CN108946692B - 一种磷酸钴纳米材料及其制备方法和应用 - Google Patents
一种磷酸钴纳米材料及其制备方法和应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 29
- 229910000152 cobalt phosphate Inorganic materials 0.000 title claims abstract description 11
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 12
- 239000010452 phosphate Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 235000021317 phosphate Nutrition 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000010411 electrocatalyst Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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Abstract
本发明公开了一种磷酸钴纳米材料及其制备方法和应用。该磷酸盐的化学通式为Co3(OH)2(HPO4)2,表面活性剂聚乙烯吡咯烷酮(PVP)的辅助制备尺寸为0.5‑1μm的纳米材料。本发明采用表面活性剂辅助水热法,制备方法简单、易操作、成本低廉、环境友好,整个反应过程不需要特殊设备,利于工业化生产,最终得到的产物质量较高。本方法制备的磷酸盐纳米材料可同时实现材料导电性高,活性位点多,电催化活性高等优点。本发明制备的材料是一种具有广泛商业化应用前景的理想析氧反应电催化材料。
Description
技术领域
本发明属于电化学催化剂的制备领域,涉及一种磷酸钴纳米材料及其制备方法和应用。
背景技术
由于全球对可持续能源的需求增长,电化学水分解产生氢气和氧气引起了很大关注。水分解反应由两个半反应组成:析氢反应(HER)和析氧反应(OER)。然而由于析氧半反应需要经历复杂的四电子转移过程,动力学过程更为缓慢,一直是限制水裂解过程效率的主要因素。
到目前为止,含铂、钌和铱贵金属元素的化合物具有良好的催化析氧反应效果。然而,由于这些贵金属在地球上的储量少,价格相对昂贵,不适合大规模生产并应用于实际生产中。因此设计合成高效的非贵金属析氧反应催化剂,对于水裂解反应在实际中的应用具有非常重要的意义。随着近年来的研究发展,过渡金属磷酸盐在析氧反应催化方面的研究受到了广泛的重视。
二维材料在电子传输或者热传递时被限制在一个平面内,这一独特的物理特性使其受到了广泛的关注。当二维材料作为电催化剂时,由于其高的比表面积与更多的活性暴露位点可促进电解质中的电荷和质量传递,从而有利于催化活性的进一步提升。与大尺寸的块材相比,纳米材料具有更快质量传输和电子转移和更多暴露出的催化活性表面等优点。在此通过表面活性剂辅助水热法,制备出堆叠的二维层状磷酸钴纳米材料。
发明内容
本发明的目的就是为了合成高产量、高品质的磷酸钴纳米材料从而解决现有催化剂存在的电流密度低、过电位高、稳定性差等问题。
本发明的目的可以通过以下技术方案来实现:
一种磷酸盐纳米材料的制备方法,其特征在于,采用表面活性剂辅助水热法,将钴源、表面活性剂和水混合,混合均匀后加入磷源水溶液形成的初始凝胶混合物,转移至内衬为聚四氟乙烯的不锈钢自压釜中晶化得到。
优选地,所述表面活性剂为聚乙烯吡咯烷酮(PVP)。分子量选择12~150KDa中的任一种。
优选地,所述初始凝胶混合物中,钴源、表面活性剂、水和磷源的质量比为0.5~2.5:0.5~5:6:0.85,其中磷源水溶液的浓度为0.86mol/L。
优选地,晶化温度为180~220℃,晶化时间6~12小时。
优选地,将钴源、表面活性剂和水混合,至少搅拌1小时,达到混合均匀的状态。加入磷源溶液后,至少搅拌2小时。
优选地,所述的钴源选自硝酸钴、乙酸钴、氯化钴、溴化钴中的至少一种。
优选地,所述的磷源任选磷酸铵、磷酸氢二铵、磷酸二氢铵、次亚磷酸、亚磷酸、磷酸中的至少一种。
根据本申请的又一方面,由上述任一方法所制备的晶体材料。
根据本申请的又一方面,提供所述电解水析氧反应的应用方法,将材料滴覆在玻碳电极表面,室温晾干。采用三电极体系用线性扫描伏安法进行测试,电解液为1M KOH。
本发明能产生的有益效果至少包括:
(1)本申请提供了一种表面活性剂辅助制备磷酸盐纳米材料的方法,制备的磷酸盐纳米材料具体尺寸小,比表面积大的优点。
(2)本申请提供了一种表面活性剂辅助制备磷酸盐纳米材料的方法,操作简单,成本低廉,反应条件温和。
(3)本申请提供的这种磷酸盐纳米材料在氢氧化钾的碱性溶液中具有优异的催化电化学析氧反应效果,能够有效地提高电化学裂解水的效率。1M KOH溶液中,扫速为5mV/s时,在过电位2.9V下,电流密度可达到10mA/cm2。
(4)与含钌元素和铱元素的贵金属催化剂相比,本发明原料廉价易得,资源丰富,催化性能稳定,可适合商业化生产。
附图说明
图1是样品1#的X射线衍射图谱。
图2是样品1#的扫描电镜图。
图3是样品1#的透射电镜图。
图4是样品1#和其他表面活性剂以及商用氧化钌,氧化铱在1M KOH电解液中获得的线性扫描伏安图。
