A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in th...A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.展开更多
Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uni...Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.展开更多
A simple calcination method was employed to prepare a Z-scheme N-doped K4Nb6O17/g-C3N4(KCN)heterojunction photocatalyst,in which the electronic structure of K4Nb6O17 was regulated by N-doping,and g-C3N4 was formed bot...A simple calcination method was employed to prepare a Z-scheme N-doped K4Nb6O17/g-C3N4(KCN)heterojunction photocatalyst,in which the electronic structure of K4Nb6O17 was regulated by N-doping,and g-C3N4 was formed both on the surface and within the interlayer spaces of K4Nb6O17.The KCN composite showed profoundly improved photocatalytic activity for both H2 generation and RhB degradation compared to its counterparts.This improved performance was attributed to the synergistic effects of N-doping,which broadened its light harvesting ability,and heterojunction formation,which increased the charge separation rate.The relatively low BET specific surface area of the KCN composite had little effect on its photocatalytic activity.Based on ESR spectroscopy studies,•O2^−,•OH,and h^+are the main active species in the photocatalytic degradation of RhB.Thus,it is reasonable to propose a Z-scheme photocatalytic mechanism over the KCN composite,which exhibits the dual advantages of efficient charge separation and high redox ability.Our work provides a simple approach for constructing large-scale Z-scheme heterojunction photocatalysts with high photocatalytic performance.展开更多
The CdS/spherical g-C3N4 n-n heterojunction photocatalyst was fabricated via a solvothermal method.The tetracycline was used to characterize the photocatalytic properties of the as-developed hybrids.The photocatalytic...The CdS/spherical g-C3N4 n-n heterojunction photocatalyst was fabricated via a solvothermal method.The tetracycline was used to characterize the photocatalytic properties of the as-developed hybrids.The photocatalytic degradation mechanism of the as-developed heterojunction photocatalyst was also analyzed.Research results show that CdS nanoparticles are well dispersed in the surface layer of spherical g-C3N4.Moreover,the mass ratio of CdS to spherical g-C3N4 will influence the photocatalytic activity of the asdeveloped composites,which shows the trend of first increasing and then decreasing as it increased.When the mass ratio is 7:1,in 25 min,the as-developed heterojunction shows 93.2%of the maximum photocatalytic efficiency and still exhibits 83.6%after 5 times cycle testing.Moreover,the as-developed hybrids can accelerate the electron transport and improve the separation efficiency of photo-generated carriers compared with pure samples.In addition,the holes and superoxide radicals are dominating active species during the photocatalytic degradation process.展开更多
Bi_2WO_6 was modified by two-dimensional g-C_3N_4(2D g-C_3N_4)via a hydrothermal method.The structure,morphology,optical and electronic properties were investigated by multiple techniques,including X-ray diffraction(X...Bi_2WO_6 was modified by two-dimensional g-C_3N_4(2D g-C_3N_4)via a hydrothermal method.The structure,morphology,optical and electronic properties were investigated by multiple techniques,including X-ray diffraction(XRD),X-ray photoelectron spectroscopy spectra(XPS),Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Ultravioletvisible diffuse reflection spectroscopy(DRS),photocurrent and electrochemical impedance spectroscopy(EIS),electron spin resonance(ESR),respectively.Rhodamine B(Rh B)was used as the target organic pollutant to research the photocatalytic performance of as-prepared composites.The Bi_2WO_6/2D g-C_3N_4exhibited a remarkable improvement compared with the pure Bi_2WO_6.The enhanced photocatalytic activity was because the photogenerated electrons and holes can quickly separate by Z-Scheme passageway in composites.The photocatalytic mechanism was also researched in detail through ESR analysis.展开更多
Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from ...Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.展开更多
A heterojunction photocatalyst based on porous tubular g-C3N4 decorated with CdS nanoparticles was fabricated by a facile hydrothermal co-deposition method.The one-dimensional porous structure of g-C3N4 provides a hig...A heterojunction photocatalyst based on porous tubular g-C3N4 decorated with CdS nanoparticles was fabricated by a facile hydrothermal co-deposition method.The one-dimensional porous structure of g-C3N4 provides a higher specific surface area,enhanced light absorption,and better separation and transport performance of charge carriers along the longitudinal direction,all of which synergistically contribute to the superior photocatalytic activity observed.The significantly enhanced catalytic efficiency is also a benefit originating from the fast transfer of photogenerated electrons and holes between g-C3N4 and CdS through a built-in electric field,which was confirmed by investigating the morphology,structure,optical properties,electrochemical properties,and photocatalytic activities.Photocatalytic degradation of rhodamine B(RhB)and photocatalytic hydrogen evolution reaction were also carried out to investigate its photocatalytic performance.RhB can be degraded completely within 60 min,and the optimum H2 evolution rate of tubular g-C3N4/CdS composite is as high as 71.6μmol h^–1,which is about 16.3 times higher than that of pure bulk g-C3N4.The as-prepared nanostructure would be suitable for treating environmental pollutants as well as for water splitting.展开更多
