English

• 1. Introduction

  Energy and good ecological environment are the cornerstone and indispensable element in today's the sustainable global development of human society [1,2]. With the rapid industrialization and globalization, energy shortage and environmental pollution have gradually escalated into hotspot issue [3-5]. However, depletable and unclean fossil fuels are still the main energy sources humans use nowadays [6]. Thus, exploring clean and inexhaustible energy is urgent to reverse the trend. The infinite and freely accessible solar energy is regarded as the most environmentally friendly and most promising new energy resource [7]. Artificial photocatalytic energy conversion supplies the promising manner for overcoming energy crisis, combating to climate change and remediating environment [6,8,9]. For instance, sustainable clean H₂ fuel, which was produced by photocatalytic water splitting [10-13], was considered as one of the most promising green energy sources due to generating water during the process of complete reaction between H₂ and O₂ [14]. The photocatalytic CO₂ reduction was widely recognized as a deployable and highly intriguing strategy to recycle the inert CO₂ into value-added substances such as CH₄ or CO [15]. The photocatalytic degradation of environmental contaminants could treat the wastewater economically and effectively [16,17]. Therefore, the development and improvement of photocatalysts that could effectively absorb photons from the sun need to be studied intensively and many encouraging achievements have been made after years of exploration.

  Among various photocatalysts of zero-dimension, one dimension, two dimension and three-dimension, polymer semiconductor g-C₃N₄ has drawn immense attraction in recent years owing to its customizable structure, excellent visible-light response activity, superiorly photochemical and thermal stability, abundance of raw materials, facile synthetic strategy, low cost and toxicity [18,19]. As an n-type organic semiconductor, g-C₃N₄ possesses an optical band gap of 2.70 eV. Therefore, g-C₃N₄ can harvest visible light of the solar spectrum up to 460 nm [20-22]. Nevertheless, the further large-scale applications of g-C₃N₄ are restricted due to low surface area, severe charge recombination rate, low mobility of charge and inadequate visible light (wavelength range, 400–760 nm) absorption. To overcome such shortcomings, the composites with high photoactivity of g-C₃N₄ are designed and developed. For example, the lifetime of the charge carriers could be prolonged by the morphology control [23]. In addition, other ways, including metal or non-metal doping [24-27], constructing heterojunctions [28-30], surface modification [31,32], have also been employed to improve the photocatalytic properties of g-C₃N₄. Among them, it is universally accepted that semiconductor surfaces modification using noble metal nanoparticles such as silver (Ag) and gold could expand the light-harvesting range of visible-near-infrared light owing to the surface plasmon resonance effects [33-35]. Besides, the noble metal nanoparticles could do duty for the electron trappers due to the low Fermi levels [36]. Compared to other noble metals, the Ag was regarded as the most economical raw materials that possessed the stronger surface plasmon resonance effect and higher sensitivity [37,38]. Thus, the Ag decoration has increasingly been considered as a promising method, which could facilitate separation/transfer of charge carriers and enhance the absorption of visible light so as to achieve the high photocatalytic energy conversion [39,40]. Currently, the synthetic methods of various Ag decorated g-C₃N₄ are generally calcination, chemical and photo-assisted reduction. Typically, Ag/g-C₃N₄ porous nanofibers was synthesized using supramolecular hydrogel of Ag-melamine as the precursor via calcination and presented highly efficient H₂ evolution [41]. The photo-assisted reduction using ultra-violet (UV) irradiation was applied to synthesize the Ag nanoparticles decorated g-C₃N₄ nanosheets [42]. Ag decorated P-doped g-C₃N₄ nanosheets, which visible-light photocatalytic activities were proved to significantly enhance by the experiments of water splitting and pollutant degradation, were constructed by silver mirror reaction and two-step calcination process [43]. Microfluidic reactors with the advantages of high heat and mass transfer, operational safety and enhanced scalability were also employed for Ag/g-C₃N₄ synthesis, achieving the higher catalytic activity for the photocatalytic water splitting [44]. Furthermore, single-atom Ag incorporated g-C₃N₄ catalyst was synthesized and presented excellent stability and higher photocatalytic activities for H₂ evolution than Ag or Pt nanoparticles decorated g-C₃N₄ [45] and so forth. As far as we know, although some excellent reviews have summarized the based-g-C₃N₄ applications such as H₂ evolution [46,47], pollutant degradation [48,49], and CO₂ reduction [50,51], the comprehensive review of g-C₃N₄ decorated with silver for photocatalytic energy conversion have not been covered.

  In this review, we began with comprehensive and in-depth introductions for the basic performances and types of g-C₃N₄. Then, the g-C₃N₄ decorated with various silvers were introduced systematically, focusing on the comprehensive summary of g-C₃N₄ decorated with silver nanoparticles and single atom silver. It was worth noting that the composites of silver and g-C₃N₄ semiconductor possess unique advantage than other g-C₃N₄ composite photocatalyst, including enhancing visible light absorption, prolonging the lifetime of the charge carriers, excellent controllability and stability, higher photocatalytic efficiency and environmentally friendly. Therefore, the photocatalysts of g-C₃N₄ decorated with various silvers have become the promising candidates for photocatalytic energy conversion and environmental remediation. As shown in Fig. 1, their applications on H₂ evolution, pollutant degradation and CO₂ reduction were summarized. Finally, some pivotal challenges and perspectives for future development were further proposed.

  Figure 1

  

  Figure 1.  Schematic illustration of the g-C₃N₄ decorated with various silvers for photocatalytic energy conversion.

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  2. Basic performances and types of g-C₃N₄

  2.1 Basic performances of g-C₃N₄

  Metal-free polymer semiconductor: The g-C₃N₄, consisting of triazine or tri-s-triazine units connected with planar amino groups in each layer and weak van der Waals force between layers, was just consist of carbon (C) and nitrogen (N) with the hybridization forms of sp², and some impurity hydrogen (H) [52], as shown in Fig. 2. The C/N stoichiometric ratio confirmed by theoretical calculation was 0.75. Nevertheless, the results of element analysis, which was different from the ideal scale model of 0.75, verified that average C/N atomic ratio was 0.72 and there were 2% H from uncondensed amino functions [53]. Besides, the photocatalytic applications of semiconductor were mainly determined by the valence band (VB) potential, conduction band (CB) potential and band gap energy (E_g). The VB and CB were severally due to the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The E_g was the energy difference between the conduction band minimum (CBM) and valence band maximum (VBM) [3]. Therefore, the degree of light response and redox capability of semiconductor were controlled by the energy band structure (Fig. 1). The VB and CB of g-C₃N₄ were severally composed of nitrogen P_Z orbitals (HOMO) and carbon P_Z orbitals (LUMO) [44]. The E_g (2.70 eV) of g-C₃N₄ was the energy difference between VB (−1.1 eV) and CB (+1.6 eV) potential [54]. Thus, the g-C₃N₄ showed a response to visible light up to 460 nm [55,56]. In short, the simple composition of g-C₃N₄ endowed its unique characteristics such as nontoxic, biocompatible, easy preparation using abundant precursors, medium band gap, and made it become the promising candidate for the application system of visible light [57].

  Figure 2

  

  Figure 2.  (A) Triazine and (B) tri-s-triazine (heptazine) structures of g-C₃N₄. Reprinted with permission [73]. Copyright 2016, American Chemical Society.

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  Stability: C₃N₄ processed five kinds of structures, including α-C₃N₄, β-C₃N₄, cubic C₃N₄, quasi-cubic C₃N₄ and graphite-like phase C₃N₄. Among them, the g-C₃N₄ was most stable due to the planar lamellae structure similar to graphene and had high thermal and chemical stability [58]. Thermal analysis showed that the heat resistance temperature was 600 ℃ in the air and complete decomposition temperature was up to 700 ℃ [53,59,60]. The chemical attack such as acid, alkali, and organic solvents except for potassium permanganate and molten alkali metal hydroxide was stable [61], which benefited from strong covalent C—N bonds in each layer and interlayer van der Waals forces [60]. Thus, the stable g-C₃N₄ was widely perceived as a promising inert material for various applications of high temperature reactions and surface science in multifarious solvents [62,63].

