CN116639729A - Symbiotic bismuth layered ferroelectric Bi 7 Ti 4 NbO 21 Preparation method and application of semiconductor material - Google Patents

Symbiotic bismuth layered ferroelectric Bi 7 Ti 4 NbO 21 Preparation method and application of semiconductor material Download PDF

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CN116639729A
CN116639729A CN202310609389.9A CN202310609389A CN116639729A CN 116639729 A CN116639729 A CN 116639729A CN 202310609389 A CN202310609389 A CN 202310609389A CN 116639729 A CN116639729 A CN 116639729A
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于洪鉴
纪媛媛
张燕
韩杰
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Abstract

The invention discloses a symbiotic bismuth layered ferroelectric Bi 7 Ti 4 NbO 21 The preparation method and application of the semiconductor material comprise the following steps:step 1: stoichiometric ratio of bismuth source and Nb 2 O 5 Adding a titanium source into water, and uniformly stirring; step 2: then pouring an alkali solution into the mixed solution obtained in the step 1, and continuously stirring uniformly; step 3: transferring the mixed solution obtained in the step (2) into a hydrothermal kettle for heating reaction; step 4: washing and drying the product obtained by the reaction in the step 3 to obtain the symbiotic ferroelectric Bi 7 Ti 4 NbO 21 A semiconductor material. The bismuth-based layered symbiotic ferroelectric Bi with large specific surface area, rich active sites, complete crystal form, uniform particle size dispersion, stronger ferroelectric property and excellent photocatalytic property is synthesized by using a solvothermal method 7 Ti 4 NbO 21 A semiconductor material.

Description

一种共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法及 其应用A kind of preparation method of intergrowth bismuth system layered ferroelectric Bi7Ti4NbO21 semiconductor material and its application

技术领域technical field

本发明涉及一种共生铋系层状铁电材料的制备方法，具体涉及共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法及其应用。The invention relates to a preparation method of a symbiotic bismuth-based layered ferroelectric material, in particular to a preparation method and application of a symbiotic bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

背景技术Background technique

随着全球工业化和现代化的高速发展，二氧化碳的过度排放打破了自然界碳循环的平衡，造成了严重的环境问题，尤其是全球变暖。通过太阳能驱动将二氧化碳转化为高附加值的含碳燃料因其能同时解决碳排放和能源危机的优势而成为科学研究的热点之一。到目前为止，尽管二氧化碳还原已经取得了很大了进展，但二氧化碳光还原在太阳能燃料中的实际应用差强人意。因此，探索合成具有高效光催化性能的新型光催化剂具有重要意义。With the rapid development of global industrialization and modernization, the excessive emission of carbon dioxide has broken the balance of the natural carbon cycle, causing serious environmental problems, especially global warming. Converting carbon dioxide into high-value-added carbon-containing fuels driven by solar energy has become one of the hotspots of scientific research because of its advantages in solving both carbon emissions and energy crises. So far, although much progress has been made in CO2 reduction, the practical application of CO2 photoreduction in solar fuels has been less than satisfactory. Therefore, it is of great significance to explore and synthesize new photocatalysts with high-efficiency photocatalytic performance.

近年来，铋系层状钙钛矿铁电材料（BLSFs）以其优良的疲劳性能，铁电特性而受到了广泛的研究和报道。众多的铋系层状钙钛矿铁电材料如Bi2WO6、SrBi2Nb2O9、Bi4Ti3O12和Bi3TiNbO9 等被报道展现出优异的光催化活性。为了进一步提升材料的光催化性能，研究者们也提出了许多的改性方法，比如形貌与晶面的调控，缺陷工程的构建，A位和B位的掺杂/取代，形成多元混合体系的固溶体等。众所周知，铁电半导体材料的自发极化电场能够有效地减少电子和空穴的复合，进而提高光催化性能，因此可以通过有效的手段提升材料的铁电性能进而提高光催化性能。据报道利用两种不同铋系层状结构单元组成新材料—共生铋系层状铁电半导体，能够显著提升材料的铁电性能。然而，目前铋系层状铁电半导体的合成多数利用高温固相法，合成过程不但耗能高，往往也难以实现形貌和微结构的调控。因此，如何利用溶剂热法合成出比表面积大，活性位点丰富，具有较强铁电性能和光催化性能的铋系层状铁电Bi7Ti4NbO21半导体材料，并将其应用于光催化领域具有重要的研究价值。In recent years, bismuth-based layered perovskite ferroelectric materials (BLSFs) have been extensively studied and reported for their excellent fatigue performance and ferroelectric properties. Numerous bismuth-based layered perovskite ferroelectric materials such as Bi 2 WO 6 , SrBi 2 Nb 2 O 9 , Bi 4 Ti 3 O 12 and Bi 3 TiNbO 9 have been reported to exhibit excellent photocatalytic activity. In order to further improve the photocatalytic performance of materials, researchers have also proposed many modification methods, such as the regulation of morphology and crystal plane, the construction of defect engineering, the doping/substitution of A-site and B-site, and the formation of multi-component hybrid systems. solid solution, etc. It is well known that the spontaneous polarization electric field of ferroelectric semiconductor materials can effectively reduce the recombination of electrons and holes, thereby improving the photocatalytic performance. It is reported that the use of two different bismuth-based layered structural units to form a new material-intergrowth bismuth-based layered ferroelectric semiconductors can significantly improve the ferroelectric properties of the material. However, most of the synthesis of bismuth-based layered ferroelectric semiconductors currently uses high-temperature solid-state methods. The synthesis process not only consumes high energy, but also often makes it difficult to control the morphology and microstructure. Therefore, how to use the solvothermal method to synthesize bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor materials with large specific surface area, rich active sites, strong ferroelectric properties and photocatalytic properties, and apply them in photocatalysis The field has important research value.

发明内容Contents of the invention

发明目的：针对上述现有技术，提出一种共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，利用溶剂热法合成出比表面积大，活性位点丰富，具有较强的铁电性能和光催化性能的铋系层状铁电Bi7Ti4NbO21半导体材料。Purpose of the invention: Aiming at the above-mentioned prior art, a method for preparing a symbiotic bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material is proposed, which is synthesized by a solvothermal method with a large specific surface area, rich active sites, and strong Bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor materials with ferroelectric and photocatalytic properties.

技术方案：一种共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，包括以下步骤：Technical solution: A method for preparing an intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material, comprising the following steps:

步骤1：按化学计量比将铋源、Nb2O5、钛源加入水中，搅拌均匀；Step 1: Add bismuth source, Nb 2 O 5 , and titanium source into water according to the stoichiometric ratio, and stir evenly;

步骤2：然后向步骤1得到的混合液中倒入碱溶液，继续搅拌均匀；Step 2: Then pour the alkali solution into the mixed solution obtained in step 1, and continue to stir evenly;

步骤3：接着将步骤2得到的混合液转移至水热釜中，进行加热反应；Step 3: Then transfer the mixed solution obtained in step 2 to a hydrothermal kettle for heating and reaction;

步骤4：将步骤3反应所得产物洗涤烘干，即为共生铁电Bi7Ti4NbO21半导体材料。Step 4: washing and drying the reaction product obtained in step 3, which is the symbiotic ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

进一步的，所述步骤1中，铋源为铋盐，选自五水合硝酸铋、硫酸铋、氯化铋、柠檬酸铋中的至少一种。Further, in the step 1, the bismuth source is a bismuth salt, at least one selected from bismuth nitrate pentahydrate, bismuth sulfate, bismuth chloride, and bismuth citrate.

进一步的，所述步骤1中，钛源选自二氧化钛、钛酸四丁酯、四氯化钛中的至少一种。Further, in the step 1, the titanium source is at least one selected from titanium dioxide, tetrabutyl titanate, and titanium tetrachloride.

进一步的，所述步骤2中，碱溶液选自氢氧化钠、氢氧化钾中的至少一种，所述碱溶液在整个反应液中的碱浓度3-6 mol/L。Further, in the step 2, the alkali solution is selected from at least one of sodium hydroxide and potassium hydroxide, and the alkali concentration of the alkali solution in the entire reaction liquid is 3-6 mol/L.

进一步的，所述步骤3中，反应温度为200～240 ℃，时间为20～30 h。Further, in the step 3, the reaction temperature is 200-240° C., and the time is 20-30 h.

