As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemic...As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4,(2) modification strategies of g-C3N4,(3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories:(1) Type I heterojunction,(2) Type II heterojunction,(3) p-n heterojunction,(4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.展开更多
Graphitic carbon nitride nanosheets （g-C3N4 NSs） hybridized nitrogen doped titanium dioxide （N-TiO2） nanofibers （GCN/NT NFs） have been synthesized in situ via a simple electrospinning process combined with a mod...Graphitic carbon nitride nanosheets （g-C3N4 NSs） hybridized nitrogen doped titanium dioxide （N-TiO2） nanofibers （GCN/NT NFs） have been synthesized in situ via a simple electrospinning process combined with a modified heat-etching method. The prepared GCN/NT NFs were characterized by a variety of methods and their photocatalytic activities were evaluated by hydrogen （H2） production from water splitting and degradation of rhodamine B in aqueous solution. It was found that the GCN/NT NFs have a mesoporous structure, composed of g-C3N4 NSs and N-doped TiO2 crystallites. The g-C3N4 NSs synthesized after heat-etching were found to be embedded in, and covered, the hybrid NFs to form stable interfaces. The partial decomposition of g-C3N4 releases its nitrogen content which eventually gets doped into the nearby TiO2 skeleton. The GCN/NT NFs give a high photocatalytic H2 production rate of 8,931.3 μmol·h^-1·g^-1 in aqueous methanol solution under simulated solar light. Such a highly efficient photocatalytic perfor- mance can be ascribed to the combined effects of g-C3N4 NSs and N-doped TiO2 with enhanced light absorption intensity and improved electron transport ability. Also, the large surface area of the mesoporous NFs minimizes light reflection on the surface and provides more surface-active sites. This work highlights the potential of quasi-one dimensional hybrid materials in the field of solar energy conversion.展开更多
光催化二氧化碳还原成烃类化合物是解决能源短缺和环境污染的重要途径。而构建复合物光催化剂可以有效地解决单一光催化剂的缺点,并且提高二氧化碳还原活性。尽管对复合物光催化剂已经做了很多研究,然而对其活性增强的内在机制还缺乏理...光催化二氧化碳还原成烃类化合物是解决能源短缺和环境污染的重要途径。而构建复合物光催化剂可以有效地解决单一光催化剂的缺点,并且提高二氧化碳还原活性。尽管对复合物光催化剂已经做了很多研究,然而对其活性增强的内在机制还缺乏理论认识。本文采用密度泛函理论计算方法研究了二维/二维BP/g-C_(3)N_(4)复合模型的电子性质和CO_(2)还原反应过程。通过对能带位置和界面电子相互作用的综合分析发现,在BP/g-C_(3)N_(4)异质结中,光生载流子的迁移遵循S型异质结光催化机制。与单一的g-C_(3)N_(4)相比,这种异质结可以实现光生载流子的高效分离并且拥有良好的氧化还原能力。此外,通过对比研究CO_(2)在g-C_(3)N_(4)和BP/g-C_(3)N_(4)还原反应过程发现,异质结使CO_(2)还原反应的最大能垒从1.48 e V降低到1.22e V。因此,BP/g-C_(3)N_(4)异质结在理论上被证明是一种优良的CO_(2)还原光催化剂。这项工作有助于了解BP改性对g-C_(3)N_(4)光催化活性的影响,也为其他高性能CO_(2)还原光催化剂的设计提供理论依据。展开更多
Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low spe...Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.展开更多
A simple one-step thermal polymerization method was developed for synthesis of holey graphitic carbon nitride nanotubes,involving direci eating of mixtures of melamine and urea or melamine and cyanuric acid in specifi...A simple one-step thermal polymerization method was developed for synthesis of holey graphitic carbon nitride nanotubes,involving direci eating of mixtures of melamine and urea or melamine and cyanuric acid in specific mass ratios.Supramolecular structures formed betweer the precursor molecules guided nanotube formation.The porous and nanotubular structure of the nanotubes facilitated efficient charge carrier nigration and separation,thereby enhancing photocatalytic Hz production in 20 vol.%lactic acid under visible light irradiation.Nanotubes synthesized using melamine and urea in a 1:10 mass ratio(denoted herein as CN-MU nanotubes)exhibited a photocatalytic hydroger production rate of 1,073.6μmol·h^-1·^-g with Pt as the cocatalyst,a rate of 4.7 and 3.1 times higher than traditional Pt/g-CN4 photocatalysts prepared from graphitic carbon nitride(g-CN4)obtained by direct thermal polymerization of melamine or urea,respectively.On the basis of their outstanding performance for photocatalytic H2 production,it is envisaged that the holey g-C3N4 nanotubes will find widespread uptake in other areas,including photocatalytic CO2 reduction,dye-sensitized solar cells and photoelectrochemical sensors.展开更多
With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4...With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.展开更多
