CN110292941A - A kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping - Google Patents
A kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping Download PDFInfo
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 52
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000013019 agitation Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract 2
- 238000007789 sealing Methods 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 229910052961 molybdenite Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910017299 Mo—O Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the technical fields of green energy resource, more particularly to a kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping, the synthetic technology process of the catalyst is simple, highly-safe, low in cost, it can be with the spherical molybdenum disulfide of a large amount of oxygen dopings of rapid synthesis, with more edge active sites, catalytic activity for hydrogen evolution is improved；(1) sodium molybdate, thiocarbamide and silica are dissolved in water；(2) above-mentioned mixing liquid is transferred to reaction kettle, forms uniform solution by magnetic agitation processing, solution carries out hydro-thermal reaction in the reaction kettle of sealing；(3) sample after hydro-thermal is used into hydrofluoric acid and naoh treatment respectively, obtained product deionized water and dehydrated alcohol wash repeatedly, are dried overnight, and obtain the molybdenum disulfide of different structure.
Description
Technical field
The present invention relates to the technical fields of green energy resource, are suitable for cathode for hydrogen evolution catalyst-oxygen more particularly to one kind and mix
The technology of preparing of miscellaneous spherical molybdenum disulfide material.
Background technique
It is well known that currently, fossil energy is in world's energy market in occupation of vital status, modern energy warp
The accelerated growth of Ji be highly dependent on may increasingly reduction fossil fuel resource.(Energies2015,8,172-216) excessive
Carbon emission already lead to global temperatures and increase 4 DEG C, this result is there is a possibility that sea level rise to being enough to flood global 460-
7600000 populations.(RenewableandSustainableEnergyReviews2018,82,3091-3106) some datas
Show, it is known that petroleum reserves it is estimated exhausted in 34 to 40 years, coal is 106 to 200 years, and natural gas is 36 to 70 years
(EnergyPolicy2009,37,181–189).It is emerging to the research of renewable energy technologies that these data excite people again
Interest.Electrochemistry evolving hydrogen reaction (HER), it is simple and efficient due to producing hydrogen purity height, process, become sustainable one kind for producing hydrogen
Method.Catalyst for electrochemistry evolving hydrogen reaction should reduce overpotential and improve the efficiency of electrochemical process.
(Chem.Rev.2010,110,6446) currently, most efficient liberation of hydrogen catalyst is Pt metal, exploitation liberation of hydrogen is efficient, content is rich
Rich, low-cost catalyst is still challenging.
It has recently been demonstrated that molybdenum disulfide (MoS2) is a kind of very promising elctro-catalyst.As a kind of typical case
Two-dimensional material, molybdenum disulfide around two S layers of one Mo layers by forming；Curing molybdenum sheet is by the model moral between adjacent S layer
Magnificent power interaction keeps together.(J.Am.Chem.Soc., 2005,127,5308-5309) is calculated and experimental result is demonstrate,proved
Real HER activity is derived from the edge site of MoS2, and (Science2007,317,100.) is currently, hinder that this material is widely used
Major influence factors are that the interaction of Van der Waals force leads to the accumulation of two-dimensional material, (J.Am.Chem.Soc., 2011,133,
7296-7299), this unavoidably reduces the quantity of active surface area and active site.(Chem.Comm.,2012,48,
7687-7689) therefore there is the nanosizing MoS2 of edge exposure to be more advantageous to evolving hydrogen reaction for preparation.Xie
(J.Am.Chem.Soc., 2014,136,17881-17888) et al. using ammonium molybdate and thiocarbamide as raw material, low temperature synthesizes oxygen doping
Molybdenum disulfide, so that (002) surface layer spacing is extended to 0.95nm, increase the unordered degree of MoS2, generate more unsaturated
The edge S- site, improves hydrogen evolution activity.Overpotential reaches 120mV, Tafel slope 55mV/dec.Deng
The team of (Nat.Commun., 2017,8:14430) prepares the MoS2 of meso-hole structure using SiO2 as template.Even mesoporous MoS2
The preparation process of foam (mPF-MoS2): firstly, ammonium molybdate molecule is equably adsorbed onto SiO2 nanometers of colloidal state by wet impregnation method
On ball.Then, the ammonium molybdate on thiocarbamide and the surface SiO2, which directly chemically reacts, is converted into MoS2.Due to monodisperse SiO2 nanosphere
The induction of template, MoS2 will further be self-assembled into the layer of vertical arrangement around SiO2 nanosphere.Finally, can be by with HF
Solution etches SiO2 to obtain mPF-MoS2.Etching process will not influence the structure of MoS2, because MoS2 cannot be molten by HF solution
Solution.The foam molybdenum disulfide prepared increases the active surface area of material, it is shown that higher liberation of hydrogen efficiency.Overpotential is
156mV, Tafel slope 74mV/dec, but equipment required for this method is more, scheme is complicated, cause its production cost compared with
It is high.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation skill suitable for making electrochemistry cathode for hydrogen evolution catalyst
The synthetic technology process of art, the catalyst is simple, highly-safe, low in cost, can be with the spherical of a large amount of oxygen dopings of rapid synthesis
Molybdenum disulfide has more edge active sites, improves catalytic activity for hydrogen evolution.
A kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping of the invention, packet
Include following steps:
(1) sodium molybdate, thiocarbamide and silica are dissolved in water；
(2) above-mentioned mixing liquid is transferred to reaction kettle, forms uniform solution by magnetic agitation processing, solution is close
Hydro-thermal reaction is carried out in the reaction kettle of envelope；
(3) sample after hydro-thermal is used into hydrofluoric acid and naoh treatment respectively, obtained product deionized water and anhydrous
Ethanol washing is multiple, is dried overnight, and obtains the molybdenum disulfide of different structure.
A kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping of the invention, institute
Stating sodium molybdate, thiocarbamide and silica molar ratios in step (1) is 1:2:1~1:2:3.
A kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping of the invention, institute
Magnetic agitation 30min after sample mixing is stated in step (2), is transferred to three 100mL water heating kettles, hydrothermal temperature is respectively
160 DEG C, 180 DEG C and 200 DEG C, target temperature is heated to by room temperature, is maintained under target temperature for 24 hours, cooled to room temperature obtains
It is target product to black powder.
Compared with prior art the invention has the benefit that (1) present invention uses hydrothermal synthesis technology, experimental program phase
To simple, easy to operate, equipment requirement is not high, can largely reduce production cost.
(2) the spherical molybdenum disulfide material of oxygen doping that the present invention is prepared extends to (002) interlamellar spacing by 0.64nm
0.95nm increases the unordered degree of molybdenum disulfide, generates more how unsaturated edge active site, has good liberation of hydrogen efficiency.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of N-M160, M160, M180, M200 sample in present invention preparation embodiment 1,2；
Fig. 2 is HF treated H-N-M160, H-M160, H-M180, H-M200 sample in present invention preparation embodiment 1
X-ray diffractogram；
Fig. 3 is HF treated (A) H-M160, (B) H-M180, (C) H-M200, (D) H- in present invention preparation embodiment 1
The scanning electron microscope (SEM) photograph of N-M160；
Fig. 4 is HF treated sample (A) LSV curve in present invention preparation embodiment 1, illustration Tafel curve in (A),
(B) impedance spectrum, (C) time-measuring electric potential curve, the relational graph of (D) current density difference and sweep speed；
Fig. 5 is NaOH treated N-N-M160, N-M160, N-M180 and N-M200 sample in present invention preparation embodiment 2
The XRD diagram of product；
Fig. 6 is NaOH treated (A) N-N-M160, (B) N-M160, (C) N-M180 in present invention preparation embodiment 2,
(D) scanning electron microscope (SEM) photograph of N-M200；
Fig. 7 is NaOH treated sample (A) LSV curve in present invention preparation embodiment 2, and illustration Tafel is bent in (A)
Line, (B) impedance spectrum, (C) time-measuring electric potential curve, the relational graph of (D) current density difference and sweep speed.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
The preparation of the spherical molybdenum disulfide of embodiment 1:2H-
It takes a certain amount of sodium molybdate, thiocarbamide and silica to sequentially add in 100mL reaction kettle, divides after magnetic agitation 30min
It is not heated under conditions of 160 DEG C, 180 DEG C and 200 DEG C of temperature, natural cooling, obtained product deionized water and anhydrous second
Repeatedly, sample is labeled as M160, M180, M200 for alcohol washing.It is handled to obtain pure 2H phase MoS2 with HF solution, is respectively labeled as H-
M160,H-M180,H-M200.It is compared simultaneously with the sample that silica is not added, implements identical step under the conditions of 160 DEG C
Suddenly, raw material only adds sodium molybdate and thiocarbamide.Label is after this sample hydrofluoric acid treatment, is marked with before hydrofluoric acid treatment
It is denoted as N-M160.The hump that Fig. 1 is shown in 2 θ=22 ° or so appearance is attributable to the presence of silica.At 160 DEG C, sample
(002) face extend to 0.95nm completely, be attributable to the doping of oxygen；At 180 DEG C, there are 0.95nm and 0.65nm in (002) face
Two kinds of structures illustrate that the content of oxygen is reduced；At 200 DEG C, (002) face shows the interlamellar spacing of 0.65nm, generates 2H-MoS2.
The XRD of each sample in comparison diagram 2, it has been found that molybdenum disulfide (002) face is returned to the 0.65nm of 2H-MoS2 by 0.95nm,
The peak of 14.2 °, 33.4 ° and 59.2 ° appearance corresponds respectively to (002), (100), (110) face of molybdenum disulfide, reference standard card
Piece (JCPDSNo.37-1492), then product is 2H-MoS2.Since hydrofluoric acid can be reacted with oxide, Mo-O key is caused to be broken,
Molybdenum disulfide is set to be restored to the stable state of standard.Illustrate that silica is dry by complete cleaning in the hump that 2 θ=22 ° or so disappear
Only.It can be seen that the molybdenum disulfide that hydro-thermal method is prepared is the spherical particle as made of small nanometer sheet heap cluster by Fig. 3, dioxy be not added
Sample (Fig. 3 A) agglomeration of SiClx is serious, and sphere size distribution is uneven.After HF is handled, H-M160, H-M180 and
For H-M200 sample in the chondritic of independent uniformly rule, H-M160 sample particle diameter is about 1 μm or so (such as Fig. 3 B), H-M180
Sample particle diameter is about at 1.3 μm or so (Fig. 3 C), and H-M200 sample particle diameter is about at 1.5~2 μm or so (Fig. 3 D).It is swept from above-mentioned
Electron microscope is retouched it can be gathered that rule, as the temperature rises, molybdenum disulfide sphere partial size is gradually increased.The addition of silica can
Agglomeration is eliminated, molybdenum disulfide is dispersed into independent uniform ball one by one.Fig. 4 shows H-N-M160, H-M160, H-
The Hydrogen Evolution Performance of M180 and H-M200 sample.When current density reaches 10mA/cm2, corresponding overpotential be respectively 493mV,
317mV, 328mV and 477mV.Under low potential, the current density of H-M160 is greater than H-M180.Tafel slope is with sample hydro-thermal
The increase of temperature gradually increases, and H-M160 and H-M180 have lesser slope.In AC impedance spectroscopy 4B, H-M160 sample
Radius it is minimum, there is minimum charge transfer resistance, promote mass transfer conduction of the electronics between electrode and molybdenum disulfide, improve
Liberation of hydrogen efficiency.It, can be thick by the size for the linear regression curves slope that contrast sample current density difference changes with sweep speed
Slightly estimation H-M160 sample has maximum active surface area.
Embodiment 2: the preparation of the spherical molybdenum disulfide of oxygen doping
It takes a certain amount of sodium molybdate, thiocarbamide and silica to sequentially add in 100mL reaction kettle, divides after magnetic agitation 30min
It is not heated under conditions of 160 DEG C, 180 DEG C and 200 DEG C of temperature, natural cooling, obtained product deionized water and anhydrous second
Repeatedly, sample is labeled as M160, M180, M200 for alcohol washing.The oxygen doping molybdenum disulfide handled with NaOH solution is marked respectively
It is denoted as N-M160, N-M180, N-M200；It is compared, is implemented under the conditions of 160 DEG C identical with the sample that silica is not added simultaneously
The step of, raw material only adds sodium molybdate and thiocarbamide.Label is after this sample naoh treatment, at sodium hydroxide
N-M160 is labeled as before reason.Fig. 5 shows the XRD diagram of different structure molybdenum disulfide after NaOH processing.N-N-M160,N-
The position interlamellar spacing of 2 θ=8.9 ° is 0.95nm in M160, N-M180 sample, corresponding to (002) face extended.N-M180's
Sample starts to have occurred in 2 θ=14.2 °, and interlamellar spacing is the diffraction maximum of 0.64nm, which is shown as two kinds of structures.Work as hydro-thermal
When temperature is 200 DEG C, the interlamellar spacing of sample 0.95nm is completely disappeared, and is converted into 0.64nm.By N-M160, to N-M200 curing
The variation that molybdenum (002) face occurs is it is found that the content of oxygen is increased with temperature and reduced.According to document (JournaloftheAmerican
ChemicalSociety, 2013,135 (47): 17881-17888) it reports, under cryogenic conditions, sodium molybdate can remain unbroken
Mo-O key generates the molybdenum disulfide of oxygen doping, and high temperature can be such that Mo-O key is broken.However, in the result of XRD, 200 DEG C
Under the conditions of, Mo-O key is not broken completely, is particularly likely that the presence of small part oxygen in the steamed bun peak that 7~8 ° occur.Fig. 6 is sample
The scanning electron microscope (SEM) photograph obtained after being handled by NaOH.Likewise, biggish reunion sphere is presented in N-N-M160, sphere is uneven
One, be it is some irregular spherical, be made of many small nanometer sheets, N-M160 sample particle diameter is about at 1 μm hereinafter, start to occur
The full spherical pattern of independent dispersion；N-M180 sample particle diameter has apparent increase between 1.3~2 μm；The sample of N-M200
About 1.5 μm of partial size, the partial size of ball increases as the temperature rises.Meanwhile the addition of silica can eliminate agglomeration,
Molybdenum disulfide is dispersed into independent uniform ball one by one.Electrochemical property test shows that N-M160 has the smallest mistake in Fig. 7
Current potential 255mV, the smallest Tafel slope 45mV/dec and the smallest Charge-transfer resistance and maximum active area.More than
As the result is shown with the sample after naoh treatment, original oxygen doping structure can be retained, the content of oxygen is increased with temperature
And reduce, the partial size of molybdenum disulfide increases with the raising of hydrothermal temperature, wherein the spherical oxygen doping molybdenum disulfide of N-M160
With best hydrogen evolution activity, the presence of oxygen increases the unordered degree of structure, generates more how unsaturated Mo atom and S atom,
Active site is increased, liberation of hydrogen efficiency is improved.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications, these improvements and modifications can also be made
Also it should be regarded as protection scope of the present invention.
Claims (3)
1. a kind of technology of preparing suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping, which is characterized in that packet
Include following steps:
(1) sodium molybdate, thiocarbamide and silica are dissolved in water；
(2) above-mentioned mixing liquid is transferred to reaction kettle, forms uniform solution by magnetic agitation processing, solution is in sealing
Hydro-thermal reaction is carried out in reaction kettle；
(3) sample after hydro-thermal is used into hydrofluoric acid and naoh treatment respectively, obtained product deionized water and dehydrated alcohol
Washing repeatedly, is dried overnight, obtains the molybdenum disulfide of different structure.
2. a kind of preparation suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping as described in claim 1
Technology, which is characterized in that sodium molybdate, thiocarbamide and silica molar ratios are 1:2:1~1:2:3 in the step (1).
3. a kind of preparation suitable for the spherical molybdenum disulfide material of cathode for hydrogen evolution catalyst-oxygen doping as claimed in claim 2
Technology, which is characterized in that magnetic agitation 30min after sample mixing in the step (2) is transferred to three 100mL water heating kettles, water
Thermal response temperature is respectively 160 DEG C, 180 DEG C and 200 DEG C, is heated to target temperature by room temperature, is maintained under target temperature for 24 hours,
Cooled to room temperature, obtaining black powder is target product.
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Cited By (5)
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| CN111099658A (en) * | 2020-01-07 | 2020-05-05 | 南开大学 | Preparation method of molybdenum disulfide nano material with different interlayer spacings |
| CN111151272A (en) * | 2020-01-14 | 2020-05-15 | 郑州大学 | Cobalt and iron doped molybdenum disulfide based material, preparation method thereof and application of cobalt and iron doped molybdenum disulfide based material in electrocatalytic hydrogen evolution |
| CN113019399A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Preparation method of supported two-dimensional sulfide |
| CN113713833A (en) * | 2021-09-15 | 2021-11-30 | 北京师范大学 | Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof |
| CN114345373A (en) * | 2020-09-27 | 2022-04-15 | 武汉理工大学 | Preparation method of oxygen-doped molybdenum disulfide nanosheet hydrogen evolution electrocatalyst rich in defects |
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| 李焕冉: ""二硫化钼及其复合材料的制备与电化学析氢性能研究"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113019399A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Preparation method of supported two-dimensional sulfide |
| CN111099658A (en) * | 2020-01-07 | 2020-05-05 | 南开大学 | Preparation method of molybdenum disulfide nano material with different interlayer spacings |
| CN111151272A (en) * | 2020-01-14 | 2020-05-15 | 郑州大学 | Cobalt and iron doped molybdenum disulfide based material, preparation method thereof and application of cobalt and iron doped molybdenum disulfide based material in electrocatalytic hydrogen evolution |
| CN114345373A (en) * | 2020-09-27 | 2022-04-15 | 武汉理工大学 | Preparation method of oxygen-doped molybdenum disulfide nanosheet hydrogen evolution electrocatalyst rich in defects |
| CN113713833A (en) * | 2021-09-15 | 2021-11-30 | 北京师范大学 | Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof |
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