CN116726970A - Sulfur-nitrogen doped MXene hydrogen storage material catalyst, hydrogen storage material containing catalyst and preparation method - Google Patents
Sulfur-nitrogen doped MXene hydrogen storage material catalyst, hydrogen storage material containing catalyst and preparation method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 148
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 148
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000011232 storage material Substances 0.000 title claims abstract description 64
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000003860 storage Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 32
- 238000000498 ball milling Methods 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000003795 desorption Methods 0.000 abstract description 29
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 17
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 229910012375 magnesium hydride Inorganic materials 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000011777 magnesium Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019080 Mg-H Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- -1 S C Ti Chemical class 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a sulfur-nitrogen doped MXene hydrogen storage material catalyst, a hydrogen storage material containing the catalyst and a preparation method thereof, and belongs to the technical field of hydrogen storage. The hydrogen storage material catalyst is sulfur-nitrogen doped Nb 2 CT x The hydrogen storage catalyst and magnesium hydride are ball milled to prepare the composite hydrogen storage material. The catalyst has excellent catalytic effect on the hydrogen absorption and desorption process of magnesium hydride, and the composite hydrogen storage material prepared by the catalyst and the magnesium hydride can realize 275 ℃ for 5 minutes of hydrogen desorption by 5.32wt.% in the hydrogen desorption dynamics test, and can realize 150 ℃ for 2 minutes of hydrogen desorption by 5.08wt.% in the hydrogen desorption dynamics test. In addition, the initial hydrogen release temperature of the composite hydrogen storage material is reduced compared with that of pure magnesium hydride105.48 ℃. The catalyst has the advantages of simple preparation method, easily available raw materials and suitability for expanded production.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage, and relates to a sulfur-nitrogen doped MXene hydrogen storage material catalyst, a hydrogen storage material containing the catalyst and a preparation method thereof.
Background
Hydrogen is considered an attractive energy carrier because it is a large-scale, sustainable and renewable energy source. However, practical application of hydrogen energy also requires breakthrough of technologies such as low-cost hydrogen production, fuel cells for converting hydrogen into electric energy with high efficiency, safe and compact hydrogen storage, and the like. The hydrogen density at normal temperature and pressure is only 0.089 kg.m -3 Therefore, safe, compact storage of hydrogen is critical for hydrogen energy applications.
Solid state hydrogen storage is a widely studied and developed process because it is safer and more compact than other processes such as storage in high pressure gas cylinders or insulated tanks. Currently, solid state hydrogen storage has multiple branches such as metal hydrides, complex metal hydrides, amino compounds, novel carbon-based adsorbents, and the like. The magnesium-based hydrogen storage material is used as a metal-based hydrogen storage material with great prospect, the theoretical hydrogen storage amount can reach 7.6wt.%, which is higher than the light vehicle-mounted hydrogen source index (5.5 wt.%) proposed by the U.S. department of energy (DOE), and the hydrogen release platform is slow, good in reversibility, light in weight, rich in resources and low in price. However, due to the defects of poor hydrogen absorption and desorption kinetics, high hydrogen desorption temperature and the like, the practical application is greatly limited. Therefore, researchers adopt methods of adding catalysts, surface treatment modification, nanocrystallization, preparing composite hydrogen storage materials and the like to improve the performance of the magnesium-based hydrogen storage materials to a certain extent, but the problem that the hydrogen desorption temperature is higher than the practical application temperature and the kinetics of hydrogen desorption and desorption is poor still exists.
In recent yearsTwo-dimensional layered mxnes, due to their layered structure, relatively large surface area, remarkable chemical durability, and high electrical conductivity, have shown great potential in many fields of catalysis, sensors, conversion, energy storage, gas adsorption, and electronics. MXnes has the general formula M n+1 X n T x Wherein M is a transition metal, e.g. S C Ti, zr, hf, V, nb, ta, cr, mo, etc., X is carbon, nitrogen or carbonium, n=1, 2, 3, T represents a surface group, e.g. O 2- ，OH - Or F - Etc. It has been studied as a catalyst for use in modifying the properties of hydrogen storage materials to further enhance the catalytic properties of the MXees materials by modifying the MXees materials themselves, but materials based on MXees (e.g., ti 2 C) Despite its excellent capacity (up to 8.5wt.% based on density functional theory), its slow hydrogen absorption and desorption kinetics still greatly restrict its hydrogen storage applications, so their potential for hydrogen storage applications still needs to be exploited further.
