CN117239154A - CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof - Google Patents
CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN117239154A CN117239154A CN202310973922.XA CN202310973922A CN117239154A CN 117239154 A CN117239154 A CN 117239154A CN 202310973922 A CN202310973922 A CN 202310973922A CN 117239154 A CN117239154 A CN 117239154A
- Authority
- CN
- China
- Prior art keywords
- ceo
- copt
- catalyst
- hydrogen
- composite
- 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
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 71
- 229910018979 CoPt Inorganic materials 0.000 title claims abstract description 66
- RAXSQXIANLNZAF-UHFFFAOYSA-N boron;hydrazine Chemical compound [B].NN RAXSQXIANLNZAF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 title claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002073 nanorod Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000011232 storage material Substances 0.000 abstract description 4
- 238000005275 alloying Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKPZIQOBDZDBRW-UHFFFAOYSA-N [Pt].[K] Chemical compound [Pt].[K] OKPZIQOBDZDBRW-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GHGNQWNTEPHORR-UHFFFAOYSA-L cobalt;dichlorocobalt Chemical compound [Co].Cl[Co]Cl GHGNQWNTEPHORR-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018936 CoPd Inorganic materials 0.000 description 1
- 229910016551 CuPt Inorganic materials 0.000 description 1
- 229910005335 FePt Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The application belongs to the technical field of hydrogen storage materials, and in particular relates to CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and its preparation process and application. CeO is prepared by the method 2 Dispersing the powder in water, adding cobalt source precursor and platinum source precursor, performing ultrasonic treatment at room temperature to obtain uniform mixed solution, and then adding sodium borohydride for reduction to obtain CoPt/CeO 2 Composite nano catalyst. CoPt/CeO prepared by the application 2 The high performance of the composite nanocatalyst can be attributed to the small size of the CoPt NPs, the alloying effect between Co and Pt, the rich basic sites on the CoPt/CeO surface, and the CoPt NPs and CeO 2 Electron-metal-carrier interactions between carriers. The method for preparing the catalyst has simple and convenient operation and costThe catalyst has the characteristics of small particle size, multiple catalytic active sites and the like, has high catalytic activity and stability, and is a catalyst with a very development prospect.
Description
Technical Field
The application belongs to the technical field of hydrogen storage materials, and in particular relates to CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and its preparation process and application.
Background
Hydrogen is widely regarded as a potential hydrogen carrier because of its advantages of high energy density, wide sources, no pollution, etc. However, finding a safe and effective hydrogen storage/generation material remains one of the most difficult challenges to move to the hydrogen-powered social road. Chemical hydrogen storage materials are receiving considerable attention due to their high hydrogen content and mild dehydrogenation temperatures.
Recently, hydrazine borane (HB, N) 2 H 4 BH 3 ) Is considered to be a very promising candidate because it is a stable and safe solid at room temperature, has a very high hydrogen content (15.4 wt%) and has a high solubility in water, especially its aqueous solution is very stable under ambient conditions. Hydrolysis of BH in aqueous solution using a suitable catalyst 3 Group (equation 1) and decomposition N 2 H 4 After part (equation 2), N 2 H 4 BH 3 A hydrogen utilization efficiency of 100% can be achieved. Theoretically, 1 mole of N 2 H 4 BH 3 Can generate 5 mol H 2 And 1 mole N 2 . However, N 2 H 4 Part can also be incompletely decomposed into NH 3 And N 2 (equation 3). To maximize N 2 H 4 BH 3 As an efficacy of the hydrogen storage material, undesirable reaction pathways must be avoided.
N 2 H 4 BH 3 + 3H 2 O → N 2 H 4 + H 3 BO 3 + 3H 2 (1)
N 2 H 4 → N 2 + 2H 2 (2)
3N 2 H 4 → 4NH 3 + N 2 (3)
It has been previously reported that nickel-based bimetallic Nanoparticles (NPs), in particular Pt-bound nanoparticles, are represented by N 2 H 4 BH 3 Is higher than the height of (2)Is effective in dehydrogenation. However, in most of these catalysts, the noble metal content is very high and these nanoparticles are decomposing N 2 H 4 In part, exhibit poor kinetics, which limit catalyst production and use in future industries. Therefore, the development of a catalyst with low noble metal content, high activity and high selectivity is of great importance for practical application.
Disclosure of Invention
The application aims to solve the defects in the prior art and provides a CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 The preparation method and application of the composite nano catalyst specifically adopts the following technical scheme:
CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 The preparation method of the composite nano catalyst comprises the following steps:
CeO is added with 2 Dispersing the powder in water, adding cobalt source precursor and platinum source precursor, performing ultrasonic treatment at room temperature to obtain uniform mixed solution, and then adding sodium borohydride for reduction to obtain CoPt/CeO 2 Composite nano catalyst.
The CeO is synthesized by taking cerium nitrate as a cerium source through a hydrothermal method 2 Nanorods and their use as supports for the preparation of CoPt/CeO by simple, green and low cost wet chemical methods 2 . Dispersing CoPt nanoparticles having an average particle size of about 3.2nm in CeO 2 In this case, since the atomic radius of Co is smaller than that of Pt, the diffraction peak shifts to a higher value after the formation of the CoPt alloy. At the same time, coPt/CeO due to the small size of the CoPt nanoparticles 2 A large number of alkaline sites on the surface, between CoPt and CeO 2 Electron transfer between them promotes catalytic performance. On the basis, ceO 2 The nano rod can reduce the agglomeration of metal particles, the interaction between metal and a carrier can efficiently catalyze hydrazine borane to produce hydrogen, the selectivity is 100 percent, and the conversion frequency (TOF) reaches 5454 h under 323K alkaline condition -1 And has high cycle stability, and is a catalyst with development prospect.
CoPt/CeO prepared by the preparation method 2 CoP in composite nanocatalystthe average particle size of the t nano particles is 3.2+/-0.4 nm. The large-area agglomeration can occur when the metal particle size is too large, and the catalytic performance is affected; the finer the metal particle size is, the higher the dispersity is, and the catalytic performance of the catalyst can be promoted; therefore, it is demonstrated that CoPt has a small particle size and a large number of exposed active sites, and thus has high catalytic activity.
As a further preferred embodiment, coPt/CeO 2 The Co content in the composite nano catalyst is more than 0 and less than 19.5%, and the Pt content is more than 0 and less than 46%. More preferably CoPt/CeO 2 The molar ratio of Co to Pt in the composite nano catalyst is 9:1. the molar ratio of Co to Pt is 0: 10. 10: 0. 3:7 and 1:9, all other nano catalysts catalyze hydrazine borane to produce hydrogen and show 100 percent of H 2 Selectivity. When the Co and Pt contents were 19.5% and 7.2%, respectively, the molar ratio of Co to Pt was 9:1 CoPt/CeO 2 Exhibits 100% hydrogen selectivity and TOF of 5454 and 5454 h -1 Its excellent properties can be due to the small size of the CoPt nanoparticles, coPt/CeO 2 A large number of alkaline sites on the surface and between Co and Pt and between CoPt and CeO 2 The electrons between them strongly interact.
As a further preferred embodiment, ceO 2 The dosage ratio of the cobalt source precursor to the platinum source precursor is 10: 1.2-10.9: 2.1 to 18.7.
As a further preferable embodiment, the cobalt source precursor is cobalt chloride; the platinum source precursor is potassium tetrachloroplatinate.
Wherein, the application also provides CeO in the preparation step 2 The preparation method of (2) comprises the following steps:
dropwise adding cerium nitrate solution into sodium hydroxide solution, vigorously stirring at room temperature for 30 min to obtain a white turbid solution, transferring the white turbid solution into an autoclave, heating at 100 ℃ for reaction for 24 h, cooling to room temperature, centrifuging, collecting pale yellow precipitate, washing with water and absolute ethyl alcohol, drying, and finally calcining at 550 ℃ in air for 2 h to obtain CeO 2 A nanorod. CeO prepared by the method 2 The performance of the nano rod for catalyzing the dehydrogenation of hydrazine borane after loading CoPt is better than that of CeO purchased directly 2 。
In another aspect of the application, there is also provided the CoPt/CeO described above for catalyzing the production of hydrogen from hydrazine borane 2 The composite nano catalyst can be applied to the preparation of a hydrogen source of a fuel cell, and the composite nano catalyst is used for catalyzing the decomposition of hydrazine borane to produce hydrogen at the temperature of 303K-333K.
The beneficial effects of the application are as follows: coPt/CeO prepared by the application 2 The high performance of the composite nanocatalyst is due to the small size of the CoPt NPs, alloying effects between Co and Pt, coPt/CeO 2 Surface rich alkaline sites and CoPt NPs and CeO 2 Electron-metal-carrier interactions between carriers. In addition, the method for preparing the catalyst is simple and convenient to operate and low in cost, and the obtained catalyst has the characteristics of small particle size, multiple catalytic active sites and the like, has very high catalytic activity and stability, and is a catalyst with very good development prospect.
Drawings
FIG. 1 shows the X-ray diffraction patterns of the composite nanocatalysts and the comparative catalysts obtained in examples 1,3 and 8;
FIG. 2 is a graph showing nitrogen adsorption test of the composite nanocatalyst obtained in example 1 and the comparative catalyst;
FIG. 3 is a graph showing the scanning electron microscope (a), the transmission electron microscope (b), the high resolution transmission electron microscope (c) and the particle diameter statistics (d) of CoPt nanoparticles of the composite nanocatalyst obtained in example 1;
FIG. 4 is a graph showing the X-ray photoelectron spectrum of the composite nanocatalyst obtained in example 1;
FIG. 5 shows CO of the composite nanocatalyst obtained in example 1 and the comparative catalyst 2 -TPD test pattern;
FIG. 6 is a graph showing the performance test of the composite nanocatalysts of examples 1 and 2 for catalyzing the production of hydrogen from hydrazine borane at 323K;
FIG. 7 is a graph showing the performance test of the composite nanocatalysts of examples 1 and 3 for catalyzing the production of hydrogen from hydrazine borane at 323K;
FIG. 8 is a graph showing the performance test of the nanocomposite catalysts of examples 1 and 4-9 and the comparative catalyst for catalyzing the production of hydrogen from hydrazine borane at 323K;
FIG. 9 is a graph showing the performance of the composite nanocatalysts of examples 1 and 10-12 and the comparative catalyst for catalyzing hydrazine borane at 323K;
FIG. 10 is a graph showing the performance of the composite nanocatalysts of examples 1 and 13-16 and the comparative catalyst for catalyzing hydrazine borane at 323K;
FIG. 11 is a graph showing the performance test of the nanocomposite catalyst of example 1 of the present application for catalyzing hydrazine borane at different temperatures;
FIG. 12 is a graph showing the recycling performance test of the nanocomposite catalyst obtained in example 1 for catalyzing hydrazine borane at 323K.
Detailed Description
The conception, specific structure, and technical effects produced by the present application will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects, and effects of the present application. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Example 1
CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 The preparation method of the composite nano catalyst specifically comprises the following steps:
step 1:1.75 g of cerium nitrate and 14.54 g of sodium hydroxide were added to 5ml and 55 ml of deionized water, respectively, and after stirring for 5 minutes, the cerium nitrate solution was added dropwise to the sodium hydroxide solution, followed by vigorous stirring at room temperature for 30 minutes. The white cloudy solution was then transferred to a 100 ml autoclave and after heating at 100 ℃ for 24 hours, the solution was allowed to cool naturally to room temperature. After centrifugation, the pale yellow precipitate was collected, washed with water and absolute ethanol, and then dried in an oven at 80 ℃ overnight. Finally calcining for 2 hours at 550 ℃ in air to obtain CeO 2 A nanorod;
step 2: ceO is added with 2 (10 mg) was dispersed in 5ml deionized water, followed by addition of CeO 2 To the suspension 10.9 mg CoCl was added 2 ·6H 2 O (0.045 mmol) and 2.1 mg of K 2 PtCl 4 (0.005 mmol) and sonicated at 298K for 30 min, 50mg NaBH 4 Rapidly adding the mixture and vigorously stirring; finally, a black product is obtained until bubble formation is stopped, and finally the CoPt/CeO is obtained 2 Composite nano catalyst.
Example 2
CeO in step 2 of embodiment 1 2 Replacement by directly purchased CeO 2 Other steps were followed in the same manner as in example 1 to obtain CoPt/commercial CeO 2 A nano catalyst.
Example 3
CeO in step 2 of embodiment 1 2 Substitution for non-calcined Ce (OH) 3 Other steps are the same as in example 1 to give CoPt/Ce (OH) 3 A nano catalyst.
Example 4
The metal molar ratio of Co to Pt in step 2 of example 1 was adjusted to 10:0, other steps are the same as in example 1 to obtain Co/CeO 2 A nano catalyst.
Example 5
The metal molar ratio of Co to Pt in step 2 of example 1 was adjusted to 7:3, other steps are the same as in example 1 to obtain CoPt/CeO 2 A nano catalyst.
Example 6
The metal molar ratio of Co and Pt in step 2 of example 1 was adjusted to 5:5, other steps are the same as in example 1 to obtain CoPt/CeO 2 A nano catalyst.
Example 7
The metal molar ratio of Co to Pt in step 2 of example 1 was adjusted to 3:7, other steps are the same as in example 1 to obtain CoPt/CeO 2 A nano catalyst.
Example 8
The metal molar ratio of Co to Pt in step 2 of example 1 was adjusted to 1:9, other steps are the same as in example 1 to obtain CoPt/CeO 2 A nano catalyst.
Example 9
The metal molar ratio of Co and Pt in step 2 of example 1 was adjusted to 0:10, other steps were the same as in example 1 to obtain Pt/CeO 2 A nano catalyst.
Example 10
The precursor cobalt chloride in step 2 of example 1 was changed to nickel chloride, and the other steps were the same as in example 1 to obtain NiPt/CeO 2 A nano catalyst.
Example 11
The precursor cobalt salt cobalt chloride in the step 2 of the example 1 is changed into copper chloride, and the other steps are the same as the example 1, so that CuPt/CeO is obtained 2 A nano catalyst.
Example 12
The precursor cobalt salt cobalt chloride in the step 2 of the example 1 is changed into ferrous sulfate, and the other steps are the same as those of the example 1, so that FePt/CeO is obtained 2 A nano catalyst.
Example 13
The procedure of example 1 was followed except that the precursor platinum salt potassium tetrachloroplatinate in step 2 of example 1 was changed to iridium chloride, and the same procedure as in example 1 was followed to obtain CoIr/CeO 2 A nano catalyst.
Example 14
The precursor platinum salt potassium tetrachloroplatinate in the step 2 of the example 1 is changed to rhodium chloride, and the other steps are the same as those in the example 1 to obtain CoRh/CeO 2 A nano catalyst.
Example 15
The precursor platinum salt potassium tetrachloroplatinate in the step 2 of the example 1 is changed into ruthenium chloride, and the other steps are the same as those in the example 1 to obtain CoRu/CeO 2 A nano catalyst.
Example 16
The procedure of example 1 was followed except that the precursor platinum salt potassium tetrachloroplatinate in step 2 of example 1 was changed to sodium tetrachloroplatinate, and CoPd/CeO was obtained 2 A nano catalyst.
Example 17
The application carries out relevant characterization data on part of the materials prepared in the embodiment, and the method is as follows:
FIG. 1 shows X-ray diffraction patterns of the composite nanocatalysts and the comparative catalyst obtained in examples 1,4 and 9 of the application; as can be seen from FIG. 1, after loading CoPt, ceO 2 Does not change significantly, indicating CeO 2 The structure is stable.
FIG. 2 is a graph showing the scanning electron microscope (a), the transmission electron microscope (b), the high resolution transmission electron microscope (c) and the particle diameter statistics (d) of CoPt nanoparticles of the composite nanocatalyst obtained in example 1 of the application; as can be seen from FIG. 2, ceO was prepared 2 The particles exhibited a regular rod shape, and the particle size of the supported CoPt was about 3.2nm.
FIG. 3 is a graph showing the X-ray photoelectron spectrum of the composite nanocatalyst obtained in example 1 of the application; as can be seen from fig. 3, C, ce, O, co and Pt elements were present in the prepared catalyst.
FIG. 4 is a graph showing nitrogen adsorption test of the composite nanocatalyst and the comparative catalyst obtained in example 1 of the application; as can be seen from FIG. 4, the specific surface area after CoPt loading was reduced, indicating that CoPt was successfully loaded to CeO 2 A surface.
FIG. 5 shows CO of the composite nanocatalyst obtained in example 1 of the application and a comparative catalyst 2 -TPD test pattern; as can be seen from FIG. 5, coPt/CeO 2 The alkaline site strength of (a) is higher than that of pure CoPt particles. The catalyst has a plurality of alkaline sites, which is favorable for the N-H fracture in hydrazine borane, thereby improving the catalyst activity.
Example 18
CoPt/CeO prepared by examples 1 and 2 of the present application 2 The nano catalyst catalyzes hydrazine borane to produce hydrogen, naOH (2M) is added into the catalyst system, 1 mmol of hydrazine borane is added under the normal pressure of 323K for reaction, the hydrogen production performance is shown in figure 6, and as can be seen from figure 6, coPt/CeO prepared by adopting the method of the application 2 The performance of the nano catalyst for catalyzing hydrazine borane to produce hydrogen is superior to commercial CeO directly purchased 2 。
Example 19
The nano-catalyst prepared in the application examples 1 and 3 is used for catalyzing hydrazine borane to produce hydrogen, naOH (2M) is added into a catalyst system, 1 mmol of hydrazine borane is added under the normal pressure of 323K for reaction, the hydrogen production performance is shown in figure 7, and as can be seen from figure 7, coPt/CeO prepared by the application 2 The performance of the nano catalyst in catalyzing hydrazine borane to produce hydrogen is superior to CoPt/Ce (OH) 3 。
Example 20
By adopting the embodiment of the application1 and 4-9 CoPt/CeO 2 The nano catalyst is used for catalyzing hydrazine borane to produce hydrogen, naOH (2M) is added into the catalyst system, 1 mmol of hydrazine borane is added under the normal pressure of 323K to react, the hydrogen production performance is shown in figure 8, and the conditions for preparing the catalysts of examples 1 and 4-9 and the catalytic reaction result are shown in table 1.
TABLE 1 CoPt/CeO prepared in examples 1,3-8 2 Nano catalyst catalytic hydrazine borane hydrogen production performance list
The results in Table 1 show that CoPt/CeO 2 In the catalyst, the molar ratio of Co to Pt is 0: 10. 10: 0. 3:7 and 1:9, all other nano catalysts catalyze hydrazine borane to produce hydrogen and show 100 percent of H 2 Selectivity, when the molar ratio of Co to Pt is 9:1, the nanocatalyst showed the best performance for hydrazine borane hydrogen production. The catalyst prepared by different molar ratios of Co and Pt has different electronic structures, so that the finally prepared CoPt/CeO has strong synergistic effect 2 The nanocatalysts differ in catalytic properties in the reaction.
Example 21
CoPt/CeO prepared by employing examples 1 and 10-16 of the present application 2 The nano catalyst catalyzes hydrazine borane to produce hydrogen, naOH (2M) is added into the catalyst system, 1 mmol of hydrazine borane is added into the catalyst system for reaction under the normal pressure of 323K, the hydrogen production performance is shown in fig. 9 and 10, and the conditions for preparing the catalysts of examples 1 and 10-16 and the catalytic reaction result are shown in table 2.
TABLE 2 CoPt/CeO prepared in examples 1 and 10-16 2 Nano catalyst catalytic hydrazine borane hydrogen production performance list
The results in Table 2 show that of the Co-noble and non-noble metals-Pt prepared, only CoPt/CeO 2 And NiPt/CeO 2 Exhibits a hydrogen selectivity of 100%, wherein CoPt/CeO 2 Higher TOF (tof=5454 h) -1 ) The synergistic effect between Co and Pt was shown to be much greater than other bimetallic combinations.
Example 22
CoPt/CeO prepared by example 1 of the present application 2 The nano catalyst is used for catalyzing hydrazine borane to generate hydrogen at different temperatures, the catalyst is placed in a 50 mL flask containing 5mL deionized water, and 1.0 mmol of hydrazine borane is added under the normal pressure of 303K, 313K, 323K and 333K respectively for reaction, the hydrogen generation performance chart is shown in fig. 11, and the conditions for preparing the catalyst and the catalytic reaction result are shown in table 3.
TABLE 3 CoPt/CeO prepared in example 1 2 Performance list of composite nano catalyst for catalyzing hydrazine borane to produce hydrogen at different catalytic temperatures
The results in Table 3 show that CoPt/CeO 2 The composite nano catalyst is used for catalyzing hydrazine borane to produce hydrogen, and all the hydrogen shows 100% of H 2 The selectivity, the catalytic reaction rate and the reaction activity are obviously improved along with the temperature rise, and under 323K, the prepared CoPt/CeO 2 The composite nano catalyst only needs 1.1 min for catalyzing hydrazine borane to produce hydrogen, and the conversion frequency (TOF) value is up to 5454 h -1 This is mainly due to the fact that high temperatures can activate the catalyst and thus can effectively increase the catalytic activity.
Example 23
CoPt/CeO prepared by example 1 of the present application 2 The composite nano catalyst is used for catalyzing hydrazine borane to generate hydrogen, the catalyst is placed in a 50 mL flask containing 5mL of deionized water, naOH (2M) is added, 1 mmol of hydrazine borane is added under the normal pressure of 323K for reaction, the reaction is circulated for 5 times, and the hydrogen generation performance diagram is shown in figure 12. As can be seen from FIG. 11, coPt/CeO 2 The composite nano catalyst has good recycling stability for producing hydrogen from hydrazine borane, and the catalyst activity and the gas yield are not obviously reduced after the catalyst is repeatedly used for 5 times, which proves that the catalyst has good catalytic activity and recycling stability.
CoPt/CeO prepared by the application 2 The high performance of the composite nanocatalyst is due to the small size of the CoPt NPs, alloying effects between Co and Pt, coPt/CeO 2 Surface rich alkaline sites and CoPt NPs and CeO 2 Electron-metal-carrier interactions between carriers.
In conclusion, the method for preparing the catalyst is simple and convenient to operate and low in cost, and the obtained catalyst has the characteristics of small particle size, multiple catalytic active sites and the like, has high catalytic activity and stability, and is a catalyst with a very development prospect.
While the present application has been described in considerable detail and with particularity with respect to several described embodiments, it is not intended to be limited to any such detail or embodiments or any particular embodiment, but is to be construed as providing broad interpretation of such claims by reference to the appended claims in view of the prior art so as to effectively encompass the intended scope of the application. Furthermore, the foregoing description of the application has been presented in its embodiments contemplated by the inventors for the purpose of providing a useful description, and for the purposes of providing a non-essential modification of the application that may not be presently contemplated, may represent an equivalent modification of the application.
Claims (10)
1. CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 The preparation method of the composite nano catalyst is characterized by comprising the following steps:
CeO is added with 2 Dispersing the powder in water, adding cobalt source precursor and platinum source precursor, performing ultrasonic treatment at room temperature to obtain uniform mixed solution, and then adding sodium borohydride for reduction to obtain CoPt/CeO 2 Composite nano catalyst.
2. The method of claim 1, wherein CoPt/CeO 2 The Co content in the composite nano catalyst is more than 0 and less than 19.5%, and the Pt content is more than 0 and less than 46%.
3. The method of claim 2, wherein CoPt/CeO 2 Composite nano-catalysisThe molar ratio of Co to Pt in the catalyst is 9:1.
4. the method according to claim 1, wherein CeO 2 The dosage ratio of the cobalt source precursor to the platinum source precursor is 10: 1.2-10.9: 2.1 to 18.7.
5. The method of claim 4, wherein the cobalt source precursor is cobalt chloride.
6. The method of claim 4, wherein the platinum source precursor is potassium tetrachloroplatinate.
7. The method according to claim 4, wherein CeO 2 The method comprises the following steps:
dropwise adding cerium nitrate solution into sodium hydroxide solution, vigorously stirring at room temperature for 30 min to obtain a white turbid solution, transferring the white turbid solution into an autoclave, heating at 100 ℃ for reaction for 24 h, cooling to room temperature, centrifuging, collecting pale yellow precipitate, washing with water and absolute ethyl alcohol, drying, and finally calcining at 550 ℃ in air for 2 h to obtain CeO 2 A nanorod.
8. CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nanocatalyst, characterized in that it is obtainable by the preparation process according to any of claims 1 to 7.
9. A CoPt/CeO for catalyzing the production of hydrogen from hydrazine borane as claimed in claim 8 2 The application of the composite nano catalyst in the preparation of a hydrogen source of a fuel cell.
10. The use of the composite nanocatalyst of claim 9 in the preparation of a hydrogen source for a fuel cell wherein the composite nanocatalyst is used to catalyze the decomposition of hydrazine borane to produce hydrogen at a temperature of 303K-333K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310973922.XA CN117239154A (en) | 2023-08-04 | 2023-08-04 | CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310973922.XA CN117239154A (en) | 2023-08-04 | 2023-08-04 | CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117239154A true CN117239154A (en) | 2023-12-15 |
Family
ID=89090058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310973922.XA Pending CN117239154A (en) | 2023-08-04 | 2023-08-04 | CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117239154A (en) |
-
2023
- 2023-08-04 CN CN202310973922.XA patent/CN117239154A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds | |
| Gao et al. | CrPd nanoparticles on NH2-functionalized metal-organic framework as a synergistic catalyst for efficient hydrogen evolution from formic acid | |
| He et al. | Air-engaged fabrication of nitrogen-doped carbon skeleton as an excellent platform for ultrafine well-dispersed RuNi alloy nanoparticles toward efficient hydrolysis of ammonia borane | |
| Chen et al. | Carbon-supported small Rh nanoparticles prepared with sodium citrate: Toward high catalytic activity for hydrogen evolution from ammonia borane hydrolysis | |
| Yang et al. | Complete dehydrogenation of hydrazine borane and hydrazine catalyzed by MIL-101 supported NiFePd nanoparticles | |
| Li et al. | Ultrafine Ru nanoparticles anchored to porous g-C3N4 as efficient catalysts for ammonia borane hydrolysis | |
| Zhou et al. | Pd-doped Cu nanoparticles confined by ZIF-67@ ZIF-8 for efficient dehydrogenation of ammonia borane | |
| Luconi et al. | H2 production from lightweight inorganic hydrides catalyzed by 3d transition metals | |
| Baydaroglu et al. | Polypyrrole supported Co–W–B nanoparticles as an efficient catalyst for improved hydrogen generation from hydrolysis of sodium borohydride | |
| CN111346677B (en) | Preparation method of palladium/amino-rich porous polymer catalyst for preparing hydrogen by catalyzing self-decomposition of formic acid | |
| CN113042085B (en) | Preparation method and application of nitrogen-phosphorus double-doped graphene-supported nickel-cobalt-palladium nano catalyst | |
| CN110026213B (en) | Formic acid hydrogen production catalyst and preparation method and application thereof | |
| Qiu et al. | Hydrolytic dehydrogenation of NH 3 BH 3 catalyzed by ruthenium nanoparticles supported on magnesium–aluminum layered double-hydroxides | |
| Qiu et al. | Hydrogen generation from ammonia borane hydrolysis catalyzed by ruthenium nanoparticles supported on Co–Ni layered double oxides | |
| Şen et al. | Binary Palladium–Nickel/Vulcan carbon-based nanoparticles as highly efficient catalyst for hydrogen evolution reaction at room temperature | |
| Gu et al. | Maximizing hydrogen production by AB hydrolysis with Pt@ cobalt oxide/N, O-rich carbon and alkaline ultrasonic irradiation | |
| CN113634256B (en) | Multi-dimensional micro-nano non-noble metal composite catalyst and preparation and application thereof | |
| Guo et al. | Surface property and spatial confinement engineering for achieving Ru nanoclusters on O/N-doped hollow carbon towards enhanced hydrogen production | |
| CN113426469B (en) | Preparation method and application of double-carrier supported nickel-palladium nano catalyst for formic acid dehydrogenation | |
| Jiang et al. | Hierarchically porous CoP@ CNR nanorod derived from metal-organic frameworks as noble-metal-free catalyst for dehydrogenization of ammonia-borane | |
| Liang et al. | Nitrogen doping excited Ru and Ti3C2− xNx support for hydrogen generation from ammonia borane | |
| Zhao et al. | Anchoring PdAg nanoparticles on ZIF-67-derived Co@ NC composite as a catalyst for efficient hydrogen evolution from formic acid | |
| CN117239154A (en) | CoPt/CeO for catalyzing hydrazine borane to produce hydrogen 2 Composite nano catalyst and preparation method and application thereof | |
| Liu et al. | Recent progress on porous catalysts for dehydrogenation of ammonia borane | |
| CN113145114A (en) | Supported noble metal boride catalyst and preparation method and application 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 |