CN102989485B - A kind of S-doped BiVO4 visible light catalytic material and preparation method thereof - Google Patents
A kind of S-doped BiVO4 visible light catalytic material and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种S掺杂BiVO4可见光催化材料及其制备方法，它包括如下步骤：1）前驱体溶液的制备：将摩尔比为1:1的Bi(NO3)3·5H2O和NH4VO3分别溶入适量醋酸溶液和去离子水中，分别混合均匀得到前驱体溶液A和B，其中前驱体B中加入了一定量硫脲和乳化剂；2）将前驱体溶液A和B充分搅拌，混合均匀；3）将混合均匀的溶液置入水热反应釜中，一定温度下保温一段时间；4）将反应釜中的反应产物经离心洗涤、冷冻干燥后得到S掺杂BiVO4可见光催化粉体材料。该制备方法工艺简单、成本低，本发明制备的S掺杂BiVO4可见光催化材料对亚甲基蓝溶液具有显著的降解效果。The invention relates to a S-doped BiVO 4 visible light catalytic material and a preparation method thereof, which comprises the following steps: 1) Preparation of a precursor solution: Bi(NO 3 ) 3 ·5H 2 O and Dissolve NH 4 VO 3 in an appropriate amount of acetic acid solution and deionized water, and mix them uniformly to obtain precursor solutions A and B, in which a certain amount of thiourea and emulsifier are added to precursor B; 2) Precursor solutions A and B Stir well and mix evenly; 3) Put the uniformly mixed solution into a hydrothermal reactor and keep it warm at a certain temperature for a period of time; 4) Centrifuge the reaction product in the reactor and freeze-dry to obtain S-doped BiVO 4 Visible light catalytic powder material. The preparation method has simple process and low cost, and the S-doped BiVO 4 visible light catalytic material prepared by the invention has a remarkable degradation effect on the methylene blue solution.
Description
技术领域 technical field
本发明涉及一种S元素掺杂BiVO4可见光催化粉末材料及其制备方法，属于光催化粉体材料制备领域。 The invention relates to an S element-doped BiVO4 visible light catalytic powder material and a preparation method thereof, belonging to the field of photocatalytic powder material preparation.
背景技术 Background technique
21世纪人类面临的最大问题仍是环境污染问题和能源的可持续发展。为此太阳能的开发成为解决问题的关键，而作为其中重要部分的半导体光催化技术有望成为解决环境和能源问题的有效方式。 The biggest problems facing mankind in the 21st century are still environmental pollution and sustainable energy development. Therefore, the development of solar energy has become the key to solving the problem, and semiconductor photocatalysis technology, which is an important part of it, is expected to become an effective way to solve environmental and energy problems.
半导体材料在光的照射下把光能转化为化学能，促进化合物的合成或使化合物降解。半导体催化剂在可见光区域具有陡峭的吸收边缘，它们具有的窄带隙有利于将电子从价带激发到导带上，产生导带电子和价带空穴，进行氧化还原降解有机污染物或分解水获取氢能。而氢能因其燃烧值高、无污染而成为最有希望替代现有化石能源的清洁能源。同时光催化能降解消除有毒有机污染物和无机污染物，不产生二次污染，而且具有能耗低，速度快，无选择性，深度氧化矿化等优点，将成为解决环境污染的一条廉价可行的途径。 Semiconductor materials convert light energy into chemical energy under the irradiation of light, which promotes the synthesis of compounds or degrades compounds. Semiconductor catalysts have steep absorption edges in the visible light region, and their narrow band gaps are conducive to exciting electrons from the valence band to the conduction band, generating conduction band electrons and valence band holes, and performing redox degradation of organic pollutants or decomposing water to obtain hydrogen energy. Hydrogen energy has become the most promising clean energy to replace existing fossil energy because of its high combustion value and no pollution. At the same time, photocatalysis can degrade and eliminate toxic organic pollutants and inorganic pollutants without secondary pollution, and has the advantages of low energy consumption, fast speed, no selectivity, deep oxidation mineralization, etc., and will become a cheap and feasible solution to environmental pollution. way.
由于一些半导体光催化剂如TiO2、NaTaO3、ZnO等带隙较宽，仅在紫外光范围有响应，而此波段的光能量占照射到地面的太阳光的5%，而波长在400~700nm的可见光范围达总能量的43%，因此高效可见光光催化剂的研究是实现光催化技术产业化应用的关键。目前，新型可见光光催化剂的研究目前有两大思路：一种是对TiO2、NaTaO3、ZnO等宽禁带半导体进行修饰改性使其响应波长红移至可见光区，主要有金属/非金属掺杂，染料光敏化、窄带隙半导体复合以及金属络合物敏化等手段；另一种是设计新型的可见光响应半导体光催化材料，其中窄禁带半导体制备是获得新型可见光催化剂的基本途径之一。因此，研究工作者设计了许多复合金属氧化物作为可见光响应的新型光催化剂，如Bi2WO6、InVO4、AgAlO2、CaIn2O4、BiVO4等，它们均可在可见光的照射下催化分解有机物。BiVO4性质稳定，经过表面稳定化处理后可以耐强酸和强碱介质，同时它具有优异的耐有机溶剂的性能，而且BiVO4的响应光波长范围可达500 nm以上。该系列材料因其利用可见光效率高、催化分解有机物能力强而受到广泛关注，主要用于光催化分解废水和降解多元环有机污染物。 Due to the wide band gap of some semiconductor photocatalysts such as TiO 2 , NaTaO 3 , ZnO, etc., they only respond in the ultraviolet range, and the light energy in this band accounts for 5% of the sunlight irradiating the ground, and the wavelength is 400~700nm The visible range of visible light reaches 43% of the total energy, so the research on high-efficiency visible light photocatalysts is the key to realize the industrial application of photocatalytic technology. At present, there are two main ideas in the research of new visible light photocatalysts: one is to modify wide bandgap semiconductors such as TiO 2 , NaTaO 3 , and ZnO to redshift the response wavelength to the visible light region, mainly including metal/nonmetal Doping, dye photosensitization, narrow-bandgap semiconductor recombination, and metal complex sensitization; the other is to design new visible light-responsive semiconductor photocatalytic materials, and the preparation of narrow-bandgap semiconductors is one of the basic ways to obtain new visible light catalysts. one. Therefore, researchers have designed many composite metal oxides as new photocatalysts responsive to visible light, such as Bi 2 WO 6 , InVO 4 , AgAlO 2 , CaIn 2 O 4 , BiVO 4 , etc., which can catalyze Break down organic matter. BiVO 4 is stable in nature and can withstand strong acid and strong alkali medium after surface stabilization treatment. At the same time, it has excellent resistance to organic solvents, and the wavelength range of BiVO 4 response light can reach more than 500 nm. This series of materials has attracted widespread attention due to its high efficiency in utilizing visible light and its strong ability to catalyze the decomposition of organic matter. It is mainly used for photocatalytic decomposition of wastewater and degradation of polycyclic organic pollutants.
BiVO4具有可见光催化分解水和降解有机污染物的能力，其响应光波长范围达到500nm之上，作为光催化材料在废水处理方面已展现出良好的可见光催化降解性能。BiVO4的可见光催化活性主要取决于它的晶相结构和制备方法。BiVO4的三种结构单斜白钨矿晶型、四方锆石型晶型和四方白钨矿型晶型中只有单斜白钨矿晶型在可见光下具有良好的光催化性能，但是在一定条件下，三种结构彼此之间可以相互转化。BiVO4的其制备方法主要有：水热合成发、溶剂热合成法、微波合成法、高温固相合成法以及化学沉淀法等，上述方法各有优缺点，但都能合成纯度较高的BiVO4粉体材料，然而广大研究人员在实验中发现，纯BiVO4的催化效果并不能满足日益增长的工业技术指标要求。鉴于纯BiVO4的吸附能力和电子-空穴对的转移能力较差，许多学者开始研究通过改性，或者制备金属氧化物和BiVO4配对的异质结来提高其活性，其中对于纳米BiVO4材料的离子掺杂是BiVO4改性的研究重点。在BiVO4中掺入外加离子可能会在BiVO4晶格中引入缺陷位置或改变结晶度，从而在BiVO4的带隙能级中引入缺陷能级和杂质能级，使能量较小的光子激发BiVO4产生光电子，从而改变半导体的激发光波长。此外，掺杂可以导致载流子的扩散长度增加，当掺杂价态高于金属离子的价态时，可以在局部生成光生电子的俘获中心从而抑制光生电子与空穴的复合，提高BiVO4的光催化活性。Xu等制备了一系列稀土(Ho、Sm、Yb、Eu、Gd、Nd、Ce、La)掺杂的BiVO4光催化剂，并在可见光下处理亚甲基蓝。实验表明，掺杂后的BiVO4光催化性能较原始材料有明显提高。 BiVO 4 has the ability to decompose water and degrade organic pollutants under visible light catalysis, and its response light wavelength range is above 500nm. As a photocatalytic material, it has shown good catalytic degradation performance under visible light in wastewater treatment. The visible-light photocatalytic activity of BiVO 4 mainly depends on its crystal phase structure and preparation method. Among the three structures of BiVO 4 , monoclinic scheelite crystal form, tetragonal zircon crystal form and tetragonal scheelite crystal form, only monoclinic scheelite crystal form has good photocatalytic performance under visible light, but in a certain Under certain conditions, the three structures can be transformed into each other. The preparation methods of BiVO 4 mainly include: hydrothermal synthesis, solvothermal synthesis, microwave synthesis, high-temperature solid-phase synthesis, and chemical precipitation. The above methods have their own advantages and disadvantages, but they can all synthesize BiVO with high purity. 4 powder materials, however, many researchers have found in experiments that the catalytic effect of pure BiVO 4 cannot meet the increasing requirements of industrial technical indicators. In view of the poor adsorption ability and electron-hole pair transfer ability of pure BiVO 4 , many scholars have begun to study the modification or preparation of metal oxide and BiVO 4 paired heterojunctions to improve its activity, among which for nano-BiVO 4 Ion doping of materials is the research focus of BiVO4 modification. The incorporation of external ions in BiVO 4 may introduce defect sites in the BiVO 4 lattice or change the crystallinity, thereby introducing defect levels and impurity levels in the bandgap energy levels of BiVO 4 , enabling the excitation of photons with less energy BiVO4 generates photoelectrons, thereby changing the excitation light wavelength of the semiconductor. In addition, doping can lead to an increase in the diffusion length of carriers. When the doping valence is higher than that of metal ions, it can locally generate a trapping center for photogenerated electrons, thereby inhibiting the recombination of photogenerated electrons and holes, and improving the BiVO 4 photocatalytic activity. Xu et al. prepared a series of rare earth (Ho, Sm, Yb, Eu, Gd, Nd, Ce, La) doped BiVO photocatalysts and treated methylene blue under visible light. Experiments show that the photocatalytic performance of doped BiVO 4 is significantly improved compared with the original material.
由上述分析可以看出，合成高纯度BiVO4粉体并对其进行离子掺杂可大幅提高其催化活性和催化剂的利用率，使BiVO4中的电子能被波长较长的光所激发，而目前尚未见到关于S离子掺杂的BiVO4可见光催化材料的研究报道。 From the above analysis, it can be seen that the synthesis of high-purity BiVO 4 powder and its ion doping can greatly improve its catalytic activity and catalyst utilization, so that the electrons in BiVO 4 can be excited by light with a longer wavelength, while So far, there is no research report on S ion-doped BiVO 4 visible light photocatalytic materials.
发明内容 Contents of the invention
本发明所要解决的技术问题是针对上述现有技术存在的不足而提供一种制备S掺杂BiVO4可见光催化材料的方法，该方法得到的S掺杂BiVO4可见光催化材料的光催化性能提高，光降解速率加快。 The technical problem to be solved by the present invention is to provide a method for preparing S-doped BiVO visible photocatalytic material for the deficiencies in the above -mentioned prior art, the photocatalytic performance of the S-doped BiVO visible photocatalytic material obtained by the method is improved, The rate of photodegradation is accelerated.
本发明为解决上述提出的问题所采用的技术方案为： The technical scheme that the present invention adopts for solving the above-mentioned problem is:
一种S掺杂BiVO4可见光催化材料，它是按照如下步骤制备得到的： A kind of S-doped BiVO visible photocatalytic material, it is prepared according to the following steps:
1）前驱体溶液的制备：将Bi(NO3)3·5H2O充分溶入醋酸溶液中得到前躯体溶液A，将NH4VO3充分溶入去离子水中，并加入硫脲和乳化剂，硫脲与NH4VO3的摩尔比为（4.8~5.2）:1，室温下混合均匀得到前躯体溶液B，满足Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，前驱体溶液A、B的体积相等，乳化剂在前躯体溶液B中的质量分数为2.8~ 3.1 wt%； 1) Preparation of precursor solution: fully dissolve Bi(NO 3 ) 3 5H 2 O in acetic acid solution to obtain precursor solution A, fully dissolve NH 4 VO 3 in deionized water, and add thiourea and emulsifier , the molar ratio of thiourea to NH 4 VO 3 is (4.8~5.2):1, mixed uniformly at room temperature to obtain precursor solution B, satisfying the molar ratio of Bi(NO 3 ) 3 ·5H 2 O to NH 4 VO 3 is 1:1, the volumes of precursor solutions A and B are equal, and the mass fraction of emulsifier in precursor solution B is 2.8~3.1 wt%;
2）将前躯体溶液A滴加入前躯体溶液B中，搅拌1.5~3h使其充分混合均匀，此时混合溶液的pH为1.3~1.7； 2) Add the precursor solution A dropwise into the precursor solution B, stir for 1.5~3h to make it fully mixed, and the pH of the mixed solution is 1.3~1.7 at this time;
3）将步骤2）所述混合溶液放入水热反应釜中进行热处理，热处理温度为130℃～150℃，保温时间为13h～17h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle for heat treatment, the heat treatment temperature is 130°C-150°C, the holding time is 13h-17h, and then cooled with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末洗涤并离心分离，再将离心分离的产物粉末于-100～-80℃下进行冷冻干燥，干燥时间为24～48h，即得到S掺杂BiVO4可见光催化粉体材料。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, wash and centrifuge the reaction product powder, and then freeze-dry the centrifuged product powder at -100～-80°C, and the drying time is 24～48h , that is, S-doped BiVO 4 visible light photocatalytic powder material is obtained.
按上述方案，所述醋酸溶液的体积分数为36wt%。 According to the above scheme, the volume fraction of the acetic acid solution is 36wt%.
按上述方案，所述乳化剂为OP-10。 According to the above scheme, the emulsifier is OP-10.
按上述方案，步骤3）所述的热处理采用电阻炉、管式炉、真空气氛炉等可提供稳定温度场的加热炉。 According to the above scheme, the heat treatment in step 3) adopts a heating furnace that can provide a stable temperature field, such as a resistance furnace, a tube furnace, and a vacuum atmosphere furnace.
按上述方案，步骤4）所述洗涤离心将反应产物粉末用去离子水洗涤离心，继而用无水乙醇洗涤离心。 According to the above scheme, wash and centrifuge the reaction product powder with deionized water in step 4), and then wash and centrifuge with absolute ethanol.
按上述方案，步骤4）所述的洗涤离心采用的溶剂介质还可以为甲醇、异丙醇或甲苯等有机溶剂。 According to the above scheme, the solvent medium used in the washing and centrifugation described in step 4) can also be an organic solvent such as methanol, isopropanol or toluene.
按上述方案，步骤4）所述离心采用转速为4500~6000r/min，离心时间为3~5min。 According to the above scheme, the centrifugation speed in step 4) is 4500~6000r/min, and the centrifugation time is 3~5min.
按上述方案，步骤4）所述冷冻干燥是-90℃干燥24~48h。 According to the above scheme, the freeze-drying in step 4) is drying at -90°C for 24-48h.
上述S掺杂BiVO4可见光催化材料的制备方法，它包括如下步骤： Above-mentioned S-doped BiVO The preparation method of visible light catalytic material, it comprises the steps:
1）前驱体溶液的制备：将Bi(NO3)3·5H2O充分溶入醋酸溶液中得到前躯体溶液A，将NH4VO3充分溶入去离子水中，并加入硫脲和乳化剂，硫脲与NH4VO3的摩尔比为（4.8~5.2）:1，室温下充分混合均匀得到前躯体溶液B，满足Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，前驱体溶液A、B的体积相等，乳化剂在前躯体溶液B中的质量分数为2.8 ~ 3.1 wt%； 1) Preparation of precursor solution: fully dissolve Bi(NO 3 ) 3 5H 2 O in acetic acid solution to obtain precursor solution A, fully dissolve NH 4 VO 3 in deionized water, and add thiourea and emulsifier , the molar ratio of thiourea to NH 4 VO 3 is (4.8~5.2):1, fully mixed at room temperature to obtain the precursor solution B, which satisfies the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, the volumes of precursor solutions A and B are equal, and the mass fraction of emulsifier in precursor solution B is 2.8 ~ 3.1 wt%;
2）将前躯体溶液A滴加入前躯体溶液B中，搅拌1.5~3h使其充分混合均匀，混合溶液的pH为1.3~1.7； 2) Add the precursor solution A dropwise into the precursor solution B, stir for 1.5~3h to make it fully mixed, and the pH of the mixed solution is 1.3~1.7;
3）将步骤2）所述混合溶液放入水热反应釜中进行热处理，热处理温度为130℃～150℃，保温时间为13h～17h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle for heat treatment, the heat treatment temperature is 130°C-150°C, the holding time is 13h-17h, and then cooled with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末洗涤并离心分离，再将离心分离的产物粉末于-80～-100℃下进行冷冻干燥，干燥时间为24～48h，即得到S掺杂BiVO4可见光催化粉体材料。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, wash and centrifuge the reaction product powder, then freeze-dry the centrifuged product powder at -80～-100°C, and the drying time is 24～48h , that is, S-doped BiVO 4 visible light photocatalytic powder material is obtained.
与现有技术相比，本发明具有以下优点： Compared with the prior art, the present invention has the following advantages:
1、BiVO4是一种较理想的光催化材料，但是纯BiVO4因为吸附能力和电子-空穴对的转移能力较差而限制了其进一步的应用，本发明采用水热反应法制备出高纯度的S掺杂BiVO4可见光催化材料，本方法制备速度快、效率高、反应转化完全。 1. BiVO 4 is an ideal photocatalytic material, but pure BiVO 4 has limited its further application because of its poor adsorption capacity and electron-hole pair transfer ability. The present invention adopts hydrothermal reaction method to prepare high Pure S-doped BiVO 4 visible light catalytic material, the preparation speed of this method is high, the efficiency is high, and the reaction conversion is complete.
2、与纯BiVO4相比，本发明制备出的S掺杂BiVO4可见光催化材料禁带宽度变小。 2. Compared with pure BiVO 4 , the bandgap width of the S-doped BiVO 4 visible photocatalytic material prepared by the present invention becomes smaller.
3、本发明制备出的S掺杂BiVO4可见光催化材料对染料的降解有明显的降解，在可见光照射下，20分钟甲基蓝溶液的降解率可达到59.7%，100分钟可以降解97%，可广泛应用于工业污水处理、纺织染料降解和半导体光催化等领域。 3. The S-doped BiVO4 visible light catalytic material prepared by the present invention has obvious degradation to the degradation of dyes. Under visible light irradiation, the degradation rate of methylene blue solution can reach 59.7% in 20 minutes, and 97% can be degraded in 100 minutes. It can be widely used in the fields of industrial sewage treatment, textile dye degradation and semiconductor photocatalysis.
4、本发明制备工艺简单，可操作性强，制备成本低，可迅速制备出符合使用要求的S掺杂BiVO4可见光催化材料，水热反应所采用的热处理炉具有很大的普遍性，适用于实验室以及工业生产。 4. The preparation process of the present invention is simple, has strong operability and low preparation cost, and can quickly prepare S-doped BiVO4 visible light catalytic materials that meet the requirements of use. The heat treatment furnace used in the hydrothermal reaction has great universality and is suitable for In laboratory and industrial production.
附图说明 Description of drawings
图1为本发明实施例1中制得的纯BiVO4可见光催化材料的SEM照片。 Fig. 1 is the SEM photo of the pure BiVO 4 visible photocatalytic material prepared in Example 1 of the present invention.
图2为本发明实施例2中制得的S掺杂BiVO4可见光催化材料的FESEM照片。 Fig. 2 is a FESEM photo of the S-doped BiVO 4 visible photocatalytic material prepared in Example 2 of the present invention.
图3为本发明实施例2中制得的S掺杂BiVO4可见光催化材料的TEM照片。 Fig. 3 is a TEM photo of the S-doped BiVO 4 visible photocatalytic material prepared in Example 2 of the present invention.
图4为本发明实施例3中制得的S掺杂BiVO4可见光催化材料的XRD图谱。 Fig. 4 is the XRD spectrum of the S-doped BiVO 4 visible photocatalytic material prepared in Example 3 of the present invention.
图5为本发明实施例4中制得的S掺杂BiVO4可见光催化材料的XPS分析图谱。 Fig. 5 is an XPS analysis spectrum of the S-doped BiVO 4 visible photocatalytic material prepared in Example 4 of the present invention.
图6为本发明实施例1和实施例5～7中所制得的S掺杂BiVO4可见光催化材料的光催化速率图(横坐标为时间，纵坐标为浓度比，即瞬时浓度与初始浓度的比值)。 Fig. 6 is the photocatalytic rate figure (abscissa is time, ordinate is concentration ratio, i.e. instantaneous concentration and initial concentration ratio).
具体实施方式 Detailed ways
为了更好地理解本发明，下面结合附图、实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。 In order to better understand the present invention, the content of the present invention will be further explained below in conjunction with the accompanying drawings and embodiments, but the content of the present invention is not limited to the following embodiments.
实施例1（该实施例为对比实例，即不添加乳化液OP-10及硫脲）： Embodiment 1 (this embodiment is comparative example, does not add emulsion OP-10 and thiourea) :
一种制备纯BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing pure BiVO4visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，室温下充分混合均匀得到前躯体溶液B； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml of acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml of deionized water, and mix well at room temperature to obtain precursor solution B;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌2h，使其充分混合均匀，此时混合溶液pH为1.4； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and use magnetic stirring at room temperature for 2 hours to make it fully mixed evenly. At this time, the pH of the mixed solution is 1.4;
3）3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为140℃，保温时间为15h，然后随炉冷却，得到反应产物溶液C； 3) 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 140°C, the holding time is 15h, and then cool with the furnace to obtain the reaction product solution C ;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行4次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行5次离心洗涤，离心机转速为4500r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-80℃下进行冷冻干燥，干燥时间为24h，干燥后即得到纯BiVO4可见光催化粉体材料，标记为BiVO4 - 1。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform 4 centrifugal washes, then mix the reaction product powder with absolute ethanol, perform 5 centrifugal washes, centrifuge The rotation speed of the machine is 4500r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then the product powder is placed in a freeze dryer and freeze-dried at -80°C for 24 hours, and the pure product powder is obtained after drying. BiVO 4 visible light photocatalytic powder material, marked as BiVO 4 - 1.
从图1可以看出所制备的纯BiVO4可见光催化粉体材料为八面棱台，颗粒表面光滑，且颗粒尺寸较大，大概为2-3μm；其比表面积按BET吸附法测定为0.17m2/g；对亚甲基蓝染料溶液20分钟内基本无降解，见图6；降解条件是甲基蓝的浓度1×10-5 mol/L，体积为100mL，可见光催化粉体材料投加量为0.1g，采用的光源为350W氙灯，其他实施例降解条件与此相同。 It can be seen from Figure 1 that the prepared pure BiVO 4 visible photocatalytic powder material is an octagonal prism, the surface of the particles is smooth, and the particle size is relatively large, about 2-3 μm; its specific surface area is 0.17m2 as measured by the BET adsorption method /g; There is basically no degradation of the methylene blue dye solution within 20 minutes, as shown in Figure 6; the degradation conditions are that the concentration of methylene blue is 1×10 -5 mol/L, the volume is 100mL, and the dosage of visible photocatalytic powder material is 0.1g , the light source that adopts is 350W xenon lamp, and other embodiment degradation conditions are identical with this.
实施例2： Embodiment 2 :
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入硫脲和乳化剂OP-10，其中硫脲与NH4VO3的摩尔比为4.8:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为2.9wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add thiourea and emulsifier OP-10, wherein the molar ratio of thiourea to NH4VO3 is 4.8 : 1, fully mixed at room temperature to obtain precursor solution B, the mass fraction of emulsifier in precursor solution B is 2.9wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌2h，使其充分混合均匀，此时混合溶液pH为1.5； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and stir it with magnetic force for 2 hours at room temperature to make it fully mixed, and the pH of the mixed solution is 1.5 at this time;
3）3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为130℃，保温时间为14h，然后随炉冷却，得到反应产物溶液C； 3) 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 130°C, the holding time is 14h, and then cool with the furnace to obtain the reaction product solution C ;
3）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行3次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行4次离心洗涤，离心机转速为5000r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-80℃下进行冷冻干燥，干燥时间为48h，干燥后即得到S掺杂BiVO4可见光催化粉体材料。 3) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform centrifugal washing for 3 times, then mix the reaction product powder with absolute ethanol, perform centrifugal washing for 4 times, centrifuge The rotation speed of the machine is 5000r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then put the product powder into a freeze dryer and freeze-dry at -80°C, the drying time is 48h, and the S Doped BiVO 4 visible light photocatalytic powder material.
从图2可以看出，所得S掺杂BiVO4可见光催化粉体材料整个形貌呈现哑铃状，是由颗粒细小的BiVO4组装而成，这种哑铃状BiVO4的形成是晶体成核与生长这两个过程共同作用后形成的结果；由图3可以看出该材料主要以疏松的聚集体形态存在，主要是由一些多面体纳米颗粒堆积在一起形成的，纳米颗粒直径约为50nm。 It can be seen from Figure 2 that the overall morphology of the obtained S-doped BiVO 4 visible photocatalytic powder material is dumbbell-shaped, which is assembled from fine-grained BiVO 4 , and the formation of this dumbbell-shaped BiVO 4 is due to crystal nucleation and growth. The result of the joint action of these two processes; it can be seen from Figure 3 that the material mainly exists in the form of loose aggregates, which are mainly formed by the accumulation of some polyhedral nanoparticles, and the diameter of the nanoparticles is about 50nm.
测定S掺杂BiVO4可见光催化粉体材料的比表面积为：13.05m2/g，对亚甲基蓝染料溶液20分钟能降解50.42%。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is: 13.05m 2 /g, which can degrade 50.42% of the methylene blue dye solution in 20 minutes.
实施例3：Example 3:
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入硫脲和乳化剂OP-10，其中，硫脲与NH4VO3的摩尔比为5:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为2.8wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add thiourea and emulsifier OP-10, wherein the molar ratio of thiourea to NH4VO3 is 5:1, fully mixed at room temperature to obtain precursor solution B, the mass fraction of emulsifier in precursor solution B is 2.8wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌1.5h，使其充分混合均匀，此时混合溶液pH为1.6； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and stir it with magnetic force for 1.5 hours at room temperature to make it fully mixed evenly. At this time, the pH of the mixed solution is 1.6;
3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为150℃，保温时间为16h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 150°C, the holding time is 16h, and then cool with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行4次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行4次离心洗涤，离心机转速为6000r/min，每次离心时间为3min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-90℃下进行冷冻干燥，干燥时间为24h，干燥后即得到S掺杂BiVO4可见光催化粉体材料。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform 4 centrifugal washes, then mix the reaction product powder with absolute ethanol, perform 4 centrifugal washes, centrifuge The rotation speed of the machine is 6000r/min, and the centrifugation time is 3min each time to obtain the product powder after cleaning; then put the product powder into a freeze dryer and freeze-dry at -90°C for 24 hours, and obtain S Doped BiVO 4 visible light photocatalytic powder material.
从图4中可以看出，所得S掺杂BiVO4可见光催化粉体材料为纯的单斜晶型的BiVO4， S的加入没有影响BiVO4的结构；从图5中可知该材料中Bi4f7/2的结合能为159.1eV，164.5eV，Bi4f5/2的结合能为164.5eV，S2p3/2的结合能为163.6eV，这分别是Bi3 +和S2-对应的谱峰，说明S元素成功的掺杂到BiVO4中，所得产物确实为S掺杂BiVO4可见光催化粉体材料。 It can be seen from Figure 4 that the obtained S-doped BiVO 4 visible photocatalytic powder material is pure monoclinic BiVO 4 , and the addition of S has no effect on the structure of BiVO 4 ; it can be seen from Figure 5 that the Bi4f7/ The binding energy of 2 is 159.1eV, 164.5eV, the binding energy of Bi4f5/2 is 164.5eV, and the binding energy of S2p3/2 is 163.6eV, which are the peaks corresponding to Bi 3 + and S 2- respectively, indicating that the S element is successfully Doped into BiVO 4 , the resulting product is indeed S-doped BiVO 4 visible photocatalytic powder material.
测定S掺杂BiVO4可见光催化粉体材料的比表面积为：12.97m2/g，对亚甲基蓝染料溶液20分钟能降解47.31%。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is: 12.97m 2 /g, which can degrade 47.31% of the methylene blue dye solution in 20 minutes.
实施例4：Example 4:
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入,硫脲和乳化剂OP-10，其中硫脲与NH4VO3的摩尔比为5.2:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为2.9wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add thiourea and emulsifier OP-10, wherein the molar ratio of thiourea to NH4VO3 is 5.2:1, fully mixed at room temperature to obtain precursor solution B, the mass fraction of emulsifier in precursor solution B is 2.9wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌3h，使其充分混合均匀，此时混合溶液pH为1.3； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and stir it with magnetic force for 3 hours at room temperature to make it fully mixed evenly. At this time, the pH of the mixed solution is 1.3;
3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为150℃，保温时间为15h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 150°C, the holding time is 15h, and then cool with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行3次离心洗涤，离心机转速为4500r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-90℃下进行冷冻干燥，干燥时间为48h，干燥后即得到S掺杂BiVO4可见光催化粉体材料。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform centrifugal washing for the first time, then mix the reaction product powder with absolute ethanol, perform three centrifugal washings, and centrifuge The rotation speed is 4500r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then put the product powder into a freeze dryer at -90°C for freeze-drying, the drying time is 48h, and the S-doped product is obtained after drying. Miscellaneous BiVO 4 visible light photocatalytic powder material.
测定S掺杂BiVO4可见光催化粉体材料的比表面积为：13.77m2/g，对亚甲基蓝染料溶液20分钟能降解52.8%。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is: 13.77m 2 /g, which can degrade 52.8% of methylene blue dye solution in 20 minutes.
实施例5： Embodiment 5 :
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入一定量硫脲和乳化剂OP-10，其中硫脲与NH4VO3的摩尔比为5:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为3wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add a certain amount of thiourea and emulsifier OP-10, wherein the molar ratio of thiourea to NH4VO3 5:1, fully mixed at room temperature to obtain the precursor solution B, the mass fraction of the emulsifier in the precursor solution B is 3wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌2h，使其充分混合均匀，此时混合溶液pH为； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and use magnetic stirring at room temperature for 2 hours to make it fully mixed evenly. At this time, the pH of the mixed solution is;
3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为140℃，保温时间为15h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 140°C, the holding time is 15h, and then cool with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行3次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行5次离心洗涤，离心机转速为5500r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-90℃下进行冷冻干燥，干燥时间为24h，干燥后即得到S掺杂BiVO4可见光催化粉体材料，标记为BiVO4 - 5。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform three centrifugal washings, then mix the reaction product powder with absolute ethanol, perform five centrifugal washings, and centrifuge The rotation speed of the machine is 5500r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then put the product powder into a freeze dryer and freeze-dry at -90°C for a drying time of 24h. After drying, S Doped BiVO 4 visible light photocatalytic powder material, marked as BiVO 4 - 5.
测定S掺杂BiVO4可见光催化粉体材料的比表面积为：14.1m2/g，对亚甲基蓝染料溶液20分钟能降解59.7%，见图6。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is: 14.1m 2 /g, and it can degrade 59.7% of the methylene blue dye solution in 20 minutes, as shown in Figure 6.
实施例6：Embodiment 6:
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入一定量硫脲和乳化剂OP-10，其中脲与NH4VO3的摩尔比为5.8:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为3.1wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add a certain amount of thiourea and emulsifier OP-10, wherein the molar ratio of urea to NH4VO3 is 5.8:1, fully mixed at room temperature to obtain precursor solution B, the mass fraction of emulsifier in precursor solution B is 3.1wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌2h，使其充分混合均匀，此时混合溶液pH为； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and use magnetic stirring at room temperature for 2 hours to make it fully mixed evenly. At this time, the pH of the mixed solution is;
3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为170℃，保温时间为15h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution described in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 170°C, the holding time is 15h, and then cool with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行3~5次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行3~5次离心洗涤，离心机转速为4500r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-90℃下进行冷冻干燥，干燥时间为24h，干燥后即得到S掺杂BiVO4可见光催化粉体材料，标记为BiVO4 - 6。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform centrifugal washing for 3 to 5 times, and then mix the reaction product powder with absolute ethanol for 3 to 5 times Centrifugal washing, the speed of the centrifuge is 4500r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then put the product powder in a freeze dryer and freeze-dry at -90°C for 24 hours, dry After that, the S-doped BiVO 4 visible photocatalytic powder material was obtained, which was marked as BiVO 4 - 6 .
测定S掺杂BiVO4可见光催化粉体材料的比表面积为：10.01m2/g，对亚甲基蓝染料溶液20分钟能降解23.8%，见图6。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is: 10.01m 2 /g, which can degrade 23.8% of the methylene blue dye solution in 20 minutes, as shown in Figure 6.
实施例7： Embodiment 7 :
一种制备S掺杂BiVO4可见光催化材料的方法，它包括如下步骤： A method for preparing S-doped BiVO 4 visible photocatalytic material, it comprises the steps:
1）前驱体溶液的制备：按Bi(NO3)3·5H2O与NH4VO3的摩尔比为1:1，称取原料粉末，将5mmol Bi(NO3)3·5H2O充分溶入25ml醋酸溶液中得到前躯体溶液A，将5mmol NH4VO3充分溶入25ml去离子水中，并加入一定量硫脲和乳化剂OP-10，其中硫脲与NH4VO3的摩尔比为4.5:1，室温下充分混合均匀得到前躯体溶液B，乳化剂在前躯体溶液B中的质量分数为3wt%； 1) Preparation of precursor solution: According to the molar ratio of Bi(NO 3 ) 3 5H 2 O to NH 4 VO 3 is 1:1, weigh the raw material powder, and fully mix 5mmol Bi(NO 3 ) 3 5H 2 O Dissolve in 25ml acetic acid solution to obtain precursor solution A, fully dissolve 5mmol NH4VO3 into 25ml deionized water, and add a certain amount of thiourea and emulsifier OP-10, wherein the molar ratio of thiourea to NH4VO3 4.5:1, fully mixed at room temperature to obtain precursor solution B, the mass fraction of emulsifier in precursor solution B is 3wt%;
2）将前躯体溶液A逐渐滴加入前躯体溶液B中，室温下采用磁力搅拌2h，使其充分混合均匀，此时混合溶液pH为； 2) Gradually add the precursor solution A to the precursor solution B dropwise, and use magnetic stirring at room temperature for 2 hours to make it fully mixed evenly. At this time, the pH of the mixed solution is;
3）将步骤2）所述混合溶液放入水热反应釜中，置于高温电阻炉内进行热处理，热处理温度为110℃，保温时间为15h，然后随炉冷却，得到反应产物溶液C； 3) Put the mixed solution in step 2) into a hydrothermal reaction kettle, place it in a high-temperature resistance furnace for heat treatment, the heat treatment temperature is 110°C, the holding time is 15h, and then cool with the furnace to obtain the reaction product solution C;
4）将反应产物溶液C进行离心分离，得到反应产物粉末，将反应产物粉末与去离子水混合，进行3次离心洗涤，然后将反应产物粉末与无水乙醇混合，进行3次离心洗涤，离心机转速为5000r/min，每次离心时间为5min，得到清洗后的产物粉末；再将产物粉末置入冷冻干燥仪中于-100℃下进行冷冻干燥，干燥时间为48h，干燥后即得到S掺杂BiVO4可见光催化粉体材料，标记为BiVO4 - 7。 4) Centrifuge the reaction product solution C to obtain the reaction product powder, mix the reaction product powder with deionized water, perform three centrifugal washings, then mix the reaction product powder with absolute ethanol, perform three centrifugal washings, and centrifuge The rotation speed of the machine is 5000r/min, and the centrifugation time is 5min each time to obtain the product powder after cleaning; then put the product powder into a freeze dryer at -100°C for freeze-drying, the drying time is 48h, and the S Doped BiVO 4 visible light photocatalytic powder material, marked as BiVO 4 - 7.
测定S掺杂BiVO4可见光催化粉体材料的比表面积为7.13m2/g，对亚甲基蓝染料溶液20分钟能降解17.35%，见图6。 The measured specific surface area of S-doped BiVO 4 visible light photocatalytic powder material is 7.13m 2 /g, and the methylene blue dye solution can be degraded by 17.35% in 20 minutes, as shown in Figure 6.
从图6可以看出，纯BiVO4可见光催化粉体材料对亚甲蓝染料溶液基本无降解，S掺杂BiVO4可见光催化粉体材料对亚甲蓝染料溶液都有一定程度的降解，当S掺杂BiVO4可见光催化粉体材料的水热合成温度为140℃，保温时间为15h（实施例5），20min对亚甲蓝染料溶液的降解可以达到59.7%，100min降解率为97%。 It can be seen from Figure 6 that the pure BiVO 4 visible light photocatalytic powder material has basically no degradation to the methylene blue dye solution, and the S doped BiVO 4 visible light photocatalytic powder material has a certain degree of degradation on the methylene blue dye solution. The hydrothermal synthesis temperature of BiVO 4 visible light catalytic powder material is 140°C, and the holding time is 15h (Example 5). The degradation rate of methylene blue dye solution can reach 59.7% in 20 minutes, and the degradation rate is 97% in 100 minutes.
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