In-situ hydrothermal synthesized γ-Al_2O_3/O-g-C_3N_4 heterojunctions with enhanced visible-light photocatalytic activity in water splitting for hydrogen

In this work,γ-Al_2O_3 and hydrogen peroxide treated g-C_3N_4(O-g-C_3N_4) were combined through a novel in-situ hydrothermal method to form heterojunction structured photocatalysts.These photocatalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),UV–vis diffuse reflectance spectroscopy and photoluminescence spectroscopy(PL).FT-IR results indicate that oxygen functional groups can be grafted on the surface of O-g-C_3N_4 by hydrogen peroxide treatment.The visible light photocatalytic hydrogen evolution rate was investigated in 10 vol% TEOA aqueous solution.The optimal Al_2O_3 mass content is set to be 20 wt% and the corresponding hydrogen evolution rate is 1288 μmol/h/g which is approximately 6,3 folds that of pristine g-C_3N_4 and O-g-C_3N_4 respectively and 1.6 folds that of mechanical mixed composite with the same Al_2O_3 mass content.The photocurrent density–time curves were carried out under visible light illumination for four on–off cycles.The electrochemical impedance spectroscopy(EIS) measurements verified the enhanced separation efficiency of electron–hole pairs.This work raised a new method to form the heterojunction structured photocatalysts and achieved a remarkable improvement of the photocatalytic activity in water splitting for hydrogen under visible light irradiation.     

Recent advances in the improvement of g-C3N4 based photocatalytic materials

g-C₃N₄ have been widely used in the fields of photocatalytic hydrogen production,photocatalytic degradation of dyes and oxidative degradation of toxic gases due to their excellent performance.It has attracted extensive attention in recent years due to its highly efficient photocatalytic capacity of hydrogen generation,water oxidation,carbon dioxide reduction and degradation of organic pollutants.Because of the abundant carbon and nitrogen composition of the earth,large-scale production and industrial applications of this material are possible.The modification of this material makes its performance more excellent so that this new material can obtain a steady stream of vitality.These outstanding works have become important materials and milestones on the road to mankind's photocatalytic hydrogen production.This review will begin with the basic idea of designing,synthesizing and improving g-C₃N₄ based photocatalytic materials,and introduce the latest development of g-C₃N₄ photocatalysts in hydrogen production from four aspects of controlling the carbon/nitrogen ratio,morphology,element doping and heterojunction structure of g-C₃N₄ materials.     

A novel P-doped and NCDs loaded g-C3N4 with enhanced charges separation for photocatalytic hydrogen evolution

Graphite carbon nitride(g-C₃N₄) is a promising non-metal photocatalyst for photocatalytic hydrogen production, but its performance is still limited due to sluggish charges separation and low utilization of light.In this work, P-doped and N-doped carbon dots(NCDs) supported g-C₃N₄were successfully prepared via hydrothermal and polymerization reactions. The sub-bandgap formed by P-doping enhances the utilization of visible light, and the high electron de...     

In-situ Construction of Sulfur-doped g-C3N4/defective g-C3N4 Iso-type Step-scheme Heterojunction for Boosting Photocatalytic H2 Evolution

The rational construction of a high-efficiency stepscheme heterojunctions is an effective strategy to accelerate the photocatalytic H₂.Unfortunately,the variant energy-level matching between two different semiconductor confers limited the photocatalytic performance.Herein,a newfangled graphitic-carbon nitride(g-C₃N₄)based isotype step-scheme heterojunction,which consists of sulfur-doped and defective active sites in one microstructural unit,is successfully developed by in-situ polymerizing N,N-dimethylformamide(DMF)and urea,accompanied by sulfur(S)powder.Therein,the polymerization between the amino groups of DMF and the amide group of urea endows the formation of rich defects.The propulsive integration of S-dopants contributes to the excellent fluffiness and dispersibility of lamellar g-C₃N₄.Moreover,the developed heterojunction exhibits a significantly enlarged surface area,thus leading to the more exposed catalytically active sites.Most importantly,the simultaneous introduction of S-doping and defects in the units of g-C₃N₄ also results in a significant improvement in the separation,transfer and recombination efficiency of photo-excited electron-hole pairs.Therefore,the resulting isotype step-scheme heterojunction possesses a superior photocatalytic H₂ evolution activity in comparison with pristine g-C₃N₄.The newly afforded metal-free isotype step-scheme heterojunction in this work will supply a new insight into coupling strategies of heteroatoms doping and defect engineering for various photocatalytic systems.     

