High visible light photocatalytic activities obtained by integrating g-C3N4 with ferroelectric PbTiO3

Graphitic carbon nitride (g-C3 N4) with the merits of high visible light absorption,proper electronic band structure with high conduction band edge and variable modulation,is viewed as a promising photocatalyst for practical use.To alleviate its high recombination rate of photo-excited charge carriers and maximize the photocatalytic performances,it is paramount to design highly effective transfer channels for photo-excited charge carriers.Ferroelectric materials can have the charge carriers transport in opposite directions owing to the internal spontaneous polarization,which may be suitable for constructing the heterostructure with g-C3N4 for efficient charge separation.Inspired by this concept,herein ferroelec tric PbTiO3,which can be the visible-light absorber,is coupled with g-C3N4 to construct PbTiO3/g-C3N4 heterostructure with close contact via Pb-N bond by the facile post thermal treatment.The optimized PbTiO3/g-C3N4 heterostructure exhibited excellent photocatalytic and photoelectrochemical activities under visible light irradiation.Moreover,the simultaneous application of ultrasound-induced mechanical waves can further improve its photocatalytic activities through reinforcing the built-in piezoelectric field.This work proposes a widely applicable strategy for the fabrication of high-performance ferroelectric based photocatalysts and also provides some new ideas for developing the understanding of ferroelectric photocatalysis.     

A novel Z-scheme CeO2/g-C3N4 heterojunction photocatalyst for degradation of Bisphenol A and hydrogen evolution and insight of the photocatalysis mechanism

CeO2/g-C3N4 heterojunction photocatalyst had been successfully fabricated through a one-step in-situ pyrolysis formation of 3D hollow CeO2 mesoporous nanospheres and 2D g-C3N4 nanosheets together with simultaneous removal of carbon sphere templates after heat treatment.The sample shows high catalytic performances for photocatalytic hydrogen generation and photocatalytic oxidation of Bisphe-nol A(BPA)under visible light irradiation,and the catalytic degradation route of BPA was suggested by the degradation products determined by GC-MS.The enhancing catalytic activity was attributed to the effective interfacial charge migration and separation.Finally,it was proposed that the CeO2/g-C3N4 het-erojunction photocatalyst could follow a more appropriate Z-scheme charge transfer mechanism,which was confirmed by the analysis of experiment and theoretical calculation results.     

可见光驱动Z-scheme g-C3N4/α-Fe2O3催化剂高效产H2

作为一种新型的具有可见光响应的半导体光催化剂,g-C3N4在光催化产氢领域得到了广泛的研究。然而,纯g-C3N4存在可见光响应范围较窄、光生电子-空穴复合率高、量子效率低等问题。针对纯g-C3N4的缺陷,采用简单的水热合成法制备出一种高效纳米晶胶体g-C3N4/α-Fe2O3复合材料。为了检测g-C3N4/α-Fe2O3的光催化产氢性能,将其引入以NaBH4为底液的体系中。结果表明,当Fe质量分数为1%,体系温度为30℃、NaBH4浓度为50 mmol/L时,产氢量为30 mL。利用PL、EIS以及PC等手段对g-C3N4/α-Fe2O3的光电响应能力进行了分析。结果表明,g-C3N4/α-Fe2O3复合材料具有较低的光致发光强度、较高的光电流密度和较小的电荷转移电阻,说明了光生电荷载流子的有效分离和快速转移。另外,Z-scheme电荷转移途径赋予了g-C3N4/α-Fe2O3较强的氧化能力,为光催化裂解NaBH4提供了较大的驱动力。主要意义在于对光催化产氢有一个新认识,为合理设计和构建Z型光催化剂提供参考。     

Metal-free π-conjugated hybrid g-C3N4 with tunable band structure for enhanced visible-light photocatalytic H2 production

Development of low-cost and efficient photocatalytic materials with visible-light response is of urgent need for solving energy and environmental problems.Here,a metal-free two-dimensional (2D) π-conjugated hybrid g-C3N4 photocatalyst with tunable band structure was prepared by a novel one-pot bottom-up method based on a supersaturated precipitation process of urea and triethanolamine (TEOA)solution.The microstructure of the hybrid g-C3N4 is revealed to be a compound of periodic tri-s-triazine units grafted with N-doped graphene (GR) fragments.From experimental evidence and theoretical calcu-lations,the two different π-conjugated fragments in the hybrid g-C3N4 material are proved to construct a 2D in-plane junction structure,thereby expanding the light absorption range and accelerating the inter-face charge transfer.The π-conjugated electron coupling in the 2D photocatalyst eliminates the grain boundary effect,and the coupled highest occupied molecular orbital (HOMO) effectively promotes the separation of photo-induced charge carriers.Compared with the g-C3N4 prepared by the conventional method,the visible-light H2 production activity of the optimized sample is enhanced by 253 ％.This work provides a new strategy of constructing metal-free g-C3N4 hybrids for efficient photocatalytic water splitting.     

Increasingπ-electron availability in benzene ring incorporated graphitic carbon nitride for increased photocatalytic hydrogen generation

Increasing the availability ofπ-electron in graphitic carbon nitride(g-C₃N₄)can reduce the band gap and thus enhance the photocatalytic hydrogen(H₂)generation activity upon exposure to visible light,However,such strategy has not yet been largely applied to increase the H₂generation of g-C₃N₄.Herein,we succes s fully increased the amount ofπ-electron in g-C₃N₄by incorporatingπ-electron-rich benzene rings through copolymerization of melamine and trimesic acid in air.The incorporation of benzene rings not only extends the light absorption of g-C₃N₄to 650 nm,but also improves the electrical conductivity due to delocalization ofπelectrons in benzene rings.As a result,a 3.4 times enhancement of photocatalytic H₂generation was achieved from the g-C₃N₄with benzene ring incorporation in comparing with that of pristine g-C₃N₄.More interestingly,H₂generation still occurs under irradiation of the light ofλ≥490 nm,above the absorption edge of pristine g-C₃N₄(~460 nm),illustrating the positive effectiveness of incorporated benzene rings on enhancing the H₂generation capacity of g-C₃N₄.The present work manifests the advantages of increasingπ-conjugated electrons on designing highly active g-C₃N₄photocatalysts.     

One step method of structure engineering porous graphitic carbon nitride for efficient visible-light photocatalytic reduction of Cr(Ⅵ)

Porous g-C3N4 nanosheets (PCN) were prepared by the nickel-assisted one-step thermal polymerization method.Hydrogen (H2) which was produced by the reaction between nickel (Ni) foam and ammonia (NH3) defined the structure and properties of PCN.During the formation of PCN,the participation of H2 not only enhanced the spacing between layers but also boosted the specific surface area that more active sites were exposed.Additionally,H2 promoted pores formation in the nanosheets,which was beneficial to the transfer of photons through lamellar structure and improved the absorption efficiency of visible light.Remarkably,the obtained PCN possessed better Cr(Ⅵ) photocatalytic reduction efficiency than pure g-C3N4.The reaction rate constant (k) of PCN (0.013 min-1) was approximately twice that of bare g-C3N4 (0.007 min-1).Furthermore,the effects of original pH and concentration of Cr(Ⅵ)-containing solution on removal efficiency of Cr(Ⅵ) were explored.A possible photocatalytic mechanism was proposed based on the experiments of radical scavengers and photoelectrochemical characterizations.     

类石墨相氮化碳二维纳米片的制备及可见光催化性能研究

以三聚氰胺为原料制备类石墨相氮化碳(g-C3N4),采用球磨与超声联用技术制备g-C3N4二维纳米片. 利用X 射线衍射光谱(XRD)、紫外-可见漫反射(UV-Vis)光谱、扫描电镜(SEM)、透射电镜(TEM)、原子力显微镜(AFM)、荧光(PL)光谱等分析手段对制备的催化剂进行了表征. 结果表明: g-C3N4二维纳米片具有与体相g-C3N4相同的晶体结构,片层结构仅有5个原子层厚.g-C3N4二维纳米片增加了对可见光的吸收,提高了光生电子-空穴对的分离效率.以染料罗丹明B的降解反应研究了g-C3N4二维纳米片在可见光下的催化性能. 结果表明,球磨超声1 h后制备的g-C3N4二维纳米片表现出最佳的光催化性能, 150 min 内对罗丹明B的降解率高达94%,是体相g-C3N4的2 倍.     

Significantly enhanced photocatalytic hydrogen production performance of g-C3N4/CNTs/CdZnS with carbon nanotubes as the electron mediators

The electron mediator can effectively improve the performance of the direct Z-scheme heterojunction photocatalysts.However,it is still a great challenge to select cheap and efficient electron mediators and to design them into the Z-scheme photocatalytic system.In the present paper,the g-C3N4/CNTs/CdZnS Z-scheme photocatalyst was prepared using carbon nanotubes (CNTs) as the electron mediators,and its photocatalytic hydrogen production performance was studied.Compared with single-phase g-C3N4,CdZnS and biphasic g-C3 N4/CdZnS photocatalysts,the photocatalytic hydrogen production performance of the prepared g-C3N4/CNTs/CdZnS has been significantly enhanced.Meanwhile,g-C3N4/CNTs/CdZnS possesses very good photocatalytic hydrogen production stability.The enhanced photocatalytic hydrogen production performance of g-C3 N4/CNTs/CdZnS is attributed to the fact that CNTs,as an electron mediator,can accelerate the recombination of the photogenerated holes in the valence band of g-C3N4 and the photogenerated electrons in the conduction band of CdZnS,which makes the g-C3N4/CNTs/CdZnS Z-scheme photocatalyst be easier to escape the photogenerated electrons,increases the concentration of the photogenerated carriers and prolongs the lifetime of the photogenerated carriers.This work provides a theoretical basis for the further development and design of CNTs as the intermediate electron mediator of the Z-scheme heterojunction photocatalyst.     

具有可见光催化活性的MoS2量子点/NH2-MIL-125复合材料的制备及性能表征

采用水热法合成金属-有机骨架材料NH₂-MIL-125, 并修饰硫化钼量子点, 从而构筑具有增强电荷分离的二硫化钼量子点/NH₂-MIL-125复合光催化材料(MoS₂ QDs/NH₂-MIL-125)。利用XRD、HRTEM、DRS、PL对材料性能进行分析, 通过降解甲基橙MO染料测试MoS₂ QDs/NH₂-MIL-125复合材料的光催化性能。结果表明：尺寸约 4 nm的MoS₂ QDs均匀分散在NH₂-MIL-125上, 在可见光照射下, MoS₂ QDs/NH₂-MIL-125复合材料的光催化性能极大优于单一的Bulk MoS₂和NH₂-MIL-125, 降解常数分别是它们的5.8和7.4倍。循环光催化实验结果表明, MoS₂ QDs/NH₂-MIL-125复合材料的光催化能力具有良好的稳定性。DRS和PL的测试结果表明, MoS₂ QDs/NH₂-MIL-125复合材料优异的可见光催化性能主要归因于异质结构的形成, 抑制了光生电子-空穴的复合, 进而提高了光催化性能。     

Template-free preparation of non-metal (B,P,S) doped g-C3N4 tubes with enhanced photocatalytic H2O2 generation

Developing environmentally friendly methods to produce hydrogen peroxide (H2O2) has received increas-ing attention.Photocatalysis has been proved to be a sustainable technology for H2O2 production.Herein,the novel non-metal elements (B,P,and S) doped g-C3N4 tubes (B-CNT,P-CNT,and S-CNT) photocata-lysts were obtained via a hydrothermal synthesis followed by thermal polymerization.By adjusting the precursor,the yield of g-C3N4 tubes (CNT) materials has been greatly improved.The as-prepared B-CNT,P-CNT,and S-CNT photocatalysts show an enhanced photocatalytic H2O2 production with the formation rate constants values of 42.31 μM min-1,24.95μM min-1,and 24.22μM min-1,respectively,which is higher than that of bulk CN (16.40 μM min-1).The doped B,P,S elements significantly enhanced the photocatalytic activity by adjusting their electronic structures and promoting the separation of electron-hole carriers.The results have shown great potential for the practical application of CNT photocatalysts.     

Extended visible light harvesting and boosted charge carrier dynamics in heterostructured zirconate–FeS<Subscript>2</Subscript> photocatalysts for efficient solar water splitting

Limited visible light absorption, slow charge transference, and high recombination are some of the main problems associated with low efficiency in photocatalytic processes. For these reasons, in the present work, we develope novel zirconate–FeS₂ heterostructured photocatalysts with improved visible light harvesting, effective charge separation and high photocatalytic water splitting performance. Herein, alkali and alkaline earth metal zirconates are prepared by a solid state reaction and coupled to FeS₂ through a simple wet impregnation method. The incorporation of FeS₂ particles induces visible light absorption and electron injection in zirconates, while the appropriate coupling of the semiconductors in the heterostructure allows an enhanced charge separation and suppression of the recombination. The obtained heterostructures exhibit high and stable photocatalytic activity for water splitting under visible light, showing competitive efficiencies among other reported materials. The highest hydrogen evolution rate (4490 µmol g^?1 h^?1) is shown for BaZrO₃–FeS₂ and corresponds to more than 20 times the activity of the bare BaZrO₃. In summary, this work proposes novel visible light active heterostructures for efficient visible light photocatalytic water splitting.     

g-C_3N_4-CdS异质结的合成及其光催化性能研究

以尿素为前驱体,550℃热聚合反应5 h,制备了块状g-C_3N_4。然后将块状g-C_3N_4超声剥离得到片状g-C_3N_4,在g-C_3N_4纳米片上原位生长Cd S(直径约130 nm),从而制备了g-C_3N_4-Cd S异质结。g-C_3N_4-Cd S异质结的吸收边约505 nm处,与g-C_3N_4(约460 nm)相比具有明显的红移,可吸收更多的可见光。此外,g-C_3N_4-Cd S异质结可降解99%的罗丹明B,具有较高的光催化活性。     

基于g–C3N4光催化型抗菌包装纸的制备及其抗菌性研究

目的 解决g–C3N4存在的比表面积小，电子–空穴复合速率快从而导致光催化性能不佳等问题。方法 以尿素和硫脲为前驱体材料，通过热解聚辅助水蒸气活化合成S掺杂石墨相氮化碳(g–C3N4)，并用界面聚合制备出光催化型抗菌包装纸。利用扫描电镜(SEM)、红外光谱(FTIR)、水接触角(WCA)、热重分析(TGA)、光催化抗菌实验等对抗菌包装纸的形态结构、表面官能团、纸张性质、光催化抗菌性进行详细研究。结果 致密的g–C3N4层有效提高了抗菌包装纸的疏水性和热稳定性。可见光照射下，光催化型抗菌包装纸对大肠杆菌和金黄色葡萄球菌的杀灭率达100%。未经可见光照射的原纸比光催化型包装纸的抗菌性差。结论 g–C3N4光催化型抗菌包装纸具有良好的广谱抗菌性，为绿色抗菌包装材料的制备提供了新思路。     

三维大孔g-C3N4吸附和光催化还原U(VI)性能研究

将易溶的U(VI)还原为微溶的U(IV)是治理放射性铀污染的有效方法。本研究以SiO₂纳米球作为硬模板, 通过热聚合-刻蚀制备具有连续贯通的三维大孔g-C₃N₄光催化剂, 用于吸附-光催化还原U(VI)。材料表征结果显示: 三维大孔g-C₃N₄比表面积显著增加, 对可见光的吸收明显增强; 同时具有三维有序大孔结构, 并呈规则的紧密堆积结构, 孔壁完整多孔, 整个结构具有良好的三维连通性。吸附实验表明: 三维大孔g-C₃N₄对U(VI)最大吸附容量可达~30.5 mg/g, 该过程更符合Langmuir吸附模型, 与块体g-C₃N₄相比吸附容量提高了~1.83倍。光催化还原实验表明: 三维大孔g-C₃N₄具有高的光催化活性和良好的稳定性, 其还原反应速率常数为~0.0142 min ^-1, 是块体g-C₃N₄ (~0.0024 min ^-1)的~5.9倍。鉴于三维大孔g-C₃N₄具有较优异的吸附-催化还原性能, 该材料有望应用于放射性废水中U(VI)的快速高效清除。     

Investigation of the Photocatalytic Hydrogen Production of Semiconductor Nanocrystal-Based Hydrogels

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.     

Construction of Infrared-Light-Responsive Photoinduced Carriers Driver for Enhanced Photocatalytic Hydrogen Evolution

Infrared light, more than 50% of the solar light energy, is long-termly ignored in the photocatalysis field due to its low photon energy. Herein, infrared-light-responsive photoinduced carriers driver is first constructed taking advantage of pyroelectric effect for enhancing photocatalytic hydrogen evolution. In order to give full play to its role, the photocatalytic reaction is localized on the surface and interface of the composite based on a new semi-immersion type heat collected photocatalytic microfiber system. The system is consisted of distinctive pyroelectric substrate poly(vinylidene fluoride-co-hexafluropropylene (PVDF-HFP), typical photothermal material carbon nanotube (CNT), and representative photocatalyst CdS. The transient photocurrent, electrochemical impedance spectroscopy, time-resolved photoluminescence and pyroelectric potential characterizations indicate that the infrared-light-responsive carriers driver significantly promotes the photogenerated charge separation, accelerates carrier migration, and prolongs carrier lifetime. The photocatalytic hydrogen evolution efficiency is remarkably improved more than five times with the highest average apparent quantum yield of 16.9%. It may open up new horizons to photocatalytic technology for the more efficient use of infrared light.     

具有三维网状结构的石墨相氮化碳/还原氧化石墨烯/钯复合材料的合成及可见光催化性能

石墨相氮化碳(g-C_3N_4)已经被认为是一种高效的非金属半导体光催化剂。为进一步优化其光催化性能,通过热解-水热两步法制备了三维网状结构的g-C_3N_4/还原氧化石墨烯(rGO)/钯纳米颗粒(Pd NPs)复合材料。该复合材料由大量超薄片组成,而且薄片上有大量直径约为10nm的Pd NPs。g-C_3N_4/rGO/Pd NPs复合材料展现了一个宽的可见光吸收(边~460nm),其在460~800nm波长范围内还有一个随波长增加的光吸收。经可见光(λ400nm)照射140 min后,g-C_3N_4/rGO/Pd NPs复合材料可降解90%罗丹明B(RhB)。此外,循环实验表明g-C_3N_4/rGO/Pd NPs复合材料具有良好的稳定性。因此,g-C_3N_4/rGO/Pd NPs复合材料有望成为一种高效稳定的光催化剂,在水污染处理领域具有潜在的应用价值。     

Defect‐Tailoring Mediated Electron–Hole Separation in Single‐Unit‐Cell Bi3O4Br Nanosheets for Boosting Photocatalytic Hydrogen Evolution and Nitrogen Fixation

Solar photocatalysis is a potential solution to satisfying energy demand and its resulting environmental impact. However, the low electron–hole separation efficiency in semiconductors has slowed the development of this technology. The effect of defects on electron–hole separation is not always clear. A model atomically thin structure of single‐unit‐cell Bi₃O₄Br nanosheets with surface defects is proposed to boost photocatalytic efficiency by simultaneously promoting bulk‐ and surface‐charge separation. Defect‐rich single‐unit‐cell Bi₃O₄Br displays 4.9 and 30.9 times enhanced photocatalytic hydrogen evolution and nitrogen fixation activity, respectively, than bulk Bi₃O₄Br. After the preparation of single‐unit‐cell structure, the bismuth defects are controlled to tune the oxygen defects. Benefiting from the unique single‐unit‐cell architecture and defects, the local atomic arrangement and electronic structure are tuned so as to greatly increase the charge separation efficiency and subsequently boost photocatalytic activity. This strategy provides an accessible pathway for next‐generation photocatalysts.     

Investigation of the optical characteristics of a combination of InP/ZnS-quantum dots with MWCNTs in a PMMA matrix

In the present study we investigated a combination of quantum dots with multi-walled carbon nanotubes as a possible future additive to the active layer of polymer solar cells. In this case the quantum dots should serve to enhance the long wavelength response of the solar cell, while the nanotubes enhance the charge carrier collection efficiency by favoring charge carrier separation and enhancement of the lateral conduction of the films. In order to clarify the interplay of the nanoparticles only, we deposited them into a non-conducting and transparent polymethyl-methalacrylate (PMMA) matrix. InP/ZnS quantum dots with an emission peak wavelength of 660 nm have been chosen in this study, because their addition can enhance the long wavelength response of conventional poly(3-hexylthiophene) (P3HT): phenyl-C61-butyric acid methyl ester (PCBM) bulk heterostructure polymer solar cells. In our study we kept the quantum dot concentration constant and varied the concentration of the carbon nanotubes (CNTs) in the deposited films. The characterization of the film morphology by scanning electron microscopy (SEM) imaging and of the optical properties by photoluminescence and transmittance revealed a rather complex interplay between nanotubes and quantum dots. In particular we found a strong quenching of the photoluminescence and an inhomogeneous CNT distribution for carbon nanotube concentrations exceeding 1%. The decrease in optical transmittance of the films with increasing CNT concentration is less pronounced, when quantum dots (QDs) are added. The optical transmittance in a wavelength range between 380 nm and 800 nm of the composites could be expressed empirically as a simple second order polynomial function.     

Probing single quantum dots by micro-photoluminescence

Using micro-photoluminescence, emissions from single CdSe quantum dots were observed from the cleaved (110) facets of ZnSe/CdSe/ZnSe heterostructures grown on GaAs (001) substrates. The emission intensity of a single quantum dot was linearly proportional to the excitation intensity, demonstrating excitonic features. Emissions from these single quantum dots were found to polarize within the (001) plane, providing information on the shapes of the quantum dots.