CN109078634A - A kind of Pt/Rh nanocomposite and its preparation method and application - Google Patents
A kind of Pt/Rh nanocomposite and its preparation method and application Download PDFInfo
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- CN109078634A CN109078634A CN201810960519.2A CN201810960519A CN109078634A CN 109078634 A CN109078634 A CN 109078634A CN 201810960519 A CN201810960519 A CN 201810960519A CN 109078634 A CN109078634 A CN 109078634A
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- nanocomposite
- nanometer sheet
- nanometers
- nanocluster
- salt
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010948 rhodium Substances 0.000 claims abstract description 260
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 227
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 102000004190 Enzymes Human genes 0.000 claims abstract description 28
- 108090000790 Enzymes Proteins 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 150000003057 platinum Chemical class 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 150000003283 rhodium Chemical class 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000004088 simulation Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000003759 clinical diagnosis Methods 0.000 claims abstract description 5
- 238000001514 detection method Methods 0.000 claims abstract description 4
- 238000003018 immunoassay Methods 0.000 claims abstract description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 92
- 229910052703 rhodium Inorganic materials 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 13
- 229910001630 radium chloride Inorganic materials 0.000 claims description 13
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- -1 acyl acetone platinum Chemical compound 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 102000003992 Peroxidases Human genes 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 4
- 108040007629 peroxidase activity proteins Proteins 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 36
- 238000006555 catalytic reaction Methods 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 241000209094 Oryza Species 0.000 description 18
- 235000007164 Oryza sativa Nutrition 0.000 description 18
- 235000009566 rice Nutrition 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 210000001624 hip Anatomy 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 238000010998 test method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052961 molybdenite Inorganic materials 0.000 description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 229910000629 Rh alloy Inorganic materials 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 2
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 240000000203 Salix gracilistyla Species 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003593 chromogenic compound Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 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
- VHRIFOUDVVZPAO-UHFFFAOYSA-N propan-2-one rhodium Chemical compound [Rh].CC(=O)C VHRIFOUDVVZPAO-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of Pt/Rh nanocomposites and its preparation method and application.Pt/Rh nanocomposite provided by the invention includes Rh nanometer sheet and the Pt nanocluster that is supported in the Rh nanometer sheet.Preparation method provided by the invention includes: that platinum salt and rhodium salt are dissolved in solvent, and surfactant and reducing agent is added, carries out heating reaction to obtained mixed solution, is separated by solid-liquid separation after reaction, obtain the Pt/Rh nanocomposite.Pt/Rh nanocomposite provided by the invention has very high activation capacity to oxygen, shows similar peroxidase activity feature, shows the activity being remarkably reinforced, maximum reaction rate (V compared to independent Rh piece and Pt nanoclustermax) up to 1.88 × 10‑7M s‑1.It can be used as oxide enzyme simulation enzyme, be applied to the fields such as immunoassay, biochemistry detection and clinical diagnosis instead of native enzyme.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of Pt based nano composite material more particularly to Pt/Rh nanometers a kind of
Composite material and preparation method and purposes.
Background technique
Support type Pt based nano composite material is widely used in heterogeneous catalysis.It is many studies have shown that due to Pt and carrier it
Between synergistic effect, composite material exhibits go out the activity and stability that are remarkably reinforced.For example, China group report MoS2Nanometer sheet is negative
The Pt nanoparticle and Tang Zhi of load bravely organize the layered double-hydroxide Ni (OH) of report2The Pt nano wire of load, as electro-catalysis
Agent in evolving hydrogen reaction (HER), than independent carrier and business Pt/C show higher activity (Nat.Commun.2013,
4,1444；Nat.Commun.2015,6,6430).Design and prepare new construction, high-performance Pt based nano composite material at
For one research hotspot of heterogeneous catalysis field.
In general, the preparation process of support type Pt based nano-material needs two steps, it may be assumed that first prepare good vector, then on carrier
Electronation is carried out to Pt salt precursor body or Pt is fixed on carrier by the methods of physical deposition.In order to increase carrier and Pt
Between contact, toward contact need in advance to carrier carry out it is surface-functionalized.Therefore, preparation procedure it is general cumbersome, time-consuming and
Higher cost.With above-mentioned preparation MoS2For the Pt nanoparticle of nanometer sheet load, it is necessary first to pass through electrochemical lithium intercalation mistake
Journey prepares MoS2Nanometer sheet, in the case where trisodium citrate is stablized, by halogen lamp radiation in MoS2Edge restores Pt nanometers
Particle is then supported on nanometer sheet surface by extensional mode growth.As it can be seen that above-mentioned Pt/MoS2Preparation contain multistep process, need
Want ready MoS2Nanometer sheet carrier and nucleation site as Pt, and prepare lamella MoS2Battery system need to be built to control
Its intercalation process.In addition, carrying out in subsequent stripping process to intercalation object, lithium and water vigorous reaction discharge hydrogen, give operation band
Carry out security risk.
CN108341979A discloses a kind of preparation method of chitosan noble metal nano composite material, it is characterised in that packet
It includes following steps: (1) chitosan being dissolved in solvent, prepare mother liquor；(2) mixing for preparing polysilsesquioxane and metal salt is molten
Liquid；(3) mixed solution of above-mentioned polysilsesquioxane and metal salt is added into above-mentioned mother liquor, after stirring 24~72h, static 4
~8h obtains chitosan/metallic compound/polysilsesquioxane mixed solution；(4) by above-mentioned chitosan/metallic compound/
The mixed solution drying and forming-film of polysilsesquioxane obtains chitosan noble metal nano composite membrane.The invention also discloses receive
The application method of nano composite material.
