WO2023134244A1 - 一种ldh微纳米胶体镀层液的一锅式制备方法 - Google Patents

一种ldh微纳米胶体镀层液的一锅式制备方法 Download PDF

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WO2023134244A1
WO2023134244A1 PCT/CN2022/125548 CN2022125548W WO2023134244A1 WO 2023134244 A1 WO2023134244 A1 WO 2023134244A1 CN 2022125548 W CN2022125548 W CN 2022125548W WO 2023134244 A1 WO2023134244 A1 WO 2023134244A1
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ldh
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齐元峰
李婧
路晓
郗斐
江波
李一凡
贺凯
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Qingdao University of Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
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    • C—CHEMISTRY; METALLURGY
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    • C01G51/00—Compounds of cobalt
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  • the invention relates to a one-pot preparation method of an LDH micro-nano colloidal coating solution in a carbon-free and oxygen-free atmosphere, and belongs to the technical field of nanomaterial preparation.
  • micro-nano colloidal coatings are widely used in the fields of catalyst materials, ceramic materials, medical materials and protective materials.
  • Low-dimensional, small-sized, functionalized micro-nano-structured colloidal surface layers can significantly change the organizational structure of materials and endow materials with new properties.
  • LDHs layered double hydroxides
  • LDH plating solution involves many fields such as medicine, catalysis, flame retardant and so on.
  • the surface effect and volume effect of the micro-nano colloidal materials on the catalyst coating determine the good catalytic activity of the catalyst and the selectivity of the catalytic reaction.
  • preparation conditions especially the oxidation of carbon dioxide and oxygen, good performance cannot be obtained.
  • most LDH preparations need to passively remove the influence of carbon dioxide and oxygen, and the processing process is quite cumbersome or ignored.
  • Chinese patent document CN101759213B discloses a method for preparing layered double metal hydroxides from metal powders, which uses divalent metal powders or their hydroxides, trivalent metal powders or their hydroxides, soluble salts and Ionized water is configured into a hydrothermal solution in a certain proportion. Then the solution is placed in a hydrothermal kettle, hydrothermally reacted in a standing state, the product is separated and washed with water, and then dried to obtain a layered double metal hydroxide.
  • Chinese patent document CN106334524B discloses a preparation method and application of a layered double metal hydroxide composite particle with a core-shell structure.
  • the method includes the following steps: (1) performing a hydrothermal reaction on the glucose solution to obtain a solid Wash, dry, and grind to obtain carbon microspheres; (2) Mix magnesium chloride and aluminum chloride and add deionized water to dissolve, add dilute ammonia water dropwise to the mixed solution, let it stand for crystallization, and then suction filter the crystallized product , washing, the filter cake is peptized to convert it into a sol; (3) carbon microspheres are dispersed in methanol to obtain solution A; the product obtained in step (2) is dispersed in methanol to obtain colloidal solution B; solution A Mixed with solution B, the obtained product is centrifuged, dried and ground to obtain layered double metal hydroxide composite particles with a core-shell structure, which is applied to remove 2,4-dichlorophenoxyacetic acid in water.
  • Chinese patent document CN107583471B discloses a layered double metal hydroxide composite nanofiltration membrane and a preparation method thereof.
  • a polydopamine functional layer is first modified on the base membrane, and then on the polydopamine modified membrane surface In situ construct double metal hydroxide functional cortex to obtain composite nanofiltration membrane.
  • the present invention provides a method for preparing a one-pot off-carbon oxygen-free LDH micro-nano colloidal coating solution with simple preparation process, low cost, environment-friendly and high purity.
  • the preparation process of the present invention is simple and efficient, actively isolates carbon and oxygen, and the prepared LDH colloidal coating solution has high purity, regular shape and structure, low cost and environmental friendliness, and has very wide application prospects.
  • a kind of one-pot preparation method of LDH micro-nano colloid coating liquid comprises steps as follows:
  • the pH of liquid A in step (1) is 1-2, and the molar ratio of M 2+ : M 3+ is (2-5): 1, preferably 3: 1; preferably, divalent M Dissolve 2+ salt and trivalent M 3+ salt in deionized water that has been acidified and boiled to decarbonate, and prepare liquid A;
  • the divalent M 2+ is Mg 2+ , Co 2+ , Ni 2+ , Mn 2+ or Cu 2+
  • the trivalent M 3+ is Al 3+ or Fe 3+ ;
  • the anion of the divalent M 2+ salt and the trivalent M 3+ salt is Cl - or can not be
  • the pH value of liquid B in step (1) is 11-13, and a further preferred configuration process is:
  • step (2) in the process of adding liquid A and liquid C to liquid B at the same time in step (2), it is carried out under constant temperature and stirring conditions, preferably constant temperature is 25-80°C, most preferably 70°C, stirring The rotating speed is 500-850r/min, most preferably 800r/min.
