CN110194486A - 一种无定型MoSx单层纳米片的制备方法 - Google Patents
一种无定型MoSx单层纳米片的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910003185 MoSx Inorganic materials 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 238000009830 intercalation Methods 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 29
- 229910002651 NO3 Inorganic materials 0.000 claims description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000002687 intercalation Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 11
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008232 de-aerated water Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
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- 238000007634 remodeling Methods 0.000 claims description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
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- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 50
- 229910003455 mixed metal oxide Inorganic materials 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011229 interlayer Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000002356 single layer Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
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- 238000010792 warming Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
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- 239000000843 powder Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 octadecylene Chemical group 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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Abstract
本发明提供一种无定型MoSx(x=2~4)单层纳米片的制备方法。以层状双金属氢氧化物(LDHs)层间为微反应器,先制备MoS4 2‑插层LDHs复合物;再通过低温煅烧使MoS4 2‑低温分解形成Mo3S13纳米簇,进而在层间进行排列形成MoSx单层纳米片,然后酸溶除去混合金属氧化物(MMO)后,获得无定型MoSx单层纳米片。本发明制备方法简单、反应条件温和、易于实现;不使用有机试剂,安全绿色环保;所得无定型MoSx为单层多孔的纳米片结构,比表面积大,表面拥有大量活性位点和缺陷,并具有优异的电催化析氢性能。
Description
技术领域
本发明涉及一种无定型MoSx单层纳米片的制备方法,属于纳米材料制备领域。
背景技术
当前化石燃料燃烧产生大量污染,氢气作为清洁能源,是一种理想的燃料。过渡金属硫化物如硫化钼在电催化以及储能材料等领域具有巨大的应用潜力而备受关注。然而密度泛函理论(DFT)计算和实验研究均已证明,结晶的MoS2催化析氢性能主要依赖于边缘活性位点,而层板并无活性,这严重限制了硫化钼作为析氢催化剂的应用。尽管大量研究者通过掺杂以及创造缺陷激活层板活性位点,但仍无法得到满意的催化析氢性能,这主要归结于不充足的活性位点以及高的氢(H)吸附自由能。最近研究表明,无定型MoSx材料拥有大量活性位点和更低的H吸附自由能,较结晶的MoS2拥有更优越的电催化析氢性能。
现有技术中已有关于无定型MoSx材料的报道。如,中国专利文献CN101024517A公开了一种非晶态硫化钼纳米粉体的制备方法;以可溶性钼酸盐、硫代乙酰胺、强酸和分散剂为原料,先将可溶性钼酸盐与硫代乙酰胺溶于去离子水中,再加入分散剂,最后在短时间内加入强酸,恒温下反应;反应所得沉淀物经过滤、洗涤、干燥,得到空心球状或颗粒状非晶态MoSx(x=2~4)纳米粉体。中国专利文献CN108529678A公开了一种MoSx及制备方法;包括步骤:将(NH4)2MoS4和油胺、十八烯、油酸中的一种或多种混合,然后对混合后的溶液通入惰性气体,接着将溶液升温到80~120℃后搅拌5~15min;继续对溶液进行加热至150~300℃后反应1~3h,然后经沉淀、洗涤,并分散于有机溶剂中,得到油溶性MoSx;最后对油溶性MoSx进行配体交换,得到水溶性MoSx。但上述方法使用到有机溶剂,不环保;所制备的无定型MoSx材料为空心球状或颗粒状,比表面积相对较小,并且上述发明中均未提到无定型MoSx在电催化析氢领域中的应用。
另外,由于无定型MoSx表面存在大量活性位点,因此制备无定型MoSx纳米片、并且减小无定型MoSx纳米片的厚度和横向尺寸,能够增加其比表面积,最大程度暴漏活性位点,提供更有效的电催化析氢性能。由于其结构的特殊性,目前还没有有效的技术方法能够实现大规模制备单层无定型MoSx材料,这严重限制了无定型MoSx材料在催化剂方面的应用。因此,寻找一种应用于电催化析氢领域,具有较大比表面积、原子层厚度(单层厚度)、大量活性缺陷位点、可控的S-Mo比例和优异电催化析氢性能、并能大规模制备的无定型MoSx纳米片材料的制备方法具有重要意义。
发明内容
针对现有技术存在的不足,本发明提供一种无定型MoSx单层纳米片的制备方法。本发明制备方法简单、反应条件温和、易于实现;不使用有机试剂,安全绿色环保;所得无定型MoSx为单层多孔的纳米片结构,比表面积大,表面拥有大量活性位点和缺陷,同时具有优异的电催化析氢性能。
术语说明:
LDHs:层状双金属氢氧化物(Layered Double Hydroxides),是水滑石(Hydrotalcite, HT)和类水滑石化合物(Hydrotalcite-like Compounds,HTlc)的统称,由这些化合物插层组装的一系列超分子材料称为水滑石类插层材料。
混合金属氧化物:英文名为MixedMetal Oxides,简写为MMO。
MoSx/MMO复合物:指MoSx和混合金属氧化物的复合物。
本发明的技术方案如下:
一种无定型MoSx单层纳米片的制备方法,包括步骤:
(1)MoS4 2-插层LDHs复合物的制备;
(2)MoS4 2-插层LDHs复合物于惰性气体中、250~350℃下煅烧1~4h,得到MoSx/MMO复合物;然后加入酸中,室温搅拌10~15h,经过滤、洗涤、真空干燥得到无定型MoSx单层纳米片。
根据本发明,无定型MoSx单层纳米片中,x取值为2~3。
根据本发明优选的,步骤(1)中所述LDHs具有水滑石晶体结构;化学式为 [M2+ 1-yM3 + y(OH)2]y+[An- y/n]y-·mH2O,其中,M2+为二价金属离子,M3+为三价金属离子,An-为n价阴离子,y为每摩尔LDHs中M3+的摩尔分数;n=1~2,y=0.15~0.35,m=0.5~6。
优选的,所述M2+为Mg2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+或Zn2+中的一种;所述M3+为Al3+、Cr3+、Mn3+、Fe3+、Co3+或Ni3+中的一种;所述An-为OH-、Cl-、CO3 2-或NO3 -中的一种;进一步优选的,所述M2+为Mg2+,M3+为Al3+,An-为Cl-、NO3 -或CO3 2-中的一种。
根据本发明,步骤(1)中,MoS4 2-插层LDHs复合物是以(NH4)2MoS4为MoS4 2-源,按现有离子交换法或结构重建法制备得到。优选的,可按下述任意一种方法制备得到:
