Construction of Embedded Sulfur-Doped g-C3N4/BiOBr S-Scheme Heterojunction for Highly Efficient Visible Light Photocatalytic Degradation of Organic Compound Rhodamine B.

Constructing S-scheme heterojunction catalysts is a key challenge in visible-light catalysed degradation of organic pollutants. Most heterojunction materials are reported to face significant obstacles in the separation of photogenerated electron-hole pairs owing to differences in the material size and energy barriers. In this study, sulfur-doped g-C3N4 oxidative-type semiconductor materials are synthesized and then coupled with BiOBr reductive-type semiconductor to form S-g-C3N4/BiOBr S-scheme heterojunction. A strong and efficient internal electric field is established between the two materials, facilitating the separation of photogenerated electron-hole pairs. Notably, in situ XPS proved that after visible light irradiation, Bi3+ is converted into Bi(3+ɑ)+, and a large number of photogenerated holes are produced on the surface of BiOBr, which oxidized and activated H2O into •OH.  â€¢OH cooperated with •O2 - and 1O2 to attack Rhodamine B (RhB) molecules to achieve deep oxidation mineralization. The composite material is designed with a LUMO energy level higher than that of RhB, promoting the sensitization of RhB by injecting photogenerated electrons into the heterojunction, thereby enhancing the photocatalytic performance to 22.44 times that of pure g-C3N4. This study provides a new perspective on the efficient degradation of organic molecules using visible light catalysis.

Engineering of Graphitic Carbon Nitride (g-C3N4) Based Photocatalysts for Atmospheric Protection: Modification Strategies, Recent Progress, and Application Challenges.

Graphitic carbon nitride (g-C3N4) is a prominent photocatalyst that has attracted substantial interest in the field of photocatalytic environmental remediation due to the low cost of fabrication, robust chemical structure, adaptable and tunable energy bandgaps, superior photoelectrochemical properties, cost-effective feedstocks, and distinctive framework. Nonetheless, the practical application of bulk g-C3N4 in the photocatalysis field is limited by the fast recombination of photogenerated e--h+ pairs, insufficient surface-active sites, and restricted redox capacity. Consequently, a great deal of research has been devoted to solving these scientific challenges for large-scale applications. This review concisely presents the latest advancements in g-C3N4-based photocatalyst modification strategies, and offers a comprehensive analysis of the benefits and preparation techniques for each strategy. It aims to articulate the complex relationship between theory, microstructure, and activities of g-C3N4-based photocatalysts for atmospheric protection. Finally, both the challenges and opportunities for the development of g-C3N4-based photocatalysts are highlighted. It is highly believed that this special review will provide new insight into the synthesis, modification, and broadening of g-C3N4-based photocatalysts for atmospheric protection.

Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45 µmol g-1 h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

P-N Bonds-Mediated Atomic-Level Charge-Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting.

Heterostructures are widely employed in photocatalysis to promote charge separation and photocatalytic activity. However, their benefits are limited by the linkages and contact environment at the interface. Herein, violet phosphorus quantum dots (VPQDs) and graphitic carbon nitride (g-C3N4) are employed as model materials to form VPQDs/g-C3N4 heterostructures by a simple ultrasonic pulse excitation method. The heterostructure contains strong interfacial P-N bonds that mitigate interfacial charge-separation issues. P-P bond breakage occurs in the distinctive cage-like [P9] VPQD units during longitudinal disruption, thereby exposing numerous active P sites that bond with N atoms in g-C3N4 under ultrasonic pulse excitation. The atomic-level interfacial P-N bonds of the Z-scheme VPQDs/g-C3N4 heterostructure serve as photogenerated charge-transfer channels for improved electron-hole separation efficiency. This results in excellent photocatalytic performance with a hydrogen evolution rate of 7.70 mmol g-1 h-1 (over 9.2 and 8.5 times greater than those of pure g-C3N4 and VPQDs, respectively) and apparent quantum yield of 11.68% at 400 nm. Using atomic-level chemical bonds to promote interfacial charge separation in phosphorene heterostructures is a feasible and effective design strategy for photocatalytic water-splitting materials.

Unraveling the Synergistic Mechanism of Boosted Photocatalytic H2O2 Production over Cyano-g-C3N4/In2S3/Ppy Heterostructure and Enhanced Photocatalysis-Self-Fenton Degradation Performance.

In this work, cyano contained g-C3N4 comodified by In2S3 and polypyrrole (C≡N─CN/IS/Ppy) materials are synthesized for the photocatalytic production of H2O2 and photocatalysis-self-Fenton reaction for highly efficient degradation of metronidazole. The results from UV-vis spectrophotometry, surface photovoltage, and Kelvin probe measurements reveal the promoted transport and separation efficiency of photoinduced charges after the introduction of In2S3 and Ppy in the heterojunction. The existence of a built-in electric field accelerates the photoinduced charge separation and preserves the stronger oxidation ability of holes at the valence band of C≡N─CN. Linear sweep voltammetry measurements, zeta potential analyzations, nitroblue tetrazolium determination, and other measurements show that Ppy improves the conversion ratio of •O2 - to H2O2 and the utilization ratio of •O2 -, as well as suppresses decomposition of H2O2. Accordingly, the H2O2 evolution rate produced via a two-step single-electron reduction reaction reaches almost 895 µmol L-1 h-1, a value 80% and 7.2-fold higher than those obtained with C≡N─CN/IS and C≡N─CN, respectively. The metronidazole removal rate obtained via photocatalysis-self-Fenton reaction attains 83.7% within 120 minutes, a value much higher than that recorded by the traditional Fenton method. Overall, the proposed synthesis materials and route look promising for the H2O2 production and organic pollutants degradation.

Design of Single-Atom Catalysts on C5N2 for Nitrogen Fixation at Ambient Conditions: A First-Principles Study.

Single atom catalysts (SACs) exhibit the flexible coordination structure of the active site and high utilization of active atoms, making them promising candidates for nitrogen reduction reaction (NRR) under ambient conditions. By the aid of first-principles calculations based on DFT, we have systematically explored the NRR catalytic behavior of thirteen 4d- and 5d-transition metal atoms anchored on 2D porous graphite carbon nitride C 5 ${_5 }$ N 2 ${_2 }$ . With high selectivity and outstanding activity, Zr, Nb, Mo, Ta, W and Re-doped C 5 ${_5 }$ N 2 ${_2 }$ are identified as potential nominees for NRR. Particularly, Mo@C 5 ${_5 }$ N 2 ${_2 }$ possesses an impressive low limiting potential of -0.39 V (corresponding to a very low temperature and atmospheric pressure), featuring the potential determining step involving *N-N transitions to *N-NH via the distal path. The catalytic performance of TM@C 5 ${_5 }$ N 2 ${_2 }$ can be well characterized by the adsorption strength of intermediate *N 2 ${_2 }$ H. Moreover, there exists a volcanic relationship between the catalytic property U L ${_{\rm{L}} }$ and the structure descriptor Ψ ${{{\Psi }}}$ , which validates the robustness and universality of Ψ ${{{\Psi }}}$ , combined with our previous study. This work sheds light on the design of SACs with eminent NRR performance.

Chlorine-Modified Soluble Melem-Based Graphitic Carbon Nitrite: Facile Synthesis, Catalytic Property and Ultrafast 2D IR Spectroscopic Characterization.

On the basis of thermal etching bulk graphitic carbon nitride (g-C3N4), a mild hydrochloric acid treatment method was used in this work to produce g-C3N4 nano-sheets (CNNS) and further carbon nitride with chloride-modification (CNCl). The latter has thinner layer and smaller particle size and exhibit greatly improved dispersibility and solubility in water, DMSO and other polar solvents. A typical photocatalytic reaction in solution driven by CNCl shows a significantly improved photocatalytic performance over bulk g-C3N4 and CNNS. Steady-state analytical tools including SEM, mass, UV-Vis and IR spectroscopies, and time-resolved two-dimensional infrared (2D IR) vibrational spectroscopy, were used together in this work. Better solubility, more flexible structure, smaller size, easier generation of free radicals and lower recombination rate of electron-hole pair, are believed to be reasons for the superior photocatalytic performance of CNCl.

Exploiting Photoinduced Atom Transfer Radical Polymerizations with Boron-Dopant and Nitrogen-Defect Synergy in Carbon Nitride Nanosheets.

Graphitic carbon nitrides (g-C3N4) possess various benefits as heterogeneous photocatalysts, including tunable bandgaps, scalability, and chemical robustness. However, their efficacy and ongoing advancement are hindered by challenges like limited charge-carrier separation rates, insufficient driving force for photocatalysis, small specific surface area, and inadequate absorption of visible light. In this study, boron dopants and nitrogen defects synergy are introduced into bulk g-C3N4 through the calcination of a blend of nitrogen-defective g-C3N4 and NaBH4 under inert conditions, resulting in the formation of BCN nanosheets characterized by abundant porosity and increased specific surface area. These BCN nanosheets promote intermolecular single electron transfer to the radical initiator, maintaining radical intermediates at a low concentration for better control of photoinduced atom transfer radical polymerization (photo-ATRP). Consequently, this method yields polymers with low dispersity and tailorable molecular weights under mild blue light illumination, outperforming previous reports on bulk g-C3N4. The heterogeneity of BCN enables easy separation and efficient reuse in subsequent polymerization processes. This study effectively showcases a simple method to alter the electronic and band structures of g-C3N4 with simultaneously introducing dopants and defects, leading to high-performance photo-ATRP and providing valuable insights for designing efficient photocatalytic systems for solar energy harvesting.

Evaluating the efficacy of recyclable nanostructured adsorbents for rapid removal of methylparaben from aqueous solutions.

In this study, we evaluate the efficiency of two novel nanostructured adsorbents - chitosan-graphitic carbon nitride@magnetite (CS-g-CN@Fe3O4) and graphitic carbon nitride@copper/zinc nanocomposite (g-CN@Cu/Zn NC) - for the rapid removal of methylparaben (MPB) from water. Our characterization methods, aimed at understanding the adsorbents' structures and surface areas, informed our systematic examination of influential parameters including sonication time, adsorbent dosage, initial MPB concentration, and temperature. We applied advanced modeling techniques, such as response surface methodology (RSM), generalized regression neural network (GRNN), and radial basis function neural network (RBFNN), to evaluate the adsorption process. The adsorbents proved highly effective, achieving maximum adsorption capacities of 255 mg g-1 for CS-g-CN@Fe3O4 and 218 mg g-1 for g-CN@Cu/Zn NC. Through genetic algorithm (GA) optimization, we identified the optimal conditions for the highest MPB removal efficiency: a sonication period of 12.00 min and an adsorbent dose of 0.010 g for CS-g-CN@Fe3O4 NC, with an MPB concentration of 17.20 mg L-1 at 42.85 °C; and a sonication time of 10.25 min and a 0.011 g dose for g-CN@Cu/Zn NC, with an MPB concentration of 13.45 mg L-1 at 36.50 °C. The predictive accuracy of the RBFNN and GRNN models was confirmed to be satisfactory. Our findings demonstrate the significant capabilities of these synthesized adsorbents in effectively removing MPB from water, paving the way for optimized applications in water purification.

Enhanced tetracycline degradation by novel Mn-FeOOH/CNNS photocatalysts in a visible-light-driven photocatalysis coupled peroxydisulfate system.

Recently, photocatalysis combined peroxydisulfate activation under visible light (PC-PDS/Vis) was developed as a promising technology for removing antibiotics in water. Herein, Mn doped FeOOH (Mn-FeOOH) nanoclusters were grown in-situ on the surface of graphitic carbon nitride nanosheets (CNNS) using a wet chemical method, which served as a visible-light-driven photocatalyst for peroxydisulfate (PDS) activation. Photovoltaic property characterizations revealed that Mn-FeOOH/CNNS owned superior light capture ability and carrier separation efficiency. According to DFT calculations, the synergistic effect between Mn and Fe species was proved to enhance the adsorption and activation of PDS. 99.7% of tetracycline (TC) was rapidly removed in 50 min in the PC-PDS/Vis system. In addition, Mn-FeOOH/CNNS exhibited high recycling stability with low iron leaching, attributed to the interaction between Mn-FeOOH clusters and carbon species. Quenching experiments and electron spin resonance (ESR) tests unveiled that •O2- played a significant role in TC removal, while •OH and SO4•- acted as additional roles contributing to the overall process. These findings given a new strategy for antibiotics degradation by photocatalysis, offering deeper insights for the advancement of sustainable and cutting-edge wastewater treatment technologies.

A critical review on non-metal doped g-C3N4 based photocatalyst for organic pollutant remediation with sustainability assessment by life cycle analysis.

Photocatalysis is recognized to be one of the most promising ways to address energy and environmental issues by utilizing visible light. Graphitic carbon nitride (g-C3N4), with a moderate band gap (∼2.7 eV) has been the flashpoint in environmental photocatalysis as it can work better under visible light, can be synthesized by a facile synthesis process using low-cost materials, thermally and chemically stable. Still the photocatalytic performance of g-C3N4 is not satisfactory because of certain limitations such as insufficient visible light absorption capacity, low electron-hole separation efficiency, high recombination rate, poor surface area. Introduction of doping, band structure engineering, defecting and designing of heterojunction, composites etc. were investigated to amplify its applications. Among all these modifications, elemental doping is a suitable and successful alternative for the enhancement of the photocatalytic activity by changing the optical and electronic properties. This review emphasizes on advancement and trends of elemental doping and its application on photocatalytic organic pollutant remediation in aqueous medium. The fundamental photocatalytic activity of heterogeneous photocatalysis and specifically g-C3N4-based photocatalysis have been discussed. The benfits of non-metal doping, enhanced photocatalytic performance by doping element, mechanism invloved in doping, advantages of co-doping has been explained. Mono, bi, and tri non-metal doped g-C3N4 and their application for the removal of organic pollutants from water medium by visible light photocatalysis has been summerized. Life cycle assessment (LCA) of photocatalytic system has been highlighted. Future research should focus on the large-scale application of the photocatalysis process considering the economic aspects. A rigorous life cycle assessment for deploying the non-metal doped g-C3N4-based photocatalysis technology for successful commercial application is recommended.

Interface engineered cascade-type electronic structure of 2D/0D/2D CdS-CdCO3/SnO2 quantum dots/g-C3N4 nanocomposite for boosting solar-driven photocatalysis.

A rational design of heterojunctions with high-quality contacts is essential for efficiently separating photogenerated charge carries and boosting the solar-driven harvesting capability. Herein, we fabricated a novel heterojunction of SnO2 quantum dots-anchored CdS-CdCO3 with g-C3N4 nanosheets as a superior photocatalyst. SnO2 quantum dots (SQDs) with positively charged surfaces were tightly anchored on the negatively charged surface of CdS nanosheets (NSs). The resulting CdS@SnO2 was finally decorated with g-C3N4 NSs, and a new crystalline phase of CdS-CdCO3 was formed during the hydrothermal decoration process, g-C3N4 decorated CdS-CdCO3@SnO2 (CdS-CdCO3@SnO2@g-C3N4). The as-synthesized photocatalysts were evaluated for the degradation of methyl orange dye under solar light conditions. The CdS-CdCO3@SnO2@g-C3N4 exhibited 7.7-fold and 2.3-fold enhancements in photocatalytic activities in comparison to those of the bare CdS and CdS@SnO2 NSs, respectively. The optimal performance of CdS-CdCO3@SnO2@g-C3N4 is primarily attributed to the cascade-type conduction band alignments between 2D/0D/2D heterojunctions, which can harvest maximum solar light and effectively separate photoexcited charge carriers. This work provides a new inspiration for the rational design of 2D/0D/2D heterojunction photocatalyst for green energy generation and environmental remediation applications.

A bifunctional MoS2/SGCN nanocatalyst for the electrochemical detection and degradation of hazardous 4-nitrophenol.

Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS2/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS2 nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS2/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K4[Fe(CN)6]3-/4- show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS2/SGCN modified glassy carbon electrode (MoS2/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 µM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS2/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10-2 s-1. The results of this study confirm that the MoS2/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.

Design of sonochemical assisted synthesis of Zr-MOF/g-C3N4-modified electrode for ultrasensitive detection of antipsychotic drug chlorpromazine from biological samples.

The rapid fabrication is described of binary electrocatalyst based on a highly porous metal-organic framework with zirconium metal core (Zr-MOF) decorated over the graphitic carbon nitride (g-C3N4) nanosheets via facile ultrasonication method. It is used for the robust determination of antipsychotic drug chlorpromazine (CLP) from environmental samples. The electrochemical behaviour of 2D Zr-MOF@g-C3N4 was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies. The crystalline and porous nature of the composite was characterized by XRD and SEM analysis. The functional groups and surface characteristics were investigated by FT-IR, Raman and XPS. The major electrochemical properties of the Zr-MOF@g-C3N4 composite towards CLP detection were analyzed by CV, chronocoulometric (CC), chronoamperometric (CA) and differential pulse voltammetry (DPV) techniques. The composite exhibits a low detection limit (LOD) of 2.45 nM with a linear range of 0.02 to 2.99 µM and attractive sensitivity for CLP. The sensor system shows higher selectivity towards the possible interferences of CLP drug and exhibits better repeatability and stability. Finally, the fabricated sensor system shows a high recovery range varying from 96.2 to 98.9% towards the real samples. The proposed electrochemical probe might be a promising alternative to the prevailing diagnostic tools for the detection of CLP.

Eco-Friendly g-C3N4/Carboxymethyl Cellulose/Alginate Composite Hydrogels for Simultaneous Photocatalytic Degradation of Organic Dye Pollutants.

The presented study was focused on the simple, eco-friendly synthesis of composite hydrogels of crosslinked carboxymethyl cellulose (CMC)/alginate (SA) with encapsulated g-C3N4 nanoparticles. The structural, textural, morphological, optical, and mechanical properties were determined using different methods. The encapsulation of g-C3N4 into CMC/SA copolymer resulted in the formation of composite hydrogels with a coherent structure, enhanced porosity, excellent photostability, and good adhesion. The ability of composite hydrogels to eliminate structurally different dyes with the same or opposite charge properties (cationic Methylene Blue and anionic Orange G and Remazol Brilliant Blue R) in both single- and binary-dye systems was examined through adsorption and photocatalytic reactions. The interactions between the dyes and g-C3N4 and the negatively charged CMC/SA copolymers had a notable influence on both the adsorption capacity and photodegradation efficiency of the prepared composites. Scavenger studies and leaching tests were conducted to gain insights into the primary reactive species and to assess the stability and long-term performance of the g-C3N4/CMC/SA beads. The commendable photocatalytic activity and excellent recyclability, coupled with the elimination of costly catalyst separation requirements, render the g-C3N4/CMC/SA composite hydrogels cost-effective and environmentally friendly materials, and strongly support their selection for tackling environmental pollution issues.

Effect of Morphology Modification of BiFeO3 on Photocatalytic Efficacy of P-g-C3N4/BiFeO3 Composites.

This current study assessed the impacts of morphology adjustment of perovskite BiFeO3 (BFO) on the construction and photocatalytic activity of P-infused g-C3N4/U-BiFeO3 (U-BFO/PCN) heterostructured composite photocatalysts. Favorable formation of U-BFO/PCN composites was attained via urea-aided morphology-controlled hydrothermal synthesis of BFO followed by solvosonication-mediated fusion with already synthesized P-g-C3N4 to form U-BFO/PCN composites. The prepared bare and composite photocatalysts' morphological, textural, structural, optical, and photocatalytic performance were meticulously examined through various analytical characterization techniques and photodegradation of aqueous rhodamine B (RhB). Ellipsoids and flakes morphological structures were obtained for U-BFO and BFO, and their effects on the successful fabrication of the heterojunctions were also established. The U-BFO/PCN composite exhibits 99.2% efficiency within 20 min of visible-light irradiation, surpassing BFO/PCN (88.5%), PCN (66.8%), and U-BFO (26.1%). The pseudo-first-order kinetics of U-BFO/PCN composites is 2.41 × 10-1 min-1, equivalent to 2.2 times, 57 times, and 4.3 times of BFO/PCN (1.08 × 10-1 min-1), U-BFO, (4.20 × 10-3 min-1), and PCN, (5.60 × 10-2 min-1), respectively. The recyclability test demonstrates an outstanding photostability for U-BFO/PCN after four cyclic runs. This improved photocatalytic activity exhibited by the composites can be attributed to enhanced visible-light utilization and additional accessible active sites due to surface and electronic band modification of CN via P-doping and effective charge separation achieved via successful composites formation.

Thermal Exfoliation and Phosphorus Doping in Graphitic Carbon Nitride for Efficient Photocatalytic Hydrogen Production.

Photocatalytic H2 evolution has been regarded as a promising technology to alleviate the energy crisis. Designing graphitic carbon nitride materials with a large surface area, short diffusion paths for electrons, and more exposed reactive sites are beneficial for hydrogen evolution. In this study, a facile method was proposed to dope P into a graphitic carbon nitride framework by calcining melamine with 2-aminoethylphosphonic acid. Meanwhile, PCN nanosheets (PCNSs) were obtained through a thermal exfoliation strategy. Under visible light, the PCNS sample displayed a hydrogen evolution rate of 700 µmol·g-1·h-1, which was 43.8-fold higher than that of pure g-C3N4. In addition, the PCNS photocatalyst also displayed good photostability for four consecutive cycles, with a total reaction time of 12 h. Its outstanding photocatalytic performance was attributed to the higher surface area exposing more reactive sites and the enlarged band edge for photoreduction potentials. This work provides a facile strategy to regulate catalytic structures, which may attract great research interest in the field of catalysis.

First-Principles Investigation of Phosphorus-Doped Graphitic Carbon Nitride as Anchoring Material for the Lithium-Sulfur Battery.

The utilization of lithium-sulfur battery is hindered by various challenges, including the "shuttle effect", limited sulfur utilization, and the sluggish conversion kinetics of lithium polysulfides (LiPSs). In the present work, a theoretical design for the viability of graphitic carbon nitride (g-C3N4) and phosphorus-doping graphitic carbon nitride substrates (P-g-C3N4) as promising host materials in a Li-S battery was conducted utilizing first-principles calculations. The PDOS shows that when the P atom is introduced, the 2p of the N atom is affected by the 2p orbital of the P atom, which increases the energy band of phosphorus-doping substrates. The energy bands of PC and Pi are 0.12 eV and 0.20 eV, respectively. When the lithium polysulfides are adsorbed on four substrates, the overall adsorption energy of PC is 48-77% higher than that of graphitic carbon nitride, in which the charge transfer of long-chain lithium polysulfides increase by more than 1.5-fold. It is found that there are powerful Li-N bonds between lithium polysulfides and P-g-C3N4 substrates. Compared with the graphitic carbon nitride monolayer, the anchoring effect of the LiPSs@P-g-C3N4 substrate is enhanced, which is beneficial for inhibiting the shuttle of high-order lithium polysulfides. Furthermore, the catalytic performance of the P-g-C3N4 substrate is assessed in terms of the S8 reduction pathway and the decomposition of Li2S; the decomposition energy barrier of the P-g-C3N4 substrate decrease by 10% to 18%. The calculated results show that P-g-C3N4 can promote the reduction of S8 molecules and Li-S bond cleavage within Li2S, thus improving the utilization of sulfur-active substances and the ability of rapid reaction kinetics. Therefore, the P-g-C3N4 substrates are a promising high-performance lithium-sulfur battery anchoring material.

AgIn5S8/g-C3N4 Composite Photocatalyst Coupled with Low-Temperature Plasma-Enhanced Degradation of Hydroxypropyl-Guar-Simulated Oilfield Wastewater.

The effective treatment and recovery of fracturing wastewater has always been one of the difficult problems to be solved in oilfield wastewater treatment. Accordingly, in this paper, photocatalytic-coupled low-temperature plasma technology was used to degrade the simulated wastewater containing hydroxypropyl guar, the main component of fracturing fluid. Results indicated that hydroxypropyl-guar wastewater could be degraded to a certain extent by either photocatalytic technology or plasma technology; the chemical oxygen demand and viscosity of the treated wastewater under two single-technique optimal conditions were 781 mg·L-1, 0.79 mPa·s-1 and 1296 mg·L-1, 1.01 mPa·s-1, respectively. Furthermore, the effective coupling of AgIn5S8/gC3N4 photocatalysis and dielectric-barrier discharge-low-temperature plasma not only enhanced the degradation degree of hydroxypropyl guar but also improved its degradation efficiency. Under the optimal conditions of coupling treatment, the hydroxypropyl-guar wastewater achieved the effect of a single treatment within 6 min, and the chemical oxygen demand and viscosity of the treated wastewater reduced to below 490 mg·L-1 and 0.65 mPa·s-1, respectively. In the process of coupled treatment, the AgIn5S8/gC3N4 could directly absorb the light and strong electric field generated by the system discharge and play an important role in the photocatalytic degradation, thus effectively improving the energy utilization rate of the discharge system and enhancing the degradation efficiency of hydroxypropyl guar.

Theoretical Study of p-Block Metal Single-Atom-Loaded Carbon Nitride Catalyst for Photocatalytic Water Splitting.

Graphitic carbon nitride (g-C3N4), recognized for its considerable potential as a heterogeneous photocatalyst in water splitting, has attracted extensive research interest. By using density functional theory (DFT) calculations, the regulatory role of p-block metal (PM) single atoms on the photocatalytic activity of g-C3N4 in overall water splitting was systematically explored. The incorporation of PM atoms (Ge, Sn and Pb) led to a reduction in the overpotentials required for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Combined with the electronic structures analysis via hybrid functional, it was found that the introduction of Ge, Sn or Pb optimizes the positions of the valence band maximum (VBM) and the conduction band minimum (CBM), providing a robust driving force for HER and ensuring substantial driving force for OER. Meanwhile, the presence of these three PMs induces the spatial separation of VBM and CBM, inhibiting the recombination of carriers. These findings have significant implications for the design and preparation of efficient photocatalysts.