CN108543536A - A kind of pucherite-calcium ferrite composite photo-catalyst, preparation method and applications - Google Patents

A kind of pucherite-calcium ferrite composite photo-catalyst, preparation method and applications Download PDF

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CN108543536A
CN108543536A CN201810208059.8A CN201810208059A CN108543536A CN 108543536 A CN108543536 A CN 108543536A CN 201810208059 A CN201810208059 A CN 201810208059A CN 108543536 A CN108543536 A CN 108543536A
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pucherite
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马爱琼
马孝瑜
高云琴
张由子
侯星
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Xian University of Architecture and Technology
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Abstract

The invention discloses a kind of pucherite calcium ferrite composite photo-catalyst, preparation method and applications, the photochemical catalyst includes m BiVO4Matrix, in the m BiVO4Matrix surface is dispersed with CaFe2O4；The CaFe2O4With the m BiVO4The mass ratio of matrix is 5~20 ︰ 95~80, and monocline pucherite/spinel-type ferrous acid calcium composite photocatalyst material is prepared using low-temperature self-propagating sol-gal process combination calcination method.And the test of photocatalysis performance is carried out to the material prepared using simulated visible light.The superior photocatalysis performance of the material is proved by degradation biological persistent organic pollutants methylene orange.The material belongs to inorganic catalysis material, and photocatalytic activity is high, there is good application prospect in terms of environmental protection.This method has monocline pucherite morphology controllable, and spinel-type ferrous acid calcium is compound good with monocline pucherite, the advantages of being uniformly dispersed, form effective p n hetero-junctions.

Description

一种钒酸铋-铁酸钙复合光催化剂、制备方法及其应用A kind of bismuth vanadate-calcium ferrite composite photocatalyst, preparation method and application thereof

技术领域technical field

本发明属无机材料制备技术领域，涉及一种光催化剂，特指一种钒酸铋-铁酸钙复合光催化剂、制备方法及其应用。The invention belongs to the technical field of inorganic material preparation, and relates to a photocatalyst, in particular to a bismuth vanadate-calcium ferrite composite photocatalyst, a preparation method and an application thereof.

背景技术Background technique

近年来，半导体光催化在水污染处理上表现突出，一直处于环境治理研究的前沿。它的优点是效率高、成本低、选择性广泛、反应温度需求低、能源需求小以及对污染物降解彻底等[1-4]。In recent years, semiconductor photocatalysis has been outstanding in water pollution treatment and has been at the forefront of environmental governance research. Its advantages are high efficiency, low cost, wide selectivity, low reaction temperature requirements, small energy requirements, and complete degradation of pollutants [1-4] .

其中,单斜钒酸铋(m-BiVO4)凭借其禁带宽度较窄(2.45eV)，化学稳定性好、制备成本低、可直接利用可见光、无毒环保等显著优点而受到广泛关注[5]，在光催化氧化降解有机染料废水等方面具有广阔的应用前景。Among them, bismuth monoclinic vanadate (m-BiVO 4 ) has attracted widespread attention because of its narrow band gap (2.45eV), good chemical stability, low preparation cost, direct use of visible light, non-toxic and environmentally friendly [ 5] , it has broad application prospects in photocatalytic oxidation degradation of organic dye wastewater.

但是，单斜钒酸铋光催化剂存在两个主要缺陷：一是光生电子和空穴容易复合导致其光催化效率低，二是分离回收困难使其应用受到限制。制备具有合适能带结构的单斜钒酸铋基复合光催化材料，可以提高单斜钒酸铋的光催化性能。尖晶石型铁酸钙(CaFe2O4)具有和单斜钒酸铋匹配的能带结构，具有磁性，容易分离回收。因此我们提出一种单斜钒酸铋/尖晶石型铁酸钙复合光催化材料的制备方法，旨在改善单斜钒酸铋的光催化性能。However, bismuth monoclinic vanadate photocatalysts have two major defects: one is that the photogenerated electrons and holes are easily recombined, resulting in low photocatalytic efficiency, and the other is that the separation and recovery are difficult, which limits its application. The photocatalytic performance of bismuth monoclinic vanadate can be improved by preparing a bismuth monoclinic vanadate-based composite photocatalytic material with a suitable energy band structure. Spinel-type calcium ferrite (CaFe 2 O 4 ) has an energy band structure matching that of bismuth monoclinic vanadate, is magnetic, and is easy to separate and recover. Therefore, we propose a preparation method of bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material, aiming at improving the photocatalytic performance of bismuth monoclinic vanadate.

参考文献：references:

[1]王健.ZnO纳米材料及核壳结构的制备和光催化性能研究[D].中国科学院大学，2016,06.[1] Wang Jian. Preparation and photocatalytic performance of ZnO nanomaterials and core-shell structure [D]. University of Chinese Academy of Sciences, 2016, 06.

[2]刘守新，刘鸿.光催化及光电催化基础与应用[M].北京：化学工业出版社，2005,8.[2] Liu Shouxin, Liu Hong. Photocatalysis and Photocatalysis Fundamentals and Applications [M]. Beijing: Chemical Industry Press, 2005, 8.

[3]Fujishima,Hondak.Electrochemical photolysis of water at asemiconductor electrode[J].Nature,1972,(238):37-38.[3] Fujishima, Hondak. Electrochemical photolysis of water at asemiconductor electrode [J]. Nature, 1972, (238): 37-38.

[4]姜妍彦，李景刚，宁桂玲等.尖晶石型CuAl2O4纳米粉体的制备及其可见光催化性能[J].硅酸盐学报，2006,34(9):1084-1087.[4] Jiang Yanyan, Li Jinggang, Ning Guiling, etc. Preparation of spinel-type CuAl 2 O 4 nanopowder and its visible light catalytic performance [J]. Chinese Journal of Ceramics, 2006,34(9):1084-1087.

[5]Chongfei Yu,Shuying Dong,Jin Zhao,etal.Preparation andcharacterization of sphere-shaped BiVO4/reduced graphene oxide photocatalystfor an augmented natural sunlight photocatalytic activity[J].Journal ofAlloys and Compounds,2016,677:219-227.[5]Chongfei Yu, Shuying Dong, Jin Zhao, etal.Preparation and characterization of sphere-shaped BiVO 4 /reduced graphene oxide photocatalyst for an augmented natural sunlight photocatalytic activity[J].Journal of Alloys and Compounds,2016,677:219-227.

