TiO2-yNx纳米光催化剂的制备及其可见光响应机理

利用溶胶-凝胶技术,以尿素为氮源,采用原位掺杂方式制备了TiO2-yNx纳米粉体;以亚甲基蓝(MB)溶液在可见光下的光催化降解评价其可见光催化活性;考察了体系初始pH值、N的掺杂量和焙烧温度对样品可见光催化活性的影响。 结合XRD、XPS、ESR和DRS测试技术,研究了N掺杂纳米TiO2的可见光响应机理。 研究结果表明,TiO2-yNx纳米粉体的优化制备工艺条件为：体系初始pH=0.52,掺杂比n(N)∶n(Ti)=1∶6,焙烧温度为440 ℃。 此条件下制备的样品N含量为0.77%,为单一的锐钛矿相,平均粒径为19.0 nm,具有良好的可见光催化活性。 N掺杂导致TiO2纳米粉体的表面羟基含量增加,形成了大量束缚单电子的氧空位;N取代晶格O形成了N-Ti-O和O-N-Ti键合结构。 N掺杂导致TiO2纳米粒子的吸收带边红移,对可见光的吸收能力明显增强,这表明N掺杂改变TiO2电子结构,使带隙窄化,降低光响应阈值。 N掺杂TiO2纳米粒子的可见光响应归因于N取代掺杂形成的掺杂能级与氧空位形成的缺陷能级共同作用所致。     

La掺杂Bi2O3的制备、表征与可见光催化活性

采用浸渍法制备了La掺杂Bi2O3(La-Bi2O3)光催化剂,利用X射线荧光光谱(XRF)、X射线衍射(XRD)、扫描电子显微镜(SEM)、傅立叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis)和光致发光谱(PL)等分析测试手段对样品的La掺杂量、晶体结构和光谱特征等进行了表征,并以2,4-二氯苯酚(2,4-DCP)水溶液的降解作为探针反应,考察了样品的可见光催化性能.结果表明,适量的La掺杂能有效抑制Bi2O3由四方相向单斜相转变,并将光吸收范围拓展到550 nm以上.掺杂的La可取代Bi2O3晶格中部分Bi,形成Bi—O—La键,并生成了少量镧铋复合氧化物(La0.176Bi0.824O1.5),它们的存在能有效抑制光生电子-空穴对的复合,从而提高光催化量子产率.可见光照射下2,4-DCP的光催化降解实验表明,La-Bi2O3具有良好的可见光催化性能,并且当La的掺杂量为3%(摩尔分数)时,催化剂的可见光催化效率最高.     

Dual C(sp3)−H Bond Functionalization of N‐Heterocycles through Sequential Visible‐Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions

Herein we describe a mild method for the dual C(sp³)?H bond functionalization of saturated nitrogen‐containing heterocycles through a sequential visible‐light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well‐established use of iminium ion and α‐amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp³)?H bonds.     

Synthesis of β‐Substituted γ‐Aminobutyric Acid Derivatives through Enantioselective Photoredox Catalysis

β‐Substituted chiral γ‐aminobutyric acids feature important biological activities and are valuable intermediates for the synthesis of pharmaceuticals. Herein, an efficient catalytic enantioselective approach for the synthesis of β‐substituted γ‐aminobutyric acid derivatives through visible‐light‐induced photocatalyst‐free asymmetric radical conjugate additions is reported. Various β‐substituted γ‐aminobutyric acid analogues, including previously inaccessible derivatives containing fluorinated quaternary stereocenters, were obtained in good yields (42–89 %) and with excellent enantioselectivity (90–97 % ee). Synthetically valuable applications were demonstrated by providing straightforward synthetic access to the pharmaceuticals or related bioactive compounds (S)‐pregabalin, (R)‐baclofen, (R)‐rolipram, and (S)‐nebracetam.     

粉煤灰漂珠负载Bi2WO6复合材料的制备及光催化性能研究

以工业固体废弃物粉煤灰漂珠(fly ash cenospheres, FACs)为载体, 采用水热法制备了新颖的漂珠负载Bi₂WO₆复合材料(Bi₂WO₆/FACs), 通过X射线衍射(XRD), 扫描电子显微镜(SEM), X-射线光电子能谱(XPS), 和紫外-可见漫反射光谱(DRS)技术对其进行了表征。XRD数据显示了正交相Bi₂WO₆的特征衍射峰。DRS结果证实了引入FACs后Bi₂WO₆对可见光的吸收增强。在可见光的照射下, 以亚甲基蓝溶液的光催化降解评价了Bi₂WO₆/FACs复合材料的光催化性能。结果表明：Bi₂WO₆/FACs的光催化性能优于纯Bi₂WO₆的, 其一级反应速率常数(k)为后者的2.4倍。尤其是由于漂珠质轻中空的特性, Bi₂WO₆/FACS复合光催化剂可长时间漂浮于水面, 既能充分吸收光能, 又有利于催化剂的回收和重复利用。     

