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1.
对硫化镉反蛋白石结构光子晶体薄膜进行了可控合成,用巯基乙酸修饰的纳米晶和P(St-MMA-SPMAP)高分子小球共组装,成功地构筑了反蛋白石结构并用于可见光光解水产氢。结果表明,在可见光(λ≥420 nm)照射下,Cd S-310反蛋白石结构薄膜的光解水产氢性能比硫化镉纳米颗粒提高了一倍。这主要是因为等级孔结构反蛋白石光子晶体特性对催化剂的光催化性能的提升:首先,反蛋白石的周期性结构增加了光子在材料中的传播,提高了催化剂对太阳光的利用率;同时,大孔孔壁是由纳米颗粒堆积而成的,在反应中提供了更多的反应活性位点;此外,孔结构有利于物质的传输和分子的吸附。  相似文献   

2.
慢光子效应在太阳能转换燃料中的应用(英文)   总被引:1,自引:0,他引:1  
随着全球性能源短缺和环境恶化问题的日益突出,能源和环境问题已成为目前人类面临和亟待解决的重大难题,研究新的替代能源和清洁环境技术备受关注.世界各国的科研工作者都在积极探索和寻找有效的对策,其中通过光催化分解水和还原CO_2将太阳能转化为有价值的氢气和碳氢燃料可有效缓解人类对可再生能源和清洁能源的需求.然而,现有催化剂的转换效率还达不到商业化的要求,主要原因是太阳光的利用率低和光生电荷的复合率高.将催化剂构造成三维有序孔状的光子晶体结构,可有效提高催化剂对光的利用率.光子晶体是一种特殊的周期性介电物质有序排列而成的微结构材料,它对光有着特殊的调控作用,可以通过光反射、光散射和慢光子效应来调控光在材料介质结构中的传播和光与介质的相互作用.三维反蛋白石结构的光子晶体不仅有光子晶体的特征还具有本身特有的结构效应,主要体现在以下两个方面:(1)光子晶体结构:光子晶体具有内部相互连接的三维框架结构和相互连通的球形孔道,三维框架结构提供大的比表面积,而有序的球形孔道有利于反应物分子的动态扩散;(2)光子晶体效应:当光波长落在光子禁带范围内,此波长的光将会被反射而不能在材料内传播;当光子晶体材料内有缺陷时可以发生多重散射,增加光的利用率;当光波长落在光子禁带红边的时候,这部分的光将会"慢下来"并且作用光子晶体的高介电物质部分;当光波长落在光子禁带蓝边的时候,这部分光也会"慢下来"并且作用于光子晶体的低介电物质部分.通过调控光子禁带的位置,可以得到不同波长的慢光子和调控作用于不同的材料物质上,增强入射光的利用率和光与材料的相互作用.基于光子晶体半导体材料既有电子能带又有光子能带的特点,利用光的反射、散射和慢光子效应来调控光在光子晶体中的传播,能显著增强光与催化剂的相互作用.尤其是光子禁带附近产生的慢光子效应对光有着特殊的调控作用,可以减慢一些特定频率的入射光在催化剂中的传输,促进催化剂对光的吸收.同时,慢光子效应还能促进光生电子-空穴对的分离,提高光解水产氢和光化学还原CO_2的活性.本文总结了光子晶体的慢光子效应促进光催化产H_2和CO_2还原的最新发展,并研究了慢光子效应在太阳能转换为燃料中的作用.基于慢光子效应对光的特殊调控作用,构造具有光子晶体结构的催化剂对促进太阳光的吸收和提高太阳能转换为燃料的效率具有重要的意义.  相似文献   

