CN106563442B - 一种超薄二水三氧化钨纳米片的制备方法及其应用 - Google Patents
一种超薄二水三氧化钨纳米片的制备方法及其应用 Download PDFInfo
- Publication number
- CN106563442B CN106563442B CN201610945842.3A CN201610945842A CN106563442B CN 106563442 B CN106563442 B CN 106563442B CN 201610945842 A CN201610945842 A CN 201610945842A CN 106563442 B CN106563442 B CN 106563442B
- Authority
- CN
- China
- Prior art keywords
- water
- organic
- acid
- tungstic
- ultra
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000009830 intercalation Methods 0.000 claims abstract description 12
- 230000002687 intercalation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 30
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 150000007513 acids Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract 2
- 239000007791 liquid phase Substances 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 150000003941 n-butylamines Chemical class 0.000 description 1
- -1 n-octyl amines Chemical class 0.000 description 1
- 125000004888 n-propyl amino group Chemical class [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种超薄二水三氧化钨纳米片光催化剂的制备方法。采用溶剂热反应制备有机胺插层的有机‑无机杂化物。将10mL1.0mol/L的钨酸钠溶液与90mL3.0mol/L的盐酸溶液混合反应,得到二水三氧化钨块材粉末。取二水三氧化钨粉末与有机胺混合,100~150℃反应2~3天,得到有机胺插层的有机‑无机杂化物,然后用有机酸液相剥离形成二水三氧化钨超薄纳米片。取有机胺插层的二水三氧化钨与有机酸溶液混合,液相超声剥离得到二水三氧化钨超薄纳米片。本发明方法简便,易于操作,所制备的二水三氧化钨超薄纳米片具有较高的光催化活性。
Description
技术领域
本发明所属技术领域为光催化、光电化学材料技术领域,特别涉及三氧化钨超薄纳米片光催化剂的制备方法。
背景技术
三氧化钨为一种宽禁带的n型半导体材料,室温下的禁带宽度为2.63eV,可吸收500nm以下的可见光及紫外光,在电致变色、气敏传感器、光催化与光电转换领域具有重要的应用价值。纳米三氧化钨与传统的半导体材料相比,禁带宽度较窄,在可见光条件下具有良好的光电响应性能,并且价格低廉、性能稳定、无害、无毒,可作为光催化剂,利用太阳光降解水中的有机污染物和空气中的废气,高效节能、清洁、无污染。然而,WO3的性能和实际应用与它的晶相、形态、尺寸、形貌、晶体缺陷以及表面性能紧密相关,而这些又主要取决于WO3的制备方法及制备条件。其中,2D超薄纳米结构是一种厚度在单分子层或少分子层范围的特殊形貌,其平铺尺寸从几十个纳米到微米以上,具有超高的比表面积,表现出高度的各向异性和量子限域效应。当这种特殊的超薄结构材料作为光催化剂时,光生载流子从体内扩散到表面所需要的时间变短,光生电荷分离效率明显提高。因此,2D超薄纳米材料将比其体相材料具有更高的光催化活性。
目前,已经报导的WO3纳米片的合成方法产率较低或需特殊仪器设备,因此,采用插层-剥离的方法制备超薄WO3纳米片,提高光催化性能,用于高效降解有机污染物,以及光电水分解制氢/制氧,对于环境治理、有效提高太阳光利用率和节约能源具有重要的意义。
发明内容
本发明的目的是提供一种二维的超薄二水三氧化钨纳米片的制备方法及其应用,本发明方法简单,易于操作,所制备的超薄二水三氧化钨纳米片具有较高的光电性能以及能够较好的应用于可见光响应光催化领域。
具体步骤为:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末;
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末和5~10mL有机胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100~150℃条件下反应2~3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL1.0~3.0mol/L的有机酸溶液中,冰水浴磁力搅拌6~10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
所述有机胺为正丙胺、正丁胺、正辛胺和甲酰胺中的一种;
所述有机酸为乙酸、酒石酸、草酸和柠檬酸中的一种;
所述化学试剂纯度均为化学纯以上纯度。
本发明的有益效果是:
本发明所制备的超薄二水三氧化钨纳米片是厚度为2~5nm,面积为1.5~5μm的少层结构,其禁带宽度为2.3~2.7eV之间,紫外区吸收增强,能够吸收可见光。超薄二水三氧化钨纳米片在可见光照射下,能够产生快速的光电流响应,与块体二水三氧化钨相比,催化性能明显增强。因此,超薄二水三氧化钨片作为一种可见光响应的纳米材料,在光催化降解有机污染物,光催化分解水制氢/制氧,太阳能电池等方面有巨大的应用潜力。
附图说明
图1是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体(a)和二水三氧化钨(WO3·2H2O)纳米片(b)的XRD衍射图谱。
图2是本发明实施例1制备的超薄二水三氧化钨(WO3·2H2O)纳米片的透射电镜(TEM)图,其中(a-d)为不同分辨率倍数的TEM图。
图3是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体和二水三氧化钨(WO3·2H2O)纳米片的紫外-可见-近红外漫反射光谱图。
图4是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体和二水三氧化钨(WO3·2H2O)超薄纳米片的电流密度-电位图。
具体实施方式
