Method for producing and purifying nanodiamond doped with carbon group elements

Abstract

The present invention provides a method for producing nanodiamonds doped with carbon group elements, the method comprising: a detonation step of exploding an explosive composition containing at least one explosive and at least one carbon group element compound in a closed container to obtain nanodiamonds doped with at least one carbon group element selected from Si, Ge, Sn and Pb; and a step of subjecting the nanodiamonds doped with carbon group elements to an alkali treatment to remove the carbon group elements and / or their oxides.

Description

Technical Field

[0001] The invention relates to a method for producing and purifying nano diamond doped with carbon group elements. Background Art

[0002] The luminescence center of diamond is a nano-sized and chemically stable fluorescent chromophore, which does not show decomposition, fading, or flickering in the body that is common in organic phosphors, and is therefore highly anticipated as a probe for fluorescence imaging. In addition, it is sometimes possible to measure the spin information of the electrons excited in the luminescence center from the outside, and thus it is also expected to be used as ODMR (Optically Detected Magnetic Resonance) and quantum bits.

[0003] SiV center, which is one type of luminescence center of diamond, has a sharp peak called ZPL (Zero Phonon Level) in the luminescence spectrum (Non-Patent Document 1).

[0004] Diamond doped with silicon is produced by a CVD (chemical vapor deposition) method or the like (Patent Documents 1 and 2).

[0005] Non-patent document 2 analyzes nanodiamonds in meteorites, but does not produce nanodiamonds with SiV (Silicon-Vacancy) centers. Non-patent document 2 shows through simulation that SiV centers are thermodynamically stable in nanodiamonds of 1.1 nm to 1.8 nm.

[0006] Non-patent document 3 Figure 1 Nanodiamonds with SiV centers shaped by CVD were revealed by AFM (atomic force microscopy). Figure 1 In the upper right curve graph, the vertical axis represents height (nm) and the horizontal axis represents position (micrometers). It can be clearly seen that the peak height is about 9nm, but the width (position) is at least 70nm.

[0007] Non-patent document 4 discloses that nanodiamonds with a diameter of 3 to 4 nm are used as a seed solution and grown on a silicon wafer by MWPECVD to obtain nanodiamonds with an average particle size of 73 nm containing SiV centers.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application No. 2014-504254

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2004-176132

[0012] Non-patent literature

[0013] Non-patent document 1: E. Neuetal. APPLIED PHYSICS LETTERS 98, 243107 (2011)

[0014] Non-patent literature 2: Nat Nanotechnol. 2014 Jan; 9(1): 54-8. doi: 10.1038 / nnano.2013.255. Epub 2013 Dec 8.

[0015] Non-patent document 3: Adv Sci Lett. 2011 Feb 1; 4(2): 512-515.

[0016] Non-patent document 4: Diamond and Related Materials, Volume 65, 2016, Pages 87-90 Summary of the invention

[0017] Problems to be solved by the invention

[0018] One of the purposes of the present invention is to provide a method for producing and purifying nanodiamonds doped with carbon group elements such as silicon (Si), germanium (Ge), and tin (Sn).

[0019] Solutions to the problem

[0020] The present invention provides the following method for producing and purifying nanodiamond doped with carbon group elements.

[0021] Item 1. A method for producing nanodiamond doped with carbon group elements, the method comprising:

[0022] A detonation step of detonating an explosive composition containing at least one explosive and at least one carbon group element compound in a closed container to obtain nanodiamonds doped with at least one carbon group element selected from Si, Ge, Sn and Pb; and

[0023] The process of treating the nanodiamond doped with carbon group elements with alkali to remove the carbon group elements and / or their oxides.

[0024] Item 2. The method for producing nanodiamond doped with carbon group elements according to Item 1, wherein:

[0025] Before or after the alkali treatment step, a mixed acid treatment step is further included in which the nanodiamond doped with carbon group elements is treated with a mixed acid of concentrated nitric acid and concentrated sulfuric acid.

[0026] Item 3. The method for producing nanodiamond doped with a carbon group element according to Item 1 or 2, wherein:

[0027] The explosive composition further comprises a compound containing at least one third element selected from the group consisting of B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

[0028] Item 4. A method for purifying nanodiamond doped with carbon group elements, the method comprising:

[0029] A step of treating a nanodiamond composition containing at least one carbon group element and / or its oxide selected from Si, Ge, Sn and Pb and the nanodiamond doped with the carbon group element with an alkali to remove the carbon group element and / or its oxide.

[0030] Item 5. The method for purifying nanodiamond doped with carbon group elements according to Item 4, wherein:

[0031] The nano-diamond composition is obtained by mixed acid treatment.

[0032] Item 6. The method for purifying nanodiamond doped with carbon group elements according to Item 4 or 5, wherein:

[0033] The nanodiamond composition further contains at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements and / or its oxide.

[0034] Item 7. The method for purifying nanodiamond doped with a carbon group element according to any one of Items 4 to 6, wherein:

[0035] The above-mentioned nanodiamond is further doped with at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

[0036] Effects of the Invention

[0037] At least one carbon group element selected from Si, Ge, Sn and Pb and its oxide cannot be easily removed by mixed acid treatment, but can be removed from the carbon group element-doped nanodiamond by alkali treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 (a) 738 nm bright spot imaging image and (b) fluorescence spectrum of the bright spot of silicon-doped nanodiamond obtained by using triphenylsilanol as the silicon compound and adding it in an amount of 1 mass % in terms of external proportion. Figure 1 In (b), a fluorescence sideband (shoulder peak) exists near 750 nm, but this sideband may not exist depending on the sample.

[0039] Figure 2 These are the XRD results before and after alkali treatment. A: after alkali treatment; B: before alkali treatment. DETAILED DESCRIPTION

[0040] The nanodiamond of the present invention may also be further doped with an element other than the carbon group element. Such an element may include: at least one element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements (hereinafter referred to as "the third element"). In the case where the nanodiamond is doped with the third element, the explosive composition further contains at least one explosive, at least one carbon group element compound and at least one third element compound.

[0041] In this specification, nanodiamond doped with a carbon group element and, if necessary, further doped with a third element may be simply referred to as "doped nanodiamond".

[0042] In one embodiment of the present invention, the manufacturing method of the present invention includes: a detonation step of exploding an explosive composition containing at least one explosive and at least one carbon group element compound, and at least one third element compound as needed, in a closed container to obtain a nanodiamond doped with a carbon group element and further doped with a third element as needed; and a step of subjecting the nanodiamond doped with a carbon group element and further doped with a third element as needed to an alkali treatment to remove the carbon group element and / or its oxide.

[0043] The carbon group element doped in the nanodiamond is at least one selected from Si, Ge, Sn and Pb, preferably Si.

[0044] The explosive is not particularly limited, and a wide range of known explosives can be used. Specific examples include trinitrotoluene (TNT), cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (octogen), trinitrobenzyl nitramine (tetryl), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triaminotrinitrobenzene, hexanitrostilbene, diaminodinitrobenzofuroxan, etc., and these can be used alone or in combination of two or more.

[0045] The carbon group element compound includes at least one selected from silicon compounds, germanium compounds, tin compounds and lead compounds.

[0046] Examples of the organic silicon compound include:

[0047] Silanes having a lower alkyl group such as acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, and trimethylphenoxysilane;

[0048] · Trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, chlorotriethylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, chlorodifluoromethylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorosilane, chlorodifluoropropylsilane, dichlorofluoro Silanes having a halogen atom such as propylsilane, trifluoromethylsilane, difluorodimethylsilane, fluorotrimethylsilane, ethyltrifluorosilane, diethyldifluorosilane, triethylfluorosilane, trifluoropropylsilane, fluorotripropylsilane, trifluorophenylsilane, difluorodiphenylsilane, fluorotriphenylsilane, tribromomethylsilane, dibromodimethylsilane, bromotrimethylsilane, bromotriethylsilane, bromotripropylsilane, dibromodiphenylsilane, and bromotriphenylsilane;

[0049] Polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, and octaphenylcyclotetrasilane;

[0050] Silazanes such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, and hexaphenylcyclotrisilazane;

[0051] Aromatic silanes such as silanol and disilanol, which are formed by introducing silicon atoms into the aromatic ring;

[0052] ·Hydroxy silanes such as trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, and diphenylsilanediol;

[0053] Alkyl or aryl substituted silanes such as tetramethylsilane, ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane and tetraphenylsilane;

[0054] ·Carboxyl-containing silanes such as triphenylsilylcarboxylic acid, trimethylsilylacetic acid, trimethylsilylpropionic acid, and trimethylsilylbutyric acid;

[0055] Siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane;

[0056] Silanes having an alkyl group or an aryl group and a hydrogen atom, such as methylsilane, dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, diphenylsilane, and triphenylsilane;

[0057] Tetrakis(chloromethyl)silane, tetrakis(hydroxymethyl)silane, tetrakis(trimethylsilyl)silane, tetrakis(trimethylsilyl)methane, tetrakis(dimethylsilanol)silane, tetrakis(tris(hydroxymethyl)silyl)silane, tetrakis(nitratemethyl)silane; and the like.

[0058] Examples of the inorganic silicon compound include silicon oxide, silicon oxynitride, silicon nitride, silicon oxycarbide, silicon carbonitride, silane, or carbon materials doped with silicon. Examples of the carbon material to be doped with silicon include graphite, graphite, activated carbon, carbon black, Ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.

[0059] The above-mentioned organic or inorganic silicon compounds may be used alone or in combination of two or more.

[0060] Examples of the germanium compound include organic germanium compounds such as methylgermane, ethylgermane, trimethylgermanium methylate, dimethylgermanium diacetate, tributylgermanium acetate, tetramethoxygermanium, tetraethoxygermanium, isobutylgermane, alkylgermanium trichloride, and dimethylaminogermanium trichloride, nitrotriphenol complex (Ge 2 (ntp) 2 O), catechol complex (Ge(cat) 2 ) or aminopyrene complex (Ge 2 (ap)2 Cl 2 ) and other germanium complexes, germanium ethanolate, germanium tetrabutoxide and other germanium alkoxides.

[0061] The above-mentioned germanium compounds may be used alone or in combination of two or more.

[0062] Examples of the tin compound include inorganic tin compounds such as tin (II) oxide, tin (IV) oxide, tin (II) sulfide, tin (IV) sulfide, tin (II) chloride, tin (IV) chloride, tin (II) bromide, tin (II) fluoride, tin acetate, and tin sulfate; alkyl tin compounds such as tetramethyl tin; monoalkyl tin oxide compounds such as monobutyl tin oxide; dialkyl tin oxide compounds such as dibutyl tin oxide; aryl tin compounds such as tetraphenyl tin; and organic tin compounds such as dimethyl tin maleate, hydroxybutyl tin oxide, and monobutyl tin tris(2-ethylhexanoate).

[0063] The above-mentioned tin compounds may be used alone or in combination of two or more.

[0064] Examples of lead compounds include lead monoxide (PbO), lead dioxide (PbO 2 ), red lead (Pb 3 O 4 )、White Lead (2PbCO 3 ·Pb(OH) 2 ), lead nitrate (Pb(NO 3 ) 2 ), lead chloride (PbCl 2 ), lead sulfide (PbS), chrome yellow (PbCrO 4 、Pb(SCr)O 4 、PbO·PbCrO 4 ), lead carbonate (PbCO 3 ), lead sulfate (PbSO 4 ), lead fluoride (PbF 2 ), lead tetrafluoride (PbF 4 ), lead bromide (PbBr 2 ), lead iodide (PbI 2 ) and other inorganic lead compounds, lead acetate (Pb(CH 3 COO 2 ), lead tetracarboxylate (Pb(OCOCH 3 ) 4 ), tetraethyl lead (Pb(CH 3 CH 2 ) 4 ), tetramethyl lead (Pb(CH 3 ) 4 ), tetrabutyl lead (Pb(C 4H 9 ) 4 ) and other organic lead compounds.

[0065] The above-mentioned lead compounds may be used alone or in combination of two or more.

[0066] Examples of the third element compound include organic third element compounds and inorganic third element compounds. The third element compound may be used alone or in combination of two or more.

[0067] The third element compounds are exemplified below.

[0068] Examples of the boron compound include inorganic boron compounds and organic boron compounds.

[0069] Examples of the inorganic boron compound include orthoboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, boron tribromide, tetrafluoroboric acid, ammonium borate, and magnesium borate.

[0070] Examples of the organic boron compound include triethylborane, (R)-5,5-diphenyl-2-methyl-3,4-propanol-1,3,2- Boric acid tris(trimethylsilyl) ester, 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole, tert-butyl N-[4-(4,4,5,5-tetramethyl-1,2,3-dioxaborolan-2-yl)phenyl]carbamate, phenylboronic acid, 3-acetylphenylboronic acid, boron trifluoride acetic acid complex, boron trifluoride sulfolane complex, 2-thiopheneboric acid, tris(trimethylsilyl) borate, etc.

[0071] Examples of the phosphorus compound include inorganic phosphorus compounds and organic phosphorus compounds. Examples of the inorganic phosphorus compound include ammonium polyphosphate and the like.

[0072] Examples of the organic phosphorus compound include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)-p-tolyl phosphate, tricresyl phosphate, didodecyl-p-tolyl phosphate, tris(2-butoxyethyl) phosphate, tricyclohexyl phosphate, triphenyl phosphate, ethyl diphenyl phosphate, di-(2-ethylhexyl)-p-tolyl phosphate, Phosphates such as butylphenyl ester, phenyl didodecyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, p-cresyl bis(2,5,5'-trimethylhexyl) phosphate, cresyl-2,6-xylyl phosphate, tri(xylyl) phosphate, hydroxyphenyl diphenyl phosphate, tri(tert-butylphenyl) phosphate, tri(isopropylphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, and phenyl dineopentyl phosphate;

[0073] Condensed phosphates such as 1,3-phenylenebis(diphenyl phosphate), 1,4-phenylenebis(di(xylyl) phosphate), 1,3-phenylenebis(3,5,5'-trimethylhexyl phosphate), bisphenol A bis(diphenyl phosphate), 4,4'-biphenylbis(di(xylyl) phosphate), 1,3,5-phenylenetris(di(xylyl) phosphate), and phosphites such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and tricresyl phosphite;

[0074] Phosphites such as 1,3-phenylenebis(diphenyl phosphite), 1,3-phenylenebis(di(xylyl)phosphite), 1,4-phenylenebis(3,5,5'-trimethylhexylphosphite), bisphenol A bis(diphenyl phosphite), 4,4'-biphenylbis(di(xylyl)phosphite), and 1,3,5-phenylene tris(di(xylyl)phosphite).

[0075] Examples of the nickel compound include divalent nickel halides such as nickel (II) chloride, nickel (II) bromide, and nickel (II) iodide; inorganic nickel compounds such as nickel (II) acetate and nickel (II) carbonate; and organic nickel compounds such as nickel bis(ethylacetoacetate) and nickel bis(acetylacetonate).

[0076] Examples of the titanium compound include inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, lead titanate, barium titanate, and potassium titanate; tetraalkoxytitanium such as tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium; tetraethylene glycol titanate, di-n-butyl bis(triethanolamine) titanate, diisopropoxytitanium bis(acetylacetonate), isopropoxytitanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tri(butylmethylpyrophosphate) titanate, tetraisopropyl di(dilaurylphosphite) titanate, dimethacryloyl acetoxy titanate, diacryloyl acetoxy titanate, di(dioctylphosphite) ethylene titanate, isopropyl tri(dioctylphosphite) titanate Titanium, tris(dioctyl pyrophosphate) isopropyl titanate, bis(dioctyl phosphite) tetraisopropyl titanate, bis(ditridecyl) phosphite) tetraoctyl titanate, bis(ditridecyl) phosphite) tetra(2,2-diallyloxymethyl-1-butyl) titanate, bis(dioctyl pyrophosphate) oxyacetoxy titanate, tris(dioctyl pyrophosphate) ethylene titanate, tri(n-dodecyl) benzenesulfonyl titanate isopropyl, trioctanoyl titanate isopropyl, dimethacryloyl isostearyl titanate isopropyl, isostearyl diacryloyl titanate isopropyl, tris(dioctyl phosphate) isopropyl titanate, tricumylphenyl titanate isopropyl, tris(N-aminoethyl-aminoethyl) titanate isopropyl and the like organic titanium compounds.

[0077] Examples of the cobalt compound include inorganic cobalt salts, cobalt halides, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt tetracarbonyl, tetracobalt dodecacarbonyl, tricobalt alkane nonacarbonyl, and the like; cobalt tris(ethylacetoacetate), cobalt tris(acetylacetonate), organic acid salts of cobalt (e.g., acetates, propionates, cyanates, naphthenates, stearates); alkyl sulfonates (e.g., methanesulfonates, ethanesulfonates, octanesulfonates, dodecylsulfonates) and the like; 6-18 benzenesulfonate, p-toluenesulfonate, naphthalenesulfonate, decylbenzenesulfonate, dodecylbenzenesulfonate, etc., optionally substituted with alkyl arylsulfonate (for example, C 6-18 Alkyl-aryl sulfonate)), organic cobalt complex, etc. Examples of the ligand constituting the complex include OH (hydroxyl group), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (acetyl group, propionyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), acetylacetonyl group, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H 2 O (hydrated), phosphorus compounds of phosphine (triphenylphosphine and other triarylphosphines, etc.), NH 3 (ammonium compound), NO, NO 2 (Nitro), NO3 (nitrate group), ethylenediamine, diethylenetriamine, pyridine, phenanthroline and other nitrogen-containing compounds, etc.

[0078] Examples of xenon compounds include XeF 2 、XeF 4 、XeF 6 、XeOF 2 、XeOF 4 、XeO 2 F 4 Fluoride, XeO 3 、XeO 4 Oxides; Xenon acid Xe(OH) 6 and its salts 3 XOt 6 etc.; Perxenic acid H 4 XOt 6 and its salt Na 4 XOt 6 ; Complex with metal carbonyl M(CO) 5 Xe (M = Cr, Mo, W), hydrates, etc.

[0079] Examples of the chromium compound include chromium acetylacetonate complexes such as chromium acetylacetonate, chromium alkoxides such as chromium (III) isopropoxide, organic acid chromium such as chromium (II) acetate and chromium (III) diacetate, tri(allyl)chromium, tri(methallyl)chromium, tri(crotyl)chromium, bis(cyclopentadienyl)chromium (i.e., chromocene), bis(pentamethylcyclopentadienyl)chromium (i.e., decamethylchromocene), bis(benzene)chromium, bis(ethylbenzene)chromium, bis(mesitylene)chromium, bis(pentadienyl)chromium, bis(2,4-dimethylpentadienyl)chromium, bis(allyl)chromium tricarbonyl, (cyclopentadienyl)(pentadienyl)chromium, tetra(1-norbornyl)chromium, (trimethylenemethane)tetracarbonylchromium, bis(butadiene)dicarbonylchromium, (butadiene)tetracarbonylchromium, and organic chromium compounds such as bis(cyclooctatetraene)chromium.

[0080] As tungsten compounds, for example, there can be listed: inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, sodium tungstate, boron atom coordinated tungsten complexes such as ethylborylethylidene ligands; carbon atom coordinated tungsten complexes such as carbonyl ligands, cyclopentadienyl ligands, alkyl ligands, olefin ligands, etc.; nitrogen atom coordinated tungsten complexes such as pyridine ligands and acetonitrile ligands; phosphorus atom coordinated tungsten complexes coordinated with phosphine ligands, phosphite ligands, etc.; organic tungsten compounds such as sulfur atom coordinated tungsten complexes coordinated with diethylthiocarbamate ligands, etc.

[0081] Examples of the thallium compound include inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide, and thallium iodide; trialkyl thallium compounds such as trimethyl thallium, triethyl thallium, and triisobutyl thallium; aryl thallium compounds such as dialkyl thallium halides, alkenyl dialkyl thallium, alkynyl dialkyl thallium, triphenyl thallium, and tritolyl thallium; diaryl thallium halides; thallium 2-ethylhexanoate, thallium malonic acid, thallium formate, thallium ethoxide, and thallium acetylacetonate.

[0082] Examples of the zirconium compound include inorganic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide and zirconium iodide; and organic zirconium compounds such as zirconium n-propoxide, zirconium n-butoxide, zirconium tert-butoxide, zirconium isopropoxide, zirconium ethoxide, zirconium acetate, zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetylacetate, zirconium acetylacetonate bisethylacetoacetate, zirconium hexafluoroacetylacetonate and zirconium trifluoroacetylacetonate.

[0083] Examples of the zinc compound include diethyl zinc, dimethyl zinc, zinc acetate, zinc nitrate, zinc stearate, zinc oleate, zinc palmitate, zinc myristate, zinc dodecanoate, zinc acetylacetonate, zinc chloride, zinc bromide, zinc iodide, and zinc carbamate.

[0084] Examples of the silver compound include organic silver compounds such as silver acetate, silver pivalate, silver trifluoromethanesulfonate, and silver benzoate; silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate, and silver hexafluorophosphate (AgPF). 6 ), silver hexafluoroantimonate (AgSbF 6 ) and other inorganic silver compounds.

[0085] Examples of the aluminum compound include inorganic aluminum compounds such as alumina; alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum; acyloxy compounds such as triacetoxyaluminum, aluminum tristearate, and aluminum tributylate; aluminum isopropionate, aluminum sec-butyrate, aluminum tert-butyrate, aluminum tri(ethylacetoacetate), aluminum tri(hexafluoroacetylacetonate), aluminum tri(ethylacetoacetate), aluminum tri(n-propylacetoacetate), aluminum tri(isopropylacetoacetate), aluminum tri(n-butylacetoacetate), aluminum trisalicylate, aluminum tri(2-ethoxycarbonylphenol), aluminum tri(acetylacetonate), aluminum trimethylaluminum, triethylaluminum, and triisobutylaluminum; aryl aluminum such as dialkylaluminum halides, alkenyldialkylaluminum, alkynyldialkylaluminum, triphenylaluminum, and tritolylaluminum; and organic aluminum compounds such as diarylaluminum halides.

[0086] Examples of vanadium compounds include vanadic acid and metavanadic acid, and inorganic vanadium compounds such as alkali metal salts thereof; alkoxides such as triethoxyvanadium, pentaethoxyvanadium, tripentoxyvanadium, and triisopropoxyvanadium; acetonates such as bisacetylacetonatovanadium, acetylacetonatovanadium, acetylacetonatovanadium, and oxyacetylacetonatovanadium; and organic vanadium compounds such as vanadium stearate, trimethylacetate, and acetate.

[0087] Examples of the niobium compound include halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobic acid, and niobates, and organic niobium compounds such as niobium alkoxides.

[0088] Examples of tantalum compounds include TaCl 5 、TaF 5 Inorganic tantalum compounds, Ta(OC 2 H 5 ) 5 、Ta(OCH 3 ) 5 、Ta(OC 3 H 7 ) 5 、Ta(OC 4 H 9 ) 5 , (C 5 H 5 ) 2 T H 3 、Ta(N(CH 3 ) 2 ) 5 And other organic tantalum compounds, etc.

[0089] Examples of the molybdenum compound include inorganic molybdenum compounds such as molybdenum trioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdic acid, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide; and organic molybdenum compounds such as dialkyl molybdenum dithiophosphates and dialkyl molybdenum dithiocarbamates.

[0090] Examples of the manganese compound include inorganic manganese compounds such as manganese hydroxide, nitrate, acetate, sulfate, chloride and carbonate; and organic manganese compounds including manganese oxalate, manganese acetylacetonate, or manganese alkoxides such as manganese methoxide, manganese ethoxide and manganese butoxide.

[0091] Examples of the iron compound include iron (II) fluoride, iron (III) fluoride, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) iodide, iron (III) iodide, iron (II) oxide, iron (III) oxide, iron (II, III) tetroxide, iron (II) sulfate, iron (III) sulfate, iron (II) nitrate, iron (III) nitrate, iron (II) hydroxide, iron (III) hydroxide, iron (II) perchlorate, iron (III) perchlorate, ammonium iron (II) sulfate, ammonium iron (III) sulfate, iron (III) tungstate oxide, iron (III) tetravanadate, iron (II) selenide, titanium iron (II) oxide, titanium iron (III) pentoxide, iron (II) sulfide, iron (III) sulfide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (II) phosphide, iron (III ... ), iron (III) phosphide and other inorganic iron compounds; iron (II) acetate, iron (III) acetate, iron (II) formate, iron (III) triformate, iron (II) tartrate, sodium iron (III) tartrate, iron (II) lactate, iron (II) oxalate, iron (III) oxalate, ammonium iron (III) citrate, iron (III) laurate, iron (III) stearate, iron (III) tripalmitate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), bis (2,4-pentanedione) iron (II) dihydrate, tris (2,4-pentanedione) iron (III), potassium tris (oxalato) iron (III), tris (trifluoromethanesulfonate) iron (III), iron (III) p-toluenesulfonate, dimethyldithiocarbamate iron (III), diethyldithiocarbamate iron (III), ferrocene and other organic iron compounds.

[0092] Examples of the copper compound include organic copper compounds such as copper oxalate, copper stearate, copper formate, copper tartrate, copper oleate, copper acetate, copper gluconate, and copper salicylate; and inorganic copper compounds such as natural minerals such as copper carbonate, copper chloride, copper bromide, copper iodide, copper phosphate, hydrotalcite, stichtite, and pyrite.

[0093] Examples of the cadmium compound include inorganic cadmium compounds such as cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, cadmium oxide, and cadmium carbonate; and organic cadmium compounds such as cadmium phthalate and cadmium naphthoate.

[0094] Examples of the mercury compound include inorganic mercury compounds such as mercuric chloride, mercuric sulfate, and mercuric nitrate; and organic mercury compounds such as methylmercury, methylmercury chloride, ethylmercury, ethylmercury chloride, phenylmercury acetate, thimerosal, p-chloromercuric benzoate, and mercuric acetate fluorescein.

[0095] Examples of the gallium compound include organic gallium compounds such as tetraphenylgallium and tetrakis(3,4,5-trifluorophenyl)gallium, and inorganic gallium compounds such as oxoacid gallium, gallium halide, gallium hydroxide, and gallium cyanide.

[0096] Examples of the indium compound include organic indium compounds such as triethoxyindium, indium 2-ethylhexanoate, and indium acetylacetonate; and inorganic indium compounds such as indium cyanide, indium nitrate, indium sulfate, indium carbonate, indium fluoride, indium chloride, indium bromide, and indium iodide.

[0097] Arsenic compounds include, for example, arsenic trioxide, arsenic pentoxide, arsenic trichloride, arsenic pentachloride, arsenous acid, arsenic acid, and inorganic arsenic compounds such as sodium arsenite, ammonium arsenite, potassium arsenite, ammonium arsenate, and potassium arsenate as their salts; and organic arsenic compounds such as dimethylarsenic acid, phenylarsonic acid, diphenylarsonic acid, p-hydroxyphenylarsonic acid, p-aminophenylarsonic acid, and sodium dimethylarsenate and potassium dimethylarsenate as their salts.

[0098] Examples of the antimony compound include antimony oxide, antimony phosphate, KSb(OH), NH 4 Sb 6 Inorganic antimony compounds such as antimony esters with organic acids, cyclic alkyl antimonite esters, and organic antimony compounds such as triphenyl antimony.

[0099] Examples of the bismuth compound include organic bismuth compounds such as triphenylbismuth, bismuth 2-ethylhexanoate, and bismuth acetylacetonate; and inorganic bismuth compounds such as bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth hydroxide, bismuth fluoride, bismuth chloride, bismuth bromide, and bismuth iodide.

[0100] Examples of the selenium compound include organic selenium compounds such as selenomethionine, selenocysteine, and selenocystine, and inorganic selenium compounds including alkali metal selenates such as potassium selenate and alkali metal selenites such as sodium selenite.

[0101] Examples of the tellurium compound include telluric acid and salts thereof, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide, and telluride alkoxides.

[0102] Examples of the magnesium compound include organic magnesium compounds such as magnesium ethylacetoacetate monoisopropionate, magnesium bis(ethylacetoacetate), magnesium alkylacetoacetate monoisopropionate, and magnesium bis(acetylacetonate); and inorganic magnesium compounds such as magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium chloride.

[0103] Examples of the calcium compound include organic calcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxide, calcium methoxide, and calcium acetylacetonate; and inorganic calcium compounds such as calcium nitrate, calcium sulfate, calcium carbonate, calcium phosphate, calcium hydroxide, calcium cyanide, calcium fluoride, calcium chloride, calcium bromide, and calcium iodide.

[0104] The elements doped in nanodiamonds include Li, Na, K, Cs, S, Sr, Ba, F, Y, and compounds of lanthanide elements, and known organic or inorganic compounds can be used.

[0105] In a composition containing an explosive, a carbon group element compound, and, if necessary, a third element compound, the proportion of the explosive is preferably 80 to 99.9999 mass%, more preferably 85 to 99.999 mass%, further preferably 90 to 99.99 mass%, and particularly preferably 95 to 99.9 mass%, the proportion of the carbon group element compound is preferably 0.0001 to 20 mass%, more preferably 0.001 to 15 mass%, further preferably 0.01 to 10 mass%, and particularly preferably 0.1 to 5 mass%, and the proportion of the third element compound is preferably 0 to 20 mass%, more preferably 0.001 to 15 mass%, further preferably 0.01 to 10 mass%, and particularly preferably 0.02 to 8 mass%. In addition, in a mixture containing an explosive, a carbon group element compound, and further containing a third element as needed, the carbon group element content is preferably 0.000005 to 10 mass%, more preferably 0.00001 to 8 mass%, further preferably 0.0001 to 5 mass%, particularly preferably 0.001 to 3 mass%, and most preferably 0.01 to 1 mass%, and the third element content is preferably 0 to 10 mass%, more preferably 0.00001 to 8 mass%, further preferably 0.00002 to 5 mass%, particularly preferably 0.00003 to 3 mass%, and most preferably 0.00004 to 2 mass%.

[0106] The preferred doped nanodiamond obtained by the production method of the present invention contains the third element in an amount of preferably 0.001 to 100 mol, more preferably 0.002 to 10 mol, and even more preferably 0.003 to 5 mol, per 1 mol of the carbon group element.

[0107] The explosive, the carbon group element compound, and the further third element compound as required can be mixed in the form of powders when they are solid, can be melted, or can be dissolved or dispersed in a suitable solvent for mixing. The mixing can be carried out by stirring, bead milling, ultrasonic waves, etc.

[0108] In a preferred embodiment, the explosive composition containing explosives, carbon group element compounds, and further containing a third element compound as needed further contains a cooling medium. The cooling medium can be in any form of solid, liquid, or gas. As a method of using a cooling medium, a method of detonating a mixture of explosives, carbon group element compounds, and a third element compound further used as needed in a cooling medium can be cited. As cooling media, inert gases (nitrogen, argon, CO), water, ice, liquid nitrogen, aqueous solutions containing carbon group element salts, crystalline hydrates, aqueous solutions containing third element salts, crystalline hydrates, etc. can be cited. As carbon group element salts, ammonium hexafluorosilicate, ammonium silicate, tetramethylammonium silicate, etc. can be cited. When the cooling medium is, for example, water or ice, it is preferably used about 5 times relative to the weight of the explosive.

[0109] In a preferred embodiment of the present invention, an explosive composition containing an explosive, a carbon group element compound, and a third element compound further used as needed is converted into diamond by compression caused by a shock wave under high pressure and high temperature conditions generated by the explosion of the explosive (detonation method). When the explosive explodes, at least one carbon group element atom is introduced into the diamond lattice, and at least one third element is further introduced as needed. The carbon source of nanodiamond can be an explosive, an organic carbon group element compound, and a third element compound further used as needed, but when the mixture containing an explosive, a carbon group element compound, and a third element compound further used as needed also contains a carbon material that does not contain a carbon group element and a third element, the carbon material may also become the carbon source of nanodiamond.

[0110] In the manufacturing method and purification method of the present invention, the purification of the nanodiamond composition doped with a carbon group element and further doped with a third element as required includes an alkali treatment step, and the alkali treatment and the mixed acid treatment may also be combined, wherein the nanodiamond composition comprises a single substance and / or an oxide of a carbon group element and further comprises a single substance and / or an oxide of a third element as required. A preferred purification step is a combination of the alkali treatment and the mixed acid treatment (regardless of the order).

[0111] The mixed acid may be a mixed acid of concentrated sulfuric acid and concentrated nitric acid, preferably a mixed acid of concentrated sulfuric acid:concentrated nitric acid=1:1 (volume ratio). The temperature of the mixed acid treatment is 50 to 200° C., and the time of the mixed acid treatment is 0.5 to 24 hours.

[0112] Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the alkali metal hydroxide include 0.1 to 10 N alkali metal hydroxide aqueous solutions. The temperature of the alkali treatment is 30 to 150° C., and the time of the alkali treatment is 0.5 to 24 hours.

[0113] When an explosive composition containing explosives, carbon group element compounds, and, if necessary, a third element is detonated in a container, graphite, metal impurities, carbon group element single substances (Si single substance, Ge single substance, Sn single substance, Pb single substance), carbon group element oxides (SiO 2 ,GeO 2 SnO 2 , PbO 2 ), a third element single substance, a third element oxide, etc. Graphite and metal impurities, a third element single substance, and a third element oxide can be removed by mixed acid treatment, and a carbon group element single substance and a carbon group element oxide can be removed by alkali treatment.

[0114] The nanodiamond doped with a carbon group element and further doped with a third element as required, obtained by the production method or purification method of the present invention, in a preferred embodiment, has a fluorescence emission peak in the range of 720 to 770 nm and satisfies the following requirements (i) and / or (ii):

[0115] (i) BET specific surface area is 20 to 900 m 2 / g;

[0116] (ii) The average size of the primary particles is 2 to 70 nm.

[0117] The doped nanodiamond obtained by the manufacturing method or purification method of a preferred embodiment of the present invention contains a carbon group element V (vacancy) center, and further contains a third element V center as needed, thereby having a fluorescence peak. When the carbon group element is Si, the wavelength of the fluorescence peak is preferably 720 to 770 nm, more preferably 730 to 760 nm, when the carbon group element contains silicon, preferably 580 to 630 nm, more preferably 590 to 620 nm, when the carbon group element contains germanium, preferably 590 to 650 nm, more preferably 600 to 640 nm, when the carbon group element contains tin, preferably 540 to 600 nm, more preferably 550 to 590 nm. In a more preferred embodiment of the present invention, the fluorescence peak of the nanodiamond whose carbon group element is Si includes a peak of about 738 nm called ZPL (zero phonon level).

[0118] In the nanodiamond doped with a carbon group element and further doped with a third element as required, the concentration of the carbon group element V center is preferably 1×10 10 / cm 3 More preferably, 2×10 10 ~1×1019 / cm 3 The concentration of the third element V center is preferably 1×10 10 / cm 3 More preferably, 2×10 10 ~1×10 19 / cm 3 It can be inferred that the concentration of the carbon group element V center and the third element V center can be identified, for example, by using a confocal laser microscope or a fluorescence absorption spectrometer. It should be noted that the determination of the concentration of the MV center (M is a carbon group element or a third element) by fluorescence absorption analysis can be referred to the literature (DOI 10.1002 / pssa.201532174).

[0119] The BET specific surface area of ​​the nanodiamond doped with a carbon group element and, if necessary, further doped with a third element obtained by the production method or purification method of the present invention is preferably 20 to 900 m 2 / g, more preferably 25 to 800 m 2 / g, more preferably 30 to 700 m 2 / g, particularly preferably 35 to 600 m 2 / g. The BET specific surface area can be measured by nitrogen adsorption. The BET specific surface area measurement device includes, for example, BELSORP-mini II (manufactured by Microtrac BEL Co., Ltd.), and the BET specific surface area can be measured, for example, under the following conditions.

[0120] ·Measured powder amount: 40mg

[0121] Pre-drying: 120℃, vacuum for 3 hours

[0122] ·Measurement temperature: -196℃ (liquid nitrogen temperature)

[0123] The average size of the primary particles of the doped nanodiamond obtained by the manufacturing method or purification method of the present invention is preferably 2 to 70 nm, more preferably 2.5 to 60 nm, further preferably 3 to 55 nm, and particularly preferably 3.5 to 50 nm. The average size of the primary particles can be obtained by the analysis results of the powder X-ray diffraction method (XRD) and by the Scherrer formula. The measuring device of XRD can include, for example, a fully automatic multifunctional X-ray diffraction device (manufactured by Rigaku Co., Ltd.).

[0124] The carbon content of the doped nanodiamond obtained by the production method or purification method of the present invention is preferably 70 to 99 mass %, more preferably 75 to 98 mass %, and even more preferably 80 to 97 mass %.

[0125] The hydrogen content of the doped nanodiamond obtained by the production method or purification method of the present invention is preferably 0.1 to 5 mass %, more preferably 0.2 to 4.5 mass %, and even more preferably 0.3 to 4.0 mass %.

[0126] The nitrogen content of the doped nanodiamond obtained by the production method or purification method of the present invention is preferably 0.1 to 5 mass %, more preferably 0.2 to 4.5 mass %, and even more preferably 0.3 to 4.0 mass %.

[0127] The contents of carbon, hydrogen and nitrogen in the doped nanodiamond obtained by the production method or purification method of the present invention can be measured by elemental analysis.

[0128] The carbon group element content of the doped nanodiamond obtained by the manufacturing method or purification method of the present invention is preferably 0.0001 to 10.0 mass %, more preferably 0.0001 to 5.0 mass %, further preferably 0.0001 to 1.0 mass %, and the third element content is preferably 0.0001 to 10.0 mass %, more preferably 0.0001 to 5.0 mass %, further preferably 0.0001 to 1.0 mass %. The carbon group element content and the third element content can be measured, for example, by inductively coupled plasma emission spectrometry (ICP-AES, XRF, SIMS (secondary ion mass spectrometry), and the doped nanodiamond can be quantitatively prepared by making an acidic solution after alkali melting.

[0129] The doped nanodiamond obtained by the manufacturing method or purification method of a preferred embodiment of the present invention can be identified by Raman spectroscopy in the Raman shift spectrum of diamond, graphite, surface hydroxyl (OH), and surface carbonyl (CO) characteristic peaks. The characteristic peak of diamond in the Raman shift spectrum is 1100-1400 cm -1 The characteristic peak of graphite is 1450~1700cm -1 The characteristic peak of surface hydroxyl (OH) is 1500~1750cm -1 The characteristic peak of the surface carbonyl (CO) is 1650-1800 cm -1 The areas of characteristic peaks of diamond, graphite, surface hydroxyl (OH), and surface carbonyl (CO) are shown by the Raman spectrometer. The laser wavelength of the Raman light source is, for example, 325 nm or 488 nm. As the Raman spectrometer, a confocal microscopic Raman spectrometer (for example, trade name: Microscopic Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) can be used.

[0130] In a preferred embodiment of the doped nanodiamond obtained by the production method or purification method of the present invention, the ratio (D / G) of the peak area of ​​diamond (D) to the peak area of ​​graphite (G) is preferably 0.2-9, more preferably 0.3-8, and further preferably 0.5-7.

[0131] In a preferred embodiment of the doped nanodiamond obtained by the production method or purification method of the present invention, the ratio (H / D) of the peak area (H) of the surface hydroxyl group (OH) to the peak area (D) of diamond is preferably 0.1 to 5, more preferably 0.1 to 4.0, and further preferably 0.1 to 3.0.

[0132] In a preferred embodiment of the doped nanodiamond obtained by the production method or purification method of the present invention, the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) to the peak area (D) of diamond is preferably 0.01 to 1.5, more preferably 0.03 to 1.2, and further preferably 0.05 to 1.0.

[0133] As a Raman analysis method for nanodiamond, reference may be made to the literature (for example, Vadym N. Mochalin et al., NATURE NANOTECHNOLOGY, 7 (2012) 11-23, especially FIG. 3 ).

[0134] In another preferred embodiment of the present invention, the surface of the doped nanodiamond obtained by the manufacturing method or purification method of the present invention may have at least one oxygen functional group terminal and / or at least one hydrogen terminal. Examples of the oxygen functional group terminal include OH, COOH, CONH 2 , C═O, CHO, etc., preferably OH, C═O, COOH. Examples of the hydrogen terminal include an alkyl group having 1 to 20 carbon atoms.

[0135] The presence of at least one oxygen functional group terminal on the surface of the doped nanodiamond suppresses the aggregation of the nanodiamond particles, which is preferred. The presence of at least one hydrogen terminal on the surface of the doped nanodiamond makes the Zeta (ζ) potential positive, and the nanodiamond is stable and highly dispersed in an acidic aqueous solution, which is preferred.

[0136] In another preferred embodiment of the present invention, the doped nano-diamond obtained by the manufacture method of the present invention or the purification method can also have a core-shell structure. The core of the doped nano-diamond of the core-shell structure is a nano-diamond particle doped with carbon group element atoms, further doped with the third element as required. Preferably, the core has a carbon group element V center, further has a third element V center as required and emits fluorescence. The shell is a non-diamond coating layer, can contain sp2 carbon, preferably further contains oxygen atoms. The shell can also be a graphite layer. The thickness of the shell is preferably below 5nm, more preferably below 3nm, and further preferably below 1nm. The shell can have a hydrophilic functional group on the surface.

[0137] The doped nanodiamond can be preferably manufactured by a detonation method. The shape of the doped nanodiamond is preferably spherical, ellipsoidal or polyhedral shapes similar thereto.

[0138] Roundness refers to a numerical value for representing the complexity of a figure depicted by an image, etc. For roundness, the maximum value is set to 1, and the more complex the figure, the smaller the numerical value. Roundness can be analyzed using image analysis software (e.g., winROOF) to analyze a TEM image of doped nanodiamond and obtained by the following formula.

[0139] Circularity = 4π×(area)÷(circumference)^2

[0140] For example, in the case of a perfect circle with a radius of 10, the calculation formula is "4π×(10×10×π)÷(10×2×π)^2". The result is that the roundness is 1 (maximum value). In other words, a perfect circle is the least complex figure in terms of roundness. The roundness of the doped nanodiamond is preferably greater than 0.2, more preferably greater than 0.3, and further preferably greater than 0.35.

[0141] In a preferred embodiment of the present invention, the center of doped nano-diamond particles has the diamond structure that comprises sp3 carbon, the carbon group element of doping and further comprises the 3rd element as required, and its surface is covered by the amorphous layer that is made of sp2 carbon.In a further preferred embodiment, the outside of amorphous layer can be covered by graphite oxide layer.In addition, also can be formed with hydration layer between amorphous layer and graphite oxide layer.

[0142] In a preferred embodiment of the present invention, the doped nanodiamond obtained by the production method or purification method of the present invention has a positive or negative Zeta potential. The Zeta potential of the doped nanodiamond is preferably -70 to 70 mV, more preferably -60 to 30 mV.

[0143] Doped nanodiamonds can be manufactured by a manufacturing method comprising the following steps: a step of mixing an explosive composition containing an explosive, a carbon group element compound, and a third element compound as required; a step of exploding the obtained mixture in a closed container. As containers, metal containers and synthetic resin containers can be listed. The explosive composition containing an explosive, a carbon group element compound, and a third element compound as required is preferably formed by pressing or casting. As methods for making individual particles (dry powders) of explosives, carbon group element compounds, and third element compounds, crystallization, crushing, and spray flash evaporation can be listed. In the case of molding the explosive composition by pressing or casting, the explosive, the carbon group element compound, and the third element compound further used as required are mixed in a dry powder or molten state or mixed using a solvent. The state of the explosive and the carbon group element compound when mixed can be any combination of the following four types:

[0144] ·Explosives (dry powder) and carbon group element compounds (dry powder)

[0145] ·Explosives (dry powder) and carbon group element compounds (molten state)

[0146] ·Explosives (molten state) and carbon group element compounds (dry powder)

[0147] ·Explosives (molten state) and carbon group element compounds (molten state)

[0148] When a third element compound is further mixed to form an explosive composition, the third element compound can be a dry powder or a molten state. Therefore, there are eight combinations of dry powder and molten state of the explosive, carbon group element compound and third element compound when mixed.

[0149] The explosive, the carbon group element compound, and the third element compound used as required may be mixed in the presence or absence of a solvent, and may be molded by a pressing method or a casting method after mixing.

[0150] The average particle size of the explosive, the carbon group element compound, and the third element compound is preferably 10 mm or less, more preferably 5 mm or less, and further preferably 1 mm or less. It should be noted that their average particle sizes can be measured by laser diffraction / scattering method, optical microscope, or Raman method.

[0151] The product obtained by the explosion may be further subjected to a purification step or a post-treatment step including an alkali treatment and, if necessary, a mixed acid treatment.

[0152] The post-treatment process may include annealing and gas phase oxidation. Through annealing, the carbon group element doped in the doped nanodiamond and the third element as needed can meet with defects (vacancy) to form a carbon group element V center and a third element V center as needed. In addition, the graphite layer formed on the surface of the doped nanodiamond can be thinned or removed by gas phase oxidation. Although it is an optional process, the hole formation process can also be performed before annealing. The hole formation process is performed by irradiation with an ion beam or an electron beam. Even if the hole formation process is not performed, the carbon group element V center and the third element V center as needed can be formed by annealing, but by annealing after the hole formation process, more carbon group element V centers and the third element V centers as needed can be formed. The upper limit of the hole density introduced by ion beam irradiation or electron beam irradiation is limited by the concentration at which the diamond is destroyed (>1×10 21 / cm 3 The lower limit is, for example, 1×10 16 / cm 3 Above, further 1×10 18 / cm 3 The ion beam is preferably a hydrogen (H) or helium (He) ion beam. For example, the energy of the hydrogen ion beam is preferably 10 to 1500 keV, and the energy of the helium ion beam is preferably 20 to 2000 keV. The energy of the electron beam is preferably 500 to 5000 keV.

[0153] The annealing temperature is preferably 800° C. or higher, and the annealing time is preferably 30 minutes or longer.

[0154] The gas phase oxidation can be performed in an air atmosphere. The gas phase oxidation temperature is preferably 300° C. or higher, and the gas phase oxidation time is preferably 2 hours or longer.

[0155] Example

[0156] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0157] Examples 1 to 6

[0158] When TNT is used as an explosive and the dopants shown in Table 1 are used as carbon group element compounds in the molar numbers shown in Table 1 relative to 1 mol of TNT, and silicon-doped nanodiamonds are manufactured by the detonation method according to the conventional method under the conditions of temperature (K) and pressure (GPa) shown in Table 1, nanodiamonds doped with silicon in the proportions shown in Table 1 can be obtained.

[0159] The names and structural formulas of dopant molecules (silicon compounds) 1 to 6 for doping silicon are shown below.

[0160] Dopant molecule 1: Silline

[0161] Dopant molecule 2: Tetramethylsilane (SiMe 4 )

[0162] Dopant molecule 3: Tetrakis(methylnitrate)silane (SiPETN)

[0163] Dopant molecule 4: Tetrakis(dimethylsilanol)silane (Si(SiMe 2 OH) 4 )

[0164] Dopant molecule 5: Tetrakis(trimethylsilyl)silane (Si(SiMe 3 ) 4 )

[0165] Dopant molecule 6: tetrakis(trimethylsilyl)methane (C(SiMe 3 ) 4 )

[0166] [Chemical formula 1]

[0167]

[0168] [Table 1]

[0169]

[0170] As is clear from Table 1, according to the present invention, nanodiamonds into which a large amount of silicon atoms are introduced can be obtained.

[0171] Example 7

[0172] Silicon-doped nanodiamonds were prepared using about 60 g of an explosive composition obtained by adding 10 parts by mass, 1 part by mass or 0.1 part by mass of triphenylsilanol as a silicon compound to 100 parts by mass of an explosive containing trinitrotoluene (TNT) and cyclotrimethylene trinitramine (RDX) respectively. The silicon-doped nanodiamonds were treated as follows. It should be noted that the amount of triphenylsilanol added to the explosive was 10%, 1% or 0.1% by mass.

[0173] (i) Mixed acid treatment

[0174] 15 g of the nanodiamond obtained in the detonation test was added to 2800 g of a mixed acid of concentrated sulfuric acid:concentrated nitric acid=11:1 (weight ratio), and the mixture was treated at 150° C. for 10 hours while being stirred.

[0175] (ii) Alkali treatment

[0176] 1 g of the nanodiamond treated with mixed acid was added to 100 mL of 8N sodium hydroxide aqueous solution, and the mixture was treated at 100° C. for 10 hours while being stirred.

[0177] (iii) Annealing

[0178] The alkali-treated nanodiamond was annealed at 800° C. for 30 minutes in a vacuum atmosphere.

[0179] (iv) Gas phase oxidation

[0180] The annealed nanodiamond was subjected to a gas phase oxidation treatment at 300° C. for 2 hours in an air atmosphere, thereby obtaining the silicon-doped nanodiamond of the present invention.

[0181] (v) Fluorescence analysis

[0182] A 10 w / v% aqueous suspension of the silicon-doped nanodiamond of the present invention obtained by gas phase oxidation was dripped onto a glass substrate and dried to prepare an evaluation sample. The obtained evaluation sample was subjected to high-speed mapping using a microscopic Raman spectrometer (trade name: Microscopic Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) and 738 nm bright spot imaging was performed. The 738 nm bright spot imaging image of the silicon-doped nanodiamond obtained by using triphenylsilanol as the silicon compound and adding 1 mass % in terms of external ratio is shown in FIG. Figure 1 (a) Figure 1 The fluorescence spectrum of the bright spot (a) is shown in Figure 1 (b). The zero phonon line (fluorescence peak) of the SiV center can be confirmed. The Si content of the obtained silicon-doped nanodiamond is 3.2 mass % when the addition amount of triphenylsilanol in the explosive is 10 mass %, 0.15 mass % when the addition amount is 1 mass %, and 0.03 mass % when the addition amount is 0.1 mass %.

[0183] according to Figure 1 (b) It was confirmed that the silicon-doped nanodiamond of the present invention has fluorescence at 738 nm originating from the SV center. Furthermore, the average size of primary particles and the BET specific surface area of ​​the obtained silicon-doped nanodiamond measured by XRD are shown in Table 2 below.

[0184] [Table 2]

[0185]

[0186] Determination of BET specific surface area

[0187] Device: BELSORP-mini II (manufactured by Microtrac BEL Co., Ltd.)

[0188] Measured powder amount: 40mg

[0189] Pre-drying: 120℃, vacuum treatment for 3 hours

[0190] Measuring temperature: -196℃ (liquid nitrogen temperature)

[0191] · Determination of the average size of primary particles (powder X-ray diffraction (XRD))

[0192] Equipment: Fully automatic multifunctional X-ray diffraction equipment (manufactured by Rigaku Corporation)

[0193] ·Determination of Si introduction amount (XRF)

[0194] Equipment: Fluorescent X-ray Analyzer ZSX Primus IV, manufactured by Rigaku Corporation

[0195] The XRF measurement results before and after the alkali treatment are shown in Table 3, and the XRD measurement results before and after the alkali treatment are shown in Table 3. Figure 2 .

[0196] [Table 3]

[0197]

[0198] ※ quality%

[0199] In Table 3, the amount of Si after the alkali treatment measured by XRF was significantly reduced compared to that before the alkali treatment. Therefore, the alkali treatment was effective in removing Si.

[0200] exist Figure 2 middle,

[0201] There is a broad peak derived from an amorphous compound at around 23°.

[0202] According to the XRF measurement results, Si is the largest in amount besides diamond, so it is considered that this peak originates from Si compounds.

[0203] In the graph after the alkali treatment, the broad peak near 23° disappeared, and thus it is considered that the Si compound was removed by the alkali treatment.

[0204] Example 8

[0205] Nanodiamond doped with silicon and boron was obtained in the same manner as in Example 7 except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of phenylboric acid were used instead of 1 part by mass of triphenylsilanol in Example 7.

[0206] Example 9

[0207] Nanodiamond doped with silicon and phosphorus was obtained in the same manner as in Example 7 except that 0.5 parts by mass of triphenylsilanol and 0.5 parts by mass of triphenylphosphine were used instead of 1 part by mass of triphenylsilanol in Example 7.

Claims

1. A method for producing nanodiamond doped with carbon group elements, the method include: A step of treating the nanodiamond composition containing at least one carbon group element selected from Si, Ge, Sn and Pb and / or its oxide, and the nanodiamond doped with the carbon group element with an alkali to remove the carbon group element and / or its oxide. The nanodiamond doped with carbon group elements satisfies the following requirements (i) to (iii): (i) The average size of the primary particles is 2 to 70 nm; (ii) the ratio H / D of the peak area H of the surface hydroxyl groups OH to the peak area D of diamond is 0.1 to 5; and (iii) The ratio C / D of the peak area C of the surface carbonyl CO to the peak area D of diamond is 0.01 to 1.

5.

2. The manufacturing method according to claim 1, in, The method includes: Detonating an explosive composition containing at least one explosive and at least one carbon group element compound in a sealed container to obtain a nanodiamond composition containing at least one carbon group element and / or its oxide selected from Si, Ge, Sn and Pb, and the nanodiamond doped with the carbon group element; and A process of treating the nanodiamond composition with alkali to remove the carbon group element and / or its oxide.

3. The manufacturing method according to claim 2, in, The explosive composition further comprises a compound containing at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

4. The manufacturing method according to claim 1 or 2, in, Before or after the alkali treatment step, a mixed acid treatment step is further included in which the nanodiamond doped with carbon group elements is treated with a mixed acid of concentrated nitric acid and concentrated sulfuric acid.

5. The manufacturing method according to claim 1 or 2, in, The nanodiamond composition further contains at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements and / or its oxide.

6. The manufacturing method according to claim 1 or 2, in, The nanodiamond is further doped with at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

7. A method for purifying nanodiamonds doped with carbon group elements, the method comprising: include: A step of treating the nanodiamond composition containing at least one carbon group element selected from Si, Ge, Sn and Pb and / or its oxide, and the nanodiamond doped with the carbon group element with an alkali to remove the carbon group element and / or its oxide. The nanodiamond doped with carbon group elements satisfies the following requirements (i) to (iii): (i) The average size of the primary particles is 2 to 70 nm; (ii) the ratio H / D of the peak area H of the surface hydroxyl groups OH to the peak area D of diamond is 0.1 to 5; and (iii) The ratio C / D of the peak area C of the surface carbonyl CO to the peak area D of diamond is 0.01 to 1.

5.

8. The purification method according to claim 7, in, Detonating an explosive composition containing at least one explosive and at least one carbon group element compound in a sealed container to obtain a nanodiamond composition containing at least one carbon group element and / or its oxide selected from Si, Ge, Sn and Pb, and the nanodiamond doped with the carbon group element; and A process of treating the nanodiamond composition with alkali to remove the carbon group element and / or its oxide.

9. The purification method according to claim 8, in, The explosive composition further comprises a compound containing at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

10. The purification method according to claim 7 or 8, in, Before or after the alkali treatment step, a mixed acid treatment step is further included in which the nanodiamond doped with carbon group elements is treated with a mixed acid of concentrated nitric acid and concentrated sulfuric acid.

11. The purification method according to claim 7 or 8, in, The nanodiamond composition further contains at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements and / or its oxide.

12. The purification method according to claim 7 or 8, in, The nanodiamond is further doped with at least one third element selected from B, P, S, Cr, Al, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y and lanthanide elements.

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