阅读说明：本技术 掺杂有碳族元素的纳米金刚石的制造方法及纯化方法 (Method for producing and purifying carbon group element-doped nanodiamond ) 是由 间彦智明 牧野有都 鹤井明彦 刘明 西川正浩 于 2020-03-16 设计创作，主要内容包括：本发明提供掺杂有碳族元素的纳米金刚石的制造方法,该方法包括：使含有至少一种炸药和至少一种碳族元素化合物的炸药组合物在密闭容器内爆炸,得到掺杂有选自Si、Ge、Sn及Pb中的至少一种碳族元素的纳米金刚石的爆轰工序；和对掺杂有碳族元素的纳米金刚石进行碱处理以除去碳族元素和/或其氧化物的工序。(The present invention provides a method for manufacturing a carbon group element-doped nanodiamond, comprising: a detonation step of exploding an explosive composition containing at least one explosive and at least one compound of a carbon group element 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 nanodiamond doped with a carbon group element to alkali treatment to remove the carbon group element and/or an oxide thereof.)

1. A method for manufacturing a nanodiamond doped with a carbon group element, the method comprising:

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

and a step of subjecting the nanodiamond doped with a carbon group element to an alkali treatment to remove the carbon group element and/or an oxide thereof.

2. The method for manufacturing a carbon group element-doped nanodiamond according to claim 1,

before or after the alkali treatment process, the method further comprises a mixed acid treatment process of treating the carbon group element-doped nano-diamond with mixed acid of concentrated nitric acid and concentrated sulfuric acid.

3. The method for producing a carbon group element-doped nanodiamond according to claim 1 or 2,

the explosive composition further comprises a compound containing at least one 3 rd 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 lanthanides.

4. A method of purifying a carbon group element-doped nanodiamond, the method comprising:

and a step of removing the carbon group element and/or the oxide thereof by subjecting the nanodiamond composition containing the carbon group element and/or the oxide thereof selected from the group consisting of Si, Ge, Sn, and Pb and the nanodiamond doped with the carbon group element to alkali treatment.

5. The method for purifying a carbon group element-doped nanodiamond according to claim 4,

the nanodiamond composition is obtained by treatment with mixed acid.

6. The method for purifying a carbon group element-doped nanodiamond according to claim 4 or 5,

the nanodiamond composition further contains at least one 3 rd 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 lanthanoid and/or an oxide thereof.

7. The method for purifying a carbon group element-doped nanodiamond according to any one of claims 4 to 6,

the nanodiamond is further doped with at least one 3 rd 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 lanthanoids.

Technical Field

The present invention relates to a method for producing and purifying a carbon group element-doped nanodiamond.

Background

Diamond has a luminescent center which is a fluorescent chromophore of nanometer size and chemical stability, and does not exhibit decomposition, discoloration, or scintillation in vivo, which is common in a fluorescent substance of an organic substance, and therefore, it is expected as a probe for fluorescence imaging. In addition, spin information of electrons excited in the luminescence center may be measured from the outside, and thus, the use as ODMR (Optically Detected Magnetic Resonance) or a qubit is expected.

An SiV center, which is one of the luminescence centers of diamond, has a peak called ZPL (Zero Phonon Level) in the luminescence spectrum (non-patent document 1).

Silicon-doped diamond is produced by a CVD (chemical vapor deposition) method or the like (patent documents 1 to 2).

Non-patent document 2 analyzes nanodiamonds in meteorites, but nanodiamonds having a Silicon-Vacancy (SiV) center have not been produced. Non-patent document 2 shows that the SiV center is thermodynamically stable in the nanodiamond with a size of 1.1nm to 1.8nm by simulation.

Fig. 1 of non-patent document 3 discloses nanodiamonds having SiV centers adjusted by a CVD method by AFM (atomic force microscope). In the upper right graph of fig. 1, the height (nm) on the vertical axis and the position (μm) on the horizontal axis are shown, and it is clear that the peak height is about 9nm, but the width (position) is at least 70 nm.

Non-patent document 4 discloses the following: as the seed solution, 3 to 4nm of nanodiamond was used, and grown on a silicon wafer by MWPECVD method to obtain nanodiamond having an average particle size of 73nm containing SiV centers.

Documents of the prior art

Patent document

Patent document 1: japanese Kokai 2014-504254

Patent document 2: japanese patent laid-open No. 2004-176132

Non-patent document

Non-patent document 1: e.neuettal.applied PHYSICS LETTERS 98,243107, 243107(2011)

Non-patent document 2: nat nanotechnol.2014jan; 9(1) 54-8.doi:10.1038/nnano.2013.255.Epub 2013Dec 8.

Non-patent document 3: adv Sci Lett.2011Feb 1; 4(2):512-515.

Non-patent document 4: diamond and Related Materials, Volume 65,2016, Pages87-90

Disclosure of Invention

Problems to be solved by the invention

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

Means for solving the problems

The present invention provides a method for producing and purifying a carbon group element-doped nanodiamond as described below.

Item 1. a method for manufacturing a nanodiamond doped with a carbon group element, the method comprising:

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

and a step of removing the carbon group element and/or the oxide thereof by subjecting the nanodiamond doped with the carbon group element to alkali treatment.

Item 2 the method of manufacturing a carbon group element-doped nanodiamond according to item 1, wherein,

before or after the alkali treatment step, the method further comprises a mixed acid treatment step of treating the carbon group element-doped nanodiamond with a mixed acid of concentrated nitric acid and concentrated sulfuric acid.

Item 3. the method for manufacturing a nanodiamond doped with a carbon group element according to item 1 or 2, wherein,

the explosive composition further comprises a compound containing at least one 3 rd 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 lanthanoids.

Item 4. a method for purifying a carbon group element-doped nanodiamond, comprising:

and removing the carbon group element and/or the oxide thereof by subjecting the nanodiamond composition containing the carbon group element and/or the oxide thereof selected from Si, Ge, Sn, and Pb and the carbon group element-doped nanodiamond to alkali treatment.

Item 5. the method for purifying a carbon group element-doped nanodiamond according to item 4, wherein,

the nanodiamond composition is obtained by treating with mixed acid.

Item 6. the method for purifying a carbon group element-doped nanodiamond according to item 4 or 5, wherein,

the nanodiamond composition further contains at least one 3 rd 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 lanthanoids and/or an oxide thereof.

Item 7. the method for purifying a carbon group element-doped nanodiamond according to any one of items 4 to 6,

the nanodiamond is further doped with at least one 3 rd 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 lanthanoids.

