CN110002416A - A kind of acid phosphate niobium oxygen monoatomic layer preparation of sections method - Google Patents
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- 239000002253 acid Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000000126 substance Substances 0.000 claims abstract description 16
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- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 239000010955 niobium Substances 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 4
- 238000013019 agitation Methods 0.000 claims 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- XTTKJDYDBXPBDJ-UHFFFAOYSA-N niobium;oxalic acid Chemical compound [Nb].OC(=O)C(O)=O XTTKJDYDBXPBDJ-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 abstract description 25
- 239000002135 nanosheet Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 6
- 238000004299 exfoliation Methods 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 229910000484 niobium oxide Inorganic materials 0.000 abstract description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- NJTILYLBOMRDKQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.P.[Nb+5] Chemical compound [O-2].[O-2].[OH-].O.P.[Nb+5] NJTILYLBOMRDKQ-UHFFFAOYSA-M 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- 238000012546 transfer Methods 0.000 description 13
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明属于化工材料合成技术领域，具体为一种酸式磷酸铌氧单原子层薄片的制备方法。本发明方法包括：采用化学液相合成法，制备酸式磷酸铌氧前驱体块体，对块体进行洗涤和烘干处理，得粉体；采用超声溶剂辅助剥离法，制备酸式磷酸铌氧单原子层薄片，为均一稳定的超薄纳米片胶体。制得的酸式磷酸铌氧单原子层薄片横向尺寸在几十纳米至几百纳米，厚度为1 nm左右，并可实现水相或乙醇溶剂中10mg/mL的高浓度稳定分散。使用该方法实现的合成和剥离产率可稳定保持在98%以上。本发明方法简单方便、安全高效，对于层状酸式磷铌氧在电化学储能、光电转换器件以及化学催化和电催化等领域的应用研究具有潜在价值。
The invention belongs to the technical field of chemical material synthesis, in particular to a preparation method of an acid niobium phosphate monoatomic layer sheet. The method of the invention comprises: using a chemical liquid phase synthesis method to prepare an acid niobium phosphate precursor block, washing and drying the block to obtain a powder; using an ultrasonic solvent-assisted stripping method to prepare an acid niobium phosphate Single atomic layer flakes are uniform and stable ultrathin nanosheet colloids. The prepared acid niobium oxide monoatomic layer flakes have lateral dimensions ranging from tens of nanometers to hundreds of nanometers and thicknesses of about 1 nm, and can achieve stable dispersion at a high concentration of 10 mg/mL in aqueous or ethanol solvents. The synthesis and exfoliation yields achieved using this method can be stably maintained above 98%. The method of the invention is simple, convenient, safe and efficient, and has potential value for the application research of the layered acid phosphorus niobium oxide in the fields of electrochemical energy storage, photoelectric conversion devices, chemical catalysis and electrocatalysis.
Description
技术领域technical field
本发明属于化工材料合成技术领域，具体涉及酸式磷酸铌氧单原子层薄片的制备方法。The invention belongs to the technical field of chemical material synthesis, and in particular relates to a preparation method of acid niobium phosphate monoatomic layer flakes.