3.
Different titanium oxide powders (ATiO2, BTiO2) were pretreated in ammonia (NH3) gas at high temperatures. After the pretreatment, the color of the titanium oxide powders changed from white to yellow or gray depending on the pretreatment temperatures. Morphologies and structures of the treated titanium oxide powders were characterized by physical chemical methods. XRD measurements showed that the crystalline structures were mainly mixture of anatase and rutile for the ATiO2 but only anatase for the BTiO2. Stronger absorption of visible light was observed for both types of samples using UV-Vis diffuse reflectance spectra.X-ray photoelectron spectroscopy demonstrated that doped nitrogen existed on the surface TiO2 after ammonia gas pretreatment. The photocatalytic activities of the treated titanium oxide samples were evaluated via the photodegradation of methyl orange and phenol in aqueous suspensions. No obvious improvement in photocatalytic activity was achieved by ammonia pretreatment although it could enhance the absorption of light. Effects of treatment temperatures on photoactivities were complete different for ATiO2 and BTiO2 (i.e. higher treated temperatures yielded higher activities for BTiO2 but lower for ATiO2). All samples yielded lower activity levels after ammonia pretreatment without regard to pretreatment temperature or the reaction light resource.  相似文献   

4.
一维La(OH)3纳米棒具有特殊的电子结构和多功能特性,特别是作为半导体光催化剂引起了人们极大的兴趣.但La(OH)3禁带宽度较大,且只能吸收紫外光,所以光催化效率较低,可见光利用能力较差,限制了La(OH)3的实际应用.因此,需要开发一种高效的改进方法来提高La(OH)3的可见光催化性能.本课题组发展了一种有效的改进La(OH)3方法,通过简易的方法将BiOI纳米颗粒沉积在La(OH)3纳米棒上,有效增强了对可见光的吸收能力和光生载流子的分离能力.本文采用X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)、光电子能谱(XPS)、电子自旋共振(ESR)、N2吸附和元素分析等手段研究了BiOI@La(OH)3纳米棒异质结的构建原理及增强可见光催化性能的原因.XRD和XPS结果表明,通过简易化学沉积法原位构建了BiOI@La(OH)3异质结,并且在异质结中没有杂相生成.由SEM图像可见,原始La(OH)3由分散的一维纳米棒组成,平均直径为30–50 nm.通过BiOI与La(OH)3表面的紧密接触成功构建异质结,但BiOI纳米颗粒未改变La(OH)3纳米棒的形貌.由TEM和HRTEM图像可见,La(OH)3纳米棒的平均长度为30–50 nm,并且在BiOI@La(OH)3异质结中可以清晰看出BiOI和La(OH)3之间紧密接触的界面和晶格间距.N2物理吸附结果显示,随着BiOI量的增加,BiOI@La(OH)3异质结的比表面积增加,但孔体积未现明显变化.UV-Vis DRS结果显示,引入BiOI后明显促进了La(OH)3对可见光的吸收能力和利用效率,从而有利于增强可见光催化活性.通过理论计算分别得到BiOI和La(OH)3的价带和导带位置,表明具有非常匹配的能带结构可以促进BiOI光生电子的有效转移.可见光催化去除NO测试结果表明,BiOI@La(OH)3异质结的光催化活性高达50.5%,明显优于BiOI和La(OH)3.ESR测试结果显示,BiOI@La(OH)3异质结可见光催化活性中起主要作用的活性物种是?OH.结合表征结果,BiOI@La(OH)3纳米棒异质结可见光催化性能增强的原因主要有三个:(1)BiOI@La(OH)3异质结增大的比表面积有利于反应物和产物在催化剂表面扩散,同时可提供更多活性位点参与光催化反应;(2)禁带宽度影响光催化效率,当BiOI与La(OH)3达到合适比例时,既可以促进可见光吸收,也可以使光生电子具有较强还原能力;(3)BiOI@La(OH)3异质结有利于光生载流子的分离,从而显著提高其光催化活性.  相似文献   

5.
Graphitic carbon nitride (g-C3N4) is a remarkable semiconductor catalyst that has attracted widespread attention as a visible light photo-responsive, metal-free, low-cost photocatalytic material. Pristine g-C3N4 suffers fast recombination of photogenerated electron-hole pairs, low surface area, and insufficient visible light absorption, resulting in low photocatalytic efficiency. This review presents the recent progress, perspectives, and persistent challenges in the development of g-C3N4-based photocatalytic materials. Several approaches employed to improve the visible light absorption of the materials including metal and non-metal doping, co-doping, and heterojunction engineering have been extensively discussed. These approaches, in general, were found to decrease the material’s bandgap, increase the surface area, reduce charge carrier recombination, and promote visible light absorption, thereby enhancing the overall photocatalytic performance. The material has been widely used for different applications such as photocatalytic hydrogen production, water splitting, CO2 conversion, and water purification. The work has also identified various limitations and weaknesses associated with the material that hinders its maximum utilization under visible illumination and presented state-of-the-art solutions that have been reported recently. The summary presented in this review would add an invaluable contribution to photocatalysis research and facilitate the development of efficient visible light-responsive semiconducting materials.  相似文献   