Photocatalytic H2 production via water splitting in a noble-metal-free photocatalytic system has attracted much attention in recent years.In this study,noble-metal-free Ni3N was used as an active cocatalyst to enhance...Photocatalytic H2 production via water splitting in a noble-metal-free photocatalytic system has attracted much attention in recent years.In this study,noble-metal-free Ni3N was used as an active cocatalyst to enhance the activity of g-C3N4 for photocatalytic H2 production under visible-light irradiation(λ>420 nm).The characterization results indicated that Ni3N nanoparticles were successfully loaded onto the g-C3N4,which accelerated the separation and transfer of photogenerated electrons and resulted in enhanced photocatalytic H2 evolution under visible-light irradiation.The hydrogen evolution rate reached^305.4μmol h^-1 g^-1,which is about three times higher than that of pristine g-C3N4,and the apparent quantum yield(AQY)was^0.45%atλ=420.Furthermore,the Ni3N/g-C3N4 photocatalyst showed no obvious decrease in the hydrogen production rate,even after five cycles under visible-light irradiation.Finally,a possible photocatalytic hydrogen evolution mechanism for the Ni3N/g-C3N4 system is proposed.展开更多
Constructing step-scheme(S-scheme)heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials.In this work,a series of sulfur-doped g-C3N4(SCN)/TiO2 S-sc...Constructing step-scheme(S-scheme)heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials.In this work,a series of sulfur-doped g-C3N4(SCN)/TiO2 S-scheme photocatalysts were synthesized using electrospinning and calcination methods.The as-prepared SCN/TiO2 composites showed superior photocatalytic performance than pure TiO2 and SCN in the photocatalytic degradation of Congo Red(CR)aqueous solution.The significant enhancement in photocatalytic activity benefited not only from the 1D well-distributed nanostructure,but also from the S-scheme heterojunction.Furthermore,the XPS analyses and DFT calculations demonstrated that electrons were transferred from SCN to TiO2 across the interface of the SCN/TiO2 composites.The built-in electric field,band edge bending,and Coulomb interaction synergistically facilitated the recombination of relatively useless electrons and holes in hybrid when the interface was irradiated by simulated solar light.Therefore,the remaining electrons and holes with higher reducibility and oxidizability endowed the composite with supreme redox ability.These results were adequately verified by radical trapping experiments,ESR tests,and in situ XPS analyses,suggesting that the electron immigration in the photocatalyst followed the S-scheme heterojunction mechanism.This work can enrich our knowledge of the design and fabrication of novel S-scheme heterojunction photocatalysts and provide a promising strategy for solving environmental pollution in the future.展开更多
Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have be...Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have been rarely reported.Herein,a CoP co-catalyst-modified graphitic-C3N4(g-C3N4/CoP)is investigated for photocatalytic water splitting to produce H2.The g-C3N4/CoP composite is synthesized in two steps.The first step is related to thermal decomposition,and the second step involves an electroless plating technique.The photocatalytic activity for hydrogen evolution reactions of g-C3N4 is distinctly increased by loading the appropriate amount of CoP quantum dots(QDs).Among the as-synthesized samples,the optimized one(g-C3N4/CoP-4%)shows exceptional photocatalytic activity as compared with pristine g-C3N4,generating H2 at a rate of 936μmol g^-1 h^-1,even higher than that of g-C3N4 with 4 wt%Pt(665μmol g^-1 h^-1).The UV-visible and optical absorption behavior confirms that g-C3N4 has an absorption edge at 451 nm,but after being composited with CoP,g-C3N4/CoP-4%has an absorption edge at 497 nm.Furthermore,photoluminescence and photocurrent measurements confirm that loading CoP QDs to pristine g-C3N4 not only enhances the charge separation,but also improves the transfer of photogenerated e--h+pairs,thus improving the photocatalytic performance of the catalyst to generate H2.This work demonstrates a feasible strategy for the synthesis of highly efficient metal phosphide-loaded g-C3N4 for hydrogen generation.展开更多
Photocatalysis. which utilizes solar energy to trigger chemical reactions, is one of the most desirable solar-energy-conversion approaches. Graphitic carbon nitride (g-C3N4). as an attractive metal-free photocatalys...Photocatalysis. which utilizes solar energy to trigger chemical reactions, is one of the most desirable solar-energy-conversion approaches. Graphitic carbon nitride (g-C3N4). as an attractive metal-free photocatalyst, has drawn worldwide research interest in the area of solar energy conversion due to its easy synthesis, earth-abundant nature, physicochemical stability and visible-light-responsive properties. Over the past ten years, g-C3N4 based photocatalysts have experienced intensive exploration, and great progress has been achieved. However, the solar conversion efficiency is still far from industrial applications due to the wide bandgap, severe charge recombination, and lack of surface active sites. Many strategies have been proposed to enhance the light absorption, reduce the recombination of charge carriers and accelerate the surface kinetics. This work makes a crucial review about the main contributions of various strategies to the light harvesting, charge separation and surface kinetics of g-C3N4 photocatalyst. Furthermore, the evaluation measurements for the enhanced light harvesting, reduced charge recombination and accelerated surface kinetics will be discussed. In addition, this review proposes future trends to enhance the photocatalytic performance of g-C3N4 photocatalyst for the solar energy conversion.展开更多
Modification of nickel sulfide cocatalysts is considered to be a promising approach for efficient enhancement of the photocatalytic hydrogen production performance of g-C3N4.Providing more NiS cocatalyst to function a...Modification of nickel sulfide cocatalysts is considered to be a promising approach for efficient enhancement of the photocatalytic hydrogen production performance of g-C3N4.Providing more NiS cocatalyst to function as active sites of g-C3N4 is still highly desirable.To realize this goal,in this work,a facile sulfur-mediated photodeposition approach was developed.Specifically,photogenerated electrons excited by visible light reduce the S molecules absorbed on g-C3N4 surface to S^2‒,and subsequently NiS cocatalyst is formed in situ on the g-C3N4 surface by a combination of Ni2+and S2‒due to their small solubility product constant(Ksp=3.2×10^‒19).This approach has several advantages.The NiS cocatalyst is clearly in situ deposited on the photogenerated electron transfer sites of g-C3N4,and thus provides more active sites for H2 production.In addition,this method utilizes solar energy with mild reaction conditions at room temperature.Consequently,the synthesized NiS/g-C3N4 photocatalyst achieves excellent hydrogen generation performance with the performance of the optimal sample(244μmol h^‒1 g^‒1)close to that of 1 wt%Pt/g-C3N4(316μmol h^‒1 g^‒1,a well-known excellent photocatalyst).More importantly,the present sulfur-mediated photodeposition route is versatile and facile and can be used to deposit various metal sulfides such as CoSx,CuSx and AgSx on the g-C3N4 surface,and all the resulting metal sulfide-modified g-C3N4 photocatalysts exhibit improved H2-production performance.Our study offers a novel insight for the synthesis of high-efficiency photocatalysts.展开更多
Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) ca...Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) can be doped into g-C3N4 through the coordination between amidogen and Fe(Ⅲ). After activity tests, it was found that this coordination doping of Fe(Ⅲ) could enhance the Rh B oxidation and Cr(Ⅵ) reduction activities of g-C3N4 in interesting ways, but it is not helpful for the NO-removal performance of g-C3N4. Characterization and calculation results show that the coordination of Fe(Ⅲ) can not only improve the transfer of photogenerated electrons, but it also can passivate the carbon site of triazine rings, which is the active site of NO-removal. This study revealed some doping mechanisms and effect mechanisms of elemental metal in photocatalysis.展开更多
G-C3N4 was supported on the surface of foamed ceramic,and the g-C3N4@foamed ceramic was packed in the photocatalytic reactor in a layered manner.Effects of urea and H2O2 concentration on NO conversion were investigate...G-C3N4 was supported on the surface of foamed ceramic,and the g-C3N4@foamed ceramic was packed in the photocatalytic reactor in a layered manner.Effects of urea and H2O2 concentration on NO conversion were investigated.Pulse experiments were carried out to investigate the change of NO conversion with time under different concentrations of H2O2.The contribution of each route that NO converted and the selectivities of products were calculated.Results showed that the photo-reduction of NO accounted for 2%,and the photo-oxidation of NO accounted for 14%,and the rest was absorbed by the humidifier.Products include ammonia(NH+4-N),nitrogen(N2),nitrite(NO-2-N)and nitrate(NO-3-N),of which N2 accounted for 9%.展开更多
A new,facile,and efficient way to prepare alkalinized g-C3N4 is presented.We calcined a mixture of KCl and melamine to obtain g-C3N4,whose in-plane structure was K+doped so that alkalinized samples could be obtained b...A new,facile,and efficient way to prepare alkalinized g-C3N4 is presented.We calcined a mixture of KCl and melamine to obtain g-C3N4,whose in-plane structure was K+doped so that alkalinized samples could be obtained by treatment with different concentrations of KOH.The different samples were used to oxidize As(Ⅲ)in both visible light and natural light.The sample treated with 10 mol/L KOH showed the highest efficiency,converting all As(Ⅲ)into As(Ⅴ)within 120 min in both visible light and natural light,as the oxidative capacity of the As(Ⅲ)in the alkalinized samples was significantly higher than that of the original samples.K+doping improved the electron transport capacity of the samples,while the alkalinized samples could destroy their edge structures,so as to improve the separation efficiency of the photogenerated carrier.The experiment confirmed that alkalinized g-C3N4 significantly improves the oxidation ability of As(Ⅲ)and plays an important role in the photocatalytic treatment of refractory nonmetallic ions.展开更多
Graphitic carbon nitride (g-C3N4) has become an attractive visible-light-responsive photocatalyst because of its semiconductor polymer compositions and easy-modulated band structure. However, the bulk g-C3N4 photocata...Graphitic carbon nitride (g-C3N4) has become an attractive visible-light-responsive photocatalyst because of its semiconductor polymer compositions and easy-modulated band structure. However, the bulk g-C3N4 photocatalyst has the low separation efficiency of photogenerated carriers and unsatisfied surface catalytic performance, which leads to poor photocatalytic performance. As for this, MgTi2O5 with high chemical stability, wide band gap and negative conduction band was used as a suitable platform for coupling with g-C3N4 to enhance charge separation and promoted the photoactivity. Different from common approaches, here, we propose an innovative method to construct g-C3N4/MgTi2O5 nanocomposites featuring “0 + 1 >1" magnification effect to improve g-C3N4 photocatalytic performance under visible light irradiation. Additionally, compositing metal oxides of MgTi2O5 with g-C3N4 has proven to be a proper strategy to accelerate surface catalytic reactions in g-C3N4, and the photoinduced carriers were modulated to maintain thermodynamic equilibrium, which convincingly promotes the photocatalytic activity. The photocatalytic performance of the nanocomposites was measured by hydrogen production and CO2 reduction under visible light. The developed g-C3N4/MgTi2O5 nanocomposites with a 5 wt.% MgTi2O5 exhibits the highest H2 and CO yield under visible light and excellent stability compare to the other MgTi2O5 contents in composites. According to surface photo-voltage spectra, electrochemical CO2 reduction, photoluminescence, etc. The superior performance can be related to an enhanced electron lifetime, the promoted charge transfer and the increased electronic separation property of g-C3N4. Our work provides an approach to overcome the defect of pure g-C3N4, which accesses to composite with the second component matched well.展开更多
Nitrogen photo fixation using g-C3N4-based photocatalysts have attracted abundant of attentions recently.Herein,in this study,holey g-C3N4(HGCN)nanosheets possess a good deal of carbon vacancies were prepared by means...Nitrogen photo fixation using g-C3N4-based photocatalysts have attracted abundant of attentions recently.Herein,in this study,holey g-C3N4(HGCN)nanosheets possess a good deal of carbon vacancies were prepared by means of thermally treating bulk g-C3 N4(BGCN)under an NH3 atmosphere.Characterization analysis revealed that the as-synthesized sample have identical crystal structure,la rger BET specific surface area,stronger reduction capability,and higher photogene rated charge carrier separation rate than that of BGCN.These properties may contribute to enhance the nitrogen photofixation activity.It was also found that the rate of NH4^+production for N2 photofixation of HGCN sample reached^25.54 mg L^-1 h^-1 g(cat)^-1,which is approximately^5.87 times higher than that of BGCN sample under optimal reactive conditions.Moreover,a plausible mechanism of HGCN for nitrogen photofixation process was illuminated in detail.展开更多
Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C3Na-based photocatalysts.To solve these problems,g-CN4/nitrogen-doped graphene quantum dots(NGQDs)/Ti...Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C3Na-based photocatalysts.To solve these problems,g-CN4/nitrogen-doped graphene quantum dots(NGQDs)/TiO2 ternary heterojunctions were facilely prepared via a one-step calcining method.The morphology.structure,optical and electrochemical properties of g-C3NA/NGQDs/TiO2 were characterized and explored.The optimal g-CN4/NGODs/TiOz composite exhibits enhanced photocatalytic degradation performance of ciprofloxacin(CIP)compared with the as-prepared g-C3Na.TiO:(P25)and g-C3N4/TiO2 heterojunction under visible light irradia-tion.The apparent rate constant of the composite is around 6.43.4.03 and 2.30 times higher than those of g-C3N4,TiOz and g-C3N4/TiO2,respectively.The enhanced photocatalytic efficiency should be mainly attributed to the improvement of light absorption and charge separation and transfer efficiency,originating from the narrow band gap and high charge carrier mobility.The active species trapping experiments results showed that the ht and'02 were the main active species in the degradation process.A possible photocatalytic reaction mechanism of the g-C3N4/NGODs/TiO2 composite for the enhanced degradation of CIP under visible light irradiation was also proposed.展开更多
The unmodified graphitic carbon nitride(g-C_3N_4) suffers from low photocatalytic activity because of the unfavourable structure.In the present work,we reported a simple self-structural modification strategy to optimi...The unmodified graphitic carbon nitride(g-C_3N_4) suffers from low photocatalytic activity because of the unfavourable structure.In the present work,we reported a simple self-structural modification strategy to optimize the microstructure of g-C_3N_4 and obtained graphene-like g-C_3N_4 nanosheets with porous structure.In contrast to traditional thermal pyrolysis preparation of g-C_3N_4,the present thermal condensation was improved via pyrolysis of thiourea in an alumina crucible without a cover,followed by secondary heat treatment.The popcorn-like formation and layer-by-layer thermal exfoliation of graphene-like porous g-C_3N_4 was proposed to explain the formation mechanism.The photocatalytic removal performance of both NO and NO_2 with the graphene-like porous g-C_3N_4 for was significantly enhanced by selfstructural modification.Trapping experiments and in-situ diffuse reflectance infrared fourier transform spectroscopy(DRIFTS) measurement were conducted to detect the active species during photocatalysis and the conversion pathway of g-C_3N_4 photocatalysis for NO_x purification was revealed.The photocatalytic activity of graphene-like porous g-C_3N_4 was highly enhanced due to the improved charge separation and increased oxidation capacity of the ·O_2^- radicals and holes.This work could not only provide a novel self-structural modification for design of highly efficient photocatalysts,but also offer new insights into the mechanistic understanding of g-C_3N_4 photocatalysis.展开更多
基金supported by the National Scientific Foundation of China(NSFC,Project no.21306119)the Provincial Natural Science Foundation of Sichuan(2013FZ0034 and 2013JY0150)the Outstanding Young Scientist Foundation of Sichuan University(2013SCU04A23)
基金supported by the National Natural Science Foundation of China(21871079,21501052)the Outstanding Youth Project of Natural Science Foundation of Heilongjiang Province(YQ2019B006)~~
文摘A possible mechanism for boosting the visible-light photoactivities of graphitic carbon nitride(g-C3N4)nanosheets for CO2 reduction via coupling with the electron donor Co-metal-organic framework(MOF)is proposed in this study.Specifically,Co-MOF as an electron donor is capable of transferring the photogenerated electrons in the lowest unoccupied molecular orbital(LUMO)to the conduction band of g-C3N4 to facilitate charge separation.As expected,the prepared Co-MOF/g-C3N4 nanocomposites display excellent visible-light-driven photocatalytic CO2 reduction activities.The CO production rate of 6.75μmol g–1 h–1 and CH4 evolution rate of 5.47μmol g–1 h–1 are obtained,which are approximately 2 times those obtained with the original g-C3N4 under the same conditions.Based on a series of analyses,it is shown that the introduction of Co-MOF not only broadens the range of visible-light absorption but also enhances the charge separation,which improves the photocatalytic activity of g-C3N4 to a higher level.In particular,the hydroxyl radical(·OH)experiment was operated under 590 nm(single-wavelength)irradiation,which further proved that the photogenerated electrons in the LUMO of Co-MOF can successfully migrate to g-C3N4.This work may provide an important strategy for the design of highly efficient g-C3N4-based photocatalysts for CO2 reduction.
基金supported by the National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(18)2025)+1 种基金Fundamental Research Funds for the Central Universities(JUSRP11905 and JUSRP51714B)Key Research and Development Program of Jiangsu Province(BE2017623)~~
文摘Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.
文摘A simple calcination method was employed to prepare a Z-scheme N-doped K4Nb6O17/g-C3N4(KCN)heterojunction photocatalyst,in which the electronic structure of K4Nb6O17 was regulated by N-doping,and g-C3N4 was formed both on the surface and within the interlayer spaces of K4Nb6O17.The KCN composite showed profoundly improved photocatalytic activity for both H2 generation and RhB degradation compared to its counterparts.This improved performance was attributed to the synergistic effects of N-doping,which broadened its light harvesting ability,and heterojunction formation,which increased the charge separation rate.The relatively low BET specific surface area of the KCN composite had little effect on its photocatalytic activity.Based on ESR spectroscopy studies,•O2^−,•OH,and h^+are the main active species in the photocatalytic degradation of RhB.Thus,it is reasonable to propose a Z-scheme photocatalytic mechanism over the KCN composite,which exhibits the dual advantages of efficient charge separation and high redox ability.Our work provides a simple approach for constructing large-scale Z-scheme heterojunction photocatalysts with high photocatalytic performance.
基金Funded by the Natural Science Foundation of Hebei Province,China(Nos.E2019210251 and B2019210331).
文摘The CdS/spherical g-C3N4 n-n heterojunction photocatalyst was fabricated via a solvothermal method.The tetracycline was used to characterize the photocatalytic properties of the as-developed hybrids.The photocatalytic degradation mechanism of the as-developed heterojunction photocatalyst was also analyzed.Research results show that CdS nanoparticles are well dispersed in the surface layer of spherical g-C3N4.Moreover,the mass ratio of CdS to spherical g-C3N4 will influence the photocatalytic activity of the asdeveloped composites,which shows the trend of first increasing and then decreasing as it increased.When the mass ratio is 7:1,in 25 min,the as-developed heterojunction shows 93.2%of the maximum photocatalytic efficiency and still exhibits 83.6%after 5 times cycle testing.Moreover,the as-developed hybrids can accelerate the electron transport and improve the separation efficiency of photo-generated carriers compared with pure samples.In addition,the holes and superoxide radicals are dominating active species during the photocatalytic degradation process.
基金supported by National Nature Science Foundation of China (21476097, 21776118)Six talent peaks project in Jiangsu Province (2014-JNHB-014)Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Bi_2WO_6 was modified by two-dimensional g-C_3N_4(2D g-C_3N_4)via a hydrothermal method.The structure,morphology,optical and electronic properties were investigated by multiple techniques,including X-ray diffraction(XRD),X-ray photoelectron spectroscopy spectra(XPS),Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Ultravioletvisible diffuse reflection spectroscopy(DRS),photocurrent and electrochemical impedance spectroscopy(EIS),electron spin resonance(ESR),respectively.Rhodamine B(Rh B)was used as the target organic pollutant to research the photocatalytic performance of as-prepared composites.The Bi_2WO_6/2D g-C_3N_4exhibited a remarkable improvement compared with the pure Bi_2WO_6.The enhanced photocatalytic activity was because the photogenerated electrons and holes can quickly separate by Z-Scheme passageway in composites.The photocatalytic mechanism was also researched in detail through ESR analysis.
基金supported by the National Natural Science Foundation of China(51572253,21771171)Scientific Research Grant of Hefei National Synchrotron Radiation Laboratory(UN2017LHJJ)+1 种基金the Fundamental Research Funds for the Central Universitiescooperation between NSFC and Netherlands Organization for Scientific Research(51561135011)~~
文摘Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.
基金support from the National Natural Science Foundation of China(51602297 and U1510109)Major Research Project of Shandong Province(2016ZDJS11A04)+3 种基金Fundamental Research Funds for the Central Universities(201612007)Postdoctoral Innovation Program of Shandong Province(201603043)Australia Research Council(ARC)under the Project DP160104089Start-up Foundation for Advanced Talents of Qingdao University of Science and Technology(010022919)~~
文摘A heterojunction photocatalyst based on porous tubular g-C3N4 decorated with CdS nanoparticles was fabricated by a facile hydrothermal co-deposition method.The one-dimensional porous structure of g-C3N4 provides a higher specific surface area,enhanced light absorption,and better separation and transport performance of charge carriers along the longitudinal direction,all of which synergistically contribute to the superior photocatalytic activity observed.The significantly enhanced catalytic efficiency is also a benefit originating from the fast transfer of photogenerated electrons and holes between g-C3N4 and CdS through a built-in electric field,which was confirmed by investigating the morphology,structure,optical properties,electrochemical properties,and photocatalytic activities.Photocatalytic degradation of rhodamine B(RhB)and photocatalytic hydrogen evolution reaction were also carried out to investigate its photocatalytic performance.RhB can be degraded completely within 60 min,and the optimum H2 evolution rate of tubular g-C3N4/CdS composite is as high as 71.6μmol h^–1,which is about 16.3 times higher than that of pure bulk g-C3N4.The as-prepared nanostructure would be suitable for treating environmental pollutants as well as for water splitting.
基金financially supported by the National Key Research and Development Program of China(2017YFA0402800)the National Natural Science Foundation of China(51772285,21473170,51878004)+1 种基金the Natural Science Fund of of Anhui Province(1808085ME139)the Fundamental Research Funds for the Central Universities~~
文摘Photocatalytic H2 production via water splitting in a noble-metal-free photocatalytic system has attracted much attention in recent years.In this study,noble-metal-free Ni3N was used as an active cocatalyst to enhance the activity of g-C3N4 for photocatalytic H2 production under visible-light irradiation(λ>420 nm).The characterization results indicated that Ni3N nanoparticles were successfully loaded onto the g-C3N4,which accelerated the separation and transfer of photogenerated electrons and resulted in enhanced photocatalytic H2 evolution under visible-light irradiation.The hydrogen evolution rate reached^305.4μmol h^-1 g^-1,which is about three times higher than that of pristine g-C3N4,and the apparent quantum yield(AQY)was^0.45%atλ=420.Furthermore,the Ni3N/g-C3N4 photocatalyst showed no obvious decrease in the hydrogen production rate,even after five cycles under visible-light irradiation.Finally,a possible photocatalytic hydrogen evolution mechanism for the Ni3N/g-C3N4 system is proposed.
文摘Constructing step-scheme(S-scheme)heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials.In this work,a series of sulfur-doped g-C3N4(SCN)/TiO2 S-scheme photocatalysts were synthesized using electrospinning and calcination methods.The as-prepared SCN/TiO2 composites showed superior photocatalytic performance than pure TiO2 and SCN in the photocatalytic degradation of Congo Red(CR)aqueous solution.The significant enhancement in photocatalytic activity benefited not only from the 1D well-distributed nanostructure,but also from the S-scheme heterojunction.Furthermore,the XPS analyses and DFT calculations demonstrated that electrons were transferred from SCN to TiO2 across the interface of the SCN/TiO2 composites.The built-in electric field,band edge bending,and Coulomb interaction synergistically facilitated the recombination of relatively useless electrons and holes in hybrid when the interface was irradiated by simulated solar light.Therefore,the remaining electrons and holes with higher reducibility and oxidizability endowed the composite with supreme redox ability.These results were adequately verified by radical trapping experiments,ESR tests,and in situ XPS analyses,suggesting that the electron immigration in the photocatalyst followed the S-scheme heterojunction mechanism.This work can enrich our knowledge of the design and fabrication of novel S-scheme heterojunction photocatalysts and provide a promising strategy for solving environmental pollution in the future.
基金supported by the National Natural Science Foundation of China(51602207)the Doctoral Scientific Research Foundation of Liaoning Province(20170520011)+3 种基金the Program for Liaoning Excellent Talents in Universities(LR2017074)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE-201810)Fuzhou University,the Scientific Research Project of the Educational Department of Liaoning Province(LQN201712)Shenyang Excellent Talents in Universities(RC180211)~~
文摘Photocatalytic water splitting is a promising method for hydrogen production.Numerous efficient photocatalysts have been synthesized and utilized.However,photocatalysts without a noble metal as the co-catalyst have been rarely reported.Herein,a CoP co-catalyst-modified graphitic-C3N4(g-C3N4/CoP)is investigated for photocatalytic water splitting to produce H2.The g-C3N4/CoP composite is synthesized in two steps.The first step is related to thermal decomposition,and the second step involves an electroless plating technique.The photocatalytic activity for hydrogen evolution reactions of g-C3N4 is distinctly increased by loading the appropriate amount of CoP quantum dots(QDs).Among the as-synthesized samples,the optimized one(g-C3N4/CoP-4%)shows exceptional photocatalytic activity as compared with pristine g-C3N4,generating H2 at a rate of 936μmol g^-1 h^-1,even higher than that of g-C3N4 with 4 wt%Pt(665μmol g^-1 h^-1).The UV-visible and optical absorption behavior confirms that g-C3N4 has an absorption edge at 451 nm,but after being composited with CoP,g-C3N4/CoP-4%has an absorption edge at 497 nm.Furthermore,photoluminescence and photocurrent measurements confirm that loading CoP QDs to pristine g-C3N4 not only enhances the charge separation,but also improves the transfer of photogenerated e--h+pairs,thus improving the photocatalytic performance of the catalyst to generate H2.This work demonstrates a feasible strategy for the synthesis of highly efficient metal phosphide-loaded g-C3N4 for hydrogen generation.
基金the Australian Research Council for the financial support through its DP and FF programsthe Australian Government for the financial support through the Australian Government Research Training Program ScholarshipThe financial support from National Science Foundation of China(No.513228201)
文摘Photocatalysis. which utilizes solar energy to trigger chemical reactions, is one of the most desirable solar-energy-conversion approaches. Graphitic carbon nitride (g-C3N4). as an attractive metal-free photocatalyst, has drawn worldwide research interest in the area of solar energy conversion due to its easy synthesis, earth-abundant nature, physicochemical stability and visible-light-responsive properties. Over the past ten years, g-C3N4 based photocatalysts have experienced intensive exploration, and great progress has been achieved. However, the solar conversion efficiency is still far from industrial applications due to the wide bandgap, severe charge recombination, and lack of surface active sites. Many strategies have been proposed to enhance the light absorption, reduce the recombination of charge carriers and accelerate the surface kinetics. This work makes a crucial review about the main contributions of various strategies to the light harvesting, charge separation and surface kinetics of g-C3N4 photocatalyst. Furthermore, the evaluation measurements for the enhanced light harvesting, reduced charge recombination and accelerated surface kinetics will be discussed. In addition, this review proposes future trends to enhance the photocatalytic performance of g-C3N4 photocatalyst for the solar energy conversion.
文摘Modification of nickel sulfide cocatalysts is considered to be a promising approach for efficient enhancement of the photocatalytic hydrogen production performance of g-C3N4.Providing more NiS cocatalyst to function as active sites of g-C3N4 is still highly desirable.To realize this goal,in this work,a facile sulfur-mediated photodeposition approach was developed.Specifically,photogenerated electrons excited by visible light reduce the S molecules absorbed on g-C3N4 surface to S^2‒,and subsequently NiS cocatalyst is formed in situ on the g-C3N4 surface by a combination of Ni2+and S2‒due to their small solubility product constant(Ksp=3.2×10^‒19).This approach has several advantages.The NiS cocatalyst is clearly in situ deposited on the photogenerated electron transfer sites of g-C3N4,and thus provides more active sites for H2 production.In addition,this method utilizes solar energy with mild reaction conditions at room temperature.Consequently,the synthesized NiS/g-C3N4 photocatalyst achieves excellent hydrogen generation performance with the performance of the optimal sample(244μmol h^‒1 g^‒1)close to that of 1 wt%Pt/g-C3N4(316μmol h^‒1 g^‒1,a well-known excellent photocatalyst).More importantly,the present sulfur-mediated photodeposition route is versatile and facile and can be used to deposit various metal sulfides such as CoSx,CuSx and AgSx on the g-C3N4 surface,and all the resulting metal sulfide-modified g-C3N4 photocatalysts exhibit improved H2-production performance.Our study offers a novel insight for the synthesis of high-efficiency photocatalysts.
文摘Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) can be doped into g-C3N4 through the coordination between amidogen and Fe(Ⅲ). After activity tests, it was found that this coordination doping of Fe(Ⅲ) could enhance the Rh B oxidation and Cr(Ⅵ) reduction activities of g-C3N4 in interesting ways, but it is not helpful for the NO-removal performance of g-C3N4. Characterization and calculation results show that the coordination of Fe(Ⅲ) can not only improve the transfer of photogenerated electrons, but it also can passivate the carbon site of triazine rings, which is the active site of NO-removal. This study revealed some doping mechanisms and effect mechanisms of elemental metal in photocatalysis.
基金supported by Shandong Electric Power Construction Third Engineering Co.,Ltd.(20173702021476)the“HUIMN Science and Technology”project of Qingdao(17-3-3-71-nsh)+1 种基金the High-concentration Organic Wastewater Adsorbent Production Process(20170903)the National Natural Science Foundation of China(51602297,U1510109)。
文摘G-C3N4 was supported on the surface of foamed ceramic,and the g-C3N4@foamed ceramic was packed in the photocatalytic reactor in a layered manner.Effects of urea and H2O2 concentration on NO conversion were investigated.Pulse experiments were carried out to investigate the change of NO conversion with time under different concentrations of H2O2.The contribution of each route that NO converted and the selectivities of products were calculated.Results showed that the photo-reduction of NO accounted for 2%,and the photo-oxidation of NO accounted for 14%,and the rest was absorbed by the humidifier.Products include ammonia(NH+4-N),nitrogen(N2),nitrite(NO-2-N)and nitrate(NO-3-N),of which N2 accounted for 9%.
基金supported by the Natural Science Foundation of Tianjin City of China (No.18JCYBJC17700)
文摘A new,facile,and efficient way to prepare alkalinized g-C3N4 is presented.We calcined a mixture of KCl and melamine to obtain g-C3N4,whose in-plane structure was K+doped so that alkalinized samples could be obtained by treatment with different concentrations of KOH.The different samples were used to oxidize As(Ⅲ)in both visible light and natural light.The sample treated with 10 mol/L KOH showed the highest efficiency,converting all As(Ⅲ)into As(Ⅴ)within 120 min in both visible light and natural light,as the oxidative capacity of the As(Ⅲ)in the alkalinized samples was significantly higher than that of the original samples.K+doping improved the electron transport capacity of the samples,while the alkalinized samples could destroy their edge structures,so as to improve the separation efficiency of the photogenerated carrier.The experiment confirmed that alkalinized g-C3N4 significantly improves the oxidation ability of As(Ⅲ)and plays an important role in the photocatalytic treatment of refractory nonmetallic ions.
基金supported by the National Natural Science Foundation of China (Nos.21871079 and 21501052).
文摘Graphitic carbon nitride (g-C3N4) has become an attractive visible-light-responsive photocatalyst because of its semiconductor polymer compositions and easy-modulated band structure. However, the bulk g-C3N4 photocatalyst has the low separation efficiency of photogenerated carriers and unsatisfied surface catalytic performance, which leads to poor photocatalytic performance. As for this, MgTi2O5 with high chemical stability, wide band gap and negative conduction band was used as a suitable platform for coupling with g-C3N4 to enhance charge separation and promoted the photoactivity. Different from common approaches, here, we propose an innovative method to construct g-C3N4/MgTi2O5 nanocomposites featuring “0 + 1 >1" magnification effect to improve g-C3N4 photocatalytic performance under visible light irradiation. Additionally, compositing metal oxides of MgTi2O5 with g-C3N4 has proven to be a proper strategy to accelerate surface catalytic reactions in g-C3N4, and the photoinduced carriers were modulated to maintain thermodynamic equilibrium, which convincingly promotes the photocatalytic activity. The photocatalytic performance of the nanocomposites was measured by hydrogen production and CO2 reduction under visible light. The developed g-C3N4/MgTi2O5 nanocomposites with a 5 wt.% MgTi2O5 exhibits the highest H2 and CO yield under visible light and excellent stability compare to the other MgTi2O5 contents in composites. According to surface photo-voltage spectra, electrochemical CO2 reduction, photoluminescence, etc. The superior performance can be related to an enhanced electron lifetime, the promoted charge transfer and the increased electronic separation property of g-C3N4. Our work provides an approach to overcome the defect of pure g-C3N4, which accesses to composite with the second component matched well.
基金the National Key Research and Development Program of China(No.2017YFA0402800)the National Natural Science Foundation of China(Nos.51772285,21473170,51878004)the Natural Science Fund of Anhui Province(No.1808085ME139)for partly funded support。
文摘Nitrogen photo fixation using g-C3N4-based photocatalysts have attracted abundant of attentions recently.Herein,in this study,holey g-C3N4(HGCN)nanosheets possess a good deal of carbon vacancies were prepared by means of thermally treating bulk g-C3 N4(BGCN)under an NH3 atmosphere.Characterization analysis revealed that the as-synthesized sample have identical crystal structure,la rger BET specific surface area,stronger reduction capability,and higher photogene rated charge carrier separation rate than that of BGCN.These properties may contribute to enhance the nitrogen photofixation activity.It was also found that the rate of NH4^+production for N2 photofixation of HGCN sample reached^25.54 mg L^-1 h^-1 g(cat)^-1,which is approximately^5.87 times higher than that of BGCN sample under optimal reactive conditions.Moreover,a plausible mechanism of HGCN for nitrogen photofixation process was illuminated in detail.
基金Supported by the National Natural Science Foundation of China(No.21373103)the Natural Science Foundation of Jiangsu Province,China(No.BK20170316)the PhD Research Startup Foundation of Jiangsu University of Technology,China(No.KYY18038).
文摘Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C3Na-based photocatalysts.To solve these problems,g-CN4/nitrogen-doped graphene quantum dots(NGQDs)/TiO2 ternary heterojunctions were facilely prepared via a one-step calcining method.The morphology.structure,optical and electrochemical properties of g-C3NA/NGQDs/TiO2 were characterized and explored.The optimal g-CN4/NGODs/TiOz composite exhibits enhanced photocatalytic degradation performance of ciprofloxacin(CIP)compared with the as-prepared g-C3Na.TiO:(P25)and g-C3N4/TiO2 heterojunction under visible light irradia-tion.The apparent rate constant of the composite is around 6.43.4.03 and 2.30 times higher than those of g-C3N4,TiOz and g-C3N4/TiO2,respectively.The enhanced photocatalytic efficiency should be mainly attributed to the improvement of light absorption and charge separation and transfer efficiency,originating from the narrow band gap and high charge carrier mobility.The active species trapping experiments results showed that the ht and'02 were the main active species in the degradation process.A possible photocatalytic reaction mechanism of the g-C3N4/NGODs/TiO2 composite for the enhanced degradation of CIP under visible light irradiation was also proposed.
基金supported by the National Natural Science Foundation of China(51478070,21501016 and 21777011)the National Key R&D Program of China(2016YFC0204702)+3 种基金the Innovative Research Team of Chongqing(CXTDG201602014)the Natural Science Foundation of Chongqing(cstc2016jcyj A0481,cstc2017jcyj BX0052)the Early Career Scheme(ECS 809813) from Hong Kongthe Internal Research Grant from Hong Kong Institute of Education(R3588)
文摘The unmodified graphitic carbon nitride(g-C_3N_4) suffers from low photocatalytic activity because of the unfavourable structure.In the present work,we reported a simple self-structural modification strategy to optimize the microstructure of g-C_3N_4 and obtained graphene-like g-C_3N_4 nanosheets with porous structure.In contrast to traditional thermal pyrolysis preparation of g-C_3N_4,the present thermal condensation was improved via pyrolysis of thiourea in an alumina crucible without a cover,followed by secondary heat treatment.The popcorn-like formation and layer-by-layer thermal exfoliation of graphene-like porous g-C_3N_4 was proposed to explain the formation mechanism.The photocatalytic removal performance of both NO and NO_2 with the graphene-like porous g-C_3N_4 for was significantly enhanced by selfstructural modification.Trapping experiments and in-situ diffuse reflectance infrared fourier transform spectroscopy(DRIFTS) measurement were conducted to detect the active species during photocatalysis and the conversion pathway of g-C_3N_4 photocatalysis for NO_x purification was revealed.The photocatalytic activity of graphene-like porous g-C_3N_4 was highly enhanced due to the improved charge separation and increased oxidation capacity of the ·O_2^- radicals and holes.This work could not only provide a novel self-structural modification for design of highly efficient photocatalysts,but also offer new insights into the mechanistic understanding of g-C_3N_4 photocatalysis.