CN109987585A - 一种电解水产氧的超薄氢氧化物纳米片的制备方法 - Google Patents
一种电解水产氧的超薄氢氧化物纳米片的制备方法 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 23
- 239000001301 oxygen Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 235000019441 ethanol Nutrition 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 239000000047 product Substances 0.000 claims abstract description 29
- 230000031709 bromination Effects 0.000 claims abstract description 28
- 238000005893 bromination reaction Methods 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 27
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000012670 alkaline solution Substances 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract 2
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- RIPUKAXZALFIMA-UHFFFAOYSA-N decan-1-amine;hydrobromide Chemical class [Br-].CCCCCCCCCC[NH3+] RIPUKAXZALFIMA-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical class Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- -1 n-octyl Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明公开了一种电解水产氧的超薄氢氧化物纳米片的制备方法,步骤为:(1)在K2[M(CN)4]·3H2O的水溶液中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇溶液,经静置扩散获得晶体,其中M为Ni、Pt或Pd;(2)将获得的晶体分散至乙醇中,充分搅拌使晶体的金属有机框架层发生剥离,过滤收集滤液;(3)将收集的滤液离心,获得纳米片;(4)将获得的纳米片分散至水中,经超声分散后,滴入碱性溶液,待溶液由无色变为深黑色后离心,产物分别经水、乙醇洗涤数次后,干燥即得到所述的氢氧化物纳米片。本发明制备的氢氧化物纳米片拥有优异的电催化性能,可降低使用贵金属导致成本高的问题。
Description
技术领域
本发明属于纳米材料领域,具体涉及一种电解水产氧的超薄氢氧化物纳米片的制备方法。
技术背景
电解水产氧在水分解和金属空气电池中起着很重要的作用,但是电解水产氧由于其四电子传输过程导致其动力学反应很缓慢。这就需要更大的过电势才能达到生产要求的电流密度。目前很多研究已经从贵金属催化剂转向过渡金属催化剂。例如:金属氧化物、金属氢氧化物及其衍生物。尽管在金属氢氧化物这方面已经取得了很大的进步,但是设计具有大量活性位点的超薄结构仍然是目前研究的热点。
二维石墨结构转化成石墨烯片层结构已成为研究的热点话题,而类似的二维结构有很多,比如金属有机框架、共价有机框架、无机金属氢氧化物层等等。然而将他们剥离成纳米片仍存在着很大的困难。唐志勇团队利用超声的方法制备了大量的尺寸在几十纳米的纳米片,但是超声过程在很大程度上破坏了纳米片的形貌,进而不能提供足够多的活性位点。
发明内容
针对现有技术存在的上述不足,本发明的目的是提供一种电解水产氧的超薄氢氧化物纳米片的制备方法,该方法将大的有机配体***金属有机框架层与层之间的间隙,进而扩大层与层之间的间隔,使得层间的作用力减弱,进而可以顺利剥离得到纳米片。
