CN114887643A - Catalyst for preparing hydrogen by ammonolysis and preparation method thereof - Google Patents
Catalyst for preparing hydrogen by ammonolysis and preparation method thereof Download PDFInfo
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- CN114887643A CN114887643A CN202210521369.1A CN202210521369A CN114887643A CN 114887643 A CN114887643 A CN 114887643A CN 202210521369 A CN202210521369 A CN 202210521369A CN 114887643 A CN114887643 A CN 114887643A
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- ruthenium
- nitrogen
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- doped carbon
- hydrogen
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000001257 hydrogen Substances 0.000 title claims abstract description 106
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 106
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000005915 ammonolysis reaction Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 94
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 63
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 63
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 238000011068 loading method Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000001354 calcination Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000004408 titanium dioxide Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 150000003303 ruthenium Chemical class 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000002815 nickel Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002071 nanotube Substances 0.000 claims description 13
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 239000007869 azo polymerization initiator Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 claims description 2
- MHQZDNQHLGFBRN-UHFFFAOYSA-N 5-ethenyl-1h-imidazole Chemical compound C=CC1=CNC=N1 MHQZDNQHLGFBRN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 29
- 239000003575 carbonaceous material Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 5
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 229910000929 Ru alloy Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052743 krypton Inorganic materials 0.000 description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- -1 nickel metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to the technical field of ammonia decomposition, in particular to a catalyst for hydrogen production by ammonia pyrolysis and a preparation method thereof. The preparation method of the catalyst for preparing hydrogen by ammonolysis comprises the following steps: the nitrogen-doped carbon nanotube NPTC is used for firstly loading ruthenium and then loading nickel, and then the product is calcined and reduced to prepare the catalyst for the hydrogen production by ammonia pyrolysis. Ruthenium is loaded on the nitrogen-doped carbon nanotube NPTC firstly and then loaded, so that the use amount of the ruthenium can be reduced, the catalytic activity of the catalyst for the hydrogen production by ammonolysis can be improved, and the prepared catalyst for the hydrogen production by ammonolysis is at 550 ℃ and at an airspeed of 6000h ‑1 The conversion catalytic efficiency of the ammonia gas can reach more than 90 percent in the state of (1). Meanwhile, the problem of excessive reduction of ruthenium on the carbon nanotube with the nitrogen-doped communicated tubular structure can be solved by loading ruthenium and then loading nickel, so that the activity of the catalyst is further improved. In addition, the prepared catalyst for preparing hydrogen by ammonolysis has high dispersion degree of ruthenium and nickel and greatly improved catalytic activity compared with pure ruthenium.
Description
Technical Field
The invention relates to the technical field of ammonia decomposition, in particular to a catalyst for hydrogen production by ammonia pyrolysis and a preparation method thereof.
Background
Hydrogen energy has received much attention as the most desirable clean renewable energy source in the twenty-first century. However, the traditional hydrogen production method has high cost, and the hydrogen is flammable and explosive, and is easy to generate hydrogen with hydrogen storage materials to cause brittleness, so that the industrial application of hydrogen energy is limited to a great extent. The ammonia gas has higher hydrogen content and boiling point far higher than that of liquid hydrogen, and the hydrogen production by ammonia decomposition provides convenient conditions for the storage and transportation of the hydrogen gas and the application in the aspect of vehicle-mounted hydrogen production. The ammonia decomposition hydrogen production can be roughly divided into two types of electrolytic hydrogen production and pyrolysis hydrogen production, wherein the ammonia pyrolysis hydrogen production has relatively wider application in industry due to the characteristics of mature process, simple reaction, short flow, high reaction conversion efficiency and the like. The reaction for producing hydrogen by pyrolyzing ammonia has low conversion rate under the condition of simple heating due to reversibility, and cannot meet the requirement of large-scale industrial production, so that the high-efficiency catalyst plays an important role in the reaction.
For the catalyst used in industrial production, efficiency and efficiency are two issues that must be considered, while the conventional catalyst for ammonia pyrolysis hydrogen production has several drawbacks that limit its large-scale application: (1) the cost of high-efficiency catalysts represented by ruthenium is high; (2) and the low-cost non-noble metal catalyst has low activity, so that the complete conversion temperature of the reaction is high and the conversion efficiency is low.
Therefore, it is highly desirable to provide a catalyst for hydrogen production by ammonolysis, which is environment-friendly, low-cost and high-efficiency, and a preparation method thereof.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the catalyst for preparing hydrogen by ammonolysis and the preparation method thereof, and the catalyst for preparing hydrogen by ammonolysis is environment-friendly, low in cost and high in efficiency.
The invention conception of the invention is as follows: ruthenium and nickel alloy are loaded on a nitrogen-doped carbon Nanotube (NPTC), so that the catalytic activity of the catalyst for preparing hydrogen through ammonolysis can be improved, and meanwhile, the problem of excessive reduction of ruthenium can be solved by loading ruthenium first and then loading nickel, so that the activity of the catalyst is further improved.
The first aspect of the invention provides a preparation method of a catalyst for producing hydrogen by ammonolysis, which comprises the following steps:
the preparation method comprises the steps of polymerizing, calcining and removing titanium dioxide by using a titanium dioxide nanotube, an imidazole substance, an amide substance and an azo polymerization initiator to prepare a nitrogen-doped carbon Nanotube (NPTC); the imidazole substance contains alkenyl, and the amide substance contains alkenyl;
loading ruthenium on the nitrogen-doped carbon Nanotube (NPTC) to prepare ruthenium-loaded nitrogen-doped carbon Nanotube (NPTC) powder; the calcining temperature in the ruthenium loading process is 100-150 ℃;
loading nickel on the ruthenium-loaded nitrogen-doped carbon Nanotube (NPTC) powder to prepare the catalyst for preparing hydrogen by ammonia pyrolysis; the calcination temperature in the nickel loading process is 600-800 ℃.
Compared with the prior art, the preparation method of the catalyst for hydrogen production by ammonolysis provided by the first aspect of the invention has the following beneficial effects: ruthenium and nickel alloy are loaded on a carbon nano tube (NPTC) with a nitrogen-doped communicated tubular structure, so that the catalytic activity of the catalyst for preparing hydrogen by ammonolysis can be improved; meanwhile, the problem of excessive reduction of ruthenium on the carbon nanotube with the nitrogen-doped communicated tubular structure can be solved by loading ruthenium and then loading nickel, so that the activity of the catalyst is further improved. In addition, the prepared catalyst for preparing hydrogen by ammonolysis has high dispersion degree of ruthenium and nickel and greatly improved catalytic activity compared with pure ruthenium.