i、离子交换法:将二价金属硝酸盐和三价金属硝酸盐按摩尔比(1~3):1溶于水中,得溶液A;将NaOH、KOH或质量浓度为20~30%的氨水溶于水中,得溶液B;在惰性气体保护、搅拌条件下,将溶液A和溶液B同时滴加入脱气水C中,并控制最终pH为9.5~10.0,室温搅拌20~40min;然后惰性气体保护下,70~90℃熟化10~15h,经过滤、洗涤、干燥得 NO3 -插层的LDHs;将NO3 -插层的LDHs与(NH4)2MoS4加入脱气水中,得悬浊液D,惰性气体保护下,20~60℃搅拌12~36h,经过滤、洗涤、真空干燥得MoS4 2-插层LDHs复合物;
ii、结构重建法:将二价金属盐、三价金属盐、尿素溶于水中,得溶液E,80~100℃下搅拌20~30h,经过滤、洗涤、干燥得CO3 2-插层的LDHs;400~550℃煅烧1~3h得到 MMO;将MMO和(NH4)2MoS4加入脱气去离子水中,得悬浊液F,惰性气体保护下,20~60℃搅拌12~36h;经过滤、洗涤、干燥得MoS4 2-插层LDHs复合物。
优选的,MoS4 2-插层LDHs复合物制备之i中,包括以下条件中的一项或多项:
a、所述二价金属硝酸盐为Mg(NO3)2,三价金属硝酸盐为Al(NO3)3;溶液A中总金属硝酸盐的摩尔浓度为0.1~1mol/L;
b、所述溶液B中NaOH、氨或KOH的摩尔浓度为1~2moL/L;溶液A中总金属硝酸盐和溶液B中NaOH、氨或KOH的摩尔比为1:(2~3);所述脱气水C与溶液A的体积比为(0.1~2):1。
c、所述NO3 -插层的LDHs与(NH4)2MoS4的质量比为1:(0.5~3);所述悬浊液D中,NO3 -插层的LDHs的质量浓度为20~30%。
优选的,MoS4 2-插层LDHs复合物制备之ii中,包括以下条件中的一项或多项:
a、所述二价金属盐为Mg(NO3)2,三价金属盐为Al(NO3)3;所述二价金属盐和三价金属盐的摩尔比为(1~3):1,尿素与总金属盐摩尔比为(3~5):1;所述溶液E中总金属盐的摩尔浓度为0.1~0.5mol/L;
b、所述MMO和(NH4)2MoS4的质量比为1:(0.5~5);所述悬浊液F中,MMO的质量浓度为10~30%。
根据本发明优选的,步骤(2)中所述酸是使用摩尔浓度为0.3~5mol/L的盐酸、硝酸、硫酸或磷酸水溶液;优选的,所述酸为盐酸水溶液。
根据本发明优选的,步骤(2)中所述MoSx/MMO复合物的质量和酸的体积比为 0.01~0.03g/mL。
根据本发明优选的,步骤(2)中,煅烧过程中的升温速率为2~10℃/min。
本发明的技术特点及有益效果如下:
1、LDHs具有层状晶体结构,层间存在可交换的阴离子;本发明以LDHs层间为微反应器,利用其“限域效应”,将MoS4 2-插入到LDHs层间,然后经低温(250~350℃)煅烧,使MoS4 2-在层间有限空间内分解-聚合形成以Mo3S13纳米簇为基元的无定型MoSx单层纳米片,获得MoSx/MMO复合物;将其中的MMO酸溶去除得无定型MoSx单层纳米片。本发明利用LDHs作为模板,制得高占比率(90~95%)的无定型MoSx单层纳米片,并可实现纳米片横向尺寸(通过控制LDHs的横向尺寸)以及S:Mo比例(S:Mo比例随温度升高而降低)的可控合成。本发明严格控制煅烧温度,低温煅烧,使MoS4 2-充分分解聚合形成无定型MoSx(实际转化率为98~100%)而非晶态MoS2(当煅烧温度升高时,MoS4 2-可分解聚合形成晶态MoS2)。本发明合成过程简单,条件温和、易于实现;首次大规模制备了原子层厚度无定形MoSx纳米片;不使用有机试剂,安全绿色环保;所需设备简单,能耗小,成本低,易于规模化生产。
2、本发明制备的MoSx单层纳米片为无定型的,是由基元Mo3S13纳米簇连接而成的MoSx单层纳米片,厚度为0.7~1.4nm,横向尺寸为5~40nm;厚度和横向尺寸较小,具有较大的比表面积,从而暴露大量S活性位点和缺陷活性位点,具有更低的H吸附自由能,从而具有优异的电催化析氢性能,电催化析氢活性优于现有方法制备的S-Mo基催化剂,甚至在具有工业意义的电位下其性能高于贵重金属Pt/C催化剂。
附图说明
图1为实施例1制备的MoS4 2-插层LDHs复合物、MoSx/MMO复合物、无定型MoSx单层纳米片的XRD图;
图2为实施例1制备的无定型MoSx单层纳米片的SEM图;
图3为实施例1制备的无定型MoSx单层纳米片的AFM图;
图4为实施例1制备的无定型MoSx单层纳米片的横向尺寸和厚度分布图;
图5为实施例1制备的无定型MoSx单层纳米片的HRTEM图;
图6为实施例1制备的无定型MoSx单层纳米片和对比例1制备的块状MoSx的Raman图;
图7为实施例1制备的无定型MoSx单层纳米片和对比例1制备的块状MoSx的BET 和孔体积图;
图8为对比例1制备的块状无定型MoSx的SEM图;
图9为实施例1制备的无定型MoSx单层纳米片、对比例1制备的块状MoSx和商用 Pt/C的LSV对比图;其中的插图为无定型MoSx单层纳米片LSV的局部放大图;
