金属相1T´ MoS2增强类石墨相C3N4的可见光催化性能

通过煅烧和静电自组装的方法制备了1T′ MoS₂超薄纳米片和类石墨烯相氮化碳(g-C₃N₄)纳米片的复合材料. 该材料在光催化实验中展现出6.24 μmol?g^?1?h^?1的产氢速率, 优于贵金属铂修饰的g-C₃N₄纳米片的性能(4.64 μmol?g^?1?h^?1). 此外, 该复合材料在光催化降解有机染料甲基橙的实验中表现出0.19 min^?1的催化速率, 而纯g-C₃N₄纳米片只有0.053 min^?1的催化速率. 材料光催化性能的提升可归结于1T′MoS₂ 和g-C₃N₄之间的协同效应, 包括光吸收的增强以及因1T′MoS₂优异电子导电性而得到的高效电荷分离.     

Fe(Ⅲ)螯合掺杂对g-C3N4光催化性能和活性位的影响(英文)

元素掺杂是一种简单有效的光催化剂改性方法.已有诸多文献报道采用非金属元素(B、P、S)或金属元素(Na⁺, Ni³⁺,Co³⁺, Cu²⁺)对g-C₃N₄进行掺杂改性,但目前对金属掺杂的模型和影响机理尚不清晰.g-C₃N₄作为层状材料,它的表面和边缘有大量的胺基,它对光生载流子的传输起到重要作用.此外,胺基可以与金属通过配位键形成螯合物;与胺基螯合的金属由于其功函数较小,可以捕获半导体的光生电子,并有利于降低光生载流子的复合.本文选用Fe(Ⅲ)对g-C₃N₄进行掺杂改性, SEM-EDS表明, C和N元素均匀分布在g-C₃N₄整个骨架上,而Fe元素主要分布在g-C₃N₄边缘部分;FTIR结果发现,掺杂Fe后, N-Hx伸缩振动峰强度随着掺杂量的增加而降低,证明Fe(Ⅲ)与g-C     

Z型g-C3N4/Pt/TiO2纳米管阵列复合电极的制备及光电氧化甲醇性能

以NH₄Cl为气体模板吹制双氰胺制备g-C₃N₄纳米片, 并将其负载于Pt/TiO₂纳米管阵列(Pt/TiO₂ NTs)上, 制备了一种新型的Z型g-C₃N₄/Pt/TiO₂NTs复合电极材料. 通过扫描电子显微镜、 X射线衍射和X射线光电子能谱对该材料的结构进行了表征, 采用电化学和光电化学方法研究了材料的性能. 研究结果显示, 在可见光照射下, g-C₃N₄/Pt/TiO₂ NTs复合材料具有高效的光电氧化甲醇的性能. 该复合材料的高性能主要归因于以下两点： (1) g-C₃N₄与Pt/TiO₂NTs的结合有效扩展了其在可见光范围的吸收; (2) Z型电荷转移保留了具有强氧化能力的空穴和强还原能力的电子, 从而使光生中间体作用于电催化过程增强了甲醇氧化效率.     

Z型光催化剂Sb2WO6/g-C3N4的制备及光催化性能

通过水热反应合成了Sb₂WO₆改性的g-C₃N₄复合材料(Sb₂WO₆ /g-C₃N₄). 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫散射反射光谱(UV-Vis DRS)和光致发光光谱(PL)等表征了样品的性质. 结果表明, Sb₂WO₆在g-C₃N₄的表面上生长, 并且复合材料光吸收能力有一定的增强, 光生电子-空穴的重组率降低. 通过罗丹明B(RhB)的光降解评价了Sb₂WO₆/g-C₃N₄复合材料的光催化性能. 结果表明, 模拟日光下Sb₂WO₆质量分数为10%的Sb₂WO₆/g-C₃N₄复合材料在60 min内对RhB的降解率为99.3%, 高于纯g-C₃N₄和Sb₂WO₆. Sb₂WO₆/g-C₃N₄复合材料的这种高度增强的光催化活性主要归因于强的界面相互作用促进了光生电子-空穴分离和迁移. 添加自由基清除剂的实验结果表明, ·O^2-和h⁺是光催化反应中的主要活性物质. Sb₂WO₆/g-C₃N₄复合材料在几个反应周期内表现出优异的稳定性. 根据实验结果提出了一种可能的Z型光催化机理.     

