一锅法合成在可见光下具有高效降解草甘膦的牡丹状Bi2S3/BiVO4(040)复合光催化剂

草甘膦是一种广谱除草剂, 2015年世界卫生组织国际癌症研究机构宣布草甘膦可能对人类致癌(2A类).单斜白钨矿型BiVO_4是一种较广泛研究的可见光光催化剂,但由于其光生电子和空穴迁移慢且容易复合而导致其光催化活性低.此外,有研究表明, BiVO_4的(040)晶面易于光生载流子分离,从而提高其光催化性能.Bi_2S_3的带隙能为1.27 eV,能被全可见光(400-800 nm)激发.Bi_2S_3的导带和价带位置与BiVO_4匹配,能形成异质结,从而提高其光催化活性.本文以EDTA为导向剂, L-半胱氨酸为硫源和软模板,采用一锅水热法制备了单斜白钨矿型BiVO_4,主要以(040)晶面为暴露面的Bi_2S_3/BiVO_4复合光催化剂.采用钼锑抗分光光度法测定草甘膦最终光催化降解产物之一PO_4~(3-)浓度,来计算草甘膦的降解率.X射线衍射(XRD)结果表明, Bi_2S_3/BiVO_4复合光催化剂只含Bi_2S_3和BiVO_4两种成分,没有其他晶相存在.场发射扫描电子显微镜(FESEM)显示,纯BiVO_4为片状结构,随着Bi_2S_3复合量增加, Bi_2S_3/BiVO_4的形貌为小片组成的牡丹状;但Bi_2S_3复合量进一步增加, Bi_2S_3/BiVO_4颗粒聚集严重.XRD, FESEM和高分辨透射电子显微镜(HRTEM)结果表明, Bi_2S_3复合量对Bi_2S_3/BiVO4样品(040)和(121)面晶生长及形貌有显著影响.Bi_2S_3的复合提高了Bi_2S_3/BiVO_4对可见光的吸收能力,经计算BiVO_4和Bi_2S_3带隙能分别为2.42和1.27 eV.随着Bi_2S_3复合量增加, Bi_2S_3/BiVO_4的光催化活性逐渐提高,至1 mmol时最高,对草甘膦的降解率为纯BiVO_4的2.2倍;但随着Bi2S3复合量进一步增加, Bi_2S_3/BiVO_4的光催化活性反而下降,可能是由于Bi_2S_3量太多包覆在BiVO_4表面而Bi_2S_3光催化性能很差的缘故.瞬态光电流测试和电化学阻抗谱的结果证实, Bi_2S_3/BiVO_4比BiVO_4具有更有效的电荷分离和更快的界面电荷转移能力.活性成分捕获剂实验表明,加入空穴捕获剂EDTA或电子捕获剂K_2Cr_2O_7完全抑制了草甘膦的降解.ESR谱证明羟基自由基·OH的存在.通过计算,得出BiVO_4的价带电位(EVB=2.87 eV vs. NHE)比Bi_2S_3 (EVB=1.69 eV vs. NHE)正,而Bi_2S_3 (EVB=0.42 eV vs. NHE)的导带电位比BiVO_4 (EVB=0.45 eV vs. NHE)负,能带匹配,即光生电子从Bi2S3迁移至Bi VO4,光生空穴从BiVO_4迁移至Bi_2S_3,从而将光生电子与空穴有效分离利用,达到提高其光催化性能的目的.Bi_2S_3/BiVO_4样品对草甘膦的光催化降解活性提高,主要是由于Bi_2S_3/BiVO_4异质结结构的形成提高了其对可见光的吸收能力和电子空穴对的分离效率.此外, Bi_2S_3/BiVO_4具有相对稳定性和可重复使用性.该方法简单,可制备用于光催化降解有机污染、光催化裂解水和光催化还原二氧化碳等不同领域的高活性复合光催化剂.     

