Nitrogen-doped pyrogenic carbonaceous matter facilitates azo dye decolorization by sulfide: The important role of graphitic nitrogen

Pyrogenic carbonaceous matter(PCM) catalyzes azo dye decolorization by sulfide, but the nitrogen doping catalytic mechanisms are poorly understood. In this study, we found that stagnate time of azo dye methyl orange(MO) decolorization was reduced to 0.54-18.28 min in the presence of various nitrogen-doped graphenes(NGs), remarkably lower compared to graphene itself. Particularly, graphitic nitrogen played a critical role in NGs-catalyzed MO decolorization by sulfide. Gas chromatography-mass spectrometry and in-situ surface Raman analysis demonstrated that doping nitrogen, especially graphite one facilitated reactive intermediate polysulfides formation. This is attributed to the improved electron conductivity through graphitic nitrogen doping, and the enhanced interactions between sulfide and carbon atoms bonded to graphitic nitrogen. This study not only provides a better understanding of PCM impact on transformations and fates of organic pollutants in natural environments, but also offer a new regulation strategy for more efficient wastewater treatment processes in PCM-catalyzed engineering systems.

Recent Advances of Graphitic Carbon Nitride-Based Structures and Applications in Catalyst, Sensing, Imaging, and LEDs

The graphitic carbon nitride(g-C_3N_4) which is a two-dimensional conjugated polymer has drawn broad interdisciplinary attention as a low-cost, metal-free, and visible-light-responsive photocatalyst in the area of environmental remediation. The g-C_3N_4-based materials have excellent electronic band structures, electron-rich properties, basic surface functionalities, high physicochemical stabilities and are ‘‘earth-abundant.'' This review summarizes the latest progress related to the design and construction of g-C_3N_4-based materials and their applications including catalysis, sensing,imaging, and white-light-emitting diodes. An outlook on possible further developments in g-C_3N_4-based research for emerging properties and applications is also included.

Synergetic effect of nitrogen‐doped carbon catalysts for high‐efficiency electrochemical CO_(2) reduction

The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.

Efficient Photoelectrochemical Water Splitting by g-C_3N_4/TiO_2 Nanotube Array Heterostructures

Well-ordered TiO_2 nanotube arrays(TNTAs)decorated with graphitic carbon nitride(g-C_3N_4) were fabricated by anodic oxidization and calcination process.First, TNTAs were prepared via the anodic oxidation of Ti foil in glycerol solution containing fluorinion and 20%deionized water. Subsequently, g-C_3N_4 film was hydrothermally grown on TNTAs via the hydrogen-bonded cyanuric acid melamine supramolecular complex. The results showed that g-C_3N_4 was successfully decorated on the TNTAs and the g-C_3N_4/TNTAs served as an efficient and stable photoanode for photoelectrochemical water splitting. The facile deposition method enables the fabrication of efficient and low-cost photoanodes for renewable energy applications.

Recent Advances in Graphitic Carbon Nitride-Based Chemiluminescence,Cataluminescence and Electrochemiluminescence

Graphitic carbon nitride(g-C3N4)has attracted considerable attention due to its special structure and properties,such as its good chemical and thermal stability under ambient conditions,low cost and non-toxicity,and facile synthesis.Recently,g-C3N4-based sensors have been demonstrated to be of high interests in the areas of sensing due to the unique optical,electronic and catalytic properties of g-C3N4.This review focuses on the most salient advances in luminescent sensors based on g-C3N4,chemiluminescence,cataluminescence and electrochemiluminescence methods are discussed.This review provides valuable information for researchers of related areas and thus may inspire the development of more practical and effective approaches for designing two-dimensional(2D)nanomaterial-assisted luminescent sensors.

Fluorescent light enhanced graphitic carbon nitride/ceria with ultralow-content platinum catalyst for oxidative decomposition of formaldehyde at ambient temperature

The complete decomposition of formaldehyde(HCHO) at ambient temperature is the most potential strategy for HCHO elimination from indoor environment.Herein,extra low content of Pt nanoparticles(0.025 wt%)supported on water-solubility carbon nitride/ceria(Pt/gC_(3)N_(4)@CeO_(2)) was prepared for gaseous HCHO removal at ambient temperature in a simulated indoor environment.Fluorescent light(8 W) illumination could visibly boost the complete decomposition of HCHO into CO_(2) over Pt/gC_(3)N_(4)@CeO_(2).The cooperative effect in the distinct heterostructure and plenty of surface reactive oxygen species contribute primarily to the enhanced catalytic performance of Pt/g-C_(3)N_(4)@CeO_(2).Moreover,the possible mechanism of HCHO oxidation over Pt/g-C_(3)N_(4)@CeO_(2) assisted by the fluorescent light irradiation was proposed based on the physicochemical and optical characterization as well as the result of in situ diffuse reflectance infrared Fourier transform spectra.This work might shed some light on the potential application of the versatile catalysts for ambient-temperature catalytic decomposition of HCHO by making full use of the indoor energies.

Porous honeycomb-like C3N4/rGO composite as host for high performance Li-S batteries

Lithium-sulfur (Li-S) batteries have attracted extensive attention along with the urgent increasing demand for energy storage owing to the high theoretical specific capacity and energy density, abundant reserves and low cost of sulfur. However, the practical application of Li-S batteries is still impeded due to the low utilization of sulfur and serious shuttle-effect of lithium polysulfides (LiPSs). Here, we fabricated the porous honeycomb-like C3N4 (PHCN) through a hard template method. As a polar material, graphitic C3N4 has abundant nitrogen content (-58%), which can provide enough active sites to mitigate shuttle-effect, and then conductive reduced graphene oxide (rGO) was introduced to combine with PHCN to form PHCN/rGO composite in order to improve the utilization efficiency of sulfur. After sulfur loading, the PHCN/rGO/S cathode exhibited an initial discharge capacity of 1,061.1 mA h g^-1 at 0.2 C and outstanding rate performance at high current density of 5 C (495.1 mA h g^-1), and also retained 519 mA h g^-1, after 400 cycles at 1 C. Even at high sulfur loading (4.3 mg cm^-2), the capacity fade rate was only 0.16% per cycle at 0.5 C for 200 cycles. The above results demonstrate that the special design of PHCN/rGO composite as sulfur host has high potential application for Li-S rechargeable batteries.

Template-free large-scale synthesis of g-C3N4 microtubes for enhanced visible light-driven photocatalytic H2 production

A template-free hydrothermal-assisted thermal polymerization method has been developed for the large-scale synthesis of one-dimensional （1D） graphitic carbon nitride （g-C3N4） microtubes. The g-C3N4 microtubes were obtained by simple thermal polymerization of melamine-cyanuric acid complex microrods under N2 atmosphere, which were synthesized by hydrothermal treatment of melamine solution at 180℃ for 24 h. The as-obtained g-C3N4 microtubes exhibited a large surface area and a unique one-dimensional tubular structure, which provided abundant active sites for proton reduction and also facilitated the electron transfer processes. As such, the g-C3N4 microtubes showed enhanced photocatalytic H2 production activity in lactic acid aqueous solutions under visible light irradiation （A 〉 420 nm）, which was - 3.1 times higher than that of bulk g-C3N4 prepared by direct thermal polymerization of the melamine precursor under the same calcination conditions.

Enhanced CH4 selectivity in CO2 photocatalytic reduction over carbon quantum dots decorated and oxygen doping g-C3N4

Graphitic carbon nitride(g-C3N4,CN)exhibits inefficient charge separation,deficient CO2 adsorption and activation sites,and sluggish surface reaction kinetics,which have been recognized as the main barriers to its application in CO2 photocatalytic reduction.In this work,carbon quantum dot(CQD)decoration and oxygen atom doping were applied to CN by a facile one-step hydrothermal method.The incorporated CQDs not only facilitate charge transfer and separation,but also provide alternative CO2 adsorption and activation sites.Further,the oxygen-atom-doped CN(OCN),in which oxygen doping is accompanied by the formation of nitrogen defects,proves to be a sustainable H^+ provider by facilitating the water dissociation and oxidation half-reactions.Because of the synergistic effect of the hybridized binary CQDs/OCN addressing the three challenging issues of the CN based materials,the performance of CO2 photocatalytic conversion to CH4 over CQDs/OCN-x(x represents the volume ratio of laboratory-used H2O2(30 wt.%)in the mixed solution)is dramatically improved by 11 times at least.The hybrid photocatalyst design and mechanism proposed in this work could inspire more rational design and fabrication of effective photocatalysts for CO2 photocatalytic conversion with a high CH4 selectivity.

Catalyzing polysulfide conversion by g-C3N4 in a graphene network for long-life lithium-sulfur batteries

The practical application of lithium-sulfur batteries with a high energy density has been plagued by the poor cycling stability of the sulfur cathode, which is a result of the insulating nature of sulfur and the dissolution of polysulfides. Much work has been done to construct nanostructured or doped carbon as a porous or polar host for promising sulfur cathodes, although restricting the polysulfide shuttle effect by improving the redox reaction kinetics is more attractive. Herein, we present a well-designed strategy by introducing graphitic carbon nitride （g-C3N4） into a three-dimensional hierarchical porous graphene assembly to achieve a synergistic combination of confinement and catalyzation of polysulfides. The porous g-CBN4 nanosheets in situ formed inside the graphene network afford a highly accessible surface to catalyze the transformation of polysulfides, and the hierarchical porous graphene-assembled carbon can function as a conductive network and provide appropriate space for g-C3N4 catalysis in the sulfur cathode. Thus, this hybrid can effectively improve sulfur utilization and block the dissolution of polysulfides, achieving excellent cycling performance for sulfur cathodes in lithium-sulfur batteries.