Preferably, the imidazole substance comprises at least one of 1-vinyl imidazole, 2-vinyl imidazole and 5-vinyl imidazole.
Preferably, the amide-type substance comprises at least one of N, N '-methylene bisacrylamide and N, N' -vinyl bisacrylamide.
Preferably, the azo polymerization initiator includes at least one of 4,4' -azobis (4-cyanovaleric acid), azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyronitrile, and azobisisoheptonitrile.
Preferably, the ruthenium loading process specifically comprises: dispersing the nitrogen-doped carbon nano tube into water to prepare nitrogen-doped carbon nano tube dispersion liquid, adding a ruthenium salt aqueous solution into the nitrogen-doped carbon nano tube dispersion liquid, heating, mixing, reacting, washing and drying to prepare nitrogen-doped carbon nano tube powder loaded with ruthenium salt; and calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium salt in a mixed atmosphere of hydrogen and protective gas to obtain the nitrogen-doped carbon nanotube powder loaded with ruthenium.
The preferable process of loading nickel is specifically as follows: adding the nitrogen-doped carbon nanotube powder loaded with ruthenium into a nickel salt aqueous solution, heating, mixing, washing and drying to prepare nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel salt; and calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel chloride in the mixed atmosphere of hydrogen and protective gas to obtain the catalyst for preparing hydrogen by ammonia pyrolysis.
Preferably, the preparation method comprises the following steps:
(1) dispersing titanium dioxide nanotubes, 1-vinyl imidazole (1-VIm, > 99%), N '-methylene bisacrylamide (MBA, > 99%) and 4,4' -azobis (4-cyanovaleric acid) (ACVA, > 98%) in water, performing freeze-thaw cycling and degassing by liquid nitrogen, heating for polymerization, and stirring to obtain a semi-finished carrier (TiNTs/P-VIm);
(2) calcining the semi-finished carrier (TiNTs/P-VIm) in a protective gas atmosphere, removing titanium dioxide by hydrofluoric acid (HF), washing and drying to obtain a nitrogen-doped carbon Nanotube (NPTC);
(3) dispersing the nitrogen-doped carbon Nanotube (NPTC) into water to prepare nitrogen-doped carbon Nanotube (NPTC) dispersion liquid, adding a ruthenium salt aqueous solution into the NPTC dispersion liquid, heating, mixing, reacting, washing and drying to prepare ruthenium salt-loaded nitrogen-doped carbon nanotube powder (ruthenium salt @ NPTC);
(4) calcining and reducing the nitrogen-doped carbon Nanotube (NPTC) powder loaded with ruthenium salt in a mixed atmosphere of hydrogen and protective gas to prepare nitrogen-doped carbon nanotube powder (Ru @ NPTC) loaded with ruthenium;
(5) adding the ruthenium-loaded nitrogen-doped carbon nanotube powder (Ru @ NPTC) into a nickel salt aqueous solution, heating, mixing, washing and drying to obtain ruthenium and nickel salt-loaded nitrogen-doped carbon nanotube powder (Ru + NiCl) 2 @NPTC);
(6) The nitrogen-doped carbon nanotube powder (Ru + NiCl) loaded with ruthenium and nickel salt is added 2 @ NPTC) under the mixed atmosphere of hydrogen and protective gas, and calcining and reducing to obtain the catalyst for preparing hydrogen by pyrolyzing ammonia.
Preferably, in the step (1), the titanium dioxide nanotube is prepared by an alkali thermal method.
Preferably, in the step (1), the 4,4 '-azobis (4-cyanovaleric acid), the N, N' -methylenebisacrylamide, the titanium dioxide nanotube, the 1-vinylimidazole and the water are 25 to 50 parts by weight of 4,4 '-azobis (4-cyanovaleric acid), 25 to 50 parts by weight of N, N' -methylenebisacrylamide, 500-1500 parts by weight of titanium dioxide nanotube, 2000-3000 parts by weight of 1-vinylimidazole and 10000-20000 parts by weight of water; further preferably, the organic solvent is composed of 30-40 parts by weight of 4,4 '-azobis (4-cyanovaleric acid), 40-50 parts by weight of N, N' -methylenebisacrylamide, 800-1200 parts by weight of titanium dioxide nanotubes, 2500-3000 parts by weight of 1-vinylimidazole and 10000-20000 parts by weight of water; still more preferably, the component(s) comprise, by weight, 35-40 parts of 4,4 '-azobis (4-cyanovaleric acid), 40-45 parts of N, N' -methylenebisacrylamide, 900-1100 parts of titanium dioxide nanotubes, 2500-2700 parts of 1-vinylimidazole and 14000-16000 parts of water.
Preferably, in the step (1), the cycle number of the liquid nitrogen freeze-thaw cycle degassing is 2-5; further preferably, the number of degassing cycles of the liquid nitrogen freeze-thaw cycle is 3.
Preferably, in the step (1), the temperature of the heating polymerization is 50-100 ℃, and the reaction time is 0.5-2 h; further preferably, the temperature of the heating polymerization is 70-90 ℃, and the reaction time is 1-2 h; more preferably, the temperature for heating polymerization is 80-90 ℃, and the reaction time is 1-2 h.
Preferably, in step (1), the stirring includes at least one of mechanical stirring, gas flow stirring, jet stirring, ultrasonic stirring and shaker stirring.
Preferably, in step (1), the TiNTs/P-VIm is further subjected to freeze drying.
Preferably, in the step (2), the protective gas comprises at least one of nitrogen, helium, neon, argon, krypton and xenon; further preferably, the protective gas is argon.
Preferably, in the step (2), the calcining temperature is 700-1000 ℃, and the calcining time is 1-3 h; further preferably, the calcining temperature is 700-900 ℃, and the calcining time is 1.5-3 h; more preferably, the calcination temperature is 750-850 ℃ and the calcination time is 1.5-2.5 h.
Preferably, in step (2), water is added to the calcined material immediately.
Preferably, in the step (2), the concentration of the hydrofluoric acid (HF) is 20-50 wt%; further preferably, the concentration of the hydrofluoric acid (HF) is 20-40 wt%; still more preferably, the concentration of hydrofluoric acid (HF) is 25 to 35 wt%.
Preferably, in the step (2), the reaction time for removing the titanium dioxide by using hydrofluoric acid (HF) is 24-72 h; further preferably, the reaction time for removing the titanium dioxide by using hydrofluoric acid (HF) is 36-60 h; still more preferably, the reaction time for removing titanium dioxide with hydrofluoric acid (HF) is 40-50 h.
Preferably, in the step (2), the washing solvent is water, and the standard of washing completion is that the pH of the waste liquor after washing is 6.5-7.5; further preferably, the washing completion criterion is that the pH of the waste liquid after washing is 7.
Preferably, in the step (2), the drying temperature is 50-70 ℃; further preferably, the drying temperature is 55-65 ℃.
Preferably, in the step (3), the concentration of the nitrogen-doped carbon Nanotube (NPTC) dispersion is 3-4 mg/mL; further preferably, the concentration of the nitrogen-doped carbon Nanotube (NPTC) dispersion liquid is 3.5-4 mg/mL; still more preferably, the concentration of the nitrogen-doped carbon Nanotube (NPTC) dispersion is 3.85 mg/mL.
Preferably, in the step (3), the ruthenium salt includes RuCl 3 (ruthenium trichloride), RuBr 3 (ruthenium bromide), Ru (NO) 3 ) 3 (ruthenium trinitronitrosyl); further preferably, the ruthenium salt is RuCl 3 。
Preferably, in the step (3), the concentration of the ruthenium salt aqueous solution is 10-30 mg/mL; further preferably, the concentration of the ruthenium salt aqueous solution is 15-25 mg/mL; still more preferably, the concentration of the aqueous ruthenium salt solution is 20 mg/mL.
Preferably, in the step (3), the ruthenium salt aqueous solution: the volume ratio of the nitrogen-doped carbon Nanotube (NPTC) dispersion liquid is 1: (5-15); further preferably, the aqueous ruthenium salt solution: the volume ratio of the nitrogen-doped carbon Nanotube (NPTC) dispersion liquid is 1: (5-10); still further preferably, the aqueous ruthenium salt solution: the volume ratio of the nitrogen-doped carbon Nanotube (NPTC) dispersion liquid is 1: (6.0-7.0).
Preferably, in the step (3), the washed solvent is an organic solvent, and the organic solvent includes at least one of ethanol, methanol, propanol, butanol, acetonitrile, n-hexane, ethyl acetate and acetone; further preferably, the solvent for washing is ethanol.
Preferably, in the step (3), the number of washing is 2 to 10; further preferably, the number of washing is 2 to 4.
Preferably, in the step (3), the drying is vacuum heating drying, the drying temperature is 50-100 ℃, and the drying time is 12-24 h; more preferably, the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
Preferably, in the step (4), the protective gas includes at least one of nitrogen, helium, neon, argon, krypton and xenon; further preferably, the protective gas is argon.
Preferably, in the step (4), the calcining temperature is 100-150 ℃ and the time is 0.5-2 h; further preferably, the calcining temperature is 100-150 ℃, and the time is 0.5-1.5 h; more preferably, the calcination temperature is 120-130 ℃ and the calcination time is 0.5-1.5 h.
Preferably, in step (5), the nickel salt comprises NiCl 2 、NiBr 2 、NiF 2 、Ni(NO 3 ) 2 At least one of; further preferably, the nickel salt is NiCl 2 。
Preferably, in the step (5), the washed solvent is an organic solvent, and the organic solvent includes at least one of ethanol, methanol, propanol, butanol, acetonitrile, n-hexane, ethyl acetate and acetone; further preferably, the solvent for washing is ethanol.
Preferably, in the step (5), the number of washing times is 2 to 10; further preferably, the number of washing is 2 to 4.
Preferably, in the step (5), the drying is vacuum heating drying, the drying temperature is 50-100 ℃, and the drying time is 12-24 h; more preferably, the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
Preferably, the ruthenium salt of the aqueous ruthenium salt solution, the aqueous nickel salt solution: the mass ratio of the nickel salt is 1: (1-3); further preferably, the ruthenium salt: the mass ratio of the nickel salt is 1: (1.5-2.5); still further preferably, the ruthenium salt: the mass ratio of the nickel salt is 1: 2.
preferably, in the step (6), the protective gas includes at least one of nitrogen, helium, neon, argon, krypton and xenon; further preferably, the protective gas is argon.
Preferably, in the step (6), the calcination temperature is 600-800 ℃, and the calcination time is 0.5-2 h; further preferably, the calcining temperature is 650-750 ℃, and the calcining time is 0.5-1.5 h; still more preferably, the temperature of the calcination is 700 ℃.
The second aspect of the invention provides an ammonolysis hydrogen production catalyst prepared by any one of the preparation methods, wherein the ammonolysis hydrogen production catalyst is prepared at 550 ℃ and at an airspeed of 6000h -1 The conversion catalytic efficiency of ammonia gas is not less than 90%.
Preferably, in the catalyst for hydrogen production by ammonolysis, the content of ruthenium is 1-10 wt% and the content of nickel is 1-15 wt%; further preferably, the ruthenium content is 2.5-7.5 wt%, and the nickel content is 1.46-13.5 wt%; more preferably, the ruthenium content is 4.0-5.0 wt% and the nickel content is 3.5-7.5 wt%; more preferably, the ruthenium content is 4.0-5.0 wt% and the nickel content is 3.5-6.0 wt%, but not limited to, the nickel content may be 3.5%, 4.5%, 5.5%, 6.0%.
The third aspect of the invention provides an ammonolysis hydrogen production catalyst, which contains the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) by loading ruthenium and nickel alloy on the nitrogen-doped carbon Nanotube (NPTC) with a communicated tubular structure, the usage amount of ruthenium can be reduced, and the catalytic activity of the catalyst for hydrogen production by ammonolysis can be improved, so that the prepared catalyst for hydrogen production by ammonolysis is at 550 ℃ and at an airspeed of 6000h -1 The conversion catalytic efficiency of the ammonia gas can reach more than 90 percent in the state of (1). Meanwhile, the problem of excessive reduction of ruthenium on the carbon nanotube with the nitrogen-doped communicated tubular structure can be solved by loading ruthenium and then loading nickel, so that the activity of the catalyst is further improved. In addition, the prepared catalyst for preparing hydrogen by ammonolysis has high dispersion degree of ruthenium and nickel and greatly improved catalytic activity compared with pure ruthenium.
(2) The catalytic effect is ensured, and simultaneously, the dosage of noble metal ruthenium is reduced, so that the production cost is reduced; the preparation process is simple, the operation is convenient, the whole reaction process is non-toxic and harmless, the environment is friendly, and the large-scale and large-area production is easy.
Drawings
FIG. 1 is an SEM photograph of NPTC prepared in example 1 of the present invention;
FIG. 2 is a TEM image of NPTC obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of Ru + Ni @ NPTC prepared in example 1 of the present invention;
FIG. 4 is an SEM image of Ru + Ni @ NPTC prepared in example 1 of the present invention;
FIG. 5 is a graph of the ammonolysis conversion efficiency at different temperatures for the catalysts for hydrogen production by ammonolysis prepared in examples 1-3 of the present invention;
FIG. 6 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 of the present invention and comparative example 1 at different temperatures;
FIG. 7 is a graph showing the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 of the present invention and comparative examples 2 to 4 at different temperatures;
FIG. 8 is a graph showing the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 of the present invention and comparative examples 5 to 6 at different temperatures.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The ammonia conversion catalysis efficiency testing method of the ammonia pyrolysis hydrogen production catalyst comprises the following steps: the ammonia pyrolysis hydrogen production catalyst is tested in a fixed bed reactor for ammonia decomposition catalytic performance at the temperature of 300-650 ℃. A Porapak Q-type chromatographic column is adopted, a TCD detector is used for detection, and argon is used as carrier gas. 100mg of the solid catalyst was loaded into a quartz tube, and the quartz tube was installed at a corresponding position of the detector. The reaction temperature is controlled by an automatic temperature controller, the heating rate is 10K/min, and the airspeed is 6000h -1 . Before reaction, the temperature is increased to 773K and reduced for 2h in Ar atmosphere of 10mL/min at constant temperature, then the catalyst is blown by air to be cooled to room temperature, ammonia gas is introduced, the temperature is increased to the set temperature at the temperature increase rate of 25K/min, and the gas flow is measured and controlled by a mass flow meter. Ammonia conversion catalytic efficiency (initial ammonia content-treated ammonia content)/initial ammonia content 100%.
Example 1
A catalyst for preparing hydrogen by ammonolysis of a ruthenium and nickel nitrogen loaded communicated tubular structure carbon material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) dispersing 1g of titanium dioxide nanotube prepared by an alkali-thermal method, 2.6g of 1-vinylimidazole (1-VIm, > 99%), 43mg of N, N '-methylenebisacrylamide (MBA, > 99%) and 38mg of 4,4' -azobis (ACVA, > 98%) in deionized water, placing the mixture in liquid nitrogen for three times of freeze-thaw cycle degassing, heating and stirring the product at 85 ℃ for polymerization for 1.5h, and freeze-drying after the reaction is finished to obtain a semi-finished product carrier TiNTs/P-VIm (jelly-shaped beige solid);
(2) calcining the freeze-dried TiNTs/P-VIm at 800 ℃ for 2h in 99.99% argon atmosphere, immediately adding deionized water, stirring in 30 wt% hydrofluoric acid (HF) for 48h, removing a titanium dioxide template, washing with deionized water to neutrality to obtain a nitrogen-doped communicated tubular carbon material, namely a nitrogen-doped carbon nanotube NPTC, and drying in an oven at 60 ℃;
(3) after NPTC grinding, uniformly dispersing 50mg of NPTC into 13mL of deionized water to prepare NPTC dispersion liquid, wherein the concentration of the NPTC dispersion liquid is 3.85 mg/mL; to the NPTC dispersion was added RuCl at a concentration of 20mg/mL 2mL 3 Heating the water solution in 70 deg.C water bath, stirring, reacting for 10min, washing the mixed solution with ethanol for three times after the reaction is finished, placing in an oven, and vacuum drying at 70 deg.C for 16h to obtain RuCl-loaded 3 NPTC powder (RuCl) 3 @NPTC);
(4) RuCl is added at 125 ℃ under a mixed atmosphere of hydrogen and argon 3 Calcining and reducing the @ NPTC for 1h, and naturally cooling after the reaction is finished to prepare Ru @ NPTC;
(5) ru @ NPTC was added to 13mL of 7.05mg/mL NiCl 2 Heating in water solution (the mass ratio of ruthenium to nickel is Ru: Ni is 1: 2) and magnetically stirring, washing the mixed solution with ethanol for three times after stirring, and placing in an oven for vacuum drying at 70 ℃ for 16h to prepare NPTC powder (Ru + NiCl) loaded with ruthenium and nickel salts 2 @NPTC);
(6) Mixing Ru + NiCl 2 And putting the @ NPTC in a hydrogen-argon mixed atmosphere, calcining at 700 ℃, reducing for 1h, naturally cooling to prepare a nitrogen-doped communicated tubular carbon material loaded with ruthenium and nickel, and preparing the ammonia pyrolysis hydrogen production catalyst loaded with the ruthenium-nickel-nitrogen-doped communicated tubular carbon material, wherein the catalyst is recorded as Ru + Ni @ NPTC.
The Ru + Ni @ NPTC of example 1 was found to have a Ru content of substantially 4.62 wt% and a Ni content of substantially 5.51 wt%.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 1 at 550 ℃ is 95%.
FIG. 1 is an SEM photograph of NPTC obtained in example 1 (step (2)) of the present invention; the figure shows that the prepared nitrogen-doped communicated tubular carbon material NPTC is a nested carbon material formed by agglomeration of a plurality of tubular structures.
FIG. 2 is a TEM image of NPTC obtained in example 1 (step (2)) of the present invention; specific connected tubular structures in the nitrogen-doped connected tubular structure carbon material NPTC can be seen from the figure.
FIG. 3 is an XRD pattern of Ru + Ni @ NPTC prepared in example 1 of the present invention, with the abscissa representing the 2 θ angle (2 θ Degree) and the ordinate representing the corresponding Intensity (Intensity, a.u.); by comparing standard PDF card maps (Ni PDF #04-0850 and Ru PDF #06-0663) corresponding to the ruthenium and nickel metals, the ruthenium and nickel metals are successfully loaded on the NPTC. In addition, since NPTC is judged to have an amorphous carbon structure from only a slow peak with a very low intensity at about 26 ° observed in the XRD curve of NPTC, the slow peak is masked by a strong characteristic diffraction peak of the metal particle after loading the ruthenium or nickel metal particle, and a diffraction peak of NPTC cannot be observed in the XRD curve of Ru + Ni @ NPTC.
FIG. 4 is an SEM image of Ru + Ni @ NPTC prepared in example 1 of the present invention; it can be seen from the figure that ruthenium and nickel metal are successfully loaded on the nested NPTC formed by the aggregation of a plurality of tubular structures, and the ruthenium and nickel metal particles have higher dispersity.
Example 2
Example 2 differs from example 1 in that: the reduction temperatures used in step (6) were 600 ℃.
The ammonia conversion catalytic efficiency test of the catalyst for preparing hydrogen by ammonolysis shows that the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 2 at 550 ℃ is 93%.
Example 3
Example 3 differs from example 1 in that: the reduction temperatures used in step (6) were 800 ℃ respectively.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in example 3 at 550 ℃ is 90%.
FIG. 5 shows an embodiment of the present inventionThe ammonolysis hydrogen production catalysts prepared in examples 1 to 3 were shown in the figure of ammonolysis conversion efficiency at different temperatures, with the abscissa representing the Reaction temperature (%), and the ordinate representing the ammonia gas conversion catalytic efficiency (NH) 3 conversion, deg.C); the ammonia conversion catalytic efficiency of the ammonia pyrolysis hydrogen production catalyst of examples 1-3 at 550 ℃ is above 90, but the reduction temperature used in step (6) of example 2 is 600 ℃, and NiCl in example 2 2 The phenomenon that the catalyst is not completely reduced exists, the reduction temperature used in the step (6) in the example 3 is 800 ℃, and the overhigh temperature in the example 3 causes the carbonization of the carrier to a certain degree, so that the overall activity of the catalyst is reduced; the reduction temperature used in step (6) of example 1 was 700 c, and the Ru + Ni @ NPTC prepared in example 1 performed the best for the optimal reduction temperature.
Comparative example 1
Comparative example 1 differs from example 1 in that: RuCl in step (3) 3 The @ NPTC is directly added into the NiCl in the step (5) without reduction in the step (4) 2 Heating and magnetically stirring the solution, and eliminating the step (4).
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 1 at 550 ℃ is 89%.
FIG. 6 is a graph of the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 and comparative example 1 of the present invention at different temperatures, with the abscissa representing the Reaction temperature (percent) and the ordinate representing the catalytic efficiency for ammonia conversion (NH) 3 conversion, deg.C); RuCl of comparative example 1 3 @ NPTC directly to NiCl without reduction 2 In aqueous solution, due to RuCl 3 The larger particles, compared to Ru, occupy more active sites on the support, which in turn may lead to NiCl 2 Reduced loading of (3), Ni agglomeration, and RuCl 3 And NiCl 2 Reduction is carried out together, although the reaction steps are simplified to a certain extent, the problem that the activity is reduced along with the over reduction of Ru is also caused; to NiCl 2 The Ru @ NPTC after reduction is added into the aqueous solution, namely the Ru + Ni @ NPTC active phase prepared in the example 1 has higher dispersity and larger particle sizeSmall, the catalytic effect is better.
Comparative example 2
Comparative example 2 differs from example 1 in that: the NPTC carries nickel (Ni) firstly and then carries ruthenium (Ru).
A catalyst for preparing hydrogen by ammonolysis of a ruthenium and nickel nitrogen loaded communicated tubular structure carbon material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) dispersing 1g of titanium dioxide nanotube prepared by an alkali-thermal method, 2.6g of 1-vinylimidazole (1-VIm, > 99%), 43mg of N, N '-methylenebisacrylamide (MBA, > 99%) and 38mg of 4,4' -azobis (ACVA, > 98%) in deionized water, placing the mixture in liquid nitrogen for three times of freeze-thaw cycle degassing, heating and stirring the product at 85 ℃ for polymerization for 1.5h, and freeze-drying after the reaction is finished to obtain TiNTs/P-VIm (jelly-shaped beige solid);
(2) calcining the freeze-dried TiNTs/P-VIm at the high temperature of 800 ℃ for 2h in the atmosphere of 99.99% argon gas, immediately adding deionized water, placing the calcined TiNTs/P-VIm in 30 wt% hydrofluoric acid (HF), stirring for 48h, removing a titanium dioxide template, washing the titanium dioxide template to be neutral by using the deionized water to obtain a nitrogen-doped communicated tubular structure carbon material NPTC, and placing the carbon material NPTC in an oven for drying at the temperature of 60 ℃.
(3) After NPTC grinding, uniformly dispersing 50mg of NPTC into 13mL of deionized water to prepare NPTC dispersion liquid, wherein the concentration of the NPTC dispersion liquid is 3.85 mg/mL; to the NPTC dispersion 15mL of 45.8mg/mL NiCl was added 2 Heating the aqueous solution in 70 ℃ water bath, stirring and reacting for 10min, washing the mixed solution with ethanol for three times after the reaction is finished, placing the mixed solution in a drying oven, and drying the mixed solution in vacuum for 16h at 70 ℃ to obtain the loaded NiCl 2 NPTC powder (NiCl) 2 @NPTC);
(4) At 125 deg.C under mixed atmosphere of hydrogen and argon, adding NiCl 2 Calcining and reducing the @ NPTC for 1h, and naturally cooling after the reaction is finished to prepare Ni @ NPTC;
(5) adding Ni @ NPTC to RuCl with the concentration of 20mg/mL 2mL 3 Heating in water solution (the mass ratio of ruthenium to nickel is Ru: Ni is 1: 2) and magnetically stirring, washing the mixed solution with ethanol for three times after stirring, and placing in an oven for vacuum drying at 70 ℃ for 16h to obtain NPTC powder (Ni + R) loaded with nickel and ruthenium saltuCl 3 @NPTC);
(6) Adding Ni + RuCl 3 Putting @ NPTC in a hydrogen-argon mixed atmosphere, calcining at 700 ℃, reducing for 1h, naturally cooling to prepare a nitrogen-doped communicated tubular carbon material loaded with ruthenium and nickel, and preparing a catalyst for ammonia pyrolysis hydrogen production, recorded as Ni + RuCl, of the carbon material loaded with the ruthenium and nickel-nitrogen-doped communicated tubular structure 3 @NPTC。
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 2 at 550 ℃ is 89%.
Comparative example 3
Comparative example 3 differs from example 1 in that: NPTC simultaneously supports ruthenium (Ru) and nickel (Ni).
A catalyst for preparing hydrogen by ammonolysis of a ruthenium and nickel nitrogen loaded communicated tubular structure carbon material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) dispersing 1g of titanium dioxide nanotube prepared by an alkali-thermal method, 2.6g of 1-vinylimidazole (1-VIm, > 99%), 43mg of N, N '-methylenebisacrylamide (MBA, > 99%) and 38mg of 4,4' -azobis (ACVA, > 98%) in deionized water, placing the mixture in liquid nitrogen for three times of freeze-thaw cycle degassing, heating and stirring the product at 85 ℃ for polymerization for 1.5h, and freeze-drying after the reaction is finished to obtain TiNTs/P-VIm (jelly-shaped beige solid);
(2) calcining the freeze-dried TiNTs/P-VIm at the high temperature of 800 ℃ for 2h in the atmosphere of 99.99% argon gas, immediately adding deionized water, placing the calcined TiNTs/P-VIm in 30 wt% hydrofluoric acid (HF), stirring for 48h, removing a titanium dioxide template, washing the titanium dioxide template to be neutral by using the deionized water to obtain a nitrogen-doped communicated tubular structure carbon material NPTC, and placing the carbon material NPTC in an oven for drying at the temperature of 60 ℃.
(3) After NPTC grinding, uniformly dispersing 50mg of NPTC into 13mL of deionized water to prepare NPTC dispersion liquid, wherein the concentration of the NPTC dispersion liquid is 3.85 mg/mL; to the NPTC dispersion was added RuCl at a concentration of 20mg/mL 2mL 3 Aqueous solution and 15mL of 45.8mg/mL NiCl 2 Heating water solution (Ru: Ni: 1: 2) at 70 deg.C in water bath, stirring, reacting for 10min, washing the mixed solution with ethanol for three times,placing in an oven, vacuum drying at 70 deg.C for 16h to obtain RuCl 3 And NiCl 2 NPTC powder (RuCl) 3 -NiCl 2 @NPTC);
(4) Adding RuCl 3 -NiCl 2 And putting the @ NPTC in a hydrogen-argon mixed atmosphere, calcining at 700 ℃, reducing for 1h, naturally cooling to prepare a nitrogen-doped communicated tubular carbon material loaded with ruthenium and nickel, and preparing the ammonia pyrolysis hydrogen production catalyst loaded with the ruthenium-nickel-nitrogen-doped communicated tubular carbon material, which is recorded as Ru-Ni @ NPTC.
According to ammonia conversion catalytic efficiency test of the catalyst for preparing hydrogen by ammonolysis, the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 3 at 550 ℃ is 85 percent.
Comparative example 4
Comparative example 4 differs from example 1 in that: NPTC carries nickel (Ni) only.
A catalyst for preparing hydrogen by ammonolysis of a carbon material with a supported nickel-nitrogen doped communicated tubular structure and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) dispersing 1g of titanium dioxide nanotube prepared by an alkali-thermal method, 2.6g of 1-vinylimidazole (1-VIm, > 99%), 43mg of N, N '-methylenebisacrylamide (MBA, > 99%) and 38mg of 4,4' -azobis (ACVA, > 98%) in deionized water, placing the mixture in liquid nitrogen for three times of freeze-thaw cycle degassing, heating and stirring the product at 85 ℃ for polymerization for 1.5h, and freeze-drying after the reaction is finished to obtain TiNTs/P-VIm (jelly-shaped beige solid);
(2) calcining the freeze-dried TiNTs/P-VIm at the high temperature of 800 ℃ for 2h in the atmosphere of 99.99% argon gas, immediately adding deionized water, placing the calcined TiNTs/P-VIm in 30 wt% hydrofluoric acid (HF), stirring for 48h, removing a titanium dioxide template, washing the titanium dioxide template to be neutral by using the deionized water to obtain a nitrogen-doped communicated tubular structure carbon material NPTC, and placing the carbon material NPTC in an oven for drying at the temperature of 60 ℃.
(3) After NPTC grinding, uniformly dispersing 50mg of NPTC into 13mL of deionized water to prepare NPTC dispersion liquid, wherein the concentration of the NPTC dispersion liquid is 3.85 mg/mL; to the NPTC dispersion was added 15mL of 45.8mg/mL NiCl 2 Heating the water solution in 70 deg.C water bath, stirring, reacting for 10min, washing with ethanol, mixing, and dissolvingThe solution is placed in an oven for three times and is dried for 16 hours in vacuum at 70 ℃ to prepare the loaded NiCl 2 NPTC powder (NiCl) 2 @NPTC);
(4) At 700 deg.C under mixed atmosphere of hydrogen and argon, adding NiCl 2 Calcining and reducing the @ NPTC for 1h, and naturally cooling after the reaction is finished to prepare the catalyst for the ammonolysis hydrogen production of the carbon material loaded with the nickel-nitrogen doped communicated tubular structure, which is marked as Ni @ NPTC.
FIG. 7 is a graph showing the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 and comparative examples 2 to 4 of the present invention at different temperatures, with the abscissa representing the Reaction temperature (percent) and the ordinate representing the catalytic efficiency for ammonia conversion (NH) 3 conversion, deg.C); in the catalyst, Ru plays a leading role, the activity, the loading amount and the loading effect of the Ru directly influence the activity of the catalyst, while in the comparative example 2, the Ru is loaded after Ni is loaded, and the loading effect of the Ru can be influenced to a certain extent; in comparative example 3, in which Ru and Ni were supported together, the particle distribution was not controlled, the particle size and the particle dispersion were not satisfactory, and there was also RuCl mentioned in comparative example 1 3 And NiCl 2 The Ru over-reduction problem occurs during co-reduction, so the order of loading Ru followed by Ni on NPTC, i.e. Ru + Ni @ NPTC prepared in example 1, performed best.
Comparative example 5
Comparative example 5 differs from example 1 in that: adding ruthenium and nickel materials according to the mass ratio of Ru: ni ═ 1: 1, Ru @ NPTC in step (5) was added to 7.5mL of 45.8mg/mL NiCl 2 An aqueous solution.
Through detection, the content of Ru in the catalyst for preparing hydrogen through ammonolysis of the comparative example 5 is actually 4.98 wt%, and the content of Ni in the catalyst for preparing hydrogen through ammonolysis is actually 2.89 wt%.
According to ammonia conversion catalytic efficiency test of the catalyst for preparing hydrogen by ammonolysis, the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 5 at 550 ℃ is 87%.
Comparative example 6
Comparative example 6 differs from example 1 in that: adding ruthenium and nickel materials according to the mass ratio of Ru: ni ═ 1: 3, Ru @ NPTC in step (5) was added to 22.5mL of 45.8mg/mL NiCl 2 An aqueous solution.
Through detection, the content of Ru in the catalyst for preparing hydrogen through ammonolysis of the comparative example 6 is actually 4.01 wt%, and the content of Ni in the catalyst for preparing hydrogen through ammonolysis is actually 7.04 wt%.
The ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis is tested, and the ammonia conversion catalytic efficiency of the catalyst for preparing hydrogen by ammonolysis in the comparative example 6 at 550 ℃ is 88 percent.
FIG. 8 is a graph showing the ammonolysis conversion efficiency of the catalysts for hydrogen production by ammonolysis prepared in example 1 and comparative examples 5 to 6 of the present invention at different temperatures, with the abscissa representing the Reaction temperature (percent) and the ordinate representing the catalytic efficiency for ammonia conversion (NH) 3 conversion, deg.C); ru: ni ═ 1: 2 (example 1) catalytic effect vs Ru: ni ═ 1: 1 (comparative example 5) is good; however, as the content of nickel is continuously increased, the agglomeration phenomenon of Ni at high temperature is more obvious in comparative example 6, and the influence of the reduction of the relative content of Ru on the catalytic activity is large, so that the quantity ratio of the Ru to the Ni is as follows in consideration of the comprehensive catalytic effect and the cost: ru: ni ═ 1: 2, (the actual loading of ruthenium metal is about 4 wt%), i.e., the Ru + Ni @ NPTC prepared in example 1 is more satisfactory.
According to the invention, ruthenium and nickel alloy are loaded on the nitrogen-doped carbon Nanotube (NPTC) with the communicated tubular structure, so that the use amount of ruthenium can be reduced, the catalytic activity of the catalyst for hydrogen production by ammonia pyrolysis can be improved, and the prepared catalyst for hydrogen production by ammonia pyrolysis can be prepared at 550 ℃ and 6000 hours at airspeed of 6000 hours -1 The conversion catalytic efficiency of the ammonia gas can reach more than 90 percent in the state of (1). On the basis of light weight, excellent electrical, mechanical and chemical properties of the traditional carbon nano tube, the substrate changes the electronic structure of the surface of the substrate through nitrogen doping, and further promotes the composite desorption of nitrogen atoms on the surface of the catalyst so as to improve the overall catalytic performance of the catalyst. And the specific surface area of the unique pipe communication-shaped structure of the substrate is more suitable for catalyzing ammonia decomposition reaction. Meanwhile, the problem of excessive reduction of ruthenium on the carbon nanotube with the nitrogen-doped communicated tubular structure can be solved by loading ruthenium and then loading nickel, so that the activity of the catalyst is further improved. In addition, the prepared catalyst for preparing hydrogen by ammonolysis has high dispersion degree of ruthenium and nickel and greatly improved catalytic activity compared with pure rutheniumNPTC pure ruthenium (the sum of the amounts of the pure ruthenium-supporting substances and the nickel-supporting substances in example 1) with an ammonia decomposition conversion of 34% at 500 ℃ (space velocity WHSV of 30000mL g -1 ·h -1 )。
Claims (10)
1. The preparation method of the catalyst for preparing hydrogen by ammonolysis is characterized by comprising the following steps of:
the nitrogen-doped carbon nanotube is prepared by polymerizing, calcining and removing titanium dioxide by using a titanium dioxide nanotube, an imidazole substance, an amide substance and an azo polymerization initiator; the imidazole substance contains alkenyl, and the amide substance contains alkenyl;
loading ruthenium on the nitrogen-doped carbon nano tube to prepare ruthenium-loaded nitrogen-doped carbon nano tube powder; the calcining temperature in the ruthenium loading process is 100-150 ℃;
loading nickel on the ruthenium-loaded nitrogen-doped carbon nanotube powder to prepare the ammonia pyrolysis hydrogen production catalyst; the calcination temperature in the nickel loading process is 600-800 ℃.
2. The method according to claim 1, wherein the imidazole-based substance includes at least one of 1-vinylimidazole, 2-vinylimidazole and 5-vinylimidazole.
3. The method according to claim 1, wherein the amide-based substance comprises at least one of N, N '-methylenebisacrylamide and N, N' -vinylbisacrylamide.
4. The production method according to claim 1, wherein the azo polymerization initiator comprises at least one of 4,4' -azobis (4-cyanovaleric acid), azobisisobutyramidine hydrochloride, azobisisobutyronitrile, azobisisoheptonitrile.
5. The preparation method according to claim 1, wherein the ruthenium loading process is specifically: dispersing the nitrogen-doped carbon nano tube into water to prepare nitrogen-doped carbon nano tube dispersion liquid, adding a ruthenium salt aqueous solution into the nitrogen-doped carbon nano tube dispersion liquid, heating, mixing, reacting, washing and drying to prepare nitrogen-doped carbon nano tube powder loaded with ruthenium salt; and calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium salt in a mixed atmosphere of hydrogen and protective gas to obtain the nitrogen-doped carbon nanotube powder loaded with ruthenium.
6. The preparation method according to claim 1, wherein the nickel loading process is specifically as follows: adding the nitrogen-doped carbon nanotube powder loaded with ruthenium into a nickel salt aqueous solution, heating, mixing, washing and drying to prepare nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel salt; and calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel chloride in the mixed atmosphere of hydrogen and protective gas to obtain the catalyst for preparing hydrogen by ammonia pyrolysis.
7. The method of claim 1, comprising the steps of:
(1) dispersing titanium dioxide nanotubes, 1-vinyl imidazole, N '-methylene bisacrylamide and 4,4' -azobis (4-cyanovaleric acid) in water, performing freeze-thaw cycling and degassing by using liquid nitrogen, heating for polymerization, and stirring to obtain a semi-finished product carrier;
(2) calcining the semi-finished carrier in the atmosphere of protective gas, removing titanium dioxide by hydrofluoric acid, washing and drying to prepare the nitrogen-doped carbon nanotube;
(3) dispersing the nitrogen-doped carbon nano tube into water to prepare nitrogen-doped carbon nano tube dispersion liquid, adding a ruthenium salt aqueous solution into the nitrogen-doped carbon nano tube dispersion liquid, heating, mixing, reacting, washing and drying to prepare nitrogen-doped carbon nano tube powder loaded with ruthenium salt;
(4) calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium salt in a mixed atmosphere of hydrogen and protective gas to prepare nitrogen-doped carbon nanotube powder loaded with ruthenium;
(5) adding the nitrogen-doped carbon nanotube powder loaded with ruthenium into a nickel salt aqueous solution, heating, mixing, washing and drying to prepare nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel salt;
(6) and calcining and reducing the nitrogen-doped carbon nanotube powder loaded with ruthenium and nickel salt in the mixed atmosphere of hydrogen and protective gas to obtain the catalyst for preparing hydrogen by ammonia pyrolysis.
8. The catalyst for preparing hydrogen by ammonia pyrolysis is characterized by being prepared by the preparation method of any one of claims 1 to 7, and the catalyst for preparing hydrogen by ammonia pyrolysis is used at 550 ℃ and at an airspeed of 6000h -1 The conversion catalytic efficiency of ammonia gas is not less than 90%.
9. The catalyst for hydrogen production by ammonia pyrolysis as recited in claim 8, wherein the catalyst for hydrogen production by ammonia pyrolysis contains 1-10 wt% of ruthenium and 1-15 wt% of nickel.
10. A catalyst for hydrogen production by ammonolysis, which comprises the catalyst for hydrogen production by ammonolysis according to claim 8 or 9.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1678523A (en) * | 2002-06-24 | 2005-10-05 | 原子能委员会 | Method and device for depositing carbon nanotubes or nitrogen-doped carbon nanotubes by means of pyrolysis |
US20090155163A1 (en) * | 2007-12-13 | 2009-06-18 | Korea Advanced Instiute Of Science And Technology | Transition Metal-Carbon Nanotube Hybrid Catalyst Containing Nitrogen, Method for Preparation Thereof, and Method for Generation of Hydrogen Using the Same |
CN106334566A (en) * | 2016-07-29 | 2017-01-18 | 湖北大学 | Core-shell structured supported carbon nanotube catalyst and preparation method thereof |
WO2018033829A1 (en) * | 2016-08-15 | 2018-02-22 | Sabic Global Technologies B.V. | Preparation of nitrogen rich three dimensional mesoporous carbon nitride and its sensing and photocatalytic properties |
CN110270338A (en) * | 2019-06-20 | 2019-09-24 | 福州大学 | A kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application |
CN110586153A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in ammonia decomposition reaction |
CN110813359A (en) * | 2019-11-22 | 2020-02-21 | 福州大学 | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof |
WO2021225254A1 (en) * | 2020-05-07 | 2021-11-11 | 한국과학기술연구원 | Catalyst in which catalytic metal is supported on hexagonal support, and preparation method therefor |
-
2022
- 2022-05-13 CN CN202210521369.1A patent/CN114887643B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1678523A (en) * | 2002-06-24 | 2005-10-05 | 原子能委员会 | Method and device for depositing carbon nanotubes or nitrogen-doped carbon nanotubes by means of pyrolysis |
US20090155163A1 (en) * | 2007-12-13 | 2009-06-18 | Korea Advanced Instiute Of Science And Technology | Transition Metal-Carbon Nanotube Hybrid Catalyst Containing Nitrogen, Method for Preparation Thereof, and Method for Generation of Hydrogen Using the Same |
CN106334566A (en) * | 2016-07-29 | 2017-01-18 | 湖北大学 | Core-shell structured supported carbon nanotube catalyst and preparation method thereof |
WO2018033829A1 (en) * | 2016-08-15 | 2018-02-22 | Sabic Global Technologies B.V. | Preparation of nitrogen rich three dimensional mesoporous carbon nitride and its sensing and photocatalytic properties |
CN110270338A (en) * | 2019-06-20 | 2019-09-24 | 福州大学 | A kind of nickel and/or ruthenium system ammonia decomposition catalyzer and its preparation method and application |
CN110586153A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in ammonia decomposition reaction |
CN110813359A (en) * | 2019-11-22 | 2020-02-21 | 福州大学 | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof |
WO2021225254A1 (en) * | 2020-05-07 | 2021-11-11 | 한국과학기술연구원 | Catalyst in which catalytic metal is supported on hexagonal support, and preparation method therefor |
Non-Patent Citations (4)
Title |
---|
F.R. GARICIA-GARCIA ET AL.: "The use of carbon nanotubes with and without nitrogen doping as support for ruthenium catalysts in the ammonia decomposition reaction", 《CARBON》, vol. 48, pages 267 - 276 * |
HONGFEI PAN ET AL: "Nitrogen-doped porous carbon with interconnected tubular structure for supercapacitors operating at sub-ambient temperatures", 《CHEMICAL ENGINEERING JOURNAL》, vol. 401, pages 1 - 11 * |
ILARIA LUCENTINI ET AL.: "Catalytic ammonia decomposition over Ni-Ru supported on CeO2 for hydrogen production: Effect of metal loading and kinetic analysis", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 286, pages 1 - 10 * |
谈俊;余皓;彭峰;: "掺氮碳纳米管的结构、制备及其催化应用", 工业催化, no. 02, pages 45 - 51 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116196952A (en) * | 2023-05-05 | 2023-06-02 | 佛山仙湖实验室 | Catalyst for producing hydrogen by ammonia pyrolysis grown on fixed bed in situ and preparation method thereof |
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