EP3038976A1 - Bulk preparation of holey carbon allotropes via controlled catalytic oxidation - Google Patents
Bulk preparation of holey carbon allotropes via controlled catalytic oxidationInfo
- Publication number
- EP3038976A1 EP3038976A1 EP13892744.7A EP13892744A EP3038976A1 EP 3038976 A1 EP3038976 A1 EP 3038976A1 EP 13892744 A EP13892744 A EP 13892744A EP 3038976 A1 EP3038976 A1 EP 3038976A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon
- graphene
- nanoparticles
- oxidation catalyst
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 89
- 230000003647 oxidation Effects 0.000 title claims abstract description 88
- 229910021387 carbon allotrope Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 230000003197 catalytic effect Effects 0.000 title description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 205
- 238000000034 method Methods 0.000 claims abstract description 78
- 239000002105 nanoparticle Substances 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000007669 thermal treatment Methods 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 153
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000002074 nanoribbon Substances 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001905 inorganic group Chemical group 0.000 claims description 2
- 238000010849 ion bombardment Methods 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 64
- 229920004738 ULTEM® Polymers 0.000 description 17
- 239000002131 composite material Substances 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 16
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- 230000007547 defect Effects 0.000 description 15
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- 230000008021 deposition Effects 0.000 description 9
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229940071536 silver acetate Drugs 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 230000033001 locomotion Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000002524 electron diffraction data Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004299 exfoliation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- -1 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000013030 3-step procedure Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- FCHAMFUEENBIDH-UHFFFAOYSA-N Severin Natural products CC1CCC2C(C)C3CCC4(O)C(CC5C4CC(O)C6CC(CCC56C)OC(=O)C)C3CN2C1 FCHAMFUEENBIDH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
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- 239000008247 solid mixture Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 238000010626 work up procedure 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
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- 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
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
Definitions
- the present invention relates to holey graphenes, graphene nanomeshes, holey carbon nanotubes, or holey carbon nanofibers, and, more particularly to holey graphenes, graphene nanomeshes, holey carbon nanotubes, or holey carbon nanofibers formed by controlled catalytic oxidation.
- Graphene sheets are two-dimensional, conjugated carbon structures which are only one or a few atoms thick. They are currently among the most studied nanomaterials for potential applications in electronics, energy harvesting, conversion, and storage, polymer composites, and others. 1"4 Graphene sheets with the most ideal structures are experimentally obtained via mechanical exfoliation (the "Scotch Tape” method), which only produces very small quantities. 1 For the bulk preparation of graphene, one of the most popular methods usually starts with strong oxidation of natural graphite into graphene oxide (GO) that is dispersible in aqueous solutions as an exfoliated monolayer or few-layered sheets.
- GO graphene oxide
- the exfoliated GO sheets may then be chemically or thermally converted into graphene - or more accurately “reduced graphene oxide” (rGO).
- rGO reduced graphene oxide
- chemically exfoliated rGO sheets usually have more defects.
- 3 ' 5,6 [05] graphene sheets prepared from any method always contain intrinsic defects. Typical types of defects on graphene surface are Stone-Wales (pentagon-heptagon pairs) or vacancy sites, which are mostly of nanometer sizes. 5 ' 6 Recently, there have been a few reports on novel types of graphene structures which are featured with large pore openings (i.e., holes) on the conjugated carbon surface.
- porous Si0 2 mask on top of a graphene flake, was then placed under oxygen plasma for the removal of exposed carbon atoms underneath. This resulted in supported or freestanding (upon lift-off) graphene nanomeshes with spherical holes of a few to tens of nm in diameter with various periodicities.
- metallic nanoparticles such as silver (Ag), gold (Au), or platinum (Pt) nanoparticles, or metallic oxide nanoparticles, or combinations thereof.
- the present invention addresses these needs by providing a method for forming holey graphenes by a controlled catalytic oxidation of the graphene surface using metallic or metal oxide nanoparticles.