图10为实施例1制备的无定型MoSx单层纳米片和商用Pt/C的Tafel对比图;
图11为实施例1制备的无定型MoSx单层纳米片循环稳定性CV图以及计时电流i-t图(插图)。
具体实施方式
下面结合具体实施例对本发明做进一步的说明,但不限于此。
同时下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
一种无定型MoSx单层纳米片的制备方法,包括步骤:
采用结构重建法制备MoS4 2-插层LDHs复合物。
取200ml去离子水、6.8gMg(NO3)2·6H2O、5.0gAl(NO3)3·9H2O及8g尿素加入三口烧瓶中,常温搅拌0.5h使固体溶解,并在90℃油浴中回流24h。经过滤、洗涤、60℃干燥 12h,得到CO3 2-插层的LDHs。将制得的LDHs在马弗炉400℃煅烧2h得到MMO模板。称取4.0gMMO和6.0g(NH4)2MoS4,放入100ml脱气去离子水中,并于氮气保护下搅拌24h,温度恒定为40℃。然后将分散液过滤、洗涤、60℃干燥12h,得到MoS4 2-插层LDHs复合物(简称MoS4 2-/LDHs)。
将5gMoS4 2-/LDHs复合物粉末置于管式炉中,N2保护下升温至300℃煅烧2h,升温速率为5℃/min。自然冷至室温后,得MoSx/MMO复合物。取2gMoSx/MMO复合物加入 100ml0.5mol/L盐酸中,室温搅拌12h,然后经过滤、水洗、冷冻干燥10h,得无定型MoSx单层纳米片。
本实施例制备的MoS4 2-/LDHs复合物、MoSx/MMO复合物、无定型MoSx单层纳米片的XRD图如图1所示。由图1可知,MoS4 2-插层LDHs拥有更大的层间距,证明MoS4 2-成功插入LDHs层间;MoSx/MMO复合物、无定型MoSx单层纳米片的峰强度较弱,表明为无定型状态。
本实施例制备的无定型MoSx单层纳米片的SEM图如图2所示,无定型MoSx的微观形貌是柔性超薄纳米片,且超薄纳米片堆叠在一起。
本实施例制备的无定型MoSx单层纳米片的AFM图如图3所示,纳米片的厚度为~1.0nm;同时本实施例制备的单层纳米片的占比以及横向尺寸分布如图4所示,其横向尺寸为5~40nm,单层纳米片占比可以达到93%。
本实施例制备的无定型MoSx单层纳米片的HRTEM图如图5所示,纳米片为无定型状态,没有明显的晶格条纹。
本实施例制备的无定型MoSx单层纳米片的Raman图如图6所示,纳米片缺少结晶态MoS2对应的特征峰。
本实施例制备的无定型MoSx单层纳米片的BET和孔体积如图7所示,本发明无定型MoSx单层纳米片的比表面积高达76m2/g,明显高于对比例1制备的块状无定型MoSx的比表面积(6.5m2/g);制备的无定型MoSx单层纳米片孔体积(0.43cm2/g)明显高于对比例1 制备的块状无定型MoSx的孔体积(0.07cm2/g)。
实施例2
一种无定型MoSx单层纳米片的制备方法,包括步骤:
采用离子交换法制备MoS4 2-插层LDHs复合物:
取10.2gMg(NO3)2·6H2O和7.6gAl(NO3)3·9H2O溶于200ml去离子水中得溶液A。取6.4gNaOH溶于200ml去离子水中得溶液B。将溶液A和B在搅拌条件下同时滴加到50ml 脱气去离子水中,氮气保护并控制pH为10.0。室温搅拌30min后,置于80℃烘箱中氮气保护下熟化12h。经过滤、洗涤、60℃真空干燥12h,得NO3 -插层的LDHs。称取5.0g所制备的LDHs与5.0g(NH4)2MoS4加入100ml脱气去离子水中,N2保护下,40℃搅拌24h。经过滤、洗涤、真空干燥得到MoS4 2-/LDHs复合物。
将5gMoS4 2-/LDHs复合物粉末置于管式炉中,N2保护下升温至300℃煅烧2h,升温速率为2℃/min。自然冷至室温后,得MoSx/MMO复合物。取2gMoSx/MMO复合物加入 100ml0.5mol/L盐酸中,室温搅拌12h,然后经过滤、水洗、冷冻干燥10h得无定型MoSx单层纳米片。
实施例3
一种无定型MoSx单层纳米片的制备方法,包括步骤:
MoS4 2-插层LDHs复合物的制备如实施例1所述;
将5gMoS4 2-插层LDHs复合物粉末置于管式炉中,N2保护下升温至280℃煅烧1h,升温速率为2℃/min。自然冷至室温后,得MoSx/MMO复合物。取2gMoSx/MMO复合物加入100ml0.5mol/L盐酸中,室温搅拌12h,然后经过滤、水洗、冷冻干燥10h得无定型 MoSx单层纳米片。
实施例4
一种无定型MoSx单层纳米片的制备方法,包括步骤:
