CN107890866A - A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition - Google Patents
A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition Download PDFInfo
- Publication number
- CN107890866A CN107890866A CN201711334968.8A CN201711334968A CN107890866A CN 107890866 A CN107890866 A CN 107890866A CN 201711334968 A CN201711334968 A CN 201711334968A CN 107890866 A CN107890866 A CN 107890866A
- Authority
- CN
- China
- Prior art keywords
- platinum catalyst
- electrode
- hydantoin derivatives
- complexant
- carbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000001469 hydantoins Chemical class 0.000 title claims abstract description 43
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 title claims abstract description 36
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims description 63
- 239000000654 additive Substances 0.000 claims description 38
- 230000000996 additive effect Effects 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 27
- 229920000557 Nafion® Polymers 0.000 claims description 18
- 238000001548 drop coating Methods 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002659 electrodeposit Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 6
- IAIWVQXQOWNYOU-FPYGCLRLSA-N nitrofural Chemical compound NC(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 IAIWVQXQOWNYOU-FPYGCLRLSA-N 0.000 claims description 6
- 229960001907 nitrofurazone Drugs 0.000 claims description 6
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 235000010241 potassium sorbate Nutrition 0.000 claims description 5
- 239000004302 potassium sorbate Substances 0.000 claims description 5
- 229940069338 potassium sorbate Drugs 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- WSDISUOETYTPRL-UHFFFAOYSA-N dmdm hydantoin Chemical compound CC1(C)N(CO)C(=O)N(CO)C1=O WSDISUOETYTPRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 2
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 230000010287 polarization Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 150000007945 N-acyl ureas Chemical class 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/23—
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Abstract
A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition, it is related to a kind of method for preparing platinum catalyst.The problem of larger the invention aims to solve the platinum catalyst particle diameter of existing method preparation, the utilization rate of the platinum catalyst of big particle diameter is low, and catalytic performance is low and catalysis cost is high.Method：First, yellow transparent solution is prepared；2nd, coat, obtain the glass-carbon electrode of surface coating carbon material；3rd, electro-deposition, platinum catalyst is obtained in working electrode surface.The present invention is 3nm or so in the average grain diameter that working electrode surface obtains platinum catalyst, and the particle diameter of platinum catalyst is smaller, and surface area is bigger, exposed avtive spot is also more, cost is reduced when being improved, and then being catalyzed so as to the catalytic performance of platinum catalyst, it is of far-reaching significance.The present invention can obtain a kind of platinum catalyst.
Description
Technical field
The present invention relates to a kind of method for preparing platinum catalyst.
Background technology
In the last few years, platinum catalyst had been developed as the most potential catalyst of commercial, and it is applied also very
Extensively：Such as oxygen reduction reaction, the oxidation reaction of alcohols and acids, oxygen evolution reaction, hydroxide reaction even some petrochemical industries
In organic reaction etc..But because platinum is noble metal, and scarcity of resources, cost is of a relatively high, how to prepare high performance platinum
Catalyst, its utilization rate is improved, reduce the problem of cost is paid close attention to the most as platinum catalyst preparation field.Wherein, electrodeposition process
Due to having the characteristics that green, the simple and convenient preparation for being usually used in platinum catalyst.
At present, electrodeposition process prepares platinum catalyst and typically uses simple salt system, and plating solution is mainly by chloroplatinic acid or chloroplatinic acid
Potassium, sulfuric acid composition.And often particle diameter is larger for platinum catalyst prepared by simple salt system, particle diameter is about more than 50nm, and it is utilized
Rate substantially reduces, it is difficult to plays efficient catalytic performance, and improves cost.
The content of the invention
It is larger the invention aims to solve the platinum catalyst particle diameter of existing method preparation, the platinum catalyst of big particle diameter
The problem of utilization rate is low, and catalytic performance is low and catalysis cost is high, and it is heavy as complexant electricity using hydantoin derivatives to provide one kind
The method that product prepares platinum catalyst.
