CN104310490A - Schwertmannite-graphene oxide composite material and preparation method thereof - Google Patents
Schwertmannite-graphene oxide composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
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- 238000001291 vacuum drying Methods 0.000 claims description 5
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- 229910002804 graphite Inorganic materials 0.000 abstract description 12
- 239000010439 graphite Substances 0.000 abstract description 12
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 7
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Abstract
本发明公开了属于新型功能复合材料技术领域的一种施氏矿物-氧化石墨烯复合材料及其制备方法。该方法首先用浓硫酸和高锰酸钾氧化可膨胀石墨得到氧化石墨烯，然后将氧化石墨烯先后与FeCl3·6H2O和Na2SO4混合，通过化学方法合成施氏矿物-氧化石墨烯复合材料。该制备方法简单、易于操作，实验条件温和，占用空间小，所用原料价廉易得，且不存在二次污染；制得的复合材料比表面积较大，可阻止氧化石墨烯的团聚，保持复合材料中各组分的反应活性，并且易于分离回收，具有广阔的应用前景。
The invention discloses a Shi's mineral-graphene oxide composite material and a preparation method thereof, which belong to the technical field of new functional composite materials. The method first oxidizes expandable graphite with concentrated sulfuric acid and potassium permanganate to obtain graphene oxide, and then successively mixes graphene oxide with FeCl 3 6H 2 O and Na 2 SO 4 to synthesize Shi’s mineral-graphite oxide by chemical method vinyl composites. The preparation method is simple and easy to operate, with mild experimental conditions, small space occupation, cheap and easy-to-obtain raw materials, and no secondary pollution; the prepared composite material has a large specific surface area, which can prevent the agglomeration of graphene oxide and maintain composite The reactivity of each component in the material, and easy separation and recovery, have broad application prospects.
Description
技术领域technical field
本发明属于新型功能复合材料技术领域，具体涉及一种施氏矿物-氧化石墨烯复合材料及其制备方法。The invention belongs to the technical field of novel functional composite materials, and in particular relates to a Shi's mineral-graphene oxide composite material and a preparation method thereof.
背景技术Background technique
施氏矿物亦称施威特曼石(Schwertmannite)，其化学式为Fe8O8(OH)8-2x(SO4)x·nH2O(其中1≤x≤1.75)，是一种低晶质羟基硫酸高铁矿物，普遍存在于硫酸根含量丰富的酸性环境中，如酸性矿山废水与酸性硫酸盐土壤。由于具有纳米级的粒度和不规则的孔道结构，其比表面积大(100–200m2/g)、反应活性强，并且含有大量羟基、硫酸根等基团，因此可将其作为催化剂或吸附剂，从而达到变废为宝的目的。Schwertmannite, also known as Schwertmannite, has a chemical formula of Fe 8 O 8 (OH) 8-2x (SO 4 ) x nH 2 O (where 1≤x≤1.75) Hydroxysulfate high-iron minerals are commonly found in acidic environments rich in sulfate radicals, such as acid mine wastewater and acid sulfate soils. Due to its nanoscale particle size and irregular pore structure, it has a large specific surface area (100–200m 2 /g), strong reactivity, and contains a large number of hydroxyl groups, sulfate groups, etc., so it can be used as a catalyst or adsorbent , so as to achieve the purpose of turning waste into treasure.
