CN109126822B - Carbon nanotube-gold copper alloy composite material and preparation method and application thereof - Google Patents
Carbon nanotube-gold copper alloy composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109126822B CN109126822B CN201811115340.3A CN201811115340A CN109126822B CN 109126822 B CN109126822 B CN 109126822B CN 201811115340 A CN201811115340 A CN 201811115340A CN 109126822 B CN109126822 B CN 109126822B
- Authority
- CN
- China
- Prior art keywords
- gold
- copper
- cnts
- carbon nanotube
- copper alloy
- 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.)
- Active
Links
- 239000010931 gold Substances 0.000 title claims abstract description 76
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 116
- 239000010949 copper Substances 0.000 claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 31
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 15
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 59
- 238000007747 plating Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 16
- 238000010306 acid treatment Methods 0.000 claims description 15
- 238000005275 alloying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000003353 gold alloy Substances 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000002071 nanotube Substances 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 229920002873 Polyethylenimine Polymers 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910002708 Au–Cu Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052927 chalcanthite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910015371 AuCu Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble 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
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a carbon nano tube-gold-copper alloy composite material, which consists of CNTs and nano-copper-gold alloy particles on the surface layer of the CNTs, wherein a copper-gold alloy layer consists of the following components in percentage by weight: 5-10 wt% of carbon nano tube, 15-65 wt% of gold and 25-75 wt% of copper. According to the invention, through the CNTs loading, the interaction between gold and copper and a carrier can be improved, the sintering resistance of gold and copper nanoparticles is greatly improved, the high specific surface area of the CNTs and the structure of mutual supporting of nanotubes in the catalyst play a role in isolating and dispersing the gold and copper nanoparticles, the distance between the gold and copper nanoparticles is increased, a certain effect on the sintering resistance of the catalyst is achieved, and the reaction stability of the catalyst is improved; the invention can obtain gold-copper particles with different crystal grain sizes by regulating and controlling process parameters, has high purity, wide particle size range and controllable particle size, and the obtained nano gold-copper alloy particles have good combination with the carbon nano tube interface and the alloy catalytic performance is superior to that of the traditional gold-copper alloy.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a carbon nanotube-gold copper alloy composite material as well as a preparation method and application thereof.
Background
With the wide application of nano-alloy in the field of catalysis, the application of the supported gold nanoparticles as a catalyst and the combination of gold-containing bimetallic catalysts and other metals are hot research. The gold-copper alloy is an alloy prepared from high-purity gold and copper, and the traditional gold-copper alloy material has the defects of weak adsorption capacity, poor single use effect, small specific surface area, easy agglomeration and poor sintering resistance.
The existing preparation method of the gold-copper alloy mainly comprises a template method, an immersion method and an explosion method, has the problems of complex preparation method, high cost, single granularity, serious particle agglomeration during alloying and the like, and the loss of the active surface area caused by the growth of metal particles in the alloying process is the main reason of the inactivation of the supported catalyst; meanwhile, in heterogeneous catalysis, the catalytic process mainly occurs on the surface of the catalyst, and the adsorption capacity of reactants on the surface of the gold-copper alloy is poor, so that the catalytic effect is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon nanotube-gold copper alloy composite material with high purity, uniform plating, large specific surface area, good sintering resistance and high catalytic efficiency, and a preparation method and application thereof.
The invention provides a carbon nanotube-gold copper alloy composite material, which consists of a matrix carbon nanotube and gold copper alloy loaded on the surface of the matrix carbon nanotube, wherein the carbon nanotube-gold copper alloy composite material consists of the following components in percentage by weight: 5-10 wt% of carbon nano tube, 15-65 wt% of gold and 25-75 wt% of copper.
Preferably, the length of the carbon nano tube is 300-1000 nm, the diameter of the carbon nano tube is 20-25 nm, and the particle size of the gold-copper alloy is 20-150 nm.
Further, the gold-copper alloy is obtained by alloying a gold plating layer and a copper plating layer, and the particle size of the gold-copper alloy is 20-50 nm.
The invention also provides a preparation method of the carbon nanotube-gold copper alloy composite material, which comprises the following steps:
(1) acid treatment: putting CNTs (carbon nanotubes) into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment, and cleaning to obtain acid-treated CNTs;
(2) surface gold plating: adding the CNTs subjected to acid treatment obtained in the step (1) into PEI, stirring at normal temperature, controlling the super-vibration frequency, uniformly mixing, adding chloroauric acid, stirring and heating, taking out the CNTs after reacting for a preset time, and cleaning to obtain gold-plated CNTs;
(3) copper plating on the surface: adding the CNTs plated with gold obtained in the step (2) into a copper plating solution, adding bipyridine and PVP, controlling the super-vibration frequency and the temperature, adding glyoxylic acid as a reducing agent, adjusting the PH, determining the reaction process according to the color change of the solution and the generation time of bubbles, taking out the CNTs after the bubbles appear for a certain time, and cleaning to obtain the CNTs plated with gold and copper;
(4) alloying treatment: and (4) adding the CNTs plated with the gold and copper obtained in the step (3) into an isopropanol solution, heating to a preset temperature to alloy a gold and copper plating layer, and washing to obtain the carbon nanotube-gold and copper alloy composite material.
