WO2022016785A1 - 掺杂的MXene量子点的制备方法以及光学薄膜和QLED - Google Patents

掺杂的MXene量子点的制备方法以及光学薄膜和QLED Download PDF

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WO2022016785A1
WO2022016785A1 PCT/CN2020/136136 CN2020136136W WO2022016785A1 WO 2022016785 A1 WO2022016785 A1 WO 2022016785A1 CN 2020136136 W CN2020136136 W CN 2020136136W WO 2022016785 A1 WO2022016785 A1 WO 2022016785A1
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mxene
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叶炜浩
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  • the present disclosure relates to the technical field of quantum dot material preparation, and in particular, to a preparation method of doped MXene quantum dots, optical films and QLEDs.
  • MXenes Because of their unique structural, electronic and chemical properties, MXenes have potential applications in many fields, including as energy storage materials, sensors, and catalysts, and quantum dots derived from 2D inorganic MXenes have begun to received considerable attention.
  • the preparation methods of MXene quantum dots mainly include chemical solution growth method, epitaxial growth method and electric field confinement method.
  • the inventors found that in addition to their respective disadvantages such as low conductivity, high cost and low yield, the above preparation methods also have a common disadvantage, that is, the MXene quantum The emission wavelengths of the dots are not controllable.
  • MXene quantum dot solution Disperse MXene in a mixed solution of concentrated nitric acid and concentrated sulfuric acid to obtain an MXene quantum dot solution
  • a sulfur source and/or a nitrogen source is added to the MXene quantum dot solution for reaction to prepare doped MXene quantum dots.
  • an optical film comprising a hydrophilic polymer and doped MXene quantum dots dispersed in the hydrophilic polymer, the doped MXene quantum dots being prepared by the method described above be made of.
  • a QLED comprising a light-emitting layer, wherein the light-emitting layer is made of the optical film as described above.
  • a preparation method capable of obtaining doped MXene quantum dots emitting light of different wavelengths.
  • FIG. 1 is a schematic flowchart of a method for preparing doped MXene quantum dots according to an embodiment of the present disclosure.
  • the preparation method of the doped MXene quantum dots according to the present disclosure includes the following steps:
  • step S100 the present disclosure does not limit the preparation method of MXene.
  • MXenes prepared by any preparation method such as chemical liquid phase etching can be provided.
  • step S100 may include the following steps:
  • the MXene powder in an inactive atmosphere such as nitrogen or an inert gas, the MXene powder is heated to 1000-1400° C. for calcination, and the powder is obtained by grinding after calcination;
  • MXene may be selected from one of Ti 2 C, Ti 3 C 2 , (Ti 0.5 , Nb 0.5 ) 2 C, (V 0.5 , Cr 0.5 ) 3 C 2 , Nb 2 C, Ti 3 CN and Ta 4 C 3 or more.
  • concentrated nitric acid refers to a nitric acid solution with a mass content of HNO 3 of 68% or more
  • concentrated sulfuric acid refers to a sulfuric acid solution with a mass content of H 2 SO 4 of 70% or more.
  • a mixed solution of concentrated nitric acid and concentrated sulfuric acid is used to disperse the MXene.
  • the inventors found that when etching is performed using, for example, an HF solution in step S100, there may be cases where the powder is not completely broken.
  • the inventors also unexpectedly found that the above mixed solution can oxidize the parts that are not completely disconnected, so that the powder is basically completely disconnected to form quantum dot particles.
  • the etching of the mixed solution is relatively mild compared to the strong etching of, for example, an HF solution, and it is easy to obtain quantum dot particles of a predetermined size.
  • the volume of concentrated nitric acid is less than the volume of concentrated sulfuric acid in the mixed solution, and in some embodiments, the concentrated nitric acid is The volume ratio of concentrated nitric acid and concentrated sulfuric acid is 1:(2-5), which makes strong oxidizing property more appropriate. In some embodiments, the volume ratio of concentrated nitric acid and concentrated sulfuric acid is 1:3, which is the most suitable for strong oxidizing property.
  • the inventors also unexpectedly found that the preparation of functionalized MXene by chemical liquid phase etching method is different from the existing chemical liquid etching method, which is affected by the concentration of the chemical etchant and the reaction time (for example, if the reaction time is too short or the etchant If the corrosiveness is too weak, MXene may not be prepared, and if the etchant is too corrosive, the MAX phase may be completely dissolved), and only two-dimensional systems with functional groups such as F, OH, etc. on the surface can be obtained.
  • the MXene is dispersed by using a mixed solution of concentrated nitric acid and concentrated sulfuric acid (for example, when MXene is prepared by chemical liquid etching method, after etching with HF solution, using the above The mixed solution is dispersed, which can prevent MXene from being corroded and dissolved by the HF solution), and the obtained MXene quantum dots are purer.
  • the obtained MXene QDs with 0D system have better dispersibility in aqueous and non-aqueous media, which is more favorable for functionalization or doping.
  • the ratio of MXene to the mixed solution is (1-5) g: 10 mL, such as 1 g: 10 mL, 2 g: 10 mL, 3 g: 10 mL, 5 g: 10 mL, and the like.
  • the strong oxidizing property of the mixed solution can be fully exerted, and MXene can be dispersed into quantum dot particles in a predetermined size. If the ratio is less than 1g:10mL, it may lead to excessive etching, so that the structure of MXene itself is destroyed, and quantum dots cannot be formed. If the ratio is greater than 5g:10mL, it may lead to insufficient etching, so that MXene is still in the bulk phase material, and no quantum dots are formed.
  • step S200 after dispersing the MXene in the mixed solution of concentrated nitric acid and concentrated sulfuric acid, the method further includes: heating, cooling to room temperature, and adjusting the pH value to neutrality to obtain an MXene quantum dot solution.
  • the heating temperature is 90 to 110°C, for example, 90°C, 100°C, 105°C, 110°C, and the like. Heating at this temperature can promote the etching of MXene by the mixed solution.
  • the heating time is 10-15h, such as 10h, 12h, 14h and 15h. Adjusting the pH to neutrality can make the resulting MXene quantum dots purer and more favorable for functionalization or doping.
  • the reaction temperature is 150-170°C, such as 150°C, 160°C, 165°C, and 170°C, etc.
  • the reaction time is 12-15h, such as 12h, 13h, 14h, and 15h. etc. for a more complete response.
  • the reaction is a hydrothermal reaction.
  • step S300 after the reaction is performed, purification treatment may also be performed.
  • the purification treatment can be performed by washing the obtained product with a dialysis membrane.
  • the molecular weight cut-off of the dialysis membrane may be 1000-2000 Da, such as 1000 Da, 1200 Da, 1500 Da and 2000 Da, etc., and the number of cleanings may be 2 to 4 times, such as 2 times, 3 times and 4 times.
  • both the sulfur source and the nitrogen source are inorganic substances.
  • the inorganic matter can make the doping more sufficient, that is, the sulfur source and the nitrogen source as the inorganic matter can enter the MXene more easily, especially when the reaction is a hydrothermal reaction.
  • the sulfur source may be selected from sodium thiosulfate (Na 2 S 2 O 3) , sulfur powder, sodium sulfide (Na 2 S), sodium sulfite (Na 2 SO 3) and sodium dithionite (Na 2 One or more of S 2 O 6 ), in some embodiments, the nitrogen source may be selected from ammonia (NH 3 ⁇ H 2 O), ammonium chloride (NH 4 Cl), and ammonium bicarbonate (NH 4 HCO) 3 ) one or more of.
  • the ratio of the MXene quantum dot solution to the sulfur source is 1mL:(0.05-0.1)g, such as 1mL:0.05g, 1mL:0.06g, 1mL:0.08g and 1mL:0.1 g, etc.
  • the ratio of MXene quantum dot solution to nitrogen source is 1 mL: (0.7-1.4) mmol, such as 1: 0.7 mmol, 1: 1.05 mmol, 1: 1.26 mmol and 1: 1.4 mmol, etc. It should be understood that the same is true for the ratio when both a sulfur source and a nitrogen source are used.
  • the effective doping of MXene quantum dots with a sulfur source and/or a nitrogen source can be achieved , which in turn changes the surface electron distribution of MXene quantum dots, produces different defects, forms hydrogen bonds with bound water, and forms a strong and ordered hydrogen bond network through COC bonds.
  • the generated hydrogen bond network changes the size of the quantum dots, thereby The obtained doped quantum dots are made to emit light of different wavelengths.
  • the doped MXene quantum dots prepared according to the embodiments of the present disclosure can emit light of different wavelengths, and can be applied to the fields of full-color quantum dot illumination and display.
  • the present disclosure also provides an optical film comprising a hydrophilic polymer and doped MXene quantum dots dispersed in the hydrophilic polymer, the doped MXene quantum dots being prepared by any of the above embodiments,
  • the mass ratio of the two can be 1:8, such as 4:7, 1:2, 1:4 and 1:5, etc.
  • the inventors found that the use of the hydrophilic polymer can achieve the effect of more uniform mixing with the doped MXene quantum dots without the need to modify the surface of the MXene quantum dots.
  • the hydrophilic polymer may be selected from one or more of polyvinylpyrrolidone, polyacrylic acid, polyvinyl alcohol, and polyethylene oxide.
  • the present disclosure also provides a QLED, including a light-emitting layer, and the light-emitting layer is made of any of the above optical films.
  • the types and fabrication methods of QLEDs are not limited, and known QLED types and fabrication methods may be employed, such as those described in CN106252522A, the entire contents of which are incorporated herein by reference.
  • the QLED may also include, but is not limited to, a cathode, an anode, and optional functional layers, such as a hole injection layer and/or a hole transport layer, an electron injection layer and/or an electron transport layer, and the like.
  • the hole injection layer and/or the hole transport layer may be provided between the anode and the light emitting layer, and the electron injection layer and/or the electron transport layer may be provided between the cathode and the light emitting layer.
  • the materials and parameters such as thicknesses of the cathode, anode, and functional layers are not limited, as long as the present disclosure can be realized, and details are not repeated here.
  • Ti 3 C 2 1 g was added to 10 mL of a mixed solution of concentrated nitric acid and concentrated sulfuric acid (volume ratio of 1:2), and heated under reflux at 100° C. for 12 h to disperse Ti 3 C 2 . Then, it was diluted with 100 mL of deionized water and cooled to 25°C in an ice bath. Next, the obtained product was added to NaOH until the pH value reached 7 to obtain a Ti 3 C 2 quantum dot solution.
  • N-doped Ti 3 C 2 quantum dots Add 0.1 g of N-doped Ti 3 C 2 quantum dots to 1 mL of water to obtain N-doped Ti 3 C 2 quantum dots solution, and then uniformly mix 1 mL of quantum dot solution and 0.5 g of polyvinylpyrrolidone (PVP), N-doped Ti 3 C 2 quantum dots/PVP composites were obtained. Next, the N-doped Ti 3 C 2 quantum dot/PVP composite material was poured into a petri dish, and cured and aged at room temperature for 3 days to obtain an N-doped Ti 3 C 2 quantum dot/PVP thin film.
  • PVP polyvinylpyrrolidone
  • (Ti 0.5 , Nb 0.5 ) 2 AlC was ball-milled into powder by ball milling, and the milling time was 15h. Then, the temperature was raised to 1300°C at 5°C/min, calcined at 1300°C for 2.5 h under argon protection, and then crushed with a mortar and pestle to obtain MXene powder. Next, 6 g of MXene powder was added to 5 mL of HF solution (50 mol%), stirred at 25° C. for 4 h, the suspension was obtained, washed twice with deionized water, and centrifuged to obtain (Ti 0.5 , Nb 0.5 ) 2 C Wet deposits. Finally, the (Ti 0.5 , Nb 0.5 ) 2 C wet deposit was dried in a vacuum oven at 70° C. for 14 h to obtain MXene: (Ti 0.5 , Nb 0.5 ) 2 C.
  • the S-doped (Ti 0.5 , Nb 0.5 ) 2 C quantum dot/PAA composite material was poured into a petri dish, and cured and aged at room temperature for 3 days to obtain S-doped (Ti 0.5 , Nb 0.5 ) 2 C Quantum dots/PAA films.
  • the Ta 4 AlC 3 was ball-milled into powder by ball milling, and the milling time was 12h. Then, the temperature was raised to 1100°C at 5°C/min, calcined at 1100°C for 4 h under argon protection, and then crushed with a mortar and pestle to obtain MXene powder. Next, 8 g of MXene powder was added to 5 mL of HF solution (50 mol%), stirred at 25 °C for 3.5 h, the suspension was obtained, washed three times with deionized water, and centrifuged to obtain a Ta 4 C 3 wet deposit . Finally, the Ta 4 C 3 wet deposit was dried in a vacuum oven at 70° C. for 14 h; MXene: Ta 4 C 3 was obtained .
  • Ta 4 C 3 powder 5 g was added to a mixed solution of 10 mL of concentrated nitric acid and concentrated sulfuric acid (volume ratio of 1:5), and heated under reflux at 90° C. for 15 h to disperse the powder. Then, it was diluted with 100 mL of deionized water and cooled to 25°C in an ice bath. Next, the obtained product was added to NaOH until the pH value reached 7 to obtain a Ta 4 C 3 quantum dot solution.
  • N/S doped Ta 4 C 3 quantum dots were added 0.4 g into 1 mL of water to obtain N/S doped Ta 4 C 3 quantum dot solution, and then uniformly mix 1 mL of quantum dot solution and 0.7 g of polyepoxy Ethane (PEO) to obtain N/S doped Ta 4 C 3 quantum dots/PEO composites.
  • PEO polyepoxy Ethane
  • the N/S doped Ta 4 C 3 quantum dots/PEO composite material was poured into a petri dish, and cured and aged at room temperature for 3 days to obtain N/S doped Ta 4 C 3 quantum dots/PEO thin films.

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Abstract

提供一种掺杂的MXene量子点的制备方法以及光学薄膜和QLED。其中，掺杂的MXene量子点的制备方法包括如下步骤：提供MXene；将MXene分散在浓硝酸和浓硫酸的混合溶液中，得到MXene量子点溶液；将硫源和/或氮源加到MXene量子点溶液中进行反应，制得掺杂的MXene量子点。通过采用浓硝酸和浓硫酸的混合溶液对MXene分散处理，得到的MXene量子点更纯净且更有利于掺杂，并且使用无机硫源和/或无机氮源对MXene量子点掺杂，能够改变量子点表面的缺陷，产生氢键以改变量子点的尺寸，从而使量子点发出不同波长的光。

Description

掺杂的MXene量子点的制备方法以及光学薄膜和QLED
优先权
本公开要求于2020年07月24日提交的中国专利申请No.202010725381.5的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及量子点材料制备技术领域，尤其涉及掺杂的MXene量子点的制备方法以及光学薄膜和QLED。
背景技术
MXene是一类外形类似于片片相叠的片状结构的、具有二维层状结构的金属碳化物和金属氮化物材料，是过渡金属碳化物或碳氮化物的二维晶体，化学式为M n+1X n，n＝1、2或3，M为前期过渡金属元素，X为碳或/和氮元素。
因为具有独特的结构性质、电子特性和化学性质，所以MXene在诸多领域具有潜在的应用价值，包括用作储能材料、传感器和催化剂等，并且由二维无机MXene衍生而来的量子点已经开始受到相当大的关注。
发明内容
目前，MXene量子点的制备方法主要包括化学溶液生长法、外延生长法和电场约束法等。
然而，在实际使用过程中，发明人发现，上述制备方法除了具有各自的诸如电导率低、成本高和产率低等的缺点以外，还具有一个共性的缺点，即上述方法制得的MXene量子点的发光波长均不可控。
基于此，根据本公开的第一方面，提供一种掺杂的MXene量子点的制备方法，包括如下步骤：
提供MXene；
将MXene分散在浓硝酸和浓硫酸的混合溶液中，得到MXene量子点溶液；
将硫源和/或氮源加到MXene量子点溶液中进行反应，制得掺杂的MXene量子点。
根据本公开的第二方面，提供一种光学薄膜，包括亲水性聚合物和分散在亲水性聚合物中的掺杂的MXene量子点，掺杂的MXene量子点由如上所述的制备方法制得。
根据本公开的第三方面，提供一种QLED，包括发光层，其中发光层由如上所述的光学薄膜制成。
根据本公开，提供能够获得发出不同波长光的掺杂的MXene量子点的制备方法。
附图说明
图1为本公开实施例提供的一种掺杂的MXene量子点的制备方法的流程示意图。
具体实施方式
应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
如图1所示，根据本公开的掺杂的MXene量子点的制备方法包括如下步骤：
S100、提供MXene；
S200、将MXene分散在浓硝酸和浓硫酸的混合溶液中，得到MXene量子点溶液；
S300、将硫源和/或氮源加到MXene量子点溶液中进行反应，制得掺杂的MXene量子点。
对于步骤S100，本公开不限制MXene的制备方法。例如，可以提供通过诸如化学液相刻蚀法等的任意制备方法制得的MXene。
例如，在一些实施方式中，步骤S100可以包括如下步骤：
S101、用球磨法将MXene单体球磨成MXene粉体；
S102、在诸如氮气或惰性气体等的非活性气氛下，将MXene粉体升温至1000～1400℃进行煅烧，煅烧后经研磨，得到粉末；
S103、将粉末加到HF溶液中，固液分离，对固体部分进行清洗和干燥处理，得到MXene。MXene可以选自Ti 2C、Ti 3C 2、(Ti 0.5,Nb 0.5) 2C、(V 0.5,Cr 0.5) 3C 2、Nb 2C、Ti 3CN和Ta 4C 3中的一种或多种。
除非另有说明，在本公开中，浓硝酸是指HNO 3的质量含量为68％以上的硝酸溶液，浓硫酸是指H 2SO 4的质量含量为70％以上的硫酸溶液。
在一些实施方式中，在步骤S200中，使用浓硝酸和浓硫酸的混合溶液来分散MXene。这是因为，发明人发现，当在步骤S100中使用例如HF溶液进行刻蚀时，可能存在粉末未被完全断开的情况。同时，发明人还意外地发现，上述混合溶液能够氧化未被完全断开的部位，使得粉末基本上完全断开，以形成量子点颗粒。此外，与例如HF溶液的强刻蚀相比，上述混合溶液的刻蚀相对温和，容易得到预定尺寸的量子点颗粒。
为了确保混合溶液具有对于使粉末基本上完全断开而言适当的强氧化性，在一些实施方式中，在混合溶液中，浓硝酸的体积小于浓硫酸的体积，在一些实施方式中，浓硝酸和浓硫酸的体积比为1:(2～5)，使得强氧化性更适当，在一些实施方式中，浓硝酸和浓硫酸的体积比为1：3，适当强氧化性最适当。
此外，发明人还意外地发现，与现有的采用化学液相刻蚀法制备官能团化的MXene因受化学刻蚀剂的浓度和反应时间的影响(例如，如果反应时间太短或刻蚀剂腐蚀性太弱，则可能制备不出MXene，而如果刻蚀剂腐蚀性太强，则可能会把MAX相完全溶解)，只能获得表面带有诸如F、OH等的官能团的具有二维体系的MXene，不能获得纯净的MXene量子点的情况相比，通过采用浓硝酸和浓硫酸的混合溶液来分散MXene(例如，在化学液相刻蚀法制备MXene时，用HF溶液腐蚀后，用上述混合溶液进行分散，能够避免MXene被HF溶液腐蚀溶解)，得到的MXene量子点更纯净。同时，与具有二维体系的MXene相比，得到的具有零维体系的MXene量子点在水和非水介质中的分散性更好，从而更有利于功能化或掺杂。
在另一些实施方式中，在步骤S200中，MXene与混合溶液的比例为(1-5)g:10mL，例如1g:10mL、2g:10mL、3g:10mL和5g:10mL等。以这样的比例，能够充分地发挥出混合溶液的强氧化性，进而能够使MXene以预定尺寸分散成量子点颗粒。如果比例小于1g:10mL，则可能导致刻蚀过度，使得MXene自身的结构被破坏，无法形成量子点。如果比例大于5g:10mL，则可能导致刻蚀不足，使得MXene还处于体相材料，没有形成量子点。
在再一些实施方式中，在步骤S200中，将MXene分散在浓硝酸和浓硫酸的混合溶液中之后，还包括：加热、冷却至室温、将pH值调节至中性，得到MXene量子点溶液。其中，加热的温度为90～110℃，例如90℃、100℃、105℃、110℃等。在该温度下加热，能够促进混合溶液对MXene的刻蚀。加热的时间为10～15h，例如10h、12h、14h和15h等。将pH值调节至中性，能够使得到的MXene量子点更纯净且更有利于功能化或掺杂。
在一些实施方式中，在步骤S300中，反应的温度为150～170℃，例如150℃、160℃、165℃和170℃等，反应的时间为12～15h，例如12h、13h、14h和15h等，以使反应更充分。在另一些实施方式中，反应为水热反应。
在另一些实施方式中，在步骤S300中，进行反应之后，还可以进行纯化处理。其中，纯化处理可以通过用透析膜清洗所得到的产物来进行。进一步地，透析膜的截留分子量可以为1000-2000Da，例如1000Da、1200Da、1500Da和2000Da等，清洗的次数可以为2～4次，例如2次、3次和4次。
在再一些实施方式中，在步骤S300中，硫源和氮源均是无机物。与有机物、特别是氮源为尿素的情况相比，无机物能够使掺杂更充分，即作为无机物的硫源和氮源更容易进入MXene，特别是在反应为水热反应时。在一些实施方式中，硫源可以选自硫代硫酸钠(Na 2S 2O 3)、硫粉、硫化钠(Na 2S)、亚硫酸钠(Na 2SO 3)和连二硫酸钠(Na 2S 2O 6)中的一种或多种，在一些实施方式中，氮源可以选自氨水(NH 3·H 2O)、氯化铵(NH 4Cl)和碳酸氢铵(NH 4HCO 3)中的一种或多种。
在又一些实施方式中，在步骤S300中，MXene量子点溶液与硫源的比例为1mL:(0.05～0.1)g，例如1mL:0.05g、1mL:0.06g、1mL:0.08g和1mL:0.1g等，进一步地，MXene量子点溶液与氮源的比例为1mL:(0.7～1.4)mmol，例如1：0.7mmol、1：1.05mmol、1：1.26mmol和1：1.4mmol等。应当理解，当使用硫源和氮源两者时，比例也是这样。
通过采用上述比例，特别是在采用浓硝酸和浓硫酸的混合溶液对MXene进行分散之后(即步骤S200和步骤S300的组合)，能够实现硫源和/或氮源对MXene量子点的有效掺杂，进而改变了MXene量子点的表面电子分布，产生不同缺陷，与结合水形成氢键，并且通过C-O-C键形成坚固且有序的氢键网络，产生的氢键网络改变了量子点的尺寸，从而使获得的掺杂量子点发出不同波长的光。
当使用本公开的硫源进行掺杂时，会在MXene量子点体系中形成OS、S 2或者C-S-C，使得电子缺陷的形成较少，相应的氢键也少，能够得到较小尺寸的S掺杂的MXene量子点，从而使得S掺杂的MXene量子点的发光波长与蓝光对应。当使用本公开的硫源进行掺杂时，N会在MXene量子点体系中除了形成C-N键外，还会形成类似吡咯(结构为
Figure PCTCN2020136136-appb-000001
)的C＝N键。由于C＝N键的形成，该电子缺陷位点具有较强的负电型，会产生电子收缩缺陷，所以容易与水分子形成更多的氢键(C-N或C＝N键的形成势垒小于 C-S键，所以掺杂N更容易形成氢键)，从而使得N掺杂的MXene量子点的发光波长与绿光对应。当使用本公开的硫源和氮源两者时，N的存在增加了类似吡咯的C-N-C键的形成，除了C＝N键外，C-S-C键也增加了电子缺陷的形成，最终形成更大的氢键网络，由于氢键的形成，颗粒的尺寸会变大，所以相应的离域π电子能级下降，导致波长红移，从而使得S/N掺杂的MXene量子点的发光波长与红光对应。
因此，根据本公开的实施方式制得的掺杂的MXene量子点能够发出不同波长的光，能够适用于全彩色量子点照明和显示领域。
此外，本公开还提供一种光学薄膜，其包括亲水性聚合物和分散在亲水性聚合物中的掺杂的MXene量子点，掺杂的MXene量子点由上述任一实施方式制得，两者的质量比可以为1:8，例如4:7、1:2、1:4和1:5等。
通过与采用疏水性聚合物的情况相比，发明人发现，采用亲水性聚合物能够实现与掺杂的MXene量子点混合更均匀，无需对MXene量子点的表面进行改性的效果。
在一些实施方式中，亲水性聚合物可以选自聚乙烯吡咯烷酮、聚丙烯酸、聚乙烯醇和聚环氧乙烷中的一种或多种。
此外，本公开还提供一种QLED，包括发光层，发光层由上述任一光学薄膜制成。
在本公开中，不限制QLED的类型和制备方法，可以采用已知的QLED类型和制备方法，例如CN106252522A中描述那些，在此通过引用将其全部内容并入本文。进一步地，QLED还可以包括但不限于阴极、阳极以及任选的功能层，例如空穴注入层和/或空穴传输层、电子注入层和/或电子传输层等。空穴注入层和/或空穴传输层可以设置在阳极与发光层之间，电子注入层和/或电子传输层可以设置在阴极与发光层之间。
在本公开中，不限制阴极、阳极和功能层的材料和诸如厚度等的参数，只要能够实现本公开即可，在此不再赘述。
下面通过具体实施例对本公开进行详细说明。
实施例1
(1)MXene：Ti 3C 2的制备
将摩尔比为1:1的Ti 2AlC和TiC用球磨法球磨成混合粉体，球磨时间为10h。然后，以5℃/min升温至1200℃，在氩气保护下1200℃煅烧3h后，用研钵和杵压碎，得到MXene粉末。接着，将5g的MXene粉末加到5mL的HF溶液(50mol％)中，在25℃下搅拌3h，得到悬浮液后用去离子水洗涤2次，离心分离，得到Ti 3C 2湿沉积物。最后， 将Ti 3C 2湿沉积物在70℃的真空烤箱中干燥14h，得到MXene：Ti 3C 2。
(2)Ti 3C 2量子点溶液的制备
将1g的Ti 3C 2加到10mL的浓硝酸和浓硫酸(体积比为1:2)的混合溶液中，在100℃下回流加热12h，使Ti 3C 2分散。然后，用100mL的去离子水稀释，在冰浴中冷却到25℃。接着，将得到的产物加入NaOH，直到pH值达到7，得到Ti 3C 2量子点溶液。
(3)N掺杂的Ti 3C 2量子点的制备
将100μL(0.7mmol)的NH 3·H 2O加到1mL的Ti 3C 2量子点溶液中，然后转移至50mL反应釜，加热至150℃保温15h。接着，在反应后用透析膜(截留分子量为1000Da)清洗产物2次，烘干，最终得到N掺杂的Ti 3C 2量子点。
(4)基于N掺杂的Ti 3C 2量子点的光学薄膜的制备
将0.1g的N掺杂Ti 3C 2量子点加入1mL的水中，得到N掺杂的Ti 3C 2量子点溶液，然后均匀混合1mL的量子点溶液和0.5g的聚乙烯吡咯烷酮(PVP)，得到N掺杂的Ti 3C 2量子点/PVP复合材料。接着，将N掺杂的Ti 3C 2量子点/PVP复合材料倒入培养皿中，在室温下养护老化3天，得到N掺杂的Ti 3C 2量子点/PVP薄膜。
实施例2
(1)MXene：(Ti 0.5,Nb 0.5) 2C的制备
将(Ti 0.5,Nb 0.5) 2AlC用球磨法球磨成粉体，球磨时间为15h。然后，以5℃/min升温至1300℃，在氩气保护下1300℃煅烧2.5h后，用研钵和杵压碎，得到MXene粉末。接着，将6g的MXene粉末加到5mL的HF溶液(50mol％)中，在25℃下搅拌4h，得到悬浮液后用去离子水洗涤2次，离心分离，得到(Ti 0.5,Nb 0.5) 2C湿沉积物。最后，将(Ti 0.5,Nb 0.5) 2C湿沉积物在70℃的真空烤箱中干燥14h，得到MXene：(Ti 0.5,Nb 0.5) 2C。
(2)(Ti 0.5,Nb 0.5) 2C量子点溶液的制备
将3g的(Ti 0.5,Nb 0.5) 2加到10mL的浓硝酸和浓硫酸(体积比为1:3)的混合溶液中，在110℃下回流加热10h使(Ti 0.5,Nb 0.5) 2分散，用100mL的去离子水稀释，在冰浴中冷却到25℃。接着，将得到的产物加入NaOH，直到pH值达到7，得到(Ti 0.5,Nb 0.5) 2C量子点溶液。
(3)S掺杂的(Ti 0.5,Nb 0.5) 2C量子点的制备
将0.05g的Na 2S 2O 3加到1mL的(Ti 0.5,Nb 0.5) 2C量子点溶液中，然后转移至50mL反 应釜，加热至160℃保温14h.接着，在反应后用透析膜(截留分子量为1500Da)清洗产物3次，烘干，最终得到S掺杂的(Ti 0.5,Nb 0.5) 2C量子点。
(4)基于S掺杂的(Ti 0.5,Nb 0.5) 2C量子点的光学薄膜的制备
将0.4g的S掺杂(Ti 0.5,Nb 0.5) 2C量子点加入1mL的水中，得到S掺杂的(Ti 0.5,Nb 0.5) 2C量子点溶液，然后均匀混合1mL的量子点溶液和0.8g的聚丙烯酸(PAA)，得到S掺杂的(Ti 0.5,Nb 0.5) 2C量子点/PAA复合材料。接着，将S掺杂的(Ti 0.5,Nb 0.5) 2C量子点/PAA复合材料倒入培养皿中，在室温下养护老化3天，得到S掺杂的(Ti 0.5,Nb 0.5) 2C量子点/PAA薄膜。
实施例3
(1)MXene：Ta 4C 3的制备
将Ta 4AlC 3用球磨法球磨成粉体，球磨时间为12h。然后，以5℃/min升温至1100℃，在氩气保护下1100℃煅烧4h后，用研钵和杵压碎，得到MXene粉末。接着，将8g的MXene粉末加到5mL的HF溶液(50mol％)中，在25℃下搅拌3.5h，得到悬浮液后用去离子水洗涤3次，离心分离，得到Ta 4C 3湿沉积物。最后，将Ta 4C 3湿沉积物在70℃的真空烤箱中干燥14h；得到MXene：Ta 4C 3。
(2)Ta 4C 3量子点溶液的制备
将5g的Ta 4C 3粉末加到10mL浓硝酸和浓硫酸(体积比为1:5)的混合溶液中，在90℃下回流加热15h，使粉末分散。然后，用100mL去离子水稀释，在冰浴中冷却到25℃。接着，将得到的产物加入NaOH，直到pH值达到7，得到Ta 4C 3量子点溶液。
(3)S/N掺杂的Ta 4C 3量子点的制备
将0.1g的Na 2S 2O 6和1.4mmol的NH 4Cl加到1mL的Ta 4C 3量子点溶液中，然后转移至50mL反应釜，加热至170℃保温13h，在反应后用透析膜(截留分子量为2000Da)清洗产物4次，烘干，最终得到N/S掺杂的Ta 4C 3量子点。
(4)基于S/N掺杂的Ta 4C 3量子点的光学薄膜的制备
将0.4g的S/N掺杂Ta 4C 3量子点加入1mL的水中，得到N/S掺杂的Ta 4C 3量子点溶液，然后均匀混合1mL的量子点溶液和0.7g的聚环氧乙烷(PEO)，得到N/S掺杂的Ta 4C 3量子点/PEO复合材料。接着，将N/S掺杂的Ta 4C 3量子点/PEO复合材料倒入培养皿中，在室温下养护老化3天，得到N/S掺杂的Ta 4C 3量子点/PEO薄膜。
虽然已经参照示例性实施方式描述了本公开，但是应当理解，本公开不限于所公开 的示例性实施方式。权利要求书的范围应当符合最宽泛的解释，以包含所有的这些变型、等同结构和功能。

Claims (17)

  1. 一种掺杂的MXene量子点的制备方法，其中，包括如下步骤：
    提供MXene；
    将MXene分散在浓硝酸和浓硫酸的混合溶液中，得到MXene量子点溶液；
    将硫源和/或氮源加到MXene量子点溶液中进行反应，制得掺杂的MXene量子点。
  2. 根据权利要求1所述的制备方法，其中，MXene与混合溶液的比例为(1～5)g:10mL，
    在混合溶液中，浓硝酸的体积小于浓硫酸的体积。
  3. 根据权利要求2所述的制备方法，其中，浓硝酸和浓硫酸的体积比为1:(2～5)。
  4. 根据权利要求3所述的制备方法，其中，浓硝酸和浓硫酸的体积比为1:3。
  5. 根据权利要求1所述的制备方法，其中，硫源和氮源均是无机物。
  6. 根据权利要求5所述的制备方法，其中，硫源选自硫代硫酸钠、硫粉、硫化钠、亚硫酸钠和连二硫酸钠中的一种或多种，
    氮源选自氨水、氯化铵和碳酸氢铵中的一种或多种。
  7. 根据权利要求1所述的制备方法，其中，MXene量子点溶液与硫源的比例为1mL:(0.05～0.1)g，
    MXene量子点溶液与氮源的比例为1mL:(0.7～1.4)mmol。
  8. 根据权利要求1所述的制备方法，其中，将MXene分散在浓硝酸和浓硫酸的混合溶液中之后，所述制备方法还包括：
    加热、冷却至室温、将pH值调节至中性，得到MXene量子点溶液，
    其中，加热的温度为90～110℃，时间为10～15h。
  9. 根据权利要求1所述的制备方法，其中，进行反应的温度为150～170℃，时间为12～15h。
  10. 根据权利要求1所述的制备方法，其中，MXene选自Ti 2C、Ti 3C 2、(Ti 0.5,Nb 0.5) 2C、(V 0.5,Cr 0.5) 3C 2、Nb 2C、Ti 3CN和Ta 4C 3中的一种或多种。
  11. 根据权利要求1所述的制备方法，其中，进行反应之后，还进行纯化处理， 制得掺杂的MXene量子点，
    纯化处理通过用透析膜清洗所得到的产物来进行。
  12. 根据权利要求11所述的制备方法，其中，透析膜的截留分子量为1000-2000Da。
  13. 一种光学薄膜，其中，包括亲水性聚合物和分散在亲水性聚合物中的掺杂的MXene量子点，
    掺杂的MXene量子点由如权利要求1～12任意一项所述的制备方法制得。
  14. 根据权利要求13所述的光学薄膜，其中，亲水性聚合物选自聚乙烯吡咯烷酮、聚丙烯酸、聚乙烯醇和聚环氧乙烷中的一种或多种。
  15. 根据权利要求13所述的光学薄膜，其中，光学薄膜由亲水性聚合物和分散在亲水性聚合物中的掺杂的MXene量子点组成。
  16. 根据权利要求13所述的光学薄膜，其中，亲水性聚合物与掺杂的MXene量子点的质量比为1：(1-8)。
  17. 一种QLED，包括发光层，其中，发光层由如权利要求8或9所述的光学薄膜制成。
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