CN113019408B - Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst - Google Patents
Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst Download PDFInfo
- Publication number
- CN113019408B CN113019408B CN202110268315.4A CN202110268315A CN113019408B CN 113019408 B CN113019408 B CN 113019408B CN 202110268315 A CN202110268315 A CN 202110268315A CN 113019408 B CN113019408 B CN 113019408B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- ammonia borane
- treatment
- hydrogen production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000001257 hydrogen Substances 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 title claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 48
- 229910003296 Ni-Mo Inorganic materials 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 16
- 239000008103 glucose Substances 0.000 claims abstract description 16
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000002161 passivation Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011278 co-treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910039444 MoC Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000001569 carbon dioxide Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 238000003860 storage Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- -1 molybdate ions Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001151 AlNi Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/615—
-
- 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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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 ammonia borane waterA preparation method and application of a catalyst for hydrogen decomposition. The invention relates to the technical field of molybdenum carbide material preparation and hydrogen production. The method comprises the following steps: (1) Dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution; (2) Dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, and sealing the solvent; (3) Standing the mixed solution subjected to ultrasonic treatment in the step (2) for a second preset time, and drying the mixed solution subjected to standing; (4) Grinding the solid obtained in the step (3) into fine powder, putting the fine powder into a porcelain boat, and carrying out staged heating heat treatment and passivation to obtain Ni-Mo 2 C/γ‑Al 2 O 3 A catalyst. The invention provides a supported Ni-Mo which has simple operation process, easy control, safety, environmental protection, low synthesis temperature and easy mass production 2 And C, synthesizing a catalyst.
Description
Technical Field
The invention relates to a preparation method of a supported catalyst and the technical field of ammonia borane hydrogen production, in particular to supported Ni-Mo 2 A preparation method of the catalyst C.
Background
Environmental problems with the excessive use of fossil energy have attracted considerable attention. Meanwhile, due to the limited reserves and non-renewable performance of fossil energy, people are forced to continuously find novel clean energy. The hydrogen energy is known as a green energy source in the 21 st century due to the characteristics of cleanness, high efficiency, wide source and high energy density, and will occupy an important place in a future energy system. The hydrogen energy is used for replacing fossil energy, so that the method is one of the best ways for solving the shortage of energy and environmental pollution in the future and promoting sustainable development of human society.Because hydrogen is a flammable and explosive gas, safe and efficient storage and preparation of hydrogen are key to realizing hydrogen energy and restricting the development of hydrogen energy economy. At present, the hydrogen storage mode mainly comprises low-temperature liquid hydrogen storage, high-pressure gaseous hydrogen storage and chemical solid hydrogen storage. The former two approaches cannot meet the needs of people in daily production and life at present due to the limitations in safety, technology and the like. In view of this, researchers began to look at solid hydrogen storage, i.e., hydrogen gas was stored in a solid material using physical or chemical adsorption. In the chemical solid hydrogen storage material, ammonia borane (NH) 3 BH 3 AB) has the advantages of higher hydrogen storage density (19.6 wt% of hydrogen storage content), safety and innocuity at normal temperature and pressure, moderate chemical stability and the like, and is widely paid attention to. After AB stores hydrogen, hydrogen needs to be released for utilization. At present, the ammonia borane hydrogen release modes mainly comprise three modes, namely high-temperature pyrolysis hydrogen production, alcoholysis hydrogen production and hydrolysis hydrogen production. Compared with pyrolysis hydrogen production and alcoholysis hydrogen production, AB hydrolysis hydrogen production has the advantages of mild reaction conditions, low hydrogen production cost and the like, and is the most main mode of ammonia borane hydrogen production at present. Ammonia borane has higher solubility in water and can stably exist in aqueous solution, after a proper catalyst is added, the ammonia borane can be decomposed to release hydrogen at 298K, and the product can be dissolved in water while generating hydrogen, so that toxic gas is hardly generated. Noble metals (Pt, rh, ru, au and Pd) exhibit excellent ammonia borane hydrolysis hydrogen production properties, however noble metal resources are scarce and costly, limiting their large-scale use. Therefore, the development of non-noble metal catalysts is imperative. Among non-noble metals, ni-based and Co-based catalysts have a good effect on ammonia borane catalytic hydrogen production, but the hydrogen production efficiency is far from the use requirement. Molybdenum carbide has properties similar to those of noble metals and has attracted extensive attention from students in hydrogenation reactions, hydrogen production reactions and CO 2 The catalyst has been widely used in catalytic reduction fields, and meanwhile, the molybdenum carbide has low price, so that it is hopeful to become the substitute of noble metal catalyst with the highest potential.
