CN111167495B - Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof - Google Patents
Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 23
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 229960003638 dopamine Drugs 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002161 passivation Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000002135 nanosheet Substances 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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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
-
- B01J35/398—
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- 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
Abstract
The invention belongs to the technical field of hydrogen production by hydrolyzing ammonia borane, and discloses a catalyst Ni for hydrogen production by ammonia borane 2‑x Fe x @ CN-G and a preparation method thereof. The catalyst has a structure that NiFe nano-particles coated by nitrogen-doped carbon grow on a graphene nano-sheet. The preparation method comprises the following steps: (1) Preparing precursor Ni 2‑x Fe x -ldh @ pda-GO composite: (1 a) dispersing GO in water to obtain a GO dispersion liquid; (1b) Adding nickel salt, ferric salt, a urea solution and a polyvinylpyrrolidone solution into the GO dispersion liquid, stirring uniformly, adding an alkaline solution, stirring uniformly, adding a dopamine solution, stirring for 24-72 h, and controlling the temperature to be 120-140 ℃ for hydrothermal reaction for 24-48 h; cooling to room temperature, then carrying out suction filtration and drying to obtain a precursor Ni 2‑x Fe x -ldh @ pda-GO composite; (2) And reacting the precursor Ni 2‑x Fe x Calcining the-LDH @ PDA-GO composite material under the protection of inert atmosphere, cooling to room temperature, adding ethanol for passivation, drying and grinding to obtain the catalyst Ni 2‑x Fe x @ CN-G. The catalyst prepared by the invention has high activity when being used for preparing hydrogen from ammonia borane.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by hydrolyzing ammonia borane, and particularly relates to a catalyst Ni for hydrogen production by ammonia borane 2- x Fe x @ CN-G and a preparation method thereof.
Background
Hydrogen energy is one of the most promising candidates to be able to replace traditional fossil fuels (coal, oil, and natural gas, etc.) as a sustainable, clean energy source. However, storage and transportation of hydrogen gas is a key issue in the development of hydrogen energy. Among the novel hydrogen storage materials, ammonia borane has the characteristics of high hydrogen content (19.6 wt%), low molecular weight (30.87 g/mol), no toxicity, high stability and good stability in air and aqueous solutions. These advantages make ammonia borane attractive as a hydrogen storage material. Meanwhile, the existence of a proper catalyst is beneficial to the ammonia borane to release hydrogen, the ammonia borane can effectively release the hydrogen after catalytic hydrolysis, and each mol of the ammonia borane releases 3 mol of hydrogen. Noble metal-based catalysts, such as Pt, pd, ru, rh, etc., have excellent catalytic ammonia borane hydrolysis activity. However, the high cost and low natural content of these precious metals greatly hinders their widespread use. Therefore, a catalyst based on elements having low manufacturing cost and abundant earth content and having higher performance is highly desirable for industrialization.
Therefore, research and development of noble metal-free catalysts are the focus and focus of research in this field. Including oxides, phosphides, borides, and the like. Of all reported noble metal-free catalysts, cobalt-based catalysts are the most attractive and active catalysts for catalyzing the hydrolysis of ammonia borane. However, cobalt-based catalysts tend to agglomerate during catalyst preparation and liquid-phase catalytic reactions. Therefore, it is necessary to develop a more stable, less costly, more active catalytic system. The nickel-based catalyst has low price and high earth element content, so the nickel-based catalyst has good cost performance. Nickel-based catalysts have not been regarded as important for a long time because of their lower activity compared to cobalt-based catalysts.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a catalyst Ni for producing hydrogen from ammonia borane 2-x Fe x @ CN-G and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
catalyst for ammonia borane hydrogen production, wherein molecular formula of catalyst is Ni 2-x Fe x @ CN-G, x is more than or equal to 0 and less than or equal to 2; the catalyst has a structure that NiFe nano particles coated with nitrogen-doped carbon grow on graphene nano sheets.
The preparation method of the catalyst for preparing hydrogen from ammonia borane comprises the following steps:
(1) Preparing precursor Ni 2-x Fe x -ldh @ pda-GO composite:
(1a) Dispersing GO in water to obtain a GO dispersion liquid;
(1b) Adding nickel salt, ferric salt, a urea solution and a polyvinylpyrrolidone solution into the GO dispersion liquid, stirring uniformly, adding an alkaline solution, stirring uniformly, adding a dopamine solution, stirring for 24-72 h, and controlling the temperature to be 120-140 ℃ for hydrothermal reaction for 24-48 h; cooling to room temperature, then carrying out suction filtration and drying to obtain a precursor Ni 2-x Fe x -ldh @ pda-GO composite;
(2) And reacting the precursor Ni 2-x Fe x Heating the-LDH @ PDA-GO composite material to 400-700 ℃ under the protection of inert atmosphere, calcining for 2-4 h, cooling to room temperature, adding ethanol to ensure that the calcined product is completely immersed into the ethanol for passivation treatment, drying and grinding to prepare the catalyst Ni 2-x Fe x @CN-G。
Preferably, in step (1 a), the concentration of GO dispersion is 1-5 mg/mL −1 (ii) a In the step (1 b), the concentration of the urea solution is 0.06-0.12 g/mL −1 The concentration of the polyvinylpyrrolidone solution is 0.005-0.01 g/mL −1 The concentration of the dopamine solution is 0.01-0.03 g/mL −1 。
Preferably, in the step (1 b), the using amount ratio of the nickel salt, the iron salt, the urea solution, the polyvinylpyrrolidone solution, the GO dispersion liquid, the alkaline solution and the dopamine solution is (2-x) mmol, (5-15) mL, (80-90) mL, (120-140) mL, (5-15) mL, and x is more than or equal to 0 and less than or equal to 2.
Preferably, in step (1 b), the alkaline solution consists of ethanol, water and ammonia and the pH of the alkaline solution =8-9.
Preferably, the alkaline solution consists of ethanol, water and ammonia water according to the volume ratio of ethanol to water to ammonia water of = (30-40) to (90-100) to (0.5-1.0); the mass concentration of the ammonia water is 25-28 wt%.
Preferably, in the step (2), the temperature rise rate is 5-10 ℃ min −1 。
Preferably, in the step (2), the passivation treatment is carried out for 1-5 h.
Compared with the prior art, the invention adopts precursor Ni 2-x Fe x Method for preparing catalyst Ni by high-temperature calcination of-LDH @ PDA-GO in inert atmosphere 2-x Fe x @ CN-G, the prepared catalyst has high activity when being used for preparing hydrogen from ammonia borane.
Drawings
FIG. 1: transmission electron micrographs of the catalysts prepared in example 1 and comparative examples 1 and 2: (a) - (h) in order of Ni @ CN-G, ni 1.6 Fe 0.4 @CN-G，Ni 1.2 Fe 0.8 @CN-G，Ni 0.8 Fe 1.2 @CN-G，Ni 0.4 Fe 1.6 @CN-G，Fe@CN-G，Ni 1.2 Fe 0.8 -G，Ni 1.2 Fe 0.8 @CN。。
FIG. 2 is a schematic diagram: x-ray powder diffraction pattern of the catalyst prepared in example 1.
FIG. 3: catalyst Ni prepared in example 1 1.2 Fe 0.8 @ CN-G and Ni catalyst prepared in comparative example 1 1.2 Fe 0.8 Catalyst Ni-G prepared in comparative example 2 1.2 Fe 0.8 Raman spectrum of @ CN.
FIG. 4: comparative example 1 and the catalysts prepared in comparative examples 1-2 are shown to catalyze the hydrolysis of ammonia borane to evolve hydrogen gas (volume of hydrogen produced versus time).
FIG. 5: catalyst Ni prepared in example 1 1.2 Fe 0.8 A comparison graph of catalytic activity of the catalyst prepared in the comparative example 3 for catalyzing ammonia borane to hydrolyze and separate out hydrogen (graph of volume of produced hydrogen changing with time).
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Catalyst Ni 2-x Fe x The preparation method of @ CN-G comprises the following steps:
(1) Firstly, dispersing 0.17 g of GO in 85 mL of deionized water, and alternately performing stirring and ultrasonic treatment for 2 hours in the dispersing process to ensure uniform dispersion to obtain a GO dispersion liquid;
(2) Adding 2-x mmol nickel nitrate, x mmol ferric nitrate, 10 mL urea aqueous solution (containing 0.60 g of urea) and 10 mL polyvinylpyrrolidone (PVP) (containing 0.10 g of PVP and MW = 10000) aqueous solution to the GO dispersion respectively, and stirring for 2 h; then, 36 mL of absolute ethyl alcohol, 94 mL of deionized water and 0.75 mL of ammonia water (28 wt%) are added into the GO dispersion liquid, and stirring is continued for 0.5 h; then, 10 mL of dopamine aqueous solution (containing 0.125 g of dopamine) is added, and the mixture is continuously stirred for 24 hours at room temperature; finally, transferring the mixture into a 500 mL polytetrafluoroethylene autoclave, keeping the temperature at 120 ℃ for 24 h, naturally cooling to room temperature, carrying out suction filtration on the obtained product, and freeze-drying in vacuum to obtain a precursor Ni 2-x Fe x -ldh @ pda-GO composite;
(3) 200 mg of Ni 2-x Fe x -LDH @ PDA-GO composite material placed in porcelain boat, in N 2 Heating to 500 deg.C at a rate of 5 deg.C/min in atmosphere, calcining for 2 h, and controlling atmosphere flow at 30 mL/min −1 Cooling to room temperature, adding absolute ethyl alcohol to ensure that the calcined product is completely immersed into the ethyl alcohol for passivation for 5 hours, drying at 30 ℃, and grinding to obtain a target catalyst;
wherein x is equal to 0,0.4,0.8,1.2,1.6,2 in sequence, and the corresponding target catalysts are numbered in sequence as follows: ni @ CN-G, ni 1.6 Fe 0.4 @CN-G，Ni 1.2 Fe 0.8 @CN-G，Ni 0.8 Fe 1.2 @CN-G，Ni 0.4 Fe 1.6 @CN-G，Fe@CN-G。
Comparative example 1
The difference from example 1 is that: x =0.8, and in step (2), the dopamine aqueous solution was not added, the others being the same as in example 1. The obtained target catalyst is numbered as Ni 1.2 Fe 0.8 -G。
Comparative example 2
The difference from example 1 is that: x =0.8 and step (1) was omitted and no GO dispersion was added in step (2), all other things being the same as in example 1. The obtained target catalyst is numbered as Ni 1.2 Fe 0.8 @CN。
Comparative example 3
The difference from example 1 is that: x =0.8, and in step (3), no ethanol is added for passivation after calcination, and the calcined product is directly used as the target catalyst.
Catalyst structural characterization
FIG. 1 is a transmission electron microscope photograph of the catalysts prepared in example 1 and comparative examples 1 and 2: (a) - (h) in turn Ni @ CN-G, ni 1.6 Fe 0.4 @CN-G，Ni 1.2 Fe 0.8 @CN-G，Ni 0.8 Fe 1.2 @CN-G，Ni 0.4 Fe 1.6 @CN-G，Fe@CN-G，Ni 1.2 Fe 0.8 -G，Ni 1.2 Fe 0.8 @ CN. As can be seen in FIGS. 1 (a-f): the nickel-iron alloy nanoparticles were grown on large sheets of graphene nanoplatelets and the particles were of different sizes when different iron contents were added, with the particles having the best dispersion when the iron content was 0.8 mmol. As can be seen in FIG. 1 (g-h): nanoparticles were larger and aggregated more severely due to no GO or dopamine addition.
FIG. 2 is an X-ray powder diffraction pattern of the catalyst prepared in example 1. As can be seen from fig. 2: the metal peak position is between that of metal nickel and metal iron, and in addition, a characteristic peak of graphene is detected in the vicinity of 26 °.
FIG. 3 shows Ni catalyst prepared in example 1 1.2 Fe 0.8 @ CN-G and Ni catalyst prepared in comparative example 1 1.2 Fe 0.8 -G, catalyst Ni prepared in comparative example 2 1.2 Fe 0.8 Raman spectrum of @ CN. At 1350 cm −1 and 1589 cm −1 The peaks at (a) are due to the presence of D-and G-bands of carbon, respectively, due to the graphitized disordered structure and the amorphous carbon, and the G-band corresponds to the crystalline nature of the graphite structure.
Testing of catalyst Performance
The catalyst prepared in example 1 and the catalysts prepared in comparative examples 1 to 3 were used for producing hydrogen from ammonia borane, and the hydrolysis of ammonia borane was measured by the water displacement method. The conditions are as follows: 20 mg of catalyst was dissolved in 5 mL of H 2 In O, 84 mg of ammonia borane was dissolved in 5 mL of NaOH solution simultaneously(containing NaOH 0.4 g). Before the hydrogen production test, the flask was placed in a water bath at 25 ℃, and the two solutions were poured into the flask and mixed and stirred at a stirring speed of 500 rpm.
FIG. 4 is a graph comparing the catalytic activity of the catalysts prepared in example 1 and comparative examples 1-2 to catalyze the hydrolysis of ammonia borane to evolve hydrogen gas (the volume of hydrogen produced versus time). As can be seen in fig. 4 (a): ni under the same conditions 1.2 Fe 0.8 @ CN-G has the best hydrogen-producing activity, and as can be seen from FIG. 4 (b): compared with catalyst Ni 1.2 Fe 0.8 -G and Ni 1.2 Fe 0.8 @ CN, catalyst Ni 1.2 Fe 0.8 The time required by the @ CN-G catalytic reaction is shortest, which shows that the activity of the catalyst in ammonia borane hydrolysis is greatly improved by the carbon coating method and the introduction of the graphene.
FIG. 5 shows Ni catalyst prepared in example 1 1.2 Fe 0.8 Comparative graph of catalytic activity of catalyst prepared in comparative example 3 for catalyzing ammonia borane to hydrolyze and separate out hydrogen (graph of volume of hydrogen produced in time). As can be seen from fig. 5: the catalyst obtained by adding ethanol for passivation has high activity compared with the catalyst obtained by not adding ethanol.
Claims (7)
1. The preparation method of the catalyst for ammonia borane hydrogen production is characterized in that the molecular formula of the catalyst is Ni 2-x Fe x @ CN-G, x is more than 0 and less than 2; the catalyst has a structure that NiFe nano particles coated by nitrogen-doped carbon grow on a graphene nano sheet; the preparation steps are as follows:
(1) And preparing a precursor Ni 2-x Fe x -ldh @ pda-GO composite:
(1a) Dispersing GO in water to obtain a GO dispersion liquid;
(1b) Adding nickel salt, ferric salt, a urea solution and a polyvinylpyrrolidone solution into the GO dispersion liquid, uniformly stirring, adding an alkaline solution, uniformly stirring, adding a dopamine solution, stirring for 24-72 h, and controlling the temperature to be 120-140 ℃ for hydrothermal reaction for 24-48 h; cooling to room temperature, then carrying out suction filtration and drying to obtain a precursor Ni 2-x Fe x -ldh @ pda-GO composite;
(2) And Ni precursor 2-x Fe x Heating the-LDH @ PDA-GO composite material to 400-700 ℃ under the protection of inert atmosphere, calcining for 2-4 h, cooling to room temperature, adding ethanol to ensure that the calcined product is completely immersed in ethanol for passivation treatment, drying and grinding to obtain the catalyst Ni 2-x Fe x @CN-G。
2. The method for preparing the catalyst for ammonia borane hydrogen production according to claim 1, characterized by comprising: in the step (1 a), the concentration of GO dispersion liquid is 1-5 mg/mL −1 (ii) a In the step (1 b), the concentration of the urea solution is 0.06-0.12 g.mL −1 The concentration of the polyvinylpyrrolidone solution is 0.005-0.01 g/mL −1 The concentration of the dopamine solution is 0.01-0.03 g/mL −1 。
3. The method for preparing the catalyst for ammonia borane hydrogen production according to claim 2, characterized in that: in the step (1 b), the dosage ratio of the nickel salt, the ferric salt, the urea solution, the polyvinylpyrrolidone solution, the GO dispersion liquid, the alkaline solution and the dopamine solution is (2-x) mmol, x mmol, (5-15) mL, (80-90) mL, (120-140) mL and (5-15) mL, and x is more than 0 and less than 2.
4. A process for producing a catalyst for ammonia borane hydrogen production according to any one of claims 1 to 3, characterized by: in step (1 b), the alkaline solution consists of ethanol, water and ammonia water and the pH of the alkaline solution =8-9.
5. The method for preparing the catalyst for ammonia borane hydrogen production according to claim 4, characterized by comprising the following steps: the alkaline solution consists of ethanol, water and ammonia water according to the volume ratio of ethanol, water and ammonia water of (30-40) to (90-100) to (0.5-1.0); the mass concentration of the ammonia water is 25-28 wt%.
6. The method for preparing the catalyst for ammonia borane hydrogen production according to claim 1, characterized in thatCharacterized in that: in the step (2), the temperature rise rate is 5-10 ℃ min −1 。
7. The method for preparing the catalyst for ammonia borane hydrogen production according to claim 1, characterized by comprising: in the step (2), passivation treatment is carried out for 1-5 h.
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| CN112044462B (en) * | 2020-09-10 | 2021-11-05 | 中山大学 | Graphene-loaded transition metal nitride nanocomposite and preparation method and application thereof |
| CN112717952B (en) * | 2021-02-25 | 2022-10-25 | 郑州大学 | Catalyst PtNiO for ammonia borane hydrogen evolution by hydrolysis x /TiO 2 -V O And method for preparing the same |
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