A kind of rhodium of CN107442134A/nickel alloy nanocatalyst and its preparation method and application, belongs to nanocatalyst
Research field；Catalyst of the invention is spherical, polyhedral rhodium/nickel alloy nanoparticles, prepared rhodium/nickel alloy nanometer
The size of catalyst granules is distributed as 12~58nm, rhodium in catalyst, nickel mol ratio be 0.01~0.05:1；The present invention with
Nickel acetate, rhodium chloride be raw material, be prepared for rhodium/nickel nanometer alloy catalyst of varying particle size, microstructure, then with
1- nitroanthraquinone, hydrogen are raw material, are reacted using the catalyst, so that reaction temperature is warming up to 100~160 DEG C, and keep the temperature
2~8h is reacted, high-purity 1- amino anthraquinones is obtained.
A kind of rhodium of CN107497448A/copper alloy nanocatalyst and its preparation method and application, the catalyst is
Rhodium/copper alloy nano particle of the more cluster structures of spherical shape of 10~120nm, rhodium in catalyst, copper mol ratio be 0.02~
0.08:1；The present invention is prepared for mole of varying particle size, microstructure and rhodium, copper using rhodium chloride, copper nitrate as raw material
The rhodium of ratio/copper nanometer alloy catalyst is reacted then using 1- nitroanthraquinone, hydrogen as raw material using the catalyst, is made anti-
It answers temperature to be warming up to 120~80 DEG C, and 1~8h of insulation reaction, obtains high-purity 1- amino anthraquinones.
Although the above method can prepare more conveniently nano metal material, it is not particularly suited for Pt based nano-material.
In view of this, it is necessary to develop a kind of simple preparation method of support type Pt base nano catalytic material.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of nano combined materials of Pt/Rh
Material and its preparation method and application.Pt/Rh nanocomposite preparation method provided by the invention is simple, passes through one kettle way
Preparation is completed, does not need preliminary support and its functionalization, simple process, period are short.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of Pt/Rh nanocomposite, the Pt/Rh nanocomposite includes Rh
Nanometer sheet and the Pt nanocluster being supported in the Rh nanometer sheet.
It is right due to the synergistic effect between Rh piece and Pt nanocluster in Pt/Rh nanocomposite provided by the invention
Oxygen has very high activation capacity, shows the catalytic activity significantly increased in the oxidation reaction, to organic chromogenic substrate 3,
The oxidation reaction of 3 ', 5,5 '-tetramethyl benzidines (TMB) has very high catalytic activity, has similar peroxidase activity special
Sign, shows the activity being remarkably reinforced, maximum reaction rate (V compared to independent Rh piece and Pt nanoclustermax) up to 1.88 ×
10-7M s-1, respectively may be about Rh piece (Vmax=1.92 × 10-8M s-1) and Pt nanocluster (Vmax=1.29 × 10-7M s-1)
10 times and 1.5 times.
In Pt/Rh nanocomposite provided by the invention, Pt nanocluster is in monodisperse.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the molar ratio of the Pt nanocluster and Rh nanometer sheet be (0.219~
0.749):1。
Preferably, the Rh nanometer sheet is two-dimension nano materials.
Preferably, the shape of the Rh nanometer sheet is trapezoidal.
Preferably, a length of 200~600 nanometers of the bottom of the Rh nanometer sheet, for example, 200 nanometers, 300 nanometers, 400 nanometers,
500 nanometers or 600 nanometers etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.The length at bottom here long i.e. trapezoidal upper bottom or bottom.
Preferably, a length of 100~300 nanometers of the waist of the Rh nanometer sheet, for example, 100 nanometers, 150 nanometers, 200 nanometers,
250 nanometers or 300 nanometers etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.Here the length of the long i.e. trapezoidal waist of waist.
Preferably, the Rh nanometer sheet with a thickness of 0.4~1.5 nanometer, such as 0.4 nanometer, 0.8 nanometer, 1 nanometer, 1.2
Nanometer or 1.5 nanometers etc., it is not limited to cited numerical value, other unlisted numerical value are equally suitable in the numberical range
With.
Preferably, the Pt nanocluster is zero dimensional nanometer materials.
Preferably, the partial size of the Pt nanocluster is 2~3 nanometers, for example, 2 nanometers, 2.2 nanometers, 2.4 nanometers, 2.6 receive
Rice, 2.8 nanometers or 3 nanometers etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range
It is applicable in.
Second aspect, the present invention provides a kind of preparation method of Pt/Rh nanocomposite as described in relation to the first aspect, described
Preparation method the following steps are included:
Platinum salt and rhodium salt are dissolved in solvent, surfactant and reducing agent is added, obtained mixed solution is added
Thermal response is separated by solid-liquid separation after reaction, obtains the Pt/Rh nanocomposite.
In preparation method provided by the invention, platinum salt presoma, which preferentially restores, forms Pt nanocluster as nucleation site simultaneously
Stablized by surfactant, and then due to charge effect, rhodium salt precursor body be adsorbed on around Pt nanocluster concurrently survive it is former, outer
Prolong formula growth, forms Rh nanometer sheet, it is final to realize Pt nanocluster in the load of Rh on piece.Therefore, system provided by the present invention
Method does not need preliminary support or to its functionalization, subsequent yet not need to restore platinum salt presoma, one pot of completion Pt nanocluster
The load of formation and Pt nanocluster in Rh on piece with Rh piece, simple process overcome the tradition system of support type Pt sill
Method needs preliminary support and surface modification, then by electronation platinum salt presoma or passes through the side such as physical deposition Pt on carrier
Method and existing multi-step, it is time-consuming the disadvantages of.
As currently preferred technical solution, the platinum salt includes in chloroplatinic acid, potassium chloroplatinate or acetylacetone,2,4-pentanedione platinum
Any one or at least two combination.It is typical but be non-limiting combination and have: the combination of chloroplatinic acid and potassium chloroplatinate, chlorine platinum
The combination of acid and acetylacetone,2,4-pentanedione platinum, potassium chloroplatinate and the combination of acetylacetone,2,4-pentanedione platinum etc..
Preferably, the rhodium salt includes radium chloride and/or acetylacetone,2,4-pentanedione rhodium.In the present invention, the radium chloride and/or acetyl
It can be radium chloride that acetone rhodium, which refers to, or acetylacetone,2,4-pentanedione rhodium can also be the combination of radium chloride and acetylacetone,2,4-pentanedione rhodium.
Preferably, the solvent includes any one in benzylalcohol, ethylene glycol or n,N-Dimethylformamide or at least two
The combination of kind.It is typical but be non-limiting combination and have: the combination of benzylalcohol and ethylene glycol, ethylene glycol and n,N-Dimethylformamide
Combination, benzylalcohol and the combination of n,N-Dimethylformamide etc..
As currently preferred technical solution, the surfactant include polyvinylpyrrolidone, polyethylene glycol or
In cetyl trimethylammonium bromide any one or at least two combination.It is typical but be non-limiting combination and have: poly-
The combination of the combination of vinylpyrrolidone and polyethylene glycol, polyethylene glycol and cetyl trimethylammonium bromide, polyvinyl pyrrole
Alkanone and the combination of cetyl trimethylammonium bromide etc..
Preferably, the reducing agent include in formaldehyde, benzaldehyde or salicylide any one or at least two combination.
It is typical but be non-limiting combination and have: the combination of the combination of formaldehyde and benzaldehyde, formaldehyde and salicylide, benzaldehyde and salicylide
Combination etc..
As currently preferred technical solution, in the mixed solution, the molar concentration of platinum salt is 0.1~3.0mmol/
L, such as 0.1mmol/L, 0.5mmol/L, 1.0mmol/L, 1.2mmol/L, 2.0mmol/L, 2.5mmol/L or 3.0mmol/L
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in the mixed solution, the molar concentration of rhodium salt is 2.8~3.3mmol/L, such as 2.8mmol/L,
2.9mmol/L, 3.0mmol/L, 3.1mmol/L, 3.2mmol/L or 3.3mmol/L etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in the mixed solution, the molar ratio of platinum salt and rhodium salt is (0.218~0.763): 1, such as 0.218:
1,0.25:1,0.3:1,0.333:1,0.455:1,0.545:1,0.654:1 or 0.763:1 etc., it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range.Within the scope of this, the Pt/Rh nanometer that can make is multiple
Condensation material has more excellent catalytic effect.
As currently preferred technical solution, in the mixed solution, the mass concentration of surfactant is 10.0~
25.0g/L, such as 10.0g/L, 12.5g/L, 15g/L, 17.2g/L, 20g/L, 22.8g/L or 25.0g/L etc., but simultaneously not only limit
It is equally applicable in other unlisted numerical value in cited numerical value, the numberical range.
Preferably, in the mixed solution, the molar concentration of reducing agent is 4~7000mmol/L, such as 4mmol/L,
10mmol/L、50mmol/L、100mmol/L、500mmol/L、1000mmol/L、2000mmol/L、3000mmol/L、
4000mmol/L, 5000mmol/L, 6000mmol/L or 7000mmol/L etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range.
As currently preferred technical solution, the temperature of the heating reaction is 140~220 DEG C, such as 140 DEG C, 150
DEG C, 160 DEG C, 170 DEG C or 180 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value in the numberical range
It is equally applicable, preferably 180 DEG C.
Preferably, it is described heating reaction time be 6~10h, such as 6h, 7h, 8h, 9h or 10h etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 8h.
Preferably, described be separated by solid-liquid separation includes centrifuge separation.
Preferably, the preparation method further include: after the completion of reaction, reaction product is washed.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
Platinum salt and rhodium salt are dissolved in solvent, surfactant and reducing agent is added, to obtained mixed solution at 180 DEG C
Under carry out heating reaction 8h, wash and be centrifugated after reaction, obtain the Pt/Rh nanocomposite；
Wherein, the platinum salt be chloroplatinic acid, potassium chloroplatinate or acetylacetone,2,4-pentanedione platinum in any one or at least two group
It closes, the rhodium salt is radium chloride and/or acetylacetone,2,4-pentanedione rhodium, and the solvent is in benzylalcohol, ethylene glycol or n,N-Dimethylformamide
Any one or at least two combination, the surfactant be polyvinylpyrrolidone, polyethylene glycol or cetyl
In trimethylammonium bromide any one or at least two combination, the reducing agent is formaldehyde, benzaldehyde or salicylide kind
Any one or at least two combination；
In the mixed solution, the molar concentration of platinum salt is 0.1~3.0mmol/L, the molar concentration of rhodium salt is 2.8~
The molar ratio of 3.3mmol/L, platinum salt and rhodium salt is (0.218~0.763): 1, the mass concentration of surfactant is 10.0~
25.0g/L, the molar concentration of reducing agent are 4~7000mmol/L.
The third aspect, the present invention provide a kind of purposes of Pt/Rh nanocomposite as described in relation to the first aspect, the Pt/
Rh nanocomposite is applied to immunoassay, biological detection or clinical diagnosis field as oxide enzyme simulation enzyme.
Based on its easy preparation method and excellent activity, Pt/Rh nanocomposite provided by the invention is very suitable to make
Above-mentioned field is used for for a kind of oxide enzyme simulation enzyme.
Compared with prior art, the invention has the following advantages:
(1) Pt/Rh nanocomposite provided by the invention has very high activation capacity to oxygen, shows similar oxidation
Object enzymatic activity profiles show the activity being remarkably reinforced, maximum reaction rate (V compared to independent Rh piece and Pt nanoclustermax)
Up to 1.88 × 10-7M s-1, respectively may be about Rh piece (Vmax=1.92 × 10-8M s-1) and Pt nanocluster (Vmax=1.29 ×
10-7M s-1) 10 times and 1.5 times.It can be used as oxide enzyme simulation enzyme, be applied to immunoassay, biochemical inspection instead of native enzyme
It surveys and the fields such as clinical diagnosis.