发明内容Contents of the invention

本发明的第一个目的在于提出一种钒酸铋-铁酸钙复合光催化剂，能够改善单斜钒酸铋的光催化性能。The first object of the present invention is to propose a bismuth vanadate-calcium ferrite composite photocatalyst, which can improve the photocatalytic performance of bismuth monoclinic vanadate.

本发明的第二个目的是提供一种钒酸铋-铁酸钙复合光催化剂的制备方法，具有合成简单、降解效率高的特点。The second object of the present invention is to provide a preparation method of bismuth vanadate-calcium ferrite composite photocatalyst, which has the characteristics of simple synthesis and high degradation efficiency.

本发明的第三个目的是提供一种钒酸铋-铁酸钙复合光催化剂用于光催化降解有机染料的应用。The third object of the present invention is to provide the application of a bismuth vanadate-calcium ferrite composite photocatalyst for photocatalytic degradation of organic dyes.

为达到上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:

一种钒酸铋-铁酸钙复合光催化剂，所述光催化剂包括m-BiVO4基体，在所述m-BiVO4基体表面分散有CaFe2O4；A kind of bismuth vanadate-calcium ferrite composite photocatalyst, described photocatalyst comprises m-BiVO 4 matrix, is dispersed with CaFe 2 O 4 on the surface of described m-BiVO 4 matrix;

所述CaFe2O4与所述m-BiVO4基体的质量比为5～20︰95～80。The mass ratio of the CaFe 2 O 4 to the m-BiVO 4 matrix is 5-20:95-80.

可选的，所述光催化剂的制备方法包括：将CaFe2O4与m-BiVO4基体经过溶胶-凝胶原位负载法得到混合凝胶，混合凝胶经干燥固化得到前驱体粉末，前驱体粉末再经高温煅烧即得。Optionally, the preparation method of the photocatalyst includes: subjecting CaFe 2 O 4 and m-BiVO 4 matrix to a sol-gel in-situ loading method to obtain a mixed gel, and drying and curing the mixed gel to obtain a precursor powder, the precursor The body powder is then calcined at high temperature.

可选的，所述的溶胶-凝胶原位负载法为将m-BiVO4基体制备成前驱体溶液，CaFe2O4分散在前驱体溶液中得到混合凝胶。Optionally, in the sol-gel in-situ loading method, the m-BiVO 4 matrix is prepared as a precursor solution, and CaFe 2 O 4 is dispersed in the precursor solution to obtain a mixed gel.

可选的，将CaFe2O4纳米粉体超声分散分散在前驱体溶液中，超声分散的时间为20～45min；Optionally, ultrasonically disperse the CaFe 2 O 4 nanopowder in the precursor solution, and the ultrasonic dispersion time is 20-45 minutes;

所述的混合凝胶经干燥固化得到前驱体粉末的干燥温度为60～90℃；The drying temperature of the precursor powder obtained by drying and curing the mixed gel is 60-90°C;

所述的高温煅烧的煅烧温度为450～600℃,煅烧时间为3～6h。The calcination temperature of the high-temperature calcination is 450-600° C., and the calcination time is 3-6 hours.

一种钒酸铋-铁酸钙复合光催化剂制备方法，包括将CaFe2O4纳米粉体与m-BiVO4基体经过溶胶-凝胶原位负载法得到混合凝胶，混合凝胶经干燥固化得到前驱体粉末，前驱体粉末再经高温煅烧即得。A method for preparing a bismuth vanadate-calcium ferrite composite photocatalyst, comprising the step of subjecting CaFe 2 O 4 nano powder and m-BiVO 4 matrix to a sol-gel in-situ loading method to obtain a mixed gel, and the mixed gel is dried and solidified The precursor powder is obtained, and the precursor powder is then calcined at a high temperature.

可选的，所述的溶胶-凝胶原位负载法为将m-BiVO4基体制备成前驱体溶液，CaFe2O4纳米粉体分散在前驱体溶液中得到混合凝胶；Optionally, the sol-gel in-situ loading method is to prepare the m-BiVO 4 matrix into a precursor solution, and disperse the CaFe 2 O 4 nanopowder in the precursor solution to obtain a mixed gel;

将CaFe2O4超声分散分散在前驱体溶液中，超声分散的时间为20～45min；Ultrasonic dispersion of CaFe 2 O 4 in the precursor solution, the time of ultrasonic dispersion is 20-45min;

所述的混合凝胶经干燥固化得到前驱体粉末的干燥温度为60～90℃；The drying temperature of the precursor powder obtained by drying and curing the mixed gel is 60-90°C;

所述的高温煅烧的煅烧温度为450～600℃,煅烧时间为3～6h。The calcination temperature of the high-temperature calcination is 450-600° C., and the calcination time is 3-6 hours.

可选的，所述的前驱体液的制备采用溶胶-凝胶法，前驱体溶液的制备原料为硝酸铋、柠檬酸、乙二醇水溶液、偏钒酸铵；Optionally, the preparation of the precursor liquid adopts the sol-gel method, and the raw materials for the preparation of the precursor solution are bismuth nitrate, citric acid, ethylene glycol aqueous solution, and ammonium metavanadate;

硝酸铋、柠檬酸、乙二醇水溶液的用量比为5.5～11.5g︰15～25g︰20～50ml；The dosage ratio of bismuth nitrate, citric acid and ethylene glycol aqueous solution is 5.5～11.5g︰15～25g︰20～50ml;

偏钒酸铵与乙二醇溶液的用量比为1.05～4.35g︰20～50ml。The dosage ratio of ammonium metavanadate to ethylene glycol solution is 1.05～4.35g︰20～50ml.

乙二醇水溶液中的乙二醇与水的体积比为1︰2。The volume ratio of ethylene glycol to water in the ethylene glycol aqueous solution is 1:2.

