WO2023015709A1 - 一种碳基无金属官能量子点及其制备和应用 - Google Patents

一种碳基无金属官能量子点及其制备和应用 Download PDF

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WO2023015709A1
WO2023015709A1 PCT/CN2021/122957 CN2021122957W WO2023015709A1 WO 2023015709 A1 WO2023015709 A1 WO 2023015709A1 CN 2021122957 W CN2021122957 W CN 2021122957W WO 2023015709 A1 WO2023015709 A1 WO 2023015709A1
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carbon
based metal
free functional
functional quantum
quantum dots
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贺提为
王肖
康振辉
陈少昂
唐康健
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Suzhou University
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

Definitions

  • the invention relates to a catalyst, in particular to a carbon-based metal-free functional quantum dot and its preparation and application.
  • Carbon quantum dots are zero-dimensional carbon-based nanomaterials. Due to their unique physicochemical properties, carbon quantum dots are considered to be a promising metal-free functional material for biological, catalytic, and optoelectronic devices.
  • CN112742366A reported carbon quantum dots doped with metal ions and its preparation method and catalytic oxidation method of cycloalkane.
  • the metal-doped carbon-based material has excellent catalytic performance for catalytic oxidation of cycloalkane.
  • a series of environmental problems such as environmental pollution, cost increase, and complex synthesis methods will inevitably occur when metal doping is involved. Therefore, a non-metal-doped carbon-based nanomaterial is urgently needed to solve this problem.
  • the present invention aims to solve the above problems, and provides a carbon-based metal-free functional quantum dot and its preparation and application.
  • the novel carbon-based metal-free functional quantum dot is used as a catalyst for preparing highly selective target products from alkanes such as cyclohexane, reducing
  • the whole catalytic process has low cost, high conversion rate selectivity, no harmful substances to human body, and no environmental pollutants.
  • the preparation method of the carbon-based metal-free functional quantum dots comprises the following steps,
  • step S1 of the present invention by preparing powdered graphite, the ultraviolet light can be fully absorbed in the later stage, and the specific surface area of the graphite can be increased as much as possible to maximize the reaction.
  • step S2 the sample placed under the irradiation of the ultraviolet irradiation device is oxidized by short-wavelength ultraviolet light, and the first 15 minutes is mainly used to clean the organic matter on the surface of the powdered graphite to modify its surface and make it hydrophilic or lipophilic
  • ultraviolet radiation is mainly used for cutting and oxidizing graphite powder to form 2-5nm carbon-based metal-free functional quantum dot particles and surface oxidation to produce oxidized functional groups such as hydroxycarboxycarbonyl and the like.
  • the carbon-based metal-free functional quantum dots are completely generated by grinding and irradiating for many times.
  • the powdered graphite is obtained by grinding graphite rods, wherein physical grinding can be used for grinding.
  • the time for the first irradiation is 1-24h, preferably 12-20h; the time for each subsequent irradiation is reduced by 0.1-6h.
  • the standing time is 0.4-0.6h. Stand still in a fume hood so that the ozone generated by the irradiation cannot remain in the carbon-based metal-free functional quantum dot sample.
  • step S3 is 2-5 times.
  • the second aspect of the present invention provides the carbon-based metal-free functional quantum dots prepared by the above preparation method.
  • the carbon-based metal-free functional quantum dots only contain two elements, C and O, and do not contain any metal elements and other heteroatoms.
  • the third aspect of the present invention provides the application of the above-mentioned carbon-based metal-free functional quantum dots as catalysts in the preparation of oxidation products from C4-C10 alkanes.
  • C4-C10 alkanes include C4-C10 alkanes and C4-C10 naphthenes.
  • SS1 dissolving the carbon-based metal-free functional quantum dots in a solvent to obtain a carbon-based metal-free functional quantum dot dispersion
  • the above application includes the following steps:
  • SS2 Reacting cyclohexane, oxygen-containing gas and the carbon-based metal-free functional quantum dot dispersion liquid at 100-160° C. to prepare adipic acid.
  • the internal pressure of the reaction system of C4-C10 alkanes, oxygen-containing gas and carbon-based metal-free functional quantum dot dispersion liquid is 1-5 MPa.
  • the solvent is one or more of methanol, ethanol, propanol, butanol, acetone and butanone.
  • step SS1 the mass volume ratio of the carbon-based metal-free functional quantum dots to the solvent is 1 g/L.
  • step SS2 the volume ratio of the C4-C10 alkane to the carbon-based metal-free functional quantum dot dispersion is 1:2-5.
  • the oxygen content in the oxygen-containing gas is 0.1%-100%, preferably air (21% oxygen content).
  • the reaction time is 10-60min.
  • step SS2 after the reaction is completed, the oxidation product is obtained through recrystallization.
  • a carbon-based metal-free functional quantum dot is prepared, which has very ideal catalytic oxidation characteristics of hydrocarbons, and can be used as a catalyst for efficient oxidation of hydrocarbons.
  • the catalytic oxidation process of the material does not require other auxiliary strong acids, high-valent oxides, etc. as oxidants, and there is no equipment corrosion in the process, and no toxic and harmful gas emissions such as NOx, SOx; no metal function, less by-products; both greatly reduce production costs, It also effectively avoids the environmental pollution problems in the material production process and the catalytic process; and greatly improves the selectivity of the target product and avoids the generation of low-value by-products.
  • Figure 1 is a transmission electron microscope image of KW-1, and the inset is the corresponding high-resolution transmission electron microscope image.
  • Figure 2 is a full spectrum diagram of the X-ray photoelectron spectrum of KW-1.
  • the graphite rod is made into black powder (fine and uniform powder particles) by physical grinding and other methods and placed in a transparent quartz cuvette, so that the surface area of the stone grinding rod powder is as large as possible and the thickness is as thin as possible;
  • KW-1 only contains two non-metallic elements, carbon and oxygen, which is an innovative discovery compared to other catalysts that produce high conversion and high selectivity. And from Figure 2, it can be found that the oxygen content is 45.8%, and the oxygen content is extremely high, showing extraordinary non-toxicity and environmental harmlessness.
  • Example 1 On the basis of Example 1, the carbon-based metal-free functional quantum dots obtained in Example 1 were replaced with carbon quantum dots (prepared by electrochemical corrosion method), and the selectivity of adipic acid was 16.8% through liquid chromatography analysis, cyclohexane The conversion per pass was 0.96%.
  • Example 2 On the basis of Example 2, the carbon-based metal-free functional quantum dots obtained in Example 1 were replaced with carbon quantum dots (prepared by electrochemical corrosion method), and the selectivity of adipic acid was 12.6% through liquid chromatography analysis, cyclohexane The conversion per pass was 13.6%.
  • Example 3 On the basis of Example 3, the carbon-based metal-free functional quantum dots obtained in Example 1 were replaced with carbon quantum dots (prepared by electrochemical corrosion method), and the selectivity of adipic acid was 14.45% through liquid chromatography analysis, cyclohexane The conversion per pass was 1.25%.
  • Example 4 On the basis of Example 4, the carbon-based metal-free functional quantum dots obtained in Example 1 were replaced with carbon quantum dots (prepared by electrochemical corrosion method), and the selectivity of adipic acid was 13.69% through liquid chromatography analysis, cyclohexane The conversion per pass was 1.34%.
  • Example 5 On the basis of Example 5, the carbon-based metal-free functional quantum dots obtained in Example 1 were replaced with carbon quantum dots (prepared by electrochemical corrosion method), and the selectivity of adipic acid was 17.23% through liquid chromatography analysis, cyclohexane The conversion per pass was 2.96%.

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Abstract

提供了一种催化剂，具体涉及一种碳基无金属官能量子点及其制备和应用，制备方法包括以下步骤：S1：制备粉末状石墨；S2：将粉末状石墨置于UV条件下辐照后静置；S3：将S2所得粉末进行研磨；S4：重复步骤S2-S3多次得到碳基无金属官能量子点。制备的碳基无金属官能量子点具有非常理想的碳氢化合物的催化氧化特性，可作为高效氧化碳氢化合物的催化剂，应用中催化氧化过程不需要其它辅助的强酸、高价氧化物等作为氧化剂，过程无设备腐蚀，且无NOx，SOx等有毒有害气体排放；无金属官能，副产物少；既大大降低了生产成本，又有效地避免材料生产过程及催化过程中的环境污染问题；且极大地提高了目标产物的选择性、避免了低值副产物的产生。

Description

一种碳基无金属官能量子点及其制备和应用 技术领域
本发明涉及一种催化剂，具体涉及一种碳基无金属官能量子点及其制备和应用。
背景技术
碳量子点(CDs)是一种零维的碳基纳米材料。由于具有本身独特的物理化学性质，碳量子点被认为是一种很有前途的生物、催化和光电器件的无金属功能材料。近年来CN112742366A报道碳量子点掺杂金属离子及其制备方法和环烷烃催化氧化方法，该金属掺杂碳基材料对环烷烃的催化氧化具有优异的催化性能。然而涉及到金属掺杂就不可避免的会出现环境污染，成本提高，合成方法复杂等一系列环境问题，因此急需一种非金属掺杂的碳基纳米材料出现来解决这一问题。
发明内容
本发明旨在解决上述问题，提供了一种碳基无金属官能量子点及其制备和应用，采用新型碳基无金属官能量子点作为环己烷等烷烃制备高选择性目标产物的催化剂，降低了成本，同时整个催化过程成本低廉，转化率选择性高，无对人体有害物质产生，无环境污染物产生。
按照本发明的技术方案，所述碳基无金属官能量子点的制备方法，包括以下步骤，
S1：制备粉末状石墨；
S2：将所述粉末状石墨置于UV(紫外光线)条件下辐照后静置；
S3：将S2所得粉末进行充分研磨；
S4：重复步骤S2-S3多次，得到所述碳基无金属官能量子点。
本发明步骤S1中，通过制备粉末状石墨，使得后期可以充分的吸收紫外光， 尽可能的增加石墨的比表面积使其最大化的反应。步骤S2中，置于紫外辐照装置辐射下的样品因为受到短波长紫外光的氧化作用，前15min主要是用于清洗粉末状石墨表面的有机物致其表面改性并使其亲水或者亲油，剩下的时间紫外辐照主要用来切割以及氧化石墨粉末作用，使其形成2-5nm碳基无金属官能量子点颗粒以及表面氧化产生氧化官能团羟基羧基羰基等。多次研磨辐照，完全生成碳基无金属官能量子点。
进一步的，所述步骤S1中，粉末状石墨由石墨棒经研磨制得，其中，研磨可以采用物理研磨。
进一步的，第一次辐照的时间为1-24h，优选为12-20h；后续每次辐照的时间减少0.1-6h。
进一步的，所述步骤S2中，静置的时间为0.4-0.6h。静置在通风橱中进行，使辐照产生的臭氧不能残留于碳基无金属官能量子点样品中。
进一步的，步骤S3中的多次为2-5次。
本发明的第二方面提供了上述制备方法制得的碳基无金属官能量子点，所述碳基无金属官能量子点只含有C、O两种元素，不含任何金属元素及其他杂原子。
本发明的第三方面提供了上述碳基无金属官能量子点作为催化剂在C4-C10烷烃制备氧化产物中的应用。
其中，C4-C10烷烃包括C4-C10链烷烃和C4-C10环烷烃。
进一步的，所述的应用包括以下步骤：
SS1：将所述碳基无金属官能量子点溶于溶剂中，得到碳基无金属官能量子点分散液；
SS2：将C4-C10烷烃、含氧气体和所述碳基无金属官能量子点分散液在100-160℃的条件下反应，制得氧化产物。
具体的，以环己烷氧化制己二酸为例，上述应用包括以下步骤：
SS1：将所述碳基无金属官能量子点溶于溶剂中，得到碳基无金属官能量子 点分散液；
SS2：将环己烷、含氧气体和所述碳基无金属官能量子点分散液在100-160℃的条件下反应，制得己二酸。
进一步的，所述步骤SS2中，C4-C10烷烃、含氧气体和碳基无金属官能量子点分散液的反应体系的内压为1-5MPa。
进一步的，溶剂为甲醇、乙醇、丙醇、丁醇、丙酮和丁酮中的一种或多种。
进一步的，步骤SS1中，碳基无金属官能量子点与溶剂的质量体积比为1g/L。
进一步的，步骤SS2中，C4-C10烷烃和碳基无金属官能量子点分散液的体积比为1：2-5。
进一步的，含氧气体中的含氧量为0.1％-100％，优选空气(含氧量21％)。
进一步的，所述步骤SS2中，反应的时间为10-60min。
进一步的，所述步骤SS2中，反应结束后，经重结晶得到氧化产物。
本发明的技术方案相比现有技术具有以下优点：制备了一种碳基无金属官能量子点，具有非常理想的碳氢化合物的催化氧化特性，可作为高效氧化碳氢化合物的催化剂，应用该材料的催化氧化过程不需要其它辅助的强酸、高价氧化物等作为氧化剂，过程无设备腐蚀，且无NOx，SOx等有毒有害气体排放；无金属官能，副产物少；既大大降低了生产成本，又有效地避免材料生产过程及催化过程中的环境污染问题；且极大地提高了目标产物的选择性、避免了低值副产物的产生。
附图说明
图1为KW-1的透射电子显微镜图片，插图是对应的高分辨率透射电子显微镜图片。
图2为KW-1的X射线光电子能谱的全谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
制备例1 碳基无金属官能量子点的制备
将石墨棒通过物理研磨等方法制成黑色粉末(粉末颗粒精细均匀)置于透明石英比色皿中，使石磨棒粉末表面积尽可能大，厚度尽量薄；
石英比色皿敞口放置于UV表面辐射装置(BZZ250G-T)中，功率100％，辐照3个小时，静置1个小时；
取出比色皿，将固体粉末置于玛瑙研钵中精细研磨(使粉末颜色均匀颗粒精细)；
重复上述步骤三次，每次辐照时间减少0.5个小时，第四次辐照之后研磨出褐色粉末，得到碳基无金属官能量子点，命名为KW-1。
如图1所示：根据KW-1的透射电子显微镜图可以发现KW-1尺寸分布均匀，粒径分布大概在3-8nm左右，高分辨率透射电子显微镜镜显示其晶格间距为0.21nm，符合碳基纳米材料的(100)晶面。
如图2所示：可以看出KW-1中只含有碳和氧两种非金属元素，这相对于其它产生高转化率以及高选择性的催化剂来说是革新性的发现。并且从图2中可以发现其氧含量为45.8％，氧含量占比极高，展示出非凡的无毒性，以及环境无害性。
实施例1
称取5g实施例1所得碳基无金属官能量子点分散于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(空气)和环己烷，在150℃、体系内压为3MPa的条件下反应15min，得到粗品己二酸，经三次重结晶得到高品质己二酸。经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经液相色谱分析己二酸选择性为97.6％，环己烷单程转化率为40.37％。
实施例2
称取5g实施例1所得碳基无金属官能量子点分散于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(由10％ 氧气和90％氮气组成)和环己烷，在130℃、体系内压为1MPa的条件下反应15min，得到粗品己二酸，经三次重结晶得到高品质己二酸。经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经液相色谱分析己二酸选择性为79.75％，环己烷单程转化率为79.75％。
实施例3
称取5g实施例1所得碳基无金属官能量子点分散于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(空气)和环己烷，在100℃、体系内压为3MPa的条件下反应15min，得到粗品己二酸，经三次重结晶得到高品质己二酸。经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经液相色谱分析己二酸选择性为90.32％，环己烷单程转化率为8.66％。
实施例4
称取5g实施例1所得碳基无金属官能量子点分散于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(空气)和环己烷，在150℃、体系内压为3MPa的条件下反应60min，得到粗品己二酸，经三次重结晶得到高品质己二酸。经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经液相色谱分析己二酸选择性为90.19％，环己烷单程转化率为91.20％。
实施例5
称取5g实施例1所得碳基无金属官能量子点分散于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(纯氧)和环己烷，在150℃、体系内压为5MPa的条件下反应15min，得到粗品己二酸，经三次重结晶得到高品质己二酸。经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经液相色谱分析己二酸选择性为94.70％，环己烷单程转化率为89.37％。
实施例6
称取10g实施例1所得碳基无金属官能量子点于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(纯氧)和正己烷，在140℃、体系内压为1.5MPa的条件下反应30min，反应得到液体经减压蒸馏、干燥、精馏得到无色液体产品2,5-己二酮的到粗产品己二酮，经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经色谱分析2,5-己二酮纯度为96.2％，正己烷单程转化率为37.2％。
实施例7
