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1.
采用介质阻挡放电等离子体法合成了氧原子掺杂的具有氮空穴的石墨相氮化碳催化剂(g-C3N4), 并对催化剂的结构和形貌进行了表征分析. 结果表明, 等离子体处理没有改变催化剂的形貌, 并同时将氮空穴和氧原子引入了g-C3N4的晶格. 在可见光条件下, 制备的共掺杂g-C3N4催化剂的铵离子产率高达5.9 mg·L -1·h -1· g cat - 1 , 分别是具有氮空穴的g-C3N4和纯g-C3N4的2.2倍和20倍, 同时还表现出优异的催化稳定性. 密度泛函理论计算结果显示, 与具有氮空穴的g-C3N4相比, 氧原子的引入能提高氮空穴对反应物氮气分子的活化能力, 提高光催化固氮性能.  相似文献   

2.
郭红霞  崔继方  刘利 《应用化学》2020,37(3):256-263
利用太阳能和半导体光催化剂,将CO2光催化还原转变成碳氢燃料,是缓解温室效应、全球变暖、环境污染和能源危机等一系列问题的理想途径。 本文对氧空位增强的光催化还原CO2反应机理进行归纳,并分别针对还原产物为C1和C2组分的光催化体系进行概括总结。 作为CO2光催化还原过程的第一步,CO2捕获光催化剂导带上的电子生成CO2·-是反应的速控步骤。 氧空位的引入及其带来的金属配位不饱和点,利于CO2捕获电子生成CO2·-,进而促进CO2光催化还原过程。 最后,提出当前氧空位增强光催化还原CO2过程仍然存在的问题,且对发展前景进行展望。  相似文献   

3.
在室温下采用离子交换法制备了四足状、 立方体状和十二面体状Ag3PO4微晶及Ag3PO4块体, 并进行了表征. 以Ag3PO4微/纳米和块体材料热力学性质的区别为基础, 结合化学热力学理论和热动力学基本原理, 导出摩尔表面热力学关系式. 在此基础上, 采用原位微量热技术获取Ag3PO4的化学反应动力学信息和表面热力学函数, 讨论了形貌和温度对表面热力学性质变化的影响. 结果表明, 四足状Ag3PO4的摩尔表面焓(Hms)、 摩尔表面Gibbs自由能(Gms)和摩尔表面熵(Sms)最大, 立方体状次之, 十二面体状最小; HmsSms随温度的升高而增大, Gms则随温度的升高而减小.  相似文献   

4.
采用溶胶-凝胶法用SO42-部分代替Li3Fe2(PO4)3中的PO43-阴离子制得Li3-xFe2(PO4)3-x(SO4)x(x=00.90)正极材料, 通过X射线衍射、 充放电技术、 循环伏安特性测试及电化学阻抗谱表征了掺杂材料的相组成及电化学性能. 结果表明, SO42-主要以固溶形式存在于Li3Fe2(PO4)3中, 产物中还伴有少量Fe2O3第二相析出. SO42-掺杂使Li3Fe2(PO4)3的放电容量呈抛物线形规律变化, 并在掺杂浓度x=0.60时达到最佳值, 该样品在0.5C倍率下的首次放电容量为111.59 mA·h/g, 比未掺杂的样品提高了18.4%; 60次循环充放电后的容量保持率为96%; 将该样品的放电倍率由0.5C逐渐提高至5C, 再降至0.5C, 并在每个倍率下循环10次, 材料的最终放电容量仍能达到首次放电容量的97%. 导致这些变化的原因是SO42-掺杂使材料的氧化还原性能增强, 电池内阻减小, 极化程度降低及Li+扩散系数增大.  相似文献   

5.
基于变色多酸P2Mo18O626-与绿光Tb3+之间的功能互补及分子间能量转移的原理, 在维生素C(VC)的还原下, P2Mo18O626-@Tb3+溶液由浅黄色变为蓝色, 发生荧光猝灭; 相反, 在H2O2氧化下, 溶液的蓝色褪去, 荧光得以恢复, P2Mo18O626-@Tb3+溶液呈现出可逆的化学响应变色及荧光开关性质. 利用紫外-可见(UV-Vis)及荧光(PL)光谱法对VC浓度进行定量检测, 分别以800 nm处的吸光度和 547 nm处荧光强度的对数值对VC浓度作图, 获得光谱法对VC检测的线性方程, 检出限分别为3.40×10-3和0.21 μmol/L; 利用UV-Vis及PL动力学方法对VC和H2O2检测的响应速度进行了考察, 响应时间分别为52和320 s; 通过UV-Vis光谱及动力学方法考察了VC检测的选择性及可重复使用性.  相似文献   

