CN114904516A - Method for preparing carbon carrier supported platinum-based nanoparticle catalyst by aid of functional small molecules - Google Patents
Method for preparing carbon carrier supported platinum-based nanoparticle catalyst by aid of functional small molecules Download PDFInfo
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- CN114904516A CN114904516A CN202110176005.XA CN202110176005A CN114904516A CN 114904516 A CN114904516 A CN 114904516A CN 202110176005 A CN202110176005 A CN 202110176005A CN 114904516 A CN114904516 A CN 114904516A
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- Prior art keywords
- carbon
- platinum
- preparing
- catalyst
- functional
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- -1 2-bipyridine Chemical compound 0.000 claims description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- BHOCTMHUVQJYHN-UHFFFAOYSA-N 1-aminoethyl dihydrogen phosphate Chemical compound CC(N)OP(O)(O)=O BHOCTMHUVQJYHN-UHFFFAOYSA-N 0.000 claims description 3
- JEPCLNGRAIMPQV-UHFFFAOYSA-N 2-aminobenzene-1,3-diol Chemical compound NC1=C(O)C=CC=C1O JEPCLNGRAIMPQV-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- WFNVGXBEWXBZPL-UHFFFAOYSA-N 3,5-diaminophenol Chemical compound NC1=CC(N)=CC(O)=C1 WFNVGXBEWXBZPL-UHFFFAOYSA-N 0.000 claims description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 3
- 229940018563 3-aminophenol Drugs 0.000 claims description 3
- KDHUXRBROABJBC-UHFFFAOYSA-N 4-Aminocatechol Chemical compound NC1=CC=C(O)C(O)=C1 KDHUXRBROABJBC-UHFFFAOYSA-N 0.000 claims description 3
- ROCVGJLXIARCAC-UHFFFAOYSA-N 4-aminobenzene-1,3-diol Chemical compound NC1=CC=C(O)C=C1O ROCVGJLXIARCAC-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- RGJOEKWQDUBAIZ-IBOSZNHHSA-N CoASH Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCS)O[C@H]1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-IBOSZNHHSA-N 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 108010024636 Glutathione Proteins 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 claims description 3
- 229960000830 captopril Drugs 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- RGJOEKWQDUBAIZ-UHFFFAOYSA-N coenzime A Natural products OC1C(OP(O)(O)=O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005516 coenzyme A Substances 0.000 claims description 3
- 229940093530 coenzyme a Drugs 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 229960002433 cysteine Drugs 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- KDTSHFARGAKYJN-UHFFFAOYSA-N dephosphocoenzyme A Natural products OC1C(O)C(COP(O)(=O)OP(O)(=O)OCC(C)(C)C(O)C(=O)NCCC(=O)NCCS)OC1N1C2=NC=NC(N)=C2N=C1 KDTSHFARGAKYJN-UHFFFAOYSA-N 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
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- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910002844 PtNi Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- 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
- KFDNQUWMBLVQNB-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KFDNQUWMBLVQNB-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910002837 PtCo Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
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- 159000000021 acetate salts Chemical class 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
The invention relates to a method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by using functional micromolecules in an auxiliary manner, which comprises the following steps: the functional small molecule comprises at least N, S, P, O one or more of the functional groups; the platinum-based metal nanoparticles can be platinum single metal or contain one or more of Pd, Au, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn and Cu. The carbon carrier supported platinum-based nanoparticle catalyst prepared by the method has the advantages of controllable preparation process, convenient operation and easy amplification, and has wide application prospects in the technical fields of hydrogen-oxygen fuel cells, hydrogen production by electrolyzing water, hydrodeoxygenation industrial catalysis and the like.
Description
Technical Field
The invention relates to a method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by using functional micromolecules for assistance. The obtained catalyst has wide application prospect in the technical fields of hydrogen-oxygen fuel cells, hydrogen production by water electrolysis, hydrodeoxygenation industrial catalysis and the like.
