WO1993004220A1 - Glassy carbon containing metal particles - Google Patents
Glassy carbon containing metal particles Download PDFInfo
- Publication number
- WO1993004220A1 WO1993004220A1 PCT/US1992/006458 US9206458W WO9304220A1 WO 1993004220 A1 WO1993004220 A1 WO 1993004220A1 US 9206458 W US9206458 W US 9206458W WO 9304220 A1 WO9304220 A1 WO 9304220A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glassy carbon
- metal particles
- less
- cross
- nanometers
- Prior art date
Links
- 239000002923 metal particle Substances 0.000 title claims abstract description 44
- 229910021397 glassy carbon Inorganic materials 0.000 title claims description 87
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 103
- 229910052697 platinum Inorganic materials 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 239000011159 matrix material Substances 0.000 claims description 17
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- RZUASTIKPBCXPU-UHFFFAOYSA-N ethene;platinum;triphenylphosphane Chemical compound [Pt].C=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RZUASTIKPBCXPU-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- -1 diacetylene metal complex Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical group C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- WRKSFOCSVUCYGJ-UHFFFAOYSA-N ethene;triphenylphosphane Chemical compound C=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WRKSFOCSVUCYGJ-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- URHURAUXXZJQAP-UHFFFAOYSA-N C=1C=CC=CC=1[Pt]C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1[Pt]C1=CC=CC=C1 URHURAUXXZJQAP-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Chemical group 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Chemical group 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the invention relates to glassy carbon.
- Glassy carbon has a unique combination of properties, including chemical and thermal inertness, hardness, impermeability to gases and liquids, and electrical conductivity. Because of these properties, glassy carbon commonly is used in carbon electrodes. It is known to use oligomers containing acetylene groups as starting materials for making glassy carbon.
- the invention features, in one aspect, glassy carbon containing a dispersion of metal particles having an average size of less than 1 micron.
- the invention features, in another aspect, an electrochemical cell in which one of the electrodes includes glassy carbon containing a dispersion of metal particles having an average particle size of less than 1 micron.
- the invention features, in another aspect, an electrochemical cell in which one or both of the electrodes includes glassy carbon containing a dispersion of metal particles having a relatively uniform size distribution.
- relatively uniform size distribution it is meant that the diameter of 70% of the metal particles are less than 5 times (more preferably 3 times) the number average diameter of the particles.
- the invention features, in another aspect, a method of producing glassy carbon containing metal particles.
- the method involves heating a metal complexed to a molecule (preferably including acetylene groups) for a sufficient period of time for the molecule to cross ⁇ link to provide glassy carbon.
- a metal complexed to a molecule preferably including acetylene groups
- cross-linking is performed at temperatures of less than 1000°C, more preferably less than 750°C most preferably less than 600°C.
- the glassy carbon can be incorporated into an electrode for an electrochemical cell.
- the invention features, in another aspect, a method of producing a cross-linked carbon matrix that includes metal particles.
- the method includes providing a metal complexed to a molecule capable of cross-linking to form an sp 2 -hybridized carbon matrix, and cross- linking (preferably by heating) the molecules sufficiently to form an sp -hybridized carbon matrix having microcrystalline graphite domains having average lattice dimensions of between 1 and 20 nanometers (more preferably between 2.5 and 7.5 nanometers).
- the invention features, in another aspect, a method of producing a cross-linked, conductive carbon matrix.
- the method includes providing a metal complexed to a molecule capable of cross-linking to form a conductive sp 2 -hybridized matrix, and cross-linking (preferably by heating) the molecules sufficiently to form an sp 2 -hybridized carbon matrix having a conductivity of at least 0.01 s/cm (more preferably at least 0.1 s/cm) .
- glassy carbon containing a dispersion of small metal particles to catalyze a chemical reaction (e.g., reforming, hydrogenations, dehydrogenations, isomerizations of hydrocarbons, oxidations, reductions, and pollutant removal) , or to catalyze an electrochemical reaction in an electrochemical cell (e.g., a fuel cell, a cell for electrochemical synthesis, or a sensor) .
- a chemical reaction e.g., reforming, hydrogenations, dehydrogenations, isomerizations of hydrocarbons, oxidations, reductions, and pollutant removal
- an electrochemical cell e.g., a fuel cell, a cell for electrochemical synthesis, or a sensor
- the preferred metals are transition metals that have desirable catalytic or electrocatal tic properties, for example, platinum, palladium, iron, cobalt, and silver.
