CN107955598A - 一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 - Google Patents
一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN107955598A CN107955598A CN201711067699.3A CN201711067699A CN107955598A CN 107955598 A CN107955598 A CN 107955598A CN 201711067699 A CN201711067699 A CN 201711067699A CN 107955598 A CN107955598 A CN 107955598A
- Authority
- CN
- China
- Prior art keywords
- core
- nitrogen
- shell structure
- nanometer sheet
- selenizing molybdenum
- 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.)
- Granted
Links
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 66
- 239000011733 molybdenum Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 20
- 239000011218 binary composite Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000013590 bulk material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 4
- 238000003786 synthesis reaction Methods 0.000 abstract 4
- 239000010410 layer Substances 0.000 description 7
- 239000002127 nanobelt Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- -1 ultrasonic 0.5h Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种硒化钼纳米片/氮掺杂碳核壳结构复合材料,具有中空结构,内核是硒化钼纳米片,外壳是中空纳米带结构的氮掺杂碳层;其制备方法包括:三氧化钼纳米带的合成,三氧化钼/聚吡咯二元复合材料的合成,硒化钼/聚吡咯核壳结构二元复合材料的合成,硒化钼纳米片/氮掺杂碳核壳结构复合材料的合成;用作可见光催化剂、电催化剂、钠/锂离子阳极材料和发光晶体管材料。本发明的硒化钼纳米片/氮掺杂碳核壳结构复合材料克服了硒化钼本体材料活性低的缺点,有效缓解硒化钼在使用过程中因体积膨胀造成的不稳定性;本发明的方法简单,易于操作,环保,成本低廉,适用于工业化生产。
Description
技术领域
本发明属于过渡金属化合物纳米材料领域,特别涉及一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用。
背景技术
作为过渡金属化合物纳米材料中的典型代表,硒化钼属于六方晶系,具有类似于三明治的二维片层状结构,层与层之间通过较弱的范德华力结合在一起。相邻的分子层通过分子间作用力结合可以相互滑动,因而具有较低的摩擦系数,常用作固体润滑剂;硒化钼中每个钼原子被六个硒原子包围,呈三角棱柱状,比表面积大,表面活性高,具有优异的催化活性,广泛用作石油加工行业的加氢脱硫催化剂以及废水处理催化剂。此外,由于具有较大层间距,一些离子如Li+和Na+可以很容易地插入到硒化钼的层间,形成插层化合物,因此在能量存储上也有广泛应用。然而,由于其自身较差的导电性以及有限的活性位点大大限制了硒化钼在光电子、新能源、生物传感等领域的应用,且单一功能的硒化钼已经完全无法满足需要,因而发展基于硒化钼复合多功能纳米材料的制备方法尤为必要。由于中空氮掺杂碳纳米带具有较高的长径比高,大的比表面积,较高的电子传输能力与优异的机械强度,从而能够提高其复合材料结构稳定性及导电性,因此将硒化钼限域在纳米带结构的氮掺杂碳纳米框架内具有重要意义。
发明内容
本发明所要解决的技术问题是提供一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用,该方法简单,易于操作,环保,提高了复合材料的稳定性。
本发明的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料,具有中空结构,内核是硒化钼纳米片,外壳是中空纳米带结构的氮掺杂碳层。
本发明的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,包括:
(1)将质量比为10:1-1:20(优选10:1-1:10)的钼酸钠和氯化钠溶于溶剂中形成混合溶液,搅拌,水热反应,冷却,抽滤,洗涤,干燥,得到三氧化钼纳米带,其中,混合溶液中钼酸钠的浓度为0.01-0.1g/mL;
(2)将步骤(1)中三氧化钼纳米带溶于溶剂中,搅拌,加入吡咯,继续搅拌,加入引发剂溶液反应,抽滤,洗涤,干燥,得到三氧化钼/聚吡咯二元复合材料,其中,三氧化钼纳米带和吡咯的质量比为1:4-15,引发剂与吡咯的摩尔比为1:1-4,三氧化钼纳米带溶液的浓度为0.2-0.6mg/mL;
(3)将步骤(2)中三氧化钼/聚吡咯二元复合材料溶于溶剂一中,超声,得到分散液,将硒溶于溶剂二中,搅拌,滴加到分散液中,水热反应,冷却,抽滤,洗涤,干燥,得到硒化钼/聚吡咯核壳结构二元复合材料,其中,三氧化钼/聚吡咯二元复合材料和硒的质量比为5:1-1:5,三氧化钼/聚吡咯二元复合材料溶液的浓度为0.001-0.02g/mL,硒溶液的浓度为0.001-0.02g/mL;
(4)将步骤(3)中硒化钼/聚吡咯核壳结构二元复合材料在惰性气体环境下退火,洗涤,抽滤,干燥,得到硒化钼纳米片/氮掺杂碳核壳结构复合材料。
所述步骤(1)中搅拌时间为10min;水热反应前加入3mol/L盐酸溶液调节pH值为0.5-1.5。
所述步骤(1)中水热反应温度为160-220℃,水热反应时间为10-48h;干燥为在烘箱中60℃干燥24h。
所述步骤(1)、(2)中溶剂均为去离子水。
所述步骤(2)中继续搅拌时间为10min;引发剂为过硫酸铵、过硫酸钾或氯化铁。
所述步骤(2)中引发剂溶液的浓度为16.5mg/ml。
所述步骤(2)中反应温度为-10-10℃,反应时间为6-48h,优选反应温度为-2-2℃,反应时间为12-24h。
所述步骤(2)中干燥为在真空条件下60℃干燥24h。
所述步骤(3)中超声时间为0.5h;溶剂一为N,N-二甲基甲酰胺;溶剂二是质量分数为50%的水合肼;搅拌时间为1-4h,搅拌温度为80℃。
所述步骤(3)中水热反应温度为160-220℃,水热反应时间为10-48h;干燥为在烘箱中60℃干燥24h。
所述步骤(4)中惰性气体为氮气;退火的工艺参数为:升温到800℃,保温时间为4h,升温的速率为2-5℃/min。
所述步骤(4)中洗涤为先用盐酸洗涤再用水洗涤;干燥为在真空条件下60℃干燥24h。
本发明的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料可以用作可见光催化剂、电催化剂、钠/锂离子阳极材料和发光晶体管材料。
本发明通过水热反应,原位聚合和水热硒化以及高温退火技术,以三氧化钼纳米带为前驱体,其外部包覆聚吡咯层,对其二元复合材料进行水热硒化,水热硒化实现内层三氧化钼的硒化转变为硒化钼,高温退火,制备得到一种新型的硒化钼纳米片/氮掺杂碳核壳结构复合材料。该复合材料在结构上表现为硒化钼纳米片限域生长在中空纳米带结构的氮掺杂碳层内,且在中空纳米带碳层内仍有多余的空间。该复合材料具有如下优势:纳米带结构赋予复合材料较大的长径比,大的比表面积以及一定的力学强度;限域生长在碳层内的硒化钼为纳米片形貌,有利于活性位点的暴露且在一定程度上避免了二硫化钼的团聚现象;外层氮掺杂碳层优良的导电性能有利于电子的传输,内部的空腔结构能够有效缓解因长时间反应引发的结构形变。因此,将硒化钼纳米片与碳材料进行有效的复合,可以达到很好的协同增强作用,以制备出性能优异的复合材料。
有益效果
(1)本发明的硒化钼纳米片/氮掺杂碳核壳结构复合材料具有中空结构,硒化钼为纳米片状,有利于增加硒化钼的活性位点数量,克服了硒化钼本体材料活性低的缺点。中空结构和碳基复合结构可以有效缓解硒化钼在使用过程中因体积膨胀造成的不稳定性。
(2)本发明的方法简单,易于操作,环保,成本低廉,适用于工业化生产,是一种有效快捷的制备方法。
附图说明
图1是实施例1中硒化钼纳米片/氮掺杂碳核壳结构复合材料的SEM图;
图2是实施例1中硒化钼纳米片/氮掺杂碳核壳结构复合材料的TEM图;
图3是实施例1中硒化钼纳米片/氮掺杂碳核壳结构复合材料、三氧化钼纳米带和聚吡咯的XRD图。
具体实施方式
下面结合具体实施例,进一步阐述本发明。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。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将1.21g钼酸钠与0.6g氯化钠加入到60mL去离子水中得到溶液,持续搅拌10min,得到均匀分散液,加入3mol/L盐酸溶液调节pH值为1,转移至水热釜中于烘箱内进行水热反应,反应温度为180℃,反应时间为24h,待反应釜冷却至室温,将所得分散液进行抽滤分离其中的淡蓝色沉淀,将所得固体用去离子水清洗,于烘箱中60℃干燥24h,得到三氧化钼纳米带。
(2)在250mL烧瓶中加入40mg步骤(1)中的三氧化钼纳米带,加入80ml去离子水,搅拌使三氧化钼均匀分散在去离子水中得到分散液,用移液管量取200μL吡咯(0.00288mol)加入上述烧瓶中,搅拌10min后,逐滴加入20ml过硫酸铵水溶液(16.5mg/ml),控制吡咯与过硫酸铵的摩尔比为2:1,将烧瓶放入低温冷冻循环泵中,设置反应温度为0±2℃,搅拌反应12h,在三氧化钼上通过原位聚合反应生长聚吡咯,反应结束后,将分散液抽滤,将所得固体用去离子水洗涤三次,在真空条件下60℃干燥24h,得到三氧化钼/聚吡咯二元复合材料。
(3)称取25mg步骤(2)中三氧化钼/聚吡咯二元复合材料分散在12.5ml N,N-二甲基甲酰胺中,超声0.5h,分散液命名为A溶液,在100ml烧瓶中加入25mg硒粉,分散在12.5ml质量分数为50%的水合肼中,水浴80℃加热,持续搅拌2h,将溶液命名为B。将B逐滴加入A中,转移至50ml水热釜中于烘箱内进行水热反应,反应温度为180℃,反应时间为12h,待反应釜冷却至室温,将所得分散液进行抽滤分离其中的淡蓝色沉淀,将所得固体用去离子水清洗,于烘箱中60℃干燥24h,得到硒化钼/聚吡咯二元复合材料。
(4)称量20mg步骤(3)中的硒化钼/聚吡咯二元复合材料,加入到长为6cm、宽为3cm的瓷方舟中,在氮气环境下于管式炉中高温退火,升温速率为5℃/min,升温至800℃,保温时间为4h。反应结束后,将所得分散液用盐酸洗涤三次,再用水洗涤三次,抽滤,所得产物在真空条件下60℃干燥24h,得到硒化钼纳米片/氮掺杂碳核壳结构复合材料。
图1表明:本实施例制备得到硒化钼纳米片/氮掺杂碳核壳结构复合材料具有纳米带结构,长约为3-8μm,宽约为100-200nm,其较好的长径比有利于电子的传输,并且纳米带结构可以形成三维互相贯穿的结构,降低了离子和电子传输路径,进一步提高材料的导电性能。
图2表明:本实施例制备得到的硒化钼纳米片/氮掺杂碳核壳结构复合材料具有独特空心结构,外部的碳层提高了材料整体的导电性,内部的硒化钼为片层结构,抑制了硒化钼自身的团聚,有利于硒化钼活性位点的充分暴露,材料整体具有空心结构,有利于缓解硒化钼在电化学过程中的体积膨胀和收缩,提高了材料的稳定性。
图3表明:本实施例中的三氧化钼纳米带的XRD衍射峰窄而高,基线平稳,MoO3属于正交晶系,晶胞参数为a=0.396nm,b=1.386nm,c=0.370nm,且(020)(040)(060)晶面具有很强的衍射强度,与JCPDS-05-0508的卡片索引值一致。纯的聚吡咯在2θ=25°的峰,对应于其(002)晶面。而三氧化钼经过包覆聚吡咯层后水热处理后制得的硒化钼纳米片/氮掺杂碳核壳结构复合材料在2θ=13.6°,27.5°,31.4°,37.8°,47.4°和55.9°出现了硒化钼的特征峰,对应于硒化钼的(002),(004),(100),(103),(105)和(110)晶面,与JCPDS-29-0914的卡片索引值一致,进一步证实了内部的片层架构是硒化钼的纳米片。
Claims (10)
1.一种硒化钼纳米片/氮掺杂碳核壳结构复合材料,其特征在于,具有中空结构,内核是硒化钼纳米片,外壳是中空纳米带结构的氮掺杂碳层。
2.一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,包括:
(1)将质量比为10:1-1:20的钼酸钠和氯化钠溶于溶剂中形成混合溶液,搅拌,水热反应,冷却,抽滤,洗涤,干燥,得到三氧化钼纳米带,其中,混合溶液中钼酸钠的浓度为0.01-0.1g/mL;
(2)将步骤(1)中三氧化钼纳米带溶于溶剂中,搅拌,加入吡咯,继续搅拌,加入引发剂溶液反应,抽滤,洗涤,干燥,得到三氧化钼/聚吡咯二元复合材料,其中,三氧化钼纳米带和吡咯的质量比为1:4-15,引发剂与吡咯的摩尔比为1:1-4,三氧化钼纳米带溶液的浓度为0.2-0.6mg/mL;
(3)将步骤(2)中三氧化钼/聚吡咯二元复合材料溶于溶剂一中,超声,得到分散液,将硒溶于溶剂二中,搅拌,滴加到分散液中,水热反应,冷却,抽滤,洗涤,干燥,得到硒化钼/聚吡咯核壳结构二元复合材料,其中,三氧化钼/聚吡咯二元复合材料和硒的质量比为5:1-1:5,三氧化钼/聚吡咯二元复合材料溶液的浓度为0.001-0.02g/mL,硒溶液的浓度为0.001-0.02g/mL;
(4)将步骤(3)中硒化钼/聚吡咯核壳结构二元复合材料在惰性气体环境下退火,洗涤,抽滤,干燥,得到硒化钼纳米片/氮掺杂碳核壳结构复合材料。
3.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(1)中搅拌时间为10min;水热反应前加入3mol/L盐酸溶液调节pH值为0.5-1.5。
4.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(1)中水热反应温度为160-220℃,水热反应时间为10-48h;干燥为在烘箱中60℃干燥24h。
5.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(1)、(2)中溶剂均为去离子水。
6.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(2)中继续搅拌时间为10min;引发剂为过硫酸铵、过硫酸钾或氯化铁;引发剂溶液的浓度为16.5mg/ml;反应温度为-10-10℃,反应时间为6-48h;干燥为在真空条件下60℃干燥24h。
7.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(3)中超声时间为0.5h;溶剂一为N,N-二甲基甲酰胺;溶剂二是质量分数为50%的水合肼;搅拌时间为1-4h,搅拌温度为80℃。
8.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(3)中水热反应温度为160-220℃,水热反应时间为10-48h;干燥为在烘箱中60℃干燥24h。
9.按照权利要求2所述的一种硒化钼纳米片/氮掺杂碳核壳结构复合材料的制备方法,其特征在于,所述步骤(4)中惰性气体为氮气;退火的工艺参数为:升温到800℃,保温时间为4h,升温的速率为2-5℃/min;洗涤为先用盐酸洗涤再用水洗涤;干燥为在真空条件下60℃干燥24h。
10.一种如权利要求1所述的硒化钼纳米片/氮掺杂碳核壳结构复合材料的应用,其特征在于,用作可见光催化剂、电催化剂、钠/锂离子阳极材料和发光晶体管材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711067699.3A CN107955598B (zh) | 2017-11-03 | 2017-11-03 | 一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711067699.3A CN107955598B (zh) | 2017-11-03 | 2017-11-03 | 一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107955598A true CN107955598A (zh) | 2018-04-24 |
CN107955598B CN107955598B (zh) | 2019-12-31 |
Family
ID=61964339
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711067699.3A Active CN107955598B (zh) | 2017-11-03 | 2017-11-03 | 一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107955598B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109244426A (zh) * | 2018-10-31 | 2019-01-18 | 北京科技大学 | 一种碳包覆超薄FeMoSe4纳米薯片状钾离子负极材料的制备方法 |
CN109786682A (zh) * | 2018-06-20 | 2019-05-21 | 信阳师范学院 | 一种二硒化钼@氮掺杂碳十二面核体钠离子电池负极材料及其制备方法、钠离子电池 |
CN112408358A (zh) * | 2020-11-17 | 2021-02-26 | 浙江理工大学 | 一种氮掺杂碳/硒化钼/石墨烯纳米盒材料、制备方法及应用 |
CN114420459A (zh) * | 2022-01-06 | 2022-04-29 | 重庆文理学院 | 一种超级电容器用的碳/二氧化锰复合材料及其制备方法 |
CN116196896A (zh) * | 2023-04-25 | 2023-06-02 | 淮安兴淮消防设备有限公司 | 一种N掺杂多孔碳-MoSe2的复合材料及在废水吸附中的应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460921A (zh) * | 2015-11-20 | 2016-04-06 | 复旦大学 | 一种硒化钼纳米片/石墨烯纳米带复合材料及其制备方法 |
CN105914374A (zh) * | 2016-05-31 | 2016-08-31 | 浙江大学 | 氮掺杂碳包覆硒化钼/石墨烯核壳阵列夹心结构的复合材料及其制备方法和应用 |
-
2017
- 2017-11-03 CN CN201711067699.3A patent/CN107955598B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460921A (zh) * | 2015-11-20 | 2016-04-06 | 复旦大学 | 一种硒化钼纳米片/石墨烯纳米带复合材料及其制备方法 |
CN105914374A (zh) * | 2016-05-31 | 2016-08-31 | 浙江大学 | 氮掺杂碳包覆硒化钼/石墨烯核壳阵列夹心结构的复合材料及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
GUICHONG JIA ET AL.: "Ultrathin MoSe2@N-doped carbon composite nanospheres for stable Na-ion storage", 《NANOTECHNOLOGY》 * |
YUNMEI PAN ET AL.: "Uniform Yolk–Shell MoS2@Carbon Microsphere Anodes for High-Performance Lithium-Ion Batteries", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109786682A (zh) * | 2018-06-20 | 2019-05-21 | 信阳师范学院 | 一种二硒化钼@氮掺杂碳十二面核体钠离子电池负极材料及其制备方法、钠离子电池 |
CN109244426A (zh) * | 2018-10-31 | 2019-01-18 | 北京科技大学 | 一种碳包覆超薄FeMoSe4纳米薯片状钾离子负极材料的制备方法 |
CN112408358A (zh) * | 2020-11-17 | 2021-02-26 | 浙江理工大学 | 一种氮掺杂碳/硒化钼/石墨烯纳米盒材料、制备方法及应用 |
CN114420459A (zh) * | 2022-01-06 | 2022-04-29 | 重庆文理学院 | 一种超级电容器用的碳/二氧化锰复合材料及其制备方法 |
CN116196896A (zh) * | 2023-04-25 | 2023-06-02 | 淮安兴淮消防设备有限公司 | 一种N掺杂多孔碳-MoSe2的复合材料及在废水吸附中的应用 |
CN116196896B (zh) * | 2023-04-25 | 2024-05-28 | 北京知投家知识产权运营有限公司 | 一种N掺杂多孔碳-MoSe2的复合材料及在废水吸附中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN107955598B (zh) | 2019-12-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107955598A (zh) | 一种硒化钼纳米片/氮掺杂碳核壳结构复合材料及其制备方法和应用 | |
CN103956473B (zh) | 一种CuO-Cu2O/石墨烯纳米复合材料及其制备方法 | |
CN105329851B (zh) | 一种纳米铁氧化物‑多层石墨烯复合材料制备方法 | |
Daneshvar et al. | Porous SnO2–CuxO nanocomposite thin film on carbon nanotubes as electrodes for high performance supercapacitors | |
CN104319395B (zh) | 一种三维氮掺杂石墨烯/CoOx复合材料的制备方法 | |
CN104448305B (zh) | 一种纳米复合吸波材料及其制备方法 | |
CN106519222A (zh) | 石墨烯/磁性粒子/聚苯胺复合多孔吸波材料及其制备方法 | |
CN104401980B (zh) | Fe2O3-SnO2/石墨烯三元复合纳米材料的水热制备方法 | |
CN107393725A (zh) | 一种多孔导电的碳材料负载NiCo2O4复合材料及其制法和应用 | |
CN105460921A (zh) | 一种硒化钼纳米片/石墨烯纳米带复合材料及其制备方法 | |
CN106025244A (zh) | 一种硒化镍/石墨烯/碳纳米管复合材料及其制备方法 | |
CN110272035A (zh) | 一种以金属离子催化有机配体制备碳纳米笼的方法及其制备的碳纳米笼和应用 | |
Liu et al. | Synthesis of multi-walled carbon nanotube supported nickel catalysts by hydrazine reduction and their electrocatalytic activity on ethanol electro-oxidation | |
CN104150469B (zh) | 一种可批量化制备少层石墨烯粉体的方法 | |
CN106496554A (zh) | 一种石墨烯/Fe3O4/聚苯胺三元吸波复合材料的制备方法 | |
CN104004496B (zh) | 一种还原氧化石墨烯/氧化镍复合吸波材料的制备方法 | |
CN103450843A (zh) | 一种三维结构的还原氧化石墨烯/四氧化三铁复合吸波水凝胶的制备方法 | |
CN106935838B (zh) | 制备单向择优生长高电化学活性的磷酸铁锂四元复合材料的方法 | |
CN106158405A (zh) | 一种氢氧化镍/石墨烯纳米复合材料及其制备方法、超级电容器电极及超级电容器 | |
CN105006379B (zh) | 一种二氧化钌纳米团簇/碳复合材料及其制备方法 | |
CN106571455A (zh) | 一种载银介孔氧化硅包覆三元正极材料及制备方法和应用 | |
Salarizadeh et al. | Synergistic effect of MoS2 and Fe3O4 decorated reduced graphene oxide as a ternary hybrid for high-performance and stable asymmetric supercapacitors | |
CN112165848A (zh) | 石墨烯负载磁性金属或其氧化物的复合吸波材料及其制备方法 | |
CN108365182B (zh) | 铁离子掺杂纳米四氧化三锰/多层石墨烯复合材料及其制备方法及应用其的锂电池 | |
Ge et al. | Nitrogen-doped porous Ag–C@ Co3O4 nanocomposite for boosting lithium ion batteries |
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 |