CN105268440A - Graphene loaded cobaltous oxide catalyst and preparation method thereof - Google Patents
Graphene loaded cobaltous oxide catalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 title 1
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000012153 distilled water Substances 0.000 claims description 26
- 230000003197 catalytic effect Effects 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
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Abstract
本发明涉及一种石墨烯负载氧化钴催化剂及其制备方法；所述制备方法为，首先制备乙酸钴水溶液和氧化石墨烯水溶液，混合后，磁力搅拌，得混合溶液A；在混合溶液A中逐滴加入氨水，磁力搅拌，得到混合溶液B；所得混合溶液B装入有聚四氟乙烯内衬的高压反应釜中，在160-190℃下水热反应10-14h，得到混合物；将所得的混合物转速离心分离后，去除上层清液，剩余固体物质进行洗涤后，转移到烘箱中，60℃干燥8h，即制备出石墨烯负载氧化钴催化剂。所制备的催化剂可应用于催化一氧化碳低温氧化中，在100℃即可将一氧化碳完全氧化为二氧化碳，在100℃下可至少维持一氧化碳完全转化为二氧化碳3000分钟。
The invention relates to a graphene-supported cobalt oxide catalyst and a preparation method thereof; the preparation method is as follows: firstly prepare an aqueous solution of cobalt acetate and an aqueous solution of graphene oxide, and after mixing, stir magnetically to obtain a mixed solution A; Ammonia water was added dropwise and magnetically stirred to obtain a mixed solution B; the obtained mixed solution B was placed in a polytetrafluoroethylene-lined autoclave, and hydrothermally reacted at 160-190°C for 10-14 hours to obtain a mixture; the obtained mixture After centrifugal separation at a rotational speed, the supernatant was removed, and the remaining solid matter was washed, then transferred to an oven, and dried at 60° C. for 8 hours to prepare a graphene-supported cobalt oxide catalyst. The prepared catalyst can be applied to low-temperature oxidation of carbon monoxide, can completely oxidize carbon monoxide to carbon dioxide at 100°C, and can maintain complete conversion of carbon monoxide to carbon dioxide for at least 3000 minutes at 100°C.
Description
技术领域 technical field
本发明涉及一种催化剂，具体的说是一种石墨烯负载氧化钴催化剂及其制备方法。 The invention relates to a catalyst, in particular to a graphene-supported cobalt oxide catalyst and a preparation method thereof.
背景技术 Background technique
一氧化碳是大气中的一种主要污染物，主要来自汽车尾气和工业生产过程。人体吸入之后可损害中枢神经系统，对人类的健康造成极大的危害。一氧化碳的催化氧化脱除是有效控制其排放的途径。在催化一氧化碳氧化的催化剂中贵金属的催化活性较高，但贵金属价格昂贵、在自然界中含量较少且一般避免不了硫中毒等缺陷，限制了其工业中的广泛应用。所以开发用非贵金属全部代替或者部分代替贵金属的催化剂是一项非常有意义的工作。 Carbon monoxide is a major pollutant in the atmosphere, mainly from automobile exhaust and industrial production processes. After inhalation, it can damage the central nervous system and cause great harm to human health. The catalytic oxidation removal of carbon monoxide is an effective way to control its emission. Among the catalysts that catalyze the oxidation of carbon monoxide, noble metals have high catalytic activity, but noble metals are expensive, less abundant in nature, and generally cannot avoid defects such as sulfur poisoning, which limits their wide application in industry. Therefore, it is very meaningful to develop catalysts that replace all or part of noble metals with non-noble metals.
石墨烯是单原子厚度的二维晶体，被认为是富勒烯、碳纳米管和石墨的基本结构单元。石墨烯具有高比表面积、突出的导热性能和力学性能、非凡的电子传输性能等一系列优异的性质，使得其作为催化剂载体的研究引起了科技工作者的广泛关注，石墨烯基复合材料在光降解、电容器等方面具有优异的性能。很多研究表明，过渡金属钴具有类似甚至高于贵金属的催化一氧化碳低温氧化性能，但是单纯组分的钴物种容易失活。 Graphene is a one-atom-thick two-dimensional crystal and is considered the basic building block of fullerenes, carbon nanotubes, and graphite. Graphene has a series of excellent properties such as high specific surface area, outstanding thermal conductivity and mechanical properties, extraordinary electron transport properties, etc., making its research as a catalyst carrier has attracted widespread attention of scientific and technological workers. It has excellent performance in degradation, capacitor and so on. Many studies have shown that the transition metal cobalt has similar or even higher catalytic performance for the low-temperature oxidation of carbon monoxide than noble metals, but the pure cobalt species are easily deactivated.
