CN109650450B - 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
- Publication number
- CN109650450B CN109650450B CN201910085058.3A CN201910085058A CN109650450B CN 109650450 B CN109650450 B CN 109650450B CN 201910085058 A CN201910085058 A CN 201910085058A CN 109650450 B CN109650450 B CN 109650450B
- Authority
- CN
- China
- Prior art keywords
- microspheres
- mos
- hollow
- source
- microsphere
- 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
- 239000004005 microsphere Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title abstract description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 33
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 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
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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
- 229910021578 Iron(III) chloride Inorganic materials 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 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
- XYWDPYKBIRQXQS-UHFFFAOYSA-N di-isopropyl sulphide Natural products CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 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
- 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
- 239000002135 nanosheet Substances 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005461 lubrication Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 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 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 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
- 230000005540 biological transmission Effects 0.000 description 3
- 235000008429 bread Nutrition 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 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 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
-
- 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
- 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
-
- 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
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
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 (6)
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Fe源为硝酸铁、氯化铁、硫酸亚铁、醋酸亚铁、或磷酸铁中的任意一种，所述Fe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。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910085058.3A CN109650450B (zh) | 2019-01-18 | 2019-01-18 | 一种中空MoS2微球的制备方法及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910085058.3A CN109650450B (zh) | 2019-01-18 | 2019-01-18 | 一种中空MoS2微球的制备方法及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109650450A CN109650450A (zh) | 2019-04-19 |
| CN109650450B true CN109650450B (zh) | 2021-03-09 |
Family
ID=66122164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910085058.3A Active CN109650450B (zh) | 2019-01-18 | 2019-01-18 | 一种中空MoS2微球的制备方法及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109650450B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841579B (zh) * | 2019-04-28 | 2022-03-11 | 中国科学院大连化学物理研究所 | 一种三维多级孔结构二硫化钼及其制备方法与应用 |
| CN110180564B (zh) * | 2019-06-19 | 2020-07-24 | 清华大学 | 一种二硫化钼催化膜及其制备和应用 |
| CN110255619B (zh) * | 2019-06-21 | 2022-04-22 | 南京工业大学 | 一种基于上转换纳米颗粒制备三维空心结构硫化钼的方法 |
| 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 |
| CN116285294A (zh) * | 2023-05-04 | 2023-06-23 | 万华化学（宁波）有限公司 | 一种低烟密度、耐刮擦的聚碳酸酯材料及其制备方法与应用 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2362854A2 (en) * | 2008-11-10 | 2011-09-07 | Yeda Research And Development Company Ltd. | Inorganic multilayered nanostructures |
| CN101704552A (zh) * | 2009-10-28 | 2010-05-12 | 无锡润鹏复合新材料有限公司 | 一种二硫化钼纳米管及其制备方法 |
| CN102583546B (zh) * | 2012-02-18 | 2013-06-19 | 长安大学 | 以介孔二氧化硅分子筛为硬模板合成介孔二硫化钼的方法 |
| CN105600824B (zh) * | 2016-01-20 | 2017-03-15 | 三峡大学 | 一种高性能微纳多级结构MoS2材料、制备方法及应用 |
| CN108128805A (zh) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | 一种二硫化钼空心球的制备方法 |
| CN107742587B (zh) * | 2017-09-29 | 2019-08-13 | 江苏科技大学 | 一种高比容量的三层Mn2O3@MoS2纳米空心球电极材料及其制备方法与应用 |
| CN108408779A (zh) * | 2017-12-29 | 2018-08-17 | 镇江创智特种合金科技发展有限公司 | 空心“蠕虫”状的MoS2材料及其制备方法 |
| CN108658128B (zh) * | 2018-08-02 | 2020-05-05 | 合肥中航纳米技术发展有限公司 | 一种具有分级结构的MoS2微纳米球的制备方法 |
-
2019
- 2019-01-18 CN CN201910085058.3A patent/CN109650450B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109650450A (zh) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109650450B (zh) | 一种中空MoS2微球的制备方法及其应用 | |
| Kathalingam et al. | Nanosheet-like ZnCo2O4@ nitrogen doped graphene oxide/polyaniline composite for supercapacitor application: effect of polyaniline incorporation | |
| CN108385124B (zh) | 一种用于析氢反应的过渡族金属/碳管/石墨烯电催化剂的制备方法 | |
| Zhao et al. | A Bi‐Co Corridor Construction Effectively Improving the Selectivity of Electrocatalytic Nitrate Reduction toward Ammonia by Nearly 100% | |
| CN105923623A (zh) | 一种三维多级孔结构的石墨烯粉体的制备方法 | |
| Wang et al. | Construction of unique ternary composite MCNTs@ CoSx@ MoS2 with three-dimensional lamellar heterostructure as high-performance bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions | |
| CN109847778B (zh) | 一种用于电解水析氧的二硫化钴/碳氮复合材料及其合成方法 | |
| Jiang et al. | Synthesis of g-C3N4/Fe3O4/MoS2 composites for efficient hydrogen evolution reaction | |
| Ji et al. | MoS2/CoS2 heterostructures embedded in N-doped carbon nanosheets towards enhanced hydrogen evolution reaction | |
| Andikaey et al. | Synthesis of engineered graphene nanocomposites coated with NiCo metal-organic frameworks as electrodes for high-quality supercapacitor | |
| CN107954483B (zh) | 一种α相氢氧化镍超薄纳米片及其制备方法 | |
| Zhang et al. | Facile synthesis of Co–Fe layered double hydroxide nanosheets wrapped on Ni-doped nanoporous carbon nanorods for oxygen evolution reaction | |
| CN106784881B (zh) | 一种贵金属/竖直生长水滑石纳米片甲醇燃料电池催化剂及其制备方法 | |
| CN107731566A (zh) | 一种三维花瓣状镍钴硫化物电极材料的制备方法和应用 | |
| Luo et al. | Controllable synthesis of nitrogen-doped carbon containing Co and Co3Fe7 nanoparticles as effective catalysts for electrochemical oxygen conversion | |
| CN104882298A (zh) | 一种微波法制备NiCo2O4/石墨烯超级电容材料的方法 | |
| CN113549935A (zh) | 杂原子掺杂过渡金属单原子催化剂及其制备方法与应用 | |
| Dong et al. | Tunable growth of perpendicular cobalt ferrite nanosheets on reduced graphene oxide for energy storage | |
| Tong et al. | Greatly improved HER electrocatalytic activity by the composite of CoSe2 and N, S-dual doped graphitic carbon | |
| Ma et al. | Lignin-derived hierarchical porous flower-like carbon nanosheets decorated with biomass carbon quantum dots for efficient oxygen reduction | |
| Gu et al. | Enhancement of the hydrogen evolution performance by finely tuning the morphology of Co-based catalyst without changing chemical composition | |
| Xie et al. | Hierarchical FeCo/C@ Ni (OH) 2 heterostructures for enhanced oxygen evolution activity | |
| Homayounfard et al. | Growth of few-layer flower-like MoS2 on heteroatom-doped activated carbon as a hydrogen evolution reaction electrode | |
| Yan et al. | Ru nanoparticles supported on Co-embedded N-doped carbon nanotubes as efficient electrocatalysts for hydrogen evolution in basic media | |
| CN108479809B (zh) | 一种MnS/Ni3S4复合材料及其制备方法和应用 |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240713 Address after: 810, 8th Floor, Building 10, Courtyard 1, Tianxing Street, Fangshan District, Beijing, 102400 Patentee after: Beijing Zhichanhui Technology Co.,Ltd. Country or region after: China Address before: 443002 No. 8, University Road, Xiling District, Yichang, Hubei Patentee before: CHINA THREE GORGES University Country or region before: China |
|
| TR01 | Transfer of patent right |