实施例1:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末与5mL正丙胺混合均匀,加入到25mL聚四氯乙烯反应釜中,在100℃反应3天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物加入到15mL 3.0mol/L的醋酸溶液中,冰水浴磁力搅拌10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
图1显示了实施例1制备的二水三氧化钨块体(a)和二水三氧化钨纳米片(b)的XRD衍射图谱,可见块体二水三氧化钨是单斜相晶体,而二水三氧化钨纳米片是正交相晶体。图2是实施例1制备的超薄二水三氧化钨纳米片的透射电镜(TEM)图,其中(a-d)为不同分辨率倍数的TEM图,几乎透明的片状结构表明成功获得了超薄二水三氧化钨纳米片。图3是实施例1制备的二水三氧化钨块体和二水三氧化钨纳米片的紫外-可见-近红外漫反射光谱图,图3显示二水三氧化钨纳米片的吸收带边明显蓝移,说明存在量子限域效应。
所制备的二水三氧化钨超薄纳米片,通过旋涂法在ITO表面做成光电极,制备电极作为工作电极,辅助电极为铂电极,饱和甘汞电极(SCE)作为参比电极,0.5mol/LNa2SO4为支持电解质溶液,在太阳光模拟器(一个太阳的光强)下测试光电化学性能,外加电压的范围为0.2V~0.8V,测试从低压开始一直扫到高压区,采用光源均为590W的氙灯(NEWPORT-9115X型太阳光模拟器),以光切换的方式来测试。从图4可以看出二水三氧化钨超薄纳米片的光电流远远高于二水三氧化钨块体粉末的光电流,由以上结果可知超薄二水三氧化钨纳米片能作为一种可见光响应的纳米材料应用于光催化领域。
实施例2:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得二水三氧化钨粉末与10mL正丁胺混合于聚四氯乙烯反应釜内胆中,在120℃反应2天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物,加入到15mL 1.0mol/L的酒石酸溶液中,冰水浴磁力搅拌6小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片。
实施例3:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得块状二水三氧化钨粉末和8mL正辛胺混合均匀,加入聚四氯乙烯反应釜中,在150℃反应2天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物,加入到15mL1.5mol/L的柠檬酸溶液中,冰水浴磁力搅拌8小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片。
实施例4:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗2~3次,然后冷冻干燥,得到二水三氧化钨块材粉末;
(2)将0.2g步骤(1)所得WO3·2H2O块材粉末和10mL甲酰胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100℃条件下反应3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL 2.0mol/L的醋酸溶液中,冰水浴磁力搅拌10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片。
以上实施例所述化学试剂纯度均为化学纯以上纯度。
Claims (1)
1.一种超薄WO3·2H2O纳米片的制备方法,其特征在于具体步骤为:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗3次,然后冷冻干燥,得到WO3·2H2O块材粉末;
(2)取0.2g步骤(1)所得WO3·2H2O块材粉末和5~10mL有机胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100~150℃条件下反应2~3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL浓度为1.0~3.0mol/L的有机酸溶液中,冰水浴磁力搅拌6~10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的WO3·2H2O超薄纳米片;
所述超薄WO3·2H2O纳米片,其特征在于:WO3·2H2O纳米片的厚度为2-5nm;
所述有机胺为正丙胺、正丁胺、正辛胺、和甲酰胺中的一种;
所述有机酸为乙酸、酒石酸、草酸和柠檬酸中的一种;
所述钨酸钠、盐酸、有机胺、有机酸均为化学纯以上纯度。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610945842.3A CN106563442B (zh) | 2016-11-02 | 2016-11-02 | 一种超薄二水三氧化钨纳米片的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610945842.3A CN106563442B (zh) | 2016-11-02 | 2016-11-02 | 一种超薄二水三氧化钨纳米片的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106563442A CN106563442A (zh) | 2017-04-19 |
CN106563442B true CN106563442B (zh) | 2018-09-11 |
Family
ID=58536562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610945842.3A Active CN106563442B (zh) | 2016-11-02 | 2016-11-02 | 一种超薄二水三氧化钨纳米片的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106563442B (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107324391B (zh) * | 2017-08-16 | 2019-01-22 | 广东工业大学 | 一种单层水合三氧化钨纳米片及其制备方法 |
CN110194487B (zh) * | 2018-02-27 | 2020-10-27 | 中国科学技术大学 | 一种表面分散有铂单原子的复合材料及其制备方法、气敏材料 |
CN108607539A (zh) * | 2018-04-23 | 2018-10-02 | 南京信息工程大学 | 一种片状三氧化钨及其制备方法和用作光催化剂的用途 |
CN110639581B (zh) * | 2019-09-01 | 2022-09-27 | 桂林理工大学 | 一种WP2/g-C3N4异质结光催化剂的制备方法 |
CN110918085A (zh) * | 2019-12-16 | 2020-03-27 | 桂林理工大学 | 一种多孔wo3/c纳米片介孔复合光催化剂的制备方法 |
CN111514911B (zh) * | 2020-05-08 | 2023-04-07 | 桂林理工大学 | 一种具有介孔结构的碳掺杂wp纳米片电催化剂及其制备方法 |
CN112499684B (zh) * | 2020-12-04 | 2022-11-08 | 合肥工业大学 | 一种基于离子斥力作用分散剥离多层wo3纳米片的方法 |
CN112844371A (zh) * | 2021-02-03 | 2021-05-28 | 黑河学院 | 一种用于光解水制氧的催化剂及其制备方法 |
CN113955803B (zh) * | 2021-11-02 | 2024-03-22 | 云南锡业集团(控股)有限责任公司研发中心 | 一种粒度可调控的氧化钨粉及钨粉的制备方法 |
CN114606510B (zh) * | 2022-03-21 | 2023-06-27 | 吉林大学 | 一种层状铱基钙钛矿纳米片催化剂、制备方法及其在电催化析氧反应中的应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4247585B2 (ja) * | 1999-03-30 | 2009-04-02 | 日産化学工業株式会社 | 変性された酸化第二スズ−酸化ジルコニウム複合ゾル及びその製造法 |
CN101318702B (zh) * | 2007-06-08 | 2011-01-19 | 郑州大学 | 一种三氧化钨纳米片及其制备方法 |
CN103030179B (zh) * | 2013-01-08 | 2014-12-24 | 江苏大学 | 水热法制备三氧化钨纳米片及其应用 |
CN103969308B (zh) * | 2014-05-05 | 2016-07-06 | 上海师范大学 | 一种可室温工作的印制式no2气敏元件及其制备方法 |
CN104874408A (zh) * | 2015-06-15 | 2015-09-02 | 桂林理工大学 | 一种二硫化锡超薄纳米片光催化剂的制备方法 |
-
2016
- 2016-11-02 CN CN201610945842.3A patent/CN106563442B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN106563442A (zh) | 2017-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106563442B (zh) | 一种超薄二水三氧化钨纳米片的制备方法及其应用 | |
CN107866234B (zh) | 一种高活性ZnIn2S4/TiO2 Z体系催化剂材料制备方法 | |
CN103708559B (zh) | 一种具有光催化性能的三氧化钨纳米薄膜及其制备方法 | |
Ju et al. | Fully blossomed WO3/BiVO4 structure obtained via active facet engineering of patterned FTO for highly efficient Water splitting | |
Tang et al. | CdS/Cu2S co-sensitized TiO2 branched nanorod arrays of enhanced photoelectrochemical properties by forming nanoscale heterostructure | |
CN104646037A (zh) | BiOXs光催化剂、石墨烯复合的BiOXs光催化剂、及其制备方法 | |
CN106000431B (zh) | 片状CdS/BiOCl复合纳米材料及其制备方法 | |
CN105536819B (zh) | 一种石墨烯/硫化锑复合光催化剂的制备方法 | |
Guo et al. | Fabrication of TiO2 nano-branched arrays/Cu2S composite structure and its photoelectric performance | |
CN102220615B (zh) | 制备CdS/ZnO纳米管阵列光电极的方法 | |
CN106498372A (zh) | 光沉积制备Bi/BiVO4复合光电阳极材料的方法 | |
CN101345140B (zh) | 染料敏化太阳能电池光阳极的制备方法 | |
Abdalla et al. | Au/Ga2O3/ZnO heterostructure nanorods arrays for effective photoelectrochemical water splitting | |
CN110368968B (zh) | NiFe-LDH/Ti3C2/Bi2WO6纳米片阵列及制法和应用 | |
CN108579765A (zh) | 硫化铜/钒酸铋双层膜复合材料的制备及作为光电阳极的应用 | |
Peng et al. | Influence of ZnO nano-array interlayer on the charge transfer performance of quantum dot sensitized solar cells | |
Li et al. | Enhanced visible light photocatalytic property of red phosphorus via surface roughening | |
CN106431005B (zh) | 一种钛酸锶-二氧化钛复合纳米管阵列薄膜及其制备方法与应用 | |
CN110368962A (zh) | 一种BiOI/WO3异质结高效光电催化电极的制备方法、产品及应用 | |
Wang et al. | Integrating the plasmonic sensitizer and electron relay into ZnO/Au/CdS sandwich nanotube array photoanode for efficient solar-to-hydrogen conversion with 3.2% efficiency | |
CN105771953B (zh) | 一种钛酸锌/二氧化钛复合纳米材料的制备方法 | |
CN101485977A (zh) | 氧化锌/氧化铟纳米异质结光催化材料及其制备方法 | |
CN105618153A (zh) | 一种基于层级组装的硅-二氧化钛-聚吡咯三维仿生复合材料及应用 | |
CN110586072A (zh) | 一种新型结构的wo3微纳米光催化材料 | |
Chang et al. | Effect of calcination induced phase transition on the photocatalytic hydrogen production activity of BiOI and Bi5O7I based photocatalysts |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |