Efficient Charge Separation between Bi and Bi2MoO6 for Photoelectrochemical Properties

Herein, porous Bi/Bi₂MoO₆ nanoparticles have been prepared by a facile in‐situ reduction approach. Moreover, the morphology and Bi content of product could be controlled by varying the reaction time. By controlled fabrication, the desired porous Bi₂MoO₆ nanostructure with incorporation of Bi was obtained and exhibited high photoelectric and photocatalytic activity. In particular, the samples yield a photocurrent density of 320 μA cm^?2, which is 3.2 times that of the pure Bi₂MoO₆ nanosheet (100 μA cm^?2) under the same conditions. UV/Vis diffuse reflectance spectroscopy analysis confirmed the surface plasmon resonance in the as‐prepared porous nanoparticles. The improved photoelectric properties could be the synergistic effect of the porous structure with large surface area and effective electron‐hole separations between Bi and Bi₂MoO₆.     

Enhanced photocatalytic properties of Bi2MoO6 nanoplates deposited with intermetallic AgPd nanoparticles by photoreduction method

Bi₂MoO₆ nanoplates modified with intermetallic AgPd nanoparticles synthesized by photoreduction deposition method were used for visible-light-driven photodegradation of rhodamine B. The as-synthesized AgPd/Bi₂MoO₆ nanocomposites were identified by XRD. The 2θ diffraction angle of the (111) plane of pure metallic cubic Ag at 38.11° of heterostructure 10% Ag/Bi₂MoO₆ nanocomposites shifted to a higher diffraction angle at 38.17° of heterostructure 10% Ag_0.7Pd_0.3/Bi₂MoO₆ nanocomposites. TEM images of the as-synthesized nanocomposites showed good metallic Ag and intermetallic AgPd nanoparticles with particle size of 10–12 nm which were fully supported on top of Bi₂MoO₆ nanoplates. Bi₂MoO₆ nanoplates deposited with intermetallic AgPd nanoparticles show significant photocatalytic activity better than Ag/Bi₂MoO₆ and Bi₂MoO₆ due to the formation of AgPd/Bi₂MoO₆ Schottky barrier.

     

Fe (III)‐grafted Bi2MoO6 nanoplates for enhanced photocatalytic activities on tetracycline degradation and HMF oxidation

Fe (III)‐grafted Bi₂MoO₆ nanoplates (Fe (III)/BMO) with varying small quantity of Fe (III) clusters modification were fabricated through a simple hydrothermal and impregnation process. The characterization results indicate that the modification of Fe (III) clusters on the surface of Bi₂MoO₆ nanoplates with intimate interfacial contact is beneficial to the expansion of visible light absorption range and the separation of photoinduced carriers during the interface charge transfer process. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) and selective aerobic oxidation of biomass‐derived chemical 5‐hydroxymethylfuraldehyde (HMF) under visible light. The 1.5 wt% Fe (III) clusters‐grafted Bi₂MoO₆ nanoplates exhibited optimum photocatalytic activity, which is the TC degradation kinetic rate constant is 5.3 times higher than that of bare BMO, and the highest HMF conversion of 32.62% can be obtained with a selectivity of 95.30%. Furthermore, a possible visible light photocatalysis mechanism over Fe (III)/BMO sample has been proposed. This study may supply some insight for the development of visible‐light‐driven Bi₂MoO₆‐based photocatalysts applicable to both environmental remediation and biomass‐derived chemical transformation.     

Fabrication of S-scheme hollow TiO2@Bi2MoO6 composite for efficiently photocatalytic CO2 reduction

Herein, an S-scheme hollow TiO₂@Bi₂MoO₆ heterojunction was synthesized for photocatalytic reduction of CO₂ under simulated sunlight. Among all prepared composites, the TiO₂@Bi₂MoO₆ with 20% of TiO₂ exhibited the highest CO yield (183.97 μmol/g within 6 h), which was 4.0 and 2.4 times higher than pristine TiO₂ and Bi₂MoO₆, respectively. The improved photocatalytic activity may be due to the formation of S-scheme heterojunction to promote the separation and transfer of photogenerated charge carriers. Additionally, this hollow structure provided abundant sites in terms of CO₂ adsorption and activation. Meanwhile, the photogenerated charge transfer mechanism of the S-scheme was verified by work function calculations, Electron paramagnetic resonance (EPR) measurements as well as X-ray photoelectron spectroscopy (XPS). This research presents a novel approach to improve photocatalytic reduction of CO₂ via morphology modulation and the fabrication of S-scheme heterojunction.     

Pd nanoparticle-modified Bi2WO6 nanoplates used for visible-light-driven photocatalyst

Pd nanoparticles supported on Bi₂WO₆ nanoplates used for visible-light-driven photocatalyst were successfully synthesized by photoreduction deposition method under visible-light irradiation. Different analytical techniques including X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and photoluminescence spectroscopy revealed that face-centered cubic metallic Pd nanoparticles were uniformly loaded on top of orthorhombic Bi₂WO₆ nanoplates to form heterostructure Pd/Bi₂WO₆ nanocomposites. Photocatalytic activities of pure Bi₂WO₆ sample and heterostructure Pd/Bi₂WO₆ nanocomposites were studied through the photodegradation of rhodamine B (RhB) under visible-light irradiation. The photocatalytic efficiency of Bi₂WO₆ was increased to the highest by being loaded with 5 wt% Pd and then decreased by being loaded with 10 wt% Pd. The improved photocatalytic efficiency caused by high-efficiency diffusion and separation of photo-generated charge carriers was explained and can lead to superior photodegradation of RhB under visible-light irradiation.

     

Bi2MoO6/BiVO4异质结的水热合成和可见光催化活性

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(λ>420 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.     

镂空Bi2MoO6微球的制备及其对氧氟沙星抗生素的降解性能

以钼酸钠以及五水合硝酸铋为原料,采用醇热法及高温退火制备了镂空Bi2MoO6微球光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FESEM)、高分辨透射电镜(HRTEM)、物理吸附分析仪、紫外-可见漫反射(UV-Vis DRS)、荧光光谱分析(PL)以及电化学测试等分析方法分别对制备材料的晶体结构、微观形貌、比表面积和光学特性进行表征。以氧氟沙星(OFX)水溶液作为目标降解物,在可见光照射的条件下,探究了Bi2MoO6对OFX的光催化降解性能。实验结果表明:醇热法合成的球状钼酸铋的平均直径为500 nm,镂空结构使得球状Bi2MoO6的比表面积提高到片状Bi2MoO6的5倍。更大的比表面积为光催化提供了大量的吸附位点,在120 min的可见光辐射下,投放量为1 g·L^-1的Bi2MoO6对p H=7、浓度为10 mg·L^-1OFX水溶液的降解效率可达64%,而片状Bi2MoO6仅为31%。镂空球状的Bi2MoO6在强碱性环境具有优异的光催化效果,对OFX的降解率达到79%,在强碱性环境中,具有更优的光催化降解性能。     

Z型异质结Cu2O/Bi2MoO6的构建及光催化降解性能

通过水热法制备出一系列Z型异质结Cu₂O/Bi₂MoO₆新型光催化剂。采用扫描电子显微镜、粉末X射线衍射、红外光谱、紫外可见吸收光谱等表征手段研究了催化剂的形貌、结构性质和光电化学性质,并以四环素(TC)为降解目标污染物,进一步探究了其催化效率。实验结果表明,Cu₂O的加入提高了复合催化剂的光催化性能,其中20% Cu₂O/Bi₂MoO₆复合催化剂(Cu₂O和Bi₂MoO₆的质量比为20%)降解效果最好,100 min内可降解95%的TC。Cu₂O与Bi₂MoO₆之间的协同作用使其可以吸收更多的可见光,所构建的Z型异质结改变了电子转移途径,提高了电子与空穴的分离效率,光催化活性显著提高。通过自由基捕获实验和能带结构,分析了Z型异质结Cu₂O/Bi₂MoO₆复合催化剂光催化降解TC可能的机理。     

Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi₂WO₆@Bi₂MoO_6-xF_2x（BWO/BMO6-xF2x）异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B（RhB）的光催化降解作为探针反应来评价Bi₂WO₆@Bi₂MoO_6-xF_2x异质结的光催化活性增强机制。形貌分析表明,所得Bi₂MoO₆微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi₂WO₆量子点均匀沉积在Bi₂MoO_6-xF_2x微球表面,形成新颖的Bi₂WO₆@Bi₂MoO_6-xF_2x异质结;与纯Bi₂MoO₆或者Bi₂WO₆相比,1∶1Bi₂WO₆@Bi₂MoO_6-xF_2x异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi₂WO₆量子点表面沉积显著提高Bi₂MoO_6-xF_2x光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O₂^-和h⁺是主要的活性物种。根据实验结果,探讨了F^-掺杂和Bi₂WO₆量子点之间的协同效应对Bi₂MoO₆的光催化活性的影响机制。     

铁电极化对层状Bi2MoO6光催化性能的增强

通过对铁电光催化剂Bi_2MoO_6和聚甲基丙烯酸甲酯(PMMA)构建的有机-无机复合膜材料施加电场极化,来探究铁电极化对Bi_2MoO_6光催化剂活性提升的影响。未极化的Bi_2MoO_6在光照40 min时降解罗丹明B(RhB)的效率为57.6%,在光照150min时对双酚A(BPA)的降解效率为33.4%。在15 V电压下极化1.5 h的Bi_2MoO_6材料在相同条件下降解罗丹明B和双酚A的效率分别达到98.1%和79.2%,光催化活性得到了较大的提升。光催化活性提升的原因归因于内部电场的增强。未极化的Bi_2MoO_6的内电场的铁电畴是无序、分布不均匀的,光生载流子非常容易发生体内复合。当外加电场极化Bi_2MoO_6时,Bi_2MoO_6的铁电畴趋于有序,极化方向趋于同一方向,表面一侧(C+区)产生正电荷,在另一侧(C-区)产生负电荷,从C-区指向C+区的极化电场推动光生电子和空穴分别迁移到C+和C-区域。这一过程促使光生电荷载流子快速从体内迁移至表面,提高和延长了光生载流子的分离效率和寿命,导致光催化活性的提升。     

Bi2WO6量子点(QDs)修饰Bi2MoO6-xF2x异质结的构筑及其催化活性增强机理

采用简单沉积-沉淀法合成了Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)(BWO/BMO_(6-x)F_(2x))异质结,借助XRD、XPS、TEM、SEM、EDS、UV-Vis-DRS、PC和EIS等测试技术对其组成、形貌、光吸收特性和光电化学性能等进行系统表征,并以模型污染物罗丹明B(Rh B)的光催化降解作为探针反应来评价Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结的光催化活性增强机制。形貌分析表明,所得Bi_2MoO_6微球由大量厚度为20~50 nm的纳米片组成;FE-SEM和HR-TEM分析表明,尺寸约为10 nm的Bi_2WO_6量子点均匀沉积在Bi_2MoO_(6-x)F_(2x)微球表面,形成新颖的Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结;与纯Bi_2MoO_6或者Bi_2WO_6相比,1∶1Bi_2WO_6@Bi_2MoO_(6-x)F_(2x)异质结表现出更好的光催化活性和光电流性质,其对RhB光催化降解的表观速率常数分别为纯BMO和BWO的6.4和11.6倍。PC和EIS图谱分析表明,Bi_2WO_6量子点表面沉积显著提高Bi_2MoO_(6-x)F_(2x)光生电子/空穴的分离效率和迁移速率;活性物种捕获实验证明了·O_2~-和h~+是主要的活性物种。根据实验结果,探讨了F-掺杂和Bi_2WO_6量子点之间的协同效应对Bi_2MoO_6的光催化活性的影响机制。     