背景技术Background technique
自2004年英国科学家从热解石墨中剥离得到单碳原子厚度的石墨烯以来，这种超薄结构的二维材料以其具有单个或者多个碳原子层厚度的结构特征、极高的电子迁移率、良好的机械柔韧性、化学稳定性和光学透明性，以及优异的导电、导热性能，开始在锂离子电池、超级电容器、太阳能电池、导热膜等方面展现出广阔的应用前景。以石墨烯为契机和突破口，一系列二维层状材料例如六方氮化硼(h-BN)，过渡金属硫化物(TMDs)，层状过渡金属氧化物(Oxides)，氢氧化物( Hydroxides)和双氢氧化物(LDHs)以及多种二维体系逐步受到科研界和产业界的关注；通过对这些新颖独特的二维层状材料的制备方法，剥离工艺及自组装技术的研究，使其优异的理化性能更好的为功能材料应用所服务，是近年来意义重大且发展迅速的一大研究领域。Since British scientists exfoliated graphene with a thickness of a single carbon atom from pyrolytic graphite in 2004, this ultra-thin two-dimensional material is characterized by its structural characteristics of single or multiple carbon atomic layers, extremely high electron mobility High efficiency, good mechanical flexibility, chemical stability and optical transparency, as well as excellent electrical and thermal conductivity, have begun to show broad application prospects in lithium-ion batteries, supercapacitors, solar cells, thermally conductive films, etc. Taking graphene as an opportunity and breakthrough, a series of two-dimensional layered materials such as hexagonal boron nitride (h-BN), transition metal dichalcogenides (TMDs), layered transition metal oxides (Oxides), hydroxides (Hydroxides) and double hydroxides (LDHs) and a variety of two-dimensional systems have gradually attracted the attention of scientific research and industrial circles; through the research on the preparation methods, exfoliation processes and self-assembly technology of these novel and unique two-dimensional layered materials, their Excellent physical and chemical properties can better serve the application of functional materials, which is a significant and rapidly developing research field in recent years.
酸式磷酸铌氧（2NbOPO4· H3PO4· H2O）作为一种在催化领域应用成熟的铌类化合物，以其绿色无毒、催化活性高等优点，在固体酸催化剂和介孔催化体系设计等方面得到了一定程度的应用。根据现有文献记载，酸式磷酸铌氧已被应用在包括催化缩合反应制备β-烯胺基酮(Wodtke F.,李瑞鹏.NbOPO4催化的β-烯胺基酮的简便制法[J].中国医药工业杂志.2017:1174.)，催化纤维素水解/醇解制备乙酰丙酸和乙酰丙酸甲酯(王艳芹,丁大千,夏启能,刘晓晖.介孔NbOPO4:酸性质调控及在纤维素水解、醇解中的作用研究[C].第18届全国分子筛学术大会.中国上海.2015.)等在内的催化反应领域。需要指出的是，现有文献报道的磷酸铌氧材料大多为三维介孔体系，聚焦于层状相酸式磷酸铌氧合成调控以及单原子薄层结构剥离的文献未有见刊。同时，基于二维结构开放的层空间特征、极大的比表面积及丰富的活性反应位点，层状磷酸铌氧和相应的超薄纳米片在电化学储能、光电转换器件、化学催化与电催化等领域尚具有巨大应用前景。因此，开发安全、环保、高产率的层状相酸式磷酸铌氧的制备方法，并得到高产率的酸式磷酸铌氧单原子层薄片，对于该体系在功能材料领域的进一步应用，具有重要意义。Niobium acid phosphate (2NbOPO 4 · H 3 PO 4 · H 2 O), as a mature niobium compound in the field of catalysis, has the advantages of green non-toxicity and high catalytic activity. It is widely used in solid acid catalysts and mesoporous catalysis. System design and other aspects have been applied to a certain extent. According to the existing literature records, acid niobium phosphate has been used in the preparation of β-enaminoketone by catalytic condensation reaction (Wodtke F., Li Ruipeng. NbOPO 4 -catalyzed β-enaminoketone simple preparation method [J] . Chinese Journal of Pharmaceutical Industry. 2017: 1174.), Catalytic cellulose hydrolysis/alcoholysis to prepare levulinic acid and methyl levulinate (Wang Yanqin, Ding Daqian, Xia Qineng, Liu Xiaohui. Mesoporous NbOPO 4 : regulation of acid properties and its application in fibers Research on the role of elemental hydrolysis and alcoholysis [C]. The 18th National Molecular Sieve Academic Conference. Shanghai, China. 2015.) and other fields of catalytic reactions. It should be pointed out that most of the niobium phosphate materials reported in the existing literature are three-dimensional mesoporous systems, and no literature focusing on the synthesis regulation of layered acid niobium phosphate and the exfoliation of single-atom thin-layer structure has been published. At the same time, based on the open layer space characteristics of the two-dimensional structure, the large specific surface area and the abundant active reaction sites, the layered niobium oxyphosphate and the corresponding ultrathin nanosheets are widely used in electrochemical energy storage, photoelectric conversion devices, chemical catalysis and other applications. Electrocatalysis and other fields still have great application prospects. Therefore, the development of a safe, environmentally friendly and high-yield preparation method of layered phase acid niobium phosphate and obtaining high-yield acid niobium phosphate monoatomic layer flakes is of great importance for the further application of this system in the field of functional materials. significance.