(2) in preparation method provided by the invention, carrier, which is formed, passes through one kettle way in supported on carriers with Pt nanocluster
It completes, preparation method is simple, and the period is short, and it is more, all to overcome step present in traditional preparation method of support type Pt based nano composite material
The disadvantages of phase is long.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of Pt/Rh nanocomposite prepared by the embodiment of the present invention 1；
Fig. 2 is the distribution diagram of element of Pt/Rh nanocomposite prepared by the embodiment of the present invention 1, and wherein Fig. 2 (a) is
Angle of elevation annular dark field scanning transmission image, Fig. 2 (b) and Fig. 2 (c) are respectively Rh, Pt distribution diagram of element, and Fig. 2 (d) is Rh and Pt member
The stacking chart of element；Scale in Fig. 2 (a), Fig. 2 (b), Fig. 2 (c) and Fig. 2 (d) is 100nm；
Fig. 3 is the X-ray energy spectrum diagram of Pt/Rh nanocomposite prepared by the embodiment of the present invention 1；
Fig. 4 is the x-ray photoelectron spectroscopy figure of Pt/Rh nanocomposite prepared by the embodiment of the present invention 1, wherein
Fig. 4 (a) is the XPS fitted figure of Rh, and Fig. 4 (b) is the XPS fitted figure of Pt；
Fig. 5 is the catalysis colorimetric photo for measuring Pt/Rh prepared by the embodiment of the present invention 1 as oxide enzyme simulation enzyme when
Figure；In figure: Fig. 5 (a) only has TMB；Fig. 5 (b) only has Pt/Rh；Fig. 5 (c) contains TMB, Pt/Rh simultaneously；
Fig. 6 be the embodiment of the present invention 1 prepared by Pt/Rh as oxide enzyme simulation enzyme when and comparative example 1, comparative example 2
The Rh piece and Pt nanocluster prepared respectively compares the TMB catalytic activity aoxidized；
Fig. 7 be the embodiment of the present invention 1 prepared by Pt/Rh as oxide enzyme simulation enzyme when and comparative example 1, comparative example 2
The Rh piece and Pt nanocluster prepared respectively compares the TMB stability kinetics aoxidized, wherein (a) is to make by dynamics data
Figure, (b) for dynamics data is pressed the figure that double reciprocal equations are made.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Chloroplatinic acid and acetylacetone,2,4-pentanedione rhodium are dissolved in benzylalcohol, polyvinylpyrrolidone and formaldehyde is added, stirs evenly, wherein
Chloroplatinic acid concentration be 0.7mmol/L, acetylacetone,2,4-pentanedione rhodium concentration be 3.2mmol/L, polyvinylpyrrolidoneconcentration concentration 16.0g/L,
Concentration of formaldehyde is 7000mmol/L.Heating reaction 8h at 180 DEG C.After reaction, be cooled to room temperature, by reactant acetone and
Ethanol washing, centrifugation removal supernatant, obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.219:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 450 nanometers, and two waists of Rh nanometer sheet are averagely about 185 nanometers, and Rh nanometer sheet is received with a thickness of 0.8
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 2.5 nanometers.
The catalysis stability kinetics test method of Pt/Rh nanocomposite provided in this embodiment is as follows:
The dispersion liquid of Pt/Rh nanocomposite is added into the Acetic acid-sodium acetate buffer of pH=4,0.1mol/L, mixes
It is even, change reaction system in TMB concentration (0.005mmol/L, 0.01mmol/L, 0.02mmol/L, 0.05mmol/L,
0.1mmol/L, 0.2mmol/L, 0.5mmol/L), it reacts 20 minutes at room temperature, wherein existing every 20 seconds measurement primary first-order equation liquid
The absorbance value of 652 nanometers.Dynamics data is used to Michaelis-Menten equation and Lineweaver-Burk respectively again
Double reciprocal equation mappings, solve kinetic constant.
The maximum reaction rate of Pt/Rh nanocomposite catalysis TMB provided in this embodiment is tested according to the above method
(Vmax) up to 1.88 × 10-7M s-1。
Fig. 1 is the transmission image of Pt/Rh nanocomposite prepared by embodiment 1, be can be clearly seen that from figure
A large amount of monodisperse nanoparticles are evenly distributed on superthin layer carrier material, and wherein the average grain diameter of Pt nanoparticle is about 2.7
Nanometer；Ultra-thin Rh piece is trapezoidal shape, and trapezoidal two bottom is averagely about 450 nanometers, and two waists are averagely about 185 nanometers.
Fig. 2 (a) is the dark field scan image of Pt/Rh prepared by embodiment 1, can be clearly seen the distribution of Pt nanocluster
In ultra-thin Rh on piece, without agglomeration；It may further see that Pt and Rh element is equal from Fig. 2 (b), Fig. 2 (c) and Fig. 2 (d)
Even distribution situation, it is consistent with the transmission image result of Pt/Rh in Fig. 1.
Fig. 3 is the X-ray energy spectrum diagram of Pt/Rh prepared by embodiment 1, can be clearly seen that composite material from figure
In only contain two kinds of metallic elements of Pt, Rh, wherein copper is from copper mesh.It is by the atomic ratio that integral measures Pt and Rh
0.219:1, and reacts the atomic ratio that feeds intake (Pt/Rh=0.218:1) closely, illustrates that most Pt atom is successfully born
It is loaded in Rh on piece, material realizes controlledly synthesis in composition.
Fig. 4 is the x-ray photoelectron spectroscopy figure of Pt/Rh prepared by embodiment 1, wherein being located in Fig. 4 (a)
Two peaks occurred at 312.07eV and 307.27eV correspond respectively to Rh3d3/2And Rh3d5/2, the small peak at 308.98eV returns
Belong to Rh3+, Rh3+Content accounts for about 3.6%.And in Fig. 4 (b), two peaks occurred at 74.17eV and 70.85eV respectively correspond
In Pt4f5/2And Pt4f7/2.Compared to metal Rh3d5/2(307.0eV) and Pt4f7/2The combination of (71.0eV) standard can be worth, and Pt/Rh receives
Rh3d in nano composite material5/2And Pt4f7/2Peak position combines the mobile 0.27eV in energy direction to height respectively and moves to low combination energy direction
Dynamic 0.15eV, illustrates that there are electron interactions between Rh and Pt atom.
It is of great significance by the oxidation reaction of oxidant of oxygen.The following are be used as to Pt/Rh prepared by embodiment 1
Colorimetric estimation (reaction total volume 1mL) with similar peroxidase activity feature when analogue enztme:
Steps are as follows similar to the colorimetric estimation of peroxidase activity feature by Pt/Rh: taking acetic acid-vinegar of pH=4,0.1mol/L
TMB solution and Pt/Rh dispersion liquid is successively added in sour sodium buffer thereto, makes the concentration difference of TMB and Pt/Rh in system
For 0.5mmol/L and 5 μm of ol/L, then above-mentioned solution is mixed；It places at room temperature after ten minutes, that is, solution can be observed from nothing
Discoloration is blue, as shown in Fig. 5 (c).These results indicate that Pt/Rh has very TMB in system in the presence of dissolved oxygen
High catalytic oxidation activity can be used as oxide enzyme simulation enzyme.As control, Fig. 5 (a) is colorimetric photo figure when only having TMB,
Solution is without obvious color in colorimetric photo figure when Fig. 5 (b) is only Pt/Rh, Fig. 5 (a) and Fig. 5 (b).
Embodiment 2
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Potassium chloroplatinate and radium chloride are dissolved in ethylene glycol, polyethylene glycol and formaldehyde is added, stirs evenly, wherein chloroplatinic acid
Potassium concn is 1.0mmol/L, and chlorination rhodium concentration is 3.0mmol/L, Polyethylene glycol 12.0g/L, and concentration of formaldehyde is
5000mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, by reactant acetone and ethanol washing,
Centrifugation removal supernatant, obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.327:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 460 nanometers, and two waists of Rh nanometer sheet are averagely about 190 nanometers, and Rh nanometer sheet is received with a thickness of 1.2
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 2.3 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.78×10-7M s-1。
Embodiment 3
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Acetylacetone,2,4-pentanedione platinum and acetylacetone,2,4-pentanedione rhodium are dissolved in benzylalcohol, polyvinylpyrrolidone and salicylide is added, stirring is equal
Even, wherein acetylacetone,2,4-pentanedione platinum concentration is 1.5mmol/L, and acetylacetone,2,4-pentanedione rhodium concentration is 3.3mmol/L, polyvinylpyrrolidoneconcentration concentration
For 25.0g/L, bigcatkin willow aldehyde concentration is 4mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, will react
Object acetone and ethanol washing, centrifugation removal supernatant, obtain the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.449:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 480 nanometers, and two waists of Rh nanometer sheet are averagely about 200 nanometers, and Rh nanometer sheet is received with a thickness of 0.8
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 2 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.72×10-7M s-1。
Embodiment 4
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Chloroplatinic acid and radium chloride are dissolved in n,N-Dimethylformamide, polyvinylpyrrolidone and salicylide is added, stirs
It mixes uniformly, wherein chloroplatinic acid concentration is 1.8mmol/L, and chlorination rhodium concentration is 3.3mmol/L, and polyvinylpyrrolidoneconcentration concentration is
20.0g/L, bigcatkin willow aldehyde concentration are 10mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, by reactant
With acetone and ethanol washing, centrifugation removal supernatant obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.538:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are about 500 nanometers, and two waists of Rh nanometer sheet are about 300 nanometers, Rh nanometer sheet with a thickness of 1.2 nanometers, the Pt
Nanocluster is zero dimensional nanometer materials, and partial size is 2.7 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.65×10-7M s-1。
Embodiment 5
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Acetylacetone,2,4-pentanedione platinum and radium chloride are dissolved in benzylalcohol, polyethylene glycol and benzaldehyde is added, stirs evenly, wherein acetyl
Acetone platinum concentration is 2.3mmol/L, and chlorination rhodium concentration is 3.0mmol/L, Polyethylene glycol 18.0g/L, benzaldehyde concentration
For 50mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, by reactant acetone and ethanol washing,
Centrifugation removal supernatant, obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.749:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 500 nanometers, and two waists of Rh nanometer sheet are about 320 nanometers, Rh nanometer sheet with a thickness of 0.8 nanometer, institute
Stating Pt nanocluster is zero dimensional nanometer materials, and partial size is 2.7 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.46×10-7M s-1。
Embodiment 6
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Chloroplatinic acid and radium chloride are dissolved in n,N-Dimethylformamide, cetyl trimethylammonium bromide and benzene first is added
Aldehyde stirs evenly, and wherein chloroplatinic acid concentration is 0.7mmol/L, and chlorination rhodium concentration is 2.8mmol/L, cetyl trimethyl bromine
Change ammonium concentration is 16.0g/L, benzaldehyde concentration 10mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room
Temperature, by reactant acetone and ethanol washing, centrifugation removal supernatant obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.246:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 430 nanometers, and two waists of Rh nanometer sheet are averagely about 180 nanometers, and Rh nanometer sheet is received with a thickness of 0.9
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 2.1 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.55×10-7M s-1。
Embodiment 7
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Acetylacetone,2,4-pentanedione platinum and radium chloride are dissolved in n,N-Dimethylformamide, polyvinylpyrrolidone and formaldehyde is added,
It stirs evenly, wherein acetylacetone,2,4-pentanedione platinum concentration is 0.96mmol/L, and chlorination rhodium concentration is 3.2mol/L, and polyvinylpyrrolidone is dense
Degree is 10.0g/L, concentration of formaldehyde 3000mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, it will be anti-
Object acetone and ethanol washing are answered, centrifugation removal supernatant obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.296:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 350 nanometers, and two waists of Rh nanometer sheet are about 140 nanometers, Rh nanometer sheet with a thickness of 1.2 nanometers, institute
Stating Pt nanocluster is zero dimensional nanometer materials, and partial size is 2.3 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.5×10-7M s-1。
Embodiment 8
The present embodiment is prepared as follows Pt/Rh nanocomposite:
Chloroplatinic acid and radium chloride are dissolved in n,N-Dimethylformamide, polyvinylpyrrolidone and benzaldehyde is added, stirs
It mixes uniformly, wherein chloroplatinic acid concentration is 2.0mmol/L, and chlorination rhodium concentration is 3.1mmol/L, and polyvinylpyrrolidoneconcentration concentration is
18.0g/L, benzaldehyde concentration 4mmol/L.Heating reaction 8h at 180 DEG C.After reaction, it is cooled to room temperature, by reactant
With acetone and ethanol washing, centrifugation removal supernatant obtains the Pt/Rh nanocomposite.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.648:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 470 nanometers, and two waists of Rh nanometer sheet are averagely about 220 nanometers, and Rh nanometer sheet is received with a thickness of 1.5
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 2.6 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.7×10-7M s-1。
Embodiment 9
Referring to embodiment 5, difference is the specific preparation method of the present embodiment, and acetylacetone,2,4-pentanedione platinum concentration is 3.0mmol/L,
Heating reaction 10h at 140 DEG C.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
The molar ratio of rice cluster composition, Pt nanocluster and Rh nanometer sheet is 0.8:1, and the shape of Rh nanometer sheet is trapezoidal, Rh nanometer sheet
Two bottoms be about 600 nanometers, two waists of Rh nanometer sheet are about 270 nanometers, Rh nanometer sheet with a thickness of 1.2 nanometers, the Pt receives
Rice cluster is zero dimensional nanometer materials, and partial size is 2.9 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.2×10-9M s-1。
Embodiment 10
Referring to embodiment 1, difference is the specific preparation method of the present embodiment, heating reaction 6h at 220 DEG C.
Pt/Rh nanocomposite provided in this embodiment is received by Rh nanometer sheet and the Pt being supported in the Rh nanometer sheet
Rice cluster composition, the molar ratio of Pt nanocluster and Rh nanometer sheet are 0.215:1, the shape of Rh nanometer sheet be it is trapezoidal, Rh nanometers
Two bottoms of piece are averagely about 460 nanometers, and two waists of Rh nanometer sheet are averagely about 190 nanometers, and Rh nanometer sheet is received with a thickness of 1.5
Rice, the Pt nanocluster are zero dimensional nanometer materials, and partial size is 3 nanometers.
According to the catalysis stability kinetics test method of embodiment 1 to Pt/Rh nanocomposite provided in this embodiment
It is tested, as a result are as follows: the maximum reaction rate (V of Pt/Rh nanocomposite catalysis TMB provided in this embodimentmax) reachable
1.6×10-7M s-1。
Comparative example 1
This comparative example prepares Rh nanometer sheet (being free of Pt), and the specific method is as follows:
Acetylacetone,2,4-pentanedione rhodium is dissolved in benzylalcohol, polyvinylpyrrolidone and formaldehyde is added, stirs evenly, wherein acetylacetone,2,4-pentanedione
Rhodium concentration is 3.2mmol/L, polyvinylpyrrolidoneconcentration concentration 16.0g/L, concentration of formaldehyde 7000mmol/L.Add at 180 DEG C
Thermal response 8h.After reaction, it is cooled to room temperature, by reactant acetone and ethanol washing, centrifugation removal supernatant supernatant is obtained
To the Rh nanometer sheet.
The Rh nanometer sheet that this comparative example provides is tested according to the catalysis stability kinetics test method of embodiment 1,
As a result are as follows: the maximum reaction rate (V of Rh nanometer sheet catalysis TMB provided in this embodimentmax) up to 1.92 × 10-8M s-1。
Comparative example 2
This comparative example prepares only Pt nanocluster (being free of Rh), and the specific method is as follows:
Chloroplatinic acid is dissolved in benzylalcohol, polyvinylpyrrolidone and formaldehyde is added, stirs evenly, wherein chloroplatinic acid concentration is
0.7mmol/L, polyvinylpyrrolidoneconcentration concentration 16.0g/L, concentration of formaldehyde 7000mmol/L.Heating reaction 8h at 180 DEG C.
After reaction, it is cooled to room temperature, by reactant acetone and ethanol washing, centrifugation removal supernatant supernatant obtains the Pt
Nanocluster.
The Pt nanocluster that this comparative example provides is surveyed according to the catalysis stability kinetics test method of embodiment 1
Examination, as a result are as follows: the maximum reaction rate (V of Pt nanocluster catalysis TMB provided in this embodimentmax) up to 1.29 × 10-8M s-1。
Fig. 6 shows that Pt/Rh and independent Rh piece, Pt nanocluster aoxidize in room temperature TMB as oxide enzyme simulation enzyme
It is lower to react the ultraviolet spectrogram collected after twenty minutes.From fig. 6, it can be seen that the Pt/Rh nanocomposite of embodiment 1 is catalyzed
The product of TMB oxidation reaction has maximum absorbance value in 652 nanometers, respectively may be about Rh piece (comparative example 1) and Pt nanoclusters
It is higher to show that Pt/Rh nanocomposite ratio Rh piece and Pt nanocluster have TMB oxidation for 3 times and 5 times of cluster (comparative example 2)
Catalytic activity.
It is living further to compare the catalysis that Pt/Rh nanocomposite aoxidizes TMB with independent Rh piece and Pt nanocluster
Property, constant other reaction conditions only change TMB concentration, absorbance of the measurement catalysis reaction in 652 nanometers.Fig. 7 display is real
The Pt/Rh nanocomposite and independent Rh piece (comparative example 1), Pt nanocluster (comparative example 2) for applying example 1 are as oxide enzyme mould
Stability kinetics curve when quasi- enzyme.From Fig. 7 (a) as can be seen that no matter using which kind of catalyst, TMB oxidation reaction kinetics
Follow Mie theory, maximum reaction rate (Vmax) up to 1.88 × 10-7M s-1, respectively may be about independent Rh piece (Vmax=1.92
×10-8M s-1) and Pt nanocluster (Vmax=1.29 × 10-7M s-1) 10 times and 1.5 times, illustrate that the activity of Pt/Rh is remote high
In the activity of Rh piece and Pt nanocluster.Dynamics data is pressed into double reciprocal equation mappings, catalysis can be seen from Fig. 7 (b)
The inverse of reaction rate is in good linear relationship with the inverse of concentration of substrate.The above results explanation, Pt/Rh catalysis TMB's
In oxidation process, there are significant synergistic effects between Pt and Rh, have very high activation capacity to oxygen, to greatly speed up
Reaction rate.
Based on the above embodiments with comparative example it is found that Pt/Rh nanocomposite provided by the invention is from the foregoing, it will be observed that this hair
Pt/Rh preparation method provided by bright is simple, has the catalysis of similar oxide enzyme when as nanometer analogue enztme, compared to independent Rh
Piece and Pt nanocluster show the activity being remarkably reinforced, maximum reaction rate (Vmax) up to 1.88 × 10-7M s-1, can be used as
A kind of new oxide enzyme simulation enzyme, i.e., Pt/Rh prepared by the present invention, which can be used as analogue enztme, to replace oxide enzyme immune
Analysis, biochemistry detection and clinical diagnosis etc. obtain broad application prospect.Comparative example does not use the solution of the present invention, thus nothing
Method obtains excellent results of the invention.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of Pt/Rh nanocomposite, which is characterized in that the Pt/Rh nanocomposite includes Rh nanometer sheet and bears
The Pt nanocluster being loaded in the Rh nanometer sheet.
2. according to Pt/Rh nanocomposite described in right 1, which is characterized in that the Pt nanocluster and Rh nanometer sheet
Molar ratio is (0.219~0.749): 1；
Preferably, the shape of the Rh nanometer sheet is trapezoidal；
Preferably, a length of 200~600 nanometers of the bottom of the Rh nanometer sheet；
Preferably, a length of 100~300 nanometers of the waist of the Rh nanometer sheet；
Preferably, the Rh nanometer sheet with a thickness of 0.4~1.5 nanometer；
Preferably, the Pt nanocluster is zero dimensional nanometer materials；
Preferably, the partial size of the Pt nanocluster is 2~3 nanometers.
3. a kind of preparation method of Pt/Rh nanocomposite as described in claim 1, which is characterized in that the method includes
Following steps:
Platinum salt and rhodium salt are dissolved in solvent, surfactant and reducing agent is added, obtained mixed solution heat anti-
It answers, is separated by solid-liquid separation after reaction, obtain the Pt/Rh nanocomposite.
4. preparation method according to claim 3, which is characterized in that the platinum salt includes chloroplatinic acid, potassium chloroplatinate or second
In acyl acetone platinum any one or at least two combination；
Preferably, the rhodium salt includes radium chloride and/or acetylacetone,2,4-pentanedione rhodium；
Preferably, the solvent includes any one in benzylalcohol, ethylene glycol or n,N-Dimethylformamide or at least two
Combination.
5. preparation method according to claim 3 or 4, which is characterized in that the surfactant includes polyvinyl pyrrole
In alkanone, polyethylene glycol or cetyl trimethylammonium bromide any one or at least two combination；
Preferably, the reducing agent include in formaldehyde, benzaldehyde or salicylide any one or at least two combination.
6. according to the described in any item preparation methods of claim 3-5, which is characterized in that in the mixed solution, platinum salt is rubbed
Your concentration is 0.1~3.0mmol/L；
Preferably, in the mixed solution, the molar concentration of rhodium salt is 2.8~3.3mmol/L；
Preferably, in the mixed solution, the molar ratio of platinum salt and rhodium salt is (0.218~0.763): 1.
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that in the mixed solution, surface-active
The mass concentration of agent is 10.0~25.0g/L；
Preferably, in the mixed solution, the molar concentration of reducing agent is 4~7000mmol/L.
8. according to the described in any item preparation methods of claim 3-7, which is characterized in that the temperature of the heating reaction is 140
~220 DEG C, preferably 180 DEG C；
Preferably, the time of the heating reaction is 6~10h, preferably 8h；
Preferably, described be separated by solid-liquid separation includes centrifuge separation；
Preferably, the preparation method further include: after the completion of reaction, reaction product is washed.