Preferably, in the step (1), the volume ratio of concentrated sulfuric acid to concentrated nitric acid is (2-4): 1.
preferably, in the step (2), the molecular weight of PEI is 600-800, the concentration is 0.5-1 mol/L, the concentration of chloroauric acid is 5-10 g/L, the concentration of CNTs is 5-10 g/L, and the adding amount of PEI, chloroauric acid and CNTs is 2:1:2 in parts by volume.
Preferably, in the step (2), the CNTs subjected to acid treatment and obtained in the step (1) are added into the PEI, stirred at normal temperature for 30-60 min, the super-vibration machine is controlled to perform super-vibration for 5-10 min under the frequency of 60HZ and 40HZ respectively, chloroauric acid is added after uniform mixing, stirring and heating are performed at the temperature of 50-80 ℃, and the reaction time is 1-2 h.
Preferably, in the step (3), the copper plating solution is obtained by: weighing 25-35 parts of CuSO by weight of raw materials4·5H2O, 70-90 parts of EDTANa225-30 parts of NaKC4H4O6·4H2Dissolving 30-35 parts of KOH in 400-450 parts of water, and uniformly stirring to obtain a copper plating solution; the EDTANA2And NaKC4H4O6As a complexing agent, the copper ion complexing agent can prevent the copper ion from generating precipitation after being complexed with the copper ion.
Preferably, in the step (3), the specific process of plating copper on the surface is as follows:
taking 20-30 parts of copper plating solution by volume, adding 10-15 parts of 2, 2-bipyridine solution, wherein the concentration of the bipyridine solution is (0.1-0.3 g)/100ml, adding 10-15 parts of PVP solution, the molecular weight of PVP is 4000, the concentration of the solution is 0.1g/100ml, adding water to dilute the solution to 80-100 parts, adding the gold-plated CNTs obtained in the step (2), stabilizing the plating solution at 15 +/-1 ℃ by using water bath, adding 1-2 parts of glyoxylic acid, adjusting the pH of the reaction solution to 11.5-13 by using 10mol/L KOH, placing the solution in an ultrasonic vibration machine to react, wherein the first ultrasonic vibration frequency is 40HZ, and then adjusting the pH to 60HZ until the reaction is finished; the PVP is a surfactant and promotes the coating of the copper particles; the 2, 2-bipyridine is used as a stabilizer in the copper plating reaction, can stabilize the plating solution, and can adjust the size of copper-plated grains to refine the grains.
Preferably, in the step (3), the reaction process is determined according to the color change of the solution and the generation time of the bubbles, and specifically, the reaction process comprises the following steps:
the color of the solution changes into: blue solution → solution turns green → dark green → reddish → grass green → yellow/orange, when bubbles appear; and timing and sampling are started when bubbles appear, the sampling time is 10-15 min when the bubbles appear, and the whole reaction time is not more than 2 h.
Preferably, in the step (4), a 100ml reaction kettle is used, the adding amount of isopropanol is 60-70 ml, the heating is carried out to 220-280 ℃, the reaction time is 10-12 h, after the mixture is fully alloyed, a sample is taken out and poured into a 1000ml beaker, water is added to 600ml, and the mixture is filtered by a 0.45um filter membrane to obtain the carbon nanotube-gold-copper alloy composite material.
The invention also provides application of the carbon nano tube-gold copper alloy composite material, and the carbon nano tube-gold copper alloy composite material is used as a catalyst for ethanol selective oxidation reaction.
Firstly, carrying out gold plating on CNTs by using Polyethyleneimine (PEI), then loading Cu nanoparticles on the gold-plated CNTs by using an ultrasonic copper plating method, and then carrying out alloying to obtain the carbon nanotube-gold-copper alloy composite material; the preparation method has the advantages of simple process, mild reaction conditions, low cost, regular and controllable appearance; the carbon nano tube-gold copper alloy composite material can be applied to catalytic degradation of toxic substances, biosensing and imaging, photothermal therapy, drug delivery, catalysis and pollution treatment, absorption in visible light and infrared regions and the like.
