CN113546656A - A kind of MXene supported Ni@C nanoparticle hydrogen storage catalyst and preparation method thereof - Google Patents
A kind of MXene supported Ni@C nanoparticle hydrogen storage catalyst and preparation method thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 160
- 239000001257 hydrogen Substances 0.000 title claims abstract description 160
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000003860 storage Methods 0.000 title claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- -1 lithium aluminum hydride Chemical compound 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 37
- 239000011232 storage material Substances 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 30
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 12
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 238000002525 ultrasonication Methods 0.000 claims 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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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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Abstract
本发明公开了一种MXene负载Ni@C纳米颗粒储氢催化剂，以Ni‑MOFs为基础碳化制备Ni@C后，再负载到MXene上制得，简称为Ni@C‑MXene；所述Ni‑MOFs由六水合硝酸镍、对苯二甲酸水热反应制得；所述MXene为Ti3C2，由Ti3AlC2和浓盐酸加氟化锂反应制得。其制备方法包括以下步骤：1）Ni@C的制备；2）MXene的制备；3）Ni@C‑MXene的制备。作为储氢材料催化剂的应用，将MXene负载Ni@C纳米颗粒储氢催化剂与和氢化铝锂满足一定的质量之比，在一定条件下进行球磨，即可得到Ni@C‑MXene掺杂氢化铝锂储氢材料；当MXene负载Ni@C纳米颗粒储氢催化剂掺杂量为7 wt%时，体系放氢温度降至56.1℃，放氢量达到6.52 wt%。本发明的储氢材料具有优异的储放氢性能，制得的MXene负载MOF衍生Ni纳米颗粒能显著改善氢化铝锂的放氢性能，使得其在较低温度下表现出优异的放氢性能。
The invention discloses an MXene-supported Ni@C nanoparticle hydrogen storage catalyst. Ni@C is prepared by carbonization on the basis of Ni-MOFs, and then loaded onto MXene to prepare, which is referred to as Ni@C-MXene for short; MOFs are prepared by the hydrothermal reaction of nickel nitrate hexahydrate and terephthalic acid; the MXene is Ti 3 C 2 and is prepared by the reaction of Ti 3 AlC 2 and concentrated hydrochloric acid plus lithium fluoride. The preparation method includes the following steps: 1) preparation of Ni@C; 2) preparation of MXene; 3) preparation of Ni@C-MXene. As the application of hydrogen storage material catalyst, Ni@C-MXene doped aluminum hydride can be obtained by ball milling MXene-supported Ni@C nanoparticle hydrogen storage catalyst with lithium aluminum hydride in a certain mass ratio under certain conditions. Lithium hydrogen storage material; when the doping amount of MXene-supported Ni@C nanoparticle hydrogen storage catalyst is 7 wt%, the hydrogen desorption temperature of the system drops to 56.1 °C, and the hydrogen desorption amount reaches 6.52 wt%. The hydrogen storage material of the invention has excellent hydrogen storage and desorption performance, and the prepared MXene-loaded MOF-derived Ni nanoparticles can significantly improve the hydrogen desorption performance of lithium aluminum hydride, so that it exhibits excellent hydrogen desorption performance at lower temperatures.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials of new energy materials, in particular to an MXene loaded Ni @ C nanoparticle hydrogen storage catalyst and a preparation method thereof.
Background
The rapid growth of the population and the development of technology have increased global energy demand. According to the energy information and regulatory agency data in the united states, global energy demand is expected to increase by 28% between 2015 and 2040 years. Global energy demand is expected to peak in 2035 years, and the global economy will experience a long-term shore after 2040 years. With the use of fossil fuels and excessive emission of carbon dioxide, people are increasingly concerned about the risk of resource exhaustion and environmental problems in the future; therefore, the development of exploring clean energy is of great importance. Furthermore, it is estimated that world fossil fuel production will soon reach a peak, and then production begins to decline. Energy systems must be more reliable, safe, low cost, clean and environmentally friendly to ensure the global environment has the ability to cope with the future. Compared with fossil fuels, renewable energy technology has sustainable development on the environment. In response to these problems, great efforts have been made to search for renewable energy sources such as solar energy, hydrogen energy, geothermal energy, wind energy, and nuclear energy. Of the above renewable energy sources, hydrogen energy is considered the most promising alternative as a "hydrogen energy economy" to overcome the ever-increasing energy demand worldwide. Hydrogen acts as a carrier for new energy implementations, ultimately allowing humans to achieve the goal of "low" or "zero" carbon in the future. With the development of hydrogen energy in recent years, particularly in transportation, it has been applied to a plurality of countries. Solid-state hydrogen storage is consistently considered the most promising form of hydrogen storage due to its advantages of high weight, high bulk density, high safety, and low cost, as compared to storage in both gas and liquid forms.