6.
半导体/石墨烯复合光催化剂的制备及应用   总被引:1,自引:0,他引:1  
首先分析了石墨烯和半导体光催化剂的特点,以及二者复合后可能具有的优越性质,接着介绍了石墨烯和半导体复合光催化剂的制备方法,归纳了石墨烯增强半导体光催化的机理,然后阐述了复合光催化剂在降解有机污染物、光催化分解水产氢、光催化还原CO2制有机燃料和光催化灭菌四个典型的应用,最后对半导体/石墨烯复合光催化剂未来的发展趋势提出了展望.  相似文献   

7.
Mesoporous multiwalled carbon nanotubes/titanium dioxide (CNTs/TiO(2)) nanocomposites with low loading amounts (0-0.5 wt%) of CNTs embedded inside mesoporous TiO(2) aggregates has been prepared by a simple one-pot hydrothermal method using titanium sulfate as titanium source. The as-prepared CNTs/TiO(2) samples are carefully characterized, analyzed and discussed. In contrast to previous reports with high CNT loading, our results indicate that a low CNT loading slightly influences the textural properties (including crystallite size, degree of crystallinity, specific surface areas, and pore volume etc.) and UV-light absorption of the mesoporous TiO(2) aggregates. The SEM and TEM results demonstrate that the CNTs are mostly embedded in the mesoporous TiO(2) aggregates. Moreover, chemical bonds are formed at the interface between CNTs and TiO(2), which is confirmed by the Raman, IR and XPS analyses. Significantly, we point out that PL analysis in terms of intensity of PL signals seems to not be a reliable way to monitor the recombination rate in the CNTs/TiO(2) composite, due to the quenching effect of CNTs. Instead, the analysis of transient photocurrent responses is introduced, which definitely reflects CNTs as fast electron transfer channels in chemically-bonded CNTs/TiO(2) composites with low CNT loading. Notably, the positive synergy effects of CNTs and TiO(2) depend on both the CNT loading amount and the state of interfacial contacts. In our study, only these chemically bonded CNTs/TiO(2) nanocomposites with appropriate loading amounts (<0.1 wt%) favor the separation of photogenerated electron-hole pairs and decrease their recombination rate and thus display significantly enhanced photocatalytic activity for degrading acetone in air under UV irradiation, as compared with pristine TiO(2) counterparts and commercial P25 photocatalyst. In contrast, a high CNT loading (>0.1 wt%) results in a decrease in photocatalytic activity; a simple mechanical mixing of CNTs and TiO(2) without forming chemical bonds at the interface also results in inferior photocatalytic performance.  相似文献   

8.
Photocatalytic hydrogen production is crucial for solar‐to‐chemical conversion process, wherein high‐efficiency photocatalysts lie in the heart of this area. A photocatalyst of hierarchically mesoporous titanium phosphonate based metal–organic frameworks, featuring well‐structured spheres, a periodic mesostructure, and large secondary mesoporosity, are rationally designed with the complex of polyelectrolyte and cathodic surfactant serving as the template. The well‐structured hierarchical porosity and homogeneously incorporated phosphonate groups can favor the mass transfer and strong optical absorption during the photocatalytic reactions. Correspondingly, the titanium phosphonates exhibit significantly improved photocatalytic hydrogen evolution rate along with impressive stability. This work can provide more insights into designing advanced photocatalysts for energy conversion and render a tunable platform in photoelectrochemistry.  相似文献   

9.
Chromium-sensitized titanium dioxide nanotubes (CTNT) with high photocatalytic activity were prepared by a chemical bath deposition technique. The resulting films were characterized by SEM, EDX, and XRD. Results showed that the fabricated films have the ordered nanotubes with diameter of 90–140 nm, wall thickness of 20–50 nm, and tube lengths in the range of 24 μm. Diffuse reflectance spectra showed an increase in the visible absorption relative to bare titanium dioxide nanotubes (TNT). The photoelectrochemical performance was examined under light irradiation in 1 M NaOH electrolyte. Photoelectrochemical characterization shows that chromium sensitizing efficiently enhances the photocatalytic water splitting performance of CTNT composite. The sample (C3TNT) exhibited better photocatalytic activity than the TNT and CTNT fabricated using other chromium concentrations. This inexpensive photoanodes prepared free of noble metals showed enhanced high photocurrent density with good stability and is a highly promising photoanode for solar hydrogen production.  相似文献   

10.
We used hybrid density-functional calculations to clarify the effect of substituting chromium for titanium (Cr(Ti)) on photocatalytic activities of Cr-doped SrTiO(3). A singly negative Cr(Ti)?, which is relevant to a lower oxidation state of Cr, is advantageous for the visible light absorption without forming electron trapping centers, while other charge states are inactive for the photocatalytic reaction. Stabilizing the desirable charge state (Cr(Ti)?) is feasible by shifting the Fermi level towards the conduction band. Our theory sheds light on the photocatalytic properties of metal-doped semiconductors.  相似文献   

11.
李旭力  李宁  高旸钦  戈磊 《催化学报》2022,43(3):679-707
随着全球经济的快速发展,能源短缺与环境污染成为当今世界共同关注的热点问题,开发和利用洁净能源成为当务之急.近年,以半导体为基础的光催化技术引起了国内外的广泛关注,其中包括光催化分解水制氢、光催化还原CO2、光催化固氮以及光催化降解污染物等.尤其太阳能驱动的光催化分解水和光催化CO2还原均可将太阳能转化为可储存和运输的化...  相似文献   

12.
以Ti(OCH2CH2CH2CH3)4为钛源,脱脂棉花纤维为模板,利用浸渍-热转化两步法制备了具有中空结构的Sn4+掺杂TiO2光催化纤维材料(Sn4+/TiO2),利用X-射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见光谱(UV-vis)等技术对其晶体结构、形貌、尺寸、光吸收特性等进行了表征.以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了样品Sn4+/TiO,在太阳光下的光催化性能.结果表明:利用该法制得的Sn4+/TiO2材料具有中空纤维结构;煅烧温度影响材料Sn4+/TiO2的相结构、组成、尺寸、形貌以及催化性能;Sn4+的掺入能够显著改善TiO2在太阳光条件下的催化性能,600℃煅烧2h所得的Sn4+掺杂量x=0.29%的TiO2中空纤维材料具有最佳的光催化活性,太阳光下2h即可使MB溶液的脱色降解率达97.28%;重复使用5次仍可使MB溶液的脱色降解率保持在90%以上,且该催化剂材料易于离心分离去除.  相似文献   

13.
In the literature it was found that titanium oxide clusters of a few metal atoms encapsulated inside the micropores of zeolite Y exhibit large blue shifts in the Ti-O ligand-to-metal charge-transfer band as compared to non-encapsulated bulk titanium dioxide particles. This blue shift of the Ti-O absorption band is believed to have a negative effect on the photocatalytic activity of zeolite-encapsulated TiO2. We report here on circumventing this problem and increasing visible-light absorption by means of a red shift of the absorption band caused by addition of some organic molecular modifiers containing acidic OH groups that can strongly bind with titanol groups TiOH. In the studied series of zeolite-encapsulated TiO2 samples, the red shift of the optical spectrum follows the order: catechol > 4-aminobenzoic acid > benzoic acid. Also N-doping of zeolite-encapsulated TiO2 clusters by thermal treatment with urea leads to a red shift of the TiO2 absorption band that depends on the annealing and hydration conditions. By comparison to the degradation of phenol in aqueous solution, we have demonstrated that these changes in the absorption spectrum on addition of the organic modifier are also reflected in the photocatalytic activity of the samples; a greater increase in photocatalytic activity (about 30%) was observed for the additive catechol.  相似文献   