6.
通过使用二丙烯基三胺为结构导向剂, 在水热体系中合成出一例具有新型三维开放骨架结构的磷酸铁化合物JU94(2H3O[Fe2P2O8(OH)2]). 单晶X射线衍射分析结果显示, 该化合物结晶在单斜晶系P21/c空间群, 晶胞参数a=0.97566(5) nm, b=0.98560(5) nm, c=1.24514(5) nm, β=129.651(3)°, V=0.92189(8) nm3. 该化合物的骨架结构是由FeO6八面体和PO4四面体连接构成, 以四核铁簇作为结构构筑单元. JU94沿[101], [1ˉ01], [010]和[111]方向含有扭曲八元环孔道, 水分子分布于孔道中. 穆斯堡尔谱研究结果表明, 该结构具有2个晶体学独立的正三价铁离子. 磁性研究结果表明, 该物质具有反铁磁性.  相似文献   

7.
半导体光催化技术不仅可以将太阳能转化为化学能,还可以直接降解和矿化有机污染物,因此其在抑制环境污染和解决能源短缺方面具有广阔的应用前景。类石墨相氮化碳(g-C3N4)具有独特的电子能带结构、优异的热稳定性以及化学稳定性,因此g-C3N4作为一种廉价的无金属光催化剂被广泛应用于光解水制氢产氧、污染物降解、光催化CO2还原、抗菌和有机官能团选择性转换等领域。然而,传统热缩聚法合成的g-C3N4光催化剂比表面积小、禁带宽度大、光生电子-空穴易于复合、光生载流子传输慢,抑制了其光催化活性。为了进一步提高g-C3N4的光催化活性,出现了多种改性方法。本文针对g-C3N4光催化剂的改性研究,综述了近年来国内外在g-C3N4光催化剂改性方面的重要研究进展,如采用模板法优化g-C3N4的纳米结构、元素掺杂及共聚合调控g-C3N4的能带结构、贵金属沉积或半导体复合提高光生载流子分离效率等。最后,本文还展望了g-C3N4光催化剂在改性方面的未来发展趋势。  相似文献   

8.
以三甲基氯硅烷、 γ-氯丙基三氯硅烷、 1,4-二氯丁烷和咪唑等为原料合成了一种新型的四硅氧烷Gemini咪唑表面活性剂([Si4-4-Si4im]Cl2), 通过质谱(MS)和核磁共振氢谱(1H NMR)证明所得产物为目标产物. 通过Wilhelmy板法测得其在25 ℃下的临界胶束浓度(cmc)为0.54 mmol/L, 水溶液的表面张力(γcmc)降至18.6 mN/m. 通过电导率法研究了其胶束形成热力学参数(ΔGm 0Hm 0和ΔSm 0), 表明在15~35 ℃下其胶束化过程是自发进行的, 且为熵驱动过程.  相似文献   

9.
研究了腐植酸(HA)存在下冰相体系中γ-六氯环己烷(γ-HCH)的光转化规律. 结果表明, HA浓度对γ-HCH的光转化率呈现低浓度促进而高浓度抑制的现象; 盐离子浓度、 NO2-及NO3-γ-HCH的光转化率均有促进作用; 低浓度Fe3+γ-HCH的光转化率有促进作用, 当Fe3+的浓度增大到50 μmol/L时, 呈现抑制效应; γ-HCH在不同pH值条件下光转化速率的大小顺序为碱性>中性>酸性. 冰相中HA通过产生单线态氧(1O2)、 羟基自由基(·OH)及三重激发态(HA*)加速γ-HCH的光转化. HA存在下γ-HCH的光转化产物主要是五氯环己烯、 邻二氯苯和对二氯苯、 一氯苯, 光转化过程中1O2通过消耗中间产物间接加速了γ-HCH的光转化过程.  相似文献   

10.
采用共沉淀法, 固定Mg2+/(Al3++Ti4+)摩尔比为3.00, 改变Ti4+/(Al3++Ti4+)摩尔比(RTi, 0~0.40), 合成了5个Mg-Al-Ti-CO3层状双氢氧化物(LDHs)样品, 并进行了表征. 采用电势滴定、 盐滴定和电势质量滴定法, 测定了其结构电荷密度(σst)、 零净电荷点(pHPZNC)和零净质子电荷点(pHPZNPC)等, 并基于普适1-pK和2-pK模型得出其表面羟基酸碱反应特征平衡常数(pK, pKa1int和pKa2int), 考察了RTi对LDHs晶体结构和界面电化学性质的影响. 研究结果表明, 随着RTi增大,晶胞常数和层间距均增大, 可归因于Ti4+离子间强静电排斥作用. pHPZNC和pHPZNPC以及pK, pKa1int和pKa2int均随RTi的增大而有增大的趋势, 表明表面羟基去质子化趋势降低. 各LDHs样品的pHPZNPC值低于其pHPZNC值, 且随电解质(NaNO3)浓度的增大而升高, 可归因于结构正电荷效应.  相似文献   

11.
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, ·O2-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.  相似文献   

12.
本文通过在双氰胺前驱体中添加聚乙二醇,在缩聚过程实现碳掺杂形成含氮空位的g-C3N4光催化剂。通过X射线衍射(XRD)、红外光谱(FTIR)、光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis)和荧光谱(FL)等表征手段,考察了原位聚合碳掺杂形成氮空位对g-C3N4物相结构、组分与化学态、光吸收性能及光催化活性的影响。研究结果表明,采用该方法可实现原位聚合碳掺杂,有效拓展g-C3N4的可见光吸收至850 nm,在紫外-可见光与可见光照射下光降解RhB及光催化产氢性能均显著提高,尤其可见光条件下的性能提升更为显著。  相似文献   

13.
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.  相似文献   

14.
使用尿素、 红磷和氯化镍为原料, 通过一种简单的焙烧方法合成了Ni5P4/g-C3N4光催化剂. 该催化剂形成的异质结可以降低界面电阻, 有效抑制光生电子-空穴对复合率. 以罗丹明B模拟污染物进行降解测试, 发现3NPC的反应速率常数最高, 几乎是g-C3N4的7倍, 并具有最高的光催化产氢能力, 制氢速率高达1013.88 μmol·g-1·h-1, 明显高于g-C3N4(664.38 μmol·g-1·h-1).  相似文献   

15.
g-C3N4 have been widely used in the fields of photocatalytic hydrogen production,photocatalytic degradation of dyes and oxidative degradation of toxic gases due to their excellent performance.It has attracted extensive attention in recent years due to its highly efficient photocatalytic capacity of hydrogen generation,water oxidation,carbon dioxide reduction and degradation of organic pollutants.Because of the abundant carbon and nitrogen composition of the earth,large-scale production and industrial applications of this material are possible.The modification of this material makes its performance more excellent so that this new material can obtain a steady stream of vitality.These outstanding works have become important materials and milestones on the road to mankind's photocatalytic hydrogen production.This review will begin with the basic idea of designing,synthesizing and improving g-C3N4 based photocatalytic materials,and introduce the latest development of g-C3N4 photocatalysts in hydrogen production from four aspects of controlling the carbon/nitrogen ratio,morphology,element doping and heterojunction structure of g-C3N4 materials.  相似文献   

16.
以双氰胺、醋酸锌、钼酸铵、醋酸镉和硫化钠为原料,采用水热法合成了一系列Zn-Mo共掺杂CdS(Zn-Mo-CdS),并与g-C3N4组成异质结催化剂(Zn-Mo-CdS/g-C3N4)。采用X射线衍射光谱(XRD)、紫外-可见(UV-Vis)光谱、电感耦合等离子体-原子发射光谱(ICP-AES)、电化学阻抗谱(EIS)、X光电子能谱(XPS)等分析手段对制备的催化剂进行了表征。结果表明, Zn-Mo-CdS与g-C3N4之间紧密结合并形成异质结,促进界面电荷迁移,抑制光生电子-空穴对的复合。以可见光下降解染料罗丹明B (RhB)为探针反应考察了催化剂性能。结果表明, Zn-Mo-CdS/g-C3N4异质结催化剂的光催化性能与单纯g-C3N4、Zn-Mo-CdS及双金属硫化物/g-C3N4异质结催化剂相比均有大幅度提高,质量比m(Zn-Mo-CdS)/m(g-C3N4) = 4 : 1时制备的异质结催化剂表现出最大的降解速率常数,是单纯g-C3N4和Zn-Mo-CdS的30倍和10倍。不仅Zn-Mo-CdS,其他三元金属复合硫化物如Mo-Ni-CdS和Ni-Sn-CdS与g-C3N4之间也能有效构筑异质结,促进电子-空穴对的分离和催化性能提升。  相似文献   

17.
Since Fujishima and Honda demonstrated the photoelectrochemical water splitting on TiO2 photoanode and Pt counter electrode, photocatalysis has been considered as one of the most promising technologies for solving both the problems of environmental pollution and energy shortage. This process can effectively use solar energy, the most abundant energy resource on the earth, to drive various catalytic reactions, such as water splitting, CO2 reduction, organic pollutant degradation, and organic synthesis, for energy generation and environmental purification. Except for the various metal-based semiconductors, such as metal oxides, metal sulfides, and metal oxynitrides, developed for photocatalysis, graphitic carbon nitride (g-C3N4) has attracted significant attention in the recent years because of its earth abundancy, non-toxicity, good stability, and relatively narrow band gap (2.7 eV) for visible light response. However, g-C3N4 suffers from insufficient absorption of visible light in the solar spectrum and rapid recombination of photogenerated electrons and holes, thus resulting in low photocatalytic activity. Until now, various strategies have been developed to enhance the photocatalytic activity of g-C3N4, including element doping, nanostructure and heterostructure design, and co-catalyst decoration. Among these methods, element doping has been found to be very effective for adjusting the unique electronic and molecular structures of g-C3N4, which could significantly expand the range of photoresponse under visible light and improve the charge separation. Especially, non-metal doping has been well investigated frequently to improve the photocatalytic activity of g-C3N4. The non-metal dopants commonly used for the doping of g-C3N4 include oxygen (O), phosphorus (P), sulfur (S), boron (B), and halogen (F, Cl, Br, I) and also carbon (C) and nitrogen (N) (for self-doping), as they are easily accessible and can be introduced into the g-C3N4 framework through different physical and chemical synthetic methods. In this review article, the structural and optical properties of g-C3N4 is introduced first, followed by a brief introduction to the modification of g-C3N4 as photocatalysts. Then, the progress in the non-metal doped g-C3N4 with improved photocatalytic activity is reviewed in detail, with the photocatalytic mechanisms presented for easy understanding of the fundamentals of photocatalysis and for guiding in the design of novel g-C3N4 photocatalysts. Finally, the prospects of the modification of g-C3N4 for further advances in photocatalysis is presented.  相似文献   

18.
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.  相似文献   

19.
兼具高光学质量和电化学性能的薄膜光电极难以制备, 限制了光电催化氧化技术在水处理中的的应用. 本文采用原位煅烧法制备了负载在氧化铟锡(ITO)玻璃上的石墨相氮化碳(g-C3N4)薄膜电极, 并通过掺杂K+提高其光电催化氧化性能; 对电极进行了表征, 研究了其光电催化氧化降解水中双氯芬酸钠(DCF)的效率及降解路径. 结果表明, 原位煅烧法能制备出高质量的K+/g-C3N4薄膜光电极, K+的掺杂并未明显改变电极上g-C3N4的晶型、 价态和多孔形貌, 但可以提高ITO玻璃上g-C3N4的负载量, 增强电极对可见光的响应; K+的最佳掺杂浓度为0.002 mol/L, K+/g-C3N4薄膜电极光电催化氧化降解DCF的速率常数是纯g-C3N4薄膜电极的1.86倍; 当初始pH值为4, 电压为1 V, 光源强度为0.96 W/cm2, 反应2 h后水中DCF降解率达到70%. K+/g-C3N4薄膜电极光电催化氧化过程中, 光催化氧化和电化学氧化之间存在协同作用, 两者相互增强, 并提高了反应过程中光生 空穴(h+)和羟基自由基(·OH)浓度, 在这两种活性物质作用下, 水中DCF分别被h+氧化生成咔唑衍生物、 与·OH发生加成反应生成多羟基芳香化合物, 最后开环生成小分子物质.  相似文献   

20.
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.  相似文献   

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