CN106186070A - 一种多孔富缺陷二硫化钼的制备方法 - Google Patents
一种多孔富缺陷二硫化钼的制备方法 Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 50
- 239000011733 molybdenum Substances 0.000 title claims abstract description 50
- 230000007547 defect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000004220 aggregation Methods 0.000 claims abstract description 8
- 230000002776 aggregation Effects 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000006698 induction Effects 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- -1 ammonium radical ion Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims 1
- 235000016768 molybdenum Nutrition 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
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- 238000005119 centrifugation Methods 0.000 abstract 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 4
- 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 4
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- 229910052961 molybdenite Inorganic materials 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229950000845 politef Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
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- 210000000232 gallbladder Anatomy 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种多孔富缺陷二硫化钼的制备方法,其特征在于:在钼酸盐的水溶液中加入可溶性酸或可溶性盐,然后加热,钼酸根离子在阳离子的诱导下逐步聚合成多孔杂合的有序聚集体;产物经离心、洗涤和烘干后,转移到反应釜中,以含负二价硫元素的化合物为硫源,通过水热‑气相原位硫化法获得多孔富缺陷二硫化钼。本发明的方法操作简单,原料廉价易得,所得产物形貌较好、比表面积大,能够规模化合成。
Description
技术领域
本发明涉及一种催化材料二硫化钼的制备技术,具体涉及一种多孔富缺陷二硫化钼的制备方法。
背景技术
随着经济的发展,化石燃料的消耗不断增长,这给人类社会带来前所未有的环境压力,其解决途径是化石能源的洁净化和开发新型绿色能源。加氢脱硫是化石能源洁净化最有效的手段之一,目前,加氢脱硫使用的催化剂是二硫化钼及其复合材料[1,2]。尽管如此,化石能源是有限且不可再生的。当前,迫切需要开发新型绿色能源。已有大量权威文献证明,以太阳光为能源,使用高效的催化剂光解水制氢是获取氢气的有效手段。MoS2的带隙结构使其具有很好的可见光吸收性能,是极好的光解水制氢的催化剂[3-5]。然而,目前光解水制氢的效率还很低,根本无法满足人类对氢能的需求,必须使用电解水制氢才能大量获得氢气。二硫化钼是一种价廉易得的材料,它作为高效电催化析氢的催化剂已经受到许多著名学者的高度关注[6-8]。
二硫化钼在上述领域所具有的高效催化性能与它的结构密切相关。二硫化钼是类石墨烯的层状化合物,这种层状结构可以形成两种不同性质的表面,即剥离面和断裂面。在晶体学上,剥离面化学性质稳定,对二硫化钼的催化性能没有贡献。与之相反,断裂面却暴露出很多Mo-S棱面,形成Mo-S悬空键,呈化学性质不稳定状态,这种边缘裸露的悬空位是MoS2在催化反应中的活性中心[9,10],对氢原子有着奇异的亲和力,在氢气参与的催化反应中具有很高的研究价值。
当前工业中所用的多孔MoS2催化剂大部分为负载型的,常见的载体有γ-Al2O3、TiO2、分子筛和多孔碳等[11]。但负载型MoS2在使用中活性组分容易流失而降低其使用寿命,并且由于催化剂活性组分是担载在高比表面积的载体上,它是二维的束缚结构,不能有效地与底物接触,不能充分发挥催化剂的本征催化活性[12]。因此,负载型MoS2催化活性难以提高,此外,随着环保趋严,负载型二硫化钼回收难度也明显增大,因此,迫切需要开发活性密度更高且更环保的非负载型二硫化钼催化剂。
参考文献
1.Nogueira A,Znaiguia R,Uzio D,et al.Applied Catalysis A General,2012,429-430(25):92-105.
2.Sang I L,Cho A,Koh J H,et al.Applied Catalysis B Environmental,2011,101(3–4):220-225.
3.Li Y,Wang H,Xie L,et al.Journal of the American Chemical Society,2011,133(19):7296-7299.
4.Wang T,Liu L,Zhu Z,et al.Energy&Environmental Science,2013,6(2):625-633.
5.Zong X,Na Y,Wen F,et al.Chemical Communications,2009,30(30):4536-4538.
6.Wang T,Liu L,Zhu Z,et al.Energy&Environmental Science,2013,6(2):625-633.
7.Guo X,Tong X,Wang Y,et al.Journal of Materials Chemistry A,2013,1(15):4657-4661.
8.Bian X,Zhu J,Liao L,et al.Electrochemistry Communications,2012,22(1):128-132.