14.
采用水热法以Hummers氧化法制备的氧化石墨和钛酸四丁酯为原料制备了部分还原的氧化石墨烯/二氧化钛(RGO/TiO2)复合光催化剂, 并研究了该复合材料在可见光以及紫外光下对亚甲基蓝的光催化降解活性.结果表明, 通过改变反应温度和氧化石墨加入量可以调控TiO2的晶相组成及其在复合材料中的分散性; 在水热反应过程中氧化石墨烯发生了部分还原; 所制备的RGO/TiO2复合材料的可见光和紫外光催化活性均高于纯TiO2; 部分还原的氧化石墨烯在复合材料中担当载体和电子受体, 同时可以使TiO2的初始吸收边向可见光区域红移, 增强了TiO2在可见光区域的吸收, 能有效提高对目标污染物的吸附性和光催化降解活性.  相似文献   

15.
TiO2-双亲共聚物复合纳米粒子的合成与紫外光敏特性   总被引:3,自引:0,他引:3  
孙镛  毕研迎  石凤 《化学学报》2007,65(1):67-71
用偶联剂乙烯基三乙氧基硅烷改性纳米粒子TiO2, 应用超声技术将TiO2 纳米粒子分散在甲醇介质中, 然后用苯乙烯(ST)原位聚合包封, 再用丙烯酰胺或乙烯基吡咯烷酮(VP)共聚, 两步原位分散聚合得到了有机聚合物为壳、TiO2为核的有机/无机复合粒子. 用红外光谱、紫外-可见光谱、透射电子显微镜等检测手段进行表征. 结果显示: 由于双亲共聚物对TiO2纳米粒子的敏化作用, 紫外-可见光谱图上两种纳米复合粒子的最大吸收峰均有明显红移, 并且吸收光谱的范围扩大了, 其中尤以TiO2/(PST-co-PVP)为甚. 意味着光敏化活性的提高, 特别是在可见光谱的范围内. 这种情形对宽带隙半导体材料如TiO2纳米粒子的光催化特性是有利的, 表明这类材料的应用空间得到了拓展.  相似文献   

16.
Silver sensitized titanium vanadium mixed Ag/TiV oxide photocatalyst was synthesized using sol-gel technique. The catalyst was characterized using XRD, SEM, EDAX, HRTEM, UV-DRS, XPS, and PL analysis which reveal the formation of a predominantly rutile mixed phase nanoparticles of 25-30 nm crystallite size. The catalyst showed a marked red-shift in the absorption spectrum compared to Degussa P25. It exhibited a remarkable enhancement in the visible light photocatalytic activity in inactivating Escherichia coli, a gram-negative pathogenic bacterium, too. The conclusions are supported by a comparison with an identically synthesized TiV oxide sample. A microbicidal photonic efficiency (MPE) has been defined and a method for its determination has been proposed to facilitate quantification of the performance of the photocatalyst and the disinfection system taking into account the response of the catalyst to the radiation intensity.  相似文献   

17.
TiO2纳米管阵列在环境领域的研究进展   总被引:1,自引:0,他引:1  
房治  周庆祥 《化学学报》2012,(17):1767-1774
TiO2纳米管阵列是一种新型的无机功能材料,具有化学惰性、气敏、介电效应、良好的生物兼容性、较强的光催化能力以及抗化学腐蚀和光腐蚀的能力,特别是具有很好的光催化活性,使其在太阳能的储存与利用、环境净化、催化剂、光催化降解环境污染物等方面有比较多的研究应用.TiO2纳米管阵列通过一定的修饰可以使其吸收光谱向可见光区迁移,同时它兼具成本低廉、环境友好等优点,是当前环境污染物削减与监控的重要研究方向之一.本文主要对近年来国内外TiO2纳米管阵列作为光催化剂降解环境污染物和作为功能材料在环境分析检测中的应用进行简要综述,为开发新型污染物监控与处理技术及拓展TiO2纳米管阵列的潜能提供重要参考.  相似文献   