Currently, transition metal carbide materials (TMCs) are typically prepared using metal oxidesTemp. -programmed carbonization of chemical compounds in gas phase, wherein the gas phase is mainly H 2 With hydrocarbons (CH) 4 、C 2 H 6 CO, etc.). But during this preparation CH 4 、H 2 The use of such materials causes a potential hazard and high costs. Therefore, a synthetic method which is simple and convenient to operate and economical is to be developed.
Disclosure of Invention
In view of the drawbacks of the prior art, an object of the present invention is to provide a novel catalyst capable of producing hydrogen with high efficiency, i.e. having a high TOF value in the hydrogen production process. To this end, the inventors of the present application have conducted a number of experiments, by combining various metallic and non-metallic materials in various ways, and finally found a composition that can achieve TOF values as high as 80.9mol H2 ·mol Ni -1 ·min -1 Hydrogen production catalyst of (a).
The catalyst prepared by the method has high TOF value, greatly reduces the cost and has huge social value and commercial popularization value. The materials used in the method of the invention are all cheap and easily available materials, including nickel acetate, ammonium paramolybdate, glucose and gamma-Al 2 O 3 . Preparation of Supported Ni-Mo Using these materials 2 The catalyst C can obviously reduce the cost and threshold of hydrogen production, and the invention adopts CO with weak oxidability for the first time 2 The synthesized catalyst is subjected to passivation treatment as an oxidizing agent.
Specifically, the invention provides a preparation method of a catalyst for preparing hydrogen by ammonia borane hydrolysis, which is characterized in that the catalyst is gamma-Al 2 O 3 Loaded Ni-Mo 2 C catalyst, the method comprising mixing Ni and Mo in a predetermined ratio 2 C is loaded on a carrier by adopting a one-step impregnation method, ni and Mo 2 The load of C is calculated according to the mass fraction of the whole catalyst; the carrier is gamma-Al 2 O 3 。
Preferably, the method comprises the steps of:
(1) Dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution;
(2) Dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, sealing the solvent, and performing ultrasonic treatment for a preset time;
(3) Standing the mixed solution subjected to ultrasonic treatment in the step (2) for a second preset time, and drying the mixed solution subjected to standing to obtain a tan solid;
(4) Grinding the solid obtained in the step (3) into fine powder, placing the fine powder into a tube furnace, and performing staged heating heat treatment and passivation under inert gas and specific passivation gas to obtain Ni-Mo 2 C/γ-Al 2 O 3 A catalyst.
Preferably, ni, mo in the catalyst 2 C. The mass of the carrier is as follows: 8-12 parts, 25-35 parts and 55-65 parts.
Preferably, the Ni, mo 2 C. The mass fraction of the carrier was 10wt%, 30wt% and 60wt%, respectively.
Preferably, in the step (1), the concentration of the ammonia water is 25-28%.
Preferably, the inert gas is Ar and the specific passivation gas is CO 2 。
Preferably, in the step (4), the temperature-programmed heat treatment is to heat up to 300 ℃ at a speed of 2 ℃/min, heat-preserving treatment is to heat up to 400 ℃ at a speed of 2 ℃/min, heat-preserving treatment is to heat up to 1h, and then heat up to 720 ℃ at a speed of 2 ℃/min, and heat-preserving treatment is to heat up to 3h.
Preferably, in the step (4), the passivation method is to naturally cool the tube furnace to 120-145 ℃ after the step-wise heating heat treatment, and then switch to CO 2 And (3) gas, wherein the passivation treatment time is 2h.