Background
Due to environmental pollution and climate warming, hydrogen energy has attracted people's attention as a clean energy source with no emission and high energy density. While the generation and conversion of hydrogen energy cannot be separated from the carbon-supported platinum-based catalyst. The carbon-supported platinum-based catalyst is an important electrocatalyst and has wide application in the fields of hydrogen-oxygen fuel cells, hydrogen production by water electrolysis and methanol fuel cells. In recent years, carbon-supported platinum-based catalysts have been further developed in selective hydrogenation and heterogeneous catalysis. Carbon-supported platinum-based catalysts have no alternative status in the field of catalysts due to their high efficiency and durability.
According to research reports, the particle size of the platinum metal and the platinum alloy has the optimal mass specific activity when the particle size is 3-4 nm, but the particle with small size has higher free energy due to the problem of thermodynamic stability, and the interaction between the surface inertia of the carbon carrier and the metal is weak. Therefore, the synthesis of carbon-supported platinum-based catalysts with uniform particle size and uniform spatial distribution has been a problem. The traditional method for preparing the platinum-based electrocatalyst mainly comprises an impregnation method and a liquid-phase reduction method. The preparation method of the platinum-based metal particle is simple, but the method is uncontrollable and cannot ensure that all the platinum-based metal particles are anchored in the hole; although the catalyst with uniform high dispersion size can be obtained in the latter, the reducing agent or the protective agent is easy to remove, the exposure of the active sites of the catalyst is influenced, and the interaction between the metal and the carrier is weak, so that the metal is dissolved in agglomeration and dissolution during catalytic reaction. In addition, in the electrochemical process, such as the cathode reaction of a hydrogen-oxygen fuel cell, active component metal particles are easy to agglomerate and dissolve when the catalyst works for a long time, so that the stability of the catalyst is reduced, and the use and maintenance cost of the fuel cell is increased. Efficient synthesis of high quality platinum-based catalysts has been a major concern in hydrogen economy. The controllable synthesis of even ultra-small platinum-based metal particles supported by a carbon carrier has been a difficult problem in the field of catalyst synthesis. The space-limited growth of the carbon carrier using micropores or mesopores is one of effective strategies for solving the problems, but how to introduce the platinum-based metal particles into the pores of the carbon carrier so as to effectively limit the growth in the pores is the key of the problem.
It is seen that there is a need to design a novel and efficient method for synthesizing a carbon-supported platinum-based catalyst, which effectively introduces platinum or a platinum alloy into pores of a carbon carrier, thereby obtaining a high-stability catalyst, solving the problems of agglomeration, shedding and loss of metal nanoparticles in the reaction process, and the synthesis process of the catalyst needs to be simple, controllable and easy to amplify.
Disclosure of Invention
In order to solve the problems of uncontrollable synthesis steps, weak action of active components and a carrier, easy agglomeration and loss and the like of the traditional synthetic carbon-supported catalyst, the invention provides a method for preparing a carbon carrier-supported platinum-based nanoparticle catalyst by using functional micromolecules, which comprises the steps of introducing the functional micromolecules into a carbon carrier, subsequently or simultaneously introducing a precursor containing platinum (other metal salts are added if necessary) into the carbon carrier, and then reducing the obtained product to obtain the carbon-supported platinum-based nanoparticle catalyst. The carbon carrier can enable the platinum-based nanoparticles to grow in a limited area, effectively control the size of the platinum-based nanoparticles, limit the migration of the platinum-based nanoparticles and prevent the platinum-based nanoparticles from agglomerating and losing in the reaction process.
The invention provides a method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by using functional micromolecules in an auxiliary manner, which is characterized by comprising the following steps of: the functional small molecule comprises at least N, S, P, O one or more of the functional groups; the platinum-based metal nanoparticles can be platinum single metal or contain one or more of Pd, Au, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn and Cu.
Further, the process comprises the following steps: a) providing a carbon support; b) respectively or simultaneously introducing functional small molecules and a platinum-containing metal salt precursor into a carbon carrier, and drying to obtain an intermediate product; c) reducing the intermediate product obtained in the step b) to obtain the carbon-supported platinum-based nanoparticle catalyst.
