CN112978679A - Preparation method of multi-metal hydrogen-containing compound - Google Patents
Preparation method of multi-metal hydrogen-containing compound Download PDFInfo
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- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
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- C—CHEMISTRY; METALLURGY
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- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
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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
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/246—Hydrides containing at least two metals; Addition complexes thereof also containing non-metals other than hydrogen
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Abstract
The application discloses a preparation method of a multi-metal hydrogen-containing compound, which at least comprises the following steps: the material containing the multi-metal nitrogen-containing compound is subjected to hydrogenation deamination in a hydrogen atmosphere to obtain the multi-metal hydrogen-containing compound. Compared with the traditional synthesis method, the method has the advantages of low temperature, low hydrogen pressure, short reaction time and the like, and the method is favorable for popularizing the application of the material in various related research fields.
Description
Technical Field
The application relates to a preparation method of a multi-metal hydrogen-containing compound, belonging to the technical field of complex hydrides.
Background
Energy crisis and environmental pollution are two major problems facing the human society today. On one hand, the traditional fossil energy is increasingly consumed and cannot be regenerated, and on the other hand, the fossil energy brings environmental problems such as air pollution, ozone layer destruction, greenhouse effect and the like in the process of using the fossil energy in large quantity. This forces people to find new sustainable energy or energy carriers, reduce the direct use of fossil energy and reduce energy consumption in various industrial fields. The metal hydrogen-containing compound has important application value in a plurality of fields, for example, the complex hydride has important application prospect in the aspect of hydrogen storage material, thereby being widely researched by people, NaBH4，NaAlH4，Mg(NH2)2LiH and other hydrogen storage systems have been studied for many years. Containing hydrogen in the catalytic fieldThe material also has important application, the synthetic ammonia industry is one of the industrial fields with the highest energy consumption, and the energy consumption for synthesizing ammonia accounts for 1-2% of the total global energy consumption every year, so that the development of the low-energy-consumption high-efficiency synthetic ammonia catalyst has important significance. In 2017, Wang et al report that ammonia can be efficiently synthesized at low temperature and low pressure by using a transition metal-LiH composite catalyst, and compared with an industrial catalyst, the energy consumption is greatly reduced. In the aspect of ion conductors, hydrogen-containing compounds also have important application, and a hydrogen negative ion conductor is a material capable of conducting H & lt- & gt and has potential application value in the fields of fuel cells, hydrogen separation membranes, sensors and the like. In 2014, Verbraeken et al reported BaH2Has good hydride ion conductivity, which can be compared with the best proton conductor. In 2016, Kobayashi et al reported the synthesis of a novel oxide La2-x-ySrx+yLiH1-x+yO3-yIt has the performance of pure hydrogen negative ion conductor.
In general, the synthesis of metal hydrogen-containing compounds is difficult, and the reaction is generally carried out at high temperature and high hydrogen pressure. As mentioned above, the oxide La2-x-ySrx+yLiH1-x+yO3-yThe synthesis of the material needs 650 ℃ and 2GPa H2The reaction is carried out under pressure, which conditions need to be achieved in a very specific apparatus. The application value of the material is greatly limited by the difficulty in synthesis, so that the exploration of the efficient synthesis of the metal hydrogen-containing compound at low temperature and low pressure is very important.
Disclosure of Invention
According to one aspect of the present application, a process for the preparation of a multi-metal hydrogen-containing compound is provided which avoids the reactions between multiple solid phases involved in conventional synthetic methods, which are slow in kinetics, and which is a major reason why high temperatures and pressures are required in conventional methods. The method adopts the multi-element metal nitrogen-containing compound or the mixture thereof as the precursor, and the gas-solid reaction between hydrogen and solid occurs, so that the dynamic performance is accelerated, and the thermodynamic performance is good, thereby the method can rapidly react at low temperature and low pressure.
The application provides a preparation method of a multi-metal hydrogen-containing compound, which at least comprises the following steps: the material containing the multi-metal nitrogen-containing compound is subjected to hydrogenation deamination in a hydrogen atmosphere to obtain the multi-metal hydrogen-containing compound.
Optionally, the multi-metal nitrogen-containing compound comprises at least one of a multi-metal amino compound, a multi-metal imino compound, and a multi-metal nitride.
Optionally, the multi-metal nitrogen-containing compound contains a metal element; the metal elements are selected from at least two of metal A, metal B and metal C; wherein the metal A represents an alkali metal or an alkaline earth metal; metal B represents a lanthanide metal or an actinide metal; the metal C represents a transition metal.
Optionally, the alkali metal comprises at least one of lithium, sodium, potassium, rubidium, and cesium.
Optionally, the alkaline earth metal comprises at least one of magnesium, calcium, strontium, barium.
Optionally, the lanthanide metal includes at least one of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium.
Optionally, the actinide metal comprises at least one of actinium, thorium, protactinium, and uranium.
Optionally, the transition metal comprises at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, ruthenium, rhodium, palladium, silver, gold.
Optionally, the conditions of the hydrodeamination are: the reaction temperature is 50-600 ℃; the reaction time is 1-60 h; the reaction pressure is 0.1-20 bar; the hydrogen flow rate is 10 to 500 mL/min.
Optionally, the multi-metal hydrogen-containing compound comprises at least one of a multi-metal hydride, a multi-metal nitrogen hydride.
Optionally, the metal element C-1 is contained in the multi-element metal hydride; the metal element C-1 is a late transition period metal; the multi-element metal nitride contains a metal element C-2; the metal element C-2 is a metal with a transition period.
Optionally, the preparation method of the multi-metal nitrogen-containing compound at least comprises the following steps: reacting a material containing a metal source with ammonia gas to obtain a multi-metal nitrogen-containing compound; the metal source comprises at least two of a metal A source, a metal B source and a metal C source.
Optionally, the metal a source comprises any one of elemental metal a, metal a hydride, metal a nitrogen-containing compound; the metal B source comprises any one of a metal B simple substance, metal B hydride and a metal B nitrogen-containing compound; the metal C source comprises any one of a metal C simple substance, a metal C hydride and a metal C nitrogen-containing compound.
Specifically, the simple substance of the metal A comprises at least one of Li, K, Sr and Ba; the metal A hydride includes LiH, KH, SrH2、BaH2At least one of; the metal A nitrogen-containing compound includes Li3N、LiNH2、Li2NH、KNH2At least one of BaNH; the simple substance of the metal B comprises at least one of La, Y, Sc and Ce; the metal B hydride comprises LaH3、YH3、ScH3At least one of; the metal B nitrogen-containing compound comprises at least one of LaN, YN and ScN; the metal C simple substance comprises at least one of Cr, Mo, Fe, Co, Ni, Zn and Pd; the metal C hydride includes NiH2、ZnH2、PdH2At least one of; the metal C nitrogen-containing compound comprises CrN, Cr (NH)2)3、Mo2N、Fe3N、Zn(NH2)2At least one of (1).
Optionally, the metal C is a late transition period metal, i.e., the metal element C-1, and the resulting product is a multi-metal hydride.
Optionally, the reaction I comprises any one of ball milling and calcining;
preferably, the conditions of the calcination are: the calcining temperature is 200-600 ℃; the calcining pressure is 0-200 bar.
Alternatively, the upper limit of the temperature of the calcination is selected from any one of 600 ℃, 550 ℃, 500 ℃, 450 ℃, 400 ℃, 350 ℃, 300 ℃ and 250 ℃, and the lower limit is selected from any one of 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 550 ℃.
Optionally, the method for preparing the metal C nitrogen-containing compound at least comprises the following steps:
reacting II with an amino compound of metal D or an ammine compound of halide of metal C to obtain a nitrogen-containing compound of metal C; alternatively, the first and second electrodes may be,
reacting II between an ammonia compound of halide of metal C or thiocyanogen salt of metal C and metal D in liquid ammonia to obtain a nitrogen-containing compound of metal C;
wherein the metal D comprises any one of alkali metals Li, Na, K, Rb and Cs.
Specifically, the ammine compound of the halide of the metal C comprises CrCl3·6NH3、FeCl2·6NH3、MoCl3·6NH3、NiCl2·6NH3At least one of (1).
Specifically, the thiocyanates of metal C include Fe (SCN)3、Co(SCN)2、Ni(SCN)2At least one of (1).
Specifically, the metal D amino compound includes LiNH2、NaNH2、KNH2At least one of (1).
Alternatively, the metal C in the method for producing a nitrogen-containing compound of metal C in the above method is referred to as a transition period metal, and the resultant product is a multi-metal nitrogen hydride.
Optionally, when the nitrogen-containing compound of metal C is prepared, after the preparation by the ball milling method is completed, the metal D halide or the thiocyanato salt in the ball-milled product needs to be removed, so as to obtain the nitrogen-containing compound of metal C.
