g-C3N4 modified Bi2O3 composites with enhanced visible-light photocatalytic activity

Novel g-C₃N₄ modified Bi₂O₃ (g-C₃N₄/Bi₂O₃) composites were synthesized by a mixing-calcination method. The samples were characterized by thermogravimetry (TG), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), UV–vis diffuse reflection spectroscopy (DRS), photoluminescence (PL) and photocurrent-time measurement (PT). The photocatalytic activity of the composites was evaluated by degradation of Rhodamine B (RHB) and 4-chlorophenol (4-CP) under visible light irradiation (>400 nm). The results indicated that the g-C₃N₄/Bi₂O₃ composites showed higher photocatalytic activity than that of Bi₂O₃ and g-C₃N₄. The enhanced photocatalytic activity of the g-C₃N₄/Bi₂O₃ composites could be attributed to the suitable band positions between g-C₃N₄ and Bi₂O₃. This leads to a low recombination between the photogenerated electron–hole pairs. The proposed mechanism for the enhanced visible-light photocatalytic activity of g-C₃N₄/Bi₂O₃ composites was proven by PL and PT analysis.     

First-principles study of nitrogen defect g-C3N4/WS2 heterojunction on photocatalytic activity

In this work, first-principles density functional theory simulations have been performed to investigate the influence of nitrogen (N) defect on the supercell structure, electronic structure and photocatalytic properties of g-C₃N₄/WS₂ heterojunctions. Analyses of calculated binding energies and the lattice mismatch ratios led us to confirm that N-deficient g-C₃N₄ and WS₂ were in parallel contact and form a stable heterojunction. Furthermore, the work functions, molecular dynamics simulations, charge density differences, band structures, DOS, electronic and optical properties and absorption spectra of different g-C₃N₄/WS₂ heterojunctions have been analyzed in detail. It is revealed that the compositing of N-deficient g-C₃N₄ with WS₂ improves the separation of photoinduced electron-hole pairs. N-defect enhances the visible light absorption of the heterojunction, due to the introduction of impurity energy levels. Moreover, the introduction of defect species further improves the photocatalytic performance of g-C₃N₄/WS₂ heterojunction in the visible region.     

rGO supported self-assembly of 2D nano sheet of (g-C3N4) into rod-like nano structure and its application in sonophotocatalytic degradation of an antibiotic

Graphitic carbon nitride (g-C₃N₄) is an analog of graphite due to its unique electronic structure. g-C₃N₄ based materials have been used in photocatalytic applications. However, pure g-C₃N₄ suffers from major shortcomings which include poor disparity, low surface area and a high recombination rate of photo generated electron-hole pairs that significantly reduce its photocatalytic activity. In this work, self-assembly of g-C₃N₄ sheet into rod shaped g-C₃N₄ was developed via a simple polymerisation method. A composite made of g-C₃N₄ nanorods and rGO (rGO-RCN) was also prepared. The band gap g-C₃N₄ was shifted from 2.77 to 2.6 eV evidented by UV-DRS data. As a result, rGO-RCN showed a relatively high absorption in the visible region. Moreover, a fast electron transfer rate was observed with rGO-RCN composite as conformed from PL analysis and photocurrent measurement. The formation of nanorod and sheet morphologies was confirmed via TEM analysis. The photocatalytic activities of prepared sheet-g-C₃N₄ (SCN)_, Rod g-C₃N₄ (RCN), reduced graphene oxide supported sheet-g-C₃N₄ (rGO-SCN) and reduced graphene oxide supported Rod-g-C₃N₄ (rGO-RCN) were evaluated using a commonly used antibiotic (tetracycline). Among these catalysts, rGO-RCN nanocomposite showed sonophotocatalytic activity 3 times higher compared to pure g-C₃N₄. This superior sonophotocatalytic activity could be due to enhanced visible light absorption of the material, active sites generated by ultrasound, and the high electron transport property of rGO.     

