CN110064410A - A method of it is extremely easy to prepare the monatomic catalyst of noble metal - Google Patents
A method of it is extremely easy to prepare the monatomic catalyst of noble metal Download PDFInfo
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- CN110064410A CN110064410A CN201910390620.3A CN201910390620A CN110064410A CN 110064410 A CN110064410 A CN 110064410A CN 201910390620 A CN201910390620 A CN 201910390620A CN 110064410 A CN110064410 A CN 110064410A
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000009938 salting Methods 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 107
- 239000000463 material Substances 0.000 claims description 65
- 229910052697 platinum Inorganic materials 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 11
- 239000010970 precious metal Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- -1 transition metal selenides Chemical class 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000010944 silver (metal) Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 230000001052 transient effect Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 43
- 229910052799 carbon Inorganic materials 0.000 description 42
- 238000006555 catalytic reaction Methods 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000004075 alteration Effects 0.000 description 14
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 13
- 229910052961 molybdenite Inorganic materials 0.000 description 13
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052798 chalcogen Inorganic materials 0.000 description 4
- 150000001787 chalcogens Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229910020700 Na3VO4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910003090 WSe2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
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 extremely easy method for preparing the monatomic catalyst of noble metal, include the following steps: (1) by Transition-metal dichalcogenide nano material with containing noble metal acid or salting liquid mix；(2) mixed solution in step (1) is placed under light source and irradiates a period of time, Transition-metal dichalcogenide nano material is separated with solution then, dries the monatomic catalyst of noble metal can be obtained, the monatomic catalyst of noble metal is the monatomic composite material in conjunction with Transition-metal dichalcogenide nano material of noble metal.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of extremely simplicity prepares the monatomic catalyst of noble metal
Method and application.
Background technique
The size of metallic particles be determine its catalytic performance key factor, catalytic activity with the reduction of particle size and
It significantly increases.Therefore, metallic catalyst to small size, it is monatomic development be inexorable trend.It is different from traditional nano particle, it is single
Catalyst atom can perform to atom utilization ultimate attainment (100% atom utilization), there is more obvious size, structure
Effect and strong interaction with carrier, while being also equipped with high catalytic activity, stability and selectivity.Thus, it prepares single former
Muonic catalysis agent can substantially reduce metal wastage while improving material catalytic efficiency, to reduce catalyst cost.
Currently, still having many challenges in terms of the controllable large scale preparation of monatomic catalyst.Main cause is when gold
Belong to when being reduced in size to monatomic level of particle, specific surface area can increase rapidly, sharply so as to cause metal surface free energy
Increase, is easy to agglomerate into nano particle.For this purpose, researcher, which has been devoted to research, prevents reuniting, obtaining for metallic
To the method for the high activity metal cluster (i.e. monatomic catalyst) of stable dispersion.Conventional monatomic method for preparing catalyst
Mainly there are solution chemical method, atomic layer deposition method, pyrolysismethod etc..But these methods or process are cumbersome or need high temperature or condition
It is harsh or involve great expense, all it is unfavorable for the large-scale promotion application of monatomic catalyst.
In addition, noble metal is still one of catalyst of greatest concern, catalysis reaction efficiency can not only be significantly improved, and
And self property is extremely stable, it is high temperature resistant, resistance to oxidation, corrosion-resistant.However, noble metal is resource very rare on the earth and valence
Lattice are expensive, are not able to satisfy the current demand of extensive catalysis reaction.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of extremely easy sides for preparing the monatomic catalyst of noble metal
Method.
Here, the present invention provides a kind of extremely easy method for preparing the monatomic catalyst of noble metal, include the following steps:
(1) by Transition-metal dichalcogenide (TMDs) nano material with containing noble metal acid or salting liquid mix；
(2) mixed solution in step (1) is placed under light source and irradiates a period of time, TMDs is separated with solution then, is done
Dry that the monatomic catalyst of noble metal can be obtained, the monatomic catalyst of noble metal is that noble metal is monatomic in conjunction with TMDs
Composite material.
This method preparation process extremely simplicity, preparation cost and lower cost for material, are suitble to large-scale industrial production and application.
Preferably, it includes at least one of Pt, Au, Ag, Pd, Ru, Ir that the noble metal is monatomic.
Preferably, the TMDs is at least one of transient metal sulfide, transition metal selenides in step (1).
Preferably, the pattern of the TMDs nano material is nanometer sheet, nano wire, nanometer rods or nano-cluster, preferably receive
Rice piece.
Preferably, in step (1), the acid or salt containing noble metal be chloroplatinic acid, gold chloride, silver nitrate, chlorine palladium acid sodium,
At least one of palladium chloride.
Preferably, precious metal atom molar concentration is in the acid or salting liquid containing noble metal in step (1)
0.01mmol/L~1mmol/L, preferably 0.1mmol/L~1mmol/L.
Preferably, in step (1), the TMDs with containing noble metal acid or salting liquid mass ratio be 1:1000~1:20,
Preferably 1:500~1:50, further preferably 1:200~1:100.
Preferably, the TMDs nano material is grown in conductive substrates, it is preferable that the conductive substrates are carbon fiber.
Preferably, the light source is at least one of xenon source, natural sunlight in step (2).
Preferably, the intensity of light source is 50mW/cm in step (2)2~200mW/cm2, preferably 100mW/cm2；Irradiation
Time is 0.5h~2h, preferably 1h.
The method that the present invention utilizes illumination, simply and effectively prepares a large amount of monatomic catalyst materials of high quality noble metal,
Noble metal consumption is substantially reduced while retaining noble metal superelevation catalytic activity, reduces cost.
Detailed description of the invention
Fig. 1 is the VS in embodiment 1 before and after the monatomic load of Pt2The x-ray diffraction pattern of nanometer sheet.
Fig. 2 be in embodiment 1 Pt for preparing it is monatomic/VS2The scanning electron microscope (SEM) photograph of catalysis material.
Fig. 3 be in embodiment 1 Pt for preparing it is monatomic/VS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material.
Fig. 4 be in embodiment 2 Pt for preparing it is monatomic/VS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material.
Fig. 5 is the MoS in embodiment 3 before and after the monatomic load of Pt2The x-ray diffraction pattern of nanometer sheet.
Fig. 6 be in embodiment 3 Pt for preparing it is monatomic/MoS2The scanning electron microscope (SEM) photograph of catalysis material.
Fig. 7 be in embodiment 3 Pt for preparing it is monatomic/MoS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material.
Fig. 8 be embodiment 4 in 1mmol/L platinum acid chloride solution preparation Pt it is monatomic/cluster-VS2Nanometer sheet is catalyzed material
The condenser spherical aberration Electronic Speculum dark field plot of material.
Fig. 9 is the scanning electron microscope (SEM) photograph for the carbon paper used in embodiment 1.
Figure 10 is the Pt nano particle-VS of 10mmol/L platinum acid chloride solution preparation in comparative example 12Nanometer sheet catalysis material
Condenser spherical aberration Electronic Speculum dark field plot.
Figure 11 is 0.1mmol/L, 0.5mmol/L, 1mmol/L, 5mmol/L, 10mmol/L in embodiment 4 and comparative example 1
Platinum acid chloride solution preparation different shape Pt/VS2The polarization curve of catalysis material.
Figure 12 is 0.1mmol/L, 0.5mmol/L, 1mmol/L, 5mmol/L, 10mmol/L in embodiment 4 and comparative example 1
Platinum acid chloride solution preparation different shape Pt/VS2The Pt activity curve of catalysis material.
Figure 13 be embodiment 4 in 1mmol/L platinum acid chloride solution preparation Pt it is monatomic/cluster-VS2Nanometer sheet is catalyzed material
Curent change figure under the 5000 circulations front and back polarization curve comparison diagram and constant voltage of material.
Figure 14 be in embodiment 5 Au for preparing it is monatomic/VS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material.
Figure 15 be in embodiment 6 Pd for preparing it is monatomic/VS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material.
Figure 16 is the schematic diagram of the method for an embodiment of the present invention.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In an embodiment of the present invention, firstly, by Transition-metal dichalcogenide (TMDs) nano material and containing noble metal
Acid or salting liquid be sufficiently mixed.
Transition-metal dichalcogenide (TMDs) has MX2Chemical formula, wherein M represents transition metal, for example, selected from Ti,
Zr, Ha, V, Nb, Ta, Cr, Mo, W etc., X represent chalcogen, generally S, Se, Te.TMDs specifically may be, for example, transition metal
Sulfide is (such as: MoS2、VS2), transition metal selenides (such as: MoSe2、WSe2At least one of).
The pattern of the TMDs nano material can be nanometer sheet, nano wire, nanometer rods or nano-cluster etc., preferably nanometer
Piece, this is because TMDs sheet is as layer structure, the synthesis condition of nanometer sheet is most simple, while TMDs nanometer sheet is in ultrasound
It is easier to be dispersed into multilayer or single layer structure, increases specific surface area, be more advantageous to and the contact of acid or salting liquid containing noble metal
And reaction.
Method commonly used in the art can be used in the preparation method of Transition-metal dichalcogenide (TMDs) nano material.It is some
In embodiment, TMDs nano material can be grown in conductive substrates.For example, conductive substrates can be placed in containing transition metal
In the solution in source and chalcogen source, hydro-thermal reaction is carried out, the TMDs nano material grown in substrate is obtained.
It, can also be by it in 300~500 DEG C of vacuum or inert atmosphere after obtaining the TMDs nano material grown in substrate
Middle annealing improves the crystallinity of TMDs in 20~60 minutes, to enhance the reactivity and catalytic activity of TMDs.
Conductive substrates can be selected from carbon fiber, nickel foam etc..Wherein preferred carbon fiber, because the specific surface area of carbon fiber is more
Greatly, more TMDs nanometer sheets can be grown under unit volume.Carbon fiber can be the carbon paper being made of carbon fiber, carbon cloth or
At least one of carbon felt is also possible to individual carbon fiber bundle.
Transition metal source can be transition metal mixtures (such as sodium vanadate, ammonium metavanadate, sodium molybdate, ammonium heptamolybdate, wolframic acid
Sodium etc.), transition metal oxide (such as vanadyl acetylacetonate, molybdenum trioxide etc.).Chalcogen source can be thioacetamide,
Thiocarbamide, cysteine etc..Transition metal source and the molar ratio in chalcogen source can be 1:2~1:4.Hydrothermal temperature can be
150~220 DEG C, the reaction time can be 18~32h, preferably for 24 hours.
Acid or salting liquid containing noble metal can be selected according to the type of precious metal element.In other words, regulation can be passed through
The type of acid or salt containing noble metal regulates and controls the monatomic type of noble metal.Specifically, precious metal element can be selected from Pt, Au,
At least one of Ag, Pd, Ru, Ir.Correspondingly, the acid containing noble metal or salting liquid can be selected from chloroplatinic acid, gold chloride, nitric acid
At least one of silver, chlorine palladium acid sodium, palladium chloride etc..
The solvent that acid or salting liquid containing noble metal use can be at least one of water or organic solvent.It is described organic
Solvent is any organic solvent that the above-mentioned acid containing noble metal or salt are not acted on and can dissolved with reactant, for example, can be selected from
One or more of alcohols solvent (such as: methanol, ethyl alcohol, isopropanol).
Precious metal atom molar concentration can be 0.01mmol/L~1mmol/L in acid or salting liquid containing noble metal, upper
It states in range, the monatomic catalyst of noble metal of high load amount can be obtained.If concentration is lower than 0.01mmol/L, obtained
Monatomic load capacity is lower.If concentration is higher than 1mmol/L, noble metal granule will form.It is highly preferred that the acid containing noble metal
Or precious metal atom molar concentration is that 0.1mmol/L~0.5mmol/L in the range can be to avoid monatomic in salting liquid
It is agglomerated into cluster.
By regulating and controlling the concentration of acid or salting liquid containing noble metal, can regulate and control expensive in the gained monatomic catalyst of noble metal
The monoatomic content of metal.Specifically, noble metal is monoatomic to be contained when the concentration of acid or salting liquid containing noble metal is higher
It measures also higher.
TMDs nano material with containing noble metal acid or salting liquid mass ratio can be 1:1000~1:20, preferably 1:500
~1:50, further preferably 1:200~1:100.Using above-mentioned mass ratio, the utilization rate of acid or salt containing noble metal is in height
Crest state, formed high load amount noble metal it is monoatomic and meanwhile as far as possible reduce noble metal consumption.
By TMDs nano material with containing noble metal acid or the well-mixed method of salting liquid can for impregnate, ultrasound, stirring,
Oscillation etc..
Then, as shown in figure 16, the mixed solution of TMDs nano material and acid or salting liquid containing noble metal is placed in light
A period of time is irradiated under source, and TMDs nano material is separated with solution then, dries that corresponding noble metal can be obtained is monatomic
Catalyst.
The light source can be continuous light source, for example, at least one of xenon source, natural sunlight.Using above-mentioned
Light source can with low energy consumption, complete to transitory efficient the preparation of the monatomic catalyst of noble metal.When especially, using nature sunlight
It can be realized and clean synthesis in the case where not consuming any additional source of energy, the large-scale low-cost for facilitating the catalyst is raw
It produces.
Since TMDs is layer structure, only supported between layers by Van der Waals force, therefore ion is easily accessible TMDs layers
Between, doping or absorption are formed, i.e. TMDs has higher reactivity compared with other materials such as carbon fiber etc., therefore is not required to
Individually high-strength ultraviolet light is wanted, reaction only can be realized by white light.
The intensity of light source can be 50mW/cm2~200mW/cm2, preferably 80~120mW/cm2, further preferred 100mW/cm2,
One times of sun light intensity under the atmosphere factor of about AM1.5G.Irradiation time can be 0.5h~2h, preferably 0.5~1h, into one
Step is preferably 1h.Using above-mentioned illumination condition, the monatomic catalyst of noble metal can be efficiently obtained, meanwhile, be conducive to prepare
It is that nature sunlight irradiates that method, which is expanded, energy saving.By regulating and controlling illumination condition, can regulating and controlling gained, noble metal is monatomic urges
The monoatomic content of noble metal in agent.Specifically, noble metal is monatomic when illumination is relatively strong and/or light application time is longer
Content it is higher.
The above-mentioned solution isolated after solid can be re-used in the preparation of the monatomic catalyst of noble metal.That is, your gold contained
The acid or salting liquid of category can be used repeatedly, and have no effect on the final performance of catalyst, significantly improve noble metal source
Utilization rate reduces the cost of raw material.
The resulting monatomic catalyst of noble metal is the monatomic composite material in conjunction with TMDs nano material of noble metal.It is expensive
The monatomic mass fraction in TMDs nano material of metal can be 0.05wt.%~1wt.%.
The monatomic interaction relationship with TMDs nano material of noble metal, can be precious metal atom and is adsorbed on TMDs table
Face can be the vacancy that precious metal atom replaces TMDs, be also possible to precious metal atom and enter in TMDs interstitial void, preferably expensive
Metallic atom enters the vacancy TMDs, is conducive to the stability of precious metal atom in the composite.Using method of the invention
When, precious metal atom preferentially enters the vacancy in TMDs structure, therefore gained composite material stability is more excellent.
In some embodiments, TMDs nano material, the difference of the different noble metal source of adjusting, different-shape can be passed through
Material rate, different intensities of illumination and light application time obtain the monatomic catalyst of different noble metals.
The present invention provides a kind of preparation methods of the monatomic catalyst of noble metal, since noble metal is in TMDs nano material
On form monatomic, improve the atom utilization of noble metal, reduce the consumption of noble metal, to be urged promoting catalyst
Material cost is reduced while changing performance.
Compared with prior art, the present invention also has a characteristic that
(1) preparation process of the present invention is extremely easy, and light source can be substituted by the sunlight in natural environment, can be realized
Synthesis is cleaned in the case where not consuming any additional source of energy, facilitates the large-scale low-cost production of the catalyst.
(2) present invention has universality, and it is monatomic in VS can be suitable for simultaneously the noble metals such as Pt, Au, Ag, Pd2、MoS2
Preparation in equal TMDs nano material.
(3) noble metal source (acid or salting liquid containing noble metal) used in the present invention can be used repeatedly, and improve
The utilization rate of noble metal source reduces the cost of raw material.
(4) catalyst prepared by the present invention monatomic load capacity with higher, and stability is good, atom form is (single former
Son or cluster) can be controlled by solution concentration, reaction time, can effectively avoid it is monatomic be grown to particle, repeat
Property is good.
(5) the monatomic catalyst material of noble metal prepared by the present invention and preparation cost are very cheap, and catalytic performance is excellent
It is different, it is suitable for large-scale production and application.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Various raw materials used in following embodiment do not illustrate such as, are commercial product, or can pass through
Known method preparation.
Embodiment 1:Pt is monatomic/VS2The preparation of catalysis material
Grow VS2The preparation of the carbon paper of nanometer sheet: by 3mmol Na3VO4·12H2O and 15mmol thioacetamide adds
Enter into 40mL deionized water, is stirred well to after being completely dissolved and is transferred in 50mL ptfe autoclave.Then, by one
The carbon paper (its SEM figure is referring to Fig. 9) that chip size is 1cm × 2cm immerses in above-mentioned solution, then seals reaction kettle, in 160 DEG C
Reaction is for 24 hours.After reaction, it is naturally cooling to room temperature, then takes out carbon paper, is cleaned multiple times with water and ethyl alcohol, it is dry
Obtain the VS grown on carbon paper2Nanometer sheet, vacuum annealing 20min improves VS at 300 DEG C2The crystallinity of nanometer sheet.
VS will be grown21cm × 2cm carbon paper of nanometer sheet is immersed in 10mL, in the platinum acid chloride solution of 0.1mmol/L, sets
In intensity be 100mW cm-2Xenon source under irradiate 0.5h.When irradiation time is more than half, overturning carbon paper surface completes the other side
Reaction.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, the monatomic-VS of Pt can be obtained2Nanometer sheet
Composite catalyzing material.
Fig. 1 is the VS in embodiment 1 before and after the monatomic load of Pt2The x-ray diffraction pattern of nanometer sheet, it was demonstrated that Pt atom
It introduces to VS2Crystal structure do not influence, while not forming Pt diffraction maximum, it was demonstrated that the not formed particle of Pt atom.
Fig. 2 be the Pt that is grown on carbon paper in embodiment 1 it is monatomic/VS2The scanning electron microscope (SEM) photograph of catalysis material, it was demonstrated that VS2Nanometer
Piece homoepitaxial is on carbon paper, while nanometer sheet surface does not have apparent Pt particle.
Fig. 3 be the Pt that is generated under 0.1mmol/L chloroplatinic acid concentration, xenon source in embodiment 1 it is monatomic/VS2It is catalyzed material
The condenser spherical aberration Electronic Speculum dark field plot of material, bright spot represent Pt atom, intuitively show VS2Middle Pt atom is successfully introduced into.
As inductively-coupled plasma spectrometer measure obtained by the monatomic-VS of Pt2Pt in nanometer sheet composite catalyzing material
Monoatomic mass fraction is 0.08%.
Embodiment 2:Pt is monatomic/VS2The preparation of catalysis material
Grow VS2The preparation of the carbon paper of nanometer sheet: with embodiment 1.
VS will be grown21cm × 2cm carbon paper of nanometer sheet is immersed in the platinum acid chloride solution of 10mL, 1mmol/L, is placed in
Intensity is 60mW cm-2Sunlight under irradiate 2h.When irradiation time is more than half, overturning carbon paper surface completes the reaction of the other side.Instead
Carbon paper is taken out after answering, is cleaned multiple times with water and ethyl alcohol, it is dry, the monatomic-VS of Pt can be obtained2Nanometer sheet composite catalyzing
Material.
Fig. 4 be the Pt that is generated under 1mmol/L chloroplatinic acid concentration, sun radiant in embodiment 2 it is monatomic/VS2It is catalyzed material
The condenser spherical aberration Electronic Speculum dark field plot of material, bright spot represent Pt atom, intuitively show VS2Surface Pt atom is successfully introduced into.
Monatomic-the VS of gained Pt2The monoatomic mass fraction of Pt is 0.47% in nanometer sheet composite catalyzing material.
Embodiment 3:Pt is monatomic/MoS2The preparation of catalysis material
Grow MoS2The preparation of the carbon paper of nanometer sheet: by 1mmol Na2MoO4·2H2O and 4mmol thiocarbamide is added to
In 40mL deionized water, it is stirred well to after being completely dissolved and is transferred in 50mL ptfe autoclave.Then, by a piece of ruler
The very little carbon paper for 1cm × 2cm immerses in above-mentioned solution, then seals reaction kettle, for 24 hours in 200 DEG C of reactions.After reaction,
It is naturally cooling to room temperature, then takes out carbon paper, is cleaned multiple times with water and ethyl alcohol, it is dry, it can be obtained and grown on carbon paper
MoS2Nanometer sheet, Ar at 350 DEG C21h anneal to improve MoS2The crystallinity of nanometer sheet.
MoS will be grown21cm × 2cm carbon paper of nanometer sheet is immersed in the platinum acid chloride solution of 10mL, 0.5mmol/L, is set
In intensity be 100mW cm-2Xenon source under irradiate 1h.When irradiation time is more than half, overturning carbon paper surface completes the anti-of the other side
It answers.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, the monatomic-MoS of Pt can be obtained2Nanometer sheet is multiple
Close catalysis material.
Fig. 5 is the MoS in embodiment 3 before and after the monatomic load of Pt2The x-ray diffraction pattern of nanometer sheet, it was demonstrated that Pt atom
It introduces to MoS2Crystal structure do not influence, while not forming Pt diffraction maximum, it was demonstrated that the not formed particle of Pt atom.
Fig. 6 be the Pt that is grown on carbon paper in embodiment 3 it is monatomic/MoS2The scanning electron microscope (SEM) photograph of catalysis material, it was demonstrated that MoS2It receives
Rice piece homoepitaxial is on carbon paper, while nanometer sheet surface does not have apparent Pt particle.
Fig. 7 be embodiment 3 in Pt it is monatomic/MoS2The condenser spherical aberration Electronic Speculum dark field plot of catalysis material, bright spot represent Pt
Atom intuitively shows MoS2Surface Pt atom is successfully introduced into.
Monatomic-the MoS of gained Pt2The monoatomic mass fraction of Pt is 0.89% in nanometer sheet composite catalyzing material.
Embodiment 4:Pt/VS2The preparation of catalysis material
Grow VS2The preparation of the carbon paper of nanometer sheet: with embodiment 1.
VS will be grown2The carbon paper of nanometer sheet is immersed in 10mL, the chloroplatinic acid of 0.1mmol/L, 0.5mmol/L, 1mmol/L
In solution, being placed in intensity is 100mW cm-2Xenon source under irradiate 1h.When irradiation time is more than half, overturning carbon paper surface is completed
The reaction of the other side.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, it is monatomic/former that Pt can be obtained
Submanifold-VS2Nanometer sheet composite catalyzing material.
Fig. 8 be embodiment 4 in 1mmol/L platinum acid chloride solution preparation Pt it is monatomic/cluster-VS2Nanometer sheet is catalyzed material
The condenser spherical aberration Electronic Speculum dark field plot of material, bright spot represent pt atom, intuitively show VS2Surface Pt atom is successfully introduced into.With
Fig. 3 comparison can see, and with the increase of chloroplatinic acid concentration, the extension in reaction time, monatomic load capacity is significantly improved, and
Gradually form cluster.
It is measured in embodiment 4 by inductively-coupled plasma spectrometer in 0.1mmol/L, 0.5mmol/L, 1mmol/L
Platinum acid chloride solution obtained in three kinds of monatomic-VS of Pt2The mass fraction difference of Pt atom in nanometer sheet composite catalyzing material
It is 0.13%, 0.36%, 0.78%.
Comparative example 1:Pt nano particle/VS2The preparation of catalysis material
VS will be grown2The carbon paper of nanometer sheet is immersed in 10mL, in the platinum acid chloride solution of 5mmol/L, 10mmol/L, is placed in
Intensity is 100mW cm-2Xenon source under irradiate 1h.When irradiation time is more than half, overturning carbon paper surface completes the anti-of the other side
It answers.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, Pt nano particle/VS can be obtained2Nanometer sheet
Composite catalyzing material.
Figure 10 is the Pt nano particle-VS of 10mmol/L platinum acid chloride solution preparation in comparative example 12Nanometer sheet catalysis material
Condenser spherical aberration Electronic Speculum dark field plot shows that Pt atom can grow into particle under high concentration.
To different shape Pt/VS prepared in embodiment 4 and comparative example 12Catalysis material carries out electrocatalytic hydrogen evolution test.
All electro-chemical tests are tested using three-electrode system as test system using electrochemical workstation (CHI660b).With
The sulfuric acid of 0.5M is as electrolyte, and saturated calomel electrode is as reference electrode, high pure graphite electrode (99.9995%, Alfa
Aesar) as to electrode, prepared is loaded with Pt/VS2The carbon paper of catalysis material constructs test body directly as working electrode
System.It with the measurement of 5mV/s swept speed and carry out polarization curve, and is the electricity relative to reversible hydrogen electrode by all voltage corrections
Pressure.
As a result referring to Figure 11 and Figure 12.Figure 11 is the Pt/VS of the different shape prepared under different chloroplatinic acid concentration2It is catalyzed material
The polarization curve of material, Figure 12 are corresponding Pt activity curve.As seen from Figure 11,0,0.1,0.5,1,5,10mmol/L
The Pt/VS prepared under chloroplatinic acid concentration2The electrocatalytic hydrogen evolution activity of catalysis material is respectively 10mA/cm2Current density descended electricity
Position is 257mV, 122mV, 94mV, 77mV, 74mV, 72mV.That is, with the introducing of Pt atom, VS2Electrocatalytic hydrogen evolution activity it is bright
Aobvious enhancing, and with the increase of chloroplatinic acid concentration, catalytic activity is gradually increased, but when chloroplatinic acid concentration is higher than 1mmol/L due to
Pt seed activity is generated no longer to increase.As seen from Figure 12 0,0.1,0.5,1,5, under the chloroplatinic acid concentration of 10mmol/L
The Pt/VS of preparation2The Pt unit mass activity of catalysis material be respectively 200mV overpotential under 16.4A/mgPt、9.2A/mgPt、
5.6A/mgPt、2.0A/mgPt、1.2A/mgPt, that is, with the increase of chloroplatinic acid concentration, the utilization rate of Pt atom is gradually decreased, chlorine
Pt/VS when platinic acid concentration is lower than 1mmol/L2The Pt unit mass activity of catalysis material is much higher than 20%Pt/C electrode.In conjunction with urging
Change Hydrogen Evolution Performance and Pt atom utilization, Pt/VS obtained under 1mmol/L chloroplatinic acid concentration2Catalysis material comprehensive performance is optimal,
It is low in cost while realizing efficient catalytic Hydrogen Evolution Performance, it is easy to large-scale production and application.
To the Pt/VS prepared in the platinum acid chloride solution of 1mmol/L in embodiment 42Catalysis material carries out stability test:
With the test and -0.1V perseverance sweeping speed and carry out 5000 cyclic voltammetry curves (CV) of 20mV/s in the range of -0.6~0.05V
The testing current of pressure.As a result referring to Figure 13.It can be seen that polarization curve does not occur obviously to deviate after 5000 circulations；
Meanwhile electric current does not occur obviously to decay yet after 12h under -0.1V constant pressure.Show that the material still has height after multiple catalysis reaction
Catalytic activity, it is reusable.
Embodiment 5:Au is monatomic/VS2The preparation of catalysis material
Grow VS2The preparation of the carbon paper of nanometer sheet: with embodiment 1.
VS will be grown21cm × 2cm carbon paper of nanometer sheet is immersed in the chlorauric acid solution of 10mL, 0.5mmol/L, is set
In intensity be 100mW cm-2Xenon source under irradiate 0.5h.When irradiation time is more than half, overturning carbon paper surface completes the other side
Reaction.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, the monatomic-VS of Au can be obtained2Nanometer sheet
Composite catalyzing material.
Figure 14 be the Au that is generated under 0.5mmol/L gold chloride concentration, xenon source in embodiment 5 it is monatomic/VS2It is catalyzed material
The condenser spherical aberration Electronic Speculum dark field plot of material, bright spot represent Au atom, intuitively show VS2Surface A u atom is successfully introduced into.
Embodiment 6:Pd is monatomic/VS2The preparation of catalysis material
Grow VS2The preparation of the carbon paper of nanometer sheet: with embodiment 1.
VS will be grown21cm × 2cm carbon paper of nanometer sheet is immersed in the chlorine palladium acid sodium solution of 10mL, 0.5mmol/L,
Being placed in intensity is 100mW cm-2Xenon source under irradiate 0.5h.When irradiation time is more than half, overturning carbon paper surface completes the other side
Reaction.Carbon paper is taken out after reaction, is cleaned multiple times with water and ethyl alcohol, it is dry, the monatomic-VS of Pd can be obtained2Nanometer
Piece composite catalyzing material.
Figure 15 be the Pd that is generated under 0.5mmol/L chlorine palladium acid na concn, xenon source in embodiment 6 it is monatomic/VS2Catalysis
The condenser spherical aberration Electronic Speculum dark field plot of material, bright spot represent Pd atom, intuitively show VS2Surface Pd atom is successfully introduced into.
More than, embodiments of the present invention are illustrated.It should be understood that example as described herein and embodiment are only
In order to illustrate being not intended to restrict the invention, those skilled in the art can make various modifications or variation according to it, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (9)
1. a kind of extremely easy method for preparing the monatomic catalyst of noble metal, which comprises the steps of:
(1) by Transition-metal dichalcogenide nano material with containing noble metal acid or salting liquid mix；
(2) mixed solution in step (1) is placed under light source and irradiates a period of time, then by Transition-metal dichalcogenide nanometer
Material separates with solution, dries the monatomic catalyst of noble metal can be obtained, and the monatomic catalyst of noble metal is noble metal
The monatomic composite material in conjunction with Transition-metal dichalcogenide nano material.
2. the method as described in claim 1, which is characterized in that the monatomic noble metal includes Pt, Au, Ag, Pd, Ru, Ir
At least one of.
3. method according to claim 1 or 2, which is characterized in that in step (1), the Transition-metal dichalcogenide is received
Rice material is at least one of transient metal sulfide, transition metal selenides；The Transition-metal dichalcogenide nanometer
The pattern of material is nanometer sheet, nano wire, nanometer rods or nano-cluster, preferably nanometer sheet.
4. method as claimed in any one of claims 1-3, which is characterized in that in step (1), the acid containing noble metal or
Salt is at least one of chloroplatinic acid, gold chloride, silver nitrate, chlorine palladium acid sodium, palladium chloride.
5. such as method of any of claims 1-4, which is characterized in that in step (1), the acid containing noble metal or
Precious metal atom molar concentration is the mmol/L of 0.01 mmol/L~1, the preferably mmol/ of 0.1 mmol/L~0.5 in salting liquid
L。
6. method according to any one of claims 1 to 5, which is characterized in that in step (1), the transition metal sulfur family
Close object nano material with containing noble metal acid or salting liquid mass ratio be 1:1000~1:20, preferably 1:500~1:50, into one
Step is preferably 1:200~1:100.
7. such as method of any of claims 1-6, which is characterized in that in step (2), the light source is xenon lamp
At least one of source, natural sunlight.
8. such as method of any of claims 1-7, which is characterized in that in step (2), the intensity of light source is 50
mW/cm2~200 mW/cm2, preferably 100 mW/cm2；Irradiation time is the h of 0.5 h~2, preferably 1 h.
9. such as method of any of claims 1-8, which is characterized in that described to cross metal chalcogenide compound nano material
It is grown in conductive substrates, it is preferable that the conductive substrates are carbon fiber.
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| CN111111738A (en) * | 2020-01-16 | 2020-05-08 | 佛山科学技术学院 | Composite photocatalytic material and preparation method thereof |
| CN111111738B (en) * | 2020-01-16 | 2022-06-28 | 佛山科学技术学院 | Composite photocatalytic material and preparation method thereof |
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| CN113617367B (en) * | 2020-05-06 | 2023-06-06 | 中国科学院城市环境研究所 | Noble metal ruthenium monoatomic supported catalyst and preparation method and application thereof |
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| CN112264047A (en) * | 2020-11-13 | 2021-01-26 | 中国科学技术大学 | Noble metal monoatomic catalyst for electrolyzing water to generate oxygen and preparation method and application thereof |
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| CN114018988A (en) * | 2021-10-28 | 2022-02-08 | 南京大学 | Two-dimensional thin-layer material gas sensor, and preparation method and application thereof |
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| CN114772643A (en) * | 2022-04-27 | 2022-07-22 | 广东省科学院生物与医学工程研究所 | Composite nano material and preparation method and application thereof |
| CN114772643B (en) * | 2022-04-27 | 2024-03-29 | 广东省科学院生物与医学工程研究所 | Composite nano material and preparation method and application thereof |
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