Explosive composition and method for manufacturing the same, and method for manufacturing heteroatom-doped nanodiamond

Abstract

To provide an explosive composition suitable for production of a nanodiamond doped with a heteroatom, a method for producing the explosive composition, and a method for producing a heteroatom-doped nanodiamond.SOLUTION: The present invention provides an explosive composition comprising at least one explosive and at least one heteroatom compound, the heteroatom compound comprising at least one heteroatom selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanoid.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an explosive composition and a method for producing the same, and a method for producing heteroatom-doped nanodiamond. [Background technology]

[0002] Diamond luminescence centers are nano-sized, chemically stable fluorescent chromophores that do not decompose, fade, or blink in vivo, as is the case with many organic fluorescent materials, and so are expected to be used as fluorescence imaging probes. In addition, because it is sometimes possible to measure the spin information of electrons excited in the luminescence center from outside, they are also expected to be used in ODMR (Optically Detected Magnetic Resonance) and as quantum bits.

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

[0004] Silicon- or boron-doped diamond is produced by a CVD method or the like (Patent Documents 1 to 4).

[0005] Patent Document 5 discloses an explosive composition for diamond synthesis, which contains one or more types of high explosives and diamond powder. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special table 2014-504254 [Patent Document 2] Patent Publication No. 2004-176132 [Patent Document 3] Patent Publication No. 2018-076216 [Patent Document 4] Patent Publication No. 2018-012612 [Patent Document 5] JP2-241536 [Non-patent literature]

[0007] [Non-Patent Document 1] E. Neu et al. APPLIED PHYSICS LETTERS 98, 243107 (2011) Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide an explosive composition suitable for producing nanodiamonds doped with foreign atoms, a method for producing the same, and a method for producing nanodiamonds doped with foreign atoms. [Means for solving the problem]

[0009] The present invention provides the following explosive composition and its manufacturing method, as well as a manufacturing method for heteroatom-doped nanodiamond. Item 1. An explosive composition comprising at least one type of explosive and at least one type of heteroatom compound, the heteroatom compound containing at least one type of heteroatom selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanides. Item 2. The explosive composition according to item 1, wherein the explosive comprises at least one selected from the group consisting of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octogen), trinitrophenylmethylnitramine (tetryl), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triamino-trinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofuroxan. Item 3. The explosive composition according to item 1 or 2, wherein the heteroatom compound is an organic heteroatom compound. Item 4. The explosive composition according to any one of Items 1 to 3, comprising 80 to 99.9999 mass% of an explosive and 0.0001 to 20 mass% of a heteroatom compound. Item 5. The explosive composition according to any one of Items 1 to 4, wherein the particle size of the explosive and / or heteroatom compound is 10 mm or less. Item 6. A method for producing an explosive composition according to any one of Items 1 to 5, comprising mixing an explosive and a heteroatom compound in a dry powder or molten state or using a solvent, and molding the mixture by a squeezing method or a pouring method. Item 7. A method for producing an explosive composition according to Item 6, in which an explosive composition is produced by mixing in a dry powder or molten state using an explosive and / or a heteroatom compound having a particle size of 10 mm or less. Item 8. A method for producing a heteroatom-doped nanodiamond, comprising a step of exploding the explosive composition according to any one of items 1 to 5 in a sealed container. Effect of the Invention

[0010] By using the explosive composition of the present invention, nanodiamonds doped with at least one kind of foreign atom can be obtained by detonation method. [Brief description of the drawings]

[0011] [Figure 1] (a) 738 nm bright spot imaging image (a) of silicon-doped nanodiamond obtained by adding 1 mass% of triphenylsilanol as a silicon compound, (b) fluorescence measurement result of the bright spot in Figure 1(a), (c) XRD measurement result of the sample after mixed acid and alkali treatment. In Figure 1(b), a fluorescent side band (shoulder peak) is present around 750 nm, but this side band may not be present depending on the sample. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The explosive composition of the present invention comprises at least one explosive and at least one heteroatom compound.

[0013] The explosive is not particularly limited, and a wide variety of known explosives can be used. Specific examples include trinitrotoluene (TNT), cyclotrimethylenetrinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octogen), trinitrophenylmethylnitramine (tetryl), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triamino-trinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofuroxan, which can be used alone or in combination of two or more.

[0014] The heteroatom compound is a compound that contains at least one type of heteroatom (atom other than carbon), and may be either an organic compound or an inorganic compound.

[0015] The heteroatom is selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanoids, preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, Ag, and lanthanoids, more preferably selected from the group consisting of Si, Ge, Sn, B, P, Ni, Ti, Co, Xe, Cr, W, Ta, Zr, and Ag.

[0016] The heteroatom compounds described below as specific examples are merely illustrative, and a wide variety of known heteroatom compounds can be used.

[0017] When the heteroatom is silicon, the organic silicon compounds are: Silanes with lower alkyl groups, such as acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, and trimethylphenoxysilane;

[0018] ·Trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, chlorotriethylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, chlorodifluoromethylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorosilane, chlorodifluoropropylsilane, dichlorofluoropropyl silanes having halogen atoms such as pyrsilane, trifluoromethylsilane, difluorodimethylsilane, fluorotrimethylsilane, ethyltrifluorosilane, diethyldifluorosilane, triethylfluorosilane, trifluoropropylsilane, fluorotripropylsilane, trifluorophenylsilane, difluorodiphenylsilane, fluorotriphenylsilane, tribromomethylsilane, dibromodimethylsilane, bromotrimethylsilane, bromotriethylsilane, bromotripropylsilane, dibromodiphenylsilane, and bromotriphenylsilane;

[0019] Polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, and octaphenylcyclotetrasilane Silazane such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, and hexaphenylcyclotrisilazane; Aromatic silanes such as silabenzene and disilabenzene, which have silicon atoms incorporated in the aromatic ring Hydroxyl-containing silanes such as trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, and diphenylsilanediol

[0020] Alkyl or aryl substituted silanes such as tetramethylsilane, ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane, and tetraphenylsilane; Carboxylic acid-containing silanes such as triphenylsilyl carboxylic acid, trimethylsilyl acetic acid, trimethylsilyl propionic acid, and trimethylsilyl butyric acid,

[0021] Siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane, Silanes having an alkyl or aryl group and a hydrogen atom, such as methylsilane, dimethylsilane, trimethylsilane, diethylsilane, triethylsilane, tripropylsilane, diphenylsilane, and triphenylsilane; Tetrakis(chloromethyl)silane, tetrakis(hydroxymethyl)silane, tetrakis(trimethylsilyl)silane, tetrakis(trimethylsilyl)methane, tetrakis(dimethylsilanolyl)silane, tetrakis(tri(hydroxymethyl)silyl)silane, tetrakis(nitratomethyl)silane, etc.

[0022] Examples of inorganic silicon compounds include silicon oxide, silicon oxynitride, silicon nitride, silicon carbide oxide, silicon carbide nitride, silane, and carbon materials doped with silicon, etc. Examples of carbon materials doped with silicon include graphite, activated carbon, carbon black, ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, and mesoporous carbon.

[0023] Examples of the boron compound include inorganic boron compounds and organic boron compounds.

[0024] Examples of inorganic boron compounds include orthoboric acid, diboron dioxide, diboron trioxide, tetraboron trioxide, tetraboron pentoxide, boron tribromide, tetrafluoroboric acid, ammonium borate, and magnesium borate.

[0025] Examples of organic boron compounds include triethylborane, (R)-5,5-diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine, triisopropyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, bis(hexylene glycolato)diboron, 4-(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 acetate complex, boron trifluoride sulfolane complex, 2-thiopheneboronic acid, and tris(trimethylsilyl)borate.

[0026] Examples of the phosphorus compound include inorganic phosphorus compounds, organic phosphorus compounds, etc. Examples of the inorganic phosphorus compound include ammonium polyphosphate.

[0027] The organic phosphorus compounds 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, tritolyl phosphate, di(dodecyl)p-tolyl phosphate, tris(2-butoxyethyl)phosphate, tricyclohexyl phosphate, triphenyl phosphate, ethyl diphenyl phosphate, dibutyl phosphoric acid esters such as phenyl phosphate, phenyl bis dodecyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, p-tolyl bis (2,5,5'-trimethylhexyl) phosphate, cresyl-2,6-xylenyl phosphate, trixylenyl phosphate, hydroxyphenyl diphenyl phosphate, tris (t-butylphenyl) phosphate, tris (i-propylphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tri (nonylphenyl) phosphate, and phenyl bis neopentyl phosphate; Condensed phosphate esters such as 1,3-phenylene bis(diphenyl phosphate), 1,4-phenylene bis(dixylenyl phosphate), 1,3-phenylene bis(3,5,5'-trimethylhexyl phosphate), bisphenol A bis(diphenyl phosphate), 4,4'-biphenyl bis(dixylenyl phosphate), and 1,3,5-phenylene tris(dixylenyl phosphate); Phosphite esters such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and tricresyl phosphite; Examples of phosphite esters include 1,3-phenylene bis(diphenyl phosphite), 1,3-phenylene bis(dixylenyl phosphite), 1,4-phenylene bis(3,5,5'-trimethylhexyl phosphite), bisphenol A bis(diphenyl phosphite), 4,4'-biphenyl bis(dixylenyl phosphite), and 1,3,5-phenylene tris(dixylenyl phosphite).

[0028] Examples of germanium compounds include organic germanium compounds such as methylgermane, ethylgermane, trimethylgermanium methoxide, dimethylgermanium diacetate, tributylgermanium acetate, tetramethoxygermanium, tetraethoxygermanium, isobutylgermane, alkylgermanium trichloride, and dimethylaminogermanium trichloride; examples of germanium compounds include germanium complexes such as nitrotriphenol complex (Ge2(ntp)2O), catechol complex (Ge(cat)2), and aminopyrene complex (Ge2(ap)2Cl2); and germanium alkoxides such as germanium ethoxide and germanium tetrabutoxide.

[0029] Examples of tin compounds 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 tetramethyltin; monoalkyl tin oxide compounds such as monobutyltin oxide; dialkyl tin oxide compounds such as dibutyltin oxide; aryl tin compounds such as tetraphenyltin; and organic tin compounds such as dimethyltin maleate, hydroxybutyltin oxide, and monobutyltin tris(2-ethylhexanoate).

[0030] Examples of nickel compounds include divalent nickel halides such as nickel chloride(II), nickel bromide(II), and nickel iodide(II); inorganic nickel compounds such as nickel acetate(II) and nickel carbonate(II); and organic nickel compounds such as nickel bis(ethylacetoacetate) and nickel bis(acetylacetonate).

[0031] Examples of titanium compounds include inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, barium titanate, and potassium titanate; tetraalkoxy titanium compounds such as tetraethoxy titanium, tetraisopropoxy titanium, and tetrabutyloxy titanium; tetraethylene glycol titanate, di-n-butyl bis(triethanolamine) titanate, di-isopropoxy titanium bis(acetylacetonate), isopropoxy titanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris(butylmethylpyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate, dimethacryloxy acetate titanate, diacryloxy acetate titanate, di(dioctylphosphate) ethylene titanate, and tri(dioctyloxy) ethylene titanate. octyl phosphate) isopropoxy titanium, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, tris(dioctyl pyrophosphate) ethylene Examples of the titanium compounds include isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, and isopropyl tri(N-aminoethyl-aminoethyl) titanate.

[0032] Examples of the cobalt compounds include inorganic cobalt compounds such as inorganic acid salts of cobalt, cobalt halides, cobalt oxide, cobalt hydroxide, dicobalt octacarbonyl, cobalt hydrogen tetracarbonyl, tetracobalt dodecacarbonyl, and alkylidynetricobalt nonacarbonyl; cobalt tris(ethylacetoacetate), cobalt tris(acetylacetonate); organic acid salts of cobalt (e.g., acetate, propionate, cyanate, naphthenate, and stearate); and alkylsulfonates such as methanesulfonate, ethanesulfonate, octane sulfonate, and dodecanesulfonate (e.g., C 6-18 alkylsulfonates; arylsulfonates which may be substituted with an alkyl group, such as benzenesulfonates, p-toluenesulfonates, naphthalenesulfonates, decylbenzenesulfonates, and dodecylbenzenesulfonates (e.g., C 6-18 Examples of the ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonate, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H2O (aquo), phosphorus compounds such as phosphine (triarylphosphine, etc.), NH3 (ammine), NO, NO2 (nitro), NO3 (nitrato), ethylenediamine, diethylenetriamine, pyridine, and nitrogen-containing compounds such as phenanthroline.

[0033] Examples of xenon compounds include fluorides such as XeF2, XeF4, XeF6, XeOF2, XeOF4, and XeO2F4, oxides such as XeO3 and XeO4, xenonic acid Xe(OH)6 and its salts Ba3XeO6, perxenic acid H4XeO6 and its salt Na4XeO6, complexes with metal carbonyls M(CO)5Xe (M = Cr, Mo, W), and hydrates.

[0034] Examples of chromium compounds include chromium acetylacetone complexes such as acetylacetonate chromium, chromium alkoxides such as chromium(III) isopropoxide, organic acid chromium compounds such as chromium(II) acetate and hydroxychromium(III) diacetate, tris(allyl)chromium, tris(methallyl)chromium, tris(crotyl)chromium, bis(cyclopentadienyl)chromium (i.e., chromocene), bis(pentamethylcyclopentadienyl)chromium (i.e., decamethylchromocene), bis(benzene)chromium, Included are organic chromium compounds such as bis(ethylbenzene)chromium, bis(mesitylene)chromium, bis(pentadienyl)chromium, bis(2,4-dimethylpentadienyl)chromium, bis(allyl)tricarbonylchromium, (cyclopentadienyl)(pentadienyl)chromium, tetra(1-norbornyl)chromium, (trimethylenemethane)tetracarbonylchromium, bis(butadiene)dicarbonylchromium, (butadiene)tetracarbonylchromium, and bis(cyclooctatetraene)chromium.

[0035] Examples of the tungsten compound include inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate, and sodium tungstate; boron atom-coordinated tungsten complexes such as ethylborylethylidene ligands; carbon atom-coordinated tungsten complexes such as carbonyl ligands, cyclopentadienyl ligands, alkyl group ligands, and olefin-based ligands; nitrogen atom-coordinated tungsten complexes such as pyridine ligands and acetonitrile ligands; phosphorus atom-coordinated tungsten complexes coordinated with phosphine ligands, phosphite ligands, and the like; and organic tungsten compounds such as sulfur atom-coordinated tungsten complexes coordinated with diethylcarbamodithiolato ligands.

[0036] Examples of thallium compounds include inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide, and thallium iodide; trialkylthallium compounds such as trimethylthallium, triethylthallium, and triisobutylthallium; arylthallium compounds such as dialkylthallium halides, alkenyldialkylthallium, alkynyldialkylthallium, triphenylthallium, and tritolylthallium; diarylthallium halides; thallium 2-ethylhexanoate, thallium malonate, thallium formate, thallium ethoxide, and thallium acetylacetonate; and organic thallium compounds such as thallium acetylacetonate.

[0037] 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 t-butoxide, zirconium isopropoxide, zirconium ethoxide, zirconyl acetate, zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, zirconium ethylacetoacetate, zirconium acetylacetonate bisethylacetoacetate, zirconium hexafluoroacetylacetonate, and zirconium trifluoroacetylacetonate.

[0038] Examples of silver compounds include organic silver compounds such as silver acetate, silver pivalate, silver trifluoromethanesulfonate, and silver benzoate; and inorganic silver compounds such as silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate, silver hexafluorophosphate (AgPF6), and silver hexafluoroantimonate (AgSbF6).

[0039] Examples of the aluminum compound include inorganic aluminum compounds such as aluminum oxide, alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum, acyloxy compounds such as triacetoxyaluminum, aluminum tristearate, and aluminum tributyrate, aluminum isopropylate, aluminum sec-butylate, aluminum tert-butylate, aluminum tris(ethylacetoacetate), tris(hexafluoroacetylacetonate)aluminum, tris(ethylacetoacetate)aluminum, and tris(n-propylacetoacetate). aluminum acetate), tris(iso-propylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, trissalicylaldehyde aluminum, tris(2-ethoxycarbonylphenolate)aluminum, tris(acetylacetonate)aluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum and other trialkylaluminums; dialkylaluminum halides; arylaluminums such as alkenyldialkylaluminum, alkynyldialkylaluminum, triphenylaluminum, and tritolylaluminum; and organic aluminum compounds such as diarylaluminum halides.

[0040] Examples of vanadium compounds include vanadic acid and metavanadic acid, as well as inorganic vanadium compounds such as alkali metal salts thereof; alkoxides such as triethoxyvanadyl, pentaethoxyvanadyl, triamyloxyvanadyl, and triisopropoxyvanadyl; acetonates such as bisacetylacetonate vanadyl, vanadium acetylacetonate, vanadyl acetylacetonate, and vanadium oxyacetylacetonate; and organic vanadium compounds such as vanadium stearate, vanadium pivalate, and vanadium acetate.

[0041] Examples of niobium compounds include halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobic acid and niobate salts, and organic niobium compounds such as niobium alkoxides.

[0042] Examples of tantalum compounds include inorganic tantalum compounds such as TaCl5 and TaF5, and organic tantalum compounds such as Ta(OC2H5)5, Ta(OCH3)5, Ta(OC3H7)5, Ta(OC4H9)5, (C5H5)2TaH3, and Ta(N(CH3)2)5.

[0043] Examples of the molybdenum compound include inorganic molybdenum compounds such as molybdenum trioxide, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, sodium phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, and molybdenum carbide; and organic molybdenum compounds such as molybdenum dialkyldithiophosphate and molybdenum dialkyldithiocarbamate.

[0044] Examples of manganese compounds include inorganic manganese compounds such as manganese hydroxide, nitrate, acetate, sulfate, chloride and carbonate; manganese oxalate; acetylacetonate compounds; and organic manganese compounds including manganese alkoxides such as methoxide, ethoxide and butoxide.

[0045] Examples of copper compounds 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 copper carbonate, copper chloride, copper bromide, copper iodide, copper phosphate, and natural minerals such as hydrotalcite, stichtite, and pyrolite.

[0046] Examples of cadmium compounds 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 naphthalate.

[0047] Examples of mercury compounds 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, mercuric parachlorobenzoate, and fluorescein mercuric acetate.

[0048] 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 gallium oxoates, gallium halides, gallium hydroxide, and gallium cyanide.

[0049] Examples of indium compounds 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.

[0050] Examples of arsenic compounds include inorganic arsenic compounds such as diarsenic trioxide, diarsenic pentoxide, arsenic trichloride, arsenic pentachloride, arsenous acid, arsenic acid, and salts thereof such as sodium arsenite, ammonium arsenite, potassium arsenite, ammonium arsenate, and potassium arsenate; and organic arsenic compounds such as cacodylic acid, phenylarsonic acid, diphenylarsonic acid, p-hydroxyphenylarsonic acid, p-aminophenylarsonic acid, and salts thereof such as sodium cacodylate and potassium cacodylate.

[0051] Examples of antimony compounds include inorganic antimony compounds such as antimony oxide, antimony phosphate, KSb(OH) and NH4SbF6, and organic antimony compounds such as antimony esters with organic acids, cyclic alkyl antimonites and triphenylantimony.

[0052] Examples of bismuth compounds 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.

[0053] Examples of selenium compounds 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.

[0054] Examples of tellurium compounds include telluric acid and its salts, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide, and tellurium alkoxides.

[0055] Examples of magnesium compounds include organic magnesium compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis(ethyl acetoacetate), alkyl acetoacetate magnesium monoisopropylate, and magnesium bis(acetylacetonate), and inorganic magnesium compounds such as magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium chloride.

[0056] Examples of calcium compounds include organic calcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxide, calcium methoxyethoxide, 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.

[0057] As the heteroatom compound having a heteroatom of Li, Na, K, Cs, S, Sr, Ba, F, Y, or a lanthanoid, a known organic or inorganic compound can be used.

[0058] The heteroatom compounds may be used alone or in combination of two or more.

[0059] The proportion of the explosive in the explosive composition containing at least one explosive and at least one heteroatom compound is preferably 80 to 99.9999 mass%, more preferably 85 to 99.999 mass%, even more preferably 90 to 99.99 mass%, particularly preferably 95 to 99.9 mass%, and the proportion of the heteroatom compound is preferably 0.0001 to 20 mass%, more preferably 0.001 to 15 mass%, even more preferably 0.01 to 10 mass%, particularly preferably 0.1 to 5 mass%. The heteroatom content in the explosive composition containing the explosive and the heteroatom compound is preferably 0.000005 to 10 mass%, more preferably 0.00001 to 8 mass%, even more preferably 0.0001 to 5 mass%, particularly preferably 0.001 to 3 mass%, and most preferably 0.01 to 1 mass%.

[0060] When at least one explosive and at least one heteroatom compound are solid, they may be mixed in powder form, melted, or dissolved or dispersed in a suitable solvent. Mixing may be performed by stirring, bead milling, ultrasonic waves, etc.

[0061] In a preferred embodiment, the explosive composition containing at least one explosive and at least one heteroatom compound further contains at least one cooling medium. The cooling medium may be any of solid, liquid, and gas. A method using a cooling medium includes a method in which an explosive composition containing an explosive and a heteroatom compound is detonated in a cooling medium. Examples of the cooling medium include inert gas (nitrogen, argon, CO), water, ice, liquid nitrogen, an aqueous solution of a salt containing a heteroatom, and a crystal hydrate. Examples of the salt containing a heteroatom when the heteroatom is silicon include ammonium hexafluorosilicate, ammonium silicate, and tetramethylammonium silicate. For example, in the case of water or ice, it is preferable to use about 5 times the weight of the explosive as the cooling medium.

[0062] In one preferred embodiment of the present invention, the explosive composition comprising at least one explosive and at least one heteroatom compound is converted into heteroatom-doped nanodiamond by compression by shock wave under high pressure and high temperature conditions generated by the explosion of the explosive (detonation method).During the explosion of the explosive, at least one heteroatom is incorporated into diamond lattice.The carbon source of the heteroatom-doped nanodiamond can be the explosive and organic heteroatom compound, but when the explosive composition comprising the explosive and at least one heteroatom compound further comprises carbon material that does not contain heteroatom, this carbon material can also be the carbon source of the heteroatom-doped nanodiamond.

[0063] The heteroatom-doped nanodiamond produced using the explosive composition of the present invention contains a heteroatom V (vacancy) center, and thus has a fluorescence emission peak. The wavelength of the fluorescence emission peak is preferably 720 to 770 nm, more preferably 730 to 760 nm, when the heteroatom contains silicon, preferably 580 to 630 nm, more preferably 590 to 620 nm, when the heteroatom contains germanium, and preferably 590 to 650 nm, more preferably 600 to 640 nm, when the heteroatom contains tin. In a more preferred embodiment of the present invention, the fluorescence emission peak of the nanodiamond whose group 14 element is Si includes a sharp peak at about 738 nm, which is called ZPL (Zero Phonon Level).

[0064] The concentration of heteroatom V centers in the heteroatom-doped nanodiamonds produced using the explosive composition of the present invention is preferably 1×10 10 / cm 3 More preferably, it is 2×10 10 ~1×10 19 / cm 3 It is assumed that the concentration of heteroatomic V centers can be determined, for example, by using a confocal laser microscope or a fluorescence absorption spectroscopy device. The determination of the concentration of heteroatomic V centers by fluorescence absorption spectroscopy can be found in the literature (DOI 10.1002 / pssa.201532174).

[0065] The BET specific surface area of ​​the heteroatom-doped nanodiamond produced using the explosive composition 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. An example of a measuring device for the BET specific surface area is BELSORP-miniII (manufactured by Microtrack-Bell Co., Ltd.), and the BET specific surface area can be measured, for example, under the following conditions. ·Measurement amount of powder: 40mg Pre-drying: 120℃, vacuum treatment for 3 hours Measurement temperature: -196℃ (liquid nitrogen temperature) The average size of the primary particles of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention is preferably 2 to 70 nm, more preferably 2.5 to 60 nm, even more preferably 3 to 55 nm, and particularly preferably 3.5 to 50 nm. The average size of the primary particles can be determined from the analysis results of powder X-ray diffraction (XRD) using Scherrer's formula. The XRD measuring device can be, for example, a fully automatic multipurpose X-ray diffractometer (manufactured by Rigaku Corporation).

[0066] The carbon content of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention is preferably 70 to 99 mass %, more preferably 75 to 98 mass %, and even more preferably 80 to 97 mass %.

[0067] The hydrogen content of the heteroatom-doped nanodiamond produced using the explosive composition 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%.

[0068] The nitrogen content of the heteroatom-doped nanodiamond produced using the explosive composition 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%.

[0069] The carbon, hydrogen and nitrogen contents of the heteroatom doped nanodiamonds can be measured by elemental analysis.

[0070] The heteroatom content of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention is preferably 0.0001 to 10.0 mass%, more preferably 0.0001 to 5.0 mass%, and even more preferably 0.0001 to 1.0 mass%. The heteroatom content can be measured, for example, by inductively coupled plasma atomic emission spectrometry (ICP-AES, XRF, SIMS (secondary ion mass spectrometry), and the heteroatom-doped nanodiamond can be quantified as an acidic solution after alkali fusion.

[0071] In a preferred embodiment of the present invention, the heteroatom-doped nanodiamond produced using the explosive composition of the present invention can be identified by Raman spectroscopy in the Raman shift chart with peaks characteristic of diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO). The peak characteristic of diamond in the Raman shift chart is 1100 to 1400 cm -1 The characteristic peak of graphite is 1450-1700 cm -1 The characteristic peak of the surface hydroxyl group (OH) is 1500-1750 cm-1 The characteristic peak of the surface carbonyl group (CO) is 1650-1800 cm -1 The areas of the peaks characteristic of diamond, graphite, surface hydroxyl groups (OH), and surface carbonyl groups (CO) are shown by a 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.

[0072] In a preferred embodiment of the present invention, in the heteroatom-doped nanodiamond produced using the explosive composition of the present invention, the ratio (D / G) of the diamond peak area (D) to the graphite peak area (G) is preferably 0.2 to 9, more preferably 0.3 to 8, and even more preferably 0.5 to 7.

[0073] In a preferred embodiment of the present invention, the ratio (H / D) of the peak area (H) of the surface hydroxyl group (OH) of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention to the peak area (D) of the diamond is preferably 0.1 to 5, more preferably 0.1 to 4.0, and even more preferably 0.1 to 3.0.

[0074] In a preferred embodiment of the present invention, the ratio (C / D) of the peak area (C) of the surface carbonyl group (CO) of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention to the peak area (D) of the diamond is preferably 0.01 to 1.5, more preferably 0.03 to 1.2, and even more preferably 0.05 to 1.0.

[0075] For Raman analysis of nanodiamonds, please refer to the literature (e.g., Vadym N. Mochalin et. al, NATURE NANOTECHNOLOGY, 7(2012)11-23, especially Figure 3).

[0076] In another preferred embodiment of the present invention, the surface of the heteroatom-doped nanodiamond produced by using the explosive composition of the present invention may have at least one type of oxygen functional group terminal and / or at least one type of hydrogen terminal. The oxygen functional group terminal may be OH, COOH, CONH2, C=O, CHO, etc., and OH, C=O, COOH are preferred. The hydrogen terminal may be an alkyl group having 1 to 20 carbon atoms.

[0077] The presence of at least one type of oxygen functional group termination on the surface of the heteroatom-doped nanodiamond is preferable because it suppresses the aggregation of nanodiamond particles. The presence of at least one type of hydrogen termination on the surface of the heteroatom-doped nanodiamond is preferable because it makes the zeta potential positive and makes the nanodiamond stable and highly dispersible in an acidic aqueous solution.

[0078] In another preferred embodiment of the present invention, the heteroatom-doped nanodiamond produced using the explosive composition of the present invention may have a core-shell structure. The core of the heteroatom-doped nanodiamond of the core-shell structure is a nanodiamond particle doped with a heteroatom. This core preferably has a SiV center and emits fluorescence. The shell is a non-diamond coating layer, which may contain sp2 carbon and preferably further contains oxygen atoms. The shell may be a graphite layer. The thickness of the shell is preferably 5 nm or less, more preferably 3 nm or less, and even more preferably 1 nm or less. The shell may have a hydrophilic functional group on the surface.

[0079] The heteroatom-doped nanodiamond can be preferably produced by the detonation method using the explosive composition of the present invention. The heteroatom-doped nanodiamond is preferably spherical, ellipsoidal, or a polyhedral shape close to them.

[0080] In this specification, the circularity is a numerical value that expresses the complexity of the figure drawn in an image or the like. The maximum circularity is 1, and the more complex the figure, the smaller the numerical value becomes. The circularity can be calculated by analyzing the TEM image of, for example, silicon-doped nanodiamond with image analysis software (for example, winROOF) and using the following formula. Circularity = 4π x (area) ÷ (perimeter) ^ 2 For example, in the case of a perfect circle with a radius of 10, the formula is "4π×(10×10×π)÷(10×2×π)^2", resulting in a circularity of 1 (maximum value). In other words, a perfect circle is the least complicated shape in terms of circularity. The circularity of the heteroatom-doped nanodiamond produced using the explosive composition of the present invention is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.35 or more.

[0081] In a preferred embodiment of the present invention, the core of the heteroatom-doped nanodiamond particle produced by using the explosive composition of the present invention has a diamond structure containing sp3 carbon and doped heteroatom, and its surface is covered with an amorphous layer composed of sp2 carbon.In a more preferred embodiment, the outside of the amorphous layer may be covered with a graphite oxide layer.In addition, a hydration layer may be formed between the amorphous layer and the graphite oxide layer.

[0082] In a preferred embodiment of the present invention, the heteroatom-doped nanodiamond produced by using the explosive composition of the present invention has a positive or negative zeta potential.The zeta potential of the heteroatom-doped nanodiamond is preferably -70 to 70mV, more preferably -60 to 30mV.

[0083] The heteroatom doped nanodiamonds are produced by a method including mixing an explosive composition containing at least one explosive and at least one heteroatom compound, and detonating the resulting explosive composition in a closed container. The container can be made of metal or synthetic resin. The explosive and the heteroatom compound are preferably formed by pressing or casting. Methods for producing particles (dry powder) of the explosive and the heteroatom compound include crystallization, crushing, and spray flash evaporation. When the explosive composition is formed by pressing or casting, the explosive and the heteroatom compound are mixed in a dry powder or molten state or using a solvent. The state of the mixture of the explosive and the heteroatom compound may be any combination of the following four: Explosives (dry powder) and heteroatom compounds (dry powder) Explosives (dry powder) and heteroatom compounds (molten state) Explosives (molten state) and heteroatomic compounds (dry powders) Explosives (molten state) and heteroatomic compounds (molten state) The explosive and the heteroatom compound may be mixed in the presence or absence of a solvent, and after mixing, the mixture can be molded by a pressing method or a pouring method.

[0084] The average particle size of each of the explosive and the heteroatom compound is preferably 10 mm or less, more preferably 5 mm or less, and further preferably 1 mm or less. These average particle sizes can be measured by a laser diffraction / scattering method, an optical microscope, or a Raman method. The product obtained by the explosion can be further subjected to a purification step and a post-treatment step. The purification step can include one or both of a mixed acid treatment and an alkali treatment. A preferred purification step is a mixed acid treatment step.

[0085] When an explosive composition containing at least one explosive and at least one heteroatom compound is detonated in a sealed container, graphite, metal impurities, heteroatom elements, heteroatom oxides, etc. are generated in addition to heteroatom-doped nanodiamonds. Graphite and metal impurities can be removed by mixed acid treatment, and heteroatom elements and heteroatom oxides can be removed by alkali treatment.

[0086] The mixed acid may be a mixture of concentrated sulfuric acid and concentrated nitric acid, preferably a mixture of concentrated sulfuric acid:concentrated nitric acid=1:1 (volume ratio). The mixed acid treatment temperature is 50 to 200° C., and the mixed acid treatment time is 0.5 to 24 hours.

[0087] The alkali may be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc. The alkali treatment temperature is 30 to 150° C., and the alkali treatment time is 0.5 to 24 hours.

[0088] The post-treatment process can include annealing and vapor phase oxidation. The annealing process allows the doped heteroatoms in the heteroatom-doped nanodiamond to meet with vacancies, forming heteroatom V centers. The vapor phase oxidation can also thin or remove the graphite layer formed on the surface of the heteroatom-doped nanodiamond. Although this is an optional process, a vacancy formation process may be performed before annealing. The vacancy formation process is performed by ion beam or electron beam irradiation. Although heteroatom V centers can be formed by annealing even without the vacancy formation process, more heteroatom V centers can be formed by annealing after the vacancy formation process. The upper limit of the vacancy density introduced by ion beam or electron beam irradiation is the concentration at which diamond is destroyed (>1×10 21 / cm 3 The lower limit is, for example, 1×10 16 / cm 3 That's it, plus 1x10 18 / cm 3That is all. 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.

[0089] The annealing temperature is preferably 800° C. or higher, and the annealing time is 30 minutes or longer.

[0090] The gas phase oxidation can be carried out in an air atmosphere, the gas phase oxidation temperature is preferably 300° C. or higher, and the gas phase oxidation time is 2 hours or longer.

[0091] In one preferred embodiment of the present invention, the explosive composition comprising at least one explosive and at least one heteroatom compound is converted into diamond by compression by shock waves under high pressure and high temperature conditions generated by the explosion of the explosive (detonation method).During the explosion of the explosive, heteroatoms are incorporated into diamond lattice.The carbon source of nanodiamond can be the explosive and organic heteroatom compound, but when the explosive composition comprising the explosive and heteroatom compound further comprises carbon material that does not contain heteroatoms, this carbon material can also be the carbon source of heteroatom-doped nanodiamond. EXAMPLES

[0092] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 6 By using TNT as the explosive and the dopant shown in Table 1 as a compound in which the hetero atom is silicon in the number of moles shown in Table 1 per mole of TNT, and producing silicon-doped nanodiamonds by the conventional detonation method under the temperature (K) and pressure (GPa) conditions shown in Table 1, nanodiamonds doped with silicon in the ratio shown in Table 1 can be obtained.

[0093] The names and structural formulas of dopant molecules (heteroatom compounds) 1 to 6 used to dope silicon are shown below. Dopant molecule 1: silline Dopant molecule 2: Tetramethylsilane (SiMe4) Dopant molecule 3: Tetrakis(nitratomethyl)silane (SiPETN) Dopant molecule 4: Tetrakis(dimethylsilanolyl)silane (Si(SiMe2OH)4) Dopant molecule 5: Tetrakis(trimethylsilyl)silane (Si(SiMe3)4) Dopant molecule 6: Tetrakis(trimethylsilyl)methane (C(SiMe3)4)

[0094] [ka]

[0095] [Table 1]

[0096] As is clear from Table 1, it is clear that the present invention makes it possible to obtain nanodiamonds having a large number of silicon atoms introduced therein.

[0097] Example 7 About 60 g of an explosive composition was used, in which 10 parts by mass of triphenylsilanol, 1 part by mass, or 0.1 part by mass of triphenylsilanol was added as a silicon compound to 100 parts by mass of explosive containing trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX), and silicon-doped nanodiamonds were produced according to a conventional method for producing nanodiamonds. The silicon-doped nanodiamonds obtained were subjected to the following treatment. The amount of triphenylsilanol added in the explosive was 10% by mass, 1% by mass, or 0.1% by mass. (i) Mixed acid treatment 15 g of nanodiamonds obtained in the detonation test were added to 2,800 g of mixed acid of concentrated sulfuric acid: concentrated nitric acid = 11:1 (weight ratio), and treated with stirring at 150°C for 10 hours. (ii) Alkaline treatment 1 g of the nanodiamond treated with mixed acid was added to 100 mL of 8N aqueous sodium hydroxide solution and treated at 100°C for 10 hours with stirring. (iii) Annealing The alkaline-treated nanodiamonds were annealed at 800°C for 30 minutes in a vacuum atmosphere. (iv) Gas Phase Oxidation The annealed nanodiamond was subjected to gas phase oxidation treatment at 300°C for 2 hours in an air atmosphere to obtain the silicon-doped nanodiamond of the present invention. (v) Fluorescence analysis A 10 w / v% water suspension of the silicon-doped nanodiamond of the present invention obtained by gas-phase oxidation was dropped 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 (product name: Microscopic Laser Raman Spectrophotometer LabRAM HR Evolution, manufactured by Horiba, Ltd.) and 738 nm bright spot imaging was performed. Figure 1(a) shows a 738 nm bright spot image of a silicon-doped nanodiamond obtained using triphenylsilanol as a silicon compound and with an external ratio of 1 mass% added. Figure 1(b) shows the fluorescence spectrum of the bright spot in Figure 1(a). The zero phonon line (fluorescence peak) of the SiV center can be confirmed. The Si content of the obtained silicon-doped nanodiamond was 3.2 mass% when the amount of triphenylsilanol added in the explosive was 10 mass%, 0.15 mass% when it was 1 mass%, and 0.03 mass% when it was 0.1 mass%. From Fig. 1(b), it was confirmed that the silicon-doped nanodiamond of the present invention has 738 nm fluorescence derived from SV center. Furthermore, the average size of the primary particles and the BET specific surface area of ​​the obtained silicon-doped nanodiamond measured by XRD are shown in Table 2 below.

[0098] [Table 2]

[0099] BET specific surface area measurement Equipment: BELSORP-miniII (Microtrack BEL Co., Ltd.) Measured powder amount: 40mg Pre-drying: 120℃, vacuum treatment for 3 hours Measurement temperature: -196℃ (liquid nitrogen temperature) -Measurement of the average size of primary particles (X-ray powder diffraction method (XRD)) Equipment: Fully automated multipurpose X-ray diffraction equipment (Rigaku Corporation) ·Measuring method for Si incorporation amount (XRF) Equipment: X-ray fluorescence analyzer ZSX Primus IV manufactured by Rigaku Corporation

[0100] Example 8 Boron-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of phenylboronic acid is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0101] Example 9 Phosphorus-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of triphenylphosphine is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0102] Example 10 Nickel-doped nanodiamonds can be obtained in the same manner as in Example 7, except that 1 part by mass of nickel bis(acetylacetonate) is used instead of 1 part by mass of triphenylsilanol in Example 7.

[0103] Example 11 Nanodiamonds doped with silicon and boron can be 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 phenylboronic acid are used instead of 1 part by mass of triphenylsilanol in Example 7.

[0104] Example 12 Nanodiamonds doped with silicon and phosphorus can be 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 are used instead of 1 part by mass of triphenylsilanol in Example 7.

Claims

1. 1. An explosive composition comprising at least one type of explosive and at least one type of organic heteroatom compound, wherein the organic heteroatom compound contains at least one heteroatom selected from the group consisting of B, P, Si, S, Cr, Sn, Al, Ge, Li, Na, K, Cs, Mg, Ca, Sr, Ba, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Ni, Cu, Ag, Cd, Hg, Ga, In, Tl, As, Sb, Bi, Se, Te, Co, Xe, F, Y, and lanthanoids, wherein the proportion of the explosive in the explosive composition is 90 to 99.99% by mass, and the proportion of the organic heteroatom compound is 0.01 to 10% by mass.

2. The explosive composition according to claim 1, wherein the explosive comprises at least one selected from the group consisting of trinitrotoluene (TNT), cyclotrimethylenetrinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octogen), trinitrophenylmethylnitramine (tetryl), pentaerythritol tetranitrate (PETN), tetranitromethane (TNM), triamino-trinitrobenzene, hexanitrostilbene, and diaminodinitrobenzofuroxan.

3. 3. The explosive composition according to claim 1, wherein the particle size of the explosive and / or heteroatom compound is 10 mm or less.

4. A method for producing an explosive composition according to any one of claims 1 to 3, characterized in that the explosive and the heteroatom compound are mixed in a dry powder or molten state or in a solvent, and molded by a squeezing method or a pouring method.

5. The method for producing an explosive composition according to claim 4, wherein the explosive composition is produced by mixing in a dry powder or molten state explosives and / or heteroatom compounds having a particle size of 10 mm or less.

6. A method for producing a heteroatom-doped nanodiamond, comprising a step of exploding the explosive composition according to any one of claims 1 to 3 in a sealed container.

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