CN111883367B - Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof - Google Patents
Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于纳米材料制备方法及电催化应用领域，具体涉及一种Cu掺杂氢氧化钴纳米片阵列结构材料及其制备方法和应用。The invention belongs to the field of nanomaterial preparation method and electrocatalysis application, and in particular relates to a Cu-doped cobalt hydroxide nanosheet array structure material, a preparation method and application thereof.
背景技术Background technique
目前，氢气因其高能量密度和环保的特点被认为是一种最具吸引力的可替代传统化石燃料的能源。水电解制氢一直被认为是一种可持续的、有发展前景的途径，但由于阳极析氧反应(OER)动力学较慢，通常需要相当大的电位才能持续产氢。并且在全水电解过程中，H2和O2同时产生，可能形成***性的H2/O2混合物。因此，非常有必要开发可行的方法，利用一种更容易进行的氧化反应代替OER实现高效、安全、大规模的生产氢气。Currently, hydrogen is considered to be the most attractive alternative to traditional fossil fuels due to its high energy density and environmental friendliness. Hydrogen production from water electrolysis has long been considered a sustainable and promising route, but due to the slow kinetics of the anodic oxygen evolution reaction (OER), considerable potentials are usually required for sustained hydrogen production. And in the whole water electrolysis process, H2 and O2 are generated at the same time, which may form an explosive H2 / O2 mixture. Therefore, it is highly necessary to develop feasible methods to utilize a more easily performed oxidation reaction instead of OER to achieve efficient, safe, and large-scale hydrogen production.
尿素氧化反应(UOR)的理论电势(0.37V vs.RHE)远小于OER的理论电势(1.23Vvs.RHE)，因此，UOR具有替代反应迟缓的OER的潜力。而且，全尿素电解在节能制氢的同时还为修复富含尿素的废水提供了广阔的前景。然而，由于阳极UOR固有的缓慢6e—转移过程，使得全尿素电解仍然面临低活性和高过电位的挑战。因此，人们致力于开发高效、地球资源丰富的UOR催化剂材料。The theoretical potential of urea oxidation reaction (UOR) (0.37 V vs. RHE) is much smaller than that of OER (1.23 V vs. RHE), therefore, UOR has the potential to replace the sluggish OER. Moreover, all-urea electrolysis provides a broad prospect for the remediation of urea-rich wastewater while energy-saving hydrogen production. However, all-urea electrolysis still faces challenges of low activity and high overpotential due to the inherently slow 6e - transfer process of anodic UOR. Therefore, efforts have been devoted to developing efficient and earth-abundant UOR catalyst materials.
目前大量研究致力于开发各种镍基材料用作UOR催化剂，认为镍基材料在电化学过程中氧化生成的Ni3+是UOR的活性位点。而一些镍基材料也具有良好的HER催化性能，能够成功应用于全尿素电催化制氢。考虑到Co2+氧化成Co3+的电位低于Ni2+氧化成Ni3+的电位，钴基材料应具有更大的UOR电催化潜力。然而钴基材料很少用于UOR和全尿素电解过程，并且其催化活性有待进一步提高。At present, a lot of research is devoted to the development of various nickel-based materials as UOR catalysts. It is believed that Ni 3+ generated by the oxidation of nickel-based materials in the electrochemical process is the active site of UOR. And some nickel-based materials also have good HER catalytic performance, which can be successfully applied to all urea electrocatalytic hydrogen production. Considering that the potential for oxidation of Co2 + to Co3 + is lower than that of Ni2 + to Ni3 + , cobalt-based materials should have a greater potential for UOR electrocatalysis. However, cobalt-based materials are rarely used in UOR and all-urea electrolysis processes, and their catalytic activity needs to be further improved.
发明内容SUMMARY OF THE INVENTION
为解决上述技术问题，本发明提供了一种Cu掺杂氢氧化钴纳米片阵列结构材料及其制备方法和应用。在泡沫镍基底上通过一步液相法合成出Cu掺杂Co(OH)2纳米片阵列结构材料，作为高效UOR、HER和全尿素电解催化剂。在Co(OH)2纳米片阵列中，二维纳米片暴露大量的表面原子，能够显著增加活性位点的数量，其相对开放的结构能保证反应物和产物的快速扩散和质子耦合电子的快速转移，使得催化活性位点易于接近。而且引入的外来金属阳离子Cu2+可以有效地调节Co(OH)2的活性金属中心Co的电子结构，增加催化剂的导电性，加快电子转移速率，提高亲水性，增加活性位点的数量，实现全尿素电解突出的催化活性和稳定性。In order to solve the above technical problems, the present invention provides a Cu-doped cobalt hydroxide nanosheet array structure material and a preparation method and application thereof. A Cu-doped Co(OH) 2 nanosheet array structure material was synthesized by a one-step liquid-phase method on a nickel foam substrate as an efficient catalyst for UOR, HER, and all-urea electrolysis. In the Co(OH) 2 nanosheet array, the 2D nanosheets expose a large number of surface atoms, which can significantly increase the number of active sites, and its relatively open structure can ensure the rapid diffusion of reactants and products and the rapidity of proton-coupled electrons. transfer, making the catalytically active site accessible. Moreover, the introduced foreign metal cation Cu 2+ can effectively adjust the electronic structure of the active metal center Co of Co(OH) 2 , increase the conductivity of the catalyst, accelerate the electron transfer rate, improve the hydrophilicity, and increase the number of active sites, Achieve outstanding catalytic activity and stability of all urea electrolysis.
本发明提供的一种Cu掺杂Co(OH)2纳米片阵列结构材料的制备方法，包括以下步骤：将铜盐、钴盐和六亚甲基四胺溶解于水和甲醇的混合溶剂中，将溶液转移至反应釜中，将泡沫镍倾斜置于溶液中，进行溶剂热反应，反应结束后冷却至室温，产物经洗涤、干燥，即可制得Cu掺杂Co(OH)2纳米片阵列结构材料。A preparation method of a Cu-doped Co(OH) 2 nanosheet array structure material provided by the present invention includes the following steps: dissolving copper salt, cobalt salt and hexamethylenetetramine in a mixed solvent of water and methanol, The solution was transferred to the reaction kettle, and the nickel foam was tilted into the solution to carry out a solvothermal reaction. After the reaction was completed, it was cooled to room temperature, and the product was washed and dried to obtain a Cu-doped Co(OH) 2 nanosheet array. Structural materials.
进一步地，所述铜盐为三水合硝酸铜；所述钴盐为六水合硝酸钴。Further, the copper salt is copper nitrate trihydrate; the cobalt salt is cobalt nitrate hexahydrate.
所述铜盐、钴盐和六亚甲基四胺的物质的量之比为0.1～0.3:2:5，优选为0.2:2:5。The substance ratio of the copper salt, the cobalt salt and the hexamethylenetetramine is 0.1-0.3:2:5, preferably 0.2:2:5.
所述六亚甲基四胺在水和甲醇混合溶剂中的浓度为0.143M。The concentration of the hexamethylenetetramine in the mixed solvent of water and methanol is 0.143M.
所述水和甲醇的体积比为4:3。The volume ratio of the water and methanol is 4:3.
所述溶剂热反应条件为120℃下反应6h。The solvothermal reaction conditions were 120° C. for 6 h.
所述泡沫镍(NF)使用前需进行清洗，具体清洗步骤为：先用6M盐酸浸泡15min除去外层的氧化膜，然后用去离子水和无水乙醇各清洗3次，自然晾干。使用时，泡沫镍裁剪成2×3cm大小。The nickel foam (NF) needs to be cleaned before use. The specific cleaning steps are as follows: soaking in 6M hydrochloric acid for 15 minutes to remove the outer oxide film, then cleaning with deionized water and absolute ethanol for 3 times each, and drying naturally. When in use, the nickel foam is cut into a size of 2×3cm.
所述洗涤为用去离子水和无水乙醇各洗涤3次。The washing was three times each with deionized water and absolute ethanol.
所述干燥为在60℃的烘箱中干燥8h。The drying was drying in an oven at 60° C. for 8 h.
本发明还提供了一种如上述制备方法制备得到的Cu掺杂Co(OH)2纳米片阵列结构材料，所述Cu掺杂Co(OH)2纳米片阵列结构材料的形貌由平均尺寸为300～400nm的纳米片组成。The present invention also provides a Cu-doped Co(OH) 2 nanosheet array structure material prepared by the above preparation method. The morphology of the Cu-doped Co(OH) 2 nanosheet array structure material has an average size of 300 ~ 400nm nanosheet composition.
本发明还提供了所述Cu掺杂Co(OH)2纳米片阵列结构材料作为尿素氧化反应或析氢反应或全尿素电解反应电催化剂的应用。The present invention also provides the application of the Cu-doped Co(OH) 2 nanosheet array structure material as an electrocatalyst for urea oxidation reaction or hydrogen evolution reaction or total urea electrolysis reaction.
所述Cu掺杂Co(OH)2纳米片阵列结构材料作为尿素氧化反应(UOR)电催化剂的应用时，具体方法为：将在泡沫镍上制备的Cu掺杂Co(OH)2纳米片阵列结构材料剪成0.5×0.5cm大小作为工作电极，以1M KOH和0.33M尿素溶液为电解液，用CHI 760E电化学工作站进行测试。用铂丝和Ag/AgCl电极分别作为对电极和参比电极。采用线性扫描伏安法(LSV)在5.0mV·s-1的扫描速率且欧姆补偿为90％下获得极化曲线；通过在恒定电压下测定电流密度时间曲线获得稳定性。电化学活性面积(ECSA)通过在无明显法拉第区域不同扫描速率下(6，8，10，12，14，16，18和20mV·s-1)的循环伏安(CV)测量双电层电容(Cdl)进行评估；电化学阻抗(EIS)在100kHz至0.1Hz的频率范围内进行测试。分别以商业Pt/C负载在泡沫镍上和在泡沫镍上制备的Co(OH)2纳米片作为工作电极，分别测量它们的UOR性能作为比较。When the Cu-doped Co(OH) 2 nanosheet array structure material is used as a urea oxidation reaction (UOR) electrocatalyst, the specific method is as follows: Cu-doped Co(OH) 2 nanosheet arrays prepared on nickel foam The structural material was cut into a size of 0.5 × 0.5 cm as the working electrode, and 1 M KOH and 0.33 M urea solution were used as the electrolyte, and the tests were carried out with a CHI 760E electrochemical workstation. A platinum wire and an Ag/AgCl electrode were used as the counter electrode and the reference electrode, respectively. Polarization curves were obtained using linear sweep voltammetry (LSV) at a scan rate of 5.0 mV·s −1 and an ohmic compensation of 90%; stability was obtained by measuring current density time curves at constant voltage. Electrochemically active area (ECSA) measurement of electric double-layer capacitance by cyclic voltammetry (CV) at different scan rates (6, 8, 10, 12, 14, 16, 18 and 20 mV·s -1 ) with no apparent Faradaic region (C dl ) was evaluated; electrochemical impedance (EIS) was measured in the frequency range from 100 kHz to 0.1 Hz. Commercial Pt/C supported on nickel foam and Co(OH) 2 nanosheets prepared on nickel foam were used as working electrodes, and their UOR performances were measured for comparison.