Photoelectrochemical(PEC)water splitting is recognized as a sustainable strategy for hydrogen generation due to its abundant hydrogen source,utilization of inexhaustible solar energy,high-purity product,and environmen...Photoelectrochemical(PEC)water splitting is recognized as a sustainable strategy for hydrogen generation due to its abundant hydrogen source,utilization of inexhaustible solar energy,high-purity product,and environment-friendly process.To actualize a practical PEC water splitting,it is paramount to develop efficient,stable,safe,and low-cost photoelectrode materials.Recently,graphitic carbon nitride(g-C3N4)has aroused a great interest in the new generation photoelectrode materials because of its unique features,such as suitable band structure for water splitting,a certain range of visible light absorption,nontoxicity,and good stability.Some inherent defects of g-C3N4,however,seriously impair further improvement on PEC performance,including low electronic conductivity,high recombination rate of photogenerated charges,and limited visible light absorption at long wavelength range.Construction of g-C3N4-based nanosized heteroarrays as photoelectrodes has been regarded as a promising strategy to circumvent these inherent limitations and achieve the high-performance PEC water splitting due to the accelerated exciton separation and the reduced combination of photogenerated electrons/holes.Herein,we summarize in detail the latest progress of g-C3N4-based nanosized heteroarrays in PEC water-splitting photoelectrodes.Firstly,the unique advantages of this type of photoelectrodes,including the highly ordered nanoarray architectures and the heterojunctions,are highlighted.Then,different g-C3N4-based nanosized heteroarrays are comprehensively discussed,in terms of their fabrication methods,PEC capacities,and mechanisms,etc.To conclude,the key challenges and possible solutions for future development on g-C3N4-based nanosized heteroarray photoelectrodes are discussed.展开更多
Ultrathin graphitic carbon nitride nanoplatelets （UGCNPs） are synthesized by a facile manner via an efficient and eco-friendly ball milling approach. The obtained UGCNPs are 2-6 nm in size and 0.35-0.7 nm in thickne...Ultrathin graphitic carbon nitride nanoplatelets （UGCNPs） are synthesized by a facile manner via an efficient and eco-friendly ball milling approach. The obtained UGCNPs are 2-6 nm in size and 0.35-0.7 nm in thickness, with improved specific surface area over that of bulk graphitic carbon nitride. Photochemical experiments show that the UGCNPs are highly active in visible-light water splitting, with a hydrogen evolution rate of 1,365 μmol·h^-1·g^-1, which is 13.7-fold greater than that of their bulk counterparts. The notable improvement in the hydrogen evolution rate observed with UGCNPs under visible light is due to the synergistic effects derived from the increased specific surface area, reduced thickness, and a negative shift in the conduction band concomitant with the exfoliation of bulk graphitic carbon nitride into UGCNPs. In addition to metal- free visible-light-driven photocatalytic hydrogen production, the UGCNPs find attractive applications in biomedical imaging and optoelectronics because of their superior luminescence characteristics.展开更多
基金supported by Xiamen University Malaysia Research Fund (XMUMRF/2019-C3/IENG/0013)financial assistance and faculty start-up grants/supports from Xiamen University~~
文摘As one of the most appealing and attractive technologies, photocatalysis is widely used as a promising method to circumvent the environmental and energy problems. Due to its chemical stability and unique physicochemical, graphitic carbon nitride (g-C3N4) has become research hotspots in the community. However, g-C3N4 photocatalyst still suffers from many problems, resulting in unsatisfactory photocatalytic activity such as low specific surface area, high charge recombination and insufficient visible light utilization. Since 2009, g-C3N4-based heterostructures have attracted the attention of scientists worldwide for their greatly enhanced photocatalytic performance. Overall, this review summarizes the recent advances of g-C3N4-based nanocomposites modified with transition metal sulfide (TMS), including (1) preparation of pristine g-C3N4,(2) modification strategies of g-C3N4,(3) design principles of TMS-modified g-C3N4 heterostructured photocatalysts, and (4) applications in energy conversion. What is more, the characteristics and transfer mechanisms of each classification of the metal sulfide heterojunction system will be critically reviewed, spanning from the following categories:(1) Type I heterojunction,(2) Type II heterojunction,(3) p-n heterojunction,(4) Schottky junction and (5) Z-scheme heterojunction. Apart from that, the application of g-C3N4-based heterostructured photocatalysts in H2 evolution, CO2 reduction, N2 fixation and pollutant degradation will also be systematically presented. Last but not least, this review will conclude with invigorating perspectives, limitations and prospects for further advancing g-C3N4-based heterostructured photocatalysts toward practical benefits for a sustainable future.