发明内容 Contents of the invention
本发明目的是为解决上述技术问题的不足，提供一种石墨烯负载氧化钴催化剂及其制备方法，所采用的制备方法操作简单所制备的石墨烯负载氧化钴催化剂中氧化钴颗粒在石墨烯表面分散均匀、粒径大小均一，该催化剂为孔径3.1-5.8纳米的介孔材料，比表面积高达210cm3/g；可用于催化一氧化碳的低温氧化。 The purpose of the present invention is to solve the deficiencies of the above-mentioned technical problems, to provide a graphene-supported cobalt oxide catalyst and a preparation method thereof, the preparation method adopted is simple to operate Uniform dispersion and uniform particle size, the catalyst is a mesoporous material with a pore diameter of 3.1-5.8 nanometers, and a specific surface area as high as 210cm 3 /g; it can be used to catalyze the low-temperature oxidation of carbon monoxide.
一种石墨烯负载氧化钴催化剂的制备方法，包括以下步骤： A preparation method of graphene supported cobalt oxide catalyst, comprising the following steps:
步骤一、常温下，按照质量比为1：20-21的比例，取乙酸钴和蒸馏水；将所取乙酸钴加入到蒸馏水中，磁力搅拌使其完全溶解，制得乙酸钴水溶液，备用； Step 1. At room temperature, take cobalt acetate and distilled water according to the mass ratio of 1:20-21; add the taken cobalt acetate into the distilled water, and magnetically stir to make it completely dissolve, so as to prepare an aqueous solution of cobalt acetate, which is set aside;
步骤二、按照质量分数为1.12%的氧化石墨烯水溶液中石墨烯与上述步骤一中所制备的氧化钴的质量比为1:4-2:3的比例，取质量分数为1.12%的氧化石墨烯水溶液；将所取氧化石墨烯水溶液加入到上述步骤一中所取蒸馏水3.7-4.6体积的蒸馏水中，置于功率168W的超声波反应器中超声60-120分钟，制得稀释后的氧化石墨烯水溶液，备用； Step 2, according to the mass fraction of 1.12% graphene oxide aqueous solution, the mass ratio of graphene and the cobalt oxide prepared in the above step 1 is a ratio of 1:4-2:3, and the mass fraction is 1.12% graphite oxide Aqueous solution of graphene oxide; the obtained graphene oxide aqueous solution is added to the distilled water of 3.7-4.6 volumes of distilled water obtained in the above step 1, and placed in an ultrasonic reactor with a power of 168W for 60-120 minutes to obtain diluted graphene oxide aqueous solution, spare;
步骤三、将所制备的乙酸钴水溶液和稀释后氧化石墨烯水溶液进行混合，磁力搅拌20-25分钟，得到混合溶液A；在所得混合溶液A中逐滴加入其体积0.09-0.11倍的质量分数为28%的氨水，磁力搅拌115-120分钟，得到混合溶液B，备用； Step 3. Mix the prepared cobalt acetate aqueous solution and the diluted graphene oxide aqueous solution, and magnetically stir for 20-25 minutes to obtain a mixed solution A; add dropwise a mass fraction of 0.09-0.11 times its volume to the obtained mixed solution A 28% ammonia water, magnetically stirred for 115-120 minutes to obtain mixed solution B, set aside;
步骤四、将步骤三所得混合溶液B装入有聚四氟乙烯内衬的高压反应釜中，混合溶液B占反应釜容积的60%-70%，在160-190℃下水热反应10-14h，反应结束后自然冷却至室温，得到混合物； Step 4. Put the mixed solution B obtained in step 3 into a high-pressure reactor lined with polytetrafluoroethylene. The mixed solution B accounts for 60%-70% of the reactor volume, and react hydrothermally at 160-190°C for 10-14h , naturally cooled to room temperature after the reaction to obtain a mixture;
步骤五、将步骤四反应后所得的混合物以3500r/min的转速离心分离5-10分钟后，去除上层清液，剩余固体物质先采用蒸馏水洗涤3-5次，再用乙醇洗涤1次，转移到烘箱中，60℃干燥8h，不需煅烧，即制备出石墨烯负载氧化钴催化剂。 Step 5. Centrifuge the mixture obtained after the reaction in Step 4 for 5-10 minutes at a speed of 3500r/min, remove the supernatant, and wash the remaining solid matter with distilled water for 3-5 times, then wash with ethanol for 1 time, transfer In an oven, dry at 60°C for 8 hours, without calcination, the graphene-supported cobalt oxide catalyst is prepared.