一步法制备Bi2MoO6/CoMoO4绣花球结构及其光催化性能

以五水硝酸铋为铋源,采用简易的一步水热法合成出Bi_2MoO_6/CoMoO_4绣花球结构。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)和电化学测试等表征对所制备催化剂的物相组成、微观形貌、光学性质以及光生电荷复合效率进行了分析。研究结果表明,引入Bi_2MoO_6之后,Bi_2MoO_6/CoMoO_4复合异质结的光吸收范围明显被拓宽,其光生电荷的分离率也得到了提升。以亚甲基蓝和头孢曲松钠为污染物来模拟废水,在可见光的条件下评估催化剂样品的光催化降解活性。在可见光下光照60 min后,Bi_2MoO_6负载量为30%(w/w)的复合物具有最佳的光催化性能,其降解速率常数约为纯CoMoO_4的2倍。基于实验的所有表征,进一步地研究了Bi_2MoO_6/CoMoO_4体系相应的光催化机理。     

Solar Light Driven H2O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

A chemically stable 2D microporous COF ( PMCR-1 ) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term stable photocatalytic H₂O₂ production rate (60 h) from pure and sea water under visible light. The H₂O₂ production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π–π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H₂O₂ formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well-defined micropores of PMCR-1 enable size-selective photocatalytic oxidation.     

Tunable and rapid crystallisation of phase pure Bi2MoO6 (koechlinite) and Bi2Mo3O12 via continuous hydrothermal synthesis

Herein, we report the rapid single step hydrothermal synthesis of phase pure Bi₂MoO₆ (koechlinite) and Bi₂Mo₃O₁₂, via a continuous hydrothermal flow synthesis (CHFS) reactor, which uses supercritical water of 375–450 °C at a pressure of 24.1 MPa as a crystallising medium. The product being obtained as highly crystalline nano-materials with high surface area. Simple variation in synthesis condition and appropriate solution stoichiometry were shown to be sufficient to select the phase of the product. The materials synthesised showed significant photcatalytic activity towards the decolourisation of methylene blue in comparison to a commercial gold standard photocatalyst.     

MOF-808/Bi2MoO6复合材料的构筑及其光催化性能

采用简单的两步水热法制备出了锆基金属有机骨架和钼酸铋的复合材料MOF-808/Bi₂MoO₆。通过X射线粉末衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱、N₂吸附-脱附测试和电化学测试对所制备材料的组成、微观结构、光学性质以及光生载流子的复合效率进行了分析。与纯Bi₂MoO₆和MOF-808相比,0.5%-MOF-808/Bi₂MoO₆复合材料展示出了较高的光催化活性,在可见光照射120 min时对抗生素环丙沙星(CIP)的降解率达89.7%。通过自由基捕获实验,证明了·O₂^-是主要活性物种,基于此我们提出了可能的光催化降解机理。     

MOF-808/Bi2MoO6复合材料的构筑及其光催化性能

采用简单的两步水热法制备出了锆基金属有机骨架和钼酸铋的复合材料MOF-808/Bi₂MoO₆。通过X射线粉末衍射、傅里叶红外光谱、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、紫外可见漫反射光谱、N₂吸附-脱附测试和电化学测试对所制备材料的组成、微观结构、光学性质以及光生载流子的复合效率进行了分析。与纯Bi₂MoO₆和MOF-808相比,0.5%-MOF-808/Bi₂MoO₆复合材料展示出了较高的光催化活性,在可见光照射120 min时对抗生素环丙沙星(CIP)的降解率达89.7%。通过自由基捕获实验,证明了·O₂^-是主要活性物种,基于此我们提出了可能的光催化降解机理。     