文摘Graphitic carbon nitride nanosheets （g-C3N4 NSs） hybridized nitrogen doped titanium dioxide （N-TiO2） nanofibers （GCN/NT NFs） have been synthesized in situ via a simple electrospinning process combined with a modified heat-etching method. The prepared GCN/NT NFs were characterized by a variety of methods and their photocatalytic activities were evaluated by hydrogen （H2） production from water splitting and degradation of rhodamine B in aqueous solution. It was found that the GCN/NT NFs have a mesoporous structure, composed of g-C3N4 NSs and N-doped TiO2 crystallites. The g-C3N4 NSs synthesized after heat-etching were found to be embedded in, and covered, the hybrid NFs to form stable interfaces. The partial decomposition of g-C3N4 releases its nitrogen content which eventually gets doped into the nearby TiO2 skeleton. The GCN/NT NFs give a high photocatalytic H2 production rate of 8,931.3 μmol·h^-1·g^-1 in aqueous methanol solution under simulated solar light. Such a highly efficient photocatalytic perfor- mance can be ascribed to the combined effects of g-C3N4 NSs and N-doped TiO2 with enhanced light absorption intensity and improved electron transport ability. Also, the large surface area of the mesoporous NFs minimizes light reflection on the surface and provides more surface-active sites. This work highlights the potential of quasi-one dimensional hybrid materials in the field of solar energy conversion.
文摘光催化二氧化碳还原成烃类化合物是解决能源短缺和环境污染的重要途径。而构建复合物光催化剂可以有效地解决单一光催化剂的缺点,并且提高二氧化碳还原活性。尽管对复合物光催化剂已经做了很多研究,然而对其活性增强的内在机制还缺乏理论认识。本文采用密度泛函理论计算方法研究了二维/二维BP/g-C_(3)N_(4)复合模型的电子性质和CO_(2)还原反应过程。通过对能带位置和界面电子相互作用的综合分析发现,在BP/g-C_(3)N_(4)异质结中,光生载流子的迁移遵循S型异质结光催化机制。与单一的g-C_(3)N_(4)相比,这种异质结可以实现光生载流子的高效分离并且拥有良好的氧化还原能力。此外,通过对比研究CO_(2)在g-C_(3)N_(4)和BP/g-C_(3)N_(4)还原反应过程发现,异质结使CO_(2)还原反应的最大能垒从1.48 e V降低到1.22e V。因此,BP/g-C_(3)N_(4)异质结在理论上被证明是一种优良的CO_(2)还原光催化剂。这项工作有助于了解BP改性对g-C_(3)N_(4)光催化活性的影响,也为其他高性能CO_(2)还原光催化剂的设计提供理论依据。
文摘Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.
基金The authors are grateful for the financial support from the National Key R&D Program of China(Nos.2018YFB1502002,2017YFA0206904,2017YFA0206900,and 2016YFB0600901)the National Natural Science Foundation of China(Nos.51825205,U1662U&51772305,51572270,21871279,and 21802154)+4 种基金the Beijing Natural Science Foundation(Nos.2191002,218207&and 2194089)the Beijing Municipal Science and Technology Project(No.Z181100005118007)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17000000)the Royal Society-Newton Advanced Fellowship(No.NA170422)the International Partnership Program of Chinese Academy of Sciences(No.GJHZ1819)and the K.C.Wong Education Foundation.G.I.N.W.acknowledges funding support from the Energy Education Trust of New Zealand and the University of Auckland Faculty Research Development Fund.
文摘A simple one-step thermal polymerization method was developed for synthesis of holey graphitic carbon nitride nanotubes,involving direci eating of mixtures of melamine and urea or melamine and cyanuric acid in specific mass ratios.Supramolecular structures formed betweer the precursor molecules guided nanotube formation.The porous and nanotubular structure of the nanotubes facilitated efficient charge carrier nigration and separation,thereby enhancing photocatalytic Hz production in 20 vol.%lactic acid under visible light irradiation.Nanotubes synthesized using melamine and urea in a 1:10 mass ratio(denoted herein as CN-MU nanotubes)exhibited a photocatalytic hydroger production rate of 1,073.6μmol·h^-1·^-g with Pt as the cocatalyst,a rate of 4.7 and 3.1 times higher than traditional Pt/g-CN4 photocatalysts prepared from graphitic carbon nitride(g-CN4)obtained by direct thermal polymerization of melamine or urea,respectively.On the basis of their outstanding performance for photocatalytic H2 production,it is envisaged that the holey g-C3N4 nanotubes will find widespread uptake in other areas,including photocatalytic CO2 reduction,dye-sensitized solar cells and photoelectrochemical sensors.