发明内容SUMMARY OF THE INVENTION
本发明针对现有二维层状材料的合成与剥离技术存在的空白，提出一种安全、环保、高产率的酸式磷酸铌氧单原子层薄片的制备方法。Aiming at the blank of the existing two-dimensional layered material synthesis and stripping technology, the invention proposes a method for preparing a safe, environment-friendly and high-yield acid niobium oxyphosphate monoatomic layer sheet.
本发明提供的酸式磷酸铌氧单原子层薄片的制备方法，具体步骤为：The preparation method of the acid niobium oxide monoatomic layer sheet provided by the invention, the specific steps are:
（1）采用化学液相合成法，制备酸式磷酸铌氧前驱体块体，对块体进行洗涤和烘干处理，得分体；(1) Using the chemical liquid phase synthesis method, the acid niobium phosphate precursor block is prepared, and the block is washed and dried to separate the blocks;
（2）采用超声溶剂辅助剥离法，制备酸式磷酸铌氧单原子层薄片，为均一稳定的超薄纳米片胶体。(2) Ultra-thin nanosheet colloids were prepared by ultrasonic solvent-assisted exfoliation method to prepare acid niobium phosphate monoatomic layer flakes.
本发明中，所述的酸式磷酸铌氧前驱体块体，其分子式为2NbOPO4· H3PO4· H2O，为边长在1-2μm, 厚度在10-100 nm的二维结构层状相；块体中各元素比为Nb:O:P=2:（12-16）:（2-4），优选Nb:O:P≈2:15:3。In the present invention, the acid niobium phosphate precursor block has a molecular formula of 2NbOPO 4 · H 3 PO 4 · H 2 O, and is a two-dimensional structure with a side length of 1-2 μm and a thickness of 10-100 nm. Layered phase; the ratio of each element in the bulk is Nb:O:P=2:(12-16):(2-4), preferably Nb:O:P≈2:15:3.
本发明中，所述的酸式磷酸铌氧单原子层薄片，边长为50-1000nm，厚度约1nm(厚度误差小于0.1nm)。薄片中各元素比为Nb:O:P=1:（4-6）:（0.8-1.2），优选Nb:O:P≈1:5:1。In the present invention, the acid niobium oxide monoatomic layer thin sheet has a side length of 50-1000 nm and a thickness of about 1 nm (thickness error is less than 0.1 nm). The ratio of each element in the sheet is Nb:O:P=1:(4-6):(0.8-1.2), preferably Nb:O:P≈1:5:1.
本发明中，块体合成和薄片结构剥离产率均超过98%。In the present invention, the yields of bulk synthesis and flake structure exfoliation both exceed 98%.
本发明中，所述的化学液相合成法，是以一定比例的铌源和磷酸为原始反应物，以去离子水作为合成溶剂环境，在三颈烧瓶中充分混合反应物，于100-200℃热油浴中加热反应体系5-20 h，完成合成反应，自然冷却至室温，将产物进行洗涤、烘干处理。In the present invention, in the chemical liquid-phase synthesis method, a certain proportion of niobium source and phosphoric acid are used as the original reactants, deionized water is used as the synthesis solvent environment, and the reactants are fully mixed in a three-necked flask, and the reactants are fully mixed in a three-necked flask. The reaction system was heated in a ℃ hot oil bath for 5-20 h to complete the synthesis reaction, then cooled to room temperature naturally, and the product was washed and dried.
