WO2017050263A1 - 一种新型纳米碳晶 - Google Patents

一种新型纳米碳晶 Download PDF

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WO2017050263A1
WO2017050263A1 PCT/CN2016/099790 CN2016099790W WO2017050263A1 WO 2017050263 A1 WO2017050263 A1 WO 2017050263A1 CN 2016099790 W CN2016099790 W CN 2016099790W WO 2017050263 A1 WO2017050263 A1 WO 2017050263A1
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carbon
crystal
nanocarbon
atom
mesh
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French (fr)
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郭留希
赵清国
张洪涛
杨晋中
刘永奇
武艳强
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郑州华晶金刚石股份有限公司
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    • 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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention belongs to the technical field of carbon materials, and particularly relates to a novel nano carbon crystal.
  • Carbon is one of the most widely used elements in the world, and carbon is currently the most widely used material in the world.
  • carbon materials such as: fullerenes, carbon nanotubes, graphene, etc., nanocarbon crystals are in the carbon material family.
  • the emergence of new materials means an improvement in the material preparation process.
  • the industrial preparation method of fullerenes is mainly a combustion method, and benzene and toluene are mainly used to obtain C 6 by incomplete combustion under the action of oxygen. With C 7 .
  • the mixture the same amount of toxic gas is discharged to pollute the environment, and subsequent purification by other organic substances is required, and the preparation process is complicated.
  • the industrial preparation method of carbon nanotubes is an arc method.
  • the graphite electrode is placed in a reaction vessel filled with nitrogen or argon gas, and an arc is generated between the two poles. Under this condition, c 6Q , amorphous c, and more are prepared.
  • the carbon nanotubes of the layer can not be purified by C 6Q to obtain high purity carbon nanotubes, and the preparation method has high energy consumption.
  • the preparation method of graphene is mainly a redox method, the graphite is oxidized by an oxidizing agent, the layer spacing of graphite is increased, and then separated by a physical method, and finally the graphene is obtained by chemical reduction, and the graphene yield by the method is obtained. High, but the quality of the product is low.
  • a novel nano carbon crystal having a spherical morphology, and C atoms on the surface of the carbon crystal and C atoms in the inner diamond phase constitute dimerization of C atoms.
  • two carbon atoms in the dimeric structure of the C atom are asymmetrically distributed.
  • the lattice spacing is 0.21 nm.
  • the average particle diameter is R, 0 ⁇ R ⁇ 10 nm.
  • the carbon crystal has a C content of 99 to 100%.
  • the nanocarbon crystal is prepared by the following method, and the steps are:
  • the diamond is sieved out of the mesh of the mechanical pulverizer by 32 mesh or more, and the granules are sieved by the multi-stage vibrating sieve to separate fine materials of 500 mesh or more.
  • the nanocarbon crystal provided by the invention has the following advantages:
  • the C content of the nanocarbon crystal is between 99% and 100%, the purity is high, the particle size range is narrow, 0 ⁇ R ⁇ 10 nm, the product has strong crystallinity, strong surface activity and strong adsorption capacity.
  • the shape is regular and controllable, the loss rate is low, and the loss rate can be controlled within 1%.
  • the nanocarbon crystal can absorb the full spectrum of solar energy and has high surface carbon atom activity. When combined with a catalyst such as Ti0 2 , it can absorb visible light under illumination and emit short-wavelength light of 325-425 nm, thereby exciting TiO.
  • the second catalyst forms an electron-hole pair, and the electron-hole pair is converted into an active group, thereby degrading the organic dye molecule. Since the nano-carbon crystal is on the surface of the catalyst such as TiO 2 , it can function to transfer electrons and promote the charge. The separation, electron transport along the surface of the nanocarbon crystal, can prolong the cavity life of the catalyst such as TiO 2 and improve the catalytic activity.
  • the surface of the nanocarbon crystal has a dimeric structure of asymmetrically distributed C atoms, has high surface activity, is easily functionalized by the surface, and can be used for various cosmetics, and has the same wear resistance. It is also used for various cleaning agents, oil additives, coating additives, etc. to increase wear resistance.
  • the nanocarbon crystal of the invention has no photoluminescence phenomenon, and can be used in the field of stealth aircraft surface coating (requires good optical concealing performance and high temperature and friction resistance), or To make special optical devices, such as optical resonators, limit displays, etc., have unique applications in the field of optics.
  • the nanometer carbon crystal has a small particle size, is easily dispersed in the plating solution, and is also easily adsorbed on the surface of the object to be plated, forming a diamond film on the surface of the plated member, and the film has good thermal conductivity. Abrasion resistant, it can be used for surface treatment of various heat and wear parts.
