CN110841658A - Preparation method of cobalt-based sulfide nanorod array - Google Patents
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 33
- 239000010941 cobalt Substances 0.000 title claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002073 nanorod Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000004073 vulcanization Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 abstract description 26
- 239000002243 precursor Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000006260 foam Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
本发明公开了一种钴基硫化物纳米棒阵列的制备方法。所述方法以简单的水热方法在泡沫镍上自生长纳米棒阵列结构的钴基前驱体，随后将前驱体加入硫化钠溶液中，通过离子交换，制备出钴基硫化物纳米棒阵列。本发明方法简单，原料成本低廉，便于工业化生产，在较为温和的条件下有效控制合成了钴基硫化物纳米棒阵列，制得的钴基硫化物纳米棒阵列具有良好自支撑能力，析氧反应活性和析氧稳定性。
The invention discloses a preparation method of a cobalt-based sulfide nanorod array. In the method, a cobalt-based precursor of nanorod array structure is self-grown on nickel foam by a simple hydrothermal method, and then the precursor is added to a sodium sulfide solution, and the cobalt-based sulfide nanorod array is prepared by ion exchange. The method of the invention is simple, the cost of raw materials is low, the industrial production is convenient, the cobalt-based sulfide nanorod array is effectively controlled and synthesized under relatively mild conditions, and the prepared cobalt-based sulfide nanorod array has good self-supporting ability, oxygen evolution reaction Activity and oxygen evolution stability.
Description
技术领域technical field
本发明属于析氧催化剂技术领域，涉及一种钴基硫化物纳米棒阵列的制备方法。The invention belongs to the technical field of oxygen evolution catalysts, and relates to a preparation method of a cobalt-based sulfide nanorod array.
背景技术Background technique
氢能作为一种绿色环保且无毒的洁净能源，由于其具有来源广泛，环境友好和热值高等优点受到广泛关注。电解水制氢由于产氢纯度高，制备过程简易，原料来源广泛的优点，被视为极具潜力的制氢技术。但是，作为电解水的半反应，发生在阳极的析氧过程涉及4电子的转移，其较差的析氧动力学反应及较高的析氧过电位导致能耗增加，水分解效率降低。因此，在其他条件不变情况下，发展高效的析氧催化剂，有效降低反应过电势是提高制氢效率/降低能耗的关键。贵金属氧化物催化剂虽然具有较高的催化活性，但是由于贵金属价格昂贵，储量较少，限制了其规模应用。因此，开发高效，廉价易得的析氧催化剂成为真正规模化电解水制氢的关键。As a green, non-toxic and clean energy, hydrogen energy has attracted extensive attention due to its wide range of sources, environmental friendliness and high calorific value. Hydrogen production by electrolysis of water is regarded as a potential hydrogen production technology due to the advantages of high hydrogen production purity, simple preparation process and wide range of raw material sources. However, as a half-reaction of water electrolysis, the oxygen evolution process at the anode involves the transfer of 4 electrons. The poor kinetics of oxygen evolution and high oxygen evolution overpotential lead to increased energy consumption and reduced water splitting efficiency. Therefore, under the condition that other conditions remain unchanged, developing an efficient oxygen evolution catalyst and effectively reducing the reaction overpotential is the key to improving hydrogen production efficiency/reducing energy consumption. Although noble metal oxide catalysts have high catalytic activity, their large-scale applications are limited due to the high price and small reserves of noble metals. Therefore, the development of efficient, inexpensive and readily available oxygen evolution catalysts has become the key to truly large-scale water electrolysis for hydrogen production.
