碳纳米管的表面修饰及TiO2-CNTs复合催化剂的光催化性能

运用酸氧化和聚乙烯醇表面修饰碳纳米管, 修饰的碳纳米管的水分散性能显著改善. 进一步地运用低温水热法合成表面修饰的碳纳米管复合TiO₂, 观察到了复合催化剂紫外及可见光激发下的光催化性能的明显提升. 红外光谱、X光电子能谱、差热-热重分析、X光衍射、Brunauer-Emmett-Teller低温氮吸附、透射电镜及紫外-可见漫反射光谱等表征表明, 复合催化剂光催化性能改善与碳纳米管良好水溶液分散性能导致的TiO₂在修饰的碳纳米管表面的均匀、致密分散和密切键合, 从而充分利用碳纳米管的功能密切关联.     

Bioinspired Hierarchical Nanotubular Titania Immobilized with Platinum Nanoparticles for Photocatalytic Hydrogen Production

A bioinspired nanocomposite composed of platinum nanoparticles and nanotubular titania was fabricated in which the titania matter was templated by natural cellulose substance. The composite possesses three‐ dimensional hierarchical structures, and ultrafine metallic platinum particles with sizes of ca. 2 nm were immobilized uniformly on the surfaces of the titania nanotubes. Such a nanocomposite with 1.06 wt % of platinum content shows the optimal photocatalytic hydrogen production activity from water splitting of 16.44 mmol h^?1 g^?1, and excessive loading of platinum results in poorer photocatalytic performance. The structural integrity of the nanocomposite upon cyclic water‐splitting processes results in its sufficient photocatalytic stability.     

石墨相氮化碳的共轭交联修饰及其对可见光催化产氢性能的影响

石墨相氮化碳(GCN)具有廉价易制和高度稳定性, 在光催化分解水制氢领域备受关注, 但其较窄的光谱响应范围和较低的光生电荷分离和转移效率制约了其光催化性能. 采用4,4'-(苯并[c][1,2,5]噻二唑-4,7-二基)二苯甲醛(BTD)与热聚法合成的GCN在260 ℃进行酸催化席夫碱反应, 使GCN片层发生共轭交联反应和表面修饰, 制备了四个BTD改性的氮化碳材料GCN-BTD_x (x为20、40、80和160, 代表每100 mg GCN原料对应BTD的毫克用量). 其中, GCN-BTD₁₆₀表现出最高的光催化还原水制氢性能, 制氢速率为863 μmol•g^–1•h^–1, 是未修饰GCN的2倍, 且展示出优秀的循环利用性能. 研究发现, BTD修饰拓宽了材料的光吸收范围, 调节了材料的能带结构, 提高了电荷分离效率并降低了界面的电荷转移阻力, 从而提高了材料的可见光催化制氢性能.     

SiO2-Coated ZnO Nanoflakes Decorated with Ag Nanoparticles for Photocatalytic Water Oxidation

Many strategies have been adopted to improve the photoinduced features of zinc oxide nanostructures for different application fields. In this work, zinc oxide has been synthesised and decorated by plasmonic metal nanoparticles to enhance its photocatalytic activity in the visible range. Furthermore, an insulating layer of SiO₂ has been grown between the surface of zinc oxide nanoflakes and silver nanoparticles. A synthetic procedure that allows the accurate modulation of the insulating layer thickness in the range 5–40 nm has been developed. Evidences highlight the crucial role of the SiO₂ layer in dramatically increasing photocatalytic water oxidation promoted by the nanostructure under both UV and visible illumination. An ideal thickness value of about 10 nm has been demonstrated to guarantee the plasmon-induced resonance energy-transfer process and to quench the Förster resonance energy-transfer mechanism; thus, optimising the local surface plasmon resonance effect and water oxidation properties.     

