A hybrid perovskite crystal for dual stimulation response by heat and guest molecules, its preparation method and application

Abstract

This invention discloses a hybrid perovskite crystal for dual stimulation response by heat and guest molecules, its preparation method, and its applications. The general molecular formula of the hybrid perovskite crystal is [C9H]. 22 PO][PbI3]·H2O, with a molecular weight of 783.1, wherein C9H 22 PO + The compound is composed of (1-hydroxy)triisopropylphosphine ions. The crystal is monoclinic with chiral space group P21. The (1-hydroxy)triisopropylphosphine organic ligand is dissolved in lead iodide using hydroiodic acid solution, and yellow, blocky one-dimensional perovskite crystals are obtained by a solution cooling method. The preparation method is simple, efficient, and reproducible. The compound exhibits piezoelectricity at room temperature. After high-temperature dehydration, the compound [C9H...]... 22 PO][PbI3]·H2O transforms into [C9H 22 [PO][PbI3], the latter undergoes two reversible phase transitions and exhibits second harmonic generation (SHG) switching and dielectric switching functions.

Description

Technical Field

[0001] This invention relates to a hybrid perovskite crystal for dual stimulation response to heat and guest molecules, its preparation method and application, belonging to the field of functional materials. Background Technology

[0002] Stimulus-responsive smart materials are materials capable of sensing and responding to their environment and possessing detection capabilities. When stimulated by environmental factors (such as temperature, pH, ionic strength, chemical properties, electric fields, magnetic fields, light, or chemical composition), certain physical or chemical properties of the material itself (such as phase, shape, surface energy, reaction rate, permeation rate, or recognition performance) will change accordingly. They have received widespread attention in fields such as medical engineering, sensors, and information storage. Despite the rapid development in this field, research on stimulus-responsive smart perovskite materials with self-powered characteristics remains largely unexplored. The three main self-powered methods are piezoelectricity, triboelectricity, and thermoelectricity. Research in the field of piezoelectricity was the earliest to be conducted, and many research results have been achieved in terms of materials, properties, and devices. When a piezoelectric material is stimulated by external stress, it undergoes an internal deformation process due to the external pressure, resulting in polarization and generating an electrical signal. Piezoelectric materials can generate an electric field through mechanical deformation, which theoretically helps to excite multiple responses in responsive smart materials. Therefore, designing smart materials with piezoelectric effects is of great significance for stimulus response.

[0003] Among various stimuli, temperature is the most commonly used trigger. Notably, introducing water as a guest is also an effective method for designing stimulus-responsive smart materials because hydrogen bonds are weaker than chemical bonds and are more prone to breakage and disorder under external stimuli. In recent years, some smart materials that achieve stimulus response by modulating water molecules have exhibited phase transition behavior and dielectric switching, with water molecules in the pores acting as controllers. However, second harmonic switching (SHG) in molecularly water-controlled phase transition materials has been rarely reported. This is because SHG signals only exist in non-centrosymmetric materials. For stimulus-responsive materials, expressing SHG switching phenomena through the loss / addition of water molecules remains a challenge. Summary of the Invention

[0004] Objectives of the Invention: The first objective of this invention is to provide a hybrid perovskite crystal that responds to both thermal and guest molecule stimuli; the second objective is to provide a method for preparing the hybrid perovskite crystal that responds to both thermal and guest molecule stimuli; the third objective is to provide the application of the hybrid perovskite crystal that responds to both thermal and guest molecule stimuli in the preparation of piezoelectric materials, SHG switches, dielectric switches, or molecular phase change materials.

[0005] Technical Solution: The present invention discloses a hybrid perovskite crystal for dual stimulation response by heat and guest molecules. The hybrid perovskite crystal comprises a one-dimensional hybrid perovskite crystal consisting of a lead iodide ion, a (1-hydroxy)triisopropylphosphine ion, and a water molecule, with the general molecular formula [C9H]. 22 PO][PbI3]·H2O, wherein the [C9H 22 [PO] represents (1-hydroxy)triisopropylphosphine ion. The molecular weight of the perovskite crystal is 783.1. The hybrid perovskite crystal belongs to the monoclinic crystal system at 293K, with space group P21 and chiral space group.

[0006] The cell parameters of the dual-hybrid perovskite crystal include:

[0007]

[0008] The method for preparing hybrid perovskite crystals with dual stimulation response to heat and guest molecules, as described in this invention, includes the following steps:

[0009] The iodide of organophosphorus is added to a hydroiodic acid solution containing H3PO2 as a stabilizer, stirred to dissolve, and then inorganic lead is added. The mixture is stirred until the solution becomes clear and allowed to stand to obtain a hybrid perovskite crystal that can respond to both heat and guest molecules.

[0010] The iodide of the organophosphorus is [(i-Pr)3POH]I (ACS No. 278614-28-1).

[0011] The hydroiodic acid solution has a mass concentration of 48-57% and contains ≤1.5% H3PO2 stabilizer.

[0012] The solid-liquid ratio of the organophosphorus iodide to the hydroiodic acid solution is 1:10-20 g / mL.

[0013] The inorganic lead is either lead iodide or lead acetate.

[0014] The molar ratio of the organophosphorus iodide to inorganic lead is 1:1.

[0015] The settling time is more than one week.

[0016] The present invention relates to the application of hybrid perovskite crystals for dual stimulation response by heat and guest molecules in the preparation of piezoelectric materials, SHG switches, dielectric switches, or molecular phase change materials.

[0017] The hybrid perovskite crystal for dual stimulation response by heat and guest molecules described in this invention is a multifunctional stimulus-responsive compound that exhibits SHG switching and dielectric switching under dual stimulation by temperature and guest water molecules.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0019] (1) The preparation method provided by the present invention is to synthesize by self-assembly of solvent through natural evaporation of solution at room temperature. The preparation method is simple and easy to operate, and the final product has high yield and good reproducibility.

[0020] (2) The hybrid perovskite crystal prepared by the present invention for dual stimulation response of heat and guest molecules exhibits piezoelectricity at room temperature.

[0021] (3) After high-temperature dehydration, the hybrid perovskite crystal prepared in this invention, compound [C9H] 22 PO][PbI3]·H2O transforms into [C9H 22 [PO][PbI3], the latter undergoes two reversible phase transitions and exhibits second harmonic generation (SHG) switching and dielectric switching functions. Attached Figure Description

[0022] Figure 1 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Crystal structure diagram of PO][PbI3]·H2O at 293K;

[0023] Figure 2 The hybrid perovskite crystal [C9H] obtained in Example 1 22 The piezoelectric coefficient d of PO][PbI3]·H2O at 293K 33 And output voltage measurement diagram;

[0024] Figure 3 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Thermogravimetric analysis diagram of PO][PbI3]·H2O;

[0025] Figure 4 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Differential scanning calorimetry curve of PO][PbI3]·H2O after dehydration;

[0026] Figure 5 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Measurement diagram of a second-order nonlinear optical switch after dehydration of PO][PbI3]·H2O;

[0027] Figure 6 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Dielectric measurement diagram of PO][PbI3]·H2O after dehydration;

[0028] Figure 7 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Diagram of the reversible dielectric switch after dehydration of PO][PbI3]·H2O. Detailed Implementation

[0029] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0030] All reagents used in the experiment were commercially available analytical grade reagents.

[0031] Example 1

[0032] Accurately weigh 1.217 g of [(i-Pr)3POH]I into a beaker, add 15 mL of hydroiodic acid solution containing H3PO2 stabilizer (containing 1.5% H3PO2), stir to dissolve, then add 1.844 g of lead iodide, stir to dissolve to obtain a clear solution. After the clear solution is allowed to stand at room temperature for one week, yellow transparent elongated crystals are obtained, which are the hybrid perovskite crystals [C9H] for dual stimulation response by heat and guest molecules. 22 PO][PbI3]·H2O.

[0033] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 Analysis was performed using PO][PbI3]·H2O. Under a microscope, a single crystal of suitable size was selected and analyzed using a variable-temperature X-ray single-crystal diffractometer (Rigaku CCD Saturn 724+) at 293 K, employing graphite-monochromatic Mo Kα rays. The X-ray diffraction structure of the single crystal was determined, and the structure was resolved and refined using the SHELXTL97 software package. The crystal structure diagram is shown below. Figure 1 As shown, the specific data of the crystal structure of this compound are shown in Table 1.

[0034] Figure 1 The hybrid perovskite crystal [C9H] obtained in Example 1 22 The crystal structure diagram of PO][PbI3]·H2O at 293K is provided by Figure 1 It can be seen that the hybrid perovskite crystal structure of this invention consists of C9H... 22 PO + It consists of a cation, a [PbI3] anion, and an H2O molecule. Notably, a water molecule is bonded to an organic cation via hydrogen bonds. Each [PbI6] cation... 4- The octahedron shares all six corners with its two adjacent solids, forming an infinite one-dimensional [(PbI3)] arranged along the b direction. - ]n chain, and simultaneously, cation C9H 22 PO + Water molecules are located between inorganic chains.

[0035] Table 1 Crystallographic data of the compounds

[0036]

[0037] The hybrid perovskite crystal [C9H] prepared in Example 1 22 The piezoelectric properties of PO][PbI3]·H2O were tested using a piezoelectric testing instrument (Institute of Acoustics, Chinese Academy of Sciences, model ZJ-4AN). The results are as follows: Figure 2 As shown. Figure 2 The hybrid perovskite crystal [C9H] obtained in Example 1 22 The piezoelectric coefficient d of PO][PbI3]·H2O at 293K 33 And the output voltage measurement diagram, by Figure 2 It can be observed that this hybrid perovskite crystal [C9H] 22 The piezoelectric coefficient of PO][PbI3]·H2O is 10 pC / N, and the output voltage is approximately 1 V. This illustrates the hybrid perovskite crystal [C9H] prepared in this embodiment. 22 PO][PbI3]·H2O has a self-powered function.

[0038] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 Thermogravimetric analysis (TGA) was performed on PO][PbI3]·H2O using a TAQ50 system. The results are as follows: Figure 3 As shown, Figure 3 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Thermogravimetric analysis chart of PO][PbI3]·H2O, by Figure 3 As can be seen, the hybrid perovskite crystal [C9H] prepared in this embodiment... 22 [PO][PbI3]·H2O begins to lose its water of crystallization at around 352K and remains stable in the temperature range of 352K-465K. 22 [PO][PbI3]. Therefore, [C9H] can be processed at 360K. 22 [PO][PbI3]·H2O is heated to dehydrate, thus obtaining [C9H 22 PO][PbI3].

[0039] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 The PO][PbI3]·H2O powder was dehydrated by heating and then analyzed by differential scanning calorimetry (DSC) using a Netzsch Model DSC 200F3 instrument. The heating / cooling rate was 20 K / min under a nitrogen atmosphere. The results are as follows: Figure 4 As shown, Figure 4 The hybrid perovskite crystal [C9H] obtained in Example 122 Differential scanning calorimetry (DSC) curves of PO₄][PbI₃]·H₂O after dehydration, from Figure 4 As can be seen, in the measurements of the heating-cooling cycle, two pairs of reversible exothermic and endothermic peaks were observed at approximately 255K / 243K and 348K / 315K. This indicates that the hybrid perovskite crystal [C9H] prepared in this embodiment... 22 PO][PbI3]·H2O is a reversible phase change material after dehydration.

[0040] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 The PO][PbI3]·H2O powder was measured using a second harmonic frequency multiplier (FLS 920, Edinburgh Instruments) after dehydration by heating. The results are as follows: Figure 5 As shown, Figure 5 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Measurement diagram of a second-order nonlinear optical switch after dehydration of PO][PbI3]·H2O, from Figure 5 It can be seen that the compound exhibits SHG switching at around 348K / 315K after heating and dehydration.

[0041] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 The PO][PbI3]·H2O powder, after being dehydrated by heating, was compressed into tablets, and conductive silver paste was applied to both sides. The dielectric properties were then studied using an impedance analyzer (Tonghui Model TH2828A). The results are as follows: Figure 6 , 7 As shown, Figure 6 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Dielectric measurement diagram of PO][PbI3]·H2O after dehydration; Figure 7 The hybrid perovskite crystal [C9H] obtained in Example 1 22 Diagram of the reversible dielectric switch after dehydration of PO][PbI3]·H2O. (From...) Figure 6 , 7 As can be seen, the hybrid perovskite crystal [C9H] prepared in this embodiment... 22 PO][PbI3]·H2O exhibits dielectric anomalies around 255K / 243K and 348K / 315K after heating and dehydration, and displays dielectric switching properties around 348K / 315K. Measurements of the dielectric switching period demonstrate the cyclic stability of the material.

[0042] Example 2

[0043] Accurately weigh 1.217 g of [(i-Pr)3POH]I into a beaker, add 20 mL of hydroiodic acid solution containing H3PO2 stabilizer (containing 1.5% H3PO2), stir to dissolve, then add 1.844 g of lead iodide, stir to dissolve to obtain a clear solution. After the clear solution is allowed to stand at room temperature for one week, yellow transparent elongated crystals are obtained, which are the hybrid perovskite crystals [C9H] that are used for dual stimulation response by heat and guest molecules. 22 PO][PbI3]·H2O.

[0044] The hybrid perovskite crystal [C9H] prepared in this embodiment 22 Analysis was performed using PO][PbI3]·H2O. Under a microscope, a single crystal of appropriate size was selected and analyzed using a variable-temperature X-ray single-crystal diffractometer (Rigaku CCD Saturn 724+) at 293 K, employing graphite-monochromatic Mo Kα rays. The X-ray diffraction structure of the single crystal was determined, and the structure was resolved and refined using the SHELXTL97 software package. The crystal structure diagram is shown below. Figure 1 As shown, the specific data of the crystal structure of this compound are shown in Table 2.

[0045] Table 2 Crystallographic data of the compounds

[0046] The results show that the general molecular formula of the hybrid perovskite crystal described in Example 2 is [C9H]. 22 PO][PbI3]·H2O, where [C9H 22 [PO] represents (1-hydroxy)triisopropylphosphine ion. The molecular weight of the perovskite crystal is 783.1. The hybrid perovskite crystal belongs to the monoclinic crystal system at 293 K, with space group P21 and chiral space group. It is the same as the crystal obtained in Example 1.

[0047] Example 3

[0048] Accurately weigh 0.609 g of [(i-Pr)3POH]I into a beaker, add 10 mL of hydroiodic acid solution containing H3PO2 stabilizer (containing 1.5% H3PO2), stir to dissolve, then add 0.922 g of lead iodide, stir to dissolve to obtain a clear solution. After the clear solution is allowed to stand at room temperature for one week, yellow transparent elongated crystals are obtained, which are the hybrid perovskite crystals [C9H] for dual stimulation response by heat and guest molecules. 22 PO][PbI3]·H2O.

[0049] The hybrid perovskite crystal [C9H] prepared in this embodiment 22Analysis was performed using PO][PbI3]·H2O. Under a microscope, a single crystal of suitable size was selected and analyzed using a variable-temperature X-ray single-crystal diffractometer (Rigaku CCD Saturn 724+) at 293 K, employing graphite-monochromatic Mo Kα rays. The X-ray diffraction structure of the single crystal was determined, and the structure was resolved and refined using the SHELXTL97 software package. The crystal structure diagram is shown below. Figure 1 As shown, the specific data of the crystal structure of this compound are shown in Table 3.

[0050] Table 3 Crystallographic data of the compounds

[0051]

[0052]

[0053] The results show that the general molecular formula of the hybrid perovskite crystal described in Example 3 is [C9H]. 22 PO][PbI3]·H2O, where [C9H 22 [PO] represents (1-hydroxy)triisopropylphosphine ion. The molecular weight of the perovskite crystal is 783.1. The hybrid perovskite crystal belongs to the monoclinic crystal system at 293 K, with space group P21 and chiral space group. It is the same as the crystals obtained in Examples 1 and 2.

Claims

1. A hybrid perovskite crystal for dual stimulation response to heat and guest molecules, characterized in that, The general molecular formula of the hybrid perovskite crystal is [C9H]. 22 PO][PbI3]·H2O, wherein the [C9H 22 [PO] represents (1-hydroxy)triisopropylphosphine ion; the molecular weight of the perovskite crystal is 783.1; the hybrid perovskite crystal is monoclinic with space group [missing information]. P 21, Chiral Space Group.

2. The hybrid perovskite crystal for dual stimulation response by heat and guest molecules according to claim 1, characterized in that, The unit cell parameters of the hybrid perovskite crystal include: 。 3. The method for preparing hybrid perovskite crystals for dual stimulation response by heat and guest molecules according to claim 1 or 2, characterized in that, Includes the following steps: Will[( i -Pr)3POH] I is added to a hydroiodic acid solution containing H3PO2 stabilizer, stirred to dissolve, then inorganic lead is added, and stirring is continued until the solution becomes clear. After standing, a hybrid perovskite crystal for dual stimulation response of heat and guest molecules is obtained.

4. The preparation method according to claim 3, characterized in that, The hydroiodic acid solution has a mass concentration of 48-57% and contains ≤1.5% H3PO2 stabilizer.

5. The preparation method according to claim 3, characterized in that, The solid-liquid ratio of the organophosphorus iodide to the hydroiodic acid solution is 1:10-20 g / mL.

6. The preparation method according to claim 3, characterized in that, The inorganic lead is lead iodide or lead acetate.

7. The preparation method according to claim 3, characterized in that, The molar ratio of the organophosphorus iodide to inorganic lead is 1:

1.

8. The preparation method according to claim 3, characterized in that, The settling time is more than one week.

9. The application of the hybrid perovskite crystal for dual stimulation response by heat and guest molecules as described in claim 1 or 2 in the preparation of piezoelectric materials, SHG switches, dielectric switches or molecular phase change materials.

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