四角星形BiVO4/Bi2O3催化剂的制备及性能

采用水热法合成具有四角星形貌的钒酸铋,再将钒酸铋浸渍在碱溶液里二次水热,制备出BiVO_4/Bi_2O_3催化剂。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM),紫外-可见漫反射(UV-Vis DRS)等方法对样品进行表征。可见光下,BiVO_4/Bi_2O_3复合物的光催化降解罗丹明B性能及光电流响应均优于纯BiVO_4。这是由于BiVO_4/Bi_2O_3复合材料形成了异质结构,有效抑制了光生电子与空穴的复合效率。     

Bi/BiVO4&Bi4V2O11复合催化剂的制备及其光催化性能

经由溶剂热反应、光辅助还原过程制备Bi/Bi VO_4Bi_4V_2O_(11)纳米复合光催化材料。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、高分辨率透射电子显微镜(HRTEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、N_2吸附-脱附等温线和光致发光(PL)等手段对该复合物进行表征。实验结果表明当金属Bi与BiVO_4Bi_4V_2O_(11)的质量比值为0.8,可见光照射30 min时,Bi/BiVO_4Bi_4V_2O_(11)复合催化剂对罗丹明B(RhB)的降解率可达95.6%。此外,Bi/BiVO_4Bi_4V_2O_(11)对四环素(TC)的降解也表现出增强的光催化性能。Bi/BiVO_4Bi_4V_2O_(11)复合材料提升的光催化性能可能归因于金属Bi的表面等离子体共振(SPR)效应、拓宽的可见光吸收范围和增大的比表面积。此外,提出了复合光催化剂可能的光催化机理。     

稀土离子Tm3+掺杂Bi2WO6的可见光催化性能

以Na_2WO_4·2H_2O和Bi(NO_3)_3·5H_2O为主要原料,采用水热法合成了稀土离子Tm~(3+)掺杂的Bi_2WO_6光催化剂。采用XRD、SEM、TEM、Raman、PL、DRS研究了Tm~(3+)掺杂Bi_2WO_6的物相,微观形貌和可见光催化性能。结果表明,Tm~(3+)掺杂有效提高了Bi_2WO_6的光催化性能,当掺杂量为6%时,样品的光催化性能最好,可见光照射30 min后,对罗丹明B的降解效率达到91.27%,而可见光照射5 h后,对焦糖色素的降解效率达45.25%。与未掺杂Bi_2WO_6相比,分别提高了27.78%和35.22%。     

球磨法制备异质结型光催化剂ZnO/Bi_4Ti_3O_(12)及催化性能

本文用水作为分散介质,掺杂一定量的ZnO于Bi_4Ti_3O_(12)中,采用高能球磨法制备了异质结型光催化剂ZnO/Bi_4Ti_3O_(12).利用UV-Vis、XRD、SEM和PL等仪器对样品进行了分析与表征.以375 W中压汞灯为光源,通过对亚甲基蓝的氧化来研究其光催化活性.结果表明,对于光氧化亚甲基蓝(MB),异质结型光催化剂ZnO/Bi_4Ti_3O_(12)光催化活性高于钛酸铋的光催化活性.当ZnO的掺杂量分别是0.0和0.5wt.%,异质结型光催化剂ZnO/Bi_4Ti_3O_(12)对亚甲基蓝光氧化率分别达到50.2和80.3 %.     

γ-Bi_2MoO_6光催化降解次甲基蓝的研究

以Bi(NO_3)_3·5H_2O和(NH_4)_6Mo_7O_(24)·4H_2O为原料,水热法合成Bi_2MoO_6粉体,采用X-射线衍射、紫外可见漫反射光谱仪对其进行表征。以次甲基蓝溶液为目标降解物,评价了Bi_2MoO_6催化剂的光催化活性。考察了光催化剂的制备反应温度、pH值以及焙烧温度、催化剂用量等对光催化反应效果的影响,确定了Bi_2MoO_6粉体的最佳制备条件。结果显示:在160℃,pH=8的条件下水热反应4h,并在160℃干燥所制得的催化剂对次甲基蓝的降解效果最佳,其脱色率可达到90%。     

层级纳米花环状Bi_2O_3/(BiO)_2CO_3复合材料光催化降解罗丹明B

通过程序升温水热法制备了层级纳米花状结构Bi_2O_3/(BiO)_2CO_3复合材料(简称BO/BCO)。采用X射线衍射(XRD)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和氮气吸附-脱附测定等方法对上述合成材料的晶型结构、组成、光吸收性质、形貌和表面物理化学性质进行了表征。结果表明,该复合材料中(BiO)_2CO_3的晶型为四方相,Bi_2O_3的晶型为单斜相,复合后的材料同时具有两者晶型结构。并且,合成时随着OH-的引入与反应时间的增加,复合材料中(BiO)_2CO_3的特征衍射峰强度逐渐降低,Bi_2O_3的特征衍射峰强度逐渐增加,证明了Bi_2O_3在样品中所占比例的增加。从UV-Vis/DRS吸收光谱分析结果显示,与单体(BiO)_2CO_3和单体Bi_2O_3相比,合成的BO/BCO复合材料的吸收边带发生偏移,且Bi_2O_3的引入有效增加其可见光区吸收。同时,样品由片状(BiO)_2CO_3生长为层级纳米花环状结构的BO/BCO-0.5,而层级结构的形成导致BO/BCO-0.5的带隙能变窄,且对于光电子的反射与散射发生改变,从而有利于光生电荷的转移与光的吸收效率。另外,以罗丹明B为模型分子,通过不同光源照射下的光催化活性实验,循环实验以及捕获实验对复合材料BO/BCO的光催化活性进行了研究。结果表明,与其他体系(单体Bi_2O_3和P25)相比,BO/BCO-0.5活性有明显提高,并且在多次循环实验后依然保持良好的稳定性。此外,根据捕获实验结果推测了BO/BCO复合材料可能的光催化反应机理。     

pH值对Bi_2MoO_6晶体形貌和可见光催化性能的影响

以(NH4)6Mo7O24·4H2O和Bi(NO3)3·5H2O为原料,采用普通水热法制备Bi2Mo O6光催化剂,研究p H值对制备该光催化剂的影响。对所制备的系列样品,采用X-射线衍射仪(XRD)、扫描电子显微镜(SEM)、比表面积分析仪、X射线光电子能谱仪(XPS)和紫外-可见漫反射(UV-Vis DRS)进行表征。结果表明:p H值对Bi2Mo O6晶体的物相组成、形貌和光催化性能均有显著影响。p H值为1~7时,所制备的样品为纯相Bi2Mo O6,p H值为9或11时,出现第二相Bi3.64Mo0.36O6.55;随着p H值的升高,形貌依次为纳米棒、纳米片和无规则纳米颗粒。在可见光(λ≥420 nm)照射下,通过光催化降解罗丹明B(Rhodamine B,Rh B),探讨了制备Bi2Mo O6的p H值对其可见光催化活性的影响。当p H=7时,制备的样品光催化效果最好,光照50 min后对初始浓度为5 mg·L-1的罗丹明B溶液的降解率为85%。     

磁性γ-Fe_2O_3/La/Bi_2WO_6复合材料的制备及其光催化性能的研究

采用γ-Fe_2O_3掺杂对La/Bi_2WO_6进行改性。通过超声-水热法合成出粒径在0.2-1.0μm,表面附着γ-Fe_2O_3球形颗粒的La/Bi_2WO_6纳米片状的磁性γ-Fe_2O_3/La/Bi_2WO_6复合光催化剂。结合XRD、SEM等表征手段对复合材料的组成、形貌、光学性质进行表征,通过光催化降解罗丹明B溶液对其光催化性能进行评价。结果表明:γ-Fe_2O_3/La/Bi_2WO_6复合光催化剂可以通过外磁场作用很容易的与反应溶液分离,且仍具有较高的可见光催化活性和稳定性,其重复使用3次后,对罗丹明B的降解率变化不明显,仍达到95.3%。     