Alternatively, the metal D halide or thiocyanide salt in the ball-milled product is removed by the following method: dissolving metal D halide or thiocyanogen salt in an organic solvent, centrifuging to remove supernatant, repeating for multiple times, and evacuating and drying the solid product to obtain the metal C nitrogen-containing compound.
Optionally, the organic solvent comprises at least one of tetrahydrofuran, diethyl ether, cyclohexane, pentane, n-butane, and toluene.
Preferably, the rotation speed of the ball mill is 100-400 r/min; the weight ratio of the grinding balls to the sample to be treated in the ball milling process is 10: 1-100: 1; the ball milling time is 1-60 hours.
Alternatively, the upper limit of the time for ball milling is selected from any one of 60 hours, 50 hours, 40 hours, 30 hours, 20 hours, 10 hours, and 5 hours, and the lower limit is selected from any one of 1 hour, 5 hours, 10 hours, 20 hours, 30 hours, 40 hours, and 50 hours.
Alternatively, the polymetallic hydrogen-containing compound is prepared by determining the reduction temperature of the polymetallic nitrogen-containing compound by temperature programmed reduction-mass spectrometry (TPR-MS) and reducing at a selected temperature.
The beneficial effects that this application can produce include:
(1) by adopting the method, the reaction temperature and pressure can be greatly reduced, and the reaction time is shortened;
(2) by adopting the method, various multi-element novel metal hydrogen-containing compounds can be developed.
Drawings
FIG. 1 shows K synthesized in example 12ZnH4XRD pattern of (a).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1: preparation of ternary hydrides K2ZnH4
(1) Weighing 5 g of a mixture of metal K and metal Zn (the molar ratio is 2: 1) in a glove box, filling the mixture into a ball milling tank, filling 8bar of ammonia gas into the ball milling tank, and mechanically milling for 20 hours at the rotating speed of 400 rpm; obtaining a multi-metal nitrogen-containing compound K2Zn(NH2)4；
(2) Taking 40mg of the ball-milled product in the step 1 to perform TPR-MS test, and heating to 600 ℃ from room temperature at a heating rate of 10 ℃/min;
(3) confirming the deamination temperature of the sample through the step 2, selecting a proper temperature of 400 ℃ for carrying out hydrogenation deamination, wherein the specific reaction is K2Zn(NH2)4+4H2＝K2ZnH4+4NH3Reacting for 15h, and collecting a solid product which is K2ZnH4。
Example 2: preparation of quaternary nitrogen hydride BaCrNH
(1) 5 g of lithium amide and ammine CrCl were weighed in a glove box3(the mol ratio is 3: 1), mechanically milling the mixture for 10 hours at the rotating speed of 400 rpm;
(2) putting the ball-milled product obtained in the step 1 into a centrifuge tube, adding 100mL of THF solvent, performing ultrasonic treatment for 30min to fully dissolve the ball-milled product, then centrifuging for 100min to fully settle the ball-milled product, pouring out the supernatant, and repeating the operation for 5 times;
(3) vacuumizing the centrifugal precipitate obtained in the step (2) to remove residual solvent, and vacuumizing for 10min to obtain a metal Cr nitrogen-containing compound Cr (NH)2)3；
(4) The nitrogen-containing compound (namely Cr (NH)) of the chromium prepared in the step 32)3) Weighing the metal Ba and the metal Ba according to a molar ratio of 1:1, putting the metal Ba and the metal Ba into a ball milling tank, filling 8bar of ammonia gas, mechanically milling the mixture for 20 hours at a rotating speed of 400rpm to obtain a multi-metal nitrogen-containing compound BaCr (NH)2)5；
(5) Taking 40mg of the ball-milled product in the step 4 to perform TPR-MS test, and heating from room temperature to 600 ℃ at a heating rate of 10 ℃/min;
(6) confirming the deamination temperature of the sample through the step 5, selecting a proper temperature (300 ℃) to carry out the hydrogenation deamination, wherein the specific reaction is BaCr (NH)2)5+1.5H2＝BaCrNH+4NH3And the reaction time is 10 hours, and the collected product is the quaternary nitrogen hydride BaCrNH.
Example 3: preparation of ternary hydride Li4FeH6
(1) 5 g of lithium amide and Fe (SCN) were weighed in a glove box2(the mol ratio is 2: 1), mechanically milling the mixture for 10 hours at the rotating speed of 400 rpm;
(2) putting the ball-milled product obtained in the step 1 into a centrifuge tube, adding 100mL of THF solvent, performing ultrasonic treatment for 30min to fully dissolve the ball-milled product, then centrifuging for 100min to fully settle the ball-milled product, pouring out the supernatant, and repeating the operation for 5 times;
(3) will step withVacuumizing the centrifugal precipitate in the step 2 to remove residual solvent, and vacuumizing for 10min to obtain a metal Fe nitrogen-containing compound Fe (NH)2)2；
(4) The nitrogen-containing compound (namely Fe (NH)) of the Fe prepared in the step 32)2) Weighing the metal Li and the nitrogen-containing compound in a molar ratio of 1:4, putting the metal Li into a ball milling tank, filling 80bar of ammonia gas, mechanically milling the mixture for 20 hours at a rotating speed of 400rpm to obtain the multi-metal nitrogen-containing compound Li4Fe(NH)2(NH2)2；
(5) Taking 40mg of the ball-milled product in the step 4 to perform TPR-MS test, and heating to 600 ℃ from room temperature at a heating rate of 10 ℃/min;
(6) confirming the deamination temperature of the sample through the step 5, selecting a proper temperature (400 ℃) to carry out hydrogenation deamination, wherein the specific reaction is Li4Fe(NH)2(NH2)2+6H2＝Li4FeH6+4NH3Reaction time is 10h, and the collected product is ternary hydride Li4FeH6。
Example 4: preparation of quaternary nitrogen hydride SrMoNH
(1) 5 g of lithium metal and ammoniated MoCl were weighed in a glove box3Namely MoCl3·6NH3Adding 100mL of liquid ammonia into the mixture (the molar ratio is 3: 1), and oscillating the reactor for 10 h;
(2) putting the product obtained in the step 1 into a centrifuge tube, adding 100mL of THF solvent, performing ultrasonic treatment for 30min to fully dissolve the product, then centrifuging for 100min to fully settle the product, pouring out the supernatant, and repeating the operation for 5 times;
(3) vacuumizing the centrifugal precipitate obtained in the step (2) to remove residual solvent, and vacuumizing for 10min to obtain a metal Mo nitrogen-containing compound Mo (NH)2)3；
(4) The nitrogen-containing compound of Mo (i.e. Mo (NH)) prepared in the step 32)3) Weighing the metal Sr and the nitrogen-containing compound in a molar ratio of 1:1, putting the metal Sr and the nitrogen-containing compound into a ball milling tank, filling 8bar of ammonia gas, mechanically milling the mixture for 20 hours at a rotating speed of 400rpm to obtain the multi-metal nitrogen-containing compound SrMo (NH)2)5；
(5) Taking 40mg of the ball-milled product in the step 4 to perform TPR-MS test, and heating to 600 ℃ from room temperature at a heating rate of 10 ℃/min;
(6) confirming the deamination temperature of the sample through the step 5, selecting a proper temperature (400 ℃) to carry out hydrogenation deamination, wherein the specific reaction is SrMo (NH)2)5+1.5H2＝SrMoNH+4NH3And reacting for 20 hours, and collecting a product, namely the quaternary nitrogen hydride SrMoNH.