- the preferred molecules are oligomers that include diacetylene and aromatic groups.
- the particles Preferably have an average size of less than 100 nanometers, more preferably less than 15 nanometers, most preferably less than 5 nanometers.
- the preferred glassy carbon has a carbon content of at least 80%. Glassy carbon is a form of sp -hybridized carbon composed of branched and entangled graphite ribbons.
- glassy carbon The structure and properties of glassy carbon are well known in the art, and are described, for example, in conventional texts such as Kinoshita, Carbon: Electrochemical and Physiochemical Properties (Wiley: New York, 1988) As is recognized by these skilled in the art, although glassy carbon is a well-known material, its properties vary somewhat based on the specific mode of preparation. For example, glassy carbons in general have good conductivity, but some forms have better conductivity than others.
- the size of the metal particles is readily regulated by controlling the initial loading of the metal in the complex; the lower the atom percent of metal in the starting complex (preferably less than 10%, more preferably less than 5%) , the smaller the resultant particle size.
- the small particle size makes a large surface area of metal available for participation in, for example, electrochemical or catalytic reactions. The invention thus provides a highly efficient mode of delivery for catalytic metals, most of which are very expensive.
- acetylenic chemical precursors of glassy carbons are soluble in organic solvents, which makes them easy to handle and form into desired shapes, such as thin films or coatings on the outside of conventional carbon electrodes.
- the amount of metal in the coating can be controlled by the dilution of the complex in the solution; the more dilute the complex, the thinner the coating formed.
- the cross-linking of the acetylene precursors occur at relatively low temperatures.
- the invention provides a convenient way to introduce more than one type of metal into glassy carbon, for example, by mixing acetyleni ⁇ molecules complexed to different metals together prior to cross-linking.
- the preferred glassy carbon are prepared from aromatic acetylene molecules, typically oligomers or even larger polymers, complexed to a transition metal. Heteroatoms such as nitrogen or boron can be included in the glassy carbon as part of the aromatic ring. Other heteroatoms such as halides or silicon can be substituted for a hydrogen atom in the aromatic ring.
- the acetylene groups cross link at a low temperature (e.g., less than 400°C) to form a highly cross-linked carbon network. Further heating at temperatures typically less than 600°C causes the microcrystalline lattice to increase in size.
- the transition metals can complex to either the acetylene groups, or aromatic rings, or other complexing groups included in the molecule, and are released from the complex during the cross-linking process. The metal remains trapped in the glassy carbon network as small particles of a relatively uniform size.
- the transition metal selected will depend on the catalytic, or electrocatalytic, properties desired, but can be, for example, platinum, palladium, titanium, ruthenium, zirconium, hafnium, iron, nickel, and silver, or combinations of these metals, if desired.
- acetylenic oligomers that are suitable for complexing with transition metals to provide precursors for glassy carbon are legion, and are well- known to those skilled in the art.
- suitable complexed oligomeric precursors include those having formula 1-10, below.
- the oligomers may be end-capped with mono-functional acetylenes (not shown) .
- the illustrated repeat unit of the oligomers is shown complexed to the metal; usually in the full oligomer, only a portion of the repeat units are complexed to metal atoms, depending on the metal loading into the reaction mixture that generated 1-10.
- Oligomers 1-10 can be prepared by standard chemical procedures. For example, the synthesis of 1 can be accomplished by reaction of 11 with butyllithiu followed by reaction with chlorodiphenylphosphine to give 12. Reaction of 12 with (PPh 3 ) 3 RhCl or Ag(PPh 3 ) 4 BF4 gives 1.
- the synthesis of 2 can be accomplished by treatment of 13 with magnesium in diethyl ether, followed by reaction with cyclopentenone, followed by dehydration to give a general cyclopentadiene ligand which can be used for complexation with various metals.
- Platinum complex 3 which serves as a precursor to metal doped glassy carbon containing a bypyridyl ligand complexed with platinum, can be prepared by reaction of 15 with 16 using bis(triphenylphosphine)palladium(II) chloride as a catalyst in toluene to give 17. Reaction of 17 with (cyclooctadiene)diphenylplatinum(II) gives 3.