纺锤形BiVO_4微米管:低温离子熔盐合成及光催化性能

以Bi(NO_3)_3·5H_2O和NH_4VO_3为原料,以氯化胆碱和尿素组成的低温离子熔盐为反应介质,采用离子热合成法成功制备出了具有纺锤状外形的BiVO_4微米管。利用XRD,SEM,UV-Vis DRS,光催化测试等手段考察了BiVO_4颗粒的物相、形貌和光催化性能。结果表明,在离子熔盐环境下可以制备出结晶良好的BiVO_4纺锤形微米管,该BiVO_4微米管长10～15μm,直径为1.5μm左右,管壁厚约为200 nm。同时,研究了pH值对BiVO_4颗粒物相与形貌的影响,发现随着pH值的变化可分别合成出具有柱状、纺锤形微米管、柱状微米管和针柱状单斜相BiVO_4颗粒。光催化测试结果表明,这些单斜白钨矿BiVO_4颗粒在可见光范围都具有一定的光催化活性,其中纺锤状微米管对罗丹明B的降解效果最佳,可见光照射4.5h后罗丹明B的降解率可达到93%。     

柠檬酸辅助水热法制备可见光高效去除甲基橙的Bi2WO6纳米片

以Bi(NO3)3·5H2O和Na2WO3 ·2H2O为原料,以柠檬酸为络合剂,采用辅助水热法制备了Bi2WO6纳米片,运用X射线衍射、扫描电镜、场发射高分辨透射电镜、拉曼光谱、红外光谱和紫外-可见漫反射光谱等手段对样品进行了表征,并考察了该催化剂光催化去除甲基橙反应性能.结果表明,通过调节体系的pH值可制得结晶度良好...     

增强可见光催化活性的Z型MoO3/Bi2O4复合光催化剂的制备（英文）

全球工业化进程的加快使人们饱受环境污染问题的困扰.半导体光催化技术作为一种高效、绿色、有潜力的新技术,在环境净化方面有着广阔的应用前景.Bi2O4是近年来新开发出的一种铋基光催化剂,在环境净化方面已有一些研究.但是,单体光催化剂通常存在光响应范围窄、光生载流子复合率高等问题,这些不足限制了Bi2O4的进一步应用.因此,需要通过适当的改性来拓宽其光响应范围和提高其载流子的分离效率,从而提高其光催化活性.构建Z型异质结被认为是提高光催化剂光生载流子分离效率并进一步提高光催化活性的有效方法.MoO3是一种宽禁带的n型半导体,具有独特的能带结构、光学特性和表面效应,是一种非常有前景的半导体光催化剂.虽然MoO3材料的光生载流子复合率高,带隙(2.7-3.2 eV)大,不利于其参与光催化反应,但MoO3与其他合适的半导体配位形成复合材料后能够有效提高其光生载流子的分离效率,从而提高其光催化活性.本研究采用简单的水热法制备了一种新型Z型MoO3/Bi2O4复合光催化剂,SEM和TEM分析结果表明,MoO3和Bi2O4紧密结合在一起.X射线光电子能谱分析表明,MoO3和Bi2O4之间存在很强的界面相互作用,这有助于电荷转移和光生载流子的分离.光致发光光谱、电阻抗和光电流测试也证明了MoO3/Bi2O4复合光催化剂的光生载流子分离效率更高,形成了更强的光电流.通过在可见光下降解RhB溶液评价了所合成光催化剂的光催化性能.15%MoO3/Bi2O4(15-MB)复合光催化剂表现出了最佳的可见光催化活性,在40 min内对10 mg/L RhB溶液的降解率达到了99.6%,其降解速率是Bi2O4的2倍.此外,15-MB复合光催化剂在经过五次循环降解RhB溶液后仍保持良好的光催化活性和稳定性,表明MoO3/Bi2O4复合光催化剂具有较强的应用潜力.通过自由基捕获实验确定了光催化反应中主要的活性自由基为 O2-和h+.通过莫特-肖特基测试和带隙计算得到MoO3和Bi2O4的价带和导带位置.最后,根据实验和分析结果提出了Z型MoO3/Bi2O4复合光催化剂在可见光下降解RhB溶液的机理.本研究为设计铋基Z型异质结光催化剂用于高效去除环境污染物提供了一种有前景的策略.     

