技术领域Technical field
本发明属于电化学领域，涉及一种纳米超结构自支撑电极的制备方法及其应用。The invention belongs to the field of electrochemistry and relates to a preparation method and application of a nano-superstructure self-supporting electrode.
背景技术Background technique
开发利用清洁能源以降低人为碳排放迫在眉睫。氢能作为一种具有能量密度高、零碳排放等优点的清洁能源，因而是替代传统化石能源理想的选择。但如何以高效、经济的方式大规模制备氢气仍面临巨大挑战。在众多制氢体系中，电解水体系可在常温、常压下制备氢气，且所需电能可由清洁能源(如太阳能、风能等)发电所提供，因而可显著降低制氢成本，以实现氢气的大规模制备。It is urgent to develop and utilize clean energy to reduce man-made carbon emissions. As a clean energy with high energy density and zero carbon emissions, hydrogen energy is an ideal choice to replace traditional fossil energy. However, how to prepare hydrogen on a large scale in an efficient and economical manner still faces huge challenges. Among many hydrogen production systems, the electrolysis water system can produce hydrogen at normal temperature and pressure, and the required electric energy can be provided by clean energy (such as solar energy, wind energy, etc.), thus significantly reducing the cost of hydrogen production to achieve hydrogen production. Large scale preparation.
常规电解水体系包括阴极析氢反应(HER)与阳极析氧反应(OER)。由于阳极OER热力学电势较大(1.23V)，且四电子反应过程动力学缓慢，使之通常需要较高的过电位，这将导致整个电解体系需要较高的电解电压，因而不利于其大规模应用。与OER相比，有机小分子氧化反应通常需要的氧化电位较低，且还可能产生高附加值的氧化产物。若以有机小分子氧化反应替代OER，构建新型电解水体系，将有望在降低电解水制氢所需能量的同时，获得高附加值的阳极氧化产物，从而可以进一步提升电解水制氢效率，因而具有重要的潜在应用价值。为了实现上述目标，开发高效、稳定的电催化剂至关重要。与常规贵金属基电催化剂(如Pt、RuO2等)相比，设计开发具有相当、甚至性能更优的新型非贵金属催化剂具有更大的现实与经济意义。据报道，层状金属氢氧化物(LDHs) 因其独特的微观形貌及电子结构而在有机小分子氧化反应耦合的电解水体系应用中受到广泛关注。但目前报道的例子中，绝大多数层状金属氢氧化物(LDHs) 催化剂都是粉体形式，使得最终制备的电极稳定性欠佳。与此同时，现有报道的层状金属氢氧化物(LDHs)鲜有能同时在分子尺度上对催化剂的微观形貌与电子结构进行精准调控，从而使得相应的层状金属氢氧化物(LDHs)的催化性能不足。因此，如何从分子尺度上对层状金属氢氧化物(LDHs)催化剂的微观形貌与电子结构进行精准调控，以获得稳定性及催化性能优异的层状金属氢氧化物 (LDHs)成为本领域亟待解决的技术难题。Conventional electrolysis water systems include cathode hydrogen evolution reaction (HER) and anode oxygen evolution reaction (OER). Due to the large thermodynamic potential of the anode OER (1.23V) and the slow kinetics of the four-electron reaction process, it usually requires a higher overpotential, which will cause the entire electrolysis system to require a higher electrolysis voltage, which is not conducive to its large-scale application. Compared with OER, the oxidation reaction of organic small molecules usually requires a lower oxidation potential and may also produce high value-added oxidation products. If the oxidation reaction of organic small molecules is used to replace OER and a new electrolytic water system is constructed, it is expected to reduce the energy required for hydrogen production by electrolyzing water and obtain high value-added anodic oxidation products, which can further improve the efficiency of hydrogen production by electrolyzing water. It has important potential application value. In order to achieve the above goals, it is crucial to develop efficient and stable electrocatalysts. Compared with conventional noble metal-based electrocatalysts (such as Pt, RuO2, etc. ), it is of greater practical and economic significance to design and develop new non-precious metal catalysts with equivalent or even better performance. It is reported that layered metal hydroxides (LDHs) have received widespread attention in the application of electrolysis water systems coupled with the oxidation reaction of organic small molecules due to their unique microscopic morphology and electronic structure. However, in the examples reported so far, the vast majority of layered metal hydroxides (LDHs) catalysts are in powder form, making the final prepared electrodes less stable. At the same time, few of the currently reported layered metal hydroxides (LDHs) can simultaneously precisely control the micromorphology and electronic structure of the catalyst at the molecular scale, thus making the corresponding layered metal hydroxides (LDHs) ) has insufficient catalytic performance. Therefore, how to precisely control the micromorphology and electronic structure of layered metal hydroxides (LDHs) catalysts at the molecular scale to obtain layered metal hydroxides (LDHs) with excellent stability and catalytic performance has become an issue in this field. Technical problems that need to be solved urgently.
