JP2008126211A - Method for producing metal support porous body - Google Patents
Method for producing metal support porous body Download PDFInfo
- Publication number
- JP2008126211A JP2008126211A JP2006317490A JP2006317490A JP2008126211A JP 2008126211 A JP2008126211 A JP 2008126211A JP 2006317490 A JP2006317490 A JP 2006317490A JP 2006317490 A JP2006317490 A JP 2006317490A JP 2008126211 A JP2008126211 A JP 2008126211A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- platinum
- porous body
- producing
- tertiary amine
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 158
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 89
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 16
- -1 platinum ions Chemical class 0.000 claims description 64
- 239000011148 porous material Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 26
- 238000006722 reduction reaction Methods 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 17
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 239000002923 metal particle Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 150000003974 aralkylamines Chemical class 0.000 description 2
- WAJRCRIROYMRKA-UHFFFAOYSA-L benzonitrile;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WAJRCRIROYMRKA-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- BVURNMLGDQYNAF-SECBINFHSA-N (1r)-n,n-dimethyl-1-phenylethanamine Chemical compound CN(C)[C@H](C)C1=CC=CC=C1 BVURNMLGDQYNAF-SECBINFHSA-N 0.000 description 1
- 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
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 description 1
- TXOFSCODFRHERQ-UHFFFAOYSA-N Dimethylphenethylamine Natural products CN(C)CCC1=CC=CC=C1 TXOFSCODFRHERQ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
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- OQHZUTFDNJOOCI-UHFFFAOYSA-J S(C#N)[Pt](SC#N)(SC#N)SC#N.[K] Chemical compound S(C#N)[Pt](SC#N)(SC#N)SC#N.[K] OQHZUTFDNJOOCI-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- CKQGCFFDQIFZFA-UHFFFAOYSA-N Undecyl acetate Chemical compound CCCCCCCCCCCOC(C)=O CKQGCFFDQIFZFA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KYHBHUGWTQLYOZ-UHFFFAOYSA-N [N+](=O)([O-])[Pt]([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-].[K] Chemical compound [N+](=O)([O-])[Pt]([N+](=O)[O-])([N+](=O)[O-])[N+](=O)[O-].[K] KYHBHUGWTQLYOZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KHCPSOMSJYAQSY-UHFFFAOYSA-L azane;dichloroplatinum Chemical compound N.N.N.N.Cl[Pt]Cl KHCPSOMSJYAQSY-UHFFFAOYSA-L 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-N dichloroplatinum;triphenylphosphanium Chemical compound Cl[Pt]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-N 0.000 description 1
- FXGFZZYDXMUETH-UHFFFAOYSA-L difluoroplatinum Chemical compound F[Pt]F FXGFZZYDXMUETH-UHFFFAOYSA-L 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- WPABBAJWZPZLPM-UHFFFAOYSA-N n,n-diethyl-2-phenylethanamine Chemical compound CCN(CC)CCC1=CC=CC=C1 WPABBAJWZPZLPM-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- RCIBIGQXGCBBCT-UHFFFAOYSA-N phenyl isocyanide Chemical compound [C-]#[N+]C1=CC=CC=C1 RCIBIGQXGCBBCT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- UIRRQIANMRREBL-UHFFFAOYSA-N platinum;triethylphosphane Chemical compound [Pt].CCP(CC)CC UIRRQIANMRREBL-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
Classifications
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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
Abstract
Description
本発明は、金属担持多孔質体の製造方法に関する。 The present invention relates to a method for producing a metal-supporting porous body.
多孔質体上に白金を担持した金属担持多孔質体は、燃料電池用電極触媒や排ガス浄化用触媒、ガス検知器のセンサー材料などに用いられる。これらの用途においては、白金金属表面において生じる触媒活性の発現を目的として白金を担持させるものであるから、電池や触媒としての機能を向上させるためには、比表面積が大きい微小粒子を多孔質上に担持させることが必要とされる。 The metal-supported porous body in which platinum is supported on the porous body is used as a fuel cell electrode catalyst, an exhaust gas purification catalyst, a sensor material for a gas detector, and the like. In these applications, platinum is supported for the purpose of expressing the catalytic activity that occurs on the surface of the platinum metal. To improve the function as a battery or catalyst, fine particles with a large specific surface area are made porous. It is required to be carried on
このような金属担持多孔質体の製造方法としては、白金コロイドを含むコロイド溶液を用いて、カーボン担体に白金粒子を担持させる方法が公知である（特許文献１〜３）。しかしながら、これらの方法は、コロイド溶液を生成する工程と、そのコロイド溶液を用いてカーボン担体に白金粒子を担持させる工程とが必要となるため、より簡便な製造方法の提供が望まれている。 As a method for producing such a metal-supporting porous body, a method of supporting platinum particles on a carbon carrier using a colloidal solution containing platinum colloid is known (Patent Documents 1 to 3). However, these methods require a step of producing a colloidal solution and a step of supporting platinum particles on a carbon support using the colloidal solution, and thus it is desired to provide a simpler production method.
特許文献４には、カーボン粉末と白金錯体とが水に分散した分散溶液を調製し、分散溶液に緩衝剤を添加した後に、還元剤を添加してカーボン粉末表面に白金を還元析出させる方法が開示されている。しかし、このような方法は、還元力が強い還元剤を使用するために、微細な白金粒子をカーボン粉末中に担持させるためには、反応条件の制御が必要となる。このため、還元剤とは別の緩衝剤を添加する工程が必要となり、そのため工程数及びコストの面から未だ改善の余地があった。 Patent Document 4 discloses a method of preparing a dispersion solution in which carbon powder and a platinum complex are dispersed in water, adding a buffering agent to the dispersion solution, and then adding a reducing agent to reduce and precipitate platinum on the surface of the carbon powder. It is disclosed. However, in such a method, since a reducing agent having a strong reducing power is used, it is necessary to control reaction conditions in order to support fine platinum particles in the carbon powder. For this reason, a step of adding a buffering agent different from the reducing agent is required, so that there is still room for improvement in terms of the number of steps and cost.
また、特許文献５には、導電性担体材料を水中に懸濁し、懸濁液に白金の溶性化合物の水溶液を添加し、かつ懸濁液のｐＨ値をアルカリ溶液の添加によって７〜９に上昇させ、還元剤を用いた還元によって白金を担体材料上に析出させる方法が開示されている。しかし、特許文献５に記載の方法は、強力な還元剤を使用することによって金属を析出させるものであり、また微小な粒子径のものとするためには、反応前にアルカリ溶液を添加する工程が更に必要であることから、工程数及びコストの面から未だ改善の余地があった。 In Patent Document 5, a conductive carrier material is suspended in water, an aqueous solution of a platinum-soluble compound is added to the suspension, and the pH value of the suspension is increased to 7 to 9 by adding an alkaline solution. And a method of precipitating platinum on a support material by reduction using a reducing agent is disclosed. However, the method described in Patent Document 5 is to deposit a metal by using a strong reducing agent, and in order to obtain a fine particle size, a step of adding an alkaline solution before the reaction. However, there is still room for improvement in terms of the number of processes and cost.
特許文献６には、白金オルガノゾルの製造方法が開示されている。特許文献６は、金属担持多孔質体の製造方法に関するものではなく、金属超微粒子オルガノゾルに関するものである。特許文献６に記載の方法は、特許文献４、５に記載の方法と同様に、強力な還元剤を添加する前に別の添加剤（アルキルアミンおよび／またはその化合物）を添加する方法である。 Patent Document 6 discloses a method for producing a platinum organosol. Patent Document 6 does not relate to a method for producing a metal-supporting porous body, but relates to a metal ultrafine particle organosol. The method described in Patent Document 6 is a method of adding another additive (alkylamine and / or a compound thereof) before adding a strong reducing agent, similarly to the methods described in Patent Documents 4 and 5. .
白金コロイド水溶液の製造方法として、特許文献７には、高分子量顔料分散剤を含有する水溶液中で、２価の白金化合物とアミン化合物とを混合し、２価の白金化合物を還元して白金コロイド粒子を得る方法が開示されている。しかしながら、特許文献７に記載の方法は、金属担持多孔質体の製造方法に関するものではなく、また還元剤の他に高分子顔料分散剤を用いる方法である。 As a method for producing a platinum colloid aqueous solution, Patent Document 7 discloses a platinum colloid obtained by mixing a divalent platinum compound and an amine compound in an aqueous solution containing a high molecular weight pigment dispersant, and reducing the divalent platinum compound. A method of obtaining particles is disclosed. However, the method described in Patent Document 7 is not related to a method for producing a metal-supporting porous body, and is a method using a polymer pigment dispersant in addition to a reducing agent.
