CN106238049B - Preparation of an Ag-doped 3DOM CeO2-ZrO2 material - Google Patents
Preparation of an Ag-doped 3DOM CeO2-ZrO2 material Download PDFInfo
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- 239000000463 material Substances 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title 1
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims abstract description 12
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 9
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 6
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明公开了一种通过减压填充合成方法制备Ag掺杂3DOM CeO2‑ZrO2复合光催化剂，属于化工行业技术领域。以聚苯乙烯(PS)胶球为大孔模板剂，并且以EO20PO70O20(P123)为介孔模板剂，采用Zr(OC4H9)4、Ce(NO3)3·6H2O、AgNO3为原料，通过减压填充后，经过干燥和煅烧得到3DOM Ag/CeO2‑ZrO2复合光催化剂。对其表面形貌、微观结构、光催化活性进行了测定，产品性能在降解刚果红和光解水制氢的光催化方面有很大提高。The invention discloses an Ag-doped 3DOM CeO 2 -ZrO 2 composite photocatalyst prepared by a decompression filling synthesis method, which belongs to the technical field of the chemical industry. Polystyrene (PS) globules were used as macroporous template agent, and EO 20 PO 70 O 20 (P123) was used as mesoporous template agent, Zr(OC 4 H 9 ) 4 , Ce(NO 3 ) 3 ·6H were used 2 O and AgNO 3 are used as raw materials. After filling under reduced pressure, 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst is obtained through drying and calcination. Its surface morphology, microstructure and photocatalytic activity were determined, and the product performance was greatly improved in the photocatalytic degradation of Congo red and photolysis of water for hydrogen production.
Description
技术领域technical field
本发明涉及一种减压填充方法制备的Ag掺杂3DOM CeO2-ZrO2复合光催化剂，属于化工行业技术领域。The invention relates to an Ag-doped 3DOM CeO 2 -ZrO 2 composite photocatalyst prepared by a decompression filling method, and belongs to the technical field of the chemical industry.
背景技术Background technique
随着能源的消耗，利用太阳能分解水制氢的技术已经引起人们的广泛关注，而环境问题也成为经济发展的因素之一。新型光催化技术由于其对环境友好等特点引起了各国科学家的广泛关注。光催化技术大都以半导体材料为光催化剂，在光的激发下能够降解污染物。然而，一般光催化剂存在对太阳光的利用率较低等缺点，所以制备高效光催化材料在光解水制氢及降解污染物方面显得非常有意义。With the consumption of energy, the technology of using solar energy to split water to produce hydrogen has attracted widespread attention, and environmental problems have also become one of the factors of economic development. The new photocatalytic technology has attracted extensive attention of scientists from all over the world due to its environmental friendliness and other characteristics. Most of the photocatalytic technologies use semiconductor materials as photocatalysts, which can degrade pollutants under the excitation of light. However, general photocatalysts have disadvantages such as low utilization of sunlight, so the preparation of high-efficiency photocatalytic materials is very meaningful in photolysis of water for hydrogen production and degradation of pollutants.
发明内容SUMMARY OF THE INVENTION
为了解决上述问题，本发明的目的在于提供一种减压填充法合成Ag掺杂3DOMCeO2-ZrO2复合光催化剂，一是由于CeO2和ZrO2都具有合适的带隙位置，能够利用光分解水产生氢气。二，通过制备三维有序大孔复合材料(3DOM)能够扩大材料的比表面积，增加反应的活性位点，同时，3DOM通透开放的大孔结构能够降低物质的传质阻力，有利于反应物分子的扩散。三，通过Ag的掺杂能够使催化的光响应范围拓宽至可见光区，提高光催化剂对太阳光的利用率，并且Ag的掺杂增加了复合材料光生电子的迁移途径，这种光生电子的多途径迁移从本质上降低了光生电子-空穴对的复合率，提高了复合材料的光催化反应效率。以聚苯乙烯(PS)胶球为大孔模板剂，并且以EO20PO70O20(P123)为介孔模板剂，采用Zr(OC4H9)4、Ce(NO3)3·6H2O、AgNO3为原料，通过减压填充后，经过干燥和煅烧得到3DOM Ag/CeO2-ZrO2复合光催化剂。In order to solve the above problems, the purpose of the present invention is to provide a kind of Ag- doped 3DOMCeO 2 -ZrO 2 composite photocatalyst synthesized by a decompression filling method. Water produces hydrogen. Second, by preparing a three-dimensional ordered macroporous composite material (3DOM), the specific surface area of the material can be expanded and the active site of the reaction can be increased. Diffusion of molecules. Third, the doping of Ag can widen the photoresponse range of the catalysis to the visible light region, improve the utilization rate of the photocatalyst to sunlight, and the doping of Ag increases the migration path of photogenerated electrons in the composite material. Pathway migration essentially reduces the recombination rate of photogenerated electron-hole pairs and improves the photocatalytic reaction efficiency of the composites. Polystyrene (PS) globules were used as macroporous template agent, and EO 20 PO 70 O 20 (P123) was used as mesoporous template agent, Zr(OC 4 H 9 ) 4 , Ce(NO 3 ) 3 ·6H were used 2 O and AgNO 3 are used as raw materials. After filling under reduced pressure, 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst is obtained through drying and calcination.
