阅读说明：本技术 一种金属卤化物钙钛矿CsPbX3在光催化仿生生物合成的应用 (Metal halide perovskite CsPbX3Application in photocatalysis bionic biosynthesis ) 是由 袁荃 王杰 李志恒 于 2020-12-17 设计创作，主要内容包括：本发明涉及发光材料的技术领域,具体涉及一种金属卤化物钙钛矿CsPbX-3在光催化仿生生物合成的应用,利用金属卤化物钙钛矿CsPbX-3的长余辉发光性质应用在光催化生物合成中。本发明中发现金属卤化物钙钛矿CsPbX-3的长余辉发光时长达1h以上。本发明将金属卤化物钙钛矿CsPbX-3的长余辉发光应用在光催化生物合成中,钙钛矿的长寿命光生电子可以提高光催化生物合成的产量。本发明可以扩大钙钛矿材料在能源方面的应用,为人工光合作用的发展带来新的启发。本发明中构建的光催化生物合成体系,光量子产率高达3.24％,体现了钙钛矿的长余辉发光性质的对光催化活性的重要价值。(The invention relates to the technical field of luminescent materials, in particular to a metal halide perovskite CsPbX 3 Application in photocatalysis bionic biosynthesis by using metal halide perovskite CsPbX 3 The long afterglow luminescence property of the compound is applied to the photocatalysis biosynthesis. The metal halide perovskite CsPbX found in the invention 3 The long afterglow of (2) can reach more than 1h when emitting light. The invention uses metal halide perovskite CsPbX 3 The long afterglow luminescence is applied to the photocatalysis biosynthesis, and the long service life photoproduction electrons of the perovskite can improve the photocatalysisYield of the synthesis of the compound. The invention can expand the application of the perovskite material in the aspect of energy and bring new inspiration for the development of artificial photosynthesis. The photocatalytic biosynthesis system constructed in the invention has the light quantum yield as high as 3.24%, and embodies the important value of the long afterglow luminescence property of perovskite on the photocatalytic activity.)

1. Metal halide perovskite CsPbX₃The application in photocatalysis bionic biosynthesis is characterized in that: using metal halide perovskites CsPbX₃The long afterglow luminescence property of the compound is applied to the photocatalysis biosynthesis.

2. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the CsPbX is pretreated by a photosensitizer₃The obtained photocatalyst nano-particles are mixed with a certain amount of electron donor, coenzyme, [ CpRh (bpy) H₂O]²⁺Mixing the oxido-reductase and the buffer solution, adding the raw materials, sealing, reacting for a certain time under the irradiation of ultraviolet light or blue light, centrifuging the obtained solution after reaction, and taking the supernatant to obtain the bionic biosynthetic product.

3. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the concentration of the coenzyme in the reaction system is 1-10mM, [ Cp ] Rh (bpy) H₂O]²⁺The concentration of the compound is 0.02-0.2mM, the concentration of the electron donor is 5% -40% w/v, the concentration of the photocatalyst nano-particles is 0.2-2mg/mL, the concentration of the oxidoreductase is 0.2-5mg/mL, the buffer solution is PBS buffer solution, the pH value of the buffer solution is 6.5-8, and the concentration is 10-1000 mM.

4. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: pretreatment of CsPbX with photosensitizer₃Comprises the steps of coating the CsPbX with a photosensitizer₃The photocatalyst nano-particles are CsPbBr₃@TiO₂、CsPbBr₃@WO₃、CsPbBr₃@ZnO、CsPbBr₃@Fe₂O₃、CsPbBr₃@Cu2O、CsPbBr₃@SnO₂At least one of (1).

5. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the electron donor is any one of triethanolamine, ethylene diamine tetraacetic acid, ascorbic acid and water.

6. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the coenzyme is nicotinamide adenine dinucleotide or nicotinamide adenine dinucleotide phosphate.

7. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the oxidoreductase is any one of formate dehydrogenase, glutamate dehydrogenase, alcohol dehydrogenase and formaldehyde dehydrogenase.

8. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the raw material is any one of carbon dioxide gas, ketoglutaric acid, ketone compounds, formic acid and formaldehyde.

9. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the bionic biosynthetic product is any one of formic acid, glutamate, alcohol compounds, formaldehyde and methanol.

10. The metal halide perovskite CsPbX of claim 1₃The application in photocatalysis bionic biosynthesis is characterized in that: the CsPbX₃Is CsPbCl₃、CsPbCl_1.5Br_1.5、CsPbBr₃、CsPbBr_1.5I_1.5、CsPbI₃At least one of (1).

Technical Field

The invention relates to the technical field of luminescent materials, in particular to a metal halide perovskite CsPbX₃Application in photocatalytic biomimetic biosynthesis.

Background

Metal halide perovskites have unique optoelectronic properties such as high carrier mobility, high quantum yield, tunable band gap, etc., and are widely used in the fields of solar cells, light emitting diodes, photodetectors, etc., wherein the photoelectric conversion efficiency of the perovskite solar cells has been developed to approach that of commercial silicon-based solar cells for a short time, and the internal quantum efficiency of the perovskite LEDs has also been approaching 100%. The photoelectric properties of perovskite materials are closely related to their microstructure. It is reported that the crystal structure, electronic structure, band gap, crystallinity and the like of the perovskite can be changed by adjusting the microstructure in the perovskite by doping and other methods, so that the properties of the perovskite, such as luminous efficiency, carrier transmission capability, stability and the like, are improved. The research on the structure-activity relationship between the microstructure and the photoelectric property of the perovskite material has important significance for deeply understanding the photoelectric property of the perovskite and promoting the application of the perovskite.

Defects are incomplete areas of the crystal that deviate from the ideal structure, one of the most common microstructures in materials. Defects also exist in the perovskite nanocrystals, and crystal defects such as halogen vacancies, lead vacancies, interstitials and the like are inevitably formed due to low energy of formation and high growth rate of the perovskite crystals. The defects have important influence on the photoelectric properties of the semiconductor material, and the defects can form new electronic transition energy levels in blank regions between the energy levels, so that the band gap of the material is changed, and the light absorption and emission properties of the material are regulated. In addition, the defects can store carriers to prolong the luminescence life of the material, and can inhibit the recombination of electrons and holes by capturing photon-generated carriers to promote the transfer of the electrons and the holes to a substrate, thereby improving the photocatalytic performance of the material. Defects in the perovskite can influence the band gap of the perovskite and can capture photogenerated carriers, and new photoelectric properties can be brought to the perovskite.

Metal halide perovskites have been synthesized by many people and have excellent optoelectronic properties such as high quantum yield, adjustable band gap, etc., but no one has reported the long afterglow luminescent properties of metal halide perovskites.

Disclosure of Invention

The invention aims to provide a metal halide perovskite CsPbX₃In the application of photocatalytic biomimetic biosynthesis, the long-afterglow luminescent property of the metal halide perovskite is utilized to be applied in the photocatalytic biosynthesis.

The scheme adopted by the invention for realizing the purpose is as follows: metal halide perovskite CsPbX₃Application in photocatalysis bionic biosynthesis by using metal halide perovskite CsPbX₃The long afterglow luminescence property of the compound is applied to the photocatalysis biosynthesis.

Preferably, CsPbX will be pretreated with a photosensitizer₃The obtained photocatalyst nano-particles are mixed with a certain amount of electron donor, coenzyme, [ CpRh (bpy) H₂O]²⁺Mixing the oxido-reductase and the buffer solution, adding the raw materials, sealing, reacting for a certain time under the irradiation of ultraviolet light or blue light, centrifuging the obtained solution after reaction, and taking the supernatant to obtain the bionic biosynthetic product.

Preferably, the concentration of the coenzyme in the reaction system is 1-10mM, [ Cp ] Rh (bpy) H₂O]²⁺The concentration of the compound is 0.02-0.2mM, the concentration of the electron donor is 5% -40% w/v, the concentration of the photocatalyst nano-particles is 0.2-2mg/mL, the concentration of the oxidoreductase is 0.2-5mg/mL, the buffer solution is PBS buffer solution, the pH value of the buffer solution is 6.5-8, and the concentration is 10-1000 mM.

Preferably, CsPbX is pretreated with a photosensitizer₃Comprises the steps of coating the CsPbX with a photosensitizer₃The photocatalyst nano-particles are CsPbBr₃@TiO₂、CsPbBr₃@WO₃、CsPbBr₃@ZnO、CsPbBr₃@Fe₂O₃、CsPbBr₃@Cu2O、CsPbBr₃@SnO₂At least one of (1).

Preferably, the electron donor is any one of triethanolamine, ethylenediamine tetraacetic acid, ascorbic acid and water.

Preferably, the coenzyme is nicotinamide adenine dinucleotide or nicotinamide adenine dinucleotide phosphate.

Preferably, the oxidoreductase is any one of formate dehydrogenase, glutamate dehydrogenase, alcohol dehydrogenase, and formaldehyde dehydrogenase.

Preferably, the raw material is any one of carbon dioxide gas, ketoglutaric acid, ketone compounds, formic acid and formaldehyde.

Preferably, the biomimetic biosynthesis product is any one of formic acid, glutamate, alcohol compounds, formaldehyde and methanol.

Preferably, the CsPbX₃Is CsPbCl₃、CsPbCl_1.5Br_1.5、CsPbBr₃、CsPbBr_1.5I_1.5、CsPbI₃At least one of (1).

The metal halide perovskite used in the invention is synthesized by adopting a hot injection method, and the method comprises the following specific steps:

1) cesium carbonate is taken as a precursor, oleic acid and octadecene are taken as solvents, and the cesium oleate precursor is synthesized under the conditions of no water and no oxygen at 140-160 ℃, wherein the reaction time is about 2-4 h.

2) Lead halides (lead chloride, lead bromide and lead iodide) are used as precursors, octadecene, oleylamine and oleic acid are used as solvents, and the drying is carried out for 0.5-1.5h under the conditions of oxygen-free temperature of 110-.

3) An appropriate amount of cesium oleate precursor in 1) was rapidly added to the mixture in 2) at 140 ℃. and rapidly cooled to room temperature.

4) Centrifuging the obtained solution, and dispersing in n-hexane to obtain CsPbX₃The dispersion of (4).

The perovskite surface coated TiO for biosynthesis of the invention₂The method comprises the following specific steps:

1) preparing a toluene solution of tetrabutyl titanate with a certain concentration, wherein the volume ratio of tetrabutyl titanate to toluene is 1-3: 100.

2) Taking 1-2mL of solution in an appropriate amount of 1), and dropwise adding the solution into CsPbBr under the stirring condition₃In the toluene solution, reacting for 2-4h at room temperature.

3) Centrifuging the obtained solution, and drying the precipitate at 60-100 deg.C under vacuum for 8-12 h.

4) Calcining the product in the step 3) at the temperature of 250-350 ℃ for 4-6 hours under argon flow, and then grinding to obtain CsPbBr₃@TiO₂。

The invention has the following advantages and beneficial effects:

(1) the metal halide perovskite CsPbX found in the invention₃The long afterglow of (2) can reach more than 1h when emitting light.

(2) The invention uses metal halide perovskite CsPbX₃The long-afterglow luminescence is applied to the photocatalytic biosynthesis, and the long-life photoproduction electrons of the perovskite can improve the yield of the photocatalytic biosynthesis. The invention can expand the application of the perovskite material in the aspect of energy and bring new inspiration for the development of artificial photosynthesis.

(3) The photocatalytic biosynthesis system constructed in the invention has the light quantum yield as high as 3.24%, and embodies the important value of the long afterglow luminescence property of perovskite on the photocatalytic activity.

Drawings

FIG. 1 shows the perovskite CsPbBr prepared in example 1 of the present invention₃Transmission electron microscopy images of;

FIG. 2 shows CsPbX perovskite prepared in example 1 of the present invention₃The afterglow decay photograph of (1);

FIG. 3 shows CsPbBr prepared in example 1 of the present invention₃Luminescence photographs before and after the excitation light was turned off;

FIG. 4 shows the composition of CO in application example 2 of the present invention₂Schematic representation of photocatalytic biosynthesis of formic acid;

FIG. 5 shows the composition of CO in application example 2 of the present invention₂The relationship graph of the formic acid amount of the photocatalysis biosynthesis and the illumination time.

Detailed Description

The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.

Example 1: perovskite CsPbX₃Preparation of nanocrystals

CsPbCl is used in the invention₃、CsPbCl_1.5Br_1.5、CsPbBr₃、CsPbBr_1.5I_1.5、CsPbI₃There are 5 kinds of perovskite nanocrystals.

1) Take 0.814g Cs₂CO₃Adding into 40mL octadecene solution, adding 2.5mL oleic acid, heating to 120 deg.C, vacuumizing for 1 hr to remove water and oxygen, heating at 150 deg.C under argon atmosphere for 2 hr to obtain Cs₂CO₃Completely reacting with oleic acid to obtain a transparent light yellow cesium oleate precursor solution;

2) with CsPbBr₃Preparation of nanocrystals is exemplified: 0.38mmol of PbBr was taken₂(140mg) was added to 10mL of octadecene solution, heated to 120 deg.C and dried under vacuum for 1 hour. 1mL of oleic acid and 1mL of oleylamine were added to PbBr under an argon atmosphere₂And completely dissolving. Then heating to 160 ℃, adding 1mL of cesium oleate precursor solution into the solution until the solution is clear and light yellow, reacting for 5-10s, taking out, and carrying out ice-water bath to completely stop the reaction to obtain CsPbBr₃And (4) a nanocrystalline solution. Centrifuging the obtained solution at 9000r/min for 5min, discarding supernatant, retaining precipitate, and dispersing the precipitate into 3-4mL n-hexane solution for use. The above PbBr is added₂PbCl in an equivalent amount₂Or PbCl₂And PbBr₂Mixture of (2) or PbBr₂And PbI₂Of PbI or PbI₂Under the condition that other raw materials and reaction conditions are the same, CsPbCl is prepared₃、CsPbCl_1.5Br_1.5、CsPbBr_1.5I_1.5、CsPbI₃And (4) nanocrystals.

The obtained perovskite CsPbX₃The nanocrystals were dispersed in n-hexane, dropped in a copper mesh, and observed by transmission electron microscopy, FIG. 1 being CsPbBr₃The transmission electron micrograph of the nanocrystal shows a uniform cubic morphology with a size of about 12 nm.

Example 2: perovskite CsPbBr₃@TiO₂Preparation of nanoparticles

20 μ L of tetrabutyl titanate was added to 1mL of toluene to obtain a toluene solution of tetrabutyl titanate, and the preparation was made1mg/mL CsPbBr₃Slowly dripping 1mL of tetrabutyl titanate toluene solution into the toluene solution under stirring, reacting for about 3h at room temperature, centrifuging the obtained solution for 5min at 5000r/min, vacuum drying the obtained precipitate for about 10h at 80 ℃, calcining the dried product for 5h at 300 ℃ under argon flow, and grinding to obtain CsPbBr₃@TiO₂And (3) nanoparticles.

Example 3: CsPbX₃Test of long afterglow luminescence property of nanocrystalline

1) The CsPbCl obtained in example 1 was taken₃、CsPbCl_1.5Br_1.5、CsPbBr₃、CsPbBr_1.5I_1.5、CsPbI₃1mL of each of the 5 perovskite nanocrystals n-hexane solutions was added to a 24-well plate, and irradiated with 365nm light from a portable ultraviolet lamp for 3 min. The ultraviolet lamp was removed and immediately placed in an IVIS Lumina small animal Living body imager (Caliper, America) to record the afterglow luminescence decay image with the exposure time set to 60 s.

2) CsPbBr obtained in example 1₃Centrifuging n-hexane solution at 9000r/min for 5min, vacuum drying the obtained precipitate overnight, and grinding to obtain CsPbBr₃And (3) nanocrystalline powder. Recording CsPbBr with a Single lens reflex (Nikon, D7100, Japan)₃The images of the nanocrystalline powder under the irradiation of an ultraviolet lamp (365nm) and after the nanocrystalline powder is turned off can obtain photoluminescence and afterglow luminescence in the graph 3.

FIG. 2 shows CsPbCl₃、CsPbCl_1.5Br_1.5、CsPbBr₃、CsPbBr_1.5I_1.5、CsPbI₃Afterglow attenuation images of 5 perovskite nanocrystals, and results show that CsPbX₃The nanocrystalline has long afterglow luminescence exceeding 1 h.

FIG. 3 shows CsPbBr₃The luminescence pictures of the nanocrystalline powder before and after the exciting light is turned off can be seen, and CsPbBr can be seen from the pictures after the ultraviolet lamp is turned off₃The nanocrystals still have bright green light, indicating CsPbBr₃The nanocrystalline has strong long afterglow luminescence.

Example 4: photocatalytic biosynthesis of formic acid

Referring to FIG. 4, in a glass bottle, phosphorus at pH 7.5 was addedAcid buffer as solvent, then Nicotinamide Adenine Dinucleotide (NAD) is added⁺)、[Cp*Rh(bpy)H₂O]²⁺Triethanolamine, CsPbBr₃@TiO₂Nanoparticles and formate dehydrogenase to a final volume of 2mL, a phosphate buffer concentration of 100mM in the reaction system, NAD⁺In a concentration of 5mM, [ Cp + Rh (bpy) H2O]²⁺In a concentration of 0.0625mM, triethanolamine in a concentration of 30% w/v, CsPbBr₃@TiO₂The concentration of the nanoparticles was 2mg/mL and the concentration of formate dehydrogenase was 2 mg/mL. Carbon dioxide gas was then bubbled through the solution for about 10 minutes, and finally the glass bottle was sealed with carbon dioxide gas. The solution was irradiated with 50W power and 450nm wavelength LED lamp as excitation light source under stirring. And taking 300 mu L of solution at 0, 30, 60, 90 and 120 minutes after the illumination is started, centrifuging for 5min at 5000r/min to obtain supernatant, and detecting the content of formic acid in the supernatant by using a formic acid detection kit.

FIG. 5 is a graph showing the relationship between the amount of formic acid produced by photocatalytic biosynthesis and the time of light irradiation, and it can be seen from the graph that the amount of formic acid produced gradually increases with the time of light irradiation, and the yield of formic acid reaches 110.55. mu. mol after 2 hours of light irradiation.

Example 5: photocatalytic biosynthesis of L-glutamate

In a glass bottle, phosphate buffer solution with pH of 6.5 is added as a solvent, followed by Nicotinamide Adenine Dinucleotide (NAD)⁺)、[Cp*Rh(bpy)H₂O]²⁺Triethanolamine, CsPbBr₃@TiO₂Nanoparticles, alpha-ketoglutarate and 40U glutamate dehydrogenase to a final volume of 2mL, wherein the concentration of phosphate buffer is 1000mM, NAD⁺The concentration was 10mM, [ Cp + Rh (bpy) H₂O]²⁺0.2mM concentration, 40% w/v triethanolamine concentration, CsPbBr₃@TiO₂The concentration of the nano particles is 1mg/mL, and the concentration of the alpha-ketoglutaric acid is 5 mM. The solution was irradiated with LED lamps at a power of 50W and a wavelength of 480nm as an excitation light source under stirring. The reaction is finished 120 minutes after the illumination is started, the reaction solution is centrifuged for 5 minutes at 5000r/min to obtain supernatant, and L-glutamate is obtained through biosynthesis.

Example 6: photocatalytic biosynthesis of formaldehyde

In a glass bottle, phosphate buffer solution with pH of 6.5 is added as a solvent, followed by Nicotinamide Adenine Dinucleotide (NAD)⁺)、[Cp*Rh(bpy)H₂O]²⁺Ascorbic acid, CsPbBr₃@TiO₂Nanoparticles, formic acid solution and 0.4mg formaldehyde dehydrogenase to a final volume of 2 mL; wherein the concentration of the phosphate buffer is 10mM, and the NAD⁺The concentration was 1mM, [ Cp + Rh (bpy) H₂O]²⁺The concentration was 0.02mM, the ascorbic acid concentration was 5% w/v, CsPbBr₃@TiO₂The concentration of the nano particles is 0.2mg/mL, and the concentration of the formic acid solution is 5 mM. The solution was irradiated with 50W power and 300nm wavelength LED lamp as excitation light source under stirring. And finishing the reaction 120 minutes after the illumination begins, centrifuging the reaction solution for 5 minutes at 5000r/min to obtain supernatant, and biosynthesizing to obtain the formaldehyde.

Example 7: photocatalytic biosynthesis of methanol

In a glass vial, phosphate buffer solution with pH 7.5 was added as a solvent, followed by nicotinamide adenine dinucleotide phosphate, [ Cp. multidot. Rh (bpy) H₂O]²⁺Ethylenediaminetetraacetic acid, CsPbBr₃@TiO₂Nanoparticles, formaldehyde solution and 5mg of alcohol dehydrogenase to a final volume of 2mL, wherein the concentration of NADP is 5mM, [ Cp Rh (bpy) H₂O]²⁺The concentration is 0.0625mM, the concentration of the ethylene diamine tetraacetic acid is 30% w/v, CsPbBr₃@TiO₂The concentration of the nano particles is 2mg/mL, and the concentration of the formaldehyde solution is 5 mM. The solution was irradiated with 50W power and 450nm wavelength LED lamp as excitation light source under stirring. And finishing the reaction 120 minutes after the illumination begins, and centrifuging the reaction solution for 5 minutes at 5000r/min to obtain supernatant fluid for biosynthesis to prepare the methanol.

While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.