/GF microelectrode was further successfully applied to the detection of TNT in lake and tap water, indicating its promise as a portable sensor for the electrochemical detection of explosive compounds.

Effect of Aging-Induced Dioxolane Polymerization on the Electrochemistry of Carbon-Coated Lithium Sulfide.

Lithium sulfide-based materials have been considered as potential positive electrodes for the next generation batteries. Lithium sulfide is the fully lithiated form of sulfur, i.e., they share the same high theoretical capacity. However, it has the benefit of already containing lithium, which allows making cells with lithium-free negative electrodes. Lithium sulfide, however, shares with sulfur the polysulfide dissolution drawback upon cycling. One possible solution to this problem is to envelop the active material particles with carbonaceous materials. In this work, we investigate the effect of a nitrogen-rich carbon coating on lithium sulfide particles. The effect of such coating on the surface properties and electrochemistry of lithium sulfide cathodes is investigated in details, in particular, regarding its interaction with fresh vs. aged electrolyte. The polymerization of dioxalane (DOL) due to aging is found to affect the electrochemistry of lithium sulfide and, interestingly, to improve the cycling performance.

Two-Dimensional NiSe2/N-Rich Carbon Nanocomposites Derived from Ni-Hexamine Frameworks for Superb Na-Ion Storage.

Design of functional carbon-based nanomaterials from metal-organic frameworks (MOFs) has attracted soaring interests in recent years. However, a MOF-derived strategy toward two-dimensional (2D) nanomaterials remains a great challenge. In this work, we develop a layered Ni-hexamine framework as efficient precursor to prepare a 2D NiSe2/N-rich carbon nanocomposite by a simple pyrolysis and subsequent selenization process. In the 2D NiSe2/N-rich carbon nanocomposite, NiSe2 nanoparticles with diameters of ca. 75 nm are homogeneously distributed in the N-rich carbon nanosheets. When serving as anode materials for sodium-ion batteries, the 2D nanocomposites exhibit a high reversible capacity of 410 mAh g-1 at 1 A g-1 and maintain a value of 255 mAh g-1 even at 10 A g-1. The excellent electrochemical performance can be attributed to the synergistic effects between the N-rich carbon nanosheets and NiSe2 nanoparticles. More importantly, the hexamine-based MOFs can be regarded as new and powerful platforms for the fabrication of 2D N-rich carbon-based nanomaterials, which is of great importance for various potential applications.

S-Doped N-Rich Carbon Nanosheets with Expanded Interlayer Distance as Anode Materials for Sodium-Ion Batteries.

2D composites with S doping into N-rich carbon nanosheets are fabricated, whose interlayer distance becomes large enough for Na+ insertion and diffusion. The large surface area and stable structure also provide more sites for Na+ adsorption, leading to high Na-storage capacity and excellent rate performance. Moreover, Faradaic reactions between Na+ and tightly bound S is beneficial for further improvement of Na-storage capacity.