Three-dimensional g-C3N4/MgO composites as a high-performance adsorbent for removal of Pb(II) from aqueous solution

ABSTRACT

A novel, three-dimensional material of g-C₃N₄/MgO was prepared by pyrolysis method. The adsorption behavior for Pb(II) onto g-C₃N₄/MgO was systematically investigated. The adsorption experiments confirmed that the g-C₃N₄/MgO exhibited remarkable adsorption performance owing to its rough morphology and abundant active sites on the surface. The maximum adsorption capacities for Pb(II) reached to 220.3, 226.2 and 235.1 mg/g at 308 K, 318 K and 328 K, respectively. The optimum adsorbent dosage was 1.0 g/L. The adsorption kinetics and isotherm could be well described by the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption process was spontaneous and endothermic.     

TiO2 photocatalyst loaded on hydrophobic Si3N4 support for efficient degradation of organics diluted in water

TiO₂ photocatalyst loaded on Si₃N₄ (TiO₂/Si₃N₄) was prepared by a conventional impregnation method and its photocatalytic performance for the degradation of organics (2-propanol) diluted in water was compared with that of TiO₂ photocatalysts (TiO₂/SiO₂, TiO₂/Al₂O₃, and TiO₂/SiC) loaded on various types of supports (SiO₂, Al₂O₃, and SiC). The formation of the well-crystallized anatase phase of TiO₂ was observed on the calcined TiO₂/Si₃N₄ photocatalyst, while a small anatase phase of TiO₂ was observed on the TiO₂/SiC photocatalyst and amorphous TiO₂ species was the main component on the TiO₂/SiO₂ and TiO₂/Al₂O₃ photocatalysts. The measurements of the water adsorption ability of photocatalysts indicated that the TiO₂/Si₃N₄ photocatalyst exhibited more hydrophobic surface properties in comparison to other support photocatalysts. Under UV-light irradiation, the TiO₂/Si₃N₄ photocatalyst decomposed 2-propanol diluted in water into acetone, CO₂, and H₂O, and finally, acetone was also decomposed into CO₂ and H₂O. The TiO₂/Si₃N₄ photocatalyst showed higher photocatalytic activity than TiO₂ photocatalyst loaded on other supports. The well-crystallized TiO₂ phase deposited on Si₃N₄ and the hydrophobic surface of Si₃N₄ support are important factors for the enhancement of photocatalytic activity for the degradation of organic compounds in liquid-phase reactions.     

Comprehensive Review on g-C3N4-Based Photocatalysts for the Photocatalytic Hydrogen Production under Visible Light

Currently, the synthesis of active photocatalysts for the evolution of hydrogen, including photocatalysts based on graphite-like carbon nitride, is an acute issue. In this review, a comprehensive analysis of the state-of-the-art studies of graphic carbon nitride as a photocatalyst for hydrogen production under visible light is presented. In this review, various approaches to the synthesis of photocatalysts based on g-C₃N₄ reported in the literature were considered, including various methods for modifying and improving the structural and photocatalytic properties of this material. A thorough analysis of the literature has shown that the most commonly used methods for improving g-C₃N₄ properties are alterations of textural characteristics by introducing templates, pore formers or pre-treatment method, doping with heteroatoms, modification with metals, and the creation of composite photocatalysts. Next, the authors considered their own detailed study on the synthesis of graphitic carbon nitride with different pre-treatments and respective photocatalysts that demonstrate high efficiency and stability in photocatalytic production of hydrogen. Particular attention was paid to describing the effect of the state of the platinum cocatalyst on the activity of the resulting photocatalyst. The decisive factors leading to the creation of active materials were discussed.     

Construction of Highly Active Zn3In2S6 (110)/g-C3N4 System by Low Temperature Solvothermal for Efficient Degradation of Tetracycline under Visible Light