Bi and S Co-doping g-C3N4 to Enhance Internal Electric Field for Robust Photocatalytic Degradation and H2 Production

By adjusting the type and proportion of doping elements in the g-C₃N₄-based photocatalyst, the internal electric field（IEF） strength of the semiconductor can be regulated. This can effectively enhance the driving force of charge separation in the photocatalytic process. It is found that the introduction of appropriate concentration of Bi and S into the skeleton structure of g-C₃N₄ can achieve efficient degradation of tetracycline（TC） and other pollutan...     

Synthesis of carbon nitride in moist environments:A defect engineering strategy toward superior photocatalytic hydrogen evolution reaction

Intimate understanding of the synthesis-structure-activity relationships is an accessible pathway to overcome the intrinsic challenges of carbon nitride(g-C₃N₄)photocatalysts.This work looks in the effects of humidity of the synthesis process to the morphology,chemical structure,band structure as well as the photocatalytic activity of g-C₃N₄ materials.Four g-C₃N₄ samples were prepared by heating melem in four gas environments:dry Ar,dry Air,moist Ar and moist Air.The photocatalytic activity measurements revealed that the samples synthesized in moist inert and oxidic gases environments displayed 20 and 10 times the photocata lytic H₂ evolution activity of the samples synthesized in dry inert and oxidic gases environments,respectively.The reasons for this remarkable variety in photocata lytic activities had been through investigated.After all,the terminations of the carbon vacancies were identified as the dominant factor in enhancing H₂ evolution performance.The work here thus demonstrating an example of defect engineering.     

Metal derivative(MD)/g-C3N4 association in hydrogen production:A study on the fascinating chemistry behind,current trend and future direction

Metal derivative/graphitic carbon nitride(g-C₃N₄) association is found promising in providing sustainable hydrogen production by photocatalytic water splitting process. Number of works reported on the synthesis and application of various metal based g-C₃N₄ composites are increasing day by day.Mechanism of charge separation varies according to the metal candidate that gets couple with g-C₃N₄.The present article thus explores the in...     

Degradation of tetracycline hydrochloride by ultrafine TiO2 nanoparticles modified g-C3N4 heterojunction photocatalyst: Influencing factors,products and mechanism insight

The unique heterojunction photocatalyst of graphite carbon nitride（g-C₃N₄） modified ultrafine TiO₂（gC₃N₄/Ti O₂） was successfully fabricated by electrochemical etching and co-annealing method. However,the effects of various environmental factors on the degradation of TC by g-C₃N₄/Ti O2and the internal reaction mechanism are still unclear. In this study, the effects of initial p H, anions, and cations on the ph...     

Study on the Different Photocatalytic Performances for Tetracycline Hydrochloride Degradation of p-block Metal Composite Oxides Sr_(1.36)Sb_2O_6 and Sr_2Sb_2O_7

p-block metal composite oxides Sr_1.36Sb₂O₆ and Sr₂Sb₂O₇ synthesized by a hydrothermal method as photocatalysts in the degradation of tetracycline hydrochloride under UV light irradiation have been extensively studied.The effects of synthesis conditions on the photocatalytic activity were discussed.The Sr_1.36Sb₂O₆-100°C-24 h-5 and Sr₂Sb₂O₇-150℃-24 h^-2 samples prepared under optimal conditions exhibited remarkably different photocatalytic activities.The essential factors influencing the difference of photocatalytic performance were revealed.The results showed that the different photocatalytic activities observed for Sr_1.36Sb₂O₆and Sr₂Sb₂O₇ could be attributed to their different electronic and crystal structures.Our work will provide a new perspective for the screening and design of p-block metal composite oxide photocatalysts to enhance the removal of organic pollutants in the environment.     

Self-assembled synthesis of oxygen-doped g-C_3N_4 nanotubes in enhancement of visible-light photocatalytic hydrogen

Currently,photocatalytic water splitting is regarded as promising technology in renewable energy generation.However,the conversion efficiency suffers great restriction due to the rapid recombination of charge carriers.Rational designed the structure and doping elements become important alternative routes to improve the performance of photocatalyst.In this work,we rational designed oxygen-doped graphitic carbon nitride(OCN)nanotubes derived from supermolecular intermediates for photocata lytic water splitting.The as prepared OCN nanotubes exhibit an outstanding hydrogen evolution rate of 73.84μmol h^-1,outperforming the most of reported one dimensional(1D)g-C₃N₄ previously.Due to the rational oxygen doping,the band structure of g-C₃N₄ is meliorated,which can narrow the band gap and reduce the recombination rate of photogene rated carriers.Furthermore,the hollow nanotube structure of OCN also provide multiple diffuse reflection during photocata lytic reaction,which can significantly promote the utilization capacity of visible light and enhance the photocatalytic water splitting performance.It is believed that our work not only rationally controls the nanostructure,but also introduces useful heteroatom into the matrix of photocatalyst,which provides an effective way to design high-efficiency g-C₃N₄ photocatalyst.     

Magnetically recoverable Cu2O/Fe3O4 composite photocatalysts：Fabrication and photocatalytic activity

A magnetically separable Cu2O/Fe3O4 magnetic composite photocatalyst was synthesized in large quantities by a fast and simple route. The as-prepared photocatalysts were characterized by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS） and X-ray diffraction （XRD）. Furthermore, the Cu2O/Fe3O4 composite photocatalysts were tested using methyl orange （MO） degradation reaction under visible light irradiation （100 mW/cm2） and demonstrated to have a high photocatalytic efficiency toward the decomposition of MO under visible light irradiation with good recyclability.     

Constructing a coplanar heterojunction through enhanced π-π conjugation in g-C3N4 for efficient solar-driven water splitting

Adjusting the electronic structure of graphitic carbon nitride（g-C₃N₄） photocatalyst through π-π conjugation is an effective method to achieve efficient photogenerated carrier separation. One key challenge ofπ-π conjugation control is to tune the degree of such conjugation without destroying the g-C₃N₄structure. Herein we report a conceptual design that achieves a coplanar heterojunction by enhancing theπ-π conjugation via the doping of crystalline g-C...     

Engineering FeS2 nanoparticles on tubular g-C3N4 for photo-Fenton treatment of paint wastewater

An efficient photo-Fenton catalyst （Fe S₂@HTCN） was designed by maximizing the synergistic effect of Fe S₂nanoparticles and hollow tubular g-C₃N₄（HTCN）.Molecule self-assembly and molten salts-assisted calcination were used to engineering the hollow structured g-C₃N₄before anchoring Fe S₂nanoparticles on the walls of HTCN via reflux method.Compared to bulk g-C₃N₄,the unique structure of HTCN and het...     

Novel polybenzimidazole/graphitic carbon nitride nanosheets composite membrane for the application of acid-alkaline amphoteric water electrolysis

It is a great challenge to develop membrane materials with high performance and long durability for acidalkaline amphoteric water electrolysis.Hence,the graphitic carbon nitride(g-C₃N₄)nanosheets were compounded with the(2,2'-m-phenylene)-5,5'-benzimidazole(m-PBI)matrix for the preparation of m-PBI/g-C₃N₄ composite membranes.The synthesis of g-C₃N₄ nanosheets and m-PBI matrix have been confirmed by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscoy(TEM)and ¹H nuclear magnetic resonance spectra(¹H NMR),respectively.The fourier transform infrared spectroscopy(FT-IR)and SEM of the composite membranes showed the g-C₃N₄ nanosheets were well dispersed in the m-PBI/g-C₃N₄ composite membrane.The mechanical properties test exhibited the good mechanical strength,and the TGA curves of m-PBI showed the high thermal stability of composite membranes.Besides,the m-PBI/g-C₃N₄ composite membrane showed excellent proton and hydroxide ion conductivity,which was higher than pure m-PBI and Nafion 115 membrane.The acid-alkaline amphoteric water electrolysis test showed m-PBI/1%g-C₃N₄ composite membrane has the best performance with a current density of 800 mA cm^-2 at cell voltage of 1.98 V at 20℃.It showed that m-PBI/g-C₃N₄ composite membrane has a good application prospect for acid-alkaline amphoteric water electrolysis.     

三维磁性复合材料ZnFe2O4/g-C3N4/rGO@Ag的制备及高效光催化降解罗丹明B的研究

光催化降解有机染料被认为是目前解决染料污染问题的一种理想策略。首先以三聚氰胺、氧化石墨烯(GO)和中空ZnFe₂O₄为前驱体通过热处理来构建3D结构ZnFe₂O₄/g-C₃N₄/rGO骨架;然后将银(Ag)作为助催化剂固定在ZnFe₂O₄/g-C₃N₄/rGO骨架上,制备了3D结构ZnFe₂O₄/g-C₃N₄/rGO@Ag复合光催化剂。并采用傅里叶变换红外(FT-IR)、X射线衍射(XRD)和扫描电子显微镜(SEM)等手段对材料的结构、形貌与化学组成进行了表征。结果表明,ZnFe₂O₄/g-C₃N₄/rGO@Ag复合催化剂在可见光的照射下对罗丹明B (RhB)的降解活性显著增强,在可见光照射下20...     

Exploring the mechanism of Ta3N5/KTaO3 photocatalyst for overall water splitting by first-principles calculations

The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta₃N₅ single crystals grown on the surface of KTaO₃ can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta₃N₅(010)/KTaO₃(110)slab models have been built according to experimental observations by considering two common terminations of KTaO₃(110)surface,named as Ta₃N₅/O₂ and Ta₃N₅/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta₃N₅/O₂ has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta₃N₅/KTaO.The light absorption of heterostructures displays the feature of KTaO₃ in the short wavelength region and the characteristic of Ta₃N₅ in the long wavelength region.The calculated band offsets show that Ta₃N₅/O₂ and Ta₃N₅/KTaO have distinct Type-II band alignments,with Ta₃N₅ as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta₃N₅ in Ta₃N₅/KTaO₃ photocatalytic system is determined by the termination property of KTaO₃(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta₃N₅ synthesized by using KTaO₃ as a precursor for the nitridation reaction.     

Photoreduction of CO_2 to methanol over Bi_2S_3/CdS photocatalyst under visible light irradiation

The Bi2S3,CdS and Bi2S3/CdS photocatalysts were prepared by direct reactions between their corresponding salt and thiourea in a hy- drothermal autoclave.The photocatalytic activities of these photocatalysts for reducing CO2 to CH3OH under visible light irradiation have been investigated.The results show that the photocatalytic activity and visible light response of Bi2S3 are higher than those of CdS.The Bi2S3 modification can enhance the photocatalytic activity and visible light response of CdS.The photocatalytic activity of Bi2S3/CdS hetero-junction photocatalyst was the highest and the highest yields of methanol was 613μmol/g when the weight proportion of Bi2S3 to CdS was 15%,which was about three times as large as that of CdS or two times of that of Bi2S3.     

Mg-induced g-C3N4 synthesis of nitrogen-doped graphitic carbon for effective activation of peroxymonosulfate to degrade organic contaminants

The nitrogen-doped carbon derived from graphitic carbon nitride （g-C₃N₄） has been widely deployed in activating peroxymonosulfate （PMS） to remove organic pollutants.However,the instability of g-C₃N₄at high temperature brings challenges to the preparation of materials.The nitrogen-doped graphitic carbon nanosheets （N-GC750） were synthesized by magnesium thermal denitrification.Magnesium undergoes the displacement reaction with small molecules produced b...     

WO3/g-C3N4异质结催化剂的制备及其氧化脱硫性能

以尿素和钨酸铵为原料采用浸渍法制备了金属氧化物三氧化钨（WO₃）与石墨相氮化碳（g-C₃N₄）异质结复合材料WO₃/g-C₃N₄。采用XRD、UV-vis、SEM、PL和XPS表征手段考察了催化剂的理化性质,发现WO₃与g-C₃N₄存在较好的相互作用和电子转移,保证了WO₃/g-C₃N₄本身所具有较高的氧化脱硫活性。以WO₃/g-C₃N₄作为催化剂,过氧化氢异丙苯为氧化剂,考察其光催化氧化脱硫性能,在反应温度80℃,O/S物质的量比为3.0的反应条件下,反应180 min,二苯并噻吩（DBT）转化率可以达到72.79%。通过游离基捕获实验,发现超氧自由基（·O₂^-）、电子（e^-）、羟基自由基（·OH）起到了促进反应速率的作用,并对该体系的反应机理进行了探讨。     

Insights into the efficient charge separation over Nb2O5/2D-C3N4 heterostructure for exceptional visible-light driven H2 evolution

Two-dimensional carbon nitride(2 D-C₃ N₄)nanosheets are promising materials in photocatalytic water splitting,but still suffer from easy agglomeration and fast photogene rated electron-hole pairs recombination.To tackle this issue,herein,a hierarchical Nb₂ O₅/2 D-C₃ N₄ heterostructure is precisely constructed and the built-in electric field between Nb₂O₅ and 2 D-C₃ N₄ can provide the driving force to separate/transfer the charge carriers efficiently.Moreover,the strongly Lewis acidic Nb₂O₅ can adsorb TEOA molecules on its surface at locally high concentrations to facilitate the oxidation reaction kinetics under irradiation,resulting in efficient photogene rated electrons-holes separation and exceptional photocatalytic hydrogen evolution.As expected,the champion Nb₂O₅/2 D-C₃N₄ heterostructure achieves an exceptional H2 evolution rate of 31.6 mmol g^-1 h^-1,which is 213.6 times and 4.3 times higher than that of pristine Nb₂O₅ and2 D-C₃N₄,respectively.Moreover,the champion heterostructure possesses a high apparent quantum efficiency(AQE)of 45.08%atλ=405 nm and superior cycling stability.Furthermore,a possible photocatalytic mechanism of the energy band alignment at the hetero-interface is proposed based on the systematical characterizations accompanied by density functional theory(DFT)calculations.This work paves the way for the precise construction of a high-quality heterostructured photocatalyst with efficient charge separation to boost hydrogen production.