为实现上述目的,本发明采用如下技术方案:
一种电解水产氧的超薄氢氧化物纳米片的制备方法,包括以下步骤:
(1)在K2[M(CN)4]·3H2O的水溶液中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇混合溶液,经静置扩散获得晶体,其中M为Ni、Pt或Pd;
(2)将获得的晶体分散至乙醇中,充分搅拌使晶体的金属有机框架层发生剥离,过滤收集滤液;
(3)将收集的滤液离心,获得纳米片;
(4)将获得的纳米片分散至水中,经超声分散后,滴入碱性溶液,待溶液由无色变为深黑色后离心,产物分别经水、乙醇洗涤数次后,干燥即得到所述的氢氧化物纳米片。
其中,上述步骤(1)静置扩散过程中,三种溶液会随着密度的作用相互进入到彼此溶液体系,期间反应物便会相互接触发生反应,从而得到晶体产物。静置扩散的时间可优选为2~4周。金属氯化物可为氯化锰、氯化亚铁、氯化钴、氯化镍或氯化铜等。
上述步骤(2)中,不宜采用高速搅拌,因为高速搅拌会破坏纳米片的整体形貌,搅拌速度可优选为50~250r/min。搅拌时间可根据需要设定,以使金属有机框架层发生剥离为准,搅拌时间宜在6h以上,可优选为6~12h。
上述步骤(4)中,洗涤后的产物,室温干燥即可。
本发明对温度未做特别说明的,均为室温下操作,即20~30℃。
作为优选,所述K2[M(CN)4]·3H2O水溶液、CH3CH2OH和H2O的混合液、金属氯化物和烷基溴化铵盐的乙醇混合溶液三者的体积比为1:2~6:1。
作为优选,所述K2[M(CN)4]·3H2O水溶液的浓度为0.04~0.16mol/L。
作为优选,所述CH3CH2OH和H2O的混合液中CH3CH2OH和H2O的体积比为1:1~3。
作为优选,所述金属氯化物和烷基溴化铵盐的乙醇混合溶液中,金属氯化物的浓度为0.04~0.12mol/L,烷基溴化铵盐的浓度为0.04~0.12mol/L。
作为优选,所述烷基溴化铵盐为四正丁基溴化铵、四癸基溴化铵或四正辛基溴化铵。
作为优选,步骤(2)中过滤后的晶体继续分散至乙醇中,充分搅拌后过滤,收集滤液,过滤后的晶体重复前述操作,优选地,获得的晶体前后共进行4~6次所述操作。
作为优选,步骤(3)中滤液先以低速离心除去大颗粒固体,再以高速离心获得纳米片。本发明中低速指在2000r/min以下,高速指在6000r/min以上。
作为优选,步骤(2)中晶体与乙醇的质量体积比为1g:5~10mL。
本发明方法制备的超薄氢氧化物纳米片可应用于电解水产氧。
相比现有技术,本发明具有如下有益效果:本发明将不同的烷基溴化铵盐***金属有机框架层与层之间的间隙,扩大了层与层之间的距离,弱化了层与层之间的作用力,实现了剥离大片的纳米片,再多次更换母液获得超薄的纳米片,将获得的超薄纳米片在碱性溶液中转化成超薄的金属氢氧化物纳米片,从而拥有优异的电催化性能;本发明所提供的氢氧化物纳米片电催化性能已经和商用的IrO2相媲美,可减少贵金属在电催化中的使用,实现了很好的降低成本的作用。
附图说明
图1为实施例1制备的晶体扫描电镜图;
图2为实施例1制备的纳米片透射电镜图;
图3为实施例1制备的超薄氢氧化物纳米片扫描电镜图;
图4为实施例1制备的超薄氢氧化物纳米片原子力电镜图;
图5为实施例1制备的超薄氢氧化物纳米片电化学性能图。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步详细说明。
实施例1
本实施例超薄氢氧化物纳米片的制备方法如下:
(1)在含有5mL K2[M(CN)4]·3H2O水溶液的试管中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇混合溶液,静置扩散三周获得晶体;
其中,金属氯化物为二氯化亚铁,M为Ni,烷基溴化铵盐为四正丁基溴化铵。
K2[M(CN)4]·3H2O的水溶液的浓度为0.06mol/L,CH3CH2OH和H2O的混合液中CH3CH2OH、H2O的体积为1:1,金属氯化物和烷基溴化铵盐的乙醇混合溶液中,金属氯化物的浓度为0.06mol/L,烷基溴化铵盐的浓度为0.06mol/L。