本发明解决其技术问题所采用的技术方案是：减压填充法合成Ag掺杂3DOM CeO2-ZrO2复合光催化剂，称取P123，质量为0.050±0.005 g，异丙醇(IPA)，体积为17 mL，PS，质量为0.500±0.010 g，Zr(OC4H9)4，体积为1.5 mL，Ce(NO3)3·6H2O，质量为0.167±0.002 g，AgNO3，质量为0.023±0.001 g。Ce(NO3)3·6H2O与AgNO3溶解于2 mL IPA中备用。将P123加入到IPA中并搅拌至完全溶解后滴加Zr(OC4H9)4，随后加入Ce(NO3)3与AgNO3溶液至形成Ag/CeO2-ZrO2溶胶，将PS模板置于Ag/CeO2-ZrO2溶胶中，搅拌一段时间后进行减压填充。将产物放入烘箱中至干燥，设定烘干温度60±2 ℃，干燥后所获产物在600 ℃下煅烧7 h，得到三维有序大孔复合材料Ag/CeO2-ZrO2 (标记为3DOM Ag/CeO2-ZrO2)。The technical scheme adopted by the present invention to solve the technical problem is as follows: the Ag-doped 3DOM CeO 2 -ZrO 2 composite photocatalyst is synthesized by a decompression filling method, and P123 is weighed, the mass is 0.050±0.005 g, the isopropanol (IPA), the volume 17 mL, PS, mass 0.500±0.010 g, Zr(OC 4 H 9 ) 4 , volume 1.5 mL, Ce(NO 3 ) 3 ·6H 2 O, mass 0.167±0.002 g, AgNO 3 , mass 0.023±0.001g. Ce(NO 3 ) 3 ·6H 2 O and AgNO 3 were dissolved in 2 mL of IPA for use. P123 was added to IPA and stirred until completely dissolved, Zr(OC 4 H 9 ) 4 was added dropwise, then Ce(NO 3 ) 3 and AgNO 3 solutions were added to form Ag/CeO 2 -ZrO 2 sol, and the PS template was placed In the Ag/CeO 2 -ZrO 2 sol, it is filled under reduced pressure after stirring for a period of time. The product was placed in an oven to dry, and the drying temperature was set at 60±2 °C. After drying, the obtained product was calcined at 600 °C for 7 h to obtain a three-dimensional ordered macroporous composite material Ag/CeO 2 -ZrO 2 (marked as 3DOM Ag/CeO 2 -ZrO 2 ).
本发明的有益效果是：采用减压填充法合成具有较高可见光响应的3DOM Ag/CeO2-ZrO2复合光催化剂。复合材料由立方相Ag、立方相CeO2和四方相ZrO2组成，且Ag的引入提高了光催化剂在可见光区的吸收。3DOM Ag/CeO2-ZrO2具有的三维有序大孔结构使材料具有较大的比表面积。与P25相比，复合光催化剂在模拟日光和可见光下对刚果红具有较好的光降解效果。另外，复合催化剂在Na2S-Na2SO3为牺牲剂的条件下具有较高的产氢效果，这是由于Ag的引入，扩大了复合材料可见光响应的范围，同时增加了光生电子的迁移途径，抑制了复合材料中光生电子-空穴对的复合，从而改善其光催化活性。The beneficial effect of the present invention is that: the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst with higher visible light response is synthesized by a decompression filling method. The composites consist of cubic Ag, cubic CeO and tetragonal ZrO , and the introduction of Ag improves the absorption of the photocatalyst in the visible light region. The three-dimensional ordered macroporous structure of 3DOM Ag/CeO 2 -ZrO 2 enables the material to have a large specific surface area. Compared with P25, the composite photocatalyst has better photodegradation effect on Congo red under simulated sunlight and visible light. In addition, the composite catalyst has a higher hydrogen production effect under the condition of Na 2 S-Na 2 SO 3 as sacrificial agent, which is due to the introduction of Ag, which expands the visible light response range of the composite material and increases the migration of photogenerated electrons. This pathway inhibits the recombination of photogenerated electron-hole pairs in the composite, thereby improving its photocatalytic activity.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明做进一步说明。The present invention will be further described below with reference to the accompanying drawings and specific embodiments.
图1是PS胶晶模板表面形貌图。Figure 1 shows the surface topography of the PS colloidal template.
图2是3DOM Ag/CeO2-ZrO2复合光催化剂表面形貌图。Figure 2 is the surface topography of the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst.
图3是3DOM Ag/CeO2-ZrO2复合光催化剂的HR-TEM照片。Figure 3 is an HR-TEM image of the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst.
图4是3DOM Ag/CeO2-ZrO2复合光催化剂的XRD图。Figure 4 is the XRD pattern of the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst.
图5是3DOM Ag/CeO2-ZrO2复合光催化剂的N2吸附-脱附等温线。Figure 5 is the N adsorption-desorption isotherm of the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst.
图6是3DOM Ag/CeO2-ZrO2复合光催化剂的XPS图。Figure 6 is an XPS image of the 3DOM Ag/CeO 2 -ZrO 2 composite photocatalyst.
图7是紫外光下直接光降解、P25、CeO2、ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2催化降解刚果红动力学结果图。Figure 7 is a graph showing the kinetic results of direct photodegradation, P25, CeO 2 , ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 catalytic degradation of Congo red under ultraviolet light.
图8是可见光下直接光降解、P25、CeO2、ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2催化降解刚果红反应结果图。Figure 8 is a graph showing the results of direct photodegradation under visible light, P25, CeO 2 , ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 catalyzing the degradation of Congo red.
图9是模拟日光下直接光降解、P25、CeO2、ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2催化降解刚果红反应结果图。Figure 9 is a graph showing the results of direct photodegradation, P25, CeO 2 , ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 catalytic degradation of Congo red under simulated sunlight.
图10是P25、ZrO2、3DOM ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2在Na2S-Na2SO3溶液中光解水制氢结果图。Figure 10 is a graph showing the results of photolysis of water for hydrogen production by P25, ZrO 2 , 3DOM ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 in Na 2 S-Na 2 SO 3 solution.
具体实施方式Detailed ways
减压填充法合成Ag掺杂3DOM CeO2-ZrO2复合光催化剂，称取购于天津科密欧化学试剂有限公司99.0%的Ce(NO3)3·6H2O，质量为Ce(NO3)3·6H2O，0.167±0.002 g，和购于天津市光复精细化工研究所99.8%的AgNO3，质量为0.023±0.001 g溶解于购于天津市光复精细化工研究所的99.7%的IPA中，体积为2 mL备用。将购于上海萨恩化学技术有限公司Mn~5800的P123，质量为0.050±0.005 g加入到体积为的15 mL IPA中并搅拌至完全溶解后滴加购于上海迈瑞尔化学技术有限公司80.0%的Zr(OC4H9)4，体积为1.5 mL，随后加入Ce(NO3)3与AgNO3溶液至形成Ag/CeO2-ZrO2溶胶，将PS模板(采用无乳化剂的乳化方法合成，并通过离心干燥获得PS胶晶模板)，质量为0.500±0.010 g置于Ag/CeO2-ZrO2溶胶中，搅拌一段时间后进行减压填充。将产物放入烘箱中至干燥，设定烘干温度60±2 ℃，干燥后所获产物使用天津泰斯特仪器有限公司的SX-2.5-12型箱式电阻炉中在600 ℃下煅烧7 h，得到三维有序大孔复合材料Ag/CeO2-ZrO2 (标记为3DOM Ag/CeO2-ZrO2)。Ag-doped 3DOM CeO 2 -ZrO 2 composite photocatalyst was synthesized by vacuum filling method, and 99.0% Ce(NO 3 ) 3 ·6H 2 O purchased from Tianjin Kemio Chemical Reagent Co., Ltd. was weighed and the mass was Ce(NO 3 ) 3 ·6H 2 O, 0.167±0.002 g, and 99.8% AgNO 3 purchased from Tianjin Guangfu Fine Chemical Research Institute, mass 0.023±0.001 g dissolved in 99.7% IPA purchased from Tianjin Guangfu Fine Chemical Research Institute , the volume is 2 mL for later use. The P123 of Mn~5800 purchased from Shanghai Saen Chemical Technology Co., Ltd., with a mass of 0.050 ± 0.005 g, was added to 15 mL of IPA with a volume of 15 mL and stirred until completely dissolved, and then added dropwise and purchased from Shanghai Merrill Chemical Technology Co., Ltd. 80.0% Zr(OC 4 H 9 ) 4 , the volume is 1.5 mL, then Ce(NO 3 ) 3 and AgNO 3 solutions were added to form Ag/CeO 2 -ZrO 2 sol, PS template (synthesized by emulsifier-free emulsification method) , and obtained the PS colloidal crystal template by centrifugal drying) with a mass of 0.500 ± 0.010 g and placed in the Ag/CeO 2 -ZrO 2 sol, stirred for a period of time, and then filled under reduced pressure. The product was placed in an oven to dry, and the drying temperature was set at 60 ± 2 °C. After drying, the obtained product was calcined at 600 °C in a SX-2.5-12 box-type resistance furnace of Tianjin Test Instrument Co., Ltd. for 7 h, three-dimensional ordered macroporous composite material Ag/CeO 2 -ZrO 2 (marked as 3DOM Ag/CeO 2 -ZrO 2 ) was obtained.
22复合光催化剂的结构及性能测定： 22 Structure and performance determination of composite photocatalysts:
一、表面形貌和微观结构1. Surface morphology and microstructure
3DOM Ag/CeO2-ZrO2样品的表面形貌和微观结构分析结果见图1—6。由图1可清楚地观察到，所合成的PS胶晶模板在三维空间内排列整齐有序，大小均一。由于在自组装过程中受到挤压，所以PS胶球呈现六边形形状。图2的SEM结果表明，样品在排列有序，呈开放通透的大孔结构，大孔排列整齐有序且为六边形形状，且由于PS胶晶模板为面心立方排列，所以能够从每个大孔处看到三个小孔。图3为样品3DOM Ag/CeO2-ZrO2的HR-TEM照片，从图中可以看到立方相Ag的(111)晶面，立方相CeO2的(111)晶面和四方相ZrO2的(011)晶面。图4为所制备的材料的XRD图，从图中可以看到，复合材料3DOM Ag/CeO2-ZrO2中存在Ag、CeO2和ZrO2的特征峰。图5为复合材料的N2吸附-脱附等温线，从图中可以明显的看到，由于具有较大的比表面积，三维有序大孔复合材料的等温线明显的向上移动。从图6的XPS图中也可以证明，在3DOM Ag/CeO2-ZrO2中Ce存在两种价态且Ag以单质的形式存在。The surface morphology and microstructure analysis results of 3DOM Ag/CeO 2 -ZrO 2 samples are shown in Figures 1-6. It can be clearly observed from Figure 1 that the synthesized PS colloidal crystal templates are neatly arranged in three-dimensional space with uniform size. Due to being squeezed during the self-assembly process, the PS glue balls assume a hexagonal shape. The SEM results in Figure 2 show that the samples are arranged in an orderly manner, showing an open and transparent macroporous structure. The macropores are arranged in an orderly and hexagonal shape, and since the PS colloidal template is in a face-centered cubic arrangement, it can be Three small holes are seen at each large hole. Figure 3 is the HR-TEM image of the sample 3DOM Ag/CeO 2 -ZrO 2 , from which we can see the (111) crystal face of the cubic Ag, the (111) crystal face of the cubic CeO 2 and the tetragonal ZrO 2 (011) crystal plane. Figure 4 is the XRD pattern of the prepared material, from which it can be seen that there are characteristic peaks of Ag, CeO 2 and ZrO 2 in the composite material 3DOM Ag/CeO 2 -ZrO 2 . Figure 5 shows the N adsorption-desorption isotherm of the composite material. It can be clearly seen from the figure that the isotherm of the three-dimensional ordered macroporous composite material is obviously shifted upward due to the larger specific surface area. It can also be proved from the XPS diagram of FIG. 6 that in 3DOM Ag/CeO 2 -ZrO 2 , Ce exists in two valence states and Ag exists in the form of elemental substance.
二、光催化性能测定2. Determination of photocatalytic performance
对所合成的3DOM Ag/CeO2-ZrO2的光催化活性进行了降解刚果红和光解水制氢的光催化实验。为了评价所合成的复合材料的光催化效果，选用市售P25、单质CeO2、单质ZrO2、Ag/CeO2-ZrO2及3DOM ZrO2作为对比实验。The photocatalytic activities of the as-synthesized 3DOM Ag/CeO 2 -ZrO 2 were carried out for the degradation of Congo red and the photocatalysis of water for hydrogen production. In order to evaluate the photocatalytic effect of the synthesized composite materials, commercially available P25, elemental CeO 2 , elemental ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM ZrO 2 were selected as comparative experiments.
、不同样品对紫外光降解刚果红速率的影响见图7所示。根据实验数据，按照公式- ln(C t /C 0 )=kt+b进行计算，其中，C t 为染料在t时刻的浓度(mg·L-1)，C 0 是染料初始浓度(mg·L-1)，k是速率常数(min-1)，b为截距。由图7可见，-ln(C t /C 0 )与反应时间t基本呈线性关系，这说明染料刚果红的降解遵循准一级反应动力学。经计算，直接光降解、P25、CeO2、ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2的紫外光光催化降解刚果红的表观反应速率常数分别为0.00053、0.00813、0.00652、0.00484、0.00902和0.01331 min-1。在可见光和模拟日光条件下降解刚果红结果见图8、图9，3DOM Ag/CeO2-ZrO2复合材料对刚果红的降解均呈现出最高的光催化活性，远超过市售P25。The effect of different samples on the rate of UV photodegradation of Congo red is shown in Figure 7. According to the experimental data, the calculation is performed according to the formula - ln(C t /C 0 )=kt+b , where C t is the concentration of the dye at time t (mg·L -1 ), and C 0 is the initial concentration of the dye (mg·L -1 ) L -1 ), k is the rate constant (min -1 ), and b is the intercept. It can be seen from Fig. 7 that -ln(C t /C 0 ) has a substantially linear relationship with the reaction time t , which indicates that the degradation of the dye Congo red follows the pseudo-first-order reaction kinetics. After calculation, the apparent reaction rate constants of UV photocatalytic degradation of Congo red by direct photodegradation, P25, CeO 2 , ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 are 0.00053 and 0.00813, respectively. , 0.00652, 0.00484, 0.00902 and 0.01331 min -1 . The results of the degradation of Congo red under visible light and simulated sunlight are shown in Figure 8 and Figure 9. The 3DOM Ag/CeO 2 -ZrO 2 composite showed the highest photocatalytic activity for the degradation of Congo red, far exceeding the commercially available P25.
2、光解水制氢P25、ZrO2、3DOM ZrO2、Ag/CeO2-ZrO2和3DOM Ag/CeO2-ZrO2不同样品在Na2S-Na2SO3溶液中产氢速率结果如图10所示。结果表明，3DOMAg/CeO2-ZrO2复合材料具有最好的产氢能力。2. The hydrogen production rate results of different samples of P25, ZrO 2 , 3DOM ZrO 2 , Ag/CeO 2 -ZrO 2 and 3DOM Ag/CeO 2 -ZrO 2 in Na 2 S-Na 2 SO 3 solution are shown in the figure 10 shown. The results show that the 3DOMAg/CeO 2 -ZrO 2 composite has the best hydrogen production capacity.
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