- the complex containing iron 4 can be prepared by reaction of l,l'-bromoacetylferrocene (18) with copper to give 19. Treatment of 19 with P0C1 3 in dimethylformamide followed by reaction with sodium hydroxide gives 20. Reaction of 20 in the presence of copper chloride and oxygen gives 4.
- Cud Glassy carbon precursor 5 which contains nickel, can be prepared by reaction of 21 with ethylene bis(triphenylphosphine)nickel(0) .
- the starting complex can also include more than one metal.
- the molecular weight of the oligomers and polymers can be controlled by suitable use of end-capping groups such as phenyl acetylene, pentafluoroacetylene and the like when the molecules are prepared.
- the level of metal incorporated in these molecules also can be controlled by the amount of metal complex added to the acetylene molecule.
- glassy carbon containing a dispersion of two or more types of metal particles also can be prepared by simply mixing different metal containing oligomeric complexes prior to cross-linking and annealling.
- the most preferred glassy carbons include a dispersion of platinum particles. Platinum is a catalyst for many important chemical reactions, including oxygen and hydrogen reduction. Glassy carbon including the dispersion of platinum particles can be used, for example, in oxygen/hydrogen or methanol/oxygen fuel cells. It is highly suitable for these uses because the platinum is provided efficiently in a stable matrix.
- the preferred glassy carbons containing platinum particles were prepared according to the following procedures.
- Ethylene bis(triphenylphosphine) latinum(0) was prepared by a three-step process.
- Triphenylphosphine (1.46 g, 5.6 mmol) was dissolved in 20 mL of absolute ethanol at 65°C. When the solution was clear, 0.14 g (0.0025 mol) of potassium hydroxide in 1 mL of water and 4 mL of ethanol was added. To this was then added 0.5 g (1.2 mmol) of potassium tetrachloroplatinate(II) dissolved in 5 mL of water while stirring at 65°C. A pale yellow solid precipated within a few minutes of the first addition. After cooling, the compound was recovered by filtration, washed with 50 L of warm ethanol, 20 mL of water and 12 mL of cold ethanol to give 1.17 g (78 %) of product.
- An alternative starting complex, tetrakis[bis[l- (3-phenylbutadiyny1)phenyl]phenylphosphine]platinum(0) which has the below formula, was prepared in two steps.
- the reaction was quenched with a saturated solution of ammonium chloride, the solids removed by decantation, and the organic layer was washed with ammonium chloride solutions and dried with anhydrous magnesium sulfate. After filtration of the solid, the solvent was removed in vacuo, and the yellow residue was purified by column chro atography on silica gel (20% CH 2 C1 2 in hexanes) to give 0.7 g (20 %) of light white crystals.
- the bis[l-(3- phenylbutadiyne)phenylJphenylphosphine (0.47 g, 0.09 mmol) was dissolved in the minimum amount of benzene (4 mL) and then diluted in 10 mL of ethanol. The solution was heated to 65°C and when the solution turned clear, 0.5 mL of a solution of 0.21 g (0.004 mol) of potassium hydroxide in 1 mL of water and 4 mL of ethanol was added. To this, was then added dropwise, 0.0832 g (0.2 mmol) of potassium tetrachloroplatinate(II) dissolved in 5 mL of water, while stirring at 65°C.
- the acetylenic complexes described above can be converted to glassy carbon at relatively low temperatures.
- the initial heating causes the acetylene groups to cross-link, forming a highly cross-linked carbon matrix.
- the cross-linking can be carried out at temperatures below 500°C (e.g., 350°C).
- the cross-linked matrix anneals, to provide glassy carbon.
- Annealization typically requires heating at a higher temperature (e.g., 550°C - 700°C) than the initial cross-linking. Both steps can be carried out simultaneously by simply heating at the higher temperature.
- the glassy carbons should have a conductivity greater than 0.01 s/cm, more preferably greater than 0.1 s/cm, and most preferably greater than 0.7 s/cm.
- the microcrystalline graphite dimensions as determined by conventional Raman spectroscopy and X-ray powder diffraction techniques, are between 1 and 20 nanometers, more preferably greater than 2 nanometers, most preferably between 2.5 and 7.5 nanometers.
- the glassy carbon electrode should function as a practical electrode.
- the oxidation-reduction separation should be ⁇ Ep ⁇ 200 V, more preferably ⁇ 150mV, and most preferably ⁇ 100mV.