The adsorption of reactants on the surface of a catalyst is particularly important, the CNTs treated by strong acid have strong chemical adsorption effect, and the CNTs used as carriers of nano binary alloy particles can exert the advantages of large specific surface area, large length-diameter ratio, strong chemical adsorption effect, uniform dispersion of metal elements on a tube and high thermal stability. The loss of the active surface area caused by the growth of metal particles in the alloying process is the main reason of the inactivation of the supported catalyst, after the CNTs are loaded with the gold-copper alloy, the interaction between the gold-copper and the carrier can be improved, the sintering resistance of the gold-copper nanoparticles is greatly improved, the CNTs have high specific surface area, the mutual supporting structure among the carbon nanotubes in the composite material plays a role in isolating and dispersing the gold-copper nanoparticles, the distance among the gold-copper nanoparticles is increased, a certain role in the sintering resistance of the catalyst is played, and the reaction stability of the catalyst is improved.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) according to the carbon nanotube-gold copper alloy composite material, the CNTs are used as a substrate, the AuCu alloy is plated on the surface of the CNTs by using a plating technology, the carbon nanotube-gold copper alloy composite material is superior to the conventional technology such as dipping, the generation of an agglomeration phenomenon is reduced, the carbon nanotube-gold copper alloy composite material has a larger specific surface area and stronger adsorption capacity, and after acid treatment, the negative charges on the surface of the CNTs are increased, so that the adsorbed metal ion effect is increased, a synergistic effect is generated between the AuCu alloy and the CNTs, and the catalytic activity of the carbon nanotube-gold copper alloy.
(2) The carbon nanotube-gold-copper alloy composite material is loaded by the CNTs, so that the interaction between the gold-copper alloy and a carrier can be improved, the sintering resistance of gold-copper nanoparticles is greatly improved, the CNTs have a structure with a high specific surface area and a structure of mutual support of catalysts, the characteristics of isolating and dispersing the gold-copper nanoparticles are achieved, the distance between the gold-copper nanoparticles is increased, the sintering resistance of the catalysts is also achieved, and the stability of the gold-copper alloy as the catalysts is improved.
(3) According to the preparation method of the carbon nanotube-gold-copper alloy composite material, the gold-copper alloy layers with different grain sizes can be obtained by regulating and controlling the process parameters, the purity is high, the coating is uniform, the thickness is controllable, the surface of the same carbon nanotube can be coated with gold-copper alloys with several grain sizes, different alloy particles have different component ranges, and multiple substances can be catalyzed; the preparation method is simple, low in cost, low in equipment requirement and suitable for large-scale production.
Drawings
FIG. 1 is a transmission electron micrograph of CNTs treated with a strong acid in example 1 according to the present invention.
FIG. 2 is a transmission electron micrograph of CNTs plated with gold in example 1 according to the present invention.
FIG. 3 is a transmission electron micrograph of the gold-copper-plated CNTs according to example 1 of the present invention.
Fig. 4 is a transmission electron microscope image of the carbon nanotube-gold copper alloy composite material obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The invention relates to a preparation method of a carbon nano tube-gold copper alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the steps of taking a multi-walled carbon nanotube as a substrate, putting CNTs with the length of about 500nm and the width of 20-25 nm into a mixed solution (volume ratio of 3: 1) of concentrated sulfuric acid and concentrated nitric acid, heating for 2h at 110 ℃, and cleaning with a large amount of deionized water to obtain the CNTs after acid treatment, wherein the concentration of the CNTs is 5g/l, and a transmission electron microscope image of the CNTs is shown in FIG. 1;
(2) surface gold plating: adding 8ml of the acid-treated CNTs obtained in the step (1) into 16ml of 1mol/L PEI, stirring for 30min at normal temperature, performing ultra-vibration for 5min respectively at the frequency of 60HZ and 40HZ by using an ultra-vibration machine, adding 6ml of chloroauric acid after uniform mixing, putting into a water bath furnace, stirring and heating for 1h, taking out the CNTs, and performing suction filtration and cleaning to obtain gold-plated CNTs, wherein a transmission electron microscope image of the CNTs is shown in FIG. 2;
(3) copper plating on the surface: adding the gold-plated CNTs obtained in the step (2) into a copper plating solution, flushing the activated CNTs with 50ml of water, pouring the CNTs into a 1000ml beaker, sequentially adding PVP 6g, copper plating solution 150ml and 0.2g/100ml 2, 2-bipyridine 144ml, adding water to 600ml, placing the CNTs into a constant-temperature super-vibration machine for super-vibration for 40min, cooling to 15 ℃, adding 10ml of glyoxylic acid serving as a reducing agent, using 40HZ for the first super-vibration, using 60HZ until the reaction is finished, generating bubbles when the solution is yellow/orange, respectively recording time and PH, sampling 15min after bubbles appear, and then carrying out suction filtration and washing with a large amount of water, wherein a transmission electron microscope picture of the CNTs is shown in FIG. 3;
preparing a copper plating solution: preparing 500ml of copper plating solution by using a volumetric flask, and sequentially adding the following medicines: 30g of CuSO4·5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O; 34g KOH and finally water to 500 ml;
(4) alloying treatment: and (3) adding the CNTs coated with gold and copper obtained in the step (3) into a 100ml reaction kettle by using isopropanol, wherein the addition amount of the isopropanol is 70ml, heating to 240 ℃, reacting for 12h, alloying the gold and copper coating, performing suction filtration and washing by using a large amount of deionized water, and drying to obtain the carbon nanotube-gold and copper alloy composite material, wherein a transmission electron microscope picture of an alloyed sample is shown in figure 4, and the structural parameters of the carbon nanotube-gold and copper alloy composite material obtained in the embodiment are shown in Table 1.
TABLE 1 structural parameters of the carbon nanotube-Au-Cu alloy composite of this example
As can be seen from fig. 1 to 4, the gold-plated layer, the copper-plated layer and the gold-copper alloy layer of the present embodiment are uniform and dense, and the coating is complete; the average components in the composite material are as follows: 10wt% of CNTs; 48 wt% of Au, 42 wt% of Cu; as can be seen from Table 1, the average particle size of the particles is 40nm, the particle sizes are distributed from 15 nm to 100nm, and the CNTs are loaded with the alloy, so that the specific surface area is large and the particle size is small; in addition, table 2 shows the ethanol conversion rate of the catalyst in the present embodiment in the selective oxidation reaction of ethanol, and it can be seen that the catalytic performance of the present invention is higher than that of the conventional gold-copper alloy particles.
TABLE 2 conversion of the catalyst to ethanol in this example
Example 2
The invention relates to a preparation method of a carbon nano tube-gold copper alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the steps of taking a multi-walled carbon nanotube as a substrate, enabling the CNTs to be about 500nm in length and 20-25 nm in width, putting the CNTs into a mixed solution (volume ratio is 2: 1) of concentrated sulfuric acid and concentrated nitric acid, heating for 2h at 90 ℃, and cleaning with a large amount of deionized water to obtain the CNTs subjected to acid treatment, wherein the concentration of the CNTs is 5 g/l;
(2) surface gold plating: adding 8ml of the acid-treated CNTs obtained in the step (1) into 16ml of 1mol/L PEI, stirring for 30min at normal temperature, performing super-vibration for 5min respectively at the frequency of 60HZ and 40HZ by using a super-vibration machine, adding 12ml of chloroauric acid after uniform mixing, putting into a water bath furnace, stirring and heating for 1.5h, taking out the CNTs, and performing suction filtration and cleaning to obtain gold-plated CNTs;
(3) copper plating on the surface: adding the gold-plated CNTs obtained in the step (2) into a copper plating solution, flushing the activated CNTs with 50ml of water, pouring the CNTs into a 1000ml beaker, sequentially adding PVP 6g, a copper plating solution 150ml and 0.2g/100ml 2, 2-bipyridine 144ml, adding water to 600ml, placing the CNTs into a constant-temperature super-vibration machine for super-vibration for 40min, cooling to 15 ℃, adding 10ml of glyoxylic acid serving as a reducing agent, using 40HZ for the first super-vibration, using 60HZ until the reaction is finished, generating bubbles when the solution is yellow/orange, respectively recording time and PH, sampling 15min after bubbles appear, and then washing with a large amount of water;
preparing a copper plating solution: preparing 500ml of copper plating solution by using a volumetric flask, and sequentially adding the following medicines: 30g of CuSO4·5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O; 34g KOH and finally water to 500 ml;
(4) alloying treatment: and (3) adding the CNTs coated with gold and copper obtained in the step (3) into a 100ml reaction kettle by using isopropanol, wherein the addition amount of the isopropanol is 60ml, heating to 240 ℃, reacting for 10 hours, alloying the gold and copper coating, performing suction filtration and washing by using a large amount of deionized water, and drying to obtain the carbon nanotube-gold and copper alloy composite material, wherein the structural parameters of the carbon nanotube-gold and copper alloy composite material obtained in the embodiment are shown in Table 3.
TABLE 3 structural parameters of the carbon nanotube-Au-Cu alloy composite in this example
The carbon nanotube-gold copper alloy composite material in the embodiment comprises the following components: 10wt% of CNTs; au65 wt%, Cu 25 wt%; as can be seen from Table 3, the average particle size of the particles is 50nm, the particle sizes are distributed from 20nm to 120nm, and the CNTs are loaded with the alloy, so that the specific surface area is large and the particle size is small; in addition, table 4 shows the ethanol conversion rate of the catalyst in the selective oxidation reaction of ethanol, and it can be seen that the catalytic performance of the present invention is higher than that of the conventional gold-copper alloy particles.
TABLE 4 conversion of the catalyst to ethanol in this example
Example 3
The invention relates to a preparation method of a carbon nano tube-gold copper alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the steps of taking a multi-walled carbon nanotube as a substrate, enabling the CNTs to be about 500nm in length and 20-25 nm in width, putting the CNTs into a mixed solution (volume ratio is 3: 1) of concentrated sulfuric acid and concentrated nitric acid, heating for 2h at 90 ℃, and cleaning with a large amount of deionized water to obtain the CNTs subjected to acid treatment, wherein the concentration of the CNTs is 5 g/l;
(2) surface gold plating: adding 8ml of the acid-treated CNTs obtained in the step (1) into 16ml of 1mol/L PEI, stirring for 30min at normal temperature, performing super-vibration for 5min respectively at the frequency of 60HZ and 40HZ by using a super-vibration machine, adding 4ml of chloroauric acid after uniform mixing, putting into a water bath furnace, stirring and heating for 1h, taking out the CNTs, and performing suction filtration and cleaning to obtain gold-plated CNTs;
(3) copper plating on the surface: adding the gold-plated CNTs obtained in the step (2) into a copper plating solution, flushing the activated CNTs with 50ml of water, pouring the CNTs into a 1000ml beaker, sequentially adding PVP 6g, a copper plating solution 150ml and 0.2g/100ml 2, 2-bipyridine 144ml, adding water to 600ml, placing the CNTs into a constant-temperature super-vibration machine for super-vibration for 40min, cooling to 15 ℃, adding 10ml of glyoxylic acid serving as a reducing agent, using 40HZ for the first super-vibration, using 60HZ until the reaction is finished, generating bubbles when the solution is yellow/orange, respectively recording time and PH, sampling 25min after bubbles appear, and then washing with a large amount of water;
preparing a copper plating solution: preparing 500ml of copper plating solution by using a volumetric flask, and sequentially adding the following medicines: 30g of CuSO4·5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O; 34g KOH and finally water to 500 ml;
(4) alloying treatment: and (3) adding the CNTs coated with gold and copper obtained in the step (3) into a 100ml reaction kettle by using isopropanol, wherein the addition amount of the isopropanol is 70ml, heating to 240 ℃, reacting for 10 hours, alloying the gold and copper coating, performing suction filtration and washing by using a large amount of deionized water, and drying to obtain the carbon nanotube-gold and copper alloy composite material, wherein the structural parameters of the carbon nanotube-gold and copper alloy composite material obtained in the embodiment are shown in Table 5.
TABLE 5 structural parameters of the carbon nanotube-Au-Cu alloy composite in this example
The carbon nanotube-gold copper alloy composite material in the embodiment comprises the following components: CNTs 8 wt%; au27 wt%, Cu 65 wt%; as can be seen from Table 5, the average particle size of the particles is 60nm, and the particles are distributed from 30 to 150 nm; table 6 shows the ethanol conversion rate of the catalyst in the selective oxidation reaction of ethanol, and it can be seen that the catalytic performance of the present invention is higher than that of the conventional gold-copper alloy particles.
TABLE 6 conversion of the catalyst to ethanol in this example
Example 4
The invention relates to a preparation method of a carbon nano tube-gold copper alloy composite material, which comprises the following steps:
(1) acid treatment: the method comprises the steps of taking a multi-walled carbon nanotube as a substrate, enabling the CNTs to be about 500nm in length and 20-25 nm in width, putting the CNTs into a mixed solution (volume ratio is 3: 1) of concentrated sulfuric acid and concentrated nitric acid, heating for 2h at 90 ℃, and cleaning with a large amount of deionized water to obtain the CNTs subjected to acid treatment, wherein the concentration of the CNTs is 5 g/l;
(2) surface gold plating: adding 8ml of the acid-treated CNTs obtained in the step (1) into 16ml of 1mol/L PEI, stirring for 30min at normal temperature, performing super-vibration for 5min respectively at the frequency of 60HZ and 40HZ by using a super-vibration machine, adding 16ml of chloroauric acid after uniform mixing, putting into a water bath furnace, stirring and heating for 2h, taking out the CNTs, and performing suction filtration and cleaning to obtain gold-plated CNTs;
(3) copper plating on the surface: adding the gold-plated CNTs obtained in the step (2) into a copper plating solution, flushing the activated CNTs with 50ml of water, pouring the CNTs into a 1000ml beaker, sequentially adding PVP 6g, a copper plating solution 150ml and 0.2g/100ml 2, 2-bipyridine 144ml, adding water to 600ml, placing the CNTs into a constant-temperature super-vibration machine for super-vibration for 40min, cooling to 15 ℃, adding 10ml of glyoxylic acid serving as a reducing agent, using 40HZ for the first super-vibration, using 60HZ until the reaction is finished, generating bubbles when the solution is yellow/orange, respectively recording time and PH, sampling 25min after bubbles appear, and then washing with a large amount of water;
preparing a copper plating solution: preparing 500ml of copper plating solution by using a volumetric flask, and sequentially adding the following medicines: 30g of CuSO4·5H2O；80g EDTANa2；28g NaKC4H4O6·4H2O; 34g KOH and finally water to 500 ml;
(4) alloying treatment: and (3) adding the CNTs coated with gold and copper obtained in the step (3) into a 100ml reaction kettle by using isopropanol, wherein the addition amount of the isopropanol is 70ml, heating to 240 ℃, reacting for 10 hours, alloying the gold and copper coating, performing suction filtration and washing by using a large amount of deionized water, and drying to obtain the carbon nanotube-gold and copper alloy composite material, wherein the structural parameters of the carbon nanotube-gold and copper alloy composite material obtained in the embodiment are shown in Table 7.
TABLE 7 structural parameters of the carbon nanotube-Au-Cu alloy composite in this example
The carbon nanotube-gold copper alloy composite material in the embodiment comprises the following components: CNTs 6 wt%; 47 wt% of Au, 47 wt% of Cu; as can be seen from Table 7, the average particle size of the particles was 70nm, and the particles were distributed from 50 to 80 nm; table 8 shows the ethanol conversion rate of the catalyst in the selective oxidation reaction of ethanol, and it can be seen that the catalytic performance of the present invention is higher than that of the conventional Au-Cu alloy particles.
TABLE 8 conversion of the catalyst to ethanol in this example
Claims (9)
1. The carbon nanotube-gold copper alloy composite material is characterized by consisting of a matrix carbon nanotube and a gold copper alloy loaded on the surface of the matrix carbon nanotube, wherein the carbon nanotube-gold copper alloy composite material consists of the following components in percentage by weight: 5-10 wt% of carbon nano tube, 15-65 wt% of gold and 25-75 wt% of copper;
the preparation method of the carbon nano tube-gold copper alloy composite material is characterized by comprising the following steps of:
(1) acid treatment: putting CNTs (carbon nanotubes) into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for ultrasonic treatment, and cleaning to obtain acid-treated CNTs;
(2) surface gold plating: adding the CNTs subjected to acid treatment obtained in the step (1) into PEI, stirring at normal temperature, controlling the super-vibration frequency, uniformly mixing, adding chloroauric acid, stirring and heating, taking out the CNTs after reacting for a preset time, and cleaning to obtain gold-plated CNTs;
(3) copper plating on the surface: adding the CNTs plated with gold obtained in the step (2) into a copper plating solution, adding bipyridine and PVP, controlling the super-vibration frequency and the temperature, adding glyoxylic acid as a reducing agent, adjusting the PH, determining the reaction process according to the color change of the solution and the generation time of bubbles, taking out the CNTs after the bubbles appear for a certain time, and cleaning to obtain the CNTs plated with gold and copper;
(4) alloying treatment: and (4) adding the CNTs plated with the gold and copper obtained in the step (3) into an isopropanol solution, heating to a preset temperature to alloy a gold and copper plating layer, and washing to obtain the carbon nanotube-gold and copper alloy composite material.
2. The carbon nanotube-gold-copper alloy composite material according to claim 1, wherein the carbon nanotubes have a length of 300 to 1000nm, and the gold-copper alloy has a particle size of 20 to 150 nm.
3. The carbon nanotube-gold copper alloy composite material of claim 1, wherein in the step (2), the molecular weight of PEI is 600-800, the concentration is 0.5-1 mol/L, the concentration of chloroauric acid is 5-10 g/L, the concentration of CNTs is 5-10 g/L, and the addition amounts of PEI, chloroauric acid and CNTs are 2:1: 2.
4. the carbon nanotube-gold-copper alloy composite material of claim 1, wherein in the step (2), the CNTs subjected to acid treatment and obtained in the step (1) are added into the PEI, the mixture is stirred at normal temperature for 30-60 min, the super-vibration machine is controlled to perform super-vibration for 5-10 min at the frequency of 60HZ and 40HZ respectively, chloroauric acid is added after the mixture is uniformly mixed, the mixture is stirred and heated at the temperature of 50-80 ℃, and the reaction time is 1-2 h.
5. The carbon nanotube-gold copper alloy composite material according to claim 1, wherein in the step (3), the copper plating solution is obtained by: weighing 25-35 parts of CuSO by weight of raw materials4·5H2O, 70-90 parts of EDTANa225-30 parts of NaKC4H4O6·4H2Dissolving 30-35 parts of KOH in 400-450 parts of water, and uniformly stirring to obtain a copper plating solution; the EDTANA2And NaKC4H4O6As a complexing agent, the copper ion complexing agent can prevent the copper ion from generating precipitation after being complexed with the copper ion.
6. The carbon nanotube-gold-copper alloy composite material according to claim 1, wherein in the step (3), the copper plating on the surface comprises:
taking 20-30 parts of copper plating solution by volume, adding 10-15 parts of 2, 2-bipyridine solution, wherein the concentration of the bipyridine solution is (0.1-0.3 g)/100ml, adding 10-15 parts of PVP solution, the molecular weight of PVP is 4000, the concentration of the solution is 0.1g/100ml, adding water to dilute the solution to 80-100 parts, adding the gold-plated CNTs obtained in the step (2), stabilizing the plating solution at 15 +/-1 ℃ by using water bath, adding 1-2 parts of glyoxylic acid, adjusting the pH of the reaction solution to 11.5-13 by using 10mol/L KOH, placing the solution in an ultrasonic vibration machine to react, wherein the first ultrasonic vibration frequency is 40HZ, and then adjusting the pH to 60HZ until the reaction is finished; the PVP is a surfactant and promotes the coating of the copper particles; the 2, 2-bipyridine is used as a stabilizer in the copper plating reaction, can stabilize the plating solution, and can adjust the size of copper-plated grains to refine the grains.
7. The carbon nanotube-gold-copper alloy composite material according to claim 1, wherein in the step (3), the reaction process is determined according to the color change of the solution and the generation time of the bubbles, and specifically comprises:
the color of the solution changes into: blue solution → solution turns green → dark green → reddish → grass green → yellow/orange, when bubbles appear; and timing and sampling are started when bubbles appear, the sampling time is 10-15 min when the bubbles appear, and the whole reaction time is not more than 2 h.
8. The carbon nanotube-gold-copper alloy composite material according to claim 1, wherein in the step (4), a 100ml reaction kettle is used, the amount of isopropanol added is 60-70 ml, the mixture is heated to 220-280 ℃ and the reaction time is 10-12 h, after the mixture is fully alloyed, a sample is taken out and poured into a 1000ml beaker, water is added to 600ml, and the mixture is subjected to suction filtration by using a 0.45um filter membrane to obtain the carbon nanotube-gold-copper alloy composite material.
9. The use of the carbon nanotube-gold copper alloy composite according to any one of claims 1 to 8, wherein the carbon nanotube-gold copper alloy composite is used as a catalyst for ethanol selective oxidation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811115340.3A CN109126822B (en) | 2018-09-25 | 2018-09-25 | Carbon nanotube-gold copper alloy composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811115340.3A CN109126822B (en) | 2018-09-25 | 2018-09-25 | Carbon nanotube-gold copper alloy composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109126822A CN109126822A (en) | 2019-01-04 |
| CN109126822B true CN109126822B (en) | 2021-05-07 |
Family
ID=64823524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811115340.3A Active CN109126822B (en) | 2018-09-25 | 2018-09-25 | Carbon nanotube-gold copper alloy composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109126822B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116898919A (en) * | 2023-07-06 | 2023-10-20 | 宁波科瑞特动物药业有限公司 | Animal insect repellent and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407132A (en) * | 2001-07-02 | 2003-04-02 | 希普雷公司 | Nonelectrolytic gold plating liquid and method thereof |
| CN1978711A (en) * | 2005-12-08 | 2007-06-13 | 中国科学院金属研究所 | Method for preparing alloy coating |
| CN101045533A (en) * | 2007-03-12 | 2007-10-03 | 清华大学 | Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof |
| CN101380584A (en) * | 2008-10-23 | 2009-03-11 | 华南理工大学 | High activity methanol-resistance direct methanol fuel cell cathode catalyst and production method thereof |
| CN101716677A (en) * | 2009-12-11 | 2010-06-02 | 哈尔滨工业大学 | Preparation method of carbon nano tube-copper oxide composite powder |
| CN101728545A (en) * | 2009-11-13 | 2010-06-09 | 上海理工大学 | Anode nanometer alloy catalyst of direct methanol fuel cell and preparation method thereof |
| CN102140668A (en) * | 2011-03-10 | 2011-08-03 | 上海交通大学 | Optimization method for carbon nanotube and metal copper composite electroplating process |
| CN102553582A (en) * | 2011-12-01 | 2012-07-11 | 昆明理工大学 | Method for preparing carbon supported Au-Pt or Au-Pd catalyst |
| CN103022418A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Carbon nano tube enhanced tin-copper-nickel alloy cathode and preparation method thereof |
| CN105606681A (en) * | 2015-12-27 | 2016-05-25 | 济南大学 | Preparation method and application of biosensor built based on gold and copper-multiwalled carbon nanotube-manganese dioxide |
| CN107557769A (en) * | 2017-07-26 | 2018-01-09 | 昆明理工大学 | A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI395710B (en) * | 2009-01-06 | 2013-05-11 | Univ Tatung | Method of preparing a carbon nanotube complex |
| KR20130054008A (en) * | 2011-11-16 | 2013-05-24 | 삼성전자주식회사 | Electrode for fuel cell, method of preparing the electrode, catalyst slurry, and fuel cell including the electrode |
-
2018
- 2018-09-25 CN CN201811115340.3A patent/CN109126822B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407132A (en) * | 2001-07-02 | 2003-04-02 | 希普雷公司 | Nonelectrolytic gold plating liquid and method thereof |
| CN1978711A (en) * | 2005-12-08 | 2007-06-13 | 中国科学院金属研究所 | Method for preparing alloy coating |
| CN101045533A (en) * | 2007-03-12 | 2007-10-03 | 清华大学 | Carbon nano tube wave absorbtion mateirla of surface carried with magnetic alloy particle and preparation method thereof |
| CN101380584A (en) * | 2008-10-23 | 2009-03-11 | 华南理工大学 | High activity methanol-resistance direct methanol fuel cell cathode catalyst and production method thereof |
| CN101728545A (en) * | 2009-11-13 | 2010-06-09 | 上海理工大学 | Anode nanometer alloy catalyst of direct methanol fuel cell and preparation method thereof |
| CN101716677A (en) * | 2009-12-11 | 2010-06-02 | 哈尔滨工业大学 | Preparation method of carbon nano tube-copper oxide composite powder |
| CN102140668A (en) * | 2011-03-10 | 2011-08-03 | 上海交通大学 | Optimization method for carbon nanotube and metal copper composite electroplating process |
| CN102553582A (en) * | 2011-12-01 | 2012-07-11 | 昆明理工大学 | Method for preparing carbon supported Au-Pt or Au-Pd catalyst |
| CN103022418A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Carbon nano tube enhanced tin-copper-nickel alloy cathode and preparation method thereof |
| CN105606681A (en) * | 2015-12-27 | 2016-05-25 | 济南大学 | Preparation method and application of biosensor built based on gold and copper-multiwalled carbon nanotube-manganese dioxide |
| CN107557769A (en) * | 2017-07-26 | 2018-01-09 | 昆明理工大学 | A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material |
Non-Patent Citations (3)
| Title |
|---|
| "Nonenzymatic glucose sensor based on gold–copper alloy nanoparticles on defect sites of carbon nanotubes by spontaneous reduction";Dengyou Liuet al.;《Synthetic Metals》;20100703;第160卷;第1745-1748页 * |
| "负载型纳米金催化剂的合成及其乙醇选择性氧化性能研究";杜宪军;《中国博士学位论文全文数据库工程科技I辑》;20171215(第12期);B014-61 * |
| Dengyou Liuet al.."Nonenzymatic glucose sensor based on gold–copper alloy nanoparticles on defect sites of carbon nanotubes by spontaneous reduction".《Synthetic Metals》.2010,第160卷第1745-1748页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109126822A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109261155B (en) | Carbon nanotube/copper-zinc alloy composite material and preparation method and application thereof | |
| Ang et al. | Decoration of activated carbon nanotubes with copper and nickel | |
| CN102773475B (en) | Copper oxide silver composite powder for conductive paste and preparation method thereof | |
| CN102664275B (en) | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof | |
| US7208437B2 (en) | Catalyst and method for its manufacture | |
| CN103007963A (en) | Method for preparing bimetallic nanometer alloy composite material by taking graphene as carrier | |
| CN104999076B (en) | The method that one kettle way prepares the controllable silver-colored copper-clad nano-powder of shell thickness | |
| CN110518257B (en) | Preparation method of carbon-supported transition metal @ Pt core-shell structure catalyst | |
| CN110649273B (en) | Method for synthesizing small-size high-dispersion intermetallic compound catalyst material and application | |
| CN102732863B (en) | Method for preparing magnetic-field-assisted graphite carbon material chemical plating magnetic metal | |
| CN109894610B (en) | Metal-coated spherical cast tungsten carbide powder and preparation method thereof | |
| JP5665743B2 (en) | Continuous production method of catalyst | |
| WO2014029210A1 (en) | Preparation method for electrical contact materials | |
| CN113477270B (en) | Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material | |
| JPH04141236A (en) | Platinoid catalyst and its manufacturing process | |
| WO2022262801A1 (en) | Nano-metal 3d printing ink and application thereof | |
| CN109126822B (en) | Carbon nanotube-gold copper alloy composite material and preparation method and application thereof | |
| JPWO2011132258A1 (en) | Catalyst production method | |
| CN108097949B (en) | A kind of production method of tin plating nickel powder | |
| CN111774579B (en) | Al/Ni composite particles and preparation method thereof | |
| CN113293393A (en) | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof | |
| CN105209660A (en) | Method for coating of carbon nanomaterials | |
| CN115283670A (en) | Ti (C, N) -Mo-Fe composite powder and preparation method and application thereof | |
| CN106910906A (en) | A kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application | |
| CN114073973A (en) | Light-weight supported magnetic metal composite catalyst 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 |