CN115094436A - A kind of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and preparation method and application thereof - Google Patents
A kind of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and preparation method and application thereof Download PDFInfo
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000011258 core-shell material Substances 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 20
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 20
- 230000010287 polarization Effects 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 229940075397 calomel Drugs 0.000 claims description 11
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000004913 activation Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于先进纳米复合材料与技术领域，具体涉及一种镧掺杂镍钴层状双氢氧化物纳米核壳结构催化材料及其制备方法与应用。The invention belongs to the field of advanced nano-composite materials and technologies, in particular to a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and a preparation method and application thereof.
背景技术Background technique
日益增长化石燃料消耗的环境问题受到了人们越来越多的关注，因此建立一个全球规模的清洁和可持续的能源体系是非常重要的。电解水制氢，是非常有前途的方法，这是由于它可以利用来自如风能，太阳能，地热能等清洁能源的电能直接制得高浓度氢气。但是该反应由于它的半反应析氧反应动力学非常缓慢，需要很大的电压去驱动反应，严重的阻碍了该反应的进行，导致研究半反应析氧的催化剂成为了很重要的课题，目前商业化所用的电解水析氧催化剂面临成本高及稳定性低等问题(I.Rodríguez-García,D.Galyamin,L.Pascual,P.Ferrer,M.A.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是：提供一种镧掺杂镍钴层状双氢氧化物纳米核壳结构催化材料及其制备方法与应用，解决现有技术中该催化剂催化性能不高且不稳定，意在通过本发明的技术进一步提高催化剂的催化性能和稳定性。The technical problem to be solved by the present invention is: to provide a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and its preparation method and application, so as to solve the problem that the catalytic performance of the catalyst in the prior art is not high and unstable , is intended to further improve the catalytic performance and stability of the catalyst through the technology of the present invention.
本发明的技术方案是：一种镧掺杂镍钴层状双氢氧化物纳米核壳结构催化材料及其制备方法(图1)如下：首先，在盐酸溶液中，浸泡铜泡沫，清洗表面污渍，然后再用水清洗干净；第二，在三参数体系中，采用恒电流极化，在氢氧化钠溶液中洗涤干净的铜泡沫表面上，形成氢氧化铜纳米阵列；第三，镍源、钴源和镧源配成溶液，在三参数体系中，利用恒电压极化，在氢氧化铜纳米阵列表面上，长出镧掺杂镍钴层状双氢氧化物，形成镧掺杂镍钴层状双氢氧化物纳米核壳结构催化材料。The technical scheme of the present invention is: a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalytic material and its preparation method (Fig. 1) are as follows: first, in a hydrochloric acid solution, soak copper foam to clean the surface stains , and then washed with water; second, in the three-parameter system, using constant current polarization, the copper foam surface was washed in sodium hydroxide solution to form copper hydroxide nanoarrays; third, nickel source, cobalt The source and the lanthanum source are formulated into a solution. In the three-parameter system, using constant voltage polarization, lanthanum-doped nickel-cobalt layered double hydroxide grows on the surface of the copper hydroxide nanoarray to form a lanthanum-doped nickel-cobalt layer. Double hydroxide nano-core-shell structure catalytic material.
优选的，在去除铜泡沫表面污渍中，盐酸溶液浓度为0.1M～0.15M。Preferably, in removing the stains on the surface of the copper foam, the concentration of the hydrochloric acid solution is 0.1M-0.15M.
优选的，优选的所用铜泡沫为0.1mm。Preferably, the preferred copper foam used is 0.1 mm.
优选的，镍源采用硝酸镍、氯化镍中的一种或者一种以上混合。Preferably, the nickel source is one or more than one of nickel nitrate and nickel chloride.
优选的，钴源采用硝酸钴、氯化钴中的一种或者一种以上混合。Preferably, one or more of cobalt nitrate and cobalt chloride are used as the cobalt source.
优选的，镧源采用硝酸镧、氯化镧中的一种或者一种以上混合。Preferably, as the lanthanum source, one or more of lanthanum nitrate and lanthanum chloride are used in combination.
优选的，在合成氢氧化铜纳米阵列体系中，氢氧化钠溶液浓度为1M～2M。在合成镧掺杂镍钴层状双氢氧化物纳米核壳结构材料体系中，镍的摩尔浓度为0.1M～0.2M，钴的摩尔浓度为0.05M～0.1M，镧的摩尔浓度为3mM～15mM。Preferably, in the synthesis of the copper hydroxide nanoarray system, the concentration of the sodium hydroxide solution is 1M-2M. In the synthesis of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure material system, the molar concentration of nickel is 0.1M～0.2M, the molar concentration of cobalt is 0.05M～0.1M, and the molar concentration of lanthanum is 3mM～ 15mM.
优选的，在三参数体系中，对电极采用铂丝或铂片，辅助电极采用甘汞电极或Ag/AgCl电极，工作电极为合成材料。Preferably, in the three-parameter system, the counter electrode is a platinum wire or a platinum sheet, the auxiliary electrode is a calomel electrode or an Ag/AgCl electrode, and the working electrode is a synthetic material.
优选的，使用恒电流极化时间控制在20min～30min之间。Preferably, the galvanostatic polarization time is controlled between 20min and 30min.
优选的，使用恒电压极化时间控制在100s～150s之间。Preferably, the constant voltage polarization time is controlled between 100s and 150s.
优选的，镍元素的电子结构偏移在X射线光电子能谱中主峰结合能分别控制在855.7eV～856.1eV和873.5eV～973.9eV之间。Preferably, the binding energy of the main peak of the electronic structure shift of nickel element in the X-ray photoelectron spectrum is controlled to be between 855.7eV～856.1eV and 873.5eV～973.9eV, respectively.
优选的，钴元素的电子结构偏移在X射线光电子能谱中主峰结合能分别控制在780.9eV～781.1eV和796.7eV～796.9eV之间。Preferably, the main peak binding energy of the electronic structure shift of the cobalt element in the X-ray photoelectron spectrum is controlled to be between 780.9eV-781.1eV and 796.7eV-796.9eV, respectively.
优选的，塔菲尔斜率控制在145mA/dec～160mA/dec之间。Preferably, the Tafel slope is controlled between 145 mA/dec and 160 mA/dec.
优选的，电化学双层电容在22mF/cm2～35mF/cm2。Preferably, the electrochemical double layer capacitance is between 22 mF/cm 2 and 35 mF/cm 2 .
优选的，掺杂镧元素调节了镧掺杂镍钴层状双氢氧化物的电子结构，提高了对析氧反应的催化活性。Preferably, doping with lanthanum adjusts the electronic structure of the lanthanum-doped nickel-cobalt layered double hydroxide, and improves the catalytic activity for the oxygen evolution reaction.
优选的，镧掺杂镍钴层状双氢氧化物的核壳结构可以暴露更多的活性位点。Preferably, the core-shell structure of the lanthanum-doped nickel-cobalt layered double hydroxide can expose more active sites.
本发明的有益效果：本发明所报道的制备方法操作简单，能够实现镧元素对镍钴层状双氢氧化物的电子调控控制、能够控制镍，钴和镧元素的比例、比表面积、活化面积、塔菲尔斜率等，提高电解水析氧活性。制备简单，反应条件温和，适合规模化生产，且制备的产品具有稳定性、电催化活性高的特点，可广泛应用于电化学能源储存与转换技术，具有较高的应用价值。Beneficial effects of the present invention: the preparation method reported in the present invention is simple to operate, can realize the electronic regulation and control of lanthanum on nickel-cobalt layered double hydroxide, and can control the ratio, specific surface area and activation area of nickel, cobalt and lanthanum. , Tafel slope, etc., to improve the oxygen evolution activity of electrolyzed water. The preparation is simple, the reaction conditions are mild, suitable for large-scale production, and the prepared product has the characteristics of stability and high electrocatalytic activity, can be widely used in electrochemical energy storage and conversion technology, and has high application value.
