CN105771962A - A near-infrared responsive carbon quantum dot/Bi2MoO6 photocatalyst and its preparation method - Google Patents
A near-infrared responsive carbon quantum dot/Bi2MoO6 photocatalyst and its preparation method Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910002900 Bi2MoO6 Inorganic materials 0.000 title claims description 5
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 230000004044 response Effects 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 230000003595 spectral effect Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 19
- 229940043267 rhodamine b Drugs 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001889 high-resolution electron micrograph Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J35/39—Photocatalytic properties
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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Abstract
一种近红外响应的碳量子点(CQDs)/Bi2MoO6复合光催化剂，由Bi2MoO6和CQDs组成，CQDs分布在Bi2MoO6上，CQDs和Bi2MoO6的质量百分比为1‑15%：85‑99%。本发明还提供了上述光催化剂的制备方法，将Bi(NO3)3·5H2O和Na2MoO4·2H2O的水溶液混合，得到浅黄色悬浮液；将CQDs的水溶液加入到浅黄色悬浮液中，然后转移到水热釜中，在140~180℃的温度下反应，所得的产物依次无水乙醇和去离子水洗涤，然后离心，将沉淀干燥，得具有近红外光催化活性的CQDs/Bi2MoO6复合光催化剂。本发明具有较宽的光谱响应范围，较高的载流子分离效率和光催化活性。
A near-infrared responsive carbon quantum dots (CQDs)/Bi 2 MoO 6 composite photocatalyst consisting of Bi 2 MoO 6 and CQDs distributed on Bi 2 MoO 6 with a mass percent of CQDs and Bi 2 MoO 6 of 1 ‑15%: 85‑99%. The present invention also provides the preparation method of the above-mentioned photocatalyst, mixing the aqueous solution of Bi(NO 3 ) 3 5H 2 O and Na 2 MoO 4 2H 2 O to obtain a light yellow suspension; adding the aqueous solution of CQDs to the light yellow suspension, then transferred to a hydrothermal kettle, and reacted at a temperature of 140~180°C. The obtained product was washed with absolute ethanol and deionized water in turn, then centrifuged, and the precipitate was dried to obtain a near-infrared photocatalytic activity CQDs/Bi 2 MoO 6 composite photocatalyst. The invention has wider spectral response range, higher carrier separation efficiency and photocatalytic activity.
Description
技术领域 technical field
本发明属于材料学领域，涉及一种光催化材料，具体来说是一种近红外响应的碳量子点/Bi2MoO6光催化剂及制备方法。 The invention belongs to the field of materials science, and relates to a photocatalytic material, specifically a near-infrared responsive carbon quantum dot/Bi 2 MoO 6 photocatalyst and a preparation method.
背景技术 Background technique
由于全球日益加重的环境污染与能源危机，半导体光催化的研究和应用引起了人们的广泛关注。光催化技术的核心问题是合适光催化剂的设计、开发与研制，特别是宽光谱响应的高性能光催化材料的研究成为当务之急。然而，目前开发出的光催化材料大多数仅能够吸收紫外光或者可见光，而不能利用占太阳光谱53%的近红外光及红外光。近年来，研究者们发现碳量子点（CQDs）具有上转换发光作用，它能够吸收近红外甚至红外光，将其转换为短波段的紫外光以及可见光。因此，将CQDs和光催化材料进行复合，就能够利用CQDs的上转换发光作用将长波段的近红外光或者红外光转化为短波段的可见光及紫外光，进而激发光催化材料，从而拓宽光催化材料对太阳光谱的吸收范围。 Due to the increasing environmental pollution and energy crisis in the world, the research and application of semiconductor photocatalysis have attracted widespread attention. The core issue of photocatalytic technology is the design, development and development of suitable photocatalysts, especially the research on high-performance photocatalytic materials with wide spectral response has become a top priority. However, most of the currently developed photocatalytic materials can only absorb ultraviolet light or visible light, but cannot utilize near-infrared light and infrared light, which account for 53% of the solar spectrum. In recent years, researchers have discovered that carbon quantum dots (CQDs) have upconversion luminescence, which can absorb near-infrared or even infrared light and convert it into short-wavelength ultraviolet and visible light. Therefore, by combining CQDs and photocatalytic materials, the up-conversion luminescence of CQDs can be used to convert long-wavelength near-infrared light or infrared light into short-wavelength visible light and ultraviolet light, and then excite photocatalytic materials, thereby broadening the scope of photocatalytic materials. The absorption range of the solar spectrum.
Bi2MoO6 光催化剂是最近研究较多的一种新型可见光催化材料，它是一种稳定、无毒的半导体材料，带隙约为2.5 ～ 2.8eV，其吸收的阈值波长大于450 nm，具有活性高，稳定性强，无毒及宽光谱响应等优点，使其成为目前最具潜力的可见光催化剂。但是，单纯的Bi2MoO6光催化材料存在光谱响应范围不够宽，以及载流子复合几率高的问题，从而限制了它的实际应用。 Bi 2 MoO 6 photocatalyst is a new type of visible light catalytic material that has been studied more recently. It is a stable and non-toxic semiconductor material with a band gap of about 2.5 to 2.8 eV, and its absorption threshold wavelength is greater than 450 nm. The advantages of high activity, strong stability, non-toxicity and wide spectral response make it the most potential visible light catalyst at present. However, the pure Bi 2 MoO 6 photocatalytic material has the problems of insufficient spectral response range and high charge carrier recombination probability, which limits its practical application.
发明内容 Contents of the invention
针对现有技术中的上述技术问题，本发明提供了一种近红外响应的碳量子点/Bi2MoO6光催化剂及制备方法，所述的这种近红外响应的碳量子点/Bi2MoO6光催化剂及制备方法要解决现有技术中的光催化材料上光谱响应范围窄，不能利用近红外光及红外光，而且光生载流子容易复合的技术问题。 Aiming at the above-mentioned technical problems in the prior art, the present invention provides a near-infrared responsive carbon quantum dot/Bi 2 MoO 6 photocatalyst and a preparation method thereof, said near-infrared responsive carbon quantum dot/Bi 2 MoO 6 The photocatalyst and its preparation method should solve the technical problems that the photocatalytic materials in the prior art have a narrow spectral response range, cannot use near-infrared light and infrared light, and are easy to recombine photogenerated carriers.
本发明提供了一种近红外响应的碳量子点/Bi2MoO6复合光催化剂，由50-100 nm的纳米片状Bi2MoO6和5-10 nm的碳量子点组成，碳量子点纳米颗粒分布在片状Bi2MoO6上，按质量百分比计算，纳米颗粒的碳量子点：纳米尺寸的片状Bi2MoO6为1-15%：85-99%。 The invention provides a near-infrared responsive carbon quantum dot/Bi 2 MoO 6 composite photocatalyst, which is composed of 50-100 nm nanosheet Bi 2 MoO 6 and 5-10 nm carbon quantum dots, and the carbon quantum dots are nanometer The particles are distributed on the sheet-like Bi 2 MoO 6 , and the ratio of carbon quantum dots of nanoparticles: nano-sized sheet-like Bi 2 MoO 6 is 1-15%: 85-99% by mass percentage.
进一步的，按质量百分比计算，纳米颗粒的碳量子点：纳米尺寸的片状Bi2MoO6为1%：99%。 Further, calculated by mass percentage, the ratio of carbon quantum dots of nanoparticles: nanometer-sized flake Bi 2 MoO 6 is 1%: 99%.
进一步的，按质量百分比计算，纳米颗粒的碳量子点：纳米尺寸的片状Bi2MoO6为3.2%：96.8%。 Further, calculated by mass percentage, the ratio of carbon quantum dots of nanoparticles: nanometer-sized flake Bi 2 MoO 6 is 3.2%: 96.8%.
进一步的，按质量百分比计算，纳米颗粒的碳量子点：纳米尺寸的片状Bi2MoO6为6%：94%。 Further, calculated by mass percentage, the ratio of nanoparticle carbon quantum dots: nanometer-sized flake Bi 2 MoO 6 is 6%: 94%.
进一步的，按质量百分比计算，纳米颗粒的碳量子点：纳米尺寸的片状Bi2MoO6为15%：85%。 Further, calculated by mass percentage, the ratio of carbon quantum dots of nanoparticles: nanometer-sized flake Bi 2 MoO 6 is 15%: 85%.
本发明还提供了上述的一种近红外响应的碳量子点/Bi2MoO6复合光催化剂的制备方法，包括以下步骤： The present invention also provides a method for preparing the above-mentioned near - infrared responsive carbon quantum dot/ Bi2MoO6 composite photocatalyst, comprising the following steps:
1）将Bi(NO3)3·5H2O溶于硝酸中，得到浓度为0.05~1 mol/L的Bi(NO3)3溶液；将Na2MoO4·2H2O溶于去离子水中，得到浓度为0.025~0.5 mol/L的Na2MoO4溶液； 1) Dissolve Bi(NO 3 ) 3 ·5H 2 O in nitric acid to obtain a Bi(NO 3 ) 3 solution with a concentration of 0.05~1 mol/L; dissolve Na 2 MoO 4 ·2H 2 O in deionized water , to obtain a Na2MoO4 solution with a concentration of 0.025~ 0.5 mol/L;
2）然后按摩尔比计算，即Bi(NO3)3溶液中的Bi3+：Na2MoO4溶液中的MoO4 2-为2:1的比例，将Bi(NO3)3溶液和Na2MoO4溶液混合均匀，得到浅黄色悬浮液； 2) Then calculated according to the molar ratio, that is, Bi 3+ in the Bi(NO 3 ) 3 solution: MoO 4 2- in the Na 2 MoO 4 solution is a ratio of 2:1, the Bi(NO 3 ) 3 solution and Na 2 The MoO 4 solution was mixed evenly to obtain a light yellow suspension;
3）将CQDs水溶液加入到步骤2）所得的浅黄色悬浮液中，超声处理20~40min，超声处理的功率为40-100 W，频率为20-40 KHz，得到灰色悬浮液； 3) Add the CQDs aqueous solution to the light yellow suspension obtained in step 2), and sonicate for 20-40min, and the power of sonication is 40-100 W, the frequency is 20-40 KHz, a gray suspension is obtained;
4）将步骤3）所得的灰色悬浮液转移到水热釜中，控制温度为140~180℃下反应15~30h，所得的产物依次用无水乙醇和去离子水洗涤，然后控制温度为60-80 ℃进行干燥，即得CQDs/Bi2MoO6纳米粉体。 4) Transfer the gray suspension obtained in step 3) to a hydrothermal kettle, control the temperature at 140-180°C for 15-30 hours, wash the obtained product with absolute ethanol and deionized water in sequence, and then control the temperature at 60 Dry at -80°C to obtain CQDs/Bi 2 MoO 6 nanometer powder.
本发明的复合光催化剂不仅对太阳光具有较好的吸收，而且具有较高的载流子分离效率和光催化性能。在波长大于700 nm的近红外光的照射下，CQDs/Bi2MoO6复合材料在10 h内对罗丹明B的降解率达到93.6%，而单纯的Bi2MoO6在同样的条件下则不能将罗丹明B降解。可见CQDs/Bi2MoO6复合光催化剂能够在近红外光下降解有机污染物，具有应用前景。 The composite photocatalyst of the invention not only has better absorption of sunlight, but also has higher carrier separation efficiency and photocatalytic performance. Under the irradiation of near-infrared light with a wavelength greater than 700 nm, the CQDs/Bi 2 MoO 6 composite can degrade 93.6% of rhodamine B within 10 h, while pure Bi 2 MoO 6 cannot Degrade Rhodamine B. It can be seen that the CQDs/Bi 2 MoO 6 composite photocatalyst can degrade organic pollutants under near-infrared light, and has application prospects.
本发明利用CQDs和Bi2MoO6进行复合，不仅能够利用CQDs的上转换发光作用增加Bi2MoO6的光谱响应范围，还能够利用CQDs的电子转移和电子储存能力增加光生载流子的分离效率，从而带来光催化性能的有效提升。 The present invention uses CQDs and Bi 2 MoO 6 to compound, not only can use the up-conversion luminescence of CQDs to increase the spectral response range of Bi 2 MoO 6 , but also can use the electron transfer and electron storage capabilities of CQDs to increase the separation efficiency of photogenerated carriers , leading to an effective improvement in the photocatalytic performance.
本发明和已有技术相比，其技术进步是显著的。本发明的CQDs/Bi2MoO6复合光催化剂具有较宽的光谱响应范围，较高的载流子分离效率和光催化活性，且制备方法简单，可控性强，容易实现规模化生产，无需特殊设备和苛刻条件。 Compared with the prior art, the technical progress of the present invention is remarkable. The CQDs/Bi 2 MoO 6 composite photocatalyst of the present invention has a wide spectral response range, high carrier separation efficiency and photocatalytic activity, and the preparation method is simple, the controllability is strong, and it is easy to realize large-scale production without special equipment and harsh conditions.
附图说明 Description of drawings
图1是实施例1所得的CQDs/Bi2MoO6复合光催化剂的XRD衍射谱图。 Fig. 1 is the XRD diffraction spectrum of the CQDs/Bi 2 MoO 6 composite photocatalyst obtained in Example 1.
图2是实施例1所得的CQDs/Bi2MoO6复合光催化剂的高分辨电镜照片。 Fig. 2 is a high-resolution electron micrograph of the CQDs/Bi 2 MoO 6 composite photocatalyst obtained in Example 1.
图3是实施例1所得的CQDs/Bi2MoO6复合光催化剂在近红外光下降解罗丹明B的过程中，不同降解时间下所得的罗丹明B的吸光度随检测波长的变化情况。 Fig. 3 shows the variation of the absorbance of Rhodamine B obtained under different degradation times with the detection wavelength during the degradation of Rhodamine B by the CQDs/Bi 2 MoO 6 composite photocatalyst obtained in Example 1 under near-infrared light.
图4是以实施例1所得的CQDs/Bi2MoO6复合光催化剂与单纯Bi2MoO6在近红外光下对罗丹明B的降解曲线对比图。 Fig. 4 is a comparison chart of degradation curves of CQDs/Bi 2 MoO 6 composite photocatalyst obtained in Example 1 and pure Bi 2 MoO 6 on rhodamine B under near-infrared light.
具体实施方式 detailed description
下面通过具体实施例并结合附图对本发明进一步阐述，但并不限制本发明。 The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings, but the present invention is not limited.
所用原料： Raw materials used:
Bi(NO3)3·5H2O(分析纯，国药集团化学试剂有限公司)； Bi(NO 3 ) 3 5H 2 O (analytical grade, Sinopharm Chemical Reagent Co., Ltd.);
Na2MoO4·2H2O(分析纯，国药集团化学试剂有限公司)； Na 2 MoO 4 2H 2 O (analytical grade, Sinopharm Chemical Reagent Co., Ltd.);
硝酸 （分析纯，国药集团化学试剂有限公司）； Nitric acid (analytical grade, Sinopharm Chemical Reagent Co., Ltd.);
无水乙醇 （分析纯，国药集团化学试剂有限公司）。 Absolute ethanol (analytical grade, Sinopharm Chemical Reagent Co., Ltd.).
实施例Example 11
一种CQDs/Bi2MoO6复合光催化剂，由50-100 nm的纳米片状Bi2MoO6和5-10 nm的碳量子点组成，且CQDs纳米颗粒分布在纳米尺寸的片状Bi2MoO6上，按质量百分比计算，纳米颗粒的CQDs：纳米尺寸的片状Bi2MoO6为3.2%：96.8%。 A CQDs/Bi 2 MoO 6 composite photocatalyst, which is composed of 50-100 nm nano-sheet Bi 2 MoO 6 and 5-10 nm carbon quantum dots, and CQDs nanoparticles are distributed in the nano-sized sheet-like Bi 2 MoO 6 , calculated by mass percentage, the CQDs of nanoparticles: nano-sized flake Bi 2 MoO 6 is 3.2%: 96.8%.
上述的一种CQDs/Bi2MoO6复合光催化剂制备方法，具体包括以下步骤： The above-mentioned preparation method of a CQDs/Bi 2 MoO 6 composite photocatalyst specifically comprises the following steps:
（1）、将Bi(NO3)3·5H2O溶于硝酸中，得到浓度为0.1 mol/L的Bi(NO3)3溶液； (1) Dissolve Bi(NO 3 ) 3 ·5H 2 O in nitric acid to obtain a Bi(NO 3 ) 3 solution with a concentration of 0.1 mol/L;
将Na2MoO4·2H2O溶于去离子水中，得到浓度为0.05 mol/L的Na2MoO4溶液； Dissolve Na 2 MoO 4 ·2H 2 O in deionized water to obtain a Na 2 MoO 4 solution with a concentration of 0.05 mol/L;
然后按摩尔比计算，即Bi(NO3)3溶液中的Bi3+：Na2MoO4溶液中的MoO4 2-为2:1的比例，将Bi(NO3)3溶液和Na2MoO4溶液混合均匀，得到浅黄色悬浮液； Then calculated by molar ratio, that is, Bi 3+ in Bi(NO 3 ) 3 solution: MoO 4 2- in Na 2 MoO 4 solution is a ratio of 2:1, Bi(NO 3 ) 3 solution and Na 2 MoO 4 The solution is mixed evenly to obtain a light yellow suspension;
（2）、将CQDs水溶液加入到步骤（1）所得的浅黄色悬浮液中，控制功率为40-100 W，频率为20-40 KHz进行超声处理30min，得到灰色悬浮液; (2) Add the CQDs aqueous solution to the light yellow suspension obtained in step (1), and control the power to 40-100 W, the frequency is 20-40 KHz to carry out ultrasonic treatment 30min, obtain gray suspension;
（3）、将步骤（2）所得的灰色悬浮液转移到水热釜中，控制温度为160℃下反应20h，所得的产物依次用无水乙醇和去离子水洗涤3次，然后控制温度为60-80 ℃进行干燥，即得CQDs/Bi2MoO6纳米粉体。 (3) Transfer the gray suspension obtained in step (2) to a hydrothermal kettle, and control the temperature at 160°C for 20 hours. The obtained product is washed with absolute ethanol and deionized water for 3 times in sequence, and then the temperature is controlled to Dry at 60-80°C to obtain CQDs/Bi 2 MoO 6 nanometer powder.
采用X射线衍射仪（D/max2200PC，日本理学株式会社）对上述所得的CQDs/Bi2MoO6复合光催化剂进行测定，所得的XRD图谱如图1所示，从图1中可以看出所得的CQDs/Bi2MoO6复合光催化剂中因CQDs的复合量较少，XRD图谱未表现出其衍射峰，仅表现出单斜相的钼酸铋峰。 The CQDs/Bi 2 MoO 6 composite photocatalyst obtained above was measured by an X-ray diffractometer (D/max2200PC, Japan Rigaku Co., Ltd.), and the obtained XRD spectrum is shown in Figure 1, from which it can be seen that the obtained In the CQDs/Bi 2 MoO 6 composite photocatalyst, due to the less complex amount of CQDs, the XRD pattern does not show its diffraction peak, but only shows the peak of bismuth molybdate in monoclinic phase.
采用场发射透射电子显微镜（FEI tecnaiG2F30，美国FEI公司）对上述所得的CQDs/Bi2MoO6复合光催化剂进行形貌和微结构表征，所得的高分辨透射电镜图如图2所示，从图2中可以看出，CQDs纳米颗粒分布在纳米尺寸的片状Bi2MoO6上，其中0.321 nm和0.275 nm分别对应于CQDs的（002）面和Bi2MoO6的（200）面的晶面间距。 The morphology and microstructure of the CQDs/Bi 2 MoO 6 composite photocatalyst obtained above were characterized by a field emission transmission electron microscope (FEI tecnaiG2F30, FEI, USA). The high-resolution transmission electron microscope image obtained is shown in Figure 2. 2, it can be seen that the CQDs nanoparticles are distributed on the nano-sized sheet - like Bi2MoO6 , where 0.321 nm and 0.275 nm correspond to the crystal planes of the (002) plane of CQDs and the ( 200 ) plane of Bi2MoO6, respectively spacing.
为了研究所制备样品的光催化性能，设计模拟太阳光下降解罗丹明B的实验。步骤如下：将0.05 g实施例1所得的CQDs/Bi2MoO6复合光催化剂加入到50 mL浓度为10-5 mol/L的罗丹明B水溶液中，避光搅拌60分钟，以达到吸附平衡，然后置于近红外光（500 W氙灯，带波长大于700 nm的滤波片）下照射，检测罗丹明B的吸光度并记录结果；通过紫外可见吸收谱测量罗丹明B溶液在552 nm的吸光度，来表征溶液中污染物浓度的变化，进而得出降解率； In order to study the photocatalytic performance of the prepared samples, an experiment was designed to simulate the degradation of rhodamine B under sunlight. The steps are as follows: add 0.05 g of the CQDs/Bi 2 MoO 6 composite photocatalyst obtained in Example 1 into 50 mL of rhodamine B aqueous solution with a concentration of 10 -5 mol/L, and stir for 60 minutes in the dark to achieve adsorption equilibrium. Then irradiate with near-infrared light (500 W xenon lamp, with a filter with a wavelength greater than 700 nm), detect the absorbance of rhodamine B and record the results; measure the absorbance of rhodamine B solution at 552 nm by UV-visible absorption spectrum, to Characterize the change of pollutant concentration in the solution, and then obtain the degradation rate;
图3为本实施例所得的CQDs/Bi2MoO6复合光催化剂在近红外光下降解罗丹明B的过程中，不同降解时间下所得的罗丹明B的吸光度随检测波长的变化情况。从图3可以看出，随着光照时间的延长，罗丹明B在552 nm处的吸光度逐渐下降，同时伴随着蓝移现象，这说明罗丹明B逐渐被CQDs/Bi2MoO6复合光催化剂降解。 Fig. 3 shows the variation of the absorbance of Rhodamine B obtained under different degradation times with the detection wavelength during the degradation of Rhodamine B by the CQDs/Bi 2 MoO 6 composite photocatalyst obtained in this example under near-infrared light. It can be seen from Figure 3 that the absorbance of Rhodamine B at 552 nm gradually decreases with the prolongation of the illumination time, accompanied by a blue shift phenomenon, which indicates that Rhodamine B is gradually degraded by the CQDs/Bi 2 MoO 6 composite photocatalyst .
图4为本实施例获得的CQDs/Bi2MoO6复合光催化材料与单纯Bi2MoO6纳米材料在近红外光下对罗丹明B降解率的对比曲线图。由图4可见：所获得的CQDs/Bi2MoO6复合光催化材料在10 h内对罗丹明B的降解率达到93.6%，而单纯Bi2MoO6在同样条件下不能将罗丹明B降解，说明CQDs/Bi2MoO6复合光催化材料具有显著的近红外光催化活性。 Fig. 4 is a comparison curve of the degradation rate of rhodamine B under near-infrared light between the CQDs/Bi 2 MoO 6 composite photocatalytic material obtained in this example and the pure Bi 2 MoO 6 nanomaterial. It can be seen from Figure 4 that the obtained CQDs/Bi 2 MoO 6 composite photocatalytic material can degrade 93.6% of Rhodamine B within 10 h, while pure Bi 2 MoO 6 cannot degrade Rhodamine B under the same conditions. It shows that the CQDs/Bi 2 MoO 6 composite photocatalytic material has remarkable near-infrared photocatalytic activity.
实施例Example 22
本实施例与实施例1的不同之处仅在于：CQDs和Bi2MoO6的质量比为1%： 99%，其余内容均与实施例1中所述完全相同。经检测分析得知：本实施例所获得的CQDs/Bi2MoO6复合光催化材料在与实施例1获得的复合材料相同条件下对罗丹明B 的降解率为80.7%。 The difference between this example and Example 1 is that the mass ratio of CQDs to Bi 2 MoO 6 is 1%:99%, and the rest of the content is exactly the same as that described in Example 1. According to the detection and analysis, the CQDs/Bi 2 MoO 6 composite photocatalytic material obtained in this example has a degradation rate of 80.7% for rhodamine B under the same conditions as the composite material obtained in Example 1.
实施例Example 33
本实施例与实施例1的不同之处仅在于：CQDs和Bi2MoO6的质量比为6%： 94%，其余内容均与实施例1中所述完全相同。经检测分析得知：本实施例所获得的CQDs/Bi2MoO6复合光催化材料在与实施例1获得的复合材料相同条件下对罗丹明B 的降解率为76.8%。 This example differs from Example 1 only in that the mass ratio of CQDs to Bi 2 MoO 6 is 6%:94%, and the rest of the content is exactly the same as that described in Example 1. According to the detection and analysis, the CQDs/Bi 2 MoO 6 composite photocatalytic material obtained in this example has a degradation rate of 76.8% for rhodamine B under the same conditions as the composite material obtained in Example 1.
实施例Example 44
本实施例与实施例1的不同之处仅在于：CQDs和Bi2MoO6的质量比为15%： 85%，其余内容均与实施例1中所述完全相同。经检测分析得知：本实施例所获得的CQDs/Bi2MoO6复合光催化材料在与实施例1获得的复合材料相同条件下对罗丹明B 的降解率为68.1%。 The difference between this example and Example 1 is that the mass ratio of CQDs to Bi 2 MoO 6 is 15%:85%, and the rest of the content is exactly the same as that described in Example 1. According to the detection and analysis, the CQDs/Bi 2 MoO 6 composite photocatalytic material obtained in this example has a degradation rate of 68.1% for rhodamine B under the same conditions as the composite material obtained in Example 1.
综上所述，本发明提供的一种CQDs/Bi2MoO6复合光催化剂，能够有效太阳光中的近红外部分，具有较高的载流子分离效率和光催化活性，可在近红外光的激发下实现有机污染物的降解，具有应用前景；且所述制备方法简单，可控性强，容易实现规模化生产。 In summary, a CQDs/Bi 2 MoO 6 composite photocatalyst provided by the present invention can be effective in the near-infrared part of sunlight, has high carrier separation efficiency and photocatalytic activity, and can be used in near-infrared light. The degradation of organic pollutants under excitation has application prospects; and the preparation method is simple, highly controllable, and easy to realize large-scale production.
以上所述仅是本发明的实施方式的举例，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。 The foregoing is only an example of the embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the technical principles of the present invention. Modifications should also be regarded as the scope of protection of the present invention.
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