所制备的石墨烯负载氧化钴催化剂中石墨烯与氧化钴质量比为1:4-2:3，优选为3:7；该石墨烯负载氧化钴催化剂为孔径3.1-5.8纳米的介孔材料，比表面积为210cm3/g。该催化剂在可应用于催化一氧化碳低温氧化中，在100℃即可将一氧化碳完全氧化为二氧化碳，并具有较高的催化一氧化碳氧化的稳定性，在100℃下可至少维持一氧化碳完全转化为二氧化碳3000分钟。 The mass ratio of graphene and cobalt oxide in the prepared graphene-supported cobalt oxide catalyst is 1:4-2:3, preferably 3:7; the graphene-supported cobalt oxide catalyst is a mesoporous material with a pore diameter of 3.1-5.8 nanometers, The specific surface area was 210 cm 3 /g. The catalyst can be applied to catalyze the low-temperature oxidation of carbon monoxide. It can completely oxidize carbon monoxide to carbon dioxide at 100°C, and has high stability in catalytic carbon monoxide oxidation. At 100°C, it can maintain the complete conversion of carbon monoxide into carbon dioxide for at least 3000 minutes. .
有益效果是： The beneficial effects are:
1、本发明提供了一种石墨烯负载氧化钴催化剂的制备方法，该方法具有操作简单、条件温和易控、成本低廉、不需高温煅烧的特点。利用石墨烯特殊的结构和优异的电子传输性能，结合氧化钴的高催化一氧化碳低温氧化活性，采用简单的方法制备出催化一氧化碳低温氧化性能优异、稳定性高的纳米石墨烯负载氧化钴催化剂。 1. The present invention provides a method for preparing a graphene-supported cobalt oxide catalyst. The method has the characteristics of simple operation, mild conditions, easy control, low cost, and no need for high-temperature calcination. Using the special structure and excellent electron transport performance of graphene, combined with the high catalytic activity of cobalt oxide for low-temperature oxidation of carbon monoxide, a nanographene-supported cobalt oxide catalyst with excellent catalytic performance and high stability for low-temperature oxidation of carbon monoxide was prepared by a simple method.
2、本发明所制备的催化剂中氧化钴颗粒在二维片层石墨烯表面均匀分散，粒径大小均一，且该催化剂为孔径3.1-5.8纳米的介孔材料，比表面积高达210cm3/g，在催化一氧化碳低温氧化方面具有高活性，100℃即可将一氧化碳完全氧化，且具有较高的稳定性，100℃的反应温度下保持一氧化碳完全转化为二氧化碳3000分钟以上。 2. In the catalyst prepared by the present invention, the cobalt oxide particles are uniformly dispersed on the surface of the two-dimensional sheet graphene, and the particle size is uniform, and the catalyst is a mesoporous material with a pore diameter of 3.1-5.8 nanometers, and the specific surface area is as high as 210cm 3 /g, It has high activity in catalyzing low-temperature oxidation of carbon monoxide. Carbon monoxide can be completely oxidized at 100°C, and it has high stability. At a reaction temperature of 100°C, carbon monoxide can be completely converted into carbon dioxide for more than 3000 minutes.
附图说明 Description of drawings
图1、本发明所制备的不同石墨烯与氧化钴质量比的石墨烯负载氧化钴催化剂的X-射线衍射图谱； Fig. 1, the X-ray diffraction spectrum of the graphene supported cobalt oxide catalyst of the prepared different graphene of the present invention and cobalt oxide mass ratio;
图2、实施例2所制备石墨烯负载氧化钴催化剂的透射电镜照片和选区电子衍射照片； The transmission electron microscope photo and the selected area electron diffraction photo of the graphene supported cobalt oxide catalyst prepared by Fig. 2, embodiment 2;
图3、实施例2和实施例3所制备石墨烯负载氧化钴催化剂的氮气吸附脱附等温线； The nitrogen adsorption-desorption isotherm of graphene supported cobalt oxide catalyst prepared by Fig. 3, embodiment 2 and embodiment 3;
图4、实施例2和实施例3所制备石墨烯负载氧化钴催化剂的孔径分布曲线； The pore size distribution curve of the prepared graphene supported cobalt oxide catalyst of Fig. 4, embodiment 2 and embodiment 3;
图5、石墨烯和不同石墨烯含量的催化剂催化一氧化碳低温氧化性能曲线； Figure 5. Graphene and catalysts with different graphene content catalytic low-temperature oxidation performance curves of carbon monoxide;
图6、实施例2所制备石墨烯负载氧化钴催化剂催化一氧化碳低温氧化稳定性曲线。 Fig. 6, the graphene-supported cobalt oxide catalyst prepared in Example 2 catalyzes the low-temperature oxidation stability curve of carbon monoxide.