  • the nanocarbon crystal phase is composed of a diamond phase, and has high hardness, high wear resistance, high thermal conductivity, high stability, oleophilic hydrophobicity, etc., and can be widely used to improve conventional grinding operations and improve Grinding efficiency and reducing costs.
  • FIG. 1 is a block diagram of a process flow of the present invention
  • Example 2 is a TEM analysis diagram of nanocarbon crystals prepared in Example 1;
  • Example 3 is an XRD spectrum of the nanocarbon crystal prepared in Example 1;
  • Example 4 is an EDS spectrum of the nanocarbon crystal prepared in Example 1;
  • Example 5 is a Raman spectrum of nanocarbon crystals prepared in Example 1.
  • Example 6 is a MAS NMR spectrum of the nanocarbon crystal prepared in Example 1.
  • a novel nano-carbon crystal having an average particle diameter of R, 0 ⁇ R ⁇ 10 nm, a C content of 99 to 100 ⁇ 3 ⁇ 4, the carbon crystal is a spheroidal morphology, a C atom on the surface of the carbon crystal and an inner diamond layer
  • the C atom of the phase constitutes a dimer structure of the C atom, and the two carbon atoms in the dimer structure of the C atom are asymmetrically distributed with a lattice spacing of 0.21 nm.
  • the nano carbon crystal is prepared by the following method, and the process flow diagram is as shown in FIG. 1 , and the steps are as follows:
  • Preliminary crushing First, the diamond raw material is sent into the crushing cavity of the mechanical crusher, and is broken by the action of the hammer head inside the crusher, and the crushed material passes through different mesh screens, larger than the sieve.
  • the material of the mesh diameter is left to be re-crushed inside the crusher, and the fine particles filtered by the finest sieve under the crusher are collected through the sieve plate (the mesh number is not less than 32 mesh), and the mesh is filtered by other meshes.
  • the material can be sold as coarse material or used to prepare other granular materials; the particles above 32 mesh are multi-layered by a multi-layer vibrating machine for initial particle size, the vibrating screen is generally controlled at 30 min ⁇ 3 h, and the mesh number is from 40 mesh.
  • the coarse material sorted by the 40 mesh screen is returned to the mechanical crusher for re-crushing (Fig. 1A), and the material collected from the 40 mesh to 500 mesh sieve is used to prepare other granular materials, passing through a 500 mesh sieve.
  • the fine material collected after the net is used to prepare nano carbon crystals. To ensure the accuracy of the sorting granularity, the collected fine materials are repeatedly sieved and selected more than once.
  • step (1) The fine material sieved in step (1) is sent into the crushing chamber of the airflow crusher, and the fine material is crushed by the high-pressure airflow, and the sieve mesh is collected at the receiving port of the airflow crusher. After the separation, the mesh number of the mesh is arranged from 1000 mesh to 10000 mesh from high to low, and the fine powder selected by the 10000 mesh screen is collected for preparing the nano carbon crystal, and the other mesh mesh is used for preparation. The other material is still returned to the airflow crusher for re-crushing, and the coarse material collected by the 1000 mesh screen is automatically returned to the airflow crusher for re-crushing (Fig. 1B).
  • Example 3 The preparation process of Example 3 is different from that of Embodiment 2 in that: the centrifugal chamber is 30 minutes, and the rotation speed is 200.
  • the prepared nanocarbon crystal has a particle size of 6 to 8 nm.
  • Example 4 The preparation process of Example 4 is different from that of Example 2 in that: the centrifugal day is lh, the rotation speed is lOOOOr pm, and the precipitation separation time is 6 days.
  • the prepared nano carbon crystal has a particle size of 5 to 6 nm.
  • Example 5 The preparation process of Example 5 is different from that of Example 2 in that: the centrifugal chamber is 2 h, the rotation speed is 20000 rpm, and the sedimentation time is 7 days.
  • the prepared nano carbon crystal has a particle size of 0 to 5 nm.
  • Example 2 is a TEM analysis diagram of the nanocarbon crystal provided in Example 1, in which: a: nanocarbon crystal; b: explosion method nanodiamond; 1 represents a partial enlarged view, 2 represents a HRTEM image, and 1 is in the upper left
  • a nanocarbon crystal
  • b explosion method nanodiamond
  • 1 represents a partial enlarged view
  • 2 represents a HRTEM image
  • 1 is in the upper left
  • SAED diagram is a SAED diagram.
  • the nanocarbon crystal prepared in the embodiment is approximately spherical, the morphology is relatively regular, the particle size is 2-5 nm, and the explosive nanodiamond is composed of some agglomerated particles. , and the morphology is not regular, the particle size is between 5-10nm.