  • the volume ratio of liquid A, liquid B and liquid C in step (2) is 1: (1-3): (1-2), most preferably 1:1:1.4;
  • the reaction time is 0.5-2h.
  • the aging temperature in step (2) is 60-80°C, most preferably 70°C; preferably, the aging time is 20-30h.
  • the product in step (2) is washed with absolute ethanol for 3-4 times after being centrifuged, and dried at 80-100° C. for 8-12 hours.
  • the anion of acid and salt in step (2) is Cl - or The cation of the salt is Na + ;
  • the LDH solid is dispersed into the mixed solution of acid and salt and purged several times with nitrogen;
  • the shaking time is 10-15h.
  • the layer spacing of LDH is different. When the value of x is between 0.17-0.33, the structurally complete LDH can be obtained.
  • the one-pot preparation method of LDH micro-nano colloid coating liquid comprises steps as follows:
  • Solution A Prepare M 2+ -M 3+ salt solution with a pH of 1-2, dissolve divalent M 2+ salt and trivalent M 3+ salt in deionized water that has been acidified and boiled to decarbonate, and keep M 2+ : M 3+ molar ratio is (2-5): 1;
  • Liquid C 25% to 28% concentrated ammonia water
  • the reason for the impurity of the product obtained by the existing method is that the existing method ignores the influence of oxygen and carbon dioxide in the air. Therefore, the whole process of the present invention is under nitrogen protection condition, has removed O in the air Oxidation, CO Dissolved in water produces containing affect the experiment. Compared with the traditional method, the process is simple, and the LDH interlayer anions prepared by separating the air are purer, the LDH crystallinity is higher, and the morphology is more regular.
  • the entire synthesis process of the carbon-free oxygen-free LDH micro-nano colloidal coating solution of the present invention is carried out in a closed environment (such as a vial), and the one-pot synthesis is more efficient, cheap and environmentally friendly.
  • the material morphology of LDH can also be controlled by controlling metal ion concentration, reaction temperature, reaction time and other conditions.
  • the whole process has no corrosion to equipment, does not pollute the environment, and is suitable for industrial production.
  • Figure 1 is a schematic flow diagram of the optimal preparation method of the present invention.
  • Fig. 2 is a photo of the appearance of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution in Example 1 to which the interlayer anion is NO 3 - .
  • Fig. 3 is a photo of the Tyndall phenomenon of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution obtained by irradiating light beams in Example 1 with NO 3 - as the interlayer anion.
  • Fig. 4 is a SEM photo of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution obtained in Example 1 with NO 3 - as the interlayer anion.
  • Fig. 5 is the appearance photo of the off-carbon oxygen-free Fe/Fe-LDH micro-nano colloidal coating solution in Example 2 to which the interlayer anion is Cl- .
  • Example 6 is a photo of the Tyndall phenomenon of the off - carbon oxygen-free Fe/Fe-LDH micro-nano colloidal coating solution obtained by irradiating the interlayer anion in Example 2 with a light beam.
  • Fig. 7 is the SEM photo of the off-carbon oxygen-free Fe/Fe-LDH micro-nano colloidal coating solution obtained in Example 2 with Cl- as the interlayer anion.
  • Fig. 8 is that the interlayer anion of embodiment 3 is Appearance photos of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution.
  • Fig. 9 is that the interlayer negative ion obtained by beam irradiation embodiment 3 is Photos of the Tyndall phenomenon of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution.
  • Fig. 10 is that the interlayer anion that embodiment 3 obtains is The SEM photo of the off-carbon oxygen-free Co/Al-LDH micro-nano colloidal coating solution.
  • Fig. 11 is that embodiment 4 arrives without Appearance photograph of Mn/Al-LDH nanosuspension with interlayer anion as NO 3- .
  • Fig. 12 is the no Photograph of the Tyndall phenomenon of Mn/Al-LDH nanosuspensions with NO 3- as the interlayer anion.
  • Fig. 13 is that embodiment 4 obtains without SEM photographs of Mn/Al-LDH nanosuspensions with NO 3- as the interlayer anion.
  • Fig. 14 is that the interlayer anion of comparative example 1 to is Appearance photos of the Mn/Al-LDH micro-nano colloid coating solution.
  • Figure 15 shows that the interlayer negative ions obtained by irradiating comparative example 1 with light beams are Tyndall phenomenon photo of the Mn/Al-LDH micro-nano colloid coating solution.
  • Figure 16 shows that the interlayer anion obtained in Comparative Example 1 is The SEM photo of the Mn/Al-LDH micro-nano colloid coating solution.
  • Fig. 17 is the XRD diffraction pattern of each sample tested in the test example.
  • FIG. 4 The SEM photo of the carbon-free oxygen-free Co/Al-LDH micro-nano colloidal coating solution obtained in this example with NO 3 ⁇ as the interlayer anion is shown in FIG. 4 . It can be seen from Figure 4 that the particles are well dispersed, and most of them present a hydrotalcite-like layered structure, and the particle size and shape show a certain degree of dispersion.
  • FIG. 7 The SEM photo of the carbon-free oxygen-free Fe/Fe-LDH micro-nano colloidal coating solution obtained in this example with Cl ⁇ as the interlayer anion is shown in FIG. 7 . It can be seen from Figure 7 that the particles are well dispersed, and most of them present a hydrotalcite-like layered structure, and the particle size and shape show a certain degree of dispersion.
  • the interlayer anion obtained in this embodiment is The photo of the appearance of the carbon-free oxygen-free Co/Al-LDH micro-nano colloidal coating solution is shown in Figure 8.
  • the interlayer anions obtained by beam irradiation in this embodiment are The off-carbon oxygen-free Co/Al-LDH micro-nano colloid coating solution, the photo of the phenomenon is shown in Figure 9. It can be seen from Figure 9 that the Co/Al-LDH coating solution has obvious Tyndall effect, which proves its colloidal characteristics.
  • the interlayer anion obtained in this embodiment is The SEM photo of the carbon-free oxygen-free Co/Al-LDH micro-nano colloidal coating solution is shown in Figure 10. It can be seen from Figure 10 that the particles are well dispersed, and most of them present a hydrotalcite-like layered structure, and the particle size and shape show a certain degree of dispersion.
  • Dissolve 33g of ammonium chloride solid in 100ml of boiled deionized water add saturated ammonium chloride solution to 25% to 28% concentrated ammonia water, adjust the pH value to 13, and obtain ammonia-ammonium chloride buffer solution as liquid B . A certain amount of 25% to 28% concentrated ammonia water is used as liquid C.
  • the interlayer anion is the Mn/Al-LDH nanosuspension of NO 3- , and the photo of the phenomenon is shown in Figure 12. It can be seen from Figure 12 that the coating solution has obvious Tyndall effect, which proves its colloidal properties.
  • the whole process is carried out in air without nitrogen protection.
  • the interlayer anion is obtained as Co/Al-LDH micro-nano colloid coating solution.
  • the interlayer anion obtained in this comparative example is The appearance photo of the Co/Al-LDH micro-nano colloidal coating solution is shown in Figure 14.
  • FIG. 16 The SEM photo of the Co/Al-LDH micro-nano colloidal coating solution obtained in this comparative example with NO 3 ⁇ as the interlayer anion is shown in FIG. 16 . It can be seen from Figure 16 that the layered structure of the obtained LDH is not obvious, tends to a rod-like structure, and has a small particle size.
  • Example 1 The purity of the products of Example 1 and Comparative Example 1 was tested, and the XRD diffraction patterns are shown in FIG. 17 .

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Abstract

本发明涉及一种LDH微纳米胶体镀层液的一锅式制备方法，属于纳米材料制备技术领域。配制M 2+-M 3+盐溶液为A液，氨-氯化铵缓冲溶液为B液，浓氨水作为C液，将B液置于密封西林瓶于恒温金属浴震荡锅在一定温度与转速下，用注射泵同时将A液和B液注入特制西林瓶中反应，而后静置老化，离心洗涤干燥后分散到盐和酸混合溶液中，氮气吹扫震荡后制得离碳无氧型LDH微纳米胶体镀层液。本发明制备方法主动隔离碳和氧，制备得的LDH胶体镀层液纯度高，形貌结构规则，有非常广泛的应用前景。

Description

一种LDH微纳米胶体镀层液的一锅式制备方法 技术领域：
本发明涉及一种在离碳无氧气氛下LDH微纳米胶体镀层液的一锅式制备方法，属于纳米材料制备技术领域。
背景技术：
微纳米胶体镀层因其具有比较高的强度和优异的耐腐蚀性能，被广泛应用于催化剂材料，陶瓷材料，医用材料及防护材料等领域。低维度、小尺寸、功能化的微纳米结构胶体表面层能够显著改变材料的组织结构并赋予材料新的性能。在反应催化应用中，层状双金属氢氧化物(LDH)作为一种良好的无机功能材料，因其特殊的结构和功能使其具有丰富的物理化学性能。现如今，LDH镀液涉及了医药，催化，阻燃等诸多领域。尤其催化剂镀层微纳米胶体材料的表面效应和体积效应决定了催化剂良好的催化活性及催化反应的选择性。但受制备条件的影响，尤其二氧化碳和氧气氧化而得不到好的性能，而今大多数LDH制备都需要被动的去除二氧化碳及氧气的影响，处理过程相当繁琐或者忽略了这一点。
例如，中国专利文件CN101759213B公开了一种金属粉制备层状双金属氢氧化物的方法，该方法利用二价金属粉或其氢氧化物、三价金属粉或其氢氧化物、可溶性盐和去离子水按一定比例配置成水热溶液。然后将该溶液放置在水热釜中，在静置状态下水热反应，产物经分离和水洗后烘干即得层状双金属氢氧化物。再比如，中国专利文件CN106334524B公开了一种一种核-壳结构层状双金属氢氧化物复合粒子制备方法及应用，该方法包含以下步骤：(1)将葡萄糖溶液进行水热反应，所得固体洗涤，干燥，研磨得到碳微球；(2)将氯化镁和氯化铝混合加入去离子水溶解，在混合溶液中滴加的稀氨水，静置晶化，再将晶化后的产物抽滤，洗涤，将滤饼进行胶溶，使其转化为溶胶；(3)将碳微球分散在甲醇中得到溶液A；将步骤(2)所得产物分散在甲醇中得到胶体溶液B；将溶液A与溶液B混合，所得产物离心分离，烘干研磨，得到核-壳结构的层状双金属氢氧化物复合粒子，应用于去除水中的2,4-二氯苯氧乙酸。再比如中国专利文件CN107583471B公开了一种层状双金属氢氧化物复合纳滤膜及其制备方法，该方法先在基膜上修饰生成一聚多巴胺功能层，然后在聚多巴胺修饰的膜表面上原位构建双金属氢氧化物功能皮层，得到复合纳滤膜。
然而，以上方法都没有在密闭环境下进行层状双金属氢氧化物的制备，且最后也没有考虑空气中CO 2的影响。得到的非
Figure PCTCN2022125548-appb-000001
插层的LDH纯度往往较差，层间阴离子不纯，容易导致所制得的材料形貌结构不规则。因此，提供纯度更好，结晶度更高，相貌结构更加规则的LDH，并且制备过程简单高效，具有重要意义。为此，提出本发明。
发明内容：
针对现有技术的不足，本发明提供一种制备工艺简单，成本低廉环境友好且纯度高的一锅式离碳无氧型LDH微纳米胶体镀层液的制备方法。本发明制备过程简单高效，主动隔离 碳和氧，制备得的LDH胶体镀层液纯度高，形貌结构规则，成本低廉环境友好，有非常广泛的应用前景。
本发明的技术方案如下：
一种LDH微纳米胶体镀层液的一锅式制备方法，包括步骤如下：
(1)在无氧无二氧化碳且氮气保护下，配制M 2+-M 3+盐溶液为A液，氨-氯化铵缓冲溶液为B液，浓氨水作为C液；
(2)在无氧无二氧化碳且氮气保护下，向B液中同时加入A液和C液，反应后静置老化；产物离心、洗涤、干燥，得到无碳酸盐LDH固体；将LDH固体分散到酸和盐的混合溶液中，震荡，即得离碳无氧型LDH微纳米胶体镀层液。
根据本发明，优选的，步骤(1)中A液pH＝1-2，M 2+：M 3+摩尔比为(2-5)：1，优选3:1；优选的，将二价M 2+盐和三价M 3+盐溶于酸化且煮沸脱碳酸的去离子水中，配置A液；
优选的，二价M 2+是Mg 2+、Co 2+、Ni 2+、Mn 2+或Cu 2+，三价M 3+是Al 3+或Fe 3+；
优选的，二价M 2+盐和三价M 3+盐的阴离子为
Figure PCTCN2022125548-appb-000002
Cl -或
Figure PCTCN2022125548-appb-000003
不能为
Figure PCTCN2022125548-appb-000004
根据本发明，优选的，步骤(1)中B液pH值为11-13，进一步优选的配置过程为：
将氯化铵固体溶于煮沸后的去离子水中，得到饱和氯化铵溶液，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到11-13，得到氨-氯化铵缓冲溶液。
根据本发明，优选的，步骤(2)向B液中同时加入A液和C液的过程中，在恒温、搅拌条件下进行，优选的恒温温度为25-80℃，最优选70℃，搅拌转速为500-850r/min，最优选800r/min。
根据本发明，优选的，步骤(2)中A液、B液和C液的体积比为1：(1-3)：(1-2),最优选1:1:1.4；
优选的，反应时间为0.5-2h。
根据本发明，优选的，步骤(2)中老化的温度为60-80℃，最优选70℃；优选的，老化时间为20-30h。
根据本发明，优选的，步骤(2)中产物离心后用无水乙醇洗涤3-4次，于80-100℃干燥8-12h。
根据本发明，优选的，步骤(2)中酸和盐的阴离子为
Figure PCTCN2022125548-appb-000005
Cl -或
Figure PCTCN2022125548-appb-000006
盐的阳离子为Na +；
优选的，LDH固体分散到酸和盐的混合溶液中后用氮气吹扫数次；
优选的，震荡时间为10-15h。
本发明制备的层状双金属氢氧化物(LDH)的化学式为：
Figure PCTCN2022125548-appb-000007
其中M 2+代表二价金属阳离子，M 3+代表三价金属阳离子，A n-为层间阴离子，n＝1、2或3，比如有机和无机离子及络合离子，层间阴离子不同，LDH的层间距不同。在x值在0.17-0.33之间时，能得到结构完整的LDH。
根据本发明，LDH微纳米胶体镀层液的一锅式制备方法，一种优选的实施方案，包括 步骤如下：
A液:配制pH为1-2的M 2+-M 3+盐溶液，将二价M 2+盐和三价M 3+盐溶于酸化且煮沸脱碳酸的去离子水中，保持M 2+：M 3+摩尔比为(2-5)：1；
B液:配制氨-氯化铵缓冲溶液，将33g氯化铵固体溶于100ml煮沸后的去离子水中，得到pH＝4.46的饱和氯化铵溶液，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到11-13，得到氨-氯化铵缓冲溶液；
C液：25％～28％的浓氨水；
(1)使用真空泵将密封西林瓶抽至负压0.07MPa，然后氮气吹扫，重复三次并再次抽真空到负压0.07MPa，保证在无氧无二氧化碳，将B液置于此密封西林瓶中氮气保护，置于恒温金属浴震荡锅中，在70℃与800r/min转速下，用注射泵同时将A液和C液缓慢注入密封西林瓶中，配置出混合溶液，A液、B液和C液的体积比为1:1:1.4；
(2)A液和C液注射完毕后，保持转速反应1h，然后调节转速为0r/min，在静置状态下于70℃恒定温度下老化24h；
(3)将产物离心，并用无水乙醇洗涤3-4次，于80-100℃干燥8-12h，得到无碳酸盐LDH固体；
(4)将制得的LDH分散到1mol/L钠盐和3.3mmol/L的酸溶液中，用氮气吹扫数次，在室温下震荡12h，得到离碳无氧型LDH微纳米胶体镀层液。
本发明的有益效果如下：
1.本发明的发明人发现，导致现有方法得到的产物不纯的原因在于，现有方法忽视了空气中氧气和二氧化碳的影响。因此，本发明制备的整个过程在氮气保护条件下，去除了空气中O 2氧化、CO 2溶于水产生含
Figure PCTCN2022125548-appb-000008
影响实验。相比较传统方法，工艺简单，隔绝空气制备的LDH层间阴离子更纯，LDH结晶度更高，形貌更加规则。
2.本发明离碳无氧型LDH微纳米胶体镀层液整个合成过程都在密闭环境(例如西林瓶)中进行，一锅法合成更加高效、廉价且环境友好。
3.本发明还可以通过控制金属离子浓度、反应温度、反应时间等条件来控制LDH的材料形貌大小。整个过程对设备无腐蚀，不会污染环境，适合工业生产。
附图说明：
图1为本发明最优制备方法的流程示意图。
图2为实施例1到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液的外观照片。
图3为用光束照射实施例1得到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液的丁达尔现象照片。
图4为实施例1得到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液的SEM照片。
图5为实施例2到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液的外 观照片。
图6为用光束照射实施例2得到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液的丁达尔现象照片。
图7为实施例2得到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液的SEM照片。
图8为实施例3到的层间阴离子为
Figure PCTCN2022125548-appb-000009
的离碳无氧型Co/Al-LDH微纳米胶体镀层液的外观照片。
图9为用光束照射实施例3得到的层间阴离子为
Figure PCTCN2022125548-appb-000010
的离碳无氧型Co/Al-LDH微纳米胶体镀层液的丁达尔现象照片。
图10为实施例3得到的层间阴离子为
Figure PCTCN2022125548-appb-000011
的离碳无氧型Co/Al-LDH微纳米胶体镀层液的SEM照片。
图11为实施例4到的无
Figure PCTCN2022125548-appb-000012
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液的外观照片。
图12为用光束照射实施例4得到的无
Figure PCTCN2022125548-appb-000013
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液的丁达尔现象照片。
图13为实施例4得到的无
Figure PCTCN2022125548-appb-000014
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液的SEM照片。
图14为对比例1到的层间阴离子为
Figure PCTCN2022125548-appb-000015
的Mn/Al-LDH微纳米胶体镀层液的外观照片。
图15为用光束照射对比例1得到的层间阴离子为
Figure PCTCN2022125548-appb-000016
的Mn/Al-LDH微纳米胶体镀层液的丁达尔现象照片。
图16为对比例1得到的层间阴离子为
Figure PCTCN2022125548-appb-000017
的Mn/Al-LDH微纳米胶体镀层液的SEM照片。
图17为试验例中测试的各样品的XRD衍射图谱。
具体实施方式：
下面通过实施例并结合附图对本发明做进一步说明，但不限于此。
实施例1：
按化学计量比精准称量Co(NO 3) 2·6H 2O和Al(NO 3) 3·9H 2O，煮沸冷却的去离子水用硝酸酸化至pH＝2，配置成Co 2+：Al 3+＝3:1，总金属离子浓度为0.1mol/l的Co-Al盐溶液作为A液。将33g氯化铵固体溶于100ml煮沸后的去离子水中，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到12，得到氨-氯化铵缓冲溶液作为B液。一定量的25％～28％的浓氨水作为C液。
密封一个干净的20ml西林瓶，氮气吹扫瓶内数次，加入B液，置于恒温金属浴震荡锅中，设置温度为70℃，转速800r/min。注射泵安装A液和C液，连接西林瓶缓慢注入到B液中，A液、B液和C液的体积比为1：1：1.4。注射完毕后，保持转速反应1h，然后调节转速为0r/min，温度不变在静置状态下于恒定温度下老化24h后，将西林瓶放入离心机(6000r/min)离心，用无水乙醇洗涤3-4次，于80℃下干燥12h。在西林瓶的固体中添加 20ml的1mol硝酸钠和3.3mmol的硝酸溶液中，用氮气吹扫数次，在室温下震荡12h，得到层间阴离子为
Figure PCTCN2022125548-appb-000018
的离碳无氧型Co/Al-LDH微纳米胶体镀层液。
本实施例得到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液的外观照片如图2所示。
用光束照射本实施例得到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液，现象照片如图3所示。由图3可知Co/Al-LDH镀层液有明显的的丁达尔效应，证明了它的胶体特性。
本实施例得到的层间阴离子为NO 3 -的离碳无氧型Co/Al-LDH微纳米胶体镀层液的SEM照片如图4所示。由图4可知颗粒分散良好，大都呈现类水滑石的层状结构，颗粒大小形状呈一定分散性。
实施例2：
按化学计量比精准称量FeCl 2·2H 2O和FeCl 3·6H 2O，煮沸冷却的去离子水用硝酸酸化至pH＝1，配置成Fe 2+：Fe 3+＝3:1，总金属离子浓度为0.01mol/l的Fe-Fe盐溶液作为A液。将33g氯化铵固体溶于100ml煮沸后的去离子水中，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到13，得到氨-氯化铵缓冲溶液作为B液。一定量的25％～28％的浓氨水作为C液。
密封一个干净的20ml西林瓶，氮气吹扫瓶内数次，加入B液，置于恒温金属浴震荡锅中，设置温度为70℃，转速800r/min。注射泵安装A液和C液，连接西林瓶缓慢注入到B液中，A液、B液和C液的体积比为1：1：1.4。注射完毕后，保持转速反应1h，然后调节转速为0r/min，温度不变在静置状态下于恒定温度下老化24h后，将西林瓶放入离心机(6000r/min)离心，用无水乙醇洗涤3-4次，于80℃下干燥12h。在西林瓶的固体中添加20ml的1mol氯化钠和3.3mmol的盐酸溶液中，用氮气吹扫数次，在室温下震荡12h，得到层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液。
本实施例得到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液的外观照片如图5所示。
用光束照射本实施例得到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液，现象照片如图6所示。由图6可知Fe/Fe-LDH镀层液有明显的的丁达尔效应，证明了它的胶体特性。
本实施例得到的层间阴离子为Cl -的离碳无氧型Fe/Fe-LDH微纳米胶体镀层液的SEM照片如图7所示。由图7可知颗粒分散良好，大都呈现类水滑石的层状结构，颗粒大小形状呈一定分散性。
实施例3：
按化学计量比精准称量CoSO 4·7H 2O和Al 2(SO 4) 3·18H 2O，煮沸冷却的去离子水用硫酸酸化至pH＝2，配置成Co 2+：Al 3+＝3:1，总金属离子浓度为0.05mol/l的Co-Al盐溶液作为A液。将33g氯化铵固体溶于100ml煮沸后的去离子水中，将饱和氯化铵溶液加入25％～28％ 的浓氨水中，调节pH值到12，得到氨-氯化铵缓冲溶液作为B液。一定量的25％～28％的浓氨水作为C液。
密封一个干净的20ml西林瓶，氮气吹扫瓶内数次，加入B液，置于恒温金属浴震荡锅中，设置温度为70℃，转速800r/min。注射泵安装A液和C液，连接西林瓶缓慢注入到B液中，A液、B液和C液的体积比为1：1：1.4。注射完毕后，保持转速反应1h，然后调节转速为0r/min，温度不变在静置状态下于恒定温度下老化24h后，将西林瓶放入离心机(6000r/min)离心，用无水乙醇洗涤3-4次，于80℃下干燥12h。在西林瓶的固体中添加20ml的1mol硫酸钠和3.3mmol的硫酸溶液中，用氮气吹扫数次，在室温下震荡12h，得到层间阴离子为
Figure PCTCN2022125548-appb-000019
的离碳无氧型Co/Al-LDH微纳米胶体镀层液。
本实施例得到的层间阴离子为
Figure PCTCN2022125548-appb-000020
的离碳无氧型Co/Al-LDH微纳米胶体镀层液的外观照片如图8所示。
用光束照射本实施例得到的层间阴离子为
Figure PCTCN2022125548-appb-000021
的离碳无氧型Co/Al-LDH微纳米胶体镀层液，现象照片如图9所示。由图9可知Co/Al-LDH镀层液有明显的的丁达尔效应，证明了它的胶体特性。
本实施例得到的层间阴离子为
Figure PCTCN2022125548-appb-000022
的离碳无氧型Co/Al-LDH微纳米胶体镀层液的SEM照片如图10所示。由图10可知颗粒分散良好，大都呈现类水滑石的层状结构，颗粒大小形状呈一定分散性。
实施例4：
按化学计量比精准称量Mn(NO 3) 2·4H 2O和Al(NO 3) 3·9H 2O，煮沸冷却的去离子水用硝酸酸化至pH＝2，配置成Mn 2+：Al 3+＝3:1，总金属离子浓度为0.01mol/l的Mn-Al盐溶液作为A液。将33g氯化铵固体溶于100ml煮沸后的去离子水中，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到13，得到氨-氯化铵缓冲溶液作为B液。一定量的25％～28％的浓氨水作为C液。
密封一个干净的20ml西林瓶，氮气吹扫瓶内数次，加入B液，置于恒温金属浴震荡锅中，设置温度为70℃，转速800r/min。注射泵安装A液和C液，连接西林瓶缓慢注入到B液中，A液、B液和C液的体积比为1：1：1.4。注射完毕后，保持转速反应1h，然后调节转速为0r/min，温度不变在静置状态下于恒定温度下老化24h后，将西林瓶放入离心机(6000r/min)离心，用无水乙醇洗涤3-4次，于80℃下干燥12h。在西林瓶的固体中添加20ml的1mol硝酸钠和3.3mmol的硝酸酸溶液中，用氮气吹扫数次，在室温下震荡12h，得到无
Figure PCTCN2022125548-appb-000023
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液。
本实施例得到的无
Figure PCTCN2022125548-appb-000024
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液的外观照片如图11所示。
用光束照射本实施例得到的无
Figure PCTCN2022125548-appb-000025
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液，现象照片如图12所示。由图12可知镀层液有明显的的丁达尔效应，证明了它的胶体特性。
本实施例得到的无
Figure PCTCN2022125548-appb-000026
层间阴离子为NO 3-的Mn/Al-LDH纳米悬浮液的SEM照片如图 13所示。由图13可知颗粒分散良好，大都呈现类水滑石的层状结构，颗粒大小形状呈一定分散性。且得到的层状结构更大。
对比例1
如实施例1所述，不同的是：
整个过程在空气中进行，没有氮气保护。得到层间阴离子为
Figure PCTCN2022125548-appb-000027
的Co/Al-LDH微纳米胶体镀层液。
本对比例得到的层间阴离子为
Figure PCTCN2022125548-appb-000028
的Co/Al-LDH微纳米胶体镀层液的外观照片如图14所示。
