WO2024121604A1 - Procédé thermochimique à base de catalyseurs hétérogènes pour production de matériaux carbonés nanocristallins - Google Patents
Procédé thermochimique à base de catalyseurs hétérogènes pour production de matériaux carbonés nanocristallins Download PDFInfo
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- WO2024121604A1 WO2024121604A1 PCT/IB2022/061916 IB2022061916W WO2024121604A1 WO 2024121604 A1 WO2024121604 A1 WO 2024121604A1 IB 2022061916 W IB2022061916 W IB 2022061916W WO 2024121604 A1 WO2024121604 A1 WO 2024121604A1
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- carbon
- oxygenic
- nanocrystalline
- ionic
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Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000008569 process Effects 0.000 title claims abstract description 67
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- 239000003575 carbonaceous material Substances 0.000 title description 2
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 239000013528 metallic particle Substances 0.000 claims abstract description 32
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 30
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 29
- 239000010432 diamond Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 229910001848 post-transition metal Inorganic materials 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000007704 transition Effects 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 150000002894 organic compounds Chemical class 0.000 claims description 22
- -1 tetrafluoroborate Chemical compound 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000009738 saturating Methods 0.000 claims description 12
- 150000005323 carbonate salts Chemical class 0.000 claims description 10
- 150000003141 primary amines Chemical class 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 229910021389 graphene Inorganic materials 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 79
- 238000001237 Raman spectrum Methods 0.000 description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 230000009467 reduction Effects 0.000 description 16
- 230000001747 exhibiting effect Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 238000004098 selected area electron diffraction Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
Definitions
- the present disclosure relates to the production of a carbon nanomaterial, including a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or a mixture thereof, particularly when said production of carbon nanomaterials involves heterogeneous catalytic thermochemical reduction.
- a carbon nanomaterial including a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or a mixture thereof, is being consumed at an accelerated rate despite its unavailability in nature.
- Such consumption trend arises in various fields of applications, especially in the electronics industry, owing to the carbon nanomaterial’s excellent properties such as superior strength and electrical properties.
- An object of the present invention is to provide a new process for industrially producing a carbon nanomaterial.
- the inventor has found that embodiments according to the concept of the present invention enable the production of such products at a significantly less energy-intensive condition, as well as satisfactory yield and reaction time.
- the present invention provides a new process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or a mixture thereof.
- Said process comprises thermochemically reducing of an oxygenic carbon source at an atmospheric pressure and an onset temperature within the range of 25 - 100 °C.
- thermochemical reduction is carried out in presence of: (a) an ionic solution comprising a solvent and an ionic salt, and (b) metallic particles acting as a heterogeneous catalyst, said metallic particles comprising one or more of the following: a post-transition element, a transition element, an oxide, and an alloy thereof.
- the metal -carbon nanomaterial composite product yield per a single run of an embodiment which depends on the type of the metal catalyst, the oxygenic carbon source and the reaction time, is approximately 10 - 100 g-L ⁇ h" 1 . Such yield is conducive to the scale-up to a mass production scale.
- the metallic particles comprise one or more of the following: the posttransition element and the transition element.
- the post-transition element is bismuth (Bi)
- the transition element is silver (Ag).
- the size of said metallic particles is within the range of 10 - 1,000 nm.
- the metallic particles are exposed to the ambient air or oxygen-containing atmosphere at 30 - 125 °C for 30 minutes to 24 hours before the reaction.
- said oxygenic carbon source is dissolved in the solvent.
- said oxygenic carbon source is dissolved in the solvent at the concentration within the range of 0. 1 - 10 M.
- said solvent is a polar solvent.
- said polar solvent is water.
- said oxygenic carbon source is water-soluble. More preferably, said oxygenic carbon source is (i) an oxygenic organic compound or (ii) a carbonate salt, a bicarbonate salt or a mixture thereof.
- oxygenic carbon source is an oxygenic organic compound
- oxygenic organic compound is a carboxylic acid, an alcohol, a ketone, an aldehyde, or a carbamate.
- the oxygenic organic compound is a carboxylic acid, it is most preferably acetic acid. In an embodiment where the oxygenic organic compound is an alcohol, it is most preferably ethanol. In an embodiment where the oxygenic organic compound is a ketone, it is most preferably acetone. In an embodiment where the oxygenic organic compound is an aldehyde, it is most preferably acetaldehyde. In an embodiment where the oxygenic organic compound is a carbamate, said carbamate is preferably prepared by saturating a primary amine aqueous solution with CO2; and in such embodiment, it is most preferred that the primary amine is mono ethanolamine and/or that the concentration of the primary amine aqueous solution is within the range of 0. 1 - 10 M.
- the carbonate salt is most preferably Na2CC>3.
- the bicarbonate salt is most preferably NH4HCO3.
- the carbonate salt is preferably prepared by saturating an aqueous solution of a strong base with CO2.
- the strong base is KOH; also most preferably, the strong base’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
- the bicarbonate salt is preferably prepared by saturating an aqueous solution of a tertiary amine, or by saturating an ammonia aqueous solution, with CO2. More preferably, the tertiary amine is dimethylethanolamine (DMAE); also more preferably, the tertiary amine’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
- DMAE dimethylethanolamine
- the ammonia’s concentration in the aqueous solution is within the range of 0.1 - 10 M.
- the ionic salt comprises a cation selected from ammonium cation, imidazolium cation, and a mixture thereof.
- said ammonium cation is ammonium cation (NH4 + ) and choline cation.
- said imidazolium cation is l-butyl-3- methylimidazolium ([bmim]).
- the anion of said ionic salt is selected from the group comprising tetrafluoroborate (BEp), hexafluorophosphate (PFr,“). halides (O’, Br, F", I"), hexafluoroantimonate (SbFr>“). sulfate (SOr 2- ). and nitrate (NO ).
- the most preferable ionic salts are: l-butyl-3- methylimidazolium tetrafluoroborate ([bmim][BF4]) or ammonium sulfate ((NFL ⁇ SCh) or choline chloride.
- the concentration of said ionic salt in the ionic solution is within the range of 0.1 - 10 M.
- H2O2 or Fe (II) ions are added to the ionic solution.
- the present invention provides a process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or a mixture thereof.
- Said process comprises steps of: (i) thermochemically reducing an oxygenic carbon source in presence of (a) an ionic solution, and (b) metallic particles suspended in said ionic solution and acting as a heterogeneous catalyst; and (ii) stirring said ionic solution.
- Said ionic solution comprises a mixture of (a) 1- butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), ammonium sulfate ((NH4)2SO4) or choline chloride, and (b) water.
- Said thermochemically reducing the oxygenic carbon source occurs at an atmospheric pressure and an onset temperature within the range of 25 - 100 °C.
- step of (ii), stirring the ionic solution may be carried out before or during the thermochemical reduction and may be carried out continuously or intermittently.
- the ionic solution is stirred continuously during the thermochemical reduction.
- Fig. 1 shows a schematic diagram of a thermochemical reactor for thermochemically reducing an oxygenic carbon source in accordance with a preferred embodiment (not to scale).
- Fig. 2A shows a Raman spectrum exhibiting merged peaks of a product of Example 1.
- Fig. 2B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 1.
- Fig. 2C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 1.
- Fig. 2D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 1.
- Fig. 2E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 1.
- Fig. 3A shows a Raman spectrum exhibiting merged peaks of a product of Example 2.
- Fig. 3B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 2.
- Fig. 3C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 2.
- Fig. 3D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 2.
- Fig. 3E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 2.
- Fig. 4A shows a Raman spectrum exhibiting merged peaks of a product of Example 3.
- Fig. 4B shows a matching of d-spacing, as obtained from Selected Area Electron Diffraction (SAED), of the product of Example 3.
- Fig. 4C shows a first Transmission Electron Microscopy (TEM) image of the product of Example 3.
- Fig. 4D shows a second Transmission Electron Microscopy (TEM) image of the product of Example 3.
- Fig. 4E shows Energy Dispersive X-ray (EDX) peaks of the product of Example 3.
- Fig. 5 shows a Raman spectrum exhibiting merged peaks of a product of Example 4.
- Fig. 6 shows a Raman spectrum exhibiting merged peaks of a product of Example 5.
- Fig. 7 shows a Raman spectrum exhibiting merged peaks of a product of Example 6.
- Fig. 8 shows a Raman spectrum exhibiting merged peaks of a product of Example 7.
- Fig. 9 shows a Raman spectrum exhibiting merged peaks of a product of Example 8.
- Fig. 10 shows a Raman spectrum exhibiting merged peaks of a product of Example 9.
- Fig. 11 shows a Raman spectrum exhibiting merged peaks of a product of Example 10.
- Fig. 12 shows a Raman spectrum exhibiting merged peaks of a product of Example 11.
- Fig. 13 shows a Raman spectrum exhibiting merged peaks of a product of Example 12.
- Fig. 14 shows a Raman spectrum exhibiting merged peaks of a product of Example 13.
- Fig. 15 shows a Raman spectrum exhibiting merged peaks of a product of Example 14.
- Fig. 16 shows a Raman spectrum exhibiting merged peaks of a product of Example 15.
- compositions and processes include the recited elements, but not excluding others.
- Consisting essentially of when used to define compositions and methods, shall mean excluding other elements of any essential significance to the combination for the stated purpose. Thus, a process or product consisting essentially of the elements as defined herein would not exclude other materials or steps that do not materially affect the basic and novel characteristic(s) of the claimed invention.
- Consisting of shall mean excluding more than trace elements of other ingredients and substantial steps. Embodiments defined by each of these transition terms are within the scope of this invention.
- Oxygenic carbon source is intended to mean a mono-molecular compound or an ionic compound containing both carbon and oxygen atoms.
- Oxygenic organic compound is intended to mean a mono-molecular organic compound having an oxygen atom.
- Fig. 1 shows a schematic diagram of a thermochemical reactor in which a process for producing a carbon nanomaterial is conducted in accordance with a preferred embodiment.
- the thermochemical reactor (10) comprises a receptacle (100), a heating element (200), a stirrer (300), and a vent (400).
- the receptacle (100) contains an ionic solution (110) in which metallic particles (120) are present and act as a heterogeneous catalyst.
- the ionic solution (110) is a mixture of an ionic salt and a solvent in which an oxygenic carbon source is dissolved.
- the heating element (200), the source of thermal energy is preferably connected to the lower part or the bottom of the receptacle (100) and configured to heat the ionic solution (110).
- the stirrer (300) is preferably disposed so as to immerse in the ionic solution (110) and configured to disperse the metallic particles (120) in the ionic solution (110).
- the stirrer (300) takes the form of a propeller having a shaft (310), an end of which is connected to multiple blades (320), and another end of which, to a motor (330).
- the shaft (310) is disposed substantially vertically so that the blades (320) are effectively immersed in the ionic solution (110) and the motor (330) is located away from the ionic solution (110).
- the vent (400), through which the gaseous byproducts leave the receptacle (100), is preferably located at the top of the receptacle (100).
- the carbon source is an oxygenic carbon source.
- a water-soluble oxygenic carbon source is used.
- the oxygenic carbon source is a carbonate salt or a bicarbonate salt.
- Preferred carbonate and bicarbonate salts include: Na2CO and NH4HCO3.
- the carbonate salt is prepared by saturating an aqueous solution of a strong base with CO2.
- the bicarbonate salt is prepared by saturating (i) an ammonia aqueous solution or (ii) an aqueous solution of a tertiary amine, with CO2.
- the concentration of the strong base, ammonia, or the tertiary amine, in their respective aqueous solution is within the range of 0.1 - 10 M.
- the oxygenic carbon source is an oxygenic organic compound.
- Preferred oxygenic organic compounds include: an alcohol, carboxylic acid, ketone, aldehyde, and carbamate.
- the carbamate is prepared by saturating primary amine aqueous solution with CO2. More preferably, the primary amine is mono ethanolamine and/or the concentration of the primary amine aqueous solution is within the range 0.1 - 10 M.
- the oxygenic carbon source may be supplied to the ionic solution in any desired form, for example, in the solid, liquid, gaseous, or solvated form, depending on the phase stability at the operating temperature and pressure.
- the oxygenic carbon source is dissolved in the ionic solution (i.e., supplied in the solvated form).
