CN105133002B - A kind of preparation method of 13 thio ammonium molybdate crystal - Google Patents
A kind of preparation method of 13 thio ammonium molybdate crystal Download PDFInfo
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- CN105133002B CN105133002B CN201510542268.2A CN201510542268A CN105133002B CN 105133002 B CN105133002 B CN 105133002B CN 201510542268 A CN201510542268 A CN 201510542268A CN 105133002 B CN105133002 B CN 105133002B
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Abstract
The invention discloses a kind of 13 thio ammonium molybdate crystals, chemical formula is (NH4)2Mo3S13, crystal molecule amount is 740.68, cell parameter： α=90 °, β=117.288 (6) °, γ=90 °,Z=2, R1=0.0459, wR2=0.1236.In addition, the invention also discloses the preparation method of the 13 thio ammonium molybdate crystal.The 13 thio ammonium molybdate crystals of the present invention are by three core molybdenum sulphur cluster [Mo3S13]2‑Anion and 2 ammonium ion compositions, its preparation method is simple to operate, it is easy to accomplish, hydrogen sulfide gas is not used in preparation process, pollution-free, blending theory research and the lubrication mechanism to the core molybdenum of later stage novel high-performance lube oil additive three have important directive significance.
Description
Technical field
The invention belongs to many ammonium thiomolybdate technical fields, and in particular to a kind of preparation side of 13 thio ammonium molybdate crystal
Method.
Background technology
In recent years due to the rise of organic molybdenum lubricating material, alkylthio carbamic acid molybdenum is added as new lubricating oil
Agent increasingly attracts attention, and the alkylthio carbamic acid molybdenum with three nuclear structures of best performance show is then most competitive
Product, this allows for precursor compound 13 ammonium thiomolybdate of the alkylthio carbamic acid molybdenum with three nuclear structures
Study on the synthesis becomes more meaningful.
On 13 ammonium thiomolybdate ((NH4)2Mo3S13) synthesising process research, only 1975 Union Carbide
Slightly introduced in the patent US7074381 of the patent US3876755 and infineum companies of company.The former mainly introduces 12 sulphur
For the synthetic method of ammonium molybdate, although yield is higher, material rate is very remote with theoretical value gap, does not have industrialization meaning；And
Use substantial amounts of hydrogen sulfide gas as sulphur source in the synthetic method of the latter, pollution is big, and environment is unfriendly, and reaction condition is difficult
To control.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of 13 molybdenum dithiophosphates for above-mentioned the deficiencies in the prior art
Sour ammonium crystal.The 13 thio ammonium molybdate crystal is by three core molybdenum sulphur cluster [Mo3S13]2-Anion and 2 ammonium ion compositions, three core molybdenums
Sulphur cluster [Mo3S13]2-Three Mo atoms can be described as two-by-two to be connected in equilateral triangle in flat state, one, center S atom
It is connected with three Mo atoms, in S2-Valence state.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of 13 thio ammonium molybdate crystals, it is special
Levy and be, chemical formula is (NH4)2Mo3S13, at a temperature of 296K, in the type single crystal X-ray diffractions of Bruker SMART APEX II
On instrument, with the MoK alpha rays through graphite monochromator monochromatizationUsing the programs of SHELX 97 by direct method and
Complete matrix least square method is parsed and amendment crystal structure, and crystal molecule amount is 740.68, cell parameter： α=90 °, β=117.288 (6) °, γ=90 °, Z=2, R1=0.0459, wR2=0.1236.
In addition, present invention also offers a kind of method for preparing above-mentioned 13 thio ammonium molybdate crystals, it is characterised in that bag
Include following steps：
Step 1: by molybdenum trioxide and water according to 1:The mass ratio of (10~15) is added in reactor, is uniformly mixing to obtain
Suspension；
Step 2: reactor described in step one is heated into 40 DEG C~60 DEG C, then to institute under the conditions of insulated and stirred
The pH value for stating dropwise addition ammoniacal liquor to suspension in reactor is 8~10, then addition ammonium sulfide, sulphur powder and second into the reactor
Alcohol；The mol ratio of the ammonium sulfide, sulphur powder and ethanol is 1:(2~3):(4~6)；The mole of the sulphur powder is in step one
10~15 times of the molybdenum trioxide mole；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.6MPa~0.8MPa, and reactor then is heated into 180 DEG C
Insulated and stirred reacts 5h~7h after~200 DEG C；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
Drying in oven is placed in after alcohol elution, the ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and monohydric alcohol in dissolving step four under the conditions of 60 DEG C~70 DEG C institute
13 ammonium thiomolybdates are stated, then stand 13 ammonium thiomolybdates after dissolving at room temperature, the crystal of precipitation is 13
Ammonium thiomolybdate crystal；The volume ratio of the tetrahydrofuran and monohydric alcohol is 3~5:1.
