α-Fe2O3/W18O49纳米复合光催化剂的制备及其光催化固氮性能研究

采用水热法合成α-Fe_2O_3/W_(18)O_(49)复合光催化剂,将α-Fe_2O_3颗粒修饰在W_(18)O_(49)颗粒表面。通过XRD、SEM、FTIR、XPS和UV-vis等表征手段分别研究了样品的物相、结构、形貌、组成和吸光特性等。并利用光催化固氮装置考察了模拟太阳光照射下,不同复合比例下样品的光催化固氮的性能。结果表明,复合后催化剂较原始催化剂具有更窄的禁带、更高的可见光响应强度;2%α-Fe_2O_3/W_(18)O_(49)纳米复合材料光催化固氮性能最佳,在3 h内的光催化反应的固氮量达到了1861.43μg·g~(-1)_(cat),为单一W_(18)O_(49)催化剂的固氮量的～1.97倍。最后,讨论了有关2%α-Fe_2O_3/W_(18)O_(49)异质结光催化固氮的可能机制。     

CoFe_2O_4磁性光催化材料的制备及其对四环素废水的降解

通过水热法成功制备了CoFe_2O_4磁性光催化材料,并将合成的CoFe_2O_4磁性材料应用于可见光照射下降解四环素(TC)模拟废水,考察了CoFe_2O_4磁性材料的光催化性能,同时考察了CoFe_2O_4制备过程中不同制备条件对其光催化活性的影响。通过捕获实验考察CoFe_2O_4光催化降解四环素的主要活性自由基;经过3次循环实验发现,采用水热法合成的CoFe_2O_4磁性光催化材料具有较好的稳定性,对四环素模拟废水的降解率达到65.78%。     

半导体光催化材料的能带结构优化和纳米复合修饰

总结了课题组通过半导体光催化材料的能带结构优化和纳米复合修饰,获得响应可见光以及具有实际应用的高效光催化材料方面所取得的一些进展工作。通过稀土元素调变光催化材料电子结构发现,K_4Ce_2M_(10)O_(30)(M:Nb,Ta)半导体复合金属氧化物及其固溶体化合物K_4Ce_2Nb_(10-x)Ta_xO_(30)具有1.8～2.2eV的禁带宽度和适合的电化学电位。对其不同负载研究表明,纳米NiOx的修饰能显著提高光解水制氢活性。同时还发现了一种负载纳米Pt/Cr_2O_3的Bi-V-(M)-O固溶体氧化物在可见光下具有完全分解纯水为H_2和O_2 (2:1)的能力,能有效利用560nm以下的太阳光,有望成为一种高效而稳定的新型实用化光解水材料。利用第一性原理研究了材料的电子结构,揭示了可见光活性机制,探讨了TiN (111)晶面取向的活性,为进一步构筑新型高效光催化剂提供了思路。通过纳米复合获得了SiO_2/NiFe_2O_4、TiO_(2-x)N_x/SiO_2/NiFe_2O_4、Bi_(12)TiO_(20)/SiO_2/NiFe_2O_4等具有可磁分离特性的复合光催化剂,首次通过反胶束法制备出具有...     

棒状α-Fe_2O_3/ZnO复合物的制备及其光催化性能

以硝酸锌(Zn(NO_3)_2)、硝酸铁(Fe(NO_3)_3)和氢氧化钠(NaOH)为原料,采用液相沸腾回流法制得了不同长径比的棒状α-Fe_2O_3异质复合ZnO光催化剂。用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)及紫外-可见漫反射光谱(UV-visDRS)等多种手段对产物进行表征。以"三致"污染物五氯酚为降解对象,考察了紫外-可见光照下样品的光催化效果。结果表明,棒状α-Fe_2O_3/ZnO复合光催化剂的性能与其α-Fe_2O_3的含量密切相关。当α-Fe_2O_3与ZnO的物质的量比为1∶5时,样品光催化活性最高,4h内即可将五氯酚降解完全。     

α-Fe2O3-ZnO/煤矸石复合光催化剂的制备及其降解五氯酚性能的研究

以氯化铁(FeCl_3)、氯化锌(ZnCl_2)、煤矸石和氢氧化钠(NaOH)为原料,采用沸腾回流法制得了一系列纳米三氧化二铁(α-Fe_2O_3)和氧化锌(ZnO)不同摩尔配合比的纳米三氧化二铁-氧化锌/煤矸石复合光催化剂(α-Fe_2O_3-ZnO/煤矸石复合光催化剂),并对产物进行了表征。以五氯酚(PCP)为目标降解物,考察了模拟太阳光照条件下样品的光催化降解效果。结果表明,将球形α-Fe_2O_3-ZnO复合物负载于改性煤矸石表面可有效提高其光催化活性,且α-Fe_2O_3-ZnO/煤矸石复合光催化剂的性能与α-Fe_2O_3和ZnO的摩尔配合比有关,在α-Fe_2O_3与ZnO的摩尔配合比为1∶5,光照4h条件下,α-Fe_2O_3-ZnO/煤矸石复合光催化剂对PCP的降解率达到100%,具有最佳的光催化降解效果,此外还具有可重复使用的特点。     