具体实施方式 detailed description
一种石墨烯负载氧化钴催化剂及其制备方法，所采用的制备方法操作简单，所制备的石墨烯负载氧化钴催化剂中氧化钴颗粒在石墨烯表面分散均匀、粒径大小均一，该催化剂为孔径3.1-5.8纳米的介孔材料，比表面积高达210cm3/g；可用于催化一氧化碳的低温氧化。 A graphene-supported cobalt oxide catalyst and a preparation method thereof, the preparation method adopted is simple to operate, cobalt oxide particles in the prepared graphene-supported cobalt oxide catalyst are uniformly dispersed on the surface of graphene, and the particle size is uniform. 3.1-5.8 nanometer mesoporous material with a specific surface area up to 210cm 3 /g; it can be used to catalyze the low-temperature oxidation of carbon monoxide.
一种石墨烯负载氧化钴催化剂的制备方法，包括以下步骤： A preparation method of graphene supported cobalt oxide catalyst, comprising the following steps:
步骤一、常温下，按照质量比为1：20-21的比例，取乙酸钴和蒸馏水；将所取乙酸钴加入到蒸馏水中，磁力搅拌使其完全溶解，制得乙酸钴水溶液，备用； Step 1. At room temperature, take cobalt acetate and distilled water according to the mass ratio of 1:20-21; add the taken cobalt acetate into the distilled water, and magnetically stir to make it completely dissolve, so as to prepare an aqueous solution of cobalt acetate, which is set aside;
步骤二、按照质量分数为1.12%的氧化石墨烯水溶液中石墨烯与上述步骤一中所制备的氧化钴的质量比为1:4-2:3的比例，取质量分数为1.12%的氧化石墨烯水溶液；将所取氧化石墨烯水溶液加入到上述步骤一中所取蒸馏水3.7-4.6体积的蒸馏水中，置于功率168W的超声波反应器中超声60-120分钟，制得稀释后的氧化石墨烯水溶液，备用； Step 2, according to the mass fraction of 1.12% graphene oxide aqueous solution, the mass ratio of graphene and the cobalt oxide prepared in the above step 1 is a ratio of 1:4-2:3, and the mass fraction is 1.12% graphite oxide Aqueous solution of graphene oxide; the obtained graphene oxide aqueous solution is added to the distilled water of 3.7-4.6 volumes of distilled water obtained in the above step 1, and placed in an ultrasonic reactor with a power of 168W for 60-120 minutes to obtain diluted graphene oxide aqueous solution, spare;
步骤三、将所制备的乙酸钴水溶液和稀释后氧化石墨烯水溶液进行混合，磁力搅拌20-25分钟，得到混合溶液A；在所得混合溶液A中逐滴加入其体积0.09-0.11倍的质量分数为28%的氨水，磁力搅拌115-120分钟，得到混合溶液B，备用； Step 3. Mix the prepared cobalt acetate aqueous solution and the diluted graphene oxide aqueous solution, and magnetically stir for 20-25 minutes to obtain a mixed solution A; add dropwise a mass fraction of 0.09-0.11 times its volume to the obtained mixed solution A 28% ammonia water, magnetically stirred for 115-120 minutes to obtain mixed solution B, set aside;
步骤四、将步骤三所得混合溶液B装入有聚四氟乙烯内衬的高压反应釜中，混合溶液B占反应釜容积的60%-70%，在160-190℃下水热反应10-14h，反应结束后自然冷却至室温，得到混合物； Step 4. Put the mixed solution B obtained in step 3 into a high-pressure reactor lined with polytetrafluoroethylene. The mixed solution B accounts for 60%-70% of the reactor volume, and react hydrothermally at 160-190°C for 10-14h , naturally cooled to room temperature after the reaction to obtain a mixture;
步骤五、将步骤四反应后所得的混合物以3500r/min的转速离心分离5-10分钟后，去除上层清液，剩余固体物质先采用蒸馏水洗涤3-5次，再用乙醇洗涤1次，转移到烘箱中，60℃干燥8h，不需煅烧，即制备出石墨烯负载氧化钴催化剂。 Step 5. Centrifuge the mixture obtained after the reaction in Step 4 for 5-10 minutes at a speed of 3500r/min, remove the supernatant, and wash the remaining solid matter with distilled water for 3-5 times, then wash with ethanol for 1 time, transfer In an oven, dry at 60°C for 8 hours, without calcination, the graphene-supported cobalt oxide catalyst is prepared.
所制备的石墨烯负载氧化钴催化剂中石墨烯与氧化钴质量比为1:4-2:3，优选为3:7；该石墨烯负载氧化钴催化剂为孔径3.1-5.8纳米的介孔材料，比表面积为210cm3/g。该催化剂在可应用于催化一氧化碳低温氧化中，在100℃即可将一氧化碳完全氧化为二氧化碳，并具有较高的催化一氧化碳氧化的稳定性，在100℃下可至少维持一氧化碳完全转化为二氧化碳3000分钟。 The mass ratio of graphene and cobalt oxide in the prepared graphene-supported cobalt oxide catalyst is 1:4-2:3, preferably 3:7; the graphene-supported cobalt oxide catalyst is a mesoporous material with a pore diameter of 3.1-5.8 nanometers, The specific surface area was 210 cm 3 /g. The catalyst can be applied to catalyze the low-temperature oxidation of carbon monoxide. It can completely oxidize carbon monoxide to carbon dioxide at 100°C, and has high stability in catalytic carbon monoxide oxidation. At 100°C, it can maintain the complete conversion of carbon monoxide into carbon dioxide for at least 3000 minutes. .
实施例1Example 1
常温下，取2.49克乙酸钴溶于50毫升蒸馏水中，磁力搅拌使其完全溶解，制得乙酸钴水溶液Ⅰ，备用。按照催化剂中石墨烯与氧化钴的质量比为1:4的比例取氧化石墨烯水溶液，加入230毫升蒸馏水，超声20分钟，制得氧化石墨烯水溶液Ⅱ，备用；其中，所述的氧化石墨烯是利用改进的Hummers方法制备氧化石墨，然后经过超声处理60分钟，制得质量百分含量为1.12%的氧化石墨烯水溶液。将溶液Ⅰ和溶液Ⅱ混合，磁力搅拌20分钟，逐滴加入26毫升质量百分含量为28%的氨水，磁力搅拌120分钟。将混合溶液装入有聚四氟乙烯内衬的高压反应釜中，180℃下水热反应12小时，自然冷却至室温；将所得混合物以3500r/min的转速离心分离5-10分钟，去除上层清液，将剩余固体物质蒸馏水洗涤3-5次，乙醇洗涤1次，将沉淀转移到烘箱中，60℃干燥8h。获得石墨烯与氧化钴质量比为1:4的石墨烯负载氧化钴催化剂。 At room temperature, 2.49 g of cobalt acetate was dissolved in 50 ml of distilled water, and magnetically stirred to completely dissolve it to obtain cobalt acetate aqueous solution I, which was set aside. Take graphene oxide aqueous solution according to the mass ratio of graphene and cobalt oxide in the catalyst being 1:4, add 230 milliliters of distilled water, ultrasonic 20 minutes, obtain graphene oxide aqueous solution II, set aside; Wherein, described graphene oxide Graphite oxide was prepared by an improved Hummers method, and then ultrasonically treated for 60 minutes to obtain an aqueous solution of graphene oxide with a mass percentage of 1.12%. Mix solution I and solution II, stir magnetically for 20 minutes, add 26 ml of ammonia water with a mass percentage of 28% dropwise, and stir magnetically for 120 minutes. Put the mixed solution into a polytetrafluoroethylene-lined autoclave, conduct a hydrothermal reaction at 180°C for 12 hours, and cool to room temperature naturally; centrifuge the resulting mixture at a speed of 3500r/min for 5-10 minutes, remove the supernatant liquid, the remaining solid matter was washed 3-5 times with distilled water and once with ethanol, and the precipitate was transferred to an oven and dried at 60°C for 8 hours. A graphene-supported cobalt oxide catalyst having a mass ratio of graphene to cobalt oxide of 1:4 was obtained.