また、白金合金を担持した多孔質体の製造方法としては、特許文献８に、カーボン担体上に白金を担持する工程と、他の金属の塩溶液にアルカリを添加して水酸化物を調製したあと保護コロイド剤を添加して水酸化物を調製する工程と、白金を担持したカーボンをここで得られたコロイド溶液に添加して混合し、濾過する工程と、濾過後の白金担持カーボンを所定の温度で熱処理して合金化する工程とを有する方法が開示されている。この方法におけるカーボン担体上に白金を担持する方法としては、塩基性に調製後、ヒドラジンによって還元する方法が記載されているのみであり、上述した方法と同様の問題を有するものである。 In addition, as a method for producing a porous body carrying a platinum alloy, in Patent Document 8, a step of carrying platinum on a carbon support and adding a alkali to a salt solution of another metal prepared a hydroxide. A step of preparing a hydroxide by adding a protective colloid agent, a step of adding and mixing platinum-supported carbon to the obtained colloid solution, filtering, and a platinum-supported carbon after filtration And a process of alloying by heat treatment at a temperature of 5 ° C. As a method of supporting platinum on a carbon support in this method, only a method of reducing with hydrazine after basic preparation is described, and it has the same problem as the method described above.
本発明は、上記現状に鑑み、工程数が少なくて簡便で、反応の制御も容易であることから、コストダウンを図ることができるような金属担持多孔質体の製造方法を提供することを目的とするものである。 In view of the above-mentioned present situation, the present invention has an object of providing a method for producing a metal-supporting porous body capable of reducing the cost because the number of steps is small and simple, and the reaction is easily controlled. It is what.
本発明は、多孔質体の存在下、溶媒中で、２価の白金イオンを第３級アミンにより白金に還元する工程を有することを特徴とする金属担持多孔質体の製造方法である。
本発明において、第３級アミンの使用量は、Ｎ量換算で、白金イオン中の白金原子１モルあたり１〜２０当量であることが好ましい。
本発明において、反応中の溶媒中における白金（金属換算量）／多孔質体の質量比は、２０／８０〜８０／２０であることが好ましい。
The present invention is a method for producing a metal-supporting porous body, comprising a step of reducing divalent platinum ions to platinum with a tertiary amine in a solvent in the presence of the porous body.
In this invention, it is preferable that the usage-amount of a tertiary amine is 1-20 equivalent per 1 mol of platinum atoms in platinum ion in conversion of N amount.
In the present invention, the mass ratio of platinum (in metal equivalent) / porous body in the solvent during the reaction is preferably 20/80 to 80/20.
本発明はまた、多孔質体の存在下、溶媒中で、２価の白金イオンと、金、銀、ルテニウム、ロジウム、パラジウム、オスミウム、レニウム、イリジウム、銅、クロム、マンガン、鉄、インジウム、モリブデン、スズ、コバルト、ニッケル、亜鉛、アンチモン、ビスマス、バナジウム、ニオブ、タンタル及びタングステンからなる群から選ばれる少なくとも１種の金属のイオン若しくは錯イオンとを、第３級アミンにより白金及び上記金属に同時に還元する工程を有することを特徴とする金属担持多孔質体の製造方法である。 The present invention also provides a divalent platinum ion, gold, silver, ruthenium, rhodium, palladium, osmium, rhenium, iridium, copper, chromium, manganese, iron, indium, molybdenum in a solvent in the presence of a porous material. At least one metal ion or complex ion selected from the group consisting of tin, cobalt, nickel, zinc, antimony, bismuth, vanadium, niobium, tantalum and tungsten is simultaneously added to platinum and the above metal by a tertiary amine. It is a manufacturing method of the metal carrying | support porous body characterized by having the process to reduce | restore.
本発明において、２価の白金イオンは、４配位の白金錯イオンであることが好ましい。
また、２価で４配位の白金錯イオンは、テトラクロロ白金（ＩＩ）酸イオンであることが好ましい。
In the present invention, the divalent platinum ion is preferably a tetracoordinate platinum complex ion.
The divalent and tetracoordinate platinum complex ion is preferably a tetrachloroplatinum (II) acid ion.
本発明において、多孔質体は、導電性を有することが好ましい。上記多孔質体は、導電性カーボンブラック又はセラミック材料であることが好ましい。
本発明においては、第３級アミンは、脂肪族、アラルキル又は脂環式の第３級アミンであり、溶媒は、水又は水性媒体であることが好ましい。
In the present invention, the porous body preferably has conductivity. The porous body is preferably conductive carbon black or a ceramic material.
In the present invention, the tertiary amine is preferably an aliphatic, aralkyl or alicyclic tertiary amine, and the solvent is preferably water or an aqueous medium.
上記多孔質体は、２００〜１５００ｍ２／ｇのＢＥＴ比表面積を有することが好ましい。また、反応時間１０分〜５０時間、反応温度１５〜１００℃で還元を行うことが好ましい。
以下に本発明を詳細に説明する。
The porous body preferably has a BET specific surface area of 200 to 1500 m 2 / g. The reduction is preferably performed at a reaction temperature of 15 to 100 ° C. for a reaction time of 10 minutes to 50 hours.
The present invention is described in detail below.
本発明の金属担持多孔質体の製造方法は、多孔質体の存在下、溶媒中で、２価の白金イオンを第３級アミンにより白金に還元する工程を有する。すなわち、本発明は白金イオンとして４価の白金イオンより還元されやすい２価の白金イオンを原料として使用するものである。このため、第３級アミン存在下という温和な還元条件で金属を析出させることができ、反応の制御が容易となり、コストダウンを図ることができるものである。 The method for producing a metal-supporting porous body of the present invention includes a step of reducing divalent platinum ions to platinum with a tertiary amine in a solvent in the presence of the porous body. That is, the present invention uses a divalent platinum ion, which is more easily reduced than a tetravalent platinum ion, as a raw material. Therefore, the metal can be deposited under mild reduction conditions in the presence of a tertiary amine, the reaction can be easily controlled, and the cost can be reduced.
本発明では、還元剤として第３級アミンを使用する。アミンによる還元反応は穏やかな条件下での進行するものであることから、微細な粒子状の金属を容易に析出させることができる。このため、比表面積が大きい微細な金属粒子を多孔質体上に効率よく担持させることができる。 In the present invention, a tertiary amine is used as the reducing agent. Since the reduction reaction with an amine proceeds under mild conditions, a fine particulate metal can be easily deposited. For this reason, fine metal particles having a large specific surface area can be efficiently supported on the porous body.
また、アミンの窒素原子上の非共有電子対は金属に対する配位子として作用するものであるから、配位することによって錯体が水溶液中で安定化してしまうと、還元反応が進行しにくくなる。このため、良好な還元性を得るためには配位能が低いアミンを使用することが必要である。第３級アミンは、窒素原子周辺に３つの脂肪族炭化水素基等が存在することから、立体的要因のために配位能が低く、このため還元反応を進行させやすいと推測される。 In addition, since the unshared electron pair on the nitrogen atom of the amine acts as a ligand for the metal, if the complex is stabilized in the aqueous solution by coordination, the reduction reaction is difficult to proceed. For this reason, in order to obtain favorable reducibility, it is necessary to use an amine with low coordination ability. The tertiary amine has three aliphatic hydrocarbon groups around the nitrogen atom, and therefore has a low coordination ability due to a steric factor, and is thus presumed to facilitate the reduction reaction.
本発明においては、上述したような反応を多孔質体存在下で行うものである。これによって、金属が担持した多孔質体を容易に製造することができる。 In the present invention, the reaction as described above is performed in the presence of a porous material. As a result, a porous body carrying a metal can be easily manufactured.
