CN109650450A - 一种中空MoS2微球的制备方法及其应用 - Google Patents
一种中空MoS2微球的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 22
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 claims 1
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 claims 1
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical compound CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 claims 1
- 231100000719 pollutant Toxicity 0.000 claims 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims 1
- 235000015393 sodium molybdate Nutrition 0.000 claims 1
- 239000011684 sodium molybdate Substances 0.000 claims 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 1
- 231100000331 toxic Toxicity 0.000 claims 1
- 230000002588 toxic effect Effects 0.000 claims 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004005 microsphere Substances 0.000 abstract description 6
- 210000003850 cellular structure Anatomy 0.000 abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000005461 lubrication Methods 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 rough surface Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- 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
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- B01J35/33—Electric or magnetic properties
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- 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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- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
本发明提供了一种表面多孔结构的大尺寸中空MoS2微球及其制备方法和应用。本发明先采用水热法制备大尺寸的Cu‑Fe2O3微球，然后以该微球为模板通过水热法在其表面垂直生长MoS2层状纳米片，最后将得到的复合材料通过腐蚀液刻蚀的方法去除内部的模板，得到具有大尺寸的中空MoS2微球。实施例的结果表明，本发明能够制备得到表具有较大尺寸的中空微球，粒度分布1～30μm；中空微球表面是超薄纳米片组装的多孔结构，具有丰富的孔道结构，孔的尺寸为2～500nm的介孔及大孔，壳层厚度可以在5～500nm之间进行调节。本发明制备的MoS2材料尺寸较大，纳米片状二硫化钼垂直生排列形成了三维多孔的结构，在催化、光/电催化、吸附、气敏传感、润滑等领域都有较优异的性能。
Description
技术领域
本技术属于二维层状材料制备领域，技术涉及水热法，特别是一种大尺寸中空MoS2微球及其制备方法和应用。
背景技术
自石墨烯的发现以来，二维层状材料因具有优异的光学、电学、磁学及力学性能，近年来得到了广泛的关注。其中过渡金属硫化物具有类石墨烯的结构特点，金属W/Mo原子层被两个S/Se原子层夹在中间，形成典型的三明治结构，其层内通过很强的化学键结合，层与层之间则以较弱的范德华力结合，是一种典型的无机层状化合物。过渡金属硫化物（TMDs）以其奇特的性能成为人们关注的热点，在众多领域如场效应晶体管、催化、气敏、锂离子电池等方面得到了广泛的应用。尤其是纳米尺寸的TMDs，晶体边缘的不饱和键具有较高的化学活性使其在很多领域具有潜在的应用价值。
得益于光催化技术的如火如荼，二维硫化钼材料近年来得到了长足的发展。越来越多的硫化钼材料被开发出来并用于光催化助催化剂应用。目前，多数已经报道的MoS2材料为超薄纳米片结构，而具有其他结构形貌的MoS2材料的报道较少。同时，由于超薄纳米片在实际使用过程中分离、收集比较困难，限制了其广泛的应用。
具有中空结构的材料具有独特的孔道结构，大的比表面积，更多的活性位点，有助于增强客体材料与分子的接触面积，用于催化、光催化，气敏等领域具有很好的应用前景。而具有大尺寸的中空结构不仅具有纳米中空结构的优势，同时该类结构又具有大尺寸粒子的易分离处理等优点，因此具有更好应用前景。因此制备出具有大尺寸的中空结构的MoS2材料具有重要的研究价值。
发明内容
本发明的目的在于提供一种大尺寸中空MoS2微球及其制备方法和应用。制备的MoS2微球具有中空结构，球壳由垂直排列的MoS2超薄纳米片组装而成，厚度可调节，具有较多的介孔及大孔结构，同时该微球具有开口结构。多孔结构有助于小分子的扩散传输，在催化、光/电催化、吸附、气敏传感、锂离子电池等领域等都有较优异的性能。
本发明还涉及一种大尺寸中空MoS2微球的制备方法，采用的是两步水热工艺，包含以下步骤：
（1）将一定量的Fe源和六亚甲基四胺加入装有乙醇与水组成的混合溶剂中，搅拌溶解。然后再加入适量的铜源，搅拌一定时间后将溶液转入水热反应釜中，水热反应一段时间后，冷却后取出样品，离心，洗涤，最后放入干燥箱中干燥，得到Cu-α-Fe2O3。
（2）将一定量的钼源、硫源溶于去离子水中，磁力搅拌完全溶解，再加入步骤（1）中得到的材料，搅拌完全分散后加入水热反应釜中，水热反应，冷却、洗涤，离心，最后放入干燥箱干燥，得到Cu-α-Fe2O3@MoS2复合材料微球。
（3）将制备得到的复合微球中加入一定浓度的腐蚀液进行搅拌腐蚀，得到MoS2表面垂直排列的多孔结构的中空MoS2微球。
所述铁源为水溶性铁源，具体包括硝酸铁、氯化铁、硫酸亚铁、醋酸亚铁、磷酸铁，所述铁源的浓度为0.1mol/L~3 mol/L，所述Fe源和六亚甲基四胺的摩尔比为0.5-2：1。
所述乙醇/水混合溶剂中两者的体积比为0.25-4：1。
所述Cu-α-Fe2O3微球中Cu的含量为1wt%~10wt%。所述水热反应的温度为120℃~240℃，所述反应时间为4h~30h。
所述的Cu-α-Fe2O3、硫源与钼源的物质的量比为0.2-10：0.5-4：1。所述钼源的浓度为0.005~0.1mol/L。
所述腐蚀溶液为稀盐酸、稀硝酸溶液，所述腐蚀液的浓度为2wt%~10wt%。所述腐蚀时间为5min~20min。所述搅拌腐蚀的搅拌速度为20r/min~50r/min。
所述步骤（1）、步骤（2）中的产物经离心分离、洗涤液为无水乙醇+水的混合溶液，洗涤后采用真空干燥的方式，产物干燥温度为30 °C ~ 100 °C，干燥时间为2~20h。
所述大尺寸中空MoS2微球的壳层厚度可以通过调节钼源与Cu-α-Fe2O3的相对量进行调节。
本发明的另一目的是将制备的大尺寸中空MoS2微球用于催化、光催化、电催化、吸附、气敏传感、锂离子电池等领域。
本发明的有益效果为：
本发明所制备得到的大尺寸中空MoS2微球，该微球由MoS2超薄纳米片垂直排列而成，微球直径为 1~30μm，壳层厚度可以在5～500nm之间进行调节，具有丰富的孔道结构，孔尺寸均匀，分散性好，表面粗糙。
该方法以无机盐为原料，通过两步水热法制备大尺寸中空MoS2微球。可以通过调整原料浓度、体积，反应温度、反应时间等调控中空微球的结构。本发明制备的大尺寸中空MoS2微球粒径均匀，分散性好，表面粗糙，微球表面为垂直排列的MoS2超薄纳米片组装而成，具有丰富的孔道结构及超薄的纳米片结构，赋予材料较大的比表面积与丰富的反应活性位点，提高其活性。同时，较大尺寸的微球有助于材料的后续分离及收集，便于工业化应用。
附图说明
图 1 是实施例 1大尺寸中空MoS2微球的 X 射线衍射图谱。
图 2 是实施例 1大尺寸中空MoS2微球的扫描电镜照片。
图 3 是实施例 1大尺寸中空MoS2微球的透射电镜照片。
图 4 是实施例1大尺寸中空MoS2微球降解对硝基苯的紫外可见吸收光谱图。
图 5 是实施例 2大尺寸中空MoS2微球的扫描电镜照片。
图 6 是实施例 2大尺寸中空MoS2微球的透射电镜照片。
具体实施方式
下面结合具体实施例，进一步阐明本发明，应理解这些实施例仅用于说明本发明而不用于限制本发明的范围，在阅读了本发明之后，本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
实施例 1
1）将4.054g的六水合氯化铁(FeCI3·6H2O)和1.2g六亚甲基四胺(HMT)加入装有30ml体积比为1:1的乙醇/水混合溶剂的烧杯中，搅拌使之完全溶解。然后再加入1.0wt％的三水合硝酸铜(Cu(NO3)2·3H2O)，搅拌30min后将溶液转入50ml的水热反应釜中，经过180℃水热反应24h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3作为模板。
2）将0.35g四水合钼酸铵（(NH4)6Mo7O24·4H2O）、0.76g硫脲(CN2H4S )溶于20ml去离子水中，并用磁力搅拌30min，使之完全溶解，再加入20mg已得到的Cu-α-Fe2O3，搅拌30min使得完全分散后加入50mL的水热反应釜中，经过180℃水热反应24h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3@MoS2微球。
3）取0.2g的步骤（2）中制备的复合材料，加入到20ml的浓度为5wt%的稀盐酸溶液中，搅拌20min进行腐蚀，腐蚀后的溶液过滤，用去离子水与乙醇洗涤后置于真空干燥箱中进行干燥，收集得到大尺寸中空MoS2微球。
上述制备的大尺寸中空MoS2微球的 X 射线衍射图谱如图 1 所示，其衍射峰主要为MoS2，明显的馒头峰说明材料的结晶性比较差。上述制备的大尺寸中空MoS2微球的扫描电镜照片（见图 2），从中可以看出MoS2微球具有中空结构。上述制备的大尺寸中空MoS2微球的透射电镜照片（见图 3），从中可以看出大尺寸中空MoS2微球的空心结构。
上述制备的大尺寸中空MoS2微球粉体的直径约为2μm。BET测试结果表明MoS2微球的比表面积为127m2/g。
将上述制备的大尺寸中空MoS2微球用于催化还原3ml浓度为14mg/L的对硝基苯酚溶液，经15min后，催化还原效率达到90％，Kapp值0.1267min-1（图4）。
上述制备的中空MoS2微球进行吸附性能测试：将3mg的MoS2粉体加入到100ml浓度为75mg/L的亚甲基蓝溶液中，1min内亚甲基蓝的降解率达94％。
将上述制备的尺寸中空MoS2微球应用于电催化产氢领域，析氢反应起始过电位为108mV，塔菲尔斜率为84mV/dec。
将上述制备的中空MoS2微球应用于锂离子电池负极上，显示电流密度为0.2A g−1时可逆容量为361 mA h g-1。
将上述制备的中空MoS2微球应用于气敏领域，当探测200ppm的甲醛时，灵敏度为13。
实施例2
1）将2.1g的六水合氯化铁(FeCI3·6H2O)和1.5g六亚甲基四胺(HMT)加入装有30ml体积比为1:1的乙醇/水混合溶剂的烧杯中，搅拌使之完全溶解。然后再加入3.0wt％的三水合硝酸铜(Cu(NO3)2·3H2O)，搅拌30min后将溶液转入50ml的水热反应釜中，经过180℃水热反应24h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3作为模板。
2）将0.5g四水合钼酸铵（(NH4)6Mo7O24·4H2O）、0.8g硫脲(CN2H4S )溶于20ml去离子水中，并用磁力搅拌30min，使之完全溶解，再加入20mg已得到的Cu-α-Fe2O3，搅拌30min使得完全分散后加入50mL的水热反应釜中，经过180℃水热反应24h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3@MoS2微球。
3）取0.2g的步骤（2）中制备的复合材料，加入到20ml的浓度为5wt%的稀盐酸溶液中，搅拌20min进行腐蚀，腐蚀后的溶液过滤，用去离子水与乙醇洗涤后置于真空干燥箱中进行干燥，收集得到大尺寸中空MoS2微球。
上述制备的大尺寸中空MoS2微球的 X 射线衍射图谱其衍射峰主要为MoS2，明显的馒头峰说明材料的结晶性比较差。上述制备的大尺寸中空MoS2微球的扫描电镜照片（见图5），从中可以看出MoS2微球具有中空结构。上述制备的大尺寸中空MoS2微球的透射电镜照片可以看出大尺寸中空MoS2微球的空心结构（图6）。
上述制备的大尺寸中空MoS2微球粉体的直径约为2.2μm。BET测试结果表明MoS2微球的比表面积为135m2/g。
将上述制备的大尺寸中空MoS2微球用于催化还原3ml浓度为20mg/L的对硝基苯酚溶液，经15min后，催化还原效率达到92％。
上述制备的中空MoS2微球进行吸附性能测试：将1mg的MoS2粉体加入到50ml浓度为50mg/L的亚甲基蓝溶液中，2min内亚甲基蓝的降解率达90％。
将上述制备的尺寸中空MoS2微球应用于电催化产氢领域，析氢反应起始过电位为116mV，塔菲尔斜率为93mV/dec。
将上述制备的中空MoS2微球应用于锂离子电池负极上，显示电流密度为0.5A g−1时可逆容量为283 mA h g-1。
将上述制备的中空MoS2微球应用于气敏领域，当探测100ppm的甲醛时，灵敏度为5.6。
实施例3
1）将3g的硝酸铁和1.5g六亚甲基四胺(HMT)加入装有50ml体积比为1:2的乙醇/水混合溶剂的烧杯中，搅拌使之完全溶解。然后再加入2.0wt％的三水合硝酸铜(Cu(NO3)2·3H2O)，搅拌30min后将溶液转入50ml的水热反应釜中，经过160℃水热反应20h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3作为模板。
2）将0.5g四水合钼酸铵（(NH4)6Mo7O24·4H2O）、0.8g硫脲(CN2H4S )溶于20ml去离子水中，并用磁力搅拌30min，使之完全溶解，再加入20mg已得到的Cu-α-Fe2O3，搅拌30min使得完全分散后加入50mL的水热反应釜中，经过180℃水热反应24h后，冷却后取出样品，用无水乙醇和去离子水洗涤，离心，最后放入干燥箱80℃下干燥10h，得到Cu-α-Fe2O3@MoS2微球。
3）取0.2g的步骤（2）中制备的复合材料，加入到20ml的浓度为8wt%的稀盐酸溶液中，搅拌20min进行腐蚀，腐蚀后的溶液过滤，用去离子水与乙醇洗涤后置于真空干燥箱中进行干燥，收集得到大尺寸中空MoS2微球。
上述制备的大尺寸中空MoS2微球的 X 射线衍射图谱其衍射峰主要为MoS2，明显的馒头峰说明材料的结晶性比较差。上述制备的大尺寸中空MoS2微球的扫描电镜照片及透射电镜照片可以看出大尺寸中空MoS2微球的空心结构。
上述制备的大尺寸中空MoS2微球粉体的直径约为1.8μm。BET测试结果表明MoS2微球的比表面积为89m2/g。
将上述制备的大尺寸中空MoS2微球用于催化还原3ml浓度为50mg/L的对硝基苯酚溶液，经10min后，催化还原效率达到87％。
上述制备的中空MoS2微球进行吸附性能测试：将1mg的MoS2粉体加入到50ml浓度为50mg/L的亚甲基蓝溶液中，3min内亚甲基蓝的降解率达94％。
将上述制备的尺寸中空MoS2微球应用于电催化产氢领域，析氢反应起始过电位为96mV，塔菲尔斜率为85mV/dec。
将上述制备的中空MoS2微球应用于锂离子电池负极上，显示电流密度为0.5A g−1时可逆容量为296 mA h g-1。
将上述制备的中空MoS2微球应用于气敏领域，当探测500ppm的甲醛时，灵敏度为26。
Claims (10)
1.一种中空MoS2微球的制备方法，其特征在于，包括以下步骤：
（1）水热法制备Cu-α-Fe2O3微球：将Fe源和六亚甲基四胺溶解于乙醇/水混合溶剂中，搅拌溶解，加入铜源，搅拌一定时间后将溶液转入水热反应釜中进行水热反应，冷却，离心，洗涤，干燥，得到Cu-α-Fe2O3；
（2）将钼源、硫源溶于去离子水中，与步骤（1）中得到的材料混合均匀，然后加入水热反应釜中，水热反应，冷却、洗涤，离心，干燥，得到复合材料微球；
（3）将步骤（2）制备得到的复合材料微球用腐蚀液进行搅拌腐蚀，得到MoS2表面垂直排列的多孔结构的中空MoS2微球。
2.根据权利要求1所述的中空MoS2微球的制备方法，其特征在于，步骤（1）中所述铁源为水溶性铁源，具体包括硝酸铁、氯化铁、硫酸亚铁、醋酸亚铁、磷酸铁等，所述铁源的浓度为0.1mol/L~3mol/L，所述Fe源和六亚甲基四胺的摩尔比为0.5-2：1。
3.根据权利要求1所述的中空MoS2微球的制备方法，其特征在于，Cu-α-Fe2O3微球中Cu的含量为1wt%~10wt%。
4.根据权利要求1所述的中空MoS2微球的制备方法，其特征在于，步骤（1）中所述的乙醇/水混合溶剂中两者的体积比为1:4~4:1，所述水热反应的温度为120℃~240℃，反应时间为4h~30h。
5.根据权利要求1所述的中空MoS2微球的制备方法，其特征在于，所述的Cu-α-Fe2O3、硫源与钼源的物质的量比为0.2-10：0.5-4：1，所述的硫源包括硫脲、硫代乙酰胺、甲基乙基硫醚、硫氢化钠、乙基苯基硫中的任意一种；所述的钼源包括钼酸钠、钼酸铵、磷钼酸铵中的任意一种。
6.根据权利要求1所述的中空MoS2微球的制备方法，其特征在于，所述的腐蚀溶液为稀盐酸、或稀硝酸溶液，腐蚀液的浓度为2wt%~5wt%，腐蚀时间为5min~20min，所述搅拌腐蚀的搅拌速度为20r/min~50r/min。
7.根据权利要求1-6任一项所述制备得到的中空MoS2微球在催化降解有毒的苯酚类化合物上的应用，具体包括对硝基苯酚。
8.根据权利要求1-6 任一项所述制备得到的中空MoS2微球作为吸附剂在吸附有机染料污染物上的应用，具体包括亚甲基蓝。
9.根据权利要求1-6 任一项所述制备得到的中空MoS2微球在电催化方面的应用具体包括电催化产氢。
10.根据权利要求1-6任一项所述制备得到的中空MoS2微球在气敏传感、锂离子电池材料领域上的应用。
Priority Applications (1)
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| CN116135311B (zh) * | 2023-04-20 | 2023-08-04 | 山西省煤炭地质物探测绘院有限公司 | 基于二硫化钼网络结构的纳米材料及其制备方法、应用 |
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