Controlled preparation of P-doped g-C3N4 nanosheets for efficient photocatalytic hydrogen production

Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy. Graphitic carbon nitride (g-C₃N₄), despite with obvious catalytic effect, is still unsatisfactory for hydrogen production. In this work, phosphorus element is incorporated to tune g-C₃N₄'s property through calcinating the mixture of g-C₃N₄ and NaH₂PO_2, sacrificial agent and co-catalyst also been supplied to help efficient photocatalytic hydrogen production. Phosphorus (P) doped g-C₃N₄ samples (PCN-S) were prepared, and their catalytic properties were studied. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and ultraviolet diffuse reflection (UV-DRS) were used to study their structures and morphologies. The results show that the reaction rate of PCN-S is 318 μmol h⁻¹ g⁻¹, which is 2.98 times as high as pure carbon nitride nanosheets (CN) can do. Our study paves a new avenue, which is simple, environment-friendly and sustainable, to synthesize highly efficient P doping g-C₃N₄ nanosheets for solar energy conversion.     

Controlled preparation of P-doped g-C3N4 nanosheets for efficient photocatalytic hydrogen production

Hydrogen production by photolysis of water by sunlight is an environmentally-friendly preparation technology for renewable energy. Graphitic carbon nitride (g-C₃N₄), despite with obvious catalytic effect, is still unsatisfactory for hydrogen production. In this work, phosphorus element is incorporated to tune g-C₃N₄'s property through calcinating the mixture of g-C₃N₄ and NaH₂PO₂, sacrificial agent and co-catalyst also been supplied to help efficient photocatalytic hydrogen production. Phosphorus (P) doped g-C₃N₄ samples (PCN-S) were prepared, and their catalytic properties were studied. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and ultraviolet diffuse reflection (UV-DRS) were used to study their structures and morphologies. The results show that the reaction rate of PCN-S is 318 μmol·h^-1·g^-1, which is 2.98 times as high as pure carbon nitride nanosheets (CN) can do. Our study paves a new avenue, which is simple, environment-friendly and sustainable, to synthesize highly efficient P doping g-C₃N₄ nanosheets for solar energy conversion.     

Rational design of MoS2/g-C3N4/ZnIn2S4 hierarchical heterostructures with efficient charge transfer for significantly enhanced photocatalytic H2 production

The rational design of hierarchical heterojunction photocatalysts with efficient spatial charge separation remains an intense challenge in hydrogen generation from photocatalytic water splitting. Herein, a noble-metal-free MoS₂/g-C₃N₄/ZnIn₂S₄ ternary heterostructure with a hierarchical flower-like architecture was developed by in situ growth of 3D flower-like ZnIn₂S₄ nanospheres on 2D MoS₂ and 2D g-C₃N₄ nanosheets. Benefiting from the favorable 2D-2D-3D hierarchical heterojunction structure, the resultant MoS₂/g-C₃N₄/ZnIn₂S₄ nanocomposite loaded with 3 wt% g-C₃N₄ and 1.5 wt% MoS₂ displayed the optimal hydrogen evolution activity (6291 μmol g^?1 h^?1), which was a 6.96-fold and 2.54-fold enhancement compared to bare ZnIn₂S₄ and binary g-C₃N₄/ZnIn₂S₄, respectively. Structural characterizations reveal that the significantly boosted photoactivity is closely associated with the multichannel charge transfer among ZnIn₂S₄, MoS₂, and g-C₃N₄ components with suitable band-edge alignments in the composites, where the photogenerated electrons migrate from g-C₃N₄ to ZnIn₂S₄ and MoS₂ through the intimate heterojunction interfaces, thus enabling efficient electron-hole separation and high photoactivity for hydrogen evolution. In addition, the introduction of MoS₂ nanosheets highly benefits the improved light-harvesting capacity and the reduced H₂-evolution overpotential, further promoting the photocatalytic H₂-evolution performance. Moreover, the MoS₂/g-C₃N₄/ZnIn₂S₄ ternary heterostructure possesses prominent stability during the photoreaction process owing to the migration of photoinduced holes from ZnIn₂S₄ to g-C₃N₄, which is deemed to be central to practical applications in solar hydrogen production.     

有机酸介导合成WO3/g-C3N4及其光催化性能

采用水热法制备了WO3/g-C3N4复合物,并探讨了草酸、柠檬酸、乙酸和水杨酸对复合物结构、形貌及催化活性的影响.结果表明,复合物中棒状WO3分布在片层状的g-C3N4上,二者结合紧密形成异质结构.以1 mol/L草酸为介导剂制备的WO3/g-C3N4的光催化活性最佳,当WO3和g-C3N4质量比为1:1时,可见光下反...     

BiOCl/g-C3N4异质结催化剂可见光催化还原CO2

以KCl、Bi（NO₃）₃和类石墨氮化碳（g-C₃N₄）为前体,采用水热法成功制备了BiOCl/g-C₃N₄异质结光催化剂,并进行可见光催化还原CO₂,考察了催化剂的活性及稳定性,同时研究BiOCl：g-C₃N₄（摩尔比）、催化剂用量和光照强度对光催化还原CO₂的影响。结果表明,在水蒸气的存在下,BiOCl/g-C₃N₄较纯BiOCl和g-C₃N₄具有更高的光催化还原CO₂活性,在催化剂用量为0.1 g,光照强度为2.413×10^-6 einstein·min^-1·cm^-2,BiOCl：g-C₃N₄摩尔比为1：1的异质结催化剂显示了最高的光催化还原CO₂活性,且可见光催化剂在5次套用实验后其活性基本不变。基于X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、比表面积测试（BET）和紫外-可见（UV-vis）吸收光谱表征,可以推断BiOCl和g-C₃N₄之间形成的p-n结能有效分离光生电子和空穴,是增强光催化剂活性的主要原因。     

Enhanced interfacial electronic transfer of BiVO4 coupled with 2D g-C3N4 for visible-light photocatalytic performance

A BiVO₄/2D g-C₃N₄ direct dual semiconductor photocatalytic system has been fabricated via electrostatic self-assembly method of BiVO₄ microparticle and g-C₃N₄ nanosheet. According to experimental measurements and first-principle calculations, the formation of built-in electric field and the opposite band bending around the interface region in BiVO₄/2D g-C₃N₄ as well as the intimate contact between BiVO₄ and 2D g-C₃N₄ will lead to high separation efficiency of charge carriers. More importantly, the intensity of bulid-in electric field is greatly enhanced due to the ultrathin nanosheet structure of 2D g-C₃N₄. As a result, BiVO₄/2D g-C₃N₄ exhibits excellent photocatalytic performance with the 93.0% Rhodamine B (RhB) removal after 40 min visible light irradiation, and the photocatalytic reaction rate is about 22.7 and 10.3 times as high as that of BiVO₄ and 2D g-C₃N₄, respectively. In addition, BiVO₄/2D g-C₃N₄ also displays enhanced photocatalytic performance in the degradation of tetracycline (TC). It is expected that this work may provide insights into the understanding the significant role of built-in electric field in heterostructure and fabricating highly efficient direct dual semiconductor systems.     

MoO3/g-C3N4复合材料的制备及光催化性能

以三聚氰胺和四水合钼酸铵为前驱体,采用水热法制备了MoO₃/g-C₃N₄复合光催化剂。利用X-射线衍射仪（XRD）、红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）及紫外-可见漫反射仪（DRS）等对制备的样品进行了表征。表征结果显示,棒状的三氧化钼负载在层状C₃N₄表面,复合材料的光吸收能力有一定的增强。材料可见光催化降解亚甲基蓝（MB）溶液的实验表明,三氧化钼和g-C₃N₄所复合产生的异质结具有较好的吸收光强度及催化降解性能,尤其是5%（质量分数）MoO₃/g-C₃N₄复合材料光催化降解率最好,达到95.7%,高于纯三氧化钼和g-C₃N₄。自由基与空穴捕获实验表明,·O₂^-是光催化反应中的主要活性物种。MoO₃/g-C₃N₄复合材料在4个循环周期内表现出了优异的稳定性。     

