CN106340394A - 一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 - Google Patents
一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 Download PDFInfo
- Publication number
- CN106340394A CN106340394A CN201610897972.4A CN201610897972A CN106340394A CN 106340394 A CN106340394 A CN 106340394A CN 201610897972 A CN201610897972 A CN 201610897972A CN 106340394 A CN106340394 A CN 106340394A
- Authority
- CN
- China
- Prior art keywords
- preparation
- composite material
- graphene
- polymer
- graphene composite
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract description 6
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 76
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 33
- 239000011733 molybdenum Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- -1 tetramethyl-para-phenylene Chemical group 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 claims description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000012047 saturated solution Substances 0.000 claims description 7
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000005349 anion exchange Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- HTRYWXJIGDXDLF-UHFFFAOYSA-L 1-(2,4-dinitrophenyl)-4-[1-(2,4-dinitrophenyl)pyridin-1-ium-4-yl]pyridin-1-ium;dichloride Chemical compound [Cl-].[Cl-].[O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1[N+]1=CC=C(C=2C=C[N+](=CC=2)C=2C(=CC(=CC=2)[N+]([O-])=O)[N+]([O-])=O)C=C1 HTRYWXJIGDXDLF-UHFFFAOYSA-L 0.000 abstract 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000005486 sulfidation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- PQNOIAHNKHBLRN-UHFFFAOYSA-P (nh4)2mos4 Chemical compound [NH4+].[NH4+].[S-][Mo]([S-])(=S)=S PQNOIAHNKHBLRN-UHFFFAOYSA-P 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 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 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法。本发明首先制备出1,1'‑双(2,4‑二硝基苯基)‑4,4'‑二氯化联吡啶BDB和氧化石墨烯,接着通过铃木反应制备出线性联吡啶类聚合物修饰的氧化石墨烯,然后通过阴离子交换法将钼酸根交换到线性联吡啶类聚合物上,再通过与硫代乙酰胺共水热硫化得到硫化钼石墨烯复合材料前驱体,最后高温脱硫得到二硫化钼石墨烯复合材料。本发明基于BDB与钼酸根之间的电荷相互作用得到分散均匀的二硫化钼石墨烯复合材料,本发明制备方法简单,所制备的材料电化学性能优异,同时具有大规模制备的潜质,可应用于电催化、析氢催化、超级电容器等领域。
Description
技术领域
本发明属于功能材料技术领域,涉及一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法。
背景技术
随着现代工业的发展和人们生活水平的提高,化石燃料燃烧排放的尾气,氢气作为一种非常有前景的新能源可替代化石燃料,但是它的大规模工业生产制约了其发展。电解水产氢作为一种节能、可循环的制氢工艺逐渐成为了研究热点。目前,常用的催化剂为铂,但是铂的昂贵的造价限制了其应用。因此开发非贵金属催化剂成为了关键。
MoS2具有很好的电催化析氢性能,二硫化钼的高催化活性与其结构有很大的关系。二硫化钼的高催化活性与它的高活性有关,而且它具有较强的抗硫中毒能力。另外,有证据表明二硫化钼的催化活性中心主要是位于片层边缘位置暴露的缺硫的三价Mo离子,因此提高边缘面积可以有效地提高催化效率。MoS2片层间较弱的范德华力以及较大的层间距,使其在电化学储氢和锂离子电池等储能领域有着广泛的应用。
2004年,A.Geim和K.Novoselov发现了石墨烯,由于独特的物理、化学性质引起了世界范围内的广泛关注。后续对石墨烯材料的研究包括:零维的石墨烯量子点,一维的石墨烯纤维,二维的石墨烯薄膜和三维的石墨烯材料,石墨烯材料实现了点线面整个三维维度的发展。石墨烯凝胶是近几年兴起的三维石墨烯材料,其具有大的比表面积、低密度、高孔隙率(可达到99%)、极好的导热性能及低介电常数等一系列优异性能吸引人们进行广泛研究。石墨烯凝胶的制备是采用还原的方法消除氧化石墨烯片层上的众多官能团,使得到的石墨烯片层发生π-π共轭形成石墨烯凝胶,其制备方法包括:化学还原法―以还原剂(如:水合肼、亚硫酸盐氢钠、维生素C等)还原氧化石墨烯制备石墨烯凝胶;模板法:采用气相沉积法(CVD)将碳源沉积到选定的模板上,再通过后续处理蚀刻除掉模板制备石墨烯气凝胶;水热还原法:清华大学的石高全教授开发的清洁简单制备石墨烯凝胶的方法,利用水热釜中水的自生压力还原氧化石墨烯制备石墨烯凝胶,水热法不添加化学还原剂,操作方法简单,设备需求小,迅速被广泛接受采用。
到目前为止,制备纳米二硫化钼有很多方法,大部分方法是根据二硫化钼的多片层结构,比如:机械剥离法、锂离子插层法、电化学锂离子插层法、液相剥离法以及激光细化技术;还有直接通过化学合成法,如溶解热法以及气相沉积法(CVD)。在高温和较高的蒸汽压下结晶而形成物质的方法称为水热(溶剂热)法,在高温高压下有较好溶解性与稳定性的前聚体较适用于此方法,水热法被经常应用于二维层状材料的合成,与物理剥离制备二硫化钼相比,水热合成法更加简单,主要为Mo和S的前聚体进行反应,随后退火处理,水热(溶剂热)法是一种高效的合成纳米二硫化钼的方法。最常用的二硫化钼前聚体硫代钼酸铵((NH4)2MoS4)和钼酸盐(XMoO4)。
发明内容
为了克服现有技术的不足,本发明的目的是提供一种新的二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法。本发明制备方法简单,得到的二硫化钼掺杂线性聚合物修饰石墨烯复合材料具有比表面积大、纳米粒子分散均匀。
本发明通过离子交换法将钼酸根阴离子交换到聚合物修饰的氧化石墨烯上,然后用硫代乙酰胺对钼酸根进行硫化,最后高温处理得到二硫化钼石墨烯复合材料,该复合材料可用于电催化、析氢催化、超级电容器等领域。
本发明具体的技术方案通过以下步骤实施:
本发明提供一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料的制备方法,具体步骤如下:
(1)将对硝基氯苯硝化得到2,4-二硝基氯苯;再将2,4-二硝基氯苯和4,4’-联吡啶回流反应,得到1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB;
(2)将氧化石墨烯分散到无水乙醇中得到氧化石墨烯分散液,再向其中加入四甲基对苯二胺和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB,回流24~72h生成沉淀,洗涤、真空干燥得到聚合物修饰的氧化石墨烯;
(3)取聚合物修饰的氧化石墨烯分散到钼酸铵饱和溶液中,回流反应,反应结束后,过滤、洗涤、真空干燥得带钼酸根的石墨烯复合材料Mo@GO;
(4)将硫代乙酰胺的水溶液和带钼酸根的石墨烯复合材料Mo@GO混合,并调节溶液pH到碱性,得到的混合溶液于水热釜中水热反应,反应结束后,过滤,真空干燥即得到二硫化钼石墨烯复合材料MoS2@GO;
(5)取二硫化钼石墨烯复合材料MoS2@GO碳化得到二硫化钼掺杂线性聚合物修饰石墨烯复合碳材料。
上述步骤(1)中,硝化时用浓硫酸和发烟硝酸。
上述步骤(1)中,2,4-二硝基氯苯和4,4’-联吡啶的质量比为1:500~1:100。
上述步骤(2)中,四甲基对苯二胺、1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB和氧化石墨烯的质量比为(0.2~1):(1~5):(0.05~1)。
上述步骤(3)中,聚合物修饰的氧化石墨烯和钼酸铵饱和溶液的质量体积比为1:5~5:1mg/mL。
上述步骤(4)中,硫代乙酰胺和带钼酸根的石墨烯复合材料Mo@GO的质量比为1:2~10:1。
上述步骤(4)中,水热反应的温度为150~180℃,水热反应时间为12~20h。
上述步骤(5)中,用N2碳化,反应条件为:管式炉中,N2流速50ml/min,以升温速率2~5℃/min升温至800~1000℃保温2~8h,再自然冷却得到二硫化钼掺杂线性聚合物修饰石墨烯复合材料。
本发明还提供一种上述的制备方法得到的二硫化钼掺杂线性聚合物修饰石墨烯复合材料。
和现有技术相比,本发明的有益效果在于:本发明以氧化石墨烯(GO)和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB单体与四甲基对苯二胺为原料,通过氧化石墨烯上的含氧官能团与BDB和四甲基对苯二胺之间的相互作用将二者聚合到氧化石墨烯上,再通过阴离子交换法将钼酸根引入聚合物修饰的石墨烯上,最后通过水热法对钼酸根进行硫化,再退火的到二硫化钼掺杂的石墨烯复合材料。本发明利用联吡啶上两个带正电的吡啶氮将钼酸根均匀的分散到聚合物修饰的氧化石墨烯中,最后的到的二硫化物纳米粒分散均匀,颗粒小。此种离子交换法引入目标元素具有分散均匀,比表面积大,电化学性能优异的特点,可用于电化学析氢催化、超级电容器等领域。
附图说明
图1是二硫化钼石墨烯复合材料的制备过程示意图。
图2是聚合物修饰石墨烯扫描电镜图片。
图3是聚合物修饰石墨烯复合材料BET图片。
具体实施方式
下面结合具体的实施例对本发明的技术方案做进一步的描述,但本发明的保护范围并不限于下述实施例。
本发明各实施例中所用的各种原料,如无特殊说明,均为市售。
图1是二硫化钼石墨烯复合材料的制备过程示意图。
实施例1
(1)石墨烯的制备:以325目的石墨粉为原料,采用改进的hummer法制备氧化石墨烯,并以XRD、XPS、AFM等方式表征所得的氧化石墨。
(2)2,4-二硝基氯苯的制备:取50g对硝基氯苯倒入2L的圆底烧瓶,磁力搅拌条件下向烧瓶中滴加120ml发烟硝酸使对硝基氯苯全部溶解,然后再滴加20ml浓硫酸反应半小时,待体系冷却至室温后,加入冰水淬灭反应得到黄色固体,再以500ml去离子水洗涤过滤后真空干燥得2,4-二硝基氯苯。
(3)BDB的制备:取50ml乙腈至于250ml圆底烧瓶中,再向烧瓶加入2g 4,4’-联吡啶和10mg 2,4-二硝基氯苯,充分搅拌得到黄色溶液,加热回流48小时,待烧瓶中生成大量白色沉淀,再以500ml去离子水洗涤过滤后真空干燥得1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB。
(4)聚合物修饰的氧化石墨烯的制备:取50mg氧化石墨烯分散到100ml无水乙醇中得到氧化石墨烯分散液,向分散液中加入1g四甲基对苯二胺和1g BDB,回流24h生成黑色沉淀,沉淀经500ml乙醇洗涤过滤后真空干燥得聚合物修饰的氧化石墨烯。
(5)带有钼酸根的石墨烯复合材料的制备:取100mg聚合物修饰的石墨烯分散到100ml钼酸铵饱和溶液中,回流12h后过滤得黑色固体,所得固体材料在去离子水中浸泡24h,最后经80℃真空干燥12h即可得到带钼酸根的石墨烯复合材料(简写为Mo@GO)。
(6)Mo@GO硫化:取50mg硫代乙酰胺溶解于去100ml离子水中,向溶液中加入20mgMo@GO并将溶液pH值调到8,将上述溶液装入聚四氟乙烯内胆的水热釜150℃水热12h,产物经过滤,80℃真空干燥12h即得到二硫化钼石墨烯复合材料MoS2@GO。
(7)MoS2@GO脱硫碳化:取20mgMoS2@GO至于石英舟内放入管式电阻炉,N2流速50ml/min,升温速率2℃/min升温至800℃保温4h,自然冷却至室温得到二硫化钼掺杂线性聚合物修饰的石墨烯复合材料MoS2@GO-800。
上述所得的二硫化钼石墨烯复合材料MoS2@GO-800,以S-4800场发射扫描电子显微镜(FE-SEM)表征其形貌和微观结构,结果如图2;以3H-2000PM2比表面及微孔分析仪测试其表面积和孔径分布,结果如图3。结果表明聚合物非常均匀的修饰到氧化石墨烯上。根据BET方程计算得出MoS2@GO-800的比表面积为119m2/g,总孔体积为1.21cm3/g(图3a);根据非定域密度泛函理论分析,MoS2@GO-800在介孔区域(2~10nm)具有两个集中的孔径分布,这种分等级孔径分布有利于物质的快速传输,并且具有更多活性位点,使其具有良好的催化性能。
实施例2
(1)石墨烯的制备:以325目的石墨粉为原料,采用改进的hummer法制备氧化石墨烯,并以XRD、XPS、AFM等方式表征所得的氧化石墨。
(2)2,4-二硝基氯苯的制备:取50g对硝基氯苯倒入2L的圆底烧瓶,磁力搅拌条件下向烧瓶中滴加150ml发烟硝酸使对硝基氯苯全部溶解,然后再滴加20ml浓硫酸反应半小时,待体系冷却至室温后,加入冰水淬灭反应得到黄色固体,再以500ml去离子水洗涤过滤后真空干燥得2,4-二硝基氯苯。
(3)BDB的制备:取50ml乙腈至于250ml圆底烧瓶中,再向烧瓶加入2g 4,4’-联吡啶和10mg 2,4-二硝基氯苯,充分搅拌得到黄色溶液,加热回流48小时,待烧瓶中生成大量白色沉淀,再以500ml去离子水洗涤过滤后真空干燥得1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB。
(4)聚合物修饰的氧化石墨烯的制备:取50mg氧化石墨烯分散到100ml无水乙醇中得到氧化石墨烯分散液,向分散液中加入1g四甲基对苯二胺和1g硝基联吡啶,回流24h生成黑色沉淀,沉淀经500ml乙醇洗涤过滤后真空干燥得聚合物修饰的氧化石墨烯。
(5)带有钼酸根的石墨烯复合材料的制备:取100mg聚合物修饰的石墨烯分散到100ml钼酸铵饱和溶液中,回流12h后过滤得黑色固体,所得固体材料在去离子水中浸泡24h,最后经80℃真空干燥12h即可得到带钼酸根的石墨烯复合材料(简写为Mo@GO)。
(6)Mo@GO硫化:取50mg硫代乙酰胺溶解于去100ml离子水中,向溶液中加入20mgMo@GO并将溶液pH值调到8,将上述溶液装入聚四氟乙烯内胆的水热釜180℃水热16h,产物经过滤,80℃真空干燥12h即得到硫化钼石墨烯复合材料MoS2@GO。
(7)MoS2@GO碳化:取20mg MoS2@GO至于石英舟内放入管式电阻炉,N2流速50ml/min,升温速率2℃/min升温至900℃保温4h,自然冷却至室温得到二硫化钼掺杂线性聚合物修饰的石墨烯复合材料MoS2@GO-900。
上述所得的二硫化钼石墨烯复合材料MoS2@GO-900,以S-4800场发射扫描电子显微镜(FE-SEM)表征其形貌和微观结构,结果如图2;以3H-2000PM2比表面及微孔分析仪测试其表面积和孔径分布,结果如图3。结果表明聚合物非常均匀的修饰到氧化石墨烯上。根据BET方程计算得出MoS2@GO-900的比表面积为69m2/g,总孔体积为0.74cm3/g(图3a);根据非定域密度泛函理论分析,MoS2@GO-900在介孔区域(2~10nm)具有两个集中的孔径分布,这种分等级孔径分布有利于物质的快速传输,并且具有更多活性位点,使其具有良好的催化性能。
实施例3
(1)石墨烯的制备:以325目的石墨粉为原料,采用改进的hummer法制备氧化石墨烯,并以XRD、XPS、AFM等方式表征所得的氧化石墨。
(2)2,4-二硝基氯苯的制备:取50g对硝基氯苯倒入2L的圆底烧瓶,磁力搅拌条件下向烧瓶中滴加120ml发烟硝酸使对硝基氯苯全部溶解,然后再滴加20ml浓硫酸反应半小时,待体系冷却至室温后,加入冰水淬灭反应得到黄色固体,再以500ml去离子水洗涤过滤后真空干燥得2,4-二硝基氯苯。
(3)BDB的制备:取50ml乙腈至于250ml圆底烧瓶中,再向烧瓶加入2g 4,4’-联吡啶和10mg 2,4-二硝基氯苯,充分搅拌得到黄色溶液,加热回流48小时,待烧瓶中生成大量白色沉淀,再以500ml去离子水洗涤过滤后真空干燥得1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB。
(4)聚合物修饰的氧化石墨烯的制备:取50mg氧化石墨烯分散到100ml无水乙醇中得到氧化石墨烯分散液,向分散液中加入1g四甲基对苯二胺和1g BDB,回流24h生成黑色沉淀,沉淀经500ml乙醇洗涤过滤后真空干燥得聚合物修饰的氧化石墨烯。
(5)带有钼酸根的石墨烯复合材料的制备:取100mg聚合物修饰的石墨烯分散到100ml钼酸铵饱和溶液中,回流12h后过滤得黑色固体,所得固体材料在去离子水中浸泡24h,最后经80℃真空干燥12h即可得到带钼酸根的石墨烯复合材料(简写为Mo@GO)。
(6)Mo@GO硫化:取50mg硫代乙酰胺溶解于去100ml离子水中,向溶液中加入20mgMo@GO并将溶液pH值调到8,将上述溶液装入聚四氟乙烯内胆的水热釜180℃水热18h,产物经过滤,80℃真空干燥12h即得到硫化钼石墨烯复合材料MoS2@GO。
(7)MoS2@GO碳化:取20mgMoS2@GO至于石英舟内放入管式电阻炉,N2流速50ml/min,升温速率2℃/min升温至1000℃保温4h,自然冷却至室温得到二硫化钼掺杂线性聚合物修饰的石墨烯复合材料MoS2@GO-1000。
上述所得的二硫化钼石墨烯复合材料MoS2@GO-1000,以S-4800场发射扫描电子显微镜(FE-SEM)表征其形貌和微观结构,结果如图2;以3H-2000PM2比表面及微孔分析仪测试其表面积和孔径分布,结果如图3。结果表明聚合物非常均匀的修饰到氧化石墨烯上。根据BET方程计算得出MoS2@GO-1000的比表面积为64m2/g,总孔体积为0.72cm3/g(图3a);根据非定域密度泛函理论分析,MoS2@GO-1000在介孔区域(2~10nm)具有两个集中的孔径分布,这种分等级孔径分布有利于物质的快速传输,并且具有更多活性位点,使其具有良好的催化性能。
以上描述了本发明的基本原理、主要特征和优点,而且本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有变化和改进,这些变化和改进都落入要求保护本发明的范围内。
Claims (9)
1.一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料的制备方法,其特征在于,具体步骤如下:
(1)将对硝基氯苯硝化得到2,4-二硝基氯苯;再将2,4-二硝基氯苯和4,4’-联吡啶回流反应,得到1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB;
(2)将氧化石墨烯分散到无水乙醇中得到氧化石墨烯分散液,再向其中加入四甲基对苯二胺和1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB,回流24~72h生成沉淀,洗涤、真空干燥得到聚合物修饰的氧化石墨烯;
(3)取聚合物修饰的氧化石墨烯分散到钼酸铵饱和溶液中,回流反应,反应结束后,过滤、洗涤、真空干燥得带钼酸根的石墨烯复合材料Mo@GO;
(4)将硫代乙酰胺的水溶液和带钼酸根的石墨烯复合材料Mo@GO混合,并调节溶液pH到碱性,得到的混合溶液于水热釜中水热反应,反应结束后,过滤,真空干燥即得到二硫化钼石墨烯复合材料MoS2@GO;
(5)取二硫化钼石墨烯复合材料MoS2@GO碳化得到二硫化钼掺杂线性聚合物修饰石墨烯复合材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,硝化时用浓硫酸和发烟硝酸。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,2,4-二硝基氯苯和4,4’-联吡啶的质量比为1:500~1:100。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,四甲基对苯二胺、1,1'-双(2,4-二硝基苯基)-4,4'-二氯化联吡啶BDB和氧化石墨烯的质量比为(0.2~1):(1~5):(0.05~1)。
5.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,聚合物修饰的氧化石墨烯和钼酸铵饱和溶液的质量体积比为1:5~5:1mg/mL。
6.根据权利要求1所述的制备方法,其特征在于,步骤(4)中,硫代乙酰胺和带钼酸根的石墨烯复合材料Mo@GO的质量比为1:2~10:1。
7.根据权利要求1所述的制备方法,其特征在于,步骤(4)中,水热反应的温度为150~180℃,水热反应时间为12~20h。
8.根据权利要求1所述的制备方法,其特征在于,步骤(5)中,用N2碳化,反应条件为:管式炉中,N2流速50ml/min,以升温速率2~5℃/min升温至800~1000℃保温2~8h,再自然冷却得到二硫化钼掺杂线性聚合物修饰石墨烯复合材料。
9.一种根据权利要求1-8之一所述的制备方法得到的二硫化钼掺杂线性聚合物修饰石墨烯复合材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610897972.4A CN106340394B (zh) | 2016-10-14 | 2016-10-14 | 一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610897972.4A CN106340394B (zh) | 2016-10-14 | 2016-10-14 | 一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106340394A true CN106340394A (zh) | 2017-01-18 |
CN106340394B CN106340394B (zh) | 2018-03-20 |
Family
ID=57838807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610897972.4A Active CN106340394B (zh) | 2016-10-14 | 2016-10-14 | 一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106340394B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106925312A (zh) * | 2017-03-22 | 2017-07-07 | 上海应用技术大学 | 一种碳化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 |
CN108014820A (zh) * | 2017-12-01 | 2018-05-11 | 济南大学 | 一种具有纳米多层膜结构的二硫化钼电催化剂及其制备方法 |
CN111446423A (zh) * | 2020-04-24 | 2020-07-24 | 深圳市海盈科技有限公司 | 一种锂离子电池电极材料及其制备方法、锂离子电池 |
CN112933980A (zh) * | 2021-01-29 | 2021-06-11 | 三明学院 | 一种噻吩选择性MoSe2-rGO泡沫复合膜及其制备方法、分离噻吩的方法 |
CN113106471A (zh) * | 2021-04-09 | 2021-07-13 | 辽宁大学 | MoS2/pyridinium-ILs/PPy/GO纳米材料及其电化学应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011052852A1 (ko) * | 2009-10-28 | 2011-05-05 | (주)퓨리켐 | Ac표면에 lto를 형성시킨 lto/ac 복합물질 제조방법과, 이에 의해 제조된 lto/ac 복합물질을 이용한 전기화학 커패시터 제조방법 |
CN102850543A (zh) * | 2012-09-28 | 2013-01-02 | 中国科学院宁波材料技术与工程研究所 | 一种石墨烯/导电聚合物复合材料及其制备方法 |
CN103117175A (zh) * | 2013-02-25 | 2013-05-22 | 中国科学院过程工程研究所 | 一种多元复合纳米材料、其制备方法及其用途 |
-
2016
- 2016-10-14 CN CN201610897972.4A patent/CN106340394B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011052852A1 (ko) * | 2009-10-28 | 2011-05-05 | (주)퓨리켐 | Ac표면에 lto를 형성시킨 lto/ac 복합물질 제조방법과, 이에 의해 제조된 lto/ac 복합물질을 이용한 전기화학 커패시터 제조방법 |
CN102850543A (zh) * | 2012-09-28 | 2013-01-02 | 中国科学院宁波材料技术与工程研究所 | 一种石墨烯/导电聚合物复合材料及其制备方法 |
CN103117175A (zh) * | 2013-02-25 | 2013-05-22 | 中国科学院过程工程研究所 | 一种多元复合纳米材料、其制备方法及其用途 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106925312A (zh) * | 2017-03-22 | 2017-07-07 | 上海应用技术大学 | 一种碳化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 |
CN108014820A (zh) * | 2017-12-01 | 2018-05-11 | 济南大学 | 一种具有纳米多层膜结构的二硫化钼电催化剂及其制备方法 |
CN108014820B (zh) * | 2017-12-01 | 2020-07-17 | 济南大学 | 一种具有纳米多层膜结构的二硫化钼电催化剂及其制备方法 |
CN111446423A (zh) * | 2020-04-24 | 2020-07-24 | 深圳市海盈科技有限公司 | 一种锂离子电池电极材料及其制备方法、锂离子电池 |
CN111446423B (zh) * | 2020-04-24 | 2022-02-22 | 贵州嘉盈科技有限公司 | 一种锂离子电池电极材料及其制备方法、锂离子电池 |
CN112933980A (zh) * | 2021-01-29 | 2021-06-11 | 三明学院 | 一种噻吩选择性MoSe2-rGO泡沫复合膜及其制备方法、分离噻吩的方法 |
CN112933980B (zh) * | 2021-01-29 | 2022-04-19 | 三明学院 | 一种噻吩选择性MoSe2-rGO泡沫复合膜及其制备方法、分离噻吩的方法 |
CN113106471A (zh) * | 2021-04-09 | 2021-07-13 | 辽宁大学 | MoS2/pyridinium-ILs/PPy/GO纳米材料及其电化学应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106340394B (zh) | 2018-03-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Rono et al. | A review of the current status of graphitic carbon nitride | |
CN106340394B (zh) | 一种二硫化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 | |
Zhou et al. | Template-free one-step synthesis of g-C3N4 nanosheets with simultaneous porous network and S-doping for remarkable visible-light-driven hydrogen evolution | |
Cai et al. | Highly efficient uranium extraction by a piezo catalytic reduction-oxidation process | |
Chen et al. | Direct Z-scheme 2D/2D MnIn2S4/g-C3N4 architectures with highly efficient photocatalytic activities towards treatment of pharmaceutical wastewater and hydrogen evolution | |
Li et al. | Confined synthesis of 2D nanostructured materials toward electrocatalysis | |
Shen et al. | Converting CO2 into fuels by graphitic carbon nitride-based photocatalysts | |
Haag et al. | Metal free graphene based catalysts: a review | |
CN104261490B (zh) | 两步法制备硫化镍的方法 | |
CN103007944A (zh) | 石墨烯基磁性复合可见光催化材料Fe3O4-G-TiO2的制备方法 | |
CN103752334A (zh) | 离子液体促进合成石墨相氮化碳纳米片可见光催化剂 | |
Aksoy et al. | Visible light-driven hydrogen evolution by using mesoporous carbon nitride-metal ferrite (MFe2O4/mpg-CN; M: Mn, Fe, Co and Ni) nanocomposites as catalysts | |
CN106925312A (zh) | 一种碳化钼掺杂线性聚合物修饰石墨烯复合材料及其制备方法 | |
Hu et al. | Freeze-dried dicyandiamide-derived g-C3N4 as an effective photocatalyst for H2 generation | |
CN104617311A (zh) | 一种氮钴掺杂介孔碳/石墨烯复合材料及其制备方法 | |
Lu et al. | In situ synthesis of cobalt alginate/ammonium perchlorate composite and its low temperature decomposition performance | |
Jiao et al. | Sulfur/phosphorus doping-mediated morphology transformation of carbon nitride from rods to porous microtubes with superior photocatalytic activity | |
CN103539106A (zh) | 一种碳材料的制备方法 | |
Liu et al. | MOF-derived B, N co-doped porous carbons as metal-free catalysts for highly efficient nitro aromatics reduction | |
CN108499584B (zh) | Ni2P@C/石墨烯气凝胶析氢复合材料及制备方法 | |
Xu et al. | Z-scheme Cu2O nanoparticle/graphite carbon nitride nanosheet heterojunctions for photocatalytic hydrogen evolution | |
Ma et al. | Anchoring dye onto 1D Nb2O5 in cooperation with TEMPO for the selective photocatalytic aerobic oxidation of amines | |
Lu et al. | Synthesis of bimetallic CoMn–alginate and synergistic effect on thermal decomposition of ammonium perchlorate | |
CN104148099A (zh) | 一种MoS2-BiPO4复合光催化剂的制备方法 | |
CN109950563A (zh) | 一种金属活性位高分散的非贵金属氧还原反应催化剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | 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 | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170118 Assignee: Shanghai Anpu Experimental Technology Co.,Ltd. Assignor: SHANGHAI INSTITUTE OF TECHNOLOGY Contract record no.: X2024980004931 Denomination of invention: A molybdenum disulfide doped linear polymer modified graphene composite material and its preparation method Granted publication date: 20180320 License type: Common License Record date: 20240426 |
|
EE01 | Entry into force of recordation of patent licensing contract |