CN111659411A - Preparation and application of rare earth cerium doped iron molybdate photocatalyst - Google Patents
Preparation and application of rare earth cerium doped iron molybdate photocatalyst Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 40
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 37
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- -1 cerium ions Chemical class 0.000 description 6
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
本发明提供了一种稀土铈掺杂钼酸铁光催化剂的制备及应用，是将Fe(NO3)・9H2O溶解于去离子水中，室温下加入Ce(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将(NH4)6Mo7O24・4H2O溶解于去离子水中并将其滴加到Fe(NO3)・9H2O和Ce(NO3)3混合溶液中，搅拌，加入氨水调节pH至3~4，于180~185℃下反应12~13h，离心洗涤，干燥，即得稀土铈掺杂钼酸铁光催化剂Ce‑Fe2(MoO4)3。本发明制备的铈掺杂钼酸铁呈均匀纳米球状结构，具有较大的比表面积；同时稀土元素的掺杂能够有效的降低光催化剂的光生电子‑空穴复合率，且能在一定程度上提高光催化剂的比表面积，有利于光催化效率的提升，这使得这种Ce‑Fe2(MoO4)3在光催化染料废水处理领域具有广阔的应用前景。The invention provides the preparation and application of a rare earth cerium doped iron molybdate photocatalyst. Fe(NO 3 )·9H 2 O is dissolved in deionized water, and Ce(NO 3 ) 3 is added at room temperature to obtain Fe ( Mixed solution of NO 3 )・9H 2 O and Ce(NO 3 ) 3 ; (NH 4 ) 6 Mo 7 O 24・4H 2 O was dissolved in deionized water and added dropwise to Fe(NO 3 )・9H 2 O and Ce(NO 3 ) 3 mixed solution, stirring, adding ammonia water to adjust pH to 3~4, reacting at 180~185 ℃ for 12~13h, centrifugal washing and drying to obtain rare earth cerium doped iron molybdate light Catalyst Ce-Fe 2 (MoO 4 ) 3 . The cerium-doped iron molybdate prepared by the invention has a uniform nano-spherical structure and has a large specific surface area; at the same time, the doping of rare earth elements can effectively reduce the photo-generated electron-hole recombination rate of the photocatalyst, and can to a certain extent Increasing the specific surface area of the photocatalyst is beneficial to the improvement of the photocatalytic efficiency, which makes the Ce-Fe 2 (MoO 4 ) 3 have broad application prospects in the field of photocatalytic dye wastewater treatment.
Description
技术领域technical field
本发明涉及一种稀土铈掺杂钼酸铁光催化剂（Ce-Fe2(MoO4)3）的制备方法，尤其涉及一种纳米球状结构铈掺杂钼酸铁（Ce-Fe2(MoO4)3）的制备方法，制备的稀土铈掺杂钼酸铁光催化剂用于染料废水中有机污染物的光催化降解，属于材料制备领域及光催化应用领域。The invention relates to a preparation method of a rare earth cerium-doped iron molybdate photocatalyst (Ce-Fe 2 (MoO 4 ) 3 ), in particular to a nano-spherical structure cerium-doped iron molybdate (Ce-Fe 2 (MoO 4 ) ) 3 ) preparation method, the prepared rare earth cerium doped iron molybdate photocatalyst is used for photocatalytic degradation of organic pollutants in dye wastewater, belonging to the field of material preparation and the field of photocatalysis application.
背景技术Background technique
钼酸铁（Fe2(MoO4)3）具有响应紫外可见光、比表面能高、可选择性、外露活性强等优异性能。更值得人们所关注的是，在钼酸铁中钼酸本身就具有催化性能，而且铁也具有催化性能，因此，二者之间可达到协同催化的效果，使得钼酸铁的催化性能更强。由于Fe2(MoO4)3具有催化、光学和磁性等优异性质，这使得钼酸铁在催化剂、磁性材料和光学纤维等领域的应用前景比较广阔。Iron molybdate (Fe 2 (MoO 4 ) 3 ) has excellent properties such as response to ultraviolet and visible light, high specific surface energy, selectivity, and strong exposure activity. What is more worthy of attention is that in iron molybdate, molybdate itself has catalytic properties, and iron also has catalytic properties. Therefore, a synergistic catalytic effect can be achieved between the two, making iron molybdate stronger catalytic performance. . Due to the excellent properties of Fe 2 (MoO 4 ) 3 such as catalysis, optics and magnetism, Fe 2 (MoO 4 ) 3 has broad application prospects in the fields of catalysts, magnetic materials and optical fibers.
