CN111097470A - 氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法 - Google Patents
氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 54
- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 50
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 34
- 239000010439 graphite Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 229910002555 FeNi Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 6
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 241000080590 Niso Species 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- 230000005540 biological transmission Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/396—Distribution of the active metal ingredient
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Abstract
本发明属于电催化领域,具体为一种氮掺杂石墨碳层包覆Fe‑Ni合金纳米方块电催化剂的制备方法。以(亚)铁氰化钠和二价金属镍盐为前驱体,通过化学方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6},通过保护气氛下高温热处理得到氮掺杂石墨碳层包覆Fe‑Ni合金纳米方块电催化剂。电催化剂的不同晶面具有不同原子和电子结构,可展现出迥异的电催化活性。本发明利用简单的化学方法和后续的热处理过程,可制备出具有特定晶面暴露的Fe‑Ni合金,为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体。且表面包覆有氮掺杂的石墨碳层可有效提高催化剂的导电性、催化活性和稳定性。
Description
技术领域
本发明属于电催化领域,具体为一种氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法。
背景技术
电催化分解水制氢是减少环境污染及实现可再生清洁能源的重要途径,其中放氧反应为水分解反应过程的速控步骤。开发高效、稳定且廉价的放氧催化剂具有重要的科学价值和现实意义。Fe、Ni过渡金属及其化合物是广泛研究且具有应用前景的非贵金属基放氧催化剂材料,Fe-Ni合金是其中的典型代表。催化剂的表面原子/电子结构直接影响水分子在其表面的吸附形式和吸附能力。因此,贵金属的表面原子/电子结构直接影响电荷的表面转移过程,最终影响贵金属电催化剂的催化活性。
贵金属不同晶面的电催化活性已被广泛、深入研究,为高效电催化剂的设计提供有效依据。因非贵金属基电催化剂晶面可控制备难以实现,故针对于非贵金属基电催化剂不同晶面的催化活性研究鲜有报道。通过晶面选择性暴露调制金属氧化物表面原子/电子结构,可有效提高光生电荷的表面转移效率,其作为光催化剂具有高的光催化活性。因此,控制制备具有特定晶面暴露的Fe-Ni合金可为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体。
发明内容
本发明的目的在于提供一种氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,通过保护气氛下对普鲁士蓝衍生物{Na2FeNi(CN)6}高温热处理得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂。制备出具有特定晶面暴露的Fe-Ni合金,为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体。
本发明的技术方案是:
一种氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,以铁氰化钠或亚铁氰化钠和二价金属镍盐为前驱体,通过化学合成方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6},通过保护气氛下高温热处理,得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,二价金属镍盐为镍的可溶性盐NiSO4、NiCl2或Ni(NO3)2。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,化学合成方法采用各种湿化学方法:化学沉淀法、水热法或溶剂热法。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,化学合成方法中,将前驱体溶于水形成前驱液,前驱液中:铁氰化钠或亚铁氰化钠的摩尔浓度范围为1mM~1M,二价金属镍盐的摩尔浓度范围为1mM~1M。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,高温热处理的保护气氛为氮气或氩气。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,高温热处理的温度为700~1100℃。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,高温热处理的时间为0.5至5小时。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,铁氰化钠或亚铁氰化钠和二价金属镍盐为前驱体,通过化学合成方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6}的主要化学反应如下:
Na4[Fe(CN)6]+Ni2+→Na2FeNi(CN)6↓+2Na+;
或Na3[Fe(CN)6]+Ni2+→NaFeNi(CN)6↓+2Na+。
所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的技术指标如下:石墨碳层中氮掺杂量为1~3at%,石墨碳层的厚度为1至20纳米。
本发明的设计思想是:
传统的贵金属催化剂的成本昂贵,开发廉价电催化材料是拓展实际应用的关键。理想的电催化材料需要有好的导电性和表面催化活性,其中氮掺杂的碳材料作为一种典型导电担载体被广泛研究。碳材料本身具有好的导电属性,而氮掺杂既可提供催化活性位点又可以作为其它催化剂的锚定位点,Fe、Ni过渡金属及其化合物是非贵金属电催化剂的典型代表。因此,氮掺杂石墨碳层包覆Fe-Ni合金纳米颗粒可作为有效的电催化剂材料,同时考虑晶面催化活性的差异,选择性暴露高催化活性晶面可进一步提升其催化活性。以普鲁士蓝衍生物{Na2FeNi(CN)6}为前驱体,利用其含有氰基(CN-)骨架和Fe、Ni元素,保护气氛下高温碳化可以一步实现氮掺杂石墨碳层包覆Fe-Ni合金纳米颗粒的制备。同时,利用碱金属Na+的作用调控颗粒的形貌,控制制备高活性晶面暴露的Fe-Ni合金纳米颗粒。
本发明的优点及有益效果在于:
1、本发明提供一种氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,制备出具有特定晶面暴露的Fe-Ni合金,为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体。
2、本发明通过保护气氛下高温热处理得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂,电催化剂的不同晶面具有不同原子和电子结构,可展现出迥异的电催化活性。
附图说明
图1:本发明实施例1中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的X射线衍射(XRD)图谱。图中,横坐标2theta为衍射角(degree),纵坐标intensity为强度(a.u.)。
图2:本发明实施例1中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的扫描电子显微镜(SEM)照片。
图3:本发明实施例1中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的透射电子显微镜(TEM)照片。
图4:本发明实施例1中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的能量色散谱(EDS)。图中,横坐标Position为(μm),纵坐标Counts为计数。
图5:本发明实施例1中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的电催化产氧活性;其中,x轴为相对于可逆氢电极施加的电压/V(vs RHE),y轴Currentdensity为产生的电流密度/mA·cm-2。
图6:本发明实施例2中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的透射电子显微镜(TEM)照片。
图7:本发明实施例2中获得的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块样品的电催化产氧活性;其中,x轴为相对于可逆氢电极施加的电压/V(vs RHE),y轴Currentdensity为产生的电流密度/mA·cm-2。
具体实施方式
在具体实施过程中,本发明氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,以(亚)铁氰化钠和二价金属镍盐为前驱体,通过化学方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6},通过保护气氛下高温热处理得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂。制备出具有特定晶面暴露的Fe-Ni合金,为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体,且表面包覆有氮掺杂的石墨碳层可有效提高催化剂的导电性、催化活性和稳定性。其中,具体的特征在于:
1、所述的金属镍盐包括NiSO4、NiCl2、Ni(NO3)2等各种镍的可溶性盐。
2、所述的化学合成方法包括各种湿化学方法,如:化学沉淀法、水(溶剂)热法等。
3、所述的化学合成的前驱液摩尔浓度范围为1mM~1M,优选范围为0.05~0.5M。
4、所述的热处理保护气氛为惰性气氛(如:氮气或氩气)。
5、所述的热处理温度为700~1100℃,优选范围为800~100℃。
6、所述的热处理时间为0.5至5小时,优选范围为1至2小时。
下面结合实施例及附图来更加详细描述本发明。
实施例1
本实施例中,将1.94g的Na4Fe(CN)6·10H2O和1.05g的NiSO4·6H2O分别溶于40ml的去离子水中,分别得到摩尔浓度为0.1M的Na4Fe(CN)6水溶液和NiSO4水溶液。将40ml摩尔浓度0.1M的Ni SO4水溶液逐滴加入摩尔浓度0.1M的Na4Fe(CN)6水溶液,产生绿色沉淀。离心收集后真空烘箱60℃干燥,得到Na2FeNi(CN)6粉体,其粒径30~60纳米。对Na2FeNi(CN)6粉体进行充分研磨后,转移至石英烧舟中,氩气气氛下在管式炉中900℃煅烧2小时,得到黑色粉体样品。
X射线衍射(XRD)分析表明生成FeNi合金,同时有石墨碳衍射峰出现(图1)。通过扫描电子显微镜(SEM)观察FeNi合金为纳米方块形貌(图2)。利用透射电子显微镜(TEM)观察发现FeNi合金纳米方块表面包有石墨碳层(图3)。能量色散谱(EDS)表征发现表面石墨碳层有氮元素掺杂,石墨碳层的厚度约为10纳米,氮元素掺杂量为1.83at%(图4)。最终证实得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块材料。在摩尔浓度1M的KOH电解液中对该材料进行电催化产氧测试,10mA·cm-2的电流是的过电势约为260mV(如图5)。
实施例2
本实施例中,将1.94g的Na4Fe(CN)6·10H2O和0.95g的Ni Cl2·6H2O分别溶于40ml的去离子水中,分别得到摩尔浓度为0.1M的Na4Fe(CN)6水溶液和NiCl2水溶液。将40ml摩尔浓度0.1M的NiCl2溶液逐滴加入摩尔浓度0.1M的Na4Fe(CN)6水溶液,产生绿色沉淀。离心收集后真空烘箱60℃干燥,得到Na2FeNi(CN)6粉体,其粒径为40~70纳米。对Na2FeNi(CN)6粉体进行充分研磨后,转移至石英烧舟中,氩气气氛下在管式炉中1000℃煅烧2小时,得到黑色粉体样品,利用透射电子显微镜(TEM)观察发现FeNi合金纳米方块表面包有石墨碳层(图6),表面石墨碳层有氮元素掺杂,石墨碳层的厚度约为10纳米,氮元素掺杂量为1.68at%。
在摩尔浓度1M的KOH电解液中对该材料进行电催化产氧测试,10mA·cm-2的电流是的过电势约为250mV(如图7)。
实施例结果表明,本发明利用简单的化学方法和后续的热处理过程,可制备出具有特定晶面暴露的Fe-Ni合金,为研究非贵金属基催化剂的表面结构与活性关系提供有效的载体。且表面包覆有氮掺杂的石墨碳层可有效提高催化剂的导电性、催化活性和稳定性。
以上实例仅为本发明中较佳结果,并不用于限制本发明,凡是在本发明原则基础上做的同等替换或修饰所获得的技术方案,均在本发明的保护范围之内。
Claims (9)
1.一种氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,以铁氰化钠或亚铁氰化钠和二价金属镍盐为前驱体,通过化学合成方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6},通过保护气氛下高温热处理,得到氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂。
2.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,二价金属镍盐为镍的可溶性盐NiSO4、NiCl2或Ni(NO3)2。
3.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,化学合成方法采用各种湿化学方法:化学沉淀法、水热法或溶剂热法。
4.按照权利要求3所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,化学合成方法中,将前驱体溶于水形成前驱液,前驱液中:铁氰化钠或亚铁氰化钠的摩尔浓度范围为1mM~1M,二价金属镍盐的摩尔浓度范围为1mM~1M。
5.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,高温热处理的保护气氛为氮气或氩气。
6.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,高温热处理的温度为700~1100℃。
7.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,高温热处理的时间为0.5至5小时。
8.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,铁氰化钠或亚铁氰化钠和二价金属镍盐为前驱体,通过化学合成方法制备得到普鲁士蓝衍生物{Na2FeNi(CN)6}的主要化学反应如下:
Na4[Fe(CN)6]+Ni2+→Na2FeNi(CN)6↓+2Na+;
或Na3[Fe(CN)6]+Ni2+→NaFeNi(CN)6↓+2Na+。
9.按照权利要求1所述的氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的制备方法,其特征在于,氮掺杂石墨碳层包覆Fe-Ni合金纳米方块电催化剂的技术指标如下:石墨碳层中氮掺杂量为1~3at%,石墨碳层的厚度为1至20纳米。
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