  Optical performances: The optical property of g-C₃N₄ was critical for visible light photocatalytic applications, which could be characterized using photoluminescence (PL) [64], ultraviolet-visible diffuse reflection spectrum (UV–vis DRS) [16] and electrochemiluminescence (ECL) [65]. According to statistics, the band-gap initial UV–vis absorption peak of g-C₃N₄ was in the 420–450 nm wavelength range, which belonged to a characteristic absorption of organic semiconductor. According to a previous report, with the increase of condensation temperature, the absorption edge of UV–vis spectrum generated bathochromic shift, indicating the condensation temperatures could affect the band gap (Fig. 3A) [66]. In addition, doping of metallic and nonmetallic elements (Fe, Mn, Au, Ag, S, P, C, I, O, and B atoms and barbituric acid) also made the adsorption edge move towards longer wavelengths [53,67]. Coincidentally, condensation temperature also played a vital role in the PL. The PL spectra of g-C₃N₄ were red shift when the condensation temperature increased (Fig. 3B). Furthermore, because of the transition of the s-triazine ring, the g-C₃N₄ dissolved in solvents emitted blue PL approximate 450 nm under UV light irradiation [68]. The ECL of g-C₃N₄ opened up a potential route for sensitive detection system, in which g-C₃N₄ acted as a donor of energy transfer [69]. In a word, the UV–vis DRS, PL and ECL properties of g-C₃N₄ were very important for applications in various fields such as catalysis, energy storage technologies, sensing, light-emitting devices, and biological imaging [70].

  Figure 3

  

  Figure 3.  (A) Ultraviolet-visible diffuse reflectance spectrum of g-C₃N₄ prepared at different temperature. Reprinted with permission [66]. Copyright 2009, Springer Nature. (B) Photoluminescence spectra of 2 h calcined g-C₃N₄ at different temperatures. Reprinted with permission [53]. Copyright 2022, Elsevier.

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  Electrochemical and photoelectrochemical performances: The strong electron acceptance ability of nitrogen atom in the heptaphane ring was in connection with the electrocatalytic performance of g-C₃N₄ and could induce the electrochemical reactions [60]. However, the single g-C₃N₄ was inert to the electrocatalysis common reactions of O₂ and H₂ evolution reaction [71]. There is no doubt that photoelectrochemical properties could endow g-C₃N₄ more excellent catalytic activity by the combination of optical and electrical performances, which opened the door for the study of photoelectrochemical performances of g-C₃N₄-based materials [72,73].

  2.2 Types of g-C₃N₄

  The types of g-C₃N₄ were still being extended due to the intense studies in the past few years. Synthetic routes, material compositions, condensation temperatures and shapes of g-C₃N₄ were pivotal for its properties and applications. The various types of g-C₃N₄ could be synthesized using various precursors, including melamine [74-76], urea [77,78], thiourea [79,80], dicyandiamide [81,82], cyanamide [83,84], and guanidinium chloride [85,86], and various suitable synthetic routes such as thermal condensation [87] and supramolecular pre-assembly [88]. In order to give a clearer picture of the morphologies, we classified herein in terms of different shapes, as shown in Fig. 4. The following was an introduction to the common and different shapes of g-C₃N₄ according to the timeline.

  Figure 4

  

  Figure 4.  Various morphologies of the g-C₃N₄. The nanocluster. Reprinted with permission [89]. Copyright 2014, Royal Society of Chemistry. The nanosphere. Reprinted with permission [97]. Copyright 2019, Royal Society of Chemistry. The nanorod. Reprinted with permission [99]. Copyright 2012, Royal Society of Chemistry. The nanotube. Reprinted with permission [103]. Copyright 2009, American Chemical Society. The nanofiber. Reprinted with permission [107]. Copyright 2008, Wiley. The nanosheet. Reprinted with permission [113]. Copyright 2012, Wiley.

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  Nanocluster and nanosphere: The strong quantum confinement effects of g-C₃N₄ nanoclusters when the size was less than 10 nm made it display the bright fluorescence. Besides, the advantages of g-C₃N₄ nanoclusters also contained good stability, non-toxicity and biocompatibility. The synthetic routes of g-C₃N₄ nanoclusters mainly contained two methods of top-down and bottom-up. The upconverted g-C₃N₄ nanoclusters were synthesized using the top-down method. Wang et al. prepare the g-C₃N₄ nanostructure by controlling the process of cutting three-dimensional bulk g-C₃N₄ into two-dimensional nanosheets, one-dimensional g-C₃N₄ nanoribbons and finally to zero-dimensional g-C₃N₄ nanostructures for the first time [89], as shown in Fig. 5A. In the same year, Xie et al. firstly prepared the g-C₃N₄ single-layered quantum dots using the top-down method which included three steps of acid treatment, hydrothermal treatment and ultrasonication [90]. Hu et al. also developed an extremely simple and green hydrothermal treatment of bulk g-C₃N₄ to form g-C₃N₄ dots for the first time [91]. The following year, the g-C₃N₄ quantum dots were prepared by bottom-up method. For example, Lin et al. developed a facile one-pot microwave-assisted solvothermal method to prepare the strong excitation-dependent photoluminescence g-C₃N₄ quantum dots [92]. Lu et al. prepared the oxygen and sulfur co-doped g-C₃N₄ quantum dots by thermal treatment of citric acid and thiourea, which had the strong blue photoluminescence [93]. Afterwards, the doping and metal modified methods were used to synthesize g-C₃N₄ quantum dots, which the emission wavelength was in the whole visible-light regime and exhibited excitation-dependent red emission peak by metal-enhanced effect [75,94]. The g-C₃N₄ nanospheres which the size was greater than 10 nm had been prepared using rapid microwave-hydrothermal method as early as in 2008 [95]. Interestingly enough, inspired by natural photosynthesis system, the spherical and multishell g-C₃N₄ nanocapsule was successfully synthesized by Shen et al., which exhibited excellent visible-light harvesting and electron transfer properties [84], as illustrated in Fig. 5B. In recent years, the g-C₃N₄ microspheres and nitrogen-doped hollow carbon nanospheres were synthesized by facile thermal heating method and the classic Stöber approach [96,97], respectively.

  Figure 5

  

  Figure 5.  (A) Schematic illustration of the controllable synthesis of g-C₃N₄ nanosheets, nanoribbons and quantum dots. Reprinted with permission [89]. Copyright 2014, Royal Society of Chemistry. (B) Overall synthetic procedure of multishell g-C₃N₄ nanocapsules. Reprinted with permission [84]. Copyright 2017, American Chemical Society. (C) Synthetic process for helical nanorod-like g-C₃N₄ and morphology characterization. Reprinted with permission [100]. Copyright 2014, John Wiley and Sons Ltd. (D) The proposed formation process of g-C₃N₄ nanotubes. Reprinted with permission [104]. Copyright 2014, Royal Society of Chemistry. (E) Preparation of porous nanofiber-like Ag/g-C₃N₄ from Ag-melamine supramolecular hydrogels. Reprinted with permission [41]. Copyright 2017, American Chemical Society. (F) Schematic illustration of liquid-exfoliation process from bulk g-C₃N₄ to ultrathin nanosheets, the photograph of bulk g-C₃N₄ and suspension of ultrathin g-C₃N₄ nanosheets. Reprinted with permission [115]. Copyright 2013, American Chemical Society.

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  Nanorod, nanotube, nanofiber/nanowire: The g-C₃N₄ nanorod, nanotube and nanofiber/nanowire belonged to the one-dimensional nanostructures and processed high surface area, smooth carrier transport and light harvesting. Thus, they were widely used in the field of photocatalysis. One's early years, the g-C₃N₄ nanorods and mesoporous g-C₃N₄ nanorods were successfully synthesized using chiral silica nanorods and SBA-15 nanorod as templates, respectively [98,99]. Interestingly enough, Zheng et al. reported a nanocasting approach to prepare twisted hexagonal rod-like C₃N₄ by using chiral silicon dioxides as templates [100], as illustrated in Fig. 5C.

  As early as in 2004, the high-quality carbon nitride nanotubes, which inner diameters and wall thicknesses were severally in the range of 50–100 nm and 20–50 nm, were successfully synthesized by a simple benzene-thermal process and without using any catalyst or template for the first time [101]. Subsequently, the g-C₃N₄ nanobelts and nanotubes were produced by polycondensation of dicyandiamide and melamine at 290 ℃ and 4.5–5 MPa [102]. The polymerization reaction between ethylenediamine and carbon tetrachloride was used to produce carbon nitride nanotubes, in which the porous anodic aluminum oxide membranes played a templated role [103]. The nanotube-type g-C₃N₄, which showed blue fluorescence and excellent visible-light photocatalytic activity, was synthesized by facile and generally feasible method of directly heating melamine [104], as illustrated in Fig. 5D. The tapered hollow g-C₃N₄ composite nanotubes were fabricated via one-step thermal condensation of polyacrylonitrile, melamine and sulfur [105]. The tubular g-C₃N₄ isotype heterojunction, which could jointly manipulate the oriented transfer of electrons and holes so as to facilitate the visible-light photocatalysis, was produced by combining the molecular self-assembly and thermal polycondensation techniques [106].

