CN111850697B - High-stability organic lead iodide crystal material and preparation method and application thereof - Google Patents
High-stability organic lead iodide crystal material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 101
- 239000013078 crystal Substances 0.000 title claims abstract description 33
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- HJDQVQXEAZRSQI-UHFFFAOYSA-N hexanedioic acid;sodium Chemical compound [Na].[Na].OC(=O)CCCCC(O)=O HJDQVQXEAZRSQI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 108
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910000464 lead oxide Inorganic materials 0.000 claims description 29
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 27
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 claims description 26
- 235000011049 sodium adipate Nutrition 0.000 claims description 26
- 229910001868 water Inorganic materials 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000002178 crystalline material Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005303 weighing Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000007789 sealing Methods 0.000 description 16
- 239000000725 suspension Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004933 hydrothermal crystal growth Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition 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
- 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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a high-stability organic lead iodide crystal material, a preparation method and application thereof, wherein the chemical formula of the crystal material is [ Pb ]2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]The crystal structure belongs to a monoclinic system, the space group is C2/C, and [ Pb ] in the crystal2I2]The inorganic components are in two-dimensional layers, and the layers are connected through an adipic acid disodium organic ligand. Compared with the prior art, the method overcomes the defects of poor stability and difficulty in realizing photocatalytic full hydrolysis of the existing hybrid organic-inorganic perovskite material, combines the advantages of simple preparation process and the like, and has potential application value in the field of photocatalysis.
Description
Technical Field
The invention belongs to the technical field of crystal materials, and relates to a high-stability organic lead iodide crystal material, and a preparation method and application thereof.
Background
With the rapid development of society, the over-exploitation and use of energy causes global energy crisis and environmental pollution problems. The construction of an effective catalytic system for the development of clean energy is one of the hot issues of global concern. Wherein a photocatalytic system is currently recognized as a simple and efficient method for converting light energy into chemical energy (H)2And O2). However, designing a single component semiconductor photocatalystThe challenge of a chemical agent and good light energy conversion efficiency is still great. The current photocatalyst is mainly a traditional inorganic or organic conjugated polymer, such as ultraviolet light-responsive metal oxide or visible light-responsive metal oxynitride. Only a few of these photocatalysts can be activated to achieve full-hydrolysis in one step, and thus the search for an efficient one-component full-hydrolysis catalyst remains a significant challenge.
In recent years, a class of hybrid organic-inorganic lead-calcium-titanium halide ores attracts much attention due to good optical properties, mainly because of the advantages of simple preparation method, accurate adjustment and control of band gap, high light absorption coefficient and the like. But the moisture-sensitive characteristics of the materials greatly limit the application of the materials in photocatalytic full-splitting water. The reason for this is that organic substances in the perovskite material, namely organic amines, can form hydrogen bonds with water molecules, resulting in the disintegration of the perovskite material. Recently, researchers have applied the high-concentration HI solution to realize photocatalytic hydrogen production in order to overcome the defect of humidity sensitivity. However, HI is a flammable, highly corrosive and highly photosensitive substance, which limits its application in the commercial production of hydrogen.
Based on the fact that carboxylic acid ligands and lead halide have stronger coordination capacity, the organic carboxylic acid is adopted to replace organic amine, and therefore the effective method for solving the problem of humidity sensitivity of the material is achieved. However, the response range of the materials reported at present to light is narrow, and solar energy cannot be effectively utilized, so that the application of the materials in the field of photocatalysis is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-stability organic lead iodide crystal material, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a high-stability organic lead iodide crystal material with a chemical formula of [ Pb ]2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]。
Furthermore, the crystal structure of the material belongs to a monoclinic system, the space group is C2/C, and [ Pb ] in the crystal2I2]The inorganic components are in two-dimensional layers, and the layers are connected through an adipic acid disodium organic ligand.
The second technical proposal of the invention provides a preparation method of the high-stability organic lead iodide crystal material, which is characterized by comprising the following steps:
(1) sequentially adding lead oxide, disodium adipate, potassium iodide and concentrated hydrochloric acid into a reaction kettle filled with deionized water, uniformly stirring, and carrying out hydrothermal reaction;
(2) after the reaction is finished, cooling to room temperature, taking out a reaction product, and then filtering, washing and drying to obtain a target product.
Further, in the step (1), the molar ratio of the lead oxide to the disodium adipate to the potassium iodide is 1: (2.5-4): (3-4).
Further, in the step (1), the molar concentration of concentrated hydrochloric acid is 12mol/L, and the addition amount ratio of the concentrated hydrochloric acid to the lead oxide is 230-: 0.23 g.
Further, in the step (1), the volume of the reaction kettle is 1.2-2 times of that of the deionized water used.
Further, in the step (1), the hydrothermal reaction conditions are specifically as follows: the reaction temperature is 170 ℃ and 200 ℃, and the reaction time is 50-100 hours.
Further, in the step (2), the cooling rate is 3-8 ℃/h.
Further, in the step (2), the washing solvent used for washing is one or both of deionized water and ethanol.
The material consists of a cationic two-dimensional lead iodide inorganic layer and adipate dianions for balancing charges between layers. In the preparation process, lead oxide and potassium iodide are respectively used as a lead source and an iodine source, concentrated hydrochloric acid is used as a pH regulator, and disodium adipate is used as a structure directing agent. The reasons for using lead oxide and potassium iodide instead of lead iodide are: 1) lead iodide has poor solubility in the reaction system; 2) in the process of mixing lead oxide and potassium iodide to form lead iodide, the lead iodide can be uniformly mixed with a structure directing agent, which is beneficial to the next step of hydrothermal crystal growth.
In addition, the invention also limits the addition amount of each raw material (such as adipic acid disodium, potassium iodide, concentrated hydrochloric acid and the like), specific reaction conditions (such as reaction temperature, reaction time, temperature reduction speed and the like) and the like, mainly because the conditions are key factors for successfully obtaining the high-quality organic lead iodide crystal material; if the content of the impurities is not within the range of the conditions defined in the present invention, the obtained crystalline material has many problems such as poor crystallinity, high impurity content, and even failure to obtain the target crystal.
The third technical scheme of the invention provides application of the high-stability organic lead iodide crystal material in photocatalytic decomposition of water. Can be used as a good photoresponse material for photocatalytic water decomposition.
Compared with the prior art, the invention has the following advantages:
(1) the preparation process of the material disclosed by the invention is simple and easy to operate, and the product has high crystallinity and high purity.
(2) The material obtained by the invention can resist corrosion of strong acid and strong alkali, has high tolerance to high-temperature environment, and can be heated to 200 ℃ in air atmosphere without decomposition.
(3) The light absorption range is wide, the material obtained by the invention is yellow crystal, the light absorption range can be extended to a visible light region, and the absorption band edge is 480 nanometers.
(4) The energy band meets the requirement of full water splitting, the valence band position of the material obtained by the invention is more positive than the oxidation position of water, and the conduction band position is more negative than the reduction position of water, thus meeting the energy band requirement of the full water splitting photocatalyst.
(5) The material is used for simulating catalytic total hydrolysis under sunlight, and the result shows that the catalyst can decompose water according to a stoichiometric ratio to generate H2And O2The aim of water decomposition of single component is fulfilled.
Drawings
FIG. 1 shows the material [ Pb ] of the present invention2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]A schematic of the crystal structure of (a);
FIG. 2 shows the material [ Pb ] of the present invention2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]An X-ray powder diffraction pattern after treatment in an acid-base solution;
FIG. 3 shows the material [ Pb ] of the present invention2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]X-ray powder diffractogram after heat treatment;
FIG. 4 shows the material [ Pb ] of the present invention2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –](ii) diffuse reflectance absorption spectrum of (d);
FIG. 5 shows the material [ Pb ] of the present invention2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]The photocatalysis effect under simulated sunlight.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the molar concentration of concentrated hydrochloric acid was 12mol/L, and unless otherwise specified, it was indicated that the starting materials and the treatment techniques were conventional and commercially available in the art.
Example 1
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
The material obtained in this example was yellow transparent crystal, and the crystal structure of the material was confirmed by single crystal ray diffraction characterization as shown in fig. 1.
Material [ Pb2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]Stability investigation of (1):
three samples prepared in this example, 0.1g each, were weighed out and soaked in hydrochloric acid at pH 2, aqueous sodium hydroxide at pH 12 and boiling water, respectively, after 24 hours the material was filtered off, rinsed with ethanol and dried. The crystallinity of the sample is characterized by ray powder diffraction (PXRD) and compared with the image of the untreated sample to examine the stability of the sample, and the comparison graph is shown in figure 2, and the prepared material has higher acid-base stability. In addition, 0.1g of the material was weighed out and calcined in a 200 ℃ tube furnace in an air atmosphere for half an hour, and PXRD as shown in FIG. 3 shows that the material has good thermal stability.
Material [ Pb2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]Investigation of optical Properties
The obtained crystal material is ground into powder, and the ultraviolet-visible diffuse reflection absorption spectrum of the crystal material is tested, as shown in figure 4, the light absorption of the material extends to a visible light region, the absorption band edge is 480nm, and the band gap is about 2.74eV, which shows that the material has the potential of photocatalysis by using sunlight.
Material [ Pb2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]Photocatalytic performance measurement of
Weighing 0.1g of photocatalyst, ultrasonically dispersing into 100mL of deionized water, evacuating the air dissolved in the solution through vacuum treatment, irradiating the system with AM1.5G simulated sunlight, detecting the gas generated by photocatalysis through gas chromatography, and obtaining a photocatalysis efficiency chart as shown in figure 5, wherein the system can be used for decomposing water with a stoichiometric ratio to generate H2And O2And one-step photocatalytic full water decomposition is realized.
Comparative example 1:
compared to example 1, most of them are the same except that the addition of concentrated hydrochloric acid is omitted in this comparative example. The main component of the obtained material is lead iodide instead of the target crystal
Comparative example 2:
compared with example 1, most of the results are the same, except that the concentrated hydrochloric acid is changed to equal H in the comparative example+Molar amount of dilute sulfuric acid. The main component of the obtained material is a mixture of the target product with a small size and lead iodide.
Comparative example 3:
compared with example 1, most of the results were the same except that the amount of concentrated hydrochloric acid used was changed to 200. mu.L in this comparative example. The main component of the resulting material is a mixture of lead iodide and the target crystal.
Comparative example 4:
compared with example 1, most of the results were the same except that the amount of concentrated hydrochloric acid used was changed to 300. mu.L in this comparative example. The main component of the obtained material is transparent crystal without I element.
Comparative example 5:
compared with example 1, the major part is the same except that the amount of disodium adipate used in this comparative example is changed to 0.38 g. The main component of the obtained material is lead iodide.
Comparative example 6:
compared with example 1, the major part is the same except that the amount of disodium adipate used in this comparative example is changed to 0.85 g. The main component of the obtained material is a colorless transparent product.
Comparative example 7:
most of them were the same as in example 1 except that the amount of potassium iodide used in this comparative example was changed to 0.42 g. The main component of the resulting material is a mixture of white powder and a small amount of target crystals.
Comparative example 8:
most of them were the same as in example 1 except that the amount of potassium iodide used in this comparative example was changed to 0.75 g. The main component of the resulting material is a mixture of lead iodide and a small amount of the target crystal.
Comparative example 9:
most of the same is true as in example 1, except that in this comparative example the hydrothermal temperature is changed to 150 ℃. The resulting material is lead iodide rather than the target crystal.
Comparative example 10:
most of the same is true as in example 1, except that in this comparative example, the hydrothermal temperature is changed to 220 ℃. The resulting material is a mixture of lead iodide and the target crystal.
Example 2
Material synthesis: weighing 0.23g of lead oxide, 0.475g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 230 mu L of concentrated hydrochloric acid, and vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 3
Material synthesis: weighing 0.23g of lead oxide, 0.76g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 275 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with ethanol for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 4
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 50 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 3 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 5
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 90 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 3 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 6
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 100 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 8 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 7
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.581g of potassium iodide, adding the materials into a reaction kettle (with the volume of 20mL) containing 15mL of deionized water, then dropwise adding 260 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 100 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 8
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.664g of potassium iodide, adding the lead oxide, the disodium adipate and the potassium iodide into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 260 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 170 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 3 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 9
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 200 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 9
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 10mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 200 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water and ethanol for three times respectively, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 10
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (with the volume of 20mL) containing 12mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then violently stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 90 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with ethanol for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 11
Material synthesis: weighing 0.23g of lead oxide, 0.665g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 10mL of deionized water, then dropwise adding 260 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 90 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with ethanol for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 12
Material synthesis: weighing 0.23g of lead oxide, 0.665g of disodium adipate and 0.5g of potassium iodide, adding the materials into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 275 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 200 ℃ for reaction for 60 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 3 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with ethanol for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 13
Material synthesis: weighing 0.23g of lead oxide, 0.665g of disodium adipate and 0.664g of potassium iodide, adding the lead oxide, the disodium adipate and the potassium iodide into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 275 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 90 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 8 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with ethanol for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 14
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.664g of potassium iodide, adding the lead oxide, the disodium adipate and the potassium iodide into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 275 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven with the constant temperature of 180 ℃ for reaction for 72 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
Example 15
Material synthesis: weighing 0.23g of lead oxide, 0.57g of disodium adipate and 0.664g of potassium iodide, adding the lead oxide, the disodium adipate and the potassium iodide into a reaction kettle (the volume is 20mL) containing 15mL of deionized water, then dropwise adding 250 mu L of concentrated hydrochloric acid, and then vigorously stirring to obtain a uniform suspension; sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven with the constant temperature of 180 ℃ for reaction for 50 hours; after the reaction is finished, the temperature of the oven is reduced to room temperature at the speed of 5 ℃/hour; and opening the high-pressure reaction kettle, transferring the obtained solid product to a beaker, washing the solid product with deionized water for three times, and finally drying the solid product in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A high-stability organic lead iodide crystal material is characterized in that the chemical formula is [ Pb ]2I2(H2O)0.75]2+[–O2C(CH2)4CO2 –]；
The crystal structure of the material belongs to a monoclinic system, the space group is C2/C, and Pb in the crystal2I2The inorganic components are in two-dimensional layers, and the layers are connected through an adipic acid disodium organic ligand.
2. The method for preparing the high-stability organolead iodide crystalline material of claim 1, comprising the steps of:
(1) sequentially adding lead oxide, disodium adipate, potassium iodide and concentrated hydrochloric acid into a reaction kettle filled with deionized water, uniformly stirring, and carrying out hydrothermal reaction;
(2) after the reaction is finished, cooling to room temperature, taking out a reaction product, and filtering, washing and drying the reaction product to obtain a target product;
in the step (1), the molar ratio of lead oxide, adipic acid disodium and potassium iodide is 1: (2.5-4): (3-4);
in the step (1), the molar concentration of the concentrated hydrochloric acid is 12mol/L, and the ratio of the molar concentration to the addition amount of the lead oxide is (230) -275) mu L: 0.23 g;
in the step (1), the hydrothermal reaction conditions are specifically as follows: the reaction temperature is 170 ℃ and 200 ℃, and the reaction time is 50-100 hours;
in the step (2), the cooling rate is 3-8 ℃/h.
3. The method for preparing high-stability organolead iodide crystalline material according to claim 2, wherein in the step (1), the volume of the reaction vessel is 1.2-2 times of the deionized water used.
4. The method for preparing the high-stability organolead iodide crystalline material of claim 2, wherein in the step (2), the washing solvent used for washing is one or both of deionized water or ethanol.
5. Use of the high stability organolead iodide crystalline material of claim 1 for photocatalytic decomposition of water.
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| JP2003036977A (en) * | 2001-07-25 | 2003-02-07 | Japan Science & Technology Corp | Electric field light-emitting element utilizing phosphorescence light of lead halide type stratified perovskite compound |
| CN107955181A (en) * | 2017-07-06 | 2018-04-24 | 同济大学 | A kind of high stability two dimension cationic halogenation lead material and its preparation and application |
| CN108864176A (en) * | 2018-07-25 | 2018-11-23 | 同济大学 | A kind of lead halide hybrid material and preparation method thereof |
| CN110305019A (en) * | 2019-08-15 | 2019-10-08 | 暨南大学 | A kind of two-dimensional layer perovskite crystal and preparation method thereof |
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| JP2003036977A (en) * | 2001-07-25 | 2003-02-07 | Japan Science & Technology Corp | Electric field light-emitting element utilizing phosphorescence light of lead halide type stratified perovskite compound |
| CN107955181A (en) * | 2017-07-06 | 2018-04-24 | 同济大学 | A kind of high stability two dimension cationic halogenation lead material and its preparation and application |
| CN108864176A (en) * | 2018-07-25 | 2018-11-23 | 同济大学 | A kind of lead halide hybrid material and preparation method thereof |
| CN110305019A (en) * | 2019-08-15 | 2019-10-08 | 暨南大学 | A kind of two-dimensional layer perovskite crystal and preparation method thereof |
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