附图说明Description of drawings
图1是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂的制备方法；Fig. 1 is the preparation method of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalyst;
图2是氢氧化铜扫描电镜图；Fig. 2 is the scanning electron microscope picture of copper hydroxide;
图3是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂扫描电镜图；3 is a scanning electron microscope image of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图4是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂EDS能谱铜、镧、镍、氧和钴元素图；Fig. 4 is the EDS energy spectrum of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst with copper, lanthanum, nickel, oxygen and cobalt elements;
图5是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂透射电镜图；Figure 5 is a transmission electron microscope image of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图6是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂X射线衍射图；Fig. 6 is the X-ray diffraction pattern of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图7是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂X射线光电子能谱Ni图谱；Fig. 7 is the Ni spectrum of X-ray photoelectron spectroscopy of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图8是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂X射线光电子能谱Co图谱；Fig. 8 is the X-ray photoelectron spectrum Co spectrum of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图9是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂线性扫描图；Fig. 9 is the linear scanning diagram of lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell structure catalyst;
图10是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂过电压图；Figure 10 is an overvoltage diagram of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图11是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂塔菲尔斜率图；Figure 11 is a Tafel slope diagram of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图12是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂阻抗图；Figure 12 is an impedance diagram of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图13是镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂电化学双层电容图；Figure 13 is an electrochemical double-layer capacitance diagram of a lanthanum-doped nickel-cobalt layered double hydroxide nano-core-shell catalyst;
图14是镧掺杂镍钴层状双氢氧化物纳米催化剂电化学双层电容图；Fig. 14 is the electrochemical double layer capacitance diagram of lanthanum-doped nickel-cobalt layered double hydroxide nanocatalyst;
图15是镧掺杂镍钴层状双氢氧化物纳米催化剂在1000圈循环伏安测试之前和之后的线性扫描图；Figure 15 is a linear scan of the lanthanum-doped nickel-cobalt layered double hydroxide nanocatalyst before and after 1000 cycles of cyclic voltammetry;
图16是镧掺杂镍钴层状双氢氧化物纳米催化剂的稳定性测试图。Figure 16 is a graph showing the stability test of the lanthanum-doped nickel-cobalt layered double hydroxide nanocatalyst.
具体实施方式Detailed ways
实施例1：Example 1:
(1)首先，将1*1.3cm2的铜泡沫放在0.1M的盐酸溶液里浸泡10min，然后再用去离子水分别超声10min三次，取出在真空干燥箱干燥。配制1.5M的氢氧化钠溶液，将铜泡沫作为工作电极(电极反应区域为1*1cm2)，铂丝作为对电极，甘汞电极作为参比电极，使用电化学工站中的恒电流极化，电沉积20min后，取下工作电解夹上合成的材料，然后用清水冲洗3次，烘干得到氢氧化铜纳米阵列。该材料作为下一步合成催化剂的前驱体，也是对比材料。(1) First, soak the 1*1.3cm 2 copper foam in 0.1M hydrochloric acid solution for 10min, then use deionized water to sonicate for 10min three times, take it out and dry it in a vacuum drying oven. Prepare 1.5M sodium hydroxide solution, use copper foam as working electrode (electrode reaction area is 1*1cm 2 ), platinum wire as counter electrode, calomel electrode as reference electrode, use galvanostatic electrode in electrochemical station After 20 min of electrodeposition, the synthesized material on the working electrolytic clip was removed, then rinsed three times with clean water, and dried to obtain copper hydroxide nanoarrays. This material is used as a precursor for the next step to synthesize catalyst, and it is also a comparative material.
(2)通过分析天平分别称取六水硝酸镍2.18g和六水硝酸钴1.16g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化120s后形成镍钴层状双氢氧化物负载氢氧化铜核壳结构纳米阵列，该材料作为对比材料。(2) Weigh 2.18 g of nickel nitrate hexahydrate and 1.16 g of cobalt nitrate hexahydrate respectively by analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 min to prepare an electrolytic solution. Under three-parameter conditions, using copper hydroxide nanoarrays as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode, the nickel-cobalt layered double hydroxide supported copper hydroxide core was formed after constant voltage polarization for 120 s. Shell-structured nanoarrays, this material was used as a comparison material.
(3)通过分析天平分别称取六水硝酸镍2.18g，六水硝酸钴1.16g，和六水硝酸镧0.15g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化120s后形成镧掺杂镍钴层状双氢氧化物负载氢氧化铜纳米核壳结构。(3) Weigh 2.18 g of nickel nitrate hexahydrate, 1.16 g of cobalt nitrate hexahydrate, and 0.15 g of lanthanum nitrate hexahydrate by an analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 min to form an electrolytic solution. Under three-parameter conditions, copper hydroxide nanoarrays were used as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode. After constant voltage polarization for 120 s, a lanthanum-doped nickel-cobalt layered double hydroxide was formed to carry hydrogen. Copper oxide nanocore-shell structure.
实施例2：Example 2:
(1)首先，将1*1.3cm2的铜泡沫放在0.15M的盐酸溶液里浸泡10min，然后再用去离子水分别超声10min三次，取出在真空干燥箱干燥。配制2M的氢氧化钠溶液，将铜泡沫作为工作电极(电极反应区域为1*1cm2)，铂丝作为对电极，甘汞电极作为参比电极，使用电化学工站中的恒电流极化，电沉积20min后，取下工作电解夹上合成的材料，然后用清水冲洗3次，烘干得到氢氧化铜纳米阵列。该材料作为下一步合成催化剂的前驱体，也是对比材料。(1) First, soak the 1*1.3cm 2 copper foam in 0.15M hydrochloric acid solution for 10min, then use deionized water to sonicate for 10min three times, take it out and dry it in a vacuum drying oven. Prepare 2M sodium hydroxide solution, use copper foam as working electrode (electrode reaction area is 1*1cm 2 ), platinum wire as counter electrode, calomel electrode as reference electrode, use galvanostatic polarization in electrochemical station , After 20 min of electrodeposition, the synthesized material on the working electrolytic clip was removed, then rinsed three times with clean water, and dried to obtain a copper hydroxide nanoarray. This material is used as a precursor for the next step to synthesize catalyst, and it is also a comparative material.
(2)通过分析天平分别称取氯化镍2.18g和氯化钴1.16g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化120s后形成镍钴层状双氢氧化物负载氢氧化铜核壳结构纳米阵列，该材料作为对比材料。(2) Weigh 2.18 g of nickel chloride and 1.16 g of cobalt chloride by analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 min to prepare an electrolytic solution. Under three-parameter conditions, using copper hydroxide nanoarrays as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode, the nickel-cobalt layered double hydroxide supported copper hydroxide core was formed after constant voltage polarization for 120 s. Shell-structured nanoarrays, this material was used as a comparison material.
(3)通过分析天平分别称取氯化镍2.18g，氯化钴1.16g，和氯化镧0.15g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化120s后形成镧掺杂镍钴层状双氢氧化物负载氢氧化铜纳米核壳结构。(3) Weigh 2.18 g of nickel chloride, 1.16 g of cobalt chloride, and 0.15 g of lanthanum chloride by analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 minutes to prepare an electrolytic solution. Under three-parameter conditions, copper hydroxide nanoarrays were used as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode. After constant voltage polarization for 120 s, a lanthanum-doped nickel-cobalt layered double hydroxide was formed to carry hydrogen. Copper oxide nanocore-shell structure.
实施例3：Example 3:
(1)首先，将1*1.3cm2的铜泡沫放在0.1M的盐酸溶液里浸泡10min，然后再用去离子水分别超声10min三次，取出在真空干燥箱干燥。配制1.5M的氢氧化钠溶液，将铜泡沫作为工作电极(电极反应区域为1*1cm2)，铂丝作为对电极，甘汞电极作为参比电极，使用电化学工站中的恒电流极化，电沉积30min后，取下工作电解夹上合成的材料，然后用清水冲洗3次，烘干得到氢氧化铜纳米阵列。该材料作为下一步合成催化剂的前驱体，也是对比材料。(1) First, soak the 1*1.3cm 2 copper foam in 0.1M hydrochloric acid solution for 10min, then use deionized water to sonicate for 10min three times, take it out and dry it in a vacuum drying oven. Prepare 1.5M sodium hydroxide solution, use copper foam as working electrode (electrode reaction area is 1*1cm 2 ), platinum wire as counter electrode, calomel electrode as reference electrode, use galvanostatic electrode in electrochemical station After 30 min of electrodeposition, the synthesized material on the working electrolytic clip was removed, then rinsed three times with clean water, and dried to obtain a copper hydroxide nanoarray. This material is used as a precursor for the next step to synthesize catalyst, and it is also a comparative material.
(2)通过分析天平分别称取六水硝酸镍2.18g和六水硝酸钴1.16g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化150s后形成镍钴层状双氢氧化物负载氢氧化铜核壳结构纳米阵列，该材料作为对比材料。(2) Weigh 2.18 g of nickel nitrate hexahydrate and 1.16 g of cobalt nitrate hexahydrate respectively by analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 min to prepare an electrolytic solution. Under three-parameter conditions, using copper hydroxide nanoarrays as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode, the nickel-cobalt layered double hydroxide supported copper hydroxide core was formed after constant voltage polarization for 150 s. Shell-structured nanoarrays, this material was used as a comparison material.
(3)通过分析天平分别称取六水硝酸镍2.18g，六水硝酸钴1.16g，和六水硝酸镧0.15g，放入烧杯中，加入50mL的水，搅拌30min,配成电解溶液。在三参数条件下，使用氢氧化铜纳米阵列作为工作电极，铂丝作为对电极，甘汞电极作为参比电极，恒电压极化150s后形成镧掺杂镍钴层状双氢氧化物负载氢氧化铜纳米核壳结构。(3) Weigh 2.18 g of nickel nitrate hexahydrate, 1.16 g of cobalt nitrate hexahydrate, and 0.15 g of lanthanum nitrate hexahydrate by an analytical balance, put them into a beaker, add 50 mL of water, and stir for 30 min to form an electrolytic solution. Under three-parameter conditions, using copper hydroxide nanoarrays as the working electrode, platinum wire as the counter electrode, and calomel electrode as the reference electrode, the lanthanum-doped nickel-cobalt layered double hydroxide was formed after constant voltage polarization for 150 s to carry hydrogen. Copper oxide nanocore-shell structure.
测试例1：表面形貌分析Test Example 1: Surface Topography Analysis
使用扫描电镜图(图2，图3和图4)和透射电镜图(图5)观察镧掺杂镍钴层状双氢氧化物纳米核壳结构催化剂的成功制备。The successful preparation of lanthanum-doped nickel-cobalt layered double hydroxide nanocore-shell catalyst was observed using scanning electron microscope images (Fig. 2, Fig. 3 and Fig. 4) and transmission electron microscope images (Fig. 5).
测试例2：结构组成和电子结构分析Test Example 2: Structural Composition and Electronic Structure Analysis
将制备样品进行X射线衍射分析，结果如图6所示，由于镍钴层状双氢氧化物的低结晶度，使得X射线衍射图中未观察到镍钴层状双氢氧化物，为了进一步验证样品，进行了X射线光电子能谱表征，如图7和图8所示，同时可以发现镍和钴的峰偏移，证明了掺杂镧元素调节了镍钴层状双氢氧化物的电子结构。The prepared sample was subjected to X-ray diffraction analysis. The results are shown in Figure 6. Due to the low crystallinity of nickel-cobalt layered double hydroxide, no nickel-cobalt layered double hydroxide was observed in the X-ray diffraction pattern. In order to further The samples were verified and X-ray photoelectron spectroscopy characterization was carried out, as shown in Figure 7 and Figure 8, and the peak shift of nickel and cobalt could be found at the same time, which proved that doping lanthanum adjusted the electrons of nickel-cobalt layered double hydroxide structure.
测试例3：催化剂性能测试Test Example 3: Catalyst Performance Test
将样品进行电化学线性扫描，如图9所示，发现镧掺杂镍钴层状双氢氧化物纳米核壳催化剂的过电压最低(254mV)，如图10所示，此外其催化剂塔菲尔斜率(图11)和阻抗半圆也都是最小的(图12)。同时，镧掺杂镍钴层状双氢氧化物纳米核壳催化剂的活化面积最大(图13)。为了证明核壳结构暴露了更多的活性位点，对比镧掺杂镍钴层状双氢氧化物直接负载在铜泡沫上的催化剂，其活化面积远远小于镧掺杂镍钴层状双氢氧化物负载氢氧化铜纳米核壳催化剂，如图14所示。The electrochemical linear scan of the sample was carried out, as shown in Figure 9. It was found that the overvoltage of the lanthanum-doped nickel-cobalt layered double hydroxide nanocore-shell catalyst was the lowest (254mV), as shown in Figure 10. In addition, its catalyst Tafel The slope (Figure 11) and impedance semicircle are also minimal (Figure 12). Meanwhile, the activation area of the lanthanum-doped nickel-cobalt layered double hydroxide nanocore-shell catalyst was the largest (Fig. 13). In order to prove that the core-shell structure exposes more active sites, the activation area is much smaller than that of the lanthanum-doped nickel-cobalt layered double hydroxides directly supported on copper foam catalysts. The oxide-supported copper hydroxide nanocore-shell catalyst is shown in Figure 14.
测试例4：催化剂性能测试Test Example 4: Catalyst Performance Test
将镧掺杂镍钴层状双氢氧化物负载氢氧化铜纳米核壳催化剂进行1000圈循环伏安测试，发现其线性扫描曲线几乎都重合(图15)，和长it稳定性测试(图16)。The lanthanum-doped nickel-cobalt layered double hydroxide-supported copper hydroxide nanocore-shell catalyst was tested for 1000 cycles of cyclic voltammetry, and it was found that its linear sweep curves almost overlapped (Fig. 15), and the long-it stability test (Fig. 16). ).
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