  Initially, the nitrogen-rich carbon nitride microfibers were large-scale synthesized by evaporating the as-synthesized graphitic carbon nitride precursor [107]. Subsequently, the g-C₃N₄ nanowires were synthesized by using diatom frustules as a substrate [108]. The following year, Tahir et al. also reported a facile, scale up, and efficient method to synthesize the g-C₃N₄ nanofibers, which could be used for energy storage and photodegradation of rhodamine B [109]. In recent years, the porous nanofiber-type g-C₃N₄ nanocomposites were fabricated by a new and facile supramolecular hydrogel self-template approach [41], as illustrated in Fig. 5E.

  Nanosheet: The g-C₃N₄ nanosheets had received tremendous attention due to a graphite-like layered structure and weak van der Waals of interlamination and had been used widely in energy conversion applications [110-112]. Similar to aforementioned synthetic routes of g-C₃N₄ nanostructures, the g-C₃N₄ nanosheets mainly had two synthetic approaches, including the top-down and bottom-up approach. Niu et al. used the top-down chemical etching approach to produce the g-C₃N₄ nanosheets with larger surface area 306 m²/g than the 50 m²/g of bulk g-C₃N₄ [113]. The following year, Yang et al. [114] and Zhang et al. [115] demonstrated the synthesis of g-C₃N₄ nanosheets by liquid phase exfoliation routes, as illustrated in Fig. 5F. Subsequently, Ma et al. developed a new approach of sonication-exfoliation to fabricate proton-functionalized ultrathin g-C₃N₄ nanosheets for the first time [116]. Schwinghammer et al. synthesized crystalline carbon nitride nanosheets by one-step liquid exfoliation of bulk material poly(triazine imide) [117]. Recently, Chen et al. reported a barbituric acid-modified graphitic carbon nitride nanosheets with blue-green fluorescence, which were prepared by the copolymerization of dicyandiamide with barbituric acid and then the chemical oxidation process [118]. For the bottom-up approach, Yang et al. demonstrated the successful fabrication of graphene-based carbon nitride nanosheets using the nanocasting technology, which the graphene-based mesoporous silica nanosheets were employed as a template for the first time [119]. In the same year, Zhang et al. developed a new, facile, sulfur-mediated method to prepare the g-C₃N₄ polymers, which the big atomic size of sulfur could influence the conformation and the connectivity of the acquired g-C₃N₄ and hence provide a template tool for tuning the texture and electronic structure [120]. In addition, other methods have also been used to synthesize g-C₃N₄ nanosheets. For example, Cheng et al. obtained g-C₃N₄ nanosheets by pyrolyzing a melamine-KBH₄ mixture for the first time, which could be used as a fluorosensor for Cu²⁺ and possessed the chemiluminescence (ECL) behavior and so on [21].

  3. The photocatalytic reactions of silver-modified g-C₃N₄

  In recent years, considerable efforts had been done in the area of silver-modified g-C₃N₄ composite materials and a lot of achievements had been accomplished. For example, the silver nanoparticles, silver nanoclusters, single atom silver and other kinds of silver such as silver halides and silver phosphate were used to decorate the various g-C₃N₄ in order to effectively improve the photocatalytic activity of g-C₃N₄. There were mainly the following reasons. Firstly, the silver was relatively inexpensive compared with other noble metals such as Au and Pt. Then, the plasma resonance effect of metal Ag could facilitate the improvement of local electromagnetic fields and improve the electron conductivity, which could promptly generate the electron and hole carriers in photocatalysts. In addition, the Schottky junction between Ag and the g-C₃N₄ could restrain the recombination of electron and hole charge carriers [121-123]. In this focused section, the synthetic strategies of miscellaneous composite materials and the applications photocatalytic energy conversion of silver-decorated g-C₃N₄ were presented in detail. Furthermore, the reports on silver-decorated g-C₃N₄ photocatalysts were summarized in Table 1 following chronological order.

  Table 1

  

  Table 1.  Recent reports on g-C3N4-based photocatalysts.

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  3.1 The g-C₃N₄ decorated with silver nanoparticles

  In recent ten years, silver (Ag) nanoparticles decorated g-C₃N₄ had drawn broad interdisciplinary attention, which could be used for photocatalytic energy conversion such as photocatalytic pollutant degradation, photocatalytic hydrogen evolution, photocatalytic N₂ (highly stable) reduction [124], and sensing. As early as in 2011, Ge et al. synthesized the g-C₃N₄ photocatalysts loaded with noble metal Ag nanoparticles by facile heating method. The as-synthesized Ag/g-C₃N₄ composite with enhanced photocatalytic property was used for the decomposition of methyl orange and hydrogen evolution [125]. Yang et al. also prepared the Ag/g-C₃N₄ plasmonic photocatalysts via thermal polymerization and photodeposition method, which were used to effectively degrade the methyl orange and p-nitrophenol [126]. Whereafter, the organic pollutants, including methyl mercaptan [127], sulfamethoxazole [122], rhodamine B [128], and methylene blue [129], also were degraded under visible light by using the Ag/g-C₃N₄ composites as the photocatalyst. For the photocatalytic hydrogen evolution, Wang et al. had further proved that the promising photocatalyst of Ag/g-C₃N₄ exhibited highly promoted photoinduced electron-hole separation capability, so giving much better hydrogen evolution activity than the pristine g-C₃N₄ [41]. Recently, a wide variety of Ag/g-C₃N₄ photocatalysts, including the g-C₃N₄ nanotubes [130], bulk g-C₃N₄ [131], two-dimensional g-C₃N₄ nanosheets [78,132] decorated with silver nanoparticles, were designed and fabricated for photocatalytic hydrogen evolution under visible light, which all showed the enhanced charge separation/transfer owing to the introduction of silver nanoparticles. For instance, Fig. 6A showed the photocatalytic mechanism of hydrogen generation of Ag/g-C₃N₄. The electrons and holes formed, and then the electron injected into Ag nanoparticles sites. Schottky barrier between Ag and g-C₃N₄ could capture the photogenerated electrons and facilitate the separation rate of electron-hole pairs. Finally, the photoelectron reacted with the H₂O and generated hydrogen. Fig. 6B showed that the hydrogen generation rate increased dramatically with the increase of the loading content [132]. In addition, Yao et al. prepared the boron and noble metal Ag modified graphitic carbon nitride via in-situ decomposition-thermal polymerization method. The obtained Ag/B-doped g-C₃N₄ composites were used for photocatalytic ammonia production and the photocatalytic property was distinguished due to inhibiting the recombination of photogenerated charge carriers by the loaded Ag nanoparticles [133]. The applications of g-C₃N₄ decorated with Ag nanoparticles had been further extended for sensing. Cheng et al. synthesized a composite of g-C₃N₄ quantum dots decorated with Ag nanoparticles, which had strong metal-enhanced fluorescence intensity and was used for ultrasensitive detection of heparin [75]. The parathion-methyl [134] and Hg²⁺ ion [135] were also detected using Ag nanoparticles decorated g-C₃N₄ as sensor. Interestingly enough, Bayan et al. fabricated a textile based triboelectric nanogenerator for the first time, which was made up of Ag nanoparticles loaded g-C₃N₄ nanosheets and carbon fibres. The superior output characteristics and thermal stability of triboelectric nanogenerator made it become potential power sources for wearable electronics [42].

  Figure 6

  

  Figure 6.  Schematic diagram (A) and H₂ generation rate of catalysts with different loading contents (B) of photocatalytic hydrogen generation of Ag/g-C₃N₄. Reprinted with permission [132]. Copyright 2022, Elsevier. Photocatalytic mechanism of Ag decorated P-doped g-C₃N₄ nanosheets under visible-light irradiation (C), time course of hydrogen evolution (D), and photocatalytic activities (E) for rhodamine B degradation under visible light irradiation. Reprinted with permission [43]. Copyright 2022, Elsevier. The possible photocatalytic mechanism (F) and photocatalytic activity (G) for degradation of bisphenol A over photocatalyst of mesoporous g-C₃N₄ decorated with isolated Ag sites. Reprinted with permission [139]. Copyright 2017, Elsevier. The proposed Z-scheme photocatalytic mechanism for the Ag₂CrO₄/g-C₃N₄/GO composite (H) and CH₃OH and CH₄ production (I) of CN (g-C₃N₄), CG (g-C₃N₄/GO), CA (Ag₂CrO₄/g-C₃N₄) and CAG (Ag₂CrO₄/g-C₃N₄/GO) samples. Reprinted with permission [158]. Copyright 2018, Elsevier.

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  3.2 The g-C₃N₄ decorated with silver nanoclusters

  During the rational design of silver-modified g-C₃N₄ photocatalysts for hydrogen evolution, researchers paid great attention to adjust the size of silver (Ag) nanoparticles to enhance the photocatalytic property. Recently, Mallikarjuna et al. successfully fabricated g-C₃N₄ decorated with Ag nanoclusters using ultrasonication method. The obtained Ag/g-C₃N₄ composite displayed the profound photocatalytic activities for hydrogen evolution. Furthermore, the effect of dye degradation and antimicrobial activity were profound [136]. Chen et al. constructed the highly efficient photocatalysts of Ag decorated P-doped g-C₃N₄ for hydrogen evolution and photocatalytic degradation of rhodamine B, which were severally 5.3 and 1.6 times that of bulk g-C₃N₄ due to the plasma resonance effect of Ag and Schottky junction between Ag and P-doped g-C₃N₄ (Figs. 6C-E) [43]. Besides, the various pollutants such as rhodamine B, tetracycline, and acetaminophen could be degraded by Ag/g-C₃N₄ composite, including the g-C₃N₄ nanosheets decorated with silver silicates dots (~5.2 nm) [55] and silver nanoclusters [137,138].

  3.3 The g-C₃N₄ decorated with single atom silver

  As a representative n-type polymer semiconductor, the g-C₃N₄ had been employed as excellent host support for producing single-atom photocatalysts due to the abundant surface trapping sites for isolated atoms. The noble metal silver (Ag) had been decorated on the g-C₃N₄ to fabricate the single atom-dispersed silver-decorated g-C₃N₄ photocatalysts for the degradation of emerging pollutants and hydrogen evolution. Wang et al. had decorated isolated Ag atoms on mesoporous g-C₃N₄ (mpg-C₃N₄) via co-condensation method. The as-synthesized Ag/mpg-C₃N₄ single-atom photocatalyst presented excellent performance for the degradation of bisphenol A (100% degradation over 0.1 g/L photocatalysts within 1 h) due to quick transfer of photoexcited electrons by adding peroxymonosulfate to accelerate the separation of electron-hole pairs, as seen from Figs. 6F and G [139]. Wang et al. reported a novel ternary photocatalyst comprised of single atom-dispersed Ag and carbon quantum dots, co-loaded with ultrathin g-C₃N₄, which presented a highly photocatalytic activity for the degradation of naproxen, mainly attributing to the surface plasmon resonance effect and the electron separation and transfer capacity of Ag [17]. Recently, Zhao et al. have further demonstrated that Ag/g-C₃N₄ single-atom photocatalyst showed the enhanced visible light absorption and accelerated charge transfer owing to the amorphous structure induced by single-atom Ag, thus giving much better photocatalytic naproxen degradation activity than the pure g-C₃N₄ [140]. Besides, Wang et al. also synthesized a single-atom dispersed Ag loaded ultrathin g-C₃N₄ hybrid by a facile co-polymerization, which was served as visible light driven photocatalyst for the degradation of sulfamethazine and exhibited higher efficiency [141]. Soon afterwards, Wang et al. synthesized the sodium ion-doped g-C₃N₄ photocatalyst decorated with ultrafine silver nanoparticles (<1 nm) via facile and efficient one-pot route, which showed enhanced photogenerated charge separation/transfer and effectively degraded rhodamine B and tetracycline hydrochloride [142]. Artificial photocatalytic hydrogen evolution was a potential path to convert the infinite and freely accessible solar energy into the green and clean energy carrier of hydrogen. Lately, Li et al. constructed the highly active photocatalyst of single-atom silver-decorated g-C₃N₄, which showed excellent activity for the photocatalytic hydrogen evolution [45].

  3.4 The g-C₃N₄ decorated with other kinds of silver

  Other kinds of silvers, including silver halides, Ag₃PO₄, Ag₂O, Ag₂CO₃, Ag₂CrO₄, Ag₂NCN, Ag/AgO, Ag-AgVO₃, Ag@AgCl, had also been applied to construct g-C₃N₄-based photocatalysts. Organic pollutants such as dyes, pharmaceuticals had undesirable hazards on human settlements and ecological balance. It was urgent to efficiently eliminate the contaminants and achieve a sustainable planet. Photocatalytic degradation provided an interesting approach to remove these contaminants by rational design of photocatalysts and harvesting solar energy to promote the generation of free radical species. Xu et al. had decorated the AgX (X = Br, I) nanoparticles onto the g-C₃N₄ for the photocatalytic degradation of methyl orange [143]. The introduction of AgX nanoparticles promoted the photocurrent and increased photocatalytic activity. In the same year, Zhang et al. developed a novel g-C₃N₄/Ag₃PO₄ bulk heterojunction for photocatalytic degradation of rhodamine B, which had two intense optical absorption edges corresponding to g-C₃N₄ and Ag₃PO₄ in the visible light region [144]. Afterwards, more and more photocatalysts, including Ag₂O-g-C₃N₄ composite [145], AgBr/g-C₃N₄ nanocomposite photocatalyst [146], g-C₃N₄ nanosheets decorated with Ag₂CO₃ nanoparticles [147], g-C₃N₄ sheets decorated with Ag₂CrO₄ nanoparticles [148], ultrathin g-C₃N₄ nanosheets decorated with Ag₂NCN nanoparticles [149], the g-C₃N₄ microspheres decorated with silver/silver(Ⅱ) oxide (Ag/AgO) [96], Ag-AgVO₃/g-C₃N₄ composite [150], poly-o-phenylenediamine modified AgCl/g-C₃N₄ nanosheets [151], Z-scheme AgBr/P-g-C₃N₄ heterojunction photocatalyst [152], AgI/g-C₃N₄ nanocomposites [153], and Ag@AgCl/g-C₃N₄ plasmonic photocatalyst [154], had been used for the photocatalytic degradation of rhodamine B [145,147,148,153], methyl orange [146,147,153], phenol [148], organic dye [149], acid violet-7 dye [96], tetracycline [150,151,154], ephedrine [152]. Furthermore, Yang et al. reported a highly efficient photocatalyst of decorating silver phosphate particles on various g-C₃N₄ for the photocatalytic hydrogen evolution [155]. The Z-scheme and p-n heterostructure of porous g-C₃N₄/graphene oxide-Ag/AgBr composite was constructed for high-efficient photocatalytic hydrogen evolution (3.69 mmol g⁻¹ h⁻¹) at the absence of Pt co-catalyst, which was higher than the largest number of existing photocatalysts [156]. Nevertheless, Bai et al. further fabricated heterojunction materials composed of Ag₂NCN and g-C₃N₄ for photocatalytic hydrogen evolution, which exhibited higher photocatalytic activity (322.35 µmol g⁻¹ h⁻¹) [157]. In addition, the ternary nanocomposite Z-scheme photocatalyst composed of Ag₂CrO₄, g-C₃N₄ and graphene oxide was fabricated for photocatalytic CO₂ reduction, which exhibited an enhanced CO₂ conversion activity owing to the broadened light absorption, higher CO₂ adsorption and more efficient charge separation, as seen from Figs. 6H and I [158]. As a consequence, the g-C₃N₄-based photocatalysts held great promise on photocatalytic energy conversion.

  4. Summary and outlook

  In conclusion, we had summarized the several desirable properties of g-C₃N₄ such as tunable electronic band structure, high physical and chemical stability, optical performances, electrochemical and photoelectrochemical performances and the multifarious types, including nanocluster, nanosphere, nanorod, nanotube, nanofiber/nanowire, nanosheet. The g-C₃N₄ nanoclusters had strong quantum confinement effects and thus displayed the bright fluorescence. Besides, the g-C₃N₄ nanosphere, nanorod, nanotube and nanofiber/nanowire were widely used for photocatalysis owing to high surface area, smooth carrier transport and light harvesting. Most important of all, the g-C₃N₄ nanosheets were the most widely used in the photocatalytic field because of graphite-like layered structure and weak van der Waals of interlamination. Furthermore, the photocatalytic reactions of various silver-modified g-C₃N₄ were summarized in detail and comprehensively, especially the g-C₃N₄ decorated with silver nanoparticles, silver nanoclusters and single atom silver for the photocatalytic hydrogen evolution, pollutants degradation and CO₂ reduction. Among them, the single atom silver could provide the 100% utilization of active metal sites due to the presence of isolated silver atoms and thus exhibited more excellent catalytic behavior compared with nanoparticles and nanoclusters. It had no doubt that silver-modified g-C₃N₄ photocatalysts were excellent candidates owing to the accelerated charge separation/transfer efficiency and promoting photocatalytic activities. Apart from the aforementioned excellent achievements, there was still certain challenges in the exploration and actual applications of various silver-modified g-C₃N₄ photocatalysts, including the achievement of long-term stability, the high loading of various silver (especially single atom silver), the practical application scope in the field of energy conversion.

  Declaration of competing interest

  The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

  Acknowledgments

  This study was financially supported by the Shenzhen Science and Technology Program (No. JCYJ20220531093205013), and the National Natural Science Foundation of China (No. 52100069).

  
  
• 1. [1]

     D. Li, X. Li, J. Gong, Chem. Rev. 116 (2016) 11529–11653. doi: 10.1021/acs.chemrev.6b00099

  2. [2]

     Y. Xing, X. Wang, S. Hao, et al., Chin. Chem. Lett. 32 (2021) 13–20. doi: 10.1016/j.cclet.2020.11.011

  3. [3]

     S. Patnaik, D.P. Sahoo, K. Parida, Carbon 172 (2021) 682–711. doi: 10.1016/j.carbon.2020.10.073

  4. [4]

     L. Zhang, Z.J. Zhao, T. Wang, J. Gong, Chem. Soc. Rev. 47 (2018) 5423–5443. doi: 10.1039/C8CS00016F

  5. [5]

     Q. Zeng, S. Chang, M. Wang, et al., Chin. Chem. Lett. 32 (2021) 2212–2216. doi: 10.1016/j.cclet.2020.12.062

  6. [6]

     B.H. Kreps, Am. J. Econ. Sociol. 79 (2020) 695–717. doi: 10.1111/ajes.12336

  7. [7]

     J.D. Xiao, H.L. Jiang, Acc. Chem. Res. 52 (2019) 356–366. doi: 10.1021/acs.accounts.8b00521

  8. [8]

     P. Zhang, X.W. Lou, Adv. Mater. 31 (2019) 1900281. doi: 10.1002/adma.201900281

  9. [9]

     Z.H. Xue, D. Luan, H. Zhang, X.W. Lou, Joule 6 (2022) 92–133. doi: 10.1016/j.joule.2021.12.011

  10. [10]

      J. Liu, H. Wu, F. Li, et al., Adv. Sustain. Syst. 4 (2020) 2000151. doi: 10.1002/adsu.202000151

  11. [11]

      J. Liang, X. Yang, Y. Wang, et al., J. Mater. Chem. A 9 (2021) 12898–12922. doi: 10.1039/d1ta00890k

  12. [12]

      Q. Zhang, Y. Xiao, L. Yang, et al., Chin. Chem. Lett. 34 (2023) 107628. doi: 10.1016/j.cclet.2022.06.051

  13. [13]

      Z. fiqar, J. Tao, T. Yang, et al., Surf. Interfaces 26 (2021) 101312. doi: 10.1016/j.surfin.2021.101312

  14. [14]

      X. Wang, H. Jiang, M. Zhu, X. Shi, Chin. Chem. Lett. 34 (2023) 107683. doi: 10.1016/j.cclet.2022.07.026

  15. [15]

      G. Xu, H. Zhang, J. Wei, et al., ACS Nano 12 (2018) 5333–5340. doi: 10.1021/acsnano.8b00110

  16. [16]

      Y. Liu, L. Chen, X. Liu, et al., Chin. Chem. Lett. 33 (2022) 1385–1389. doi: 10.3390/cryst12101385

  17. [17]

      F. Wang, Y. Wang, Y. Feng, et al., Appl. Catal. B: Environ. 221 (2018) 510–520. doi: 10.1016/j.apcatb.2017.09.055

  18. [18]

      G. Mamba, A.K. Mishra, Appl. Catal. B: Environ. 198 (2016) 347–377. doi: 10.1016/j.apcatb.2016.05.052

  19. [19]

      J. Liu, Y. Liu, N. Liu, et al., Science 347 (2015) 970–974. doi: 10.1126/science.aaa3145

  20. [20]

      S. Patnaik, D.P. Sahoo, K.M. Parida, J. Colloid Interface Sci. 560 (2020) 519–535. doi: 10.1016/j.jcis.2019.09.041

  21. [21]

      N. Cheng, P. Jiang, Q. Liu, et al., Analyst 139 (2014) 5065–5068. doi: 10.1039/C4AN00914B

  22. [22]

      S. Patnaik, K.K. Das, A. Mohanty, K. Parida, Catal. Today 315 (2018) 52–66. doi: 10.1016/j.cattod.2018.04.008

  23. [23]

      P. Xia, B. Zhu, J. Yu, S. Cao, M. Jaroniec, J. Mater. Chem. A 5 (2017) 3230–3238. doi: 10.1039/C6TA08310B

  24. [24]

      J. Zhao, L. Ma, H. Wang, et al., Appl. Surf. Sci. 332 (2015) 625–630. doi: 10.1016/j.apsusc.2015.01.233

  25. [25]

      R. Zhang, S. Niu, X. Zhang, et al., Appl. Surf. Sci. 489 (2019) 427–434. doi: 10.1016/j.apsusc.2019.05.362

  26. [26]

      N. Sagara, S. Kamimura, T. Tsubota, T. Ohno, Appl. Catal. B: Environ. 192 (2016) 193–198. doi: 10.1016/j.apcatb.2016.03.055

  27. [27]

      W. Chen, T.Y. Liu, T. Huang, X.H. Liu, X.J. Yang, Nanoscale 8 (2016) 3711–3719. doi: 10.1039/C5NR07695A

  28. [28]

      S.P. Adhikari, Z.D. Hood, VW. Chen, et al., Sustain. Energy Fuels 2 (2018) 2507–2515. doi: 10.1039/c8se00319j

  29. [29]

      W. Zhao, Y. Li, P. Zhao, et al., Chem. Eng. J. 405 (2021) 126555. doi: 10.1016/j.cej.2020.126555

  30. [30]

      Q. Chen, C. Yuan, C. Zhai, Chin. Chem. Lett. 33 (2022) 983–986. doi: 10.1016/j.cclet.2021.07.047

  31. [31]

      H. Liu, X. Liu, W. Yang, et al., J. Mater. Chem. A 7 (2019) 2022–2026. doi: 10.1039/c8ta11172c

  32. [32]

      I.F. Teixeira, E.C.M. Barbosa, S.C.E. Tsang, P.H.C. Camargo, Chem. Soc. Rev. 47 (2018) 7783–7817. doi: 10.1039/c8cs00479j

  33. [33]

      Y. Bu, Z. Chen, W. Li, Appl. Catal. B: Environ. 144 (2014) 622–630. doi: 10.1016/j.apcatb.2013.07.066

  34. [34]

      J.M. Luther, P.K. Jain, T. Ewers, A.P. Alivisatos, Nat. Mater. 10 (2011) 361–366. doi: 10.1038/nmat3004

  35. [35]

      F. Wu, C. Pu, M. Zhang, B. Liu, J. Yang, Surf. Interfaces 25 (2021) 101298. doi: 10.1016/j.surfin.2021.101298

  36. [36]

      Y. Yang, W. Guo, Y. Guo, et al., J. Hazard. Mater. 271 (2014) 150–159. doi: 10.1016/j.jhazmat.2014.02.023

  37. [37]

      S. Ren, G. Zhao, Y. Wang, B. Wang, Q. Wang, Nanotechnology 26 (2015) 125403. doi: 10.1088/0957-4484/26/12/125403

  38. [38]

      A. Jakab, C. Rosman, Y. Khalavka, et al., ACS Nano 5 (2011) 6880–6885. doi: 10.1021/nn200877b

  39. [39]

      C. Clavero, Nat. Photonics 8 (2014) 95–103. doi: 10.1038/nphoton.2013.238

  40. [40]

      K. Huang, C. Li, L. Wang, W. Wang, X. Meng, Chem. Eng. J. 425 (2021) 131493. doi: 10.1016/j.cej.2021.131493

  41. [41]

      J. Wang, J. Cong, H. Xu, et al., ACS Sustain. Chem. Eng. 5 (2017) 10633–10639. doi: 10.1021/acssuschemeng.7b02608

  42. [42]

      S. Bayan, S. Pal, S.K. Ray, Nano Energy 94 (2022) 106928. doi: 10.1016/j.nanoen.2022.106928

  43. [43]

      Y. Chen, X. Ren, X. Wang, et al., Int. J. Hydrog. Energy 47 (2022) 250–263. doi: 10.1016/j.ijhydene.2021.10.024

  44. [44]

      I. Majeed, U. Manzoor, F.K. Kanodarwala, et al., Catal. Sci. Technol. 8 (2018) 1183–1193. doi: 10.1039/C7CY02219K

  45. [45]

      X. Li, S. Zhao, X. Duan, et al., Appl. Catal. B: Environ. 283 (2021) 119660. doi: 10.1016/j.apcatb.2020.119660

  46. [46]

      S. Lv, C. Wu, Y.H. Ng, et al., Int. J. Hydrog. Energy 47 (2022) 42136–42149. doi: 10.1016/j.ijhydene.2021.06.214

  47. [47]

      A. Mishra, A. Mehta, S. Basu, et al., Carbon 149 (2019) 693–721. doi: 10.1016/j.carbon.2019.04.104

  48. [48]

      A. Balakrishnan, M. Chinthala, Chemosphere 297 (2022) 134190. doi: 10.1016/j.chemosphere.2022.134190

  49. [49]

      J. Fu, J. Yu, C. Jiang, B. Cheng, Adv. Energy Mater. 8 (2018) 1701503. doi: 10.1002/aenm.201701503

  50. [50]

      S. Cao, J. Low, J. Yu, M. Jaroniec, Adv. Mater. 27 (2015) 2150–2176. doi: 10.1002/adma.201500033

  51. [51]

      Y. Zheng, L. Lin, B. Wang, X. Wang, Angew. Chem. Int. Ed. 54 (2015) 12868–12884. doi: 10.1002/anie.201501788

  52. [52]

      T. Xiong, W. Cen, Y. Zhang, F. Dong, ACS Catal. 6 (2016) 2462–2472. doi: 10.1021/acscatal.5b02922

  53. [53]

      S. Wang, L. Wang, H. Cong, et al., J. Environ. Chem. Eng. 10 (2022) 108189. doi: 10.1016/j.jece.2022.108189

  54. [54]

      P. Ding, H. Ji, P. Li, et al., Appl. Catal. B: Environ. 300 (2022) 120633. doi: 10.1016/j.apcatb.2021.120633

  55. [55]

      S. Zhang, H. Gao, X. Liu, et al., ACS Appl. Mater. Interfaces 8 (2016) 35138–35149. doi: 10.1021/acsami.6b09260

  56. [56]

      Z. Cai, J. Chen, S. Xing, D. Zheng, L. Guo, J. Hazard. Mater. 416 (2021) 126195. doi: 10.1016/j.jhazmat.2021.126195

  57. [57]

      L. Liu, J. Zhang, B. Zhang, et al., Green Chem. 20 (2018) 4206–4209. doi: 10.1039/c8gc01666f

  58. [58]

      Y. Ren, Q. Han, Y. Zhao, H. Wen, Z. Jiang, J. Hazard. Mater. 404 (2021) 124153. doi: 10.1016/j.jhazmat.2020.124153

  59. [59]

      X. Wang, S. Blechert, M. Antonietti, ACS Catal. 2 (2012) 1596–1606. doi: 10.1021/cs300240x

  60. [60]

      J. Liu, H. Wang, M. Antonietti, Chem. Soc. Rev. 45 (2016) 2308–2326. doi: 10.1039/C5CS00767D

  61. [61]

      J. He, X. Wang, S. Jin, Z.Q. Liu, M. Zhu, Chin. J. Catal. 43 (2022) 1306–1315. doi: 10.1016/S1872-2067(21)63936-0

  62. [62]

      B.V. Lotsch, M. Döblinger, J. Sehnert, et al., Chem. Eur. J. 13 (2007) 4969–4980. doi: 10.1002/chem.200601759

  63. [63]

      Z. Gu, Y. Asakura, S. Yin, Nanotechnology 31 (2019) 114001.

  64. [64]

      D. Das, S.L. Shinde, K.K. Nanda, ACS Appl. Mater. Interfaces 8 (2016) 2181–2186. doi: 10.1021/acsami.5b10770

  65. [65]

      Q.X. Luo, Y. Li, R.P. Liang, et al., Electroanal. Chem. 856 (2020) 113706. doi: 10.1016/j.jelechem.2019.113706

  66. [66]

      X. Wang, K. Maeda, A. Thomas, et al., Nat. Mater. 8 (2009) 76–80. doi: 10.1038/nmat2317

  67. [67]

      J.S. Zhang, X.F. Chen, K. Takanabe, et al., Angew. Chem. Int. Ed. 49 (2010) 441–444. doi: 10.1002/anie.200903886

  68. [68]

      A. Thomas, A. Fischer, F. Goettmann, et al., J. Mater. Chem. 18 (2008) 4893–4908. doi: 10.1039/b800274f

  69. [69]

      Q.M. Feng, Y.Z. Shen, M.X. Li, et al., Anal. Chem. 88 (2016) 937–944. doi: 10.1021/acs.analchem.5b03670

  70. [70]

      A. Wang, C. Wang, L. Fu, W. Wong-Ng, Y. Lan, Nano-Micro Lett. 9 (2017) 47. doi: 10.1007/s40820-017-0148-2

  71. [71]

      X. Wang, A. Vasileff, Y. Jiao, Y. Zheng, S.Z. Qiao, Adv. Mater. 31 (2019) 1803625. doi: 10.1002/adma.201803625

  72. [72]

      Y. Zhang, M. Antonietti, Chem. Asian J. 5 (2010) 1307–1311. doi: 10.1002/asia.200900685

  73. [73]

      W.J. Ong, L.L. Tan, Y.H. Ng, S.T. Yong, S.P. Chai, Chem. Rev. 116 (2016) 7159–7329. doi: 10.1021/acs.chemrev.6b00075

  74. [74]

      L. Shi, T. Wang, H. Zhang, K. Chang, J. Ye, Adv. Funct. Mater. 25 (2015) 5360–5367. doi: 10.1002/adfm.201502253

  75. [75]

      Q. Cheng, Y. He, Y. Ge, J. Zhou, G. Song, Microchim. Acta 185 (2018) 332. doi: 10.1007/s00604-018-2864-9

  76. [76]

      T. Alizadeh, F. Rafiei, Mater. Chem. Phys. 227 (2019) 176–183. doi: 10.1016/j.matchemphys.2019.01.060

  77. [77]

      S.M. Abdel Moneim, T.A. Gad-Allah, M.F. El-Shahat, A.M. Ashmawy, H.S. Ibrahim, J. Environ. Chem. Eng. 4 (2016) 4165–4172. doi: 10.1016/j.jece.2016.08.034

  78. [78]

      X. Deng, X. Kuang, J. Zeng, et al., Nanotechnology 33 (2022) 175401. doi: 10.1088/1361-6528/ac493d

  79. [79]

      K. Wang, Q. Li, B. Liu, et al., Appl. Catal. B: Environ. 176–177 (2015) 44–52.

  80. [80]

      J. Xiao, Y. Xie, F. Nawaz, et al., Appl. Catal. B: Environ. 183 (2016) 417–425. doi: 10.1016/j.apcatb.2015.11.010

  81. [81]

      X.D. Sun, Y.Y. Li, J. Zhou, et al., J. Colloid Interf. Sci. 451 (2015) 108–116. doi: 10.1016/j.jcis.2015.03.059

  82. [82]

      G. Liu, T. Wang, H. Zhang, et al., Angew. Chem. 127 (2015) 13765–13769. doi: 10.1002/ange.201505802

  83. [83]

      Y. Shiraishi, Y. Kofuji, H. Sakamoto, et al., ACS Catal. 5 (2015) 3058–3066. doi: 10.1021/acscatal.5b00408

  84. [84]

      Z. Tong, D. Yang, Z. Li, et al., ACS Nano 11 (2017) 1103–1112. doi: 10.1021/acsnano.6b08251

  85. [85]

      J. Xu, H.T. Wu, X. Wang, et al., Phys. Chem. Chem. Phys. 15 (2013) 4510–4517. doi: 10.1039/c3cp44402c

  86. [86]

      L. Shi, L. Liang, F. Wang, J. Ma, J. Sun, Catal. Sci. Technol. 4 (2014) 3235–3243. doi: 10.1039/C4CY00411F

  87. [87]

      F. Dong, L. Wu, Y. Sun, et al., J. Mater. Chem. 21 (2011) 15171–15174. doi: 10.1039/c1jm12844b

  88. [88]

      J.P. Mathias, E.E. Simanek, J.A. Zerkowski, C.T. Seto, G.M. Whitesides, J. Am. Chem. Soc. 116 (1994) 4316–4325. doi: 10.1021/ja00089a021

  89. [89]

      W. Wang, J.C. Yu, Z. Shen, D.K.L. Chan, T. Gu, Chem. Commun. 50 (2014) 10148–10150. doi: 10.1039/C4CC02543A

  90. [90]

      X. Zhang, H. Wang, H. Wang, et al., Adv. Mater. 26 (2014) 4438–4443. doi: 10.1002/adma.201400111

  91. [91]

      S. Zhang, J. Li, M. Zeng, et al., Nanoscale 6 (2014) 4157–4162. doi: 10.1039/c3nr06744k

  92. [92]

      X. Cao, J. Ma, Y. Lin, et al., Spectrochim. Acta A 151 (2015) 875–880. doi: 10.1016/j.saa.2015.07.034

  93. [93]

      Y.C. Lu, J. Chen, A.J. Wang, et al., J. Mater. Chem. C 3 (2015) 73–78. doi: 10.1039/C4TC02111H

  94. [94]

      J. Wu, S. Yang, J. Li, et al., Adv. Optical Mater. 4 (2016) 2095–2101. doi: 10.1002/adom.201600570

  95. [95]

      R. Cui, C. Liu, J. Shen, et al., Adv. Funct. Mater. 18 (2008) 2197–2204. doi: 10.1002/adfm.200701340

  96. [96]

      D. Vidyasagar, S.G. Ghugal, A. Kulkarni, et al., Appl. Catal. B: Environ. 221 (2018) 339–348. doi: 10.1016/j.apcatb.2017.09.030

  97. [97]

      J. Ruan, X. Wu, Y. Wang, et al., J. Mater. Chem. A 7 (2019) 19305–19315. doi: 10.1039/c9ta05205d

  98. [98]

      J. Liu, J. Huang, H. Zhou, M. Antonietti, ACS Appl. Mater. Interfaces 6 (2014) 8434–8440. doi: 10.1021/am501319v

  99. [99]

      X.H. Li, X. Wang, M. Antonietti, Chem. Sci. 3 (2012) 2170–2174. doi: 10.1039/c2sc20289a

  100. [100]

       Y. Zheng, L. Lin, X. Ye, F. Guo, X. Wang, Angew. Chem. Int. Ed. 53 (2014) 11926–11930. doi: 10.1002/anie.201407319

  101. [101]

       Q. Guo, Y. Xie, X. Wang, et al., Chem. Commun. 4 (2004) 26–27.

  102. [102]

       J. Li, C. Cao, H. Zhu, Nanotechnology 18 (2007) 115605. doi: 10.1088/0957-4484/18/11/115605

  103. [103]

       S.W. Bian, Z. Ma, W.G. Song, J. Phys. Chem. C 113 (2009) 8668–8672. doi: 10.1021/jp810630k

  104. [104]

       S. Wang, C. Li, T. Wang, et al., J. Mater. Chem. A 2 (2014) 2885–2890. doi: 10.1039/c3ta14576j

  105. [105]

       F. He, G. Chen, J. Miao, et al., ACS Energy Lett. 1 (2016) 969–975. doi: 10.1021/acsenergylett.6b00398

  106. [106]

       Z. Tong, D. Yang, Y. Sun, Y. Nan, Z. Jiang, Small 12 (2016) 4093–4101. doi: 10.1002/smll.201601660

  107. [107]

       Y. Zhao, Z. Liu, W. Chu, et al., Adv. Mater. 20 (2008) 1777–1781. doi: 10.1002/adma.200702230

  108. [108]

       J. Liu, J. Huang, D. Dontosova, M. Antonietti, RSC Adv. 3 (2013) 22988–22993. doi: 10.1039/c3ra44490b

  109. [109]

       M. Tahir, C. Cao, N. Mahmood, et al., ACS Appl. Mater. Interfaces 6 (2014) 1258–1265. doi: 10.1021/am405076b

  110. [110]

       Y. Hou, Z. Wen, S. Cui, X. Feng, J. Chen, Nano Lett. 16 (2016) 2268–2277. doi: 10.1021/acs.nanolett.5b04496

  111. [111]

       X. Yuan, C. Zhou, Y. Jin, et al., J. Colloid Interface Sci. 468 (2016) 211–219. doi: 10.1016/j.jcis.2016.01.048

  112. [112]

       Q. Han, F. Zhao, C. Hu, et al., Nano Res. 8 (2015) 1718–1728. doi: 10.1007/s12274-014-0675-9

  113. [113]

       P. Niu, L. Zhang, G. Liu, H.M. Cheng, Adv. Funct. Mater. 22 (2012) 4763–4770. doi: 10.1002/adfm.201200922

  114. [114]

       S. Yang, Y. Gong, J. Zhang, et al., Adv. Mater. 25 (2013) 2452–2456. doi: 10.1002/adma.201204453

  115. [115]

       X. Zhang, X. Xie, H. Wang, et al., J. Am. Chem. Soc. 135 (2013) 18–21. doi: 10.1021/ja308249k

  116. [116]

       T.Y. Ma, Y. Tang, S. Dai, S.Z. Qiao, Small 10 (2014) 2382–2389. doi: 10.1002/smll.201303827

  117. [117]

       K. Schwinghammer, M.B. Mesch, V. Duppel, et al., J. Am. Chem. Soc. 136 (2014) 1730–1733. doi: 10.1021/ja411321s

  118. [118]

       L. Chen, Z. Song, X. Liu, et al., Analyst 143 (2018) 1609–1614. doi: 10.1039/C7AN02089A

  119. [119]

       S. Yang, X. Feng, X. Wang, K. Müllen, Angew. Chem. Int. Ed. 50 (2011) 5339–5343. doi: 10.1002/anie.201100170

  120. [120]

       J. Zhang, J. Sun, K. Maeda, et al., Energy Environ. Sci. 4 (2011) 675–678. doi: 10.1039/C0EE00418A

  121. [121]

       O. Fontelles-Carceller, M.J. Muñoz-Batista, M. Fernández-García, A. Kubacka, ACS Appl. Mater. Interfaces 8 (2016) 2617–2627. doi: 10.1021/acsami.5b10434

  122. [122]

       Y. Song, J. Qi, J. Tian, S. Gao, F. Cui, Chem. Eng. J. 341 (2018) 547–555. doi: 10.1016/j.cej.2018.02.063

  123. [123]

       M.J. Muñoz-Batista, O. Fontelles-Carceller, M. Ferrer, M. Fernández-García, A. Kubacka, Appl. Catal. B: Environ. 183 (2016) 86–95. doi: 10.1016/j.apcatb.2015.10.024

  124. [124]

       S. Gao, H. Ji, P. Yang, et al., Small 19 (2023) 2206114. doi: 10.1002/smll.202206114

  125. [125]

       L. Ge, C. Han, J. Liu, Y. Li, Appl. Catal. A: Gen. 409-410 (2011) 215–222. doi: 10.1016/j.apcata.2011.10.006

  126. [126]

       Y. Yang, Y. Guo, F. Liu, et al., Appl. Catal. B: Environ. 142-143 (2013) 828–837. doi: 10.1016/j.apcatb.2013.06.026

  127. [127]

       T. Sano, K. Koike, T. Hori, et al., Appl. Catal. B: Environ. 198 (2016) 133–141. doi: 10.1016/j.apcatb.2016.05.057

  128. [128]

       K.Z. Qi, Y. Li, Y.b. Xie, et al., Front. Chem. 7 (2019) 91. doi: 10.3389/fchem.2019.00091

  129. [129]

       M.E. Khan, T.H. Han, M.M. Khan, M.R. Karim, M.H. Cho, ACS Appl. Nano Mater. 1 (2018) 2912–2922. doi: 10.1021/acsanm.8b00548

  130. [130]

       T. Ishaq, M. Yousaf, I.A Bhatti, et al., Int. J. Hydrog. Energy 45 (2020) 31574–31584. doi: 10.1016/j.ijhydene.2020.08.191

  131. [131]

       T. Ren, Y. Dang, Y. Xiao, et al., Inorg. Chem. Commun. 123 (2021) 108367. doi: 10.1016/j.inoche.2020.108367

  132. [132]

       H. Zhu, K.J. Wu, C.H. He, Chem. Eng. J. 429 (2022) 132412. doi: 10.1016/j.cej.2021.132412

  133. [133]

       X. Yao, W. Zhang, J. Huang, et al., Appli. Catal. A: Gen. 601 (2020) 117647. doi: 10.1016/j.apcata.2020.117647

  134. [134]

       Y. Li, M. Wan, G. Yan, P. Qiu, X. Wang, J. Pharm. Anal. 11 (2021) 183–190. doi: 10.1016/j.jpha.2020.04.007

  135. [135]

       E. Murugan, S. Santhoshkumar, S. Govindaraju, M. Palanichamy, Spectrochim. Acta A 246 (2021) 119036. doi: 10.1016/j.saa.2020.119036

  136. [136]

       K. Mallikarjuna, S.V.P. Vattikuti, R. Manne, et al., Nanomaterials 11 (2021) 2918. doi: 10.3390/nano11112918

  137. [137]

       T.M.O. Le, T.H. Lam, T.N. Pham, et al., Polymers 10 (2018) 633. doi: 10.3390/polym10060633

  138. [138]

       Y. Ling, G. Liao, P. Xu, L. Li, Sep. Purif. Technol. 216 (2019) 1–8. doi: 10.1016/j.seppur.2019.01.057

  139. [139]

       Y. Wang, X. Zhao, D. Cao, Y. Wang, Y. Zhu, Appl. Catal. B: Environ. 211 (2017) 79–88. doi: 10.1016/j.apcatb.2017.03.079

  140. [140]

       Z. Zhao, W. Zhang, W. Liu, et al., Sci. Total Environ. 742 (2020) 140642. doi: 10.1016/j.scitotenv.2020.140642

  141. [141]

       F. Wang, Y. Wang, Y. Li, et al., Dalton Trans. 47 (2018) 6924–6933. doi: 10.1039/C8DT00919H

  142. [142]

       K.L. Wang, Y. Li, T. Sun, et al., Appl. Surf. Sci. 476 (2019) 741–748. doi: 10.3390/catal9090741

  143. [143]

       H. Xu, J. Yan, Y. Xu, et al., Appl. Catal. B: Environ. 129 (2013) 182–193. doi: 10.1016/j.apcatb.2012.08.015

  144. [144]

       F.J. Zhang, F.Z. Xie, S.F. Zhu, et al., Chem. Eng. J. 228 (2013) 435–441. doi: 10.1016/j.cej.2013.05.027

  145. [145]

       L. Shi, L. Liang, J. Ma, F. Wang, J. Sun, Catal. Sci. Technol. 4 (2014) 758–765. doi: 10.1039/c3cy00871a

  146. [146]

       Y. Feng, J. Shen, Q. Cai, H. Yang, Q. Shen, New J. Chem. 39 (2015) 1132–1138. doi: 10.1039/C4NJ01433B

  147. [147]

       Y. Li, L. Fang, R. Jin, et al., Nanoscale 7 (2015) 758–764. doi: 10.1039/C4NR06565D

  148. [148]

       L. Shi, L. Liang, F. Wang, M. Liu, J. Sun, Dalton Trans. 45 (2016) 5815–5824. doi: 10.1039/C5DT04644K

  149. [149]

       B. Jia, W. Zhao, L. Fan, et al., Catal. Sci. Technol. 8 (2018) 1447–1453. doi: 10.1039/C7CY02325A

  150. [150]

       D. Chen, B. Li, Q. Pu, et al., J. Hazard. Mater. 373 (2019) 303–312. doi: 10.1016/j.jhazmat.2019.03.090

  151. [151]

       L. Sun, C. Liu, J. Li, et al., Chin. J. Catal. 40 (2019) 80–94. doi: 10.1016/S1872-2067(18)63172-9

  152. [152]

       M. Chen, C. Guo, S. Hou, et al., Appl. Catal. B: Environ. 266 (2020) 118614. doi: 10.1016/j.apcatb.2020.118614

  153. [153]

       Y. Orooji, M. Ghanbari, O. Amiri, M. Salavati-Niasari, J. Hazard. Mater. 389 (2020) 122079. doi: 10.1016/j.jhazmat.2020.122079

  154. [154]

       D. Sun, Y. Zhang, Y. Liu, et al., Chem. Eng. J. 384 (2020) 123259. doi: 10.1016/j.cej.2019.123259

  155. [155]

       X. Yang, Z. Chen, J. Xu, et al., ACS Appl. Mater. Interfaces 7 (2015) 15285–15293. doi: 10.1021/acsami.5b02649

  156. [156]

       W. Li, X. Wang, M. Li, et al., Appl. Catal. B: Environ. 268 (2020) 118384. doi: 10.1016/j.apcatb.2019.118384

  157. [157]

       C. Bai, J. Bi, J. Wu, Y. Han, X. Zhang, New J. Chem. 42 (2018) 16005–16012. doi: 10.1039/c8nj02991a

  158. [158]

       D. Xu, B. Cheng, W. Wang, C. Jiang, J. Yu, Appl. Catal. B: Environ. 231 (2018) 368–380. doi: 10.1016/j.apcatb.2018.03.036

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  Figure 1  Schematic illustration of the g-C₃N₄ decorated with various silvers for photocatalytic energy conversion.

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  Figure 2  (A) Triazine and (B) tri-s-triazine (heptazine) structures of g-C₃N₄. Reprinted with permission [73]. Copyright 2016, American Chemical Society.

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  Figure 3  (A) Ultraviolet-visible diffuse reflectance spectrum of g-C₃N₄ prepared at different temperature. Reprinted with permission [66]. Copyright 2009, Springer Nature. (B) Photoluminescence spectra of 2 h calcined g-C₃N₄ at different temperatures. Reprinted with permission [53]. Copyright 2022, Elsevier.

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  Figure 4  Various morphologies of the g-C₃N₄. The nanocluster. Reprinted with permission [89]. Copyright 2014, Royal Society of Chemistry. The nanosphere. Reprinted with permission [97]. Copyright 2019, Royal Society of Chemistry. The nanorod. Reprinted with permission [99]. Copyright 2012, Royal Society of Chemistry. The nanotube. Reprinted with permission [103]. Copyright 2009, American Chemical Society. The nanofiber. Reprinted with permission [107]. Copyright 2008, Wiley. The nanosheet. Reprinted with permission [113]. Copyright 2012, Wiley.

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  Figure 5  (A) Schematic illustration of the controllable synthesis of g-C₃N₄ nanosheets, nanoribbons and quantum dots. Reprinted with permission [89]. Copyright 2014, Royal Society of Chemistry. (B) Overall synthetic procedure of multishell g-C₃N₄ nanocapsules. Reprinted with permission [84]. Copyright 2017, American Chemical Society. (C) Synthetic process for helical nanorod-like g-C₃N₄ and morphology characterization. Reprinted with permission [100]. Copyright 2014, John Wiley and Sons Ltd. (D) The proposed formation process of g-C₃N₄ nanotubes. Reprinted with permission [104]. Copyright 2014, Royal Society of Chemistry. (E) Preparation of porous nanofiber-like Ag/g-C₃N₄ from Ag-melamine supramolecular hydrogels. Reprinted with permission [41]. Copyright 2017, American Chemical Society. (F) Schematic illustration of liquid-exfoliation process from bulk g-C₃N₄ to ultrathin nanosheets, the photograph of bulk g-C₃N₄ and suspension of ultrathin g-C₃N₄ nanosheets. Reprinted with permission [115]. Copyright 2013, American Chemical Society.

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  Figure 6  Schematic diagram (A) and H₂ generation rate of catalysts with different loading contents (B) of photocatalytic hydrogen generation of Ag/g-C₃N₄. Reprinted with permission [132]. Copyright 2022, Elsevier. Photocatalytic mechanism of Ag decorated P-doped g-C₃N₄ nanosheets under visible-light irradiation (C), time course of hydrogen evolution (D), and photocatalytic activities (E) for rhodamine B degradation under visible light irradiation. Reprinted with permission [43]. Copyright 2022, Elsevier. The possible photocatalytic mechanism (F) and photocatalytic activity (G) for degradation of bisphenol A over photocatalyst of mesoporous g-C₃N₄ decorated with isolated Ag sites. Reprinted with permission [139]. Copyright 2017, Elsevier. The proposed Z-scheme photocatalytic mechanism for the Ag₂CrO₄/g-C₃N₄/GO composite (H) and CH₃OH and CH₄ production (I) of CN (g-C₃N₄), CG (g-C₃N₄/GO), CA (Ag₂CrO₄/g-C₃N₄) and CAG (Ag₂CrO₄/g-C₃N₄/GO) samples. Reprinted with permission [158]. Copyright 2018, Elsevier.

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  Table 1.  Recent reports on g-C3N4-based photocatalysts.

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