Constructing Built‐in Electric Field in Ultrathin Graphitic Carbon Nitride Nanosheets by N and O Codoping for Enhanced Photocatalytic Hydrogen Evolution Activity

Codoping of N and O in ultrathin graphitic carbon nitride (g‐C₃N₄) nanosheets leads to an inner electric field. This field restrains the recombination of photogenerated carriers and, thus, enhances hydrogen evolution. The layered structure of codoped g‐C₃N₄ nanosheets (N‐O‐CNNS) not only provides abundant sites of contact with the reaction medium, but also decreases the distance over which the photogenerated electron–hole pairs are transported to the reaction interface. Quantum confinement in the ultrathin structure results in an increased bandgap and makes the photocatalytic reaction more favorable than bulk g‐C₃N₄. Under visible light irradiation, N‐O‐CNNS with 3 wt% Pt achieves a hydrogen evolution rate of 9.2 mmol g^?1 h^?1 and a value of 46.9 mmol g^?1 h^?1 under AM1.5 with 5 wt% Pt. Thus, this work paves the way for designing efficient nanostructures with increased separation/transfer efficiency of photogenerated carriers and, hence, increased photocatalytic activities.     

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.     

Merging Single‐Atom‐Dispersed Iron and Graphitic Carbon Nitride to a Joint Electronic System for High‐Efficiency Photocatalytic Hydrogen Evolution

Scalable and sustainable solar hydrogen production via photocatalytic water splitting requires extremely active and stable light‐harvesting semiconductors to fulfill the stringent requirements of suitable energy band position and rapid interfacial charge transfer process. Motivated by this point, increasing attention has been given to the development of photocatalysts comprising intimately interfaced photoabsorbers and cocatalysts. Herein, a simple one‐step approach is reported to fabricate a high‐efficiency photocatalytic system, in which single‐site dispersed iron atoms are rationally integrated on the intrinsic structure of the porous crimped graphitic carbon nitride (g‐C₃N₄) polymer. A detailed analysis of the formation process shows that a stable complex is generated by spontaneously coordinating dicyandiamidine nitrate with iron ions in isopropanol, thus leading to a relatively complicated polycondensation reaction upon thermal treatment. The correlation of experimental and computational results confirms that optimized electronic structures of Fe@g‐C₃N₄ with an appropriate d‐band position and negatively shifting Fermi level can be achieved, which effectively gains the reducibility of electrons and creates more active sites for the photocatalytic reactions. As a result, the Fe@g‐C₃N₄ exhibits a highlighted intramolecular synergistic effect, performing greatly enhanced solar‐photon‐driven activities, including excellent photocatalytic hydrogen evolution rate (3390 µmol h^?1 g^?1, λ > 420 nm) and a reliable apparent quantum efficiency value of 6.89% at 420 nm.     

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.     

介孔石墨相氮化碳吸附材料在环境中的应用

石墨相氮化碳(Graphitic carbon nitride,g-C_3N_4)是一种由碳(C)和氮(N)元素组成的共轭聚合物材料,具有平面的三嗪聚合物(Poly(tri-s-triazine))网络结构。比起大部分其他碳材料,氮化碳是富电子体,因而赋予了其特殊的性质。然而目前对于g-C_3N_4的研究主要集中在其相关催化作用(光催化,电催化和光电催化),对于g-C_3N_4的吸附作用的研究相对很少涉及。本文探讨了g-C_3N_4材料在吸附领域中的应用,简要综述了G-C_3N_4的性质、制备方法及其作为吸附材料的应用现状,最后展望了石墨型氮化碳在吸附应用领域的未来发展方向。     

Acetamide- or Formamide-Assisted In Situ Approach to Carbon-Rich or Nitrogen-Deficient Graphitic Carbon Nitride for Notably Enhanced Visible-Light Photocatalytic Redox Performance

Acetamide- or formamide-assisted in situ strategy is designed to synthesize carbon atom self-doped g-C₃N₄ (AHCN_x) or nitrogen vacancy-modified g-C₃N₄ (FHCN_x). Different from the direct copolymerization route that suffers from the problem of mismatched physical properties of acetamide (or formamide) with urea, the synthesis of AHCN_x (or FHCN_x) starts from a crucial preorganization step of acetamide (or formamide) with urea via freeze drying-hydrothermal treatment so that the chemical structures as well as C-doping level in AHCN_x and N-vacancy concentration in FHCN_x can be precisely regulated. By using various structural characterization methods, well-defined AHCN_x and FHCN_x structures are proposed. At the optimal C-doping level in AHCN_x or N-vacancy concentration in FHCN_x, both AHCN_x and FHCN_x exhibit remarkably improved visible-light photocatalytic performance in oxidation of emerging organic pollutants (acetaminophen and methylparaben) and reduction of proton to H₂ in comparison of unmodified g-C₃N₄. Combination of the experimental results with theoretical calculations, it is confirmed that AHCN_x and FHCN_x show different charge separation and transfer mechanisms, while the enhanced visible-light harvesting capacity and the localized charge distributions on HOMO and LUMO are responsible for this excellent photocatalytic redox performance of AHCN_x and FHCN_x.     

Synergistic Functionality of Dopants and Defects in Co-Phthalocyanine/B-CN Z-Scheme Photocatalysts for Promoting Photocatalytic CO2 Reduction Reactions

The realization of solar-light-driven CO₂ reduction reactions (CO₂ RR) is essential for the commercial development of renewable energy modules and the reduction of global CO₂ emissions. Combining experimental measurements and theoretical calculations, to introduce boron dopants and nitrogen defects in graphitic carbon nitride (g-C₃N₄), sodium borohydride is simply calcined with the mixture of g-C₃N₄ (CN), followed by the introduction of ultrathin Co phthalocyanine through phosphate groups. By strengthening H-bonding interactions, the resultant CoPc/P-BNDCN nanocomposite showed excellent photocatalytic CO₂ reduction activity, releasing 197.76 and 130.32 µmol h⁻¹ g⁻¹ CO and CH₄, respectively, and conveying an unprecedented 10-26-time improvement under visible-light irradiation. The substantial tuning is performed towards the conduction and valance band locations by B-dopants and N-defects to modulate the band structure for significantly accelerated CO₂ RR. Through the use of ultrathin metal phthalocyanine assemblies that have a lot of single-atom sites, this work demonstrates a sustainable approach for achieving effective photocatalytic CO₂ activation. More importantly, the excellent photoactivity is attributed to the fast charge separation via Z-scheme transfer mechanism formed by the universally facile strategy of dimension-matched ultrathin (≈4 nm) metal phthalocyanine-assisted nanocomposites.     

3D Aerogel of Graphitic Carbon Nitride Modified with Perylene Imide and Graphene Oxide for Highly Efficient Nitric Oxide Removal under Visible Light

3D materials are considered promising for photocatalytic applications in air purification because of their large surface areas, controllability, and recyclability. Here, a series of aerogels consisting of graphitic‐carbon nitride (g‐C₃N₄) modified with a perylene imide (PI) and graphene oxide (GO) are prepared for nitric oxide (NO) removal under visible‐light irradiation. All of the photocatalysts exhibit excellent activity in NO removal because of the strong light absorption and good planarity of PI–g‐C₃N₄ coupled with the favorable charge transport properties of GO, which slow the recombination of electron–hole pairs. The aerogel containing thiophene displays the most efficient NO removal of the aerogel series, with a removal ratio of up to 66%. Density functional theory calculations are conducted to explain this result and recycling experiments are carried out to verify the stability and recyclability of these photocatalysts.     

Band Engineering and Morphology Control of Oxygen‑Incorporated Graphitic Carbon Nitride Porous Nanosheets for Highly Efficient Photocatalytic Hydrogen Evolution

Graphitic carbon nitride(g-C3N4)-based photocatalysts have shown great potential in the splitting of water.However,the intrinsic drawbacks of g-C3N4,such as low surface area,poor diffusion,and charge separation efficiency,remain as the bottleneck to achieve highly efficient hydrogen evolution.Here,a hollow oxygen-incorporated g-C3N4 nanosheet(OCN)with an improved surface area of 148.5 m2 g^−1 is fabricated by the multiple thermal treatments under the N2/O2 atmosphere,wherein the C–O bonds are formed through two ways of physical adsorption and doping.The physical characterization and theoretical calculation indicate that the O-adsorption can promote the generation of defects,leading to the formation of hollow morphology,while the O-doping results in reduced band gap of g-C3N4.The optimized OCN shows an excellent photocatalytic hydrogen evolution activity of 3519.6μmol g^−1 h^−1 for~20 h,which is over four times higher than that of g-C3N4(850.1μmol g^−1 h^−1)and outperforms most of the reported g-C3N4 catalysts.     

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。     

Evolution of Irradiation‐Induced Vacancy Defects in Boron Nitride Nanotubes

Irradiation‐induced vacancy defects in multiwalled (MW) boron nitride nanotubes (BNNTs) are investigated via in situ high‐resolution transmission electron microscope operated at 80 kV, with a homogeneous distribution of electron beam intensity. During the irradiation triangle‐shaped vacancy defects are gradually generated in MW BNNTs under a mediate electron current density (30 A cm^?2), by knocking the B atoms out. The vacancy defects grow along a well‐defined direction within a wall at the early stage as a result of the curvature induced lattice strain, and then develop wall by wall. The orientation or the growth direction of the vacancy defects can be used to identify the chirality of an individual wall. With increasing electron current density, the shape of the irradiation‐induced vacancy defects changes from regular triangle to irregular polygon.     

Cobalt Sulfide Nanowires Core Encapsulated by a N,S Codoped Graphitic Carbon Shell for Efficient Oxygen Reduction Reaction

Exploration of economical electrocatalysts for highly efficient and stable oxygen reduction reaction (ORR) is believed to be essential for diverse future renewable energy applications. Herein, cobalt sulfide nanowire core encapsulated in a N, S codoped graphitic carbon shell (CoS NWs@NSC) is successfully fabricated via the calcination of polydopamine‐coated Co(CO₃)_0.5(OH)_0.11H₂O NWs with sulfur powder under argon atmosphere. The uniform encapsulation of CoS core by N, S codoped graphitic carbon shell favors the interaction of the core–shell structure for generating stable and numerous ORR active sites homogeneously dispersed throughout the materials. Meanwhile, the wire‐like CoS NWs@NSC stacks to form 3D mesoporous conductive networks, which improves the mass and charge transport capability of catalyst. Accordingly, the resultant CoS NWs@NSC electrocatalysts possess excellent ORR activity through the four‐electron pathway with superior stability and methanol tolerance over the Pt/C in 0.1 m KOH. This strategy can offer inspiration for designing and fabricating novel core–shell‐structured nanomaterials with active sites derived from uniform morphology as potential electrocatalysts for various vital renewable energy devices.