石墨烯是一种由碳原子六元环的平面结构构成的新型二维碳纳米材料，其理论比表面积非常大(2630m2/g)；其表面存在大量的环氧基团、羟基、羧基等含氧基团，具有独特的纳米结构和优异的吸附反应性能。但是由于氧化石墨烯的表面能较高，易发生团聚，并且分散于水中后难以从水溶液中分离出来，因此有必要对其进行表面改性。石墨烯具有优异的物理化学性能，以其作为基体负载氧化物得到的复合材料近年来受到了广泛关注。若能制备一种复合材料，结合氧化石墨烯和施氏矿物的优点，既易于分离回收，又能避免氧化石墨烯的团聚，且工艺简单，可以大规模生产，这种复合材料将会具有极大的应用前景(如催化剂、污水处理、电池材料等领域)。Graphene is a new type of two-dimensional carbon nanomaterial composed of a planar structure of six-membered rings of carbon atoms. Its theoretical specific surface area is very large (2630m 2 /g); there are a large number of epoxy groups, hydroxyl groups, carboxyl groups, etc. on its surface. Oxygen-containing groups, with a unique nanostructure and excellent adsorption reaction performance. However, due to the high surface energy of graphene oxide, it is easy to agglomerate, and it is difficult to separate from the aqueous solution after being dispersed in water, so it is necessary to modify its surface. Graphene has excellent physical and chemical properties, and composite materials obtained by using it as a matrix to support oxides have received extensive attention in recent years. If a composite material can be prepared, combining the advantages of graphene oxide and Schwartz minerals, it is easy to separate and recycle, and can avoid the agglomeration of graphene oxide, and the process is simple, and it can be produced on a large scale. Large application prospects (such as catalysts, sewage treatment, battery materials, etc.).
发明内容Contents of the invention
本发明的目的在于提供一种施氏矿物-氧化石墨烯复合材料及其制备方法。The object of the present invention is to provide a Shi's mineral-graphene oxide composite material and a preparation method thereof.
一种施氏矿物-氧化石墨烯复合材料的制备方法，具体步骤如下：A preparation method of Shi's mineral-graphene oxide composite material, the specific steps are as follows:
将氧化石墨烯于去离子水中超声分散；加入FeCl3·6H2O搅拌；然后加入Na2SO4，在60-85℃水浴条件下保温；自然冷却至室温后离心，弃去上清液；采用pH 2.5的稀盐酸溶液作为清洗液，将沉淀离心洗涤；最后真空干燥即制得施氏矿物-氧化石墨烯复合材料。Ultrasonic disperse graphene oxide in deionized water; add FeCl 3 6H 2 O to stir; then add Na 2 SO 4 , keep warm in a water bath at 60-85°C; naturally cool to room temperature, centrifuge, and discard the supernatant; Dilute hydrochloric acid solution with a pH of 2.5 was used as a cleaning solution, and the precipitate was centrifugally washed; finally, vacuum-dried to obtain the Schwartz mineral-graphene oxide composite material.
其中，FeCl3·6H2O与氧化石墨烯的质量比为5:1-10:1，FeCl3·6H2O与Na2SO4的质量比为3:1-4:1。Wherein, the mass ratio of FeCl 3 ·6H 2 O to graphene oxide is 5:1-10:1, and the mass ratio of FeCl 3 ·6H 2 O to Na 2 SO 4 is 3:1-4:1.
所述搅拌的时间为1-3h。The stirring time is 1-3h.
所述保温的时间为12-60min。The time of the heat preservation is 12-60min.
所述离心条件为在10000-12000r/min下离心3-10min。The centrifugation condition is centrifugation at 10000-12000r/min for 3-10min.
所述氧化石墨烯可以用如下方法制备：首先将可膨胀石墨1–2g加入反应容器中，加入浓硫酸，浓硫酸与石墨的质量比为70:1–200:1，在冰水浴中搅拌10–30min；缓缓加入高锰酸钾，高锰酸钾与石墨的质量比为1.5:1–6:1，保持体系温度不超过15℃；反应完毕后撤出冰水浴，在温度34-36℃下恒温搅拌3天；然后分三次加入去离子水，第一次加入40mL，在59-61℃下搅拌30–60min，第二次加入40mL，在89-91℃下保持30–60min，第三次直接加入40mL去离子水；最后加入H2O2，所用H2O2为30wt％，H2O2与石墨的质量比为4.5:1–13.5:1。趁热在10000–12000r/min下离心30min，弃去上清液，用体积比为1:10的盐酸和蒸馏水离心洗涤，制得氧化石墨烯，冷冻干燥备用。The graphene oxide can be prepared as follows: first, 1-2g of expandable graphite is added to a reaction vessel, and concentrated sulfuric acid is added, the mass ratio of concentrated sulfuric acid to graphite is 70:1-200:1, and stirred in an ice-water bath for 10 –30min; slowly add potassium permanganate, the mass ratio of potassium permanganate to graphite is 1.5:1–6:1, and keep the system temperature not exceeding 15°C; Stir at constant temperature at ℃ for 3 days; then add deionized water three times, add 40mL for the first time, stir at 59-61℃ for 30-60min, add 40mL for the second time, keep at 89-91℃ for 30-60min, the second time Add 40 mL of deionized water three times directly; finally add H 2 O 2 , the amount of H 2 O 2 used is 30 wt%, and the mass ratio of H 2 O 2 to graphite is 4.5:1–13.5:1. Centrifuge at 10000-12000r/min for 30min while hot, discard the supernatant, wash with hydrochloric acid and distilled water with a volume ratio of 1:10 to prepare graphene oxide, and freeze-dry it for later use.
