Preparation of sulfur-containing metal organic coordination polymer material and application thereof in photocatalytic hydrogen production
阅读说明：本技术 一种含硫金属有机配位聚合物材料的制备及其光催化制氢应用 (Preparation of sulfur-containing metal organic coordination polymer material and application thereof in photocatalytic hydrogen production ) 是由 于岩 卓嘉宁 徐维晨 吴安海 冯亚南 于 2021-10-22 设计创作，主要内容包括：本申请涉及一种新型含硫金属有机配位聚合物材料的制备方法及其在光催化制氢方面的应用。其化学式为[Ni(4,4’-dipy)(PySH)-(2)]-(n),可通过水热法得到蓝色晶体,正交晶系,空间群为P 2-(1)2-(1)2-(1),晶胞参数a=9.784(2)Å,b=17.742(4)Å,c=26.376(5)Å,α=90°,β=90°,γ=90°,Z=2,晶胞体积V=4578.4(16)Å～(3)。该配位聚合物材料在可见光照射下表现出良好的制氢性能。(The application relates to a preparation method of a novel sulfur-containing metal organic coordination polymer material and application thereof in photocatalytic hydrogen production. The chemical formula is [ Ni (4,4' -copy) (PySH) 2 ] n Blue crystals, orthorhombic, having a space group of P 2 1 2 1 2 1 Cell parameter a =9.784(2)Å， b =17.742(4)Å， c =26.376(5)Å， α =90°， β =90°， γ =90 °, Z =2, cell volume V =4578.4(16)Å 3 . The coordination polymer material shows good hydrogen production performance under the irradiation of visible light.)
1. A sulfur-containing metal-organic coordination polymer material characterized by its conversion to a sulfur-containing metal-organic coordination polymerHas the chemical formula of [ Ni (4,4' -copy) (PySH)2]nOrthorhombic, space group ofP 212121Cell parametera = 9.784(2) Å，b = 17.742(4) Å，c = 26.376(5) Å，α= 90°，β= 90°，γ=90 °, Z =2, cell volumeV = 4578.4(16) Å3(ii) a Wherein 4,4'-dipy is 4,4' - (1, 3-propanediyl) bipyridine, PySH is 2-mercaptopyridine, and n is a positive integer.
2. The method for synthesizing the sulfur-containing organometallic complex polymer material according to claim 1, wherein the method comprises the steps of weighing 2-mercaptopyridine, 4' - (1, 3-propanediyl) bipyridine, a nickel source and an alkali source, adding deionized water, stirring, sealing in a reaction kettle, and carrying out hydrothermal reaction; and after the reaction is finished, washing with deionized water and ethanol to obtain a blue target crystal, namely the sulfur-containing metal organic coordination polymer material.
3. The synthesis method according to claim 2, wherein the 2-mercaptopyridine, the 4,4' - (1, 3-propanediyl) bipyridine, the nickel source and the alkali source are blended in a molar ratio of 0.9 to 1:0.45 to 0.5: 1.
4. The method of synthesis according to claim 2, characterized in that the nickel source is NiCl2•6H2O。
5. The method of claim 2, wherein the source of alkalinity is potassium hydroxide.
6. The method of claim 2, wherein the amount of deionized water added is 8 mL.
7. The synthesis method according to claim 2, wherein the hydrothermal reaction is carried out under the conditions of heating from room temperature to 180 ℃, then cooling from 180 ℃ to 150 ℃, and then cooling from 150 ℃ to room temperature for the second time.
8. The synthesis method according to claim 7, wherein the temperature rise rate is 37.5 ℃/h and the first temperature fall rate is 0.625 ℃/h.
9. The synthesis method according to claim 7, wherein the secondary cooling rate is 2.5 ℃/h.
10. The use of the sulfur-containing metal-organic coordination polymer material of claim 1 in a photocatalytic hydrogen production reaction.
Technical Field
The invention belongs to the field of coordination polymer materials, and particularly relates to a preparation method of a sulfur-containing metal organic coordination polymer material and application of the sulfur-containing metal organic coordination polymer material in the field of photocatalytic hydrogen production.
Background
With the rapid development of economy, energy and environmental issues have become the focus of common attention in countries around the world. The photocatalytic hydrogen production reaction can effectively utilize solar energy to convert water resources into clean hydrogen energy, and is one of effective methods for solving energy crisis and environmental problems. The metal organic coordination polymer is widely concerned in the field of photocatalytic hydrogen production due to the advantages of precise structure, easy design and regulation and the like. Part of coordination polymer materials based on non-noble metals are designed to be used as catalysts for photocatalytic hydrogen production reaction, but the problems of low stability, low efficiency and the like generally exist.
The coordination mode of the sulfur-containing ligand is various and is easy to be mixed with transition metal ions Ni2+Coordination assemblies produce coordination polymers of novel structure and generally exhibit relatively high stability in aqueous solutions. In addition, NiS catalytic sites with high activity are introduced, which is beneficial to improving the catalytic activity. Therefore, the application selects sulfur-containing ligand and non-noble metal ion Ni2+The prepared novel metal organic coordination polymer material is used for photocatalytic hydrogen production reaction.
Disclosure of Invention
The invention provides a preparation method of a sulfur-containing metal organic coordination polymer material and application thereof in the field of photocatalytic hydrogen production.
The chemical formula of the sulfur-containing metal organic coordination polymer material is [ Ni (4,4' -dipy) (PySH)2]nOrthorhombic, space group ofP 212121Cell parametera = 9.784(2) Å，b = 17.742(4) Å，c = 26.376(5) Å，α= 90°，β= 90°，γ=90 °, Z =2, cell volumeV = 4578.4(16) Å3. Wherein 4,4'-dipy is 4,4' - (1, 3-propanediyl) bipyridine, PySH is 2-mercaptopyridine.
The sulfur-containing metal-organic coordination polymer material [ Ni (4,4' -dip)y)(PySH)2]nThe preparation method comprises the step of preparing the compound by a hydrothermal method, namely mixing and stirring 2-mercaptopyridine, 4' - (1, 3-propanediyl) bipyridine, a nickel source, an alkali source and water uniformly, and crystallizing at a specific temperature to obtain the compound.
Wherein the molar ratio of the 2-mercaptopyridine to the 4,4' - (1, 3-propanediyl) bipyridine to the nickel source to the alkali source is 0.9-1: 0.45-0.5: 1, and the nickel source is NiCl2•6H2And O, the alkali source is potassium hydroxide. The conditions of the hydrothermal reaction are that the temperature is increased from room temperature to 180 ℃ through the temperature rising rate of 37.5 ℃/h, then is reduced from 180 ℃ to 150 ℃ at the rate of 0.625 ℃/h, and then is reduced from 150 ℃ to room temperature at the rate of 2.5 ℃/h.
The present invention provides the above-mentioned material [ Ni (4,4' -copy) (PySH)2]nThe material has good catalytic hydrogen production performance under the irradiation of visible light under the combined action of a photosensitizer and a sacrificial agent.
The application technical scheme has the beneficial effects that:
the invention obtains a metal organic coordination polymer material [ Ni (4,4' -dipy) (PySH) with novel structure by a simple preparation method2]n. Under the combined action of the photosensitizer and the sacrificial agent, the metal organic coordination polymer material shows good catalytic hydrogen production performance under the irradiation of visible light.
Drawings
FIG. 1 shows a metal-organic coordination polymer material [ Ni (4,4' -dipyry) (PySH) prepared in example 1 of the present invention2]nThe crystal is coordinated with Ni through N atoms at two ends of a 4,4' - (1, 3-propanediyl) bipyridine ligand and is not extended in an limited way.
FIG. 2 shows a metal-organic coordination polymer material [ Ni (4,4' -dipyry) (PySH) prepared in example 1 of the present invention2]nX-ray powder diffraction pattern of (a). Wherein a is a diffraction pattern obtained by fitting the resolved crystal structure; b is a spectrum obtained by grinding a sample and then performing X-ray powder diffraction.
FIG. 3 shows a metal-organic coordination polymer material [ Ni (4,4' -dipyry) ((II))PySH)2]nThe performance of photocatalytic hydrogen production in the presence of a photosensitizer and a sacrificial agent.
Detailed Description
EXAMPLE 1 Synthesis of [ Ni (4,4' -dipy) (PySH) by hydrothermal method2]nCrystal
Weighing 2-mercaptopyridine, 4' - (1, 3-propanediyl) bipyridine and NiCl according to a certain molar ratio2•6H2Adding 8mL of deionized water into the O and the potassium hydroxide in a hydrothermal reaction tank, stirring, sealing and heating, wherein the hydrothermal reaction condition is that the temperature is increased from room temperature to 180 ℃ at the heating rate of 37.5 ℃/h, then the temperature is decreased from 180 ℃ to 150 ℃ at the rate of 0.625 ℃/h, and then the temperature is decreased from 150 ℃ to room temperature at the rate of 2.5 ℃/h. After the reaction is finished, the mixture is washed alternately by deionized water and ethanol to obtain blue crystals. The compounding ratio of each raw material and the sample number are shown in Table 1.
TABLE 1 samples [ Ni (4,4' -dipy) (PySH)2]nConditions for the synthesis of
Example 2 photocatalytic Hydrogen production Performance study
Weighing 10mg of [ Ni (4,4' -dipy) (PySH)2]nAdded to an aqueous solution containing 5mM eosin (photosensitizer) and 15% TEOA (sacrificial agent), and the solution pH =8.5 was adjusted. Then the solution is transferred to a reaction bottle for photocatalytic reaction, and the photocatalytic hydrogen production performance is shown in figure 3.
The above description is only for the purpose of illustrating the present invention and is not intended to limit the present invention in any way, and the present invention is not limited to the above description, but rather should be construed as being limited to the scope of the present invention.