The properties and applications of nanodiamonds

Journal name:
Nature Nanotechnology
Volume:
7,
Pages:
11–23
Year published:
DOI:
doi:10.1038/nnano.2011.209
Published online

Abstract

Nanodiamonds have excellent mechanical and optical properties, high surface areas and tunable surface structures. They are also non-toxic, which makes them well suited to biomedical applications. Here we review the synthesis, structure, properties, surface chemistry and phase transformations of individual nanodiamonds and clusters of nanodiamonds. In particular we discuss the rational control of the mechanical, chemical, electronic and optical properties of nanodiamonds through surface doping, interior doping and the introduction of functional groups. These little gems have a wide range of potential applications in tribology, drug delivery, bioimaging and tissue engineering, and also as protein mimics and a filler material for nanocomposites.

At a glance

Figures

  1. Detonation synthesis of nanodiamonds.
    Figure 1: Detonation synthesis of nanodiamonds.

    a, To synthesize nanodiamonds, explosives with a negative oxygen balance (for example a mix of 60 wt% TNT (C6H2(NO2)3CH3) and 40 wt% hexogen (C3H6N6O6)) are detonated in a closed metallic chamber in an atmosphere of N2, CO2 and liquid or solid H2O. After detonation, diamond-containing soot is collected from the bottom and the walls of the chamber. b, Phase diagram showing that the most stable phase of carbon is graphite at low pressures, and diamond at high pressures, with both phases melting when at temperatures above 4,500 K (with the precise melting temperature for each phase depending on the pressure). The phase diagrams for nanoscale carbon are similar, but the liquid phase is found at lower temperatures38, 39. During detonation, the pressure and temperature rise instantaneously, reaching the Jouguet point (point A), which falls within the region of liquid carbon clusters of 1–2 nm in size for many explosives. As the temperature and pressure decrease along the isentrope (red line), carbon atoms condense into nanoclusters, which further coalesce into larger liquid droplets and crystallize39. When the pressure drops below the diamond–graphite equilibrium line, the growth of diamond is replaced by the formation of graphite. c, Schematic of the detonation wave propagation showing (I) the front of the shock wave caused by the explosion; (II) the zone of chemical reaction in which the explosive molecules decompose; (III) the Chapman–Jouguet plane (where P and T correspond to point A in Fig. 1b, indicating the conditions when reaction and energy release are essentially complete); (IV) the expanding detonation products; (V) the formation of carbon nanoclusters; (VI) the coagulation into liquid nanodroplets; and (VII) the crystallization, growth and agglomeration of nanodiamonds39.

  2. Structure of a single nanodiamond particle.
    Figure 2: Structure of a single nanodiamond particle.

    a, Schematic model illustrating the structure of a single ~5-nm nanodiamond after oxidative purification. The diamond core is covered by a layer of surface functional groups, which stabilize the particle by terminating the dangling bonds. The surface can also be stabilized by the conversion of sp3 carbon to sp2 carbon. A section of the particle has been cut along the amber dashed lines and removed to illustrate the inner diamond structure of the particle. b,c, Close-up views of two regions of the nanodiamond shown in a. The sp2 carbon (shown in black) forms chains and graphitic patches (b). The majority of surface atoms are terminated with oxygen-containing groups (c; oxygen atoms are shown in red, nitrogen in blue). Some hydrocarbon chains (green, lower left of a,c) and hydrogen terminations (hydrogen atoms are shown in white) are also seen. d, Each nanodiamond is made up of a highly ordered diamond core. Some nanodiamonds are faceted, such as the one shown in this transmission electron micrograph, whereas most have a rounded shape, as shown in a. The inset is a fast Fourier transform of the micrograph, which confirms that this nanodiamond has a highly ordered diamond core. Panel d, reproduced with permission from ref. 19, © 2011 ACS.

  3. Raman spectroscopy and structure of nanodiamond.
    Figure 3: Raman spectroscopy and structure of nanodiamond.

    Electron micrographs showing detonation soot (bottom), purified nanodiamond (middle) and oxidized nanodiamond (top). The diamond cores in detonation soot seem to be completely covered by graphitic shells, and this is confirmed by the Raman spectrum (black line), which is dominated by the G-band of graphitic carbon at 1,590 cm−1 and has no diamond peak. Purified nanodiamonds are partially covered by a thin layer of graphite, so a diamond peak can be seen at 1,328 cm−1 in the Raman spectrum (blue line). This thin layer of graphite is completely removed by oxidation in air, so the Raman spectrum of oxidized nanodiamonds has an even stronger diamond peak (red line). The diamond peak in the Raman spectrum of purified and air oxidized nanodiamond (inset a) is a combination of peaks originating from larger (I) and smaller (II) coherence scattering domains. The phonon confinement model84 gives a good fit (blue line) to experimental data (open circles). The broad feature at 1,500−1,800 cm−1 in the spectrum of air oxidized nanodiamond (inset b) originates from surface functional groups and adsorbed molecules, with some contribution from sp2 carbon atoms. The Raman spectra were recorded following excitation by an ultraviolet laser (325 nm).

  4. Optical properties of nanodiamonds.
    Figure 4: Optical properties of nanodiamonds.

    a,b, De-aggregation by salt-assisted dry milling reduces the size of diamond particles from ~1 μm to less than 10 nm (a), and makes suspensions of the particles both darker and more transparent (b). The changes in colour are not related to the presence of graphitic carbon56. c, Photonic structures formed by centrifugation of suspensions of nanodiamonds in deionized water. d,e, Covalently attaching ODA to nanodiamonds changes their optical properties. ND–ODA absorbs and re-emits light over a wide range of wavelengths, as can be seen in these excitation (purple) and emission (blue) spectra (d). Moreover, and in contrast to non-functionalized nanodiamond, ND–ODA is strongly blue fluorescent when illuminated with ultraviolet light (e). f, ND–ODA can be used for bio-imaging, as illustrated by this confocal micrograph of the fluorescent scaffold made of ND–ODA–PLLA with 7F2 osteoblasts grown on it (see main text for details). Panel c, reproduced with permission from ref. 62, © 2008 IOP.

  5. Surface modification.
    Figure 5: Surface modification.

    Precise control over surface chemistry requires a sample of purified nanodiamond with only one kind of functional group attached to its surface. Nanodiamond terminated with carboxylic groups (ND–COOH; green region) is a common starting material (and is made by air oxidation or ozone treatment of nanodiamond, followed by treatment in aqueous HCl to hydrolyse anhydrides and remove metal impurities). The surface of ND–COOH can be modified by high-temperature gas treatments (red) or ambient-temperature wet chemistry techniques (blue). Heating in NH3, for example, can result in the formation of a variety of different surface groups including NH2, C–O–H, C≡N and groups containing C=N (refs 9, 48). Heating in Cl2 produces acylchlorides, and F2 treatment forms C–F groups (not shown)67, 137, 138. Treatment in H2 completely reduces C=O to C–O–H and forms additional C–H groups. Hydroxyl (OH) groups may be removed at higher temperatures or with longer hydrogenation times, or by treatment in hydrogen plasma66. Annealing in N2, Ar or vacuum completely removes the functional groups and converts the nanodiamonds into graphitic carbon nano-onions139, 140. A wide range of surface groups and functionalized nanodiamonds can also be produced using wet chemistry treatments.

  6. Advanced atomic-level composite design with nanodiamond.
    Figure 6: Advanced atomic-level composite design with nanodiamond.

    a, Three examples of the interfaces between nanodiamond and different matrices. Nanodiamond can bind to SiC through C–Si bonds between the surface of the nanodiamond and the Si atoms in the SiC to produce ND–SiC (left). Carboxylic groups present on the nanodiamond surface can form salts by ion exchange reactions with different metal ions, such as Cu2+ (middle; ref. 141). Metal ions can be later reduced, forming an atomically thin metal layer around the particle. These metallized particles can be used as a means to disperse nanodiamonds in metals that do not wet carbon, and also to produce wear-resistant ND–Cu sliding contacts. Nanodiamonds with surface carboxylic groups can be functionalized through covalent attachment of ODA by amide bond formation (right). b, Stress–strain curves for six ND–ODA–PLLA composites that contain different amounts of ND–ODA11. The Young's modulus of a given composite is proportional to the slope of its stress–strain curve. c, Aminated nanodiamond, produced through covalent attachment of ethylenediamine to carboxylic groups on the surface of the nanodiamond, can replace traditional epoxy curing agents (amines) in reaction with epoxy resin. This results in the covalent incorporation of the nanodiamond into the epoxy polymer network at a molecular level, improving the mechanical properties of the polymer matrix14.

  7. Nanodiamonds and drug delivery.
    Figure 7: Nanodiamonds and drug delivery.

    a, DNA can be electrostatically attached to nanodiamonds by first covering negatively charged carboxylated nanodiamonds with positively charged PEI800 molecules. A similar electrostatic binding strategy has been used to attach siRNA and doxorubicin (Dox) to nanodiamond104. b, Schematic representation of a proposed mechanism for ND–Dox complexes interacting with a cell. 1, Endocytosis of the ND–drug complexes. 2, Diffusion of free drug molecules across the cell membrane. 3, ABC transporter proteins efflux free drug molecules out of the cell, whereas ND–drug complexes are able to remain inside the cell and deliver a steady, lethal dose of the drug to the tumour. c, Photographs of breast-cancer tumours after treatment with ND–Dox (top), Dox (middle) and a control (PBS; bottom). Two representative tumours are shown in each case. The large size of the tumours excised after long-term treatment with Dox or PBS illustrates a reduced ability of Dox to inhibit tumour growth owing to the extreme resistance of the 4T1 breast cancer to chemotherapy. In contrast, treatment with ND–Dox clearly reduces the size of the tumours. Figure reproduced with permission from: a, ref. 127, © 2009 ACS; b, ref. 142, © 2011 AAAS; c, ref. 104, © 2011 AAAS.

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Affiliations

  1. Department of Materials Science and Engineering and A. J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, Pennsylvania 19104, USA

    • Vadym N. Mochalin &
    • Yury Gogotsi
  2. International Technology Center, Raleigh, North Carolina 27617, USA

    • Olga Shenderova
  3. Departments of Biomedical and Mechanical Engineering, Northwestern University, Evanston, Illinois 60208, USA

    • Dean Ho
  4. Institute for BioNanotechnology in Medicine (IBNAM) and Robert H. Lurie Comprehensive Cancer Center, Northwestern University, Chicago, Illinois 60611, USA

    • Dean Ho

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