可选的，所述的CaFe2O4纳米粉体采用自蔓延溶胶-凝胶结合高温煅烧法制备得到，包括将硝酸铁、硝酸镁、乙二醇水溶液和柠檬酸原料混合后得到凝胶，凝胶采用低温自蔓延燃烧得到CaFe2O4前驱体粉末，将所得前驱体粉末煅烧得到CaFe2O4纳米粉体；Optionally, the CaFe 2 O 4 nanopowder is prepared by self-propagating sol-gel combined with high-temperature calcination, including mixing ferric nitrate, magnesium nitrate, ethylene glycol aqueous solution and citric acid raw materials to obtain a gel, The gel adopts low-temperature self-propagating combustion to obtain CaFe 2 O 4 precursor powder, and the obtained precursor powder is calcined to obtain CaFe 2 O 4 nano-powder;

硝酸铁、硝酸镁与乙二醇溶液的用量比为18.05～27.45g︰3.98～11.35g︰10～30ml；The dosage ratio of ferric nitrate, magnesium nitrate and ethylene glycol solution is 18.05～27.45g︰3.98～11.35g︰10～30ml;

柠檬酸与乙二醇溶液的用量比为40.13～60.65g︰30～50ml；The dosage ratio of citric acid and ethylene glycol solution is 40.13～60.65g︰30～50ml;

乙二醇水溶液中的乙二醇与水的体积比为1︰2。The volume ratio of ethylene glycol to water in the ethylene glycol aqueous solution is 1:2.

可选的，所述低温自蔓延燃烧的温度为160～220℃；Optionally, the temperature of the low-temperature self-propagating combustion is 160-220°C;

所述煅烧的温度为700～900℃，升温速率为2.5～5℃/min，保温时间为5h。The calcining temperature is 700-900° C., the heating rate is 2.5-5° C./min, and the holding time is 5 hours.

所述的钒酸铋-铁酸钙复合光催化剂或者所述的钒酸铋-铁酸钙复合光催化剂制备方法制备得到的钒酸铋-铁酸钙复合光催化剂用于光催化降解有机染料的应用。The bismuth vanadate-calcium ferrite composite photocatalyst or the bismuth vanadate-calcium ferrite composite photocatalyst prepared by the preparation method of the bismuth vanadate-calcium ferrite composite photocatalyst is used for photocatalytic degradation of organic dyes application.

本发明的技术效果为：Technical effect of the present invention is:

(1)本发明描述了一种高分散的可回收的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料及其应用，m-BiVO4是一种性能优异的可见光催化剂，CaFe2O4纳米粉体的引入体现了其与m-BiVO4的半导体耦合作用，可以有效促进光生电子空穴分离，提高可见光催化效率，使得本发明制备的高分散复合光催化材料在短时间内即可达到很高的催化效率，最高可达85％。同时CaFe2O4纳米粉体具有磁性，方便粉体分离回收利用，降低了其使用成本。(1) The present invention describes a highly dispersed and recyclable bismuth monoclinic vanadate/spinel-type calcium ferrite composite photocatalytic material and its application. m-BiVO 4 is a visible light catalyst with excellent performance, and CaFe The introduction of 2 O 4 nanopowder reflects its semiconducting coupling effect with m-BiVO 4 , which can effectively promote the separation of photogenerated electrons and holes, improve the catalytic efficiency of visible light, and make the highly dispersed composite photocatalytic material prepared by the present invention in a short time A high catalytic efficiency can be achieved, up to 85%. At the same time, the CaFe 2 O 4 nanometer powder is magnetic, which facilitates the separation and recycling of the powder, and reduces its use cost.

(2)在制备CaFe2O4纳米粉体与m-BiVO4前驱体液的过程中，由于采用了自蔓延溶胶-凝胶法，并以乙二醇与去离子水作为复合分散剂，使得所制备的粉体分散性更好，纯度更高。(2) In the process of preparing CaFe 2 O 4 nanopowder and m-BiVO 4 precursor liquid, the self-propagating sol-gel method was adopted, and ethylene glycol and deionized water were used as composite dispersants, so that the The prepared powder has better dispersibility and higher purity.

(3)在制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料时，由于采用了原位负载复合结合煅烧法，使得CaFe2O4纳米粉体在m-BiVO4前驱体液中分散均匀，复合良好，光催化效果更佳。(3) When preparing bismuth monoclinic vanadate/spinel-type calcium ferrite composite photocatalytic materials, due to the in-situ loading composite combined with calcination method, the CaFe 2 O 4 nanopowders in the m-BiVO 4 precursor liquid Uniform dispersion, good compounding, and better photocatalytic effect.

附图说明Description of drawings

图1为实施例1所制备CaFe2O4样品的XRD图谱；Fig. 1 is the XRD collection of patterns of CaFe2O4 sample prepared by embodiment 1;

图2为实施例1所制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料的XRD图谱；Fig. 2 is the XRD spectrum of bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material prepared in embodiment 1;

图3为实施例1所制备CaFe2O4样品的SEM与EDS分析图；Fig. 3 is the SEM and EDS analysis figure of CaFe2O4 sample prepared in embodiment 1;

图4为实施例1所制备的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料对亚甲基橙的光催化5次循环实验；Fig. 4 is that the bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material prepared in embodiment 1 is to the photocatalytic cycle experiment of 5 times of methylene orange;

图5为实施例1～4所制备的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料光催化降解亚甲基橙的降解效果图；Fig. 5 is the degradation effect figure of the photocatalytic degradation methylene orange of bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material prepared in embodiment 1～4;

图6为实施例1～4所制备的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料光催化降解亚甲基橙的机理示意图。6 is a schematic diagram of the mechanism of photocatalytic degradation of methylene orange by the bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material prepared in Examples 1-4.

具体实施方式Detailed ways

本发明所述的有机染料包括亚甲基橙、亚甲基蓝、罗丹明B等常见的有机染料。The organic dyes described in the present invention include common organic dyes such as methylene orange, methylene blue, and rhodamine B.

下面结合具体实施实例对本发明做进一步说明：Below in conjunction with specific implementation examples the present invention will be further described:

实施例1：Example 1:

步骤1：溶胶-凝胶技术制备m-BiVO4前驱体液：按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取五水合硝酸铋9.7g、柠檬酸15.37g，溶入25ml乙二醇水溶液中，不断搅拌得到溶液A；称取偏钒酸铵2.34g溶入溶入25ml乙二醇水溶液中不断搅拌得到溶液B。在持续搅拌的条件下将溶液B以30滴/分的速率逐滴加入溶液A中，并用氨水调节pH值等于9，水浴加热搅拌蒸发部分溶剂得到m-BiVO4前驱体液。Step 1: Preparation of m-BiVO 4 precursor body fluid by sol-gel technique: prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2, weigh 9.7g of bismuth nitrate pentahydrate and 15.37g of citric acid , dissolved in 25ml of ethylene glycol aqueous solution, and stirred continuously to obtain solution A; weighed 2.34g of ammonium metavanadate and dissolved in 25ml of ethylene glycol aqueous solution, and continuously stirred to obtain solution B. Solution B was added dropwise to solution A at a rate of 30 drops/min under continuous stirring, and the pH value was adjusted to 9 with ammonia water, heated and stirred in a water bath to evaporate part of the solvent to obtain m-BiVO 4 precursor liquid.

