CN111686752B - Taraxacum-shaped load type amorphous alloy catalyst and preparation method and application thereof - Google Patents
Taraxacum-shaped load type amorphous alloy catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 27
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 241000245665 Taraxacum Species 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 31
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- -1 zeolite imidazole ester Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000011943 nanocatalyst Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000006227 byproduct Substances 0.000 description 2
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- 238000012827 research and development Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000005280 amorphization Methods 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/40—
-
- 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
-
- 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 discloses a dandelion shapeA load type amorphous alloy catalyst, a preparation method thereof and application thereof in catalyzing hydroboron or ammonia borane hydrolysis to prepare hydrogen. The catalyst takes ZIF-67 as a carrier, and Co, Mo and Ni precursors are subjected to NaBH according to a regulation and control ratio4Reducing and completely wrapping the ZIF-67 nano particles to obtain the amorphous alloy supported nano catalyst with excellent catalytic performance. The obtained catalyst has a dandelion-shaped structure, is uniformly distributed, has a large specific surface area and a plurality of catalytic active sites, has good catalytic activity in the field of hydrogen production by hydrolysis of borohydride or ammonia borane, and has the catalytic performance which is increased by 150 percent compared with that of a pure unsupported CoMoNi-B catalyst and can reach 7120mL of H2min/g Co, the apparent activation energy is 35.01kJ/mol, and after 5 times of cyclic reaction, 86 percent of catalytic activity is maintained. Compared with the traditional noble metal catalyst, the catalyst has the advantages of simple preparation, low cost, easily obtained raw materials, suitability for industrial production and wide application prospect.
Description
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a dandelion-shaped supported amorphous alloy catalyst and a preparation method and application thereof.
Background
With the continuous consumption and utilization of resources, how to develop, store and convert novel renewable green energy and efficient clean energy has become a key factor of sustainable development in future society. In recent years, scientists and researchers have continuously made efforts to develop energy systems, and research on renewable energy sources has been carried out more deeply. The hydrogen energy is considered as the available next generation green energy source due to the characteristics of abundant reserves, high energy density, environmental friendliness and the like.
Solid-state hydrogen storage with metal hydrides (such as sodium borohydride and the like) has very high hydrogen storage density, can be operated at relatively low temperature and pressure, and is safer than mechanical storage. The sodium borohydride has the characteristics of high hydrogen release density (the hydrogen storage capacity is up to 10.8 wt%), low hydrogen release temperature, high hydrogen release speed and the like. The hydrolysis catalyst can react with water at normal temperature to release hydrogen, and can be regenerated through chemical processes such as ball milling and the like after hydrolysis hydrogen release is realized, and meanwhile, for borohydride, the efficient hydrolysis catalyst can realize controllable hydrogen release at room temperature, so that the research and development of practical mobile hydrogen sources are possible.
The development of a catalyst with excellent performance and low price is the key for promoting the application of sodium borohydride in hydrogen production by hydrolysis. At present, noble metals Pt and Ru and alloys thereof have excellent catalytic activity on the hydrogen production reaction by sodium borohydride hydrolysis. Despite their excellent performance, the use of noble metals as catalysts is hardly feasible on an industrial level due to their high cost and scarcity, which has led researchers to focus more on non-noble metal catalysts, especially Co-based catalysts.
At present, it has been reported that, compared with a single metal catalyst, three or more specific metal elements can form a synergistic effect by combining with each other, so that the catalytic performance of the catalyst is greatly improved. Taking a cobalt-based catalyst as an example, by adding other specific elements (such as Ni, Mo, etc.), a common electron pair is formed, so that cobalt becomes more active, and the deactivation of the catalyst is avoided. These third metals are present in the ternary alloy catalyst primarily as metal oxides. In addition, they also promote the overall catalytic reaction by acting as acidic sites, increasing the absorption of reactive species on the surface; the added metal can also act as an electron donor ligand, enhancing the kinetic activity of the reaction. However, too high surface energy of the unsupported catalyst can cause easy agglomeration of catalyst particles and reduce the performance of the catalyst. Therefore, the research and development of a proper carrier which is adaptive to the metal active component can effectively inhibit the agglomeration phenomenon, and the service life and the performance of the catalyst are further improved, thereby having important significance.