２価の白金イオンは、２価の白金イオン前駆体（白金化合物）が溶媒に溶解することにより生じる。２価の白金イオン前駆体としては、白金原子１つに対して２つの電子供与体又は電子供与官能基から構成されるものと、白金原子１つに対して４つの電子供与体又は電子供与官能基から構成されるものとを挙げることができる。
白金原子１つに対して２つの電子供与体もしくは電子供与官能基から構成される２価の白金イオン前駆体としては、例えば、フッ化白金（ＩＩ）、塩化白金（ＩＩ）、臭化白金（ＩＩ）、ヨウ化白金（ＩＩ）、酸化白金（ＩＩ）、シアン化白金（ＩＩ）等を挙げることができる。
白金原子１つに対して４つの電子供与体又は電子供与官能基から構成される２価の白金イオン前駆体としては、例えば、テトラクロロ白金（ＩＩ）酸ナトリウム四水和物、テトラクロロ白金（ＩＩ）酸カリウム、テトラクロロ白金（ＩＩ）酸アンモニウム、テトラブロモ白金（ＩＩ）酸二水和物、テトラニトロ白金（ＩＩ）酸カリウム、ビス（２，４−ペンタンジオナト）白金（ＩＩ）、ジクロロジアンミン白金（ＩＩ）、テトラクロロ白金（ＩＩ）酸、テトラアンミン白金（ＩＩ）、テトラアンミン白金（ＩＩ）塩化物ｎ水和物、ジニトロジアンミン白金（ＩＩ）、ジクロロビス（ベンゾニトリル）白金（ＩＩ）、ビス（エチレンジアミン）白金（ＩＩ）塩化物、テトラキス（チオシアナト）白金（ＩＩ）酸カリウム、テトラシアノ白金（ＩＩ）酸カリウム三水和物、テトラシアノ白金（ＩＩ）酸バリウム四水和物、ジクロロビス（トリフェニルホスフィン）白金（ＩＩ）、ヨード（メチル）ビス（トリエチルホスフィン）白金（ＩＩ）、ジフェニルビス（トリエチルホスフィン）白金（ＩＩ）、ジクロロ（フェニルイソシアニド）（トリエチルホスフィン）白金（ＩＩ）、ビス（アリル）白金（ＩＩ）、ジクロロ（１，５−シクロオクタジエン）白金（ＩＩ）、トランス−ｌ−シクロヘキサンジアミンジクロロ白金（ＩＩ）、トランス−ｄ−シクロヘキサンジアミンジクロロ白金(ＩＩ)、ジクロロビス（ベンゾニトリル）白金（ＩＩ）、ジクロロ（η−エチレン）白金（ＩＩ）ダイマー、ジクロロ（η−シクロヘキセン）白金（ＩＩ）ダイマー等が挙げられる。
The divalent platinum ion is generated by dissolving a divalent platinum ion precursor (platinum compound) in a solvent. Examples of the divalent platinum ion precursor include those composed of two electron donors or electron donating functional groups for one platinum atom, and four electron donors or electron donating functional groups for one platinum atom. And those composed of groups.
Examples of the divalent platinum ion precursor composed of two electron donors or electron donating functional groups for one platinum atom include platinum fluoride (II), platinum chloride (II), platinum bromide ( II), platinum iodide (II), platinum oxide (II), platinum cyanide (II) and the like.
Examples of the divalent platinum ion precursor composed of four electron donors or electron donating functional groups for one platinum atom include sodium tetrachloroplatinate (II) tetrahydrate, tetrachloroplatinum ( II) Potassium acid, Tetrachloroplatinum (II) ammonium, Tetrabromoplatinum (II) acid dihydrate, Potassium tetranitroplatinum (II), Bis (2,4-pentanedionato) platinum (II), Dichlorodiammine Platinum (II), tetrachloroplatinum (II) acid, tetraammineplatinum (II), tetraammineplatinum (II) chloride n-hydrate, dinitrodiammineplatinum (II), dichlorobis (benzonitrile) platinum (II), bis ( Ethylenediamine) platinum (II) chloride, potassium tetrakis (thiocyanato) platinum (II), tetracyanoplatinum ( I) Potassium acid trihydrate, tetracyanoplatinum (II) barium acid tetrahydrate, dichlorobis (triphenylphosphine) platinum (II), iodo (methyl) bis (triethylphosphine) platinum (II), diphenylbis (triethyl) Phosphine) platinum (II), dichloro (phenylisocyanide) (triethylphosphine) platinum (II), bis (allyl) platinum (II), dichloro (1,5-cyclooctadiene) platinum (II), trans-1-cyclohexane Diamine dichloroplatinum (II), trans-d-cyclohexanediamine dichloroplatinum (II), dichlorobis (benzonitrile) platinum (II), dichloro (η-ethylene) platinum (II) dimer, dichloro (η-cyclohexene) platinum (II ) Dimers and the like.
白金原子１つに対して４つの電子供与体又は電子供与官能基から構成される２価の白金イオン前駆体のなかでは、４配位の白金錯イオンのアルカリ金属塩又はアンモニウム塩が好ましい。これらの塩は、水性媒体中への溶解性が高いので、還元工程において好適に使用され得るからである。 Among the divalent platinum ion precursors composed of four electron donors or electron donating functional groups for one platinum atom, alkali metal salts or ammonium salts of tetracoordinate platinum complex ions are preferable. This is because these salts have high solubility in an aqueous medium and can be suitably used in the reduction step.
溶媒としては、特に限定されるものではなく、例えば、水性媒体や、有機溶媒等を挙げることができる。
水性媒体としては、水又は水と有機溶媒との混合物を挙げることができる。
これらのなかでは、水が好ましい。製造工程上安全であり、また生成して得られた金属担持多孔質体も爆発等のおそれがなくて安全だからである。
また、有機溶媒としては、水溶性のものが好ましく、具体的には、１価又は多価のアルコール、エーテルを挙げることができる。
本発明の金属担持多孔質体の製造方法は、反応中の溶媒中において白金の含有量が金属量換算で０．００５ｍｏｌ／ｌ以上で行うことが好ましい。
白金の含有量が０．００５ｍｏｌ／ｌ未満であると、白金粒子を充分に多孔質体に担持させることが困難である。
The solvent is not particularly limited, and examples thereof include an aqueous medium and an organic solvent.
Examples of the aqueous medium include water or a mixture of water and an organic solvent.
Of these, water is preferred. This is because it is safe in the manufacturing process, and the metal-supported porous body obtained by the production is also safe without the risk of explosion.
Moreover, as an organic solvent, a water-soluble thing is preferable, and can specifically mention monohydric or polyhydric alcohol and ether.
The method for producing a metal-supported porous body of the present invention is preferably carried out at a platinum content of 0.005 mol / l or more in terms of metal amount in the solvent during the reaction.
If the platinum content is less than 0.005 mol / l, it is difficult to sufficiently support the platinum particles on the porous body.
本発明の金属担持多孔質体の製造方法は、反応中の溶媒中において白金（金属換算量）／多孔質体の質量比が２０／８０〜８０／２０であることが好ましい。上記範囲内であることが、燃料電池や排ガス浄化用触媒としての好適である。上記質量比が２０／８０未満であると、金属担持多孔質体を燃料電池用電極触媒等として用いる場合に触媒層を厚くしなければならないため、燃料ガス等の拡散性が低下し、触媒能が充分に得られないおそれがある。一方、上記質量比が８０／２０を超えると、燃料電池用電極触媒等として用いる場合に触媒活性が高くなりすぎて発火するおそれがある。 In the method for producing a metal-supporting porous body of the present invention, the mass ratio of platinum (metal equivalent amount) / porous body in the solvent during the reaction is preferably 20/80 to 80/20. It is suitable for the fuel cell and exhaust gas purification catalyst to be within the above range. When the mass ratio is less than 20/80, the catalyst layer must be thickened when the metal-supported porous body is used as an electrode catalyst for a fuel cell. May not be sufficiently obtained. On the other hand, if the mass ratio exceeds 80/20, when used as a fuel cell electrode catalyst or the like, the catalytic activity becomes too high and there is a risk of ignition.
本発明の金属担持多孔質体の製造方法はまた、多孔質体の存在下、溶媒中で、２価の白金イオンと、金、銀、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、銅、クロム、マンガン、鉄、インジウム、モリブデン、スズ、コバルト、ニッケル、亜鉛、アンチモン、ビスマス、バナジウム、ニオブ、タンタル、レニウム及びタングステンからなる群から選ばれる少なくとも１種の金属（以下、第２成分金属）のイオン若しくは錯イオンとを、第３級アミンにより白金及び第２成分金属に同時に還元する工程を有するものである。目的によっては、白金に加えてこれらの金属を併用することが必要とされる場合があるものであるが、このような場合にはこれらの金属の存在下で上記還元反応を行うことによって、所望の物性を得ることができる。この方法では１段階で少なくとも２種の金属を担持する金属担持多孔質体を得ることができる。ここでいう金属担持多孔質体は、白金を少なくとも含む金属担持多孔質体で、上記第二成分金属を１種又はそれ以上有する金属担持多孔質体である。換言すると、ここでの金属担持多孔質体とは、金属微粒子が多孔質体の表面に担持された構造を有するものをいう。また、その担持される金属微粒子とは、白金と第２成分金属である１種類又は２種類以上の金属とが、粒子内で合金化された（複合化された）構造を持つものや、白金微粒子と第２成分金属の金属微粒子とが混合した状態で担持されるものをいい、合金微粒子と単独金属微粒子とが混在するような形態で担持されているものを含むものをいう。また、担持される金属微粒子とは、個々の金属微粒子が独立した状態で担持されるものや、金属微粒子同士が集合した形態を含む状態で担持されるものも含むものをいう。 The method for producing a metal-supported porous body of the present invention also includes divalent platinum ions, gold, silver, ruthenium, rhodium, palladium, osmium, iridium, copper, chromium, in a solvent in the presence of the porous body. Ion of at least one metal selected from the group consisting of manganese, iron, indium, molybdenum, tin, cobalt, nickel, zinc, antimony, bismuth, vanadium, niobium, tantalum, rhenium and tungsten (hereinafter referred to as second component metal) Or it has the process of reduce | restoring a complex ion to platinum and a 2nd component metal simultaneously with a tertiary amine. Depending on the purpose, it may be necessary to use these metals in combination with platinum. In such a case, the above reduction reaction is performed in the presence of these metals. The physical properties can be obtained. In this method, it is possible to obtain a metal-supporting porous body that supports at least two kinds of metals in one step. The metal-supporting porous body here is a metal-supporting porous body containing at least platinum and having one or more of the second component metals. In other words, the metal-supporting porous body here has a structure in which metal fine particles are supported on the surface of the porous body. Further, the supported metal fine particles include those having a structure in which platinum and one or more kinds of metals as the second component metal are alloyed (composited) in the particles, or platinum. This refers to those supported in a state where fine particles and metal fine particles of the second component metal are mixed, including those supported in a form in which alloy fine particles and single metal fine particles are mixed. The supported metal fine particles include those in which individual metal fine particles are supported in an independent state and those supported in a state including a form in which metal fine particles are aggregated.
第２成分金属としては、ルテニウムが好ましい。金属担持多孔質体を燃料電池用電極触媒として使用する場合、アノードにおいてルテニウムの存在下で上記還元反応を行うことによって、一酸化炭素による被毒に対する耐性を向上させることができるからである。 As the second component metal, ruthenium is preferable. This is because when the metal-supported porous body is used as an electrode catalyst for a fuel cell, the resistance to poisoning by carbon monoxide can be improved by performing the above reduction reaction in the presence of ruthenium at the anode.
上記第２成分金属の存在下で還元反応を行う場合、溶媒中における白金及び第２成分金属の含有量は、次の関係を満たすことが好ましい。すなわち、白金及び第２成分金属と多孔質体との質量比は、（白金＋第２成分金属；金属量換算）／多孔質体＝２０／８０〜８０／２０であることが好ましい。上記範囲に金属含有量を調整することにより、一酸化炭素による被毒に対する耐性と触媒活性とを充分に有する金属担持多孔質体を製造することができるからである。白金と第２成分金属との金属換算での質量比は、当該金属担持多孔質体の用途や第２成分金属の種類により異なり、特に限定されるものではないが、白金／第２成分金属の質量比は、２０／８０〜９９．５／０．５であることが好ましい。 When the reduction reaction is performed in the presence of the second component metal, the content of platinum and the second component metal in the solvent preferably satisfies the following relationship. That is, the mass ratio of platinum and the second component metal to the porous body is preferably (platinum + second component metal; metal amount conversion) / porous body = 20/80 to 80/20. This is because by adjusting the metal content within the above range, a metal-supporting porous body having sufficient resistance to poisoning by carbon monoxide and catalytic activity can be produced. The mass ratio of platinum and the second component metal in terms of metal varies depending on the use of the metal-supported porous body and the type of the second component metal, and is not particularly limited. The mass ratio is preferably 20/80 to 99.5 / 0.5.
本発明では、多孔質体の存在下で還元を行う。上記多孔質体を用いるのは、反応面積を大きくすることにより、触媒活性を高めるためである。また、多孔質体とは、２ｎｍ未満のマイクロ孔又は２〜３０ｎｍのメソ孔を有し、比表面積が２００〜１５００ｍ２／ｇのものであることが好ましい。
上記多孔質体としては、特に限定されるものではなく、例えば、カーボン、セラミック材料、粘土鉱物等の無機物、金属若しくは半金属の単一若しくは複合酸化物、硫化物等を挙げることができる。上記多孔質体は、特に電極材料として使用する場合には導電性を有することが好ましく、具体的にはカーボンが好ましい。
In the present invention, the reduction is performed in the presence of the porous body. The reason for using the porous body is to increase the catalytic activity by increasing the reaction area. The porous body preferably has a micropore of less than 2 nm or a mesopore of 2 to 30 nm and a specific surface area of 200 to 1500 m 2 / g.
The porous body is not particularly limited, and examples thereof include inorganic substances such as carbon, ceramic materials and clay minerals, single or complex oxides of metals or metalloids, and sulfides. The porous body preferably has electrical conductivity, particularly when used as an electrode material, and specifically carbon is preferred.
上記カーボンとしては、通常使用されるカーボン材料を使用することができる。なかでも、チャンネルブラック、ファーネスブラック、アセチレンブラック、ケッチェンブラック等のカーボンブラック、グラファイト、ナノチューブ、フラーレン、活性炭等が好ましい。なお、上記カーボンとして、親水化処理が施されたものを用いることとしてもよい。そのようなカーボンとしては、例えば、表面に酸性基が導入されたもの等を挙げることができる。
さらに、金属担持多孔質体を、排ガスを浄化する触媒として使用する場合には、多孔質体は、熱やガスに対する劣化耐性などを有するものが好ましく、具体的にはセラミック材料や粘土鉱物等の無機物、金属若しくは半金属の単一若しくは複合酸化物、硫化物、カルコゲン化物などが好ましい。なかでもゼオライト、アパタイト、リン酸ジルコニウム、粘土鉱物などの無機物；酸化ケイ素、酸化アルミニウム、酸化バナジウム、酸化チタン、酸化鉄、酸化ニッケル、酸化コバルト、酸化モリブデン、酸化ニオブ、酸化セリウム、酸化ランタン、酸化ホウ素、酸化ジルコニウム、酸化タンタル、酸化タングステン、酸化マグネシウム等の金属若しくは半金属の単一若しくは複合酸化物；硫化物；カルコゲン化物等が好ましい。上述したような多孔質体を用いて得られた金属担持多孔質体の使用にあたっての形状は特に限定されるものではなく、例えば、ペレット状に加工してから使用することができる。また、上記金属担持多孔質体を、支持体（例えば、ハニカム支持体等）に成形したり、支持体に塗布したりして使用することができる。
As the carbon, a commonly used carbon material can be used. Of these, carbon black such as channel black, furnace black, acetylene black, and ketjen black, graphite, nanotube, fullerene, activated carbon, and the like are preferable. In addition, it is good also as using the thing to which the hydrophilic treatment was given as said carbon. Examples of such carbon include those having an acidic group introduced on the surface.
Further, when the metal-supported porous body is used as a catalyst for purifying exhaust gas, the porous body preferably has heat resistance and gas degradation resistance, and specifically, ceramic materials, clay minerals, etc. Inorganic, metal or metalloid single or complex oxides, sulfides, chalcogenides and the like are preferred. Among them, inorganic substances such as zeolite, apatite, zirconium phosphate, clay minerals; silicon oxide, aluminum oxide, vanadium oxide, titanium oxide, iron oxide, nickel oxide, cobalt oxide, molybdenum oxide, niobium oxide, cerium oxide, lanthanum oxide, oxidation Single or complex oxides of metals or metalloids such as boron, zirconium oxide, tantalum oxide, tungsten oxide and magnesium oxide; sulfides; chalcogenides and the like are preferable. The shape of the metal-supporting porous body obtained using the porous body as described above is not particularly limited, and for example, it can be used after being processed into a pellet shape. The metal-supporting porous body can be used by forming it on a support (for example, a honeycomb support or the like) or applying it to the support.
上記多孔質体のＢＥＴ比表面積は、特に限定されるものではないが、前述のように、２００〜１５００ｍ２／ｇであることが好ましい。触媒活性に優れた金属担持多孔質体を得ることができるからである。 The BET specific surface area of the porous body is not particularly limited, but is preferably 200 to 1500 m 2 / g as described above. This is because a metal-supporting porous body having excellent catalytic activity can be obtained.
上記第３級アミンとしては、水溶性の脂肪族第３級アミンを用いることが好ましい。水性媒体中で反応を行う際に、容易に反応を進行させることができるためである。水溶性の脂肪族第３級アミンとしては、アルキル基中に水酸基、カルボニル基等の官能基を１又は２以上有するものであってもよく、例えばアルカノールアミン類であってもよい。また、水溶性の脂肪族第３級アミンとしては、例えば、ジエチルメチルアミン、トリエチルアミン、ジメチルアミノエタノール、ジエチルアミノエタノール、トリエタノールアミン、メチルジエタノールアミン、ジメチルアミノプロパノールを挙げることができる。これらのうち、アルカノールアミンが好ましく、モノアルカノールアミンがより好ましく、２−ジメチルアミノエタノールがさらに好ましい。上記脂肪族第３級アミンの置換基は、アルキル基、エーテル基、ポリエーテル基が好ましく、置換基の末端は、水素基又は水酸基であることが好ましい。なお、本発明においては、水溶性の第３級アミンとして、アラルキルアミン又は脂環式アミンを用いることも可能である。アラルキルアミンとしては、例えば、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジエチルベンジルアミン、Ｎ，Ｎ−ジメチルフェネチルアミン、Ｎ，Ｎ−ジエチルフェネチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルキシレンジアミン等を挙げることができる。上記脂環式アミンとしては、例えば、Ｎ−メチルピペリジン、ピペラジン、ピロリジン等を挙げることができる。
上記脂肪族第３級アミンとしては、市販されているものを使用することもできる。上記市販品としては、例えば、エソミンＣ／１２、エソミンＣ／１５、エソミンＣ／２５、エソミンＴ／１２、エソミンＴ／１５、エソミンＴ／２５、エソミンＳ／１５、エソミンＳ／２５、エソミンＯ／１２、エソミンＯ／１７、エソミンＯ／２０、エソミンＨＴ／１２、エソミンＨＴ／１４、エソミンＨＴ／１７、エソミンＳＡＪ−１０３、エソミンＳＡ２Ｙ−１０３（以上ライオン・アクゾ社製）等を挙げることができる。これらは単独で使用してもよく、２種以上を併用してもよい。上記市販品のなかでは、エソミンＣ／１５、エソミンＣ／２５、エソミンＴ／１５、エソミンＴ／２５、エソミンＳ／２５、エソミンＳＡＪ−１０３又はエソミンＳＡ２Ｙ−１０３が好ましい。これらの市販品は、水溶性を示すからである。
As the tertiary amine, a water-soluble aliphatic tertiary amine is preferably used. This is because the reaction can easily proceed when the reaction is carried out in an aqueous medium. The water-soluble aliphatic tertiary amine may have one or more functional groups such as a hydroxyl group and a carbonyl group in the alkyl group, and may be, for example, an alkanolamine. Examples of the water-soluble aliphatic tertiary amine include diethylmethylamine, triethylamine, dimethylaminoethanol, diethylaminoethanol, triethanolamine, methyldiethanolamine, and dimethylaminopropanol. Of these, alkanolamines are preferred, monoalkanolamines are more preferred, and 2-dimethylaminoethanol is even more preferred. The substituent of the aliphatic tertiary amine is preferably an alkyl group, an ether group or a polyether group, and the terminal of the substituent is preferably a hydrogen group or a hydroxyl group. In the present invention, an aralkylamine or an alicyclic amine can be used as the water-soluble tertiary amine. Examples of aralkylamines include N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylphenethylamine, N, N-diethylphenethylamine, N, N, N ′, N′-tetramethylxylene. A diamine etc. can be mentioned. Examples of the alicyclic amine include N-methylpiperidine, piperazine, and pyrrolidine.
As the aliphatic tertiary amine, those commercially available can also be used. Examples of the commercially available products include Esomine C / 12, Esomin C / 15, Esomin C / 25, Esomine T / 12, Esomine T / 15, Esomine T / 25, Esomine S / 15, Esomine S / 25, Esomine O / 12, Esomin O / 17, Esomin O / 20, Esomin HT / 12, Esomin HT / 14, Esomin HT / 17, Esomin SAJ-103, Esomin SA2Y-103 (manufactured by Lion Akzo) it can. These may be used alone or in combination of two or more. Among the above commercially available products, esomine C / 15, esomine C / 25, esomine T / 15, esomine T / 25, esomine S / 25, esomine SAJ-103 or esomine SA2Y-103 are preferred. This is because these commercially available products exhibit water solubility.
溶媒中に第２成分金属を含まない場合、第３級アミンの使用量は、Ｎ量換算で、白金イオン中の白金金属１モルに対して１〜２０当量であることが好ましい。１当量未満であると、還元が充分に行われないおそれがある。２０当量を超えると、後処理としての水洗工程で大量の洗浄水が必要となる。 When the second component metal is not included in the solvent, the amount of the tertiary amine used is preferably 1 to 20 equivalents per 1 mole of platinum metal in platinum ions in terms of N amount. If the amount is less than 1 equivalent, the reduction may not be performed sufficiently. If it exceeds 20 equivalents, a large amount of washing water is required in the washing step as a post-treatment.
本発明では、上記第３級アミン以外の還元剤を併用することも可能である。そのような還元剤としては、例えば、ヒドラジン化合物、クエン酸、酒石酸、アスコルビン酸、ギ酸、リンゴ酸、スルホキシル酸、それらの誘導体等を挙げることができる。
上記従来からの還元剤の中で、クエン酸、酒石酸、アスコルビン酸、ギ酸、リンゴ酸が入手容易なことから好ましい。なお、クエン酸、酒石酸、アスコルビン酸は、そのまま系に加えると、上記アミン化合物と塩を形成し、アミン化合物の機能発現を抑制するおそれがあるので、塩の形のものを用いることが好ましい。ただし、工程数の削減やコストダウンを考慮すると、これらの化合物は使用しないことが好ましい。
In the present invention, a reducing agent other than the tertiary amine can be used in combination. Examples of such a reducing agent include hydrazine compounds, citric acid, tartaric acid, ascorbic acid, formic acid, malic acid, sulfoxylic acid, and derivatives thereof.
Among the conventional reducing agents, citric acid, tartaric acid, ascorbic acid, formic acid, and malic acid are preferable because they are easily available. In addition, when citric acid, tartaric acid, and ascorbic acid are added to the system as they are, they may form a salt with the amine compound and suppress the functional expression of the amine compound. Therefore, it is preferable to use a salt form. However, it is preferable not to use these compounds in consideration of reduction in the number of steps and cost reduction.
上記還元工程は、溶媒に含まれる２価の白金イオンを、多孔質体の存在下で、第３級アミンにより還元するものである。これらを溶媒に添加する順序は、特に限定されるものではないが、上記白金イオン若しくは上記第３級アミンのいずれか一方と上記多孔質体とを含む溶媒に、他方を添加することが好ましい。なかでも、上記第３級アミンと上記多孔質体とを含む溶媒に上記白金イオンを添加することが好ましい。第３級アミンが多孔質体の濡れ性助剤や分散助剤として機能するからである。 In the reduction step, divalent platinum ions contained in the solvent are reduced with a tertiary amine in the presence of a porous material. The order of adding these to the solvent is not particularly limited, but it is preferable to add the other to the solvent containing either the platinum ion or the tertiary amine and the porous body. Especially, it is preferable to add the platinum ion to a solvent containing the tertiary amine and the porous body. This is because the tertiary amine functions as a wettability aid or a dispersion aid for the porous body.
上記還元工程では、２価の白金イオンと第３級アミンとの混合により、静置後の上澄み液が無色から黄色を呈することで還元反応の進行を確認することができる。
上記還元工程では、反応時間１０分〜５０時間、反応温度１５〜１００℃で還元を行うことが好ましい。これらの条件で還元を行うことにより、微細な粒子状の金属を容易に析出させることができるからである。
In the reduction step, the progress of the reduction reaction can be confirmed by mixing the divalent platinum ion and the tertiary amine so that the supernatant after standing exhibits a colorless to yellow color.
In the reduction step, reduction is preferably performed at a reaction temperature of 15 to 100 ° C. for a reaction time of 10 minutes to 50 hours. It is because fine particulate metal can be easily deposited by performing the reduction under these conditions.
このようにして得られた金属担持多孔質体を含有する溶媒は、白金を担持した多孔質体以外に、還元で生じた塩や、場合によってはアミン化合物を含んでいる。これらの成分は、金属担持多孔質体の触媒活性に悪影響を及ぼすおそれがあるので、除去しておくことが好ましい。これらの成分の除去は、例えば、限外濾過や電気透析等の公知の方法により、濾液の電気伝導度が目標とする値になるまで行うことができる。この目標値としては、特に限定されるものではないが、１０μＳ／ｃｍ以下が好ましい。充分な触媒活性を有する金属担持多孔質体を得ることができるからである。 The solvent containing the metal-supported porous material thus obtained contains a salt generated by reduction or, in some cases, an amine compound in addition to the porous material supporting platinum. Since these components may adversely affect the catalytic activity of the metal-supported porous body, it is preferable to remove them. These components can be removed by a known method such as ultrafiltration or electrodialysis until the electric conductivity of the filtrate reaches a target value. The target value is not particularly limited, but is preferably 10 μS / cm or less. This is because a metal-supporting porous material having sufficient catalytic activity can be obtained.
上述した製造方法で得られた金属担持多孔質体における白金の平均粒子径は、５ｎｍ未満であることが好ましい。５ｎｍ以上であると、触媒として利用することが困難になる。より好ましい平均粒子径は２〜３ｎｍである。なお、平均粒子径は、例えば、白金粒子の電子顕微鏡写真等から読み取ったり、Ｘ線回折、分析機器等により測定したりすることにより決定することができる。 The average particle diameter of platinum in the metal-supported porous body obtained by the above-described production method is preferably less than 5 nm. When it is 5 nm or more, it becomes difficult to use as a catalyst. A more preferable average particle diameter is 2 to 3 nm. In addition, an average particle diameter can be determined by reading from the electron micrograph etc. of platinum particle | grains, or measuring with X-ray diffraction, an analytical instrument etc., for example.
金属担持多孔質体の白金の担持量は、２０〜８０質量％であることが好ましい。充分な触媒活性を発揮することができるからである。２０質量％未満であると、燃料電池用電極触媒として用いる場合に触媒層を厚くしなければならないため、燃料ガス等の拡散性が低下し、触媒能が充分に得られないおそれがある。一方、８０質量％を超えると、燃料電池用電極触媒等として用いる場合に触媒活性が高くなりすぎて発火するおそれがある。 The amount of platinum supported on the metal-supporting porous body is preferably 20 to 80% by mass. This is because sufficient catalytic activity can be exhibited. If it is less than 20% by mass, the catalyst layer must be thickened when used as an electrode catalyst for a fuel cell, so that the diffusibility of fuel gas or the like is lowered, and there is a possibility that sufficient catalytic performance may not be obtained. On the other hand, when it exceeds 80 mass%, when used as a fuel cell electrode catalyst or the like, the catalytic activity becomes too high and there is a risk of ignition.
上記金属担持多孔質体のＢＥＴ比表面積は、特に限定されるものではないが、５０〜１０００ｍ２／ｇであることが好ましい。この範囲内のＢＥＴ比表面積を有する金属担持多孔質体は、優れた触媒活性を有するからである。 The BET specific surface area of the metal-supporting porous body is not particularly limited, but is preferably 50 to 1000 m 2 / g. This is because a metal-supporting porous body having a BET specific surface area within this range has excellent catalytic activity.
上記製造方法によれば、工程数を少なくして簡便に金属担持多孔質体を製造することができる。また、乾燥等の乾式工程が不要であり、湿式工程のみで、金属担持多孔質体を分散した組成物を得ることができる。多孔質体が、導電性を有する粉状のものである場合、上記製造方法により得られる組成物から溶媒を除去せず、その組成物に導電性樹脂を混合することにより、他の溶媒を用いることなく、インク状の電極触媒（触媒インク）を得ることができる。また、金属担持多孔質体を分散した組成物中の溶媒を他の溶媒に溶媒置換し、得られた組成物に導電性樹脂を混合することにより、インク化してもよい。このようにして得られた触媒インクは、例えば、固体高分子型燃料電池用電極の製造に用いられ得る。また、多孔質体が粉状である場合、上記製造方法により得られる組成物を乾燥させ、得られた粉状の金属担持多孔質体を加熱成形することにより、金属担持多孔質体の成形物を製造することも可能である。 According to the said manufacturing method, a metal carrying | support porous body can be manufactured simply, reducing the number of processes. Moreover, a dry process such as drying is unnecessary, and a composition in which the metal-supported porous body is dispersed can be obtained only by a wet process. When the porous body is in the form of a conductive powder, other solvent is used by mixing the conductive resin into the composition without removing the solvent from the composition obtained by the above production method. An ink-like electrode catalyst (catalyst ink) can be obtained without any problems. Alternatively, the solvent in the composition in which the metal-supported porous body is dispersed may be replaced with another solvent, and the resulting composition may be mixed with a conductive resin to form an ink. The catalyst ink thus obtained can be used, for example, in the production of a polymer electrolyte fuel cell electrode. When the porous body is powdery, the composition obtained by the above production method is dried, and the resulting powdery metal-carrying porous body is heat-molded to form a molded product of the metal-carrying porous body. Can also be manufactured.
本発明の金属担持多孔質体の製造方法によれば、少ない工程で簡便に金属担持多孔質体を製造することができ、コストダウンが可能である。 According to the method for producing a metal-supporting porous body of the present invention, the metal-supporting porous body can be easily produced with few steps, and the cost can be reduced.
以下に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.
［実施例１］
導電性カーボン（Ｃａｂｏｔ社製 ＶｕｌｃａｎＸＣ７２Ｒ）１．７６ｇに脱イオン水３６．１４ｇを加え混合し、更に２−ジメチルアミノエタノールを２．６８ｇ添加した後、マグネットスターラーで攪拌（７００ｒｐｍ）しながら、８０℃まで昇温し、水溶液Ａを得た。
テトラクロロ白金（ＩＩ）酸カリウム（Ｋ２ＰｔＣｌ４）２．５０ｇを脱イオン水２５．００ｇに溶解させて、水溶液Ｂを得た。
水溶液Ａ全量中の導電性カーボンと水溶液Ｂ全量中のテトラクロロ白金（ＩＩ）酸カリウム中の白金（金属量）との質量比は６０／４０であった。
水溶液Ｂ全量を水溶液Ａ全量に攪拌しながら瞬時に加え、８０℃に保ちながら７００ｒｐｍで７５分間攪拌した。
その後、加熱を停止して攪拌しながら室温まで冷却した後、白金担持多孔質体を含有した溶液をろ過した。
これに３０ｇの脱イオン水を加えてろ過を行い、白金担持多孔質体に付着した雑イオン化合物の除去のための洗浄を施した。この作業をろ液の電気伝導度が１０μＳ／ｃｍ以下になるまで行った。
得られた生成物を別の容器に移し、真空乾燥機を用いて乾燥することで白金担持多孔質体を得た。
[Example 1]
36.14 g of deionized water was added to 1.76 g of conductive carbon (Cabot Vulcan XC72R), mixed, and 2.68 g of 2-dimethylaminoethanol was further added, followed by stirring with a magnetic stirrer (700 rpm) at 80 ° C. The aqueous solution A was obtained.
An aqueous solution B was obtained by dissolving 2.50 g of potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) in 25.00 g of deionized water.
The mass ratio of the conductive carbon in the total amount of the aqueous solution A and the platinum (metal amount) in the potassium tetrachloroplatinate (II) in the total amount of the aqueous solution B was 60/40.
The entire amount of the aqueous solution B was added to the total amount of the aqueous solution A while stirring, and the mixture was stirred at 700 rpm for 75 minutes while maintaining at 80 ° C.
Then, after stopping heating and cooling to room temperature with stirring, the solution containing the platinum-supporting porous material was filtered.
To this, 30 g of deionized water was added and filtered, and washing was performed to remove miscellaneous ion compounds adhering to the platinum-supporting porous material. This operation was performed until the electric conductivity of the filtrate was 10 μS / cm or less.
The obtained product was transferred to another container and dried using a vacuum dryer to obtain a platinum-supporting porous material.
［実施例２］
２−ジメチルアミノエタノールを３．５２ｇ添加すること以外は実施例１の水溶液Ａを得る調製法にしたがって、水溶液Ｃを得た。
テトラクロロ白金（ＩＩ）酸カリウム（Ｋ２ＰｔＣｌ４）１．６７ｇと塩化ルテニウム（ＩＩＩ）三水和物（ＲｕＣｌ３・３Ｈ２Ｏ）１．０１５ｇとを脱イオン水２５．００ｇに室温下で溶解させ、水溶液Ｄを得た。
水溶液Ｄ全量中のテトラクロロ白金酸（ＩＩ）カリウム中の白金（金属量）と塩化ルテニウム（ＩＩＩ）三水和物中のルテニウム（金属量）との質量比は２／１であった。
水溶液Ｃ全量中のカーボンと、水溶液Ｄ全量中のテトラクロロ白金（ＩＩ）酸カリウム中の白金及び塩化ルテニウム（ＩＩＩ）三水和物中のルテニウムの合計（金属量）との質量比は６０／４０であった。
水溶液Ｄ全量を水溶液Ｃ全量に、攪拌しながら瞬時に加え、８０℃に保ちながら７００ｒｐｍで１５０分攪拌した。
その後、加熱を停止して攪拌しながら室温まで冷却した後、白金／ルテニウム複合体担持多孔質体を含有した溶液をろ過した。
これに３０ｇの脱イオン水を加えてろ過を行い、白金／ルテニウム複合体担持多孔質体に付着した雑イオン化合物の除去のための洗浄を施した。この作業をろ液の電気伝導度が１０μＳ／ｃｍ以下になるまで行った。
得られた生成物を別の容器に移し、真空乾燥機を用いて乾燥することで白金／ルテニウム複合体担持多孔質体を得た。
[Example 2]
An aqueous solution C was obtained according to the preparation method for obtaining the aqueous solution A of Example 1 except that 3.52 g of 2-dimethylaminoethanol was added.
1.67 g of potassium tetrachloroplatinate (II) (K 2 PtCl 4 ) and 1.015 g of ruthenium (III) chloride trihydrate (RuCl 3 .3H 2 O) were added to 25.00 g of deionized water at room temperature. An aqueous solution D was obtained by dissolution.
The mass ratio of platinum (metal amount) in potassium tetrachloroplatinate (II) in the total amount of aqueous solution D to ruthenium (metal amount) in ruthenium (III) chloride trihydrate was 2/1.
The mass ratio of the carbon in the total amount of the aqueous solution C to the total (metal amount) of platinum in the potassium tetrachloroplatinate (II) in the total amount of the aqueous solution D and ruthenium in the ruthenium (III) chloride trihydrate (metal amount) is 60 / 40.
The total amount of the aqueous solution D was added to the total amount of the aqueous solution C while stirring, and the mixture was stirred at 700 rpm for 150 minutes while maintaining at 80 ° C.
Then, after stopping heating and cooling to room temperature with stirring, the solution containing the platinum / ruthenium composite-supported porous material was filtered.
To this, 30 g of deionized water was added, followed by filtration, and washing was performed to remove miscellaneous ion compounds adhering to the platinum / ruthenium composite-supported porous body. This operation was performed until the electric conductivity of the filtrate was 10 μS / cm or less.
The obtained product was transferred to another container and dried using a vacuum dryer to obtain a porous body supporting a platinum / ruthenium complex.
［実施例３］
導電性カーボンの代わりに酸化ケイ素（日本アエロジル社製 ＡＥＲＯＰＥＲＬ ３００／３０）を用いる以外は実施例Ａを得る調製法に従って、水溶液Ｅを得た。
水溶液Ｅ全量中の酸化ケイ素と水溶液Ｂ全量中のテトラクロロ白金（ＩＩ）酸カリウム中の白金（金属量）との質量比は６０／４０であった。
水溶液Ｂ全量を水溶液Ｅ全量に撹拌しながら瞬時に加え、８０℃に保ちながら７００ｒｐｍで７５分撹拌した。
その後、加熱を停止して攪拌しながら室温まで冷却した後、白金担持多孔質体を含有した溶液をろ過した。
これに３０ｇの脱イオン水を加えてろ過を行い、白金担持多孔質体に付着した雑イオン化合物の除去のための洗浄を施した。この作業をろ液の電気伝導度が１０μＳ／ｃｍ以下になるまで行った。
得られた生成物を別の容器に移し、真空乾燥機を用いて乾燥することで白金担持多孔質体を得た。
[Example 3]
An aqueous solution E was obtained according to the preparation method for obtaining Example A, except that silicon oxide (AEROPERL 300/30 manufactured by Nippon Aerosil Co., Ltd.) was used instead of conductive carbon.
The mass ratio of silicon oxide in the total amount of the aqueous solution E to platinum (metal amount) in the potassium tetrachloroplatinate (II) in the total amount of the aqueous solution B was 60/40.
The total amount of the aqueous solution B was added to the total amount of the aqueous solution E while stirring, and the mixture was stirred at 700 rpm for 75 minutes while maintaining at 80 ° C.
Then, after stopping heating and cooling to room temperature with stirring, the solution containing the platinum-supporting porous material was filtered.
To this, 30 g of deionized water was added and filtered, and washing was performed to remove miscellaneous ion compounds adhering to the platinum-supporting porous material. This operation was performed until the electric conductivity of the filtrate was 10 μS / cm or less.
The obtained product was transferred to another container and dried using a vacuum dryer to obtain a platinum-supporting porous material.
［比較例１］
導電性カーボン（Ｃａｂｏｔ社製 ＶｕｌｃａｎＸＣ７２Ｒ）１．７６ｇに脱イオン水３６．１４ｇを加え混合し、さらに２−ジメチルアミノエタノールを３．７５ｇ添加した後、マグネットスターラーで攪拌（７００ｒｐｍ）しながら、８０℃まで昇温し、水溶液Ｆを得た。
ヘキサクロロ白金（ＩＶ）酸六水和物（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）３．１２ｇを脱イオン水２５．００ｇに溶解させ、水溶液Ｇを得た。
水溶液Ｂにかえて水溶液Ｇを用い、水溶液Ａにかえて水溶液Ｆを用いた以外は、実施例１と同様にした。
[Comparative Example 1]
36.14 g of deionized water was added to 1.76 g of conductive carbon (Cabot Vulcan XC72R), mixed, and 3.75 g of 2-dimethylaminoethanol was further added, followed by stirring with a magnetic stirrer (700 rpm) at 80 ° C. The aqueous solution F was obtained.
Hexachloroplatinic (IV) acid hexahydrate and (H 2 PtCl 6 · 6H 2 O) 3.12g was dissolved in deionized water 25.00 g, to obtain an aqueous solution G.
Example 1 was repeated except that the aqueous solution G was used instead of the aqueous solution B, and the aqueous solution F was used instead of the aqueous solution A.
［比較例２］
導電性カーボン（Ｃａｂｏｔ社製 ＶｕｌｃａｎＸＣ７２Ｒ）１．７６ｇに脱イオン水３６．１４ｇを加え混合し、さらに２−アミノエタノールを１．８４ｇ添加した後、マグネットスターラーで攪拌（７００ｒｐｍ）しながら、８０℃まで昇温し、水溶液Ｈを得た。水溶液Ａにかえて水溶液Ｈを用いた以外は、実施例１と同様にした。
[Comparative Example 2]
After adding 36.14 g of deionized water to 1.76 g of conductive carbon (VulcanXC72R manufactured by Cabot) and adding 1.84 g of 2-aminoethanol, the mixture was stirred at 700 rpm and heated to 80 ° C. The temperature was raised to obtain an aqueous solution H. Example 1 was repeated except that the aqueous solution H was used instead of the aqueous solution A.
［比較例３］
導電性カーボン（Ｃａｂｏｔ社製 ＶｕｌｃａｎＸＣ７２Ｒ）１．７６ｇに脱イオン水３６．１４ｇを加え混合し、さらに２−アミノエタノールを２．５８ｇ添加した後、マグネットスターラーで攪拌（７００ｒｐｍ）しながら、８０℃まで昇温し、水溶液Ｉを得た。水溶液Ｂにかえて水溶液Ｇを用い、水溶液Ａにかえて水溶液Ｉを用いた以外は、実施例１と同様にした。
[Comparative Example 3]
After adding 36.14 g of deionized water to 1.76 g of conductive carbon (Cabot Vulcan XC72R) and adding 2.58 g of 2-aminoethanol, stirring to 700 ° C. with a magnetic stirrer (700 rpm). The temperature was raised to obtain an aqueous solution I. Example 1 was repeated except that the aqueous solution G was used instead of the aqueous solution B, and the aqueous solution I was used instead of the aqueous solution A.
［評価方法］
実施例１〜３及び比較例１〜３で得られた水溶液を用いて、以下の方法で評価した。
（１）透過型電子顕微鏡を用いた観察及び粒子径の測定
得られた多孔質体を、透過型電子顕微鏡（日本電子社製 ＪＥＭ−２０００）を用いて観察・撮影した。その結果、実施例１〜３に係る多孔質体では金属粒子を観察することができたので、ノギスで平均粒子径を計測した。平均粒子径は、任意に選んだ１０粒子の平均値を用いた。その一方で、比較例１〜３に係る多孔質体では金属粒子を観察することができなかった。
[Evaluation methods]
Using the aqueous solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the following methods were used for evaluation.
(1) Observation using transmission electron microscope and measurement of particle diameter The obtained porous body was observed and photographed using a transmission electron microscope (JEM-2000 manufactured by JEOL Ltd.). As a result, since the metal particles could be observed in the porous bodies according to Examples 1 to 3, the average particle diameter was measured with a caliper. As the average particle diameter, an average value of arbitrarily selected 10 particles was used. On the other hand, metal particles could not be observed in the porous bodies according to Comparative Examples 1 to 3.
図１及び図２は、実施例１により得られた金属担持多孔質体の透過型電子顕微鏡写真である。図中には、大きな粒子とその粒子に付着した小さな粒子とが存在しているが、この大きな粒子が導電性カーボンであり、小さな粒子が白金粒子である。図１及び図２によれば、導電性カーボンの表面に白金粒子が均一に担持している様子を確認することができる。 1 and 2 are transmission electron micrographs of the metal-supporting porous material obtained in Example 1. FIG. In the figure, there are large particles and small particles attached to the particles. The large particles are conductive carbon, and the small particles are platinum particles. 1 and 2, it can be confirmed that platinum particles are uniformly supported on the surface of the conductive carbon.
（２）ＢＥＴ比表面積の測定
金属粒子を確認することができた実施例１〜３に係る多孔質体について、ＢＥＴ法（窒素吸着法）により比表面積を測定した。
評価方法（１）、（２）の結果を表１に示す。
(2) Measurement of BET specific surface area For the porous bodies according to Examples 1 to 3 in which metal particles could be confirmed, the specific surface area was measured by the BET method (nitrogen adsorption method).
Table 1 shows the results of the evaluation methods (1) and (2).
表１に示すように実施例１〜３では多孔質体に金属粒子を担持させることができたが、比較例１、２、３では金属粒子を担持させることができなかった。
比較例１においては、ヘキサクロロ白金（ＩＶ）酸六水和物（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）を溶解することで溶液中に生成する４価の白金イオンを、脂肪族第３級アミンでは白金金属に還元することができなかったため、導電性カーボンに金属粒子を担持させることができなかったと考えられる。
すなわち、４価の白金イオンを還元するには、白金原子１つあたりに４個の電子を供与する必要があるため、より高い反応性を有する還元剤を適用しなければならない。しかし、脂肪族第３級アミンでは還元能が不充分であったと考えられる。
また、ヘキサクロロ白金（ＩＶ）酸は、６配位であるため、４配位の錯体よりも安定性の高い錯体であると考えられる。したがって、脂肪族第３級アミンが６配位の４価の白金イオンに作用したとしても、脂肪族第３級アミンと４価の白金イオンとが安定な錯体を形成することによって反応が終結し、還元反応が起こらなかったために白金担持多孔質体が得られなかったものと推定される。
As shown in Table 1, in Examples 1 to 3, metal particles could be supported on the porous body, but in Comparative Examples 1, 2, and 3, metal particles could not be supported.
In Comparative Example 1, the tetravalent platinum ions generated in the solution by dissolving hexachloroplatinic the (IV) acid hexahydrate (H 2 PtCl 6 · 6H 2 O), aliphatic tertiary amines It is considered that the metal particles could not be supported on the conductive carbon because the metal could not be reduced to platinum metal.
That is, in order to reduce tetravalent platinum ions, it is necessary to donate four electrons per platinum atom, so a reducing agent having higher reactivity must be applied. However, it is considered that the reducing ability of the aliphatic tertiary amine was insufficient.
Further, since hexachloroplatinum (IV) acid is 6-coordinated, it is considered to be a complex having higher stability than a 4-coordinated complex. Therefore, even when an aliphatic tertiary amine acts on a hexacoordinate tetravalent platinum ion, the reaction is terminated by forming a stable complex between the aliphatic tertiary amine and the tetravalent platinum ion. It is presumed that the platinum-supporting porous body was not obtained because no reduction reaction occurred.
比較例２においては、２価の白金イオンを、脂肪族第１級アミンである２−アミノエタノールでは白金金属に還元することができなかったため、多孔質体に金属粒子を担持させることができなかったと考えられる。
従って当然ながら、比較例３においては、４価の白金イオンを、脂肪族第１級アミンでは白金金属に還元することができなかったため、多孔質体に金属粒子を担持させることができなかったと考えられる。
これらに関しては、上述したように、アミンの窒素原子上の孤立電子対が、金属イオンに対して配位子として作用するものであるため、配位によって金属錯体が溶媒中で安定化してしまうと、還元反応が進行し難くなることが原因にあると考えられる。
すなわち、２−アミノエタノールのような第１級アミンは、置換基が一つしかなくて窒素原子周辺の立体障害が小さいため、４配位の白金錯体であっても、安定な白金錯体を形成したと考えられ、そのため、白金イオンへの電子供与による白金の還元反応には至らず、白金担持多孔質体が得られなかったものと推定される。
In Comparative Example 2, bivalent platinum ions could not be reduced to platinum metal with 2-aminoethanol, which is an aliphatic primary amine, so that metal particles could not be supported on the porous body. It is thought.
Therefore, of course, in Comparative Example 3, it was considered that tetravalent platinum ions could not be reduced to platinum metal with an aliphatic primary amine, so that metal particles could not be supported on the porous body. It is done.
Regarding these, as described above, since the lone electron pair on the nitrogen atom of the amine acts as a ligand for the metal ion, the metal complex is stabilized in the solvent by coordination. It is thought that this is because the reduction reaction is difficult to proceed.
That is, a primary amine such as 2-aminoethanol has only one substituent and has a small steric hindrance around the nitrogen atom, so that even if it is a 4-coordinate platinum complex, a stable platinum complex is formed. Therefore, it is presumed that the platinum-reducing porous body was not obtained because the platinum reduction reaction due to electron donation to platinum ions was not achieved.
比較例３については、より還元され難い４価の白金イオンに、安定な錯体を形成し易い脂肪族第１級アミンを作用させても、白金イオンの還元反応は更に起こり難いため、金属粒子が多孔質体に担持されなかったものと推定される。 In Comparative Example 3, even when an aliphatic primary amine that easily forms a stable complex is allowed to act on tetravalent platinum ions that are more difficult to be reduced, the reduction reaction of platinum ions is less likely to occur. It is presumed that the porous body was not supported.
本発明は、炭化水素の水素化や脱水素、自動車等の排気ガス中窒素酸化物の浄化、燃料電池、水素と酸素とによる電気発生を伴った水の生成等の酸化還元触媒、化学センサーや太陽電池の電極のドープ材の製造方法として好適に利用することができる。 The present invention relates to hydrogenation and dehydrogenation of hydrocarbons, purification of nitrogen oxides in exhaust gas of automobiles, etc., fuel cells, oxidation-reduction catalysts such as water generation with electricity generation by hydrogen and oxygen, chemical sensors, It can utilize suitably as a manufacturing method of the dope material of the electrode of a solar cell.
Claims (11)
溶媒は、水又は水性媒体である請求項１〜８のいずれか１に記載の金属担持多孔質体の製造方法。 The tertiary amine is an aliphatic, aralkyl or alicyclic tertiary amine,
The method for producing a metal-supporting porous body according to any one of claims 1 to 8, wherein the solvent is water or an aqueous medium.
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