CN117443409A - Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof - Google Patents
Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof Download PDFInfo
- Publication number
- CN117443409A CN117443409A CN202311464855.5A CN202311464855A CN117443409A CN 117443409 A CN117443409 A CN 117443409A CN 202311464855 A CN202311464855 A CN 202311464855A CN 117443409 A CN117443409 A CN 117443409A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- hydrogen
- lani
- absorption
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 239000001257 hydrogen Substances 0.000 title claims abstract description 127
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 127
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- 238000003795 desorption Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 241000219782 Sesbania Species 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 8
- 230000002457 bidirectional effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910002335 LaNi5 Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of hydrogen storage and catalysis, and particularly relates to a catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier and a preparation method thereof. The catalyst comprises a catalyst carrier and a noble metal active catalytic component loaded on the catalyst carrier, wherein the catalyst carrier is formed and contains nano LaNi 5 The noble metal active catalytic component is Pd or Ru; the loading of the noble metal active catalytic component is 0.3% -1% of the mass of the catalyst carrier. Compared with the existing noble metal catalyst technology, the invention has the following advantages: (1) The catalyst is a bidirectional catalyst, the carrier is a nano hydrogen storage material, the hydrogen absorption and desorption processes can be completed, and the catalytic performance of the noble metal active catalytic component in the hydrogen absorption and desorption processes can be improved in an auxiliary manner; (2) The catalyst prepared by the invention has excellent performance and can reach even super-high performance under the condition of using a small amount of noble metalThe higher the noble metal loading catalyst, the hydrogen absorption and desorption catalytic performance.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage and catalysis, and particularly relates to a catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier and a preparation method thereof.
Background
Liquid Organic Hydrogen Carrier (LOHC) hydrogen storage is a technology for storing hydrogen in an organic liquid, and is an emerging method for storing hydrogen energy. Compared with solid high-pressure hydrogen storage, the technology has the advantages of higher quality hydrogen storage density, good reversibility of hydrogen absorption and desorption, good heat conduction performance, nonflammability of the material, and the like. Based on the advantages, the liquid organic hydrogen carrier LOHC has potential wide application market in the aspect of large-scale hydrogen storage and transportation.
Among the liquid organic hydrogen carriers LOHC, N-ethyl carbazole is the liquid organic hydrogen carrier with the most development potential and market application due to the fact that the mass hydrogen storage density is high and the hydrogen absorption and desorption temperature is low. However, the dynamics of LOHC absorption and desorption of hydrogen by liquid organic hydrogen carriers are generally poor, and high-loading Ru and Pd noble metal catalysts are generally needed. In addition, two different catalysts are needed in the hydrogen absorption and desorption processes of the liquid organic hydrogen carrier LOHC, so that the development and application of the liquid organic hydrogen carrier LOHC in the hydrogen energy market are greatly limited.
The university of Beijing Li Xingguo professor team successfully developed nano-scale LaNi by molten salt method 5 Through team test, the prepared nanometer LaNi 5 Is not sensitive to water and oxygen, and is a bidirectional catalyst for catalyzing the hydrogen absorption and desorption process of N-ethyl carbazole. The catalyst has excellent performance on N-ethyl carbazole hydrogen release, is comparable to Pd-based catalyst, but has poor catalytic performance on hydrogen absorption, and the time for approaching saturation of hydrogen absorption is required to be more than 6 hours.
Therefore, in order to promote the development of N-ethylcarbazole in the hydrogen storage field, so that the N-ethylcarbazole can be applied to industrial large scale, a high-efficiency low-cost bidirectional catalyst with excellent hydrogen absorption and desorption catalytic performance is needed.
Disclosure of Invention
In order to solve the problems in the prior art, one of the purposes of the invention is to provide a catalyst for catalyzing the absorption and the release of hydrogen of a liquid organic hydrogen carrier, which can greatly improve the absorption performance while not losing the high-efficiency release performance, thereby greatly shortening the absorption and release process time of the liquid organic hydrogen carrier and further meeting the large-scale industrial actual production requirement.
Another object of the present invention is to provide a method for preparing a catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a catalyst for catalyzing hydrogen absorption and hydrogen release of a liquid organic hydrogen carrier, which comprises a catalyst carrier and a noble metal active catalytic component loaded on the catalyst carrier, wherein the catalyst carrier is formed and contains nanometer LaNi 5 The method comprises the steps of carrying out a first treatment on the surface of the The noble metal active catalytic component is Pd or Ru, and the loading of the noble metal active catalytic component is 0.3% -1% of the mass of the catalyst carrier.
Preferably, the catalyst of the invention is prepared from formed nano LaNi-containing catalyst 5 The catalyst carrier is obtained by dipping the catalyst carrier in a noble metal precursor salt solution for reaction, washing and drying.
Further preferably, the formed nano LaNi-containing material of the invention 5 The catalyst carrier is prepared by the following steps:
step 1), 50-200 meshes of LaNi 5 Placing alloy powder, ammonium fluoride dilute solution, zirconia balls and grinding aid into a ball milling tank;
step 2), vacuumizing a ball milling tank, filling argon for protection, and then starting a ball mill for ball milling;
step 3), after ball milling is completed, washing the obtained product with deionized water, and then obtaining the nano LaNi through centrifugation and vacuum drying 5 A powder;
step 4), the nano LaNi prepared in the step 3) is prepared 5 Mixing the powder, the binder, the oxide carrier and deionized waterStirring to obtain viscous mixture, wherein the nanometer LaNi 5 The mass ratio of the powder to the binder to the oxide carrier to the deionized water is (5-10): (2-4): (20-40): (40-50);
step 5), placing the viscous mixture obtained in the step 4) in an extrusion molding device to obtain a wet strip-shaped catalyst carrier;
step 6), placing the wet strip-shaped catalyst carrier prepared in the step 5) in a drying device to obtain a dried strip-shaped catalyst carrier, namely the formed nano LaNi-containing catalyst carrier 5 A catalyst support.
Further preferably, the noble metal precursor salt solution is selected from one of palladium acetate, palladium nitrate, palladium chloride, ruthenium trichloride, ruthenium acetylacetonate or ruthenium acetate solution.
The invention relates to a preparation method of a catalyst for catalyzing hydrogen absorption and hydrogen desorption of a liquid organic hydrogen carrier, which comprises the following preparation steps:
(one) formed nanometer LaNi-containing 5 Preparation of catalyst support
Step 1), 50-200 meshes of LaNi 5 Placing alloy powder, ammonium fluoride dilute solution, zirconia balls and grinding aid into a ball milling tank;
step 2), vacuumizing a ball milling tank, filling argon for protection, and then starting a ball mill for ball milling;
step 3), after ball milling is completed, washing the obtained product with a large amount of deionized water, and then obtaining the nano LaNi through centrifugation and vacuum drying 5 A powder;
step 4), the nano LaNi prepared in the step 3) is prepared 5 Mixing and stirring the powder, the binder, the oxide carrier and deionized water to obtain a viscous mixture;
step 5), placing the viscous mixture obtained in the step 4) in an extrusion molding device to obtain a wet strip-shaped catalyst carrier;
step 6), placing the wet strip-shaped catalyst carrier prepared in the step 5) in a drying device to obtain a dried strip-shaped catalyst carrier, namely the formed nano LaNi-containing catalyst carrier 5 A catalyst carrier;
(II) preparation of catalyst for catalyzing absorption and desorption of hydrogen by liquid organic hydrogen carrier
Selecting metal precursor salt of Pd or Ru, metal precursor salt solvent and formed nano LaNi-containing material obtained in the step (one) 5 Mixing the catalyst carriers, stirring for 0.5-4 h at the temperature of 20-80 ℃, standing for 6-12 h after stirring, and sequentially washing and drying to obtain the catalyst for catalyzing the absorption and release of hydrogen by the liquid organic hydrogen carrier.
Further preferably, in the step 1), the mass concentration of the ammonium fluoride dilute solution is 5-20%; the grinding aid is selected from NaCl, KCl or CaCl 2 Is one of (a); the LaNi 5 The mass ratio of the alloy powder to the ammonium fluoride dilute solution to the zirconia balls to the grinding aid is 1: (0.5-1): (5-10): (0.5-1); and 2) setting the rotating speed of the ball mill to be 200-400 rpm, wherein the ball milling time is 3-6 h.
Further preferably, the nano LaNi in step 4) 5 The mass ratio of the binder, the oxide carrier and the deionized water is (5-10): (2-4): (20-40): (40-50); the binder is selected from sesbania gum powder, dry starch or sodium carboxymethyl cellulose, and the oxide carrier is selected from gamma-Al 2 O 3 、CeO 2 Or SiO 2 One of them.
Further preferably, the length of the dried strip-shaped catalyst carrier is 2-8 mm.
Further preferably, the metal precursor salt of Pd of the present invention is selected from one of palladium acetate, palladium nitrate or palladium chloride; the metal precursor salt of Ru is selected from one of ruthenium trichloride, ruthenium acetylacetonate or ruthenium acetate; the metal precursor salt solvent is selected from one of hydrochloric acid, acetylacetone or tetrahydrofuran.
Compared with the prior art, the invention has the following advantages:
(1) The catalyst is a bidirectional catalyst, can catalyze the hydrogen absorption of N-ethyl carbazole and the dehydrogenation process, and can reduce the catalyst usage amount and the catalyst cost in practical application.
(2) The catalyst has excellent performance in the aspects of hydrogen absorption and hydrogen release, and can reach and even exceed the catalytic performance of higher noble metal loading under the condition of low noble metal loading.
(3) The preparation method is simple, can be used for mass production, and is easy to popularize and use in industrialization.
Drawings
FIG. 1 is a diagram of a 0.5% Pd/LaNi5 catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph showing the hydrogen absorption kinetics of example 1, example 2, example 3, comparative example 1 and comparative example 2 of the present invention;
FIG. 3 is a graph showing the kinetics of hydrogen release for example 1, example 2, example 3, comparative example 1 and comparative example 2 of the present invention;
FIG. 4 is a schematic diagram of an apparatus for testing the hydrogen absorption and desorption kinetics curves of a liquid organic hydrogen carrier in accordance with the present invention.
Detailed Description
The invention will be described in further detail with reference to specific examples.
The invention relates to a catalyst for catalyzing hydrogen absorption and hydrogen release of a liquid organic hydrogen carrier, which comprises a catalyst carrier and a noble metal active catalytic component loaded on the catalyst carrier, wherein the catalyst carrier is formed and contains nano LaNi 5 A catalyst carrier; the noble metal active catalytic component is Pd or Ru. The catalyst is prepared from formed nano LaNi-containing catalyst 5 The catalyst carrier is obtained by dipping the catalyst carrier in a noble metal precursor salt solution for reaction, washing and drying.
Commercially available LaNi selected for use in the present invention 5 Alloy powder and 1% Pd/Al 2 O 3 The catalyst is commercially available.
Examples
(1) 10g of commercially available 100-mesh LaNi 5 Alloy powder, 5g of ammonium fluoride dilute solution with the mass percentage of 20%, 100g of zirconia balls and 5g of NaCl are placed into a ball milling tank, the ball milling tank is vacuumized and protected by argon, then the ball milling tank is opened, the rotating speed is set at 300rpm, and the ball milling is carried out for 3 hours, so that a ball milling product is obtained. Washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering the upper liquid,drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 5g of the obtained nanometer LaNi 5 Powder, re-weighing 2g sesbania gum powder, 45g gamma-Al 2 O 3 And 40mL of deionized water, placing the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, placing into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain the long strip-shaped wet-shaped nano LaNi-containing material with the length of 4-6 mm 5 And then dried at 60 c for 3 hours by a boiling dryer for use.
(3) Adding 0.316g of palladium acetate and 100mL of tetrahydrofuran into a beaker, magnetically stirring for 30min at 60 ℃, and drying the formed nano LaNi-containing material in the step (2) 5 Adding the catalyst carrier into a beaker, continuing to magnetically stir for 2 hours, standing for 8 hours, and then drying in a 120 ℃ oven to obtain 0.3% Pd/LaNi 5 A catalyst.
For the 0.3% Pd/LaNi 5 The catalyst is used for evaluating the performance of catalyzing N-ethyl carbazole to absorb and release hydrogen, and the hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 1.6H under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of (2) 4 and h, the hydrogen release is close to 99 percent. The apparatus for testing the absorption and desorption kinetics curves of the liquid organic hydrogen carrier is shown in FIG. 4.
Examples
(1) 20g of commercially available 200 mesh LaNi 5 Alloy powder, 10g of ammonium fluoride dilute solution with the mass percentage of 20%, 200g of zirconia balls and 10g of KCl are put into a ball milling tank, the ball milling tank is vacuumized and protected by argon, then the ball milling tank is opened, the rotating speed is set at 300rpm, and ball milling is carried out for 3 hours, so that a ball milling product is obtained. Washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering to remove upper liquid, and drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 10g of the obtained nanometer LaNi 5 Powder, reweighed 2g dry starch, 40g CeO 2 And 40g deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min,kneading into clusters after uniformly stirring, putting into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain the long strip-shaped wet-shaped nano LaNi-containing material with the length of 4-6 mm 5 The catalyst support was then dried by a boiling dryer at 60℃for 3h.
(3) Adding 0.527g of palladium acetate and 100mL of tetrahydrofuran into a beaker, magnetically stirring at 60 ℃ for 30min, adding the catalyst carrier dried in the step 1 into the beaker, magnetically stirring for 2h, standing for 8h, and drying in a 120 ℃ oven to obtain 0.5% Pd/LaNi 5 A catalyst.
For the 0.5% Pd/LaNi 5 The catalyst is used for evaluating the performance of catalyzing N-ethyl carbazole to absorb and release hydrogen, and the hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 1.5H under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of 3.1 and h, the hydrogen release rate is close to 99 percent. The apparatus for testing the absorption and desorption kinetics curves of the liquid organic hydrogen carrier was the same as in example 1.
Examples
(1) 10g of commercially available 50 mesh LaNi 5 Alloy powder, 5g of 20% ammonium fluoride diluted solution, 100g of zirconia balls and 5g of CaCl 2 Placing the mixture into a ball milling tank, vacuumizing the ball milling tank and filling argon for protection, then opening the ball milling machine, setting the rotating speed to 300rpm, and performing ball milling for 3 hours to obtain a ball milling product. Washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering to remove upper liquid, and drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 5g of the obtained nanometer LaNi 5 Powder, 2g of sodium carboxymethylcellulose, 45g of SiO are weighed again 2 And 40g of deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, putting into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain the long strip-shaped wet-shaped LaNi-containing material with the length of 4-6 mm 5 The catalyst support was then dried by a boiling dryer at 60℃for 4 h.
(3) 1.054g of ruthenium trichloride, 100mL of tetrahydrofuran, were added to a beaker and the mixture was magnetically stirred at 60 ℃Stirring for 30min, adding the catalyst carrier dried in the step (2) into a beaker, continuing magnetic stirring for 4h, standing for 12h, and drying in an oven at 80 ℃ to obtain 1% Ru/LaNi 5 A catalyst.
For the 1% Ru/LaNi 5 The catalyst is used for evaluating the performance of catalyzing N-ethyl carbazole to absorb and release hydrogen, and the hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 1.3H under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of 2.5h, the hydrogen release is close to 99 percent. The apparatus for testing the absorption and desorption kinetics curves of the liquid organic hydrogen carrier was the same as in example 1.
Comparative example
With commercially available 1% Pd/Al 2 O 3 (Shaanxi Kaika chemical Co., ltd.) as a catalyst, hydrogen absorption and desorption test conditions and test apparatus the same as in example 1, hydrogen absorption reaction was carried out at 180℃and 8 MPa H 2 Is carried out for 2.5H under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of 6.5 h, the hydrogen release is close to 99 percent. Although commercial 1% Pd/Al compared to example 1 2 O 3 The noble metal loading of the catalyst was higher than that of example 1, 0.3% Pd/LaNi 5 Catalysts, however, have significant differences in either hydrogen absorption or dehydrogenation properties.
Comparative example
(1) Weighing 2g sesbania gum powder and 50g gamma-Al 2 O 3 And 40g of deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, putting into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain strip gamma-Al with the length of 4-6 mm 2 O 3 The support was then dried by a boiling dryer at 60℃for 3h for use.
(2) Adding 0.316g of palladium acetate and 100mL of tetrahydrofuran into a beaker, magnetically stirring for 30min at 60 ℃, and drying the bar-shaped gamma-Al in the step (1) 2 O 3 Adding the carrier into a beaker, continuing to magnetically stir for 2 hours, standing for 8 hours, and then drying in a 120 ℃ oven to obtain 0.3% Pd/Al 2 O 3 A catalyst.
For the 0.3% Pd/Al 2 O 3 The catalyst was subjected to performance evaluation of catalyzing the absorption and desorption of hydrogen by N-ethylcarbazole, and the conditions and apparatus for the measurement of the absorption and desorption of hydrogen were the same as those in example 1. The hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 2.5H under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of 8.5 and h, the hydrogen release rate is close to 99 percent. In comparison with example 1, the support is free of nano LaNi 5 The composition of this comparative catalyst was slightly inferior in terms of hydrogen absorption properties, and the dehydrogenation properties were greatly different from those of the catalyst of example 1. When the catalyst carrier contains nano LaNi 5 When the active component Pd is used for preparing the hydrogen-containing organic liquid carrier (H x -LOHC, x=0-12) is activated, nano LaNi 5 The catalyst carrier has the auxiliary dissociation and transfer functions of hydrogen, and the synergistic effect of the two can lead the free hydrogen to be released rapidly, so the dehydrogenation performance can be greatly improved, and the catalyst carrier does not contain nano LaNi 5 At the time, H cannot be formed efficiently 2 And thus there is a significant difference in dehydrogenation performance.
Comparative example
(1) 10g of commercially available 100-mesh LaNi 5 Alloy powder, 100g of zirconia balls and 5g of NaCl are placed in a ball milling tank, the ball milling tank is vacuumized and protected by argon, then the ball milling tank is opened, the rotating speed is set at 300rpm, and the ball milling is carried out for 3 hours. Washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering to remove upper liquid, and drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 5g of the obtained nanometer LaNi 5 Powder, re-weighing 2g sesbania gum powder, 45g gamma-Al 2 O 3 And 40g of deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, putting into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain 4-6 mm long bar-shaped wet gamma-Al 2 O 3 The support was then dried by a boiling dryer at 60℃for 3h for use.
(3) In a beaker was added 0.316g palladium acetate, 100mL tetrahydrofuran, inMagnetically stirring at 60deg.C for 30min, adding the catalyst carrier dried in step (2) into beaker, magnetically stirring for 2 hr, standing for 8 hr, and oven drying at 120deg.C to obtain 0.3% Pd/LaNi 5 A catalyst.
For the 0.3% Pd/LaNi 5 The catalyst was subjected to performance evaluation of catalyzing the absorption and desorption of hydrogen by N-ethylcarbazole, and the conditions and apparatus for the measurement of the absorption and desorption of hydrogen were the same as those in example 1. The hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 1.8H under the condition of 200 ℃ and 0.1 MPa H 2 The hydrogen release is close to 99% in 5 hours under the condition of (2). In comparison to example 1, the comparative catalyst had slightly poorer hydrogen absorption and dehydrogenation properties than the catalyst of example 1 without the addition of a dilute ammonium fluoride solution during ball milling. Dilute ammonium fluoride solution can make LaNi 5 Formation of loose LaF 3 And a Ni-rich subsurface layer, while the surface structure becomes loose, and cracks are increased, so that the LaNi can be improved 5 And the Ni-rich subsurface layer also helps to adsorb H 2 Is dissociated from the (c). These effective gains cannot be obtained without adding a dilute ammonium fluoride solution, and thus the hydrogen absorption and dehydrogenation properties are slightly inferior.
Comparative example
(1) 10g of commercially available 100-mesh LaNi 5 Placing alloy powder, 5g of ammonium fluoride dilute solution with the mass percentage of 20%, 100g of zirconia balls and 5g of NaCl into a ball milling tank, vacuumizing the ball milling tank and filling argon for protection, then opening the ball milling machine, setting the rotating speed of 300rpm, and performing ball milling for 3 hours to obtain a ball milling product; washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering to remove upper liquid, and drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 5g of the obtained nanometer LaNi 5 Powder, re-weighing 5g sesbania gum powder, 95g gamma-Al 2 O 3 And 40g of deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, putting into an extrusion molding machine, setting the rotating speed to be 120rpm, and extruding to obtain wet strip gamma-Al with the length of 4-6 mm 2 O 3 The support was then dried by a boiling dryer at 60℃for 3h for use.
(3) Adding 0.316g of palladium acetate and 100mL of tetrahydrofuran into a beaker, magnetically stirring for 30min at 60 ℃, adding the catalyst carrier dried in the step (2) into the beaker, magnetically stirring for 2h, standing for 8h, and drying in a 120 ℃ oven to obtain 0.3% Pd/Al 2 O 3 A catalyst.
For the 0.3% Pd/Al 2 O 3 The catalyst was subjected to performance evaluation of catalyzing the absorption and desorption of hydrogen by N-ethylcarbazole, and the conditions and apparatus for the measurement of the absorption and desorption of hydrogen were the same as those in example 1. The hydrogen absorption reaction can be carried out at 180 ℃ and 8 MPa H 2 Is carried out for 3 hours under the condition of 200 ℃ and 0.1 MPa H 2 Under the condition of 8h, the hydrogen release is close to 99 percent. The comparative catalyst was prepared with more binder and oxide support than in example 1, and the test results showed that the hydrogen absorption performance and dehydrogenation performance were significantly different from example 1. This is because the Lani is supported when the binder and the oxide support are excessive 5 The fraction is small and too dispersed, and the partially dissociated H cannot effectively pass through the LaNi 5 Release is carried out, H is increased 2 Is a competitive adsorption effect of (a).
Comparative example
(1) 10g of commercially available LaNi 5 Alloy powder, 5g of ammonium fluoride dilute solution with the mass percentage of 20%, 100g of zirconia balls and 5g of NaCl are placed into a ball milling tank, the ball milling tank is vacuumized and protected by argon, then the ball milling tank is opened, the rotating speed of 300rpm is set, and the ball milling is carried out for 3 hours, so that a ball milling product is obtained. Washing the ball-milled product with deionized water for 3 times, centrifuging in a centrifuge, filtering to remove upper liquid, and drying at 80deg.C under vacuum for 8 hr to obtain nanometer LaNi 5 And (3) powder.
(2) Weighing 5g of the obtained nanometer LaNi 5 Powder, re-weighing 2g sesbania gum powder and 45g MgAl 2 O 4 And 40g of deionized water, putting the weighed materials into a beaker, mixing and stirring for 15min, kneading into a mass after stirring uniformly, putting into an extrusion molding machine, and setting a rotary drumThe speed is 120rpm, and the strip MgAl with the length of 4-6 mm is obtained by extrusion 2 O 4 The support was then dried by a boiling dryer at 60℃for 3h for use.
(3) Adding 0.527g of palladium acetate and 100mL of tetrahydrofuran into a beaker, magnetically stirring at 60 ℃ for 30min, adding the catalyst carrier dried in the step 1 into the beaker, magnetically stirring for 2h, standing for 8h, and drying in a 120 ℃ oven to obtain 0.5% Pd/MgAl 2 O 4 A catalyst.
For the 0.5% Pd/MgAl 2 O 4 The catalyst was subjected to performance evaluation of catalyzing the absorption and desorption of hydrogen by N-ethylcarbazole, and the conditions and apparatus for the measurement of the absorption and desorption of hydrogen were the same as those in example 1. The hydrogen absorption reaction is carried out at 180 ℃ and 8 MPa H 2 Under the condition of (1) that the hydrogen absorption saturation is not reached yet for 6 hours, the corresponding hydrogen release reaction is carried out at 200 ℃ and 0.1 MPa H 2 The hydrogen evolution at 10h failed to approach 99%. The oxide support was modified compared to example 2, which catalyst had poor levels of both hydrogen absorption and dehydrogenation properties. This is probably due to MgAl 2 O 4 The partial basic sites provided by themselves impair the number of acidic sites and thus H 2 Adsorption and dissociation with N-ethylcarbazole to prevent it from being combined with LaNi 5 An effective dissociation H conveying channel is formed, so that the hydrogen absorption and desorption performance of the catalyst is reduced.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.
Claims (10)
1. A catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier, the catalyst comprising a catalyst carrier and a noble metal active catalytic component supported on the catalyst carrier, characterized in that: the catalyst carrier is formed nano LaNi-containing catalyst 5 The method comprises the steps of carrying out a first treatment on the surface of the The noble metal active catalytic component is Pd or Ru, and the loading of the noble metal active catalytic component is the carrier quality of the catalyst0.3% -1% of the amount.
2. The catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 1, wherein: the catalyst is formed by nano LaNi 5 The catalyst carrier is obtained by dipping the catalyst carrier in a noble metal precursor salt solution for reaction, washing and drying.
3. The catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 1 or 2, wherein: the formed nanometer LaNi-containing material 5 The catalyst carrier is prepared by the following steps:
step 1), 50-200 meshes of LaNi 5 Placing alloy powder, ammonium fluoride dilute solution, zirconia balls and grinding aid into a ball milling tank;
step 2), vacuumizing a ball milling tank, filling argon for protection, and then starting a ball mill for ball milling;
step 3), after ball milling is completed, washing the obtained product with deionized water, and then obtaining the nano LaNi through centrifugation and vacuum drying 5 A powder;
step 4), the nano LaNi prepared in the step 3) is prepared 5 Mixing and stirring the powder, the binder, the oxide carrier and deionized water to obtain a viscous mixture, wherein the nano LaNi 5 The mass ratio of the powder to the binder to the oxide carrier to the deionized water is (5-10): (2-4): (20-40): (40-50);
step 5), placing the viscous mixture obtained in the step 4) in an extrusion molding device to obtain a wet strip-shaped catalyst carrier;
step 6), placing the wet strip-shaped catalyst carrier prepared in the step 5) in a drying device to obtain a dried strip-shaped catalyst carrier, namely the formed nano LaNi-containing catalyst carrier 5 A catalyst support.
4. The catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 2, wherein: the noble metal precursor salt solution is selected from one of palladium acetate, palladium nitrate, palladium chloride, ruthenium trichloride, ruthenium acetylacetonate or ruthenium acetate solution.
5. A catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier as set forth in claim 3, wherein: the mass concentration of the ammonium fluoride dilute solution in the step 1) is 5-20%; the grinding aid is selected from NaCl, KCl or CaCl 2 Is one of (a); the LaNi 5 The mass ratio of the alloy powder to the ammonium fluoride dilute solution to the zirconia balls to the grinding aid is 1: (0.5-1): (5-10): (0.5-1);
the binder is one of sesbania gum powder, dry starch or sodium carboxymethyl cellulose; the oxide carrier is gamma-Al 2 O 3 、CeO 2 Or SiO 2 One of them.
6. A method of preparing the catalyst for catalyzing the absorption and desorption of hydrogen from a liquid organic hydrogen carrier according to claim 1, wherein: the preparation method comprises the following steps:
(one) formed nanometer LaNi-containing 5 Preparation of catalyst support
Step 1), 50-200 meshes of LaNi 5 Placing alloy powder, ammonium fluoride dilute solution, zirconia balls and grinding aid into a ball milling tank;
step 2), vacuumizing a ball milling tank, filling argon for protection, and then starting a ball mill for ball milling;
step 3), after ball milling is completed, washing the obtained product with a large amount of deionized water, and then obtaining the nano LaNi through centrifugation and vacuum drying 5 A powder;
step 4), the nano LaNi prepared in the step 3) is prepared 5 Mixing and stirring the powder, the binder, the oxide carrier and deionized water to obtain a viscous mixture;
step 5), placing the viscous mixture obtained in the step 4) in an extrusion molding device to obtain a wet strip-shaped catalyst carrier;
step 6) placing the wet strip-shaped catalyst carrier prepared in the step 5)In the drying device, the dried strip-shaped catalyst carrier is obtained, and the formed nano LaNi-containing catalyst carrier is obtained 5 A catalyst carrier;
(II) preparation of catalyst for catalyzing absorption and desorption of hydrogen by liquid organic hydrogen carrier
Selecting metal precursor salt of Pd or Ru, metal precursor salt solvent and formed nano LaNi-containing material obtained in the step (one) 5 Mixing the catalyst carriers, stirring for 0.5-4 h at the temperature of 20-80 ℃, standing for 6-12 h after stirring, and sequentially washing and drying to obtain the catalyst for catalyzing the absorption and release of hydrogen by the liquid organic hydrogen carrier.
7. The method according to claim 6, wherein: the mass concentration of the ammonium fluoride dilute solution in the step 1) is 5-20%; the grinding aid is selected from NaCl, KCl or CaCl 2 Is one of (a); the LaNi 5 The mass ratio of the alloy powder to the ammonium fluoride dilute solution to the zirconia balls to the grinding aid is 1: (0.5-1): (5-10): (0.5-1); and 2) setting the rotating speed of the ball mill to be 200-400 rpm, wherein the ball milling time is 3-6 h.
8. The method according to claim 6, wherein: the nano LaNi in the step 4) 5 The mass ratio of the binder, the oxide carrier and the deionized water is (5-10): (2-4): (20-40): (40-50); the binder is selected from sesbania gum powder, dry starch or sodium carboxymethyl cellulose, and the oxide carrier is selected from gamma-Al 2 O 3 、CeO 2 Or SiO 2 One of them.
9. The method according to claim 6, wherein: the length of the dried strip-shaped catalyst carrier is 2-8 mm.
10. The method according to claim 6, wherein: the metal precursor salt of Pd is selected from one of palladium acetate, palladium nitrate or palladium chloride; the metal precursor salt of Ru is selected from one of ruthenium trichloride, ruthenium acetylacetonate or ruthenium acetate; the metal precursor salt solvent is selected from one of hydrochloric acid, acetylacetone or tetrahydrofuran; the loading amount of the active catalytic component in the metal precursor salt of Pd or Ru is 0.3-1% of the mass of the strip-shaped catalyst carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311464855.5A CN117443409A (en) | 2023-11-07 | 2023-11-07 | Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311464855.5A CN117443409A (en) | 2023-11-07 | 2023-11-07 | Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117443409A true CN117443409A (en) | 2024-01-26 |
Family
ID=89587153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311464855.5A Pending CN117443409A (en) | 2023-11-07 | 2023-11-07 | Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117443409A (en) |
-
2023
- 2023-11-07 CN CN202311464855.5A patent/CN117443409A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | MOF-derived Co embedded into N-doped nanotube decorated mesoporous carbon as a robust support of Pt catalyst for methanol electrooxidation | |
| CN108714431B (en) | Nano-cellulose reinforced composite photocatalyst and preparation method and application thereof | |
| CN106694018A (en) | Cobalt-nitrogen co-doped carbon oxygen reduction catalyst with gradient pore structure, and preparation method and application thereof | |
| CN113106491B (en) | Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof | |
| CN111883773B (en) | Preparation method of Ni/Co-CNT/NHPC lithium-sulfur battery positive electrode material | |
| CN110813363B (en) | Nitrogen-sulfur-doped porous carbon modified carbon nanotube supported Pt-Ni alloy catalyst and preparation method thereof | |
| CN107224981B (en) | PdNi alloy nano catalyst for ammonia borane hydrolysis hydrogen release and preparation method thereof | |
| CN112510221B (en) | Fuel cell electrocatalyst and preparation method and application thereof | |
| CN113013427A (en) | High-performance electrocatalyst carrier derived based on Metal Organic Framework (MOF) material and preparation method thereof | |
| CN111785980A (en) | Biomass-based catalyst for direct formic acid fuel cell anode and preparation method thereof | |
| CN114300693A (en) | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier | |
| CN111342070A (en) | High-performance low-Pt-loading fuel cell oxygen reduction catalyst and preparation method thereof | |
| CN110534754B (en) | Carbon nanotube coated with Fe3C nanocrystalline and preparation method and application thereof | |
| CN114284516A (en) | Catalyst with low Pt loading capacity, preparation method and application thereof | |
| CN116137331A (en) | Three-dimensional ordered porous oxygen reduction catalyst and preparation method and application thereof | |
| CN110890551A (en) | Coated catalyst, preparation method thereof and application thereof in fuel cell | |
| CN113546660A (en) | Alloy catalyst and application thereof in efficient hydrogen production of borane derivative | |
| CN115064704A (en) | Nitrogen-sulfur-doped iron-monoatomic-supported porous carbon catalyst and preparation method thereof | |
| CN114566657A (en) | Platinum-based ordered alloy catalyst for fuel cell and preparation method thereof | |
| CN110993966A (en) | Fuel cell electrocatalyst and preparation method thereof | |
| CN113201755A (en) | Preparation method of monatomic aerogel electrocatalyst | |
| CN115872355B (en) | Pd-X modified X element doped mesoporous carbon hydrogen storage and hydrogen oxidation catalyst dual-function material, and preparation method and application thereof | |
| CN117443409A (en) | Catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof | |
| CN107369839A (en) | Ruthenium-oxide composite diatomite loads the preparation method of fuel-cell catalyst | |
| CN115608375B (en) | Catalyst for ammonia borane hydrolysis hydrogen evolution 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 |