Further, the carbon carrier in the step a) is selected from one of mesoporous carbon, hollow carbon spheres, carbon nanotubes, carbon black, graphitic carbon and graphene.
Further, step a) comprises surface modification of the carbon support, the surface modification method comprising an oxidation treatment or a high temperature activation treatment under a gas atmosphere.
Further, the functional small molecule is selected from one or more of imidazole, dimethylimidazole, 2-bipyridine, dopamine hydrochloride, dicyandiamide, cyanamide, melamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate, urotropine, 4-aminocatechol, 2-amino-1, 3-benzenediol, 4-amino-1, 3-benzenediol, 3, 5-diaminophenol, elemental sulfur, 1-propanethiol, 1, 3-propanedithiol, cysteine, captopril, coenzyme A, glutathione, phytic acid, phosphomolybdic acid, triphenylphosphine, alpha-aminoethyl phosphate, trimesic acid, oleic acid, sodium oleate and the like.
Further, the platinum-containing metal salt precursor in step b) may be selected from one of chloroplatinic acid salt, nitrate, halide salt, acetylacetone salt, sulfate, cyanide salt, acetate salt and carbonyl salt.
Further, the metal salt precursor containing platinum in step b) may further contain one or more metal salts of Au, Pd, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn, and Cu in addition to the platinum metal salt.
Further, the method for introducing the functional small molecule into the carbon support in step b) may be solid grinding or evaporative adsorption or impregnation.
Further, the method of introducing the platinum-containing metal salt precursor into the carbon support in step b) may be solid milling, or impregnation after dissolving the platinum-containing metal salt precursor with a solvent.
The invention also relates to a carbon-supported platinum-based nanoparticle catalyst prepared by the method.
Further, the metal loading mass of the carbon-supported platinum-based nanoparticle catalyst is 0.1-70%.
The carbon-supported platinum-based nanoparticle catalyst obtained by the method has the characteristics of uniform size distribution of metal particles and uniform size of the metal particles, is simple in preparation process and easy to amplify, can be used for synthesizing various carbon-supported platinum-based nanoparticle catalysts, and has wide application prospects in the fields of fuel cells, electrolyzed water, hydrogenation and deoxidation industrial catalysis and the like.
Additional aspects and advantages will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice.
Detailed Description
The invention relates to a method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by using functional small molecules for assistance, which is described in detail below.
The invention provides a method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by utilizing the assistance of functional small molecules, wherein the functional small molecules at least comprise one or more of N, S, P, O functional groups; the platinum-based metal nanoparticles can be platinum single metal or contain one or more of Pd, Au, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn and Cu.
The preparation method of the invention is described in detail as follows:
firstly, a carbon carrier is provided, and the carbon carrier is preferably one of mesoporous carbon, hollow carbon spheres, carbon nanotubes, carbon black, graphitic carbon and graphene. Further alternatively, the carbon support may be surface modified. The method of surface modification may comprise one or more of: oxidation treatment, e.g. with ozone, H 2 O 2 Or nitric acid treatment; high-temperature activation treatment under gas atmosphere, e.g. NH 3 、CO 2 Or H 2 High-temperature treatment is carried out under O atmosphere, and the temperature range can be 300-1000 ℃.
The functional small molecule and platinum salt precursor (optionally with the addition of other metal salts) are then introduced separately or simultaneously into the carbon support. After drying, an intermediate product, such as a powdered intermediate product, is obtained.
The functional small molecule at least comprises N, S, P, O functional groups, and can be selected from imidazole, dimethyl imidazole, 2-bipyridine, dopamine hydrochloride, dicyandiamide, cyanamide, melamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, tetrasodium ethylenediamine tetraacetic acid, urotropine, 4-aminocatechol, 2-amino-1, 3-benzenediol, 4-amino-1, 3-benzenediol, 3, 5-diaminophenol, elemental sulfur, 1-propanethiol, 1, 3-propanethiol, cysteine, captopril, coenzyme A, glutathione, phytic acid, phosphomolybdic acid, triphenyl phosphorus, alpha-aminoethyl phosphoric acid, trimesic acid, Oleic acid, sodium oleate, etc. More preferred are dimethylimidazole, 2-bipyridine, dicyandiamide, melamine, elemental sulfur, and phosphomolybdic acid.
The platinum salt precursor can be selected from one or more of chloroplatinic acid salt, nitrate, halide salt, acetylacetone salt, sulfate, cyanide salt, acetate and carbonyl salt.
The precursor of the other metal salt may comprise one or more of Au, Pd, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn, Cu. The other metal salt precursor may be selected from one or more of nitrate, halide, acetylacetonate, sulfate, cyanide, acetate, and carbonyl salts.
The method for introducing the functional small molecule into the carbon support can be solid grinding or evaporative adsorption or impregnation. Alternatively, the functional small molecule is dissolved with a solvent selected from one or more of water, methanol, ethanol, isopropanol, ether, acetone, N-dimethylformamide, chloroform, toluene, N-hexane, cyclohexane, etc., and then introduced onto the carbon support by impregnation.
The functional small molecule and the platinum salt (optionally with other metal salts) precursor can be introduced into the carbon carrier simultaneously or sequentially. For example, the precursor of the platinum salt (optionally with the addition of other metal salts) and the functional small molecule are mixed with the carbon carrier simultaneously or separately by a solid grinding process. For example, the functional small molecule is introduced into the carbon carrier through an evaporation adsorption or impregnation process, the platinum and other metal salt precursors are dissolved by a solvent (one or more solvents selected from water, methanol, ethanol, isopropanol, diethyl ether, acetone, N-dimethylformamide, chloroform, toluene, N-hexane, and cyclohexane), and the platinum salt (optionally other metal salt) is introduced into the carbon carrier through an impregnation process.
The mass of the functional small molecule added per 1 part by mass of the carbon support is 0 or more, preferably 0.1 or more, more preferably 1 or more, and further preferably 2 or more.
The mass ratio of the platinum to other metal salt precursors can be selected from 1: 0 to 1: 20, preferably 1: 0 to 1: 10, more preferably 1: 0 to 1: 5, or more.
The mass of the functional small molecule added is 0 or more, preferably 1 or more per 1 part by mass of the total metal salt precursor. The mass ratio of the total metal salt precursor to the functional small molecule can be selected from 1: 0 to 1: 30, preferably 1: 0 to 1: 20, more preferably 1: 0 to 1: 10, respectively.
And finally, reducing the obtained intermediate product to obtain the carbon-supported platinum-based nanoparticle catalyst.
The reduction process may be selected from one or more of the following methods: liquid phase reduction methods, such as reducing agents such as sodium borohydride, formaldehyde, or lower alcohols; by thermal reduction, e.g. with the reducing agent being H 2 Or H 2 The reducing temperature of the mixed gas with other inert atmosphere is selected from 100 to 1000 ℃, preferably 200 to 800 ℃, and more preferably 200 to 500 ℃.
The metal loading mass of the carbon-supported platinum-based nanoparticle catalyst can be adjusted to be 0.1-70% by adjusting the mass ratio of the carbon carrier to the platinum salt precursor.
The carbon-supported platinum-based nanoparticle catalyst obtained by the method has the characteristics of uniform size distribution of metal particles and uniform size of the metal particles, is simple in preparation process and easy to amplify, can be used for synthesizing various carbon-supported platinum-based nanoparticle catalysts, and has wide application prospects in the fields of fuel cells, electrolyzed water, hydrogenation and deoxidation industrial catalysis and the like.
For a clearer understanding of the technical features, objects, and advantages of the present invention, reference will now be made in detail to the following embodiments of the present invention, which are intended to illustrate the present invention and not to limit the scope of the present invention.
[ example 1]
Preparing a mesoporous carbon supported Pt nanoparticle catalyst:first 1g of mesoporous carbon support was placed in a vessel and 2g of dimethylimidazole was added and isolated with a ceramic vessel. The vacuum degree is kept in the range of 100mbar to 200 mbar. Heating at 145 deg.C for 6h, washing, and filtering. Dispersing the obtained mesoporous carbon adsorbing dimethyl imidazole into 50ml ethanol solution containing 658mg chloroplatinic acid, evaporating the solvent to dryness, and then carrying out H 2 Reducing under the atmosphere, and finally obtaining the mesoporous carbon supported platinum carbon catalyst with the load of 20 percent at the reduction temperature of 400 ℃.
[ example 2]
Preparing a mesoporous carbon supported PtCo nanoparticle catalyst: first 1g of mesoporous carbon support was placed in a vessel, and 2g of dimethylimidazole was added and isolated with a ceramic vessel. The vacuum degree is kept in the range of 100mbar to 200 mbar. Heating at 145 deg.C for 6h, washing, and filtering. Dispersing the obtained mesoporous carbon adsorbing the dimethyl imidazole into 50ml of ethanol solution containing 2.02g of chloroplatinic acid and 1.15g of cobalt nitrate, evaporating the solvent to dryness, and then carrying out H 2 Reducing at 400 ℃ in the atmosphere, and finally synthesizing the mesoporous carbon supported platinum-cobalt alloy catalyst with the loading of 50%.
[ example 3]
Preparing a mesoporous carbon supported PtNi nano particle catalyst: immersing 1g of mesoporous carbon into an ethanol solution containing 2g of 2, 2-bipyridyl, stirring and dispersing uniformly, removing the solvent ethanol by rotary evaporation, dispersing the obtained product into 50ml of ethanol solution containing 1.15g of nickel nitrate and 2.02g of chloroplatinic acid, stirring, washing and drying. Reducing for 4H at 400 ℃ in the atmosphere of H2/Ar to obtain the mesoporous carbon supported PtNi nano-particle catalyst with the supported mass of 50%.
[ example 4]
Preparing a carbon nanotube supported Pt nanoparticle catalyst: firstly, 1g of carbon nanotube material is placed in a container, 10g of melamine is added, heating is carried out for 12h at 200 ℃ under the condition of vacuumizing, and the carbon nanotube material is washed and dried after the heating is finished. Obtaining carbon nano tube adsorbing melamine, dispersing the carbon nano tube in 50ml ethanol solution containing 3.95g chloroplatinic acid, stirring for 1H, removing solvent ethanol by rotary evaporation, drying and then performing Ar/H 2 Reducing under gas, wherein the reduction temperature is 200 ℃. Finally obtaining the carbon nano tube loaded Pt nano particles with the loading capacity of 60%.
[ example 5]
Preparing a hollow sphere carbon-loaded Pt nanoparticle catalyst: firstly, 1g of hollow spherical carbon material (purchased from Yifei Ke crystal materials technology Co., Ltd.) is put into a container, 2g of ethylenediamine acetic acid is added, the mixture is heated for 24 hours at 200 ℃ under the condition of vacuumizing, and the heating is finished, washed and dried. Obtaining carbon nano tube adsorbing melamine, dispersing the carbon nano tube in 50ml acetone solution containing 0.1g of acetylacetone platinum salt, stirring for 1H, removing solvent acetone by rotary evaporation, drying, and then performing Ar/H 2 Reducing the catalyst under gas at the reduction temperature of 600 ℃ to finally obtain the hollow sphere carbon supported Pt nanoparticle catalyst with the load of 5%.
[ example 6]
Preparing a mesoporous carbon supported Pt nanoparticle catalyst: 1g of spherical mesoporous carbon and 7g of elemental sulfur are fully mixed and ground, the mixture is heated in a closed container at 155 ℃ for 10 hours, the obtained sample is dispersed into an acetone solution containing 2.01g of platinum acetylacetonate, and the solvent is removed after the mixture is stirred for 1 hour. Finally at H 2 Reducing for 5h at 500 ℃ in the atmosphere to obtain the mesoporous carbon supported Pt nano particle catalyst with the loading of 50%.