- the method includes the steps of providing a carbon allotrope in solid form, depositing carbon oxidation catalyst nanoparticles on the surface of the carbon allotrope sheet in a facile, controllable, and solvent-free process to yield an carbon oxidation catalyst-carbon allotrope material, subjecting the resulting carbon oxidation catalyst-carbon allotrope material to a thermal treatment in air, selectively oxidizing the carbons in contact with the carbon oxidation catalyst nanoparticles into gaseous byproducts, and removing the carbon oxidation catalyst nanoparticles such that the holes remain in the surface of the carbon allotrope.
- the carbon allotrope is preferably graphene, graphene oxide, reduced graphene oxide, thermal exfoliated graphene, graphene nanoribbons, graphite, exfoliated graphite, expanded graphite, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon fibers, carbon black, amorphous carbon, or fullerenes.
- the carbon oxidation catalyst may be a transition metal, a rare earth metal, an oxides, or a
- the carbon oxidation catalyst is Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, or Au.
- the carbon oxidation catalyst nanoparticle -carbon allotrope is prepared by heating a mixture of a metal salt precursor and a carbon allotrope at an elevated temperature whereby the metal salt precursor is decomposed in an inert atmosphere with the elevated temperature being between 100 to 500°C and most preferably 350°C.
- the metal salt precursor is preferably a compound with organic groups or inorganic groups and more preferably metal acetate, metal acetyl acetonate, metal nitrate, metal halides, or combinations thereof.
- the heating may be provided by energy input such as thermal, electrical, mechanochemical, electrochemical, electron bombardment, ion bombardment, electromagnetic, or combinations of those.
- the carbon oxidation catalyst nanoparticle is in a concentration of between 0.1 mol% and 20 mol%.
- the oxidation step preferably occurs at a temperature between 150°C and 500°C.
- the carbon oxidation catalyst nanoparticles may preferably be removed by treatment in acid at temperatures between ambient and the temperature to reflux the acid and the acid is most preferably nitric acid, hydrochloric acid, sulfuric acid, acetic acid, chlorosulfonic acid, phosphorous acid or combinations thereof.
- the resulting holey carbon allotrope is incorporated into an electrode as a platform for an electrochemical device. Electrodes may be prepared according to the method described herein. In particular, this method may be use to form hole graphene by providing a graphene sheet and depositing Ag
- the steps are as set out previously.
- the Ag nanoparticles are in the form of metallic silver in a concentration of between 0.1 mol% and 20 mol%.
- the Ag nanoparticles are removed by treatment in diluted nitric acid at temperatures between ambient and the temperature to reflux the acid.
- Fig. la shows a TEM image of (Ag-G)i samples
- Fig. lb shows a TEM image of (Ag-G) !0 samples, the inset is a SEM image showing the flat interface morphology of a Ag nanoparticle on a graphene sheet;
- Fig. lc shows XRD patterns of the same samples: (Ag-G)i (bottom) and (Ag-G)io
- Fig. Id shows an XPS spectrum in the Ag 4d core level region for the (Ag-G)io sample
- Fig. 2a shows a lower magnification SEM image of a (Ag-G)io sample subjected to air oxidation at 300°C for 3 hours showing both holes and tracks;
- FIG. 2b shows SEM images of a (Ag-G)io sample subjected to air oxidation at 300°C for 3 hours showing areas enriched with lower aspect ratio holes;
- Fig. 2c shows SEM images of a (Ag-G)io sample subjected to air oxidation at 300°C for 3 hours showing areas enriched with high aspect ratio holes (i.e., tracks);
- Fig. 2d shows a TEM image at higher magnification of a (Ag-G) 10 sample subjected to air oxidation at 300°C for 3 hours showing the morphology of a hole;
- Fig. 3a shows DTG curves (air, 5.4°C/min) of the (Ag-G)io (top) and (Ag-G)i (middle) samples in comparison with the starting graphene sample (G, bottom);
- Fig. 3b shows the isothermal regions of the TGA traces of the same (Ag-G)io sample heated to and held at the denoted temperatures (from top to bottom: 250, 300, 350, 400, 450, 500°C) in air for 3-10 h;
- Fig. 4a shows a TEM image of the same (Ag-G)io sample oxidized in air at
- Fig. 4b shows a TEM image of the same (Ag-G)io sample oxidized in air at
- Fig. 4c shows a TEM image of the same (Ag-G)]o sample oxidized in air at 400°C, shown in the inset are two graphene sheets with small ( ⁇ 500 nm) lateral dimensions as a result of catalytic oxidation;
- Fig. 5a shows XRD patterns of a (Ag-G)io sample before (black) and after (red) catalytic oxidation in air, the inset shows the enlarged Ag (1 11) peak region;
- Fig. 5b shows XPS Ag 4d spectra of the same (Ag-G)io sample after catalytic oxidization in air at various temperatures: 250, 300, 350 and 400°C (from bottom to top);
- Fig. 6a shows a SEM image of a hGj sample
- Fig. 6b shows a TEM image of a hGj sample acquired at the exactly the same location as the corresponding image shown in Fig. 6a;
- Fig. 6c shows a SEM image of a hG 10 sample
- Fig. 6d shows a TEM image of a hGjo sample acquired at the exactly the same location as the corresponding image shown in Fig. 6c;
- Fig. 6e shows a SEM image of a control graphene sample
- Fig. 6f shows a TEM image of a control graphene sample acquired at the exactly the same location as the corresponding image shown in Fig. 6e;
- Fig. 7a shows a TEM image of a hGio sheet
- Fig. 7b shows an electron diffraction pattern taken from the area indicated in Fig.
- Fig. 7c shows an electron diffraction partem taken from the area indicated in Fig.
- Fig. 7d shows an electron diffraction pattern taken from the area indicated in Fig.
- Fig. 8a shows XPS C Is spectra of a hGio sample (top, red), a hGj sample
- Fig. 8b shows Raman spectra of a hGio sample (top), a hGi sample (middle), and a control graphene sample that was only refluxed in nitric acid under the same Step III conditions (bottom);
- Fig. 9a shows a SEM image of a hG 10 sheet obtained from a larger scale (-2.1 g) preparation
- Fig. 9b shows a photo of melt-extruded ribbons of neat Ultem (golden colored) and 1% hGio-filled Ultem composite (black colored);
- Fig. 9c shows a comparison of the ultimate strengths of neat Ultem, 1 wt% graphene-filled Ultem composite (1% G-Ultem), and 1 wt% hGio-filled Ultem composite (1% hGio-Ultem);
- Fig. 9d shows a comparison of Young's moduli of neat Ultem, 1 wt% graphene- filled Ultem composite (1% G-Ultem), and 1 wt% hG 10 -filled Ultem composite (1% hGio- Ultem);
- Fig. 10a shows a SEM image showing the catalytic oxidation of MWNTs in air at 300°C of with 10 mol% Ag;
- Fig. 10b shows a SEM image showing the catalytic oxidation of MWNTs in air at 300°C of with 5 mol% Au;
- Fig. 10c shows a SEM image showing the catalytic oxidation of graphene in air at 300°C of with 5 mol% Au;
- Fig. lOd shows a SEM image showing the catalytic oxidation of graphene in air at 300°C of with 5 mol% Pt;
- Fig. 11 shows a SEM image of a (Ag-G)io sample subjected to thermal treatment at 300°C in air for 10 hours;
- Fig. 12 shows DTG curves (air, 5.4°C/min) of the hGlO and hGl samples in comparison with the starting graphene sample;
- Fig. 13a shows preliminary electrochemical evaluations in the form of cyclic voltammetry curves of a hGl 0 electrode at scanning rates from 10 (most inner curve) to 500 mV s-1 (most outer curve);
- Fig. 13b shows preliminary electrochemical evaluations in the form of specific capacitance values of hGl 0 in comparison with those of a control graphene sample (with 2 hours nitric acid reflux only);
- Fig. 14 shows the steps of the method described herein.
- a straightforward yet highly scalable method is described to prepare bulk quantities of "holey graphenes", which are graphene sheets with holes ranging from a few to over 100 nm in diameter.
- the approach to their preparation takes advantage of the catalytic properties of certain metal oxides or metals, such as silver (Ag), nanoparticles toward the air oxidation of graphitic carbons.
- Ag nanoparticles were first deposited onto the graphene sheet surface in a facile, controllable, and solvent-free process. The catalyst- loaded graphene samples were then subjected to thermal treatment in air.
- the graphitic carbons in contact with the Ag nanoparticles were selectively oxidized into gaseous byproducts such as CO or C0 2 , leaving the graphene surface with holes.
- the Ag catalysts were then removed via refluxing in diluted nitric acid to obtain the final holey graphene products.
- the average size of the holes on the graphene was found to strongly correlate with the size of the Ag nanoparticles and thus could be conveniently controlled as previously established by adjusting the silver precursor concentration.
- the temperature and time of the air oxidation step as well as the catalyst removal treatment conditions were found to strongly affect the morphology of the holes. Characterization results of the holey graphene products suggested that the hole generation might have started from defect-rich regions present on the starting graphene sheets. As a result, the remaining graphitic carbons on the holey graphene sheets were highly crystalline, with no significant increase of the overall defect density despite the presence of structural holes.
- This invention is a facile and well controllable procedure to prepare holey graphene structures, which contain holes on the graphene surfaces etched via catalytic oxidation of graphitic carbon by deposited metal oxide or metallic nanoparticles.
- the technique described herein is not only versatile in that it provides controlled hole sizes on the graphitic surface, but also readily scalable. This enables more convenient use of these materials in many applications that require bulk quantities, such as polymeric composites and energy storage.
- the commercially available starting graphene material is prepared from a process similar to the thermal reduction/exfoliation of GO ["thermally exfoliated graphene” (TEG) 19 ].
- the preparation of holey graphenes (hG) is a 3-step process from the starting graphene material, namely the catalyst deposition, the catalytic oxidation, and the catalyst removal. Detailed observations from each step are discussed below.
- Step I Catalyst Deposition.
- catalytic nanoparticles such as Ag
- MWNTs multi-walled carbon nanotubes
- the nanoparticle growth in the Ag-G samples appears to use the local graphene surface as a template, as suggested by the flat interface indicating an intimate contact between Ag nanoparticles and the graphene support.
- a scanning electron microscopy (SEM) image of an example with an Ag nanoparticle "sitting" on a wrinkled part of graphene is shown in the Figure lb inset.
- the contact angle between the Ag nanoparticle and the graphene surface is smaller than 90°. In other words, the diameter of the contact area is somewhat smaller than that of the Ag nanoparticle. This is typically seen for all Ag-G samples as well as those using other metal salt precursors such as gold acetate, palladium acetate, or platinum acetyl acetonate .
- Step II Catalytic Oxidation.
- the metal oxide or metal nanoparticle decorated graphene samples are subjected to controlled air oxidation via heating in an open- ended tube furnace.
- a significant number of holes appeared on the originally intact graphene surfaces. Most of the holes are associated with at least one Ag nanoparticle. Some holes also appeared as tracks, which are apparently associated with the directional movements of the attached Ag nanoparticles under the given conditions ( Figure 2b), likely due to etching-induced motions (see more below). Nevertheless, Ag nanoparticles with larger sizes typically yield holes of larger diameters (or tracks of larger widths).
- the diameter of the Ag-graphene contact area is smaller than the corresponding Ag nanoparticle
- the diameters of the holes could be equivalent or even slightly larger than the diameter of the corresponding Ag nanoparticles at higher oxidation degrees. This might be due to the unbalanced etching- induced motions of non-spherical Ag nanoparticles.