还原氧化石墨烯/介孔TiO2复合材料的合成及其光解水制氢性能

采用溶胶凝胶法,以钛酸四异丙酯(TTIP)为钛源,十六烷基三甲基溴化铵(CTAB)为模板剂合成了介孔二氧化钛样品mTiO_2,考察了合成温度、水量、模板剂用量和焙烧温度对其在紫外光条件下光催化产氢活性的影响。结果显示,在350℃下焙烧后,样品由无定形结构转变为锐钛矿相;随着焙烧温度的提高,锐钛矿相结构产物的结晶度提高,当焙烧温度超过550℃后,样品大部分转变为金红石相。以合成温度为30℃,模板剂用量(nCTAB/nTiO_2)为0.2,水量(nH2O/nTiO_2)为100,焙烧温度为450℃条件下合成的m-TiO_2样品为催化剂,当催化剂用量为0.4 g·L-1,体系中甲醇浓度高于20%(V/V)时,其紫外光条件下的光催化产氢活性达170 mmol·g-1·h-1。采用水热法将氧化石墨烯(GO)与m-TiO_2复合制备了一系列还原氧化石墨烯/介孔TiO_2复合材料(rGO/m-TiO_2),其晶相结构为锐钛矿相。当r GO复合量(wGO/wTiO_2)为0.01时,样品在紫外光下的产氢活性为241 mmol·g-1·h-1,能量转化效率达7.4%,较未复合样品提高了42.3%;在可见光条件下,其产氢活性达9 mmol·g-1·h-1。     

一步法制备二氧化钛-金复合材料及其光解水制氢性能

以钛粉为还原剂,氯金酸为氧化剂,将二者在180 ℃水热反应釜中发生氧化还原反应,最终生成直径800 nm左右的TiO₂,比表面积为3.5 m²/g左右,其表面均匀担载了直径20 nm左右的金纳米颗粒。 采用X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、X射线光电子能谱分析(XPS)、紫外可见漫反射光谱、光电流密度、光催化制氢性能等测试表征了该复合催化剂的结构及性能。 结果表明,一步法制备的复合催化剂形貌规整,TiO₂为锐钛矿晶型,金纳米颗粒的局域表面等离子体共振(LSPR)作用促进了催化剂对可见光有较强的吸收,催化剂催化产氢性能伴随金含量增大存在先增后减规律,可见光下最大产氢速率为0.1 μmol/(g·h),光催化活性表现稳定。     

Alloyed ZnS–CuInS2 Semiconductor Nanorods and Their Nanoscale Heterostructures for Visible‐Light‐Driven Photocatalytic Hydrogen Generation

A promising photocatalytic system in the form of heterostructured nanocrystals (HNCs) is presented wherein alloyed ZnS–CuInS₂ (ZCIS) semiconductor nanorods are decorated with Pt and Pd₄S nanoparticles. This is apparently the first report on the colloidal preparation and photocatalytic behavior of ZCIS–Pt and ZCIS–Pd₄S nanoscale heterostructures. Incorporation of Pt and Pd₄S cocatalysts leads to considerable enhancement of the photocatalytic activity of ZCIS for visible‐light‐driven hydrogen production.     

Construction of Shallow Surface States through Light Ni Doping for High‐Efficiency Photocatalytic Hydrogen Production of CdS Nanocrystals

Ni‐doped CdS nanowires were synthesized by a simple one‐step method. X‐ray diffraction, X‐ray photoelectron spectroscopy, and photoluminescence spectroscopy confirmed that light Ni doping can form shallow surface states due to the presence of substitutional Ni ions, and heavy Ni doping can form deep surface states due to the presence of interstitial Ni ions. Surface photovoltage spectroscopy and transient photovoltage measurements revealed that the shallow surface states can prolong the lifetime of the photogenerated charge carriers, whereas the deep surface states lead to recombination of the photogenerated charge carriers. The relationship between different surface states and the photocatalytic performance of CdS nanocrystals are discussed. The enhanced density of shallow surface states due to light Ni doping significantly promotes photocatalytic H₂ production.     