本发明的方法制备的施氏矿物-氧化石墨烯复合材料表面具有针状毛刺，长约50nm，宽度在10nm左右；其比表面积为196.26m2/g，孔径为3.87nm，孔体积为0.37cm3/g。The surface of the Shi's mineral-graphene oxide composite material prepared by the method of the present invention has needle-like burrs about 50nm in length and about 10nm in width; its specific surface area is 196.26m2 /g, the pore diameter is 3.87nm, and the pore volume is 0.37cm 3 /g.
本发明的有益效果主要体现在：施氏矿物-氧化石墨烯复合材料的制备方法简单，实验条件温和，对外界环境条件无特殊要求，占用空间小，所用原料价廉易得，且不存在二次污染；制得的复合材料比表面积较大，可阻止氧化石墨烯的团聚，保持复合材料中各组分的反应活性，并且易于分离回收，具有广阔的应用前景。The beneficial effects of the present invention are mainly reflected in: the preparation method of the Shi's mineral-graphene oxide composite material is simple, the experimental conditions are mild, there is no special requirement for the external environmental conditions, the occupied space is small, the raw materials used are cheap and easy to obtain, and there is no secondary secondary pollution; the prepared composite material has a large specific surface area, which can prevent the agglomeration of graphene oxide, maintain the reactivity of each component in the composite material, and is easy to separate and recycle, and has broad application prospects.
附图说明Description of drawings
图1施氏矿物-氧化石墨烯复合物的XRD表征谱图。Fig. 1 XRD characterization spectrum of the Shi's mineral-graphene oxide composite.
图2施氏矿物-氧化石墨烯复合物的HRTEM谱图：(a)标尺200nm；(b)标尺50nm；(c)标尺10nm；(d)选区电子衍射(SAED)图。Fig. 2 HRTEM spectrum of the Shi's mineral-graphene oxide composite: (a) scale bar 200nm; (b) scale bar 50nm; (c) scale bar 10nm; (d) selected area electron diffraction (SAED) pattern.
图3施氏矿物-氧化石墨烯复合物的EDX谱图及元素组成表。Fig. 3 EDX spectrum and elemental composition table of Shi's mineral-graphene oxide composite.
图4施氏矿物-氧化石墨烯复合物的吸附-脱附等温线(a)及孔径分布图(b)。Fig. 4 Adsorption-desorption isotherm (a) and pore size distribution diagram (b) of the Shi's mineral-graphene oxide composite.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步描述。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
首先制备氧化石墨烯(GO)，步骤如下：将106mL浓硫酸和1.0g可膨胀石墨加入反应容器中，在冰水浴中搅拌30min；缓缓加入5g高锰酸钾，保持体系温度不超过15℃；反应完毕后撤出冰水浴，在温度35±1℃下恒温搅拌3天；然后分三次加入去离子水，第一次加入40mL，在60±1℃下搅拌60min，第二次加入40mL，在90±1℃下保持30min，第三次直接加入40mL去离子水；最后加入10mL30wt％的H2O2，趁热在12000r/min下离心30min，弃去上清液，用体积比1:10的盐酸(质量分数36–38％)和蒸馏水离心洗涤数次，冷冻干燥备用。First prepare graphene oxide (GO), the steps are as follows: add 106mL of concentrated sulfuric acid and 1.0g of expandable graphite into the reaction vessel, stir in an ice-water bath for 30min; slowly add 5g of potassium permanganate, and keep the system temperature not exceeding 15°C After the reaction is completed, withdraw from the ice-water bath, and stir at a constant temperature of 35±1°C for 3 days; then add deionized water three times, add 40mL for the first time, stir at 60±1°C for 60min, add 40mL for the second time, Keep at 90±1°C for 30min, add 40mL of deionized water directly for the third time; finally add 10mL of 30wt% H 2 O 2 , centrifuge at 12000r/min for 30min while it is hot, discard the supernatant, and use a volume ratio of 1: 10% hydrochloric acid (mass fraction 36-38%) and distilled water, centrifuged and washed several times, and freeze-dried for later use.
然后制备施氏矿物-氧化石墨烯复合材料，步骤如下：将0.108g氧化石墨烯置于100mL去离子水中，超声分散3h，加入0.54g FeCl3·6H2O，搅拌1h；然后加入0.15g Na2SO4，在60℃水浴条件下保温12min；自然冷却至室温后，在10000–12000r/min下离心3min，弃去上清液；将沉淀离心洗涤，为控制施氏矿物的溶解和转化，采用pH 2.5的稀盐酸溶液作为清洗液；最后真空干燥即制得施氏矿物-氧化石墨烯复合材料。Then prepare Shi's mineral-graphene oxide composite material, the steps are as follows: put 0.108g graphene oxide in 100mL deionized water, ultrasonically disperse for 3h, add 0.54g FeCl 3 6H 2 O, stir for 1h; then add 0.15g Na 2 SO 4 , kept in a water bath at 60°C for 12 minutes; after naturally cooling to room temperature, centrifuged at 10,000–12,000 r/min for 3 minutes, discarded the supernatant; washed the precipitate by centrifugation, in order to control the dissolution and transformation of the Schwartz minerals, A dilute hydrochloric acid solution with a pH of 2.5 was used as a cleaning solution; finally, the Schwartz mineral-graphene oxide composite material was obtained by vacuum drying.
对所制得的施氏矿物-氧化石墨烯复合材料进行X射线衍射(XRD)分析，结果如图1a所示。从图中可以看出，以氧化石墨的特征衍射峰为主；在2θ为12°附近出现很强的衍射峰，对应于氧化石墨(001)面的衍射峰。施氏矿物的结晶度往往很低，因此复合物的XRD谱图中未出现很好的施氏矿物的衍射峰。X-ray diffraction (XRD) analysis was carried out on the prepared Shi's mineral-graphene oxide composite material, and the results are shown in Figure 1a. It can be seen from the figure that the characteristic diffraction peaks of graphite oxide are the main ones; a strong diffraction peak appears near 2θ of 12°, corresponding to the diffraction peak of graphite oxide (001) plane. The crystallinity of Shi's minerals is often very low, so no good diffraction peaks of Shi's minerals appear in the XRD spectrum of the composite.
实施例2Example 2
首先制备氧化石墨烯(GO)，步骤如下：将106mL浓硫酸和1.0g可膨胀石墨加入反应容器中，在冰水浴中搅拌30min；缓缓加入5g高锰酸钾，保持体系温度不超过15℃；反应完毕后撤出冰水浴，在温度35±1℃下恒温搅拌3天；然后分三次加入去离子水，第一次加入40mL，在60±1℃下搅拌60min，第二次加入40mL，在90±1℃下保持30min，第三次直接加入40mL去离子水；最后加入10mL30wt％的H2O2，趁热在12000r/min下离心30min，弃去上清液，用体积比1:10的盐酸(质量分数36–38％)和蒸馏水离心洗涤数次，冷冻干燥备用。First prepare graphene oxide (GO), the steps are as follows: add 106mL of concentrated sulfuric acid and 1.0g of expandable graphite into the reaction vessel, stir in an ice-water bath for 30min; slowly add 5g of potassium permanganate, and keep the system temperature not exceeding 15°C After the reaction is completed, withdraw from the ice-water bath, and stir at a constant temperature of 35±1°C for 3 days; then add deionized water three times, add 40mL for the first time, stir at 60±1°C for 60min, add 40mL for the second time, Keep at 90±1°C for 30min, add 40mL of deionized water directly for the third time; finally add 10mL of 30wt% H 2 O 2 , centrifuge at 12000r/min for 30min while it is hot, discard the supernatant, and use a volume ratio of 1: 10% hydrochloric acid (mass fraction 36–38%) and distilled water, centrifuged and washed several times, and freeze-dried for later use.
然后制备施氏矿物-氧化石墨烯复合材料，步骤如下：将0.054g氧化石墨烯置于100mL去离子水中，超声分散2h，加入0.54g FeCl3·6H2O，搅拌3h；然后加入0.15g Na2SO4，在85℃水浴条件下保温30min；自然冷却至室温后，在10000–12000r/min下离心10min，弃去上清液；将沉淀离心洗涤，为控制施氏矿物的溶解和转化，采用pH 2.5的稀盐酸溶液作为清洗液；最后真空干燥即制得施氏矿物-氧化石墨烯复合材料。Then prepare Shi's mineral-graphene oxide composite material, the steps are as follows: put 0.054g graphene oxide in 100mL deionized water, ultrasonically disperse for 2h, add 0.54g FeCl 3 6H 2 O, stir for 3h; then add 0.15g Na 2 SO 4 , kept at 85°C for 30 minutes in a water bath; after naturally cooling to room temperature, centrifuged at 10,000–12,000 r/min for 10 minutes, discarded the supernatant; washed the precipitate by centrifugation, in order to control the dissolution and transformation of Schwartz minerals, A dilute hydrochloric acid solution with a pH of 2.5 was used as a cleaning solution; finally, the Schwartz mineral-graphene oxide composite material was obtained by vacuum drying.
对所制得的施氏矿物-氧化石墨烯复合材料进行X射线衍射(XRD)分析，结果如图1b所示。从图中可以看出，FeCl3·6H2O与氧化石墨烯的质量比从5:1增加到10:1后，氧化石墨烯的特征衍射峰不明显；在2θ为35°附近出现衍射峰，对应于施氏矿物的衍射峰。施氏矿物的晶形较差，接近无定形状态。由图1a和1b对比可知，不同的反应条件得到的施氏矿物-氧化石墨烯复合材料有区别。X-ray diffraction (XRD) analysis was carried out on the prepared Shi's mineral-graphene oxide composite material, and the results are shown in Figure 1b. It can be seen from the figure that after the mass ratio of FeCl 3 6H 2 O to graphene oxide increases from 5:1 to 10:1, the characteristic diffraction peaks of graphene oxide are not obvious; the diffraction peak appears around 2θ of 35° , corresponding to the diffraction peaks of the Shi's mineral. The crystalline form of Shi's mineral is poor, close to the amorphous state. From the comparison of Figures 1a and 1b, it can be seen that the Shi's mineral-graphene oxide composites obtained under different reaction conditions are different.
实施例3Example 3
首先制备氧化石墨烯(GO)，步骤如下：将106mL浓硫酸和1.0g可膨胀石墨加入反应容器中，在冰水浴中搅拌20min；缓缓加入5g高锰酸钾，保持体系温度不超过15℃；反应完毕后撤出冰水浴，在温度35±1℃下恒温搅拌3天；然后分三次加入去离子水，第一次加入40mL，在60±1℃下搅拌60min，第二次加入40mL，在90±1℃下保持30min，第三次直接加入40mL去离子水；最后加入10mL30wt％的H2O2，趁热在12000r/min下离心30min，弃去上清液，用体积比1:10的盐酸(质量分数36–38％)和蒸馏水离心洗涤数次，冷冻干燥备用。First prepare graphene oxide (GO), the steps are as follows: add 106mL of concentrated sulfuric acid and 1.0g of expandable graphite into the reaction vessel, stir in an ice-water bath for 20min; slowly add 5g of potassium permanganate, and keep the system temperature not exceeding 15°C After the reaction is completed, withdraw from the ice-water bath, and stir at a constant temperature of 35±1°C for 3 days; then add deionized water three times, add 40mL for the first time, stir at 60±1°C for 60min, add 40mL for the second time, Keep at 90±1°C for 30min, add 40mL of deionized water directly for the third time; finally add 10mL of 30wt% H 2 O 2 , centrifuge at 12000r/min for 30min while it is hot, discard the supernatant, and use a volume ratio of 1: 10% hydrochloric acid (mass fraction 36-38%) and distilled water, centrifuged and washed several times, and freeze-dried for later use.
然后制备施氏矿物-氧化石墨烯复合材料，步骤如下：将0.054g氧化石墨烯置于100mL去离子水中，超声分散3h，加入0.54g FeCl3·6H2O，搅拌3h；然后加入0.15g Na2SO4，在60℃水浴条件下保温12min；自然冷却至室温后，在10000–12000r/min下离心3min，弃去上清液；将沉淀离心洗涤，为控制施氏矿物的溶解和转化，采用pH 2.5的稀盐酸溶液作为清洗液；最后真空干燥即制得施氏矿物-氧化石墨烯复合材料。Then prepare Shi's mineral-graphene oxide composite material, the steps are as follows: put 0.054g graphene oxide in 100mL deionized water, ultrasonically disperse for 3h, add 0.54g FeCl 3 6H 2 O, stir for 3h; then add 0.15g Na 2 SO 4 , kept in a water bath at 60°C for 12 minutes; after naturally cooling to room temperature, centrifuged at 10,000–12,000 r/min for 3 minutes, discarded the supernatant; washed the precipitate by centrifugation, in order to control the dissolution and transformation of the Schwartz minerals, A dilute hydrochloric acid solution with a pH of 2.5 was used as a cleaning solution; finally, the Schwartz mineral-graphene oxide composite material was obtained by vacuum drying.
对其进行高分辨率透射电镜(HRTEM)扫描分析，结果如图2所示。由图可知，合成的施氏矿物-氧化石墨烯复合物表面具有针状毛刺(图2a)，长约50nm(图2b)，宽度在10nm左右(图2c)。施氏矿物-氧化石墨烯复合物的选区电子衍射(SAED)图(图2d)呈圆环，其中圆环上有六个亮斑的为氧化石墨烯，另外两个圆环对应的是施氏矿物。It was analyzed by high-resolution transmission electron microscopy (HRTEM), and the results are shown in Figure 2. It can be seen from the figure that the surface of the synthesized Schwartz mineral-graphene oxide composite has needle-like burrs (Figure 2a), which are about 50nm long (Figure 2b) and about 10nm wide (Figure 2c). The selected area electron diffraction (SAED) pattern of Shi's mineral-graphene oxide composite (Fig. 2d) is a ring, in which there are six bright spots on the ring are graphene oxide, and the other two rings correspond to Shi's mineral.
对其进行高分辨率透射电镜扫描分析得到EDX谱图及元素组成表，结果如图3所示。施氏矿物-氧化石墨烯复合物的EDX谱图证实了复合物的组分，其中C、O、S和Fe的重量百分数分别为29.77％、15.40％、4.28％和49.93％。The EDX spectrum and elemental composition table were obtained by high-resolution transmission electron microscope scanning analysis, and the results are shown in Figure 3. The EDX spectrum of the Schwartz mineral-graphene oxide composite confirmed the composition of the composite, in which the weight percentages of C, O, S, and Fe were 29.77%, 15.40%, 4.28%, and 49.93%, respectively.