Lithium aluminum hydride (LiAlH)4) Due to its existenceHigher hydrogen content (10.5 wt%, 0.92 g/cm)3) But is considered to be a potential solid-state hydrogen storage material. However, its higher hydrogen evolution reaction temperature, slow dehydrogenation kinetics and irreversibility under mild conditions have hindered its wider application. Several strategies have been implemented in order to lower the reaction temperature of the hydrogen evolution reaction and improve the dehydrogenation kinetics of complex hydrides, such as reducing the particle size by mechanical milling, producing reactive hydride composites (mixed with other hydride materials), doping catalysts or additives, and hydrolytic regeneration processes. It can be seen from the literature that doping the catalyst or additive by using a ball milling process is the most effective method for modifying the hydrogen storage material. Such as transition metals (Ti, Fe and Ni), metal oxides (TiO)2、Fe2O3NiO and LaFeO3) Metal halides (ScCl)3、FeCl2、NiCl2And TiF3) Carbon-based materials (TiC, Ni/C, MOFs and MWCNTs). Among them, since Ni and Ti have good dispersibility and catalytic activity, in LiBH4、LiAlH4、NaAlH4And MgH2The catalyst has excellent catalytic activity in both isocomplex hydride and alloy hydride.
In research, some transition metal groups have better catalytic effect on lithium aluminum hydride. Prior document 1[ Kojima Y, Kawai Y, Matsumoto M, et al. Hydrogen release of catalyzed lithium aluminum hydride by a mechanochemical reaction [ J]. Journal of Alloys and Compounds, 2008, 462(1-2):275-278.]Y Kojima et al indicated that a large amount of transition metal chloride was added to LiAlH by ball milling chlorides of four metals, Ti, Zr, V, Ni4As a catalyst, which greatly improves the hydrogen evolution kinetics and reduces the LiAlH4Effective hydrogen desorption temperature. However, metal chlorides are not ideal catalysts as they will react with LiAlH4The local reaction forms nano-sized metal salts and free metallic elements or intermetallic compounds. Since hydrogen atoms tend to form covalent bonds with transition metal elements, Ni-based catalysts have been demonstrated in LiAlH4Has potential in the system due to the optimized morphology of Ni or the interaction effect by introducing another phaseThe catalyst can effectively change the catalytic activity by controlling the size, shape, dispersion and other shapes of the catalyst, and is also suitable for the LiAlH doped with a Ni system4。
Meanwhile, researches show that the hydrogen release performance of lithium aluminum hydride can be greatly improved by directly adding the nano-sized element metal, and the nano metal powder is particularly prominent. Prior document 2[ Varin R A, Zbroniec L, Czujko T, et al, The effects of nano additive on The de-composition of complex metal hydride LiAlH4(lithium alanate)[J]. International Journal of Hydrogen Energy, 2011, 36(1):1167-1176.]RA Varin et al used 97% pure Ni nanopowder and LiAlH4Direct ball milling, LiAlH by ball milling4The +5 wt% n-Ni material is hydrogen-released at 120 ℃ for about 4.8 wt% in 33 minutes, and hydrogen-released at 140 ℃ for about 7 wt% in 116-166 minutes. In the ball milling process, the energy and the duration time generated by ball milling can not ensure that the nano Ni powder is fully doped into LiAlH4The authors show that if the milling time is extended beyond 1 hour, the catalytic significance is not evident from a technical point of view, since it cannot be speculated whether an excessively long milling time would ultimately lead to LiAlH4Decomposition of (3). In order to prevent the hydrogen storage material from directly discharging hydrogen due to overheating during ball milling, the ball milling time and the rotation speed should be strictly controlled. Therefore, it is necessary to find a support material for stabilizing Ni and LiAlH during ball milling4The change of the interphase reduces the agglomeration degree and improves the catalytic activity.
Due to Ni and LiAlH4Load in LiAlH which is difficult to stabilize in the ball milling process4In the above, it is necessary to find a nano-scaffold to stabilize the structure of Ni. However, for many carbon materials, not every carbon material may be catalytically active towards lithium aluminum hydride. Prior document 3[ Ismail M, ZHao Y, Yu X B, et al, Improved hydrogen storage property of LiAlH4 by milling with carbon based additives[J]. electroactive materials society, 2013.]M Ismail et al have studied the doping of carbon black, nano-carbon powder, graphite, graphene, single-walled carbon nanotubes and multi-walled carbon nanotubes to LiAlH, respectively4The impact of performance. Found not to beCarbon material doped with same kind of LiAlH4The hydrogen release performance is improved to a certain extent, but the effect is limited. Among them, single-walled carbon nanotubes (SWCNTs) exhibit the best performance improvement. LiAlH4The first two steps of hydrogen evolution temperature of-5 wt% SWCNT were reduced to 98 ℃ and 145 ℃ respectively, and the activation energies were 79 kJ/mol and 89 kJ/mol. Although the doping catalytic effect of the pure carbon material is not obvious, the carbon material has the characteristics of light weight, high dispersity, high specific surface area, high thermal conductivity and the like, so that the carbon material has certain research value in the field of catalysis. By compounding the metal and the carbon material, various forms such as surface loading, carbon coating and the like are formed, and the material with certain catalytic activity and good dispersibility can be obtained. The research on the aspect has been reported for a long time, and is to improve LiAlH4An important method of hydrogen evolution performance.