Patent specification CN 107930697 a discloses a Pt/ZIF-67 composite material for catalyzing ammonia borane hydrolysis to produce hydrogen, which can provide higher specific surface area and adsorption capacity by using ZIF-67 to compound with Pt, so that metal nanoparticles are more uniformly dispersed on the surface of MOF material. Wherein ZIF-67 is obtained by the hydrothermal reaction of cobalt acetate tetrahydrate and 2-methylimidazole. The Pt/ZIF-67 composite material prepared by the patent technology is used for catalyzing ammonia borane to hydrolyze and release hydrogen, and the activation energy is 30-40kJ mol-1The activation energy corresponds to the active groupIs classified as a noble metal Pt. And the catalyst structure obtained by the patent technology has no specificity.
Therefore, there is still a great challenge to develop a simple and convenient method for preparing a borohydride or ammonia borane hydrolysis catalyst with a unique structure and high performance.
Disclosure of Invention
The invention aims to provide a dandelion-shaped load type amorphous alloy catalyst with high circulation stability, a preparation method and application thereof, aiming at the defects of high price, low catalytic activity and poor circulation stability of the existing sodium borohydride hydrolysis catalyst. Compared with the traditional catalyst, the catalyst can reduce the cost, simplify the synthesis method and greatly improve the catalytic performance.
A dandelion-shaped supported amorphous alloy catalyst is obtained by loading an active ingredient on a zeolite imidazole ester framework material ZIF-67, wherein the active ingredient is an amorphous alloy consisting of Co, Mo, Ni and B.
As a general inventive concept, the present invention also provides a preparation method of the taraxacum-shaped supported amorphous alloy catalyst, comprising the steps of:
(1) dissolving cobalt nitrate hexahydrate in absolute methanol, performing ultrasonic dispersion to obtain a first material, dissolving 2-methylimidazole in absolute methanol, and performing ultrasonic dispersion to obtain a second material;
(2) adding the second material into the first material under stirring, and continuously stirring for 11-13 hours to obtain a ZIF-67 precursor solution;
(3) centrifugally washing the ZIF-67 precursor solution with absolute ethyl alcohol, and carrying out vacuum drying at 45-55 ℃ to obtain a carrier ZIF-67;
(4) sealing, stirring and dispersing the carrier ZIF-67 prepared in the step (3) in deionized water, then adding metal salt, continuing to seal and stir for 0.5-1.5 hours, and performing ice-water bath for 10-20 minutes after stirring is completed to obtain an ion impregnation liquid; the metal salt is cobalt salt, molybdenum salt and nickel salt;
(5) under the environment of ice-water bath, NaBH is added4Dropwise adding the aqueous solution into the ionic impregnation solution, and continuously stirring for 0.5-1.5 hours in a sealed manner, wherein the maximum time isThen centrifuging, washing and vacuum drying to obtain the dandelion-shaped load type amorphous alloy catalyst.
The key of the preparation method is that NaBH is dropwise added in ice water bath in the step (5)4Aqueous solution, otherwise, the taraxacum-shaped supported amorphous alloy catalyst can not be formed.
The invention effectively inhibits the generation of agglomeration phenomenon and improves the service life and performance of the catalyst by loading the specific metal active component on a proper carrier and combining a special preparation method. The ZIF-67 used in the invention is of a rhombic dodecahedron structure, has a high specific surface area, and can improve the effective contact area of the loaded amorphous alloy and a reactant, thereby greatly improving the catalytic activity of the loaded amorphous alloy. Particularly, due to the fact that a dandelion-shaped structure is formed, the specific flocculent amorphous alloy uniformly wrapped on the surface of the carrier can improve the electron transfer capability of the whole catalyst through interaction with the carrier, the specific flocculent amorphous alloy and the carrier are combined together, the catalytic activity and the cycle life of the catalyst can be greatly improved, and no relevant report that the catalyst with a similar structure is applied to sodium borohydride hydrolysis research exists at present.
Compared with a pure supported nano catalyst, the dandelion type catalyst with the special structure can effectively prevent nano particles from agglomerating and inactivating and improve the controllability of the catalyst, and can further realize the integration and integration of various active sites by adjusting the components, the proportion, the structure, the size and the like of an 'internal bud' (carrier) or 'flocculent crown hair' (amorphous alloy) so as to adapt to more complex and diversified catalytic reaction systems. In the catalyst, the surface/interface effect and synergistic effect between the ZIF-67 nanostructure and the uniformly dispersed amorphous alloy endow the material with excellent catalytic performance of hydrogen production by hydrolysis of borohydride or ammonia borane.
The invention regulates and controls the optimal components of the catalyst by changing the metal ratio, takes ZIF-67 as a carrier, and passes Co, Mo and Ni precursors through NaBH according to a certain regulation and control proportion4Reduction to obtain catalytic propertiesThe excellent dandelion-shaped load type amorphous alloy nano catalyst CoMoNi-B/ZIF-67, wherein NaBH4On one hand, the boron source is used as a reducing agent to reduce metal ions, and on the other hand, the boron source is used to form boride with non-noble metals.
Preferably, in the step (1), the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 1: 1.7.
Preferably, in the step (4), the ratio of the mass of the carrier ZIF-67 to the total mass of the metal salt to the volume of the deionized water is 100mg:57.7mg:20 mL;
the cobalt salt is CoCl2·6H2O, molybdenum salt is Na2MoO4·2H2O, the nickel salt being NiCl2·6H2O。
Preferably, the mass ratio of cobalt in the cobalt salt, molybdenum in the molybdenum salt, and nickel in the nickel salt is 5.85:4.17: 1. The proportion has the best catalytic performance and cycling stability.
According to the invention, a Co-reduction method is adopted, and the Co, Mo and Ni precursors are completely wrapped with ZIF-67 according to a regulation and control ratio to form a dandelion-shaped structure. Preferably, in step (5), NaBH4The molar ratio to metal salt was 10: 1.
Preferably, the dandelion-shaped supported amorphous alloy catalyst is formed by uniformly wrapping flocculent amorphous alloy on the surface of the carrier ZIF-67, is in a dandelion-shaped structure and has the size of 850-950 nm, wherein the size of the carrier ZIF-67 is 450-550 nm. The dandelion-shaped structure of the invention obtains a very large specific surface area and can effectively inhibit the agglomeration and growth of the transition metal nano catalyst.
The invention also provides application of the dandelion-shaped load type amorphous alloy catalyst in catalyzing hydroboron or ammonia borane hydrolysis to prepare hydrogen.
The dandelion-shaped load type amorphous alloy catalyst is used for catalyzing NaBH4Hydrolysis to produce hydrogen, and apparent activation energy can be reduced to 35.01 kJ/mol.
Compared with the prior art, the invention has the main advantages that:
(1) the prepared catalyst has a dandelion structure, and the activity and the cycle life of the catalyst are greatly improved by utilizing the electron transfer in the multielement metal and the dispersion effect of the carrier. In addition, the invention firstly wraps the amorphous CoMoNi-B alloy with high amorphization degree around the ZIF-67 with high crystallization degree by a dropwise adding co-reduction method to obtain the dandelion-shaped nano catalyst with the diameter of about 900 nanometers, and can further realize the integration and integration of various active sites by adjusting the components and structures of the 'internal buds' or the 'flocculent crowns' to adapt to more complex and diversified catalytic reaction systems.
(2) The dandelion-shaped load type amorphous alloy catalyst can present a macroporous honeycomb structure after catalytic reaction, is favorable for dispersion, is not easy to cause the aggregation of the by-product sodium metaborate, and can not obstruct a reaction channel, thereby prolonging the cycle life of the catalyst. Compared with the unsupported catalyst, the catalytic activity is improved by 150 percent, and the NaBH is added to the catalyst at room temperature4The hydrolysis hydrogen production rate is as high as 7120mL H2min/g Co, the apparent activation energy was 35.01 kJ/mol.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a dandelion-like CoMoNi-B catalyst prepared in example 2 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of a dandelion-like CoMoNi-B catalyst prepared in example 2 of the present invention;
FIG. 3 is a graph showing performance test of a CoMoNi-B/ZIF-67 series catalyst prepared in examples 1-3 of the present invention in catalyzing hydrolysis of sodium borohydride at room temperature to release hydrogen;
FIG. 4 is an SEM photograph of a CoMoNi-B/ZIF-67 catalyst prepared in example 2 of the present invention after five cycles at room temperature;
FIG. 5 is a graph showing calculation of Arrhenius activation energy for catalyzing hydrolysis of sodium borohydride to release hydrogen at 25 ℃, 35 ℃, 45 ℃ and 55 ℃ in a CoMoNi-B/ZIF-67 catalyst prepared in example 2 of the present invention;
FIG. 6 is a graph fitting the reaction rate of the CoMoNi-B/ZIF-67 catalyst prepared in example 2 of the present invention to hydrolyze sodium borohydride at room temperature with 10mg, 20mg, 30mg, and 40mg, respectively;
FIG. 7 is an XRD pattern of 5 cycles of reaction of the CoMoNi-B/ZIF-67 catalyst prepared in example 2 of the present invention, the CoMoNi-B catalyst prepared in comparative example 1, the ZIF-67 carrier, and the CoMoNi-B/ZIF-67 catalyst;
FIG. 8 is a graph showing the performance of the catalysts of comparative examples 1 to 2, example 2 and carrier ZIF-67 for hydrogen release from sodium borohydride hydrolysis at room temperature;
FIG. 9 is a TEM image of a CoMoNi-B/ZIF-67 catalyst of conventional morphology prepared in comparative example 3 of the present invention;
FIG. 10 is a performance test chart of the dandelion-shaped CoMoNi-B/ZIF-67 catalyst prepared in example 2 and the common-morphology CoMoNi-B/ZIF-67 catalyst prepared in comparative example 3 for catalyzing hydrolysis of sodium borohydride to release hydrogen at room temperature.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
And (3) preparing a 5% amorphous alloy loaded CoMoNi-B/ZIF-67 nano catalyst.
(1) 2.9g Co (NO) are weighed out3)2·6H2Dissolving O and 2-methylimidazole in 25mL of anhydrous methanol respectively, ultrasonically dispersing for 30 minutes, and slowly pouring the methanol solution of 2-methylimidazole into Co (NO) under the magnetic stirring environment of 500r/min3)2·6H2And (4) stirring the mixture for 12 hours in the methanol solution of O at the same rotating speed to obtain a ZIF-67 precursor solution. And (3) centrifuging the purple ZIF-67 precursor solution at the rotating speed of 8000r/min, adding absolute ethyl alcohol for cleaning, repeatedly centrifuging and cleaning for four times, and vacuum-drying the obtained solid at the temperature of 50 ℃ for 12h to obtain the ZIF-67.
(2) And (3) putting 100mg of ZIF-67 in a beaker, adding 20mL of deionized water, sealing the membrane at 500r/min and stirring for 10 min. 0.0035g of NiCl was weighed out separately2·6H2O，0.0106g Na2MoO4·2H2O，0.0241g CoCl2·6H2Dissolving O in the stirred ZIF-67 aqueous solution, sealing the membrane at 500r/min, stirring for 1h, and carrying out ice-water bath for 10-20 min after stirring to obtain the ionic impregnation liquid. Weighing a certain amount of NaBH4Adding 10mL of deionized water to prepare 0.17mol/L NaBH4A reducing agent solution. And (3) dropwise adding a reducing agent into the ionic impregnation liquid in an ice-water bath environment, and continuously stirring for 1h to obtain an aqueous solution of the CoMoNi-B/ZIF-67. The solution is centrifuged at 8000r/min and deionized water is added for cleaning. And repeatedly centrifuging and cleaning the catalyst for three times, and drying the obtained solid in vacuum at 50 ℃ to obtain the catalyst CoMoNi-B/ZIF-67.
Example 2
Preparation of a CoMoNi-B/ZIF-67 nano catalyst with 7.5% amorphous alloy loading.
The only difference from example 1 is that 0.0053g of NiCl was weighed in step (2)2·6H2O，0.0159g Na2MoO4·2H2O，0.0362g CoCl2·6H2O, the same procedure as in example 1 was repeated, to obtain a catalyst CoMoNi-B/ZIF-67.
The scanning electron micrograph of the CoMoNi-B/ZIF-67 catalyst prepared in this example is shown in FIG. 1, which shows that the composite catalyst macroscopically appears to be a spherical structure, and the surface is flocculent CoMoNi-B amorphous alloy. The size is uniform and the arrangement is compact.
The TEM image of the CoMoNi-B/ZIF-67 catalyst prepared in this example is shown in FIG. 2, and it can be directly seen by TEM that the supported catalyst is in a dandelion-like structure, and a layer of amorphous CoMoNi-B alloy uniformly wraps the ZIF-67.
Example 3
And (3) preparing a 10% amorphous alloy loaded CoMoNi-B/ZIF-67 nano catalyst.
The only difference from example 1 is that 0.0071g of NiCl was weighed in step (2)2·6H2O，0.0213g Na2MoO4·2H2O，0.0483g CoCl2·6H2O, the same procedure as in example 1 was repeated, to obtain a catalyst CoMoNi-B/ZIF-67.
Example 4
Sodium borohydride under catalyst conditions explains the hydrogen experiment:
in order to investigate the catalytic effect of the catalyst on the hydrolysis hydrogen release of sodium borohydride, the invention carries out the hydrolysis hydrogen release experiment of sodium borohydride under the condition of the catalyst, and the experimental process is as follows:
the catalytic experiments were performed in a 50mL single neck round bottom flask. 100mg of catalyst and 2mL of deionized water are transferred into a round-bottom flask, the port of the flask is connected with a 500mL measuring cylinder filled with water through a rubber tube, when hydrogen is generated, the generated gas can remove the water with the same volume in the measuring cylinder, and the generation amount of the hydrogen can be read out through the height change of the liquid level. The experimental device is transferred into a hydrothermal pot with the temperature of 25 ℃ and is stirred by magnetic force, and the stirring speed is 500 r/min. 0.3783g of sodium borohydride and 2g of sodium hydroxide were dissolved in 10mL of deionized water and 0.2mL of basic sodium borohydride solution was added each time via syringe to the round bottom flask, at which time the reaction started and counted every 3 seconds until the end of the reaction. After one test, the catalyst is taken out, centrifugal washing is carried out by absolute ethyl alcohol, the catalyst is weighed before each test, and the next test is carried out under the same conditions.
The performance diagram of the CoMoNi-B/ZIF-67 catalysts with different loading amounts obtained in examples 1-3 for catalyzing hydrolysis of sodium borohydride and hydrogen release is shown in FIG. 3.
The catalyst of example 2 still maintains 86% of the initial activity after five times of cyclic reaction, and the SEM photograph is shown in fig. 4, and the catalyst shows a macroporous honeycomb structure after catalytic reaction, which is favorable for dispersion, and does not easily cause aggregation of the by-product sodium metaborate, and does not obstruct the reaction channel, thereby improving the cycle life of the catalyst.
Example 5
Hydrogen release rate and activation energy of the catalyst under different temperature conditions were tested:
the samples prepared in example 2 were used at different temperatures (25 ℃, 35 ℃, 45 ℃ and 55 ℃) to catalyze the hydrolysis of sodium borohydride to release hydrogen by the method of example 4.
The CoMoNi-B/ZIF-67 catalyst prepared in example 2 was catalyzed at 25 deg.C, 35 deg.C, 45 deg.C and 55 deg.CAn arrhenius activation energy test chart of hydrogen release of sodium borohydride hydrolysis is shown in fig. 5, and the result shows that the hydrogen release rate is in positive correlation with the temperature, and the higher the temperature is, the faster the hydrogen release rate is. The activation energy of the CoMoNi-B/ZIF-67 catalytic reaction is calculated to be 35.01kJ mol by an Arrhenius formula-1。
Example 6
Hydrogen release rate test for different catalyst dosages:
the samples prepared in example 2 were used to catalyze the hydrolysis of sodium borohydride to produce hydrogen by the method of example 4 at different catalyst masses (10mg, 20mg, 30mg, and 40 mg).
The fitting curve of the reaction rates of the CoMoNi-B/ZIF-67 catalyst prepared in example 2, which is 10mg, 20mg, 30mg and 40mg respectively for catalyzing hydrolysis and hydrogen release of sodium borohydride is shown in FIG. 6, and the result shows that the influence of the catalyst dosage on the hydrogen production rate is very obvious, and the hydrogen production rate is faster when the catalyst dosage is larger. The reason is that the use amount of the catalyst is increased, the probability of contact of reactants and the catalyst is increased, so that the hydrolysis reaction of sodium borohydride is promoted, and the result shows that NaBH4The hydrolysis reaction follows first order kinetics with respect to the CoMoNi-B/ZIF-67 catalyst concentration.
Comparative example 1
Preparation of an unsupported CoMoNi-B nano catalyst: the catalyst was obtained as CoMoNi-B, except that the catalyst was identical to that of example 2 except that the catalyst was changed to the unsupported ZIF-67.
XRD patterns of the catalyst CoMoNi-B/ZIF-67 prepared in example 2, the catalyst prepared in comparative example 1 and the carrier ZIF-67 prepared according to the step (1) of example 2 are shown in FIG. 7.
Comparative example 2
CoMoNi-B/TiO2Preparing a nano catalyst: the difference from the example 2 is only that nano TiO with equal mass is adopted2(particle size 5 to 10nm) in place of the carrier ZIF-67, the rest being the same as in example 2, to obtain a catalyst CoMoNi-B/TiO2。
The performance graph of the catalyst for hydrolyzing hydrogen from sodium borohydride of the CoMoNi-B/ZIF-67 catalyst prepared in example 2 and the carrier ZIF-67 prepared in comparative example 1, comparative example 2 and according to step (1) of example 2 is shown in fig. 8.
Comparative example 3
Preparing a common-morphology CoMoNi-B/ZIF-67 nano catalyst: the only difference from example 2 is that an equal amount of NaBH was added rapidly at room temperature4The same solution of the reducing agent as in example 2 was used to obtain a CoMoNi-B/ZIF-67 catalyst.
The TEM image of the CoMoNi-B/ZIF-67 catalyst of the general morphology prepared in comparative example 3 is shown in FIG. 9. The supported catalyst does not have a special shape and a large amount of metal Co particles without catalytic activity are generated, ZIF-67 and CoMoNi-B in the comparative example are separated, most CoMoNi-B catalytic components are aggregated, the specific surface area is relatively small, and the progress of catalytic reaction cannot be remarkably improved.
The performance graphs of the taraxacum-shaped CoMoNi-B/ZIF-67 catalyst prepared in example 2 and the common morphology CoMoNi-B/ZIF-67 catalyst prepared in comparative example 3 are shown in FIG. 10.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A dandelion-shaped supported amorphous alloy catalyst is characterized in that the catalyst is obtained by loading active ingredients on a zeolite imidazole ester framework material ZIF-67, wherein the active ingredients are amorphous alloys consisting of Co, Mo, Ni and B;
the preparation method of the dandelion-shaped load type amorphous alloy catalyst comprises the following steps:
(1) dissolving cobalt nitrate hexahydrate in absolute methanol, performing ultrasonic dispersion to obtain a first material, dissolving 2-methylimidazole in absolute methanol, and performing ultrasonic dispersion to obtain a second material;
(2) adding the second material into the first material under stirring, and continuously stirring for 11-13 hours to obtain a ZIF-67 precursor solution;
(3) centrifugally washing the ZIF-67 precursor solution with absolute ethyl alcohol, and carrying out vacuum drying at 45-55 ℃ to obtain a carrier ZIF-67;
(4) sealing, stirring and dispersing the carrier ZIF-67 prepared in the step (3) in deionized water, then adding metal salt, continuing to seal and stir for 0.5-1.5 hours, and performing ice-water bath for 10-20 minutes after stirring is completed to obtain an ion impregnation liquid; the metal salt is cobalt salt, molybdenum salt and nickel salt;
(5) under the environment of ice-water bath, NaBH is added4And dropwise adding the aqueous solution into the ionic impregnation solution, continuously sealing and stirring for 0.5-1.5 hours, and finally centrifuging, washing and vacuum drying to obtain the dandelion-shaped supported amorphous alloy catalyst.
2. The taraxacum-containing amorphous alloy catalyst of claim 1, wherein in step (1), the mass ratio of said cobalt nitrate hexahydrate to 2-methylimidazole is 1: 1.7.
3. The dandelion-like supported amorphous alloy catalyst according to claim 1, wherein in step (4), the ratio of the mass of the carrier ZIF-67, the total mass of the metal salt and the volume of the deionized water is 100mg:57.7mg:20 mL;
the cobalt salt is CoCl2·6H2O, molybdenum salt is Na2MoO4·2H2O, the nickel salt being NiCl2·6H2O。
4. The dandelion-like supported amorphous alloy catalyst according to claim 3, characterized in that the mass ratio of cobalt in the cobalt salt, molybdenum in the molybdenum salt and nickel in the nickel salt is 5.85:4.17: 1.
5. The taraxacum-containing amorphous alloy catalyst of claim 1, wherein in step (5), NaBH4The molar ratio to metal salt was 10: 1.
6. The dandelion-like supported amorphous alloy catalyst according to any one of claims 1 to 5, wherein the flocculent amorphous alloy is uniformly coated on the surface of the carrier ZIF-67, and has a dandelion-like structure with a size of 850 to 950nm, wherein the size of the carrier ZIF-67 is 450 to 550 nm.
7. The use of the dandelion-like supported amorphous alloy catalyst according to any of claims 1-6 in catalyzing the hydrolysis of borohydride or ammonia borane to produce hydrogen.
8. The use of claim 7, wherein the taraxacum-like supported amorphous alloy catalyst is used for catalyzing NaBH4The hydrolysis produces hydrogen, and the apparent activation energy is 35.01 kJ/mol.
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