实施例4Example 4
首先制备氧化石墨烯(GO)，步骤如下：将106mL浓硫酸和1.0g可膨胀石墨加入反应容器中，在冰水浴中搅拌30min；缓缓加入5g高锰酸钾，保持体系温度不超过15℃；反应完毕后撤出冰水浴，在温度35±1℃下恒温搅拌3天；然后分三次加入去离子水，第一次加入40mL，在60±1℃下搅拌60min，第二次加入40mL，在90±1℃下保持30min，第三次直接加入40mL去离子水；最后加入10mL30wt％的H2O2，趁热在12000r/min下离心30min，弃去上清液，用体积比1:10的盐酸(质量分数36–38％)和蒸馏水离心洗涤数次，冷冻干燥备用。First prepare graphene oxide (GO), the steps are as follows: add 106mL of concentrated sulfuric acid and 1.0g of expandable graphite into the reaction vessel, stir in an ice-water bath for 30min; slowly add 5g of potassium permanganate, and keep the system temperature not exceeding 15°C After the reaction is completed, withdraw from the ice-water bath, and stir at a constant temperature of 35±1°C for 3 days; then add deionized water three times, add 40mL for the first time, stir at 60±1°C for 60min, add 40mL for the second time, Keep at 90±1°C for 30min, add 40mL of deionized water directly for the third time; finally add 10mL of 30wt% H 2 O 2 , centrifuge at 12000r/min for 30min while it is hot, discard the supernatant, and use a volume ratio of 1: 10% hydrochloric acid (mass fraction 36-38%) and distilled water, centrifuged and washed several times, and freeze-dried for later use.
然后制备施氏矿物-氧化石墨烯复合材料，步骤如下：将0.054g氧化石墨烯置于100mL去离子水中，超声分散3h，加入0.54g FeCl3·6H2O，搅拌3h；然后加入0.18g Na2SO4，在60℃水浴条件下保温12min；自然冷却至室温后，在10000–12000r/min下离心5min，弃去上清液；将沉淀离心洗涤，为控制施氏矿物的溶解和转化，采用pH 2.5的稀盐酸溶液作为清洗液；最后真空干燥即制得施氏矿物-氧化石墨烯复合材料。Then prepare Shi's mineral-graphene oxide composite material, the steps are as follows: put 0.054g graphene oxide in 100mL deionized water, ultrasonically disperse for 3h, add 0.54g FeCl 3 6H 2 O, stir for 3h; then add 0.18g Na 2 SO 4 , keep warm in a water bath at 60°C for 12 minutes; after naturally cooling to room temperature, centrifuge at 10,000–12,000 r/min for 5 minutes, discard the supernatant; wash the precipitate by centrifugation, in order to control the dissolution and transformation of Schwartz minerals, A dilute hydrochloric acid solution with a pH of 2.5 was used as a cleaning solution; finally, the Schwartz mineral-graphene oxide composite material was obtained by vacuum drying.
由施氏矿物-氧化石墨烯复合物的吸附-脱附等温线图(图4a)可知，根据BDDT分类法(the Brunauer–Deming–Deming–Teller classification)，施氏矿物-氧化石墨烯复合物呈现V型H2型滞后环吸脱附等温曲线，说明该复合物具有典型的介孔特征。采用BJH脱附技术得到的孔径分布图(图4b)表明施氏矿物-氧化石墨烯复合物孔径分布主要集中在3.87nm左右，也说明了该复合物为介孔结构。施氏矿物-氧化石墨烯复合物的比表面积、孔径和孔体积分别为196.26m2/g、3.87nm和0.37cm3/g。According to the adsorption-desorption isotherm diagram (Fig. 4a) of the Schwartz mineral-graphene oxide composite, according to the BDDT classification method (the Brunauer–Deming–Deming–Teller classification), the Schwartz mineral-graphene oxide composite presents The V-type H2-type hysteresis ring adsorption-desorption isotherms indicate that the composite has typical mesoporous characteristics. The pore size distribution diagram (Fig. 4b) obtained by using the BJH desorption technique shows that the pore size distribution of the Shi's mineral-graphene oxide composite is mainly concentrated around 3.87nm, which also shows that the composite is a mesoporous structure. The specific surface area, pore diameter and pore volume of the Shi's mineral-graphene oxide composite are 196.26m 2 /g, 3.87nm and 0.37cm 3 /g, respectively.
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