研究表明，钴基硫化物在碱性溶液中具有较好的OER活性(J.Alloys Compd.,2017,723(5):772-778)。但是已有文献报道的制备的镍钴基硫化物析氧催化剂，采用高温硫化方法，在制备过程中可能会带来尾气处理问题(J.Mater.Chem.A,2018,6(26),12506–12514)。同样采用两步法制备的钴基硫化物的方法中，某些前驱体合成时间较长，不利于实际生产的需要(Electrochimica Acta,2018,278,219-225)。此外，水热方法制备的钴基硫化物催化剂呈现粉末状，电催化过程中需要nafion试剂将其粘接在电极上，限制了催化剂的催化性能。因此，选择一种安全环保且简单易得的方法制备出较高析氧活性的钴基硫化物析氧催化剂是拓展钴基硫化物析氧催化剂应用的关键。Studies have shown that cobalt-based sulfides have better OER activity in alkaline solutions (J.Alloys Compd., 2017, 723(5):772-778). However, the nickel-cobalt-based sulfide oxygen evolution catalysts reported in the literature use high-temperature sulfidation methods, which may cause tail gas treatment problems during the preparation process (J.Mater.Chem.A, 2018, 6(26), 12506 –12514). In the method of cobalt-based sulfide prepared by the two-step method, the synthesis time of some precursors is long, which is not conducive to the needs of actual production (Electrochimica Acta, 2018, 278, 219-225). In addition, the cobalt-based sulfide catalyst prepared by the hydrothermal method is in powder form, and nafion reagent is required to bond it to the electrode during the electrocatalysis process, which limits the catalytic performance of the catalyst. Therefore, choosing a safe, environmentally friendly and simple and easy-to-obtain method to prepare cobalt-based sulfide oxygen evolution catalysts with high oxygen evolution activity is the key to expanding the application of cobalt-based sulfide oxygen evolution catalysts.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种提高其析氧反应催化活性的钴基硫化物纳米棒阵列的制备方法。The purpose of the present invention is to provide a preparation method of a cobalt-based sulfide nanorod array which improves the catalytic activity of the oxygen evolution reaction.
实现本发明目的的技术方案如下：The technical scheme that realizes the object of the present invention is as follows:
钴基硫化物纳米棒阵列的制备方法，以泡沫镍为基底，利用水热方法制备出具有纳米棒阵列结构的钴基前驱体，然后以简单的水热硫化方法，制备出具有高催化活性的自支撑的钴基硫化物纳米棒阵列催化剂，具体步骤如下：The preparation method of cobalt-based sulfide nanorod array is based on foamed nickel, and a cobalt-based precursor with a nanorod array structure is prepared by a hydrothermal method, and then a simple hydrothermal vulcanization method is used to prepare a high catalytic activity. Self-supporting cobalt-based sulfide nanorod array catalyst, the specific steps are as follows:
将泡沫镍浸入硝酸钴、尿素和氟化氨的混合溶液中，在100～150℃下进行水热反应，反应结束后，水洗，加入Na2S溶液，90～140℃下反应，反应结束后，水洗，干燥，得到钴基硫化物纳米棒阵列，所述的混合溶液中，硝酸钴的浓度为0.02～0.07mol/L。Immerse the nickel foam in a mixed solution of cobalt nitrate, urea and ammonium fluoride, and perform a hydrothermal reaction at 100-150 ° C. After the reaction, wash with water, add Na 2 S solution, and react at 90-140 ° C. After the reaction is completed , washed with water, and dried to obtain a cobalt-based sulfide nanorod array. In the mixed solution, the concentration of cobalt nitrate is 0.02-0.07 mol/L.
优选地，所述的混合溶液中，尿素的浓度0.25～0.29mol/L，氟化铵的浓度为0.1～0.28mol/L，Na2S溶液的浓度为7～9mmol/L。Preferably, in the mixed solution, the concentration of urea is 0.25-0.29 mol/L, the concentration of ammonium fluoride is 0.1-0.28 mol/L, and the concentration of Na 2 S solution is 7-9 mmol/L.
优选地，所述的水热反应时间为10～14小时。Preferably, the hydrothermal reaction time is 10-14 hours.
优选地，所述的硫化反应时间为8～10小时。Preferably, the vulcanization reaction time is 8-10 hours.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)方法简单，原料成本低廉，便于工业化生产，在较为温和的条件下有效控制合成了钴基硫化物纳米棒阵列；(1) The method is simple, the cost of raw materials is low, and it is convenient for industrial production, and the cobalt-based sulfide nanorod array is effectively controlled and synthesized under relatively mild conditions;
(2)制得的钴基硫化物纳米棒阵列具有良好自支撑能力，有效地避免了使用Nafion等粘结剂的影响；(2) The prepared cobalt-based sulfide nanorod array has good self-supporting ability, effectively avoiding the influence of using Nafion and other binders;
(3)制备的钴基硫化物纳米棒阵列具有较好的析氧反应活性，在1M KOH的电解液中，进行析氧反应，达到100mA cm-2的电流密度，所需的过电势仅为328mV，此外以20mA cm-2的电流密度进行恒电流测试，反应时间15小时，过电势仅增大了10mV，催化剂具有良好的析氧稳定性。(3) The prepared cobalt-based sulfide nanorod array has good oxygen evolution reaction activity. In the electrolyte of 1M KOH, the oxygen evolution reaction is carried out to reach a current density of 100 mA cm -2 , and the required overpotential is only In addition, the galvanostatic test was performed at a current density of 20 mA cm -2 , the reaction time was 15 hours, the overpotential increased by only 10 mV, and the catalyst had good oxygen evolution stability.
附图说明Description of drawings
图1为实施例1中棒状阵列结构的钴基前驱体(a)和钴基硫化物纳米棒阵列(b)的扫描电镜图。FIG. 1 is a scanning electron microscope image of the cobalt-based precursor (a) and the cobalt-based sulfide nanorod array (b) of the rod-like array structure in Example 1. FIG.
图2为实施例1，2，3的钴基硫化物析氧催化剂的线性扫描伏安图。2 is a linear sweep voltammogram of the cobalt-based sulfide oxygen evolution catalysts of Examples 1, 2, and 3.
图3为实施例1的钴基硫化物析氧催化剂促进氧气析出反应的稳定性图。3 is a stability diagram of the cobalt-based sulfide oxygen evolution catalyst of Example 1 promoting the oxygen evolution reaction.
图4为实施例1和对比例1的钴基硫化物析氧催化剂的线性扫描伏安图。4 is a linear sweep voltammogram of the cobalt-based sulfide oxygen evolution catalysts of Example 1 and Comparative Example 1.
图5为实施例1和对比例2的钴基硫化物析氧催化剂的线性扫描伏安图。5 is a linear sweep voltammogram of the cobalt-based sulfide oxygen evolution catalysts of Example 1 and Comparative Example 2.
具体实施方式Detailed ways
下面通过结合实施例和附图对本发明作进一步详述。The present invention will be described in further detail below with reference to the embodiments and accompanying drawings.
实施例1Example 1
步骤1，配制硝酸钴、尿素和氟化氨的混合溶液，其中硝酸钴，尿素和氟化铵的浓度分别为0.0475mol/L，0.25mol/L和0.1mol/L，将混合溶液转移至反应釜中；Step 1, prepare a mixed solution of cobalt nitrate, urea and ammonium fluoride, wherein the concentrations of cobalt nitrate, urea and ammonium fluoride are respectively 0.0475mol/L, 0.25mol/L and 0.1mol/L, and the mixed solution is transferred to the reaction in the kettle;
步骤2，将洗涤后的泡沫镍浸入到上述混合液中，120℃下水热反应12小时；In
步骤3，将生长有钴基前驱体的泡沫镍用水冲洗，随后转移至浓度为0.007mol/L的Na2S水溶液中，100℃下反应12小时，反应结束后，水洗，真空干燥，得到钴基硫化物纳米棒阵列。In step 3, the nickel foam on which the cobalt-based precursor was grown was rinsed with water, then transferred to an aqueous Na 2 S solution with a concentration of 0.007 mol/L, and reacted at 100° C. for 12 hours. After the reaction, washed with water and vacuum-dried to obtain cobalt based sulfide nanorod arrays.
图1(a)为水热方法制备的棒状阵列结构的钴基前驱体，图1(b)为水热硫化后获得的钴基硫化物纳米棒阵列的扫描电镜图。从图中可以看出，水热硫化后，仍然呈现出阵列结构，这种形貌有利于提供较多的电催化活性面积。在1mol/L的KOH电解液中，达到100mA cm-2的电流密度，实施例1，2和3所需的过电势分别为328mV，346mV和356mV(图2)。可以看出实施例1表现出优异的碱性条件下的析氧性能。采用恒电流方法测试稳定性，电解液为1mol/L的KOH进行析氧反应，电流密度为20mA cm-2，测试15小时，过电势变化小于10mV(图3)，说明该方法制备的钴基硫化物纳米棒阵列具有较高的析氧稳定性。Figure 1(a) is a cobalt-based precursor with a rod-like array structure prepared by a hydrothermal method, and Figure 1(b) is a scanning electron microscope image of the cobalt-based sulfide nanorod array obtained after hydrothermal vulcanization. It can be seen from the figure that after hydrothermal vulcanization, it still presents an array structure, which is beneficial to provide more electrocatalytic active area. In 1 mol/L KOH electrolyte, to achieve a current density of 100 mA cm −2 , the overpotentials required for Examples 1, 2 and 3 were 328 mV, 346 mV and 356 mV, respectively (Figure 2). It can be seen that Example 1 exhibits excellent oxygen evolution performance under alkaline conditions. The stability was tested by the galvanostatic method. The electrolyte was 1 mol/L KOH for oxygen evolution reaction, the current density was 20 mA cm -2 , and the overpotential change was less than 10 mV for 15 hours (Fig. 3). Sulfide nanorod arrays have high oxygen evolution stability.
实施例2Example 2
本实施例与实施例1基本相同，不同的是硝酸钴浓度为0.07mol/L，氟化铵的浓度为0.12mol/L，其他条件保持一致。This example is basically the same as Example 1, except that the concentration of cobalt nitrate is 0.07 mol/L, the concentration of ammonium fluoride is 0.12 mol/L, and other conditions remain the same.
实施例3Example 3
本实施例与实施例1基本相同，不同的是硝酸钴浓度为0.02mol/L，尿素的浓度为0.28mol/L，其他条件保持一致。This example is basically the same as Example 1, except that the concentration of cobalt nitrate is 0.02 mol/L, the concentration of urea is 0.28 mol/L, and other conditions remain the same.
对比例1Comparative Example 1
本实施例与实施例1基本相同，不同的是硝酸钴浓度为0.095mol/L，其他条件保持一致。This example is basically the same as Example 1, except that the concentration of cobalt nitrate is 0.095 mol/L, and other conditions remain the same.
对比例2Comparative Example 2
本实施例与实施例1基本相同，不同的是硝酸钴浓度为0.006mol/L，其他条件保持一致。This example is basically the same as Example 1, except that the concentration of cobalt nitrate is 0.006 mol/L, and other conditions remain the same.
图4和图5分别为对比例1和对比例2的钴基硫化物析氧催化剂的线性扫描伏安图。由图可以看出，以1mol/L的KOH为电解液，进行析氧反应，达到100mA cm-2的电流密度，对比例1和对比例2所需的过电势分别为420mV和380mV。4 and 5 are linear sweep voltammograms of the cobalt-based sulfide oxygen evolution catalysts of Comparative Example 1 and Comparative Example 2, respectively. It can be seen from the figure that the oxygen evolution reaction was carried out with 1 mol/L KOH as the electrolyte, and the current density of 100 mA cm -2 was achieved. The overpotentials required for Comparative Example 1 and Comparative Example 2 were 420 mV and 380 mV, respectively.
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| CN114204218A (en) * | 2021-11-22 | 2022-03-18 | 大连理工大学 | A kind of preparation method of positive electrode side separator for lithium-sulfur battery loaded with hollow Co3O4 cube |
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| CN114204218A (en) * | 2021-11-22 | 2022-03-18 | 大连理工大学 | A kind of preparation method of positive electrode side separator for lithium-sulfur battery loaded with hollow Co3O4 cube |
| CN115029721A (en) * | 2022-05-06 | 2022-09-09 | 海南大学 | Self-supporting partial sulfur substituted Co 3 O 4 Preparation method and application of nanowire array catalyst |
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