- a process according to the concept of the present invention may be carried out in various conditions which may be adjusted according to the circumstantial requirements.
- the applicable pressure is within the range of about 1 to about 20 atm.
- the pressure in accordance with the preferred embodiment is an ambient pressure.
- the ambient pressure refers to a common or usual condition surrounding any person in a room.
- An ambient pressure for operating the process is preferably 1 atm. Because a process in accordance with the preferred embodiment allows the catalytic thermochemical reduction to occur effectively at such ambient pressure, it obviates the need to pressurize, depressurize, vacuumize or control the pressure at any part of the thermochemical reactor (10) and thus substantially simplifies the production.
- the onset temperature of the thermochemical reactor (10) is at least of the thermal energy sufficient to initiate the catalytic thermochemical reduction of the oxygenic carbon source.
- the onset temperature of the ionic solution (110) is substantially constant during the catalytic thermochemical reduction.
- thermochemical reactor (10) depends on the carbon source and the metallic particles being selected.
- the thermochemical reactor (10) comprises a heating element (200) to provide the onset temperature, which is preferably within a range of about 25 - 100 °C.
- the heating element (200) is adapted to monitor and control the onset temperature.
- the catalytic thermochemical reduction occurred in an autoclave which is capable of both monitoring and regulating the onset temperature.
- the autoclave is commonly used as an industry-scale thermochemical reactor, which is applicable to the concept of the present invention.
- the ionic solution (110) comprises a solvent and an ionic salt.
- the solvent is a polar solvent, and more preferably is water.
- ionic salts may be part of the mixture that forms the ionic solution (110).
- the ionic salts in an embodiment are compounds represented by Formula (I):
- n ‘ is selected from the group comprising tetrafluoroborate (
- [A] + is selected from —
- R 1 , R 2 , R 3 , and R 4 being selected from hydrogen atom, Cl-C6-alkyl, Cl-C6-alkoxy, Cl- C6-aminoalkyl, Cl-C6-hydroxylalkyl, C5-C12-aryl, and C5-C12-aryl-Cl-C6-alkyl groups; and
- R, R 1 , and R 2 being selected from Cl-C6-alkyl, Cl-C6-alkoxy, Cl-C6-aminoalkyl, C5- C12-aryl, and C5-C12-aryl-Cl-C6-alkyl groups.
- the preferred combination of the ionic salt, the oxygenic carbon source, and water is as follows: (a) the ionic salt being a mixture of l-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), ammonium sulfate ((NH ⁇ SCh) or choline chloride, (b) an oxygenic carbon source, and (c) water.
- the ionic salt also functions as a stabilizer of nanoparticles/carbon nanomaterial formed at the metallic particles (120) during the catalytic thermochemical reduction of the oxygenic carbon source in the thermochemical reactor (10).
- the ionic salt is selected from ([bmim][BF4]), (NFL ⁇ SCh, and choline chloride.
- the metallic particles (120) act as a heterogeneous catalyst for the catalytic thermochemical reduction.
- the metallic particles (120) comprise one or more of the following: the posttransition element and the transition element. More preferably, the post-transition element is Bi and the transition element is Ag.
- the size of the metallic particles is within the range of 10 - 1,000 nm.
- the metallic particles are exposed to the ambient air or oxygencontaining atmosphere at 30 - 125 °C for 30 minutes to 24 hours in order to create a thin oxide layer before the start of thermochemical reduction.
- the catalytic thermochemical reduction occurs in the thermochemical reactor (10) as a batch operation.
- the crystal structure and crystal size of the resulting product depends on the nature of metallic particles (120), the carbon source used, the energy supplied, and the reaction time, among others. Prolonging the reaction time results in a larger crystallite size being formed.
- the reaction time for each batch of production can be ranged from about 5 minutes to 300 minutes. Preferably, the reaction time for each batch of production is about 15 minutes to 75 minutes.
- Nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite said composite containing a post-transition metal or a transition metal, and/or a mixture thereof
- the process for producing a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon and/or a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal, and/or mixture thereof in the thermochemical reactor (10) is a batch operation.