NaF浸泡处理对BiOBr光催化降解有机染料罗丹明B的影响

以五水硝酸铋(Bi(NO_3)_3·5H_2O)和溴代十六烷基吡啶(CPB)为原料,通过水热法合成溴氧化铋(BiOBr)光催化剂,并在pH=3.3的条件下分别用0.01 mol/L、0.1 mol/L、0.3 mol/L NaF溶液对其进行浸泡氟化处理得新催化剂BiOBr-F_(0.01)、BiOBr-F_(0.1)和BiOBr-F_(0.3).运用XRD(X-射线衍射)、SEM(扫描电镜)、UV-Vis DRS(紫外-可见漫反射光谱)、XPS(X-射线光电子能谱)、FL(荧光光谱)等技术对催化剂的物理结构及性质进行表征并研究了其在可见光(λ≥420 nm)下对有机染料罗丹明B(Rhodamine B,RhB)的催化降解活性.结果表明,随着NaF浓度增加,催化剂的结构及性质均发生一定程度的改变.氟化使得BiOBr对RhB的矿化能力减弱;但BiOBr-F_(0.1)使RhB褪色加快.RhB在降解过程中涉及到超氧自由基(O_2~(·-))、羟基自由基(·OH)及空穴(h~+)氧化,矿化率减小归因于活性物种产量降低,BiOBr-F_(0.1)使褪色加速则是加快了RhB的脱烷基过程,使最大吸收峰快速蓝移.     

Bi_(12)O_(17)Br_2和Bi_4O_5Br_2纳米片的简易制备及光催化氧化NO机理的原位漫反射红外光谱研究(英文)

BiOBr因具有合适的能带结构和独特的层状纳米结构而广泛应用于可见光催化领域,但其低的可见光利用率和高的光生电子-空穴对复合率,限制了其实际应用.最近,非整比BiOBr纳米材料表现出了良好的可见光催化性能.本课题组分别采用简易水热法和常温法制备得Bi_(12)O_(17)Br_2和Bi_4O_5Br_2纳米片,并表现出良好的可见光催化性能.然而,对于Bi_(12)O_(17)Br_2和Bi_4O_5Br_2的可见光催化氧化NO的转化路径及反应机理还不清楚.基于此,本文采用射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、电子自旋共振(ESR)、电子顺磁共振(EPR)和比表面积-孔结构(BET-BJH)等手段研究了Bi_(12)O_(17)Br_2和Bi_4O_5Br_2的理化性能,通过原位红外光谱(in situ DRIFTS)研究了Bi_(12)O_(17)Br_2和Bi_4O_5Br_2的可见光催化氧化NO的转化路径及反应机理.XRD结果表明,在常温碱性环境下,OH~-离子逐步取代BiOBr中的Br-离子制备得单斜晶相Bi_4O_5Br_2;在水热碱性环境下,OH-离子进一步取代Bi_4O_5Br_2中的Br-离子制备得四方晶相Bi_(12)O_(17)Br_2.SEM和TEM结果表明,Bi_(12)O_(17)Br_2是由不规则纳米片堆叠形成的紧密且厚实的层状结构,Bi_4O_5Br_2是由纳米片和纳米颗粒无序堆积形成的多孔疏松结构.BET-BJH测试结果显示,Bi_4O_5Br_2的比表面积和孔容(37.2 m~2/g,0.215 cm~3/g)显著高于Bi_(12)O_(17)Br_2(8.7 m~2/g,0.04 cm~3/g).UV-Vis DRS测试结果显示,Bi_(12)O_(17)Br_2和Bi_4O_5Br_2均显示了良好的可见光吸收能力.可见光催化去除NO的测试结果表明,Bi_4O_5Br_2(41.8%)的光催化活性明显高于Bi_(12)O_(17)Br_2(28.3%).并且,在5次可见光催化循环实验后,Bi_4O_5Br_2(41.1%)表现出良好可见光催化稳定性.ESR测试结果表明,Bi_(12)O_(17)Br_2和Bi_4O_5Br_2参与反应的主要活性物种均为·OH自由基,Bi_4O_5Br_2产生·OH自由基明显强于Bi_(12)O_(17)Br_2.EPR测试结果表明,Bi_4O_5Br_2的氧空位明显多于Bi_(12)O_(17)Br_2,丰富的氧空位更有利于NO的有效吸附.由此可见,Bi_(12)O_(17)Br_2和Bi_4O_5Br_2表现出不同的理化特性.可见光催化氧化NO的原位红外光谱表明,只在Bi_(12)O_(17)Br_2光催化氧化NO的转化路径中会生成中间产物N2O3,表明Bi_(12)O_(17)Br_2和Bi_4O_5Br_2具有不同的NO光催化转化路径.结合上述表征结果认为,Bi_4O_5Br_2比Bi_(12)O_(17)Br_2表现出更优异可见光催化性能的主要原因有以下四个方面为:(1)Bi_4O_5Br_2拥有更高的比表面积和更大的孔容,有利于NO的吸附、反应中间产物的转移和提供更多的活性位点参与光催化反应;(2)Bi_4O_5Br_2可以生成更多的·OH自由基和拥有更强的价带空穴氧化能力;(3)NO中的O原子可以与Bi_4O_5Br_2的氧空位结合,从而提供更多的反应位点;(4)Bi_4O_5Br_2的光催化反应中可以生成中间产物N_2O_3,可以降低NO转化成NO_3~-的反应活化能.     

双功能S-型g-C3N4/Bi/BiVO4复合光催化剂驱动人工碳循环（英文）

长期以来,陆地、大气和海洋之间的碳循环维持了大自然碳平衡.随着密集人类活动和高度工业发展,碳燃料、碳化学品和碳材料广泛应用于各个领域,导致碳排放过量,碳平衡已被严重破坏,碳污染已成为一个严峻问题.例如,持久性有机污染物和挥发性有机化合物过量排放到环境中,威胁着人类的健康和生态平衡.人们陆续开发出各种先进的环境技术,如微生物分解,去除空气和水中的碳基污染物,将有毒有害的有机化合物转化为无害CO2.但是,CO2本身是大气中的主要温室气体,它在大气中的浓度早超过了天然碳循环所能维持的环境自洁净能力.基于先进催化技术建立人工碳循环,将有机污染物矿化生成的CO2进一步转化为有价值的有机化学品(如太阳能燃料)是一种理想的低碳方法.光合作用是自然碳循环中核心过程之一,是降低大气中CO2浓度的关键.受到光合作用启发,科学家们积极开发人工光合成技术推动CO2资源化.人工光合成技术本质上基于半导体光催化过程.半导体光催化过程具有双重作用.一方面,基于有氧光催化氧化过程,有机污染物可以矿化生成无毒CO2.另一方面,基于缺氧光催化还原过程,CO2可以转化为碳氢化合物太阳能燃料.理论上,结合上述两个过程,为建立人工碳循环奠定基础,但是,至今很少有人成功建立有氧氧化-无氧还原串联光催化工艺,实现人工碳循环.难点在于有机污染物的有氧氧化反应和CO2的无氧还原反应的操作条件与反应机制是完全不同的,目前缺乏同时适用于上述两种反应的双功能光催化剂.本文成功构建了具有双功能的g-C3N4/Bi/BiVO4三元复合光催化剂,它不仅在降解有机污染物方面表现出优异的有氧光催化氧化性能(以降解染料罗丹明B为例),而且还表现出优异的缺氧CO2光催化还原性能.此外,基于“一锅法”厌氧耦合氧化-还原反应,g-C3N4/Bi/BiVO4三元复合光催化剂成功实现同步罗丹明B降解与太阳能燃料生成,构建了从毒害有机污染物到高品质太阳燃料的碳循环.结合牺牲剂实验分析与密度泛函理论理论计算,作者提出g-C3N4/Bi/BiVO4复合光催化剂的双功能性与g-C3N4与BiVO4界面内建S-型复合异质结有关.S-型复合异质结既促进界面电荷转移与分离,又维持了最佳电荷氧化还原电位.此外,S型g-C3N4/Bi/BiVO4复合光催化剂中原位生成的具有等离子体效应的Bi纳米颗粒具有双重作用,既促进界面电荷定向转移,又促进可见光吸收.本文开发的新型双功能S-型g-C3N4/Bi/BiVO4复合光催化剂系统为进一步开发集成式有氧-缺氧光催化碳循环反应系统奠定基础.     

Kinetic and product study of the gas-phase reactions of OH radicals, NO(3) radicals, and O(3) with (C(2)H(5)O)(2)P(S)CH(3) and (C(2)H(5)O)(3)PS

Rate constants for the reactions of OH radicals and NO3 radicals with O,O-diethyl methylphosphonothioate [(C(2)H(5)O)(2)P(S)CH(3); DEMPT] and O,O,O-triethyl phosphorothioate [(C(2)H(5)O)(3)PS; TEPT] have been measured using relative rate methods at atmospheric pressure of air over the temperature range 296-348 K for the OH radical reactions and at 296 +/- 2 K for the NO(3) radical reactions. At 296 +/- 2 K, the rate constants obtained for the OH radical reactions (in units of 10(-11) cm(3) molecule(-1) s(-1)) were 20.4 +/- 0.8 and 7.92 +/- 0.27 for DEMPT and TEPT, respectively, and those for the NO(3) radical reactions (in units of 10(-15) cm(3) molecule(-1) s(-1)) were 2.01 +/- 0.20 and 1.03 +/- 0.10, respectively. Upper limits to the rate constants for the reactions of O(3) with DEMPT and TEPT of <6 x 10(-20) cm(3) molecule(-1) s(-1) were determined in each case. Rate constants for the OH radical reactions, measured relative to k(OH + alpha-pinene) = 1.21 x 10(-11) e(436/T) cm(3) molecule(-1) s(-1), resulted in the Arrhenius expressions k(OH + DEMPT) = 1.08 x 10(-11) e(871+/-25)/T cm(3) molecule(-1) s(-1) and k(OH + TEPT) = 8.21 x 10(-13) e(1353+/-49)/T cm(3) molecule(-1) s(-1) over the temperature range 296-348 K, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the reference rate constant. Diethyl methylphosphonate was identified and quantified from the OH radical and NO(3) radical reactions with DEMPT, with formation yields of 21 +/- 4%, independent of temperature, from the OH radical reaction and 62 +/- 11% from the NO(3) radical reaction at 296 +/- 2 K. Similarly, triethyl phosphate was identified and quantified from the OH radical and NO(3) radical reactions with TEPT, with formation yields of 56 +/- 9%, independent of temperature, from the OH radical reaction and 78 +/- 15% from the NO(3) radical reaction at 296 +/- 2 K.     

Controlled synthesis of olive-shaped Bi2S3/BiVO4 microspheres through a limited chemical conversion route and enhanced visible-light-responding photocatalytic activity

Well-defined olive-shaped Bi(2)S(3)/BiVO(4) microspheres were synthesized through a limited chemical conversion route (LCCR), where olive-shaped BiVO(4) microspheres and thioacetamide (TAA) were used as precursors and sulfur source, respectively. The as-synthesized products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission microscope (HRTEM), X-ray photoelectron spectra (XPS), UV-visible diffuse-reflectance spectroscopy (UV-vis DRS), and photoluminescence (PL) spectra in detail. Compared with pure BiVO(4) microspheres and Bi(2)S(3) nanorods, the Bi(2)S(3)/BiVO(4) products showed obviously enhanced photocatalytic activity for the degradation of rhodamine B (Rh B) in aqueous solution under visible-light irradiation (λ > 400 nm). In addition, the Bi(2)S(3)/BiVO(4) composite microspheres showed good visible-light-driven photocatalytic activity for the degradation of refractory oxytetracycline (OTC) as well. On the basis of UV-vis DRS, the calculated energy band positions, and PL spectra, the mechanism of enhanced photocatalytic activity of Bi(2)S(3)/BiVO(4) was proposed. The present study provides a new strategy to design composite materials with enhanced photocatalytic performance.     

From hollow olive-shaped BiVO4 to n-p core-shell BiVO4@Bi2O3 microspheres: controlled synthesis and enhanced visible-light-responsive photocatalytic properties

In this study, hollow olive-shaped BiVO(4) and n-p core-shell BiVO(4)@Bi(2)O(3) microspheres were synthesized by a novel sodium bis(2-ethylhexyl)sulfosuccinate (AOT)-assisted mixed solvothermal route and a thermal solution of NaOH etching process under hydrothermal conditions for the first time, respectively. The as-obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, Brunauer-Emmett-Teller surface area, and UV-vis diffuse-reflectance spectroscopy in detail. The influence of AOT and solvent ratios on the final products was studied. On the basis of SEM observations and XRD analyses of the samples synthesized at different reaction stages, the formation mechanism of hollow olive-shaped BiVO(4) microspheres was proposed. The photocatalytic activities of hollow olive-shaped BiVO(4) and core-shell BiVO(4)@Bi(2)O(3) microspheres were evaluated on the degradation of rhodamine B under visible-light irradiation (λ > 400 nm). The results indicated that core-shell BiVO(4)@Bi(2)O(3) exhibited much higher photocatalytic activities than pure olive-shaped BiVO(4). The mechanism of enhanced photocatalytic activity of core-shell BiVO(4)@Bi(2)O(3) microspheres was discussed on the basis of the calculated energy band positions as well. The present study provides a new strategy to enhancing the photocatalytic activity of visible-light-responsive Bi-based photocatalysts by p-n heterojunction.     

Urea-based hydrothermal growth, optical and photocatalytic properties of single-crystalline In(OH)3 nanocubes

Nearly monodisperse single-crystalline In(OH)(3) nanocubes were successfully synthesized using In(NO(3))(3) x 4.5 H(2)O as indium source in the presence of urea and cetyltrimethyl ammonium bromide (CTAB) by a two-step hydrothermal process: the stock solution was heated at 70 degrees C for 24 h and then at 120 degrees C for 12 h. The structure and morphology of the resultant In(OH)(3) samples were determined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results revealed that most of as-synthesized In(OH)(3) nanocubes were uniform in size, with the average edge length of approximately 700 nm. The influences of the reaction temperature, the reaction time, the mineralizer, and the surfactant on the morphology of the obtained products were discussed in detail. Room-temperature photoluminescence (PL) spectrum of the In(OH)(3) nanocubes showed a peculiar strong emission peak centered at 480 nm. Furthermore, the photocatalytic properties of the In(OH)(3) nanocubes were tested. It was found that In(OH)(3) exhibited not only higher activity for benzene removal, but also better H(2) evolution from water than the commercial Degussa P25 TiO(2).     

Controllable synthesis and visible-light-responsive photocatalytic activity of Bi2WO6 fluffy microsphere with hierarchical architecture

Bismuth tungstate (Bi(2)WO(6)) has attracted great research interest as an important visible-light-responsive photocatalyst. In this paper, we report a facile hydrothermal route for the shape-controlled synthesis of micro/nanostructured Bi(2)WO(6), without adding surfactants or templates. The results show that various morphologies of Bi(2)WO(6) including coralloid spherical particles, packed nanosheets, fluffy microspheres, and plates can be obtained by adjusting the pH values of the precursors. The as-prepared porous fluffy microspheres with a hierarchical architecture synthesized at pH 8 exhibit the highest photocatalytic activity for the degradation of Rhodamine (RhB) under visible light irradiation. The photodegradation efficiency reaches as high as 99% within 20 min irradiation. This enhanced photocatalytic activity can be attributed to the unique porous structure and high BET surface area of fluffy microspheres with hierarchical architecture.