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1.
We recently reported that Ag(3)PO(4) exhibits excellent photooxidative capabilities for O(2) evolution from water and organic dye decomposition under visible-light irradiation. However, very little is known about the shape and facet effects of Ag(3)PO(4) crystals on their photocatalytic properties. Herein we have developed a facile and general route for high-yield fabrication of single-crystalline Ag(3)PO(4) rhombic dodecahedrons with only {110} facets exposed and cubes bounded entirely by {100} facets. Moreover, studies of their photocatalytic performance have indicated that rhombic dodecahedrons exhibit much higher activities than cubes for the degradation of organic contaminants, which may be primarily ascribed to the higher surface energy of {110} facets (1.31 J/m(2)) than of {100} facets (1.12 J/m(2)). 相似文献
2.
随着现代工业的迅猛发展,人类面临的能源危机和环境污染问题日益严重.光催化剂技术有望利用太阳能同时解决这两大问题,其关键在于设计高效的光催化体系.传统光催化材料TiO2具有价廉、活性高及稳定性好等优点,然而其带隙宽(Eg=3.2 eV),仅能利用占太阳光谱约4%的紫外光,从而限制其利用太阳能.可见光占太阳光谱的40%以上,因此开发可见光响应的光催化材料成为光催化领域研究焦点.2010年,叶金花课题组报道了Ag3PO4在可见光照射下可高效分解水产氧及降解水体中有机污染物,从而使其迅速成为研究热点.Ag3PO4是目前为止报道的光量子效率最高的可见光响应的催化材料,带隙能在2.3~2.5 eV范围内,其高效的光催化活性归结于其独特的电子结构利于光生电荷的分离及转移.然而,由于Ag3PO4本身易光蚀,稳定性差,必然限制其实际应用.近年来,为在进一步提升Ag3PO4活性的基础上增强稳定性,研究者通过多种方法对其进行修饰,包括贵金属沉积、碳材料修饰、负载及半导体异质复合等.相对于前面几种修饰方法,半导体复合相对高效且成本低.半导体复合主要构成II型异质结构和Z型光催化体系.II型异质结构由于内建电场的存在可以促进光生电荷的定向转移,从而提高光生电荷的分离效率,进而提高光催化活性.然而,这种电荷的定向迁移会降低光生电荷的氧化还原能力.模拟绿色植物的光合作用过程,一种全固态Z型光催化体系应运而生,其是将两种导带和价带位置匹配的可见光驱动的催化剂分别作为光催化系统I(PS I)和光催化系统II(PS II),同时选用导电性能优良的材料(Ag,Au和RGO等)作为电子介体.可见光照条件下,PS I和PS II均被激发产生电子和空穴,PS II导带上的电子通过电子介质与PS I价带空穴复合,一方面抑制了PS I和PS II本身电子和空穴的复合,另一方面保留了PS I导带电子的强还原性和PS II价带空穴的强氧化性.另外,PS I和PS II紧密结合形成具有准连续能级的固-固接触界面,PS II导带上的电子直接与PS I价带空穴复合,形成无电子介体的直接Z型光催化体系.Ag3PO4价带顶相对靠下,氧化能力强,往往作为PS II组分,其与导带顶相对靠上的催化剂(PS I)构成Z型体系,这样Ag3PO4导带电子可与PS I的价带空穴复合,减弱电子对Ag3PO4本身的还原,提高其稳定性;另一方面,Ag3PO4价带空穴可参与氧化反应.基于Ag3PO4的Z型体系主要以Ag作为电子介体,归因于在制备及光催化过程中原位产生的少量Ag可直接作为电子介体.此外,还原氧化石墨烯(RGO)也可作为电子介体,并且其存在可进一步提高Ag3PO4的稳定性.需要指出的是,基于Ag的等离子体共振效应,Ag3PO4基等离子体Z型光催化体系也受到关注.目前,Z型光催化体系处在发展阶段,必然存在一些问题,比如,II型异质光催化体系与直接Z型光催化体系如何区分,有待进一步研究.另外,报道的基于Ag3PO4的Z型体系主要用来光催化降解水体中的有机污染物,催化剂的回收再利用受到限制,今后可开发磁性Ag3PO4基Z型体系,解决回收再利用的问题;另外,通过能带调控,可将基于Ag3PO4的Z型体系多用于光催化产氢、还原CO2及处理有害气体. 相似文献
3.