- the motions of Ag nanoparticles on graphitic surfaces should be self-rotations along with movements in a slightly spiral and sometimes zigzag fashion.
- the rather rough edges of the holes and tracks might also have originated from such unbalanced movements of Ag.
- the weight loss threshold significantly reduces to ⁇ 370°C (peak at 534°C) for a (Ag-G)i sample and further to ⁇ 250°C (peak at 468°C) for a (Ag-G)io sample.
- the remaining weight percentages of the (Ag-G)io samples heated to 250 and 350°C in air and held for 3 hours were 93 and 83 wt%, respectively.
- the weight loss after 3 hours is ⁇ 50 wt%, indicating that there was a nearly complete oxidation of graphene with essentially no carbon left behind considering that Ag consisted of -47 wt% of the starting (Ag-G)io sample.
- Step III Catalyst Removal.
- the partially oxidized Ag-G samples from Step II (oxidation temperature at 300°C) are refluxed with diluted (2.6 M) nitric acid.
- the solid is then extensively washed with water followed by drying.
- the catalytic Ag nanoparticles are completely removed from the samples since nitric acid oxidized metallic Ag into Ag + (i.e., AgN0 3 ).
- the Ag salt is soluble in the aqueous dispersion and effectively removed with repeated washing. No Ag nanoparticle is found by microscopic analysis of the final products.
- the lack of Ag signals for these samples analyzed using both XPS and XRD confirms the complete removal of the metal.
- Electron microscopy images shown in Figure 6 are from an instrument (Hitachi S- 5200) that is equipped with capabilities of acquiring images under both secondary electron (SE) and transmitted electron (TE) modes (i.e., SEM and TEM) conveniently at the same area.
- SE secondary electron
- TE transmitted electron
- the SEM images ( Figure 6 left side, a, c, e) emphasize the top surface morphology, while the corresponding TEM images of the same area ( Figure 6 right side, b, d, f) allow observations through the thickness of the specimens. It is apparent from these images (Figure 6a - d) that the final samples after Step III catalyst removal exhibit distinct hole structures on the Ag-free graphitic surfaces. Therefore, these samples are referred to as "holey graphene" samples, or hGs.
- the relative sizes of the holes in the hG samples inherit such dependence.
- the hole sizes of the hG sample from a (Ag-G) ⁇ sample (designated as hGio) ranges from -10 to over 100 nm ( ⁇ 22 nm in average diameter), much larger than that of one started with (Ag-G)i (designated as hGj), which is ⁇ 5 nm in average diameter.
- the hGi sample has a lower oxidation degree with the same treatment temperature, making its average hole size closer to the Ag-graphene contact area (smaller than the average diameter of catalytic Ag nanoparticles).
- the hG 10 sample with a higher oxidation degree - due to large Ag- graphene contact area as well as lower oxidation threshold - has holes with diameters closer (and sometimes even larger due to hole merging) than the sizes of the original catalytic Ag
- the wider size distribution of the holes in the hGio sample is a combined result from the initial wide distribution of the catalytic Ag nanoparticles and the inhomogeneous etching of the graphene sheets due to the irregular shapes of the catalysts as previously discussed. Nevertheless, this result demonstrates that the hole sizes of the hG samples can be controlled, to a consistent degree, by varying the loading, and thus the average size, of the catalytic Ag nanoparticles.
- the retained graphitic crystallinity of the hG samples in this study suggests that many important properties of the starting graphene sample, such as electron mobility, electrical conductivity, thermal conductivity, and mechanical properties, are largely preserved. It is these properties of graphene that make it such an attractive material, so the fact that the hG samples retain them is very important for their subsequent applications that are dependent upon these properties.
- the above 3 -step procedure to prepare hG samples is readily scalable. The first two steps are both conducted in the solid-state, so the limitations only come from the sizes of the mixing and heating devices. The last step, catalyst removal via nitric acid treatment, is a straightforward wet process that can be very conveniently scaled up to the level of multiple grams.
- This large scale hGio product also shows comparable microscopic and spectroscopic characteristics as compared to the samples from the smaller scale batches discussed above.
- the average hole size for the hGio sheets in the sample is -20 nm ( Figure 9a), comparable to that for a sample prepared from a smaller scale ( Figure 6c).
- the Raman spectrum and the XPS spectrum of the sample are also very similar (not shown).
- the hG sheets may be viewed as "graphene nets" that are more flexible than plain sheets, just like the comparison of a netbag vs. a regular bag but at a microscopic scale.
- hGs might also be advantageous to intact graphene sheets.
- the hole structures might allow polymer penetration or enhanced entanglement sites leading to more enhanced interactions, which could potentially be further improved by hole-edge functionalization.
- the 3-step method to prepare hGs is versatile and applicable to various carbon allotropes since the Ag-catalyzed air oxidation of carbon is not unique to graphene sheets. For example, by heating a Ag nanoparticle-decorated multi-walled carbon nanotube ("MWNT”) sample at 300°C for 3 hours, significant Ag-induced oxidation of the nanotubes is observed ( Figure 10a). This method may also be followed to use these partially oxidized samples to prepare "holey carbon nanotubes".
- MWNT multi-walled carbon nanotube
- graphene oxide examples include graphene oxide, reduced graphene oxide, thermal exfoliated graphene, graphene nanoribbons, graphite, exfoliated graphite, expanded graphite single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon fibers, carbon black, amorphous carbon, and fullerenes.
- the carbon oxidation catalyst is not restricted to Ag; transition metals including rare earth metals, and their oxides may also be used as the catalyst.
- the metals from Group VIIIA Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt
- Group IB Cu, Ag, and Au
- Pt and Au nanoparticles are both effective catalysts toward MWNTs and graphene under similar experimental conditions ( Figure 10b - d). More surveys are being conducted on the search for lower cost replacements for the noble metal catalysts. 23 It is interesting to note that some transition metal nanoparticles (such as Fe, Ni, and Co) have been used for graphene surface etching under reductive conditions in hydrogen atmosphere. 29"32 The movements of these nanoparticles on the highly crystalline graphene surface seemed to follow chirality patterns, as similarly observed by Booth et al.
- the metals can be deposited onto the carbon allotropes in various ways, including but not limited to sputtering, electrochemical deposition, replacement reaction, spontaneous deposition, and solventless deposition. Solventless deposition is especially preferred for bulk preparation. It is preferable to use a metal compound as the precursor.
- the preferable metal compounds include but are not limited to halides, nitrates, carboxylates, oxalates, acetates, acetylacetonates, and those with any other inorganic or organic functional groups.
- the preferred range of temperature for carrying out the catalytic oxidation is between 150°C and 500°C.
- the specific surface area (in m 2 g _1 ) of a hG sheet should be the same as an intact graphene sheet.
- the actual surface area of carbon nanomaterials is strongly affected by post-processing methods. 34"38
- the starting graphene sample is from a thermal exfoliation process and thus very lightweight and fluffy with a reasonably high specific surface area of -590 m 2 g " ' measured from the nitrogen adsorption-desorption isotherms using the Brunauer-Emmett-Teller (BET) method.
- BET Brunauer-Emmett-Teller
- the method disclosed herein is a straightforward procedure to controllably prepare hG sheets with holes of various sizes.
- the 3-step procedure includes the deposition of Ag nanoparticles onto graphene sheets, the Ag-catalyzed oxidation of graphene in air under elevated temperature (typically at 300°C), and the refluxing with dilute nitric acid to remove Ag catalysts.
- elevated temperature typically at 300°C
- the hole sizes of the hG sheet products could be tuned in a wide range (average diameter from ⁇ 5 to tens of nm demonstrated in current work).
- the air oxidation temperature and time duration in the second step and the intensity of the acid treatment in the last step may also affect the hole morphology of the final hG sheets.
- the procedure was found highly scalable and used to produce multiple grams of hG sheets routinely. It is important that the hG sheets, despite their holey structures, largely retain the two- dimensional graphitic crystallinity as evidenced from a combination of microscopic and spectroscopic analyses. Therefore, the hG sheets have preserved the important properties of intact graphene sheets such as electrical, thermal, and mechanical properties. This finding has profound implications on the potential applications of hGs. For example, the preliminary experiments show that the hG sheets are better reinforcements for polymer composites than the starting intact graphene sheets due to their lower volume density but retained mechanical strength, as well as possible contributions from their unique "graphene net' ike structures in addition to enhanced matrix-filler interactions with the presence of the holes. The conductive nature of hG sheets and their porous structure may allow them to be used as advanced electrode materials in energy storage applications, for which more detailed research is currently underway.
- XPS spectra were obtained on a ThermoFisher ESCAlab 250 X-ray Photoelectron Spectrometer.
- Raman spectra were acquired on a Thermo-Nicolet-Almega Dispersive Raman Spectrometer equipped with excitation lasers with wavelengths of 532 and 785 nm.
- BET surface area measurements were conducted on a Quantachrome Nova 2200e Surface Area and Pore Size Analyzer system.
- Thermogravimetric (TGA) and differential thermogravimetric (DTG) traces were obtained on a Seiko TG/DTA 220 (SSC/5200) system.
- Polymer ribbons specimens were cut into strips of ⁇ 5 cm ⁇ 5 mm for mechanical tests, which were conducted at room temperature using at least 5 specimens on an Instron 5848 Microtester at a gauge length and a crosshead speed at 20 mm and 10 mm min "1 , respectively.
- Step I Catalyst Deposition: Ag Nanoparticle-Decorated Graphene (Ag-G).
- the as-obtained graphene powder (100 mgj and silver acetate powder of the desired ratio (1 or 10 mol% Ag-to-C, corresponding to ⁇ 9 or ⁇ 47 wt%) were mechanically mixed for 5 min using a zirconia vial-ball set (SPEX CertiPrep, ⁇ 20 cm mixing load, 2 balls) with a SPEX CertiPrep 8000D high-energy shaker mill.
- the solid mixture was then transferred to an appropriate container (e.g.
- Step II Catalytic Oxidation: Air-Oxidized Ag-G.
- a Ag-G sample 100 mg
- a given temperature 250 - 400°C
- Step HI - Catalyst Removal Holey Graphene (hG).
- an air-oxidized Ag-G sample 50 mg was refluxed in diluted nitric acid (2.6 M, 30 mL) for 2 hours to remove Ag.
- diluted nitric acid 2.6 M, 30 mL
- the slurry was centrifuged and the supernatant was discarded.
- the solid was then repeatedly washed with water in up to ten more redispersion - centrifugation cycles until the supernatant reached neutral (pH > 6).
- the solid was then carefully dried to obtain the final hG product.
- Typical overall yields in terms of carbon weight were approximately 80% and 68% for hG] and hGio samples (air oxidation at 300°C for 3 h), respectively.
- the mixing equipment used was a 30 mL half sized mixer equipped with roller blades (C.W. Brabender) attached to a RS7500 drive/ data collection system (Rheometer
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WO2016036888A1 (en) | 2014-09-02 | 2016-03-10 | Lockheed Martin Corporation | Hemodialysis and hemofiltration membranes based upon a two-dimensional membrane material and methods employing same |
JP2018528144A (en) | 2015-08-05 | 2018-09-27 | ロッキード・マーチン・コーポレーション | Perforable sheet of graphene-based material |
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- 2013-08-28 EP EP13892744.7A patent/EP3038976A4/en not_active Withdrawn
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WO2015030698A1 (en) | 2015-03-05 |
EP3038976A4 (en) | 2017-04-19 |
KR20160092987A (en) | 2016-08-05 |
CA2932452A1 (en) | 2015-03-05 |
JP2016538228A (en) | 2016-12-08 |
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