所述Cu掺杂Co(OH)2纳米片阵列结构材料作为析氢反应(HER)电催化剂的应用时，具体方法为：将在泡沫镍上制备的Cu掺杂Co(OH)2纳米片阵列结构材料剪成0.5×0.5cm大小作为工作电极，以1M KOH和0.33M尿素溶液为电解液，用CHI 760E电化学工作站进行测试。用碳棒和Ag/AgCl电极分别作为对电极和参比电极。采用线性扫描伏安法(LSV)在5.0mV·s-1的扫描速率且欧姆补偿为90％下获得极化曲线；通过在恒定电压下测定电流密度时间曲线获得稳定性。电化学活性面积(ECSA)通过在无明显法拉第区域不同扫描速率下(6，8，10，12，14，16，18和20mV·s-1)的循环伏安(CV)测量双电层电容(Cdl)进行评估；电化学阻抗(EIS)在100kHz至0.1Hz的频率范围内进行测试。分别以商业Pt/C负载在泡沫镍上和在泡沫镍上制备的Co(OH)2纳米片作为工作电极，分别测量它们HER的性能作为比较。When the Cu-doped Co(OH) 2 nanosheet array structure material is used as a hydrogen evolution reaction (HER) electrocatalyst, the specific method is as follows: the Cu-doped Co(OH) 2 nanosheet array structure prepared on the nickel foam The material was cut into a size of 0.5 × 0.5 cm as the working electrode, 1M KOH and 0.33M urea solution were used as the electrolyte, and the tests were carried out with a CHI 760E electrochemical workstation. Carbon rods and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Polarization curves were obtained using linear sweep voltammetry (LSV) at a scan rate of 5.0 mV·s −1 and an ohmic compensation of 90%; stability was obtained by measuring current density time curves at constant voltage. Electrochemically active area (ECSA) measurement of electric double-layer capacitance by cyclic voltammetry (CV) at different scan rates (6, 8, 10, 12, 14, 16, 18 and 20 mV·s -1 ) with no apparent Faradaic region (C dl ) was evaluated; electrochemical impedance (EIS) was measured in the frequency range from 100 kHz to 0.1 Hz. Commercial Pt/C supported on nickel foam and Co(OH) 2 nanosheets prepared on nickel foam were used as working electrodes, and their HER performance was measured for comparison.
所述Cu掺杂Co(OH)2纳米片阵列结构材料作为全尿素电解反应电催化剂的应用时，具体方法为：将在泡沫镍上制备的Cu掺杂Co(OH)2纳米片阵列结构材料剪成2个0.5×0.5cm大小分别作为阴极和阳极组装在双电极电解槽中，通过90％iR补偿的LSV极化曲线和在恒定电压下电流密度时间曲线测试全尿素电解性能。作为对比，研究了商业Pt/C负载在泡沫镍上和在泡沫镍上制备的Co(OH)2纳米片分别作为阴极和阳极的全尿素电解的LSV极化曲线。When the Cu-doped Co(OH) 2 nanosheet array structure material is used as an electrocatalyst for a full urea electrolysis reaction, the specific method is as follows: the Cu-doped Co(OH) 2 nanosheet array structure material prepared on the foamed nickel is used. Cut into two 0.5 × 0.5 cm in size and assembled in a two-electrode electrolytic cell as cathode and anode, respectively, and test the performance of full urea electrolysis by 90% iR-compensated LSV polarization curve and current density-time curve at constant voltage. As a comparison, the LSV polarization curves of commercial Pt/C supported on nickel foam and Co(OH) 2 nanosheets prepared on nickel foam as cathode and anode, respectively, were investigated.
本发明中，Cu掺杂能够调节催化剂的电子结构，促进高氧化态Co3+的产生，增大电化学活性面积，减小电阻。Cu掺杂诱导产生的缺陷能够有效地暴露更多开放的活性位点吸附反应中间体，加快界面电荷转移速率。而且Cu掺杂提高了催化剂的亲水性，增进电解液渗透，进一步加快电解质和催化剂之间的电荷转移速率，提高催化活性。该材料在碱性电解液中对尿素氧化反应、析氢反应和全尿素电解反应均表现出优异的活性和卓越的耐久性，对研究尿素辅助的产氢电催化电极材料的实际应用非常具有价值。In the present invention, Cu doping can adjust the electronic structure of the catalyst, promote the production of high oxidation state Co 3+ , increase the electrochemical active area, and reduce the resistance. The defects induced by Cu doping can effectively expose more open active sites for adsorption reaction intermediates and accelerate the interfacial charge transfer rate. Moreover, Cu doping improves the hydrophilicity of the catalyst, improves the penetration of the electrolyte, further accelerates the charge transfer rate between the electrolyte and the catalyst, and improves the catalytic activity. The material exhibits excellent activity and excellent durability for urea oxidation reaction, hydrogen evolution reaction and total urea electrolysis reaction in alkaline electrolyte, which is very valuable for the research on the practical application of urea-assisted hydrogen production electrocatalytic electrode materials.
与现有技术相比，本发明采用简单的一步溶剂热法，利用六亚甲基四胺分解产生NH3，NH3溶于水生成OH-和NH4 +，Co2+离子与OH-离子生成Co(OH)2，同时Cu2+掺入晶格中。选择水和甲醇混合溶液作溶剂，控制Co2+的水解速度，获得尺寸均匀的薄纳米片阵列结构。Cu掺杂Co(OH)2纳米片阵列结构材料对尿素氧化反应、析氢反应和全尿素电解反应均表现出卓越的催化活性以及稳定性，而且制备工艺环境友好、简单、成本低。Compared with the prior art, the present invention adopts a simple one-step solvothermal method, utilizes hexamethylenetetramine to decompose to generate NH 3 , NH 3 dissolves in water to generate OH - and NH 4 + , Co 2+ ions and OH - ions Co(OH) 2 is formed, while Cu 2+ is incorporated into the crystal lattice. A mixed solution of water and methanol was selected as the solvent to control the hydrolysis rate of Co 2+ to obtain a thin nanosheet array structure with uniform size. The Cu-doped Co(OH) 2 nanosheet array structure material exhibits excellent catalytic activity and stability for urea oxidation reaction, hydrogen evolution reaction and total urea electrolysis reaction, and the preparation process is environmentally friendly, simple and low-cost.
附图说明Description of drawings
图1为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的X-射线粉末衍射(XRD)图；1 is an X-ray powder diffraction (XRD) pattern of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图2为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的能量色散X射线光谱(EDX)图；2 is an energy dispersive X-ray (EDX) spectrum of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图3为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的扫描电子显微镜(SEM)图；3 is a scanning electron microscope (SEM) image of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图4为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的透射电子显微镜(TEM)图；4 is a transmission electron microscope (TEM) image of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图5为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的高分辨透射电子显微镜(HRTEM)图；5 is a high-resolution transmission electron microscope (HRTEM) image of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图6为实施例1制备的Cu掺杂Co(OH)2纳米片阵列结构材料的扫描透射电子显微镜(STEM)图和相应的元素分布图；6 is a scanning transmission electron microscope (STEM) image and a corresponding element distribution map of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 1;
图7为实施例1中Cu掺杂Co(OH)2纳米片阵列结构材料接触角测量结果图；7 is a graph showing the measurement result of the contact angle of the Cu-doped Co(OH) 2 nanosheet array structure material in Example 1;
图8为实施例2制备的Cu掺杂量为3.6％和9.7％的Cu掺杂Co(OH)2纳米片阵列结构材料的X-射线粉末衍射(XRD)图；8 is an X-ray powder diffraction (XRD) pattern of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 2 with a Cu doping amount of 3.6% and 9.7%;
图9为实施例2制备的Cu掺杂量为3.6％和9.7％的Cu掺杂Co(OH)2纳米片阵列结构材料的能量色散X射线光谱(EDX)图；FIG. 9 is an energy dispersive X-ray spectroscopy (EDX) diagram of the Cu-doped Co(OH) 2 nanosheet array structure material prepared in Example 2 with a Cu doping content of 3.6% and 9.7%;
图10为实施例2制备的Cu掺杂量为3.6％的Cu掺杂Co(OH)2纳米片阵列结构材料的扫描电子显微镜(SEM)图；10 is a scanning electron microscope (SEM) image of the Cu-doped Co(OH) 2 nanosheet array structure material with a Cu doping amount of 3.6% prepared in Example 2;
图11为实施例2制备的Cu掺杂量为9.7％的Cu掺杂Co(OH)2纳米片阵列结构材料的扫描电子显微镜(SEM)图；11 is a scanning electron microscope (SEM) image of the Cu-doped Co(OH) 2 nanosheet array structure material with a Cu doping amount of 9.7% prepared in Example 2;
图12为实施例1和实施例2制备的不同Cu含量(3.6％，6.2％和9.7％)的Cu掺杂Co(OH)2纳米片阵列结构材料尿素氧化反应(UOR)的LSV曲线图；Fig. 12 is the LSV curve diagram of urea oxidation reaction (UOR) of Cu-doped Co(OH) 2 nanosheet array structure materials prepared in Example 1 and Example 2 with different Cu contents (3.6%, 6.2% and 9.7%);
图13为实施例3中Cu掺杂Co(OH)2纳米片阵列结构材料、Co(OH)2纳米片、Pt/C和泡沫镍尿素氧化反应(UOR)的LSV曲线图(插图为高电流密度下的极化曲线)；13 is the LSV curve diagram of Cu-doped Co(OH) 2 nanosheet array structure material, Co(OH) 2 nanosheet, Pt/C and foamed nickel urea oxidation reaction (UOR) in Example 3 (inset is high current polarization curve at density);
图14为实施例3中Cu掺杂Co(OH)2纳米片阵列结构材料尿素氧化反应(UOR)的电流密度时间曲线图；14 is a current density time curve diagram of the urea oxidation reaction (UOR) of the Cu-doped Co(OH) 2 nanosheet array structure material in Example 3;
图15为实施例3中Cu掺杂Co(OH)2纳米片阵列结构材料和Co(OH)2纳米片在尿素氧化反应(UOR)条件下不同扫速下的电容电流图；Fig. 15 is the capacitive current diagram of Cu-doped Co(OH) 2 nanosheet array structure material and Co(OH) 2 nanosheet in Example 3 under different scan rates under urea oxidation reaction (UOR) conditions;
图16为实施例3中Cu掺杂Co(OH)2纳米片阵列结构材料和Co(OH)2纳米片在尿素氧化反应(UOR)条件下的阻抗图；Figure 16 is the impedance diagram of Cu-doped Co(OH) 2 nanosheet array structure material and Co(OH) 2 nanosheet in Example 3 under urea oxidation reaction (UOR) conditions;
图17为实施例1和实施例2制备的不同Cu含量(3.6％，6.2％和9.7％)的Cu掺杂Co(OH)2纳米片阵列结构材料析氢反应(HER)的LSV曲线图；Fig. 17 is the LSV curve diagram of the hydrogen evolution reaction (HER) of Cu-doped Co(OH) 2 nanosheet array structure materials with different Cu contents (3.6%, 6.2% and 9.7%) prepared in Example 1 and Example 2;
图18为实施例4中Cu掺杂Co(OH)2纳米片阵列结构材料、Co(OH)2纳米片、Pt/C和泡沫镍析氢反应(HER)的LSV曲线图(插图为高电流密度下的极化曲线)；Figure 18 is the LSV curve of the Cu-doped Co(OH) 2 nanosheet array structure material, Co(OH) 2 nanosheet, Pt/C and foamed nickel hydrogen evolution reaction (HER) in Example 4 (inset is the high current density the polarization curve below);
图19为实施例4中Cu掺杂Co(OH)2纳米片阵列结构材料析氢反应(HER)的电流密度时间曲线图；19 is a current density time curve diagram of the hydrogen evolution reaction (HER) of the Cu-doped Co(OH) 2 nanosheet array structure material in Example 4;
图20为实施例4中Cu掺杂Co(OH)2纳米片阵列结构材料和Co(OH)2纳米片在析氢反应(HER)条件下不同扫速下的电容电流图；Fig. 20 is the capacitive current diagram of Cu-doped Co(OH) 2 nanosheet array structure material and Co(OH) 2 nanosheet in Example 4 under different scan rates under hydrogen evolution reaction (HER) conditions;
图21为实施例4中Cu掺杂Co(OH)2纳米片阵列结构材料和Co(OH)2纳米片在析氢反应(HER)条件下的阻抗图；21 is the impedance diagram of the Cu-doped Co(OH) 2 nanosheet array structure material and the Co(OH) 2 nanosheet in Example 4 under hydrogen evolution reaction (HER) conditions;
图22为实施例5中Cu掺杂Co(OH)2纳米片阵列结构材料、Co(OH)2纳米片和Pt/C在两电极***中全尿素电解的极化曲线图(插图为高电流密度下的极化曲线)；Figure 22 shows the polarization curves of Cu-doped Co(OH) 2 nanosheet array structure material, Co(OH) 2 nanosheets and Pt/C in the two-electrode system for full urea electrolysis in Example 5 (inset is high current polarization curve at density);
图23为实施例5中Cu掺杂Co(OH)2纳米片阵列结构材料在两电极***中全尿素电解的电流密度时间曲线图。FIG. 23 is a current density-time curve diagram of the Cu-doped Co(OH) 2 nanosheet array structure material in the two-electrode system for full urea electrolysis in Example 5. FIG.
具体实施方式Detailed ways
下面结合实施例和说明书附图对本发明进行详细说明。The present invention will be described in detail below with reference to the embodiments and the accompanying drawings.
实施例1Example 1
一种Cu掺杂Co(OH)2纳米片阵列结构材料的制备方法，包括以下步骤：A preparation method of a Cu-doped Co(OH) 2 nanosheet array structure material, comprising the following steps:
将2×3cm大小的泡沫镍浸泡在6M盐酸溶液中，15min后，用去离子水和无水乙醇分别清洗泡沫镍3次，自然晾干，获得表面清洁的泡沫镍。准确量取20mL去离子水和15mL甲醇加入洁净的烧杯中，然后分别称取0.2mmol Cu(NO3)2·3H2O，2mmol Co(NO3)2·6H2O以及5mmol六亚甲基四胺加入烧杯中，获得均匀溶液。将溶液转移至50mL聚四氟乙烯为内衬的不锈钢反应釜中，把预先处理好的泡沫镍斜***溶液中，密封并在120℃烘箱中反应6h，待反应结束后自然冷却至室温，将覆盖样品的泡沫镍用去离子水及无水乙醇各洗涤3次，然后将泡沫镍放在60℃的烘箱中干燥8h，即可得到Cu掺杂Co(OH)2纳米片阵列结构材料。The nickel foam with a size of 2 × 3 cm was soaked in a 6M hydrochloric acid solution. After 15 minutes, the nickel foam was washed with deionized water and anhydrous ethanol for 3 times, and air-dried naturally to obtain a clean surface of the nickel foam. Accurately measure 20mL of deionized water and 15mL of methanol into a clean beaker, then weigh 0.2mmol Cu(NO 3 ) 2 ·3H 2 O, 2mmol Co(NO 3 ) 2 ·6H 2 O and 5mmol hexamethylene respectively. Tetraamine was added to the beaker to obtain a homogeneous solution. The solution was transferred to a 50 mL PTFE-lined stainless steel reaction kettle, and the pretreated nickel foam was obliquely inserted into the solution, sealed and reacted in an oven at 120 °C for 6 h. After the reaction was completed, it was naturally cooled to room temperature, and the The nickel foam covering the sample was washed three times with deionized water and anhydrous ethanol each, and then the nickel foam was dried in an oven at 60 °C for 8 h to obtain a Cu-doped Co(OH) 2 nanosheet array structure material.
用X-射线粉末衍射仪对实施例1所得产物进行物相表征，结果如图1所示，所有衍射峰均与JCPDS no.51-1731卡片中的Co(OH)2吻合。The product obtained in Example 1 was characterized by X-ray powder diffractometer. The results are shown in Figure 1. All diffraction peaks are consistent with Co(OH) 2 in JCPDS no.51-1731 card.
使用能量色散X-射线光谱(EDX)对产物进行分析，如图2所示，Cu和Co元素原子百分比为0.096:1，表明Cu元素成功掺杂到样品中，据此计算出Cu掺杂量为6.2％。The product was analyzed using energy dispersive X-ray spectroscopy (EDX), as shown in Figure 2, the atomic percentage of Cu and Co elements was 0.096:1, indicating that the Cu element was successfully doped into the sample, and the Cu doping amount was calculated accordingly. was 6.2%.
使用扫描电子显微镜(SEM)对实施例1制备的样品进行形貌分析，如图3所示，表明样品由纳米片阵列组成，纳米片平均尺寸为300～400nm。The morphology of the sample prepared in Example 1 was analyzed using a scanning electron microscope (SEM), as shown in FIG. 3 , which indicated that the sample was composed of nanosheet arrays, and the average size of the nanosheets was 300-400 nm.
使用透射电子显微镜(TEM)进一步观察样品的形貌，结果如图4所示，进一步表明样品由纳米薄片组成。The morphology of the sample was further observed using a transmission electron microscope (TEM), and the results are shown in Figure 4, further indicating that the sample is composed of nanoflakes.
纳米片的高分辨透射电子显微镜(HRTEM)图像如图5所示，显示了其结晶性质，但也存在一些缺陷，表明纳米片具有丰富的缺陷结构。其中0.275nm的晶面间距对应于Co(OH)2的(110)晶面。The high-resolution transmission electron microscopy (HRTEM) image of the nanosheets is shown in Fig. 5, showing their crystalline nature, but there are also some defects, indicating that the nanosheets have an abundant defect structure. The interplanar spacing of 0.275 nm corresponds to the (110) plane of Co(OH) 2 .
图6的扫描透射电子显微镜元素分布图说明Cu掺杂Co(OH)2纳米片阵列结构材料中Co、O和Cu元素均匀分布。The scanning transmission electron microscope element distribution map of FIG. 6 illustrates the uniform distribution of Co, O and Cu elements in the Cu-doped Co(OH) 2 nanosheet array structure material.
采用接触角法测定了Cu掺杂Co(OH)2纳米片结构的表面润湿性。图7表示水滴滴到Cu掺杂Co(OH)2样品表面后瞬间的水滴轮廓图。Cu掺杂Co(OH)2样品的接触角为16°，表明产物的亲水性。The surface wettability of Cu-doped Co(OH) 2 nanosheet structures was measured by contact angle method. Figure 7 shows the profile of the water droplet at the moment after the droplet is dropped onto the surface of the Cu-doped Co(OH) 2 sample. The contact angle of the Cu-doped Co(OH) 2 sample is 16°, indicating the hydrophilicity of the product.
实施例2Example 2
Cu掺杂Co(OH)2纳米片阵列结构材料的制备方法，包括以下步骤：The preparation method of Cu-doped Co(OH) 2 nanosheet array structure material includes the following steps:
准确量取20mL去离子水和15mL甲醇加入洁净的烧杯中，然后分别称取0.1mmol或0.3mmol Cu(NO3)2·3H2O，2mmol Co(NO3)2·6H2O以及5mmol六亚甲基四胺加入烧杯中，搅拌均匀。将晾干后的泡沫镍斜***50mL聚四氟乙烯为内衬的不锈钢反应釜中，待溶液充分溶解后转移至反应釜中，密封后在烘箱中120℃反应6h。待反应结束自然冷却至室温，将覆盖样品的泡沫镍用去离子水及无水乙醇各洗涤3次，然后将覆盖样品的泡沫镍放在60℃的烘箱中干燥8h。Cu(NO3)2·3H2O的加入量为0.1mmol时，得到的是Cu掺杂量为3.6％的Cu掺杂Co(OH)2纳米片阵列结构材料；Cu(NO3)2·3H2O的加入量为0.3mmol时，得到的是Cu掺杂量为9.7％的Cu掺杂Co(OH)2纳米片阵列结构材料。Accurately weigh 20mL of deionized water and 15mL of methanol into a clean beaker, then weigh 0.1mmol or 0.3mmol Cu(NO 3 ) 2 ·3H 2 O, 2mmol Co(NO 3 ) 2 ·6H 2 O and 5mmol Hexa Methylenetetramine was added to the beaker and stirred well. The dried nickel foam was inserted obliquely into a 50 mL PTFE-lined stainless steel reaction kettle. After the solution was fully dissolved, it was transferred to the reaction kettle. After sealing, it was reacted in an oven at 120 °C for 6 h. After the reaction was completed, it was naturally cooled to room temperature, the nickel foam covering the sample was washed three times with deionized water and anhydrous ethanol, and then the nickel foam covering the sample was dried in an oven at 60 °C for 8 h. When the addition amount of Cu(NO 3 ) 2 ·3H 2 O was 0.1 mmol, a Cu-doped Co(OH) 2 nanosheet array structure material with a Cu doping amount of 3.6% was obtained; Cu(NO 3 ) 2 · When the added amount of 3H 2 O is 0.3 mmol, a Cu-doped Co(OH) 2 nanosheet array structure material with a Cu doping amount of 9.7% is obtained.
用X-射线粉末衍射仪对实施例2所得产物进行物相表征，结果如图8所示，所有衍射峰均与JCPDS no.51-1731卡片中的Co(OH)2吻合。The product obtained in Example 2 was characterized by X-ray powder diffractometer. The results are shown in Figure 8. All diffraction peaks are consistent with Co(OH) 2 in JCPDS no.51-1731 card.
使用能量色散X-射线光谱(EDX)对所合成的纳米片进行分析，如图9所示，Cu和Co元素原子百分比分别为0.054:1和0.16:1，据此计算出Cu掺杂量为3.6％和9.7％。The synthesized nanosheets were analyzed using energy dispersive X-ray spectroscopy (EDX). As shown in Figure 9, the atomic percentages of Cu and Co elements were 0.054:1 and 0.16:1, respectively, and the Cu doping amount was calculated as 3.6% and 9.7%.
使用扫描电子显微镜(SEM)对实施例2制备的样品形貌进行分析，图10和图11分别是Cu掺杂量为3.6％和9.7％的Cu掺杂Co(OH)2的SEM图，表明样品均为纳米片组成的阵列结构。Scanning electron microscope (SEM) was used to analyze the morphology of the sample prepared in Example 2. Figure 10 and Figure 11 are the SEM images of Cu-doped Co(OH) 2 with Cu doping amount of 3.6% and 9.7%, respectively, indicating that The samples are all array structures composed of nanosheets.
实施例3Example 3
一种Cu掺杂Co(OH)2纳米片阵列结构材料作为尿素氧化反应(UOR)催化剂的应用。Application of a Cu-doped Co(OH) 2 nanosheet array structure material as a catalyst for urea oxidation reaction (UOR).
具体应用方法为：将面积0.5×0.5cm的Cu掺杂Co(OH)2纳米片阵列结构材料作为工作电极，用Pt丝和Ag/AgCl电极分别作为对电极和参比电极在1.0M KOH和0.33M尿素电解质溶液中使用CHI760E电化学工作站进行测试。分别以商业Pt/C负载在泡沫镍上和泡沫镍上制备的Co(OH)2纳米片作为工作电极，分别测量它们的UOR性能作为比较，Co(OH)2的制备是在实施例1的基础上省去了原料中的Cu(NO3)2·3H2O制备得到的。采用线性扫描伏安法(LSV)在5.0mV·s-1的扫描速率且欧姆补偿为90％下获得极化曲线。The specific application method is as follows: the Cu-doped Co(OH) 2 nanosheet array structure material with an area of 0.5 × 0.5 cm is used as the working electrode, and the Pt wire and the Ag/AgCl electrode are used as the counter electrode and the reference electrode, respectively. 0.33M urea electrolyte solution was used for testing using CHI760E electrochemical workstation. The commercial Pt/C supported on nickel foam and Co(OH) 2 nanosheets prepared on nickel foam were used as working electrodes, respectively, and their UOR performance was measured for comparison. Co(OH) 2 was prepared in Example 1. It is prepared by omitting Cu(NO 3 ) 2 ·3H 2 O in the raw material. Polarization curves were obtained using linear sweep voltammetry (LSV) at a scan rate of 5.0 mV·s −1 and an ohmic compensation of 90%.
图12为具有3.6％，6.2％和9.7％不同Cu含量的Cu掺杂Co(OH)2纳米片的尿素氧化反应(UOR)极化曲线。表明Cu掺杂量显著地影响UOR活性，Cu掺杂量为6.2％的样品优于3.6％和9.7％的样品。Figure 12 is the urea oxidation reaction (UOR) polarization curves of Cu-doped Co(OH) 2 nanosheets with different Cu contents of 3.6%, 6.2% and 9.7%. It is shown that the amount of Cu doping significantly affects the UOR activity, and the samples with a Cu doping amount of 6.2% are better than those of 3.6% and 9.7%.
图13为Cu掺杂Co(OH)2纳米片阵列结构材料、Co(OH)2纳米片、Pt/C和泡沫镍的尿素氧化反应(UOR)极化曲线，从图中可以看出，Cu掺杂Co(OH)2纳米片阵列结构材料只需要1.31V低的电位就可以实现10mA·cm-2的电流密度，分别比Co(OH)2和商业Pt/C小65mV和58mV。此外，Cu掺杂Co(OH)2纳米片阵列结构材料可以在1.418V和1.486V较小的电位下达到500mA·cm-2和1000mA·cm-2的大电流密度。Figure 13 shows the urea oxidation reaction (UOR) polarization curves of Cu-doped Co(OH) 2 nanosheet array structure materials, Co(OH) 2 nanosheets, Pt/C and nickel foam. It can be seen from the figure that Cu The doped Co(OH) 2 nanosheet array structure material only needs a low potential of 1.31 V to achieve a current density of 10 mA cm -2 , which is 65 mV and 58 mV smaller than that of Co(OH) 2 and commercial Pt/C, respectively. In addition, the Cu-doped Co(OH) 2 nanosheet array structure material can reach large current densities of 500 mA·cm -2 and 1000 mA·cm -2 at small potentials of 1.418 V and 1.486 V.
图14是在不同电位下采用电流密度时间曲线评估UOR电催化稳定性。从图中可以看出，在1.317V的电位下UOR电流密度在前7小时内下降10％，可能是由于随着电解时间的延长，电解液中尿素含量逐渐降低。而在第7h将原来的电解质溶液更换为新鲜电解质溶液后，阳极电流密度显著恢复到最初(0h)电流密度的98％。同样的，在第14h时再次更换新鲜电解质溶液后电流密度依然能够恢复到最初电流密度的94％。另外在1.362和1.418V电位下催化剂具有相似的长期耐久性。说明Cu6.2％-Co(OH)2电极具有优异的UOR稳定性。Figure 14 is the evaluation of UOR electrocatalytic stability using current density time curves at different potentials. It can be seen from the figure that the UOR current density decreased by 10% in the first 7 hours at the potential of 1.317 V, which may be due to the gradual decrease of the urea content in the electrolyte with the extension of the electrolysis time. However, after replacing the original electrolyte solution with a fresh electrolyte solution at the 7th hour, the anode current density remarkably recovered to 98% of the initial (0h) current density. Similarly, the current density could still recover to 94% of the original current density after the fresh electrolyte solution was replaced again at 14 h. Additionally the catalysts have similar long-term durability at 1.362 and 1.418 V potentials. It shows that the Cu 6.2% -Co(OH) 2 electrode has excellent UOR stability.
用双电层电容评估材料在UOR条件下的电化学活性面积，如图15所示。Cu掺杂Co(OH)2双电层电容为20.4mF·cm-2，大于Co(OH)2的10.9mF·cm-2，表明Cu掺杂增大了样品的电化学活性面积。The electrochemically active area of the material under UOR conditions was evaluated with electric double-layer capacitance, as shown in Figure 15. The electric double-layer capacitance of Cu-doped Co(OH) 2 is 20.4 mF·cm -2 , which is larger than 10.9 mF·cm -2 of Co(OH) 2 , indicating that Cu doping increases the electrochemical active area of the sample.
图16的电化学阻抗(EIS)图表明Cu掺杂Co(OH)2纳米片阵列结构材料的半圆直径小，说明其电阻小，具有更快速的催化动力学。The electrochemical impedance (EIS) diagram of FIG. 16 shows that the semicircular diameter of the Cu-doped Co(OH) 2 nanosheet array structure material is small, indicating its small resistance and faster catalytic kinetics.
实施例4Example 4
一种Cu掺杂Co(OH)2纳米片阵列结构材料作为析氢反应(HER)催化剂的应用。Application of a Cu-doped Co(OH) 2 nanosheet array structure material as a catalyst for hydrogen evolution reaction (HER).
具体应用方法为：将面积0.5×0.5cm的Cu掺杂Co(OH)2纳米片阵列结构材料作为工作电极，用碳棒和Ag/AgCl电极分别作为对电极和参比电极，在1.0M KOH和0.33M尿素电解质溶液中使用CHI760E电化学工作站进行测试。分别以商业Pt/C负载在泡沫镍上和在泡沫镍上制备的Co(OH)2纳米片作为工作电极，测量它们的HER性能作为比较。Co(OH)2的制备是在实施例1的基础上省去了原料中的Cu(NO3)2·3H2O制备得到的。采用线性扫描伏安法(LSV)在5.0mV·s-1的扫描速率且欧姆补偿为90％下获得极化曲线。The specific application method is as follows: the Cu-doped Co(OH) 2 nanosheet array structure material with an area of 0.5×0.5 cm is used as the working electrode, the carbon rod and the Ag/AgCl electrode are used as the counter electrode and the reference electrode, respectively. and 0.33M urea electrolyte solution were tested using CHI760E electrochemical workstation. Commercial Pt/C supported on nickel foam and Co(OH) 2 nanosheets prepared on nickel foam were used as working electrodes, respectively, and their HER performance was measured for comparison. The preparation of Co(OH) 2 was prepared on the basis of Example 1 without Cu(NO 3 ) 2 ·3H 2 O in the raw material. Polarization curves were obtained using linear sweep voltammetry (LSV) at a scan rate of 5.0 mV·s −1 and an ohmic compensation of 90%.
图17为具有3.6％，6.2％和9.7％不同Cu含量的Cu掺杂Co(OH)2纳米片的析氢反应(HER)极化曲线。表明Cu掺杂量也显著影响催化剂的HER活性，Cu掺杂量为6.2％的样品达到最佳。Figure 17 is the hydrogen evolution reaction (HER) polarization curves of Cu-doped Co(OH) 2 nanosheets with different Cu contents of 3.6%, 6.2% and 9.7%. It is shown that the Cu doping amount also significantly affects the HER activity of the catalyst, and the sample with Cu doping amount of 6.2% achieves the best.
图18为Cu掺杂Co(OH)2纳米片阵列结构材料、Co(OH)2纳米片、Pt/C和泡沫镍的析氢反应(HER)极化曲线。从图中可以看出，Cu掺杂Co(OH)2纳米片阵列结构材料在76mV的过电位下就能达到10mA·cm-2电流密度，远小于Co(OH)2催化剂的131mV。尽管Pt/C电极在低电流密度下显示出突出的HER活性，但在高电流密度下，材料极易脱落而影响活性。此外，Cu掺杂Co(OH)2纳米片阵列结构材料可以在234mV和261mV较小的过电位下分别达到500mA·cm-2和1000mA·cm-2的大电流密度。Figure 18 shows the hydrogen evolution reaction (HER) polarization curves of Cu-doped Co(OH) 2 nanosheet array structure materials, Co(OH) 2 nanosheets, Pt/C and nickel foam. It can be seen from the figure that the Cu-doped Co(OH) 2 nanosheet array structure material can reach a current density of 10 mA cm -2 at an overpotential of 76 mV, which is much lower than the 131 mV of the Co(OH) 2 catalyst. Although Pt/C electrodes show outstanding HER activity at low current densities, at high current densities, the material is easily exfoliated and affects the activity. In addition, the Cu-doped Co(OH) 2 nanosheet array structure material can reach large current densities of 500 mA·cm -2 and 1000 mA·cm- 2 at small overpotentials of 234 mV and 261 mV, respectively.
采用恒定过电位76，194，234mV下电流密度时间曲线评估HER电催化的稳定性，如图19所示。经过21小时的连续电解反应，电流密度均保持为最初的92.3％以上，表现出良好的HER电催化稳定性。The stability of HER electrocatalysis was evaluated using the current density-time curves at constant overpotentials of 76, 194, and 234 mV, as shown in Figure 19. After 21 hours of continuous electrolysis, the current densities remained above 92.3% of the initial value, showing good HER electrocatalytic stability.
用双电层电容评估材料在HER条件下的电化学活性面积，如图20所示。Cu掺杂Co(OH)2双电层电容为7.2mF·cm-2，大于Co(OH)2的3.6mF·cm-2，表明Cu掺杂增大了样品的电化学活性面积。The electrochemically active area of the material under HER conditions was evaluated with electric double-layer capacitance, as shown in Figure 20. The electric double layer capacitance of Cu-doped Co(OH) 2 is 7.2mF·cm -2 , which is larger than 3.6mF·cm -2 of Co(OH) 2 , indicating that Cu-doping increases the electrochemical active area of the sample.
图21的电化学阻抗(EIS)图表明Cu掺杂Co(OH)2纳米片阵列结构材料的半圆直径小，说明其电阻小，具有更快速的催化动力学。The electrochemical impedance (EIS) map of Figure 21 shows that the Cu-doped Co(OH) 2 nanosheet array structure material has a small semicircle diameter, indicating its small resistance and faster catalytic kinetics.
实施例5Example 5
一种Cu掺杂Co(OH)2纳米片阵列结构材料作为全尿素电解反应催化剂的应用。Application of a Cu-doped Co(OH) 2 nanosheet array structure material as a catalyst for all-urea electrolysis reaction.
具体应用方法为：将2个面积为0.5×0.5cm的Cu掺杂Co(OH)2纳米片阵列结构材料分别作为阳极和阴极组装在双电极电解槽中，在1.0M KOH和0.33M尿素电解质溶液中测试全尿素电解性能。并以Co(OH)2纳米片和Pt/C作为阳极和阴极组成的电对作为比较。The specific application method is as follows: 2 Cu-doped Co(OH) 2 nanosheet array structure materials with an area of 0.5 × 0.5 cm were assembled in a two-electrode electrolytic cell as anode and cathode, respectively, in 1.0 M KOH and 0.33 M urea electrolyte. The electrolytic performance of total urea was tested in solution. The galvanic pairs composed of Co(OH) 2 nanosheets and Pt/C as anode and cathode were used for comparison.
图22为90％iR补偿的电极LSV极化曲线。从图中可以看出，Cu掺杂Co(OH)2纳米片阵列结构材料在1.389V的电压下就能达到10mA·cm-2电流密度，仅需要1.781V的电压就能驱动500mA·cm-2的大电流密度。明显比商业Pt/C组成的电对活性高，而且商业Pt/C因材料极易脱落而无法达到500mA·cm-2的大电流密度。Figure 22 is a 90% iR compensated electrode LSV polarization curve. It can be seen from the figure that the Cu-doped Co(OH) 2 nanosheet array structure material can reach a current density of 10 mA cm -2 at a voltage of 1.389 V, and only needs a voltage of 1.781 V to drive 500
图23为恒定电压下电流密度时间曲线。从图中可以看出，Cu掺杂Co(OH)2纳米片阵列结构材料在恒定电压1.457V下持续电解7h电流密度下降了16％。而在第7h时将原来的电解质溶液更换为新鲜电解质溶液后，电流密度能显著恢复到最初(0h)电流密度的92.5％。同样的，在第14h时再次更换新鲜电解质溶液后电流密度依然能恢复到最初电流密度的90.5％。另外在1.65和1781V电位下催化剂具有相似的长期耐久性。说明Cu6.2％-Co(OH)2电极具有优异的长期稳定性。Figure 23 is a current density time curve at constant voltage. It can be seen from the figure that the current density of Cu-doped Co(OH) 2 nanosheet array structure material decreased by 16% under constant voltage of 1.457V for 7h. However, after replacing the original electrolyte solution with a fresh electrolyte solution at the 7th hour, the current density can remarkably recover to 92.5% of the initial (0h) current density. Similarly, the current density can still recover to 90.5% of the original current density after replacing the fresh electrolyte solution again at 14 h. Additionally the catalysts have similar long-term durability at 1.65 and 1781 V potentials. It shows that the Cu 6.2% -Co(OH) 2 electrode has excellent long-term stability.
上述参照实施例对一种Cu掺杂氢氧化钴纳米片阵列结构材料及其制备方法和应用进行的详细描述，是说明性的而不是限定性的，可按照所限定范围列举出若干个实施例，因此在不脱离本发明总体构思下的变化和修改，应属本发明的保护范围之内。The detailed description of a Cu-doped cobalt hydroxide nanosheet array structure material and its preparation method and application with reference to the above examples is illustrative rather than limiting, and several examples can be listed according to the limited scope. Therefore, changes and modifications without departing from the general concept of the present invention should fall within the protection scope of the present invention.
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