Fullerene‐C 60‐modified Ag 3PO 4 photocatalysts (C 60/Ag 3PO 4) were prepared via facile chemical precipitation. The structures, morphology and photocatalytic properties of C 60/Ag 3PO 4 were characterized by X‐ray diffractometry (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectrometry, and ultraviolet–visible (UV–vis) absorption spectrometry. C 60/Ag 3PO 4 exhibits considerably higher photocatalytic activity for degradation of Methyl Orange. The degradation conversion reached 93% after 8 min of light irradiation. Besides, the enhancement of photocatalytic activity could be attributed to the active species ?OH , which can be ascribed to strong synergistic effect between Fullerene C 60 and Ag 3PO 4. 相似文献
4.
半导体光催化材料既可以利用太阳能催化分解水制氢和降解各种有机污染物,同时还可以将温室气体CO2还原成有机低碳烷烃燃料,因此光催化是解决当今能源和环境问题最理想的途径之一.然而,目前所报道的可见光光催化材料大多具有较高的光生载流子复合率和较差的可见光吸收,导致其量子效率较低.因此,开发新型高效可见光光催化材料,拓展半导体材料光谱响应范围以及促进光生电子和空穴有效分离,成为目前光催化材料研究领域急需解决的科学问题.2010年Ye等首次报道了Ag3PO4在光催化中的应用,该材料表现出优异的光催化分解水制氧及降解有机污染物性能,在光吸收波长大于420 nm时的量子效率达到90%.然而,作为一种新型光催化材料,其组成、结构和晶面等对光催化性能的影响尚不清楚.因此,我们开展了Ag3PO4半导体纳米材料的表面微观结构调控研究,创制了一系列具有特殊形貌和选择暴露晶面的Ag3PO4基可见光催化材料,其表现出独特的光催化氧化性能.例如,利用金属络合法制备了具有(100),(110),(111),(221)和(332)等晶面的Ag3PO4晶体,发现通过调控其暴露晶面可进一步提高光催化性能.利用Ag纳米材料所具有的独特表面等离子体共振效应以及良好的导电性,构建了Ag/Ag3PO4核壳型纳米线、项链状Ag/Ag3PO4纳米线、项链状及均匀分布的Ag3PO4/PAN纳米复合纤维等异质光催化材料,提高了光生电子-空穴的分离效率,实现了有机污染物的高效催化氧化消除.然而,由于Ag3PO4在光催化反应过程中的稳定性较差以及成本较高,严重限制了其实际应用.因此,设计和制备具有高稳定性、低成本的Ag3PO4光催化材料成为目前急需开展的研究领域.本文以Ba3(PO4)2纳米片为模板和磷酸离子源,通过阳离子置换法一步制备了具有中空结构的Ba离子掺杂Ag3PO4光催化材料. 光催化结果表明, Ba离子的掺杂不但可以有效提高Ag3PO4光催化活性,并且可改变降解有机污染物甲基橙(MO)和罗丹明B(RhB)的选择性,实现优先降解MO.另外,此法制备的Ag3PO4材料经重复使用多次后仍表现出较高的光催化性能.进一步研究表明, Ba离子掺杂增强了Ag3PO4的表面电负性,因而吸附具有负电性的MO能力增加,使其光催化性能提高,此外,该法还可用于制备Ba3(PO4)2/Ag3PO4复合光催化材料,当Ag3PO4含量为40%时,该复合材料具有与纯相Ag3PO4相同的光催化剂活性.由此可见,通过合理掺杂金属离子及形成复合结构可以有效提高Ag3PO4光催化材料的活性和稳定性,降低Ag3PO4用量,这对Ag3PO4光催化材料的设计与改进具有一定指导意义. 相似文献
5.
以亚甲基蓝(MB)为模拟废水污染物,Ag3PO4为光催化剂,固定污染物初始浓度、催化剂用量、光照强度和照射时间等,探讨不同浓度的无机阴、阳离子(NO-3、Cl-、SO2-4、Na+、Ca2+、Mg2+、Al 3+)对Ag3PO4光催化降解偶氮染料MB的影响.结果表明,Na+和NO-3对Ag3PO4光催化降解MB没有明显的影响;Cl-在一定程度上对MB的降解具有促进作用;SO2-4、Ca2+、Mg2+、Al3+在不同程度上抑制了该光催化反应的进行,且抑制顺序为SO2-4Ca2+Mg2+Al 3+. 相似文献
6.
Research on Chemical Intermediates - Ag3PO4/Cu2O composites were prepared by a facile wet chemical method. The specimens were examined by X-ray diffraction, scanning electron microscopy,... 相似文献
7.
半导体光催化氧化技术作为一种“绿色技术”,被广泛应用于环境污染物治理和太阳能转化领域.高效、稳定、可回收利用的催化剂的开发是光催化技术发展的一个重要方向. Ag系半导体光催化剂因在可见光分解水制氢及降解有机污染物等方面表现出优异的催化性能而广受关注.然而,该催化剂失活快制约了其应用.因此,提高Ag系半导体材料的光催化稳定性成为近年来研究的一个热点.研究发现,在半导体的表面或者界面形成p–n异质结是提高催化剂光催化性能和稳定性的有效途径.理论上讲,当p型半导体和n型半导体形成p–n结以后,在两种半导体接触边缘的附近处存在着正、负空间电荷分列两边的偶极层,产生了从n型半导体指向p型半导体的内建电场.内建电场的存在使得p型半导体与n型半导体之间产生了电位差,即内建电势差.这种电势差能够有效促进电子和空穴的分离,达到光生电子和空穴对分离、转移和传递的目的,从而抑制电子和空穴的复合,提高光催化效率. Ag2CO3是p型半导体,其导带为0.21 eV,价带为2.83 eV; Ag3PO4是n型半导体,其导带为0.43 eV,价带为2.86 eV.两者能带结构匹配,能形成p–n异质结.因此,本文采用简单的共沉淀法,制备了不同比例的Ag3PO4/Ag2CO3复合光催化剂,并通过X射线衍射、透射电镜、X射线光电子能谱、紫外-可见漫反射光谱以及瞬态光电压谱等对其进行了表征.透射电镜照片显示,粒径较小的Ag3PO4颗粒均匀的分布在粒径较大的Ag2CO3周围. P元素和C元素的摩尔比接近于投料比. Ag3PO4/Ag2CO3复合催化剂的吸收光谱体现出两种催化剂的混合特征,在可见光区的吸收强度增加.瞬态光电压表征不仅证实了Ag2CO3是p型半导体, Ag3PO4是n型半导体,更说明了40%-Ag3PO4/Ag2CO3复合光催化剂的载流子寿命较长.罗丹明B(RhB)的降解实验证实40%-Ag3PO4/Ag2CO3(Ag3PO4与Ag2CO3的摩尔比为40%:60%)复合催化剂的光催化效率最高,500 W氙灯(附加420 nm截止波长的滤光片)照射15 min后, RhB就能被完全降解,而纯的Ag3PO4和Ag2CO3对RhB的降解率只有40%和10%.循环实验发现,前两次循环中由于单质银的生成导致催化剂活性下降,但从第三次循环开始其催化活性趋于稳定.此外,还通过添加草酸钠(空穴的清除剂)、异丙醇(羟基自由基的清除剂)和对苯醌(超氧自由基的淬灭剂)等来判断光催化过程中起主要作用的活性自由基.实验证实空穴是Ag3PO4/Ag2CO3光催化剂在降解RhB过程中产生的主要活性自由基物种. Ag3PO4/Ag2CO3光催化剂相对于单纯的Ag3PO4和Ag2CO3有更高的空穴产生能力.当可见光照射到复合催化剂表面时, Ag2CO3导带上的激发电子能够快速转移到Ag3PO4的导带上,同时Ag3PO4价带上的光生空穴能够快速转移到Ag2CO3的价带上. p–n结的形成提高了光生电子和空穴的分离效率,抑制了电子和空穴的再结合,因此,复合光催化剂光催化降解效率提高.综上所述, Ag3PO4/Ag2CO3之间能形成有效p–n结,40%-Ag3PO4/Ag2CO3复合光催化剂表现出最佳的光催化性能. 相似文献
8.
采用共沉淀法制备了Ag_3PO_4/NaNbO_3复合半导体光催化剂,利用X-射线衍射、X射线光电子能谱、紫外漫反射和扫描电镜等方法对合成样品进行表征.测试了样品对亚甲基蓝溶液的光催化降解活性,复合材料的催化活性远高于单体的Ag_3PO_4和NaNbO_3. 相似文献
10.
The phase formation in the subsolidus region of the Ag 3PO 4-ScPO 4 quasi-binary system was studied by X-ray powder diffraction and differential thermal analyses throughout the range of concentration ratios of the initial components at an interval of 10 mol % within the temperature range 20–1000°C in air at atmospheric pressure. A T-x section was constructed. The formation of the binary phosphate Ag 3Sc 2(PO 4) 3 melting incongruently at 1300 ± 5°C was detected. The composition of an eutectic (with the melting point 900 ± 5°C) is between those of the compounds Ag 3PO 4 and Ag 3Sc 2(PO 4) 3. 相似文献
11.
Single crystals of ammonium trisilver bis[fluorophosphate(V)], NH 4Ag 3(PO 3F) 2, were obtained from an aqueous solution and the structure was refined from a racemically twinned crystal. The asymmetric unit contains seven crystallographically distinct Ag atoms (two of which are located on twofold axes), four PO 3F tetrahedra and two ammonium cations. The layered structure is composed of silver–monofluorophosphate sheets, [Ag 3(PO 3F) 2] −, that extend parallel to (100). The F atoms of the PO 3F tetrahedra point towards the ammonium cations, which are located in the interlayer space and stabilize the structure via moderate N—H...O and N—H...F hydrogen bonds. 相似文献
12.
Herein, we demonstrate a complex-precipitation strategy for high-yield fabrication of single-crystalline Ag(3)PO(4) sub-microcubes with sharp corners, edges, and smooth surfaces, which exhibit much higher photocatalytic activities and photoelectric conversion properties than spherical Ag(3)PO(4) particles and commercial N-doped TiO(2) under visible light irradiation. 相似文献
13.
A high‐activity AgBr/Ag 3PO 4 heterojunction photocatalyst was synthesized based on hexadecyltrimethylammonium bromide. Its microspheres were characterized using X‐ray diffractometry, transmission electron microscopy and ultraviolet–visible diffuse reflectance spectroscopy. The new photocatalyst with high photocatalytic activity exceptionally outperforms pure Ag 3PO 4 and AgBr in methyl orange degradation. The enhancement of photocatalytic activity is attributed to the efficient separation of electron–hole pairs. In this photocatalytic reaction, h + and ?O 2? are the main reactive species that induce visible‐light‐driven degradation. 相似文献
14.
采用简单的化学偏聚法合成出Ag3PO4纳米颗粒、磷酸钴(Co3(PO4)2,CoP)纳米片以及它们两者的纳米复合结构(CoP/Ag3PO4),同时还比较了它们的可见光催化活性.采用场发射扫描电镜(FESEM)、X射线衍射(XRD)、紫外-可见(UV-Vis)吸收光谱以及光致发光谱等手段对其形貌、结构、光学以及可见光催化性能等进行表征.结果表明,CoP/Ag3PO4复合纳米结构的可见光降解甲基橙(MO)的速率和循环稳定性均明显优于其它两种物质.这表明CoP应该起着共催化剂的作用,它能够抑制光生电子与空穴之间的复合,并且提供大量高活性的光生空穴.此外,我们还发现CoP/Ag3PO4降解另一种阳离子型染料——罗丹明B(RhB)的能力则远不如纯Ag3PO4,这可能是与光催化剂的表面性质发生改变有关,造成更低的RhB吸附能力.本文提供了一种廉价制备高效可见光催化剂的新方法. 相似文献
15.
采用简单的化学偏聚法合成出Ag3PO4纳米颗粒、磷酸钴(Co3(PO4)2,CoP)纳米片以及它们两者的纳米复合结构(CoP/Ag3PO4),同时还比较了它们的可见光催化活性.采用场发射扫描电镜(FESEM)、X射线衍射(XRD)、紫外-可见(UV-Vis)吸收光谱以及光致发光谱等手段对其形貌、结构、光学以及可见光催化性能等进行表征.结果表明,CoP/Ag3PO4复合纳米结构的可见光降解甲基橙(MO)的速率和循环稳定性均明显优于其它两种物质.这表明CoP应该起着共催化剂的作用,它能够抑制光生电子与空穴之间的复合,并且提供大量高活性的光生空穴.此外,我们还发现CoP/Ag3PO4降解另一种阳离子型染料——罗丹明B(RhB)的能力则远不如纯Ag3PO4,这可能是与光催化剂的表面性质发生改变有关,造成更低的RhB吸附能力.本文提供了一种廉价制备高效可见光催化剂的新方法. 相似文献
16.
Graphene-supported BiPO 4/Ag/Ag 3PO 4 photocatalyst has been fabricated by simple hydrothermal and impregnation reaction. In BiPO 4/Ag/Ag 3PO 4 based on Reduced Graphene Oxide (RGO), this network renders numerous pathways for rapid mass transport, strong adsorption and multireflection of incident light; meanwhile, the interface between BiPO 4/Ag/Ag 3PO 4 and RGO increases the active sites and electron transfer rate. BiPO 4/Ag/Ag 3PO 4 based on RGO noticeably exhibited high photocatalytic activity than that of BiPO 4/Ag/Ag 3PO 4 and P25 under visible light irradiation for cationic dye (Rhodamine B), anionic dye (methyl orange) and 4-chlorophenol (4-CP) as a neutral pollutant, which are usually difficult to be degraded over the other catalysts. This enhanced photocatalytic activity of Graphene-supported BiPO 4/Ag/Ag 3PO 4 for all pollutants could be mainly ascribed to the reinforced charge transfer from BiPO 4/Ag/Ag 3PO 4 to RGO, which suppresses the recombination of electron/hole pairs. Besides that, this photocatalyst can be used repetitively with a high photocatalytic activity and no apparent loss of activity occurs. The results reveal that the RGO nanosheets work as a photocatalyst promoter during the photocatalytic reaction, leading to an improved photocatalytic activity. 相似文献
17.
Thermal stability of Ag3PO4 crystals was explored, and the calcination treatment was used to diminish the growth defect inside the Ag3PO4 crystals and improve their photoelectric properties. The results of in situ XRD and TG-DSC patterns indicated that Ag3PO4 crystals could maintain the integrality of their crystal structure under 400 °C. Photocatalytic efficiency and life of Ag3PO4-30-400 was improved by 138 and 800 %, respectively, compared with the pure Ag3PO4 crystals. The XPS patterns of P and O elements showed that hydroxyl groups in Ag3PO4 increased after the thermal treatment, from which it could be concluded that the hydroxyl groups filled up the Ag–O bonds after absorbing the energy in the heating process to re-optimize the lattice structure and were converted into hydroxyl radicals in the photocatalytic process, which generated a higher photocatalytic efficiency and chemical stability. 相似文献
18.
Ag 3PO 4 is widely used in the field of photocatalysis because of its unique activity. However, photocorrosion limits its practical application. Therefore, it is very urgent to find a solution to improve the light corrosion resistance of Ag 3PO 4. Herein, the Z-scheme WO 3(H 2O) 0.333/Ag 3PO 4 composites are successfully prepared through microwave hydrothermal and simple stirring. The WO 3(H 2O) 0.333/Ag 3PO 4 composites are characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. In the degradation of organic pollutants, WO 3(H 2O) 0.333/Ag 3PO 4 composites exhibit excellent performance under visible light. This is mainly attributed to the synergy of WO 3(H 2O) 0.333 and Ag 3PO 4. Especially, the photocatalytic activity of 15%WO 3(H 2O) 0.333/Ag 3PO 4 is the highest, and the methylene blue can be completely degraded in 4 min. In addition, the stability of the composites is also greatly enhanced. After five cycles of testing, the photocatalytic activity of 15%WO 3(H 2O) 0.333/Ag 3PO 4 is not obviously decreased. However, the degradation efficiency of Ag 3PO 4 was only 20.2%. This indicates that adding WO 3(H 2O) 0.333 can significantly improve the photoetching resistance of Ag 3PO 4. Finally, Z-scheme photocatalytic mechanism is investigated. 相似文献
19.
The binary Ag 3PO 4/MIL-125-NH 2 (AMN-X) composites were synthesized through ion exchange-solution method, and the ternary Ag/Ag 3PO 4/MIL-125-NH 2 (AAMN-X) Z-scheme heterojunctions were prepared via the photo chemical reduction deposition strategy. The photocatalytic hexavalent chromium (Cr(VI)) sequestration over AMN-X and AAMN-X were investigated under visible light. AAMN-120 accomplished superior reduction performance due to that Ag nanoparticles (NPs) act as electrons transfer bridge to enhance the separation efficiency of photogenerated e −-h + pairs, in which the reaction rates ( k value) were 2.77 and 124.2 fold higher than those of individual MIL-125-NH 2 and Ag 3PO 4, respectively. The influences of different pH values, small organic acids and coexisting ions on the photocatalytic performance of AAMN-120 were also investigated. In addition, the AAMN-120 heterojunction expressed great reusability and stability in cycling experiments. The mechanism of photocatalytic Cr(VI) was investigated and verified through photoluminescence (PL), electrochemistry, electron spin resonance (ESR), active species capture, and Pt element deposition experiments. 相似文献
20.
作为一种绿色技术,半导体光催化氧化广泛应用于环境污染物治理和太阳能转化领域.高效、稳定、可回收利用催化剂的开发是光催化技术发展的一个重要方向.Ag系半导体光催化剂因在可见光分解水制氢及降解有机污染物等方面表现出优异的催化性能而广受关注.然而,该催化剂失活快,制约了其应用.因此,提高Ag系半导体材料的光催化稳定性成为近年研究热点.在各种Ag基光催化剂中,Ag3PO4光催化剂因其在可见光下光氧化水产生O2以及有机染料的光催化分解中有着高的量子效率,引起了人们广泛关注.如何进一步提升Ag3PO4光催化剂性能及在光催化过程中的稳定性成为研究焦点,包括Ag3PO4光催化剂的特殊形貌和晶体结构控制生长以及复合材料控制制备.但是Z型Ag3PO4基可见光催化剂的构筑仍然是一个挑战.本文利用Ag2MoO4和Ag3PO4的溶液相反应法合成了Z型Ag3PO4/Ag2MoO4复合光催化剂,通过Ag3PO4/Ag2MoO4异质结光催化剂在可见光下降解罗丹明B(RhB)、亚甲基橙(MO)、亚甲基蓝(MB)和苯酚研究了其光催化性能,采用X射线衍射(XRD)、能谱、傅立叶变换红外光谱(FT-IR)、拉曼光谱、场发射扫描电子显微镜(FE-SEM)以及紫外可见漫反射光谱(UV-vis)等手段表征了该催化剂.XRD,FTIR和拉曼光谱结果表明,复合材料由Ag3PO4,Ag2MoO4和单质银组成,表面成功合成了Z构型Ag3PO4/Ag/Ag2MoO4复合材料.SEM结果发现纯Ag3PO4是规则的球状,纯Ag2MoO4则是多面体状块的颗粒,在Ag3PO4/Ag2MoO4复合材料中可以看到规则的球状体Ag3PO4和Ag2MoO4纳米颗粒,并且随着Ag2MoO4含量的增加,Ag3PO4颗粒的尺寸逐渐减小.UV-vis结果发现Ag2MoO4的加入拓展了复合材料对可见光的吸收范围.光催化性能测试结果表明,8%Ag2MoO4/Ag3PO4在可见光下具有优异的光催化性能:可见光照射5 min,RhB,MO和MB的降解效率分别可达95%,97%和90%.复合材料样品经过4个循环实验后,其降解RhB的效率仍然保持在84%,证明了其具有较高的稳定性.为了进一步研究Ag3PO4/Ag2MoO4的光催化机理,我们用对苯醌、乙二胺四乙酸二钠和丁醇进行了捕捉剂实验.结果表明,超氧自由基和光生空穴在降解有机染料过程中起主要作用.通过光电流测试、复合材料价带导带位置计算以及循环过程样品XRD分析并结合文献结果认为,Z构型Ag3PO4/Ag/Ag2MoO4异质结光催化体系以及可见光照射初期金属Ag纳米颗粒的生成是其具有高光催化活性和稳定性的原因. 相似文献
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