步骤2：自蔓延溶胶-凝胶结合高温煅烧法制备CaFe2O4纳米粉体。按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取将九水合硝酸铁20.2g、四水合硝酸钙5.91g溶于25ml乙二醇水溶液中，溶解搅拌均匀，得到溶液A；称取46.65g一水柠檬酸溶于35ml乙二醇水溶液中搅拌均匀得到溶液B，在持续搅拌条件下将溶液B以30滴/分的速率逐滴加入溶液A中，用氨水调节pH值等于2，静置陈化得到湿凝胶，将湿凝胶置于恒温干燥箱中于200℃低温自蔓延燃烧得到CaFe2O4前驱体粉末，将所得前驱体粉末在高温炉内以升温速率4℃/min升至900℃煅烧5h后随炉自然冷却得到CaFe2O4纳米粉体。Step 2: Prepare CaFe 2 O 4 nanometer powder by self-propagating sol-gel combined with high-temperature calcination. Prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2, weigh 20.2 g of ferric nitrate nonahydrate and 5.91 g of calcium nitrate tetrahydrate in 25 ml of ethylene glycol aqueous solution, dissolve and stir evenly, Obtain solution A; take by weighing 46.65g citric acid monohydrate and dissolve it in 35ml ethylene glycol aqueous solution and stir to obtain solution B evenly; under continuous stirring condition, solution B is added dropwise in solution A at a rate of 30 drops/min; Adjust the pH value to be equal to 2, let it stand for aging to obtain wet gel, place the wet gel in a constant temperature drying oven at 200°C for low-temperature self-propagating combustion to obtain CaFe 2 O 4 precursor powder, and place the obtained precursor powder in a high-temperature furnace Calcined at 900°C at a heating rate of 4°C/min for 5 hours, then cooled naturally with the furnace to obtain CaFe 2 O 4 nanopowder.

步骤3：制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料：将步骤2中所制备的CaFe2O4纳米粉体按20wt％的加入量加入到步骤1所制备的m-BiVO4前驱体液中，超声振动分散30min在80℃恒温搅拌均匀得到凝胶。置于恒温干燥箱中于200℃低温自蔓延燃烧得到前驱体粉末。将前驱体粉末置于高温炉内550℃煅烧4h后冷却至室温，洗涤、烘干得到单斜钒酸铋/尖晶石型铁酸钙复合光催化材料。Step 3: Prepare bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material: add the CaFe 2 O 4 nanopowder prepared in step 2 to the m prepared in step 1 in an amount of 20 wt%. -In BiVO 4 precursor liquid, ultrasonic vibration dispersion for 30min and constant temperature stirring at 80°C to obtain a gel. The precursor powder was obtained by self-propagating combustion at a low temperature of 200°C in a constant temperature drying oven. The precursor powder was calcined at 550°C for 4 hours in a high-temperature furnace, cooled to room temperature, washed and dried to obtain a bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material.

步骤4：称取0.15g步骤3中的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料加入到100ml浓度为10-5mol/L的亚甲基橙溶液中，磁力搅拌器遮光搅拌30min达到吸附-脱附平衡，打开氙光灯源进行光催化反应，每20min取样一次，每次取10ml离心分离得上清液，用紫外可见分光光度计测量上清液的吸光度，通过吸光度换算为浓度变化，120min后得到本实施例所制备的材料对亚甲基橙的降解率为85％。Step 4: Weigh 0.15 g of the bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material in step 3 and add it to 100 ml of methylene orange solution with a concentration of 10 -5 mol/L. Shade and stir for 30 minutes to reach the adsorption-desorption equilibrium, turn on the xenon light source to carry out the photocatalytic reaction, take a sample every 20 minutes, take 10ml centrifugation each time to obtain the supernatant, measure the absorbance of the supernatant with a UV-visible spectrophotometer, and pass The absorbance was converted into concentration change, and after 120 minutes, the degradation rate of methylene orange by the material prepared in this example was 85%.

实验结果：Experimental results:

图1为实施例1所制备的尖晶石型铁酸钙的XRD衍射图谱，从图中可以看出CaFe2O4的特征衍射峰2θ＝33.47°、33.57°、35.50°与标准卡片(JCPDS No.32-0168)相对应，说明尖晶石型铁酸钙成功制备。Fig. 1 is the XRD diffraction spectrum of the spinel type calcium ferrite prepared in embodiment 1, can find out from the figure CaFe 2 O 4 characteristic diffraction peaks 2θ=33.47 °, 33.57 °, 35.50 ° and standard card (JCPDS No.32-0168) corresponded, indicating that spinel calcium ferrite was successfully prepared.

图2为实施例1所制备的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料XRD衍射图谱，从图中可以看出，m-BiVO4的特征衍射峰位于2θ＝28.97°、30.53°、18.99°，相应的衍射晶面为(121),(040),(011)，与单斜钒酸铋标准卡片(m-BiVO4，JCPDS No.14-0688)相对应。由于CaFe2O4的加入量较少，因此，其衍射峰强度相对较弱，但是，其三个特征衍射峰位置没有变化，这说明，CaFe2O4与m-BiVO4成功复合，单斜钒酸铋/尖晶石型铁酸钙复合光催化材料制备成功。Figure 2 is the XRD diffraction pattern of the bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material prepared in Example 1. It can be seen from the figure that the characteristic diffraction peak of m-BiVO is located at 2θ=28.97° , 30.53°, 18.99°, the corresponding diffraction crystal planes are (121), (040), (011), corresponding to the standard card of bismuth monoclinic vanadate (m-BiVO 4 , JCPDS No.14-0688). Due to the small amount of CaFe 2 O 4 added, the intensity of its diffraction peaks is relatively weak, but the positions of the three characteristic diffraction peaks have not changed, which shows that CaFe 2 O 4 and m-BiVO 4 are successfully compounded, monoclinic Bismuth vanadate/spinel-type calcium ferrite composite photocatalytic material was successfully prepared.

图3为实施例1所制备的CaFe2O4纳米粉体的SEM与EDS分析图，由图可知，所制备的CaFe2O4纳米粉体晶型发育较完整，能谱分析表明，其原子个数比符合CaFe2O4的化学计量关系。Fig. 3 is the SEM and EDS analysis graph of the CaFe2O4 nanopowder prepared in Example 1, as can be seen from the figure, the prepared CaFe2O4 nanopowder crystal form is relatively complete, and energy spectrum analysis shows that its atomic The number ratio conforms to the stoichiometric relationship of CaFe 2 O 4 .

实施例1制备得到的单斜钒酸铋尖晶石型铁酸钙复合光催化材料循环使用效果如图4所示。由图可见，催化剂在经过5次重复使用后，其催化活性几乎没有减退，一方面说明催化剂具有很好的稳定性，另一方面说明此复合光催化材料在工业废水等污染治理方面有一定的潜在应用价值。The recycling effect of bismuth monoclinic vanadate spinel-type calcium ferrite composite photocatalytic material prepared in Example 1 is shown in Figure 4. It can be seen from the figure that after 5 times of repeated use, the catalytic activity of the catalyst has hardly decreased. On the one hand, it shows that the catalyst has good stability. potential application value.

实施例2：Example 2:

步骤1：溶胶-凝胶技术制备m-BiVO4前驱体液：按乙二醇与去离子水的体积比为1︰2.5配制乙二醇溶液，称取五水合硝酸铋6.7g、柠檬酸15g溶入20ml乙二醇水溶液中，不断搅拌得到溶液A；偏钒酸铵1.05g溶入溶入20ml乙二醇水溶液中不断搅拌得到溶液B。在持续搅拌的条件下将溶液B以30滴/分的速率逐滴加入溶液A中，并用氨水调节pH值等于7，水浴加热搅拌蒸发部分溶剂得到m-BiVO4前驱体液。Step 1: Preparation of m-BiVO 4 precursor body fluid by sol-gel technique: Prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2.5, weigh 6.7g of bismuth nitrate pentahydrate, and dissolve 15g of citric acid 1.05 g of ammonium metavanadate was dissolved in 20 ml of ethylene glycol aqueous solution and continuously stirred to obtain solution B. Solution B was added dropwise to solution A at a rate of 30 drops/min under continuous stirring, and the pH value was adjusted to 7 with ammonia water, heated and stirred in a water bath to evaporate part of the solvent to obtain m-BiVO 4 precursor liquid.

步骤2：自蔓延溶胶-凝胶结合高温煅烧法制备CaFe2O4纳米粉体。按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取将九水合硝酸铁18.05g、四水合硝酸钙6.37g溶于10ml乙二醇水溶液中，溶解搅拌均匀，得到溶液A；称取40.13g一水柠檬酸溶于30ml乙二醇水溶液中搅拌均匀得到溶液B，在持续搅拌条件下将溶液B以20滴/分的速率逐滴加入溶液A中，用氨水调节pH值等于3，静置陈化得到湿凝胶，将湿凝胶置于恒温干燥箱中于160℃低温自蔓延燃烧得到CaFe2O4前驱体粉末，将所得前驱体粉末在高温炉内以升温速率5℃/min升至700℃煅烧4h后随炉自然冷却得到CaFe2O4纳米粉体。Step 2: Prepare CaFe 2 O 4 nanometer powder by self-propagating sol-gel combined with high-temperature calcination. Prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2, weigh 18.05 g of ferric nitrate nonahydrate and 6.37 g of calcium nitrate tetrahydrate in 10 ml of ethylene glycol aqueous solution, dissolve and stir evenly, Obtain solution A; take 40.13g citric acid monohydrate and dissolve it in 30ml ethylene glycol aqueous solution and stir to obtain solution B evenly; under continuous stirring condition, solution B is added dropwise in solution A at a rate of 20 drops/min; Adjust the pH value to be equal to 3, let it stand and age to obtain a wet gel, put the wet gel in a constant temperature drying oven at a low temperature of 160 ℃ and self-propagating combustion to obtain a CaFe 2 O 4 precursor powder, and put the obtained precursor powder in a high-temperature furnace Calcined at 700°C for 4 hours at a heating rate of 5°C/min, then cooled naturally with the furnace to obtain CaFe 2 O 4 nanopowder.

步骤3：制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料：将步骤2中所制备的CaFe2O4纳米粉体按5wt％的加入量加入到步骤1所制备的m-BiVO4前驱体液中，超声振动分散20min在60℃恒温搅拌均匀得到凝胶。置于恒温干燥箱中于180℃低温自蔓延燃烧得到前驱体粉末。将前驱体粉末置于高温炉内450℃煅烧3h后冷却至室温，洗涤、烘干得到单斜钒酸铋/尖晶石型铁酸钙复合光催化材料。Step 3: Preparation of bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material: the CaFe 2 O 4 nanopowder prepared in step 2 is added to the m prepared in step 1 in an amount of 5 wt%. - In BiVO 4 precursor liquid, disperse by ultrasonic vibration for 20min and stir at constant temperature at 60°C to obtain a gel. The precursor powder was obtained by self-propagating combustion at a low temperature of 180°C in a constant temperature drying oven. The precursor powder was calcined at 450°C for 3 hours in a high-temperature furnace, cooled to room temperature, washed and dried to obtain a bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material.

步骤4：称取0.15g步骤3中的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料加入到100ml浓度为10-5mol/L的亚甲基橙溶液中，磁力搅拌器遮光搅拌30min达到吸附-脱附平衡，打开氙光灯源进行光催化反应，每20min取样一次，每次取10ml离心分离得上清液，用紫外可见分光光度计测量上清液的吸光度，通过吸光度换算为浓度变化，120min后得到本实施例所制备的材料对亚甲基橙的降解率为57％。Step 4: Weigh 0.15 g of the bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material in step 3 and add it to 100 ml of methylene orange solution with a concentration of 10 -5 mol/L. Shade and stir for 30 minutes to reach the adsorption-desorption equilibrium, turn on the xenon light source to carry out the photocatalytic reaction, take a sample every 20 minutes, take 10ml centrifugation each time to obtain the supernatant, measure the absorbance of the supernatant with a UV-visible spectrophotometer, and pass The absorbance was converted into concentration change, and after 120 minutes, the degradation rate of methylene orange by the material prepared in this example was 57%.

实施例3：Example 3:

步骤1：溶胶-凝胶技术制备m-BiVO4前驱体液：按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取五水合硝酸铋8.54g、柠檬酸19g，溶入35ml乙二醇水溶液中，不断搅拌得到溶液A；偏钒酸铵3.52g溶入溶入35ml乙二醇水溶液中不断搅拌得到溶液B。在持续搅拌的条件下将溶液B以30滴/分的速率逐滴加入溶液A中，并用氨水调节pH值等于8.5，水浴加热搅拌蒸发部分溶剂得到m-BiVO4前驱体液。Step 1: Preparation of m-BiVO 4 precursor body fluid by sol-gel technique: prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2, weigh 8.54g of bismuth nitrate pentahydrate, 19g of citric acid, Dissolve in 35ml of ethylene glycol aqueous solution and keep stirring to obtain solution A; dissolve 3.52g of ammonium metavanadate in 35ml of ethylene glycol aqueous solution and keep stirring to obtain solution B. Solution B was added dropwise to solution A at a rate of 30 drops/min under continuous stirring, and the pH value was adjusted to 8.5 with ammonia water, heated and stirred in a water bath to evaporate part of the solvent to obtain m-BiVO 4 precursor liquid.

步骤2：自蔓延溶胶-凝胶结合高温煅烧法制备CaFe2O4纳米粉体。按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取将九水合硝酸铁22.52g、四水合硝酸钙8.36g溶于20ml乙二醇水溶液中，溶解搅拌均匀，得到溶液A；称取50.25g一水柠檬酸溶于40ml乙二醇水溶液中搅拌均匀得到溶液B，在持续搅拌条件下将溶液B以35滴/分的速率逐滴加入溶液A中，用氨水调节pH值等于4，静置陈化得到湿凝胶，将湿凝胶置于恒温干燥箱中于180℃低温自蔓延燃烧得到CaFe2O4前驱体粉末，将所得前驱体粉末在高温炉内以升温速率4℃/min升至800℃煅烧4h后随炉自然冷却得到CaFe2O4纳米粉体。Step 2: Prepare CaFe 2 O 4 nanometer powder by self-propagating sol-gel combined with high-temperature calcination. The ethylene glycol solution was prepared according to the volume ratio of ethylene glycol and deionized water as 1:2, and 22.52 g of ferric nitrate nonahydrate and 8.36 g of calcium nitrate tetrahydrate were dissolved in 20 ml of ethylene glycol aqueous solution, dissolved and stirred evenly. Obtain solution A; take 50.25g citric acid monohydrate and dissolve it in 40ml ethylene glycol aqueous solution and stir to obtain solution B evenly; under continuous stirring condition, solution B is added dropwise in solution A at a rate of 35 drops/min; Adjust the pH value to be equal to 4, leave it to stand and age to obtain a wet gel, put the wet gel in a constant temperature drying oven at a low temperature of 180 ℃ and self-propagating combustion to obtain a CaFe 2 O 4 precursor powder, and put the obtained precursor powder in a high temperature furnace Calcined at 800°C for 4 hours at a heating rate of 4°C/min, then cooled naturally with the furnace to obtain CaFe 2 O 4 nanopowder.

步骤3：制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料：将步骤2中所制备的CaFe2O4纳米粉体按10wt％的加入量加入到步骤1所制备的m-BiVO4前驱体液中，超声振动分散35min在75℃恒温搅拌均匀得到凝胶。置于恒温干燥箱中于200℃低温自蔓延燃烧得到前驱体粉末。将前驱体粉末置于高温炉内520℃煅烧4.5h后冷却至室温，洗涤、烘干得到单斜钒酸铋/尖晶石型铁酸钙复合光催化材料。Step 3: Prepare bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material: add the CaFe 2 O 4 nanopowder prepared in step 2 to the m prepared in step 1 in an amount of 10 wt%. -In BiVO 4 precursor liquid, ultrasonic vibration dispersion for 35min and constant temperature stirring at 75°C to obtain a gel. The precursor powder was obtained by self-propagating combustion at a low temperature of 200°C in a constant temperature drying oven. The precursor powder was calcined at 520°C for 4.5 hours in a high-temperature furnace, cooled to room temperature, washed and dried to obtain a bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material.

步骤4：称取0.15g步骤3中的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料加入到100ml浓度为10-5mol/L的亚甲基橙溶液中，磁力搅拌器遮光搅拌30min达到吸附-脱附平衡，打开氙光灯源进行光催化反应，每20min取样一次，每次取10ml离心分离得上清液，用紫外可见分光光度计测量上清液的吸光度，通过吸光度换算为浓度变化，120min后得到本实施例所制备的材料对亚甲基橙的降解率为63％。Step 4: Weigh 0.15 g of the bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material in step 3 and add it to 100 ml of methylene orange solution with a concentration of 10 -5 mol/L. Shade and stir for 30 minutes to reach the adsorption-desorption equilibrium, turn on the xenon light source to carry out the photocatalytic reaction, take a sample every 20 minutes, take 10ml centrifugation each time to obtain the supernatant, measure the absorbance of the supernatant with a UV-visible spectrophotometer, and pass The absorbance was converted into the concentration change, and after 120 minutes, the degradation rate of methylene orange by the material prepared in this example was 63%.

实施例4：Example 4:

步骤1：溶胶-凝胶技术制备m-BiVO4前驱体液：按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取五水合硝酸铋11.5g、柠檬酸23.95g溶入48ml乙二醇水溶液中，不断搅拌得到溶液A；偏钒酸铵4.34g溶入溶入45ml乙二醇水溶液中不断搅拌得到溶液B。在持续搅拌的条件下将溶液B以30滴/分的速率逐滴加入溶液A中，并用氨水调节pH值等于9.5，水浴加热搅拌蒸发部分溶剂得到m-BiVO4前驱体液。Step 1: Preparation of m-BiVO 4 precursor body fluid by sol-gel technique: prepare ethylene glycol solution according to the volume ratio of ethylene glycol and deionized water as 1:2, weigh 11.5g of bismuth nitrate pentahydrate and 23.95g of citric acid Dissolve in 48ml of ethylene glycol aqueous solution and keep stirring to obtain solution A; dissolve 4.34g of ammonium metavanadate in 45ml of ethylene glycol aqueous solution and keep stirring to obtain solution B. Solution B was added dropwise to solution A at a rate of 30 drops/min under continuous stirring, and the pH value was adjusted to 9.5 with ammonia water, heated and stirred in a water bath to evaporate part of the solvent to obtain m-BiVO 4 precursor liquid.