In another aspect, the present invention provides a gamma-Al 2 O 3 Loaded Ni-Mo 2 The use of a catalyst for producing hydrogen from C ammonia borane is characterized in that the catalyst is Ni-Mo 2 A C ammonia borane hydrogen production catalyst for catalytic treatment of ammonia borane hydrogen production processes, the application comprising: (1) Ni-Mo 2 C/γ-Al 2 O 3 The catalyst is placed in the containerMixing with water in a mixer, and vibrating uniformly; (2) preparing ammonia borane alkali solution; (3) Adding the solution prepared in the step (2) into the solution prepared in the step (1).
More specifically, the application method is as follows: in the prepared Ni-Mo 2 C/γ-Al 2 O 3 The material is used as a catalyst for producing hydrogen by ammonia borane, the solvent is distilled water, and a water draining and gas collecting method is used for collecting hydrogen.
Catalyst 10mg was placed in a round bottom flask, 2.5mL of distilled water was added, sonicated for 2min, and placed in a 30℃water bath for preheating with a magnetic stirrer rotation speed of 568r/min.0.2g NaOH was placed in a beaker, 2.5mL water was added, sonicated until complete dissolution, and 45mg ammonia borane was added to the NaOH solution and the beaker was shaken to complete dissolution. The solution was added to a round bottom flask and the hydrogen was collected by a water and gas trap. When the first bubble emerges from the air outlet, the timing is started, and every 5mL of timing is performed until the reaction is finished.
The invention has the advantages that:
(1) Ni-Mo in the present invention 2 C/γ-Al 2 O 3 The process for preparing the catalyst is significantly superior to existing schemes, such as those mentioned in the background. The method for synthesizing the catalyst has the advantages of simple process, easy control and easy operation.
(2) Ni-Mo synthesized by the invention 2 C/γ-Al 2 O 3 The catalyst particles are more uniform and fine, ni and Mo are uniformly dispersed on the carrier, and the specific surface area is large and is 132.2m 2 And/g, the catalyst has a rich mesoporous structure, and is favorable for the diffusion of reactants and the exposure of active sites in the catalytic reaction process.
(3) The method is more beneficial to Ni and Mo in the preparation process 2 C, the interaction between the two components is that nickel acetate, ammonium molybdate and glucose are dissolved in ammonia water in the dipping process, and the nickel acetate, the ammonium molybdate and the glucose are fully mixed in the solution. Since ammonia can complex Ni 2+ And molybdate ions, ni and Mo are well dispersed in the solution. During the drying process, along with NH 3 And H 2 Evaporation of O, the Ni and Mo precursors can achieve a sufficient contact effect.
(4) The invention is thatThe catalyst prepared by the method has high porosity and good ammonia borane hydrogen production performance, and the TOF value of ammonia borane hydrogen production catalyzed by the catalyst can reach 80.9mol H2 ·mol Ni -1 ·min -1 Is obviously higher than the prior similar method.
Drawings
FIG. 1 shows Ni-Mo obtained by the method of the present invention 2 C/γ-Al 2 O 3 Powder X-ray diffraction (XRD) pattern of the catalyst. 34.5 °, 37.9 °, 39.5 °, 52.2 °, 61.6 °, 69.6 ° and 74.7 ° in the figure are Mo 2 The standard diffraction peak of C is matched with the standard card JCPDS No. 00-011-0680. At the same time, there is AlNi in the spectrogram 3 Alloy and Al 2 O 3 The diffraction peak of (2) appears, and no obvious metallic Ni diffraction peak is observed in the spectrogram.
FIG. 2 is a diagram of Ni-Mo prepared according to the present invention 2 C/γ-Al 2 O 3 Scanning Electron Microscope (SEM) image of the catalyst. As can be seen from FIG. 2, ni and Mo 2 The C particles are fine and uniformly dispersed in gamma-Al 2 O 3 And (3) on a carrier.
FIG. 3 shows mesoporous Ni-Mo obtained by the method of the present invention 2 C/γ-Al 2 O 3 N of the catalyst at 77K temperature 2 Isothermal adsorption-desorption profiles; the specific surface area of the catalyst prepared by the invention is 132.2m 2 /g。
FIG. 4 shows Ni-Mo obtained in the example of the present invention 2 C/γ-Al 2 O 3 The catalyst obtains a pore size distribution diagram according to an isothermal desorption curve. The graph shows that the pore diameter is intensively distributed at about 6.1nm, which indicates that the prepared catalyst material has typical mesoporous structure characteristics.
FIG. 5 is Ni-Mo 2 C/γ-Al 2 O 3 Ammonia borane hydrogen production profile of the catalyst. The TOF value of the catalyst for catalyzing ammonia borane to produce hydrogen can reach 80.9mol H2 ·mol Ni -1 ·min -1 。
FIG. 6 is an illustration of an undelivered CO 2 Passivated 10Ni30Mo 2 C/γ-Al 2 O 3 The ammonia borane hydrolysis hydrogen production performance diagram of the catalyst.
Detailed Description
The chemical reagents used in the invention are as follows: nickel acetate (Ni (CH) 3 COO) 2 ·4H 2 O), ammonium paramolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), glucose, gamma-Al 2 O 3 Ammonia (25-28%), argon (Ar), carbon dioxide (CO) 2 ) Ammonia borane (NH) 3 BH 3 ) Sodium hydroxide (NaOH), distilled water.
The Ni-Mo of the present invention is exemplified below 2 C/γ-Al 2 O 3 The preparation and use of the catalyst are further described, and the carrier used in the present invention is not limited to gamma-Al 2 O 3 Other metal oxides such as SiO 2 、ZrO 2 The same applies.
Example 1: ni-Mo 2 C/γ-Al 2 O 3 Preparation and deactivation of the catalyst
(1) 0.2598g of ammonium paramolybdate, 0.2120g of nickel acetate and 0.1547g of glucose are weighed by an electronic balance, placed in a small 10mL beaker, 1.5mL of ammonia water is measured by a measuring cylinder, added into the beaker, and stirred until the ammonia water is completely dissolved to form a uniform mixed solution;
(2) Weighing 0.3g of gamma-Al 2 O 3 Put into a small 25mL beaker. Then dripping the blue mixed solution obtained in the step (1) into the mixture containing gamma-Al 2 O 3 In the small beaker, a glass rod is used for stirring uniformly, the small beaker is sealed by a preservative film, the small beaker is placed in an ultrasonic instrument for ultrasonic treatment for 20min, and then the mixed solution is kept stand for 12h. The mixture after standing was then dried in an oven at 110 ℃ for 24 hours to give a tan solid. Grinding the obtained solid into fine powder with agate mortar, placing into a porcelain boat, placing into a tube furnace under Ar (100 mL/min) atmosphere, heating to 300deg.C at a heating rate of 2deg.C/min, heat-preserving for 1h, heating to 400deg.C at a heating rate of 2deg.C/min, heat-preserving for 1h, then heating to 72deg.C at a heating rate of 2deg.C/min, heat-preserving for 3h, naturally cooling to 135deg.C under Ar atmosphere, and switching to CO 2 (100 mL/min) gas, passivating for 2h, and finally placing the tube furnace in CO 2 Cooling to room temperature in (100 mL/min) atmosphere to obtain Ni-Mo 2 C/γ-Al 2 O 3 Catalyst powder.
(2) For the prepared Ni-Mo 2 C/γ-Al 2 O 3 The catalyst is characterized by surface morphology, phase structure and physical and chemical properties:
crystalline phase analysis was performed by XRD, see fig. 1 for specific results;
SEM observation of sample morphology, and specific results are shown in FIG. 2;
by N 2 Isothermal adsorption-desorption analysis of specific surface area, pore size distribution, see fig. 3 and 4 for specific results. Example 2: ni-Mo of the invention 2 C/γ-Al 2 O 3 Performance test as ammonia borane hydrogen production catalyst:
(1) Preparation of the catalyst:
10mg of Ni-Mo prepared by the present invention 2 C/γ-Al 2 O 3 The catalyst is placed in a 50mL single-neck round-bottom flask, 2.5mL of distilled water is measured by a cylinder, poured into the round-bottom flask containing the catalyst, the round-bottom flask is placed in an ultrasonic instrument for ultrasonic treatment for 2min, and then placed in a 30 ℃ warm water bathtub for standby.
(2) Preparation of ammonia borane aqueous solution:
accurately weighing 0.2g of NaOH, placing in a 25mL beaker, adding 2.5mL of water, carrying out ultrasonic treatment for 30s to completely dissolve the NaOH, then adding 45mg of ammonia borane into the beaker, and stirring until the ammonia borane is completely dissolved.
(3) Adding the solution obtained in the step (2) into the round-bottom flask in the step (1), collecting hydrogen by adopting a water draining and gas collecting method, using a measuring cylinder of 100mL when collecting hydrogen, starting timing when the first bubble is emitted from the gas outlet, and timing once every 5mL when collecting until the reaction is finished. The ammonia borane hydrogen production performance of the catalyst is shown in figure 5.
In conclusion, the Ni-Mo of the invention 2 The catalyst C takes nickel acetate as a nickel source, ammonium paramolybdate as a molybdenum source and glucose as a carbon source, and is prepared from Ni and Mo 2 C in a mass ratio of 1:3, mo 2 Mixing materials with the mass ratio of C to glucose being 1:7, dissolving in ammonia water, and stirring and dissolving to obtain a mixed solution; dropwise adding the mixed solution into a mixture containing gamma-Al 2 O 3 In the small beaker of the (c),ultrasonic treatment is carried out for 20min, and drying is carried out for 24h at 110 ℃ to obtain tan solid; the obtained solid product is placed in an argon protection atmosphere, and is subjected to heat treatment for 3 hours at 720 ℃ and then is subjected to CO 2 Passivating the gas at 135 deg.C (which temperature may have a suitable float) for 2h to obtain the gamma-Al 2 O 3 Loaded Ni-Mo 2 And C, a catalyst. Ni and Mo prepared by the method 2 The catalyst has the advantages of small particle size, uniform particle distribution on a metal oxide carrier, high porosity, large specific surface area and good ammonia borane hydrogen production performance, and the TOF value of the catalyst for catalyzing ammonia borane to produce hydrogen can reach 80.9mol as calculated from data in a graph H2 ·mol Ni -1 ·min -1 。
Comparative example 1
The inventors of the present application also synthesized 30Ni10Mo in exactly the same way as in example 1 2 C/γ-Al 2 O 3 And 10NiMo 2 And C, a catalyst.
(1) According to Ni, mo by an electronic balance 2 C、γ-Al 2 O 3 The mass fractions of the carrier are 30wt%, 10wt% and 60wt% respectively, ammonium paramolybdate, nickel acetate and glucose with corresponding mass are weighed, placed in a small beaker with the volume of 10mL, 1.5mL of ammonia water is measured by a measuring cylinder, added into the beaker, and stirred until the ammonia water is completely dissolved to form a uniform mixed solution;
(2) Weighing 0.3g of gamma-Al 2 O 3 Put into a small 25mL beaker. Then dripping the blue mixed solution obtained in the step (1) into the mixture containing gamma-Al 2 O 3 In the small beaker, a glass rod is used for stirring uniformly, the small beaker is sealed by a preservative film, the small beaker is placed in an ultrasonic instrument for ultrasonic treatment for 20min, and then the mixed solution is kept stand for 12h. The mixture after standing was then dried in an oven at 110 ℃ for 24 hours to give a tan solid. Grinding the obtained solid into fine powder with agate mortar, placing into a porcelain boat, placing into a tube furnace under Ar (100 mL/min) atmosphere, heating to 300deg.C at a heating rate of 2deg.C/min, heat-preserving for 1h, heating to 400deg.C at a heating rate of 2deg.C/min, heat-preserving for 1h, then heating to 72deg.C at a heating rate of 2deg.C/min, heat-preserving for 3h, naturally cooling to 135deg.C under Ar atmosphere, and switching to CO 2 (100 mL/min) gas, passivating for 2h, and finally placing the tube furnace in CO 2 Cooling to room temperature in (100 mL/min) atmosphere to obtain Ni-Mo 2 C/γ-Al 2 O 3 Catalyst powder
The same conditions were used for the synthesized catalyst to test its ammonia borane hydrolysis hydrogen production performance.