  • both materials have polycrystalline structure, and the corresponding HRTEM image can measure the crystal of nano-carbon crystal.
  • FIG. 3 is an XRD spectrum of the nanocarbon crystal prepared in Example 1, in which: a: an explosion method nanodiamond; b: a nanocarbon crystal.
  • the peak positions of the two materials are all at about 44°, and compared with the standard PDF card, the diamond-like Miller index corresponds to the (111) crystal plane, which proves again.
  • Both of these materials are composed of diamond phase, but it can be seen that nano-carbon crystals have a large amorphous package between 20° and 40°, and the crystallinity of nano-carbon crystals is better than that of explosive nano-diamonds. Weak, but still have strong crystallinity. According to Xie Le formula
  • the grain size of the nanodiamond synthesized by the explosion method is about 2.4 of the nanometer carbon crystal. Therefore, it can be seen that the nano-carbon crystal grains prepared by the invention are smaller than the nano-diamonds synthesized by the explosion method, and have many grain boundaries. Different degrees of distortion occur inside the small crystal grains, thereby affecting the properties of the material. Therefore, the nano carbon crystal synthesized by the present invention is superior in activity to the nano diamond synthesized by the explosion method.
  • Example 4 is an EDS spectrum of the nanocarbon crystal prepared in Example 1, in which: a: nanocarbon crystal; b: explosive method nanodiamond.
  • the nanocarbon crystals prepared by the present invention are basically composed of C elements, and the purity is high.
  • a an explosion-type nano-diamond
  • b a nano-carbon crystal prepared in Example 1.
  • the two carbon materials obviously have different Raman spectra
  • the nano-diamond synthesized by the explosion method also has the characteristic Raman peak D peak and G peak typical of the C material, and the present invention
  • the synthesized nanocarbon crystals do not have any Raman peak, which indicates that the nanocarbon crystals prepared by the present invention have different carbon atom arrangements from the explosive nanodiamonds.
  • Infrared spectroscopy only has a strong absorption signal for molecules with infrared activity. For pure C element crystals, the structure cannot be detected by infrared spectroscopy.
  • infrared activity refers to a structure in which the dipole change is not zero and the structure is more symmetrical, so the dipole change is smaller, for example.
  • CC, C C, C ⁇ C, 0-0, N ⁇ N, etc.
  • These homonuclear diatomic pairs are infrared inactive, so it is difficult to observe these homonuclear diatomic pairs in the infrared spectrum.
  • Telescopic vibration characteristic peaks if such homonuclear diatomic atoms are to be observed, a relatively weak infrared absorption peak can be detected by attaching an asymmetric group around them).
  • the Raman activity of the homonuclear diatomic pair with weak infrared activity is relatively strong, so it can be concluded that the nanocarbon crystal is different from the C atom arrangement of the explosive nanodiamond.
  • Example 6 is a MAS NMR spectrum of the nanocarbon crystal and the explosive nanodiamond prepared in Example 1, wherein: a: the nanocarbon crystal prepared in Example 2; b: the explosion method nanodiamond.
  • both the carbon nanocrystals and the explosive nanodiamonds have two C peaks, which indicates that there are two different carbon atoms C ⁇ nC 2 in the nanocarbon crystal and the explosive nanodiamond sample.
  • the 0 C of the sp 3 orbital hybrid carbon is usually 0 to 60 ppm
  • the ⁇ c of the sp 2 orbital hybrid carbon is usually 100 to 220 ppm
  • the ⁇ c of the sp orbital hybrid carbon is usually 60 to 90 ppm.
  • the peak positions are 4ppm apart, and the positions are very close, which indicates that the chemical environment of C ⁇ nC 2 is relatively close.
  • the nano-carbon crystals and the explosive nano-diamond samples are composed of C elements, so C, and C 2 has a different structure.
  • Raman spectroscopy results it is known that the nanocarbon crystal synthesized by the invention does not have any Raman spectral peak, and the nanodiamond synthesized by the explosion method has the characteristic Raman peak of the C material. Based on the above analysis, we can infer the nano carbon crystal synthesized by the invention and the explosion method.
  • the surface of the nanodiamond is different in C atom arrangement.
  • the C atom on the surface of the carbon crystal synthesized by the present invention and the C atom of the inner diamond phase constitute a dimer structure of C atoms, and the two carbon atoms are asymmetrically distributed.
  • the C atom of the nanodiamond surface synthesized by the explosion method and the C atom of the diamond phase also constitute a dimer structure of C atoms, and the two C atoms are symmetrically distributed, so that two distinct ones appear.
  • Raman Peak Asymmetric C atom arrangement is more active than symmetrically arranged C atoms, and it is easier to recombine with different groups.
  • the C atom on the surface of the same particle is more active and easy to agglomerate. For diamonds, surface functionalization is easier to perform.
  • the nanocarbon crystal provided by the invention can absorb the full spectrum of solar energy and has high surface carbon atom activity.
  • a catalyst such as Ti0 2 When combined with a catalyst such as Ti0 2 , it can absorb visible light under illumination and emit short-wavelength light of 325-425 nm.
  • the catalyst such as TiO 2 is excited to form an electron-hole pair, and the electron-hole pair is converted into an active group, thereby degrading the organic dye molecule.
  • the nano-carbon crystal is on the surface of the catalyst such as TiO 2 , it can transmit electrons.
  • the action which promotes the separation of charges, and the transport of electrons along the surface of the nanocarbon crystal, can prolong the hole lifetime of the catalyst such as Ti0 2 and improve the catalytic activity.
  • the carbon atom arrangement on the surface of the nanocarbon crystal synthesized in the present application is asymmetric, and the carbon atoms of the surface layer and the carbon atoms of the inner layer constitute an asymmetric dimer structure, which is relative to the explosion method nanodiamond. , more active, more easily surface-functionalized, easier to recombine with other materials in the form of covalent or non-covalent bonds.
  • This carbon crystal can be used in extreme displays due to its special photoluminescence properties.
  • Optical resonators, etc. due to their small particle size and large specific surface area, can be used to prepare various adsorption membranes, such as seawater desalination membrane, brackish water desalination membrane, deionized water to prepare membranes, etc., and also have strong catalytic action. , can be used to prepare non-metal catalyzed Qi 1J.
  • the carbon crystal synthesized by the invention is a material with very good biocompatibility, has no toxic and side effects, can be compounded with the active component of the drug, and can be used for directed drug conduction, so that the effective molecule of the drug can rapidly pass through the phospholipid bilayer of the human body.
  • Carbon crystal can also be used in a variety of daily cosmetics, such as: facial cleanser, soap, soap, toothpaste, etc., to achieve the purpose of less whitening effect, can effectively remove melanin from human skin and make teeth whiter .
  • the nanocarbon crystal synthesized by the invention has strong surface activity, strong composite property with other materials, and has wear resistance, so it can be used for compounding with various lubricating oils, improving lubricity of lubricating oil and preparing various coatings. Agent.
  • the carbon crystal synthesized by the invention has a small particle size, it is easy to disperse in the plating solution, and is also easily adsorbed onto the surface of the object to be plated, and a diamond film is formed on the surface of the plated part, and the film has good thermal conductivity and wear resistance. It can be used for surface treatment of all kinds of heat-generating and wearable parts (including non-stick pan).

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Abstract

本发明公开了一种新型纳米碳晶，属于碳材料制备领域，平均粒径为R，0＜R≤10nm，C含量为99～100%，该碳晶为类球形形貌，碳晶表面的C原子与内层金刚石相的C原子构成C原子的二聚体结构，C原子的二聚体结构中的两个碳原子为非对称分布。该新型纳米碳晶产品结晶性强，表面活性强，吸附能力强，形貌规整可控，损失率低，损失率可控制在1%以内，能够吸收太阳能的全谱，且表面碳原子活性高。

Description

说明书 发明名称：一种新型纳米碳晶
技术领域
[0001] 本发明属于碳材料技术领域， 具体涉及一种新型纳米碳晶。
背景技术
[0002] 碳是世界上含量最广的一种元素， 碳材料是目前世界上应用最为广泛的一种材 料。 随着吋代的变迁和科学的进步， 人们不断地利用碳和发现碳， 又发明了许 多碳材料， 例如： 富勒烯、 碳纳米管、 石墨烯等， 纳米碳晶便是碳材料家族中 新的一员。 新材料的出现意味着材料制备工艺的改进。 富勒烯的工业制备方法 主要是燃烧法， 主要用苯、 甲苯在氧气作用下通过不完全燃烧得到 C 6。与 C 7。的 混合物， 同吋还有大量有毒气体排出而污染环境， 后续还需要用其它有机物进 行提纯， 制备工艺过程复杂。 碳纳米管的工业制备方法是电弧法， 将石墨电极 置于充满氮气或氩气的反应容器中， 在两极之间发出电弧， 在这种条件下制备 出的是 c 6Q、 无定型 c、 多层的碳纳米管， 后续的提纯处理也无法将 C 6Q提纯干净 得到纯度高的碳纳米管， 而且这种制备方法能耗高。 石墨烯的制备方法主要是 氧化还原法， 通过氧化剂将石墨氧化， 增大石墨的层间距， 再通过物理方法将 其分离， 最后通过化学法进行还原得到石墨烯， 这种方法得到的石墨烯产量高 ， 但是产品质量低。
技术问题
[0003] 本发明的目的在于提供一种新型的纳米碳晶。
问题的解决方案
技术解决方案
[0004] 基于上述目的， 本发明采用以下技术方案： 一种新型纳米碳晶， 该碳晶为类球 形形貌， 碳晶表面的 C原子与内层金刚石相的 C原子构成 C原子的二聚体结构， C 原子的二聚体结构中的两个碳原子为非对称分布。
[0005] 优选地， 晶格间距为 0.21nm。
[0006] 优选地， 平均粒径为 R， 0 < R≤10nm。 [0007] 优选地， 该碳晶的 C含量为 99〜100%。
[0008] 该纳米碳晶采用以下方法制备， 步骤为：
[0009] (1) 初步破碎： 将金刚石原料机械破碎后， 筛分出 500目以上的细料， 将该细 料重复过筛一次以上， 以保证分选粒度的准确性；
[0010] (2) 再次破碎： 将筛分出 500目以上细料输送至气流破碎机内， 利用高压气流 对细料粉碎后筛分出 10000目以上的细粉， 筛余物返回气流破碎机进行重新破碎
[0011] (3) 酸洗： 将 10000目以上的细粉依次采用浓硫酸与浓硝酸混合液、 稀盐酸、 氢氟酸对该细粉酸洗， 然后使用去离子水清洗至清洗液 pH接近于 7; 所述浓硫酸 与浓硝酸混合液由质量分数为 98%浓硫酸和质量分数为 10%浓硝酸按照质量比为 5:1混合而成；
[0012] (4) 分选： 将清洗后的物料进行离心分离， 取上层液体进行 4-7天沉淀分选， 去除上层清液， 将下层沉淀物干燥后即得成品纳米碳晶； 离心分离步骤中， 离 心吋间为 30min-2h， 转速为 8000rpm-20000rpm。
[0013] 进一步地， 在步骤 （1) 中， 金刚石经机械粉碎机的筛网筛出 32目以上的颗粒 ， 颗粒经多级振筛机筛分出 500目以上的细料。
发明的有益效果
有益效果
[0014] 与现有技术相比， 本发明提供的纳米碳晶的具有以下优点：
[0015] (1) 该纳米碳晶的 C含量在 99〜100%之间， 纯度很高， 粒度范围分布窄， 0< R≤10nm, 产品结晶性较强， 表面活性强， 吸附能力强， 形貌规整可控， 损失率 低， 损失率可控制在 1%以内。
[0016] (2) 该纳米碳晶能够吸收太阳能的全谱， 且表面碳原子活性高， 与 Ti0 2等催 化剂结合后可在光照下吸收可见光， 发出 325-425nm的短波长光， 从而激发 TiO 2 等催化剂形成电子空穴对， 电子空穴对转化成活性基团， 从而降解有机染料分 子， 同吋由于纳米碳晶在 TiO 2等催化剂的表面， 故而可以起到传递电子的作用 ， 促使电荷的分离， 电子沿纳米碳晶表面传输， 可以延长 TiO 2等催化剂的空穴 寿命， 提高催化活性。 [0017] (3) 纳米碳晶表面具有非对称分布的 C原子的二聚体结构， 具有很高的表面活 性， 很容易被表面功能化处理， 可用于各种化妆品， 同吋由于具有耐磨性强的 特点， 还可以用于各种清洗剂、 机油添加剂、 涂层添加剂等， 增加耐磨性。
[0018] (4) 根据 Raman测试结果， 本发明的纳米碳晶无任何光致发光现象， 可用于 隐形飞机表面涂层领域 （要求有良好的光学隐蔽性能和耐高温耐摩擦性能） ， 或用来制备特殊的光学器件， 例如光学谐振器、 极限显示器等， 在光学领域有 着独特的应用。
[0019] (5) 纳米碳晶粒径小， 很容易在镀液中进行分散， 也很容易吸附到被镀件表 面， 在被镀件表面形成一层金刚石膜， 这种膜导热性好、 耐磨， 可用于各种发 热易磨损零件的表面处理。
[0020] (6) 纳米碳晶物相构成为金刚石相， 具备硬度高、 耐磨性强、 导热率高、 稳 定高、 亲油疏水等特性， 可广泛用于改善传统的磨削作业， 提高磨削效率， 降 低成本。
对附图的简要说明
附图说明
[0021] 图 1是本发明的工艺流程框图；
[0022] 图 2是实施例 1制备的纳米碳晶的 TEM分析图；
[0023] 图 3是实施例 1制备的纳米碳晶的 XRD谱图；
[0024] 图 4是实施例 1制备的纳米碳晶的 EDS谱图；
[0025] 图 5是实施例 1制备的纳米碳晶的 Raman光谱图；
[0026] 图 6是实施例 1制备的纳米碳晶的 MAS NMR谱图。
本发明的实施方式
[0027] 下面结合实施例对本发明进行详细说明。
[0028] 实施例 1
[0029] 一种新型纳米碳晶， 平均粒径为 R， 0< R≤10nm， C含量为 99〜100<¾， 该碳晶 为类球形形貌， 碳晶表面的 C原子与内层金刚石相的 C原子构成 C原子的二聚体 结构， C原子的二聚体结构中的两个碳原子为非对称分布， 晶格间距为 0.21nm。 [0030] 实施例 2
[0031] 采用以下方法制备该纳米碳晶， 其工艺流程框图如图 1所示， 步骤为：
[0032] (1) 初步破碎： 首先将金刚石原料送入机械破碎机的破碎腔内， 经过破碎机 内部高速回转的锤头作用而破碎， 破碎后的料经过不同目数的筛网， 大于筛网 直径的料留在破碎机内部重新破碎， 经破碎机下层最细的筛网过滤的颗粒料经 筛板收集（筛网目数不低于 32目）， 而经其它目数筛网过滤的料可当做粗料出售或 用于制备其它粒度的料； 32目以上的颗粒利用多层振筛机进行粒度初分， 振筛 吋间一般控制在 30min~3h， 筛网目数依次从 40目到 500目排布， 40目筛网分选出 的粗料返回机械破碎机进行重新破碎（图 1A)， 40目至 500目的筛网收集的料用于 制备其它粒度的料， 过 500目筛网后收集的细料用于制备纳米碳晶， 为保证分选 粒度的准确性， 对收集到的细料重复筛分选一次以上。
[0033] (2) 再次破碎： 将步骤 （1) 筛分出的细料送入气流破碎机破碎腔内， 利用高 压气流对细料进行破碎， 在气流破碎机收料口收集经筛网筛分后的料， 筛网目 数从 1000目到 10000目从高到低依次排布， 收集 10000目筛网筛选的细粉用于制 备纳米碳晶， 其它目数筛网收集的料用于制备其它料或仍返回气流破碎机进行 重新破碎， 1000目筛网收集的粗料自动返回气流破碎机进行重新破碎（图 1 B)。
[0034] (3) 酸洗： 将收集的气流破碎后 10000目的细粉置于浓硫酸与浓硝酸混合液中 酸洗 l~5h、 过滤、 清洗， 所述浓硫酸与浓硝酸混合液由质量分数为 98%浓硫酸和 质量分数为 10%浓硝酸按照质量比为 7:1.2混合而成； 然后将细粉置于 120°C~180 °C质量分数为 5<¾~10<¾的稀盐酸中 4~l lh、 过滤； 再将该细粉置于氢氟酸中 5~20 h， 去除料中的金属杂质以及在机械破碎、 气流破碎过程中附着在料上的杂质， 然后使用去离子水清洗至清洗液 pH接近于 7。
[0035] (4) 分选： 将清洗后的物料进行离心分离， 离心吋间为 lh， 转速为 lOOOOrpm ， 经离心分选后分离心管上部混合液和离心管底部沉积料两种； 取上层混合液 进行 5天沉淀分选， 沉淀吋间越长， 分选到料的粒径就越细， 沉淀分选后去除上 层清液， 下层沉淀物经粒度检测合格后烘干后即可得到成品纳米碳晶。 离心管 底部沉积料可以返回气流破碎机继续破碎也可以当成较粗粒度的成品料出售。 测得制备的纳米碳晶的粒度为 9-10nm， 该处所述的粒度为一个很小的范围内的 粒度峰值， 该峰值的粒度在对应的分选吋间分选出的粒度中所占的比例至少在 9 8%以上。
[0036] 实施例 3
[0037] 实施例 3的制备工艺与实施例 2的不同之处在于： 离心吋间为 30min， 转速为 200
OOrpm, 沉淀分选吋间为 4天。
[0038] 制备出的纳米碳晶的粒度为 6~8nm。
[0039] 实施例 4
[0040] 实施例 4的制备工艺与实施例 2的不同之处在于： 离心吋间为 lh， 转速为 lOOOOr pm， 沉淀分选吋间为 6天。
[0041] 制备出的纳米碳晶的粒度为 5~6nm。
[0042] 实施例 5
[0043] 实施例 5的制备工艺与实施例 2的不同之处在于： 离心吋间为 2h， 转速为 20000r pm， 沉淀分选吋间为 7天。
[0044] 制备出的纳米碳晶的粒度为 0~5nm。
[0045] 性能测试
[0046] (1) TEM分析
[0047] 图 2是实施例 1提供的纳米碳晶的 TEM分析图， 图中： a: 纳米碳晶； b: ***法 纳米金刚石； 1代表局部放大图， 2代表 HRTEM图， 1图中左上角的插图为对应 的 SAED图。
[0048] 由图 2的 TEM分析图可以看出， 实施例制备的纳米碳晶近似于球形， 形貌较为 规整， 粒径在 2-5nm， 而***法纳米金刚石都由一些团聚的颗粒组成的， 且形貌 也不规整， 粒径都在 5-10nm之间， 通过对应的 SAED图可以看出这两种材料都具 有多晶结构， 而对应的 HRTEM图中可测量出纳米碳晶的晶格间距均为 0.21nm， 这与金刚石相 (111)晶面的晶格间距 d=0.206nm非常接近， 这说明本发明制备的纳 米碳晶具有金刚石相结构。
[0049] (2) XRD分析
[0050] 图 3是实施例 1制备的纳米碳晶的 XRD谱图， 图中： a: ***法纳米金刚石； b: 纳米碳晶。 [0051] 从图 3可以看出， 这两种材料的出峰位置均在 44°左右， 经过与标准的 PDF卡片 比对， 与金刚石相密勒指数为 (111)晶面相对应， 这再次证明了这两种材料均是 由金刚石相构成的， 但是可以看到纳米碳晶在 20°~40°之间存在着一个较大的非 晶包， 纳米碳晶的结晶性要比***法纳米金刚石弱一些， 但依然具有较强的结 晶性。 根据谢乐公式
[数]
， K为常数， β为半高宽， λ为 Cu的 Κα射线波长， 计算结果 D BZ=8.5nm， D c =3.5nm, ***法合成的纳米金刚石的晶粒大小约是纳米碳晶的 2.4倍， 由此可见 ， 本发明制备出的纳米碳晶晶粒比***法合成的纳米金刚石小， 晶界多。 小晶 粒内部会发生不同程度畸变， 从而影响材料的性质， 因此本发明合成的纳米碳 晶的活性上优于***法合成的纳米金刚石。
[0052] (3) EDS分析
[0053] 图 4是实施例 1制备的纳米碳晶的 EDS谱图， 图中： a: 纳米碳晶； b: ***法纳 米金刚石。
[0054] 从图 4可以看出， 本发明制备的纳米碳晶基本上都是由 C元素组成的， 纯度很高
， 这点与***法制备的纳米金刚石类似， 都属于 C材料。
[0055] (4) Raman分析
[0056] 图 5是***法纳米金刚石和纳米碳晶的 Raman光谱图， 图中： a: ***法纳米金 刚石， b: 实施例 1制备的纳米碳晶。
[0057] 从图 5上可以非常明显地看到这两种碳材料明显具有不同的 Raman光谱图， 爆 炸法合成的纳米金刚石还具有 C材料典型的特征 Raman峰 D峰和 G峰， 而本发明合 成的纳米碳晶没有任何 Raman峰， 这表明本发明制备的纳米碳晶与***法纳米金 刚石具有不同的碳原子排布。 红外光谱只能对具有红外活性的分子有强的吸收 信号， 对于纯 C元素的晶体， 无法使用红外光谱检测其结构。 所谓红外活性， 是 指偶极变化不为零， 结构越对称的结构， 那么偶极的变化就越小， 比如 C-C， C=C， C≡C， 0-0， N≡N等， 这类同核双原子对都是红外非活性的， 因此 ， 在红外光谱上很难观测到这些同核双原子对的伸缩振动特征峰 (如果要观测这 类同核双原子， 在其周围接上不对称的基团后才能检测到相对微弱的红外吸收 峰)。 但是， 一般而言， 红外活性弱的同核双原子对， 其 Raman活性会比较强， 因此可以断定纳米碳晶与***法纳米金刚石的 C原子排布不同。
[0058] (5) MAS NMR分析
[0059] 图 6是实施例 1制备的纳米碳晶和***法纳米金刚石的 MAS NMR谱图， 图中： a ： 实施例 2制备的纳米碳晶； b: ***法纳米金刚石。
[0060] 从图 6可以看到纳米碳晶和***法纳米金刚石均出现两个 C峰， 这说明纳米碳晶 和***法纳米金刚石样品中均有两种不同的碳原子 C ^nC 2， 位置分别在 34ppm 和 30ppm。 一般来说， sp 3轨道杂化碳的 0 C通常在 0〜60ppm， sp 2轨道杂化碳的 δ c通常在 100〜220ppm， sp轨道杂化碳的 δ c通常在 60〜90ppm， 从图上我们可以 看出 a、 b两种种样品的C 1和C 2的δ c都在0〜60ppm之间， 在其它位置并没有出峰 ， 虽然这两个峰的出峰位置都在 0〜60ppm之间， 但是 C ^nC 2
的出峰位置相差 4ppm， 位置很接近， 说明 C ^nC 2所处的化学环境比较接近， 结 合 EDS分析可知纳米碳晶和***法纳米金刚石样品都是由 C元素构成的， 所以 C , 和 C 2具有不同的结构。 根据 Raman光谱结果知道本发明合成的纳米碳晶没有任 何 Raman光谱峰， 而***法合成的纳米金刚石具有 C材料的特征 Raman峰， 综合 以上分析我们可以推断出本发明合成的纳米碳晶与***法纳米金刚石的表面 C原 子排布不同， 本发明合成的碳晶表面的 C原子与里层的金刚石相的 C原子构成了 一种 C原子的二聚体结构， 这两个碳原子是非对称分布的， 而***法合成的纳米 金刚石表面的 C原子和金刚石相的 C原子也构成了一种 C原子的二聚体结构， 这 两个 C原子是对称分布的， 因此才会出现两种截然不同的 Raman峰。 非对称的 C 原子排布相对于对称排布的 C原子来说更具有活性， 更加容易与不同的基团进行 复合， 同吋颗粒表面的 C原子活性强也容易团聚在一起， 较***法纳米金刚石而 言更加容易进行表面功能化处理。
[0061] 本发明提供的纳米碳晶能够吸收太阳能的全谱， 且表面碳原子活性高， 与 Ti0 2 等催化剂结合后可在光照下吸收可见光， 发出 325-425nm的短波长光 ， 从而激发 TiO 2等催化剂形成电子空穴对， 电子空穴对转化成活性基团， 从而 降解有机染料分子， 同吋由于纳米碳晶在 TiO 2等催化剂的表面， 故而可以起到 传递电子的作用， 促使电荷的分离， 电子沿纳米碳晶表面传输， 可以延长 Ti0 2 等催化剂的空穴寿命， 提高催化活性。 本申请合成的纳米碳晶表面的碳原子排 布是非对称的， 表层的碳原子与里层的碳原子构成了一种非对称二聚体的结构 ， 这种结构相对于***法纳米金刚石而言， 更具有活性， 更加容易被表面功能 化处理， 更加容易与其它材料以共价键或非共价键的形式进行复合， 这种碳晶 由于具有特殊的光致发光性能， 可用于极限显示器、 光学谐振器等， 同吋由于 粒径小， 比表面积大， 可用于制备各种吸附膜， 例如海水淡化膜、 苦咸水淡化 膜、 去离子水制备膜等， 同吋还具备强大的催化作用， 可用于制备非金属催化 齐 1J。 本发明合成的碳晶是一种生物兼容性非常好的材料， 无毒副作用， 可与药 物的有效成分进行复合， 可用于药物定向传导， 使得药物有效分子能够快速穿 过人体磷脂双分子层， 快速达到病灶部位， 实现药物的靶向治疗， 提高药物的 利用率， 减少治疗周期。 碳晶这种材料还可以用于各种日用化妆品， 例如： 洗 面奶、 香皂、 肥皂、 牙膏等， 达到使用量较少美白效果增强的目的， 可有效去 除人体皮肤中黑色素以及使得牙齿更加美白。 本发明合成的纳米碳晶由于表面 活性强， 与其它材料复合性能强， 同吋还具有耐磨作用， 因此可用于与各种润 滑油进行复合， 提高润滑油的润滑性能以及制备各种涂层剂。 由于本发明合成 的碳晶粒径小， 很容易在镀液中进行分散， 也很容易吸附到被镀件表面， 在被 镀件表面形成一层金刚石膜， 这种膜导热性好、 耐磨， 可用于各种发热易磨损 零件的表面处理 (包括不粘锅)。

Claims

权利要求书
[权利要求 1] 一种新型纳米碳晶， 其特征在于， 该碳晶为类球形形貌， 碳晶表面的
C原子与内层金刚石相的 C原子构成 C原子的二聚体结构， C原子的二 聚体结构中的两个碳原子为非对称分布。
[权利要求 2] 根据权利要求 1所述的新型纳米碳晶， 其特征在于， 晶格间距为 0.21η m。
[权利要求 3] 根据权利要求 1或 2所述的新型纳米碳晶， 其特征在于， 平均粒径为 R
， 0< R≤10nm。
[权利要求 4] 根据权利要求 3所述的新型纳米碳晶， 其特征在于， 该碳晶的 C含量 为 99〜100<¾。
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