Fabrication of g-C3N4/NiO heterostructured nanocomposite modified glassy carbon electrode for quercetin biosensor

Herein, we report a one-pot synthesis of structurally uniform and electrochemically active graphitic carbon nitride/nickel oxide (g-C₃N₄/NiO) nanocomposite and an investigation on the electrocatalytic oxidation of quercetin (QR). The synthesized g-C₃N₄/NiO nanocomposite has uniform surface distribution, which was characterized with scanning electron microscopy (SEM). Moreover, the composition of synthesized g-C₃N₄/NiO nanocomposite was characterized by UV–vis-spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR spectra), BET, SEM and HRTEM. The g-C₃N₄/NiO was electrochemically treated in 0.1 MPBS solution through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The peak current response increases linearly with QR concentration from 0.010 μM to 250 µM with a fast response time of less than 2 s and a detection limit of 0.002 μM. To further evaluate the feasibility of using this sensor for real sample analysis, QR content in various real samples including green tea, green apple, honey suckle were determined and satisfactory results were achieved.     

Synthesis of CuO/g-C3N4 Composite with High Anti-Interference Ability for Enhanced Fenton-Like Catalysis

The combination of semiconductors and transition metal compounds for Fenton-like application has been widely reported. However, there are still some problems that can be further studied such as the optimization of metal species and in-depth research of mechanism. In this paper, using melamine and copper acetate as raw materials, a kind of composite of copper oxide and graphitic carbon nitride (CuO/g-C₃N₄) is synthesized by a facile hydrothermal method. The synthetic conditions such as type of transition metal salt and ratio of raw material are further optimized. With the presence of H₂O₂, the CuO/g-C₃N₄ composite shows exceptional broad-spectrum Fenton-like catalytic performance against the organic dyes in aqueous solution within a wide pH range, and the highest degradation rate of organic dyes can reach 99% within 10 min. After eight times of recycling, the catalytic activity of the composite can still remain more than 85%. More importantly, the CuO/g-C₃N₄ composite presented excellent anti-interference ability toward heavy metal ions and complex pollutants. Finally, the enhanced Fenton-like catalytic mechanism is illustrated in detail.     

Modified g-C3N4/TiO2 nanosheets/ZnO ternary facet coupled heterojunction for photocatalytic degradation of p-toluenesulfonic acid (p-TSA) under visible light

Novel ternary nanocomposites with facet coupled structure were synthesized by using modified g-C₃N₄, TiO₂ nanosheets and nano-ZnO. Nanosheet/nanosheet heterojunction structure was investigated by TEM, XPS and XRD. FT–IR and Nitrogen adsorption were illustrated for chemical/physical structure analyses. Solution of p-Toluenesulfonic acid (p-TSA) was chosen as target pollutant for visible light photodegradation and the excellent removal efficiency was achieved by this structurally modified g-C₃N₄/TiO₂/ZnO hybrid. The visible light absorption improvement and quantum efficiency enhancement, which were testified by UV–vis DRS, PL and p-TSA photodegradation measurements, due to the facet coupled structure and appropriate quantity of modified g-C₃N₄ in the nanocomposites.     

Impact of Extracellular Polymeric Substance in the Inactivation of Harmful Algae by Ag2O/g-C3N4 under Visible Light

Photocatalysis has attracted much attention as an emerging algae removal technology, but the inactivation performance is inevitably affected by the extracellular polymeric substance (EPS) produced by algae. In this study, a photocatalyst (Ag₂O/g-C₃N₄) with efficient algae inactivation is adopted to investigate the interactions with EPS, and the impact of EPS on photocatalytic algae removal is studied. The results show that EPS can adhere to the surface of Ag₂O/g-C₃N₄ by electrostatic force. The interaction with EPS decreases the surface zeta potential of the Ag₂O/g-C₃N₄ from 7.71 to −22.3 mV with the increase in EPS concentration, and the maximum ratio of particle size increases from 825 to 1281 nm. In addition, the interaction with EPS inhibits the release of Ag⁺ in Ag₂O/g-C₃N₄ by half, thus, the toxicity of metal ions will be alleviated. Meanwhile, EPS can also be degraded by Ag₂O/g-C₃N₄, indicating that EPS can work as a radical scavenger to protect the algae cells. Without the protection of EPS, 97.8% of algae cells are inactivated after 5 h photocatalysis. Therefore, more attention should be given to the interaction between EPS and photocatalyst to promote the design and application of the photocatalytic.     