Herein, Zn₃In₂S₆ photocatalyst with (110) exposed facet was prepared by low temperature solvothermal method. On this basis, a highly efficient binary Zn₃In₂S₆/g-C₃N₄ was obtained by low temperature solvothermal method and applied to the degradation of tetracycline (TC). The samples of the preparation were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, UV–vis diffuse reflection spectroscopy, and photoluminescence spectroscopy. Furthermore, the degradation performance of photocatalysts on TC was investigated under different experimental conditions. Finally, the mechanism of Zn₃In₂S₆/g-C₃N₄ composite material degrading TC is discussed. The results show that Zn₃In₂S₆ and Zn₃In₂S₆/g-C₃N₄ photocatalysts with excellent performance could be successfully prepared at lower temperature. The Zn₃In₂S₆/g-C₃N₄ heterojunction photocatalyst could significantly improve the photocatalytic activity compared with g-C₃N₄. After 150 min of illumination, the efficiency of 80%Zn₃In₂S₆/g-C₃N₄ to degrade TC was 1.35 times that of g-C₃N₄. The improvement of photocatalytic activity was due to the formation of Zn₃In₂S₆/g-C₃N₄ heterojunction, which promoted the transfer of photogenerated electron–holes. The cycle experiment test confirmed that Zn₃In₂S₆/g-C₃N₄ composite material had excellent stability. The free radical capture experiment showed that ·O₂⁻ was the primary active material. This study provides a new strategy for the preparation of photocatalysts with excellent performance at low temperature.     

Sorption of Cadmium from Aqueous Solution with a Highly Effective Sorbent – B-Doped g-C3N4

B-doped g-C₃N₄ was prepared in the laboratory via heating a mixture of melamine and boric acid. The synthesized material was characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) analysis, which revealed the high specific surface area and large amount of active groups on the surface of B-doped g-C₃N₄. The sorption of cadmium from aqueous solutions by B-doped g-C₃N₄ was studied under equilibrium conditions in the concentration range of 0.01?5.0 mmol/L. The pH of the solution was varied over a range of 2?6. The sorption of cadmium on the material was determined to be pH-dependent, and the Lagergren-second-order kinetic model was suitable to simulate the sorption process. The maximum sorption capacity from the Langmuir model was determined to be 1.4162 mmol/g (about 159.2 mgCd/g). XPS and FTIR data suggest that cadmium ions were mainly attached to the N-H and O-H groups on the surface of B-doped g-C₃N₄.     

Review on photocatalytic conversion of carbon dioxide to value-added compounds and renewable fuels by graphitic carbon nitride-based photocatalysts

Photocatalytic reduction of CO₂ is known as one of the most promising methods to produce valuable fuels and value-added compounds. To overcome selectivity and efficiency downsides, various photocatalysts have been designed and developed. This review discusses the state-of-the-art in photo-conversion of CO₂ over graphitic carbon nitride (g-C₃N₄)-based composites. The modification strategies to improve photocatalytic activity of g-C₃N₄ were classified into different categories and discussed as structural modifications, elemental doping, copolymerization, fabricating heterojunctions between g-C₃N₄ and other semiconductors, Z-scheme heterojunctions, noble metal/g-C₃N₄ photocatalysts, and design of ternary nanocomposites based on g-C₃N₄. Finally, perspectives and future research works in this field were also outlined.     

Efficient solar photocatalyst based on cobalt oxide/iron oxide composite nanofibers for the detoxification of organic pollutants

A Co₃O₄/Fe₂O₃ composite nanofiber-based solar photocatalyst has been prepared, and its catalytic performance was evaluated by degrading acridine orange (AO) and brilliant cresyl blue (BCB) beneath solar light. The morphological and physiochemical structure of the synthesized solar photocatalyst was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). FESEM indicates that the Co₃O₄/Fe₂O₃ composite has fiber-like nanostructures with an average diameter of approximately 20 nm. These nanofibers are made of aggregated nanoparticles having approximately 8.0 nm of average diameter. The optical properties were examined by UV-visible spectrophotometry, and the band gap of the solar photocatalyst was found to be 2.12 eV. The as-grown solar photocatalyst exhibited high catalytic degradation in a short time by applying to degrade AO and BCB. The pH had an effect on the catalytic performance of the as-grown solar photocatalyst, and it was found that the synthesized solar photocatalyst is more efficient at high pH. The kinetics study of both AO and BCB degradation indicates that the as-grown nanocatalyst would be a talented and efficient solar photocatalyst for the removal of hazardous and toxic organic materials.     

A comparative study of elastic recoil detection analysis (ERDA), electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) for structural analysis of amorphous carbon nitride films

A set of carbon and carbon nitride films has been prepared by ion-beam-assisted filtered cathodic vacuum arc deposition. The films were examined by elastic recoil detection analysis (ERDA), electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS). ERDA provides the stoichiometry and mass density of the samples. This study covers the range of 0 up to 29 at.% N and 2.9 g cm⁻³ down to 2.0 g cm⁻³ respectively. The carbon K-edge and the plasmon loss were examined by EELS. The C 1s and N 1s core level spectra were recorded by XPS. The main result is that for significant nitrogen contents the mass density, and hence the plasmon energy and very likely the sp³-fraction, is reduced considerably. The C 1s signals of the carbon nitride layers show a multi-peak structure but the peaks are rather broad and an accurate determination of peak positions is not possible. The splitting of the N 1s signal in four contributions at about 398, 400, 400.6 and 402 eV is observed only for the low density carbon nitrides. A CN_x sample with a density of 2.6 g cm⁻³ and equal amounts of sp²- and sp³-bonded carbon shows only a single peak. We show that the components in the N 1s multi-peak structure can be related to atomic arrangements in a fully sp²-bonded network. In particular, the component at 398 eV does not necessarily indicate the presence of a material similar to β-C₃N₄.     