MoS4 2-插层LDHs复合物的制备如实施例2所述;
将5gMoS4 2-插层LDHs复合物粉末置于管式炉中,N2保护下升温至250℃煅烧3h,升温速率为5℃/min。自然冷至室温后,得MoSx/MMO复合物。取2gMoSx/MMO复合物加入100ml0.5mol/L硫酸中,室温搅拌12h,然后经过滤、水洗、冷冻干燥10h得无定型 MoS2单层纳米片。
对比例1
一种块状无定型MoSx的制备方法,其制备方法是:直接将(NH4)2MoS4粉末置于管式炉中,N2保护下升温至300℃煅烧2h,升温速率为5℃/min。
由于没有LDHs作为模板,其直接分解聚合为块状无定型MoSx纳米粒子。其Raman谱如图6所示,表明其为无定型MoSx;图7为其BET与孔体积图,其比表面积很小,仅为6.7m2/g,孔体积仅为0.07cm2/g;图8为其SEM图,为块状材料。
对比例2
一种单层纳米片的制备方法,如实施例1所述,所不同的是:MoS4 2-插层LDHs复合物在空气中锻烧,其它条件与实施例1一致。
空气能够氧化MoS4 2-,因此无法得到无定型MoSx单层纳米片。
应用例
将本发明实施例1得到的无定型MoSx单层纳米片、对比例1得到的块状无定型MoSx纳米粒子和商用Pt/C催化剂(Pt的含量为20wt%)进行电催化析氢性能评价。
采用三电极体系对上述样品的电催化析氢反应性能进行测试。以饱和甘汞电极(SCE) 为参比电极,碳棒电极为对电极,以表面涂覆复合材料的1cm2碳布为工作电极,以0.5mol/L N2饱和的H2SO4为电解液,采用上海辰华的CHI 760e型电化学工作站进行测试。
工作电极的制备方法为:称取10mg样品,分散于1ml超纯水/乙醇(体积比为4:1)的混合溶剂中,然后加入30μL5%的Nafion膜溶液和0.5mg炭黑作为导电剂。常温条件下用超声波处理器超声分散30min获得均一的催化剂分散体,向已经经过亲水处理的1×1cm2碳布表面滴涂100μL上述催化剂分散体,待表面彻底干燥后形成催化剂负载量为1g/cm2的工作电极。将工作电极、参比电极、以及对电极组成三电极体系进行线性扫描伏安法(LSV)以及循环稳定性CV、计时电流i-t测试,测试结果如图9-11所示。
测试参数:LSV测试时电压扫速为5mV/s,扫描范围为0.2~-0.25V(相对于标准氢电位(简称RHE))。循环伏安测试时其扫速为100mV/s,扫描范围为0~-3V(相对于RHE)。
本发明实施例1制备的无定型MoSx单层纳米片和商用贵金属Pt/C催化剂(Pt的含量为20wt%)的LSV结果如图9所示。可以看出,块状无定形MoSx展现了较弱的电催化活性;无定型MoSx单层纳米片展现了超低的过电位,在-129mV实现了10mA/cm2电流密度,在-230mV实现了400mA/cm-2。由本领域技术知识可知,其电催化性能优于当前Mo-S基催化剂,甚至在具有工业意义的高电位下,其电流密度超越Pt/C,性能明显优于商用贵金属Pt/C催化剂。
本发明实施例1制备的无定型MoSx单层纳米片的Tafel图如图10所示,由图10可知极低的Tafel保证了其卓越的电催化效率,同时几乎不变的Tafel斜率也表明了其在高电位下,电流密度必将超过商用贵金属Pt/C催化剂(Pt的含量为20wt%)的电流密度。
本发明实施例1制备的无定型MoSx单层纳米片的CV图以及计时电流i-t图(插图)如图11所示,表明其具有优越的稳定性,其LSV性能在2000圈CV后基本无变化;另外 i-t曲线表明,经催化反应12h后,电流密度基本无变化,这表明本发明制备的无定型MoSx单层片制备的电极具有优越的催化稳定性。
本发明实施例1制备的无定型MoSx单层纳米片材料作为电催化析氢反应的催化剂时,由于其超薄的特性及高暴露活性位点的优势,展现了卓越的电催化性能,显著优于文献报道的Mo-S基材料(见表1)。特别是,如图9所示当电位超过220mV时,其电流密度高于目前公认性能最优的贵重金属Pt/C催化剂(Pt的含量为20wt%)。而现有技术(如中国专利文献CN 106960948 A公开的方法)制备的块状无定型MoSx,多是通过增加结构缺陷或负载其他高活性催化材料而增强催化性能,但不能暴露内部的大量活性位点,故催化性能增强有限,且材料制备方法复杂,成本高,不能满足实际工业应用要求。本发明设计的单层无定型材料,能够最大程度暴露活性位点,且制备过程简单,条件温和,绿色环保,电催化性能卓越,可满足工业生产需求。
表1实施例1制备的无定型MoSx单层片与文献报道的Mo-S基材料的催化性能比较
表1中各参考文献如下:
[1]H.Wang,H.Zhou,W.Zhang,S.Yao,J.Mater.Sci.2018,53,8951.