水热法制备N-TiO_2/RGO复合材料及光催化性能研究

采用一步水热法制备氮掺杂负载石墨烯(RGO)的二氧化钛(TiO_2)复合光催化材料(N-TiO_2/RGO),对样品进行XRD、SEM、UV-Vis等表征并以甲基橙为目标降解物进行可见光光催化活性测试。结果表明:N-TiO_2/RGO比同条件下制得的N-TiO_2和TiO_2/RGO具有更好的可见光光催化性能,可见光下照射5h,对甲基橙的降解率可达到95%。     

溶胶-凝胶法原位制备还原氧化石墨烯/二氧化钛复合材料及光催化性能

采用溶胶-凝胶法和改进的Hummers法制备了还原氧化石墨烯/二氧化钛(RGO/TiO_2)复合光催化剂。对该光催化剂的形貌、结构进行了表征与分析,并以亚甲基蓝(MB)模拟有机废水,研究了该复合材料的光催化性能。结果表明,大量TiO_2粒子负载在RGO片层表面形成膜层,分散均匀;在RGO/TiO_2中,TiO_2为锐钛矿型,RGO仍保留部分含氧官能团;RGO的引入使得RGO/TiO_2吸收带发生红移,能带宽度由3.2 eV降低至3.0 eV;RGO/TiO_2复合光催化剂具有良好的光催化降解性及循环稳定性,在持续光照MB溶液30 min后,最高降解率可达96.9%,5次循环光催化降解后,RGO/TiO_2仍有近90%的降解效率。     

Fe_3O_4/G-BiOCl纳米复合光催化剂的制备及光催化性能研究

以自制的氧化石墨烯、BiOCl/Fe_3O_4为原料,以水合肼为还原剂,制备出Fe_3O_4/石墨烯(G)-BiOCl复合光催化剂。运用X射线衍射、透射电镜和扫描电镜对Fe_3O_4/G-BiOCl的组成和形貌进行了表征,运用振动样品磁强计对其磁性进行了测试;对照研究了Fe_3O_4/G-BiOCl、BiOCl/Fe_3O_4和纯BiOCl对罗丹明B的光催化降解能力以及Fe_3O_4/G-BiOCl光催化活性的循环稳定性。结果表明:Fe_3O_4/G-BiOCl复合光催化剂分布均匀,具有超顺磁性;Fe_3O_4/G-BiOCl的光催化性能优于纯BiOCl和BiOCl/Fe_3O_4,可回收再利用,并具有良好的循环稳定性。     

MIL-101前驱体制备MnO_x-Cr_2O_3催化剂及其对苯的催化氧化性能

以硝酸铬、对苯二甲酸、氢氟酸为原料,水热法制备MIL-101(Cr);经KMnO_4预浸渍、H_2O_2还原对其进行MnO_x负载,再经热解制备MnO_x-Cr_2O_3复合催化剂;借助BET、XRD、SEM、TEM、XPS等测试手段,研究不同MnO_x负载量的MnO_x-Cr_2O_3复合催化剂对苯的催化氧化活性。结果表明:氢氟酸的添加量对MIL-101(Cr)孔结构影响显著,添加125μL的氢氟酸制备的MIL-101(Cr)具有最佳的多孔性,经甲醇多次活化后,其比表面积达到3 447 m~2/g;MnO_x-Cr_2O_3复合催化剂,比表面积为89.30 m~2/g,远大于市售的Cr_2O_3载体的,对苯催化氧化的活性T_(90%)为280℃;MnO_x负载量质量分数为5%时,催化苯的T_(90%)为266℃,但增加MnO_x负载量对复合催化剂的催化活性影响不大;MnO_x-Cr_2O_3复合催化剂的高催化氧化活性归因于Mn与Cr之间的电子迁移与表面晶格氧含量高;其良好催化活性和无毒MnO_x包覆可抑制毒性Cr元素析出。     

磁性黏土基TiO2复合材料的制备及其光催化性能

采用溶剂热法将酸改性凹凸棒黏土(AATP)和Fe_3O_4纳米粒子复合,制备出磁性凹凸棒黏土复合载体(MATP);采用水热法在MATP上负载活性组分TiO_2,制成新型磁性复合光催化剂(TiO_2/MATP)。采用X射线衍射(XRD)、透射电镜(TEM)、X射线能谱(EDS)、比表面积分析和振动磁强计(VSM)等对样品进行了表征。结果表明,TiO_2/MATP复合材料包含Fe_3O_4磁性组分和锐钛矿相TiO_2活性组分,保持了凹凸棒黏土的纳米棒状和多孔结构,BET比表面积为130.88m~2/g,饱和磁化强度为14.40emu/g。对罗丹明B染料降解实验表明,TiO_2/MATP复合材料具有较高暗吸附特征和光催化活性,20min暗吸附率可达39.0%;在紫外光照射下,50min降解率达到97.2%。     

New photocatalysts based on MIL-53 metal-organic frameworks for the decolorization of methylene blue dye

The photocatalytic decolorization of methylene blue dye in aqueous solution using a novel photocatalyst MIL-53(Fe) metal-organic frameworks was investigated under UV-vis light and visible light irradiation. The effect of electron acceptor H(2)O(2), KBrO(3) and (NH(4))(2)S(2)O(8) addition on the photocatalytic performance of MIL-53(Fe) was also evaluated. The results show that MIL-53(Fe) photocatalyst exhibited photocatalytic activity for MB decolorization both under UV-vis light and visible light irradiation, and the MB decolorization over MIL-53(Fe) photocatalyst followed the first-order kinetics. The addition of different electron acceptors all enhances the photocatalytic performance of MIL-53(Fe) photocatalyst, and the enhanced rate follows the order of H(2)O(2)>(NH(4))(2)S(2)O(8)>KBrO(3) under UV-vis light irradiation, while in the order of (NH(4))(2)S(2)O(8)>H(2)O(2)>KBrO(3) under visible light irradiation. Moreover, MIL-53(Fe) did not exhibit any obvious loss of the activity for MB decolorization during five repeated usages. The photocatalytic activities over MIL-53(M) (M=Al, Fe), the isostructure to MIL-53(Fe), indicate that the metal centers show nil effect on the photocatalytic activity of MIL-53(M) photocatalysts.     

纳米α-Fe2O3/TiO2光催化剂的制备及其光催化性能研究

以硝酸铁为铁源,NaOH为沉淀剂合成单分散性良好的纳米α-Fe2O3粒子,然后与纳米TiO2胶体复合制备了纳米α-Fe2O3/TiO2光催化剂。利用动态光散射粒径分析仪、扫描电子显微镜、紫外-可见分光光度计、X射线衍射仪对光催化剂的物相、形貌进行了表征。在室温条件下,以甲醛作为有机污染物,在可见光照射下探讨了纳米α-Fe2O3粒径、α-Fe2O3摩尔分数等对甲醛光催化降解的影响。结果表明,在一定范围内,随着粒径的减小,纳米α-Fe2O3光催化活性增强,在120min内粒径40nm的纳米α-Fe2O3对甲醛的降解效果最好,降解率约为93.05%。与纯TiO2相比,纳米α-Fe2O3/TiO2光催化剂的可见光催化活性明显增强,纳米α-Fe2O3最佳含量为0.20%(摩尔分数)。纳米α-Fe2O3含量过大,纳米α-Fe2O3/TiO2光催化剂的催化活性将降低。     

Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites

Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Br?nsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed MIL101/PTA composites appear to be feasible for industrial catalytic applications.     

磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能

应用水热合成法制备了来瓦希尔骨架材料（MIL-101（Cr））,通过后磺化法将磺酸（SO₃H）基团引入MIL-101（Cr）的笼状结构中,得到具有质子传导功能的MIL-101（Cr）-SO₃H。FTIR结果表明,磺酸基团成功引入到MIL-101（Cr）中。SEM和XRD结果表明,磺化前后材料的粒径在纳米尺寸范围,且MIL-101（Cr）-SO₃H颗粒的晶体结构无坍塌。元素分析结果表明,MIL-101（Cr）-SO₃H的磺化度为0.36。然后将MIL-101（Cr）-SO₃H掺杂到磺化酚酞侧基聚芳醚砜（SPES-C）中制备了MIL-101（Cr）-SO₃H/SPES-C燃料电池用杂化质子交换膜。SEM结果说明,MIL-101（Cr）-SO₃H/SPES-C杂化膜内MIL-101（Cr）-SO₃H分散均匀,SPES-C与MIL-101（Cr）-SO₃H两相相容性较好,膜内无缺陷。TGA分析结果表明,MIL-101（Cr）-SO₃H/SPES-C杂化膜热稳定性优良。MIL-101（Cr）-SO₃H的引入可以提高MIL-101（Cr）-SO₃H/SPES-C杂化膜吸水率并降低甲醇渗透性。随填充物MIL-101（Cr）-SO₃H的含量增加和测试温度升高,MIL-101（Cr）-SO₃H/SPES-C杂化膜的质子传导率随之增大。当温度为80℃时,MIL-101（Cr）-SO₃H填充量为5wt%的MIL-101（Cr）-SO₃H/SPES-C杂化膜的质子传导率达到0.162 S·cm-1,比商用Nafion膜的质子传导率（0.134 S·cm-1）提高了20.1%。      

RGO-MIL-68(Fe)复合材料的静电自组装合成及光催化还原Cr(Ⅵ)的性能

采用静电自组装方法制备氧化石墨烯（GO）-MIL-68（Fe）复合物,并通过简单溶剂热处理,将GO还原为还原氧化石墨烯（RGO）,首次制得RGO-MIL-68（Fe）复合物。通过XRD、FESEM、紫外-可见漫反射光谱（UV-Vis DRS）等方法对RGO-MIL-68（Fe）复合催化剂的晶体结构、形貌、光吸收性能等物理化学性质进行表征。在可见光照射下,以草酸铵（（NH₄）₂C₂O₄）为牺牲剂,对RGO-MIL-68（Fe）复合材料进行光催化还原Cr（Ⅵ）性能评价,结果表明,只需复合少量的RGO,MIL-68（Fe）的光催化活性就能显著地提高。当RGO含量为1wt%时,RGO-MIL-68（Fe）复合材料表现出最优的光催化活性,反应60 min,体系中的Cr（Ⅵ）的还原率高达81%。结合电化学分析可知,这主要是由于RGO的引入在增强MIL-68（Fe）光吸收性能的同时也促进了光生载流子的分离。      

PT／TiO2复合粒子光催化降解有机污染物的性能

在CHCl3中以FeCl3为氧化剂通过原位化学氧化方法制备了聚噻吩/二氧化钛(PT/TiO2)复合粒子。通过X射线光电子能谱(XPS)和紫外可见漫反射光谱(DRS)分析,分别研究了PT/TiO2复合粒子的结构和光响应特性。结果表明,复合粒子是由PT包裹在TiO2粒子表面而形成的具有核-壳结构的粒子;复合粒子能吸收200 nm~800 nm波长的光。分别以甲基橙和苯酚为目标污染物,研究了PT/TiO2复合粒子光催化降解污染物的性能。结果表明,具有一定含量聚噻吩的复合粒子光催化降解污染物的性能优于TiO2。     

Ag3PO4/ZnO@碳球三元异质结的合成及可见光催化性能

以片花状的ZnO@碳球(ZnO@C)为前驱物,采用原位沉淀法使Ag3PO4颗粒生长在其表面形成Ag3PO4/ZnO@碳球(Ag3PO4/ZnO@C)三元复合物。利用XRD,SEM,Raman,UV-VisDRS及瞬态光电流响应等技术对合成样品进行表征,并测试其可见光催化性能。结果表明:ZnO@C的引入能够显著提高Ag3PO4的光催化性能,其中5%(质量分数)ZnO@C与Ag3PO4的复合物AP-Z-5光催化效果最佳。在5mg/LFe(NO3)3牺牲剂存在的情况下,AP-Z-5在20min内能完全降解亚甲基蓝,光催化循环4次后仍保持86%的降解能力。AP-Z-5在Cr(VI)与亚甲基蓝混合废水中对亚甲基蓝依然能保持较高的光催化降解能力。     

磁性纳米TiO2/SiO2/Fe3O4光催化剂的制备及表征

以纳米Fe3O4磁粉为核心，采用溶胶一凝胶法制备了TiO2／SiO2／Fe3O4复合光催化剂．用XRD、TEM及元素分析对其结构和表面形貌进行了表征．以具有偶氮染料结构的甲基橙水溶液为目标反应物，评价其光催化活性．结果表明，所制TiO2／SiO2／FeaO4样品为双层包覆型结构，SiO2为中间层，最外层是锐钛矿型的TiO2,该复合光催化剂对甲基橙溶液有较高的光催化活性，并具有可利用其磁性回收重用的特点，应用前景广泛。     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

TiO2/活性炭复合体超临界沉淀法制备及其光催化性能

以活性炭为载体、超临界二氧化碳为流体、钛酸丁酯为前驱体,用超临界流体沉积法制备TiO2/活性炭（TiO2/AC）复合体。用X射线衍射（XRD）、扫描电镜（SEM）、比表面积分析（BET）、热重-差热（TG-DTA）对TiO2/AC进行表征。以紫外灯为光源,偶氮类染料亚甲基蓝为标准降解物,考察TiO2/AC复合体的光催化...