可见光响应型Bi2WO6光催化剂

Bi₂WO₆作为一种新型半导体光催化剂,具有较窄的带隙宽度和特殊的层状结构,因而显示出良好的可见光催化性能。本文综述了围绕提高Bi₂WO₆的光催化活性和实用性而开展的相关研究成果,包括:纳米结构Bi₂WO₆材料;分级超结构Bi₂WO₆材料;Bi₂WO₆光催化剂的系列修饰改性,如金属氧化物复合、碳烯和金属单质的表面沉积,以及金属离子和非金属离子的掺杂等。此外,还从回收角度综述了Bi₂WO₆的固定化技术。最后对Bi₂WO₆光催化剂的发展趋势进行了展望,强调对Bi₂WO₆进行带隙调控,并加强对其异质结构界面状态的研究,通过理论计算可深入理解光催化机制,以从制备入手指导现有催化剂的改良和设计新型光催化剂。     

Facile Electrospinning of CeO2/Bi2WO6 Heterostructured Nanofibers with Excellent Visible‐light‐driven Photocatalytic Performance

One‐dimensional (1D) CeO₂/Bi₂WO₆ heterostructured nanofibers with a diameter of about 300 nm were successfully synthesized by using a straightforward strategy combining an electrospinning technique with a sintering process. The acquired products were characterized by thermogravimetric and differential scanning calorimetric (TG‐DSC), Fourier transform infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) surface area measurements, and UV/Vis spectroscopy. The obtained CeO₂/Bi₂WO₆ heterostructured nanofibers exhibited an excellent photocatalytic property for the degradation of Rhodamine B (RhB) dye driven by visible light due to the promoted separation of photoelectrons and holes and the large contact area between the photocatalyst and organic pollutant.     

亚硫酸盐协助中空Bi2WO6微球的光催化性能

本文利用亚硫酸盐与Bi2WO6协同作用,有效地提升其光催化活性。以甲基橙和抗生素环丙沙星(CIP)作为被降解物对该体系的光催化降解性能和机理进行了研究。结果表明:光催化活性增强主要原因为亚硫酸盐能与Bi2WO6的光生空穴及羟基自由基反应,不仅能生成新的活性物质亚硫酸自由基(SO3^2-),还能促进Bi2WO6光生电子—空穴对的分离。此外,还考察了催化剂的用量、和污染物的浓度对该体系光催化性能的影响。     

增强光催化活性的3D分级结构Bi2W06微球及表面酸性

以KNO3为矿化剂,用水热法制备了3D分级结构Bi2WO6微球,通过XRD、SEM、BET对产物进行了表征．探讨了3D分级结构Bi2WO6微球可能的形成机理．以罗丹明B为模型污染物,研究了合成产物的光催化性质．结果表明：在紫外光下,RhB的降解以共轭结构断裂的光催化反应为主;而在可见光照射下,RhB的降解可能是光催化和光敏化共同作用的结果．进一步以吡啶为探针分子,通过吸附吡啶红外光谱探讨了Bi2W06表面酸性与光催化降解RhB之间的关系．研究显示,Bi2W06具有较强的表面酸性,增强了Bi2WO6与RhB分子之间吸附作用,有利于染料分子上的电子跃迁至催化剂上,易于发生光敏化和光催化反应。     

盐辅助-超生喷雾热分解法合成中空Bi2WO6纳米微球去除NO的应用

氮氧化物(简称NOx,包括NO和NO2等)是形成二次有机气溶胶的重要前体物,其存在会严重影响空气质量并危害人类健康.目前用于NOx的去除的方法主要有过滤、物理吸附、热催化等.然而,这些技术存在高能耗及产生二次污染等缺点,严重制约其实际应用.近年来,光催化技术作为一种有效处理NOx的环保技术,因其具备在常温下高效处理低浓度NOx(大气污染浓度水平)的优点而获得广泛关注.最近,Bi2WO6光催化剂因其独特的层状结构以及特有的催化性质,表现出良好的可见光催化性能.Bi2WO6光催化性能与催化剂的形貌及尺寸大小密切相关,目前报道的Bi2WO6的形貌有片状、颗粒状、花状、中空微球等.其中,由小纳米颗粒堆积成的中空Bi2WO6微球因其大的比表面积和高的荷质传输速率,表现出显著优于其它形貌的光催化性能.目前已有少量关于中空结构Bi2WO6微球的制备方法的报道,这些方法均需引入纳米球状的"核"作为模板,并在其上生长Bi2WO6胶体颗粒,然后去除"核",从而得到中空结构.譬如,Shang等采用碳纳米球作为"核"制备出Bi2WO6微球,再通过煅烧手段去除碳"核".Thillai与合作者用硅球作为"核",为了得到中空结构Bi2WO6微球,用NaOH将硅"核"刻蚀.然而这类方法均涉及到复杂的制备过程和高昂的运行成本.超生喷雾热分解法是一种常见的制备尺寸可控的纳米球的方法.在之前的工作中,本研究组成功使用超声喷雾热解法制备出具有优良光催化活性的Bi2WO6实心微球.我们首次加入NaCl盐为模板,使用简单的超声喷雾热分解方法制备出具有中空结构的Bi2WO6微球光催化剂,合成过程无需采用复杂的除"核"手段.一系列表征表明:该微球由直径为41?148 nm的纳米片自组装而成,并在表面形成了不均匀分布的孔结构;并对Bi2WO6中空微球的生长机制做了详细的研究,考察了所制备Bi2WO6催化剂去除NO的效率.生长机制研究结果表明,NaCl盐在中空Bi2WO6微球的形成过程中发挥着关键性作用:(1)NaCl盐溶液在超生喷雾热分解法的高温过程中形成NaCl单晶并作为"核"模板,参与中空Bi2WO6微球的形成;(2)Na+离子有助于Bi2WO6微球的微结构-纳米片的生长;(3)Cl?离子有利于Bi2WO6微球表面微孔的形成;(4)NaCl模板水洗后留下中空结构的Bi2WO6微球;(5)NaCl盐也充当着多孔诱发剂,其水洗溢出过程会造成Bi2WO6微球表面的孔结构.性能测试表明,以NaCl盐为模板所制备的中空Bi2WO6微球表现出优异的光催化性能,其在模拟太阳光下去除NO的效率是未添加模板的1.7倍、以KCl为模板的1.5倍、以Na2SO4为模板的1.2倍.BET和DRS分析表明,中空结构Bi2WO6微球具有大的比表面积和高的可见光吸收,对提高催化性能起到重要作用.ESR测试结果表明,?OH和?O2?是中空Bi2WO6微球的光催化反应过程的主要活性物种,?O2?的产生有助于提高光催化剂降解NO的耐受性.     

制备方法对复合氧化物Bi_2WO_6-ZrO_2-TiO_2光催化性能的影响

采用一积沉淀法和两积沉淀法分别制备了Bi2WO6-ZrO2-TiO2复合催化剂。利用X射线衍射(XRD),N2吸附(BET),傅里叶变换(FT-IR)光谱技术,X光电子能谱(XPS),紫外-可见(UV-Vis)漫反射光谱等分析技术对样品进行了表征。结果显示,两积沉淀法的Bi、W离子存在于催化剂表面,而一积沉淀法是进入催化剂晶格。利用气相苯进行催化剂的紫外和可见光活性实验,结果表明,两积沉淀法制备的复合催化剂活性最高。     

钨酸铋担载钯纳米粒子光催化甲苯及其衍生物到醛的氧化反应

甲苯及其衍生物的选择性氧化是化学工业中重要的一环.氧化产物醛、酮和酸类化合物是各种农药、染料、防腐剂、阻燃剂、香料、塑料的合成中间体.在传统的化工过程中,通常在苛刻的条件下,如高温、高压以及酸性溶剂中进行甲苯的选择性氧化.光催化有机合成作为一种"绿色"的合成方法受到越来越多的关注.我们发现钨酸铋作为可见光响应的光催化剂,可以利用氧气作为氧化剂,对甲苯及其衍生物进行催化氧化反应.通过调节水热法合成钨酸铋的酸碱条件,控制其成核生长过程,改变其形貌,发现在pH值为0.49时,得到花状钨酸铋粉末活性最高.X射线衍射、扫描电镜、紫外可见吸收光谱和比表面测定结果发现,花状钨酸铋粉末表现出最佳的甲苯氧化活性很可能是与它最大的比表面积有关系.为了进一步提高催化的活性,我们将助催化剂担载在钨酸铋粉末上,发现Pd的担载量为0.1 wt%时甲苯氧化反应活性最高.将邻、间、对位甲基取代以及对位甲氧基和氯取代的甲苯衍生物进行反应,发现均可高选择性地得到目标产物.在加入电子牺牲剂硝酸银和空穴牺牲剂草酸铵到反应体系后,发现反应被完全禁阻,说明在甲苯氧化反应过程中电子和空穴都起到了相应的作用.通过电化学测试发现,钯作为助催化剂担载在钨酸铋表面后,产生更强的氧化和还原信号,说明其在电子和空穴发生反应的过程中都起到了相应的促进作用.由此推测,在甲苯的氧化反应中,钨酸铋材料表面吸收可见光,产生光生电子和空穴,而钯的担载则促进了电子和空穴进行氧气还原和甲苯氧化的过程.     

网状钼酸铋的可见光催化活性

采用无助剂、无模板的水热法成功合成网状Bi2MoO6. pH值对这一形貌的形成起重要作用. 所制备的网状Bi2MoO6样品表现出优异的可见光催化活性,其光催化活性比固相法合成的块状Bi2MoO6样品高得多.     

Enhanced visible‐light‐driven photocatalytic activity of F doped reduced graphene oxide ‐ Bi2WO6 photocatalyst

The reduced graphene oxide‐Bi₂WO₆ (rGO‐BWO) photocatalysts with the different R_F/O values (molar ratio of the F molar mass and the O's molar mass of Bi₂WO₆) had been successfully synthesized via one‐step hydrothermal method. The F‐doped rGO‐BWO samples were characterized by X‐ray diffraction patterns (XRD), field‐emission scanning electron microscopy (FE‐ESEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area (BET), X‐ray photoelectron spectroscopy (XPS) and UV–vis diffuse reflectance spectra (DRS). The results indicate that F^? ions had been successfully doped into rGO‐BWO samples. With the increasing of the R_F/O values from 0 to 2%, the evident change of the morphology and the absorption edges of F‐doped rGO‐BWO samples and the photocatalytic activities had been enhanced. Moreover, the photocatalytic activity of F‐doped rGO‐BWO with R_F/O = 0.05 were better than rGO‐BWO and the other F‐doped rGO‐BWO under 500 W Xe lamp light irradiation. The enhanced photocatalytic activity can be attributed to the morphology of the intact microsphere that signify the bigger specific surface area for providing more possible reaction sites for the adsorption–desorption equilibrium of photocatalytic reaction, the introduction of F^? ions that may cause the enhancement of surface acidity and creation of oxygen vacancies under visible light irradiation, the narrower band gap which means needing less energy for the electron hole pair transition.     

圆盘状Bi2WO6-BiPO4异质结的水热合成及光催化性能

采用水热法制备Bi2WO6-BiPO4异质结光催化剂．利用模拟太阳光照射下的罗丹明B降解实验评价了Bi2WO6-BiPO4复合物的光催化性能．结果表明,Bi2WO6-BiPO4光催化活性比Bi2WO6和BiPO4高得多．当Bi2WO6与BiPO4的摩尔比为1：1时复合光催化剂对罗丹明B的降解率最高．Bi2WO6-BiPO4催化活性增强主要归结为两者之间形成了有效的异质结结构,其内建电场能够促进光生载流子的分离．同时,Bi2WO6的加入增强了其对可见光的吸收．研究表明O2^· -和h^＋在光催化降解过程中是主要的活性物种.     

Visible‐Light Photocatalytic Hydrogen Production Activity of ZnIn2S4 Microspheres Using Carbon Quantum Dots and Platinum as Dual Co‐catalysts

ZnIn₂S₄ microspheres (ZIS MSs) were for the first time decorated with carbon quantum dots (CQDs) and platinum nanoparticles (NPs) as dual co‐catalysts of for photocatalytic H₂ production. The ZIS MSs co‐loaded with CQDs and Pt exhibited a high photocatalytic H₂ production rate of 1032.2 μmol h^?1 g^?1 with an apparent quantum efficiency of 2.2 % (420 nm) in triethanolamine aqueous solution under visible‐light irradiation, which was much higher than the respective photocatalytic rates of pure ZIS, Pt loaded ZIS, and CQDs‐decorated ZIS. Such a great enhancement was attributed to the integrative effect of good crystallization, enhanced light absorption, high electrical conductivity of CQDs, and the vectorial electron transfer from ZIS to CQDs and Pt NPs (ZIS→CQDs→Pt).     

水热反应条件对多孔球状Bi2WO6光催化剂结构及性能的影响

采用水热法制备了Bi₂WO₆光催化剂, 考察了水热反应温度、 水热反应时间及前驱体溶液pH值等条件对其对乙烯可见光催化活性的影响, 并通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫反射光谱(UV-Vis DRS)和比表面积分析等对催化剂的晶相组成、 微观形貌和光学性质等进行表征. 结果表明, 在水热反应温度为120 ℃、 水热反应时间为12 h、 前驱体溶液pH=0.5条件下, Bi₂WO₆光催化剂经过各向异性生长以及自组装奥斯特瓦尔德成熟(Ostwald ripening)过程, 形成由二维纳米薄片自组装的多孔微球状结构, 有效增大了与乙烯气体的接触面积, 禁带宽度降至2.86 eV, 可见光响应范围拓宽, 表现出优异的光催化性能, 在可见光下240 min内对乙烯的降解率达到13.69%.     

Novel hydrostable Z-scheme Ag/CsPbBr3/Bi2WO6 photocatalyst for effective degradation of Rhodamine B in aqueous solution

In this study, a hydrostable Z-scheme Ag/CsPbBr₃/Bi₂WO₆ photocatalyst was designed and fabricated for the degradation of Rhodamine B (RhB). The structural instability of CsPbX₃ perovskites in water is one of the main obstacles that restrict their practical application in photocatalytic wastewater treatment. The photocatalyst was prepared in three steps: passivation of CsPbBr₃ nanocrystals (NCs) with 3-mercaptopropionic acid (MPA), construction of a heterojunction between MPA-passivated CsPbBr₃ NCs and Bi₂WO₆ ultrathin nanosheets, and doping Ag nanoparticles as charge mediators in the heterojunction. The as-obtained 5%Ag/20%CsPbBr₃/Bi₂WO₆ exhibits good stability and excellent photocatalytic activity. The degradation rate is 93.9% in 120 min, which is 4.41 times than that of Bi₂WO₆.     

Z型光催化剂Sb2WO6/g-C3N4的制备及光催化性能

通过水热反应合成了Sb₂WO₆改性的g-C₃N₄复合材料(Sb₂WO₆ /g-C₃N₄). 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)、 紫外-可见漫散射反射光谱(UV-Vis DRS)和光致发光光谱(PL)等表征了样品的性质. 结果表明, Sb₂WO₆在g-C₃N₄的表面上生长, 并且复合材料光吸收能力有一定的增强, 光生电子-空穴的重组率降低. 通过罗丹明B(RhB)的光降解评价了Sb₂WO₆/g-C₃N₄复合材料的光催化性能. 结果表明, 模拟日光下Sb₂WO₆质量分数为10%的Sb₂WO₆/g-C₃N₄复合材料在60 min内对RhB的降解率为99.3%, 高于纯g-C₃N₄和Sb₂WO₆. Sb₂WO₆/g-C₃N₄复合材料的这种高度增强的光催化活性主要归因于强的界面相互作用促进了光生电子-空穴分离和迁移. 添加自由基清除剂的实验结果表明, ·O^2-和h⁺是光催化反应中的主要活性物质. Sb₂WO₆/g-C₃N₄复合材料在几个反应周期内表现出优异的稳定性. 根据实验结果提出了一种可能的Z型光催化机理.     

Bi_2MoO_6/BiVO_4异质结的水热合成和可见光催化活性(英文)

采用一步水热法制备Bi2MoO6/BiVO4复合光催化剂.利用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、高分辨透射电子显微镜(HRTEM)等手段对其晶体结构和微观结构进行了表征.结果表明,Bi2MoO6纳米粒子沉积在BiVO4纳米片表面从而形成异质结结构.紫外-可见漫反射光谱(UV-Vis DRS)表明所制备的Bi2MoO6/BiVO4异质结较纯相Bi2MoO6和BiVO4对可见光吸收更强.由于形成异质结结构及其光吸收性能使Bi2MoO6/BiVO4光催化活性有较大提高.可见光下(λ420 nm)光催化降解罗丹明B(RhB)实验结果表明,Bi2MoO6/BiVO4光催化活性较纯相Bi2MoO6和BiVO4高.Bi2MoO6/BiVO4样品光催化性能提高的原因是Bi2MoO6和BiVO4形成异质结,从而有效抑制光生电子-空穴对的复合,增大了可见光吸收范围及比表面积.     

Bi3+‐Er3+ and Bi3+‐Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near‐Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f‐electron emission at 1540 nm (suitable for low‐loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺‐Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature‐dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

微波液相法一步合成H3PW12O40/Bi2WO6光催化剂及其脱氮性能

采用微波液相法一步合成了固载型H₃PW₁₂O₄₀/Bi₂WO₆光催化剂. 通过紫外-可见漫反射光谱(UV-Vis)、 场发射扫描电子显微镜(SEM)、 表面积及孔隙度(BET)测定、 氨气程序升温脱附(NH₃-TPD)、 吡啶吸附红外光谱(Py-FTIR)和X射线衍射(XRD)对所合成催化剂的结构和性质进行了考察, 并以吡啶浓度为15 mg/g的模拟油对光催化剂的脱氮效果进行评价. 结果表明, 与传统浸渍固载法相比, 微波液相一步法不仅能高效合成H₃PW₁₂O₄₀/Bi₂WO₆光催化剂, 且所合成的催化剂能被低能量的光激发. 固载H₃PW₁₂O₄₀不但能提高Bi₂WO₆纳米颗粒的表面酸量, 还能通过改变Bi₂WO₆前驱液的酸强度来调控催化剂形貌. 在H₃PW₁₂O₄₀固载量为15%(质量分数), 微波功率为800 W, 反应时间为90 min条件下得到的H₃PW₁₂O₄₀/Bi₂WO₆的光催化脱氮活性最高, 在催化剂与模拟油质量比为1/300, 500 W氙灯光照60 min的最佳光催化反应条件下, 模拟油脱氮率达到92.63%.     

Template‐free Fabrication of Hierarchical Macro‐/mesoporous N‐doped TiO2/graphene Oxide Composites with Enhanced Visible‐light Photocatalytic Activity

Hierarchical macro‐/mesoporous N‐doped TiO₂/graphene oxide (N‐TiO₂/GO) composites were prepared without using templates by the simple dropwise addition mixed solution of tetrabutyl titanate and ethanol containg graphene oxide (GO) to the ammonia solution, and then calcined at 350 °C. The as‐prepared samples were characterized by scanning electron microscopy (SEM), Brunauer‐Emmett‐Teller (BET) surface area, X‐ray diffraction (XRD), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis absorption spectroscopy. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible‐light irradiation. The results show that N‐TiO₂/GO composites exhibited enhanced photocatalytic activity. GO content exhibited an obvious influence on photocatalytic performance, and the optimal GO addition content was 1 wt%. The enhanced photocatalytic activity could be attributed to the synergetic effects of three factors including the improved visible light absorption, the hierarchical macro‐mesoporous structure, and the efficient charge separation by GO.     

Construction of a 2D Graphene‐Like MoS2/C3N4 Heterojunction with Enhanced Visible‐Light Photocatalytic Activity and Photoelectrochemical Activity

A novel graphene‐like MoS₂/C₃N₄ (GL‐MoS₂/C₃N₄) composite photocatalyst has been synthesized by a facile ethylene glycol (EG)‐assisted solvothermal method. The structure and morphology of this GL‐MoS₂/C₃N₄ photocatalyst have been investigated by a wide range of characterization methods. The results showed that GL‐MoS₂ was uniformly distributed on the surface of GL‐C₃N₄ forming a heterostructure. The obtained composite exhibited strong absorbing ability in the ultraviolet (UV) and visible regions. When irradiated with visible light, the composite photocatalyst showed high activity superior to those of the respective individual components GL‐MoS₂ and GL‐C₃N₄ in the degradation of methyl orange. The enhanced photocatalytic activity of the composite may be attributed to the efficient separation of electron–hole pairs as a result of the matching band potentials between GL‐MoS₂ and GL‐C₃N₄. Furthermore, a photocatalytic mechanism for the composite material has been proposed, and the photocatalytic reaction kinetics has been measured. Moreover, GL‐MoS₂/C₃N₄ could serve as a novel sensor for trace amounts of Cu²⁺ since it exhibited good selectivity for Cu²⁺ detection in water.     

Preparation and Photocatalytic Activity of Mesoporous TiO2 Photocatalyst Co‐doped with Fe and H3PW12O40

The mesoporous titanium dioxide (MTiO₂) photocatalysts co‐doped with Fe and H₃PW₁₂O₄₀ were synthesized by template method using tetrabutyl titanate (Ti(OC₄H₉)₄), Fe(NO₃)k₃9H₂Oand H₃PW₁₂O₄₀ as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N₂ adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO₂ exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO₂ under UV and visible light irradiation. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H₃PW₁₂O₄₀ co‐doping played an important role in improving the photocatalytic activity.