CN107601548A - Preparation of a small-sized cubic cuprous oxide nanomaterial - Google Patents
Preparation of a small-sized cubic cuprous oxide nanomaterial Download PDFInfo
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- CN107601548A CN107601548A CN201710025559.3A CN201710025559A CN107601548A CN 107601548 A CN107601548 A CN 107601548A CN 201710025559 A CN201710025559 A CN 201710025559A CN 107601548 A CN107601548 A CN 107601548A
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- 239000001509 sodium citrate Substances 0.000 claims abstract description 11
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明涉及一种小尺寸立方体纳米氧化亚铜的制备方法。先采用柠檬酸三钠络合铜离子再加入一定量的氢氧化钠溶液最后用抗坏血酸还原生成立方体纳米氧化亚铜，用无水乙醇洗涤烘干。即可得到淡黄色的纯立方体纳米氧化亚铜。本发明可通过调节柠檬酸三钠的量、抗坏血酸的量以及控制晶核的生成数量以及纳米颗粒的生长速率获得小尺寸立方体纳米氧化亚铜，所制备出的立方体纳米氧化亚铜其尺寸大小范围为25‑40nm。本发明方法操作步骤简单，合成出的小尺寸立方体纳米颗粒用于催化、传感等领域能取得明显效果，而且能作为小尺寸模型材料对于推动基础科学研究具有重要意义。The invention relates to a method for preparing small-sized cubic nano-cuprous oxide. First use trisodium citrate to complex copper ions, then add a certain amount of sodium hydroxide solution, and finally use ascorbic acid to reduce to generate cubic nano cuprous oxide, wash and dry with absolute ethanol. The light yellow pure cubic nano-cuprous oxide can be obtained. The present invention can obtain small-size cubic nano-cuprous oxide by adjusting the amount of trisodium citrate, the amount of ascorbic acid, and controlling the number of crystal nuclei and the growth rate of nanoparticles, and the prepared cubic nano-cuprous oxide has a size range for 25‑40nm. The method of the invention has simple operation steps, and the synthesized small-sized cubic nanoparticles can achieve obvious effects in fields such as catalysis and sensing, and can be used as a small-sized model material, which is of great significance for promoting basic scientific research.
Description
技术领域technical field
本发明涉及一种小尺寸立方体氧化亚铜纳米材料的制备方法，属于无机功能材料制备技术领域。The invention relates to a preparation method of a small-sized cubic cuprous oxide nanometer material, belonging to the technical field of preparation of inorganic functional materials.
背景技术Background technique
氧化亚铜纳米颗粒作为P型半导体材料，在可见光范围内有很好的吸收，尤其在光催化、太阳能电池及电解质材料等领域有广泛的应用。立方体纳米氧化亚铜是纳米氧化亚铜中典型的代表，因其可作为理想的模型材料在研究其热力学性质、电化学性质以及光催化性质而受到广泛关注；As a P-type semiconductor material, cuprous oxide nanoparticles have good absorption in the visible light range, and are widely used in the fields of photocatalysis, solar cells, and electrolyte materials. Cubic nano-cuprous oxide is a typical representative of nano-cuprous oxide, which has attracted widespread attention because it can be used as an ideal model material to study its thermodynamic properties, electrochemical properties and photocatalytic properties;
目前，纳米氧化亚铜的合成普遍合成方法为液相沉淀法和干法煅烧，液相沉淀法通常在水相中，利用水合肼、甲醛、葡萄糖等为还原剂，还原铜离子，得到纳米氧化亚铜。此方法合成简单，粒径大小均一，但合成的纳米颗粒较大，对于研究其尺寸规律存在较大困难。因此，采用合适的方法合成一种小尺寸的纳米立方体氧化亚铜对于推动基础科学研究具有重大的科学意义。At present, the common synthesis methods for the synthesis of nano-cuprous oxide are liquid phase precipitation and dry calcination. The liquid phase precipitation method is usually in the water phase, using hydrazine hydrate, formaldehyde, glucose, etc. as reducing agents to reduce copper ions to obtain nano-cuprous oxide. Copper. This method is simple to synthesize, and the particle size is uniform, but the synthesized nanoparticles are relatively large, and it is difficult to study their size rules. Therefore, adopting a suitable method to synthesize a small-sized nanocube cuprous oxide has great scientific significance for promoting basic scientific research.
发明内容Contents of the invention
本发明目的在于针对现有研究的空缺，提出一种小尺寸立方体氧化亚铜纳米材料的制备方法，工艺过程简单，原料价廉，无需表面活性剂，得到的大小均一尺寸可控的。The purpose of the present invention is to address the vacancies in the existing research, and propose a method for preparing small-sized cubic cuprous oxide nanomaterials, which has a simple process, cheap raw materials, no need for surfactants, and the obtained ones are uniform in size and controllable in size.
为实现这一目的，本发明采用控制柠檬酸三钠的浓度进行调控以及对反应成核阶段进行稀释阻止和延缓纳米颗粒的生长速率，用无水乙醇洗涤晶体，用真空干燥箱烘干纳米材料。本发明的方法包括如下具体步骤：In order to achieve this goal, the present invention uses the concentration of trisodium citrate to regulate and dilute the reaction nucleation stage to prevent and delay the growth rate of nanoparticles, wash the crystals with absolute ethanol, and dry the nanomaterials with a vacuum drying oven . Method of the present invention comprises following specific steps:
1、纳米晶的合成：在烧杯中依次加入去离子水、柠檬酸三钠溶液用保鲜膜封住并在30℃恒温搅拌30min然后依次加入硫酸铜、氢氧化钠溶液待溶液混合均匀且温度保持在30℃不变，再快速加入抗坏血酸溶液约20秒后快速倒入一定体积30℃的去离子水，用保鲜膜密封烧杯口，反应20min。其中烧杯第一次去离子水用量为200ml，柠檬酸三钠用量0.5ml(浓度为0.3-0.05Mol/L)，硫酸铜用量为0.5ml（浓度为1.2Mol/L），氢氧化钠用量为0.5ml（浓度4.8Mol/L）：抗坏血酸为0.5ml(浓度0.6-1.2Mol/L) ,第二次加入去离子水体积为100-200ml； 1. Synthesis of nanocrystals: Add deionized water and trisodium citrate solution to the beaker in turn, seal with plastic wrap and stir at 30°C for 30 minutes, then add copper sulfate and sodium hydroxide solution in turn until the solution is mixed evenly and the temperature is maintained Keep the temperature constant at 30°C, then quickly add ascorbic acid solution for about 20 seconds, then quickly pour a certain volume of deionized water at 30°C, seal the mouth of the beaker with plastic wrap, and react for 20 minutes. Among them, the amount of deionized water for the first time in the beaker is 200ml, the amount of trisodium citrate is 0.5ml (concentration is 0.3-0.05Mol/L), the amount of copper sulfate is 0.5ml (concentration is 1.2Mol/L), and the amount of sodium hydroxide is 0.5ml (concentration 4.8Mol/L): Ascorbic acid is 0.5ml (concentration 0.6-1.2Mol/L), and the volume of deionized water added for the second time is 100-200ml;
2、洗涤、烘干：收集反应产生的橙黄色浑浊溶液，离心后分别用去离子水、无水乙醇多次洗涤，然后洗涤离心后的固体溶于适量的乙醇中体置于真空干燥箱里60℃烘干。最后收集的淡黄色粉末状样品，即为立方体纳米氧化亚铜。2. Washing and drying: collect the orange-yellow turbid solution produced by the reaction, wash it with deionized water and absolute ethanol several times after centrifugation, and then dissolve the centrifuged solid in an appropriate amount of ethanol and place it in a vacuum drying oven Dry at 60°C. The light yellow powder sample collected at last is cubic nano-cuprous oxide.
本发明具有以下特点：The present invention has the following characteristics:
1、本发明可以通过在一定范围内调节柠檬酸三钠的浓度或控制纳米材料晶种的形成与生长阶段获得不同尺寸的纳米立方体氧化亚铜材料。所制备出的立方体氧化亚铜的尺寸大小为25-40nm，此方法制备出的立方体纳米氧化亚铜尺寸远小于传统方法；1. The present invention can obtain nano-cubic cuprous oxide materials of different sizes by adjusting the concentration of trisodium citrate within a certain range or controlling the formation and growth stages of nano-material seeds. The size of the prepared cubic cuprous oxide is 25-40nm, and the size of the cubic nano cuprous oxide prepared by this method is much smaller than the traditional method;
2、本发明提供的制备方法，其原料价廉，操作简单，在推动以立方体氧化亚铜为模型材料的基础科学研究等具有重要的现实意义。 2. The preparation method provided by the present invention has cheap raw materials and simple operation, and has important practical significance in promoting basic scientific research using cubic cuprous oxide as a model material.
附图说明Description of drawings
图1为本发明实施例1所得到的立方体Cu2O的场发射扫描电镜照片。Fig. 1 is a field emission scanning electron micrograph of cubic Cu 2 O obtained in Example 1 of the present invention.
图2为本发明实施例2所得到的Cu2O的场发射扫描电镜照片。Fig. 2 is a field emission scanning electron micrograph of Cu 2 O obtained in Example 2 of the present invention.
具体实施方式detailed description
本发明下述实施例中所使用的柠檬酸三钠、硫酸铜、氢氧化钠、抗坏血酸、无水乙醇均为分析纯。下述实施例中，采用的场发射扫描电子显微镜（FE-SEM,SUPRA 55Sapphire, 德国卡尔蔡司公司）Trisodium citrate, copper sulfate, sodium hydroxide, ascorbic acid, and dehydrated alcohol used in the following examples of the present invention are all analytically pure. In the following examples, the field emission scanning electron microscope (FE-SEM, SUPRA 55Sapphire, Carl Zeiss, Germany) used
实施例1Example 1
（1）在300ml的烧杯中加入200ml去离子水，用恒温搅拌器搅拌维持温度为30℃，20min后依次向烧杯中加入0.5ml柠檬酸三钠（0.1mol/L)）、硫酸铜(1.2mol/L)、氢氧化钠(4.8mol/L)、抗坏血酸（1.2mol/L）时间间隔均为5min,用同样的方法平行再制备两份；(1) Add 200ml of deionized water into a 300ml beaker, stir with a constant temperature stirrer to maintain the temperature at 30°C, add 0.5ml of trisodium citrate (0.1mol/L)) and copper sulfate (1.2 mol/L), sodium hydroxide (4.8mol/L), and ascorbic acid (1.2mol/L) at a time interval of 5 minutes, prepare two more in parallel in the same way;
（2）收集以上橙黄色溶液，离心后用适量去离子水和无水乙醇各洗涤3次，然后将其置于真空干燥箱里60℃烘干。 (2) Collect the above orange-yellow solution, centrifuge, wash with appropriate amount of deionized water and absolute ethanol three times each, and then place it in a vacuum drying oven to dry at 60°C.
实施例2Example 2
（1）在500ml的烧杯中加入200ml去离子水，用恒温搅拌器搅拌维持温度为30℃，20min后依次向烧杯中加入0.5ml柠檬酸三钠（0.1mol/L)）、硫酸铜(1.2mol/L)、氢氧化钠(4.8mol/L)、时间间隔均为5min,待加入氢氧化钠5min后快速加入0.5ml抗坏血酸（1.2mol/L）反应5s后立即加入200ml去离子水，反应20min溶液变成橙黄色；(1) Add 200ml of deionized water into a 500ml beaker, stir with a constant temperature stirrer to maintain the temperature at 30°C, and add 0.5ml of trisodium citrate (0.1mol/L)) and copper sulfate (1.2 mol/L), sodium hydroxide (4.8mol/L), and the time interval is 5min. After adding sodium hydroxide for 5min, quickly add 0.5ml ascorbic acid (1.2mol/L) to react for 5s, then immediately add 200ml deionized water, and react After 20 minutes, the solution turned orange-yellow;
（2）收集以上橙黄色溶液，离心后用适量去离子水和无水乙醇各洗涤3次，然后将其置于真空干燥箱里60℃烘干。(2) Collect the above orange-yellow solution, centrifuge, wash with appropriate amount of deionized water and absolute ethanol three times each, and then place it in a vacuum drying oven to dry at 60°C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112429763A (en) * | 2020-11-20 | 2021-03-02 | 江苏南创化学与生命健康研究院有限公司 | Method for large-batch synthesis of cuprous oxide nano-cubic blocks based on continuous kettle type device |
| CN114684848A (en) * | 2022-04-25 | 2022-07-01 | 延安大学 | Cu2Preparation method of O nanometer quadrangular bipyramid |
| CN114908413A (en) * | 2022-04-21 | 2022-08-16 | 微冻眠(厦门)科技有限公司 | Preparation method and application of nano cuprous oxide cubic single crystal and refrigerating fluid |
| CN116003989A (en) * | 2022-12-26 | 2023-04-25 | 浙江理工大学 | A kind of antibacterial reinforced waterborne polyurethane composite material and its preparation method and application |
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- 2017-01-13 CN CN201710025559.3A patent/CN107601548A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112429763A (en) * | 2020-11-20 | 2021-03-02 | 江苏南创化学与生命健康研究院有限公司 | Method for large-batch synthesis of cuprous oxide nano-cubic blocks based on continuous kettle type device |
| CN114908413A (en) * | 2022-04-21 | 2022-08-16 | 微冻眠(厦门)科技有限公司 | Preparation method and application of nano cuprous oxide cubic single crystal and refrigerating fluid |
| CN114908413B (en) * | 2022-04-21 | 2024-12-10 | 微冻眠(厦门)科技有限公司 | Preparation method, application and freezing liquid of nano cuprous oxide cubic single crystal |
| CN114684848A (en) * | 2022-04-25 | 2022-07-01 | 延安大学 | Cu2Preparation method of O nanometer quadrangular bipyramid |
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