Example 5: preparation of quaternary nitrogen hydrides Sr3LaNH
(1) Weighing 5 g of a mixture of metal Sr and LaN (the molar ratio is 3: 1) in a glove box, and calcining the mixture in nitrogen for 10 hours at the temperature of 500 ℃ and the nitrogen pressure of 50 bar; obtaining the multi-metal nitrogen-containing compound Sr3LaN3；
(2) Taking Sr prepared in the step 13LaN3Carrying out TPR-MS test on 40mg, heating from room temperature to 600 ℃, wherein the heating rate is 10 ℃/min;
(3) confirming the deamination temperature of the sample through the step 2, selecting proper temperature (400 ℃) to carry out hydrogenation deamination, wherein the specific reaction is Sr3LaN3+5H2＝Sr3LaNH+3NH3The reaction time is 10 hours, and the collected product is the quaternary nitrogen hydride Sr3LaNH。
Example 6: preparation of ternary hydride BaPdH2
(1) 5 g of metal Ba and PdH are weighed in a glove box2(the molar ratio is 1: 1) is put into a ball milling tank, ammonia gas is filled in for 8bar, mechanical ball milling is carried out for 20h at the rotating speed of 400rpm, and the multi-metal nitrogen-containing compound BaPd (NH) is obtained2)4；
(2) Taking BaPd (NH) prepared in the step 12)4Carrying out TPR-MS test on 40mg, heating from room temperature to 600 ℃, wherein the heating rate is 10 ℃/min;
(3) confirming the deamination temperature of the sample through the step 2, selecting a proper temperature (300 ℃) to carry out hydrogenation deamination, wherein the specific reaction is BaPd (NH)2)4+3H2＝BaPdH2+4NH3The reaction time is 10h, and the collected product is the ternary hydride BaPdH2。
Example 7 structural characterization of samples
XRD structure characterization was performed on the products of examples 1-6, typically as for K in example 12ZnH4A sample is shown, FIG. 1 shows K synthesized in example 12ZnH4XRD pattern of (A) from FIG. 1, K synthesized by the method2ZnH4Diffraction peaks of the samples and K in the XRD database2ZnH4The standard card (PDF #01-083-0494) is completely matched, and the sample purity is very high, and diffraction peaks are very sharp, which shows that the product crystallinity is very good.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for producing a multi-metal hydrogen-containing compound, the method comprising at least: the material containing the multi-metal nitrogen-containing compound is subjected to hydrogenation deamination in a hydrogen atmosphere to obtain the multi-metal hydrogen-containing compound.
2. The method of claim 1, wherein the multi-metal nitrogen-containing compound comprises at least one of a multi-metal amino compound, a multi-metal imino compound, and a multi-metal nitride.
3. The method of claim 1, wherein the multi-metal nitrogen-containing compound comprises a metal element;
the metal elements are selected from at least two of metal A, metal B and metal C;
wherein the metal A represents an alkali metal or an alkaline earth metal;
metal B represents a lanthanide metal or an actinide metal;
the metal C represents a transition metal.
4. The method of claim 1, wherein the conditions for hydrodeamination are: the reaction temperature is 50-600 ℃;
the reaction time is 1-60 h;
the reaction pressure is 0.1-20 bar;
the hydrogen flow rate is 10 to 500 mL/min.
5. The method of claim 1, wherein the multi-metal hydrogen-containing compound comprises at least one of a multi-metal hydride and a multi-metal nitrogen hydride.
6. The method according to claim 5, wherein the polyvalent metal hydride contains a metal C-1;
the metal C-1 is a late transition period metal;
the multi-metal nitrogen hydride contains a metal C-2;
the metal C-2 is a metal with a transition period.
7. The method of claim 1, wherein the method of preparing the multi-metal nitrogen-containing compound comprises at least the steps of: reacting a material containing a metal source with ammonia gas to obtain a multi-metal nitrogen-containing compound;
the metal source comprises at least two of a metal A source, a metal B source and a metal C source;
preferably, the metal A source comprises any one of simple metal A, metal A hydride and metal A nitrogen-containing compound;
the metal B source comprises any one of a metal B simple substance, metal B hydride and a metal B nitrogen-containing compound;
the metal C source comprises any one of a metal C simple substance, a metal C hydride and a metal C nitrogen-containing compound.
8. The method according to claim 7, wherein the reaction I comprises any one of ball milling and calcining;
the ball milling comprises ball milling in an ammonia environment;
preferably, the ball milling conditions are as follows: ball milling pressure is 8-80 bar; ball milling time is 2-60 h; the ball milling speed is 100-400 r/min; the ball mass ratio is 10: 1-100: 1;
preferably, the conditions of the calcination are: the calcining temperature is 200-600 ℃; the calcining pressure is 0-200 bar.
9. The method of claim 8, wherein the method of preparing the metal C nitrogen-containing compound comprises at least the steps of:
reacting II with an amino compound of metal D or an ammine compound of halide of metal C to obtain a nitrogen-containing compound of metal C; alternatively, the first and second electrodes may be,
reacting II between an ammonia compound of halide of metal C or thiocyanogen salt of metal C and metal D in liquid ammonia to obtain a nitrogen-containing compound of metal C;
wherein the metal D is an alkali metal;
preferably, the reaction II is ball milling.
10. The method according to claim 8 or 9, wherein the rotation speed of the ball mill is 100-400 rpm;
the weight ratio of the grinding balls to the sample to be treated in the ball milling process is 10: 1-100: 1;
the ball milling time is 1-60 hours.
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