用光束照射本对比例得到的层间阴离子为NO 3 -的Co/Al-LDH微纳米胶体镀层液，现象照片如图15所示。由图15可知此方法也可得到较明显的丁达尔效应，有胶体特性。
本对比例得到的层间阴离子为NO 3 -的Co/Al-LDH微纳米胶体镀层液的SEM照片如图16所示。由图16可知所制得LDH层状结构不明显，趋于棒状结构，且粒径小。
可以看出，没有氮气的保护所得产物没有很好的层状结构，且杂质较多。
试验例
测试实施例1和对比例1产物的纯度，XRD衍射图谱如图17所示。
由图17XRD衍射图谱结果可以看出，样品中出现了水滑石(003)、(006)、(012)、(015)、(018)、(110)、(118)的特征衍射峰，实施例样品结晶度较好，衍射强度强，峰型尖锐。而对比例1峰型衍射强度弱，峰型较缓，说明对比例的结晶度较差。进一步说明了本发明得到的产物结晶度好，纯度也更高。

Claims (14)

  1. 一种LDH微纳米胶体镀层液的一锅式制备方法，包括步骤如下：
    (1)在无氧无二氧化碳且氮气保护下，配制M 2+-M 3+盐溶液为A液，氨-氯化铵缓冲溶液为B液，浓氨水作为C液；
    (2)在无氧无二氧化碳且氮气保护下，向B液中同时加入A液和C液，反应后静置老化；产物离心、洗涤、干燥，得到无碳酸盐LDH固体；将LDH固体分散到酸和盐的混合溶液中，震荡，即得离碳无氧型LDH微纳米胶体镀层液。
  2. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中A液pH＝1-2，M 2+：M 3+摩尔比为(2-5)：1。
  3. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中将二价M 2+盐和三价M 3+盐溶于酸化且煮沸脱碳酸的去离子水中，配置A液。
  4. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中二价M 2+是Mg 2+、Co 2+、Ni 2+、Mn 2+或Cu 2+，三价M 3+是Al 3+或Fe 3+。
  5. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中二价M 2+盐和三价M 3+盐的阴离子为
    Figure PCTCN2022125548-appb-100001
    Cl -或
    Figure PCTCN2022125548-appb-100002
    不能为
    Figure PCTCN2022125548-appb-100003
  6. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中B液pH值为11-13。
  7. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(1)中B液的配置过程为：
    将氯化铵固体溶于煮沸后的去离子水中，得到饱和氯化铵溶液，将饱和氯化铵溶液加入25％～28％的浓氨水中，调节pH值到11-13，得到氨-氯化铵缓冲溶液。
  8. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)向B液中同时加入A液和C液的过程中，在恒温、搅拌条件下进行，恒温温度为25-80℃，搅拌转速为500-850r/min。
  9. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中A液、B液和C液的体积比为1：(1-3)：(1-2)。
  10. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中A液、B液和C液的反应时间为0.5-2h。
  11. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中老化的温度为60-80℃，老化时间为20-30h。
  12. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中产物离心后用无水乙醇洗涤3-4次，于80-100℃干燥8-12h。
  13. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中酸和盐的阴离子为
    Figure PCTCN2022125548-appb-100004
    Cl -或
    Figure PCTCN2022125548-appb-100005
    盐的阳离子为Na +。
  14. 根据权利要求1所述的LDH微纳米胶体镀层液的一锅式制备方法，其特征在于，步骤(2)中LDH固体分散到酸和盐的混合溶液中后用氮气吹扫数次，震荡时间为10-15h。
PCT/CN2022/125548 2022-01-14 2022-10-17 一种ldh微纳米胶体镀层液的一锅式制备方法 Ceased WO2023134244A1 (zh)

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