It is attractive that LiAlH can be further enhanced by using carbon materials as co-dopants4Hydrogen storage performance of (1). Prior document 4[ Tan C Y, Tsai W T. Effects of Ni and Co-purified MWCNTs addition on the purification catalyst and stability of LiAlH4[J]. International Journal of Hydrogen Energy, 2015, 40(40):14064-14071.]Tan C Y et al prepared Co-supporting multi-walled carbon nanotubes (MWCNTs) by chemical reduction, and found that LiAlH was converted to LiAlH when 20 wt% MWCNTs/0.4 Co was added4The hydrogen release temperature is about 103 ℃ ahead of time; when 20 wt% MWCNT/0.4Ni was added, the hydrogen evolution temperature was lowered to 77 ℃. When Ni and Co are loaded on MWCNT, the catalytic activity of Ni is greatly enhanced, but the hydrogen release amount is reduced due to the large addition amount of catalyst, so that the Ni loaded MWCNT is used for LiAlH4The catalytic effect of (b) is not ideal. Although the equipment for preparing the material by the chemical reduction method is simple and low in cost, the chemical reaction degree is difficult to control, and a large amount of impurities exist in the case of incomplete reaction. Therefore, for the nickel-based catalyst, there is an urgent need to find a catalytic phase having a high catalytic activity as well as a dispersant having a large surface area like a carbon material. However, the improvement of the catalytic activity of the nickel-based catalyst is limited by the problems of the carbon material having a relatively single elemental composition and limited catalytic activity, compared to metals and compounds thereof.
The synthesis of the load matrix with stability, high dispersibility and high specific surface area is an effective way for improving the hydrogen releasing performance of the lithium aluminum hydride. Prior document 5[ Zang L, Liu S, Guo H, et al, In Situ Synthesis of 3D Flower-Like Nanocrystalline Ni/C and its Effect on Hydrogen Storage Properties of LiAlH4[J]. Chemistry – An Asian Journal, 2017.]Zang L et al prepared 3D flower-like nanocrystalline Ni/C material and found LiAlH with 10 wt% Ni/C addition4The sample began to bleed hydrogen at approximately 50 c, with a hydrogen bleed of 6.2 wt% and at 100 c, about 2.90 wt% hydrogen evolved over 60 minutes. Therefore, carbon is used as a material with strong plasticity and high electronegativity and can weaken Li+And (AlH4)-The charge transfer between the two is carried out, so that the bond energy of Al-H is reduced, and the release of hydrogen is facilitated.
MOFs is a new porous solid material, has the advantages of flexible tailorability, excellent designability, unique pore channel structure and the like, and is easy to absorb water and LiAlH due to the fact that oxygen-containing functional groups such as amino and carboxyl are rich in the pore channels when Ni-MOFs are not carbonized4The reaction consumes part of hydrogen to make the structure unstable during ball milling, so that organic ligands are removed or converted into carbon by calcination, the MOFs can be converted into high-activity metal compounds or metal-carbon composites after thermal decomposition, and the MOFs after thermal decomposition can keep consistent with the initial form thereof, form stably maintained porosity and rigidity thereof, and orderly arrangement of metals, so that relatively stable form can be maintained during ball milling.
Studies have shown that although Ni exhibits excellent catalytic activity for lithium aluminum hydride, additional phases such as transition metals and oxides and fluorides thereof have relatively few studies on improving the overall catalytic activity of the nickel-based catalyst. Prior document 6[ Song Y, Dai J H, Liang X M, et al. infiluence of pages Ti and Ni on binding interactions and hydrolysis properties of lithium aluminate [ J]. Physical Chemistry Chemical Physics Pccp, 2010, 12(36):10942-10949.]Y, Song et al analyzed by first principles computational theory that Ti and Ni are more likely to occupy relatively small energy interstitial sites, 0.591 and 0.144 eV, respectively. [ AlH4]Radical geometry and stability in doped LiAlH4The bonding interaction between Al and H atoms is also significantly reduced. The electronic structure analysis shows that [ AlH4]The bond between Al and H atoms in the group is ionic in nature, whereas Li atoms and [ AlH ]4]The linkage between the groups is a covalent bond.
Therefore, a synergistic catalytic material can be designed, so that the material has the advantages of catalytic activity of two elements, and the hydrogen release performance of lithium aluminum hydride is greatly improved.
Among the numerous Ti-based materials, Ti3C2As a typical two-dimensional material containing abundant Ti element, a layered material Ti3C2Tx(MXene) can be prepared by reacting from the corresponding Ti3AlC2(MAX) phase exfoliation of the Al layer. After further delamination, Ti having more radicals on the surface can be obtained3C2Tx. Prior document 7[ Y, Xia, L, Sun, F, Xu, et al, Dehydration effect in improved hydrolysis of LiAlH4 by doping with two-dimensional Ti3C2 - ScienceDirect[J]. Materials Today Nano, 8:100054-100054.]Using 5 wt% Ti for Y.Xia et al3C2Doping catalytic LiAlH4The initial hydrogen release temperature of the system is 55.8 ℃, the hydrogen release amount reaches 6.5 wt percent, and 3.9 wt percent of hydrogen is released in 40 minutes at 120 ℃ for LiAlH4Exhibit excellent catalytic activity. The authors' study showed that two-dimensional Ti3C2Doping of reduced LiAlH4The dissociation energy barrier of the middle Al-H bond accelerates the fracture of the Al-H bond through the charge transfer of the interface and the impurity removal effect of the Al-H cluster. . However, the material obtained by the technical scheme uses hydrofluoric acid as an etching agent, the hydrofluoric acid used by the method has poor safety performance, the etching process is uncontrollable, and the prepared Ti3C2The hydrogen release amount is low at low temperature, and due to the existence of fluoride ions, the delamination can not be realized in the centrifugal process (the help of a delaminating agent is needed), which causes great problems for future application and operation.
Since the use of HF as an etchant is potentially hazardous,the new method (the MILD method) used LiF and HCl instead of hazardous hydrofluoric acid in 2014. By using this method, Li+Can be used as an intercalator to increase the interlayer spacing of MXene. Prior document 8[ Rj A, Xxa B, Jz A, et al, Remarkable hydrogen adsorption/desorption derivatives and mechanism of sodium aldehydes in-situ with Ti-based 2D MXene-scientific direct [ J]. Materials Chemistry and Physics, 242.]RC Jiang et al used MILD to prepare Ti with good morphology and high purity3C2And reacting with NaH/Al and ball-milling to synthesize NaH/Al-Ti3C2A composite material. Ti which has not been prepared by the MILD method3C2In LiAlH4The above study, but as lithium aluminum hydride having very similar property characteristics to sodium aluminum hydride, it can be predicted that Ti prepared using the MILD method3C2In LiAlH4Will have excellent properties.
Therefore, the patent carbonizes Ni-MOFs, removes oxygen-containing functional groups and organic ligands, and Ni nanoparticles derived from Ni-MOFs are dispersed in the exfoliated Ti3C2In the above, a novel bimetallic-based catalyst was constructed. Since there is no Ti3C2And the carbonized Ni-MOFs compound catalytic LiAlH4The present patent combines the advantages of both, and by utilizing the synergistic effect between them, is characterized in that the ultra-dispersed Ni nano-particles are electrostatically self-assembled in Ti3C2On a sheet. The unique catalyst structure changes the surface characteristics of 2D MXenes, which are marked as Ni @ C-MXene and added into LiAlH4In (1). In the work, the Ni @ C-MXene catalyst with a good structure is designed for the first time, not only can uniform distribution of Ni nano ions on MXene be effectively realized, but also sufficient Ni and Ti bimetallic catalytic sites can be provided, so that the dispersity is further improved, the agglomeration phenomenon possibly generated by nickel particles serving as a catalytic phase is reduced, the ball-milling efficiency is improved, the electron transfer is promoted, and the hydrogen evolution kinetics and thermodynamics of lithium aluminum hydride are greatly improved.
Disclosure of Invention
The invention aims to provide an MXene loaded Ni @ C nanoparticle hydrogen storage catalyst and a preparation method thereof.
By doping Ni @ C-MXene, two-dimensional metal carbide (Ti) is utilized3C2) And the catalytic superiority of Ni nano-meter (Ni @ C) derived from Ni-MOF can promote the decomposition of intermediate products in the reaction process, control the hydrogen releasing process of the intermediate products, and simultaneously realize 3 technical effects:
1. the process is simple, the synthesis is convenient, and the prepared catalyst can greatly improve the hydrogen release kinetics and thermodynamics of the lithium aluminum hydride;
2. using LiAlH4The + Ni @ C-MXene is used as a hydrogen source material, and a large amount of high-purity hydrogen can be obtained at a lower heating temperature (to 90 ℃);
3. the induction period of the second hydrogen releasing process is greatly reduced, the hydrogen releasing temperature of the second hydrogen releasing process is reduced, the two hydrogen releasing processes are coordinated, and finally a large amount of hydrogen releasing processes are realized, and 6.4 wt% of hydrogen is released from the hydrogen storage material at 200 ℃.
In order to achieve the aim, the specific technical scheme for achieving the aim of the invention is as follows:
an MXene-loaded Ni @ C nanoparticle hydrogen storage catalyst is prepared by carbonizing Ni-MOFs as a base to prepare Ni @ C and then loading the Ni @ C-MOFs onto MXene, and is referred to as Ni @ C-MXene for short.
The Ni-MOFs is prepared by the hydrothermal reaction of nickel nitrate hexahydrate and terephthalic acid; the MXene is Ti3C2From Ti3AlC2And concentrated hydrochloric acid plus lithium fluoride.
A preparation method of MXene loaded Ni @ C nanoparticle hydrogen storage catalyst comprises the following steps:
step 1) preparing Ni @ C, dissolving nickel nitrate hexahydrate in water to prepare a solution A, and dissolving terephthalic acid in N, N-dimethylformamide to prepare a solution B; then, mixing nickel nitrate hexahydrate and terephthalic acid according to a certain substance quantity ratio, and carrying out solvothermal reaction under certain conditions; after the reaction is finished, filtering, washing and drying the product, and calcining under certain conditions to obtain Ni @ C;
the ratio of the nickel nitrate hexahydrate to the terephthalic acid in the step 1 is 1.3: 1; in the step 1, the concentration of the aqueous solution of nickel nitrate hexahydrate is 0.0465 g/mL, and the concentration of the DMF solution of terephthalic acid is 0.0199 g/mL;
the condition of the solvothermal reaction in the step 1 is that the reaction is carried out for 24 hours at 110 ℃ in a blast oven; the calcination condition in the step 1 is calcination in an argon atmosphere, the heating rate is 5-7 ℃/min, the calcination temperature is 700 ℃, the calcination time is 1-2 hours, and then the room temperature is cooled; drying at 60 deg.C under vacuum for 12-14 hr;
step 2) MXene preparation, namely dissolving lithium fluoride in concentrated hydrochloric acid to obtain etching solution by using the lithium fluoride and the concentrated hydrochloric acid to meet a certain mass ratio, and then dissolving Ti3AlC2Placing the MXene into an etching solution, carrying out centrifugal treatment and ultrasonic treatment under certain conditions, and carrying out freeze drying to obtain MXene;
in the step 2, the mass ratio of the lithium fluoride to the concentrated hydrochloric acid is 1:108, and the concentration of the concentrated hydrochloric acid is 38-40 wt%; subsequently, Ti3AlC2Adding concentrated hydrochloric acid and lithium fluoride etching solution, Ti3AlC2The mass ratio of the etching solution to the etching solution is 1: 1;
in the step 2, the lithium fluoride powder is added with concentrated hydrochloric acid, the temperature in the etching process is 40 ℃, the rotating speed in the etching process is 600 rmp, and the etching time is 45 hours; to prevent overheating, a trace amount of Ti should be gradually added every 5 minutes3AlC2To a mixed solution of concentrated hydrochloric acid and lithium fluoride; centrifuging at 3000rmp for 5min for 10-20 times until pH of the supernatant is close to 6; then carrying out ultrasonic treatment for 1.5 hours under argon atmosphere, and centrifuging again at the rotating speed of 4000 rpm for 30 min;
step 3) preparing Ni @ C-MXene, mixing Ni @ C and MXene in a methanol solution according to a certain mass ratio of Ni @ C obtained in the step 1 and MXene obtained in the step 2, performing ultrasonic treatment, and drying after ultrasonic treatment to obtain Ni @ C-MXene, namely the MXene loaded Ni @ C nano-particle hydrogen storage catalyst;
the mass ratio of Ni @ C to MXene in the step 3 is 1:1, and the concentration of a dispersion liquid in methanol is 0.005 mg/ml;
the ultrasonic time of the step 3 is 2 hours; the drying condition is vacuum condition of 60 deg.C, and drying for 3-4 hr.
The application of the MXene-loaded Ni @ C nanoparticle hydrogen storage catalyst comprises the steps of enabling the MXene-loaded Ni @ C nanoparticle hydrogen storage catalyst to meet a certain mass ratio with lithium aluminum hydride, and carrying out ball milling under a certain condition to obtain a Ni @ C-MXene-doped lithium aluminum hydride hydrogen storage material;
the mass ratio of the MXene loaded Ni @ C nanoparticle hydrogen storage catalyst to the lithium aluminum hydride is 3-10 wt% of the Ni @ C-MXene added amount in the total mass;
the ball milling condition is that under the argon atmosphere, the ball-material ratio is 100-200:1, the ball milling rotation speed is 200-250 rpm, and the ball milling time is 30-40 minutes.
When the doping amount of the MXene loaded Ni @ C nanoparticle hydrogen storage catalyst is 7 wt%, the hydrogen release temperature of the system is reduced to 56.1 ℃, and the hydrogen release amount reaches 6.52 wt%.
XRD diffraction analysis experiment detection shows that the Ni @ C-MXene is successfully prepared by a simple physical mixing method. Only obvious Ti can be seen on the XRD pattern of the synthesized product3C2Peak sum very weak Li3AlF6Impurity peaks, indicating very high purity of the synthesized MXene. The peaks of MXene, Ni @ C and Ni @ C-MXene all correspond to each other and meet the standard card.
Through detection of a field emission scanning electron microscope and a transmission electron microscope, in the Ni @ C-MXene prepared by the method, the organic framework collapses to form reduced carbon in the calcining process, the reduced carbon covers the surface of the nickel particle (Ni @ C), and the Ni nano particles are uniformly distributed on the stripped MXene.