Fe3O4纳米颗粒的表面改性

通过实验对Fe3O4纳米颗粒表面改性的最佳条件进行了摸索.并根据表面改性的包覆机理对不同酸度,温度和表面活性剂的用量对Fe3O4纳米颗粒的尺寸,磁性和稳定性的影响进行了理论上的分析.     

钕掺杂对纳米TiO2光催化分解水制氢活性的影响

 采用溶胶-凝胶法制备了一系列纳米TiO2和掺杂Nd3+ 的纳米TiO2光催化剂,并通过XRD, UV-Vis, TEM和N2吸附等技术对其进行了表征和分析,考察了样品光催化分解水制氢的活性. 结果表明, Nd3+的掺杂使TiO2的相变温度从600 ℃提高到800 ℃, 同时有效抑制了TiO2的粒径增长,提高了粒子的分散性和样品的比表面积, Nd3+掺杂量越大,催化剂的比表面积越大. 掺杂Nd3+ 后, TiO2的光催化制氢活性提高,本实验中Nd3+的最佳掺杂量为0.1%, 此时催化剂的活性比未掺杂TiO2提高了3.5倍. 随着焙烧温度升高, TiO2和Nd3+/TiO2样品的光催化活性均下降,但同时一定量的金红石相与锐钛矿相共存所产生的协同效应也使样品的光催化活性有所提高.     

Photocatalytic Hydrogen Evolution Coupled with Production of Highly Value-Added Organic Chemicals by a Composite Photocatalyst CdIn2S4@MIL-53-SO3Ni1/2

Photocatalytic water splitting coupled with the production of highly value-added organic chemicals is of significant importance, which represents a very promising pathway for transforming green solar energy into chemical energy. Herein, we report a composite photocatalyst CdIn₂S₄@MIL-53-SO₃Ni_1/2, which is highly efficient on prompting water splitting for the production of H₂ in the reduction half-reaction and selective oxidation of organic molecules for the production of highly value-added organic chemicals in the oxidation half-reaction under visible light irradiation. The superior photocatalytic properties of the composite photocatalyst CdIn₂S₄@MIL-53-SO₃Ni_1/2 should be ascribed to coating suspended ion catalyst (SIC), consisting of redox-active Ni^II ions in the anionic pores of coordination network MIL-53-SO₃⁻, on the surface of photoactive CdIn₂S₄, which endows photogenerated electron-hole pairs separate more efficiently for high rate production of H₂ and selective production of highly value-added organic products, demonstrating great potential for practical applications.     

铂纳米颗粒修饰的多孔卟啉基金属-有机框架化合物高效光催化产氢

通过双溶剂法及其后续的光还原法成功地将2.5 nm的Pt纳米颗粒嵌入到卟啉基金属-有机框架化合物PCN-222的介孔中（Pt@PCN-222）。该复合材料Pt@PCN-222上的卟啉官能团可以有效地吸收可见光并促进光解水制氢,氢气产量为253μmol ·g^-1·h^-1。     

铂纳米颗粒修饰的多孔卟啉基金属-有机框架化合物高效光催化产氢

通过双溶剂法及其后续的光还原法成功地将2.5 nm 的Pt纳米颗粒嵌入到卟啉基金属-有机框架化合物PCN-222的介孔中（Pt@PCN-222）。该复合材料Pt@PCN-222上的卟啉官能团可以有效地吸收可见光并促进光解水制氢,氢气产量为253 μmol ·g^-1·h^-1。     

载有C60的TiO2纳米粒子光催化活性

以水溶性C₆₀和TiO₂粒子为前驱体,采用水热法制备了载有C₆₀的锐钛矿型TiO₂纳米粒子。应用X射线衍射、透射电子显微镜、红外光谱、紫外-可见漫反射光谱、荧光光谱对产物进行了表征。以对-硝基苯酚为模型污染物研究了产物的光催化活性,结果表明适量负载C₆₀可以提高TiO₂纳米粒子的光催化活性,C₆₀起着传输电子、促进TiO₂光生载流子分离的作用,且经7次循环使用后对-硝基苯酚的降解效率仍能达到74%。讨论了载有C₆₀的TiO₂纳米粒子光催化降解对-硝基苯酚的机理。     

Enhanced Photocatalytic Efficiency of TiO2 by Combining the Modification of Ag Nanoparticles with the Application of Anodic Bias

Ag-TiO2/TTO film electrode was used as photoanode to investigate the feasibility of a hybrid technology of Ag nanoparticles combined with the application of anodic bias.The results showed that the deposited Ag and applied anodic bias have an apparent additive effect.     

Enhancement of the Surface Activity for Some Monomeric and Polymeric Thiol Surfactants Using Silver Nanoparticles

In the present work, the self-assembling of some synthesized thiol surfactants namely (6-(3-amino phenoxy) hexane-1-thiol, 8-(3-amino phenoxy) octane-1-thiol, 10-(3-amino phenoxy) decane-1-thiol, 12-(3-amino phenoxy) dodecane-1-thiol, and their polymers on silver nanoparticles was investigated. The self-assembling of these surfactants on silver nanoparticles was characterized using different techniques such as ultraviolet (UV) spectroscopy, powder x-ray diffraction (XRD), electrone diffraction (ED), and transmission electron microscopy (TEM). The effect of the self-assembling of these surfactants on the stabilization of the silver nanoparticles (AgNPs) was studied using TEM images. The growth of the silver nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The effect of silver nanoparticles on the surface, interfacial tension, and the emulsion stability of these surfactants with paraffin oil was studied. The results show that the silver nanoparticles have the ability to effect on the behavior of these surfactants in solution and improve their surface activity.     

纳米TiO2光催化降解聚乙二醇反应

纳米TiO2光催化降解聚乙二醇反应;纳米二氧化钛; 光催化; 聚乙二醇     

Enhanced Photocatalytic Hydrogen‐Production Performance of Graphene–ZnxCd1−xS Composites by Using an Organic S Source

In response to the increasing concerns over energy and environmental sustainability, photocatalytic water‐splitting technology has attracted broad attention for its application in directly converting solar energy to valuable hydrogen (H₂) energy. In this study, high‐efficiency visible‐light‐driven photocatalytic H₂ production without the assistance of precious‐metal cocatalysts was achieved on graphene–Zn_xCd_1?xS composites with controlled compositions. The graphene‐Zn_xCd_1?xS composites were for the first time fabricated by a one‐step hydrothermal method with thiourea as an organic S source. It was found that thiourea facilitates heterogeneous nucleation of Zn_xCd_1?xS and in situ growth of Zn_xCd_1?xS nanoparticles on graphene nanosheets. Such a scenario results in abundant and intimate interfacial contact between graphene and Zn_xCd_1?xS nanoparticles, efficient transfer of the photogenerated charge carriers, and enhanced photocatalytic activity for H₂ production. The highest H₂‐production rate of 1.06 mmol h^?1 g^?1 was achieved on a graphene–Zn_0.5Cd_0.5S composite photocatalyst with a graphene content of 0.5 wt %, and the apparent quantum efficiency was 19.8 % at 420 nm. In comparison, the graphene–Zn_xCd_1?xS composite photocatalyst prepared by using an inorganic S source such as Na₂S exhibited much lower activity for photocatalytic H₂ production. In this case, homogeneous nucleation of Zn_xCd_1?xS becomes predominant and results in insufficient and loose contact with the graphene backbone through weak van der Waals forces and a large particle size. This study highlights the significance of the choice of S source in the design and fabrication of advanced graphene‐based sulfide photocatalytic materials with enhanced activity for photocatalytic H₂ production.