9. according to the described in any item preparation methods of claim 3-8, which is characterized in that the described method comprises the following steps:
Platinum salt and rhodium salt are dissolved in solvent, surfactant and reducing agent is added, to obtained mixed solution at 180 DEG C into
Row heating reaction 8h, washs after reaction and is centrifugated, obtain the Pt/Rh nanocomposite；
Wherein, the platinum salt be chloroplatinic acid, potassium chloroplatinate or acetylacetone,2,4-pentanedione platinum in any one or at least two combination, institute
Stating rhodium salt is radium chloride and/or acetylacetone,2,4-pentanedione rhodium, and the solvent is any in benzylalcohol, ethylene glycol or n,N-Dimethylformamide
It is a kind of or at least two combination, the surfactant be polyvinylpyrrolidone, polyethylene glycol or cetyl trimethyl
In ammonium bromide any one or at least two combination, the reducing agent be formaldehyde, benzaldehyde or salicylide kind it is any one
Kind or at least two combination；
In the mixed solution, the molar concentration of platinum salt is 0.1~3.0mmol/L, the molar concentration of rhodium salt is 2.8~
The molar ratio of 3.3mmol/L, platinum salt and rhodium salt is (0.218~0.763): 1, the mass concentration of surfactant is 10.0~
25.0g/L, the molar concentration of reducing agent are 4~7000mmol/L.
10. a kind of purposes of Pt/Rh nanocomposite as claimed in claim 1 or 2, which is characterized in that Pt/Rh nanometers described
Composite material is applied to immunoassay, biological detection or clinical diagnosis field as oxide enzyme simulation enzyme.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830702A (en) * | 2019-02-13 | 2019-05-31 | 深圳市雄韬电源科技股份有限公司 | A kind of fuel-cell catalyst and its preparation method and application |
| CN112206771A (en) * | 2019-07-12 | 2021-01-12 | 华南理工大学 | Ternary metal Pd-M-Ir nanoenzyme and preparation method and application thereof |
| CN112695223A (en) * | 2020-12-07 | 2021-04-23 | 青岛大学 | Method for synthesizing small-particle-size platinum-rhodium nanocrystals |
| CN113304748A (en) * | 2020-03-04 | 2021-08-27 | 青岛大学 | Copper nanocluster with multiple enzyme-like activities and preparation method and application thereof |
| CN114618482A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of platinum-rhodium alloy, preparation method of platinum-rhodium alloy catalyst and application of platinum-rhodium alloy catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423708A (en) * | 2011-08-12 | 2012-04-25 | 南京大学 | Nickel-based composite nanomaterial and preparation method thereof as well as porous nickel nanomaterial and preparation method and application thereof |
| US8540796B1 (en) * | 2008-04-23 | 2013-09-24 | Sandia Corporation | Sintering and ripening resistant noble metal nanostructures |
| CN104551000A (en) * | 2014-12-23 | 2015-04-29 | 国家纳米科学中心 | Platinum-cobalt nano-alloy mimic enzyme and preparing method and purpose thereof |
| CN106694900A (en) * | 2016-12-20 | 2017-05-24 | 浙江大学 | Preparation method for multi-metal-core-shell nanosheet |
| CN107442134A (en) * | 2017-08-30 | 2017-12-08 | 江苏大学 | A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application |
| CN107727858A (en) * | 2017-09-30 | 2018-02-23 | 山东理工大学 | A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors |
| CN108326284A (en) * | 2018-02-07 | 2018-07-27 | 中南民族大学 | A kind of Rh nano-nails cluster and its synthetic method |
-
2018
- 2018-08-22 CN CN201810960519.2A patent/CN109078634B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8540796B1 (en) * | 2008-04-23 | 2013-09-24 | Sandia Corporation | Sintering and ripening resistant noble metal nanostructures |
| CN102423708A (en) * | 2011-08-12 | 2012-04-25 | 南京大学 | Nickel-based composite nanomaterial and preparation method thereof as well as porous nickel nanomaterial and preparation method and application thereof |
| CN104551000A (en) * | 2014-12-23 | 2015-04-29 | 国家纳米科学中心 | Platinum-cobalt nano-alloy mimic enzyme and preparing method and purpose thereof |
| CN106694900A (en) * | 2016-12-20 | 2017-05-24 | 浙江大学 | Preparation method for multi-metal-core-shell nanosheet |
| CN107442134A (en) * | 2017-08-30 | 2017-12-08 | 江苏大学 | A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application |
| CN107727858A (en) * | 2017-09-30 | 2018-02-23 | 山东理工大学 | A kind of preparation method and application based on Rh@Pt nanodendrites composite immunosensors |
| CN108326284A (en) * | 2018-02-07 | 2018-07-27 | 中南民族大学 | A kind of Rh nano-nails cluster and its synthetic method |
Non-Patent Citations (2)
| Title |
|---|
| JEONG YOUNG PARK ET AL: "Tuning of Catalytic CO Oxidation by Changing Composition of Rh-Pt Bimetallic Nanoparticles", 《NANO LETTERS》 * |
| 郑丽等: "纳米材料过氧化物模拟酶在比色分析及电化学传感器中的应用", 《材料导报A：综述篇》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830702A (en) * | 2019-02-13 | 2019-05-31 | 深圳市雄韬电源科技股份有限公司 | A kind of fuel-cell catalyst and its preparation method and application |
| CN112206771A (en) * | 2019-07-12 | 2021-01-12 | 华南理工大学 | Ternary metal Pd-M-Ir nanoenzyme and preparation method and application thereof |
| CN113304748A (en) * | 2020-03-04 | 2021-08-27 | 青岛大学 | Copper nanocluster with multiple enzyme-like activities and preparation method and application thereof |
| CN112695223A (en) * | 2020-12-07 | 2021-04-23 | 青岛大学 | Method for synthesizing small-particle-size platinum-rhodium nanocrystals |
| CN114618482A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of platinum-rhodium alloy, preparation method of platinum-rhodium alloy catalyst and application of platinum-rhodium alloy catalyst |
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