[2]X.Xue,J.Zhang,I.A.Saana,J.Sun,Q.Xu,S.Mu,Nanoscale2018,10, 16531.
[3]G.Wang,J.Tao,Y.Zhang,S.Wang,X.Yan,C.Liu,F.Hu,Z.He,Z.Zuo,X. Yang,ACS Appl.Mater.Interfaces2018,10,25409.
[4]Y.Shang,X.Xu,Z.Wang,B.Jin,R.Wang,Z.Ren,B.Gao,Q.Yue,ACS SustainableChem.Eng.2018,6,6920.
[5]Z.Ji,C.Trickett,X.Pei,O.M.Yaghi,J.Am.Chem.Soc.2018,140,13618.
[6]B.Li,L.Jiang,X.Li,Z.Cheng,P.Ran,P.Zuo,L.Qu,J.Zhang,Y.Lu,Adv.Funct.Mater.2019,29,1806229.
[7]S.Reddy,R.Du,L.Kang,N.Mao,J.Zhang,Appl.Catal.,B2016,194,16.
[8]S.-K.Park,J.K.Kim,Y.C.Kang,ACS Sustainable Chem.Eng.2018,6, 12706.
[9]t.A.N.M.Abstracts of Papers,Washington,DC,United States,Aug.28-Sept. 1,2005Xu,Qiucheng,Y.Liu,H.Jiang,Y.Hu,H.Liu,C.Li,Adv.Energy Mater.2019,9.
[10]A.Y.Lu,X.Yang,C.C.Tseng,S.Min,S.H.Lin,C.L.Hsu,H.Li,H.Idriss,J.L.Kuo,K.W.Huang,L.J.Li,Small2016,12,5530.
[11]J.Deng,H.Li,J.Xiao,Y.Tu,D.Deng,H.Yang,H.Tian,J.Li,P.Ren,X. Bao,Energy Environ.Sci.2015,8,1594.
[12]L.Chen,H.Zhu,ChemCatChem2018,10,459. 。
[13]Q.Gao,Y.Jin,Y.Jin,X.Wang,Z.Ye,Z.Hong,M.Zhi,J.Sol-Gel Sci.Technol.2018,88,227.