我国稀土资源储量丰富，其中铈元素的丰量最高、最为廉价，同时铈元素因具有独特的4f1，5d1，6S2 电子排布结构，故而可以+4 价，亦可以+3价形式稳定存在，价态不同会影响原子的配位结构，铈元素这种独特的价态配置为其材料性能的提升大有助益。材料的形貌，尺寸，比表面积和氧空位共同影响其光催化性能，其中氧缺陷与铈离子的电子结构有关，不同价态铈离子的转变过程中，伴随着O2的存储和释放，释放的同时形成氧空位可直接参与反应，故而表现出氧化还原性能，同时铈元素的掺杂能够有效的降低光催化剂的光生电子-空穴复合率，所以铈元素掺杂到钼酸铁中能够显著的提升其光催化性能。China is rich in rare earth resources, among which cerium is the most abundant and cheapest element. At the same time, cerium has a unique 4f 1 , 5d 1 , 6S 2 electronic arrangement structure, so it can be stable in the form of +4 or +3. The existence of different valence states will affect the coordination structure of atoms, and the unique valence state configuration of cerium element is of great help to the improvement of its material properties. The morphology, size, specific surface area and oxygen vacancies of the material together affect its photocatalytic performance, in which the oxygen vacancies are related to the electronic structure of cerium ions . At the same time, the formation of oxygen vacancies can directly participate in the reaction, so it shows redox performance. At the same time, the doping of cerium can effectively reduce the photogenerated electron-hole recombination rate of the photocatalyst, so the doping of cerium into iron molybdate can significantly to enhance its photocatalytic performance.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种稀土铈掺杂钼酸铁光催化剂的制备方法及应用。The purpose of the present invention is to provide a preparation method and application of a rare earth cerium doped iron molybdate photocatalyst.
一、稀土铈掺杂钼酸铁光催化剂（Ce-Fe2(MoO4)3）的制备1. Preparation of rare earth cerium-doped iron molybdate photocatalyst (Ce-Fe 2 (MoO 4 ) 3 )
本发明稀土铈掺杂钼酸铁光催化剂的制备方法，是将Fe(NO3)・9H2O溶解于去离子水中，室温下加入Ce(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将(NH4)6Mo7O24・4H2O溶解于去离子水中并将其滴加到Fe(NO3)・9H2O和Ce(NO3)3混合溶液中，25℃水浴下持续搅拌4~6h，加入氨水调节pH至3~4，于180~185℃下反应12~13h，离心洗涤，80~85℃下干燥，即得稀土铈掺杂钼酸铁光催化剂Ce-Fe2(MoO4)3。其中，Ce(NO3)3和Fe(NO3)・9H2O的摩尔比为0.01~0.06:1；Fe(NO3)・9H2O和(NH4)6Mo7O24・4H2O的摩尔比为1:0.2~1:0.25。The preparation method of the rare earth cerium doped iron molybdate photocatalyst of the present invention is that Fe(NO 3 )·9H 2 O is dissolved in deionized water, and Ce(NO 3 ) 3 is added at room temperature to obtain Fe(NO 3 )·9H Mixed solution of 2 O and Ce(NO 3 ) 3 ; (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in deionized water and added dropwise to Fe(NO 3 )·9H 2 O and Ce( NO 3 ) 3 mixed solution, continue stirring for 4~6h in a water bath at 25°C, add ammonia water to adjust the pH to 3~4, react at 180~185°C for 12~13h, wash by centrifugation, and dry at 80~85°C to obtain Rare earth cerium doped iron molybdate photocatalyst Ce-Fe 2 (MoO 4 ) 3 . Among them, the molar ratio of Ce(NO 3 ) 3 and Fe(NO 3 )·9H 2 O is 0.01~0.06:1; Fe(NO 3 )·9H 2 O and (NH 4 ) 6 Mo 7 O 24 ·4H 2 The molar ratio of O is 1:0.2~1:0.25.
二、稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）的形貌2. Morphology of rare earth cerium doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 )
1、扫描电镜分析1. Scanning electron microscope analysis
图1为本发明制备的稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）Ce掺杂量为2%和钼酸铁（Fe2(MoO4)3）的扫描电镜图。从图1A中可以看到，稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）呈均匀纳米颗粒状，具有较大比表面积、其粒径可达110-220nm。由图1B可以看出，钼酸铁（Fe2(MoO4)3）为纳米片组装的微米花。FIG. 1 is a scanning electron microscope image of rare earth cerium-doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 ) with a Ce doping content of 2% and iron molybdate (Fe 2 (MoO 4 ) 3 ) prepared by the present invention. It can be seen from FIG. 1A that the rare earth cerium doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 ) is in the form of uniform nanoparticles, with a large specific surface area and a particle size of 110-220 nm. It can be seen from Fig. 1B that iron molybdate (Fe 2 (MoO 4 ) 3 ) is a microflower assembled by nanosheets.
2、XRD分析2. XRD analysis
图2为本发明制备的纯钼酸铁、稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）：1%-Ce、稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）：2%-Ce的XRD图，由图可知所有衍射峰均于标准卡片PDF#35-0183衍射峰相一致，表明样品合成成功。掺杂稀土元素铈之后并没有额外的衍射峰出现，这表明Fe2(MoO4)3在引入稀土离子之后晶体结构没有发生变化。引入稀土元素掺杂之后的Fe2(MoO4)3的XRD 峰相较于没有稀土元素掺杂的Fe2(MoO4)3，其部分峰位发生位移，这可能是因为稀土元素离子的掺入，取代了催化剂晶体中Fe3+的位置，引起Fe2(MoO4)3晶格变形。Figure 2 shows pure iron molybdate, rare earth cerium doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 ): 1%-Ce, rare earth cerium doped iron molybdate (Ce-Fe 2 (MoO ) prepared by the present invention 4 ) 3 ): XRD pattern of 2%-Ce, it can be seen from the figure that all diffraction peaks are consistent with the diffraction peaks of standard card PDF#35-0183, indicating that the sample was successfully synthesized. No additional diffraction peaks appeared after doping rare earth element cerium, which indicated that the crystal structure of Fe 2 (MoO 4 ) 3 did not change after the introduction of rare earth ions. Compared with Fe 2 (MoO 4 ) 3 without rare earth element doping, the XRD peaks of Fe 2 (MoO 4 ) 3 after introducing rare earth element doping are partially shifted, which may be due to the doping of rare earth element ions. The Fe 3+ was substituted into the catalyst crystal, resulting in the deformation of Fe 2 (MoO 4 ) 3 lattice.
三、稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）的催化性能3. Catalytic performance of rare earth cerium doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 )
图3为所制备样品中Ce3+与Fe3+的物质量之比分别为1%、2%、4%、6%的光催化性能研究图，使用上海兰仪LY-GHX-Xe-300型光催化反应器，此处氙灯光源用北京纽比特科技有限公司HSX-F300氙灯，光源处使用滤光片，滤掉紫外光(λ<400 nm)，反应装置循环水恒温并持续搅拌，分别在黑暗条件和可见光照射下进行光催化性能测试。从图中可以发现稀土铈元素的掺杂可有效的提高Fe2(MoO4)3的光催化性能，催化剂材料Ce-Fe2(MoO4)3对亚甲基蓝的降解能力顺序依次为Ce-2%/Fe2(MoO4)3>Ce-1%/Fe2(MoO4)3>Ce-4%/Fe2(MoO4)3>Ce-6%/Fe2(MoO4)3>Fe2(MoO4)3。其中Ce-2%/Fe2(MoO4)3的光催化性能最强，未掺杂铈的催化剂材料的光催化性能最弱。在4h的光催化反应后，Ce-2%/Fe2(MoO4)3对亚甲基蓝溶液的降解率达到95.7%，而未掺杂铈的催化剂材料对亚甲基蓝溶液的降解率仅为63.29%。Figure 3 shows the photocatalytic performance of the prepared samples with the ratios of Ce 3+ and Fe 3+ being 1%, 2%, 4%, and 6%, respectively. Shanghai Lanyi LY-GHX-Xe-300 was used. Type photocatalytic reactor, where the xenon lamp light source is HSX-F300 xenon lamp of Beijing Newbit Technology Co., Ltd., a filter is used at the light source to filter out ultraviolet light (λ<400 nm), the reaction device circulates water at a constant temperature and continuously stirs, respectively. The photocatalytic performance tests were carried out under dark conditions and visible light irradiation. It can be found from the figure that the doping of rare earth cerium element can effectively improve the photocatalytic performance of Fe 2 (MoO 4 ) 3 , and the degradation ability of the catalyst material Ce-Fe 2 (MoO 4 ) 3 to methylene blue is in the order of Ce-2% /Fe 2 (MoO 4 ) 3 >Ce-1%/Fe 2 (MoO 4 ) 3 >Ce-4%/Fe 2 (MoO 4 ) 3 >Ce-6%/Fe 2 (MoO 4 ) 3 >Fe 2 (MoO 4 ) 3 . Among them, the photocatalytic performance of Ce-2%/Fe 2 (MoO 4 ) 3 is the strongest, and the photocatalytic performance of the catalyst material without cerium is the weakest. After 4 h of photocatalytic reaction, the degradation rate of Ce-2%/Fe 2 (MoO 4 ) 3 to methylene blue solution reached 95.7%, while the degradation rate of undoped cerium catalyst material to methylene blue solution was only 63.29%.
综上所述，本发明制备的铈掺杂钼酸铁呈均匀纳米球状结构，具有较大的比表面积；同时稀土元素的掺杂能够有效的降低光催化剂的光生电子-空穴复合率，且能在一定程度上提高光催化剂的比表面积，有利于光催化效率的提升，这使得这种Ce-Fe2(MoO4)3在光催化染料废水处理领域具有广阔的应用前景。To sum up, the cerium-doped iron molybdate prepared by the present invention has a uniform nano-spherical structure and has a large specific surface area; at the same time, the doping of rare earth elements can effectively reduce the photo-generated electron-hole recombination rate of the photocatalyst, and The specific surface area of the photocatalyst can be increased to a certain extent, which is beneficial to the improvement of the photocatalytic efficiency, which makes the Ce-Fe 2 (MoO 4 ) 3 have broad application prospects in the field of photocatalytic dye wastewater treatment.
附图说明Description of drawings
图1为稀土铈掺杂钼酸铁Ce-Fe2(MoO4)3：2%-Ce和钼酸铁的扫描电镜图。FIG. 1 is a scanning electron microscope image of rare earth cerium doped iron molybdate Ce-Fe 2 (MoO 4 ) 3 : 2%-Ce and iron molybdate.
图2为本发明所制备样品的XRD图。Fig. 2 is the XRD pattern of the sample prepared by the present invention.
图3为本发明所制备样品光催化降解亚甲基蓝的光催化性能图。FIG. 3 is a photocatalytic performance diagram of the photocatalytic degradation of methylene blue of the sample prepared in the present invention.
具体实施方式Detailed ways
下面通过具体实例对本发明一种稀土铈掺杂钼酸铁（Ce-Fe2(MoO4)3）的制备和性能作进一步说明。The preparation and properties of a rare earth cerium-doped iron molybdate (Ce-Fe 2 (MoO 4 ) 3 ) of the present invention will be further described below through specific examples.
实施例1Example 1
将1.0 mmol Fe(NO3)・9H2O溶解于20mL去离子水中，然后在室温下加入0.01mmolCe(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将0.22 mmol (NH4)6Mo7O24・4H2O溶解于20mL去离子水中，在磁力搅拌下将其逐滴滴加到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液中，25℃恒温水浴持续搅拌6h，加入氨水调节pH至4；最后转移至含有50mL聚四氟乙烯内胆的高压反应釜中，于180℃下反应12h，待反应结束后用去离子水离心洗涤三次，再用无水乙醇离心洗涤两次，然后在80℃下干燥，得到稀土铈掺杂钼酸铁Ce-Fe2(MoO4)3光催化剂：1%-Ce。Dissolve 1.0 mmol Fe(NO 3 )·9H 2 O in 20 mL of deionized water, and then add 0.01 mmol Ce(NO 3 ) 3 at room temperature to obtain a mixture of Fe(NO 3 )·9H 2 O and Ce(NO 3 ) 3 mixed solution; 0.22 mmol (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 20 mL of deionized water, and added dropwise to Fe(NO 3 )·9H 2 O and Ce(NO ) under magnetic stirring 3 ) In the mixed solution of 3 , keep stirring in a constant temperature water bath at 25°C for 6h, add ammonia water to adjust the pH to 4; finally transfer to a high pressure reaction kettle containing 50mL polytetrafluoroethylene liner, react at 180°C for 12h, and wait for the reaction to end After centrifugation and washing with deionized water three times, centrifugation and washing with absolute ethanol for two times, and then drying at 80 °C, a rare earth cerium-doped iron molybdate Ce-Fe 2 (MoO 4 ) 3 photocatalyst was obtained: 1%-Ce .
催化性能：在亚甲基蓝溶液中加入上述制备材料，在4h的光催化反应后，溶液中亚甲基蓝的降解率达到92.85%。Catalytic performance: The above prepared materials were added to the methylene blue solution. After 4 h of photocatalytic reaction, the degradation rate of methylene blue in the solution reached 92.85%.
实施例2Example 2
将1.0 mmol Fe(NO3)・9H2O溶解于20mL去离子水中，然后在室温下加入0.02mmolCe(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将0.22 mmol (NH4)6Mo7O24・4H2O溶解于20mL去离子水中，在磁力搅拌下将其逐滴滴加到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液中，25℃恒温水浴持续搅拌6h，加入氨水调节pH至4；最后转移至含有50mL聚四氟乙烯内胆的高压反应釜中，于180℃下反应12h，待反应结束后用去离子水离心洗涤三次，再用无水乙醇离心洗涤两次，然后在80℃下干燥，得到稀土铈掺杂钼酸铁光催化剂Ce-Fe2(MoO4)3：2%-Ce。Dissolve 1.0 mmol Fe(NO 3 )·9H 2 O in 20 mL of deionized water, and then add 0.02 mmol Ce(NO 3 ) 3 at room temperature to obtain a mixture of Fe(NO 3 )·9H 2 O and Ce(NO 3 ) 3 mixed solution; 0.22 mmol (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 20 mL of deionized water, and added dropwise to Fe(NO 3 )·9H 2 O and Ce(NO ) under magnetic stirring 3 ) In the mixed solution of 3 , keep stirring in a constant temperature water bath at 25°C for 6h, add ammonia water to adjust the pH to 4; finally transfer to a high pressure reaction kettle containing 50mL polytetrafluoroethylene liner, react at 180°C for 12h, and wait for the reaction to end After centrifugation and washing with deionized water for three times, centrifugation and washing with absolute ethanol for two times, and then drying at 80° C., the rare earth cerium doped iron molybdate photocatalyst Ce-Fe 2 (MoO 4 ) 3 : 2%-Ce was obtained .
催化性能：在亚甲基蓝溶液中加入上述制备材料，在4h的光催化反应后，溶液中亚甲基蓝的降解率达到95.7%。Catalytic performance: The above prepared materials were added to the methylene blue solution. After 4 h of photocatalytic reaction, the degradation rate of methylene blue in the solution reached 95.7%.
实施例3Example 3
将1.0 mmol Fe(NO3)・9H2O溶解于20mL去离子水中，然后在室温下加入0.04mmolCe(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将0.22mmol (NH4)6Mo7O24・4H2O溶解于20mL去离子水中，在磁力搅拌下将其逐滴滴加到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液中，25℃恒温水浴持续搅拌6h，加入氨水调节pH至4；最后转移至含有50mL聚四氟乙烯内胆的高压反应釜中，于180℃下反应12h，待反应结束后用去离子水离心洗涤三次，再用无水乙醇离心洗涤两次，然后在80℃下干燥，得到稀土铈掺杂钼酸铁光催化剂Ce-Fe2(MoO4)3：4%-Ce。Dissolve 1.0 mmol Fe(NO 3 )·9H 2 O in 20 mL of deionized water, and then add 0.04 mmol Ce(NO 3 ) 3 at room temperature to obtain a mixture of Fe(NO 3 )·9H 2 O and Ce(NO 3 ) 3 Mixed solution; 0.22mmol (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 20 mL of deionized water, and added dropwise to Fe(NO 3 )·9H 2 O and Ce(NO ) under magnetic stirring 3 ) In the mixed solution of 3 , keep stirring in a constant temperature water bath at 25°C for 6h, add ammonia water to adjust the pH to 4; finally transfer to a high pressure reaction kettle containing 50mL polytetrafluoroethylene liner, react at 180°C for 12h, and wait for the reaction to end After centrifugation and washing with deionized water for three times, centrifugation and washing with absolute ethanol for two times, and then drying at 80 °C, the rare earth cerium doped iron molybdate photocatalyst Ce-Fe 2 (MoO 4 ) 3 : 4%-Ce was obtained .
催化性能：在亚甲基蓝溶液中加入上述制备材料，在4h的光催化反应后，溶液中亚甲基蓝的降解率达到67.39%。Catalytic performance: The above prepared materials were added to the methylene blue solution. After 4 h of photocatalytic reaction, the degradation rate of methylene blue in the solution reached 67.39%.
实施例4Example 4
将1.0 mmol Fe(NO3)・9H2O溶解于20mL去离子水中，然后在室温下加入0.06mmolCe(NO3)3，得到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液；将0.22mmol (NH4)6Mo7O24・4H2O溶解于20mL去离子水中，在磁力搅拌下将其逐滴滴加到Fe(NO3)・9H2O和Ce(NO3)3的混合溶液中，25℃恒温水浴持续搅拌6h，加入氨水调节pH至4；最后转移至含有50mL聚四氟乙烯内胆的高压反应釜中，于180℃下反应12h，待反应结束后用去离子水离心洗涤三次，再用无水乙醇离心洗涤两次，然后在80℃下干燥，得到稀土铈掺杂钼酸铁光催化剂Ce-Fe2(MoO4)3：6%-Ce。Dissolve 1.0 mmol Fe(NO 3 )·9H 2 O in 20 mL of deionized water, and then add 0.06 mmol Ce(NO 3 ) 3 at room temperature to obtain a mixture of Fe(NO 3 )·9H 2 O and Ce(NO 3 ) 3 Mixed solution; 0.22mmol (NH 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 20 mL of deionized water, and added dropwise to Fe(NO 3 )·9H 2 O and Ce(NO ) under magnetic stirring 3 ) In the mixed solution of 3 , keep stirring in a constant temperature water bath at 25°C for 6h, add ammonia water to adjust the pH to 4; finally transfer to a high pressure reaction kettle containing 50mL polytetrafluoroethylene liner, react at 180°C for 12h, and wait for the reaction to end After centrifugation and washing with deionized water for three times, centrifugation and washing with absolute ethanol for two times, and then drying at 80 °C, the rare earth cerium doped iron molybdate photocatalyst Ce-Fe 2 (MoO 4 ) 3 : 6%-Ce was obtained .
催化性能：在亚甲基蓝溶液中加入上述制备材料，在4h的光催化反应后，溶液中亚甲基蓝的降解率达到65.65%。Catalytic performance: The above prepared materials were added to the methylene blue solution. After 4 h of photocatalytic reaction, the degradation rate of methylene blue in the solution reached 65.65%.
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