称取10g实施例1所得碳基无金属官能量子点于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(纯氧)和正己烷，在140℃、体系内压为1.5MPa的条件下反应45min，反应得到液体经减压蒸馏、干燥、精馏得到无色液体产品2,5-己二酮的到粗产品己二酮，经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经色谱分析2,5-己二酮纯度为94.9％，正己烷单程转化率为25.6％。
实施例8
称取10g实施例1所得碳基无金属官能量子点于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(纯氧)和金刚烷，在140℃、体系内压为1.5MPa的条件下反应20min，所得液体经结晶、过滤、干燥、重结晶得到白色结晶性固体1-金刚烷醇，经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经色谱分析1-金刚烷醇纯度为98.4％，金刚烷单程转化率为62.5％。
实施例9
称取10g实施例1所得碳基无金属官能量子点于5L丙酮中，得到碳基无金属官能量子点分散液；将碳基无金属官能量子点分散液、含氧气体(纯氧)和金刚烷，在150℃、体系内压为1.5MPa的条件下反应20min，所得液体经结晶、过滤、干燥、重结晶得到白色结晶性固体1-金刚烷醇，经气相色谱检测尾气中不含有N XO气体产生，无环境污染。经色谱分析1-金刚烷醇纯度为98.9％，金 刚烷单程转化率为30.6％。
对比例1
在实施例1的基础上，将实施例1所得碳基无金属官能量子点替换为碳量子点(电化学腐蚀法制备)，经液相色谱分析己二酸选择性为16.8％，环己烷单程转化率为0.96％。
对比例2
在实施例2的基础上，将实施例1所得碳基无金属官能量子点替换为碳量子点(电化学腐蚀法制备)，经液相色谱分析己二酸选择性为12.6％，环己烷单程转化率为13.6％。
对比例3
在实施例3的基础上，将实施例1所得碳基无金属官能量子点替换为碳量子点(电化学腐蚀法制备)，经液相色谱分析己二酸选择性为14.45％，环己烷单程转化率为1.25％。
对比例4
在实施例4的基础上，将实施例1所得碳基无金属官能量子点替换为碳量子点(电化学腐蚀法制备)，经液相色谱分析己二酸选择性为13.69％，环己烷单程转化率为1.34％。
对比例5
在实施例5的基础上，将实施例1所得碳基无金属官能量子点替换为碳量子点(电化学腐蚀法制备)，经液相色谱分析己二酸选择性为17.23％，环己烷单程转化率为2.96％。
对比实施例1-5和对比例1-5中己二酸选择性和环己烷单程转化率，可知相比于电化学腐蚀法制备的碳量子点，本发明制得的碳基无金属官能量子点能够显著的提高了环己烷的转化率和己二酸的选择性。同时，目前还没有非金属催化剂可以产生如此高的环己烷转化率以及极高的己二酸选择性。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限 定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种碳基无金属官能量子点的制备方法，其特征在于，包括以下步骤，
    S1：制备粉末状石墨；
    S2：将所述粉末状石墨置于UV条件下辐照后静置；
    S3：将S2所得粉末进行研磨；
    S4：重复步骤S2-S3多次，得到所述碳基无金属官能量子点。
  2. 如权利要求1所述的碳基无金属官能量子点的制备方法，其特征在于，所述步骤S1中，粉末状石墨由石墨棒经研磨制得。
  3. 如权利要求1所述的碳基无金属官能量子点的制备方法，其特征在于，第一次辐照的时间为1-24h，后续每次辐照的时间减少0.1-6h。
  4. 如权利要求1所述的碳基无金属官能量子点的制备方法，其特征在于，所述步骤S2中，静置的时间为0.4-0.6h。
  5. 如权利要求1-4中任一项所述的制备方法制得的碳基无金属官能量子点。
  6. 如权利要求5所述的碳基无金属官能量子点作为催化剂在C4-C10环烷烃制备氧化产物中的应用。
  7. 如权利要求6所述的应用，其特征在于，包括以下步骤：
    SS1：将所述碳基无金属官能量子点溶于溶剂中，得到碳基无金属官能量子点分散液；
    SS2：将C4-C10烷烃、含氧气体和所述碳基无金属官能量子点分散液在100-160℃的条件下反应，制得氧化产物。
  8. 如权利要求7所述的应用，其特征在于，所述步骤SS2中，C4-C10烷烃、含氧气体和碳基无金属官能量子点分散液的反应体系的内压为1-5MPa。
  9. 如权利要求7或8所述的应用，其特征在于，所述步骤SS2中，反应的时间为10-60min。
  10. 如权利要求7所述的应用，其特征在于，所述步骤SS2中，反应结束 后，经重结晶得到氧化产物。
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