Above-mentioned method, it is characterised in that the mass concentration of ammoniacal liquor described in step 2 is 15%~20%.
Above-mentioned method, it is characterised in that the pH value of dropwise addition ammoniacal liquor to suspension is into the reactor in step 2
9。
Above-mentioned method, it is characterised in that the mol ratio of ammonium sulfide described in step 2, sulphur powder and ethanol is 1:2.4:5.
Above-mentioned method, it is characterised in that the mole of sulphur powder described in step 2 is molybdenum trioxide described in step one
12 times of mole.
Above-mentioned method, it is characterised in that reacting kettle inner pressure described in step 3 is 0.7MPa, reactor is heated to
Insulated and stirred reacts 6h after 190 DEG C.
Above-mentioned method, it is characterised in that the temperature of baking oven described in step 4 is 70 DEG C~90 DEG C.
Above-mentioned method, it is characterised in that monohydric alcohol described in step 5 is methanol or ethanol.
The present invention has advantages below compared with prior art：
1st, 13 thio ammonium molybdate crystals of the invention are by three core molybdenum sulphur cluster [Mo3S13]2-Anion and 2 ammonium ion groups
Into three core molybdenum sulphur cluster [Mo3S13]2-Three Mo atoms can be described as two-by-two to be connected in equilateral triangle in flat state, center
One S atom is connected with three Mo atoms, in S2-Valence state.Six, space S atom formed two-by-two after S -- S respectively with three Mo originals
Son forms plane triangle and perpendicular to former planar delta, and each S atom is in S2 2-Valence state.Six S atoms of last residue shape two-by-two
Respectively at two Mo atoms formation space positive tetrahedron after into S -- S, wherein S -- S is perpendicular to former triangle projective planum, each S atom
In S2-In valence state, the part of formation, Mo atoms are in Mo4+Valence state.
2nd, 13 thio ammonium molybdate crystals of the invention are purple, and fusing point is 215 DEG C~216 DEG C, passes through XPS photoelectron energy
Analysis of spectrum, is that (229.5eV, 232.8eV) Mo3d characteristic peak occurs in electronic energy, 4+ oxygen is mainly presented in Mo on this position
Change state, S mainly by two it is overlapping it is bimodal constitute (2p3/2,2p1/2), the region peak that wherein electronic energy is 162.3eV is
S2 2-With body region, the region peak position of (164.6eV, 163.6eV) with higher electronic energy is S2 2-And S2-Mixed ligand is overlapping
Region, the region peak that last electronic energy is 165.5eV is S2-With body region.
3rd, preparation method of the invention is simple to operate, it is easy to accomplish, hydrogen sulfide gas, no dirt are not used in preparation process
Dye.
4th, the present invention is using water and ethanol as reaction dissolvent, and the presence of ethanol can make reaction raw materials more in course of reaction
Good is dispersed in reaction dissolvent, is conducive to the production of product, and product looser, crystal grain can be made longer；In addition, in production
In thing forming process, ethanol has the effect of cleaning to solid particles surface, and the step of reducing purifying is cost-effective, enters one
Step improves the purity of product.
5th, synthesis of the 13 thio ammonium molybdate crystals of the invention to the core molybdenum of later stage novel high-performance lube oil additive three
Theoretical research and the lubrication mechanism have important directive significance.
Below by drawings and examples, technical scheme is described in further detail.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of 13 thio ammonium molybdate crystals of the embodiment of the present invention 1.
Fig. 2 is the Mo valence states and electricity of the XPS XPS Analysis of 13 thio ammonium molybdate crystals of the embodiment of the present invention 1
Sub- energy collection of illustrative plates.
Fig. 3 is the S valence states and electricity of the XPS XPS Analysis of 13 thio ammonium molybdate crystals of the embodiment of the present invention 1
Sub- energy collection of illustrative plates.
Fig. 4 is the stereoeffect figure of 13 thio ammonium molybdate crystals of the embodiment of the present invention 1.
Embodiment
Embodiment 1
The 13 thio ammonium molybdate crystals of the present embodiment, chemical formula is (NH4)2Mo3S13, at a temperature of 296K, in Bruker
On the type single crystal X-ray diffraction instrument of SMART APEX II, with the MoK alpha rays through graphite monochromator monochromatizationParsed using the programs of SHELX 97 by direct method and complete matrix least square method and amendment crystal knot
Structure, crystal molecule amount is 740.68, cell parameter：α
=90 °, β=117.288 (6) °, γ=90 °,Z=2, R1=0.0459, wR2=0.1236.
The preparation method of the 13 thio ammonium molybdate crystals of the present embodiment comprises the following steps：
Step 1: 0.14mol molybdenum trioxides and 242g water are added in reactor, suspension is uniformly mixing to obtain；
Step 2: reactor described in step one is heated into 50 DEG C, then to the reaction under the conditions of insulated and stirred
The pH value that ammoniacal liquor to suspension that mass concentration is 17% are added dropwise in kettle is 9, then the addition 0.7mol vulcanizations into the reactor
Ammonium, 1.68mol sulphur powders and 3.5mol ethanol；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.7MPa, reactor then is heated into insulation after 190 DEG C stirs
Mix reaction 6h；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
80 DEG C of drying in oven are placed in after alcohol elution, the crystalline thing of kermesinus, the as ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and methanol under the conditions of 60 DEG C ten trithios described in dissolving step four
For ammonium molybdate, then 13 ammonium thiomolybdates after dissolving are stood at room temperature, the crystal of precipitation is 13 thio molybdic acids
Ammonium crystal；The volume ratio of the tetrahydrofuran and methanol is 5:1.
XRD crystallographic analysis are carried out to manufactured in the present embodiment 13 thio ammonium molybdate crystals, as a result as shown in figure 1,
It can be seen that impurity peaks are less, illustrate that product purity is higher；Further it can be seen that attached 2 θ=10.1 ° and 10.8 °
It is near to have 2 very strong peaks, there is strong one time peak at 2 θ=16.4 °, this and the ammonium thiomolybdate marks of PDF01-071-1291 13
Quasi- collection of illustrative plates is completely the same.Prove that the product prepared is the thio ammonium molybdate crystal of target product 13.
Pass through the electrovalence of Mo and S in the thio ammonium molybdate crystal of XPS XPS Analysis manufactured in the present embodiment 13
State and electronic energy, are as a result shown in Fig. 2 and Fig. 3.XPS analysis show：As shown in Fig. 2 being that (229.5eV, 232.8eV) goes out in electronic energy
Existing Mo3d characteristic peak ,+4 valency states of oxidation are mainly presented in Mo on this position.As shown in figure 3, S is main overlapping by two
Bimodal composition (2p3/2,2p1/2), the region peak that wherein electronic energy is 162.3eV is S2 2-With body region, with higher electronic energy
(164.6eV, 163.6eV) region peak position be S2 2-And S2-Mixed ligand overlapping region, last electronic energy is 165.5eV's
Region peak is S2-With body region.
The 13 thio ammonium molybdate crystals that the present embodiment is prepared pass through X-ray single crystal diffractometer and corresponding software
Measure its stereoeffect (see Fig. 4).X-ray single crystal diffraction result shows：The molecular formula of compound is (NH4)2Mo3S13,
Its structure is by three core molybdenum sulphur cluster [Mo3S13]2-Anion and 2 ammonium ion compositions, three core molybdenum sulphur cluster [Mo3S13]2-It can be described as
Three Mo atoms are connected two-by-two is in flat state in equilateral triangle, and one, center S atom is connected with three Mo atoms, in S2-Valency
State.Six, space S atom forms after S -- S and forms plane triangles and flat perpendicular to former triangle with three Mo atoms respectively two-by-two
Face, each S atom is in S2 2-Valence state.Six S atoms of last residue form after S -- S and form space with two Mo atoms respectively two-by-two
Positive tetrahedron, wherein S -- S are perpendicular to former triangle projective planum, and each S atom is in S2-In valence state, the part of formation, Mo atoms are in
Mo4+Valence state.
Embodiment 2
The 13 thio ammonium molybdate crystals of the present embodiment are same as Example 1.
The preparation method of the 13 thio ammonium molybdate crystals of the present embodiment comprises the following steps：
Step 1: 0.14mol molybdenum trioxides and 200g water are added in reactor, suspension is uniformly mixing to obtain；
Step 2: reactor described in step one is heated into 40 DEG C, then to the reaction under the conditions of insulated and stirred
The pH value that ammoniacal liquor to suspension that mass concentration is 15% are added dropwise in kettle is 8, then the addition 0.7mol vulcanizations into the reactor
Ammonium, 1.4mol sulphur powders and 4.2mol ethanol；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.6MPa, reactor then is heated into insulation after 200 DEG C stirs
Mix reaction 5h；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
70 DEG C of drying in oven are placed in after alcohol elution, the crystalline thing of kermesinus, the as ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and ethanol under the conditions of 65 DEG C ten trithios described in dissolving step four
For ammonium molybdate, then 13 ammonium thiomolybdates after dissolving are stood at room temperature, the crystal of precipitation is 13 thio molybdic acids
Ammonium crystal；The volume ratio of the tetrahydrofuran and ethanol is 4:1.
Manufactured in the present embodiment 13 thio ammonium molybdate crystals are carried out with XRD crystallographic analysis, XPS photoelectron spectroscopies point
Analysis and the analysis of X-ray single crystal diffraction, it is as a result identical with result described in embodiment 1.
Embodiment 3
The 13 thio ammonium molybdate crystals of the present embodiment are same as Example 1.
The preparation method of the 13 thio ammonium molybdate crystals of the present embodiment comprises the following steps：
Step 1: 0.14mol molybdenum trioxides and 300g water are added in reactor, suspension is uniformly mixing to obtain；
Step 2: reactor described in step one is heated into 60 DEG C, then to the reaction under the conditions of insulated and stirred
The pH value that ammoniacal liquor to suspension that mass concentration is 20% are added dropwise in kettle is 10, then the addition 0.7mol vulcanizations into the reactor
Ammonium, 2.1mol sulphur powders and 2.8mol ethanol；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.8MPa, reactor then is heated into insulation after 180 DEG C stirs
Mix reaction 7h；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
90 DEG C of drying in oven are placed in after alcohol elution, the crystalline thing of kermesinus, the as ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and methanol under the conditions of 70 DEG C ten trithios described in dissolving step four
For ammonium molybdate, then 13 ammonium thiomolybdates after dissolving are stood at room temperature, the crystal of precipitation is 13 thio molybdic acids
Ammonium crystal；The volume ratio of the tetrahydrofuran and methanol is 3:1.
Manufactured in the present embodiment 13 thio ammonium molybdate crystals are carried out with XRD crystallographic analysis, XPS photoelectron spectroscopies point
Analysis and the analysis of X-ray single crystal diffraction, it is as a result identical with result described in embodiment 1.
Embodiment 4
The 13 thio ammonium molybdate crystals of the present embodiment are same as Example 1.
The preparation method of the 13 thio ammonium molybdate crystals of the present embodiment comprises the following steps：
Step 1: 0.14mol molybdenum trioxides and 242g water are added in reactor, suspension is uniformly mixing to obtain；
Step 2: reactor described in step one is heated into 50 DEG C, then to the reaction under the conditions of insulated and stirred
The pH value that ammoniacal liquor to suspension that mass concentration is 17% are added dropwise in kettle is 9, then the addition 0.7mol vulcanizations into the reactor
Ammonium, 1.4mol sulphur powders and 2.8mol ethanol；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.7MPa, reactor then is heated into insulation after 190 DEG C stirs
Mix reaction 6h；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
80 DEG C of drying in oven are placed in after alcohol elution, the crystalline thing of kermesinus, the as ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and methanol under the conditions of 60 DEG C ten trithios described in dissolving step four
For ammonium molybdate, then 13 ammonium thiomolybdates after dissolving are stood at room temperature, the crystal of precipitation is 13 thio molybdic acids
Ammonium crystal；The volume ratio of the tetrahydrofuran and methanol is 4:1.
Manufactured in the present embodiment 13 thio ammonium molybdate crystals are carried out with XRD crystallographic analysis, XPS photoelectron spectroscopies point
Analysis and the analysis of X-ray single crystal diffraction, it is as a result identical with result described in embodiment 1.
Embodiment 5
The 13 thio ammonium molybdate crystals of the present embodiment are same as Example 1.
The preparation method of the 13 thio ammonium molybdate crystals of the present embodiment comprises the following steps：
Step 1: 0.14mol molybdenum trioxides and 260g water are added in reactor, suspension is uniformly mixing to obtain；
Step 2: reactor described in step one is heated into 55 DEG C, then to the reaction under the conditions of insulated and stirred
The pH value that ammoniacal liquor to suspension that mass concentration is 17% are added dropwise in kettle is 9, then the addition 0.7mol vulcanizations into the reactor
Ammonium, 2.1mol sulphur powders and 4.2mol ethanol；
Sky in nitrogen, question response kettle is passed through in the reactor of ammonium sulfide, sulphur powder and ethanol Step 3: being added into step 2
Reactor is sealed after gas emptying, holding reacting kettle inner pressure is 0.8MPa, reactor then is heated into insulation after 200 DEG C stirs
Mix reaction 5h；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, by the filter cake second
70 DEG C of drying in oven are placed in after alcohol elution, the crystalline thing of kermesinus, the as ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and ethanol under the conditions of 70 DEG C ten trithios described in dissolving step four
For ammonium molybdate, then 13 ammonium thiomolybdates after dissolving are stood at room temperature, the crystal of precipitation is 13 thio molybdic acids
Ammonium crystal；The volume ratio of the tetrahydrofuran and ethanol is 5:1.
Manufactured in the present embodiment 13 thio ammonium molybdate crystals are carried out with XRD crystallographic analysis, XPS photoelectron spectroscopies point
Analysis and the analysis of X-ray single crystal diffraction, it is as a result identical with result described in embodiment 1.
It is described above, only it is presently preferred embodiments of the present invention, any limitation is not done to the present invention, it is every according to invention skill
Any simple modification, change and equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (8)
1. a kind of preparation method of 13 thio ammonium molybdate crystal, the chemical formula of the 13 thio ammonium molybdate crystal is (NH4)2Mo3S13, at a temperature of 296K, on the type single crystal X-ray diffraction instrument of Bruker SMART APEX II, with through graphite monochromator list
The MoK alpha rays of colorParsed using the programs of SHELX 97 by direct method and complete matrix least square method
With amendment crystal structure, crystal molecule amount is 740.68, cell parameter： α=90 °, β=117.288 (6) °, γ=90 °,Z=2, R1=0.0459,
WR2=0.1236, it is characterised in that preparation method comprises the following steps：
Step 1: by molybdenum trioxide and water according to 1:The mass ratio of (10~15) is added in reactor, is uniformly mixing to obtain suspended
Liquid；
Step 2: reactor described in step one is heated into 40 DEG C~60 DEG C, then to described anti-under the conditions of insulated and stirred
The pH value for answering dropwise addition ammoniacal liquor to suspension in kettle is 8~10, then addition ammonium sulfide, sulphur powder and ethanol into the reactor；Institute
The mol ratio for stating ammonium sulfide, sulphur powder and ethanol is 1:(2~3):(4~6)；The mole of the sulphur powder is three described in step one
10~15 times of molybdenum oxide mole；
Arranged Step 3: being added into step 2 and air in nitrogen, question response kettle being passed through in the reactor of ammonium sulfide, sulphur powder and ethanol
Reactor is sealed after net, holdings reacting kettle inner pressure is 0.6MPa~0.8MPa, then by reactor be heated to 180 DEG C~
Insulated and stirred reacts 5h~7h after 200 DEG C；
Step 4: the reacted material of insulated and stirred in step 3 is filtered while hot, filter cake is obtained, the filter cake ethanol is drenched
Drying in oven is placed in after washing, the ammonium thiomolybdate of product 13 is obtained；
Step 5: using the mixed solvent of tetrahydrofuran and monohydric alcohol under the conditions of 60 DEG C~70 DEG C ten described in dissolving step four
Three ammonium thiomolybdates, then stand 13 ammonium thiomolybdates after dissolving at room temperature, and the crystal of precipitation is 13 thio
Ammonium molybdate crystal；The volume ratio of the tetrahydrofuran and monohydric alcohol is 3~5:1.
2. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 2
The mass concentration of the ammoniacal liquor is 15%~20%.
3. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 2
The pH value that ammoniacal liquor to suspension are added dropwise into the reactor is 9.
4. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 2
The mol ratio of the ammonium sulfide, sulphur powder and ethanol is 1:2.4:5.
5. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 2
The mole of the sulphur powder is 12 times of molybdenum trioxide mole described in step one.
6. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 3
The reacting kettle inner pressure is 0.7MPa, and reactor is heated to insulated and stirred after 190 DEG C and reacts 6h.
7. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 4
The temperature of the baking oven is 70 DEG C~90 DEG C.
8. the preparation method of a kind of 13 thio ammonium molybdate crystal according to claim 1, it is characterised in that in step 5
The monohydric alcohol is methanol or ethanol.
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| 2H2O and (NH4)2Mo3S13•2H2O.《J. Mater. Chem.》.2001,第11卷 * |
| Simon J. Hibble, et al..An in situ structural study of the thermal decomposition reactions of the ammonium thiomolybdates, (NH4)2Mo2S12• * |
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