碳自掺杂g-C3N4光催化性能的原位光微量热-荧光光谱研究

通过在尿素前驱体中添加单宁酸, 原位缩聚形成碳自掺杂石墨相氮化碳(g-C₃N₄). 利用X射线光电子能谱(XPS)、 场发射扫描电子显微镜(FESEM)、 X射线衍射(XRD)仪和同步热分析(TG-DSC)等方法对碳自掺杂 g-C₃N₄的形貌、 物相结构和能带价态组分进行表征分析, 结合紫外-可见吸收光谱(UV-Vis)和原位光微量热-荧光光谱联用仪获得碳自掺杂g-C₃N₄降解罗丹明B的原位热/动力学信息和三维荧光光谱信息, 探讨了光催化降解罗丹明B的微观机制. 结果表明, 单宁酸浓度≤10 mg/mL时, 碳会取代七嗪单元结构的氮原子形成g-C₃N₄骨架碳自掺杂; 单宁酸浓度≥ 20 mg/mL时, 碳以无定形形式沉积负载在g-C₃N₄表面上形成无定形碳自掺杂. 骨架碳自掺杂g-C₃N₄形成的π电子有效缩短了禁带宽度, 减小了光生电子-空穴复合几率, 比无定形C掺杂g-C₃N₄显示出更优异的光催化性能, 催化主要活性物种为h⁺和·O{}_{\mathrm{2}}^{-}. 碳自掺杂g-C₃N₄光催化降解过程可分为光响应吸热、 降解污染物放热平衡过程和稳定放热3个过程. 其中骨架碳自掺杂g-C₃N₄(C/N摩尔比为0.844)在光照1000 s内, 三维荧光光谱检测的RhB降解率锐减, 光照1000 s后, 其RhB降解率为87.6%, 分别是原始g-C₃N₄和无定形碳自掺杂g-C₃N₄的3.13倍和1.95倍. 光照1000 s后, 光微量热计显示以矿化和降解非荧光发色中间产物为主, 并保持以热变速率为(0.9799±0.5356) μJ/s稳定放热, 为拟零级反应过程, 是光催化反应的决速步骤.     

Z-机制g-C3N4/Bi/BiOBr异质结光催化剂制备及其可见光降解甲醛气体研究

通过将BiOBr纳米片与g-C₃N₄复合,然后原位还原,合成了具有纳米花状结构的三元异质结光催化剂g-C₃N₄/Bi/BiOBr.对g-C₃N₄/Bi/BiOBr的结构、形貌、元素价态和光学性能等进行了表征和研究.评估了g-C₃N₄/Bi/BiOBr对气体甲醛的光催化降解活性. g-C₃N₄/Bi/BiOBr在可见光照射下降解甲醛的活性与g-C₃N₄、 BiOBr单体和g-C₃N₄/BiOBr二元复合物相比显著提高. 20%-g-C₃N₄/Bi/BiOBr复合物可以在60 min内(λ> 400 nm)降解80%的气态甲醛(初始浓度0.16 mg·L^-1).     