In all the synthesized catalysts, although 30Ni10Mo 2 C/γ-Al 2 O 3 The catalyst showed a relatively fast hydrogen production rate, but had a hydrogen production TOF value of 58.3mol H2 ·mol Ni -1 ·min -1 Obviously lower than 10Ni30Mo 2 C/γ-Al 2 O 3 。
From this comparative example, it can be seen that the ratio of the raw materials has a large influence on the hydrogen production performance.
Comparative example 2
In the same manner as in step (1) of example 1, the inventors synthesized 10NiMo 2 C catalyst, wherein Ni, mo 2 The mass fractions of C are respectively 10wt% and 90wt%, and step (2) is omitted.
The same conditions were used for the synthesized catalyst to test its ammonia borane hydrolysis hydrogen production performance.
The results demonstrate that 10NiMo is not alumina loaded 2 C exhibits poor ammonia borane hydrolysis hydrogen production activity.
The hydrogen generating effect pairs of comparative examples 1 and 2 and example 1 are shown in fig. 6.
Comparative example 3
In this example, the exact same material ratios and processes as in example 1 were used, except that the switch to CO was omitted in the final stage 2 Is performed in the passivation process.
Specifically, in this example, the catalyst prepared was 10Ni30Mo 2 C/γ-Al 2 O 3 Wherein Ni, mo 2 C、γ-Al 2 O 3 The mass fractions of the carrier are respectively 10wt%, 30wt% and 60wt%. The preparation method comprises the following steps:
(1) Dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, stirring until the ammonium paramolybdate, nickel acetate and glucose are completely dissolved, and forming a uniform blue mixed solution, wherein the concentration of the ammonia water is 25-28%;
(2) Dropwise adding the uniform solution obtained in the step (1) into a container containing metal oxide, uniformly stirring, sealing the solvent, and then placing the solvent in an ultrasonic instrument for ultrasonic treatment for a preset time;
(3) Standing the mixed solution subjected to ultrasonic treatment in the step (2) for a second preset time, and drying the mixed solution subjected to standing to obtain a tan solid;
(4) Grinding the solid obtained in the step (3) into fine powder, putting the fine powder into a porcelain boat, putting the porcelain boat into a tube furnace, and carrying out stage heating heat treatment under inert gas to obtain Ni-Mo 2 C/γ-Al 2 O 3 A catalyst.
In the step (4), the programmed heating heat treatment is to heat to 300 ℃ at a speed of 2 ℃/min, heat preservation is carried out for 1h, heat to 400 ℃ at a speed of 2 ℃/min, heat preservation is carried out for 1h, then heat to 720 ℃ at a speed of 2 ℃/min, and heat preservation is carried out for 3h. And naturally cooling the temperature of the reaction tube to room temperature, and taking out to obtain the target catalyst.
FIG. 6 shows that the comparative example has not passed CO 2 Passivated 10Ni30Mo 2 C/γ-Al 2 O 3 The hydrogen production performance of the catalyst by ammonia borane hydrolysis is shown in the graph comparing the passivated curves in FIG. 6 and FIG. 5, and it is obvious that the invention adopts CO 2 The passivation effect of hydrogen production has obvious advantages. Its hydrogen production TOF value is 38.3mol H2 ·mol Ni -1 ·min -1 Having a value significantly lower than that of CO 2 Passivating the obtained 10Ni30Mo 2 C/γ-Al 2 O 3 A catalyst.
While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it should be understood by those skilled in the art that the foregoing embodiments are merely illustrative of the implementations of the invention and are not intended to limit the scope of the invention. The details of the embodiments are not to be taken as limiting the scope of the invention, and any obvious modifications based on equivalent changes, simple substitutions, etc. of the technical solution of the invention fall within the scope of the invention without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of a catalyst for preparing hydrogen by ammonia borane hydrolysis is characterized in that the catalyst is gamma-Al 2 O 3 Loaded Ni-Mo 2 C catalyst, the method comprising mixing Ni and Mo in a predetermined ratio 2 C is loaded on a carrier by adopting a one-step impregnation method, and Ni and Mo are used as the components 2 C. The mass fraction of the carrier calculated as the mass fraction of the whole catalyst is respectively 10wt%, 30wt% and 60 wt%; the carrier is gamma-Al 2 O 3 The preparation method of the catalyst comprises the following steps:
(1) Dissolving ammonium paramolybdate, nickel acetate and glucose in ammonia water, and stirring until the ammonium paramolybdate, the nickel acetate and the glucose are completely dissolved to form a uniform blue mixed solution;
(2) Dropwise adding the uniform solution obtained in the step (1) into a solution containing gamma-Al 2 O 3 Stirring uniformly, sealing the container, and performing ultrasonic treatment for a preset time;
(3) Standing the mixed solution subjected to ultrasonic treatment in the step (2) for a second preset time, and drying the mixed solution subjected to standing to obtain a tan solid;
(4) Grinding the solid obtained in the step (3) into fine powder, placing the fine powder into a tube furnace, performing step-wise heating heat treatment under inert gas, and then performing passivation gas CO treatment 2 Under passivation to obtain Ni-Mo 2 C/γ-Al 2 O 3 The catalyst, wherein in the step (4), the step-type heating heat treatment is to heat up to 300 ℃ at the speed of 2 ℃/min, heat preservation treatment is 1h, heat up to 400 ℃ at the speed of 2 ℃/min, heat preservation is 1h, then heat up to 720 ℃ at the speed of 2 ℃/min, and heat preservation treatment is 3h.
2. The preparation method according to claim 1, wherein Ni and Mo in the catalyst 2 C. The mass of the carrier is as follows: 8-12 parts, 25-35 parts and 55-65 parts.
3. The method according to claim 1, wherein in the step (1), the concentration of the aqueous ammonia is 25 to 28%.
4. The method according to claim 1, wherein in the step (4), the inert gas is Ar.
5. The process of claim 4, wherein in step (4), the passivation is performed by naturally cooling the tube furnace to 120-145 ℃ after the stepwise elevated temperature heat treatment, followed by switching to CO 2 The passivation time was 2h for the gas.
6. The use of the catalyst prepared by the preparation method of claim 1, wherein the Ni-Mo is as follows 2 C/γ-Al 2 O 3 An ammonia borane hydrogen production catalyst for catalytic treatment of ammonia borane hydrogen production processes, the application comprising: (1) Ni-Mo 2 C/γ-Al 2 O 3 The catalyst is placed in a container, and is mixed with water and vibrated uniformly; (2) preparing ammonia borane alkali solution; (3) Adding the solution prepared in the step (2) into the solution prepared in the step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110268315.4A CN113019408B (en) | 2021-03-12 | 2021-03-12 | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110268315.4A CN113019408B (en) | 2021-03-12 | 2021-03-12 | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113019408A CN113019408A (en) | 2021-06-25 |
| CN113019408B true CN113019408B (en) | 2023-06-20 |
Family
ID=76470382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110268315.4A Active CN113019408B (en) | 2021-03-12 | 2021-03-12 | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113019408B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116618071B (en) * | 2023-07-21 | 2023-09-29 | 河南理工大学鄂尔多斯煤炭清洁开发利用研究院 | Preparation method of catalyst for ammonia borane hydrolysis hydrogen evolution |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6070136A (en) * | 1983-09-14 | 1985-04-20 | Honda Motor Co Ltd | Surface treatment of work |
| US8420267B2 (en) * | 2008-10-31 | 2013-04-16 | Alliant Techsystems Inc. | Methods and systems for producing hydrogen and system for producing power |
| CN103433042B (en) * | 2013-08-26 | 2015-07-08 | 河南理工大学 | Red mud supported nickel catalyst used for ammonia decomposition for hydrogen production and preparation method thereof |
| CN105107515B (en) * | 2015-09-24 | 2017-04-19 | 成都理工大学 | Nickel-molybdenum carbide composite catalyst for preparing synthesis gas through dry reforming of methane |
| CN109894133B (en) * | 2019-03-15 | 2020-06-02 | 大连理工大学 | Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming |
| CN110980639B (en) * | 2019-12-31 | 2021-10-26 | 湘潭大学 | Method for directly producing hydrogen by methane conversion under microwave catalysis |
| CN111167495B (en) * | 2020-01-07 | 2022-11-04 | 郑州大学 | Catalyst Ni for ammonia borane hydrogen production 2-x Fe x @ CN-G and preparation method thereof |
-
2021
- 2021-03-12 CN CN202110268315.4A patent/CN113019408B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113019408A (en) | 2021-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Aqueous electrocatalytic N 2 reduction for ambient NH 3 synthesis: recent advances in catalyst development and performance improvement | |
| CN109967099B (en) | Co with hollow nano structure2P @ C composite material and preparation method and application thereof | |
| WO2016173285A1 (en) | Supported catalyst having core-shell structure, preparation method therefor, and application thereof | |
| CN101462058B (en) | Catalyst for producing synthesis gas by reforming natural gas-carbon dioxide for industry | |
| CN110479280B (en) | CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof | |
| CN109126844B (en) | Molybdenum carbide nanosheet and preparation method and application thereof | |
| JP2019155227A (en) | Co2 methanation catalyst and carbon dioxide reduction method using the same | |
| CN112108148A (en) | Supported copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof | |
| CN113171776A (en) | Supported catalyst for preparing hydrogen by hydrolyzing sodium borohydride solution, preparation method and application | |
| CN110302799B (en) | Catalyst for electrochemically reducing carbon dioxide into carbon monoxide and preparation method thereof | |
| CN113621987A (en) | Cobalt-molybdenum alloy and cobalt-molybdenum mixed oxide electrocatalyst and preparation method and application thereof | |
| CN113262781A (en) | Metal platinum catalyst and preparation method and application thereof | |
| CN113019408B (en) | Preparation method and application of ammonia borane hydrolysis hydrogen production catalyst | |
| CN109647369B (en) | Porous carbon nano-catalyst, preparation method and application thereof | |
| CN101733089B (en) | Catalyst for preparing hydrogen gas, method for preparing same and application thereof | |
| Hu et al. | Synthesis of a novel Co-B/CTAB catalyst via solid-state-reaction at room temperature for hydrolysis of ammonia-borane | |
| Kumar et al. | Methanolysis of ammonia borane using binder‐free hierarchical Co@ Ni metal‐organic framework nanocolumn arrays catalyst for hydrogen generation | |
| CN107376936B (en) | Platinum-cobalt/attapulgite catalyst and preparation method and application thereof | |
| Xie et al. | Effect of oxygen vacancy influenced by CeO2 morphology on the methanol catalytic reforming for hydrogen production | |
| KR20220075530A (en) | A Catalyst for dehydrogenation of liquid organic hydrogen carriers and method for producing the same | |
| CN115608375B (en) | Catalyst for ammonia borane hydrolysis hydrogen evolution and preparation method thereof | |
| Wu et al. | Surface Oxygen Vacancies Induced by Calcium Substitution in Macroporous La2Ce2–x Ca x O7− δ Catalysts for Boosting Low-Temperature Oxidative Coupling of Methane | |
| Wu et al. | CeO 2 modified Ni-MOF as an efficient catalyst for electrocatalytic urea oxidation | |
| Sankir et al. | Hydrogen generation from chemical hydrides | |
| CN112779550B (en) | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |