CN110026241B - Three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and preparation method thereof - Google Patents
Three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 79
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 30
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000013110 organic ligand Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention aims to provide a catalytic electrolysis water hydrogen evolution material with low cost and good stability, which makes a contribution to solving the problem of high price of an electrolysis water hydrogen evolution catalyst. The invention designs a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material with a molecular formula of H by utilizing a one-step hydrothermal synthesis method 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 . 12H 2 O, wherein C 2 N 4 H 4 Is 4-amino-4H-1, 2, 4-triazole. The crystal system is cubic crystal system, and the space group is
Cell parameters α =90, β =90, γ = 90; a =25.3919(4) A, b =25.3919(4) A, c =25.3919(4) A,Zand = 4. The preparation method comprises the steps of mixing phosphotungstic acid (H) 3 PO 4 . 12WO 3 . xH 2 O), dissolving metal nickel salt and 4-amino-4H-1, 2, 4-triazole in deionized water, stirring, adjusting pH to 3.2-4.8 with NaOH solution and HCl solution, placing the reaction solution in a polytetrafluoroethylene reaction kettle, and placing the reaction kettle in an oven at the temperature of 160 ℃ for reaction for 4 days. Then cooling to room temperature. The invention can obtain a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
Description
Technical Field
The invention relates to a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and a preparation method thereof.
Background
Polyacids, i.e., Polyoxometalates (POMs), are a class of inorganic polyoxometalate compounds, which are metal-oxygen cluster compounds formed by connecting early transition metal ions (e.g., V, Mo, W, etc.) with oxygen atoms, and are classified into isopolyacids and heteropoly acids (central heteroatoms include P, B, Al, Co, etc.) according to elemental compositions, and have uniform nano-size, compositional structure adjustability and unique physicochemical properties based on the structure, and thus have wide applications in the research fields of adsorption, catalysis, biology, photoelectricity, etc.
After the development of the polyacid for over two centuries, especially in the last decade, the invention of various analysis methods and characterization methods fully excavates each basic research field of the polyacid. In the field of catalysis, the most successful developments are photocatalysis and electrocatalysis. However, as a catalyst, polyacids, although having their unique redox properties, face inevitable disadvantages: small specific surface area, non-recoverable and the like. Based on the situation, the experiment designs and synthesizes the polyacid based nickel metal crystalline hydrogen evolution material with a three-dimensional structure, and the material can improve the specific surface area of the polyacid catalyst; meanwhile, the existence of the pore channel structure can promote and selectively enable reactant molecules to approach active polyacid catalytic species; more importantly, the polyacid is monodisperse at the molecular level, and the homogeneous catalytic reaction of the heterogeneous catalyst is realized.
As early as many years ago, polyazole compounds have been widely used as protective layers for metal surfaces because they can form metal azole coordination polymers on the metal surfaces. The nitrogen atoms of the azole are all sp 2 And in a hybridization mode, the azole compound can be deprotonated under certain conditions to form corresponding azole anions. Since the nitrogen atom is an electron withdrawing group, the more nitrogen atoms contained on the azole, the more acidic it is, and the more easily it is deprotonated on the surface. Deprotonation not only allows all nitrogen atoms to participate in coordination, but also allows the basicity of the nitrogen atoms to be enhanced. So that the metal azole skeleton has very high thermal stability and chemical stability. Meanwhile, because the azole compounds have small steric hindrance, a plurality of coordination points and flexible and variable coordination modes, various high-dimensional coordination structures are easy to form.
The experiment takes metallic nickel as a center, 4-amino-4H-1, 2, 4-triazole as an organic ligand, and Keggin type phosphotungstic acid is introduced to design and synthesize the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material. Through a large amount of literature research, it is not difficult to find that materials coordinated with metallic nickel are less in the crystal material taking 4-amino-4H-1, 2, 4-triazole as an organic ligand, meanwhile, the crystal material is connected in a mode that the metallic nickel and oxygen atoms in polyacid are alternately connected to form an eight-membered ring structure, and the eight-membered ring structures are mutually overlapped and staggered to form a three-dimensional structure, so that a novel structure is added for the development of organic and inorganic crystal materials. On the basis, the redox performance of the polyacid is fully utilized, and the research on the electrocatalytic hydrolysis performance of the crystal material is carried out, wherein the electrocatalytic hydrolysis is to generate H by cracking water through electric energy 2 And O 2 The method is an ideal hydrogen production method, and the best electro-catalytic hydrolysis catalyst is a Pt-based material at present, however, the expensive price and the small storage amount of the Pt-based material greatly limit the industrial application, so that the search for a non-noble metal catalyst with low price and high activity is still a great challenge. In recent years, the polyacid and the derivative composite material thereof have shown good development prospect when being used as a catalyst for producing hydrogen by electrolyzing water.
Disclosure of Invention
The invention aims to provide a hydrogen evolution material with low cost and good stability, which makes a contribution to solving the problem of high price of a hydrogen evolution catalyst.
A three-dimensional polyacid-based nickel metal-organic crystalline catalytic material with molecular formula of H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 O, wherein C 2 N 4 H 4 Is 4-amino-4H-1, 2, 4-triazole, the crystal system is a cubic crystal system, and the space group is
The unit cell parameter is alpha-90, beta-90, gamma-90;
Z＝4。
a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
firstly, preparing a reaction solution with a pH value of 3.2-4.8: dissolving phosphotungstic acid, metal nickel salt and 4-amino-4H-1, 2, 4-triazole in deionized water, and stirring for several hours at normal temperature to obtain a reaction solution; then adjusting the pH value of the reaction solution to 3.2-4.8 by using a sodium hydroxide solution and a hydrochloric acid solution to obtain a reaction solution with the pH value of 3.0-4.8;
the molar ratio of the phosphotungstic acid to the nickel chloride hexahydrate in the step one is 0.1: (0.4-0.9);
the molar ratio of the phosphotungstic acid to the 4-amino-4H-1, 2, 4-triazole organic ligand in the step one is 0.1: 0.1;
the volume ratio of the phosphotungstic acid substance to the distilled water in the step one is as follows: 0.1mmol:10 mL;
secondly, adding the reaction solution with the pH value of 3.2-4.8 into a polytetrafluoroethylene reaction kettle, reacting for 4 days at the temperature of 160 ℃, cooling to room temperature to obtain a green triangular pyramid crystal, namely the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
The three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and the preparation method thereof. A three-dimensional polyacid-based nickel metal-organic crystalline catalytic material is designed and prepared, and the molecular formula is H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 And O. The crystal system is cubic crystal system, and the space group is
The unit cell parameter is alpha-90, beta-90, gamma-90;
Z＝4。
compared with the prior art, the invention has the following characteristics:
the crystal material is synthesized by Keggin type phosphotungstic acid, 4-amino-4H-1, 2, 4-triazole and metal nickel salt according to a certain molar ratio through a one-step hydrothermal method, and is a crystal material with a novel triangular structure, in the structure, two nitrogen atoms positioned on No. 1 and No. 2 on an organic ligand are coordinated with metal nickel, every three ligands are combined with two metal ions, each No. 1 metal ion is coordinated with polyacid in three different directions, No. 2 metal ion is coordinated with oxygen atoms in water molecules, four terminal oxygen atoms positioned on different directions are coordinated in each polyacid, so that the crystal forms a three-dimensional network structure by directly taking polyacid as a center without a one-dimensional or two-dimensional connection mode, and is a three-dimensional polyacid-based nickel metal-organic catalytic material, meanwhile, the redox performance of the polyacid is 0.5M H 2 SO 4 The electro-catalytic hydrolysis performance of the crystal material is studied in the solution at the scanning speed of 100mV/s, and the result shows that the current density is 10mA cm -2 Corresponding to a potential of 0.66V.
Drawings
Fig. 1 is a schematic diagram of an asymmetric structure of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first embodiment, where 1 is N, 2 is C, 3 is O, 4 is W, 5 is Ni, and 6 is P in fig. 1;
FIG. 2 is a schematic diagram of the coordination of a ligand and a metal of a three-dimensional polyacid based nickel metal-organic crystalline catalytic material prepared in the first embodiment;
FIG. 3 is the metal nickel ions and the oxygen atoms in the polyacid coordinated with the metal in different coordination situations of the three-dimensional polyacid based nickel metal-organic crystalline catalytic material prepared in the first embodiment;
FIG. 4 is a three-dimensional structure topology diagram of a three-dimensional polyacid based nickel metal-organic crystalline catalytic material prepared in the first embodiment;
FIG. 5 is an infrared spectrum of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first example;
FIG. 6 is a PXRD pattern of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in accordance with one of the examples;
FIG. 7 is a cyclic voltammogram of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first example;
FIG. 8 is a linear scanning voltammogram of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first example;
FIG. 9 is a schematic diagram of a three-dimensional polyacid based nickel metal-organic crystalline catalytic material prepared in the first embodiment;
Detailed Description
The process parameters and process routes of the present invention are not limited to the specific embodiments listed below, which are illustrative only and are not limiting of the process parameters and process routes described in the examples of the present invention. It should be understood by those skilled in the art that the present invention can be modified or substituted with equivalents in practical applications to achieve the same technical effects. As long as the application requirements are met, the invention is within the protection scope.
The first specific implementation way is as follows: the embodiment is a three-dimensional polyacid group nickel metal-organic crystalline catalytic material with a molecular formula of H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 And (O). The crystal system is cubic crystal system, and the space group is
The unit cell parameter is alpha-90, beta-90, gamma-90;
Z＝4。
h in the present embodiment 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 The valence of Ni in O is +2, and the coordination mode is 6 coordination; the Keggin type polyacid participates in metal coordination by four terminal oxygen atoms in different directions, and each No. 1 metallic nickel is respectively connected with three polyacids and three ligands, so that a three-dimensional network structure is formed.
Compared with the prior art, the implementation mode has the following characteristics:
the crystal material is synthesized by Keggin type phosphotungstic acid, 4-amino-4H-1, 2, 4-triazole and metallic nickel according to a certain molar ratio through a one-step hydrothermal method, and a single crystal X-ray diffraction result shows that the crystal material is a crystal material with a novel triangular structure, in the structure, two nitrogen atoms positioned on No. 1 and No. 2 on an organic ligand are coordinated with metallic nickel, every three ligands are combined with two metal ions, each No. 1 metal ion is coordinated with polyacid in three different directions, No. 2 metal ion is coordinated with oxygen atoms in water molecules, and four terminal oxygen atoms positioned in different directions are coordinated in each polyacid, so that the crystal does not adopt a one-dimensional or two-dimensional connection mode, but directly takes the polyacid as a center to form a three-dimensional network structure, the method is characterized in that the hydrogen evolution material is a polyacid-based nickel metal crystalline state hydrogen evolution material with a three-dimensional structure, and powder X-ray diffraction results show that the tested X-ray diffraction peak is completely consistent with the simulated single crystal X-ray diffraction peak through the synthesis method of the step one and the step two, and that the synthesized large amount of single crystal materials are high in purity. Electrocatalytic hydrolysis test shows that the polyacid-based nickel metal organic-inorganic crystal material has certain hydrogen evolution performance.
The embodiment can obtain the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
The second embodiment is as follows: the embodiment is a preparation method of a three-dimensional polyacid group nickel metal-organic crystalline catalytic material, which is completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 3.2-4.8: dissolving phosphotungstic acid, metal nickel salt and 4-amino-4H-1, 2, 4-triazole in deionized water, and stirring for several hours at normal temperature to obtain a reaction solution; then adjusting the pH value of the reaction solution to 3.2-4.8 by using a sodium hydroxide solution and a hydrochloric acid solution to obtain a reaction solution with the pH value of 3.2-4.8;
the molar ratio of the phosphotungstic acid to the metal nickel salt in the step one is 0.1: (0.4-0.9);
the molar ratio of the phosphotungstic acid to the 4-amino-4H-1, 2, 4-triazole organic ligand in the step one is 0.1: 0.1;
the volume ratio of the phosphotungstic acid substance to the distilled water in the step one is as follows: 0.1mmol:10 mL;
secondly, adding the reaction solution with the pH value of 3.2-4.8 into a polytetrafluoroethylene reaction kettle, reacting for 4 days at the temperature of 160 ℃, cooling to room temperature to obtain a green triangular pyramid crystal, namely the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
And the binuclear polyacid-based metal organic inorganic crystal material taking polyacid as a template and the preparation method thereof are described in the second step. Is designed and prepared with a molecular formula of H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 And (O). The crystal system is cubic crystal system, and the space group is
The unit cell parameter is alpha-90, beta-90, gamma-90;
Z＝4。
compared with the prior art, the implementation mode has the following characteristics:
the crystal material is synthesized by Keggin phosphotungstic acid, 4-amino-4H-1, 2, 4-triazole and metal nickel salt according to a certain molar ratio through a one-step hydrothermal method,the crystal material is a novel crystal material with a triangular structure, in the structure, two nitrogen atoms positioned on No. 1 and No. 2 on an organic ligand are coordinated with metallic nickel, every three ligands are combined with two metal ions, each No. 1 metal ion is coordinated with three polyacid in different directions, No. 2 metal ion is coordinated with oxygen atoms in water molecules, and four terminal oxygen atoms positioned on different directions are coordinated in each polyacid, so the crystal does not adopt a one-dimensional or two-dimensional connection mode, but directly takes the polyacid as a center to form a three-dimensional network structure, is a polyacid-based nickel metal crystalline hydrogen evolution material with a three-dimensional structure, and simultaneously aims at the redox performance of the polyacid at 0.5M H 2 SO 4 The research on the electrocatalytic hydrolysis performance of the crystal material in the solution shows that the current density is 10mA cm -2 Corresponding to a potential of 0.66V.
The embodiment can obtain the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: the metal silver salt in the step one is nickel chloride, nickel sulfate and nickel nitrate. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second to third embodiments in that: the molar ratio of the phosphotungstic acid to the metal nickel salt in the first step is as follows: 0.1: (0.4-0.9). The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the present embodiment differs from the second to fourth embodiments in that: the molar ratio of the phosphotungstic acid to the 4-amino-4H-1, 2, 4-triazole in the first step is as follows: 0.1:0.1. The rest is the same as the second to fourth embodiments.
The sixth specific implementation mode: the present embodiment differs from the second to fifth embodiments in that: the volume ratio of the phosphotungstic acid substance in the step one to the distilled water is as follows: 0.1mmol:10 ml. The rest is the same as the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from the second to sixth embodiments in that: in the first step, the pH value of the reaction solution is adjusted to 3.2-4.8 by using 0.1-2 mol/L hydrochloric acid solution and 0.1-2 mol/L NaOH solution. The rest is the same as the second to sixth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material is completed according to the following steps:
firstly, preparing a reaction solution with a pH value of 3.2-4.8: dissolving 0.1mmol of phosphotungstic acid and (0.4-0.9) mmol of metal nickel salt into 10ml of deionized water, and then adding 0.1mol of 4-amino-4H-1, 2, 4-triazole organic ligand into the solution to obtain a reaction solution: using 1mol/L HNO 3 Regulating the pH value of the reaction solution to 3.2-4.8 by using the solution and 1mol/L NaOH solution to obtain reaction solution with the pH value of 3.2-4.8;
the volume ratio of the phosphotungstic acid substance in the step one to the deionized water is 0.1mmol:10 ml;
secondly, adding the reaction solution with the pH value of 3.2-4.8 into a polytetrafluoroethylene reaction kettle, reacting for 4 days at 160 ℃, cooling to room temperature to obtain green triangular pyramid crystals, namely the polyacid nickel metal crystalline hydrogen evolution material with the three-dimensional structure.
The analytical data of the X-single crystal diffraction structure of the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first embodiment are shown in the table 1, and the used instrument is an ApexII single crystal diffractometer of Bruker company; table 1 shows the analytical data of X-single crystal diffraction structure of polyacid-based metal-organic inorganic crystal material prepared in example one.
TABLE 1
a R 1 ＝∑║F o │─│F c ║/∑│F o │, b wR 2 ＝∑[w(F o 2 ─F c 2 ) 2 ]/∑[w(F o 2 ) 2 ] 1/2
As shown in Table 1, the formula of the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first example is H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 O, molecular formula is H 124 P 3 W 36 Ni 8 O 156 C 24 N 48 In the structure of the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in example one, two nitrogen atoms located on the numbers 1 and 2 on the organic ligand are coordinated with the metal nickel, each three ligands are combined with two metal ions, each metal ion number 1 is coordinated with three polyacid in different directions, metal ion number 2 is coordinated with an oxygen atom in a water molecule, and four terminal oxygen atoms located on different directions are coordinated in each polyacid, so that the crystal does not adopt a one-dimensional or two-dimensional connection mode, but directly uses the polyacid as a center, thereby forming a three-dimensional network structure.
X-ray single crystal diffraction analysis shows that the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material H prepared in the first embodiment 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 The unit cell of O has three multi-negative ions [ PW 12 O 40 ] 3- (abbreviated as PW) 12 ) 2 nickel ions and 3 4-amino-4H-1, 2, 4-triazole organic ligands, as shown in figure 1: fig. 1 is a schematic diagram of an asymmetric structural unit of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first embodiment, where 1 is N, 2 is C, 3 is O, 4 is W, 5 is Ni, and 6 is P in fig. 1;
the structure of the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first embodiment has 2 crystallographically independent Ni ions, and the same coordination mode is adopted; adopting a coordination mode of six coordination to form two inverted triangle shapes, each Ni ion is coordinated with three oxygen atoms and three nitrogen atoms, and each polyacidFour terminal oxygen atoms positioned in different directions are coordinated, and polyacid, ligand and metal are coordinated with each other to form a three-dimensional network crystal structure. While the Ni-O bond length ranges
The range of the bond length of Ni-N is
All of these bond lengths are within reasonable ranges.
A three-dimensional polyacid-based nickel metal-organic crystalline catalytic material H prepared in example one 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 In O, a specific structural feature is that the asymmetric unit has a three-dimensional structure, and such a nickel-metal structure is rare in the structure of the conventional triazole crystal.
Fig. 4 is a three-dimensional topological structure diagram of the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first embodiment, as shown in the figure, a Keggin type phosphotungstic acid structural unit is simplified into four connected nodes, a ligand and metallic nickel are regarded as three connected nodes, the two nodes are connected with each other to form a closed eight-membered ring, and rings are overlapped in a three-dimensional space in a staggered manner to form a three-dimensional network structure.
FIG. 5 is an infrared spectrum of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in the first example; as can be seen from FIG. 5, the v (P-O) is assigned at 972.5, 959, 812, 612 a )，v(W＝O t )，v as (W-O b -W) and v as (W-O c -W) telescopic vibration; at 1000- -1 A vibrational peak within the range ascribed to an organic ligand vibrational peak; at 1635, 1551, 1229 and 1056cm -1 The absorption peak is the vibration absorption peak of the skeleton ring of triazole molecule. Further, the vibration peak was 3120cm -1 Belongs to the vibration expansion peak of water molecules in the compound.
FIG. 6 is a powder X-ray diffraction pattern of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material prepared in example one; as shown in the figure, the measured data of the crystal material obtained by the experiment is basically superposed with the simulation data obtained by the software according to the standard structure, and the crystal material obtained by the experiment is proved to be the analyzed structure;
in conclusion, the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material is successfully synthesized at 160 ℃ by using a one-step hydrothermal synthesis method and organic ligand 4-amino-4H-1, 2, 4-triazole, metal nickel salt and Keggin type phosphotungstic acid as reactants; meanwhile, the material has certain electrocatalytic hydrolysis performance.
Claims (9)
1. A three-dimensional polyacid-based nickel metal-organic crystalline catalytic material is prepared by a one-step hydrothermal synthesis method, taking metal nickel as a center, adopting 4-amino-4H-1, 2, 4-triazole as an organic ligand and introducing phosphotungstic acid, and has a molecular formula of H 5 [PW 12 O 40 ] 3 [Ni 2 (OH) 3 ] 4 [C 2 N 4 H 4 ] 12 ·12H 2 O, wherein C 2 N 4 H 4 Is 4-amino-4H-1, 2, 4-triazole, the crystal system is a cubic crystal system, and the space group is
The unit cell parameter is alpha-90, beta-90, gamma-90;
Z＝4。
2. a preparation method of a three-dimensional polyacid-based nickel metal-organic crystalline catalytic material comprises the following steps:
firstly, preparing a reaction solution with a pH value of 3.2-4.8: dissolving phosphotungstic acid, metal nickel salt and 4-amino-4H-1, 2, 4-triazole in deionized water, and stirring for several hours at normal temperature to obtain a reaction solution; then adjusting the pH value of the reaction solution to 3.2-4.8 by using a sodium hydroxide solution and a hydrochloric acid solution to obtain a reaction solution with the pH value of 3.2-4.8;
the molar ratio of the phosphotungstic acid to the metal nickel salt in the step one is 0.1 (0.4-0.9);
the molar ratio of the phosphotungstic acid to the 4-amino-4H-1, 2, 4-triazole organic ligand in the step one is 0.1: 0.1;
the volume ratio of the phosphotungstic acid substance in the step one to the distilled water is 0.1mmol:10 mL;
secondly, adding the reaction solution with the pH value of 3.2-4.8 into a polytetrafluoroethylene reaction kettle, reacting for 4 days at the temperature of 160 ℃, cooling to room temperature to obtain a green triangular pyramid crystal, namely the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material.
3. The method as claimed in claim 2, wherein the metal salt in step one is nickel chloride hexahydrate or nickel nitrate.
4. The method for preparing the three-dimensional polyacid based nickel metal-organic crystalline catalytic material according to claim 2, wherein the structural formula of the organic ligand 4-amino-4H-1, 2, 4-triazole in the step one is shown as
5. The method for preparing the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material according to claim 2, wherein the molar ratio of the phosphotungstic acid to the metal nickel salt in the step one is 0.1 (0.4-0.9).
6. The method for preparing the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material according to claim 2, wherein the volume ratio of the amount of the phosphotungstic acid substance to the distilled water in the step one is 0.1mmol:10 mL.
7. The method for preparing the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material according to claim 2, wherein the molar ratio of the phosphotungstic acid to the 4-amino-4H-1, 2, 4-triazole organic ligand in the step one is 0.1: 0.1.
8. The method for preparing the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material according to claim 2, wherein the phosphotungstic acid in the step one is Keggin type phosphotungstic acid.
9. The method for preparing the three-dimensional polyacid-based nickel metal-organic crystalline catalytic material according to claim 2, wherein the pH value of the reaction solution in the step one is adjusted to 3.2-4.8 by using 0.1-2 mol/L HCl solution and 0.1-2 mol/L NaOH solution.
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