Ag3PO4/g-C3N4复合材料制备及其光催化性能

采用原位沉淀法制备了Ag3PO4/g-C3N4复合材料，利用XRD、SEM、TEM、UV-Vis DRS和PL等技术对其进行表征。结果显示，g-C3N4呈现二维片状结构，Ag3PO4为立方晶相的类球状结构，且均匀分布在g-C3N4表面。以亚甲基蓝（MB）为模拟污染物，考察g-C3N4与Ag3PO4的不同摩尔比对MB降解率的影响。结果表明，在Ag3PO4/g-C3N4的摩尔比为1:0.7时，Ag3PO4/g-C3N4复合材料的光催化活性最佳，可见光照30 min后MB降解率即达到100%。光催化剂稳定性较好，重复使用5次，MB降解率仍达到85.24%。降解机理研究表明，h 和e-是降解MB的主要活性物质。     

Ag3PO4/g-C3N4复合材料的制备及其光催化性能

以硝酸银和三聚氰胺为原料,采用原位沉淀法制备了Ag3PO4/g-C3N4复合材料,利用XRD、SEM、TEM、UV-Vis DRS和PL等技术对其进行了表征.结果显示,g-C3N4呈二维片状结构,Ag3PO4为立方晶相的类球状结构,且均匀分布在g-C3N4表面.以亚甲基蓝(MB)为模拟污染物,考察g-C3N4与Ag3P...     

Co-doping g-C3N4 with P and Mo for efficient photocatalytic tetracycline degradation under visible light

Although g-C₃N₄ (CN) materials have been extensively explored for the photocatalytic degradation of organic pollutants, their weak response to visible light and fast recombination of photoexcited electron-hole pairs restrain their practical applications. Herein, we deeply mediated the CN's energy-band structure, morphology, and surface properties by non-metal (P) and metal (Mo) co-doping based on the thermal treatment of a phosphomolybdic acid hydrate and dicyandiamide mixture in a straightforward one-step manner. Meanwhile, cyano groups and nitrogen vacancies were generated as a result of the co-doping, and the resulting P, Mo co-doped CN (PM-CN) exhibited thinner layers, smaller sizes, and superior visible-light harvesting capacity and charge separation efficiency. Consequently, highly active PM-CN was obtained for photocatalytic tetracyclines (TC) degradation, and the rate was calculated to be 0.01 min^?1, 3.3 times greater than that of the pure CN, outstripping the single P- and Mo-doped counterparts. A free radical scavenging test demonstrated that the reactive species ?O^2? and h⁺ were critical in TC degradation. The present work is expected to shed light on co-doping CN with non-metal and metal elements to obtain high-performance, visible-light-responsive photocatalysts for practical environmental remediation.     

Developing controllable mesoporous CoTiO3/C3N4 heterostructures for enhanced photocatalytic performances

Excellent charge carrier kinetics and high light absorption capability are key factors in increasing photocatalytic efficiency. Here, novel mesoporous CoTiO₃/g-C₃N₄ heterostructures at varying CoTiO₃ percentages were synthesized utilizing an easy soft and hard template approach for the degradation of acridine orange (AO) under visible light exposure. The TEM images exhibited irregular nanocrystals containing stacked g-C₃N₄ layers with crimped nanosheets, and spherical CoTiO₃ NPs (10 nm) were uniformly distributed throughout the g-C₃N₄ layers. The results indicated that the mesoporous 3%CoTiO₃/g-C₃N₄ heterostructure exhibited the highest degradation of AO dye (100%) within 60 min compared to g-C3N4 (10%) and CoTiO3 (18%). Furthermore, the 3% CoTiO₃/g-C₃N₄ heterostructure had a better degradation rate, approximately 10.75- and 6.93-fold larger than those of g-C₃N₄ and CoTiO₃ NPs, respectively. The enhanced mesoporous CoTiO₃/g-C₃N₄ exhibited effective photoinduced carrier separation, a widened light harvesting range, and synergistic effects. Additionally, the 3% CoTiO₃/g-C₃N₄ heterostructure revealed superior photocatalytic stability in AO dye recycling degradation for long-life regeneration. A direct Z-scheme mechanism was suggested for the degradation of AO dye over mesoporous CoTiO₃/g-C₃N₄, and it was further supported by photoluminescence (PL) spectroscopy and photoelectrochemical responses. The present work demonstrates new insight and an approach to synthesizing mesoporous CoTiO₃/g-C₃N₄ heterostructures for various potential applications.     

g-C_3N_4/BiVO_4复合光催化剂的制备与光催化性能研究

通过原位复合的方法制备不同配比的g-C3N4/BiVO4复合光催化剂,利用傅里叶红外光谱(FTIR)、X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外-可见光漫反射光谱(UV-Vis DRS)和N2吸附-脱附对所制备的材料进行表征。并通过光催化降解有机染料罗丹明B对其光催化活性进行测试。结果表明,部分g-C3N4附着在BiVO4表面,g-C3N4/BiVO4复合光催化剂比纯的BiVO4光催化效果要好,并且确定了最佳复合比例,同时对复合光催化剂性能提高的机理进行了讨论。     

0D CoP cocatalyst/ 2D g-C3N4 nanosheets: An efficient photocatalyst for promoting photocatalytic hydrogen evolution

In this work, cobalt phosphide (CoP) nanoparticles were successfully decorated on an ultrathin g-C₃N₄ nanosheet photocatalysts by in situ chemical deposition. The built-in electric field formed by heterojunction interface of the CoP/g-C₃N₄ composite semiconductor can accelerate the transmission and separation of photogenerated charge-hole pairs and effectively improve the photocatalytic performance. TEM, HRTEM, XPS, and SPV analysis showed that CoP/g-C₃N₄ formed a stable heterogeneous interface and effectively enhanced photogenerated electron-hole separation. UV-vis DRS analysis showed that the composite had enhanced visible light absorption than pure g-C₃N₄ and was a visible light driven photocatalyst. In this process, NaH₂PO₂ and CoCl₂ are used as the source of P and Co, and typical preparation of CoP can be completed within 3 hours. Under visible light irradiation, the optimal H₂ evolution rate of 3.0 mol% CoP/g-C₃N₄ is about 15.1 μmol h⁻¹. The photocatalytic activity and stability of the CoP/g-C₃N₄ materials were evaluated by photocatalytic decomposition of water. The intrinsic relationship between the microstructure of the composite catalyst and the photocatalytic performance was analyzed to reveal the photocatalytic reaction mechanism.     

Cu3P and Ni2P co-modified g-C3N4 nanosheet with excellent photocatalytic H2 evolution activities

Copper-nickel phosphides/ graphite-like phase carbon nitride (Cu₃P-Ni₂P/g-C₃N₄) composites were obtained through a facile one-pot in situ solvothermal approach. The coexistence of Cu₃P and Ni₂P plays an important role in enhancing the catalytic activity of g-C₃N₄. The 7 wt% Cu₃P-Ni₂P/g-C₃N₄ bimetallic phosphide photocatalyst demonstrates the best photocatalytic hydrogen (H₂) evolution rate of 6529.8 μmol g⁻¹ h⁻¹, which is 80.7-fold higher than that of g-C₃N₄. The apparent quantum yield (AQE) was determined to be 18.5% at 400 nm over the 7% Cu₃P-Ni₂P/g-C₃N₄. This in situ growth strategy produced intimate contact interfaces, leading to a significantly promoted separation of charge carriers, and hence strengthened the photocatalytic H₂ production. Moreover, the coexistence of Cu₃P and Ni₂P reduced the overpotential of H₂ during the evolution process, further benefiting H₂ production. Finally, the photocatalytic enhancement mechanism was proposed and verified by fluorescence and electrochemical analysis. This work provides a low-cost strategy to synthesize nonprecious bimetallic phosphides/carbon nitride photocatalyst with outstanding H₂ production activity. © 2020 Society of Chemical Industry     