[ example 7]
Preparing a mesoporous carbon supported Pt nanoparticle catalyst: adding 1g of mesoporous carbon carrier into 50ml of phosphomolybdic acid aqueous solution, stirring, standing for 2 hours, adding 31mg of tetrachloroplatinate-tetramine platinate, stirring for 2 hours, filtering, drying, and pyrolyzing at 800 ℃ for 5 hours in Ar atmosphere to finally obtain the mesoporous carbon supported Pt nanoparticle catalyst with the load of 1%.
Experiments show that the catalysts prepared in examples 1,3, 4 and 6 have excellent catalytic activity in electrochemical oxygen reduction reaction, electrochemical methanol oxidation reaction and electrochemical hydrogen evolution reaction, and the catalysts prepared in examples 2, 5 and 7 have excellent durability in electrochemical oxygen reduction reaction, electrochemical methanol oxidation reaction and electrochemical hydrogen evolution reaction.
The present invention has been made in view of the above description, and the preparation conditions of the catalyst of the present invention are clearly disclosed. It will be apparent, however, to one skilled in the art that certain modifications and improvements can be made to the invention. Therefore, any modifications and improvements made to the present invention should be within the scope of the present invention as long as they do not depart from the spirit of the present invention.
Claims (10)
1. A method for preparing a carbon carrier supported platinum-based nanoparticle catalyst by using functional micromolecules is characterized by comprising the following steps: the functional small molecule at least comprises N, S, P, O one or more functional groups; the platinum-based metal nanoparticles can be platinum single metal or contain one or more of Pd, Au, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn and Cu.
2. The method of claim 1, the process comprising:
a) providing a carbon support; b) respectively or simultaneously introducing functional small molecules and a platinum-containing metal salt precursor into a carbon carrier, and drying to obtain an intermediate product; c) reducing the intermediate product obtained in the step b) to obtain the carbon-supported platinum-based nanoparticle catalyst.
3. The method for preparing a catalyst according to claim 2, characterized in that the carbon support in step a) is selected from one of mesoporous carbon, hollow carbon spheres, carbon nanotubes, carbon black, graphitic carbon and graphene.
4. The method for preparing a catalyst according to claim 2, characterized in that the step a) comprises surface modification of the carbon support, said surface modification method comprising an oxidation treatment or a high-temperature activation treatment under a gas atmosphere.
5. The method for preparing a catalyst according to claim 1, characterized in that the functional small molecule is selected from the group consisting of imidazole, dimethylimidazole, 2-bipyridine, dopamine hydrochloride, dicyandiamide, cyanamide, melamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, urotropin, 4-aminocatechol, 2-amino-1, 3-benzenediol, 4-amino-1, 3-benzenediol, 3, 5-diaminophenol, elemental sulfur, 1-propanethiol, 1, 3-propanethiol, cysteine, captopril, coenzyme A, glutathione, phytic acid, phosphomolybdic acid, triphenylphosphine, alpha-aminoethyl phosphoric acid, trimesic acid, One or more of oleic acid and sodium oleate.
6. The method for preparing a catalyst according to claim 2, wherein the platinum-containing metal salt precursor in step b) is selected from one of chloroplatinate, nitrate, halide, acetylacetonate, sulfate, cyanide, acetate, and carbonyl salts.
7. The method for preparing a catalyst according to claim 2, characterized in that the platinum-containing metal salt precursor in step b) may further comprise one or more metal salts of Au, Pd, Ag, Ru, Rh, Ir, Fe, Re, Mo, Ni, Co, Zn, Cu, in addition to the platinum metal salt.
8. The method for preparing a catalyst according to claim 2, characterized in that the method for introducing the functional small molecule into the carbon support in step b) may be solid grinding or evaporative adsorption or impregnation.
9. The method for preparing a catalyst according to claim 2, wherein the method for introducing the platinum-containing metal salt precursor into the carbon support in the step b) is solid milling, or impregnation after dissolving the platinum-containing metal salt precursor with a solvent.
10. A carbon-supported platinum-based nanoparticle catalyst prepared by the method according to any one of claims 1 to 9, wherein the metal loading mass of the carbon-supported platinum-based nanoparticle catalyst is between 0.1 and 70%.
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