进一步的，所述步骤4中，产物分别通过无水乙醇、去离子水各清洗3次并离心若干次。Further, in step 4, the product was washed three times with absolute ethanol and deionized water respectively and centrifuged several times.

进一步的，所述步骤4中，50～70 ℃下烘干12～24 h。Further, in step 4, drying is carried out at 50-70° C. for 12-24 h.

根据所述方法制备得到的共生铋系层状铁电Bi7Ti4NbO21半导体材料。The intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material prepared according to the method.

所述共生铋系层状铁电Bi7Ti4NbO21半导体材料作为铁电材料在光催化中的应用。The application of the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material as a ferroelectric material in photocatalysis.

进一步的，所述光催化包括光催化将CO2还原为含碳燃料、裂解水得到氢气和氧气、降解水中的污染物。Further, the photocatalysis includes photocatalytic reduction of CO2 into carbon-containing fuels, splitting water to obtain hydrogen and oxygen, and degrading pollutants in water.

有益效果Beneficial effect

1、本发明通过溶剂热法合成共生铋系层状铁电Bi7Ti4NbO21半导体材料，制备方法操作简单，成本低廉、无需高温反应过程和复杂试剂，反应物比表面积大，活性位点丰富，晶型完整、粒度分散均匀，具有较高的稳定性。1. The present invention synthesizes the symbiotic bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material through the solvothermal method. The preparation method is simple to operate, low in cost, does not require high-temperature reaction process and complex reagents, and the specific surface area of the reactant is large, and the active sites Rich, complete crystal form, uniform particle size dispersion, and high stability.

2、本发明制备的共生铋系层状铁电Bi7Ti4NbO21半导体材料具有优异的光催化性能，尤其是在光催化还原CO2为CO过程中具有较高的光催化活性。2. The intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material prepared by the present invention has excellent photocatalytic performance, especially high photocatalytic activity in the process of photocatalytic reduction of CO 2 to CO.

附图说明Description of drawings

图1为实施例及对比例制备的光催化材料的XRD图谱；Fig. 1 is the XRD spectrum of the photocatalytic material prepared by embodiment and comparative example;

图2为实施例及对比例制备的光催化材料的SEM图像；Fig. 2 is the SEM image of the photocatalytic material prepared by embodiment and comparative example;

图3为实施例及对比例制备的光催化材料的CO产率柱状图；Fig. 3 is the CO production rate histogram of the photocatalytic material prepared by embodiment and comparative example;

图4为实施例的制备方法的流程图。Fig. 4 is a flow chart of the preparation method of the embodiment.

具体实施方式Detailed ways

下面结合附图对本发明做更进一步的解释。以下实施例，用于说明本发明，但不止用来限制本发明的范围。所述方法如无特别说明均为常规方法。所述材料如无特别说明均能从公开商业途径而得。The present invention will be further explained below in conjunction with the accompanying drawings. The following examples are used to illustrate the present invention, but not to limit the scope of the present invention. The methods are conventional methods unless otherwise specified. The materials can be obtained from public commercial sources unless otherwise specified.

下述实施例Bi7Ti4NbO21和对比例Bi4Ti3O12、Bi3TiNbO9的性能评价方法如下：The performance evaluation methods of the following example Bi 7 Ti 4 NbO 21 and comparative examples Bi 4 Ti 3 O 12 and Bi 3 TiNbO 9 are as follows:

Bi4Ti3O12、Bi3TiNbO9、Bi7Ti4NbO21的物相评价方法：Phase evaluation method of Bi 4 Ti 3 O 12 , Bi 3 TiNbO 9 , Bi 7 Ti 4 NbO 21 :

X射线衍射（XRD）：将制备的Bi4Ti3O12、Bi3TiNbO9、Bi7Ti4NbO21材料在德国Bruker公司D8 Advance系列广角X射线衍射仪分析样品的晶体结构，扫描速度为5 °/min，扫描范围为20 °~ 70 °。X-ray diffraction (XRD): The crystal structure of the prepared Bi 4 Ti 3 O 12 , Bi 3 TiNbO 9 , Bi 7 Ti 4 NbO 21 materials was analyzed on a D8 Advance series wide-angle X-ray diffractometer from Bruker, Germany, with a scanning speed of 5 °/min, the scanning range is 20 °~ 70 °.

Bi4Ti3O12、Bi3TiNbO9、Bi7Ti4NbO21的微观形貌评价方法：Microscopic morphology evaluation method of Bi 4 Ti 3 O 12 , Bi 3 TiNbO 9 , Bi 7 Ti 4 NbO 21 :

扫描电镜（SEM）：将制备的Bi4Ti3O12、Bi3TiNbO9、Bi7Ti4NbO21材料在日本JEOL公司JSM-IT300系列扫描电镜上测试，加速电压：5-20 kV。Scanning electron microscope (SEM): The prepared Bi 4 Ti 3 O 12 , Bi 3 TiNbO 9 , and Bi 7 Ti 4 NbO 21 materials were tested on a JSM-IT300 series scanning electron microscope from JEOL, Japan, with an accelerating voltage of 5-20 kV.

Bi4Ti3O12、Bi3TiNbO9、Bi7Ti4NbO21的CO2还原性能评价方法：CO 2 reduction performance evaluation method of Bi 4 Ti 3 O 12 , Bi 3 TiNbO 9 , Bi 7 Ti 4 NbO 21 :

光催化CO2还原实验在定制的石英玻璃反应器( 300 mL )中进行。将50 mg的Bi7Ti4NbO21均匀分散在定制的石英玻璃反应器上，并在反应器底部放置三角形玻璃支撑体。然后将1.0900 g NaHCO3置于反应器底部并抽真空。随后将10 mL H2SO4 ( 0.65 mol/L )注入反应器底部，与NaHCO3粉末反应生成CO2 ( 1 atm )。用氙灯（300 W）作为光源 (北京泊菲莱科技有限公司)，通过冷凝循环保持反应器温度为20 ℃。最后，采用GC7920气相色谱(北京华光教育科技有限公司)对每小时抽取的1 mL反应气体进行定性定量分析，共反应4小时。Photocatalytic CO2 reduction experiments were carried out in a custom-made quartz glass reactor (300 mL). 50 mg of Bi7Ti4NbO21 was uniformly dispersed on a custom-made quartz glass reactor, and a triangular glass support was placed at the bottom of the reactor. Then 1.0900 g of NaHCO3 was placed at the bottom of the reactor and vacuumed. Then 10 mL of H 2 SO 4 (0.65 mol/L) was injected into the bottom of the reactor to react with NaHCO 3 powder to generate CO 2 (1 atm). A xenon lamp (300 W) was used as the light source (Beijing Pofilai Technology Co., Ltd.), and the reactor temperature was maintained at 20 °C through a condensation cycle. Finally, a GC7920 gas chromatograph (Beijing Huaguang Education Technology Co., Ltd.) was used for qualitative and quantitative analysis of 1 mL of reaction gas extracted per hour, and the reaction lasted for 4 hours.

Bi4Ti3O12、Bi3TiNbO9的CO2还原性能评价方法过程与上述一致。The CO 2 reduction performance evaluation method process of Bi 4 Ti 3 O 12 and Bi 3 TiNbO 9 is consistent with the above.

实施例1 制备共生铋系层状铁电Bi7Ti4NbO21半导体材料及其性能测试Example 1 Preparation of intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material and its performance test

如图4所示，在室温下，首先将3.3955 g Bi(NO3)3·5H2O、1.3700 ml钛酸四丁酯、0.1329 g Nb2O5分散在盛有30 mL的去离子水烧杯中搅拌，然后将9.600 g NaOH溶解在30mL去离子水后倒入上述反应液中继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为220 ℃，反应24 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，60 ℃下烘12 h，得到共生层状铋系铁电Bi7Ti4NbO21半导体材料。As shown in Figure 4, at room temperature, firstly, 3.3955 g Bi(NO 3 ) 3 5H 2 O, 1.3700 ml tetrabutyl titanate, 0.1329 g Nb 2 O 5 were dispersed in a 30 mL deionized water beaker Stir in medium, then dissolve 9.600 g NaOH in 30 mL deionized water and pour it into the above reaction solution to continue magnetic stirring, and finally transfer the resulting mixed solution to a polytetrafluoroethylene stainless steel hydrothermal kettle for heating and reaction, the reaction temperature is 220°C, react for 24 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 60 ℃ for 12 h to obtain intergrown layered bismuth-based ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

取制备的共生Bi7Ti4NbO21光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4 h下，CO的产率为11.92 μmol g-1。50 mg of the as-prepared symbiotic Bi 7 Ti 4 NbO 21 photocatalytic material was used for the gas-solid photocatalytic CO 2 reduction experiment. Under full light irradiation for 4 h, the CO yield was 11.92 μmol g -1 .

XRD图谱如图1所示；SEM图像如图2所示；CO产率如图3所示。The XRD spectrum is shown in Figure 1; the SEM image is shown in Figure 2; the CO yield is shown in Figure 3.

对比例1制备铋系层状铁电Bi4Ti3O12半导体材料及其性能测试Comparative Example 1 Preparation of bismuth-based layered ferroelectric Bi 4 Ti 3 O 12 semiconductor material and its performance test

在室温下，首先将1.9400 g Bi(NO3)3·5H2O、1.02 ml钛酸四丁酯分散在盛有30mL的去离子水烧杯中搅拌，然后将9.600 g NaOH溶解在30 mL去离子水后倒入上述反应液中继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为180 ℃，反应24 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，60℃下烘18h，得到共生层状铋系铁电Bi4Ti3O12半导体材料。At room temperature, firstly, 1.9400 g Bi(NO 3 ) 3 5H 2 O and 1.02 ml tetrabutyl titanate were dispersed in a 30 mL deionized water beaker and stirred, then 9.600 g NaOH was dissolved in 30 mL deionized Pour water into the above reaction solution and continue magnetic stirring, and finally transfer the resulting mixture to a polytetrafluoroethylene-lined stainless steel hydrothermal kettle for heating and reaction at a reaction temperature of 180 °C for 24 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 60° C. for 18 hours to obtain intergrown layered bismuth-based ferroelectric Bi 4 Ti 3 O 12 semiconductor material.

取制备的Bi4Ti3O12光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4h下，CO的产率为6.48 μmol g-1。50 mg of the prepared Bi 4 Ti 3 O 12 photocatalytic material was used for gas-solid phase photocatalytic CO 2 reduction experiment. Under full light irradiation for 4 hours, the yield of CO was 6.48 μmol g -1 .

XRD图谱如图1所示；SEM图像如图2所示；CO产率如图3所示。The XRD spectrum is shown in Figure 1; the SEM image is shown in Figure 2; the CO yield is shown in Figure 3.

对比例2制备铋系层状铁电Bi3TiNbO9材料及其性能测试Comparative Example 2 Preparation of bismuth-based layered ferroelectric Bi 3 TiNbO 9 material and its performance test

在室温下，首先将1.4550 g Bi(NO3)3·5H2O、0.3500 ml钛酸四丁酯、0.1329 gNb2O5分散在盛有30 mL的去离子水烧杯中搅拌，然后加入4.8000 g NaOH继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为220 ℃，反应24 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，60 ℃下烘12 h，得到共生层状铋系铁电Bi3TiNbO9半导体材料。At room temperature, first disperse 1.4550 g Bi(NO 3 ) 3 5H 2 O, 0.3500 ml tetrabutyl titanate, 0.1329 g Nb 2 O 5 in a 30 mL deionized water beaker and stir, then add 4.8000 g NaOH continued magnetic stirring, and finally the resulting mixture was transferred to a polytetrafluoroethylene-lined stainless steel hydrothermal kettle for heating and reaction at a reaction temperature of 220 °C for 24 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 60 ℃ for 12 h to obtain intergrown layered bismuth-based ferroelectric Bi 3 TiNbO 9 semiconductor material.

取制备的Bi3TiNbO9光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4 h下，CO的产率为8.59 μmol g-1。50 mg of the prepared Bi 3 TiNbO 9 photocatalytic material was used for gas-solid phase photocatalytic CO 2 reduction experiment. Under full light irradiation for 4 h, the yield of CO was 8.59 μmol g -1 .

XRD图谱如图1所示；SEM图像如图2所示；CO 产率如图3所示。The XRD spectrum is shown in Figure 1; the SEM image is shown in Figure 2; the CO yield is shown in Figure 3.

对于图1，通过对样品进行XRD测试，实施例1、对比例1和对比例2分别与Bi7Ti4NbO21、Bi4Ti3O12和Bi3TiNbO9的标准卡片PDF﹟(31-0202)、PDF﹟(43-0973)、PDF﹟(39-0233)相对应，说明合成的催化剂为纯相，无其它杂质。 For Fig. 1 , by XRD test on samples , the standard card PDF ﹟ (31- 0202), PDF﹟(43-0973), and PDF﹟(39-0233), which indicate that the synthesized catalyst is a pure phase without other impurities.

对于图2，通过对样品进行SEM测试，可以发现，溶剂热法合成的三种催化剂都由片状纳米片堆叠而成的纳米花球，样品的厚度范围约为15-50 nm，此外，可以明显的看出共生Bi7Ti4NbO21的片更大更薄，在等质量相同光源照射下，共生材料暴露更多的活性位点，增加了底物与CO2的接触概率，从而实现光催化CO2还原。As for Figure 2, through the SEM test of the samples, it can be found that the three catalysts synthesized by the solvothermal method are all composed of nano-flower balls stacked by sheet-like nano-sheets, and the thickness of the samples ranges from about 15-50 nm. In addition, it can be It is obvious that the sheets of symbiotic Bi 7 Ti 4 NbO 21 are larger and thinner. Under the illumination of the same mass and same light source, the symbiotic material exposes more active sites, which increases the contact probability between the substrate and CO 2 , thus realizing the light Catalytic CO2 reduction.

本发明共生铋系层状铁电Bi7Ti4NbO21导体材料的光催化原理：共生铋系层状铁电Bi7Ti4NbO21半导体材料的光催化CO2还原反应可被分为以下三个主要过程，首先是光吸收过程，当共生铋系层状铁电Bi7Ti4NbO21半导体材料受到光照射时，价带上的电子跃迁到导带，同时价带上产生空穴；接着是光生电子-空穴对的迁移到材料表面与CO2和H2O发生氧化还原反应过程，共生铋系层状铁电Bi7Ti4NbO21半导体材料由于内部存在较大的自发极化电场，可以作为促进电子和空穴有效分离的强大驱动力进而提高光催化反应活性；最后，材料表面吸附的CO2经过电子/质子传输过程及中间产物的转换过程最直接最终被还原成CO。The photocatalytic principle of the symbiotic bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 conductor material of the present invention: the photocatalytic CO 2 reduction reaction of the symbiotic bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material can be divided into the following three The first is the light absorption process. When the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material is irradiated by light, the electrons in the valence band transition to the conduction band, and holes are generated in the valence band; then It is the migration of photogenerated electron-hole pairs to the surface of the material and the redox reaction process of CO 2 and H 2 O. The intergrown bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material has a large spontaneous polarization electric field inside , can be used as a strong driving force to promote the effective separation of electrons and holes, thereby improving the photocatalytic reactivity; finally, the CO 2 adsorbed on the surface of the material is most directly reduced to CO through the process of electron/proton transport and conversion of intermediate products.

对于图3，通过对样品进行光催化CO2还原性能测试，可以看出光照4 h后，实施例Bi7Ti4NbO21和对比例Bi4Ti3O12、Bi3TiNbO9的CO产率分别为11.92 μmol g-1、6.48 μmol g-1、8.59 μmol g-1。As for Figure 3, by testing the photocatalytic CO 2 reduction performance of the samples, it can be seen that after 4 h of light irradiation, the CO yields of the example Bi 7 Ti 4 NbO 21 and the comparative examples Bi 4 Ti 3 O 12 and Bi 3 TiNbO 9 They are 11.92 μmol g -1 , 6.48 μmol g -1 , and 8.59 μmol g -1 , respectively.

由此可见，本发明提出溶剂热法合成共生铋系层状铁电Bi7Ti4NbO21半导体材料具有优异的光催化CO2还原性能。It can be seen that the present invention proposes a solvothermal synthesis of intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material with excellent photocatalytic CO 2 reduction performance.

实施例2Example 2

在室温下，首先将2.4715 g Bi2(SO4)3、0.3195 g TiO2、0.1329 g Nb2O5分散在盛有30 mL的去离子水烧杯中搅拌，然后将10.0998 g KOH溶解在30 mL去离子水后倒入上述反应液中继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为200 ℃，反应30 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，50 ℃下烘24 h，得到共生层状铋系铁电Bi7Ti4NbO21半导体材料。At room temperature, firstly 2.4715 g Bi 2 (SO 4 ) 3 , 0.3195 g TiO 2 , 0.1329 g Nb 2 O 5 were dispersed in a 30 mL deionized water beaker and stirred, then 10.0998 g KOH was dissolved in 30 mL Deionized water was poured into the above reaction solution to continue magnetic stirring, and finally the resulting mixture was transferred to a polytetrafluoroethylene-lined stainless steel hydrothermal kettle for heating and reaction at a reaction temperature of 200 °C for 30 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 50 ℃ for 24 h to obtain intergrown layered bismuth-based ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

取制备的共生Bi7Ti4NbO21光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4 h下，CO的产率为12.56 μmol g-1。50 mg of the as-prepared symbiotic Bi 7 Ti 4 NbO 21 photocatalytic material was used for gas-solid phase photocatalytic CO 2 reduction experiments. Under full light irradiation for 4 h, the CO yield was 12.56 μmol g -1 .

实施例3Example 3

在室温下，首先将2.2073 g BiCl3、0.7587 g TiCl4、0.1329 g Nb2O5分散在盛有30 mL的去离子水烧杯中搅拌，然后将20.1996 g KOH溶解在30 mL去离子水后倒入上述反应液中继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为240 ℃，反应20 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，70℃下烘12 h，得到共生层状铋系铁电Bi7Ti4NbO21半导体材料。At room temperature, first disperse 2.2073 g BiCl 3 , 0.7587 g TiCl 4 , and 0.1329 g Nb 2 O 5 in a 30 mL deionized water beaker and stir, then dissolve 20.1996 g KOH in 30 mL deionized water and pour into the above reaction solution and continued magnetic stirring, and finally transferred the obtained mixed solution to a polytetrafluoroethylene-lined stainless steel hydrothermal kettle for heating and reaction at a reaction temperature of 240 °C for 20 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 70°C for 12 h to obtain intergrown layered bismuth-based ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

取制备的共生Bi7Ti4NbO21光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4 h下，CO的产率为10.38 μmol g-1。50 mg of the as-prepared symbiotic Bi 7 Ti 4 NbO 21 photocatalytic material was used for the gas-solid phase photocatalytic CO 2 reduction experiment. Under full light irradiation for 4 h, the CO yield was 10.38 μmol g -1 .

实施例4Example 4

在室温下，首先将2.7866 g C6H5BiO7、1.3700 ml钛酸四丁酯、0.1329 g Nb2O5分散在盛有30 mL的去离子水烧杯中搅拌，然后将9.600 g NaOH溶解在30 mL去离子水后倒入上述反应液中继续磁力搅拌，最后将所得混合液转移到内衬为聚四氟乙烯不锈钢水热釜中加热反应，反应温度为220 ℃，反应24 h。反应结束后分别用无水乙醇、去离子水各清洗离心3次，60 ℃下烘18 h，得到共生层状铋系铁电Bi7Ti4NbO21半导体材料。At room temperature, firstly 2.7866 g C 6 H 5 BiO 7 , 1.3700 ml tetrabutyl titanate, 0.1329 g Nb 2 O 5 were dispersed in a 30 mL deionized water beaker and stirred, then 9.600 g NaOH was dissolved in 30 mL of deionized water was poured into the above reaction solution to continue magnetic stirring, and finally the resulting mixture was transferred to a polytetrafluoroethylene-lined stainless steel hydrothermal kettle for heating and reaction at a reaction temperature of 220 °C for 24 h. After the reaction, wash and centrifuge three times with absolute ethanol and deionized water respectively, and bake at 60 °C for 18 h to obtain intergrown layered bismuth-based ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material.

取制备的共生Bi7Ti4NbO21光催化材料50 mg进行气-固相光催化CO2还原实验，全光照射4 h下，CO的产率为12.03 μmol g-1。50 mg of the as-prepared symbiotic Bi 7 Ti 4 NbO 21 photocatalytic material was used for the gas-solid phase photocatalytic CO 2 reduction experiment. Under full light irradiation for 4 h, the yield of CO was 12.03 μmol g -1 .

以上制备得到的Bi7Ti4NbO21光催化材料还用于光催化裂解水得到氢气和氧气、降解水中的各类污染物。The Bi 7 Ti 4 NbO 21 photocatalytic material prepared above can also be used for photocatalytic cracking of water to obtain hydrogen and oxygen, and to degrade various pollutants in water.

以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1.一种共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：包括以下步骤：1. A method for preparing an intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material, characterized in that: comprising the following steps: 步骤1：按化学计量比将铋源、Nb2O5、钛源加入水中，搅拌均匀；Step 1: Add bismuth source, Nb 2 O 5 , and titanium source into water according to the stoichiometric ratio, and stir evenly; 步骤2：然后向步骤1得到的混合液中倒入碱溶液，继续搅拌均匀；Step 2: Then pour the alkali solution into the mixed solution obtained in step 1, and continue to stir evenly; 步骤3：接着将步骤2得到的混合液转移至水热釜中，进行加热反应；Step 3: Then transfer the mixed solution obtained in step 2 to a hydrothermal kettle for heating and reaction; 步骤4：将步骤3反应所得产物洗涤烘干，即为共生铁电Bi7Ti4NbO21半导体材料。Step 4: washing and drying the reaction product obtained in step 3, which is the symbiotic ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material. 2.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤1中，铋源为铋盐，选自五水合硝酸铋、硫酸铋、氯化铋、柠檬酸铋中的至少一种。2. The preparation method of intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1, characterized in that: in the step 1, the bismuth source is a bismuth salt selected from bismuth nitrate pentahydrate , bismuth sulfate, bismuth chloride, bismuth citrate at least one. 3.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤1中，钛源选自二氧化钛、钛酸四丁酯、四氯化钛中的至少一种。3. The preparation method of intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1, characterized in that: in the step 1, the titanium source is selected from titanium dioxide, tetrabutyl titanate, At least one of titanium tetrachloride. 4.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤2中，碱溶液选自氢氧化钠、氢氧化钾中的至少一种，所述碱溶液在整个反应液中的碱浓度3-6 mol/L。4. The preparation method of intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1, characterized in that: in the step 2, the alkali solution is selected from sodium hydroxide and potassium hydroxide The alkali concentration of the alkali solution in the entire reaction liquid is 3-6 mol/L. 5.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤3中，反应温度为200～240 ℃，时间为20～30 h。5. The method for preparing the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1, characterized in that: in the step 3, the reaction temperature is 200-240 °C, and the time is 20-20 °C 30 h. 6.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤4中，产物分别通过无水乙醇、去离子水各清洗3次并离心若干次。6. The preparation method of the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1, characterized in that: in the step 4, the products are respectively cleaned by absolute ethanol and deionized water. 3 times and centrifuge several times. 7.根据权利要求1所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料的制备方法，其特征在于：所述步骤4中，50～70 ℃下烘干12～24 h。7 . The method for preparing the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material according to claim 1 , characterized in that: in the step 4, dry at 50-70° C. for 12-24 h. 8.根据权利要求1-7任一所述的方法制备得到的共生铋系层状铁电Bi7Ti4NbO21半导体材料。8. The intergrown bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material prepared by the method according to any one of claims 1-7. 9.根据权利要求8所述的共生铋系层状铁电Bi7Ti4NbO21半导体材料作为铁电材料在光催化中的应用。9. The application of the intergrowth bismuth-based layered ferroelectric Bi 7 Ti 4 NbO 21 semiconductor material as a ferroelectric material in photocatalysis according to claim 8. 10.根据权利要求9所述的应用，其特征在于：所述光催化包括光催化将CO2还原为含碳燃料、裂解水得到氢气和氧气、降解水中的污染物。10. The application according to claim 9, characterized in that: the photocatalysis includes photocatalytic reduction of CO2 to carbon-containing fuels, cracking of water to obtain hydrogen and oxygen, and degradation of pollutants in water.
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