所述改进的Hummers方法制备氧化石墨的方法为：取66毫升浓硫酸加入到500毫升的三颈烧瓶中，缓慢加入1.5克石墨、1.5克硝酸钠，控制温度4℃以下反应90分钟；升温至35℃反应30分钟；逐滴加入蒸馏水132毫升，控制温度70℃反应15分钟；逐滴加入双氧水至溶液变为亮黄色，离心分离、盐酸洗涤、蒸馏水洗涤。 The method for preparing graphite oxide by the improved Hummers method is: get 66 milliliters of concentrated sulfuric acid and join in a 500 milliliter three-necked flask, slowly add 1.5 grams of graphite, 1.5 grams of sodium nitrate, and control the temperature below 4° C. for 90 minutes; React at 35°C for 30 minutes; add 132 ml of distilled water dropwise, and react at a controlled temperature of 70°C for 15 minutes; add hydrogen peroxide dropwise until the solution turns bright yellow, centrifuge, wash with hydrochloric acid, and wash with distilled water.
实施例2Example 2
常温下，取2.49克乙酸钴溶于50毫升蒸馏水中，磁力搅拌使其完全溶解，制得乙酸钴水溶液Ⅰ，备用。按照催化剂中石墨烯与氧化钴的质量比为3:7的比例取氧化石墨烯水溶液，加入215毫升蒸馏水，超声20分钟，制得氧化石墨烯水溶液Ⅱ，备用；其中，所述的氧化石墨烯是利用改进的Hummers方法制备氧化石墨，然后经过超声处理60分钟，制得质量百分含量为1.12%的氧化石墨烯水溶液。将溶液Ⅰ和溶液Ⅱ混合，磁力搅拌20分钟，逐滴加入26毫升质量百分含量为28%的氨水，磁力搅拌120分钟。将混合溶液装入有聚四氟乙烯内衬的高压反应釜中，180℃下水热反应12小时，自然冷却至室温；将所得混合物以3500r/min的转速离心分离5-10分钟，去除上层清液，将剩余固体物质蒸馏水洗涤3-5次，乙醇洗涤1次，将沉淀转移到烘箱中，60℃干燥8h。获得石墨烯与氧化钴质量比为3:7的石墨烯负载氧化钴催化剂。 At room temperature, 2.49 g of cobalt acetate was dissolved in 50 ml of distilled water, and magnetically stirred to completely dissolve it to obtain cobalt acetate aqueous solution I, which was set aside. Take graphene oxide aqueous solution according to the mass ratio of graphene and cobalt oxide in the catalyst being 3:7, add 215 milliliters of distilled water, ultrasonic 20 minutes, obtain graphene oxide aqueous solution II, standby; Wherein, described graphene oxide Graphite oxide was prepared by an improved Hummers method, and then ultrasonically treated for 60 minutes to obtain an aqueous solution of graphene oxide with a mass percentage of 1.12%. Mix solution I and solution II, stir magnetically for 20 minutes, add 26 ml of ammonia water with a mass percentage of 28% dropwise, and stir magnetically for 120 minutes. Put the mixed solution into a polytetrafluoroethylene-lined autoclave, conduct a hydrothermal reaction at 180°C for 12 hours, and cool to room temperature naturally; centrifuge the resulting mixture at a speed of 3500r/min for 5-10 minutes, remove the supernatant liquid, the remaining solid matter was washed 3-5 times with distilled water and once with ethanol, and the precipitate was transferred to an oven and dried at 60°C for 8 hours. The graphene-supported cobalt oxide catalyst whose mass ratio of graphene and cobalt oxide is 3:7 is obtained.
实施例3Example 3
常温下，取2.49克乙酸钴溶于50毫升蒸馏水中，磁力搅拌使其完全溶解，制得乙酸钴水溶液Ⅰ，备用。按照催化剂中石墨烯与氧化钴的质量比为2:3的比例取氧化石墨烯水溶液，加入186毫升蒸馏水，超声20分钟，制得氧化石墨烯水溶液Ⅱ，备用；其中，所述的氧化石墨烯是利用改进的Hummers方法制备氧化石墨，然后经过超声处理60分钟，制得质量百分含量为1.12%的氧化石墨烯水溶液。将溶液Ⅰ和溶液Ⅱ混合，磁力搅拌20分钟，逐滴加入26毫升质量百分含量为28%的氨水，磁力搅拌120分钟。将混合溶液装入有聚四氟乙烯内衬的高压反应釜中，180℃下水热反应12小时，自然冷却至室温；将所得混合物以3500r/min的转速离心分离5-10分钟，去除上层清液，将剩余固体物质蒸馏水洗涤3-5次，乙醇洗涤1次，将沉淀转移到烘箱中，60℃干燥8h。获得石墨烯与氧化钴质量比为2:3的石墨烯负载氧化钴催化剂。 At room temperature, 2.49 g of cobalt acetate was dissolved in 50 ml of distilled water, and magnetically stirred to completely dissolve it to obtain cobalt acetate aqueous solution I, which was set aside. According to the ratio of the mass ratio of graphene and cobalt oxide in the catalyst to 2:3, take the graphene oxide aqueous solution, add 186 milliliters of distilled water, and ultrasonicate for 20 minutes to obtain the graphene oxide aqueous solution II, which is set aside; wherein, the graphene oxide Graphite oxide was prepared by an improved Hummers method, and then ultrasonically treated for 60 minutes to obtain an aqueous solution of graphene oxide with a mass percentage of 1.12%. Mix solution I and solution II, stir magnetically for 20 minutes, add 26 ml of ammonia water with a mass percentage of 28% dropwise, and stir magnetically for 120 minutes. Put the mixed solution into a polytetrafluoroethylene-lined autoclave, conduct a hydrothermal reaction at 180°C for 12 hours, and cool to room temperature naturally; centrifuge the resulting mixture at a speed of 3500r/min for 5-10 minutes, remove the supernatant liquid, the remaining solid matter was washed 3-5 times with distilled water and once with ethanol, and the precipitate was transferred to an oven and dried at 60°C for 8 hours. The graphene-supported cobalt oxide catalyst whose mass ratio of graphene and cobalt oxide is 2:3 is obtained.
检测实验：Detection experiment:
1、取实施例1、实施例2和实施例3所制备的石墨烯负载氧化钴催化剂进行X-射线粉末衍射（XRD）检测，结果如图1所示，表明制备出的氧化石墨烯被成功还原，催化剂中所有衍射峰均与Co3O4的特征衍射峰相对应，说明成功制备了石墨烯负载氧化钴催化剂。 1. Take the graphene-supported cobalt oxide catalyst prepared in Example 1, Example 2 and Example 3 for X-ray powder diffraction (XRD) detection, the results are shown in Figure 1, indicating that the prepared graphene oxide was successfully Reduction, all the diffraction peaks in the catalyst correspond to the characteristic diffraction peaks of Co 3 O 4 , indicating that the graphene-supported cobalt oxide catalyst was successfully prepared.
2、取实施例2所制备的石墨烯负载氧化钴催化剂进行透射电镜特征，结果如图2所示，表明通过该方法所制备的石墨烯负载氧化钴催化剂中Co3O4纳米粒子粒径均一、在石墨烯表面分布均匀；选取电子衍射再次证明石墨烯上负载的是Co3O4纳米粒子。 2, get the graphene-supported cobalt oxide catalyst prepared by embodiment 2 to carry out transmission electron microscope characteristics, the result as shown in Figure 2, shows that Co in the graphene-supported cobalt oxide catalyst prepared by this method O The particle size of the nanoparticle is uniform , evenly distributed on the surface of graphene; selected electron diffraction proves again that Co 3 O 4 nanoparticles are supported on graphene.
3、实施例2和实施例3所制备的石墨烯负载氧化钴催化剂的氮气吸附脱附等温线如图3所示，孔分布曲线如图4所示。图3表明，所制备石墨烯负载氧化钴催化剂的等温线属于IV型等温线，表明样品具有典型的介孔结构；样品具有完整的H3型滞后环，表明样品具有狭缝状孔结构存在。图4表明，所制备的石墨烯负载氧化钴催化剂的最可几孔径集中在4纳米左右，分布均一。 3. The nitrogen adsorption and desorption isotherms of the graphene-supported cobalt oxide catalysts prepared in Examples 2 and 3 are shown in Figure 3, and the pore distribution curves are shown in Figure 4. Figure 3 shows that the isotherm of the prepared graphene-supported cobalt oxide catalyst belongs to type IV isotherm, indicating that the sample has a typical mesoporous structure; the sample has a complete H3 type hysteresis ring, indicating that the sample has a slit-like pore structure. Figure 4 shows that the most probable pore size of the prepared graphene-supported cobalt oxide catalyst is concentrated at about 4 nanometers, and the distribution is uniform.
4、取实施例1、实施例2和实施例3所制备的石墨烯负载氧化钴催化剂进行催化一氧化碳低温氧化性能评价。先在反应器恒温区间下沿垫一层石英棉，将0.4克催化剂装入反应器中，轻敲反应器，使催化剂表面平整、厚度均匀。所有催化性能测试前，室温吹扫30分钟，控制反应气体空速为11000mL/h/g；反应气体由空气和一氧化碳组成，一氧化碳含量占反应气体总流量的10%；然后，在室温至160的温度下，选取各温度点进行连续活性测试；测试时，在具体的反应温度稳定30分钟后，通过六通阀将产物导入色谱在线分析。分析结果如图5和图6所示。图5说明在测试温度范围内石墨烯对一氧化碳氧化无催化活性，在所有复合催化剂中石墨烯与氧化钴质量比为3:7的催化剂具有最高的催化活性，在100℃即可实现一氧化碳的完全氧化脱除。图6所示为实施例3所制备的石墨烯负载氧化钴催化剂对一氧化碳低温氧化稳定性曲线，可看出该催化剂90-150℃下催化效果佳，在100℃的反应温度下效果最好，可保持一氧化碳完全转化为二氧化碳3000分钟以上，说明其具有较高的稳定性。 4. Take the graphene-supported cobalt oxide catalyst prepared in Example 1, Example 2 and Example 3 to evaluate the performance of catalytic low-temperature oxidation of carbon monoxide. First place a layer of quartz wool along the constant temperature range of the reactor, put 0.4 grams of catalyst into the reactor, and tap the reactor to make the surface of the catalyst flat and uniform in thickness. Before all catalytic performance tests, room temperature was purged for 30 minutes, and the reaction gas space velocity was controlled to be 11000mL/h/g; the reaction gas was composed of air and carbon monoxide, and the carbon monoxide content accounted for 10% of the total flow rate of the reaction gas; Under the temperature, select each temperature point for continuous activity test; during the test, after the specific reaction temperature is stable for 30 minutes, the product is introduced into the chromatogram for online analysis through the six-way valve. The analysis results are shown in Figure 5 and Figure 6. Figure 5 shows that graphene has no catalytic activity for carbon monoxide oxidation within the tested temperature range. Among all composite catalysts, the catalyst with a mass ratio of graphene to cobalt oxide of 3:7 has the highest catalytic activity, and complete oxidation of carbon monoxide can be achieved at 100°C. Oxidation removal. Figure 6 shows the graphene-supported cobalt oxide catalyst prepared in Example 3 to the low-temperature oxidation stability curve of carbon monoxide. It can be seen that the catalyst has a good catalytic effect at 90-150 ° C, and the best effect at a reaction temperature of 100 ° C. It can keep carbon monoxide completely converted into carbon dioxide for more than 3000 minutes, which shows that it has high stability.
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| CN111602276A (en) * | 2017-12-07 | 2020-08-28 | 法国电力公司 | Method of manufacturing graphene oxide-based compounds for air electrodes of metal-air batteries and related compounds |
| CN111545211A (en) * | 2020-04-26 | 2020-08-18 | 闽南师范大学 | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof |
| CN111545211B (en) * | 2020-04-26 | 2023-01-10 | 闽南师范大学 | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof |
| CN113559929A (en) * | 2021-08-16 | 2021-10-29 | 南昌航空大学 | Membrane catalyst loaded with cobalt tetroxide and preparation method and application thereof |
| CN113559929B (en) * | 2021-08-16 | 2024-08-27 | 南昌航空大学 | Film catalyst loaded with cobaltosic oxide and preparation method and application thereof |
| CN118384896A (en) * | 2023-11-13 | 2024-07-26 | 山东嘉盛博纳环保科技有限公司 | High-efficiency catalyst for low-temperature removal of carbon monoxide and preparation method thereof |
| CN118384896B (en) * | 2023-11-13 | 2024-11-05 | 山东嘉盛博纳环保科技有限公司 | High-efficiency catalyst for low-temperature removal of carbon monoxide and preparation method thereof |
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