18.
Solar energy-harvesting materials have significantly contributed to the development of energy-saving applications for several decades. We have mainly used a new concept composed of the electrophoretic deposition technique and photonic crystal structural engineering to understand the tunable light-absorption and electronic conduction properties. A hexamolybdenum cluster compound (denoted as the Mo6 cluster) was successfully functionalized on a tin pyrophosphate semiconductor integrated within an inverse opal photonic crystal. The size of the periodical pores, surface modification, and chemical composition of the infiltration material of the inverse opal film have been investigated to control the photonic bandgap in the visible range and the efficiency of the deposited Mo6 cluster. The photoactive Mo6 clusters act as a visible light harvester and generate an efficient photo-induced current upon light absorption that is enhanced by a slow photon effect occurring at the photonic stopband edges. The electron and proton are transferred in the inorganic-organic network via hydrogen bonds by a hopping mechanism to generate a rapid photoconductivity response during light irradiation. Specific attention focused on the role of humidity and temperature regarding the reproducibility of the experiments and the photosensitivity of the nanocomposite. The suitable tunable photo-induced conduction property in organic-inorganic materials opens a new opportunity for the applicability of cluster-based compounds in visible optoelectronic devices.  相似文献   

19.
《中国化学快报》2021,32(9):2617-2628
The composite catalytic materials based on the mineral kaolinite are considered to be a potential approach for solving global energy scarcity and environmental pollution, which have excellent catalytic performance, low cost and excellent chemical stability. However, pure kaolinite does not have visible light absorption ability and cannot be used as a potential photocatalytic material. Fortunately, the unique physical and chemical properties of kaolinite can be acted as a good semiconductor carrier. Herein, this paper firstly presents the mineralogical characteristics of kaolinite. Next, kaolinite-based photocatalysts (such as TiO2/kaolinite, g-C3N4/kaolinite, g-C3N4/TiO2/kaolinite, ZnO) are discussed in detail from the formation of heterostructures, synthesis-modification methods, photocatalytic mechanisms, and electron transfer pathways. Furthermore, the specific role of kaolinite in photocatalytic materials is summarized and discussed. In addition, the photocatalytic applications of kaolinite-based photocatalysts in the fields of water decomposition, pollutant degradation, bacterial disinfection are reviewed. However, the modification of kaolinite is hard, the manufacture of a large number of kaolinite-based photocatalysts is difficult, the cost of doping noble metals is expensive, and the utilization rate of visible light is low, which limits its application in industrial practice. Finally, this paper presents some perspectives on the future development of kaolinite-based photocatalysts.  相似文献   

20.
分别采用NaBiO3和Bi(NO3)3为Bi源制备了Bi掺杂NaTaO3光催化剂,研究了Bi离子的价态对NaTaO3光催化分解水制氢性能的影响.采用X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)和紫外-可见吸收光谱研究了催化剂的晶体结构、Bi离子的化学状态和催化剂的光学吸收性能.以光催化分解水制氢反应研究了Bi离子掺杂NaTaO3的催化性能. XRD结果表明,对于两个不同Bi源掺杂的NaTaO3样品, Bi离子的掺杂没有改变催化剂的单斜相结构,但拉曼光谱证实Bi离子的掺杂致使Ta–O–Ta键角偏离了180o. XPS结果表明,以Bi(NO3)3为Bi源时, Bi离子以Bi3+掺杂于NaTaO3的A位;当以NaBiO3为原料时, Bi3+和Bi5+共掺杂于NaTaO3的A位.两种不同Bi源掺杂得到的样品在紫外-可见吸收光谱中给出了相似的光学吸收,但Bi3+的掺杂对NaTaO3光催化性能影响不大,而Bi3+和Bi5+共掺杂大大提高了NaTaO3的光解水制氢性能. Bi离子取代Na离子在A位的掺杂,在NaTaO3结构中引入了能够促进载流子分离的空位和缺陷;与此同时, Bi的掺杂导致Ta–O–Ta键角偏离180o而不利于载流子迁移.对于Bi3+掺杂的NaTaO3样品,这两种作用相互抵消,使得其催化性能与NaTaO3相比没有变化;而Bi3+和Bi5+的共掺杂和高价态Bi5+的掺杂引入了更多的空位和缺陷,提高了光生电子-空穴的分离效率,从而提高了光催化产氢性能.研究表明,光催化过程中载流子的迁移是影响催化性能的重要因素,而在ABO3钙钛矿结构的A位引入高价态离子是促进光生载流子分离的有效途径.  相似文献   

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