Through the detection of a temperature rise dehydrogenation experiment, the invention effectively improves LiAlH4When the doping amount of the catalyst is 3 wt%, the hydrogen releasing temperature of the system is reduced to 72.8 ℃, and the hydrogen releasing amount reaches 6.97 wt%; when the doping amount of the catalyst is 10 wt%, the hydrogen releasing temperature of the system is reduced to 54.9 ℃, and the hydrogen releasing amount reaches 6.14 wt%; the temperature is reduced by 48.2-66.1 ℃ compared with that of pure lithium aluminum hydride, and LiAlH is greatly reduced4The hydrogen releasing performance of the system is greatly improved at the hydrogen releasing temperature.
Through detection of an isothermal dehydrogenation experiment, 3.27 wt% of hydrogen is released by the hydrogen storage material in 60 minutes when the experiment is carried out at 90 ℃; the hydrogen storage material of the present invention evolved 5.70 wt% hydrogen gas for 20 minutes at 200 ℃ of the experiment.
The results of Differential Scanning Calorimetry (DSC) test and Kissinger equation calculation show that the hydrogen evolution reaction activation energy E of the first step and the second step of the inventiona64.998 kJ/mol and 75.696 kJ/mol respectively, which are reduced by 35.492 kJ/mol and 90.99 kJ/mol compared with undoped lithium aluminum hydride, so that the kinetic barrier of the hydrogen discharge reaction of the lithium aluminum hydride is obviously reduced, and the hydrogen discharge performance of the lithium aluminum hydride is improved.
Therefore, compared with the prior art, the invention has the following advantages:
1. the Ni nano-particles derived from the MOF prepared by the invention are dispersed on a functional MXene carrier to construct an effective double-transition metal-based catalyst for LiAlH4The material can be fully combined with lithium aluminum hydride, so that the hydrogen storage performance of the hydrogen storage material is improved, and the hydrogen storage material has low cost, simple synthesis method and process and easy large-scale production;
2. the hydrogen storage material prepared by the invention effectively improves the hydrogen storage performance of the lithium aluminum hydride. When the doping amount of Ni @ C-MXene is 7 wt%, the hydrogen release temperature of the system is reduced to 56.1 ℃, and the hydrogen release amount reaches 6.52 wt%;
3. the hydrogen storage material prepared by the invention has good hydrogen storage dynamic performance. 3.27% by weight of hydrogen were evolved at 90 ℃ for 60 minutes and 5.70% by weight at 200 ℃ for 20 minutes.
Therefore, the invention has wide application prospect in the field of new energy hydrogen storage materials.
Description of the drawings:
FIG. 1 is an XRD pattern of Ni @ C and Ni @ C-MXene obtained by pyrolysis of Ni-MOFs prepared in examples of the present invention;
FIG. 2 is a field emission scanning electron microscope image of Ni @ C-MXene prepared in an example of the present invention;
FIG. 3 is a transmission electron micrograph of Ni @ C-MXene prepared in an example of the present invention;
FIG. 4 shows LiAlH with doped Ni @ C-MXene contents of 3 wt%, 7 wt% and 10 wt%, respectively, in an example of the present invention4Temperature rising dehydrogenation curve diagram;
FIG. 5 shows LiAlH in an example of the present invention4+7 wt% Ni @ C-MXene series hydrogen storage material constant temperature dehydrogenation curve;
FIG. 6 is LiAlH in an example of the present invention4(iii) Differential Scanning Calorimeter (DSC) measurements of +7 wt% Ni @ C-MXene hydrogen storage material and a plot fitted thereto;
FIG. 7 shows LiAlH in an example of the present invention4Differential Scanning Calorimeter (DSC) testing of hydrogen storage materials and graphs fitted thereto;
FIG. 8 shows LiAlH in comparative example of the present invention4+ 7% by weight MXene and LiAlH4Temperature rising dehydrogenation profile of +7 wt% Ni @ C series hydrogen storage materials.
Detailed Description
The invention is further described in detail by the embodiments and the accompanying drawings, but the invention is not limited thereto.
Example (b):
a preparation method of MXene loaded Ni @ C nanoparticle hydrogen storage catalyst comprises the following steps:
step 1) preparation of Ni @ C, precisely weighing 1.1628 g of nickel nitrate hexahydrate (Ni (NO)3)2⋅6H2O), dissolved in 25 mL of deionized water to prepare solution A with a concentration of 0.0465 g/mL. Accurately weighing 0.498 g of terephthalic acid, dissolving in 25 mL of N, N-Dimethylformamide (DMF), and preparing a solution B with the concentration of 0.0199 g/mL; wherein, nickel nitrate hexahydrate and terephthalic acid meet the requirement of the mass ratio of 1.3:1, then mixing, then loading into a polytetrafluoroethylene reaction kettle, and then carrying out solvothermal reaction for 24 hours under the reaction condition of 110 ℃ in an oven; centrifuging the reaction product, washing with deionized water, DMF and ethanol, and filtering; and (3) drying the product after centrifugal washing in a vacuum drying oven at 60 ℃ for 12 hours, calcining in an argon atmosphere at the heating rate of 5 ℃/min at the calcining temperature of 700 ℃, preserving heat for 1 hour, and then cooling to room temperature to obtain the Ni @ C.