Sonocatalytic degradation of tetracycline hydrochloride with CoFe2O4/g-C3N4 composite

In this work, different mass percent ratios of CoFe₂O₄ coupled g-C₃N₄ (w%-CoFe₂O₄/g-C₃N₄, CFO/CN) nanocomposites were integrated through a hydrothermal process for the sonocatalytic eradication of tetracycline hydrochloride (TCH) from aqueous media. The prepared sonocatalysts were subjected to various techniques to investigate their morphology, crystallinity, ultrasound wave capturing activity and charge conductivity. From the investigated activity of the composite materials, it has been registered that the best sonocatalytic degradation efficiency of 26.71 % in 10 min was delivered when the amount of CoFe₂O₄ was 25% in the nanocomposite. The delivered efficiency was higher than that of bare CoFe₂O₄ and g-C₃N₄. This enriched sonocatalytic efficiency was credited to the accelerated charge transfer and separation of e⁻-h⁺ pair through the S-scheme heterojunctional interface. The trapping experiments confirmed that all the three species i.e. ^•OH, h⁺ and ^•O₂⁻ were involved in the eradication of antibiotics. A strong interaction was shown up between CoFe₂O₄ and g-C₃N₄ in the FTIR study to support charge transfer as confirmed from the photoluminescence and photocurrent analysis of the samples. This work will provide an easy approach for fabricating highly efficient low-cost magnetic sonocatalysts for the eradication of hazardous materials present in our environment.     

石墨相C_3N_4压致结构相变研究

将有机物三聚氰胺(C3N6H6)高温热解,得到了石墨相C3N4(g-C3N4)。利用同步辐射X射线衍射和金刚石对顶砧(DAC)高压技术,在室温下对g-C3N4进行了结构变化研究。实验结果表明,在16.57 GPa压力范围内,g-C3N4发生了压致结构相变,在6.6 GPa压力下,晶体结构由原来的石墨相转变为三斜相。使用Birch-Murnagha等温状态方程拟合出了样品的等温状态方程。     

Ultrasonic-assisted preparation and characterization of magnetic ZnFe2O4/g-C3N4 nanomaterial and their applications towards electrocatalytic reduction of 4-nitrophenol

Nanoball-structured ferromagnetic zinc ferrite nanocrystals (ZnFe₂O₄ NPs) entrapped with graphitic-carbon nitride (g-C₃N₄) was produced via straightforward and facile sonochemical synthetical technique (titanium probe; 100 W/cm² and 50 KHz). The morphological (SEM), elemental (EDS), diffraction (XRD), XPS, and electrochemical studies (CV) have been carry out to verify the nanostructure and shape of the materials. The ZnFe₂O₄ NPs/g-C₃N₄ electrode (GCE) was constructed which displayed outstanding electrochemical ability towards toxic 4-nitrophenol (NTP). A sensitive, selective, reproducible, and durable electrochemical NTP sensor was developed by ZnFe₂O₄ NPs/g-C₃N₄ modified electrode. The modified sensor exhibited a high sensitivity and 4.17 nanomolars of LOD. It’s greater than the LOD of previously reported NTP modified sensors. The real-time experiments of the modified electrochemical (ZnFe₂O₄ NPs/g-C₃N₄ electrode) sensor were successfully explained in various water (river and drinking) samples and its showed high standard recoveries. Therefore, sonochemical synthetical method and fabrication of modified electrode were developed this work based on environmental analysis of NTP sensor.     

DFT study of the oxidation of Hg0 by O2 on an Mn-doped buckled g-C3N4 catalyst

Due to the water-insoluble nature of Hg⁰, its oxidization to Hg²⁺, which is water-soluble, is a viable approach for its effective removal at coal-fired plants using existing flue gas desulfurization (FGD) unit. In this study, the adsorption and oxidation of elemental mercury on an Mn-doped g-C₃N₄ material were investigated. The spin-polarized density functional theory method was adapted to optimize the geometry structures and then to determine the corresponding electronic structures, while the CI-NEB method was adopted to search for the stable intermediates during the reaction(s). The analysis of energy and project density of states shows that the Mn-g-C₃N₄ exhibits an excellent affinity to Hg atoms. It is found that it is feasible for Hg atoms to oxidize on the Mn-g-C₃N₄ surface via two possible E-R paths, but with relatively high energy barriers. This research provides insights into a viable way for mercury removal using O₂ as the oxidizing agent.     

Ultrasonic irradiation preparation of graphitic-C3N4/polyaniline nanocomposites as counter electrodes for dye-sensitized solar cells

In this research, polyaniline/graphitic carbon nitride (PANI/g-C₃N₄) nanocomposites were synthesized via in-situ electrochemical polymerization of aniline monomer whit different number of cyclic voltammetry scans (10, 20 and 30 cycles) after electrode surface pre-preparation using a potential shock under ultrasonic irradiation. PANI/g-C₃N₄ nanocomposites with two values of g-C₃N₄ (0.010 wt% and 0.015 wt%) were deposited on the surface of the transparent conducting film (FTO glass) by immersing FTO into the aniline solution and g-C₃N₄ during the electro-polymerization. The resulting PANI/g-C₃N₄ films were characterized by Fourier transformed infra-red (FTIR), power X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) techniques. The prepared electrodes were applied as counter electrode in dye-sensitized solar cells. Among them, the prepared electrode with 10 cycles and 0.01 wt% g-C₃N₄ showed the best efficiency. These hybrids show good catalytic activity in elevating tri-iodide reduction and due to the synergistic effect of PANI and g-C₃N₄, PANI/g-C₃N₄ nanocomposite electrode shows power conversion efficiency about 1.8%.     

Combination of ultrasound-treated 2D g-C3N4 with Ag/black TiO2 nanostructure for improved photocatalysis

Herein, nanosheets of g-C₃N₄ (CN), prepared using a green ultrasonication process under various conditions, were combined with Ag/black TiO₂ nanocomposites (AgBT) to create two-dimensional (2D) CN/Ag/black TiO₂ tri-composites (CNAgBT). The thickness of the CN sheets varied with the ultrasonication conditions. The CNAgBT sample prepared using ultrasound-treated CN exhibited the highest average photocatalytic efficiencies for the degradation of two model pollutants, followed in decreasing order by AgBT, black TiO₂ (BT), sheet CN, bulk CN, and TiO₂. The order of pollutant degradation efficiencies by the photocatalysts was consistent with that of the charge carrier separation efficiencies. The degradation efficiency of the CNAgBT increased as the CN-to-AgBT ratio increased from 0.05 to 0.1, but decreased gradually for higher ratios between 0.15 and 0.20, indicating a lower optimal CN-to-AgBT ratio. A plausible photocatalytic degradation mechanism for the CNAgBT nanocomposites was proposed. Additionally, CNAgBT with a CN-to-AgBT ratio of 0.1 displayed a higher hydrogen generation rate with a maximum value of 21.5 mmol g⁻¹ over 5 h than those of the AgBT and BT. Overall, the CNAgBT prepared using ultrasonication-treated CNs showed enhanced photocatalytic performance for both pollutant degradation and hydrogen generation.     

New template for metal decoration and hydrogen adsorption on graphene-like C3N4

From density functional theory calculations we identify a graphene-like C₃N₄ (g-C₃N₄) as an excellent template for stable and well dispersed decoration of alkali (Li) and 3d transition metal (TM) atoms. The porous sites of g-C₃N₄ accommodate excessive N lone-pair electrons and promote hybridization between the orbitals of N and the metal atoms. The most stable TM decorations (Ti and Sc) on g-C₃N₄ exhibit high capacities of hydrogen adsorption with binding energies suitable for mobile applications. These metal decorated g-C₃N₄ may also prove useful in catalytic and sensing applications for their unique nanoscale structural features unavailable in conventional nano-clusters.     

Ultrasound wave assisted removal of Ceftriaxone sodium in aqueous media with novel nano composite g-C3N4/MWCNT/Bi2WO6 based on CCD-RSM model

The aim of this study was ultrasound assisted removal of Ceftriaxone sodium (CS) based on CCD model. Using sonochemical synthesized Bi₂WO₆ implanted on graphitic carbon nitride/Multiwall carbon nanotube (g-C₃N₄/MWCNT/Bi₂WO₆). For this purpose g-C₃N₄/MWCNT/Bi₂WO₆ was synthesized and characterized using diverse approaches including XRD, FE-SEM, XPS, EDS, HRTEM, FT-IR. Then, the contribution of conventional variables including pH, CS concentration, adsorbent dosage and ultrasound contact time were studied by central composite design (CCD) under response surface methodology (RSM). ANOVA was employed to the variable factors, and the most desirable operational conditions mass provided. Drug adsorption yield of 98.85% obtained under these defined conditions. Through conducting five experiments, the proper prediction of the optimum point were examined. The respective results showed that RSD% was lower than 5% while the t-test confirmed the high quality of fitting. Langmuir isotherm equation fits the experimental data best and the removal followed pseudo-second order kinetics. The estimation of the experimentally obtained maximum adsorption capacities was 19.57 mg.g⁻ of g-C₃N₄/MWCNT/Bi₂WO₆ for CS. Boundary layer diffusion explained the mechanism of removal via intraparticle diffusion.     

Synergistic effect of efficient adsorption g-C3N4/ZnO composite for photocatalytic property

Novel g-C₃N₄/ZnO composite photocatalyst was synthesized from an oxygen-containing precursor by direct thermal decomposition urea in air without any other templates assistance. Different percentages of g-C₃N₄ were hybridized with ZnO via the monolayer-dispersed method. The prepared g-C₃N₄/ZnO composites were characterized by XRD, SEM, UV–vis diffuse reflectance spectra (DRS), FT-IR, TEM and XPS. The composites showed much higher efficiency for degradation of Rhodamine B (RhB) than ZnO under UV and visible light irradiation. Especially, the photocatalytic efficiency was the highest under UV light irradiation when the percentage of g-C₃N₄ was 6%. The improved photocatalytic activity may be due to synergistic effect of photon acquisition and direct contact between organic dyestuff and photocatalyst. Then, effective separation of photogenerated electron–hole pairs at the interface of g-C₃N₄ is an important factor for improvement of photocatalytic activity. This work indicates that g-C₃N₄ hybrid semiconductors photocatalyst is a promising material in pollutants degradation.     

High vis-light photocatalytic property of g-C3N4 on four pollutants (RhB,MB, TC-HCl and P-Nitrophenol)

The g-C₃N₄ nanosheets were synthesized by a multistage program calcination with different heating rate, which was an easy, low-cost, and quick method. The morphology and structure of samples were characterized by various techniques. The performance evaluation of the samples was tested by degrading Rhodamine B, Methylene Blue, Tetracycline Hydrochloride and P-Nitrophenol in visible light. The results show that the photodegradation properties of TP-g-C₃N₄ prepared by multistage program calcination are the best than others. In particular, the degradation rate of TP-g-C₃N₄ to Rhodamine B reached 99.6% in just 4 min. TP-g-C₃N₄ catalyst has excellent stability and recycling performance. According to free radical capture experiments, •O₂⁻ may be the main active species for pollutant degradation. The possible photocatalytic degradation mechanism was also discussed. Due to the high specific surface area and a narrow band gap, the TP-g-C₃N₄ becomes a promising photocatalyst.     

g-C3N4/SnS2异质结构:一类有潜力的光解水催化剂

采用第一性原理方法研究了层间耦合作用对g-C₃N₄/SnS₂异质结构的电子结构和吸光性质的影响.发现g-C₃N₄/SnS₂是一类典型的范德瓦异质结构,能有效吸收可见光,其价带顶和导带底与水的氧化还原势匹配,且由于电荷转移而导致的界面处极化场有利于光生载流子的分离.这些理论研究结果表明g-C₃N₄/SnS₂异质结构是一类非常有潜力的光解水催化材料.     

A facile one-pot solvothermal route to tubular forms of luminescent polymeric networks [(C3N3)2(NH)3]n

A facile one-pot solvothermal route has been developed for the synthesis of tubular luminescent polymeric networks [(C₃N₃)₂(NH)₃]_n, structurally related to the proposed g-C₃N₄. XRD patterns showed a characteristic 002 basal plane diffractions, indicating an interlayer d spacing of 3.23 Å. XPS spectra show that the C1s and N1s have a symmetric peak and an asymmetric peak at 288.10 and 399.00 eV, respectively. The bulk composition C₆N_8.9H_4.5 determined by elemental analysis is comparable to the calculated value C₆N₉H₃ for this proposed polymer. FTIR spectra indicated the presence of s-triazine ring, which was further supported by the luminescent and UV-vis absorption characteristics probably depending on π→π^* electronic transition. The tubular structure has been studied by TEM, SAED, and HREM.     

石墨相氮化碳的制备条件优化用以提高其在可见光下的光催化活性

通过染料的光降解实验和敏感性数学分析探讨了石墨相氮化碳(g-C₃N₄)的制备条件与其稳定性和光催化活性之间的联系. 结果表明,相比于焙烧时间,焙烧温度的改变更为显著地影响了g-C₃N₄ 的光催化活性. 制备条件优化之后的g-C₃N₄在可见光照射下催化降解罗丹明B(RhB)的活性比未优化时提高了约100倍,归因于材料比表面积的增大和表面光生电子-空穴迁移速度的增强.