- nanocrystalline carbon with the ID, 2D, or 3D structure and/or the nanocrystalline diamond and/or the amorphous carbon and/or the metal-carbon nanomaterial composite, said composite containing a post-transition metal or transition metal, and/or the mixture thereof is formed at the metallic particles (120).
- the carbon product obtained from a process in accordance with a preferred embodiment comprises a graphite and/or a graphene and/or a graphitic carbon and/or the nanocrystalline diamond and/or the amorphous carbon, and/or the metal-carbon nanomaterial composite, said composite containing the post-transition metal or the transition metal, and/or the mixture thereof.
- the carbon product being produced is further separated from the metallic particles (120) by a known separation process.
- said separation process is a mechanical removal process, such as mechanical abrasion, or ultrasonication.
- the carbon product may contain metallic material residues, which can be further removed from the carbon product by means of a conventional chemical removal process, preferably acid leaching.
- acid leaching involves the use of nitric acid (HNO3), hydrochloric acid (HC1), or a mixture thereof.
- the separation process of the carbon product from the metallic particles (120) comprises the following steps:
- step (2) placing the solid product that was removed by step (1) in a microcentrifuge tube
- the mixture of nitric acid and hydrochloric acid is in a molar ratio of 1:3 in 0.3 ml of the solution
- DI water deionized water
- a nanocrystalline carbon with a ID, 2D, or 3D structure and/or a nanocrystalline diamond and/or an amorphous carbon product and/or a metal- carbon nanomaterial composite said composite containing a post-transition metal or a transition metal, and/or a mixture thereof, which is a mixture having various carbon structures.
- Said structures are inclusive of, and selectable from: an amorphous carbon, a graphite, a graphene, a nanocrystalline diamond, and a metal-carbon nanomaterial composite, said composite containing a post-transition metal or a transition metal.
- thermochemical reactor 10
- the thermochemical reactor (10) further contained the ionic solution (110), the onset temperature of which was generated and measured by the heating element (200).
- the ionic solution (110) was dispersed with the metallic particles (120) and stirred by the stirrer (300) at the agitation rate of 10 - 1,000 rpm.
- the reaction was carried out under a pressure of about 1 atm. After the reaction time, the carbon nanomaterial product was formed at the metallic particles (120), which was then removed from the ionic solution (110) and dried.
- the metallic particles (120) were exposed to the ambient air or oxygencontaining atmosphere at 30 - 125 °C for 30 minutes to 24 hours before being used in the thermochemical reduction.
- Some oxygenic carbon sources were prepared by saturating the ionic solution (110) with carbon dioxide gas (CO2) at ambient conditions. More particularly, where the oxygenic carbon source was a carbonate salt, the ionic solution (110) contained KOH (a strong base); where the oxygenic carbon source was a bicarbonate salt, the ionic solution (110) contained ammonia or dimethylethanolamine (a tertiary amine); where the oxygenic carbon source was a carbamate, the ionic solution (110) contained mono ethanolamine (a primary amine).
- the flow rate of CO 2 per volume of the ionic solution (110) was within the range of 0.04 - 40 cm 3 CO2 per cm 3 ionic solution per minute.
- the CO2 purging time was within 1-1,000 minutes.
- Table 1 in the next sheet shows the particulars of Examples 1-15. Description of the product obtained from each Example shall follow Table 1.
- Example 1 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
- Fig. 2A shows the Raman spectrum of the product of Example 1.
- SAED Selected Area Electron Diffraction
- TEM Transmission Electron Microscopy
- EDX Energy Dispersive X-ray
- Example 2E revealed the following atomic percentages of said product: 91.34 % carbon; 1.65 % oxygen; 1.86 % copper; 0.5 % silver; 0.33 % iodine; and 4.31 % mercury. All the foregoing results confirmed that the product of Example 1 comprised nanocrystalline diamond comprising n-diamond, hexagonal diamond, i-Carbon, graphitic carbon, and amorphous carbon structures.
- Example 2 produced a metal-carbon composite product in the form of nanocrystalline carbon with a 2D structure.
- Fig. 3A shows the Raman spectrum of the product of Example 2.
- SAED Selected Area Electron Diffraction
- TEM Transmission Electron Microscopy
- EDX Energy Dispersive X-ray
- Example 3 produced a metal -carbon composite product in the form of metallic Bi/Bi oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
- Fig. 4A shows the Raman spectrum of the product of Example 3.
- SAED Selected Area Electron Diffraction
- TEM Transmission Electron Microscopy
- EDX Energy Dispersive X-ray
- Example 4E revealed the following atomic percentages of said product: 53.34 % carbon; 27.1 % oxygen; 3.44 % fluorine; 15.19 % tin; and 0.93 % bismuth. All the foregoing results confirmed that the product of Example 3 comprised graphitic carbon, and amorphous carbon structures.
- Example 4 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 5, as observed from the shown Raman spectrum, the carbon product obtained from Example 4 comprised graphitic carbon, and amorphous carbon structures.
- Example 5 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 6, as observed from the shown Raman spectrum, the carbon product obtained from Example 5 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 6 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 7, as observed from the shown Raman spectrum, the carbon product obtained from Example 6 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 7 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 8, as observed from the shown Raman spectrum, the carbon product obtained from Example 7 comprised graphitic carbon, and amorphous carbon structures.
- Example 8 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 9, as observed from the shown Raman spectrum, the carbon product obtained from Example 8 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 9 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 10, as observed from the shown Raman spectrum, the carbon product obtained from Example 9 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 10 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 11, as observed from the shown Raman spectrum, the carbon product obtained from Example 10 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 11 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
- the carbon product obtained from Example 11 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 12 produced a metal -carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure.
- the carbon product obtained from Example 12 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 13 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 14, as observed from the shown Raman spectrum, the carbon product obtained from Example 13 comprised graphitic carbon, and amorphous carbon structures.
- Example 14 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 15, as observed from the shown Raman spectrum, the carbon product obtained from Example 14 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
- Example 15 produced a metal-carbon composite product in the form of metallic Ag/Ag oxides and nanocrystalline carbon with a ID, 2D, and 3D structure. According to Fig. 16, as observed from the shown Raman spectrum, the carbon product obtained from Example 15 comprised nanocrystalline diamond, graphitic carbon, and amorphous carbon structures.
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Abstract
L'invention concerne un nouveau procédé de production d'un carbone nanocristallin à structure 1D, 2D ou 3D et/ou d'un diamant nanocristallin et/ou d'un carbone amorphe et/ou d'un composite métal-carbone nanomatériau, ledit composite contenant un métal post-transition ou un métal de transition, et/ou un mélange de ceux-ci, par réduction thermochimique d'une source de carbone oxygénique à une pression atmosphérique et à une température de départ comprise entre 25 et 100 °C en présence (a) d'une solution ionique comprenant un solvant et un sel ionique, et (b) de particules métalliques jouant le rôle de catalyseur hétérogène. Lesdites particules métalliques comprennent un ou plusieurs des éléments suivants : un élément de post-transition, un élément de transition, un oxyde et un de leurs alliages. La pression atmosphérique et la faible température d'amorçage permises par les modes de réalisation simplifient la production, et le rendement en carbone nanocristallin peut être augmenté pour atteindre une échelle de production de masse. Un produit obtenu selon le nouveau procédé comprend un carbone nanocristallin ayant une structure 1D, 2D ou 3D et/ou un diamant nanocristallin et/ou un carbone amorphe et/ou un composite de nanomatériau métal-carbone, ledit composite contenant un métal de post-transition ou un métal de transition. Un tel produit peut être un mélange qui contient diverses structures de carbone, comprenant : un diamant nanocristallin, un carbone amorphe, un carbone graphitique et un composite de nanomatériau métal-carbone, ledit composite contenant un métal de post-transition ou un métal de transition. Ledit produit peut en outre comprendre un graphite ou un graphène.
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WO2022185098A1 (fr) * | 2021-03-04 | 2022-09-09 | Crystallyte Co., Ltd. | Procédé électrolytique pour produire un carbone nanocristallin avec une structure 1d, 2d, ou 3d et/ou un diamant nanocristallin et/ou un carbone amorphe et/ou un composite de nanomatériau métal-carbone et/ou un mélange de ceux-ci dans des conditions ambiantes |
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