Merging Visible‐Light Photocatalysis and Palladium Catalysis for C−H Acylation of Azo‐ and Azoxybenzenes with α‐Keto Acids

An efficient C?H acylation of azo‐ and azoxybenzenes with α‐keto acids has been developed by a combination of palladium catalysis and visible‐light photoredox catalysis at room temperature under 1.5 W blue LED irradiation. This method tolerates a variety of disubstituted azo‐ and azoxybenzenes, as well as α‐keto acids regardless of the nature of the substituents. A number of aryl ketones were obtained in good yields under mild reaction conditions.     

Facile Synthesis of Porous g-C3N4 with Enhanced Visible-Light Photoactivity

Porous graphitic carbon nitride (g-C₃N₄) was prepared by dicyandiamide and urea via the pyrolysis method, which possessed enhanced visible-light-driven photocatalytic performance. Its surface area was increased from 17.12 to 48.00 m²/g. The porous structure not only enhanced the light capture capacity, but also accelerated the mass transfer ability. The Di (Dicyandiamide)/Ur (Urea) composite possessed better photocatalytic activity for Rhodamine B in visible light than that of g-C₃N₄. Moreover, the Di/Ur-4:5 composite showed the best photoactivity, which was almost 5.8 times that of g-C₃N₄. The enhanced photocatalytic activity showed that holes and superoxide radical played a key role in the process of photodegradation, which was ascribed to the enhanced separation of photogenerated carriers. The efficient separation of photogenerated electron-hole pairs may be owing to the higher surface area, O dopant, and pore volumes, which can not only improve the trapping opportunities of charge carriers but also the retarded charge carrier recombination. Therefore, it is expected that the composite would be a promising candidate material for organic pollutant degradation.     

Mo掺杂对纳米TiO2结构和活性的影响

利用Mo6 的掺杂在TiO2中引入缺陷,从而扩大TiO2催化剂的光谱响应范围。运用UV-Vis、XRD、XPS、TG-DTA等测试技术考察了钼离子掺杂浓度对于TiO2光催化剂吸收光谱范围、晶型、晶胞和晶粒的影响,分析了钼进入TiO2品格的方式、价态和掺杂催化剂在热处理过程中发生的物理和化学变化。以亚甲蓝溶液的光催化降解为模型反应,考察了掺杂量对这种新型光催化剂的光催化活性的影响。结果表明,Mo6 可进入TiO2晶格中形成杂质缺陷,引起TiO2品格膨胀,Mo6 的掺杂量影响TiO2晶粒尺寸和晶相转化。Mo6 掺杂的质量分数为4．5％时,样品的吸收带边可达460 nm,对40 mg/L亚甲蓝反应2 h的降解率为58．3％,矿化率为52．5%。而Mo6 的掺杂质量分数为3．0％和6．0％时,形成的TiO2晶粒尺寸较小,TiO2晶粒中锐钛矿相与金红石相的比例接近4:1时,对亚甲蓝降解率分别为56．6％和52．0％,矿化率分别为49．2％和44．2％。     

Bi/TiO2复合纳米纤维制备及可见光催化性能

以电纺TiO₂纳米纤维为基质,EDTA为鳌合剂和吸附剂,采用溶剂热法制备Bi/TiO₂复合纳米纤维光催化材料,利用X射线粉末衍射（XRD）、扫描电镜（SEM）、X射线能量色散谱（EDS）、透射电镜（TEM）、紫外-可见漫反射光谱（UV-Vis DRS）和荧光光谱（PL）等分析测试手段对样品的物相、形貌和光学性能等进行表征,以罗丹明B（RhB）为模拟有机污染物,考察了样品的光催化性能。结果表明：EDTA在复合纳米纤维的合成过程中起到关键作用,通过改变EDTA的用量可以有效控制纤维表面构筑单质Bi纳米球的大小和覆盖密度。所制备的复合纳米纤维具有良好的可见光催化活性和稳定性,当单质Bi的负载量为65%时光催化活性最强,可见光照射180 min,RhB的降解率达到96.40%,循环使用5次降解率仍保持在91%以上。