9.Jaramillo TF,Jorgensen KP,Bonde J,et al.Science,2007,317(5834):100-102.
10.Karunadasa HI,Montalvo E,Sun Y,et al.Science,2012,335(6069):698-702.
11.Surisetty V R,Eswaramoorthi I,Dalai A K.Fuel,2012,96(1):77-84.
12.Surisetty V R,Eswaramoorthi I,Dalai AK.Fuel,2012,96(1):77-84.
发明内容
本发明是为避免上述现有技术所存在的不足,提供一种非负载型的多孔富缺陷二硫化钼催化剂的制备方法,所要解决的问题是如何使多孔杂合的钼酸聚集体的多孔结构在硫化后得到完整的保留,从而获得性能更加优异的多孔富缺陷二硫化钼。
本发明解决技术问题,采用如下技术方案:
一种多孔富缺陷二硫化钼的制备方法,其特点在于:
(1)在钼酸盐的水溶液中加入可溶性酸或可溶性盐,然后加热,钼酸根离子在阳离子的诱导下逐步聚合成多孔杂合的有序聚集体,产物经分离、洗涤、烘干后,获得纳米级多孔聚钼酸盐;
多孔杂合的钼酸聚集体的合成方法参见[Yu S H,Liu B,Mo M S,et al.AdvancedFunctional Materials,2003,13(13):639-647;Zhuo S,Xu Y,Zhao W,et al.AngewandteChemie International Edition,2013,52(33):8602-6.]。
(2)将步骤(1)所得纳米级多孔聚钼酸盐转移到反应釜中,以含负二价硫元素的化合物为硫源,通过水热-气相原位硫化法获得多孔富缺陷二硫化钼。
具体的,所述水热-气相原位硫化法的具体步骤是:
如图1所示,在高压反应釜的聚四氟乙烯内胆中放置一个耐高温容器;将纳米级多孔聚钼酸盐放入耐高温容器中,将硫源的水溶液放入聚四氟乙烯内胆中、且在耐高温容器外,使纳米级多孔聚钼酸盐和硫源的水溶液分开,从而在硫化后保持纳米级多孔聚钼酸盐的多孔结构;
然后在100~300℃的温度下水热反应12~84h,所得产物经分离、洗涤和干燥,即获得多孔富缺陷的二硫化钼。
在水热-气相原位硫化法中,硫源在水热体系下水解成硫化氢,与水蒸气结合并发生电离,因此,与直接气相硫化相比,该法提高了气相硫化的效率。
在上述方法中,通过阳离子调控聚集体的多孔结构,通过水热-气相原位硫化法保持前驱体的多孔结构,通过杂合阳离子的去除提高二硫化钼的缺陷。
优选的,所述钼酸盐为钼酸铵、钼酸钠或钼酸钾。
优选的,步骤(1)所述的阳离子是可溶性酸或可溶性盐中的阳离子,为氢离子、铵根离子、有机铵根阳离子或金属离子。
优选的,步骤(1)中的加热温度为50~300℃。
优选的,步骤(2)中所述的含负二价硫元素的化合物为硫脲、硫醇、硫代乙酰胺、硫化钠或L-半胱氨酸。
优选的,步骤(2)中的钼、硫的摩尔比为1:2.0~10.0。
优选的,步骤(2)中所述的洗涤是依次用氨水、去离子水和乙醇进行洗涤,所述干燥的温度为60~120℃。
与已有技术相比,本发明的优点在于:
1、本发明采用新的硫化方法,即水热-气相硫化法,在高压反应釜的聚四氟乙烯内胆中放置一个耐高温容器,与高压釜内胆成嵌套关系,使作为前驱体的多孔杂合的钼酸聚集体与水热体系下的硫源完全隔开,利用硫源在水热体系下受热分解生成的H2S与多孔钼酸聚集体反应,实现了原位硫化,保证前驱体的孔道结构不被破坏,通过杂合阳离子的去除提高二硫化钼晶体结构的缺陷。同时,与高温直接气相硫化相比,水热-气相还具有如下优点:(1)硫化氢气体处于密闭的反应釜中,避免气体浪费,节约了硫源,(2)H2S气体与水蒸气反应发生电离,提高了硫化效率。
2、本发明的方法操作简单、原料廉价易得,所得产物形貌较好、比表面积大,能够规模化合成。
附图说明
图1为本发明所用水热-气相反应装置示意图;
图2为本发明实施例1中所得纳米级多孔聚钼酸盐NaNH4MoO10·H2O的TEM;
图3为本发明实施例1中所得纳米级多孔聚钼酸盐NaNH4MoO10·H2O的XRD;
图4为本发明实施例1中所得多孔富缺陷二硫化钼的TEM;
图5为本发明实施例1中所得多孔富缺陷二硫化钼的HRTEM;
图6为本发明实施例1中所得多孔富缺陷二硫化钼的XRD;
图7为本发明实施例1中所得多孔富缺陷二硫化钼的比表面积;
图8为本发明实施例4中所得多孔富缺陷二硫化钼的TEM;
图9为本发明实施例4中所得多孔富缺陷二硫化钼的HRTEM;
图10为本发明实施例4中所得多孔富缺陷二硫化钼的XRD;
图11为本发明实施例4中所得多孔富缺陷二硫化钼的比表面积。
具体实施方式
实施例1
本实施例按如下步骤制备多孔富缺陷二硫化钼:
(1)称取四水合钼酸铵3.0g、氯化钠6.0g,分别溶解于50mL的去离子水中,在磁力搅拌下将二者混匀,将温度升温至70℃时,澄清溶液开始变浑浊,几分钟后析出白色絮状物,反应30分钟停止,趁热抽滤,用去离子水多次洗涤,得到白色絮状固体,室温干燥,即得到纳米级多孔聚钼酸盐。
(2)称取0.5070g纳米级多孔聚钼酸盐NaNH4MoO10·H2O和2.5095g硫脲,将纳米级多孔聚钼酸盐NaNH4MoO10·H2O放入聚四氟乙烯烧杯中,硫脲加入到聚四氟乙烯反应釜内衬中,倒入少量水,形成浆料。后将盛放纳米级多孔聚钼酸盐NaNH4MoO10·H2O的烧杯放入聚四氟乙烯反应釜中成嵌套关系,180℃反应48h。反应结束后冷却至室温,所得产物依次使用氨水、去离子水和无水乙醇洗涤多次,最后在60℃干燥后得到多孔富缺陷二硫化钼。
本实施例中纳米级多孔聚钼酸盐NaNH4MoO10·H2O的TEM和XRD如图2、3所示,所制备的多孔富缺陷二硫化钼的TEM、HRTEM、XRD和比表面积分别如图4、5、6和7所示,从图中可以看出,所制备的多孔富缺陷二硫化钼形貌较好,比表面积为85.87m2/g。
实施例2
本实施例按如下步骤制备多孔富缺陷二硫化钼:
(1)称取四水合钼酸铵3.0g、氯化钠6.0g,分别溶解于50mL的去离子水中,在磁力搅拌下将二者混匀,将温度升温至70℃时,澄清溶液开始变浑浊,几分钟后析出白色絮状物,反应30分钟停止,趁热抽滤,用去离子水多次洗涤,得到白色絮状固体,室温干燥,即得到纳米级多孔聚钼酸盐。
(2)称取0.5070g纳米级聚钼酸盐NaNH4MoO10·H2O和1.5095g硫脲,将纳米级多孔聚钼酸盐NaNH4MoO10·H2O放入聚四氟乙烯烧杯中,硫脲加入到聚四氟乙烯反应釜内衬中,倒入少量水,形成浆料。后将盛放纳米级多孔聚钼酸盐NaNH4MoO10·H2O的烧杯放入聚四氟乙烯反应釜中成嵌套关系,180℃反应48h。反应结束后冷却至室温,所得产物依次使用氨水、去离子水和无水乙醇洗涤多次,最后在60℃干燥后得到多孔富缺陷二硫化钼。
经表征,本实施例所得产物确为多孔富缺陷二硫化钼,比表面积为65.32m2/g。
对比实施例1和实施例2可知,本发明通过调节硫源的用量可以控制多孔富缺陷二硫化钼的比表面积的大小,减少硫源用量使部分聚钼酸盐不能充分硫化,从而降低材料的比表面积。
实施例3
本实施例按如下步骤制备多孔富缺陷二硫化钼:
(1)称取四水合钼酸铵3.0g、氯化钠6.0g,分别溶解于50mL的去离子水中,在磁力搅拌下将二者混匀,将温度升温至70℃时,澄清溶液开始变浑浊,几分钟后析出白色絮状物,反应30分钟停止,趁热抽滤,用去离子水多次洗涤,得到白色絮状固体,室温干燥,即得到纳米级多孔聚钼酸盐。
(2)称取0.5070g纳米级多孔聚钼酸盐NaNH4MoO10·H2O和2.5095g硫脲,将纳米级多孔聚钼酸盐NaNH4MoO10·H2O放入聚四氟乙烯烧杯中,硫脲加入到聚四氟反应釜内衬中,倒入少量水,形成浆料。后将盛放纳米级多孔聚钼酸盐NaNH4MoO10·H2O的烧杯放入聚四氟乙烯反应釜中成嵌套关系,180℃反应24h。反应结束后冷却至室温,所得产物依次使用氨水、去离子水和无水乙醇洗涤多次,最后在60℃干燥后得到多孔富缺陷二硫化钼。
经表征,本实施例所得产物确为多孔富缺陷二硫化钼,比表面积为60.44m2/g。
对比实施例1和实施例3可知,本发明通过调节纳米级聚钼酸盐的原位硫化时间也可以控制多孔富缺陷二硫化钼的比表面,减少硫化时间会使部分聚钼酸盐不能充分硫化,从而降低材料的比表面积。
实施例4
本实施例按如下步骤制备多孔富缺陷二硫化钼:
(1)称取四水合钼酸铵3.0g、氯化钠6.0g,分别溶解于50mL的去离子水中,在磁力搅拌下将二者混匀,调节溶液pH到2~3,将温度升温至70℃时,澄清溶液开始变浑浊,几分钟后析出白色絮状物,反应30分钟停止,趁热抽滤,用去离子水多次洗涤,得到白色絮状固体,室温干燥,即得到纳米级多孔聚钼酸盐。
(2)称取0.5070g纳米级多孔聚钼酸盐NaNH4MoO10·H2O和2.5095g硫脲,将纳米级多孔聚钼酸盐NaNH4MoO10·H2O放入聚四氟乙烯烧杯中,硫脲加入到聚四氟反应釜内衬中,倒入少量水,形成浆料。后将盛放纳米级多孔聚钼酸盐NaNH4MoO10·H2O的烧杯放入聚四氟乙烯反应釜中成嵌套关系,180℃反应48h。反应结束后冷却至室温,所得产物依次使用氨水、去离子水和无水乙醇洗涤多次,最后在60℃干燥后得到多孔富缺陷二硫化钼。
本实施例中所制备的多孔富缺陷二硫化钼的TEM、HRTEM、XRD和比表面积分别如图8、9、10和11所示,从图中可以看出,所制备的多孔富缺陷二硫化钼形貌较好,比表面积为118.34m2/g。
对比实施例1和实施例4可知,本发明通过改变溶液的pH来调节钼酸盐的聚合,并进而控制多孔富缺陷二硫化钼催化剂的比表面积,溶液的pH在2~3时能够制备性能最佳的钼酸聚集体原料。
Claims (8)
1.一种多孔富缺陷二硫化钼的制备方法,其特征在于:
(1)在钼酸盐的水溶液中加入可溶性酸或可溶性盐,然后加热,钼酸根离子在阳离子的诱导下逐步聚合成多孔杂合的有序聚集体,产物经分离、洗涤、烘干后,获得纳米级多孔聚钼酸盐;
(2)将步骤(1)所得纳米级多孔聚钼酸盐转移到反应釜中,以含负二价硫元素的化合物为硫源,通过水热-气相原位硫化法获得多孔富缺陷二硫化钼。
2.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述的水热-气相原位硫化法的具体步骤是:
在高压反应釜的聚四氟乙烯内胆中放置一个耐高温容器;将纳米级多孔聚钼酸盐放入耐高温容器中,将硫源的水溶液放入聚四氟乙烯内胆中、且在耐高温容器外,使纳米级多孔聚钼酸盐和硫源的水溶液分开;
然后在100~300℃的温度下水热反应12~84h,所得产物经分离、洗涤和干燥,即获得多孔富缺陷的二硫化钼。
3.根据权利要求1或2所述的制备方法,其特征在于:所述钼酸盐为钼酸铵、钼酸钠或钼酸钾。
4.根据权利要求1或2所述的制备方法,其特征在于:步骤(1)中所述的阳离子是所述可溶性酸或可溶性盐中的阳离子,为氢离子、铵根离子、有机铵根阳离子或金属离子。
5.根据权利要求1或2所述的制备方法,其特征在于:步骤(1)中的加热温度为50~300℃。
6.根据权利要求1或2所述的制备方法,其特征在于:步骤(2)中所述的含负二价硫元素的化合物为硫脲、硫醇、硫代乙酰胺、硫化钠或L-半胱氨酸。
7.根据权利要求1或2所述的制备方法,其特征在于:步骤(2)中的钼、硫的摩尔比为1:2.0~10.0。
8.根据权利要求1或2所述的制备方法,其特征在于:步骤(2)中所述的洗涤是依次用氨水、去离子水和乙醇进行洗涤,所述干燥的温度为60~120℃。
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