图5是上述催化剂通过在1M KOH电解液中扫描线性伏安曲线,获得的Tafel图。
具体实施方式
下面结合实施例,进一步阐述本申请。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。
作为一个制备磷酸盐纳米材料优选Co3(OH)2(HPO4)2的优选实施方案,典型方法如下:将原料钴源、磷源、表面活性剂和水密封于水热反应釜中进行水热反应,反应温度为180~220℃,反应时间为6~12h,然后缓慢降温至30℃,降温时间是4h,过滤清洗,即可获得紫色片状的Co3(OH)2(HPO4)2纳米片。
实施例1样品制备
将钴源、表面活性剂和水混合,搅拌至少1h,混合均匀后加入磷源水溶液,搅拌至少2h,形成初始凝胶混合物,将初始凝胶混合物密封于30mL的聚四氟乙烯内衬的水热反应釜中,放入箱式电阻炉中,在晶化温度下晶化一段时间后,经过滤、清洗、干燥,得到紫色片状Co3(OH)2(HPO4)2纳米材料。初始凝胶混合物中原料的种类及配比、晶化温度、晶化时间与样品编号的关系如表1所示。
表1样品合成条件与样品编号的关系
实施例2样品的结构解析
采用粉末X射线衍射方法,对样品1#~10#进行结构解析。
粉末X射线衍射在日本RIGAKU公司Miniflex II型的X射线粉末衍射仪上进行,测试条件为固定靶单色光源Cu-Kα,波长 电压电流为30kV/15A,狭缝DivSlit/RecSlit/SctSlit分别为1.25deg/0.3mm/1.25deg,扫描范围5-50°,扫描步长0.02°。
结果显示,样品1#~10#具有相同的化学结构式和晶体结构,化学式均为Co3(OH)2(HPO4)2。以样品1#为典型代表,如图1所示与图2中样品1#研磨成粉末后X射线衍射测试得到的图谱,峰位置和峰强度一致。说明所得样品均有很高纯度。
实施例3样品的形貌表征
采用扫描电子显微镜和透射电子显微镜的方法,对样品1#进行形貌表征。
扫描电镜图和透射电镜图分别在Hitachi公司S4800型的扫描电子显微镜和日本电子株式会社JEM-2100F型的透射电子显微镜上进行。
结果显示,如图2扫描电镜图和图3透射电镜图所示,样品1#具有很好的纳米片形貌,并且材料的形貌均一、分散性好,尺寸为0.5-1μm。
实施例4电化学析氧反应测试
样品1#的电化学析氧反应测试在上海辰华公司CHI760E型电化学工作站上进行,采用三电极体系用线性扫描伏安法进行测试,参比电极和对电极分别是Hg/HgO电极和Pt丝电极。将5mg样品1#,0.5mL水,0.5mL乙醇和10μLNafion溶液混合,超声处理2h以保证催化剂分散均匀,然后取6μL即混合液滴在直径为0.7cm的玻碳电极上,自然晾干,作为工作电极。电解液为1M KOH,扫描速率为5mV/s。由获得的线性扫描伏安图可以得到反映催化过程动力学参数的Tafel图。
如图4线性扫描伏安图和图5Tafel图所示,样品1#催化发生析氧反应的电流密度10mA/cm2时过电位为290mV,斜率为82mV/dec。与十二烷基苯磺酸钠,十六烷基三甲基溴化铵作为表面活性剂制备的Co3(OH)2(HPO4)2材料以及商用的贵金属氧化钌,氧化铱催化剂相比较,本发明用PVP制备的Co3(OH)2(HPO4)2纳米材料具有明显更好的电催化性能。
本发明研究发现,本发明在磷酸盐中选择磷酸钴、本发明磷酸钴纳米材料的辅助表面活性剂选择聚乙烯吡咯烷酮(PVP),其催化活性明显优于选择表面活性剂十二烷基硫酸钠(SDS)或十六烷基三甲基溴化铵(CTAB),本发明研究大量的表面活性剂辅助修饰磷酸盐纳米材料后,最终选择PVP辅助制备磷酸钴纳米材料,并调整钴源、表面活性剂、水和磷源的质量比(四者质量配比对材料性能有非常大的影响),本发明先将钴盐、表面活性剂和水混合,之后再入磷酸盐水溶液形成初始凝胶,晶化制备,使得本发明制备的Co3(OH)2(HPO4)2纳米材料明显优于现有技术使用贵金属的催化剂。
以上所述,仅是本发明的几个实施例,并非对本发明做任何形式的限制,虽然本发明以较佳实施例揭示如上,然而并非用以限制本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (8)
2.制备权利要求1所述纳米材料的方法,其特征在于:将钴源、表面活性剂和水混合,混合均匀后加入磷源水溶液形成的初始凝胶混合物,通过水热反应,在晶化温度下晶化制备得到。
3.根据权利要求2所述的方法,其特征在于:所述初始凝胶混合物中,钴源、表面活性剂、水和磷源的质量比为0.5~2.5:0.5~5:6:0.85。
4.根据权利要求2或3所述的方法,其特征在于:所述表面活性剂为聚乙烯吡咯烷酮、十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵中的至少一种。
5.根据权利要求2或3所述的方法,其特征在于:所选钴源任选硝酸钴、乙酸钴、氯化钴、溴化钴中的至少一种。
6.根据权利要求2或3所述的方法,其特征在于:所述磷源任选磷酸铵、磷酸氢二铵、磷酸二氢铵、磷酸中的至少一种。
7.根据权利要求2或3所述的方法,其特征在于:所述晶化温度为180~220℃,晶化时间6~12h。
8.一种磷酸钴纳米材料在电化学析氧纳米材料中的应用,其特征在于:所述电化学析氧纳米材料含有权利要求1所述的纳米材料和/或根据权利要求2-7任一项所述方法制备得到的纳米材料。
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