Constructing 0D/1D/2D Z-scheme heterojunctions of Ag nanodots/SiC nanofibers/g-C3N4 nanosheets for efficient photocatalytic water splitting

Efficiently constructing nanostructured Z-scheme heterojunctions with good interface contact is a desired route to optimize the photocatalytic property of the materials. In this work, novel 0D/1D/2D Z-scheme silver/silicon carbide/graphitic carbon nitride (Ag/SiC/CN) photocatalysts were prepared from Ag nanodots loaded on SiC nanofibers/CN nanosheets (SiC/CN) composite, using the calcination and chemical reduction routes. The Ag/SiC/CN composite with an optimal 3% Ag loading dose performs the best H₂ evolution rate of 2971 μmol g^?1 h^?1, which is approximately 8.8, 1.5 and 4.5 times compared to CN, SiC/CN and 3% Ag/CN, respectively. Besides the Ag/SiC/CN composite presents a high apparent quantum efficiency (7.3%) and outstanding photo-corrosion resistance stability. The Ag nanodots are served as efficient carriers transfer center and cocatalyst to construct Z-scheme heterojunction interface, which can help to generate more photo-generated carries, shorten the electron transmission distance and increase the electron transfer rate, certifying that 0D/1D/2D Z-scheme photocatalytic system is high-efficiency and has great advantages in photocatalytic applications.     

Selective photocatalytic degradation of organic pollutants by CuxS/ZnO/TiO2 heterostructures

Photoactive heterostructures containing Cu_xS/ZnO/TiO₂ have been obtained by spray pyrolysis deposition followed by post-deposition thermal treatment. The ZnO middle layer morphology was tailored by using chemical additives during the deposition. The samples have crystalline structure with average crystallite size around 80 Å for metal oxides and 90 Å for Cu_xS. The roughness varies from 27.5 nm for Cu_xS/dZnO/TiO₂ to 33.6 nm for Cu_xS/pZnO/TiO₂ samples. The wettability properties were tested based on the contact angle measurements. The highest surface energy value (106.4 mN/m) corresponding to Cu_xS/pZnO/TiO₂ with 30 min UV irradiation, with a predominant polar component of 85.3 mN/m. The photocatalytic efficiency under UV–Vis light irradiation was evaluated using methylene blue and phenol as pollutants. The highest photocatalytic values (93.4% for methylene blue and 72.3% for phenol) were obtained for Cu_xS/pZnO/TiO₂ heterostructure with successive 30 min UV irradiation at 2 h intervals. The mineralization efficiency was tested using total organic carbon analysis and the results are slightly lower compared with photocatalytic efficiency.     

新型g-C3N4/CuS复合材料的制备及光催化研究

一步水热法合成CuS修饰的石墨相氮化碳(g-C3N4/CuS)复合光催化剂,通过FE-SEM、XRD、FTIR、UV-Vis-DRS等手段对其进行了表征,利用Cr(VI)溶液考察了g-C3N4/CuS在可见光下的光催化还原性能.实验结果表明,g-C3N4/CuS复合光催化剂的光催化活性明显优于单一的g-C3N4和CuS.可见光照射下,180 min内Cr(VI)的去除率可达70％以上.CuS的引入不仅扩宽了g-C3N4的可见光吸收范围,而且降低了g-C3N4光生电子和空穴的复合率,从而显著提高g-C3N4的光催化活性.该复合材料的催化活性受溶液的pH值影响较大,酸性条件下更有利于光催化反应的进行;共存低浓度腐殖酸对Cr(VI)的去除没有显著影响.g-C3N4/CuS具有良好的可见光催化活性,可用于废水中Cr(VI)的光催化还原去除.