所述的充分混合反应物，是以磁力搅拌子作为搅拌媒介，在磁力搅拌***上将混合反应物体系搅拌至形成透明澄清溶液。The fully mixed reactant system uses a magnetic stirring bar as a stirring medium, and the mixed reactant system is stirred on a magnetic stirring system until a transparent and clear solution is formed.
所述的洗涤处理，是将经化学液相合成得到的产物转移到内部覆盖有两层滤纸的紧密固定在抽滤瓶上的布氏漏斗中，以去离子水冲刷产物并注满漏斗内容积，再以外接的真空泵抽净洗涤液，并以此操作流程，反复进行3-6次。The washing treatment is to transfer the product obtained by chemical liquid phase synthesis to a Buchner funnel which is covered with two layers of filter paper and tightly fixed on the suction filter bottle, rinse the product with deionized water and fill the inner volume of the funnel. , and then use an external vacuum pump to clean up the washing liquid, and repeat this operation process 3-6 times.
所述的烘干处理，是将经过洗涤处理的产物以滤纸托放，转移至鼓风干燥烘箱中以60-80℃温度干燥12-24h。In the drying treatment, the washed product is placed on filter paper, and then transferred to a blast drying oven for drying at a temperature of 60-80° C. for 12-24 hours.
本发明中，所述的铌源，是商品级草酸铌粉末(质量分数≥98%)，使用量为0.5 -1.0g；所述的磷酸，是商品级磷酸的水溶液(质量分数≥85%), 使用量为3-8 mL；所述的去离子水，是高纯度的商品级去离子水，使用量为80-150mL。In the present invention, the niobium source is commercial grade niobium oxalate powder (mass fraction≥98%), and the usage amount is 0.5-1.0g; the phosphoric acid is an aqueous solution of commercial grade phosphoric acid (mass fraction≥85%) , the usage amount is 3-8 mL; the deionized water is high-purity commercial grade deionized water, and the usage amount is 80-150 mL.
本发明中，所述的超声溶剂辅助剥离法，是将经化学液相合成所得粉末产物分散在水相或有机相当中，分散浓度为1g/L—10 g/L；随后将分散体系置于注有适量水的超声波清洗器中，以中度超声处理分散体系30 -60min。In the present invention, the ultrasonic solvent-assisted peeling method is to disperse the powder product obtained by chemical liquid phase synthesis in an aqueous phase or an organic equivalent, and the dispersion concentration is 1 g/L-10 g/L; then the dispersion system is placed in In an ultrasonic cleaner filled with an appropriate amount of water, moderately ultrasonically treat the dispersion for 30-60min.
本发明中，所述的水相，是高纯度的去离子水；所述的有机相，是商品级无水乙醇(质量分数≥99.8%)、商品级甲醇(≥99.9%)或商品级丙酮(≥99.7%)。In the present invention, the water phase is high-purity deionized water; the organic phase is commercial grade absolute ethanol (mass fraction≥99.8%), commercial grade methanol (≥99.9%) or commercial grade acetone (≥99.7%).
与现有技术相比，本发明的技术效果：Compared with the prior art, the technical effects of the present invention:
（1）本发明中，采用的原料草酸铌(铌源)及磷酸，绿色环保、安全无毒、成本低廉；所选用的液相合成方法和纳米薄片剥离方法，简便易行、效率较高；(1) In the present invention, the raw materials used are niobium oxalate (niobium source) and phosphoric acid, which are environmentally friendly, safe, non-toxic, and low in cost; the selected liquid phase synthesis method and nanosheet peeling method are simple and easy to implement and have high efficiency;
（2）本发明得到的酸式磷酸铌氧层状相，具有稳定的二维层结构，相对于此前文献报道的磷酸铌氧块体，更易于剥离实现超薄化纳米片；(2) The acid niobium phosphate layered phase obtained in the present invention has a stable two-dimensional layer structure, and is easier to peel off to achieve ultra-thin nanosheets than the niobium phosphate blocks reported in the literature before;
（3）本发明得到的磷酸铌氧胶体溶液，其剥离产率超过98%，且厚度均匀分布在1nm左右，具有剥离产率高、单层化比例高、制备得到的纳米片胶体溶液浓度高等特点。(3) The niobium phosphate colloidal solution obtained by the present invention has a peeling yield of more than 98%, and the thickness is uniformly distributed at about 1 nm, with high peeling yield, high monolayer ratio, and high concentration of the prepared nanosheet colloidal solution Features.
本发明方法对于层状酸式磷铌氧在电化学储能、光电转换器件以及化学催化和电催化等领域的应用研究具有潜在价值，对于其他二维层状纳米材料的制备和单层结构的高效剥离方法也具有借鉴意义。The method of the invention has potential value for the application research of layered acid phosphorus niobium oxide in electrochemical energy storage, photoelectric conversion devices, chemical catalysis and electrocatalysis, etc. Efficient stripping methods are also instructive.
附图说明Description of drawings
图1为合成得到的层状酸式磷酸铌氧2NbOPO4· H3PO4· H2O的X射线粉末衍射图谱和相应的扫描电子显微镜照片。Fig. 1 is the X-ray powder diffraction pattern and the corresponding scanning electron microscope photograph of the synthesized layered acid niobium phosphate 2NbOPO 4 · H 3 PO 4 · H 2 O.
图2为本发明制备的酸式磷酸铌氧单原子层薄片胶体溶液的宏观照片。Fig. 2 is a macrophotograph of the colloidal solution of acid niobium phosphate monoatomic layer flakes prepared by the present invention.
图3为本发明制备的酸式磷酸铌氧单原子层薄片胶体溶液的丁达尔现象照片和相应纳米薄片的原子力显微镜照片。Fig. 3 is a photo of Tyndall's phenomenon of a colloidal solution of acid niobium oxyphosphate monoatomic layer flakes prepared by the present invention and an atomic force microscope photo of the corresponding nano flakes.
具体实施方式Detailed ways
下面通过具体实施例进一步介绍本发明。 但本发明不限于这些实施例。The present invention is further described below through specific embodiments. However, the present invention is not limited to these examples.
实施例1：Example 1:
称取0.5g商品级草酸铌粉末，转移至经过预清洗与烘干的250mL三颈烧瓶中，并依次加入80mL去离子水和5mL商品级磷酸；向三颈瓶中加入磁力搅拌子后，将三颈瓶转移并固定在配有冷凝回流装置的油浴锅反应体系上，持续搅拌反应液直到形成透明澄清溶液后，将反应温度调至120℃进行15h反应。反应结束后待体系冷却到室温，取瓶底白色沉淀产物转移到内部覆盖有两层滤纸的完整密封在抽滤瓶上的布氏漏斗中，使用去离子水对白色产物进行重复五次的抽滤洗涤操作，并将充分洗涤后的产物转移至鼓风干燥烘箱中在60℃条件下干燥8h，得到酸式磷酸铌氧层状相；取0.01g干燥后的粉末转移至装有10mL去离子水的烧杯中，将烧杯置于超声波清洗器中并以中度超声持续作用30min，得到剥离为单原子层的磷酸铌氧纳米薄片胶体,胶体溶液浓度为1g/L。Weigh 0.5 g of commercial grade niobium oxalate powder, transfer it to a 250 mL three-necked flask that has been pre-cleaned and dried, and add 80 mL of deionized water and 5 mL of commercial grade phosphoric acid in turn; The three-necked flask was transferred and fixed on the oil bath reaction system equipped with a condensation reflux device, and the reaction solution was continuously stirred until a transparent and clear solution was formed, and then the reaction temperature was adjusted to 120 ° C for 15 hours of reaction. After the reaction, the system was cooled to room temperature, and the white precipitated product at the bottom of the bottle was taken and transferred to a Buchner funnel completely sealed on the suction filter bottle with two layers of filter paper inside, and the white product was repeatedly pumped five times with deionized water. Filter and wash, and transfer the fully washed product to a blast drying oven and dry it at 60 °C for 8 hours to obtain an acid niobium phosphate layered phase; take 0.01 g of the dried powder and transfer it to a room containing 10 mL of deionized water. In a beaker of water, place the beaker in an ultrasonic cleaner and continue to act with moderate ultrasonic waves for 30 minutes to obtain a niobium phosphate nanosheet colloid exfoliated into a single atomic layer, and the concentration of the colloid solution is 1 g/L.
实施例2：Example 2:
称取0.5g商品级草酸铌粉末，转移至经过预清洗与烘干的250mL三颈烧瓶中，并依次加入80mL去离子水和5mL商品级磷酸；向三颈瓶中加入磁力搅拌子后，将三颈瓶转移并固定在配有冷凝回流装置的油浴锅反应体系上，持续搅拌反应液直到形成透明澄清溶液后，将反应温度调至120℃进行15h反应。反应结束后待体系冷却到室温，取瓶底白色沉淀产物转移到内部覆盖有两层滤纸的完整密封在抽滤瓶上的布氏漏斗中，使用去离子水对白色产物进行重复五次的抽滤洗涤操作，并将充分洗涤后的产物转移至鼓风干燥烘箱中在60℃条件下干燥8h，得到酸式磷酸铌氧层状相；取0.1g干燥后的粉末转移至装有10mL去离子水的烧杯中，将烧杯置于超声波清洗器中并以中度超声持续作用30min，得到剥离为单原子层的磷酸铌氧纳米薄片胶体，胶体溶液浓度为10g/L。Weigh 0.5 g of commercial grade niobium oxalate powder, transfer it to a 250 mL three-necked flask that has been pre-cleaned and dried, and add 80 mL of deionized water and 5 mL of commercial grade phosphoric acid in turn; The three-necked flask was transferred and fixed on the oil bath reaction system equipped with a condensation reflux device, and the reaction solution was continuously stirred until a transparent and clear solution was formed, and then the reaction temperature was adjusted to 120 ° C for 15 hours of reaction. After the reaction, the system was cooled to room temperature, and the white precipitated product at the bottom of the bottle was taken and transferred to a Buchner funnel completely sealed on the suction filter bottle with two layers of filter paper inside, and the white product was repeatedly pumped five times with deionized water. Filter and wash, and transfer the fully washed product to a blast drying oven and dry it at 60 °C for 8 hours to obtain a layered phase of acid niobium phosphate; take 0.1 g of the dried powder and transfer it to a room containing 10 mL of deionized water. In a beaker of water, place the beaker in an ultrasonic cleaner and continue to use moderate ultrasonic waves for 30 minutes to obtain a niobium phosphate nanosheet colloid exfoliated into a single atomic layer, and the concentration of the colloid solution is 10 g/L.
实施例3：Example 3:
称取0.5g商品级草酸铌粉末，转移至经过预清洗与烘干的250mL三颈烧瓶中，并依次加入80mL去离子水和5mL商品级磷酸；向三颈瓶中加入磁力搅拌子后，将三颈瓶转移并固定在配有冷凝回流装置的油浴锅反应体系上，持续搅拌反应液直到形成透明澄清溶液后，将反应温度调至120℃进行15h反应。反应结束后待体系冷却到室温，取瓶底白色沉淀产物转移到内部覆盖有两层滤纸的完整密封在抽滤瓶上的布氏漏斗中，使用去离子水对白色产物进行重复五次的抽滤洗涤操作，并将充分洗涤后的产物转移至鼓风干燥烘箱中在60℃条件下干燥8h，得到酸式磷酸铌氧层状相；取0.01g干燥后的粉末转移至装有10mL商品级无水乙醇的烧杯中，将烧杯置于超声波清洗器中并以中度超声持续作用30min，得到剥离为单原子层的磷酸铌氧纳米薄片胶体，胶体溶液浓度为1g/L。Weigh 0.5 g of commercial grade niobium oxalate powder, transfer it to a 250 mL three-necked flask that has been pre-cleaned and dried, and add 80 mL of deionized water and 5 mL of commercial grade phosphoric acid in turn; The three-necked flask was transferred and fixed on the oil bath reaction system equipped with a condensation reflux device, and the reaction solution was continuously stirred until a transparent and clear solution was formed, and then the reaction temperature was adjusted to 120 ° C for 15 hours of reaction. After the reaction, the system was cooled to room temperature, and the white precipitated product at the bottom of the bottle was taken and transferred to a Buchner funnel completely sealed on the suction filter bottle with two layers of filter paper inside, and the white product was repeatedly pumped five times with deionized water. Filter and wash, and transfer the fully washed product to a blast drying oven and dry it at 60 °C for 8 hours to obtain an acid niobium phosphate layered phase; take 0.01 g of the dried powder and transfer it to a commercial grade containing 10 mL In a beaker of absolute ethanol, place the beaker in an ultrasonic cleaner and continue to use moderate ultrasonic waves for 30 minutes to obtain a niobium phosphate nanosheet colloid exfoliated into a single atomic layer, and the concentration of the colloid solution is 1 g/L.
实施例4：Example 4:
称取0.5g商品级草酸铌粉末，转移至经过预清洗与烘干的250mL三颈烧瓶中，并依次加入80mL去离子水和5mL商品级磷酸；向三颈瓶中加入磁力搅拌子后，将三颈瓶转移并固定在配有冷凝回流装置的油浴锅反应体系上，持续搅拌反应液直到形成透明澄清溶液后，将反应温度调至120℃进行15h反应。反应结束后待体系冷却到室温，取瓶底白色沉淀产物转移到内部覆盖有两层滤纸的完整密封在抽滤瓶上的布氏漏斗中，使用去离子水对白色产物进行重复五次的抽滤洗涤操作，并将充分洗涤后的产物转移至鼓风干燥烘箱中在60℃条件下干燥8h，得到酸式磷酸铌氧层状相；取0.1g干燥后的粉末转移至装有10mL商品级无水乙醇的烧杯中，将烧杯置于超声波清洗器中并以中度超声持续作用30min，得到剥离为单原子层的磷酸铌氧纳米薄片胶体，胶体溶液浓度为10g/L。Weigh 0.5 g of commercial grade niobium oxalate powder, transfer it to a 250 mL three-necked flask that has been pre-cleaned and dried, and add 80 mL of deionized water and 5 mL of commercial grade phosphoric acid in turn; The three-necked flask was transferred and fixed on the oil bath reaction system equipped with a condensation reflux device, and the reaction solution was continuously stirred until a transparent and clear solution was formed, and then the reaction temperature was adjusted to 120 ° C for 15 hours of reaction. After the reaction, the system was cooled to room temperature, and the white precipitated product at the bottom of the bottle was taken and transferred to a Buchner funnel completely sealed on the suction filter bottle with two layers of filter paper inside, and the white product was repeatedly pumped five times with deionized water. Filter and wash, and transfer the fully washed product to a blast drying oven and dry it at 60 °C for 8 hours to obtain an acid niobium phosphate layered phase; take 0.1 g of the dried powder and transfer it to a commercial grade containing 10 mL In a beaker of absolute ethanol, place the beaker in an ultrasonic cleaner and continue to act with moderate ultrasonic waves for 30 minutes to obtain a monoatomic layer of niobium phosphate nanosheet colloid with a concentration of 10 g/L.
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