- Glassy carbon pellets were made in two steps. Approximately 150 mg of a precursor were submitted to a pressure of 3500 psi at a temperature of 350°C for 2 hours in a 1 cm diameter steel die. A Carver laboratory press model C was used. The sample was allowed to cool slowly. At the end of this period, a 1 cm diameter black disc of cross-linked carbon solid was obtained. The pellets were then sealed in vacuo in a quartz tube and heated to 600°C at a rate of l°C/min for a total period of 15 hours in a Thermolyne type 6000 furnace, and then allowed to cool at a rate of l°C/min to room temperature. b) Glassy carbon films
- a toluene solution of a precursor was spin-coated (Headway Research, PWM101 model) on an Atomergic V25 glassy carbon disc. The solvent was evaporated and the disc was sealed in vacuo and thermally treated to 600°C under the same conditions as that for the pellets.
- a similar procedure can be used to coat a variety of materials, including carbon felt, carbon filters, other metals, silica, and alumina. Importantly, this provides the uses with the ability to take a variety of backings and turn them into, e.g., a platinum electrode, by simple coating procedures.
- Raman analysis confirms the glassy carbon microcrystalline structure of these carbon solids exhibiting bands at approximately 1580 cm -1 and 1360 cm "1 , consistent with the formation of an sp 2 -hybridized carbon lattice.
- X-ray photoelectron spectroscopic analyses and icroprobe analysis confirmed the incorporation of approximately 0.5 to 1 atom % of platinum(0) in glassy carbon.
- the size of platinum particles can be determined by standard transmission microscopic analysis. For example, a thin film of the glassy carbon containing dispersed platinum particles was prepared by evaporation of a glassy carbon precursor onto a sodium chloride disc to give a 2-3 micron thick coating. The disc was then heated to 600°C to provide a film of glassy carbon. The film was then lifted from the disc, and a transmission electron micrograph of the edge of the film is taken, and the diameters of the particles (or clusters) are recorded, and a mean obtained. The average platinum particle size in the glassy carbons obtained from the previously described precursors in the range of 1.4 to 2.1 nanometers.
- glassy carbons of the invention are useful in a wide variety of catalytic and electrochemical applications.
- glassy carbon containing dispersed platinum particles when used in place of platinum in a platinum disc electrode and studied for its effect on the reduction of H + to H 2 , exhibited a performance close to that of a pure platinum disc.
- An electrode was also prepared by applying 5 drops of a saturated solution of a 1:2 platinum:diyne ratio of poly[ (phenylenediacetylene) bis(tri ⁇ phenylphosphine) platinu (0) ] in toluene to each side of a carbon felt electrode, which consisted of a matrix of carbon fibers.
- the electrode was heated under vacuum to 600°C (l°C/min) , and cured at 600°C for 6 hours to provide the glassy carbon.
- the resulting electrode was used in place of a standard platinum disc electrode. Voltrametry was taken in a 1M H 2 S0 solution at different scan rates in the range of 0.2V to -0.6V versus a conventional Ag/AgCl reference electrode.
- the activity of the platinum dispersed in glassy carbon was compared to a polycrystalline platinum electrode and a conventional glassy carbon electrode for oxygen reduction.
- a 1 atom % platinum in glassy carbon thin film on conventional glassy carbon was exposed to oxygen in 1M HC10 4 buffer and scanned at 50 mV/sec from 1.0 to -0.5 V vs SSCE.
- the current density and potential for 0 2 reduction with the platinum in glassy carbon electrode exhibited a performance close to that of a pure platinum disc.
- the carbon felt electrode including a thin coating of glassy carbon containing platinum particles the porosity, stability, and catalytic efficiency of the electrode should be very useful for electrochemical applications.
- glassy carbons containing heteroatoms such as N can be prepared, for example, by cross-linking and annealling a complex having formulae 3.
- Glassy carbons containing dispersions of metal particles can be prepared from acetylenic oligomers lacking aromatic groups, for example, some of the acetylenic oligomers described in Hay, U.S. 3,332,916, which is hereby incorporated by reference.
- the glassy carbons can be prepared from other, non- acetylenic precursors, such as phenolic formaldehyde oligomers, that are complexed to a metal.
- the activity of the platinum dispersed in glassy carbon was compared to a polycrystalline platinum electrode and a conventional glassy carbon electrode for oxygen reduction.
- a 1 atom % platinum in glassy carbon thin film on conventional glassy carbon was exposed to oxygen in 1M HC10 4 buffer and scanned at 50 mV/sec from 1.0 to -0.5 V vs SSCE.
- the current density and potential for 0 2 reduction with the platinum in glassy carbon electrode exhibited a performance close to that of a pure platinum disc.
- the carbon felt electrode including a thin coating of glassy carbon containing platinum particles the porosity, stability, and catalytic efficiency of the electrode should be very useful for electrochemical applications.
- glassy carbons containing heteroatoms such as N can be prepared, for example, by cross-linking and annealling a complex having formulae 3.
- Glassy carbons containing dispersions of metal particles can be prepared from acetylenic oligomers lacking aromatic groups, for example, some of the acetylenic oligomers described in Hay, U.S. 3,332,916, which is hereby incorporated by reference.
- the glassy carbons can be prepared from other, non- acetylenic precursors, such as phenolic formaldehyde oligomers, that are complexed to a metal.
Abstract
Description
Claims
Priority Applications (1)
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EP93903695A EP0705232A1 (en) | 1991-08-21 | 1992-08-04 | Glassy carbon containing metal particles |
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US74826391A | 1991-08-21 | 1991-08-21 | |
US748,263 | 1991-08-21 |
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WO1993004220A1 true WO1993004220A1 (en) | 1993-03-04 |
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PCT/US1992/006458 WO1993004220A1 (en) | 1991-08-21 | 1992-08-04 | Glassy carbon containing metal particles |
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EP (1) | EP0705232A1 (en) |
CA (1) | CA2116112A1 (en) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000015576A1 (en) * | 1998-09-15 | 2000-03-23 | National Power Plc | Vitrified carbon compositions |
WO2023079029A3 (en) * | 2021-11-03 | 2023-06-15 | Norwegian University Of Science And Technology (Ntnu) | Dimensionally stable amorphous carbon structures |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518488A (en) * | 1983-02-28 | 1985-05-21 | Standard Oil Company (Indiana) | Metal-containing active carbon and methods for making and using same |
US4970189A (en) * | 1988-06-24 | 1990-11-13 | Somar Corporation | Porous, metal-containing carbonaceous material |
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JPH05249514A (en) * | 1992-03-06 | 1993-09-28 | Ricoh Co Ltd | Nonlinear optical material |
-
1992
- 1992-08-04 EP EP93903695A patent/EP0705232A1/en not_active Withdrawn
- 1992-08-04 CA CA002116112A patent/CA2116112A1/en not_active Abandoned
- 1992-08-04 WO PCT/US1992/006458 patent/WO1993004220A1/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518488A (en) * | 1983-02-28 | 1985-05-21 | Standard Oil Company (Indiana) | Metal-containing active carbon and methods for making and using same |
US4970189A (en) * | 1988-06-24 | 1990-11-13 | Somar Corporation | Porous, metal-containing carbonaceous material |
Non-Patent Citations (2)
Title |
---|
See also references of EP0705232A4 * |
Yoshuda, "New Carbon Composites Containing Ultra furo re, co or ni particles. 1. Facile Synthesis by Pyrolysis of Organometallic Polymers", Journal of Inorganic and organometallic Polymers, vol. 1, No. 1, 1991, pg. 135-141, (see pages 135-137). * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000015576A1 (en) * | 1998-09-15 | 2000-03-23 | National Power Plc | Vitrified carbon compositions |
GB2343195A (en) * | 1998-09-15 | 2000-05-03 | Nat Power Plc | Vitrified carbon compositions |
GB2343195B (en) * | 1998-09-15 | 2001-01-31 | Nat Power Plc | Vitrified carbon compositions |
AU761411B2 (en) * | 1998-09-15 | 2003-06-05 | Regenesys Technologies Limited | Vitrified carbon compositions |
US6624108B1 (en) | 1998-09-15 | 2003-09-23 | Regenesys Technologies Limited | Vitrified carbon compositions |
WO2023079029A3 (en) * | 2021-11-03 | 2023-06-15 | Norwegian University Of Science And Technology (Ntnu) | Dimensionally stable amorphous carbon structures |
Also Published As
Publication number | Publication date |
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EP0705232A4 (en) | 1995-05-09 |
EP0705232A1 (en) | 1996-04-10 |
CA2116112A1 (en) | 1993-03-04 |
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