基金supported by the National Basic Research Program of China(2011CB933700)the National Natural Science Foundation of China(21271165)~~
文摘With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide（Vo-ZnO） with graphitic carbon nitride（g-C3N4）. The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation（λ≥ 400 nm）. In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.
基金This study was supported by Developed and Applied Funding of Tianjin Normal University(135202XK1702)Program for Innovative Research in the University of Tianjin(TD13-5077)+1 种基金National Natural Science Foundation of China(Number 21905202)Australian Research Council(ARC)through Discovery Early Career Researcher Awards(DECRA,DE170100871).
文摘Photoelectrochemical(PEC)water splitting is recognized as a sustainable strategy for hydrogen generation due to its abundant hydrogen source,utilization of inexhaustible solar energy,high-purity product,and environment-friendly process.To actualize a practical PEC water splitting,it is paramount to develop efficient,stable,safe,and low-cost photoelectrode materials.Recently,graphitic carbon nitride(g-C3N4)has aroused a great interest in the new generation photoelectrode materials because of its unique features,such as suitable band structure for water splitting,a certain range of visible light absorption,nontoxicity,and good stability.Some inherent defects of g-C3N4,however,seriously impair further improvement on PEC performance,including low electronic conductivity,high recombination rate of photogenerated charges,and limited visible light absorption at long wavelength range.Construction of g-C3N4-based nanosized heteroarrays as photoelectrodes has been regarded as a promising strategy to circumvent these inherent limitations and achieve the high-performance PEC water splitting due to the accelerated exciton separation and the reduced combination of photogenerated electrons/holes.Herein,we summarize in detail the latest progress of g-C3N4-based nanosized heteroarrays in PEC water-splitting photoelectrodes.Firstly,the unique advantages of this type of photoelectrodes,including the highly ordered nanoarray architectures and the heterojunctions,are highlighted.Then,different g-C3N4-based nanosized heteroarrays are comprehensively discussed,in terms of their fabrication methods,PEC capacities,and mechanisms,etc.To conclude,the key challenges and possible solutions for future development on g-C3N4-based nanosized heteroarray photoelectrodes are discussed.
基金This project is sponsored by NSFC （Nos. 21325415, 21174019, 21301018, 51161120361）, National Basic Research Program of China （2011CB013000）, Basic Research Foundation of Beijing Institute of Technology （20121942008）, Fok Ying Tong Education Foundation （No. 131043）, the 111 Project B07012, Beijing Natural Science Foundation （2152028） and the Beijing Key Laboratory for Chemical Power Source and Green Catalysis under the contract no. 2013CX02031.
文摘Ultrathin graphitic carbon nitride nanoplatelets （UGCNPs） are synthesized by a facile manner via an efficient and eco-friendly ball milling approach. The obtained UGCNPs are 2-6 nm in size and 0.35-0.7 nm in thickness, with improved specific surface area over that of bulk graphitic carbon nitride. Photochemical experiments show that the UGCNPs are highly active in visible-light water splitting, with a hydrogen evolution rate of 1,365 μmol·h^-1·g^-1, which is 13.7-fold greater than that of their bulk counterparts. The notable improvement in the hydrogen evolution rate observed with UGCNPs under visible light is due to the synergistic effects derived from the increased specific surface area, reduced thickness, and a negative shift in the conduction band concomitant with the exfoliation of bulk graphitic carbon nitride into UGCNPs. In addition to metal- free visible-light-driven photocatalytic hydrogen production, the UGCNPs find attractive applications in biomedical imaging and optoelectronics because of their superior luminescence characteristics.
基金supported by Beijing Municipal Natural Science Foundation(JQ20003)the National Natural Science Foundation of China(21771021,21822501,and 22061130206)+3 种基金the Newton Advanced Fellowship award(NAFR1201285)the Fok Ying-Tong Education Foundation(171008)the Measurements Fund of Beijing Normal Universitythe State Key Laboratory of Heavy Oil Processing。