ADVANTAGEOUS EFFECTS OF INVENTION

At least one carbon group element simple substance selected from Si, Ge, Sn, and Pb and an oxide thereof cannot be easily removed by mixed acid treatment, but they can be removed from the carbon group element-doped nanodiamond by alkali treatment.

Drawings

Fig. 1 shows fluorescence spectra of (a) a 738nm bright point image and (b) a bright point of a silicon-doped nanodiamond obtained by using triphenyl silanol as a silicon compound and adding the amount of the triphenylsilanol as 1 mass% in terms of the external ratio. In FIG. 1B, a fluorescence sideband (shoulder) is present at about 750nm, but this sideband may not be present depending on the sample.

FIG. 2 shows XRD measurement results before and after the alkali treatment. A: after alkali treatment; b: before the alkali treatment.

Detailed Description

The nanodiamond of the present invention may be further doped with an element other than a carbon group element. Examples of such elements include: at least one element (hereinafter referred to As "element 3") 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 lanthanoids. In the case of nanodiamonds doped with element 3, the explosive composition further comprises at least one explosive, at least one compound of a carbon group element and at least one compound of element 3.

In this specification, the nanodiamond doped with a carbon group element and further doped with a 3 rd element as necessary may be simply referred to as "doped nanodiamond" in some cases.

In one embodiment of the present invention, a manufacturing method of the present invention includes: a detonation step of exploding an explosive composition containing at least one explosive, at least one compound of a carbon group element, and, if necessary, at least one compound of an element 3 in a closed container to obtain a nanodiamond doped with a carbon group element and, if necessary, a further element 3; and a step of removing the carbon group element and/or the oxide thereof by subjecting the nanodiamond doped with the carbon group element and further doped with the 3 rd element as necessary to an alkali treatment.

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

The explosive is not particularly limited, and a known explosive can be widely used. Specific examples thereof include: trinitrotoluene (TNT), cyclotrimethylenetrinitramine (hexogen, RDX), cyclotetramethylenetetranitramine (octoxygen), trinitronitrobenzonitril (terbutamine), pentaerythritol tetranitrate (PETN), Tetranitromethane (TNM), triaminotrinitrobenzene, hexanitrostilbene, diaminodinitrobenzofuroxan, and the like, and these may be used singly or in combination of two or more.

The carbon group element compound contains at least one selected from the group consisting of a silicon compound, a germanium compound, a tin compound and a lead compound.

As organic silicon compounds, mention may be made of:

lower alkyl-containing silanes such as acetoxytrimethylsilane, diacetoxydimethylsilane, triacetoxymethylsilane, acetoxytriethylsilane, diacetoxydiethylsilane, triacetoxyethylsilane, acetoxytripropropylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane, triethoxymethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, and trimethylphenoxysilane;

trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, chlorotriethylsilane, trichlorophenylsilane, dichlorodiphenylsilane, chlorotritylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, dichloroethylphenylsilane, chlorodifluoromethylsilane, dichlorofluoromethylsilane, chlorofluorodimethylsilane, chloroethyldifluorosilane, dichloroethylfluorofluorosilicone, chlorodifluoropropylsilane, dichlorofluoropropylsilane, trifluoromethylsilane, difluorodimethylsilane, fluorotrimethylsilane, ethyltrifluorosilane, diethyldifluorosilane, triethylfluorosilane, trifluoropropylsilane, fluoropropylsilane, trifluorophenylsilane, difluorodiphenylsilane, fluorotriphenylsilane, tribromomethylsilane, dibromodimethylsilane, bromotrimethylsilane, bromotriethylsilane, bromotrimethylsilane, dichlorodiphenylsilane, and a mixture of, Silanes having a halogen atom such as bromotripropylsilane, dibromodiphenylsilane, bromotriphenylsilane, etc.;

polysilanes such as hexamethyldisilane, hexaethyldisilane, hexapropyldisilane, hexaphenyldisilane, and octaphenylcyclotetrasilane;

silazanes such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane and hexaphenylcyclotrisilazane;

aromatic silanes obtained by introducing a silicon atom into an aromatic ring, such as silabenzene and disilabenzene;

hydroxyl-containing silanes such as trimethylsilanol, dimethylphenylsilanol, triethylsilanol, diethylsilanediol, tripropylsilanol, dipropylsilanediol, triphenylsilanol, and diphenylsilanediol;

alkyl-or aryl-substituted silanes such as tetramethylsilane, ethyltrimethylsilane, trimethylpropylsilane, trimethylphenylsilane, diethyldimethylsilane, triethylmethylsilane, methyltriphenylsilane, tetraethylsilane, triethylphenylsilane, diethyldiphenylsilane, ethyltriphenylsilane and tetraphenylsilane;

carboxyl-containing silanes such as triphenylsilyl carboxylic acid, trimethylsilylacetic acid, trimethylsilylpropionic acid, and trimethylsilylbutanoic acid;

siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, and hexaphenyldisiloxane;

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

tetrakis (chloromethyl) silane, tetrakis (hydroxymethyl) silane, tetrakis (trimethylsilyl) methane, tetrakis (dimethylsilyl) silane, tetrakis (tris (hydroxymethyl) silyl) silane, tetrakis (nitrolmethyl) silane; and so on.

As the inorganic silicon compound, there may be mentioned: silicon oxide, silicon oxynitride, silicon nitride, silicon oxycarbide, silicon carbonitride, silane, or a carbon material doped with silicon, or the like. As the carbon material to be doped with silicon, graphite (graphite), activated carbon, carbon black, ketjen black, coke, soft carbon, hard carbon, acetylene black, carbon fiber, mesoporous carbon, and the like can be cited.

The organic or inorganic silicon compounds may be used singly or in combination of two or more.

As the germanium compound, there can be mentioned: organic germanium compounds such as methyl germane, ethyl germane, methyl trimethyl germanium, dimethyl germanium diacetate, tributyl germanium acetate, tetramethoxy germanium, tetraethoxy germanium, isobutyl germane, alkyl germanium trichloride, dimethyl amino germanium trichloride, etc., and nitrotriphenol complex (Ge, etc.)₂(ntp)₂O), catechol complex (Ge (cat)₂) Or aminopyrene complex (Ge)₂(ap)₂Cl₂) Germanium complex, germanium alcoholate such as germanium ethoxide and germanium tetrabutoxide.

The germanium compound may be used alone or in combination of two or more.

Examples of the tin compound include: tin (II) oxide, tin (IV) oxide, tin (II) sulfide, tin (IV) sulfide, tin (II) chloride, tin (IV) chloride, tin (II) bromide, tin (II) fluoride, inorganic tin compounds such as 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, organotin compounds such as dimethyl tin maleate, hydroxybutyl tin oxide and monobutyl tin tris (2-ethylhexanoate), and the like.

The tin compound may be used alone or in combination of two or more.

Examples of the lead compound include: lead monoxide (PbO) and lead dioxide (PbO)₂) Lead (Pb)₃O₄) White lead (2 PbCO)₃·Pb(OH)₂) Lead nitrate (Pb (NO))₃)₂) Lead chloride (PbCl)₂) Lead sulfide (PbS), chrome yellow (PbCrO)₄、Pb(SCr)O₄、PbO·PbCrO₄) 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 inorganic lead compound, lead acetate (Pb (CH)₃COO)₂) Lead tetracarboxylate (Pb (OCOCH)₃)₄) Tetraethyl lead (Pb (CH)₃CH₂)₄) Tetramethyl lead (Pb (CH)₃)₄) Tetrabutyl lead (Pb (C)₄H₉)₄) And the like.

The lead compound may be used alone or in combination of two or more.

The 3 rd element compound includes an organic 3 rd element compound and an inorganic 3 rd element compound, and one 3 rd element compound or two or more kinds thereof may be used in combination.

The compound of element 3 is exemplified below.

Examples of the boron compound include: inorganic boron compounds, organic boron compounds, and the like.

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

Examples of the organoboron compound include: triethylborane, (R) -5, 5-diphenyl-2-methyl-3, 4-propanol-1, 3,2-Azoborane, triisopropyl borate, 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane, bis (hexenylglycolic acid) diboron, 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) -1H-pyrazole, N- [4- (4,4,5, 5-tetramethyl-1, 2, 3-dioxaborane-2-yl) phenyl]Tert-butyl carbamate, phenylboronic acid, 3-acetylphenylboronic acid, boron trifluoride acetate complex, boron trifluoride sulfolane complex, 2-thiopheneboronic acid, tris (trimethylsilyl) borate, and the like.

Examples of the phosphorus compound include: inorganic phosphorus compounds, organic phosphorus compounds, and the like. Examples of the inorganic phosphorus compound include ammonium polyphosphate and the like.

As the organic phosphorus compound, there can be mentioned: trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, dimethylethyl phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tricresyl phosphate, bis (dodecyl) p-tolyl phosphate, tris (2-butoxyethyl) phosphate, tricyclohexyl phosphate, triphenyl phosphate, ethyldiphenyl phosphate, dibutylphenyl phosphate, phenylbisdodecyl phosphate, tolyldiphenyl phosphate, tricresyl phosphate, p-tolylbis (2,5, 5' -trimethylhexyl) phosphate, tolyl-2, 6-ditolyl phosphate, trixylyl phosphate, hydroxyphenyl diphenyl phosphate, trihexyl diphenyl phosphate, ditexyl phosphate, and the like, Phosphoric acid esters such as tris (t-butylphenyl) phosphate, tris (isopropylphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tris (nonylphenyl) phosphate, and phenyl bisneopentyl phosphate;

condensed phosphates such as 1, 3-phenylenebis (diphenyl phosphate), 1, 4-phenylenebis (dixylyl) phosphate, 1, 3-phenylenebis (3,5,5 '-trimethylhexyl phosphate), bisphenol a bis (diphenyl phosphate), 4' -biphenylbis (dixylyl) phosphate, 1,3, 5-phenylenetris (dixylyl) phosphate), and phosphites such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, and tricresyl phosphite;

phosphites such as 1, 3-phenylenebis (diphenyl phosphite), 1, 3-phenylenebis (dixylyl phosphite), 1, 4-phenylenebis (3,5,5 '-trimethylhexyl phosphite), bisphenol a bis (diphenyl phosphite), 4' -biphenylbis (dixylyl phosphite), 1,3, 5-phenylenetris (dixylyl phosphite).

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).

Examples of the titanium compound include: inorganic titanium compounds such as titanium dioxide, titanium nitride, strontium titanate, lead titanate, barium titanate, and potassium titanate, and tetraalkoxytitanium such as tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium; tetraethylene glycol titanate, di-n-butyl bis (triethanolamine) titanate, diisopropoxytitanium bis (acetylacetonate), isopropoxytitanium octanoate, isopropyltitanium trimethacrylate, isopropyltitanium triacrylate, triisostearoyl titanium isopropoxide, isopropyl tridecylphenylsulfonyl titanium isopropoxide, tris (butylmethylphosphonato) titanium isopropoxide, tetraisopropyl bis (dilaurylphosphato) titanate, dimethylacryloyloxyacetyl titanate, diacryloyloxyacetoxy titanate, dioctylphosphato ethylene titanate, trioctylphosphonato titanium isopropoxide, tetraisopropyl bis (dioctylphosphato) titanate, tetraoctyl bis (ditridecylato) phosphite titanate, tetrakis (2) bis (ditridecylo) phosphite acyloxy) titanate, 2-diallyloxymethyl-1-butyl) titanate, bis (dioctylphosphoato) oxyacetoxy titanate, tris (dioctylphosphoato) ethylene titanate, isopropyl tri (N-dodecyl) benzenesulfonyl titanate, isopropyl trioctyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl isostearyldiacryloyl titanate, isopropyl trioctylphosphoato) titanate, isopropyl tricumylphenyl titanate, isopropyl tris (N-aminoethyl) titanate and other organic titanium compounds.

Examples of the cobalt compound include: cobalt inorganic acid salts, cobalt halides, cobalt oxide, cobalt hydroxide, cobaltosic octacarbonyl, cobaltosic tetracarbonyl, cobaltosic dodecacarbonyl, tricobalt nonalkarbonyl, etc., cobalt tris (ethylacetoacetate), cobalt tris (acetylacetonate), organic acid salts of cobalt (e.g., acetate, propionate, cyanate, naphthenate, stearate), and alkylsulfonic acid salts (e.g., C) such as methanesulfonate, ethanesulfonate, octanesulfonate, dodecylsulfonate, etc_6-18Alkyl sulfonates); benzenesulfonates, p-toluenesulfonates, naphthalenesulfonates, decylbenzenesulfonates, dodecylbenzenesulfonates and the like aryl sulfonates optionally substituted with alkyl (e.g., C_6-18Alkyl-aryl sulfonates)), organic cobalt complexes, and the like. Examples of the ligand constituting the complex include OH (hydroxyl group), alkoxy (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl (acetyl group, propionyl group, etc.), alkoxycarbonyl (methoxycarbonyl group, ethoxycarbonyl group, etc.), acetylacetonyl group, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H₂O (hydrated), phosphine (triarylphosphine such as triphenylphosphine), or NH₃(ammine compound), NO₂(nitro), NO₃And nitrogen-containing compounds such as (nitrate), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline.

As the xenon compound, for example: XeF₂、XeF₄、XeF₆、XeOF₂、XeOF₄、XeO₂F₄Isofluoride, XeO₃、XeO₄And oxides, etc.; xe (OH)₆And its salt Ba₃XeO₆Etc.; high xenon acid H₄XeO₆And salts thereof Na₄XeO₆(ii) a Complex with Metal carbonyl M (CO)₅Xe (M ═ Cr, Mo, W), hydrates, and the like.

Examples of the chromium compound include: chromium acetylacetonate complexes such as chromium acetylacetonate, chromium alkoxides such as chromium (III) isopropoxide, organic chromium compounds such as chromium (II) acetate and chromium (III) hydroxydiacetate, chromium (II) tris (allyl) chromium, chromium (III) trimethacrylate, chromium (crotyl) tris (crotyl) bis (cyclopentadienyl) chromium (i.e., chromocene), chromium (pentamethylcyclopentadienyl) bis (i.e., decamethyldiocyclopentadienyl) chromium, chromium (bis (phenyl) bis (ethylbenzene) chromium, chromium (mesitylene), chromium (bis (pentadienyl) bis, chromium (2, 4-dimethylpentadienyl) bis (allyl) tricarbonyl, (cyclopentadienyl) (pentadienyl) chromium, chromium (1-norbornyl) chromium, (trimethylmethane) tetracarbonylchromium, chromium (butadiene) dicarbonyl, (butadiene) tetracarbonylchromium, and chromium (cyclooctatetraene).

Examples of the tungsten compound include: inorganic tungsten compounds such as tungsten trioxide, ammonium tungstate and sodium tungstate, and boron atom-coordinated tungsten complexes such as ethylboroethylidene ligands; carbon atom coordinated tungsten complexes such as carbonyl ligands, cyclopentadienyl ligands, alkyl ligands and olefin 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 an organic tungsten compound such as a sulfur atom-coordinated tungsten complex coordinated with a diethylthiocarbamate ligand or the like.

Examples of thallium compounds include: inorganic thallium compounds such as thallium nitrate, thallium sulfate, thallium fluoride, thallium chloride, thallium bromide, and thallium iodide, trialkylalialium such as trimethylthallium, triethylthallium, and triisobutylthallium, arylthallium such as dialkylthallium halides, dialkylthallium alkenyls, dialkylthallium alkynyls, triphenylthallium, and tritolylalium, organic thallium compounds such as diarylthallium halides, thallium 2-ethylhexanoate, thallium malonate, thallium formate, thallium ethanolate, and thallium acetylacetonate.

Examples of the zirconium compound include: and organic zirconium compounds such as zirconium nitrate, zirconium sulfate, zirconium carbonate, zirconium hydroxide, zirconium fluoride, zirconium chloride, zirconium bromide, zirconium iodide, and the like, zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium isopropoxide, zirconium ethoxide, zirconium acetate, zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetoacetate, zirconium ethylacetoacetate, zirconium bisacetoacetate (zirconium acetylacetonate bisbenzothiazoacetate), zirconium hexafluoroacetylacetonate, zirconium trifluoroacetoacetate, and the like.

Examples of the zinc compound include: diethyl zinc, dimethyl zinc, zinc acetate, zinc nitrate, zinc stearate, zinc oleate, zinc palmitate, zinc myristate, zinc laurate, zinc acetylacetonate, zinc chloride, zinc bromide, zinc iodide, zinc carbamate, and the like.

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, silver hexafluorophosphate (AgPF)₆) Silver hexafluoroantimonate (AgSbF)₆) And inorganic silver compounds, and the like.

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 triacetoxy aluminum, aluminum tristearate, and aluminum tributyrate; aluminum isopropoxide, aluminum sec-butoxide, aluminum tert-butoxide, aluminum tris (ethylacetoacetate), aluminum tris (hexafluoroacetylacetonate), aluminum tris (ethylacetoacetate), aluminum tris (n-propylacetoacetate), aluminum tris (isopropylacetoacetate), aluminum tris (n-butylacetoacetate), aluminum trisalicylaldehyde, aluminum tris (2-ethoxycarbonylphenoxide), aluminum tris (acetylacetonate), trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, arylaluminum such as dialkylaluminum halide, dialkylaluminum alkenylate, dialkylaluminum alkynylaluminum, triphenylaluminum and tritylaluminum, and organoaluminum compound such as diarylaluminum halide.

Examples of the vanadium compound include: vanadic acid, metavanadic acid, and alkali metal salts thereof such as inorganic vanadium compounds, alkoxides of triethoxy vanadic acid, pentaethoxy vanadic acid, tripentoxy vanadic acid, triisopropoxy vanadic acid, and the like; acetonates such as vanadyl bisacetoacetonate, vanadium acetylacetonate, vanadyl acetylacetonate, and vanadyl oxyacetoacetonate; organic vanadium compounds such as vanadium stearate, vanadium pivalate, vanadium acetate and the like.

Examples of the niobium compound include: halides such as niobium pentachloride and niobium pentafluoride, inorganic niobium compounds such as niobium sulfate, niobic acid, and niobate, and organic niobium compounds such as niobium alkoxides.

Examples of the tantalum compound include: TaCl₅、TaF₅Iso-inorganic tantalum compound, Ta (OC)₂H₅)₅、Ta(OCH₃)₅、Ta(OC₃H₇)₅、Ta(OC₄H₉)₅、(C₅H₅)₂TaH₃、Ta(N(CH₃)₂)₅And organic tantalum compounds.

As the molybdenum compound, for example: 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 phosphomolybdate, silicomolybdic acid, molybdenum disulfide, molybdenum diselenide, molybdenum ditelluride, molybdenum boride, molybdenum disilicide, molybdenum nitride, molybdenum carbide, and organic molybdenum compounds such as molybdenum dialkyldithiophosphate and molybdenum dialkyldithiocarbamate.

Examples of the manganese compound include: inorganic manganese compounds such as hydroxides, nitrates, acetates, sulfates, chlorides, and carbonates of manganese; including manganese oxalate, manganese acetylacetonate, or manganese alkoxide organic compounds such as manganese methoxide, manganese ethoxide, manganese butoxide, etc.

Examples of the iron compound include: inorganic iron compounds such as 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) tetraoxide, iron (II) sulfate, iron (III) sulfate, iron (II) nitrate, iron (III) nitrate, iron (II) hydroxide, iron (III) hydroxide, iron (II) perchlorate, iron (III) perchlorate, iron (II) ammonium sulfate, iron (III) tungstate oxide, iron (III) tetravanadate, iron (II) selenide, iron (II) trioxide, iron (III) pentoxide, iron (II) sulfide, iron (III) sulfide, iron (II) phosphide, iron (III) phosphide and the like; organic iron compounds such as iron (II) acetate, iron (III) acetate, iron (II) formate, iron (III) tricarboxylate, iron (II) tartrate, iron (III) sodium tartrate, iron (II) lactate, iron (II) oxalate, iron (III) ammonium citrate, iron (III) laurate, iron (III) stearate, iron (III) tripalmitate, iron (II) hexacyanide, iron (III) bis (2, 4-pentanedione) iron (II) dihydrate, iron (III) tris (2, 4-pentanedione), iron (III) tris (oxalato) potassium, iron (III) tris (trifluoromethanesulfonate), iron (III) p-toluenesulfonate, iron (III) dimethyldithiocarbamate, iron (III) diethyldithiocarbamate, and ferrocene.

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, stehitite, and mantle rock.

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.

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 chloride, phenylmercury acetate, thimerosal, mercury p-chlorobenzoate and mercury acetate fluorescein.

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 oxoate, gallium halide, gallium hydroxide and gallium cyanide.

Examples of the indium compound include: organic indium compounds such as triethoxy indium, 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.

Examples of the arsenic compound include: arsenic trioxide, arsenic pentoxide, arsenic trichloride, arsenic pentachloride, arsenous acid, arsenic acid, and salts thereof, inorganic arsenic compounds such as sodium arsenite, ammonium arsenite, potassium arsenite, ammonium arsenate, and potassium arsenate, and organic arsenic compounds such as arsenous acid, phenylarsonic acid, diphenylarsonic acid, p-hydroxyphenylarsonic acid, and p-aminophenylarsonic acid, and salts thereof, sodium arsenate, and potassium arsenate.

Examples of the antimony compound include: antimony oxide, antimony phosphate, KSb (OH), NH₄SbF₆Inorganic antimony compounds, antimony esters with organic acids, cyclic alkyl antimonite esters, and organic antimony compounds such as triphenylantimony.

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.

Examples of selenium compounds include: organic selenium compounds such as selenomethionine, selenocysteine, and selenocystine, and inorganic selenium compounds containing alkali metal selenate such as potassium selenate and alkali metal selenite such as sodium selenite.

As the tellurium compound, for example: telluric acid and its salts, tellurium oxide, tellurium chloride, tellurium bromide, tellurium iodide and tellurium alkoxide.

Examples of the magnesium compound include: organic magnesium compounds such as magnesium monoisopropoxide ethyl acetoacetate, magnesium bis (ethyl acetoacetate), magnesium monoisopropoxide alkyl acetoacetate, and magnesium bis (acetylacetonate), and inorganic magnesium compounds such as magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium chloride.

Examples of the calcium compound include: organic calcium compounds such as calcium 2-ethylhexanoate, calcium ethoxide, calcium methoxide ethoxide, 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.

The compound in which the element doped in the nanodiamond is Li, Na, K, Cs, S, Sr, Ba, F, Y, or a lanthanoid element may be a known organic or inorganic compound.

In the composition containing the explosive, the carbon group element compound, and if necessary, the 3 rd element compound, the proportion of the explosive is preferably 80 to 99.9999% by mass, more preferably 85 to 99.999% by mass, further preferably 90 to 99.99% by mass, and particularly preferably 95 to 99.9% by mass, the proportion of the carbon group element compound is preferably 0.0001 to 20% by mass, more preferably 0.001 to 15% by mass, further preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, and the proportion of the 3 rd element compound is preferably 0 to 20% by mass, more preferably 0.001 to 15% by mass, further preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 8% by mass. In addition, in the mixture containing the explosive, the compound of the carbon group element, and if necessary, the 3 rd element, the content of the carbon group element 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%, most preferably 0.01 to 1 mass%, and the content of the 3 rd element 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%, most preferably 0.00004 to 2 mass%.

The doped nanodiamond obtained by the production method of the present invention preferably contains the 3 rd element in an amount of preferably 0.001 to 100 mol, more preferably 0.002 to 10 mol, and further preferably 0.003 to 5 mol based on 1 mol of the carbon group element.

The explosive, the carbon group element compound, and if necessary, the compound of the further element 3 may be mixed in powder form when they are solid, may be melted, or may be dissolved or dispersed in an appropriate solvent. The mixing may be performed by stirring, bead mill, ultrasonic wave, or the like.

In a preferred embodiment, the explosive composition comprising an explosive, a compound of an element of the carbon group, and, if desired, a compound of element 3, further comprises a cooling medium. The cooling medium may be in any form of solid, liquid, or gas. As a method of using the cooling medium, there is a method of detonating a mixture of an explosive, a carbon group element compound, and, if necessary, a 3 rd element compound in the cooling medium. Examples of the cooling medium include inert gas (nitrogen, argon, and CO), water, ice, liquid nitrogen, an aqueous solution containing a salt of a carbon group element, a crystalline hydrate, an aqueous solution containing a salt of an element No. 3, and a crystalline hydrate. Examples of the salts containing a carbon-group element include ammonium hexafluorosilicate, ammonium silicate, tetramethylammonium silicate and the like. When the cooling medium is, for example, water or ice, it is preferably used about 5 times the weight of the explosive.

In a preferred embodiment of the present invention, an explosive composition containing an explosive, a compound of an element of the carbon group, and, if necessary, a compound of element 3 is further used, is converted into diamond by compression by a shock wave under high-pressure and high-temperature conditions generated by the explosion of the explosive (detonation method). Upon detonation of the explosive, at least one carbon group element atom and, if necessary, at least one 3 rd element are introduced into the diamond lattice. The carbon source of the nanodiamond may be an explosive, an organic carbon group element compound, and if necessary, a 3 rd element compound, but in the case where a mixture containing the explosive, the carbon group element compound, and if necessary, the 3 rd element compound further contains a carbon material containing no carbon group element and no 3 rd element, the carbon material may also be a carbon source of the nanodiamond.

In the manufacturing method and the purification method of the present invention, the purification of the nanodiamond composition doped with a carbon group element and further doped with the 3 rd element as necessary includes an alkali treatment step, and the alkali treatment and the mixed acid treatment may be combined, and the nanodiamond composition may further contain a simple substance and/or an oxide of a carbon group element and a simple substance and/or an oxide of the 3 rd element as necessary. The purification step is preferably a combination of an alkali treatment and a mixed acid treatment (in any order).

The mixed acid may be a mixed acid of concentrated sulfuric acid and concentrated nitric acid, and preferably includes concentrated sulfuric acid: concentrated nitric acid is mixed acid with the volume ratio of 1: 1. The temperature of the mixed acid treatment is 50-200 ℃, and the time of the mixed acid treatment is 0.5-24 hours.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The alkali metal hydroxide is an aqueous solution of 0.1 to 10N alkali metal hydroxide. The temperature of the alkali treatment is 30-150 ℃, and the time of the alkali treatment is 0.5-24 hours.

If an explosive composition containing an explosive, a carbon group element compound, and if necessary, an element 3 is exploded in a container, graphite, metal impurities, a simple substance of a carbon group element (a simple substance of Si, a simple substance of Ge, a simple substance of Sn, and a simple substance of Pb), and an oxide of a carbon group element (SiO) are generated in addition to the doped nanodiamond₂、GeO₂、SnO₂、PbO₂) Elemental form 3, elemental oxide form 3, and the like. Graphite and metal impurities, a 3 rd element simple substance and a 3 rd element oxide can be removed by mixed acid treatment, and a carbon group element simple substance and a carbon group element oxide can be removed by alkali treatment.

The nanodiamond according to a preferred embodiment, which is doped with a carbon group element and, if necessary, a 3 rd element, and obtained by the production method or the purification method of the present invention, has a fluorescence emission peak in a range of 720 to 770nm, and satisfies the following requirements (i) and/or (ii):

(i) the BET specific surface area is 20 to 900m²/g；

(ii) The primary particles have an average size of 2 to 70 nm.

The doped nanodiamond obtained by the manufacturing method or the purification method according to one preferred embodiment of the present invention has a fluorescence emission peak by including a center of a carbon group element V (vacancy) and, if necessary, a center of a 3 rd element V. When the carbon group element is Si, the wavelength of the fluorescence emission peak is preferably 720 to 770nm, more preferably 730 to 760nm when the carbon group element contains silicon, 580 to 630nm, more preferably 590 to 620nm when the carbon group element contains germanium, 590 to 650nm, more preferably 600 to 640nm when the carbon group element contains tin, and 540 to 600nm, more preferably 550 to 590nm when the carbon group element contains lead. In a more preferred embodiment of the present invention, the fluorescence peak of nanodiamond whose carbon group element is Si comprises a peak of about 738nm called ZPL (Zero Phonon Level).

In the nanodiamond doped with a carbon group element and further doped with a 3 rd element as necessary, which is obtained by the production method or the purification method of the present invention, the concentration of V center of the carbon group element is preferably 1 × 10¹⁰/cm³Above, more preferably 2 × 10¹⁰～1×10¹⁹/cm³The concentration of the 3 rd element V center is preferably 1X 10¹⁰/cm³Above, more preferably 2 × 10¹⁰～1×10¹⁹/cm³The above. It is presumed that the concentration of the center of the group-carbon element V or the center of the group-3 element V can be identified by, for example, a confocal laser microscope or a fluorescence absorption spectrometer. Note that, the concentration of MV center (M is a carbon group element or a 3 rd element) can be determined by fluorescence absorption analysis with reference to literature (DOI 10.1002/pssa.201532174).

The BET specific surface area of the nanodiamond doped with a carbon group element and further doped with a 3 rd element as required, which is obtained by the production method or the purification method of the present invention, is preferably 20 to 900m²A concentration of 25 to 800m²(iv)/g, more preferably 30 to 700m²A specific preferred range is 35 to 600m²(ii) in terms of/g. The BET specific surface area can be determined by nitrogen adsorption. The BET specific surface area can be measured, for example, under the following conditions using a device such as BELSORP-mini II (manufactured by Microtrac BEL Co., Ltd.).

Determination of powder amount: 40mg of

Pre-drying: treating at 120 deg.C under vacuum for 3 hr

Measurement temperature: 196 ℃ (liquid nitrogen temperature)

The average size of primary particles of the doped nanodiamond obtained by the production method or the purification method of the present invention is preferably 2 to 70nm, more preferably 2.5 to 60nm, further preferably 3 to 55nm, and particularly preferably 3.5 to 50 nm. The average size of the primary particles can be determined from the analysis result of powder X-ray diffraction (XRD) and by the scherrer equation. Examples of the XRD measuring device include a fully automatic multifunction X-ray diffraction device (manufactured by japan corporation).

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

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

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

The content of carbon, hydrogen, and nitrogen in the doped nanodiamond obtained by the manufacturing method or the purification method of the present invention can be measured by elemental analysis.

The content of the carbon group element in the doped nanodiamond obtained by the production method or the purification method of the present invention is preferably 0.0001 to 10.0% by mass, more preferably 0.0001 to 5.0% by mass, and even more preferably 0.0001 to 1.0% by mass, and the content of the 3 rd element is preferably 0.0001 to 10.0% by mass, more preferably 0.0001 to 5.0% by mass, and even more preferably 0.0001 to 1.0% by mass. The content of the carbon group element and the content of the 3 rd element can be measured by, for example, inductively coupled plasma emission spectrometry (ICP-AES, XRF, SIMS (secondary ion mass spectrometry)), and the doped nanodiamond can be quantified by preparing an acidic solution after melting with an alkali.

The doped nanodiamond obtained by the manufacturing method or the purification method according to a preferred embodiment of the present invention may identify characteristic peaks of diamond, graphite, surface hydroxyl (OH), and surface Carbonyl (CO) in a raman-shifted spectrum by raman spectroscopy. The characteristic peak of diamond in the Raman shift spectrum is 1100-1400 cm^-1The characteristic peak of the graphite is 1450-1700 cm^-1The characteristic peak of surface hydroxyl (OH) is 1500-1750 cm^-1The characteristic peak of surface Carbonyl (CO) is 1650-1800 cm^-1. The areas of characteristic peaks of diamond, graphite, surface hydroxyl (OH), surface Carbonyl (CO) are shown by raman spectroscopy. The laser wavelength of the Raman light source is, for example, 325nm or 488 nm. As the Raman spectrometer, a confocal micro-Raman spectrometer (for example, trade name: micro laser Raman spectrometer LabRAM HR Evolution, horiba, manufactured by horiba Ltd.) can be used.

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

In the doped nanodiamond according to a preferred embodiment obtained by the production method or the 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 the diamond is preferably 0.1 to 5, more preferably 0.1 to 4.0, and further preferably 0.1 to 3.0.

In the doped nanodiamond according to one preferred embodiment obtained by the production method or the 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 the diamond is preferably 0.01 to 1.5, more preferably 0.03 to 1.2, and further preferably 0.05 to 1.0.

As a raman analysis method of nanodiamonds, reference can be made to literature (for example, Vadym n. mocalin et al, NATURE NANOTECHNOLOGY,7(2012)11-23, particularly fig. 3).

In another preferred embodiment of the present invention, the doped nanodiamond may have at least one oxygen functional group terminal and/or at least one hydrogen terminal on the surface thereof obtained by the manufacturing method or the purification method of the present invention. Examples of the terminal oxygen functional group include OH, COOH and CONH₂C is O, CHO, etc., preferably OH and C is O, COOH. The hydrogen terminal includes an alkyl group having 1 to 20 carbon atoms.

The presence of at least one kind of oxygen functional group terminal on the surface of the doped nanodiamond suppresses the aggregation of the nanodiamond particles, and is therefore preferable. The presence of at least one hydrogen termination on the surface of the doped nanodiamond is preferable because the Zeta (ζ) potential is positive, and the dispersion is stable and high in an acidic aqueous solution.

In another preferred embodiment of the present invention, the doped nanodiamonds obtained by the manufacturing method or the purification method of the present invention may also have a core-shell structure. The core of the core-shell structure doped with the nanodiamond is a nanodiamond particle doped with a carbon group element atom and further doped with a 3 rd element as required. The core is preferably a portion that emits fluorescence having a center of a carbon group element V and, if necessary, a center of a 3 rd element V. The shell is a non-diamond coating layer and may contain sp2 carbon, preferably further containing oxygen atoms. The shell may also be a graphite layer. The thickness of the shell is preferably 5nm or less, more preferably 3nm or less, and further preferably 1nm or less. The shell may have a hydrophilic functional group on the surface.

The doped nanodiamonds may preferably be manufactured by a detonation method. The shape of the doped nanodiamond is preferably spherical, ellipsoidal, or polyhedral similar to them.

The circularity is a numerical value indicating the complexity of a figure drawn by an image or the like. The maximum value is 1 for the circularity, and the numerical value becomes smaller as the figure becomes more complex. The circularity can be obtained by analyzing a TEM image of the doped nanodiamond with image analysis software (e.g., winROOF) and using the following equation.

Roundness 4 π × (area) ÷ (length around) ÷ 2

For example, in the case of a perfect circle with a radius of 10, it is a calculation formula of "4 π × (10 × 10 × π) ÷ (10 × 2 × π) ^ 2". The roundness was 1 (maximum value). That is, for roundness, perfect circles are the least complex figures. The circularity of the doped nanodiamond is preferably 0.2 or more, more preferably 0.3 or more, and further preferably 0.35 or more.

In a preferred embodiment of the present invention, the doped nanodiamond particle has a diamond structure including sp3 carbon, a doped carbon group element, and further including element No. 3 as necessary at the center thereof, and the surface thereof is covered with an amorphous layer composed of sp2 carbon. In a further preferred embodiment, the outer side of the amorphous layer may be covered by an oxidized graphite layer. Further, a hydrated layer may be formed between the amorphous layer and the graphite oxide layer.

In a preferred embodiment of the present invention, the doped nanodiamond obtained by the manufacturing method or the purification method of the present invention has a positive or negative Zeta potential. The Zeta potential of the doped nano-diamond is preferably-70 mV, and more preferably-60-30 mV.

The doped nanodiamond may be manufactured by a manufacturing method including the steps of: mixing an explosive composition containing an explosive, a carbon group element compound, and if necessary, a 3 rd element compound; and exploding the obtained mixture in a closed container. Examples of the container include a metal container and a synthetic resin container. The explosive composition containing the explosive, the carbon group element compound, and if necessary, the 3 rd element compound is preferably formed by pressing or casting. Examples of the method for producing the respective particles (dry powder) of the explosive, the carbon group element compound, and the 3 rd element compound include a crystallization method, a crushing method, and a spray flash evaporation method. In the case of forming an explosive composition by a pressing method or a filling method, the explosive, the carbon group element compound, and, if necessary, a 3 rd element compound are mixed in a dry powder or molten state or mixed using a solvent. The state of the explosive when mixed with the carbon group element compound may be any combination of four kinds:

explosive (dry powder) and carbon group element compound (dry powder)

Explosive (dry powder) and compound of carbon group element (molten state)

Explosive (molten state) and compound of carbon group element (dry powder)

Explosive (molten state) and compound of carbon group element (molten state)

When the 3 rd element compound is further mixed to form the explosive composition, the 3 rd element compound may be in a dry powder state or a molten state, and therefore eight kinds of the explosive, the carbon group element compound, and the 3 rd element compound are combined in a dry powder state and a molten state at the time of mixing.

The mixture of the explosive, the carbon group element compound, and, if necessary, the 3 rd element compound may be carried out in any condition in the presence or absence of a solvent, and may be molded by a pressing method or a filling method after the mixture.

The average particle diameter of the explosive, the carbon group element compound, and the 3 rd element compound is preferably 10mm or less, more preferably 5mm or less, and still more preferably 1mm or less. The average particle size can be measured by a laser diffraction/scattering method, an optical microscope, or a raman method.

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

The post-treatment process may include annealing, gas phase oxidation. By the annealing treatment, the carbon group element doped in the doped nanodiamond, if necessary, the 3 rd element may meet the defect (vacacy) to form a carbon group element V center, if necessary, a 3 rd element V center. In addition, the graphite layer formed on the surface of the doped nanodiamond may be thinned or removed by gas phase oxidation. Although this is an optional step, the hole forming step may be performed before annealing. The hole forming step is performed by irradiation with an ion beam or an electron beam. The carbon group element V center and, if necessary, the 3 rd element V center can be formed by annealing without performing the hole forming step, but more carbon group element V centers and, if necessary, the 3 rd element V centers can be formed by annealing after the hole forming step. The upper limit of the hole density introduced by ion beam irradiation or electron beam irradiation is the concentration (> 1X 10) at which diamond is destroyed²¹/cm³Hole concentration of) about the lower limit, for example, 1 × 10¹⁶/cm³Above, further 1X 10¹⁸/cm³The above. The ion beam is preferably an ion beam of hydrogen (H) or helium (He). For example, hydrogenThe energy of the ion beam is preferably 10 to 1500keV, 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.

The annealing temperature is preferably 800 ℃ or higher, and the annealing time is preferably 30 minutes or longer.

The gas phase oxidation may be carried out in an atmospheric atmosphere, and the gas phase oxidation temperature is preferably 300 ℃ or higher, and the gas phase oxidation time is 2 hours or longer.

Examples

The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 6

When the silicon-doped nanodiamonds were produced by the conventional method using TNT as an explosive and the dopants shown in table 1 as carbon group element compounds in the number of moles shown in table 1 based on the number of moles of TNT 1 under the conditions of temperature (K) and pressure (GPa) shown in table 1, nanodiamonds doped with silicon in the proportions shown in table 1 could be obtained.

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

Dopant molecule 1: silabenzene (silline)

Dopant molecule 2: tetramethylsilane (SiMe)₄)

Dopant molecule 3: tetrakis (nitroestermethyl) Silane (SiPETN)

Dopant molecule 4: tetrakis (dimethylsiloxy) silane (Si (SiMe)₂OH)₄)

Dopant molecule 5: tetrakis (trimethylsilyl) silane (Si (SiMe)₃)₄)

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

[ chemical formula 1]

[ Table 1]

As is clear from table 1, according to the present invention, a nanodiamond into which a large amount of silicon atoms is introduced can be obtained.

Example 7

Silicon-doped nanodiamonds were produced by a conventional method for producing nanodiamonds using about 60g of the explosive composition obtained by adding 10 parts by mass, 1 part by mass or 0.1 part by mass of triphenyl silanol as a silicon compound to 100 parts by mass of an explosive containing trinitrotoluene (TNT) and cyclotrimethylenetrinitramine (RDX). The obtained silicon-doped nanodiamond was subjected to the following treatment. The amount of triphenyl silanol added to the explosive is 10 mass%, 1 mass%, or 0.1 mass%.

(i) Mixed acid treatment

To 2800g of mixed acid (concentrated sulfuric acid: concentrated nitric acid: 11:1 by weight) was added 15g of nanodiamond obtained in the detonation test, and the mixture was treated at 150 ℃ for 10 hours while stirring.

(ii) Alkali treatment

1g of acid-mixed nanodiamond was added to 100mL of 8N aqueous sodium hydroxide solution, and the mixture was stirred and treated at 100 ℃ for 10 hours.

(iii) Annealing

The alkali-treated nanodiamond was annealed at 800 ℃ for 30 minutes in a vacuum atmosphere.

(iv) Gas phase oxidation

The annealed nanodiamond was subjected to gas phase oxidation treatment at 300 ℃ for 2 hours in an atmospheric atmosphere, thereby obtaining a silicon-doped nanodiamond according to the present invention.

(v) Fluorescence analysis

An aqueous suspension of 10 w/v% of the silicon-doped nanodiamond according to the present invention obtained by vapor phase oxidation was dropped on a glass substrate and dried to prepare an evaluation sample. The obtained evaluation sample was subjected to high-speed mapping using a micro-Raman spectrometer (trade name: LabRAM HR Evolution, horiba, manufactured by horiba Ltd.) to image a 738nm bright point. An image of 738nm bright spots of silicon-doped nanodiamond obtained using triphenyl silanol as the silicon compound and an addition amount of 1 mass% in terms of an external ratio is shown in fig. 1 (a). The fluorescence spectrum of the bright point in FIG. 1(a) is shown in FIG. 1 (b). A zero phonon line (fluorescence peak) at the center of SiV can be confirmed. The Si content of the obtained silicon-doped nanodiamond was 3.2 mass% when the amount of triphenyl silanol added in the explosive was 10 mass%, 0.15 mass% when the amount of addition was 1 mass%, and 0.03 mass% when the amount of addition was 0.1 mass%.

From fig. 1(b), it can be confirmed that the silicon-doped nanodiamond of the present invention has fluorescence of 738nm derived from SV center. Table 2 shows the average size and BET specific surface area of the primary particles of the obtained silicon-doped nanodiamond by XRD measurement.

[ Table 2]

Measurement of BET specific surface area

The device comprises the following steps: BELSORP-mini II (manufactured by Microtrac BEL Co., Ltd.)

Measurement of powder amount: 40mg of

Pre-drying: treating at 120 deg.C under vacuum for 3 hr

Measuring temperature: 196 ℃ (liquid nitrogen temperature)

Measurement of average size of Primary particles (powder X-ray diffraction (XRD))

The device comprises the following steps: full-automatic multifunctional X-ray diffraction device (manufactured by Kyowa Co., Ltd.)

Measurement of Si incorporation quantity (XRF)

The device comprises the following steps: fluorescent X-ray analyzer ZSX Primus IV, manufactured by Nippon Kogyo Co., Ltd

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 fig. 2.

[ Table 3]

^※Mass%

In table 3, the amount of Si after the alkali treatment as measured by XRF was significantly reduced as compared to that before the alkali treatment, and therefore the alkali treatment was effective for Si removal.

In the context of figure 2 of the drawings,

a broad peak originating from an amorphous compound exists around 23 °.

According to XRF measurements, the amount of Si is the greatest, except for diamond, and therefore: this peak is derived from the Si compound.

In the graph after the alkali treatment, since a broad peak near 23 ° disappears, it is considered that: the removal of the Si compound is achieved by alkali treatment.

Example 8

Nanodiamonds doped with silicon and boron were obtained in the same manner as in example 7, except that 0.5 part by mass of triphenyl silanol and 0.5 part by mass of phenyl boronic acid were used instead of 1 part by mass of triphenyl silanol in example 7.

Example 9

Silicon-and phosphorus-doped nanodiamonds were obtained in the same manner as in example 7, except that 0.5 part by mass of triphenyl silanol and 0.5 part by mass of triphenyl phosphine were used instead of 1 part by mass of triphenyl silanol in example 7.