Step 2) MXene preparation, namely precisely weighing 1.98 g of lithium fluoride (LiF) powder by taking lithium fluoride and concentrated hydrochloric acid in a mass ratio of 1:108, and dissolving the lithium fluoride powder inStirring the mixture in 30 mL of concentrated hydrochloric acid (to 40 wt%) at the speed of 600 rpm for 5 minutes to obtain etching solution; then press Ti3AlC2Precisely weighing 1 g of Ti according to the condition that the mass ratio of the Ti to the etching solution is 1:13AlC2Placing in etching solution, and gradually adding small amount of Ti every 5min to prevent overheating3AlC2Etching reaction is carried out for 45 hours at 40 ℃, and stirring is carried out for 45 hours at the speed of 600 rpm; centrifuging the reaction product and washing the reaction product for 10 to 20 times by using deionized water until the pH value of a supernatant is close to 6, and carrying out ultrasonic treatment on the obtained sample for 1.5 hours under the argon atmosphere to complete stripping; the samples were washed with deionized water and centrifuged at 4000 rpm for 30 minutes; and (3) carrying out freeze drying treatment on the colloidal solution to obtain MXene.
Step 3) preparation of Ni @ C-MXene, wherein 0.05 g of Ni @ C obtained in the step 1 and 0.05 g of MXene obtained in the step 2 are weighed and added into 20 mL of methanol solution under the condition that the mass ratio of the Ni @ C to the MXene is 1:1 to prepare a methanol dispersion liquid with the concentration of the Ni @ C and the MXene of 0.005 mg/mL; and then carrying out mixed ultrasonic treatment for 2 hours, and carrying out vacuum drying for 4 hours at 60 ℃ after ultrasonic treatment is finished to obtain Ni @ C-MXene.
Application of MXene loaded Ni @ C nanoparticle hydrogen storage catalyst; under the protection of argon atmosphere, precisely weighing 0.2790 g of lithium aluminum hydride and 0.0210 g of Ni @ C-MXene in the condition that the mass ratio of the Ni @ C-MXene to the lithium aluminum hydride obtained in the step (3) is 1:32.33, putting the weighed materials into a ball milling tank, putting 15 ball milling beads into the ball milling tank, and sealing the ball milling tank; putting the ball milling tank into a ball mill, wherein the ball milling rotating speed is 250 rpm, and the ball milling time is 30 minutes; and then taking out the ball-milled product from a glove box filled with argon to obtain the Ni @ C-MXene doped lithium aluminum hydride hydrogen storage material.
XRD analysis was performed on Ni @ C prepared in step 1), MXene prepared in step 2), and Ni @ C-MXene prepared in step 3) in the examples, and the results are shown in FIG. 1. The spectrogram of Ni @ C-MXene contains Ti loaded with strong Ni @ C characteristic peak3C2A characteristic peak; and in Ti3C2In the diffraction peak of (2), very weak Li was found3AlF6Impurity peaks, indicating very high purity of the synthesized MXene.
The Ni @ C-MXene prepared in the step 3) in the example is detected by a field emission scanning electron microscope and a transmission electron microscope, and the results are shown in FIGS. 2 and 3. According to the invention, Ni nanoparticles are uniformly distributed on the stripped MXene by a simple physical mixing method.
Lithium aluminum hydride, 3 wt%, 7 wt%, 10 wt% LiAlH4In the hydrogen storage material temperature programming dehydrogenation experiment, a proper amount of sample (600-800 mg) is taken, the temperature rise rate is 3 ℃/min, and the temperature is raised from 25 ℃ to 300 ℃.
The experimental result is shown in figure 4, the initial hydrogen releasing temperature is 54.9-72.8 ℃, the total hydrogen releasing amount is 6.14-6.97 wt%, and the hydrogen releasing temperature is reduced by 48.2-66.1 ℃ compared with pure lithium aluminum hydride.
Mixing 7 wt% of Ni @ C-MXene-LiAlH4The results of the isothermal dehydrogenation experiments at 90 ℃ and 200 ℃ are shown in FIG. 5. In the 90 ℃ experiment, the hydrogen storage material of the invention releases 3.27 wt% hydrogen in 60 minutes; the hydrogen storage material of the present invention evolved 5.70 wt% hydrogen gas for 20 minutes at 200 ℃ of the experiment.
For LiAlH4And 7 wt% Ni @ C-MXene-LiAlH4Differential Scanning Calorimetry (DSC) test and Kissinger's equation calculation were performed, and the results are shown in fig. 6 and 7. Activation energy E of the Hydrogen evolution reaction of the first and second steps of the present inventiona64.998 kJ/mol and 75.696 kJ/mol respectively, which are reduced by 35.492 kJ/mol and 90.99 kJ/mol compared with undoped lithium aluminum hydride, which shows that the addition of the Ni @ C-MXene catalyst can obviously reduce the kinetic barrier of the hydrogen discharge reaction of the lithium aluminum hydride and improve the hydrogen discharge performance of the lithium aluminum hydride.
To demonstrate the effect of the presence of MXene material in Ni @ C-MXene on the hydrogen evolution performance of lithium aluminum hydride, an MXene-doped lithium aluminum hydride hydrogen storage material was prepared by comparative example 1.
Comparative example 1
MXene nano-particle hydrogen storage catalyst and its preparation method, the steps not specially described are the same as the examples, except that; the preparation of the catalyst only comprises the step 2) and the application of MXene loaded Ni @ C nanoparticle hydrogen storage catalyst; in the application of the MXene loaded Ni @ C nanoparticle hydrogen storage catalyst, MXene instead of Ni @ C-MXene is weighed to obtain the MXene doped lithium aluminum hydride hydrogen storage material.
The obtained MXene-doped lithium aluminum hydride hydrogen storage material was subjected to a temperature rise dehydrogenation test in the same manner as in example, and the test results are shown in FIG. 8, wherein the initial hydrogen desorption temperature was 105.10 ℃, and the hydrogen desorption amount was 6.50 wt% when the temperature was raised to 300 ℃. Through the examples and the comparative example 1, the hydrogen release amount was reduced by 0.1 wt%, and the hydrogen release temperature was increased by 48.94 ℃, which preliminarily proved that Ti was used3C2The addition of the catalyst has better catalysis effect on the second-stage hydrogen release of the lithium aluminum hydride.
To demonstrate the effect of the presence of the Ni @ C material in Ni @ C-MXene on the hydrogen evolution performance of lithium aluminum hydride, a Ni @ C doped lithium aluminum hydride hydrogen storage material was prepared by comparative example 2.
Comparative example 2
The steps which are not particularly described are the same as the steps in the examples, except that the Ni @ C nanoparticle hydrogen storage catalyst is prepared by the following steps; the preparation of the catalyst only comprises the step 1) and the application of MXene loaded Ni @ C nanoparticle hydrogen storage catalyst; in the application of the MXene loaded Ni @ C nanoparticle hydrogen storage catalyst, Ni @ C is weighed instead of Ni @ C-MXene, and the Ni @ C doped lithium aluminum hydride hydrogen storage material can be obtained.
The obtained Ni @ C-doped lithium aluminum hydride hydrogen storage material was subjected to a temperature rise dehydrogenation test in the same manner as in the example, and the test results are shown in fig. 8, where the initial hydrogen desorption temperature is 55.4 ℃, and the hydrogen desorption amount is 6.16 wt% when the temperature is raised to 300 ℃. By the examples, the hydrogen discharge temperature was increased by 0.76 ℃ and the hydrogen discharge amount was decreased by 0.36 wt% as compared with comparative example 2.
Both Ni @ C and MXene improved the hydrogen evolution kinetics by comparing the examples with comparative example 1 and comparative example 2. Wherein, when the temperature is higher than 130 ℃, Ni @ C is gradually agglomerated at high temperature, so that the catalytic activity of the nickel-based catalyst is limited, and the hydrogen release kinetics is obviously slowed down; however, for MXene, the hydrogen evolution kinetics of MXene are significantly enhanced above 150 ℃ due to Ti3C2The Ti-C bond is broken to generate Ti when the Ti-C bond is chemically reacted with lithium aluminum hydride by ball milling0And Ti3+，Ti0Reaction with lithium aluminum hydride to form Ti0Conversion to Ti3+Thereby allowing Ti to stand3C2The addition of (2) improves the second stage hydrogen evolution reaction of the lithium aluminum hydride. Therefore, the Ni @ C and MXene are proved to be capable of improving the hydrogen release performance of the lithium aluminum hydride by the synergistic catalysis, and realizing low-temperature hydrogen release and high-capacity hydrogen release.
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| CN114906801A (en) * | 2022-05-26 | 2022-08-16 | 重庆大学 | A kind of MgH2@Fe-ZIF hydrogen storage material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114906801A (en) * | 2022-05-26 | 2022-08-16 | 重庆大学 | A kind of MgH2@Fe-ZIF hydrogen storage material and preparation method thereof |
| CN114906801B (en) * | 2022-05-26 | 2023-10-10 | 重庆大学 | A kind of MgH2@Fe-ZIF hydrogen storage material and its preparation method |
| CN115285935A (en) * | 2022-06-20 | 2022-11-04 | 国网江苏省电力有限公司电力科学研究院 | Hydrogen storage material of LDH and MXene composite modified magnesium hydride and preparation method thereof |
| CN115285935B (en) * | 2022-06-20 | 2023-11-14 | 国网江苏省电力有限公司电力科学研究院 | Hydrogen storage material of LDH and MXene composite modified magnesium hydride and preparation method thereof |
| CN116281849A (en) * | 2023-03-03 | 2023-06-23 | 桂林电子科技大学 | A hollow flower-like M-NC@TiO2 composite material and its preparation method and application |
| CN116553478A (en) * | 2023-07-11 | 2023-08-08 | 长春理工大学 | Hydrogen storage material and preparation method thereof |
| CN116553478B (en) * | 2023-07-11 | 2023-10-20 | 长春理工大学 | Hydrogen storage material and preparation method thereof |
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