Cross-band light absorption vacant shell material based on nano thin layer copper sulfide as well as preparation method and application of cross-band light absorption vacant shell material

Abstract

The invention belongs to the technical field of functional materials, and particularly relates to a cross-band light absorption empty shell material based on nano thin-layer copper sulfide and a preparation method and application of the cross-band light absorption empty shell material. The nano thin layer copper sulphide empty shell material is prepared based on a sacrificial template, the three-dimensional space geometrical shape of template crystal grains can be reserved, and regulation and control of the shape, the outer wall thin layer thickness and the band gap of the empty shell material can be achieved. The light absorption empty shell material is composed of copper sulfide and cuprous sulfide p-type semiconductor composite polycrystalline phases, the surface of a thin shell layer is constructed by a large number of nanosheet layered small single crystals, and compared with a solid material, the free carrier concentration of the empty shell light absorption material is remarkably improved, so that a remarkable light limiting effect is caused; meanwhile, due to the hollow morphology characteristic, incident light waves can be repeatedly reflected and absorbed at the shell layer of the inner wall of the cavity, and the light absorption capacity of the material is enhanced. In addition, due to hollowing, the material has low density and high specific absorption rate, and practical application requirements are met.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional materials, and particularly relates to a cross-band light absorption hollow material based on nanometer thin-layer copper sulfide as well as a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of industrialization and informationization, the electronic communication technology industry is booming. Various digital high-frequency electronic and electrical equipment has been widely and deeply applied, providing great convenience for human life. However, the problems of electromagnetic interference and electromagnetic pollution are increasingly prominent. Traditional magnetic metals and alloys, spinel ferrites, carbon materials and other electromagnetic wave absorbing materials have the problems of single absorption mechanism, narrow frequency band, low specific absorption rate and so on due to their core structure, and it is increasingly difficult to meet the actual application requirements. In order to solve this problem, new high-efficiency electromagnetic absorbing materials with the characteristics of "thin, light, wide and strong" need to be developed.

[0003] Copper sulfide (Cu 2-x S, 0 < x < 1) is an important transition metal chalcogenide semiconductor compound. According to the difference in crystal structure and stoichiometric ratio, copper sulfide has adjustable electrical conductivity and band gap. In particular, copper vacancies can produce free holes in the valence band of copper sulfide material, making it a self-doped p-type semiconductor, and thus generating free carriers, exhibiting localized surface plasmon resonance effect. Combined with the low toxicity characteristics of the material itself, copper sulfide has great application potential in the field of electromagnetic absorbing materials. However, compared with mature carbon material and other electromagnetic wave absorbing material systems, copper sulfide has the problems of high density, small specific surface area, poor magnetic and dielectric performance regulation ability, and non-significant Maxwell-Wagner effect and interface polarization effect, which restrict its application as electromagnetic absorbing material.

[0004] Therefore, how to prepare copper sulfide material with wave-absorbing performance through reasonable structure design on the basis of fully utilizing surface plasmon effect is still a great challenge. SUMMARY

[0005] The purpose of the present application is to provide a cross-band light absorption hollow material based on nanometer thin-layer copper sulfide as well as a preparation method and application thereof, which overcomes the problems in the background art and the prepared hollow material has the advantages of light weight and excellent light absorption capacity.

[0006] In order to achieve the above-mentioned purpose of the application, the technical scheme of the present application is as follows:

[0007] In a first aspect, the present application provides a preparation method of a cross-band light absorption hollow material based on nanometer thin-layer copper sulfide, comprising the following steps:

[0008] SS1. adding Cu 2+The Cu2O template material is obtained by adding a strong alkali solution and a reducing agent solution into an aqueous solution containing Cu2+ ions, and then separating, cleaning, and vacuum drying the reaction product.

[0009] The alkali in the strong alkali solution reacts with the Cu 2+ in a molar ratio of 600:1 to 30:1, and the reducing agent reacts with the Cu 2+ in a molar ratio of 0.5:1 to 2.5:1.

[0010] The reducing agent solution is selected from a glucose solution, an ascorbic acid solution, or a hydroxylamine hydrochloride solution.

[0011] SS2. The Cu2O template material obtained in step SS1 is uniformly dispersed in water, and a sulfur source is added thereto under the protection of an inert atmosphere. After reaction, the Cu2O / CuO / Cu x S core-shell material is obtained by separation and cleaning.

[0012] The sulfur source is selected from one or more than two mixtures of a sodium sulfide solution, a thiourea solution, an ammonium sulfide solution, a thioacetamide solution, or a sodium thiosulfate solution.

[0013] The molar ratio of the sulfur source to Cu2O is 1:1 to 1:2.

[0014] SS3. The Cu2O / CuO / Cu x S core-shell material obtained in step SS2 is dispersed in water, and an aqueous ammonia solution is added thereto. After reaction, the Cu2O / CuO / Cu x S core-shell material with hollowed Cu2O is obtained by separation.

[0015] SS4. The Cu2O / CuO / Cu x S core-shell material obtained in step SS3 is dispersed in deionized water, and concentrated hydrochloric acid is added thereto. After centrifugal cleaning and vacuum drying, the Cu x S hollow shell material is obtained.

[0016] Preferably, the strong alkali solution is sodium hydroxide or potassium hydroxide.

[0017] Preferably, in step SS1, the concentration of the aqueous solution containing Cu 2+ ions is 0.1-1 mol / L, and the aqueous solution containing Cu 2+ ions is selected from a CuSO4 aqueous solution or a CuCl2 aqueous solution.

[0018] Preferably, in step SS1, the reaction temperature is 25-70℃, and the reaction time is 3-60 mins.

[0019] Preferably, in step SS2, the reaction time is 1-24 h, and the reaction temperature is 0-30℃.

[0020] Preferably, in the step SS3, Cu2O / CuO / Cu x The concentration of the S core-shell material in the solution is 0.05-0.5 mol / L; the concentration of the ammonia water after the addition of the ammonia water is 20-200 g / L; the reaction temperature is 0-30 DEG C; and the reaction time is 0.5-12 h.

[0021] Preferably, in the step SS4, the concentration of the hydrochloric acid is 300-450 g / L; the reaction temperature is 0-30 DEG C; and the reaction time is 10-60 s.

[0022] Preferably, the cleaning solvent used in the centrifugal cleaning in the steps SS1, SS2, SS3 and SS4 is selected from one or more of anhydrous ethanol and deionized water.

[0023] In a second aspect, the application provides a cross-band light absorption hollow shell material based on nanometer thin-layer copper sulfide obtained by the preparation method according to the first aspect, wherein the light absorption hollow shell material is composed of a copper sulfide and cuprous sulfide p-type semiconductor composite polycrystalline phase, and a large number of nanometer sheet layer small single crystals are constructed on the surface of the thin shell layer.

[0024] In a third aspect, the application provides an application of the cross-band light absorption hollow shell material based on nanometer thin-layer copper sulfide obtained by the preparation method to laser protection and electromagnetic wave shielding and absorption.

[0025] The concept of the application is that: by preparing and regulating the Cu2O sacrificial template, the three-dimensional morphology of the final light absorption hollow shell material can be effectively regulated; by adjusting the type of sulfur source and the sulfuration time, the thickness of the nanometer thin-layer shell can be effectively controlled; by the strong coordination of the ammonia water, the oxide inner core can be effectively removed, and the cross-band light absorption hollow shell material based on nanometer thin-layer copper sulfide can be prepared. After the hollow shell formation, the free carrier concentration of the light absorption material is significantly improved, thereby causing a significant optical limiting effect; at the same time, the hollow morphology is also conducive to the repeated reflection and absorption of the incident light wave at the inner wall shell layer, thereby enhancing the light absorption capacity of the material. The synergistic promotion effect of multiple light absorption mechanisms in one material is achieved, and the light absorption capacity of the material is significantly improved.

[0026] Compared with the prior art, the application has the following beneficial effects:

[0027] (1) In the application, Cu2O is used as a sacrificial template, and a rich polyhedral three-dimensional morphology can be obtained, including but not limited to a cube, a rhombic dodecahedron, an octahedron and the like with diversified sizes, thereby providing an efficient and reliable process route for the cavity structure and size design of the hollow shell material.

[0028] (2) The present application can continuously control the wall thickness of the hollow shell material by adjusting process parameters such as sulfur source type and sulfurization time, build a sulfurized copper nanometer thin layer hollow shell material, significantly enhance the multiple reflection and scattering performance of the hollow absorber, realize the synergy of multiple light absorption mechanisms, and effectively solve the problem of single absorption mechanism and insufficient absorption efficiency regulation ability of the solid structure.

[0029] (3) The hollow shell material prepared by the present application not only has strong light absorption performance, but also significantly reduces the material density and increases the volume fraction by building a hollow or core-shell structure, greatly improves the specific absorption rate, and can meet the actual application requirements of lightweight electromagnetic absorption or shielding field.

[0030] (4) The preparation process of the present application is simple and controllable, has good universality, is easy to industrialize, and has high practical value and popularization value in the field of functional materials technology. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The preparation flow chart of the cross-band light absorption hollow shell material based on nanometer thin layer sulfurized copper of the present application.

[0032] Figure 2 The morphology diagram of the cross-band light absorption hollow shell material based on nanometer thin layer sulfurized copper of the present application;

[0033] a-e are respectively examples 1-5; 1-3 are respectively electron microscope graphs under the scale of 500nm, 200nm and 100nm.

[0034] Figure 3 The ultraviolet-visible-near infrared cross-band light absorption performance of the cross-band light absorption hollow shell material based on nanometer thin layer sulfurized copper of the present application examples 1-5. DETAILED DESCRIPTION

[0035] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0036] Example 1

[0037] 250mL of copper sulfate solution with a concentration of 1.0M, 10M of sodium hydroxide solution, 0.7M of glucose solution, 0.05M of sodium sulfide solution, 150g / L of ammonia solution and 400g / L of hydrochloric acid solution were prepared in advance.

[0038] Deionized water and the previously prepared copper sulfate, sodium hydroxide and glucose solutions were added in the volume ratio of 6:1:2:1, continuously stirred at room temperature for 1h, and then centrifuged and washed to obtain Cu2O template material.

[0039] Cu2O template material was dispersed in 70 mL of deionized water, 30 mL of previously prepared sodium sulfide aqueous solution was added under argon atmosphere, and the reaction was continued for 1 h. After centrifugal cleaning, Cu2O / CuO / Cu x CuO / Cu core-shell material was obtained by adding 60 mL of deionized water and 40 mL of previously prepared aqueous ammonia solution thereto, and reacting for 0.5 h. After centrifugal cleaning, CuO / Cu x CuO / Cu core-shell material was obtained by adding 60 mL of deionized water and 40 mL of previously prepared aqueous ammonia solution thereto, and reacting for 0.5 h. After centrifugal cleaning, CuO / Cu

[0040] Example 2

[0041] 250 mL of copper sulfate solution with a concentration of 1.0 M, 10 M of sodium hydroxide solution, 0.12 M of hydroxylamine hydrochloride solution, 0.05 M of thiourea solution, 200 g / L of aqueous ammonia solution, and 300 g / L of hydrochloric acid solution were prepared in advance, respectively.

[0042] Deionized water and previously prepared copper sulfate, sodium hydroxide, and hydroxylamine hydrochloride solutions were sequentially added in a volume ratio of 6:1:3:2, and stirring was continued at room temperature for 30 mins. After centrifugal cleaning, Cu2O template material was obtained.

[0043] Cu2O / CuO / Cu core-shell material was obtained by dispersing 10 mmol of Cu2O template material in 70 mL of deionized water, adding 50 mL of previously prepared thiourea aqueous solution under argon atmosphere, and continuing the reaction for 6 h. After centrifugal cleaning, Cu2O / CuO / Cu x CuO / Cu core-shell material was obtained by adding 60 mL of deionized water and 20 mL of previously prepared aqueous ammonia solution thereto, and reacting for 6 h. After centrifugal cleaning, CuO / Cu x CuO / Cu core-shell material was obtained by adding 60 mL of deionized water and 20 mL of previously prepared aqueous ammonia solution thereto, and reacting for 6 h. After centrifugal cleaning, CuO / Cu

[0044] Example 3

[0045] 250 mL of copper sulfate solution with a concentration of 1.0 M, 10 M of sodium hydroxide solution, 0.12 M of hydroxylamine hydrochloride solution, 0.05 M of thiourea solution, 200 g / L of aqueous ammonia solution, and 300 g / L of hydrochloric acid solution were prepared in advance, respectively.

[0046] Deionized water and previously prepared copper sulfate, sodium hydroxide, and hydroxylamine hydrochloride solutions were sequentially added in a volume ratio of 6:1:3:2, and stirring was continued at room temperature for 30 mins. After centrifugal cleaning, Cu2O template material was obtained.

[0047] Cu2O template material was dispersed in 70 mL of deionized water, 30 mL of pre-prepared ammonium sulfide solution was added under argon atmosphere, and the reaction was continued for 12 h. After centrifugal cleaning, Cu2O / CuO / Cu x CuO / Cu core-shell material; 60 mL of deionized water and 25 mL of pre-prepared ammonia solution were added thereto, and the reaction was continued for 12 h. After centrifugal cleaning, CuO / Cu x CuO / Cu core-shell material; 10 mL of pre-prepared hydrochloric acid solution was added thereto, and the mixture was vigorously shaken for 20 s. After centrifugal cleaning and drying, a dark green nano-thin-layer copper sulfide hollow shell powder sample was obtained.

[0048] Example 4

[0049] 250 mL of copper chloride solution with a concentration of 1.0 M, 10 M of sodium hydroxide solution, 0.15 M of glucose solution, 0.1 M of thioacetamide solution, 150 g / L of ammonia solution, and 400 g / L of hydrochloric acid solution were pre-prepared respectively.

[0050] Deionized water and pre-prepared copper chloride, sodium hydroxide, and glucose solutions were sequentially added in a volume ratio of 6:1:3:2, and the mixture was continuously stirred at room temperature for 8 mins. After centrifugal cleaning, Cu2O template material was obtained.

[0051] Cu2O template material was dispersed in 50 mL of deionized water, 20 mL of pre-prepared thioacetamide solution was added under argon atmosphere, and the reaction was continued at 0°C for 1 h. After centrifugal cleaning, Cu2O / CuO / Cu x CuO / Cu core-shell material; 50 mL of deionized water and 30 mL of pre-prepared ammonia solution were added thereto, and the mixture was magnetically stirred at 0°C for 1 h. After centrifugal cleaning, CuO / Cu x CuO / Cu core-shell material; 10 mL of pre-prepared hydrochloric acid solution was added thereto, and the mixture was vigorously shaken for 20 s. After centrifugal cleaning and drying, a dark green nano-thin-layer copper sulfide hollow shell powder sample was obtained.

[0052] Example 5

[0053] 250 mL of copper sulfate solution with a concentration of 1.0 M, 10 M of sodium hydroxide solution, 0.7 M of glucose solution, 0.05 M of sodium thiosulfate solution, 200 g / L of ammonia solution, and 300 g / L of hydrochloric acid solution were pre-prepared respectively.

[0054] Cu2O / CuO / CuS core-shell material; 100 mL of deionized water and 20 mL of pre-prepared ammonia solution were added thereto, and the mixture was stirred at 20°C for 12 h. After centrifugal washing, CuO / Cu2O / CuS core-shell material was obtained. x CuO / Cu2O / CuS core-shell material; 20 mL of pre-prepared hydrochloric acid solution was added thereto, and the mixture was vigorously shaken for 60 s. After centrifugal washing and drying, a dark green nanosheet CuS hollow shell powder sample was obtained. x CuO / Cu2O / CuS core-shell material; 20 mL of pre-prepared hydrochloric acid solution was added thereto, and the mixture was vigorously shaken for 60 s. After centrifugal washing and drying, a dark green nanosheet CuS hollow shell powder sample was obtained.

[0055] Test results

[0056] The CuS hollow shell material samples prepared in Examples 1-5 were subjected to morphology characterization and wall thickness evaluation, and the characterization results are shown in Figure 2 .

[0057] The CuS hollow shell material samples prepared in Examples 1-5 were subjected to light absorption performance test, and the test results are shown in Figure 3 .

[0058] As can be seen from the test results, the construction of the CuS nanosheet hollow shell material significantly enhances the multiple reflection and scattering performance of the hollow absorption body, realizes the synergy of multiple light absorption mechanisms, and effectively solves the problem of single absorption mechanism and insufficient absorption performance regulation ability of the solid structure.

Claims

1. A method for preparing a cross-band light absorption hollow shell material based on nanosheet copper sulfide, characterized in that, The method comprises the following steps: SS1. To the aqueous solution containing Cu 2+ ions, a strong base solution and a reducing agent solution are added, and after reaction, Cu2O template material is obtained by separation, cleaning, and vacuum drying. SS2. The Cu2O template material obtained in step SS1 is uniformly dispersed in water, and a sulfur source is added thereto under the protection of an inert atmosphere. After reaction, Cu2O / CuO / Cu is obtained by separation and washing x S core-shell material; The sulfur source is selected from one or more than two mixtures of sodium sulfide solution, thiourea solution, ammonium sulfide solution, thioacetamide solution or sodium thiosulfate solution; The molar ratio of the sulfur source to the Cu2O substance is 1:1-1:2; SS3. The Cu2O / CuO / Cu obtained in step SS2 is dispersed into water and an ammonia solution is added, and after reaction, CuO / Cu with Cu2O hollowed out is separated x S core-shell material is dispersed into water, and an ammonia solution is added, and after reaction, CuO / Cu with Cu2O hollowed out is separated x S core-shell material SS4. The CuO / Cu obtained in step SS3 was dispersed in deionized water, concentrated hydrochloric acid was added, and the mixture was dispersed in the hydrochloric acid solution. The mixture was centrifuged, washed, and vacuum dried to obtain Cu x S core-shell material was dispersed in deionized water, concentrated hydrochloric acid was added, and the mixture was dispersed in the hydrochloric acid solution. The mixture was centrifuged, washed, and vacuum dried to obtain Cu x S empty-shell material.

2. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, The strong alkali solution is sodium hydroxide or potassium hydroxide; the alkali in the strong alkali solution and the Cu 2+ The molar ratio of the Cu 2+ The molar ratio of the Cu 2+ The molar ratio of the Cu 3. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, In the step SS1, the Cu-containing 2+ The aqueous solution of ions has a concentration of 0.1-1 mol / L and contains Cu 2+ The aqueous solution of ions is selected from an aqueous solution of CuSO4 or an aqueous solution of CuCl2.

4. The method for preparing a cross-band optical absorption hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, The reaction temperature in the step SS1 is 25-70℃, and the reaction time is 3-60 mins.

5. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, In the step SS2, the reaction time is 1-24h, and the reaction temperature is 0-30℃.

6. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, In the step SS3, Cu2O / CuO / Cu x The concentration of the S core-shell material in the solution is 0.05-0.5 mol / L; the concentration of the ammonia water after the ammonia water is added is 20-200 g / L; the reaction temperature is 0-30 ℃, and the reaction time is 0.5-12 h.

7. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, In the step SS4, the concentration of the hydrochloric acid is 300-450g / L, the reaction temperature is 0-30℃, and the reaction time is 10-60s.

8. The method for preparing a trans-band optically absorbing hollow material based on a nano-thin layer of copper sulfide according to claim 1, characterized in that, The washing solvent used in the centrifugal washing in the steps SS1, SS2, SS3 and SS4 is selected from one or more than two of anhydrous ethanol and deionized water.

9. A cross-band light absorption hollow shell material based on nanometer thin-layer copper sulfide prepared by the preparation method in any one of claims 1-8.

10. Application of the cross-band light absorption hollow shell material based on nanometer thin-layer copper sulfide in claim 9 in laser protection and electromagnetic wave shielding and absorption.

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