K2[M(CN)4]·3H2O的水溶液、CH3CH2OH和H2O的混合液、金属氯化物和烷基溴化铵盐的乙醇混合溶液三者的体积比为1:2:1。
(2)将获得的晶体分散至乙醇中,室温缓慢搅拌(80r/min)6h,过滤收集滤液,过滤后的晶体继续分散至乙醇中缓慢搅拌6h,然后过滤收集滤液,过滤后的晶体继续分散至乙醇中重复前述操作,步骤(1)中获得的晶体前后共重复所述操作5次;
其中,晶体与乙醇的质量体积比为1mg:6mL。
(3)将收集的滤液离心,获得纳米片。
其中,滤液先以2000r/min离心除去大颗粒后,再以8000r/min离心。
(4)将得到的纳米片分散至水中,经超声分散后,滴入0.1M KOH溶液,待溶液颜色无色变为深黑色后离心,产物先用水洗涤,再用乙醇洗涤三次后,室温干燥得到所述的超薄氢氧化物纳米片。
图1为本实施例步骤1得到的晶体扫描电镜图像,图2为本实施例步骤2得到的纳米片透射电镜图像,图3为本实施例步骤4得到的超薄氢氧化物纳米片扫描电镜图像,图4为本实施例步骤4得到的超薄氢氧化物纳米片原子力显微镜图像。
由图1~4可观察到,图1是砖块晶体的扫描电镜图,可以看出它的层状结构;图2是剥离纳米片的透射电镜图,可以看出它的片层结构和清晰的边缘;图3可以看出氢氧化物的纳米片结构,结合图4原子力显微镜可以看出该氢氧化物纳米片厚度约为0.9nm。
电解水产氧实验
将本实施例制备的3mg超薄氢氧化物纳米片,配合80μL的5%Nifion粘胶剂和1mL乙醇,取100uL涂覆在电极上,用于电解水产氧实验。
电解水实验是在辰华760E电化学工作中测试,测试采用三电极***。他们是由参比电极Hg/HgO、对电极Pt电极和工作电极组成的。电解液是氧气饱和的1M KOH溶液,工作电极是泡沫镍,且它的面积是1cm2。
极化曲线(图5)是通过线性扫描伏安法以5mV/s的扫描速率获得的。如图5所示,Fe-NS在10mA/cm2电流密度下的电压仅1.49V,与理论电压1.23V相比,过电势仅260mV,同时它与商用IrO2拥有相当的电解水产氧性能。
实施例2
本实施例超薄氢氧化物纳米片的制备方法如下:
(1)在含有8mL K2[M(CN)4]·3H2O水溶液的试管中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇混合溶液,静置扩散三周获得晶体;
其中,金属氯化物为二氯化锰,M为Pd,烷基溴化铵盐为四癸基溴化铵。
K2[M(CN)4]·3H2O的水溶液的浓度为0.08mol/L,CH3CH2OH和H2O的混合液中CH3CH2OH、H2O的体积为1:2,金属氯化物和烷基溴化铵盐的乙醇混合溶液中,金属氯化物的浓度为0.08mol/L,烷基溴化铵盐的浓度为0.08mol/L。
K2[M(CN)4]·3H2O的水溶液、CH3CH2OH和H2O的混合液、金属氯化物和烷基溴化铵盐的乙醇混合溶液三者的体积比为1:3:1。
(2)将获得的晶体分散至乙醇中,室温缓慢搅拌(80r/min)6h,过滤收集滤液,过滤后的晶体继续分散至乙醇中缓慢搅拌6h,然后过滤收集滤液,过滤后的晶体继续分散至乙醇中重复前述操作,步骤(1)中获得的晶体前后共重复所述操作5次;
其中,晶体与乙醇的质量体积比为1mg:7mL。
(3)将收集的滤液离心,获得纳米片。
其中,滤液先以2000r/min离心除去大颗粒后,再以8000r/min离心。
(4)将得到的纳米片分散至水中,经超声分散后,滴入0.1M KOH溶液,待溶液颜色无色变为深黑色后离心,产物先用水洗涤,再用乙醇洗涤三次后,室温干燥得到所述的超薄氢氧化物纳米片。
经测试,本实施例制备的超薄氢氧化物纳米片厚度约为0.9nm,与实施例1制备的超薄氢氧化物纳米片具有相同的电催化性能。
实施例3
本实施例超薄氢氧化物纳米片的制备方法如下:
(1)在含有10mL K2[M(CN)4]·3H2O水溶液的试管中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇混合溶液,静置扩散三周获得晶体;
其中,金属氯化物为二氯化钴,M为Pt,烷基溴化铵盐为四正辛基溴化铵。
K2[M(CN)4]·3H2O的水溶液的浓度为0.12mol/L,CH3CH2OH和H2O的混合液中CH3CH2OH、H2O的体积为1:3,金属氯化物和烷基溴化铵盐的乙醇混合溶液中,金属氯化物的浓度为0.12mol/L,烷基溴化铵盐的浓度为0.12mol/L。
K2[M(CN)4]·3H2O的水溶液、CH3CH2OH和H2O的混合液、金属氯化物和烷基溴化铵盐的乙醇混合溶液三者的体积比为1:4:1。
(2)将获得的晶体分散至乙醇中,室温缓慢搅拌(100r/min)6h,过滤收集滤液,过滤后的晶体继续分散至乙醇中缓慢搅拌6h,然后过滤收集滤液,过滤后的晶体继续分散至乙醇中重复前述操作,步骤(1)中获得的晶体前后共重复所述操作5次;
其中,晶体与乙醇的质量体积比为1mg:8mL。
(3)将收集的滤液离心,获得纳米片。
其中,滤液先以2000r/min离心除去大颗粒后,再以8000r/min离心。
(4)将得到的纳米片分散至水中,经超声分散后,滴入0.1M KOH溶液,待溶液颜色无色变为深黑色后后离心,产物先用水洗涤,再用乙醇洗涤三次后,室温干燥得到所述的超薄氢氧化物纳米片。
经测试,本实施例制备的超薄氢氧化物纳米片厚度约为0.9nm,与实施例1制备的超薄氢氧化物纳米片具有相同的电催化性能。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (10)
1.一种电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,包括以下步骤:
(1)在K2[M(CN)4]·3H2O的水溶液中加入CH3CH2OH和H2O的混合液以形成分层,再缓慢加入金属氯化物和烷基溴化铵盐的乙醇混合溶液,静置扩散获得晶体,其中M为Ni、Pt或Pd;
(2)将获得的晶体分散至乙醇中,充分搅拌使晶体的金属有机框架层发生剥离,过滤收集滤液;
(3)将收集的滤液离心,获得纳米片;
(4)将获得的纳米片分散至水中,经超声分散后,滴入碱性溶液,待溶液由无色变为深黑色后离心,产物分别经水、乙醇洗涤数次后,干燥即得到所述的氢氧化物纳米片。
2.根据权利要求1所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,所述K2[M(CN)4]·3H2O水溶液、CH3CH2OH和H2O的混合液、金属氯化物和烷基溴化铵盐的乙醇混合溶液三者的体积比为1:2~6:1。
3.根据权利要求2所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,所述K2[M(CN)4]·3H2O水溶液的浓度为0.04~0.16mol/L。
4.根据权利要求2所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,所述CH3CH2OH和H2O的混合液中CH3CH2OH和H2O的体积比为1:1~3。
5.根据权利要求2所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,所述金属氯化物和烷基溴化铵盐的乙醇混合溶液中,金属氯化物的浓度为0.04~0.12mol/L,烷基溴化铵盐的浓度为0.04~0.12mol/L。
6.根据权利要求1所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,所述烷基溴化铵盐为四正丁基溴化铵、四癸基溴化铵或四正辛基溴化铵。
7.根据权利要求1所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,步骤(2)中过滤后的晶体继续分散至乙醇中,充分搅拌后过滤,收集滤液,过滤后的晶体重复前述操作,优选地,获得的晶体前后共进行4~6次所述操作。
8.根据权利要求1所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,步骤(3)中滤液先以低速离心除去大颗粒固体,再以高速离心获得纳米片。
9.根据权利要求1所述的电解水产氧的超薄氢氧化物纳米片的制备方法,其特征在于,步骤(2)中晶体与乙醇的质量体积比为1mg:5~10mL。
10.权利要求1~9任一项所述方法制备的超薄氢氧化物纳米片在电解水产氧中的应用。
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