发明内容Contents of the invention
为改善上述技术问题，本发明提供一种电极的制备方法，包括：将钴盐与有机配体溶解在溶剂中，通过液相反应在基底上原位生长Co-MOFs前驱体，然后将其浸入含过渡金属离子的溶液中，通过自牺牲模板溶剂热反应，制备得到负载LDHs材料的电极。In order to improve the above technical problems, the present invention provides a method for preparing an electrode, which includes: dissolving cobalt salt and organic ligands in a solvent, growing the Co-MOFs precursor in situ on the substrate through liquid phase reaction, and then immersing it in the In a solution containing transition metal ions, an electrode loaded with LDHs material is prepared through a self-sacrificial template solvothermal reaction.
根据本发明，所述钴盐与有机配体的反应摩尔比为1:(0.01～20)，如1:0.01、 1:0.1、1:0.5、1:1、1:2、1:4、1:8、1:10、1:20。According to the present invention, the reaction molar ratio of the cobalt salt and the organic ligand is 1: (0.01~20), such as 1:0.01, 1:0.1, 1:0.5, 1:1, 1:2, 1:4, 1:8, 1:10, 1:20.
根据本发明，所述钴盐为钴的硝酸盐、卤化盐、硫酸盐、有机酸盐或有机盐及其水合物中的至少一种，如六水硝酸钴、氯化钴、六水氯化钴、硫酸钴、七水硫酸钴、乙酸钴、乙酰丙酮钴等中的至少一种。According to the present invention, the cobalt salt is at least one of cobalt nitrates, halide salts, sulfates, organic acid salts or organic salts and hydrates thereof, such as cobalt nitrate hexahydrate, cobalt chloride, chloride hexahydrate At least one of cobalt, cobalt sulfate, cobalt sulfate heptahydrate, cobalt acetate, cobalt acetylacetonate, etc.
根据本发明，所述有机配体为2-甲基咪唑、1,4-萘二羧酸、1,4-对苯二甲酸、 2-氨基对苯二甲酸、2,5-二羟基对苯二甲酸、1,3,5-均苯三甲酸、2,6-吡啶二羧酸、咪唑-4,5-二羧酸和3,4-吡啶二羧酸等中的至少一种。According to the present invention, the organic ligands are 2-methylimidazole, 1,4-naphthalenedicarboxylic acid, 1,4-terephthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxy-terephthalic acid. At least one of dicarboxylic acid, 1,3,5-trimesoic acid, 2,6-pyridinedicarboxylic acid, imidazole-4,5-dicarboxylic acid, 3,4-pyridinedicarboxylic acid, and the like.
根据本发明，所述溶剂为水、甲醇、乙醇、乙二醇、N,N-二甲基甲酰胺(DMF) 和N,N-二甲基乙酰胺(DMA)等中的至少一种。According to the present invention, the solvent is at least one of water, methanol, ethanol, ethylene glycol, N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA).
根据本发明，所述含过渡金属离子的溶液为含V、Cr、Mn、Fe、Co、Ni、 Cu、Zn、Nb、Mo、W等中的至少一种过渡金属离子的硝酸盐、卤化盐、硫酸盐、有机酸盐或有机盐及其水合物溶液。示例性为六水硝酸镍溶液。According to the present invention, the solution containing transition metal ions is a nitrate or halide salt containing at least one transition metal ion among V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, W, etc. , sulfates, organic acid salts or organic salts and their hydrate solutions. An example is nickel nitrate hexahydrate solution.
根据本发明，所述钴盐与含过渡金属离子的溶液中的过渡金属离子的盐的摩尔比为1：(0.01～10)，如1:0.01、1:0.1、1:0.5、1:1、1:2、1:5、1:8、1:10。According to the present invention, the molar ratio of the cobalt salt to the salt of transition metal ions in the solution containing transition metal ions is 1: (0.01~10), such as 1:0.01, 1:0.1, 1:0.5, 1:1 , 1:2, 1:5, 1:8, 1:10.