Synthesis and crystal structure of the binary molybdate Li8Bi2(MoO4)7

Single crystals of Li₈Bi₂(MoO₄)₇ were synthesized; the composition and crystal structure of this compound were determined from X-ray diffraction data (CAD-4 automatic diffractometer, MoK_a radiation, 1767 reflections, R = 0.031). The parameters of the tetragonal unit cell are as follows: a = 21.130, c = 5.287 Å, Z = 4, space group -14. The structure of the binary molybdate is a three-dimensional mixed framework of MoO₄ tetrahedra of four varieties, Bi eight-vertex potyhedra, and Li(l)O₆ and Li(2)O₆ octahedra. The large channels of the framework along the c axis contain MoO₄ tetrahedra of the fifth variety with Li(3)O₄ and Li(4)O₄ tetrahedra attached to them via common vertices and forming four symmetrically related chains of pyroxene type. The structure of Li₈Bi₂(MoO₄)₇ involves structural fragments of Li₃Fe(MoO₄)₃ and a-RbPr(MoO₄)₂ and is a new structural type in the class of binary molybdates and tungstates of uniand trivalent metals.     

Selective oxidation of toluene over layered structures of Bi2MoO6 and La2MoO6

The vapor phase catalytic aerial oxidation of toluene to benzaldehyde (B_zH) was carried out over La₂MoO₆ containing the same kind of layered structure as Bi₂MoO₆. The overall kinetic analysis indicated the oxidation of toluene to B_zH to be first order with a frequency factor of log 0.63 and activation energy (E_a) of 26.3 kJ mol^–1 and 34.0 kJ mol^–1, respectively, for Bi₂MoO₆ and La₂MoO₆ catalysts. A relation between the activity and activation energy of conduction (E) is shown.     

Effcient Removal Phenol Red over Ternary Heterostructured Ag-Bi2MoO6/BiPO4 Composite Photocatalyst

The fabrication of multicomponent composite systems may provide bene ts in terms of charge separation and the retardation of charge pair recombination. In this work, a ternary heterostructured Ag-Bi₂MoO₆/BiPO₄ composite was fabricated through a low-temperature solution-phase route for the rst time. The XRD, SEM, EDX and XPS results indicated the prepared sample is a three-phase composite of BiPO₄, Bi₂MoO₆, and Ag. Ag nanopar-ticles were photodeposited on the surface of Bi₂MoO₆/BiPO₄ nanosheets, which not only increase visible-light absorption via the surface plasmon resonance, but also serve as good electron acceptor for facilitating quick photoexcited electron transfer. The interface between Bi₂MoO₆ and BiPO₄ facilitates the migration of photoinduced electrons from Bi₂MoO₆ to BiPO₄, which is also conductive to reduce the recombination of electron-holes. Thus, the ternary heterostructured Ag-Bi₂MoO₆/BiPO₄ composite showed signi cant photocatalytic activity, higher than pure Bi₂MoO₆, BiPO₄, and Bi₂MoO₆/BiPO₄. Moreover, the possible photocatalytic mechanism of the Ag-Bi₂MoO₆/BiPO₄ heterostructure related to the band positions of the semiconductors was also discussed. In addition, the quenching effects of di erent scavengers revealed that the reactive ·OH and O₂^·- play a major role in the phenol red decolorization.     

Ag/Ag2MoO4/Bi2MoO6复合光催化剂的制备及其光催化性能

采用水热、化学沉积和原位光还原的方法成功制备了新型Ag/Ag₂MoO₄/Bi₂MoO₆三元复合光催化剂。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)等技术对材料的组成、形貌、光吸收特性和光电化学性能等进行系统分析。以四环素为目标污染物,研究Ag/Ag₂MoO₄/Bi₂MoO₆在可见光下的光催化性能。研究结果表明,相比于纯Ag₂MoO₄和Bi₂MoO₆,Ag的表面等离子体共振(SPR)效应显著拓宽了催化体系对可见光的吸收能力及响应范围。当Ag₂MoO₄理论负载量(质量分数)为24.6%时,Ag/Ag₂MoO₄/Bi₂MoO₆复合材料在20 min内可将四环素完全降解,且5次循环使用后仍保持较高的催化活性,表现出良好的循环稳定性。