WO3/g-C3N4异质结催化剂的制备及其氧化脱硫性能

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

具有高效界面电荷转移的0D/2D Bi4V2O11/g-C3N4梯形异质结的设计合成及抗生素降解性能研究

随着工业技术的飞速发展,大量有机污染物被应用于生活的各个领域,由此带来了严重的环境问题。众所周知,半导体光催化技术是一种有效且环境友好的降解去除典型污染物的方法,而光催化剂在该技术的应用中起着关键作用。因此,在光催化污染物降解领域,人们已经尝试研究了各种半导体材料。其中石墨相氮化碳(g-C₃N₄)是近年来公认的“明星”材料之一。因其独特的二维层状结构和良好的可见光响应而引起了人们的极大兴趣。由于带隙较窄(~2.7 eV)、能带结构可调以及良好的物理化学稳定性,g-C₃N₄对太阳光谱的吸收可达450 nm,具有一定的可见光光催化性能。然而,g-C₃N₄在去除抗生素和染料方面的降解效率仍然存在不足,例如光生电荷的快速复合以及空穴的氧化能力弱等。为了优化这种有前景的光催化材料,人们尝试了多种方法来改善g-C₃N₄的电子能带结构,例如金属/非金属元素掺杂、形貌调控和官能团修饰等。最近,人们提出了由两种N型半导体光催化剂组成的梯形异质结理念,它可以利用半导体材料更正的价带和更负的导带。相关结果表明,构筑梯形异质结是提高g-C₃N₄光催化活性的最有效方法之一。因此,本文通过简单的原位溶剂热生长法制备了新型0D/2D Bi₄V₂O₁₁/g-C₃N₄梯形异质结光催化剂。Bi₄V₂O₁₁/g-C₃N₄复合材料对去除土霉素(OTC)和活性红染料展示出了优异的光催化活性。尤其是BVCN-50复合材料对OTC和活性红的降解效率高达74.1%和84.2%,该过程的主要活性物种为·O₂^-。大幅增强的光催化性能归因于Bi₄V₂O₁₁和g-C₃N₄之间形成的梯形异质结保持了光催化体系的强氧化还原能力(Bi₄V₂O₁₁的强氧化能力和g-C₃N₄的强还原能力),并促进了光生电荷的空间分离。此外,金属Bi⁰的表面等离子共振效应可以拓宽异质结系统的光吸收范围。此外,基于高效液相色谱-质谱联用(LC-MS)分析,我们研究了OTC降解过程中可能的中间体和降解路径。这项工作为设计和制备g-C₃N₄基梯形异质结用于抗生素和活性染料降解提供了一种新的策略。     

可见光诱导提升Pt/g-C3N4纳米片甲酸氧化性能的研究

以半导体材料类石墨氮化碳纳米片(g-C₃N₄纳米片)为载体,通过微波-多元醇法构筑了Pt/g-C₃N₄纳米片催化剂. 通过TEM、XRD、XPS、紫外-可见吸收光谱等方法对Pt/g-C₃N₄纳米片催化剂的粒径尺寸、组成、结构、光学等性质进行分析. 通过对比可见光照和暗室条件下的甲酸电氧化活性,Pt/g-C₃N₄纳米片催化剂在可见光照射下展现出良好的催化性能. 该性能的提高一方面可能是由于g-C₃N₄纳米片在可见光照射下加速了电子从Pt转移给g-C₃N₄纳米片,Pt处于“电子匮乏”状态,可削弱CO与Pt之间的化学键能,减弱CO在Pt表面的吸附能力,促进了CO的氧化,提高了催化剂抗中毒能力;另一方面,g-C₃N₄纳米片在光照条件下分离出的空穴可有效氧化甲酸分子,提高甲酸氧化活性. 因此,可见光条件下可有效提高Pt/g-C₃N₄纳米片催化剂甲酸催化氧化活性,这为直接甲酸燃料电池的发展提供了新思路.     

熔盐辅助法制备g-C3N4纳米结构及其光催化制氢性能

以尿素作为原料, 采用熔盐辅助热聚合法在KCl-NaCl-BaCl₂体系中制备了带隙可调的g-C₃N₄纳米结构. 采用X射线衍射仪、 扫描电子显微镜、 X射线光电子能谱仪、 紫外-可见漫反射光谱仪及荧光光谱仪对产物的结构、 形貌、 成分及光学性能进行了表征. 对g-C₃N₄纳米结构可见光条件下的光催化制氢性能进行了测试, 研究了不同的尿素/熔盐比对其光催化性能的影响. 结果表明, 熔盐辅助热聚合法制备的g-C₃N₄ 纳米结构吸收光谱出现明显宽化, 吸收边由普通热聚合法制备g-C₃N₄的约450 nm红移至约500 nm左右. 同时光生载流子复合几率明显降低, 从而有效提升其光催化制氢性能. 最优化的g-C₃N₄(60)样品析氢速率达到12301.1 μmol?g^?1?h^?1, 为普通热聚合法制备g-C₃N₄析氢速率的4倍.     

双功能复合材料g-C3N4/CdS/Ni催化光解水产氢和5-羟甲基糠醛氧化性能

采用高温煅烧法、 原位生长法和光还原法分三步制备出双功能复合光催化剂g-C₃N₄/CdS/Ni. 材料中CdS的引入可以增强光生电子和空穴的分离效率, Ni可以进一步提高光致产氢速率. 在以三乙醇胺(TEOA)为电子给体的水溶液中对所制备的材料进行了催化产氢性能测试, 并对材料中CdS的含量进行了优化. 结果表明, 25% (质量分数)CdS负载量的复合材料催化产氢性能最佳, 其催化产氢速率为4134.5 μmol·g^-1·h^-1, 是 g-C₃N₄/Ni催化产氢速率的115倍. 且Ni是一种良好的质子催化剂. 在此基础上, 以5-羟甲基糠醛(HMF)替代TEOA作为体系的电子给体, 其可以被选择性地催化氧化为增值化学品2, 5-二甲酰基呋喃(DFF). 当体系中HMF的转化率为82.3%, DFF的选择性为69.4%时, DFF的产率(57.2%)达到最高, 体系中H₂的产量为 51.8 μmol/g. g-C₃N₄/CdS/Ni复合材料可以在同一体系中进行催化光致产氢和HMF的选择性氧化.     

Enhanced Visible-light Photocatalytic Activity of g-C3N4/Nitrogen-doped Graphene Quantum Dots/TiO2 Ternary Heterojunctions for Ciprofloxacin Degradation with Narrow Band Gap and High Charge Carrier Mobility

Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C₃N₄-based photocatalysts. To solve these problems, g-C₃N₄/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-C₃N₄/NGQDs/TiO₂ were characterized and explored. The optimal g-C₃N₄/NGQDs/TiO₂ composite exhibits enhanced photocatalytic degradation performance of ciprofloxacin (CIP) compared with the as-prepared g-C₃N₄, TiO₂(P25) and g-C₃N₄/TiO₂ heterojunction under visible light irradiation. The apparent rate constant of the composite is around 6.43, 4.03 and 2.30 times higher than those of g-C₃N₄, TiO₂ 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 h⁺ and ^·O₂^- were the main active species in the degradation process. A possible photocatalytic reaction mechanism of the g-C₃N₄/NGQDs/TiO₂ composite for the enhanced degradation of CIP under visible light irradiation was also proposed.     

负载型Pd-Cu催化剂的制备及富氢气氛下CO优先氧化性能

分别以Al₂O₃, SiO₂和C₃N₄为载体, 通过简单浸渍法制备了3种负载型Pd-Cu催化剂(PC-Al₂O₃, PC-SiO₂, PC-C₃N₄), 考察了其在室温下富氢气氛中CO优先氧化反应性能. 采用X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 氮气物理吸附仪(N₂-physisorption)、 氢气程序升温还原(H₂-TPR)、 二氧化碳程序升温脱附(CO₂-TPD)、 X射线光电子能谱(XPS)和原位漫反射傅里叶变换红外光谱(In situ DRIFTS)等手段对其进行了表征. 结果表明, 与PC-SiO₂和PC-C₃N₄相比, PC-Al₂O₃具有更高的CO优先氧化性能. 这是由于PC-Al₂O₃上形成了大量与Pd物种具有强相互作用的Cu₂Cl(OH)₃物种; 而PC-SiO₂中仅有少量的Cu₂Cl(OH)₃, 且与Pd物种相互作用较弱; PC-C₃N₄中Cu物种则更易与C₃N₄基质配位, 由此削弱了Pd, Cu之间的相互作用. 在反应气氛下PC-Al₂O₃表面还易形成具有更强CO活化能力的Pd⁺物种, 通过与大量Cu⁺物种紧密相互作用, 在一定程度上抑制Pd⁺被过度还原为Pd⁰, 从而维持了其催化活性. 与SiO₂和C₃N₄相比, Al₂O₃更适合负载Pd-Cu用于富氢气氛下CO优先氧化反应.     

In situ Carbon Modification of g-C3N4 from Urea co-Crystal with Enhanced Photocatalytic Activity Towards Degradation of Organic Dyes Under Visible Light

An in situ strategy was introduced for synthesizing carbon modified graphitic carbon nitride(g-C₃N₄) by using urea/4-aminobenzoic acid(PABA) co-crystal(PABA@Urea) as precursor materials. Via co-calcination of the PABA co-former and the urea in PABA@Urea co-crystals, C guest species were generated and compounded into g-C₃N₄ matrix in situ by replacing the lattice N of the carbon nitride and forming carbon dots onto its layer surface. The carbon modification dramatically enhanced visible-light harvesting and charge carrier separation. Therefore, visible light photo-catalytic oxidation of methylene blue(MB) pollution in water over the carbon modified g-C₃N₄(C/g-C₃N₄) was notably improved. Up to 99% of methylene blue(MB) was eliminated within 60 min by the optimal sample prepared from the PABA@Urea co-crystal with a PABA content of 0.1%(mass ratio), faster than the degradation rate over bare g-C₃N₄. The present study demonstrates a new way to boost up the photocatalysis performance of g-C₃N₄, which holds great potential concerning the degradation of organic dyes from water.     

Cu2+改性g-C3N4光催化剂的光催化性能

Photocatalytic technology can effectively solve the problem of increasingly serious water pollution, the core of which is the design and synthesis of highly efficient photocatalytic materials. Semiconductor photocatalysts are currently the most widely used photocatalysts. Among these is graphitic carbon nitride (g-C₃N₄), which has great potential in environment management and the development of new energy owing to its low cost, easy availability, unique band structure, and good thermal stability. However, the photocatalytic activity of g-C₃N₄ remains low because of problems such as wide bandgap, weakly absorb visible light, and the high recombination rate of photogenerated carriers. Among various modification strategies, doping modification is an effective and simple method used to improve the photocatalytic performance of materials. In this work, Cu/g-C₃N₄ photocatalysts were successfully prepared by incorporating Cu²⁺ into g-C₃N₄ to further optimize photocatalytic performance. At the same time, the structure, morphology, and optical and photoelectric properties of Cu/g-C₃N₄ photocatalysts were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, UV-Vis diffuse reflectance spectroscopy (DRS), and photoelectric tests. XRD and XPS were used to ensure that the prepared photocatalysts were Cu/g-C₃N₄ and the valence state of Cu was in the form of Cu²⁺. Under visible light irradiation, the photocatalytic activity of Cu/g-C₃N₄ and pure g-C₃N₄ photocatalysts were investigated in terms of the degradation of RhB and CIP by comparing the amount of introduced copper ions. The experimental results showed that the degradation ability of Cu/g-C₃N₄ photocatalysts was stronger than that of pure g-C₃N₄. The N₂ adsorption-desorption isotherms of g-C₃N₄ and Cu/g-C₃N₄ demonstrated that the introduction of copper had little effect on the microstructure of g-C₃N₄. The small difference in specific surface area indicates that the enhanced photocatalytic activity may be attributed to the effective separation of photogenerated carriers. Therefore, the enhanced photocatalytic degradation of RhB and CIP over Cu/g-C₃N₄ may be due to the reduction of carrier recombination rate by copper. The photoelectric test showed that the incorporation of Cu²⁺ into g-C₃N₄ could reduce the electron-hole recombination rate of g-C₃N₄ and accelerate the separation of electron-hole pairs, thus enhancing the photocatalytic activity of Cu/g-C₃N₄. Free radical trapping experiments and electron spin resonance indicated that the synergistic effect of superoxide radicals (O₂^•−), hydroxyl radicals (•OH) and holes could increase the photocatalytic activity of Cu/g-C₃N₄ materials.     

Ni,Co基硒化物修饰g-C3N4光催化产氢研究

Developing novel and efficient catalysts is a significant way to break the bottleneck of low separation and transfer efficiency of charge carriers in pristine photocatalysts. Here, two fresh photocatalysts, g-C₃N₄@Ni₃Se₄ and g-C₃N₄@CoSe₂ hybrids, are first synthesized by anchoring Ni₃Se₄ and CoSe₂ nanoparticles on the surface of well-dispersed g-C₃N₄ nanosheets. The resulting materials show excellent performance for photocatalytic in situ hydrogen generation. Pristine g-C₃N₄ has poor photocatalytic hydrogen evolution activity (about 1.9 μmol·h^-1) because of the rapid recombination of electron-hole pairs. However, the hydrogen generation activity is well improved after growing Ni₃Se₄ and CoSe₂ on the surface of g-C₃N₄, owing to the unique effect of these selenides in accelerating the separation and migration of charge carriers. The hydrogen production activities of G-C₃N₄@Ni₃Se₄ and g-C₃N₄@CoSe₂ are about 16.4 μmol·h^-1 and 25.6 μmol·h^-1, which are 8-fold and 13-fold that of pristine g-C₃N₄, respectively. In detail, coupling Ni₃Se₄ and CoSe₂ with g-C₃N₄ greatly improves the light absorbance density and extends the light response region. The photoluminescence intensity of the photoexcited Eosin Y dye in the presence of g-C₃N₄@Ni₃Se₄ and g-C₃N₄@CoSe₂ is weaker than that in the presence of pure g-C₃N₄. On the other hand, the upper limit of the electron-transfer rate constants in the presence of g-C₃N₄@Ni₃Se₄ and g-C₃N₄@CoSe₂ is greater than that in the presence of pure g-C₃N₄. Among the g-C₃N₄@Ni₃Se₄@FTO, g-C₃N₄@CoSe₂@FTO, and g-C₃N₄@FTO electrodes, the g-C₃N₄@FTO electrode has the lowest photocurrent density and the highest electrochemical impedance, implying that the introduction of CoSe₂ and Ni₃Se₄ onto the surface of g-C₃N₄ enhances the separation and transfer efficiency of photogenerated charge carriers. In other words, the formation of two star metals selenide based on g-C₃N₄ can efficiently inhibit the recombination of photogenerated charge carriers and accelerate photocatalytic water splitting to generate H₂. Meanwhile, the right shift of the absorption band edge effectively reduces the transition threshold of the photoexcited electrons from the valence band to the conduction band. In addition, the more negative zeta potential for the g-C₃N₄@Ni₃Se₄ and g-C₃N₄@CoSe₂ catalysts as compared with that for pure g-C₃N₄ leads to a notable enhancement in the adsorption of protons by the sample surface. Moreover, the results of density functional theory calculations indicate that the hydrogen adsorption energy of the N sites in g-C₃N₄ is -0.22 eV; further, the hydrogen atoms are preferentially adsorbed at the bridge site of two selenium atoms to form a Se―H―Se bond, and the adsorption energy is 1.53 eV. In-depth characterization has been carried out by transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, transient photocurrent measurements, and Fourier transform infrared spectroscopy; the results of these experiments are in good agreement with one another.