US4308171A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method of preparing di and poly chalcogenides of group VIIb by low temperature precipitation from nonaqueous solution and small crystallite size stoichiometric layered dichalcogenides of rhenium and technetium
Assignee: ExxonMobil Technology and Engineering Co
•
Filing: 1980-07-16
•
Granted: 1981-12-29
•
Expires: 2000-07-16
Abstract
Abstract Finely divided, small particle (0.1 micron or less) small crystallite (about 50 Ax100 A or less) chalcogenides of manganese, rhenium and technetium are described. These compositions are prepared by mixing the absence of an aqueous solvent, a manganese, rhenium or technetium salt with a source of chalcogenide yielding a precipitate. The manganese, rhenium or technetium salt and the source of chalcogen can be mixed either neat or in the presence of a nonaqueous aprotic solvent. The precipitate which results before removal of the anion salt is a finely divided product. In the case of rhenium dichalcogenide the product possesses a layered structure. The anion salt may be removed by any technique common to the art, pumping under vacuum being one such technique, washing with a suitable solvent being another. A method is described for the preparation of di- and poly-chalcogenides of the formula MXy wherein M is a metal selected from the group consisting of mangangese, rhenium and technetium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 1.5 to about 4, preferably about 2, comprising the low temperature, nonaqueous precipitation of said MXy compounds from mixtures of the salts of said manganese, rhenium and technetium. Said precipitation occurs in the absence of aqueous solvents. The process of the instant invention permits the preparation of materials uncontaminated by water, oxygen or hydrolysis products.
Inventors
- 👤 Martin B. Dines
- 👤 Russell R. Chianelli
- 👤 Theresa A. Pecoraro
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 10:45
CPC Classifications
B; B82; B82Y; B82Y30/00; B01; B01J; B01J27/00; B01J27/02; B01J27/04; B01J27/057; B01J27/0573; B01J27/0576; C; C01; C01B; C01B19/00; C01B19/007; C01G; C01G45/00; C01G45/20; C01G47/00; C01G55/00; C01G99/00; C01G99/006; C01P; C01P2002/00; C01P2002/02; C01P2002/20; C01P2002/22; C01P2002/60; C01P2002/70; C01P2002/72; C01P2004/00; C01P2004/60; C01P2004/62; C01P2004/64; C01P2006/00; C01P2006/12; C01P2006/80; Y; Y10; Y10S; Y10S65/00; Y10S65/15
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
65 words
Chalcogenides amorphous to X-ray having a particle size of less than 0.1 micron and a crystallite size of about 50 A×100 A or less of the formula MX y wherein M is a metal selected from the group consisting of technetium and rhenium X is a chalcogen selected from the group consisting of sulfur, selenium and tellurium and y is about 1.5 to about 4.
Claim 2
Dependent Claim
65 words
Chalcogenides amorphous to X-ray having a particle size of less than 0.1 micron and a crystallite size of about 50 A×100 A or less of the formula MX y wherein M is a metal selected from the group consisting of technetium and rhenium X is a chalcogen selected from the group consisting of sulfur, selenium and tellurium and y is about 1.5 to about 4.
Claim 3
Dependent Claim
184 words
Chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of Tc and Re, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 1.5 to about 4 prepared by mixing, at a temperature of from -78° C. to 400° C. for a time sufficient for reaction to occur, in the absence of aqueous or protic solvent, solutions of: (A) metal salts, the metal being selected from the group consisting of Tc and Re, and (B) sources of sulfide, selenide or telluride ions, said source being selected from the group consisting of K 2 X, Li 2 X, Na 2 X, NaHX, (NH 4 ) 2 X, LiHX, KHX, (NH 4 )HX, (RR'NH 2 ) 2 X, (RNH 3 ) 2 X, (R,R'R"NH) 2 X wherein R, R' and R" are the same or different C 1 -C 20 alkyl or C 6 to C 20 aryl and X is the chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof.
Claim 4
Dependent Claim
184 words
Chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of Tc and Re, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 1.5 to about 4 prepared by mixing, at a temperature of from -78° C. to 400° C. for a time sufficient for reaction to occur, in the absence of aqueous or protic solvent, solutions of: (A) metal salts, the metal being selected from the group consisting of Tc and Re, and (B) sources of sulfide, selenide or telluride ions, said source being selected from the group consisting of K 2 X, Li 2 X, Na 2 X, NaHX, (NH 4 ) 2 X, LiHX, KHX, (NH 4 )HX, (RR'NH 2 ) 2 X, (RNH 3 ) 2 X, (R,R'R"NH) 2 X wherein R, R' and R" are the same or different C 1 -C 20 alkyl or C 6 to C 20 aryl and X is the chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof.
Claim 5
Dependent Claim
14 words
Chalcogenides prepared as in claim 2, wherein y is 2 and X is sulfur.
Claim 6
Dependent Claim
19 words
Chalcogenides prepared by the process of claim 2, wherein the temperature of reaction is between 25° to 300° C.
Claim 7
Dependent Claim
98 words
Chalcogenides prepared as in claim 2, wherein the sources of sulfur, selenium and tellurium ions are selected from the group consisting of K 2 S, Li 2 S, (NH 4 ) 2 S, Na 2 S, NaHS, KHS, LiHS, (NH 4 )HS, Li 2 Se, (NH 4 ) 2 Se, Li 2 Te, (RNH 3 ) 2 S, (R,R'NH 2 ) 2 S, (R,R'R"NH) 2 S, wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 to C 20 alkyl and C 6 to C 20 aryl groups.
Claim 8
Dependent Claim
13 words
Chalcogenides of Re and Tc prepared as in claim 2 which are stoichiometric.
Claim 9
Dependent Claim
87 words
Chalcogenides prepared as in claim 2 wherein the reaction is carried out in a nonaqueous aprotic solvent selected from the group consisting of C 4 to C 8 ethers, acetonitrile, benzonitrile, acetone, pyridine, propionitrile, N-methyl-formamide, dimethylformamide, 1,2-dimethoxyethane, propylene carbonate, ammonia, C 6 -C 20 aromatics, molten sulfur, sulfur dioxide, diglyme ethylacetate, C 4 to C 5 esters, sulfolane, dimethylsulfite, tributylphosphate, C 1 -C 20 amines, C 5 -C 12 alkanes, anhydrous formic acid, glacial acetic acid, C 1 -C 20 alkyl halides, C 6 -C 20 arylhalides.
Claim 10
Dependent Claim
43 words
Chalcogenides prepared as in claim 2 wherein the anion of the metal salt is selected from the group comprising halides, sulfates, nitrates, carboxylates and perfluorocarboxylates, wherein the carbonaceous moiety of the anion is a C 1 to C 8 hydrocarbon or fluorocarbon radical.
Claim 11
Independent Claim
188 words
A method for the preparation of chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of technetium and rhenium, X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 1.5 to about 4, which comprises reacting, in the absence of aqueous or protic solvent, at a temperature of from -78° to 400° C. for a time sufficient for reaction to occur, a solution of a transition metal salt, the transition metal being selected from the group consisting of manganese, technetium and rhenium, with a source of sulfide, selenide or telluride ions, said source being selected from the group consisting of K 2 X, KHX, Li 2 X, LiHX, NaHX, (NH 4 ) 2 X, Na 2 S, (RNH 3 ) 2 X, (R,R'NH 2 ) 2 X, (R,R'R"NH) 2 X wherein R, R' and R" are the same or different C 1 -C 20 alkyl or C 6 to C 20 aryl and X is the chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof.
Claim 12
Independent Claim
188 words
A method for the preparation of chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of technetium and rhenium, X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 1.5 to about 4, which comprises reacting, in the absence of aqueous or protic solvent, at a temperature of from -78° to 400° C. for a time sufficient for reaction to occur, a solution of a transition metal salt, the transition metal being selected from the group consisting of manganese, technetium and rhenium, with a source of sulfide, selenide or telluride ions, said source being selected from the group consisting of K 2 X, KHX, Li 2 X, LiHX, NaHX, (NH 4 ) 2 X, Na 2 S, (RNH 3 ) 2 X, (R,R'NH 2 ) 2 X, (R,R'R"NH) 2 X wherein R, R' and R" are the same or different C 1 -C 20 alkyl or C 6 to C 20 aryl and X is the chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof.
Claim 13
Dependent Claim
15 words
The method of claim 9 further characterized by isolating the product after the reaction occurs.
Claim 14
Dependent Claim
42 words
The method of claim 10 further characterized by the step of contacting the isolated product with an intercalating solvent, thereby forming an intercalated chalcogenide and then driving the solvent off by means of heat, thereby generating a chalcogenide of increased surface area.
Claim 15
Dependent Claim
44 words
The method of claim 11 wherein the intercalating solvent is selected from the group consisting of pyridine, ammonia, C 1 -C 20 amines, aldehydes, ketones, amides, heterocyclic bases, and amidines, and the solvent is subsequently driven off at a temperature of between 75°-200° C.
Claim 16
Dependent Claim
12 words
The method of claim 9 wherein the product is a stoichiometric chalcogenide.
Claim 17
Dependent Claim
18 words
The method of claim 9 wherein the chalcogen is selected from the group consisting of sulfur and selenium.
Claim 18
Dependent Claim
10 words
The method of claim 9 wherein the chalcogen is sulfur.
Claim 19
Dependent Claim
11 words
The method of claim 9 wherein the product is a dichalcogenide.
Claim 20
Dependent Claim
11 words
The method of claim 9 wherein the product is a disulfide.
Claim 21
Dependent Claim
16 words
The method of claim 9 wherein the temperature of reaction is between 25° to 300° C.
Claim 22
Dependent Claim
94 words
The method of claim 9 wherein the source of sulfur, selenium and tellurium is selected from the group consisting of Li 2 S, LiHS, NaHS, KHS, (NH 4 )HS, (NH 4 ) 2 S, Na 2 S, K 2 S, Li 2 Se, Li 2 Te, (NH 4 ) 2 Se, (RNH 3 ) 2 S, (RR'NH 2 ) 2 S, (RR'R"NH) 2 S wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 -C 20 alkyl and C 6 -C 20 aryl groups.
Claim 23
Dependent Claim
12 words
The method of claim 10 wherein the isolation step utilizes excess solvent.
Claim 24
Dependent Claim
17 words
The method of claim 10 wherein the isolation step utilizes vacuum pumping to draw off volatile byproducts.
Claim 25
Dependent Claim
38 words
The method of claim 10 further characterized by including the step of annealing the isolated product at a temperature of over about 450° C. thereby generating a product having low surface area, moderate particle size and high crystallinity.
Claim 26
Dependent Claim
70 words
Homogeneous dispersions of compounds of the formula MXy wherein M is a transition metal selected from the group consisting of Re and Tc, X is selected from the group consisting of sulfur, selenium and tellurium and y is a number from about 1.5 to about 4 prepared as in claim 9 in solvents selected from the group consisting of propylene carbonate, dimethylformamide, pyridine, acetonitrile, benzonitrile, propionitrile, 1,2 dimethoxyethane, diglyme, N-methylformamide.
Claim 27
Dependent Claim
14 words
The homogeneous dispersions of claim 23 wherein the compound dispersed is ReS 2 .
Claim 28
Dependent Claim
32 words
Compositions comprising the homogeneous dispersion of claim 23 deposited on high surface area supports, said supports being selected from the group consisting of high surface area carbon, high surface area refractory oxides.
Claim 29
Dependent Claim
31 words
The compositions of claim 25 wherein the high surface area support is selected from the group consisting of CaO, MgO, Al 2 O 3 , silica-alumina and high surface area carbon.
Claim 30
Dependent Claim
86 words
The method of claim 9 wherein the reaction is carried out in a nonaqueous aprotic solvent selected from the group consisting of C 4 to C 8 ethers, acetonitrile, benzonitrile, acetone, pyridine, propionitrile, N-methylformamide, dimethylformamide, 1,2-dimethoxyethane, propylene carbonate, ammonia, C 6 -C 20 aromatics, molten sulfur, sulfur dioxide, diglyme, ethylacetate, C 4 to C 5 esters, sulfolate, dimethylsulfite, tributylphosphate, C 1 -C 20 amines, C 5 -C 12 alkanes, anhydrous formic acid, glacial acetic acid, C 1 -C 20 alkyl halides, C 6 -C 20 arylhalides.
Claim 31
Dependent Claim
42 words
The method of claim 9 wherein the anion of the metal salt is selected from the group comprising halides, sulfates, nitrates, carboxylates and perfluorocarboxylates wherein the carbonaceous moiety of the anion is a C 1 to C 8 hydrocarbon or fluorocarbon radical.
References Cited (Backward Citations)
GB358180A
Cited
GB362354A
Cited
FR728913A
Cited
US1948408A
Cited
US2145657A
Cited
US2354742A
Cited
US2448740A
Cited
US2654696A
Cited
US2647858A
Cited
US2805917A
Cited
US3026175A
Cited
US3140994A
Cited
US3306701A
Cited
US3161585A
Cited
US3336386A
Cited
US3252895A
Cited
US3291720A
Cited
US3338822A
Cited
US3320157A
Cited
US3331769A
Cited
US3509213A
Cited
US3453217A
Cited
US3538162A
Cited
US3538161A
Cited
FR2034431B1
Cited
US3714339A
Cited
US3766064A
Cited
US3622497A
Cited
US3688109A
Cited
US3793081A
Cited
US3763043A
Cited
US3840389A
Cited
GB1471589A
Cited
US4009052A
Cited
US4055630A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-12-28 | 1985-06-29 | 1985-12-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-12-28 | 1989-06-29 | 1989-12-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-12-28 | 1993-06-29 | 1993-12-29 | $7700.00 | Window Closed / Lapsed |