[14]M.Li,M.Yu,X.Li,Appl.Surf.Sci.2018,439,343 。
Claims (9)
1.一种无定型MoSx单层纳米片的制备方法,包括步骤:
(1)MoS4 2-插层LDHs复合物的制备;
(2)MoS4 2-插层LDHs复合物于惰性气体中、250~350℃下煅烧1~4h,得MoSx/MMO复合物;然后加入酸中,室温搅拌10~15h,经过滤、洗涤、真空干燥得无定型MoSx单层纳米片。
2.根据权利要求1所述的无定型MoSx单层纳米片的制备方法,其特征在于,步骤(1)中所述LDHs具有水滑石晶体结构;化学式为[M2+ 1-yM3+ y(OH)2]y+[An- y/n]y-·mH2O,其中,M2+为二价金属离子,M3+为三价金属离子,An-为n价阴离子,y为每摩尔LDHs中M3+的摩尔分数;n=1~2,y=0.15~0.35,m=0.5~6。
3.根据权利要求2所述的无定型MoSx单层纳米片的制备方法,其特征在于,所述M2+为Mg2 +、Mn2+、Fe2+、Co2+、Ni2+、Cu2+或Zn2+中的一种;所述M3+为Al3+、Cr3+、Mn3+、Fe3+、Co3+或Ni3+中的一种;所述An-为OH-、Cl-、CO3 2-或NO3 -中的一种;优选的,所述M2+为Mg2+,M3+为Al3+,An-为Cl-、NO3 -或CO3 2-中的一种。
4.根据权利要求1所述的无定型MoSx单层纳米片的制备方法,其特征在于,步骤(1)中,MoS4 2-插层LDHs复合物是以(NH4)2MoS4为MoS4 2-源,按下述任意一种方法制备得到:
i、离子交换法:将二价金属硝酸盐和三价金属硝酸盐按摩尔比(1~3):1溶于水中,得溶液A;将NaOH、KOH或质量浓度为20~30%的氨水溶于水中,得溶液B;在惰性气体保护、搅拌条件下,将溶液A和溶液B同时滴加入脱气水C中,并控制最终pH为9.5~10.0,室温搅拌20~40min;然后惰性气体保护下,70~90℃熟化10~15h,经过滤、洗涤、干燥得NO3 -插层的LDHs;将NO3 -插层的LDHs与(NH4)2MoS4加入脱气水中,得悬浊液D,惰性气体保护下,20~60℃搅拌12~36h,经过滤、洗涤、真空干燥得MoS4 2-插层LDHs复合物;
ii、结构重建法:将二价金属盐、三价金属盐、尿素溶于水中,得溶液E,80~100℃下搅拌20~30h,经过滤、洗涤、干燥得CO3 2-插层的LDHs;400~550℃煅烧1~3h得到MMO;将MMO和(NH4)2MoS4加入脱气去离子水中,得悬浊液F,惰性气体保护下,20~60℃搅拌12~36h;经过滤、洗涤、干燥得MoS4 2-插层LDHs复合物。
5.根据权利要求4所述的无定型MoSx单层纳米片的制备方法,其特征在于,MoS4 2-插层LDHs复合物制备之i中,包括以下条件中的一项或多项:
a、所述二价金属硝酸盐为Mg(NO3)2,三价金属硝酸盐为Al(NO3)3;溶液A中总金属硝酸盐的摩尔浓度为0.1~1mol/L;
b、所述溶液B中NaOH、氨或KOH的摩尔浓度为1~2moL/L;溶液A中总金属硝酸盐和溶液B中NaOH、氨或KOH的摩尔比为1:(2~3);所述脱气水C与溶液A的体积比为(0.1~2):1;
c、所述NO3 -插层的LDHs与(NH4)2MoS4的质量比为1:(0.5~3);所述悬浊液D中,NO3 -插层的LDHs的质量浓度为20~30%。
6.根据权利要求4所述的无定型MoSx单层纳米片的制备方法,其特征在于,MoS4 2-插层LDHs复合物制备之ii中,包括以下条件中的一项或多项:
a、所述二价金属盐为Mg(NO3)2,三价金属盐为Al(NO3)3;所述二价金属盐和三价金属盐的摩尔比为(1~3):1,尿素与总金属盐摩尔比为(3~5):1;所述溶液E中总金属盐的摩尔浓度为0.1~0.5mol/L;
b、所述MMO和(NH4)2MoS4的质量比为1:(0.5~5);所述悬浊液F中,MMO的质量浓度为10~30%。
7.根据权利要求1所述的无定型MoSx单层纳米片的制备方法,其特征在于,步骤(2)中所述酸是使用摩尔浓度为0.3~5mol/L的盐酸、硝酸、硫酸或磷酸水溶液;优选的,所述酸为盐酸水溶液。
8.根据权利要求1所述的无定型MoSx单层纳米片的制备方法,其特征在于,步骤(2)中所述MoSx/MMO复合物的质量和酸的体积比为0.01~0.03g/mL。
9.根据权利要求1所述的无定型MoSx单层纳米片的制备方法,其特征在于,步骤(2)中,煅烧过程中的升温速率为2~10℃/min。
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