Polymeric Photocatalysts Based on Graphitic Carbon Nitride

Semiconductor‐based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g‐C₃N₄) for visible‐light photocatalytic water splitting, g‐C₃N₄‐based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g‐C₃N₄‐based photocatalysts, including the fabrication and nanostructure design of pristine g‐C₃N₄, bandgap engineering through atomic‐level doping and molecular‐level modification, and the preparation of g‐C₃N₄‐based semiconductor composites. Also, the photo­catalytic applications of g‐C₃N₄‐based photocatalysts in the fields of water splitting, CO₂ reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non‐noble‐metal cocatalysts, and Z‐scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g‐C₃N₄‐based photocatalysts are highlighted.     

A Composite Polymeric Carbon Nitride with In Situ Formed Isotype Heterojunctions for Highly Improved Photocatalysis under Visible Light

Introducing heterojunction is an effective way for improving the intrinsic photocatalytic activity of a graphitic carbon nitride (GCN) semiconductor. These heterostructures are mostly introduced by interfacing GCN with foreign materials that normally have entirely different physicochemical properties and show unfavorable compatibility, thus resulting in a limited improvement of the photocatalytic performance of the resultant materials. Herein, a composite polymeric carbon nitride (CPCN) that contains both melon‐based GCN and triazine‐based crystalline carbon nitride (CCN) is prepared by a simple thermal reaction between lithium chloride and GCN. Thanks to the intimate contact and good compatibility between GCN and CCN, an in situ formed heterojunction acts as a driving force for separating the photogenerated charge carriers in CPCN. As a result, CPCN exhibits a significantly improved photocatalytic performance under visible light irradiation, which is, respectively, 10.6 and 5.3 times as high as those of the GCN and CCN alone. This well designed isotype heterojunction by a coupling of CCN presents an effective avenue for developing efficient GCN photocatalysts.     

Sulfur‐Modified Graphitic Carbon Nitride Nanostructures as an Efficient Electrocatalyst for Water Oxidation

There is an urgent need to develop metal‐free, low cost, durable, and highly efficient catalysts for industrially important oxygen evolution reactions. Inspired by natural geodes, unique melamine nanogeodes are successfully synthesized using hydrothermal process. Sulfur‐modified graphitic carbon nitride (S‐modified g‐CN _x ) electrocatalysts are obtained by annealing these melamine nanogeodes in situ with sulfur. The sulfur modification in the g‐CN _x structure leads to excellent oxygen evolution reaction activity by lowering the overpotential. Compared with the previously reported nonmetallic systems and well‐established metallic catalysts, the S‐modified g‐CN _x nanostructures show superior performance, requiring a lower overpotential (290 mV) to achieve a current density of 10 mA cm^?2 and a Tafel slope of 120 mV dec^?1 with long‐term durability of 91.2% retention for 18 h. These inexpensive, environmentally friendly, and easy‐to‐synthesize catalysts with extraordinary performance will have a high impact in the field of oxygen evolution reaction electrocatalysis.     

3D Gold‐Modified Cerium and Cobalt Oxide Catalyst on a Graphene Aerogel for Highly Efficient Catalytic Formaldehyde Oxidation

A hard template method is used to prepare porous gold‐doped cerium and cobalt oxide (Au‐Ce_xCo_y) materials. A series of 3D Au‐Ce _xCo_y/graphene aerogel (GA) composites is then fabricated by a facile heating method. The obtained catalysts possess a well‐defined structure of ordered arrays of nanotubes and good performance in formaldehyde (HCHO) oxidation. The composition and surface elemental valence states of the catalysts are modulated by the Ce/Co molar ratio. The Au‐Ce_xCo_y catalyst and graphene oxide sheets are well compounded within 60 s through a diamine cross‐linker to form 3D Au‐Ce_xCo_y/GA composites. In addition, the resulting catalyst of 3 wt% Au‐Ce₃Co/GA achieves ≈55% conversion at room temperature and 100% conversion when the reaction temperature is raised at 60 °C. The synergistic effect between CeO₂ and Co₃O₄ promotes the migration of oxygen species and the activation of Au, which facilitates HCHO oxidation. The method used to prepare the 3D catalyst could be used to produce other catalytic materials with good replication of the template. In addition, these findings provide a simple method for rapid fabrication of catalyst/GA composites. The superior activity and stability of the 3D Au‐Ce₃Co/GA catalyst make it potentially applicable in HCHO removal.     

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g‐C₃N₄) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g‐C₃N₄. The resultant boron‐doped and nitrogen‐deficient g‐C₃N₄ exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h^?1 g^?1, much higher than previously reported g‐C₃N₄. It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g‐C₃N₄, the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C–N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g‐C₃N₄ with simultaneous introduction of dopants and defects for high‐performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.     

Increasing Solar Absorption of Atomically Thin 2D Carbon Nitride Sheets for Enhanced Visible‐Light Photocatalysis

Atomically thin 2D carbon nitride sheets (CNS) are promising materials for photocatalytic applications due to their large surface area and very short charge‐carrier diffusion distance from the bulk to the surface. However, compared to their bulk counterpart, CNS' applications always suffer from an enlarged bandgap and thus narrowed solar absorption range. Here, an approach to significantly increase solar absorption of the atomically thin CNS via fluorination followed by thermal defluorination is reported. This approach can greatly increase the visible‐light absorption of CNS by extending the absorption edge up to 578 nm. The modulated CNS loaded with Pt cocatalyst as a photocatalyst shows a superior photocatalytic hydrogen production activity under visible‐light irradiation to Pt‐CNS. Combining experimental characterization with theoretical calculations shows that this approach can introduce cyano groups into the framework of CNS as well as the accompanied nitrogen vacancies at the edges, which leads to both narrowing the bandgap and changing the charge distribution. This study will provide an effective strategy to increase solar absorption of carbon‐nitride‐based photocatalysts for solar energy conversion applications.     

Impact of Interfacial Electron Transfer on Electrochemical CO2 Reduction on Graphitic Carbon Nitride/Doped Graphene

Effective electrocatalysts are required for the CO₂ reduction reaction (CRR), while the factors that can impact their catalytic activity are yet to be discovered. In this article, graphitic carbon nitride (g‐C₃N₄) is used to investigate the feasibility of regulating its CRR catalytic performance by interfacial electron transfer. A series of g‐C₃N₄/graphene with and without heteroatom doping (C₃N₄/XG, XG = BG, NG, OG, PG, G) is comprehensively evaluated for CRR through computational methods. Variable adsorption energetics and electronic structures are observed among different doping cases, demonstrating that a higher catalytic activity originates from more interfacial electron transfer. An activity trend is obtained to show the best catalytic performance of CRR to methane on C₃N₄/XG with an overpotential of 0.45 V (i.e., ?0.28 V vs reverse hydrogen electrode [RHE]). Such a low overpotential has never been achieved on any previously reported metallic CRR electrocatalysts, therefore indicating the availability of C₃N₄/XG for CO₂ reduction and the applicability of electron transfer modulation to improve CRR catalytic performance.     

Co@CNT复合电磁波吸收剂的制备及其吸波性能

以石墨相氮化碳(g-C₃N₄)和六水合硝酸钴为原料制备Co@CNT复合电磁波吸收剂,调节Co元素含量以提高其电磁波吸收性能。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱、扫描电镜(SEM)、能谱分析(EDS)和透射电镜(TEM)等手段表征其微结构和物相组成,使用矢量网络分析仪测量复合物电磁参数并进行Matlab模拟得到反射损耗图。结果表明,Co@CNT-1与石蜡质量比为1：3的材料,其吸波性能最优,厚度为4.1 mm时对电磁波的吸收最强,最小反射损耗(RL_min)为-45.5 dB;厚度仅为1.5 mm的材料,有效吸收带宽(RL<-10 dB)最大为4.42 GHz。     

ZIF‐67‐Derived 3D Hollow Mesoporous Crystalline Co3O4 Wrapped by 2D g‐C3N4 Nanosheets for Photocatalytic Removal of Nitric Oxide

ZIF‐67‐derived 3D hollow mesoporous crystalline Co₃O₄ wrapped by 2D graphitic carbon nitride (g‐C₃N₄) nanosheets are prepared by low temperature annealing, and are used for the photocatalytic oxidation of nitric oxide (NO) at a concentration of 600 ppb. The p–n heterojunction between Co₃O₄ and g‐C₃N₄ forms a spatial conductive network frame and results in a broad visible light response range. The hollow mesoporous structure of Co₃O₄ contributes to the circulation and adsorption of NO, and the large specific surface area exposes abundant active sites for the reaction of active species. A maximum NO degradation efficiency of 57% is achieved by adjusting the mass of the Co₃O₄ precursor. Cycling tests and X‐ray diffraction indicate the high stability and recyclability of the composite, making it promising in environmental purification applications.     

Drastic Enhancement of Photocatalytic Activities over Phosphoric Acid Protonated Porous g‐C3N4 Nanosheets under Visible Light

A simple method is developed to fabricate protonated porous graphitic carbon nitride nanosheets (P‐PCNNS) by protonation–exfoliation of bulk graphitic carbon nitride (BCN) with phosphoric acid (H₃PO₄). The H₃PO₄ treatment not only helps to exfoliate the BCN into 2D ultrathin nanosheets with abundant micro‐ and mesopores, endowing P‐PCNNS with more exposed active catalytic sites and cross‐plane diffusion channels to facilitate the mass and charge transport, but also induces the protonation of carbon nitride polymer, leading to the moderate removal of the impurities of carbon species in BCN for the optimization of the aromatic π‐conjugated system for better charge separation without changing its chemical structure. As a result, the P‐PCNNS show much higher photocatalytic performance for hydrogen evolution and CO₂ conversion than bare BCN and graphitic carbon nitride nanosheets.     

Partial Sulphidation to Regulate Coordination Structure of Single Nickel Atoms on Graphitic Carbon Nitride for Efficient Solar H2 Evolution

To develop a non-precious highly efficient cocatalyst to replace Pt on graphitic carbon nitride (g-C₃N₄) for solar H₂ production is great significant, but still remains a huge challenge. The emerging single-atom catalyst presents a promising strategy for developing highly efficient non-precious cocatalyst owing to its unique adjustability of local coordination environment and electronic structure. Herein, this work presents a facile approach to achieve single Ni sites (Ni₁-N₂S) with unique local coordination structure featuring one Ni atom coordinated with two nitrogen atoms and one sulfur atom, confirmed by high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, and density functional theory calculation. Thanks to the unique electron structure of Ni₁-N₂S sites, the 1095 µmol g⁻¹ h⁻¹ of high H₂ evolution rate with 4.1% of apparent quantum yield at 420 nm are achieved. This work paves a pathway for designing a highly efficient non-precious transition metal cocatalyst for photocatalytic H₂ evolution.     

Dibenzothiophene‐S,S‐Dioxide‐Based Conjugated Polymers: Highly Efficient Photocatalyts for Hydrogen Production from Water under Visible Light

Three dibenzothiophene‐S,S‐dioxide‐based alternating copolymers were synthesized by facile Suzuki polymerization for visible light–responsive hydrogen production from water (> 420 nm). Without addition of any cocatalyst, FluPh2‐SO showed a photocatalytic efficiency of 3.48 mmol h^?1 g?¹, while a larger hydrogen evolution rate (HER) of 4.74 mmol h^?1 g^?1 was achieved for Py‐SO, which was ascribed to the improved coplanarity of the polymer that facilitated both intermolecular packing and charge transport. To minimize the possible steric hindrance of FluPh2‐SO by replacing 9,9′‐diphenylfluorene with fluorene, Flu‐SO exhibited a more red‐shifted absorption than FluPh2‐SO and yielded the highest HER of 5.04 mmol h^?1 g^?1. This work highlights the potential of dibenzothiophene‐S,S‐dioxide as a versatile building block and the rational design strategy for achieving high photocatalytic efficiency.