步骤2：自蔓延溶胶-凝胶结合高温煅烧法制备CaFe2O4纳米粉体。按乙二醇与去离子水的体积比为1︰2配制乙二醇溶液，称取将九水合硝酸铁27.45g、四水合硝酸钙10.24g溶于30ml乙二醇水溶液中，溶解搅拌均匀，得到溶液A；称取58.74g一水柠檬酸溶于50ml乙二醇水溶液中搅拌均匀得到溶液B，在持续搅拌条件下将溶液B以45滴/分的速率逐滴加入溶液A中，用氨水调节pH值等于4，静置陈化得到湿凝胶，将湿凝胶置于恒温干燥箱中于200℃低温自蔓延燃烧得到CaFe2O4前驱体粉末，将所得前驱体粉末在高温炉内以升温速率3.5℃/min升至850℃煅烧4h后随炉自然冷却得到CaFe2O4纳米粉体。Step 2: Prepare CaFe 2 O 4 nanometer powder by self-propagating sol-gel combined with high-temperature calcination. The ethylene glycol solution was prepared according to the volume ratio of ethylene glycol and deionized water as 1:2, and 27.45 g of ferric nitrate nonahydrate and 10.24 g of calcium nitrate tetrahydrate were dissolved in 30 ml of ethylene glycol aqueous solution, dissolved and stirred evenly. Obtain solution A; take by weighing 58.74g citric acid monohydrate and dissolve it in 50ml ethylene glycol aqueous solution and stir to obtain solution B; under continuous stirring, solution B is added dropwise in solution A at a rate of 45 drops/minute; Adjust the pH value to be equal to 4, let it stand for aging to obtain a wet gel, place the wet gel in a constant temperature drying oven at 200°C for low-temperature self-propagating combustion to obtain a CaFe 2 O 4 precursor powder, and place the obtained precursor powder in a high-temperature furnace Calcined at 850°C for 4 hours at a heating rate of 3.5°C/min, then cooled naturally with the furnace to obtain CaFe 2 O 4 nanopowder.

步骤3：制备单斜钒酸铋/尖晶石型铁酸钙复合光催化材料：将步骤2中所制备的CaFe2O4纳米粉体按20wt％的加入量加入到步骤1所制备的m-BiVO4前驱体液中，超声振动分散45min在80℃恒温搅拌均匀得到凝胶。置于恒温干燥箱中于190℃低温自蔓延燃烧得到前驱体粉末。将前驱体粉末置于高温炉内580℃煅烧6h后冷却至室温，洗涤、烘干得到单斜钒酸铋/尖晶石型铁酸钙复合光催化材料。Step 3: Prepare bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material: add the CaFe 2 O 4 nanopowder prepared in step 2 to the m prepared in step 1 in an amount of 20 wt%. -In the BiVO 4 precursor liquid, disperse by ultrasonic vibration for 45 minutes and stir at a constant temperature of 80°C to obtain a gel. The precursor powder was obtained by self-propagating combustion at a low temperature of 190°C in a constant temperature drying oven. The precursor powder was calcined at 580°C for 6 hours in a high-temperature furnace, cooled to room temperature, washed and dried to obtain a bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material.

步骤4：称取0.15g步骤3中的单斜钒酸铋/尖晶石型铁酸钙复合光催化材料加入到100ml浓度为10-5mol/L的亚甲基橙溶液中，磁力搅拌器遮光搅拌30min达到吸附-脱附平衡，打开氙光灯源进行光催化反应，每20min取样一次，每次取10ml离心分离得上清液，用紫外可见分光光度计测量上清液的吸光度，通过吸光度换算为浓度变化，120min后得到本实施例所制备的材料对亚甲基橙的降解率为52％。Step 4: Weigh 0.15 g of the bismuth monoclinic vanadate/spinel type calcium ferrite composite photocatalytic material in step 3 and add it to 100 ml of methylene orange solution with a concentration of 10 -5 mol/L. Shade and stir for 30 minutes to reach the adsorption-desorption equilibrium, turn on the xenon light source to carry out the photocatalytic reaction, take a sample every 20 minutes, take 10ml centrifugation each time to obtain the supernatant, measure the absorbance of the supernatant with a UV-visible spectrophotometer, and pass The absorbance was converted into concentration change, and after 120 minutes, the degradation rate of methylene orange by the material prepared in this example was 52%.

对比结果及机理分析：Comparative results and mechanism analysis:

图5为所制备样品的光催化降解效率图。说明：在制备复合光催化材料过程中，CaFe2O4与m-BiVO4的用量比为20︰80时，所制备的复合光催化剂具有最好的催化效果，并且降解速率高，在2h内对亚甲基橙的降解率达到85％。CaFe2O4的加入量过少，体现不出CaFe2O4的优良性质，导致光生电子和空穴不能有效分离，光催化降解效果不理想；CaFe2O4加入量过多，将会包裹在m-BiVO4表面，无法发挥m-BiVO4的光催化活性，无法建立有效的异质结，使得光催化效果下降。Figure 5 is a graph of the photocatalytic degradation efficiency of the prepared samples. Explanation: In the process of preparing composite photocatalytic materials, when the dosage ratio of CaFe 2 O 4 and m-BiVO 4 is 20:80, the prepared composite photocatalyst has the best catalytic effect, and the degradation rate is high, within 2h The degradation rate of methylene orange reaches 85%. If the amount of CaFe 2 O 4 added is too small, the excellent properties of CaFe 2 O 4 cannot be reflected, resulting in the ineffective separation of photogenerated electrons and holes, and the photocatalytic degradation effect is not ideal; On the surface of m-BiVO 4 , the photocatalytic activity of m-BiVO 4 cannot be exerted, and an effective heterojunction cannot be established, resulting in a decline in the photocatalytic effect.

单斜钒酸铋/尖晶石型铁酸钙复合光催化材料的催化机理如图6所示。在可见光照射下，一方面，CaFe2O4与m-BiVO4吸收可见光，其价带上的电子吸收光子获得能量跃迁到导带上；另一方面，由于CaFe2O4的导带与价带位置低于m-BiVO4，因此，光生电子受激跃迁到m-BiVO4的导带上，光生电子空穴从m-BiVO4的价带位置跃迁到CaFe2O4的价带位置，形成了有效地p-n异质结，使复合体系的电子空穴对复合几率显著降低提高光催化活性，从而对目标污染物的降解效率大幅度提高。The catalytic mechanism of bismuth monoclinic vanadate/spinel calcium ferrite composite photocatalytic material is shown in Figure 6. Under visible light irradiation, on the one hand, CaFe 2 O 4 and m-BiVO 4 absorb visible light , and the electrons in the valence band absorb photons to obtain energy transitions to the conduction band; on the other hand, due to the conduction band and valence The band position is lower than that of m-BiVO 4 , therefore, the photogenerated electrons are stimulated to jump to the conduction band of m-BiVO 4 , and the photogenerated electron holes transition from the valence band position of m-BiVO 4 to the valence band position of CaFe 2 O 4 , An effective pn heterojunction is formed, which significantly reduces the recombination probability of electron-hole pairs in the composite system and improves the photocatalytic activity, thereby greatly improving the degradation efficiency of target pollutants.

所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的前提下，本领域技术人员能够做出的任何显而易见的改进、替换或变型属于本发明的保护范围。The described embodiment is a preferred implementation of the present invention, but the present invention is not limited to the above-mentioned implementation, without departing from the essential content of the present invention, any obvious improvement, replacement or modification that those skilled in the art can make Modifications belong to the protection scope of the present invention.

Claims (10)

1. a kind of pucherite-calcium ferrite composite photo-catalyst, which is characterized in that the photochemical catalyst includes m-BiVO4Matrix, The m-BiVO4Matrix surface is dispersed with CaFe2O4；
The CaFe2O4With the m-BiVO4The mass ratio of matrix is 5~20 ︰ 95~80.
2. pucherite according to claim 1-calcium ferrite composite photo-catalyst, which is characterized in that the photochemical catalyst Preparation method includes：By CaFe2O4With m-BiVO4Matrix obtains mixed gel by sol-gel original position load method, and mixing is solidifying Glue obtains precursor powder through dry solidification, precursor powder again through high-temperature calcination to obtain the final product.
3. pucherite according to claim 2-calcium ferrite composite photo-catalyst, which is characterized in that the sol-gel Load method in situ is by m-BiVO4Matrix is prepared into precursor solution, CaFe2O4It is dispersed in precursor solution to obtain mixing and coagulate Glue.
4. pucherite according to claim 3-calcium ferrite composite photo-catalyst, which is characterized in that by CaFe2O4Ultrasound point It is dispersed in precursor solution, the time of ultrasonic disperse is 20~45min；
The drying temperature that the mixed gel obtains precursor powder through dry solidification is 60~90 DEG C；
The calcination temperature of the high-temperature calcination is 450~600 DEG C, and calcination time is 3~6h.
5. a kind of pucherite-calcium ferrite composite photo-catalyst preparation method, which is characterized in that including by CaFe2O4Nano-powder with m-BiVO4Matrix obtains mixed gel by sol-gel original position load method, and mixed gel obtains precursor through dry solidification End, precursor powder again through high-temperature calcination to obtain the final product.
6. pucherite according to claim 5-calcium ferrite composite photo-catalyst preparation method, which is characterized in that described Sol-gel original position load method is by m-BiVO4Matrix is prepared into precursor solution, CaFe2O4Nano-powder is dispersed in presoma Mixed gel is obtained in solution；
By CaFe2O4For nano-powder ultrasonic disperse in precursor solution, the time of ultrasonic disperse is 20~45min；
The drying temperature that the mixed gel obtains precursor powder through dry solidification is 60~90 DEG C；
The calcination temperature of the high-temperature calcination is 450~600 DEG C, and calcination time is 3~6h.
7. pucherite according to claim 6-calcium ferrite composite photo-catalyst preparation method, which is characterized in that described The preparation of precursor liquid uses sol-gel method, and the raw material for preparing of precursor solution is that bismuth nitrate, citric acid, ethylene glycol are water-soluble Liquid, ammonium metavanadate；
Bismuth nitrate, citric acid, glycol water amount ratio be 5.5~11.5g ︰ 15~25g ︰, 20~50ml；
The amount ratio of ammonium metavanadate and ethylene glycol solution is 1.05~4.35g ︰, 20~50ml.
The volume ratio of ethylene glycol and water in glycol water is 1 ︰ 2.
8. pucherite according to claim 6-calcium ferrite composite photo-catalyst preparation method, which is characterized in that described CaFe2O4Nano-powder is prepared using self- propagating combination of sol-gel high-temperature calcination, including by ferric nitrate, magnesium nitrate, Gel is obtained after glycol water and the mixing of lemon acid starting material, gel obtains CaFe using low temperature self-propagating combustion2O4Presoma Powder calcines gained precursor powder to obtain CaFe2O4Nano-powder；
The amount ratio of ferric nitrate, magnesium nitrate and ethylene glycol solution is 18.05~27.45g ︰ 3.98~11.35g ︰, 10~30ml；
The amount ratio of citric acid and ethylene glycol solution is 40.13~60.65g ︰, 30~50ml；
The volume ratio of ethylene glycol and water in glycol water is 1 ︰ 2.
9. pucherite according to claim 8-calcium ferrite composite photo-catalyst preparation method, which is characterized in that described low The temperature of warm self-propagating combustion is 160~220 DEG C；
The temperature of the calcining is 700~900 DEG C, and heating rate is 2.5~5 DEG C/min, soaking time 5h.
10. pucherite-calcium ferrite composite photo-catalyst according to claim 1-4 any claims or according to right It is required that pucherite-iron that pucherite-calcium ferrite composite photo-catalyst preparation method described in 5-9 any claims is prepared Sour calcium composite photo-catalyst is used for the application of photocatalytically degradating organic dye.
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