CN111389442A - 负载于泡沫镍表面的p-n异质结复合材料及其制备方法与应用 - Google Patents
负载于泡沫镍表面的p-n异质结复合材料及其制备方法与应用 Download PDFInfo
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- CN111389442A CN111389442A CN202010313573.5A CN202010313573A CN111389442A CN 111389442 A CN111389442 A CN 111389442A CN 202010313573 A CN202010313573 A CN 202010313573A CN 111389442 A CN111389442 A CN 111389442A
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- Prior art keywords
- composite material
- foamed nickel
- nickel
- loaded
- material loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 40
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002135 nanosheet Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000002070 nanowire Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 26
- 239000003344 environmental pollutant Substances 0.000 claims description 24
- 231100000719 pollutant Toxicity 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 230000001699 photocatalysis Effects 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 10
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- 150000001868 cobalt Chemical class 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 239000006260 foam Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
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- 239000012046 mixed solvent Substances 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
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- 230000005684 electric field Effects 0.000 description 5
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- 239000013543 active substance Substances 0.000 description 4
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- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- -1 preferably Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明公开了一种负载于泡沫镍表面的P‑N异质结复合材料及其制备方法与应用,为可用于光电催化去除水体中污染物的负载型催化剂。首先通过水热的方法在表面洁净的泡沫镍表面修饰层状镍铁双金属氢氧化物纳米片;然后通过混合溶剂热的方式在层状镍铁双金属氢氧化物纳米片的表面修饰四氧化三钴纳米线,得到负载于泡沫镍表面的P‑N异质结催化剂复合材料(Ni foam@NiFe‑LDH/Co3O4)。该复合材料对可见光具有良好的响应,可大大增强材料对光的吸收和利用率,进而有利于增强催化剂的性能。
Description
技术领域
本发明涉及纳米复合材料及光电催化技术领域,具体涉及一种负载于泡沫镍上的二维层状镍铁双金属氢氧化物纳米片和一维四氧化三钴纳米线P-N异质结复合材料的制备方法及其用于光电催化有效去除水体中污染物的应用。
背景技术
近年来,随着科技进步和经济发展,人们的生活水平达到了一个新高度,但也带来了能源短缺与环境污染等问题。如何合理利用已有资源消除环境污染并很好的保护环境是目前需要关注的问题。以半导体材料为核心的光催化技术为我们提供了一种较理想的污染治理思路,其本质是利用廉价、清洁和无穷尽的太阳光能为能源,在污染体系中加入催化剂,当半导体催化剂吸收能量等于或大于其带隙能的光子时,产生光生载流子,进而形成各种不同种类的活性物质,这些活性物质中具有氧化性质的可以降解有机污染物使其分解直到矿化,而具有还原性质的物质可以用于处理环境中的重金属离子。在此过程中,光催化剂受光激发产生活性物质和活性物质与环境污染物的反应是光催化技术应用的基础和关键。但是,目前大多数光催化剂的催化效率远远达不到实际应用的需求,其主要缺陷集中在催化剂对光的吸收和利用范围,光生载流子的分离和迁移,以及催化剂的稳定性和重复利用等问题上。因此,目前围绕半导体光催化技术的研究热点主要集中在解决上述问题上。
发明内容
本发明的目的是提供一种负载于泡沫镍表面的P-N异质结催化剂复合材料(Nifoam@NiFe-LDH/Co3O4)及其制备方法,构建可见光响应的光催化复合材料,并通过光电催化的方法实现水体中污染物的有效去除。本发明构建了一种负载型具有可见光响应的P-N异质结复合材料,在半导体复合材料的内部形成内建电场加速了光生载流子的迁移速率,进而可以避免光生载流子的复合而增强催化活性,与此同时,该负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)可直接用作光阳极,应用于光电催化反应,在外加电场的驱动下将光生电子转移至对电极,更进一步增强了光生载流子的分离。综上所述,这一设计不仅提高了材料对光的吸收和利用,也有利于光生载流子的分离、迁移,同时光电催化的方式可进一步增进催化活性。在催化性能方面,上述制备的复合材料表现出对污染物的有效去除,且由于P-N异质结催化剂负载于宏观泡沫镍表面,在实际的催化过程中表现出便利且良好的分离效果。
为了达到上述目的,本发明采用如下具体技术方案:
一种负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4)及其制备方法,包括以下步骤,采用混合溶剂热的方法在负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4),可作为催化剂。
本发明公开了光电催化净化水体中的污染物的方法,包括以下步骤,采用混合溶剂热的方法在负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料;将负载于泡沫镍表面的P-N异质结复合材料加入含有污染物的水体中,光催化和/或电催化,完成水体中的污染物的净化。
本发明中,光催化为可见光催化;电催化在电化学工作站进行。两种催化具体的操作方法都是常规技术,本发明创造性在于公开了负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4)作为催化剂净化水体中的污染物。
本发明进一步公开了上述负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4)作为催化剂在净化水体中污染物的应用。
水体中的污染物可以为无机物还可以为有机物,比如铬离子、油、有机溶剂、双酚化合物等。
本发明中,以泡沫镍为载体,通过水热法在泡沫镍的表面修饰层状镍铁双金属氢氧化物纳米片,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片;具体的,将前驱体溶液与泡沫镍混合,然后120~180 ℃下水热反应20~30 h,得到层状镍铁双金属氢氧化物纳米片,负载于泡沫镍的表面;前驱体溶液由镍盐、铁盐、水、尿素组成,优选的,镍盐为六水合硝酸镍、铁盐为九水合硝酸铁;进一步的,前驱体溶液中,二价金属离子Ni2+与三价金属离子Fe3+的摩尔比为2:1,尿素的摩尔数为二价金属离子Ni2+与三价金属离子Fe3+摩尔数总和的3.8~4.2倍,优选4倍。
本发明中,将层状镍铁双金属氢氧化物纳米片与含钴溶液混合,然后80~100 ℃下水热反应6~10 h,再热处理,得到负载于泡沫镍表面的P-N异质结复合材料;含钴溶液由水、乙醇、钴盐、尿素组成,优选的,钴盐为六水合硝酸钴;进一步的,水和乙醇的体积比为1:1,尿素和钴盐的摩尔比为4:1;优选的,钴盐的浓度为0.003~0.008g/mL ,优选0.004~0.005g/mL;热处理为在空气气氛下于250℃下保温1.5~2.5 h,优选2h。
本发明以宏观材料泡沫镍(Ni foam)为载体,首先通过水热的方法在泡沫镍的表面修饰层状镍铁双金属氢氧化物(NiFe-LDH)纳米片,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH);然后通过混合溶剂热的方法在层状镍铁双金属氢氧化物纳米片表面修饰针状一维四氧化三钴(Co3O4)纳米线,得到负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)。以上述复合材料作为光阳极,通过光电催化的方法对双酚A(BPA)和六价铬(Cr(VI))进行催化处理。本发明所提供的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)可以通过光电催化的方法对水体中污染物实现高效净化。
本发明负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4)的制备方法可如下进行:
(1) 层状镍铁双金属氢氧化物前驱体溶液的制备:首先,在单口圆底烧瓶中依次加入去离子水、六水合硝酸镍和九水合硝酸铁(二价金属离子Ni2+与三价金属离子Fe3+的摩尔比为2:1,Fe3+在去离子水中的摩尔浓度为0.1 mol/L),搅拌均匀后加入尿素(尿素的投料摩尔数为二价与三价金属离子摩尔数总和的4倍),搅拌均匀后于90~110℃下回流20~30 h,即得到NiFe-LDH的前驱体溶液;
(2) 负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)的制备:本发明采用水热法合成上述负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)。将表面洁净的泡沫镍放入聚四氟乙烯内衬的高压反应釜中,加入制备好的层状镍铁双金属氢氧化物的前驱体溶液。将反应釜置于预先设定好温度的烘箱内,在120~180 ℃下恒温水热反应20~30 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行离心分离并用去离子水洗涤3~5次,置于60 ℃鼓风烘箱中干燥20~30 h,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH);
(3) 负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)的制备:本发明采用混合溶剂热法合成上述负载于泡沫镍表面的P-N异质结催化剂复合材料(Nifoam@NiFe-LDH/Co3O4)。首先,在烧杯中依次加入去离子水、无水乙醇、六水合硝酸钴和尿素(去离子水和无水乙醇的体积比为1:1,尿素和六水合硝酸钴的摩尔比为4:1),超声分散得到均一的混合溶液。将上述(2)中制备得到的负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)放入聚四氟乙烯内衬的高压反应釜中,加入一定量的上述混合溶液。将反应釜置于预先设定好温度的烘箱内,在80~100 ℃下恒温水热反应6~10 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行分离并用去离子水洗涤3~5次,干燥后置于管式炉中,在空气气氛下于250℃条件下保温2 h,升温速率为2-5℃/min,得到负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)。
本发明的优点:
1. 本发明公开的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)具有广泛的光响应范围,是一种可见光光催化复合材料。
2. 本发明公开的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)中的P-N异质结可提供额外的电场来加速电子-空穴迁移,从而改善催化性能。
3. 本发明公开的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)中二维纳米片NiFe-LDH与一维Co3O4纳米线的复合,可增大比表面积,进而扩展光响应面积,更有利于污染物的吸附和光的吸收利用。
4. 本发明公开的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)中Co3O4为一维结构,可增强材料的电子传输能力。
5. 本发明公开的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4)结构稳定,制备方法简单,重复利用简便快捷。因此,本发明中所制备的材料简单易得,并可有效利用光源,通过光电催化净化水体中的污染物,有利于其进一步的推广应用。
附图说明
图1为负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)的扫描电镜照片;
图2为实施例四中所得负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)的扫描电镜照片;
图3为实施例四中所得负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)对污染物的光电催化去除效果图;
图4为实施例四中所得负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)通过光催化、电催化和光电催化的方式对污染物的去除效果对比图。
具体实施方式
本发明公开的负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4)的制备方法为,采用混合溶剂热的方法在层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4),可作为催化剂。
实施例一
层状镍铁双金属氢氧化物前驱体溶液的制备,具体步骤如下:
首先,在单口圆底烧瓶中依次加入15 ml去离子水、0.6979 g六水合硝酸镍和0.4803 g九水合硝酸铁,搅拌均匀后加入0.8647 g尿素,搅拌均匀后于100 ℃下回流24 h,即得到层状镍铁双金属氢氧化物的前驱体溶液,其中二价金属离子Ni2+与三价金属离子Fe3+的摩尔比为2:1,Fe3+的摩尔浓度为0.1 mol/L,尿素的摩尔数为二价金属离子Ni2+与三价金属离子Fe3+摩尔数总和的4倍。
实施例二
水热法制备负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH),具体步骤如下:
本发明采用水热法合成上述负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)。将泡沫镍放入聚四氟乙烯内衬的高压反应釜中,加入3 ml实施例一中制备好的层状镍铁双金属氢氧化物前驱体溶液和32 ml去离子水。将反应釜置于预先设定好温度的烘箱内,在160 ℃下恒温水热反应24 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行离心分离并用去离子水洗涤3次,置于60 ℃鼓风烘箱中干燥24 h,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)。其扫描电镜图如图1所示,从图中可以看出,在泡沫镍的表面上均匀负载了形貌规整的层状镍铁双金属氢氧化物纳米片,参照实施例七的方法,100 min后水溶液中六价铬去除率为22.3 %。
实施例三
混合溶剂热法制备负载于泡沫镍表面的P-N异质结复合材料(Ni foam@NiFe-LDH/Co3O4-1)催化剂,具体步骤如下:
本发明采用混合溶剂热法合成上述负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-1)。首先,在烧杯中依次加入40 ml去离子水、40 ml无水乙醇、0.87 g六水合硝酸钴和0.7206 g尿素,超声分散得到均一的混合溶液。将实施例二中得到的负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)放入聚四氟乙烯内衬的高压反应釜中,加入10 ml的上述混合溶液及25 ml去离子水和无水乙醇的混合溶液(体积比为1:1)。将反应釜置于预先设定好温度的烘箱内,在90 ℃下恒温水热反应8 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行分离并用去离子水洗涤3次,干燥后置于管式炉中,在空气气氛下于250 ℃条件下保温2 h,升温速率为3℃/min,得到负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-1)。所得的产物仅在均匀生长的层状镍铁双金属氢氧化物纳米片表面负载少量的四氧化三钴纳米线,参照实施例七的方法,100 min后水溶液中六价铬去除率为30.1 %。
实施例四
混合溶剂热法制备负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2),具体步骤如下:
本发明采用混合溶剂热法合成上述负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)。首先,在烧杯中依次加入40 ml去离子水、40 ml无水乙醇、0.87 g六水合硝酸钴和0.7206 g尿素,超声分散得到均一的混合溶液。将实施例二中得到的负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)放入聚四氟乙烯内衬的高压反应釜中,加入15 ml的上述混合溶液及20 ml去离子水和无水乙醇的混合溶液(体积比为1:1),此时六水合硝酸钴的浓度为0.0047g/mL(按投料比计,以所有液体体积为基数)。将反应釜置于预先设定好温度的烘箱内,在90 ℃下恒温水热反应8h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行分离并用去离子水洗涤3次,干燥后置于管式炉中,在空气气氛下于250 ℃条件下保温2 h,升温速率为℃/min,得到负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)。其扫描电镜图如图2所示,从图中可以看出,四氧化三钴纳米线均匀的负载于层状镍铁双金属氢氧化物纳米片的表面。
将上述250 ℃条件下保温2 h调整为300 ℃条件下保温2 h,其余不变,得到Nifoam@NiFe-LDH/Co3O4-2-1,参照实施例七的方法,100 min后水溶液中六价铬去除率为38.5%。
实施例五
混合溶剂热法制备负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-3),具体步骤如下:
本发明采用混合溶剂热法合成上述负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-3)。首先,在烧杯中依次加入40 ml去离子水、40 ml无水乙醇、0.87 g六水合硝酸钴和0.7206 g尿素,超声分散得到均一的混合溶液。将实施例二中得到的负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片复合材料(Ni foam@NiFe-LDH)放入聚四氟乙烯内衬的高压反应釜中,加入20 ml的上述混合溶液及15 ml去离子水和无水乙醇的混合溶液(体积比为1:1)。将反应釜置于预先设定好温度的烘箱内,在90 ℃下恒温水热反应8 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行分离并用去离子水洗涤3次,干燥后置于管式炉中,在空气气氛下于250 ℃条件下保温2 h,升温速率为3℃/min,得到负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-3)。所得的产物完全被四氧化三钴纳米线覆盖,参照实施例七的方法,100 min后水溶液中六价铬去除率为36.7 %。
实施例六
混合溶剂热法制备负载于泡沫镍表面的四氧化三钴纳米线复合材料(Ni foam@Co3O4),具体步骤如下:
本发明采用混合溶剂热法合成上述负载于泡沫镍表面的四氧化三钴纳米线复合材料(Ni foam@Co3O4)。首先,在烧杯中依次加入40 ml去离子水、40 ml无水乙醇、0.87 g六水合硝酸钴和0.7206 g尿素,超声分散得到均一的混合溶液。将表面洁净的泡沫镍放入聚四氟乙烯内衬的高压反应釜中,加入35 ml的上述混合溶液。将反应釜置于预先设定好温度的烘箱内,在90 ℃下恒温水热反应8 h。反应结束后,停止加热,待反应釜自然冷却至室温后对产物进行分离并用去离子水洗涤3次,干燥后置于管式炉中,在空气气氛下于250 ℃条件下保温2 h,升温速率为3℃/min。经扫描电镜表征,发现四氧化三钴纳米线均匀的负载于泡沫镍的表面,参照实施例七的方法,100 min后水溶液中六价铬去除率为31.3 %。
实施例七
负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)对污染物的光催化实验,具体步骤如下:
对50 mL含六价铬离子(由重铬酸钾配制,浓度为10 mg/L)的水溶液进行光催化实验。将负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)浸入污染物溶液中,避光搅拌半小时达到吸附-解吸平衡后,使用300 W氙灯光源作为模拟太阳光进行光催化实验,每隔20分钟取样3 mL。采用显色法用紫外-可见分光光度计测试水样在540nm波长下的吸光度,得到相应水样中六价铬的浓度。从附图4中可以看出,负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)在光照下,100 min后水溶液中六价铬去除率为43.6 %。
实施例八
负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)对污染物的光催化实验,具体步骤如下:
对50 mL含有机污染物(由BPA配制,浓度为10 mg/L)的水溶液进行光催化实验。将负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)浸入污染物溶液中,避光搅拌半小时达到吸附-解吸平衡后,使用300 W氙灯光源作为模拟太阳光进行光催化实验,每隔20分钟取样3 mL。采用高效液相测得溶液中BPA的残留浓度。从附图4中可以看出,负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)在光照下,100 min后水溶液中BPA的去除率为45.2 %。
实施例九
负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)对污染物的电催化实验,具体步骤如下:
采用三电极体系(上述实施例四中所得的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)作为工作电极、饱和甘汞电极作为参比电极、铂片电极作为对电极、0.2 M的Na2SO4为电解质溶液)进行电催化实验,在光电反应池中分别加入50 mL含六价铬离子(由重铬酸钾配制,浓度为10 mg/L)和有机污染物(由BPA配制,浓度为10 mg/L)的水溶液,中间用质子交换膜隔开。避光搅拌半小时达到吸附-解吸平衡后,使用电化学工作站给工作电极施加0.7 V大小的偏压进行电催化实验,每隔20分钟取样3 mL。然后,采用高效液相测得溶液中BPA的残留浓度,使用显色法用紫外-可见分光光度计测试水样在540 nm波长下的吸光度,得到相应水样中六价铬和BPA的浓度。从附图4中可以看出,负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)在外加电压的作用下,100 min后水溶液中六价铬去除率为5.3 %,BPA的去除率为13.1 %。
实施例十
负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)对污染物的光电催化实验,具体步骤如下:
采用三电极体系(上述实施例四中所得的负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)作为工作电极、饱和甘汞电极作为参比电极、铂片电极作为对电极、0.2 M的Na2SO4为电解质溶液)进行光电催化实验,在光电反应池中分别加入50mL含六价铬离子(由重铬酸钾配制,浓度为10 mg/L)和有机污染物(由BPA配制,浓度为10mg/L)的水溶液,中间用质子交换膜隔开。避光搅拌半小时达到吸附-解吸平衡后,使用300W氙灯光源作为模拟太阳光,使用电化学工作站给工作电极施加0.7 V大小的偏压进行光电催化实验,每隔20分钟取样3 mL。然后,采用高效液相测得溶液中BPA的残留浓度,使用显色法用紫外-可见分光光度计测试水样在540 nm波长下的吸光度,得到相应水样中六价铬和BPA的浓度。从附图3和附图4中可以看出,负载于泡沫镍表面的P-N异质结催化剂复合材料(Ni foam@NiFe-LDH/Co3O4-2)在光照和外加电压的协同作用下,100 min后水溶液中六价铬去除率为97.5 %,BPA(双酚A)的去除率为98.1 %,去除效率较单纯的光催化或电催化明显提高。
本发明公开的复合材料已被证实是提高材料催化活性的有效手段,就P-N异质结而言,当具有不同费米能级的两种不同类型的半导体接触时,载流子会自发地在半导体间流动,直至达到平衡状态。在半导体结的界面处,由于载流子的流动会形成两个荷电相反的空间电荷区,产生相应的内建电场。半导体结的内建电场被广泛应用于促进光生载流子的分离,如太阳能电池和光催化体系等。此外,光电催化技术——通过外加电压使半导体材料受光激发产生的光生电荷被有效分离而增强催化活性,是实现太阳能高效利用的有效方法之一,有望解决目前所面临的环境问题与能源危机。
Claims (10)
1.一种负载于泡沫镍表面的P-N异质结复合材料,其特征在于,所述负载于泡沫镍表面的P-N异质结复合材料的制备方法包括以下步骤,采用混合溶剂热的方法在负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料。
2.根据权利要求1所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,以泡沫镍为载体,通过水热法在泡沫镍的表面修饰层状镍铁双金属氢氧化物纳米片,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片;再采用混合溶剂热的方法在层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料。
3.根据权利要求2所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,将前驱体溶液与泡沫镍混合,然后120~180 ℃下水热反应20~30 h,得到负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片;前驱体溶液由镍盐、铁盐、水、尿素组成。
4.根据权利要求3所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,前驱体溶液中,二价金属离子Ni2+与三价金属离子Fe3+的摩尔比为2:1,尿素的摩尔数为二价金属离子Ni2+与三价金属离子Fe3+摩尔数总和的3.8~4.2倍。
5.根据权利要求1所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,将层状镍铁双金属氢氧化物纳米片与含钴溶液混合,然后80~100 ℃下水热反应6~10 h,再热处理,得到负载于泡沫镍表面的P-N异质结复合材料;含钴溶液由水、乙醇、钴盐、尿素组成。
6.根据权利要求5所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,水和乙醇的体积比为1:1,尿素和钴盐的摩尔比为4:1;钴盐的浓度为0.003~0.008g/mL。
7.根据权利要求5所述负载于泡沫镍表面的P-N异质结复合材料,其特征在于,热处理为在空气气氛下于250℃下保温1.5~2.5 h。
8.一种催化净化水体中的污染物的方法,包括以下步骤,采用混合溶剂热的方法在负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料;将负载于泡沫镍表面的P-N异质结复合材料加入含有污染物的水体中,光催化和/或电催化,完成水体中的污染物的净化。
9.一种负载于泡沫镍表面的P-N异质结复合材料的制备方法,包括以下步骤,采用混合溶剂热的方法在负载于泡沫镍表面的层状镍铁双金属氢氧化物纳米片表面修饰一维四氧化三钴纳米线,得到负载于泡沫镍表面的P-N异质结复合材料。
10.权利要求1所述负载于泡沫镍表面的P-N异质结复合材料作为催化剂在净化水体中污染物的应用。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101775468B1 (ko) * | 2016-09-30 | 2017-09-06 | 전북대학교산학협력단 | 슈퍼 커패시터용 전극 및 이의 제조 방법 |
CN108855102A (zh) * | 2018-06-21 | 2018-11-23 | 肇庆市华师大光电产业研究院 | 一种Co掺杂Zn(OH)2纳米片复合材料及其制备方法和应用 |
CN109201065A (zh) * | 2018-09-27 | 2019-01-15 | 苏州大学 | 一种泡沫镍复合材料及其制备方法与在光电催化去除水体污染物中的应用 |
CN110106517A (zh) * | 2019-04-22 | 2019-08-09 | 江苏大学 | 硫化钴/层状双金属氢氧化物复合电催化剂及其制备方法 |
CN110201670A (zh) * | 2019-05-21 | 2019-09-06 | 山东大学 | 基于三氯化铁/尿素低共熔溶剂的镍铁双金属氢氧化物/泡沫镍催化剂、其制备方法及应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111389442B (zh) * | 2020-04-20 | 2021-12-28 | 苏州大学 | 负载于泡沫镍表面的p-n异质结复合材料及其制备方法与应用 |
-
2020
- 2020-04-20 CN CN202010313573.5A patent/CN111389442B/zh active Active
- 2020-12-31 WO PCT/CN2020/142581 patent/WO2021212923A1/zh active Application Filing
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101775468B1 (ko) * | 2016-09-30 | 2017-09-06 | 전북대학교산학협력단 | 슈퍼 커패시터용 전극 및 이의 제조 방법 |
CN108855102A (zh) * | 2018-06-21 | 2018-11-23 | 肇庆市华师大光电产业研究院 | 一种Co掺杂Zn(OH)2纳米片复合材料及其制备方法和应用 |
CN109201065A (zh) * | 2018-09-27 | 2019-01-15 | 苏州大学 | 一种泡沫镍复合材料及其制备方法与在光电催化去除水体污染物中的应用 |
CN110106517A (zh) * | 2019-04-22 | 2019-08-09 | 江苏大学 | 硫化钴/层状双金属氢氧化物复合电催化剂及其制备方法 |
CN110201670A (zh) * | 2019-05-21 | 2019-09-06 | 山东大学 | 基于三氯化铁/尿素低共熔溶剂的镍铁双金属氢氧化物/泡沫镍催化剂、其制备方法及应用 |
Non-Patent Citations (1)
Title |
---|
WANG, SHANPENG等: "Improved Electrocatalytic Performance in Overall Water Splitting with Rational Design of Hierarchical Co3O4@NiFe Layered Double Hydroxide Core-Shell Nanostructure", 《CHEM ELECTRO CHEM》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021212923A1 (zh) * | 2020-04-20 | 2021-10-28 | 苏州大学 | 负载于泡沫镍表面的 p-n 异质结复合材料及其制备方法与应用 |
WO2022014377A1 (ja) * | 2020-07-17 | 2022-01-20 | パナソニックIpマネジメント株式会社 | 触媒、水電解セル用触媒、水電解セル、水電解装置、および触媒の製造方法 |
JP7029687B1 (ja) * | 2020-07-17 | 2022-03-04 | パナソニックIpマネジメント株式会社 | アノード触媒、水電解セル用触媒、水電解セル、水電解装置、およびアノード触媒の製造方法 |
CN115812007A (zh) * | 2020-07-17 | 2023-03-17 | 松下知识产权经营株式会社 | 催化剂及其制造方法、水电解单元用催化剂、水电解单元、水电解装置 |
CN113387419A (zh) * | 2021-06-29 | 2021-09-14 | 南华大学 | 一种g-C3N4-Sn3O4-Ni电极材料及其制备方法和应用 |
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