Disclosure of Invention
It is therefore an object of the present invention to provide sulfur-nitrogen doped Nb 2 CT x A hydrogen storage material catalyst; second object is to provide sulfur-nitrogen doped Nb 2 CT x A preparation method of a hydrogen storage material catalyst; a third object is to provide a hydrogen storage material containing the catalyst; the fourth object is to provide a method for producing a hydrogen storage material containing the catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. sulfur-nitrogen doped MXene hydrogen storage material catalyst, wherein the hydrogen storage material catalyst is sulfur-nitrogen doped Nb 2 CT x 。
Preferably, the nitrogen doping amount is 5 to 7wt.% of the total mass of the hydrogen storage catalyst, and the sulfur doping amount is 0.5 to 1.2wt.% of the total mass of the hydrogen storage catalyst.
2. A preparation method of a sulfur-nitrogen doped MXene hydrogen storage material catalyst, which comprises the following steps:
(1) Dissolving LiF in concentrated hydrochloric acid to obtain etching solution, and then Nb 2 AlC is placed in the etching liquid, and is hydrothermalCentrifugal washing after reaction, and vacuum drying to obtain Nb 2 CT x ；
(2) Dissolving thiourea in ethanol, and then adding Nb prepared in the step (1) 2 CT x Mixing, vacuum drying to obtain Nb 2 CT x And (3) calcining the mixture with thiourea in a protective atmosphere in a tube furnace.
Preferably, in step (1), the LiF, nb 2 The mass volume ratio of AlC to concentrated hydrochloric acid is as follows: 1-1.4:0.8-1.2:10-30, g: mL; the hydrothermal reaction specifically comprises the following steps: reacting for 12-36 h at 100-150 ℃ in a reaction kettle; the centrifugal washing is specifically as follows: centrifugal washing with deionized water at 3000-8000 rpm until the mixed system is neutral; the vacuum drying is specifically as follows: vacuum drying at 60-100 deg.c for 8-16 hr.
Preferably, in step (2), the Nb 2 CT x The mass volume ratio of thiourea to ethanol is as follows: 10:10-40:1-2, mg:mL; the vacuum drying is specifically as follows: vacuum drying at 60-100 deg.c for 8-16 hr; the calcination is specifically as follows: calcining for 1-4 h in the argon atmosphere in a tube furnace at 200-600 ℃.
3. MgH (MgH) 2 Sulfur nitrogen doped Nb 2 CT x The composite hydrogen storage material comprises the following components in percentage by mass: sulfur nitrogen doped Nb 2 CT x 1wt.％～15wt.％，MgH 2 85wt.％～99wt.％。
Preferably, the composite hydrogen storage material comprises, in mass percent: sulfur nitrogen doped Nb 2 CT x 3wt.％～10wt.％，MgH 2 90wt.％～97wt.％。
Preferably, the composite hydrogen storage material comprises, in mass percent: sulfur nitrogen doped Nb 2 CT x 4wt.％～6wt.％，MgH 2 94wt.％～96wt.％。
4. MgH (MgH) 2 Sulfur nitrogen doped Nb 2 CT x The preparation method of the composite hydrogen storage material comprises the following steps: mgH is processed 2 And sulfur nitrogen doped Nb 2 CT x In the argon atmosphere, according to the ball-to-material ratioAnd (2) carrying out intermittent ball milling for 8-24 h at a rotating speed of 200-800 rpm in a positive and reverse rotation mode in a ratio of 10-60:1.
Preferably, the positive and negative rotation batch ball milling specifically comprises: and suspending for 5-30 min after each ball milling for 5-20 min.
The invention has the beneficial effects that: the invention provides sulfur nitrogen doped Nb 2 CT x The catalyst is two-dimensional particles with a layered structure, the particle length is between 5 and 30 mu M, the nitrogen doping amount is between 5 and 7wt percent, the sulfur doping amount is between 0.5 and 1.2wt percent, and the catalyst has excellent catalytic effect on the hydrogen absorption and desorption process of magnesium hydride due to M 2 Nb of X structure 2 CT x The MXene has a small number of structural layers, so that the MXene has a high specific surface area and provides more catalytic active sites, thereby being beneficial to the smooth proceeding of the hydrogen absorption and desorption reactions. In addition, nb and NbO are generated in situ 2 The substance can lengthen Mg-H bond and promote the rapid release of hydrogen. The doping of S element mainly expands Nb 2 CT x The effect of interlayer spacing, too much doping will destroy the layered structure to the detriment of electron transport and transfer, nb at a doping level of 0.5-1.2 wt.% 2 CT x The layered structure can be maintained; the doping of N element mainly plays a role in improving Nb 2 CT x The conductivity is achieved, and the doping amount of the N element is determined by the S element because thiourea is used as an S source and an N source at the same time. Doping of N, S element further enhances Nb 2 CT x Surface-present polyvalent forms of Nb (NbO) 2 Nb-C, nb) promote Mg 2+ The ability of electron transfer with H-to effectively accelerate dissociation of hydrogen molecules and breaking of magnesium hydrogen bonds, and has better catalytic effect on magnesium hydride. The particle size of the composite hydrogen storage material prepared by the catalyst and magnesium hydride is between 1 and 15 mu m, and sulfur and nitrogen are doped with Nb 2 CT x Uniformly distributed in MgH 2 The surface of the particles is the subsequent MgH 2 The hydrogen absorption and desorption process of the particles provides uniformly distributed active catalytic sites, so that MgH 2 Can rapidly and efficiently release and absorb hydrogen through the sites, thus MgH during the hydrogen release kinetics test 2 Can realize the hydrogen release within 5 minutes at 275 DEG C32wt.% hydrogen uptake of 5.08wt.% can be achieved at 150 ℃ in 2 minutes at the time of the hydrogen uptake kinetics test. In addition, compared with pure magnesium hydride, the initial hydrogen release temperature of the composite hydrogen storage material is reduced by 105.48 ℃, and the composite hydrogen storage material is visible to be doped with Nb by sulfur and nitrogen 2 CT x Has excellent catalytic effect on the hydrogen absorption and desorption process of magnesium hydride. The catalyst has the advantages of simple preparation method, easily available raw materials and suitability for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is Nb prepared in example 1 2 CT x SEM images of (a);
FIG. 2 shows sulfur-nitrogen doped Nb prepared in example 1 2 CT x SEM images of (a);
FIG. 3 is MgH prepared in example 5 2 +5wt.％Nb 2 CT x SEM image of SN composite hydrogen storage material;
FIG. 4 is MgH prepared in examples 4-6 2 +y wt.％Nb 2 CT x SN (y=3, 5, 10) composite hydrogen storage material and ball-milled MgH prepared in comparative example 2 TPD curve of (2);
FIG. 5 is MgH prepared in example 5 2 +5wt.％Nb 2 CT x Preparation of ball-milled MgH by SN composite Hydrogen storage Material and comparative example 2 275 ℃ hydrogen evolution curve;
FIG. 6 is MgH prepared in example 5 2 +5wt.％Nb 2 CT x Preparation of ball-milled MgH by SN composite Hydrogen storage Material and comparative example 2 Hydrogen absorption curve at 150 ℃;
FIG. 7 is MgH prepared in example 6 2 +5wt.％Nb 2 CT x Nb 3d XPS diagram of the SN composite hydrogen storage material in different states.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
Preparation of sulfur-nitrogen doped Nb 2 CT x
(1) 1g LiF is dissolved in 20mL of concentrated hydrochloric acid with the concentration of 12mol/L to obtain etching solution, and then 1g Nb is added 2 AlC is placed in the etching solution, reacted for 24 hours at 125 ℃ in a 100mL high-pressure reaction kettle, centrifugally washed by deionized water at a rotation speed of 5000rpm until a mixed system is neutral, and finally vacuum dried for 12 hours at 60 ℃ to prepare Nb 2 CT x ；
(2) Dissolving 1200mg of thiourea in 50mL of ethanol, stirring in a water bath at 60 ℃ until the thiourea is dissolved, and then adding 300mg of Nb prepared in the step (1) 2 CT x Stirring for 1h, mixing, and vacuum drying at 80deg.C for 12h to obtain Nb 2 CT x Calcining the mixture with thiourea in a tubular furnace under argon atmosphere at 400 ℃ for 3 hours to obtain sulfur-nitrogen doped Nb 2 CT x Wherein the S doping amount is 0.69wt.%, and the N doping amount is 6.39wt.%.
Respectively pairing the prepared Nb by using a scanning electron microscope 2 CT x And sulfur nitrogen doped Nb 2 CT x Characterization is performed, FIG. 1 is Nb 2 CT x From SEM image of (C), it can be seen that Nb 2 CT x The typical two-dimensional lamellar structure particles are between 5 and 30 μm in length. FIG. 2 is a sulfur nitrogen doped Nb 2 CT x From the SEM image of (C), nb after sulfur-nitrogen doping 2 CT x The two-dimensional layered structure is maintained, and the catalyst has a high specific surface area, thereby providing more catalytic active sites. Table 1 shows a sweepSulfur-nitrogen doped Nb under electron microscope statistics 2 CT x The mass ratio of each element in the composition.
TABLE 1 Sulfur nitrogen doped Nb in example 1 2 CT x Mass ratio of each element in (C)
| C | N | S | Nb |
| 25.72wt.％ | 6.39wt.％ | 0.69wt.％ | 67.2wt.％ |
Example 2
Preparation of sulfur-nitrogen doped Nb 2 CT x
(1) 1g LiF is dissolved in 30mL of concentrated hydrochloric acid with the concentration of 12mol/L to obtain etching solution, and then 1.2g Nb is added 2 AlC is placed in the etching solution, reacted for 36 hours at 100 ℃ in a 100mL high-pressure reaction kettle, centrifugally washed by deionized water at a rotating speed of 3000rpm until a mixed system is neutral, and finally vacuum dried for 16 hours at 80 ℃ to prepare Nb 2 CT x ；
(2) Dissolving 300mg of thiourea in 30mL of ethanol, stirring in a water bath at 60 ℃ until the thiourea is dissolved, and then adding 300mg of Nb prepared in the step (1) 2 CT x Stirring for 1h, mixing, and vacuum drying at 60deg.C for 16h to obtain Nb 2 CT x Calcining the mixture with thiourea in a tube furnace under argon atmosphere at 600 ℃ for 1h to obtain sulfur-nitrogen doped Nb 2 CT x Wherein the S doping amount is 0.58wt.%, and the N doping amount is 5.64wt.%.
Example 3
Preparation of sulfur-nitrogen doped Nb 2 CT x
(1) 1.4g LiF is dissolved in 10mL of concentrated hydrochloric acid with the concentration of 12mol/L to obtain etching solution, and then 0.8g Nb is added 2 AlC is placed in the etching solution, reacted for 12 hours at 150 ℃ in a 100mL high-pressure reaction kettle, centrifugally washed by deionized water at 8000rpm until a mixed system is neutral, and finally vacuum dried for 8 hours at 100 ℃ to prepare Nb 2 CT x ；
(2) Dissolving 750mg of thiourea in 60mL of ethanol, stirring in a water bath at 60 ℃ until the thiourea is dissolved, and then adding 300mg of Nb prepared in the step (1) 2 CT x Stirring for 1h, mixing, and vacuum drying at 100deg.C for 8h to obtain Nb 2 CT x Calcining the mixture with thiourea in a tubular furnace under argon atmosphere at 200 ℃ for 4 hours to obtain sulfur-nitrogen doped Nb 2 CT x Wherein the S doping amount is 0.76wt.%, and the N doping amount is 6.67wt.%.
Example 4
Preparation of MgH 2 -3wt.% sulfur nitrogen doped Nb 2 CT x Composite hydrogen storage material (MgH) 2 +3wt.％Nb 2 CT x SN composite hydrogen storage material
MgH was performed in a vacuum glove box 2 And sulfur nitrogen doped Nb prepared in example 1 2 CT x Weighing and mixing according to a mass ratio of 97:3, wherein the total mass is 1g, pouring the mixture into a ball milling tank, wherein the ball material ratio of the mixture to a 304 stainless steel ball is 20:1, filling 0.2Mpa argon into the ball milling tank, mounting the ball milling tank on a high-energy ball mill, and carrying out forward running at a rotating speed of 400rpm for 10min and intermittent 10min, and carrying out reverse running for 10min and intermittent 10min, so that the ball milling is carried out for 10 h.
Example 5
Preparation of MgH 2 -5wt.% sulfur nitrogen doped Nb 2 CT x Composite hydrogen storage material (MgH) 2 +5wt.％Nb 2 CT x SN composite hydrogen storage material
The difference from example 4 is that: will beMgH 2 And sulfur nitrogen doped Nb prepared in example 1 2 CT x Weighing and mixing according to a mass ratio of 95:5, wherein the total mass is 1g, and preparing MgH 2 +5wt.％Nb 2 CT x SN composite hydrogen storage material.
MgH prepared in example 5 was subjected to scanning electron microscopy 2 +5wt.％Nb 2 CT x Characterization of the composite hydrogen storage material of SN, FIG. 3 is MgH 2 +5wt.％Nb 2 CT x SEM image of SN composite hydrogen storage material shows that the average particle size is 1-15 μm, and the average particle size is greatly reduced compared with the original magnesium hydride (30-50 μm). The reduction of the particle size is beneficial to improving the hydrogen absorption and desorption kinetics of the magnesium hydride, because when the particle size of the magnesium hydride is greatly reduced, the specific surface area is also increased, and the increase of the specific surface area can improve the reactivity of the particles, so that the release and the absorption and desorption of hydrogen are easier; in addition, the decrease in particle size shortens the diffusion path of hydrogen atoms from the inside to the surface or from the surface to the inside of the particles, thereby accelerating the release and desorption of hydrogen gas.
Example 6
Preparation of MgH 2 -10wt.% sulfur nitrogen doped Nb 2 CT x Composite hydrogen storage material (MgH) 2 +10wt.％Nb 2 CT x SN composite hydrogen storage material
The difference from example 4 is that: mgH is processed 2 And sulfur nitrogen doped Nb prepared in example 1 2 CT x Weighing and mixing according to a mass ratio of 90:10, wherein the total mass is 1g, and preparing MgH 2 +10wt.％Nb 2 CT x SN composite hydrogen storage material.
Comparative examples
Preparation of ball-milled MgH 2
1g of MgH was taken up in a vacuum glove box 2 Pouring into ball mill tank, mgH 2 Charging 0.2Mpa argon gas into a ball milling tank and mounting the ball milling tank on a high-energy ball mill, forward running at 400rpm for 10min and intermittent for 10min, and reverse running for 10min and intermittent for 10min, wherein the ball milling time is 10 h.
200mg of the preparations in examples 4 to 6 were weighed out respectively in a glove boxIs a composite hydrogen storage material (MgH) 2 +y wt.％Nb 2 CT x SN (y=3, 5, 10)), and ball-milled MgH prepared in comparative example 2 Respectively placing the sample tubes into a special sample tube of a high-pressure gas adsorption and desorption instrument, and then respectively loading the sample tubes into the instrument for TPD test. As shown in FIG. 4, it can be seen that Nb is doped with sulfur and nitrogen 2 CT x Increase of catalyst addition amount, mgH 2 The initial hydrogen release temperature of (a) is reduced to different degrees. The composite hydrogen storage materials (MgH) prepared in examples 4 to 6 2 +y wt.％Nb 2 CT x Starting hydrogen desorption temperatures of/SN (y=3, 5, 10)) were 248.05 ℃, 212.58 ℃ and 209.91 ℃, respectively, compared to ball-milled MgH prepared in comparative example 2 70.01 ℃, 105.48 ℃ and 108.15 ℃ are respectively reduced. Wherein MgH 2 +5wt.％Nb 2 CT x The SN composite hydrogen storage material shows the optimal catalytic effect: on the one hand, compared with MgH 2 +3wt.％Nb 2 CT x SN composite hydrogen storage material with initial hydrogen desorption temperature reduced by 35.47 ℃; on the other hand, compared with MgH 2 +10wt.％Nb 2 CT x Although the initial hydrogen release temperature of the SN composite hydrogen storage material is not quite different (2.67 ℃), the hydrogen release amount of the SN composite hydrogen storage material is more, and the hydrogen release rate is faster.
Respectively for MgH prepared in example 5 2 +5wt.％Nb 2 CT x Preparation of ball-milled MgH by SN composite Hydrogen storage Material and comparative example 2 The hydrogen desorption performance test was performed at 275℃and the hydrogen absorption performance test was performed at 150℃and the results are shown in FIG. 5 and FIG. 6 and Table 2. Wherein, FIG. 5 is a graph showing the hydrogen release at 275 ℃, FIG. 6 is a graph showing the hydrogen release at 150 ℃, and FIG. 5 shows the ball milling MgH 2 Only about 0.03wt.% hydrogen, mgH, can be evolved within 5 minutes 2 +5wt.％Nb 2 CT x 5.31wt.% of hydrogen can be released within 5 minutes of the SN composite hydrogen storage material, which is ball milling MgH 2 Nearly 177 times the amount of hydrogen released, indicating sulfur nitrogen doped Nb 2 CT x The addition of the hydrogen storage catalyst can greatly improve the hydrogen release rate of the magnesium hydride. As can be seen from FIG. 6, mgH after hydrogen desorption 2 +5wt.％Nb 2 CT x SN composite hydrogen storage materialAbout 5.08wt.% of hydrogen is absorbed within 120s at 150 ℃ while MgH is ball milled 2 Only 3.51wt.% of hydrogen can be absorbed under the same conditions, and only 4.15wt.% of hydrogen can be absorbed for a period of 20 minutes. The above results indicate that sulfur nitrogen doped Nb 2 CT x The addition of the catalyst can promote dissociation and recombination of hydrogen molecules, so that MgH 2 Has rapid hydrogen absorption and desorption rate.
TABLE 2MgH 2 +5wt.％Nb 2 CT x SN composite hydrogen storage material and ball-milling MgH 2 Hydrogen absorption and desorption performance test data
For MgH prepared in example 5 2 +5wt.％Nb 2 CT x As shown in FIG. 7, the results of the energy spectrum analysis of Nb 3d of the SN composite hydrogen storage material in different states show that the phase composition of the ball milling state, the hydrogen releasing state, the hydrogen absorbing state and the cyclic hydrogen releasing state is Nb, nb-C and Nb oxide, wherein the ball milling state is Nb 2 O 5 While the other three states are NbO 2 Indicating that after hydrogen release, nb in high valence state 2 O 5 NbO reduced to a lower valence state 2 And the hydrogen absorption and desorption cycle thereafter remains unchanged. In general, the phase composition during the hydrogen absorption and desorption cycle is Nb, nb-C and NbO 2 Wherein the presence of Nb-C indicates sulfur-nitrogen doped Nb 2 CT x Catalyst in MgH 2 The stable two-dimensional layered structure is maintained in the hydrogen absorption and desorption process, and is MgH 2 A large number of active catalytic sites are provided, which is beneficial to the hydrogen absorption and desorption reaction; nb and NbO simultaneously generated in situ 2 The substance can lengthen Mg-H bond and promote the rapid release of hydrogen; in addition, doping of N, S element can further enhance Nb 2 CT x Surface-present polyvalent forms of Nb (NbO) 2 Nb-C, nb) promote Mg 2+ And H is - The ability to transfer electrons between them, thereby effectively accelerating dissociation of hydrogen molecules and cleavage of magnesium hydrogen bonds.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. A sulfur-nitrogen doped MXene hydrogen storage material catalyst is characterized in that the hydrogen storage material catalyst is sulfur-nitrogen doped Nb 2 CT x 。
2. A sulfur nitrogen doped MXene hydrogen storage material catalyst of claim 1, wherein the nitrogen doping amount is 5 to 7wt.% of the total mass of the hydrogen storage catalyst and the sulfur doping amount is 0.5 to 1.2wt.% of the total mass of the hydrogen storage catalyst.
3. The preparation method of the sulfur-nitrogen doped MXene hydrogen storage material catalyst is characterized by comprising the following steps of:
(1) Dissolving LiF in concentrated hydrochloric acid to obtain etching solution, and then Nb 2 AlC is placed in the etching liquid, centrifugally washed after hydrothermal reaction, and finally vacuum dried to obtain Nb 2 CT x ；
(2) Dissolving thiourea in ethanol, and then adding Nb prepared in the step (1) 2 CT x Mixing, vacuum drying to obtain Nb 2 CT x And (3) calcining the mixture with thiourea in a protective atmosphere in a tube furnace.
4. The method of claim 3, wherein in step (1), the LiF and Nb are mixed with each other 2 The mass volume ratio of AlC to concentrated hydrochloric acid is as follows: 1-1.4:0.8-1.2:10-30, g: mL; the hydrothermal reaction specifically comprises the following steps: reacting for 12-36 h at 100-150 ℃ in a reaction kettle; the centrifugal washing is specifically as follows: centrifugal washing with deionized water at 3000-8000 rpm until the mixed system is neutral; the vacuum drying is specifically as follows: at 60-100 DEG CVacuum drying for 8-16 h.
5. The method of claim 3, wherein in step (2), the Nb is as follows 2 CT x The mass volume ratio of thiourea to ethanol is as follows: 10:10-40:1-2, mg:mL; the vacuum drying is specifically as follows: vacuum drying at 60-100 deg.c for 8-16 hr; the calcination is specifically as follows: calcining for 1-4 h in the argon atmosphere in a tube furnace at 200-600 ℃.
6. MgH (MgH) 2 Sulfur nitrogen doped Nb 2 CT x The composite hydrogen storage material is characterized by comprising the following components in percentage by mass: sulfur nitrogen doped Nb 2 CT x 1wt.％～15wt.％，MgH 2 85wt.％～99wt.％。
7. The MgH of claim 6 2 Sulfur nitrogen doped Nb 2 CT x The composite hydrogen storage material is characterized by comprising the following components in percentage by mass: sulfur nitrogen doped Nb 2 CT x 3wt.％～10wt.％，MgH 2 90wt.％～97wt.％。
8. The MgH of claim 6 2 Sulfur nitrogen doped Nb 2 CT x The composite hydrogen storage material is characterized by comprising the following components in percentage by mass: sulfur nitrogen doped Nb 2 CT x 4wt.％～6wt.％，MgH 2 94wt.％～96wt.％。
9. MgH (MgH) 2 Sulfur nitrogen doped Nb 2 CT x The preparation method of the composite hydrogen storage material is characterized by comprising the following steps: mgH is processed 2 And sulfur nitrogen doped Nb 2 CT x Under argon atmosphere, the ball-milling is carried out for 8 to 24 hours in a forward and reverse rotation way at the rotating speed of 200 to 800rpm according to the ball-material ratio of 10 to 60:1.
10. The method for preparing the ball mill according to claim 9, wherein the counter-rotating batch ball milling is specifically as follows: and suspending for 5-30 min after each ball milling for 5-20 min.
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