双模板法CeO2/g-C3N4形貌结构特征及湿式催化性能

利用微波辅助双模板法、软模板法制备了一系列的CeO₂/g-C₃N₄复合催化材料,通过XRD、N₂吸附-脱附、XPS、SEM和TEM等方式对材料进行表征,并对其湿式催化性能进行研究。结果表明,双模板法制备的D-CeO₂/g-C₃N₄复合材料表现出立方相CeO₂和层叠g-C₃N₄的特征,比表面积和孔径较大,属于介孔结构,表面存在Ce^₃₊和Ce^₄₊,有利于氧空位的形成。加入1 g嵌段共聚物 F127,使用无水乙醇溶液为溶剂,调节混合液呈碱性,微波辐射反应120 min后得到的D-CeO₂/g-C₃N₄(7.5)样品,结构完整均匀,具有最佳形貌特征。控制反应温度75 ℃,D-CeO₂/g-C₃N₄(7.5)投加0.7 g,H₂O₂投加 0.5 mL,初始pH值为5时,100 mg/L的苯酚溶液COD去除率可达80%以上。 D-CeO₂/g-C₃N₄(7.5) 复合催化材料使用五次以后仍可达60%以上的催化降解效果。     

H2+CO2 Synergistic Plasma Positioning Carboxyl Defects in g-C3N4 with Engineered Electronic Structure and Active Sites for Efficient Photocatalytic H2 Evolution

Defective functional-group-endowed polymer semiconductors, which have unique photoelectric properties and rapid carrier separation properties, are an emerging type of high-performance photocatalyst for various energy and environmental applications. However, traditional oxidation etching chemical methods struggle to introduce defects or produce special functional group structures gently and controllably, which limits the implementation and application of the defective functional group modification strategy. Here, with the surface carboxyl modification of graphitic carbon nitride (g-C₃N₄) photocatalyst as an example, we show for the first time the feasibility and precise modification potential of the non-thermal plasma method. In this method, the microwave plasma technique is employed to generate highly active plasma in a combined H₂+CO₂ gas environment. The plasma treatment allows for scalable production of high-quality defective carboxyl group-endowed g-C₃N₄ nanosheets with mesopores. The rapid H₂+CO₂ plasma immersion treatment can precisely tune the electronic and band structures of g-C₃N₄ nanosheets within 10 min. This conjoint approach also promotes charge-carrier separation and accelerates the photocatalyst-catalyzed H₂ evolution rate from 1.68 mmol h⁻¹g⁻¹ (raw g-C₃N₄) to 8.53 mmol h⁻¹g⁻¹ (H₂+CO₂-pCN) under Xenon lamp irradiation. The apparent quantum yield (AQY) of the H₂+CO₂-pCN with the presence of 5 wt.% Pt cocatalyst is 4.14% at 450 nm. Combined with density functional theory calculations, we illustrate that the synergistic N vacancy generation and carboxyl species grafting modifies raw g-C₃N₄ materials by introducing ideal defective carboxyl groups into the framework of heptazine ring g-C₃N₄, leading to significantly optimized electronic structure and active sites for efficient photocatalytic H₂ evolution. The 5.08-times enhancement in the photocatalytic H₂ evolution over the as-developed catalysts reveal the potential and maneuverability of the non-thermal plasma method in positioning carboxyl defects and mesoporous morphology. This work presents new understanding about the defect engineering mechanism in g-C₃N₄ semiconductors, and thus paves the way for rational design of effective polymeric photocatalysts through advanced defective functional group engineering techniques evolving CO₂ as the industrial carrier gas.     

Effective Removal of Methylene Blue on EuVO4/g-C3N4 Mesoporous Nanosheets via Coupling Adsorption and Photocatalysis

In this study, we first manufactured ultrathin g-C₃N₄ (CN) nanosheets by thermal etching and ultrasonic techniques. Then, EuVO₄ (EV) nanoparticles were loaded onto CN nanosheets to form EuVO₄/g-C₃N₄ heterojunctions (EVCs). The ultrathin and porous structure of the EVCs increased the specific surface area and reaction active sites. The formation of the heterostructure extended visible light absorption and accelerated the separation of charge carriers. These two factors were advantageous to promote the synergistic effect of adsorption and photocatalysis, and ultimately enhanced the adsorption capability and photocatalytic removal efficiency of methylene blue (MB). EVC-2 (2 wt% of EV) exhibited the highest adsorption and photocatalytic performance. Almost 100% of MB was eliminated via the adsorption–photocatalysis synergistic process over EVC-2. The MB adsorption capability of EVC-2 was 6.2 times that of CN, and the zero-orderreaction rate constant was 5 times that of CN. The MB adsorption on EVC-2 followed the pseudo second-order kinetics model and the adsorption isotherm data complied with the Langmuir isotherm model. The photocatalytic degradation data of MB on EVC-2 obeyed the zero-order kinetics equation in 0–10 min and abided by the first-order kinetics equation for10–30 min. This study provided a promising EVC heterojunctions with superior synergetic effect of adsorption and photocatalysis for the potential application in wastewater treatment.     

Melamine-(H2SO4)3/melamine-(HNO3)3 instead of H2SO4/HNO3: a safe system for the fast oxidation of thiols and sulfides under solvent-free conditions

Melamine reacted with neat sulfuric acid and fuming nitric acid readily to form two new organic solid acids, namely melamine-(H₂SO₄)₃ and melamine-(HNO₃)₃. Mixture of them acts as a unique powerful system instead of a hazardous H₂SO₄/HNO₃ system for the direct oxidation of thiols. Also, this system can oxidize the sulfides in the presence of a catalytic amount of KBr and few drops of water. This procedure offers advantages such as very low reaction time, simple work-up, excellent yield and matching with some green chemistry protocols.     

Influence of H2/NH3 mixtures on the composition of SiCNYO and SiCNAl(O) nanopowders

We performed pyrolysis of SiCNAlH and SiCNYOH nanopowder precursors under a reactive atmosphere (Ar/NH₃/H₂) with various compositions of ammonia (NH₃) and dihydrogen (H₂) to diminish C content, which is deleterious for thermal stability and sintering of the powders. This paper continues a previous work on the fabrication of an Si₃N₄/SiC composite without free C by studying the effect of H₂ on the C/N atomic ratio of the powder. We studied the influence of the nature of the gaseous mixture (Ar/NH₃/H₂) on the powder composition. Elemental analysis showed that the introduction of H₂ in the pyrolysis atmosphere limited the decomposition of NH₃ and allowed for control of the C/N ratio. This behaviour can be explained by the structural evolution observed by ²⁹Si NMR spectrometry but also by Fourier transform infrared and Raman spectroscopy. An Si₃N₄/SiC composite, with traces of free C, was obtained after post-pyrolysis heat treatment of the powders synthesized with 10 wt.% of H₂ and 25 wt.% NH₃.     

Mixed oxides as catalysts for the selective reduction of nitrobenzene

The catalytic behaviour of the PbO-Mn₃O₄ and the Bi₂O₃-MoO₃ systems was investigated in the selective reduction of nitrobenzene to nitrosobenzene. Lead compounds appeared to be good catalysts, and co-catalysts when used with Mn₃O₄. Different from oxidations by di-oxygen, Bi₃O₃ alone is a good catalyst and formation of mixed Bi-Mo-O compounds does not enhance the catalytic activity. It is suggested that the difference between these catalysts in the mentioned reaction is related to the way in which the oxygen vacancy is represented by the oxygen donor.     

Influence of Co3O4, Fe2O3 and SiC on microstructure and properties of glass foam from waste cathode ray tube display panel (CRT)

Abstract

In the present study, the effect of temperature and oxidising agents such as Fe₂O₃ and Co₃O₄ on physical and mechanical properties of glass foam is investigated. The glass foam is made of panel glass from dismantled cathode ray tubes and SiC as a foaming agent. In the process, powdered waste glass (mean particle size below 63 μm) in addition to 4 wt-% SiC powder (mean particle size below 45 μm) are combined with Fe₂O₃ and Co₃O₄ (0·4, 0·8 and 1·2 wt-%) have been sintered at 950 and 1050°C. The glass foamed containing 1·2 wt-% Co₃O₄ has good physical properties, with porosity more than 80% and bending strength more than 1·57±0·12 MPa. However, by adding different amounts of Fe₂O₃ in comparison with samples without iron oxide, little changes in porosity and strength are obtained.     

Green synthesis of thiiranes from epoxides catalyzed by magnetically separable CuFe2O4/Mg(OH)2 nanocomposite in water under benign conditions

The magnetically separable CuFe₂O₄/Mg(OH)₂ nanocomposite was prepared and characterized by FT-IR, XRD, SEM, EDS, and VSM techniques. The synthesized nanoparticles were used as a new and efficient heterogeneous catalyst for the conversion of various epoxides to the corresponding thiiranes with thiourea in water solvent at room temperature. The reactions were completed within 1–3.7?h to give thiiranes in 70–99% yields. The applied CuFe₂O₄/Mg(OH)₂ nanocomposite was separated easily using an external magnet and reused for several times without any considerable loss of activity.     

Effect of TiO2 addition on the microstructures,mechanical and dielectric properties of porous Si3N4-based ceramics

Porous Si₃N₄-based ceramics with different TiO₂ contents were prepared by gas pressure sintering method. The effects of TiO₂ addition ranging from 0 to 25?wt-% on the phase compositions, microstructures, mechanical performance and dielectric properties were investigated. The addition of TiO₂ significantly promoted the density which increased from 1.64 to about 2.3?g?cm^?3. The mechanical properties of porous Si₃N₄-based ceramics with TiO₂ addition decreased first and then increased with the increase of TiO₂ content, and the flexural strength and elastic modulus are more than 167.4?MPa and 72.8?GPa, respectively, which were higher than that of the Si₃N₄ ceramic without TiO₂ addition. With the increase of TiO₂ content, both the dielectric constant and dielectric loss increased, and the dielectric constant enhanced obviously. These results suggested that the TiO₂ was beneficial for the improvement of mechanical properties and dielectric constant of porous Si₃N₄-based ceramics.     

Quartz crystal microbalance study of the growth of indium(III) sulphide films from a chemical solution

The growth of indium(III) sulphide thin films from aqueous thioacetamide (TA)-In(III) solution has been studied with a quartz crystal microbalance (QCM). It is found that the growth of the film consists in the parallel deposition of In₂S₃ and In₂O₃. Both processes are induced by sulphide anions (S²⁻) produced after decomposition of thioacetamide. In₂S₃ is deposited by precipitation of crystallites formed in the bulk solution. On stirred solutions this reaction is hindered due to the disruption of the nucleation centres. On the other hand, In₂O₃ is deposited by electrochemical reduction of naturally dissolved oxygen (O₂) by the S²⁻ anions, followed by chemical reaction with In³⁺. This process is of electroless-chemical nature and has important consequences on the properties of the films. Both reaction mechanisms, chemical and electroless-chemical, compete under different experimental conditions: temperature, solution composition, stirring. For instances, the deposit of In₂O₃ is favoured at low bath temperature, in aerated solutions, giving rise to films with higher oxide proportion. Additives like hydrochloric acid and acetic acid also favour In₂O₃ deposition. The system has easy possibility to tune chemical and physical properties of the films, like composition, transparency and absorption edge, of interest for photovoltaic applications.     

Preparation, characterization and electrocatalytic properties of poly(luminol) and polyoxometalate hybrid film modified electrodes

Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻ have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study in situ growth of the hybrid poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻. Both the poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻ hybrid films showed four redox couples and the electrochemical properties were compared to SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of two hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO₃⁻, BrO₃⁻, IO₃⁻, S₂O₈²⁻ and NO₂⁻ by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO₃⁻ > BrO₃⁻ and ClO₃⁻. The electrocatalytic oxidation of dopamine and epinephrine by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film was also investigated.     

Hydrothermal synthesis of Co3O4 nanosheets and its application in photoelectrochemical water splitting

In this study, Co₃O₄ nanosheets were synthesized through hydrothermal method using cobalt nitrate hexahydrate. X-ray diffraction, diffuse reflectance spectra, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and field emission scanning electron microscopy were applied to investigate the properties of as-synthesized samples. Ultimately, the electrochemical and photoelectrochemical properties were evaluated by Mott–Schottky analysis and measuring photoconversion efficiency of Co₃O₄ nanosheets. The results indicated that Co₃O₄ nanosheets exhibited a maximum efficiency of 0.92% for water electrolysis under simulated 1.5 global sunlight air mass, which further suggests the excellent potential of Co₃O₄ nanosheets for application in hydrogen generation through photocatalytic water splitting.