A kind of method using hydantoins and its derivative as complexant preparing platinum catalyst by electrodeposition, specifically by following
What step was completed：
First, by hydantoin derivatives and additive be added to 2mmol/L~4mmol/L chloroplatinic acid or 2mmol/L~
In 4mmol/L potassium chloroplatinate solution, it is well mixed, obtains electroplate liquid；Concentration is that 1.5g/L~5g/L potassium carbonate is molten
Liquid adjusts the pH value of electroplate liquid to 9.5~10, obtains yellow transparent solution；
The mol ratio of hydantoin derivatives and chloroplatinic acid is (1~6) in electroplate liquid described in step 1:1 or second in
The mol ratio of ureide derivative and potassium chloroplatinate is (1~6):1；
Additive described in step 1 is lauric acid amide of ethanol, anthraquinone-2-sodium, 1- NADs, 1,2-
One or more of mixtures in methylimidazole, nitrofurazone, acrylic urea, potassium sorbate and FAS；
The concentration of additive is 1g/L~8g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be (4mg~6mg):1mL；
Step 2 1. described in carbon material be CNT, VulcanXC-72, graphene and Ketjen black in one kind or
Wherein several mixtures；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, deposited under being -1V~-0.5V in room temperature and deposition potential
10s~300s, platinum catalyst is obtained in working electrode surface.
The principle and advantage of the present invention：
First, hydantoin derivatives are contained in electrodeposit liquid of the present invention, hydantoin derivatives are complexant, in metal electricity
In deposition process, the addition of complexant enables to the metal ion in solution to form more stable complex ion with complexant,
Increase the cathodic polarization potential of solution, nucleus nucleation rate is more than its growth rate, and then refined crystal grain, effectively reduce
The particle diameter of catalyst；
2nd, the present invention is 3nm or so, the particle diameter of platinum catalyst in the average grain diameter that working electrode surface obtains platinum catalyst
Smaller, surface area is bigger, and exposed avtive spot is also more, is improved so as to the catalytic performance of platinum catalyst, and then is catalyzed
When reduce cost, it is of far-reaching significance.
The present invention can obtain a kind of platinum catalyst.
Brief description of the drawings
Fig. 1 is the cathodic polarization curve of electroplate liquid, and 1 is the yellow transparent solution obtained in the step 1 of embodiment one in Fig. 1
Cathodic polarization curve, 2 be the cathodic polarization curve of yellow transparent solution obtained in the step 1 of comparative example one, and 3 are
The cathodic polarization curve of 3mmol/L chloroplatinic acid；
Fig. 2 is the SEM figures of platinum catalyst prepared by comparative example two；
Fig. 3 is the SEM figures of platinum catalyst prepared by embodiment two；
Fig. 4 is the TEM figures of platinum catalyst prepared by embodiment three；
Fig. 5 is the particle diameter distribution statistical chart of platinum catalyst prepared by embodiment three；
Fig. 6 is 0.1mol/L HClO of the platinum catalyst in oxygen saturation4The linear scan of hydrogen reduction performance in solution is bent
Line, 1 is 0.1mol/L HClO of the platinum catalyst for preparing of example IV in oxygen saturation in Fig. 64Hydrogen reduction performance in solution
Linear scan curve, 2 be comparative example two prepare platinum catalyst oxygen saturation 0.1mol/L HClO4In solution
Hydrogen reduction performance linear scan curve.
Embodiment
Embodiment one：Present embodiment is a kind of using hydantoins and its derivative as complexant electro-deposition preparation
The method of platinum catalyst, is specifically realized by the following steps：
First, by hydantoin derivatives and additive be added to 2mmol/L~4mmol/L chloroplatinic acid or 2mmol/L~
In 4mmol/L potassium chloroplatinate solution, it is well mixed, obtains electroplate liquid；Concentration is that 1.5g/L~5g/L potassium carbonate is molten
Liquid adjusts the pH value of electroplate liquid to 9.5~10, obtains yellow transparent solution；
The mol ratio of hydantoin derivatives and chloroplatinic acid is (1~6) in electroplate liquid described in step 1:1 or second in
The mol ratio of ureide derivative and potassium chloroplatinate is (1~6):1；
Additive described in step 1 is lauric acid amide of ethanol, anthraquinone-2-sodium, 1- NADs, 1,2-
One or more of mixtures in methylimidazole, nitrofurazone, acrylic urea, potassium sorbate and FAS；
The concentration of additive is 1g/L~8g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be (4mg~6mg):1mL；
Step 2 1. described in carbon material be CNT, VulcanXC-72, graphene and Ketjen black in one kind or
Wherein several mixtures；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, deposited under being -1V~-0.5V in room temperature and deposition potential
10s~300s, platinum catalyst is obtained in working electrode surface.
The principle and advantage of present embodiment：
First, hydantoin derivatives are contained in present embodiment electrodeposit liquid, hydantoin derivatives are complexant, in gold
Belong in electrodeposition process, additions of complexant enable to metal ion in solution and complexant formed it is more stable with from
Son, increase the cathodic polarization potential of solution, nucleus nucleation rate is more than its growth rate, and then refined crystal grain, effectively
Reduce the particle diameter of catalyst；
2nd, present embodiment is 3nm or so in the average grain diameter that working electrode surface obtains platinum catalyst, platinum catalyst
Particle diameter is smaller, and surface area is bigger, and exposed avtive spot is also more, is improved so as to the catalytic performance of platinum catalyst, and then
Cost is reduced during catalysis, it is of far-reaching significance.
Present embodiment can obtain a kind of platinum catalyst.
Embodiment two：Present embodiment is with the difference of embodiment one：In second described in step 1
Ureide derivative is 5,5- dimethyl hydantoins, the bromo- 5,5- dimethyl hydantoins of 1,3- bis-, 1,3- dihydroxymethyls -5,5-
Dimethyl hydantoin and one kind in 5,5- diphenyl hydantoins or wherein several mixtures.Other steps and specific reality
It is identical to apply mode one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Will in step 1
Hydantoin derivatives and additive are added to 2mmol/L~3mmol/L chloroplatinic acid or 2mmol/L~3mmol/L chlorine platinum
In sour potassium solution, it is well mixed, obtains electroplate liquid；Concentration is 3g/L~5g/L solution of potassium carbonate by the pH value of electroplate liquid
Regulation obtains yellow transparent solution to 9.5~10.Other steps are identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Institute in step 1
The mol ratio of hydantoin derivatives and chloroplatinic acid is (1~4) in the electroplate liquid stated:1 or hydantoin derivatives and chloroplatinic acid
The mol ratio of potassium is (1~4):1.Other steps are identical with embodiment one to three.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Institute in step 1
The mol ratio of hydantoin derivatives and chloroplatinic acid is (3~6) in the electroplate liquid stated:1 or hydantoin derivatives and chloroplatinic acid
The mol ratio of potassium is (3~6):1.Other steps are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Institute in step 1
The concentration of additive is 1g/L~4g/L in the electroplate liquid stated.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Institute in step 1
The concentration of additive is 5g/L~8g/L in the electroplate liquid stated.Other steps are identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Step 2 1. in
The quality of described carbon material and the volume ratio of solvent are (5mg~6mg):1mL.Other steps and embodiment one to seven
It is identical.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：In step 3 with
Saturated calomel electrode is reference electrode, and platinized platinum is that the glass-carbon electrode of surface coating carbon material is working electrode, with step to electrode
One obtained yellow transparent solution is electrodeposit liquid, and 10s~150s is deposited under being -1V~-0.8V in room temperature and deposition potential,
Working electrode surface obtains platinum catalyst.Other steps are identical with embodiment one to eight.
Embodiment ten：Present embodiment is with one of embodiment one to nine difference：In step 3 with
Saturated calomel electrode is reference electrode, and platinized platinum is that the glass-carbon electrode of surface coating carbon material is working electrode, with step to electrode
One obtained yellow transparent solution is electrodeposit liquid, and 200s~240s is deposited under being -1V~-0.9V in room temperature and deposition potential,
Platinum catalyst is obtained in working electrode surface.Other steps are identical with embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of method using hydantoins and its derivative as complexant preparing platinum catalyst by electrodeposition, tool
Body is completed according to the following steps：
First, 5,5- dimethyl hydantoins and additive are added in 3mmol/L chloroplatinic acid, are well mixed, obtain
Electroplate liquid；Concentration is that 5g/L solution of potassium carbonate adjusts the pH value of electroplate liquid to 10, obtains yellow transparent solution；
The mol ratio of 5,5- dimethyl hydantoins and chloroplatinic acid described in step 1 is 6:1；
Additive described in step 1 is the mixture of lauric acid amide of ethanol, 1- NADs and nitrofurazone；
The mass ratio of lauric acid amide of ethanol, 1- NADs and nitrofurazone is 2 in described additive:1:1；
The concentration of additive is 5g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be Ketjen black；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, 180s is deposited under being -0.9V in room temperature and deposition potential,
Platinum catalyst is obtained in working electrode surface.
Embodiment two：A kind of method using hydantoins and its derivative as complexant preparing platinum catalyst by electrodeposition, tool
Body is completed according to the following steps：
First, DBDMH and additive are added in 3mmol/L chloroplatinic acid, mixed
Uniformly, electroplate liquid is obtained；Concentration is that 4g/L solution of potassium carbonate adjusts the pH value of electroplate liquid to 10, obtains yellow transparent
Solution；
The mol ratio of the bromo- 5,5- dimethyl hydantoins of 1,3- bis- and chloroplatinic acid is 3 in electroplate liquid described in step 1:
1；
Additive described in step 1 is the mixture of anthraquinone-2-sodium, DMIZ 1,2 dimethylimidazole and acrylic urea；
The mass ratio of anthraquinone-2-sodium, DMIZ 1,2 dimethylimidazole and acrylic urea is 1 in described additive:2:2；
The concentration of additive is 5g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be CNT；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, 240s is deposited under being -1V in room temperature and deposition potential,
Working electrode surface obtains platinum catalyst.
Embodiment three：A kind of method using hydantoins and its derivative as complexant preparing platinum catalyst by electrodeposition, tool
Body is completed according to the following steps：
First, 1,3- dihydroxymethyls -5,5- dimethyl hydantoin and additive are added in 3mmol/L chloroplatinic acid,
It is well mixed, obtain electroplate liquid；Concentration is that 3g/L solution of potassium carbonate adjusts the pH value of electroplate liquid to 10, obtains yellow
Clear solution；
The mol ratio of DMDMH and chloroplatinic acid in electroplate liquid described in step 1
For 1:1；
Additive described in step 1 is lauric acid amide of ethanol, 1- NADs, DMIZ 1,2 dimethylimidazole and mountain
Potassium sorbate；Lauric acid amide of ethanol in described additive, 1- NADs, the matter of DMIZ 1,2 dimethylimidazole and potassium sorbate
Amount is than being 1:2:1:1；
The concentration of additive is 2g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be VulcanXC-72；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, 20s is deposited under being -0.8V in room temperature and deposition potential,
Working electrode surface obtains platinum catalyst.
Example IV：A kind of method using hydantoins and its derivative as complexant preparing platinum catalyst by electrodeposition, tool
Body is completed according to the following steps：
First, 5,5- diphenyl hydantoins and additive are added in 3mmol/L chloroplatinic acid, are well mixed, obtain
Electroplate liquid；Concentration is that 2.5g/L solution of potassium carbonate adjusts the pH value of electroplate liquid to 10, obtains yellow transparent solution；
The mol ratio of hydantoin derivatives and chloroplatinic acid is 1 in electroplate liquid described in step 1:1；
Additive described in step 1 is the mixing in 1- NADs, DMIZ 1,2 dimethylimidazole and FAS
Thing；The mass ratio of 1- NADs, DMIZ 1,2 dimethylimidazole and FAS is 1 in described additive:2:1；
The concentration of additive is 4g/L in electroplate liquid described in step 1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be graphene；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, 300s is deposited under being -0.7V in room temperature and deposition potential,
Platinum catalyst is obtained in working electrode surface.
Comparative example one：The method that unused additive prepares platinum catalyst, is specifically realized by the following steps：
First, 5,5- dimethyl hydantoins are added in 3mmol/L chloroplatinic acid, are well mixed, obtain electroplate liquid；Make
The pH value of electroplate liquid is adjusted to 10 with the solution of potassium carbonate that concentration is 5g/L, obtains yellow transparent solution；
The mol ratio of 5,5- dimethyl hydantoins and chloroplatinic acid described in step 1 is 6:1；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be Ketjen black；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the yellow transparent solution that step 1 obtains as electrodeposit liquid, 180s is deposited under being -0.9V in room temperature and deposition potential,
Platinum catalyst is obtained in working electrode surface.
Comparative example two：The method that complexant and additive prepare platinum catalyst is not used, specifically according to the following steps
Complete：
First, using 3mmol/L chloroplatinic acid as electrodeposit liquid；
2nd, coat：
1., carbon material is dissolved into solvent, obtain slurry；
Step 2 1. described in the quality of carbon material and the volume ratio of solvent be 5mg:1mL；
Step 2 1. described in carbon material be Ketjen black；
Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent,
The volume ratio of water and 5%Nafion solution is 14:10:1；
2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glass-carbon electrode
The uniform μ L slurries of drop coating 6 in surface, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；
3rd, electro-deposition：
Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is work to electrode
Electrode, using the chloroplatinic acid of 3mmol/L in step 1 as electrodeposit liquid, 180s is deposited under being -0.9V in room temperature and deposition potential,
Working electrode surface obtains platinum catalyst.
Using a diameter of 3mm glass-carbon electrode as working electrode, platinum filament is reference electrode, and platinized platinum is to electrode, is used
CHI760E electrochemical workstations to obtained in the step 1 of embodiment one yellow transparent solution, in the step 1 of comparative example one
Obtained yellow transparent solution and 3mmol/L chloroplatinic acid carry out cathodic polarization test, and sweep speed is 10mV/s during test,
As shown in Figure 1；
Fig. 1 is the cathodic polarization curve of electroplate liquid, and 1 is the yellow transparent solution obtained in the step 1 of embodiment one in Fig. 1
Cathodic polarization curve, 2 be the cathodic polarization curve of yellow transparent solution obtained in the step 1 of comparative example one, and 3 are
The cathodic polarization curve of 3mmol/L chloroplatinic acid；
As seen from Figure 1,5,5- dimethyl hydantoins (complexant) and additive (coconut oil diethanol acyl be with the addition of
The mixture of amine, 1- NADs and nitrofurazone) the step 1 of embodiment one in the obtained negative electrode pole of yellow transparent solution
The negative shifting of electrochemical potential is the most obvious, next to that 5 are only added, the step 1 of comparative example one of 5- dimethyl hydantoins (complexant)
In obtained yellow transparent solution, this explanation complexant exists with additive to act synergistically, when in electrodeposit liquid complexant with adding
In the presence of adding agent common, platinum cathode overpotential in electrodeposition process is maximum, and larger cathode overpotential can make the nucleation of nucleus
Speed is more than its growth rate, therefore can reduce the particle diameter of platinum, increases avtive spot, is advantageous to prepared platinum catalyst
Catalytic performance raising.
Fig. 2 is the SEM figures of platinum catalyst prepared by comparative example two；
Fig. 3 is the SEM figures of platinum catalyst prepared by embodiment two；
It was found from Fig. 2 and Fig. 3, platinum catalyst particle diameter prepared by complexant and additive is with the addition of in embodiment two and is substantially subtracted
It is small.
Fig. 4 is the TEM figures of platinum catalyst prepared by embodiment three；
Fig. 5 is the particle diameter distribution statistical chart of platinum catalyst prepared by embodiment three；
It was found from Fig. 4 and Fig. 5, the particle size dispersion of platinum catalyst prepared by embodiment three is uniform, and particle diameter is smaller, average out to
3.09nm。
Using a diameter of 5mm glass-carbon electrode as working electrode, using saturated calomel electrode as reference electrode, using platinized platinum as pair
Electrode, the platinum catalyst and comparative example two prepared at room temperature to example IV using rotating disk electrode (r.d.e) test device are made
Standby platinum catalyst progress hydrogen reduction performance test, sweep speed 10mV/s, as shown in Figure 6；
Fig. 6 is 0.1mol/L HClO of the platinum catalyst in oxygen saturation4The linear scan of hydrogen reduction performance in solution is bent
Line, 1 is 0.1mol/L HClO of the platinum catalyst for preparing of example IV in oxygen saturation in Fig. 64Hydrogen reduction performance in solution
Linear scan curve, 2 be comparative example two prepare platinum catalyst oxygen saturation 0.1mol/L HClO4In solution
Hydrogen reduction performance linear scan curve.
It will be evident that with the addition of the oxygen for the platinum catalyst that complexant is prepared with additive in example IV also from Fig. 6
Former take-off potential is substantially corrected with half wave potential, and obvious electric current platform be present, and limiting current density is also larger, shows it
Hydrogen reduction catalytic performance is better than to be not added with being coordinated platinum catalyst prepared by agent addition agent in comparative example two；Add in example IV
The hydrogen reduction take-off potential of complexant and the platinum catalyst of additive preparation is added about in 0.61V (vs.SCE), half wave potential
About it is not added with being coordinated the hydrogen reduction starting of platinum catalyst prepared by agent addition agent in 0.5V (vs.SCE), comparative example two
Current potential about about with the addition of complexant with adding in 0.5V (vs.SCE), half wave potential in 0.27V (vs.SCE), example IV
Platinum catalyst either hydrogen reduction take-off potential or the half wave potential for adding agent to prepare are corrected, and show that its catalytic performance is more preferable.
Claims (10)
- A kind of 1. method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition, it is characterised in that one kind is with second Interior uride and its derivative are specifically realized by the following steps for the method for complexant preparing platinum catalyst by electrodeposition：First, by hydantoin derivatives and additive be added to 2mmol/L~4mmol/L chloroplatinic acid or 2mmol/L~ In 4mmol/L potassium chloroplatinate solution, it is well mixed, obtains electroplate liquid；Concentration is that 1.5g/L~5g/L potassium carbonate is molten Liquid adjusts the pH value of electroplate liquid to 9.5~10, obtains yellow transparent solution；The mol ratio of hydantoin derivatives and chloroplatinic acid is (1~6) in electroplate liquid described in step 1:1 or hydantoins The mol ratio of derivative and potassium chloroplatinate is (1~6):1；Additive described in step 1 is lauric acid amide of ethanol, anthraquinone-2-sodium, 1- NADs, 1,2- diformazans One or more of mixtures in base imidazoles, nitrofurazone, acrylic urea, potassium sorbate and FAS；The concentration of additive is 1g/L~8g/L in electroplate liquid described in step 1；2nd, coat：1., carbon material is dissolved into solvent, obtain slurry；Step 2 1. described in the quality of carbon material and the volume ratio of solvent be (4mg~6mg):1mL；Step 2 1. described in carbon material be one kind or wherein in CNT, VulcanXC-72, graphene and Ketjen black Several mixtures；Step 2 1. described in solvent be isopropanol, water and 5%Nafion solution mixed liquor, isopropanol in solvent, water with The volume ratio of 5%Nafion solution is 14:10:1；2., by the glassy carbon electrode surface of the 6 uniform drop coatings of μ L slurries to a diameter of 5mm, then naturally dry, then in glassy carbon electrode surface The uniform μ L slurries of drop coating 6, standing are dried, and obtain the glass-carbon electrode of surface coating carbon material；3rd, electro-deposition：Using saturated calomel electrode as reference electrode, platinized platinum is that the glass-carbon electrode of surface coating carbon material is working electrode to electrode, Using the yellow transparent solution that step 1 obtains as electrodeposit liquid, deposited in the case where room temperature and deposition potential are -1V~-0.5V 10s~ 300s, platinum catalyst is obtained in working electrode surface.
- A kind of 2. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that the hydantoin derivatives described in step 1 are 5,5- dimethyl hydantoins, bromo- 5, the 5- bis- of 1,3- bis- Methyl hydantoin, DMDMH and one kind in 5,5- diphenyl hydantoins or its In several mixture.
- A kind of 3. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that in step 1 by hydantoin derivatives and additive be added to 2mmol/L~3mmol/L chloroplatinic acid or In 2mmol/L~3mmol/L potassium chloroplatinate solution, it is well mixed, obtains electroplate liquid；Concentration is 3g/L~5g/L carbon Sour potassium solution adjusts the pH value of electroplate liquid to 9.5~10, obtains yellow transparent solution.
- A kind of 4. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that the mol ratio of hydantoin derivatives and chloroplatinic acid is (1~4) in the electroplate liquid described in step 1:1 or The mol ratio of hydantoin derivatives and potassium chloroplatinate is (1~4):1.
- A kind of 5. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that the mol ratio of hydantoin derivatives and chloroplatinic acid is (3~6) in the electroplate liquid described in step 1:1 or The mol ratio of hydantoin derivatives and potassium chloroplatinate is (3~6):1.
- A kind of 6. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that the concentration of additive is 1g/L~4g/L in the electroplate liquid described in step 1.
- A kind of 7. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that the concentration of additive is 5g/L~8g/L in the electroplate liquid described in step 1.
- A kind of 8. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that step 2 1. described in the quality of carbon material and the volume ratio of solvent be (5mg~6mg):1mL.
- A kind of 9. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that using saturated calomel electrode as reference electrode in step 3, platinized platinum is to coat the glass of carbon material to electrode, surface Carbon electrode is working electrode, is -1V in room temperature and deposition potential using the yellow transparent solution that step 1 obtains as electrodeposit liquid 10s~150s is deposited under~-0.8V, platinum catalyst is obtained in working electrode surface.
- A kind of 10. side using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition according to claim 1 Method, it is characterised in that using saturated calomel electrode as reference electrode in step 3, platinized platinum is to coat the glass of carbon material to electrode, surface Carbon electrode is working electrode, is -1V in room temperature and deposition potential using the yellow transparent solution that step 1 obtains as electrodeposit liquid 200s~240s is deposited under~-0.9V, platinum catalyst is obtained in working electrode surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711334968.8A CN107890866B (en) | 2017-12-13 | 2017-12-13 | Method for preparing platinum catalyst by electrodeposition with hydantoin derivative as complexing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711334968.8A CN107890866B (en) | 2017-12-13 | 2017-12-13 | Method for preparing platinum catalyst by electrodeposition with hydantoin derivative as complexing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107890866A true CN107890866A (en) | 2018-04-10 |
| CN107890866B CN107890866B (en) | 2020-07-31 |
Family
ID=61807812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711334968.8A Active CN107890866B (en) | 2017-12-13 | 2017-12-13 | Method for preparing platinum catalyst by electrodeposition with hydantoin derivative as complexing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107890866B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| CN101906649A (en) * | 2010-08-11 | 2010-12-08 | 哈尔滨工业大学 | Cyanogens-free gold plating solution and method for plating gold by adopting same |
| TW201137185A (en) * | 2010-03-12 | 2011-11-01 | Univ Leuven Kath | Liquid metal salts |
| CN103556190A (en) * | 2013-10-29 | 2014-02-05 | 常熟市伟达电镀有限责任公司 | Cost-saving electroplating solution |
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
| CN103913496A (en) * | 2014-02-28 | 2014-07-09 | 汕头大学 | Preparation method and application of modified glassy carbon electrode |
| CN105350037A (en) * | 2015-12-17 | 2016-02-24 | 宏正（福建）化学品有限公司 | Alkaline non-cyanide zinc plating nickel alloy plating solution and electroplating process thereof |
-
2017
- 2017-12-13 CN CN201711334968.8A patent/CN107890866B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259410A (en) * | 2008-04-14 | 2008-09-10 | 北京科技大学 | Method for preparing platinum catalyst by electrodeposition |
| TW201137185A (en) * | 2010-03-12 | 2011-11-01 | Univ Leuven Kath | Liquid metal salts |
| CN101906649A (en) * | 2010-08-11 | 2010-12-08 | 哈尔滨工业大学 | Cyanogens-free gold plating solution and method for plating gold by adopting same |
| CN103556190A (en) * | 2013-10-29 | 2014-02-05 | 常熟市伟达电镀有限责任公司 | Cost-saving electroplating solution |
| CN103741180A (en) * | 2014-01-10 | 2014-04-23 | 哈尔滨工业大学 | Cyanide-free bright electrogilding additive and application thereof |
| CN103913496A (en) * | 2014-02-28 | 2014-07-09 | 汕头大学 | Preparation method and application of modified glassy carbon electrode |
| CN105350037A (en) * | 2015-12-17 | 2016-02-24 | 宏正（福建）化学品有限公司 | Alkaline non-cyanide zinc plating nickel alloy plating solution and electroplating process thereof |
Non-Patent Citations (3)
| Title |
|---|
| A.A. MIKHAYLOVA ET AL.: ""Electrocatalytic and adsorption properties of platinum microparticles electrodeposited onto glassy carbon and into Nafion® films"", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| 穆劲: "《高等无机化学》", 31 July 2007 * |
| 罗龚等: ""乙内酰脲类化合物在无氰电镀中的应用"", 《电镀与涂饰》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107890866B (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Self-growing Cu/Sn bimetallic electrocatalysts on nitrogen-doped porous carbon cloth with 3D-hierarchical honeycomb structure for highly active carbon dioxide reduction | |
| CN111501060B (en) | Copper-doped bismuth bimetallic material and preparation and application thereof | |
| CN109686990B (en) | Preparation method and application of Ni-Zn/nitrogen-sulfur double-doped three-dimensional graphene electrode material | |
| CN102088091A (en) | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof | |
| CN108554426B (en) | Difunctional cobalt diselenide material and preparation and application thereof | |
| CN111790415B (en) | B-P co-doped double transition metal catalyst and preparation method and application thereof | |
| CN107321385B (en) | Preparation method of polyethyleneimine functionalized multi-branched nano triangular Pt catalyst | |
| CN106623969A (en) | Method of preparing nanometer nickel-sulfur alloy through replacement deposition of low eutectic ionic liquid | |
| CN108654657B (en) | Nickel-phosphorus-copper electrocatalyst and preparation method thereof | |
| CN106011959A (en) | Electrolytic preparation method for nano reticular nickel-copper alloy through eutectic ionic liquid | |
| CN107308940A (en) | A kind of preparation method of ultra-thin porous Co nanometer sheets | |
| CN103165914B (en) | Pt/Au/PdCo/C catalyst, and preparation and application thereof | |
| Salomé et al. | Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition | |
| CN1958856B (en) | Preparation of electrocatalysis electrode of nano carbon fiber in use for organic electrochemical synthesis process | |
| CN116145193B (en) | Copper-based catalyst for electrocatalytic reduction of nitrate radical into ammonia and preparation method thereof | |
| CN107890866A (en) | A kind of method using hydantoin derivatives as complexant preparing platinum catalyst by electrodeposition | |
| Li et al. | High performance Sn-In cathode for the electrochemical reduction of carbon dioxide to formic acid | |
| CN104034778A (en) | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof | |
| CN115747860A (en) | Oxidation modified cuprous oxide catalyst, preparation method and electrode | |
| CN113235130B (en) | Low-platinum composite material based on tungsten oxide/graphene aerogel and preparation method and application thereof | |
| CN113463119B (en) | Bismuth-based-silver-based composite material and preparation method and application thereof | |
| CN110453256B (en) | Polyhedral cobalt-iridium nanoparticle hydrogen evolution electrocatalyst, plating solution and preparation method thereof | |
| CN114908357A (en) | Method for producing hydrogen by adopting bismuth vanadate photoelectrode | |
| CN111020675B (en) | Preparation method of titanium dioxide nanotube-doped cobalt-tungsten alloy electrodeposition coating | |
| CN114134535A (en) | MoS2-Co3S4NF hydrogen evolution material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231222 Address after: Room 111, 1st Floor, Songbei Park Building, Heilongjiang University of Science and Technology Science Park, No. 2468 Puyuan Road, Songbei District, Harbin City, Heilongjiang Province, 150022 Patentee after: Heilongjiang Yuke Technology Co.,Ltd. Address before: 150022 No. 2468 Puyuan Road, Songbei District, Harbin City, Heilongjiang Province Patentee before: HEILONGJIANG University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right |