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%.     

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.     

Preparation and characterization of reduced graphene oxide supported nickel oxide nanoparticle-based platform for sensor applications

A nanostructured composite film comprising reduced graphene oxide (rGO) and nickel oxide (NiO) nanoparticles (NPs) has been prepared and utilized for development of a simple yet efficient sensor for detection of dopamine and epinephrine in a single run. The hybrid material rGO-NiO nanocomposite was synthesized chemically, and the formation of nanocomposite was confirmed via X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman, UV-Vis, and Fourier transform infrared (FTIR) spectroscopic techniques. The incorporation of NiO NPs on rGO support was found to provide improved sensing characteristics at electrode interface due to enhanced electron mobility on rGO sheet and high catalytic activity of NiO NPs. Subsequently, the synthesized rGO-NiO nanocomposite was deposited onto indium tin oxide (ITO)-coated glass substrate by simple drop-casting method, and the electrode was characterized through atomic force microscopy (AFM) and scanning electron microscopic (SEM) studies. After optimization of experimental conditions electrochemically for its high sensitivity, the fabricated rGO-NiO/ITO electrode was used for simultaneous detection of dopamine and epinephrine by square wave voltammetry (SWV) method. The results showed high sensitivity of 0.545 and 0.638 μA/μM for dopamine and epinephrine respectively in a broad linear range of 0.5–50 μM. Moreover, remarkable detection limits of 0.495 and 0.423 μM were found for dopamine and epinephrine, and the developed sensor exhibited a wide separation of 380 mV between the respective detection peaks of dopamine and epinephrine. Beside this, the proposed sensor was successfully applied in presence of high concentration of interfering agents, ascorbic acid and uric acid, and validated with real serum samples.     

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.     

Sonochemical synthesis of graphitic carbon nitrides‐wrapped bimetal oxide nanoparticles hybrid materials and their electrocatalytic activity for xanthine electro-oxidation

A novel network-like magnetic nanoparticle was fabricated on a graphitic carbon nitride through a facile sonochemical route at frequency 20 kHz and power 70 W. To enhance the electrocatalytic activity of the modified materials, the graphitic carbon nitrides (g-C₃N₄) was prepared from melamine. Monitoring of xanthine concentration level in biological fluids is more important for clinical diagnosis and medical applications. As modified CuFe₂O₄/g-C₃N₄ nanocomposite exhibits better electrochemical activity towards the oxidation of xanthine with higher anodic current compared to other modified and unmodified electrode for the detection of xanthine with larger linear range (0.03–695 µM) and lower limit of detection (13.2 nM). To compare with these methods, the electrochemical techniques may be an alternative high sensitive method due to their simplicity and rapid detection time. In addition, the practical feasibility of the sensor was inspected with biological samples, reveals the acceptable recovery of the sensor in real samples.     

Characterization and optimization of Ce0.6Zr0.4−x Mn x O2 (x ≤ 0.4)

In situ synthesis method is used to synthesize g-C₃N₄-P25 composite photocatalysts with different mass rations. The experiment result shows that P25 particles with diameter at range of 20–30 nm were embedded homogenously in the sheets of g-C₃N₄. Coupling g-C₃N₄ with P25 can not only improve the visible light absorption, but also improve the visible light photocatalytic activity of P25. The g-C₃N₄-P25 nanocomposite has the higher photocatalytic activity than g-C₃N₄ under visible light. The optimal g-C₃N₄ content with the highest photocatalytic activity is determined to be 84 %, which is almost 3.3 times higher than that of individual g-C₃N₄ under the visible light. The enhanced visible light photocatalytic activity could be ascribed to the formation of g-C₃N₄ and TiO₂ heteojunction, which results in an efficient separation and transfer of photo-induced charge carriers. The electron spin resonance results show that the ^·O₂ ^? radicals are main active species for g-C₃N₄ and the g-C₃N₄-P25 nanocomposites.     

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.     

Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine

Graphitic carbon nitride (g-C₃N₄) has been synthesized via a two-step pyrolysis of melamine (C₃H₆N₆) at 800°C for 2 h under vacuum conditions. X-ray diffraction (XRD) patterns strongly indicate that the synthesized sample is g-C₃N₄. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) morphologies indicate that the product is mainly composed of graphitic carbon nitride. The stoichiometric ratio of C:N is determined to be 0.72 by elemental analysis (EA). Chemical bonding of the sample has been investigated by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Electron energy loss spectroscopy (EELS) verifies the bonding state between carbon and nitrogen atoms. Optical properties of the g-C₃N₄ were investigated by PL (photoluminescence) measurements and UV–Vis (ultraviolet–visible) absorption spectra. We suppose its luminescent properties may have potential application as component of optical nanoscale devices. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were also performed.     

First-principles prediction of an intrinsic half-metallic graphitic hydrogenated carbon nitride

The electronic properties of an experimentally realized graphitic carbon nitride (g-C₃N₃) layer has been studied via first-principles calculations. Unlike the recently reported ferromagnetic g-C₄N₃ structure, the g-C₃N₃ system is nonmagnetic. Based on the two-dimensional g-C₃N₃ structure, we predicts a new graphitic hydrogenated carbon nitride (g-H₃C₃N₃) for the first time, which shows 100% half-metallic property around Fermi energy. It would be a kind of important material in spintronics if it could be synthesized experimentally in the future.     

Preparation of graphitic carbon nitride with large specific surface area and outstanding N2 photofixation ability via a dissolve-regrowth process

Nitrogen fixation is the second most important chemical process in nature next to photosynthesis. Here, we report a convenient dissolve-regrowth method for synthesizing graphitic carbon nitride (g-C₃N₄) with a large surface area and nitrogen vacancies by HCl treatment. XRD, N₂adsorption, SEM, TEM, UV–Vis spectroscopy, EPR, N₂-TPD, Photoluminescence and Photocurrent were used to characterize the prepared catalysts. The results indicate that HCl treatment does not influence the crystal phase of g-C₃N₄ but change the morphology and optical property, leading to the smaller particle size, larger surface area and increased bang gap energy. It is deduced by N₂-TPD, Photoluminescence, Photocurrent and DFT simulations that the nitrogen vacancies formed by the HCl treatment not only serve as active sites to adsorb and activate N₂ molecules but also promote interfacial charge transfer from g-C₃N₄to N₂ molecules. The HCl treated g-C₃N₄ catalyst exhibits outstanding nitrogen photofixation ability under visible light, which is 13.4-fold higher than that of bulk g-C₃N₄ without nitrogen vacancy. The possible reaction mechanism is proposed.     

Ultrasound-assisted synthesis of 3D flower-like zinc oxide decorated fMWCNTs for sensitive detection of toxic environmental pollutant 4-nitrophenol

Sonochemical synthesis of functionalized multi-walled carbon nanotubes (fMWCNTs) embellished 3D flower-like zinc oxide (ZnO) nanocomposite based novel electrochemical sensor for the detection of toxic environmental pollutant 4-nitrophenol (4-NP) is detailed in this paper. We have used laser-assisted synthesis technique in the development of 3D flower-like ZnO nanoparticles (NPs) and ultrasonication method was employed in preparation of ZnO NPs@fMWCNTs nanocomposite using a high-intensity ultrasonic bath DC200H with power of 200 W/cm² and 40 KHz frequency. The nanocomposite was meticulously fabricated on screen printed carbon electrode (SPCE) to carry out various electrochemical analysis. Different characterizations such as Raman spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, UV visible spectroscopy (UV–Vis), X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) of the materials used in this work were taken. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques are used in electrochemical investigations. We have observed well-defined oxidation and reduction peak currents representing electrochemical mechanism of 4-NP at very low potentials for ZnO NPs@fMWCNTs/SPCE. Furthermore, we were able to achieve efficient electrochemical determination of 4-NP using the developed sensor with a high sensitivity of 11.44 μA μM⁻¹ cm⁻² and very low detection limit (LOD) of 0.013 μM in a broad linear range of 0.06–100 μM. All the significant features of a good sensor including anti-interference, good stability, excellent repeatability, and reproducibility were exhibited by the sensor. Moreover, we have tested practical feasibility of sensor by carrying out real sample analysis on different water samples.     

Synthesis and characterization of nitrogen-rich carbon nitride nanobelts by pyrolysis of melamine

Nitrogen-rich g-C₃N₄ nanobelts were successfully synthesized via pyrolysis of melamine (C₃N₆H₆). The as-synthesized nanobelts are structurally uniform, and each belt is uniform in width and thickness along its length direction. The typical width is in the range of 600 nm and 1.5 μm, respectively. The typical length of belts is in the range of several hundreds of micrometers; some of them even have lengths on the order of millimeters. The structure and morphology were researched by XRD, SEM, TEM, CEA, XPS, FTIR, and TG measurements. The theoretical FTIR spectra are calculated to compare with experiment value. It is found that the NH₂ edges in the nanobelts are precisely for the reason of rich nitrogen. The photoluminescence (PL) spectrum was carried out. Two peaks at 443 and 500 nm were observed in the spectrum. In addition, a possible growth mechanism is also inferred by principle of VLS.     

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.     

A facile in situ solvothermal method for two-dimensional layered g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/SnS<Subscript>2</Subscript> p-n heterojunction composites with efficient visible-light photocatalytic activity

To overcome the fast recombination rate of electron-hole pairs of individual SnS₂, p-n heterojunction g-C₃N₄/SnS₂ composites were fabricated as high-efficiency visible-light photocatalyst to photodegradate the organic dye MB. The morphologies, structures, compositions, and photocatalytic properties were characterized. The SnS₂ shows two-dimensional layer structure with an average thickness of 20 nm and diameter size of about 2 μm, and the g-C₃N₄ nanoflakes were uniformly deposited on the surface of SnS₂ nanosheets. In comparison with the bare g-C₃N₄ and SnS₂, the composites show improved photocatalytic activity under visible light, which is sensitive to the content of g-C₃N₄. In particular, the 15% g-C₃N₄/SnS₂ composites exhibit the highest photocatalytic activity and outstanding reusability, which can degrade 88.01% MB after only 1 h in the visible light (λ?>?420 nm) range. The g-C₃N₄/SnS₂ heterojunction composites show outstanding reusability after four times cycling experiments. The improved photocatalytic activities of composites are attributed to abundant active species, increased charge separation, and decreased electron-hole pair recombination, which originated from the large specific surface area and efficient interfacial transport of photo-induced charge carriers between SnS₂ and g-C₃N₄. These results suggest that the two-dimensional layered g-C₃N₄/SnS₂ p-n heterojunction composites are promised to be a high-efficiency visible-light photocatalyst.     

Ultrasonically assisted synthesis of barium stannate incorporated graphitic carbon nitride nanocomposite and its analytical performance in electrochemical sensing of 4-nitrophenol

We describe the ultrasonic assisted preparation of barium stannate-graphitic carbon nitride nanocomposite (BSO-gCN) by a simple method and its application in electrochemical detection of 4-nitrophenol via electro-oxidation. A bath type ultrasonic cleaner with ultrasonic power and ultrasonic frequency of 100 W and 50 Hz, respectively, was used for the synthesis of BSO-gCN nanocomposite material. The prepared BSO-gCN nanocomposite was characterized by employing several spectroscopic and microscopic techniques such as X-ray diffraction, X-ray photoelectron spectroscopy, fourier transform infra-red, field emission scanning electron microscopy, and high resolution transmission electron microscopy, to unravel the structural and electronic features of the prepared nanocomposite. The BSO-gCN was drop-casted on a pre-treated glassy carbon electrode (GCE), and their sensor electrode was utilized for electrochemical sensing of 4-nitrophenol (4-NP). The BSO-gCN modified GCE exhibited better electrochemical sensing behavior than the bare GCE and other investigated electrodes. The electroanalytical parameters such as charge transfer coefficient (α = 0.5), the rate constant for electron transfer (k_s = 1.16 s⁻¹) and number of electron transferred were calculated. Linear sweep voltammetry (LSV) exhibited increase in peak current linearly with 4-NP concentration in the range between 1.6 and 50 μM. The lowest detection limit (LoD) was calculated to be 1 μM and sensitivity of 0.81 μA μM⁻¹ cm⁻²_. A 100-fold excess of various ions, such as Ca²⁺, Na⁺, K⁺, Cl⁻, I⁻, CO₃²⁻, NO₃, NH₄⁺ and SO₄²⁻ did not able to interfere with the determination of 4-NP and high sensitivity for detecting 4-NP in real samples was achieved. This newly developed BSO-gCN could be a potential candidate for electrochemical sensor applications.     

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.     

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.     

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.     

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.     

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.