根据本发明，所述含过渡金属离子的溶液中还含有尿素。优选地，过渡金属离子的盐与尿素的摩尔比为1：(5～100)，如1:5、1:10、1:20、1:50、1:80、1:100。According to the present invention, the solution containing transition metal ions further contains urea. Preferably, the molar ratio of the transition metal ion salt to urea is 1: (5-100), such as 1:5, 1:10, 1:20, 1:50, 1:80, 1:100.
根据本发明，所述基底为导电基底。优选地，所述基底包括但不限于为金属泡沫、金属网和导电碳基底，如泡沫镍铁、泡沫镍、泡沫铜、泡沫铁、泡沫钴、镍网、铜网、钛网、不锈钢网、碳布、碳纸等中的至少一种。According to the invention, the substrate is an electrically conductive substrate. Preferably, the substrate includes but is not limited to metal foam, metal mesh and conductive carbon substrate, such as ferronickel foam, nickel foam, copper foam, iron foam, cobalt foam, nickel mesh, copper mesh, titanium mesh, stainless steel mesh, At least one of carbon cloth, carbon paper, etc.
根据本发明，所述制备方法还包括对基底进行预处理。例如，将基底置于酸溶液中超声处理，然后洗涤、干燥。According to the present invention, the preparation method further includes pre-treating the substrate. For example, the substrate is sonicated in an acid solution, then washed and dried.
根据本发明，所述液相反应的反应温度为-10～100℃，如-10℃、0℃、4℃、 10℃、20℃、50℃、80℃、100℃；所述液相反应的反应时间为1～150h，如1h、 12h、24h、48h、100h、150h。According to the present invention, the reaction temperature of the liquid phase reaction is -10~100°C, such as -10°C, 0°C, 4°C, 10°C, 20°C, 50°C, 80°C, 100°C; the liquid phase reaction The reaction time is 1 to 150h, such as 1h, 12h, 24h, 48h, 100h, 150h.
根据本发明，所述溶剂热反应的温度为80～200℃，如80℃、100℃、120℃、 150℃、200℃；所述溶剂热反应的时间为1～120h，如1h、12h、24h、48h、100h、 120h。According to the present invention, the temperature of the solvothermal reaction is 80-200°C, such as 80°C, 100°C, 120°C, 150°C, 200°C; the time of the solvothermal reaction is 1-120h, such as 1h, 12h, 24h, 48h, 100h, 120h.
根据本发明，所述电极为具有纳米超结构的自支撑电极。According to the present invention, the electrode is a self-supporting electrode with a nano-superstructure.
本发明还提供由上述制备方法制备得到的电极。The present invention also provides electrodes prepared by the above preparation method.
根据本发明，所述基底具有如上文所述的定义和选择。According to the invention, said substrate has the definition and selection as described above.
根据本发明，所述电极包括基底及负载于基底上的LDHs材料。优选地，所述电极上LDHs材料的负载量为0.5～40mg cm–2。According to the present invention, the electrode includes a substrate and LDHs material supported on the substrate. Preferably, the loading amount of LDHs material on the electrode is 0.5 to 40 mg cm–2 .
本发明还提供上述电极在电解水制氢体系、环境污水处理的氧化反应(如 UOR)、有机小分子升级反应等中的应用。优选地，所述电极应用于有机小分子氧化反应耦合的电解水制氢体系。The present invention also provides applications of the above-mentioned electrodes in water electrolysis hydrogen production systems, oxidation reactions (such as UOR) in environmental sewage treatment, organic small molecule upgrading reactions, etc. Preferably, the electrode is used in an electrolysis water hydrogen production system coupled with an oxidation reaction of organic small molecules.
根据本发明，所述电极的尺寸为(0.5cm*0.5cm)～(10cm*10cm)。According to the present invention, the size of the electrode is (0.5cm*0.5cm) ~ (10cm*10cm).
根据本发明，所述有机小分子氧化反应为尿素氧化反应(UOR)、水合肼氧化反应(HzOR)、甲醇氧化反应(MOR)、乙醇氧化反应(EOR)、乙二醇氧化反应、甘油氧化反应(GOR)、葡萄糖氧化反应、5-羟甲基糠醛氧化反应等中的至少一种。According to the present invention, the organic small molecule oxidation reaction is urea oxidation reaction (UOR), hydrazine hydrate oxidation reaction (HzOR), methanol oxidation reaction (MOR), ethanol oxidation reaction (EOR), ethylene glycol oxidation reaction, and glycerol oxidation reaction. (GOR), glucose oxidation reaction, 5-hydroxymethylfurfural oxidation reaction, and the like.
本发明的有益效果：Beneficial effects of the present invention:
本发明使用Co基MOFs作为前驱体，通过自牺牲模板溶剂热法制备得到了具有纳米超结构的自支撑LDHs基电极材料。具体为：初级结构—LDH结构单元；二级结构—超薄LDH纳米针；三级结构—由LDH纳米针组成的空心板阵列；四级结构—由空心板阵列修饰的三维导电基底框架。这种纳米超结构显著增加了活性位点的数量跟本征活性，进而提升了传质、传荷能力，最终显著增强了其在有机小分子氧化反应及其耦合的新型电解水制氢体系中的电化学性能。以 UOR为例，本发明的自支撑电极仅需1.368V电压即可获得100mA cm-2的电流密度，且具有优异的稳定性。此外，与常规电解水体系相比，在UOR耦合的电解水体系中，获得100mA cm-2的电流密度所需的输入电压可降低213mV。The present invention uses Co-based MOFs as a precursor and prepares a self-supporting LDHs-based electrode material with a nano-superstructure through a self-sacrificial template solvothermal method. Specifically: primary structure - LDH structural unit; secondary structure - ultra-thin LDH nanoneedles; tertiary structure - hollow plate array composed of LDH nanoneedles; quaternary structure - three-dimensional conductive base frame modified by hollow plate array. This nano-superstructure significantly increases the number and intrinsic activity of active sites, thereby improving the mass transfer and charge transfer capabilities, and ultimately significantly enhances its performance in the oxidation reaction of organic small molecules and its coupled new electrolytic water hydrogen production system. electrochemical properties. Taking UOR as an example, the self-supporting electrode of the present invention can obtain a current density of 100mA cm-2 with only a voltage of 1.368V and has excellent stability. In addition, compared with the conventional electrolyzed water system, the input voltage required to obtain a current density of 100mA cm-2 can be reduced by 213mV in the UOR-coupled electrolyzed water system.
本发明通过改变前驱体合成中钴盐、有机配体以及反应溶剂的种类和比例，和/或改变溶剂热反应中添加的过渡金属离子种类与浓度，可以控制所制备的 LDH的组分、大小、厚度等参数，进而改变催化活性点位的数量跟本征活性。同时，由于电极材料所用的原料丰富，合成方法简单，催化效果优异，因而使本发明的电极材料更适用于工业应用。此外，本发明所制备的自支撑电极，可用于环境污水处理的氧化反应(如UOR)、有机小分子升级反应等。不仅如此，本发明制备的电极材料还可用于设计新的电解系统，该系统使用新型阳极反应耦合阴极还原反应，其中阴极反应包括但不仅限于HER、CO2还原反应(CO2RR)、 N2还原反应(NRR)、氧还原反应(ORR)等。The present invention can control the composition and size of the prepared LDH by changing the types and proportions of cobalt salts, organic ligands and reaction solvents in precursor synthesis, and/or changing the types and concentrations of transition metal ions added in the solvothermal reaction. , thickness and other parameters, thereby changing the number and intrinsic activity of catalytic active sites. At the same time, since the raw materials used in the electrode material are abundant, the synthesis method is simple, and the catalytic effect is excellent, the electrode material of the present invention is more suitable for industrial applications. In addition, the self-supporting electrode prepared by the present invention can be used for oxidation reactions (such as UOR) in environmental sewage treatment, organic small molecule upgrading reactions, etc. Not only that, the electrode materials prepared in the present invention can also be used to design new electrolysis systems that use new anode reactions to couple cathode reduction reactions, where the cathode reactions include but are not limited to HER, CO2 reduction reaction (CO2 RR), N2 reduction reaction (NRR), oxygen reduction reaction (ORR), etc.
附图说明Description of the drawings
图1是实施例1、2中实验测得Co-MOF的粉末XRD图谱。Figure 1 is the powder XRD pattern of Co-MOF experimentally measured in Examples 1 and 2.
图2是实施例1、2中Co-MOF的扫描电镜(SEM)图。Figure 2 is a scanning electron microscope (SEM) image of Co-MOF in Examples 1 and 2.
图3是实施例1制备的NiCo-ZLDH/NF(1.0)电极的扫描电镜图。Figure 3 is a scanning electron microscope image of the NiCo-ZLDH/NF (1.0) electrode prepared in Example 1.
图4是实施例1制备的NiCo-ZLDH/NF(1.0)电极的原子力显微镜(AFM)图，标尺为100nm。Figure 4 is an atomic force microscope (AFM) image of the NiCo-ZLDH/NF (1.0) electrode prepared in Example 1. The scale bar is 100 nm.
图5是实施例2制备的NiCo-ZLDH/NF(0.2)电极的扫描电镜图。Figure 5 is a scanning electron microscope image of the NiCo-ZLDH/NF (0.2) electrode prepared in Example 2.
图6是实施例3制备的NiCo-ZLDH/NF(2.0)电极的扫描电镜图。Figure 6 is a scanning electron microscope image of the NiCo-ZLDH/NF (2.0) electrode prepared in Example 3.
图7是实施例4中UOR电化学性能图。Figure 7 is a graph of UOR electrochemical performance in Example 4.
图8是实施例4中HER测试图。Figure 8 is a HER test chart in Example 4.
图9是实施例4中恒电压稳定性测试图。Figure 9 is a constant voltage stability test chart in Example 4.
图10是实施例5全解系统性能测试图。Figure 10 is a performance test chart of the full solution system of Embodiment 5.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步描述。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明内容所实现的技术均涵盖在本发明旨在保护的范围内。The present invention will be further described below with reference to specific embodiments. It should be understood that the following examples are only illustrative and explain the present invention and should not be construed as limiting the scope of the present invention. All technologies implemented based on the content of the present invention are covered by the scope of protection intended by the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1Example 1
(1)泡沫镍(NF)基底的预处理：取20*30mm的NF用1mol/L盐酸溶液超声处理10分钟，并用去离子水和无水乙醇冲洗数次，以去除表面氧化层及有机物，然后于60℃烘箱中烘干备用。(1) Pretreatment of nickel foam (NF) substrate: take 20*30mm NF and ultrasonically treat it with 1mol/L hydrochloric acid solution for 10 minutes, and rinse it several times with deionized water and absolute ethanol to remove the surface oxide layer and organic matter. Then dry it in an oven at 60°C for later use.
(2)Co-MOF(ZIF-67/NF)阵列的合成：ZIF-67/NF的制备通过一步简单的低温合成策略。将2mmol的六水硝酸钴和8mmol的2-甲基咪唑分别溶解于20mL的去离子水中。然后将两种溶液快速混合并加入一片经步骤(1)预处理过的泡沫镍(2*3cm)。随后用封口膜密封，并放入4℃冰箱中反应18h。反应结束后即可得到ZIF-67涂覆的镍泡沫，取出后用去离子水和无水乙醇冲洗数次后于60℃烘箱中烘干制备得到的Co-MOF(ZIF-67/NF)阵列前驱体，备用。(2) Synthesis of Co-MOF (ZIF-67/NF) array: ZIF-67/NF was prepared through a simple one-step low-temperature synthesis strategy. Dissolve 2 mmol of cobalt nitrate hexahydrate and 8 mmol of 2-methylimidazole in 20 mL of deionized water respectively. Then mix the two solutions quickly and add a piece of nickel foam (2*3cm) pretreated in step (1). Then seal it with parafilm and place it in a 4°C refrigerator for reaction for 18 hours. After the reaction is completed, the ZIF-67-coated nickel foam can be obtained. After taking it out, rinse it several times with deionized water and absolute ethanol, and then dry the prepared Co-MOF (ZIF-67/NF) array in a 60°C oven. Precursor, spare.
对步骤(2)制备得到的Co-MOF(ZIF-67/NF)阵列前驱体样品的结构组成及形貌进行分析。图1为ZIF-67/NF的XRD谱图，图中结果表明：本发明成功制备得到了样品Co-MOF(ZIF-67/NF)阵列前驱体。图2的SEM图可以看出：MOF 阵列均匀的生长在镍泡沫基底上。Analyze the structural composition and morphology of the Co-MOF (ZIF-67/NF) array precursor sample prepared in step (2). Figure 1 is the XRD spectrum of ZIF-67/NF. The results in the figure show that the present invention successfully prepared the sample Co-MOF (ZIF-67/NF) array precursor. The SEM image in Figure 2 shows that the MOF array grows uniformly on the nickel foam substrate.
(3)纳米超结构集成电极的合成：自支撑NiCo-ZLDH/NF电极的制备采用刻蚀半牺牲模板过程。首先，将10mmol尿素和1.0mmol NiCl2·6H2O溶解在5.0mL 去离子水(DI)和10mL N,N-二甲基甲酰胺的混合溶液中(体积比DI：DMF ＝1:2)。然后将上述溶液转移到聚四氟乙烯高压釜内衬中，并浸入一片步骤(2) 合成的ZIF-67/NF(2*3cm)，于120℃烘箱中水热反应24h。待自然冷却至室温后，取出样品用去离子水和无水乙醇冲洗，然后于60℃干燥过夜，制备得到自支撑NiCo-ZLDH/NF(1.0)电极。(3) Synthesis of nano-superstructure integrated electrode: The self-supporting NiCo-ZLDH/NF electrode is prepared by etching a semi-sacrificial template process. First, dissolve 10 mmol urea and 1.0 mmol NiCl2 ·6H2 O in a mixed solution of 5.0 mL deionized water (DI) and 10 mL N,N-dimethylformamide (volume ratio DI: DMF = 1:2) . Then transfer the above solution to the lining of a polytetrafluoroethylene autoclave, immerse a piece of ZIF-67/NF (2*3cm) synthesized in step (2), and perform a hydrothermal reaction in a 120°C oven for 24 hours. After naturally cooling to room temperature, the sample was taken out, rinsed with deionized water and absolute ethanol, and then dried at 60°C overnight to prepare a self-supporting NiCo-ZLDH/NF (1.0) electrode.
图3和图4为本实施例制备得到的自支撑NiCo-ZLDH/NF(1.0)电极样品的 SEM图和AFM图，由图可以看出：超结构电极由约7.0nm的纳米片组成。Figures 3 and 4 are SEM images and AFM images of the self-supporting NiCo-ZLDH/NF (1.0) electrode sample prepared in this example. It can be seen from the images that the superstructure electrode is composed of nanosheets of approximately 7.0nm.
实施例2Example 2
(1)泡沫镍基底的预处理，与实施例1中步骤(1)相同。(1) The pretreatment of the nickel foam substrate is the same as step (1) in Example 1.
(2)Co-MOF微阵列的合成，与实施例1中步骤(2)相同。(2) Synthesis of Co-MOF microarray is the same as step (2) in Example 1.
(3)纳米超结构集成电极的制备：自支撑NiCo-ZLDH/NF电极的制备使用刻蚀半牺牲模板方法。首先，将10mmol尿素和0.2mmol NiCl2·6H2O溶解在5.0mL 去离子水和10mL N,N-二甲基甲酰胺的混合溶液中。然后将上述溶液转移到聚四氟乙烯高压釜内衬中，并浸入一片步骤(2)合成的ZIF-67/NF(2*3cm)，于120 ℃烘箱中水热反应24h。待自然冷却至室温后，取出样品用去离子水和无水乙醇冲洗，然后于60℃干燥过夜，制备得到自支撑NiCo-ZLDH/NF(0.2)电极。(3) Preparation of nano-superstructure integrated electrodes: The preparation of self-supporting NiCo-ZLDH/NF electrodes uses the etching semi-sacrificial template method. First, 10 mmol urea and 0.2 mmol NiCl2 ·6H2 O were dissolved in a mixed solution of 5.0 mL deionized water and 10 mL N,N-dimethylformamide. The above solution was then transferred to the lining of a polytetrafluoroethylene autoclave, immersed in a piece of ZIF-67/NF (2*3cm) synthesized in step (2), and hydrothermally reacted in an oven at 120°C for 24 hours. After naturally cooling to room temperature, the sample was taken out, rinsed with deionized water and absolute ethanol, and then dried at 60°C overnight to prepare a self-supporting NiCo-ZLDH/NF (0.2) electrode.
本实施例制备得到的自支撑NiCo-ZLDH/NF(0.2)电极样品的SEM图如图5所示。由图可以看出表面密集分布的纳米片层，其厚度约为5-10nm。The SEM image of the self-supporting NiCo-ZLDH/NF (0.2) electrode sample prepared in this example is shown in Figure 5. It can be seen from the figure that the nanosheets are densely distributed on the surface, and their thickness is about 5-10nm.
实施例3Example 3
与实施例1相比，不同之处仅在于：步骤(3)中采用2.0mmol NiCl2·6H2O，从而制备得到自支撑NiCo-ZLDH/NF(2.0)电极。Compared with Example 1, the only difference is that 2.0 mmol NiCl2 ·6H2 O is used in step (3) to prepare a self-supporting NiCo-ZLDH/NF (2.0) electrode.
图6是实施例3制备的NiCo-ZLDH/NF(2.0)电极的扫描电镜图，从图6所示 SEM图可以看出密集分布的纳米片层，其厚度约7.0nm。Figure 6 is a scanning electron microscope image of the NiCo-ZLDH/NF (2.0) electrode prepared in Example 3. From the SEM image shown in Figure 6, it can be seen that the densely distributed nanosheet layer has a thickness of about 7.0nm.
实施例4Example 4
具有纳米超结构集成电极(NiCo-ZLDH/NF)的电化学性能测试。Electrochemical performance testing of integrated electrodes with nano-superstructure (NiCo-ZLDH/NF).
纳米超结构集成电极的电化学性能表征：尿素氧化(UOR)的电化学性能采用由参比电极(Ag/AgCl)，工作电极(实施例1、实施例2和实施例3中制备的电极，1.0*1.0cm2)和辅助电极(铂网)组成的三电极池中进行。电解液使用1.0M KOH或1.0M KOH和0.5M尿素(Urea)。所测的电位转化为相对于可逆氢电极(RHE)的电位值：ERHE＝EAg/AgCl+0.197+0.059pH。线性扫描伏安曲线 (LSV)和循环伏安曲线(CV)都以5mV s–1的扫速记录。如无具体的说明，电化学数据进行IR补偿。电化学阻抗谱(EIS)测试在交流振幅5mV的0.05至105Hz的频率范围内进行。Characterization of the electrochemical performance of nano-superstructure integrated electrodes: The electrochemical performance of urea oxidation (UOR) adopts the reference electrode (Ag/AgCl), the working electrode (the electrode prepared in Example 1, Example 2 and Example 3, 1.0*1.0cm2 ) and auxiliary electrode (platinum mesh) in a three-electrode cell. The electrolyte solution uses 1.0M KOH or 1.0M KOH and 0.5M urea (Urea). The measured potential is converted into a potential value relative to the reversible hydrogen electrode (RHE): ERHE = EAg/AgCl + 0.197 + 0.059 pH. Both linear sweep voltammetry (LSV) and cyclic voltammetry (CV) were recorded at a sweep rate of 5mV s–1 . Unless otherwise specified, electrochemical data were IR compensated. Electrochemical impedance spectroscopy (EIS) tests were performed in the frequency range from 0.05 to 105 Hz with an AC amplitude of 5 mV.
图7是电极NiCo-ZLDH/NF使用不同的镍含量合成催化剂的UOR性能图(电解液使用的是1.0M KOH和0.5M尿素(Urea))。由图可以看出电流密度在 200mA cm-2时，NiCo-ZLDH/NF(1.0)的电位为1.36V，对UOR有最优的催化效果。Figure 7 is a UOR performance diagram of the electrode NiCo-ZLDH/NF using different nickel contents to synthesize catalysts (the electrolyte uses 1.0M KOH and 0.5M urea (Urea)). It can be seen from the figure that when the current density is 200mA cm-2 , the potential of NiCo-ZLDH/NF (1.0) is 1.36V, which has the optimal catalytic effect on UOR.
图8是电极NiCo-ZLDH/NF(1.0)分别在1.0M KOH、1.0M KOH+0.5M尿素的电解液中的HER性能图，从图中可以看出尿素的添加对析氢过程没有显著影响。Figure 8 is the HER performance diagram of the electrode NiCo-ZLDH/NF (1.0) in the electrolyte of 1.0M KOH and 1.0M KOH + 0.5M urea. It can be seen from the figure that the addition of urea has no significant impact on the hydrogen evolution process.
图9为实施例1中所制备得到的自支撑电极(NiCo-ZLDH/NF)的UOR和HER 恒电压稳定性测试，测试结果表明所制备的多级集成电极具有良好的结构稳定性。Figure 9 shows the UOR and HER constant voltage stability tests of the self-supporting electrode (NiCo-ZLDH/NF) prepared in Example 1. The test results show that the prepared multi-level integrated electrode has good structural stability.
实施例5Example 5
具有纳米超结构自支撑电极(NiCo-ZLDH/NF)尿素氧化反应耦合析氢全解池性能测试。Performance test of urea oxidation reaction coupled hydrogen evolution total decomposition cell with nano-superstructured self-supporting electrode (NiCo-ZLDH/NF).
纳米超结构自支撑电极的全池电化学性能测试过程：UOR//HER和 OER//HER使用两电极体系测试(两电极均为实施例1制备得到的自支撑电极 (NiCo-ZLDH/NF))，工作电极面积为1.0cm2，电解液分别为1.0M KOH (UOR//HER)、1.0M KOH附加0.5M尿素(OER//HER)。Full-cell electrochemical performance testing process of nano-superstructured self-supporting electrodes: UOR//HER and OER//HER were tested using a two-electrode system (both electrodes were self-supporting electrodes (NiCo-ZLDH/NF) prepared in Example 1) ), the working electrode area is 1.0cm2 , and the electrolytes are 1.0M KOH (UOR//HER) and 1.0M KOH plus 0.5M urea (OER//HER).
图10为实施例5中UOR//HER和OER//HER在单池中的全解性能测试结果，可以明显看出UOR//HER系统的活性高于OER//HER体系。Figure 10 shows the full solution performance test results of UOR//HER and OER//HER in a single pool in Example 5. It can be clearly seen that the activity of the UOR//HER system is higher than that of the OER//HER system.
以上，对本发明的实施方式进行了示例性说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been illustratively described above. However, the present invention is not limited to the above-described embodiment. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210521054.7ACN117089874A (en) | 2022-05-12 | 2022-05-12 | Preparation method and application of self-supporting electrode with nano-super structure |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210521054.7ACN117089874A (en) | 2022-05-12 | 2022-05-12 | Preparation method and application of self-supporting electrode with nano-super structure |
| Publication Number | Publication Date |
|---|---|
| CN117089874Atrue CN117089874A (en) | 2023-11-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210521054.7APendingCN117089874A (en) | 2022-05-12 | 2022-05-12 | Preparation method and application of self-supporting electrode with nano-super structure |
| Country | Link |
|---|---|
| CN (1) | CN117089874A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118925729A (en)* | 2024-10-11 | 2024-11-12 | 浙江大学 | Copper-cobalt based heterogeneous catalyst, preparation method and application thereof, and method for electrocatalytic oxidation of 5-hydroxymethylfurfural |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118925729A (en)* | 2024-10-11 | 2024-11-12 | 浙江大学 | Copper-cobalt based heterogeneous catalyst, preparation method and application thereof, and method for electrocatalytic oxidation of 5-hydroxymethylfurfural |
| Publication | Publication Date | Title |
|---|---|---|
| CN108716008B (en) | Three-dimensional nickel-iron layered double hydroxide array and room-temperature preparation method and application thereof | |
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN112080759B (en) | Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea | |
| CN107267124A (en) | A kind of nitrogenous graphitized carbon material containing the bimetallic MOFs of Ni/Fe | |
| CN112951623B (en) | Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof | |
| CN114540831B (en) | A nickel-iron bimetallic coordination polymer catalyst for electrolysis of water and preparation method thereof | |
| CN111883367A (en) | A kind of Cu-doped cobalt hydroxide nanosheet array structure material, preparation method and application thereof | |
| CN115404511A (en) | A kind of nickel foam self-supporting cobalt-nickel bimetallic sulfide heterostructure anode electrocatalyst and its preparation method and application | |
| CN116876032B (en) | Method for synthesizing organic acid ligand hybrid nickel cobalt hydroxide catalyst by one-step hydrothermal method and application | |
| CN118345429A (en) | Nitrogen-doped carbon-modified self-supporting La-doped Co3O4Preparation method of oxygen evolution catalyst | |
| CN117512676A (en) | Hierarchical iron doped nickel-carbon structure nanotube and preparation method and application thereof | |
| CN118186400A (en) | A method for preparing a transition metal-based electrocatalytic water decomposition anode catalyst material and its application | |
| CN117230475A (en) | Preparation method of Ni and Mn bimetallic electrocatalyst and small molecule electrooxidation application thereof | |
| CN115505949A (en) | A kind of iridium-doped metal-organic framework derivative material and its preparation method and application in electrocatalytic oxygen evolution | |
| CN117089874A (en) | Preparation method and application of self-supporting electrode with nano-super structure | |
| CN118773654A (en) | A transition metal-based high-activity alkaline water electrolysis oxygen evolution reaction catalyst and its preparation method and application | |
| CN116516392B (en) | A CoSe nanosheet electrocatalyst with cation vacancies and its preparation method and application | |
| CN118704031A (en) | A NiCo alloy hydrogen evolution catalyst modified by rare earth oxide Eu2O3 supported on carbon cloth and its preparation method and application | |
| CN117431583A (en) | Organic ligand modified transition metal oxyhydroxide nano array electrode and preparation method and application thereof | |
| CN109012673A (en) | A kind of preparation method and application of oxygen-separating catalyst | |
| CN114574900A (en) | Co-N-C composite material with self-supporting multi-stage structure, preparation method and application | |
| CN114045521A (en) | A kind of preparation method of nano-scale electrocatalyst | |
| CN112813451A (en) | Preparation method of Fe-MOF nanosheet growing on foamed nickel in situ | |
| CN119465251A (en) | Preparation method and application of supported FeRu alloy electrocatalyst | |
| CN119980319A (en) | Preparation and application method of nickel-based electrode for electrolyzing water to generate hydrogen |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |