CN115533117A - Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods - Google Patents
Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods Download PDFInfo
- Publication number
- CN115533117A CN115533117A CN202211138766.7A CN202211138766A CN115533117A CN 115533117 A CN115533117 A CN 115533117A CN 202211138766 A CN202211138766 A CN 202211138766A CN 115533117 A CN115533117 A CN 115533117A
- Authority
- CN
- China
- Prior art keywords
- sio
- capillary electrode
- printing
- preparing
- limited
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 45
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 238000010146 3D printing Methods 0.000 title claims abstract description 18
- 230000008878 coupling Effects 0.000 title claims abstract description 15
- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- 238000007599 discharging Methods 0.000 title claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 229910052786 argon Inorganic materials 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 31
- 230000033001 locomotion Effects 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000010891 electric arc Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000026058 directional locomotion Effects 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a method for preparing Pt/SiO by coupling 3D printing and limited-area discharging technology 2 Apparatus and methods for nanoparticles. The method uses Pt ion solution to dope nano SiO 2 Is a precursor, argon is a discharge gas, and the Pt/SiO with uniform particles, controllable thickness and ordered arrangement is deposited on the surface of a large-size carrier substrate by coupling 3D printing and a limited-area discharge technology under atmospheric pressure 2 And (3) nanoparticles. The method is simple, efficient, environment-friendly and safe, other chemical reagents are not introduced, and the obtained composite nano particles are high in purity, small in size, narrow in particle size distribution and adjustable in components.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a method for preparing Pt/SiO by utilizing a movable discharge technology under normal pressure 2 Apparatus and methods for nanoparticles.
Background
Pt is one of the most important noble metal catalysts in industry. Among the numerous forms of Pt, pt nanoparticles, which are characterized by small size and high specific surface area, exhibit remarkable catalytic performance and are widely used in chemical reactions such as hydrogenation, dehydrogenation, isomerization, cyclization, dehydration, dehalogenation, oxidation, cracking, and the like. Due to the factors of synthesis process, technical level, equipment facilities and the like, the Pt nanoparticles are often aggregated in the synthesis process, and the catalytic performance of a single nanoparticle is limited. Therefore, a series of synthetic methods for dispersing Pt nanoparticles on a carrier material are proposed at home and abroad. The selection of inert carrier materials and the method for compounding the inert carrier materials with the noble metal nano-particles become hot spots for research. Among the numerous support materials, the inert support SiO is typical 2 Exhibit excellent properties and are often used in heterogeneous catalysis to stabilize supported metal nanoparticles. Most of the Pt composite SiO proposed at present 2 The method has complex reaction process and needs a large amount of pretreatment and post-treatment, thereby causing chemical substance residue and influencing the catalytic performance of the product. Therefore, the key to the development of the synthesis process of the supported Pt-based catalyst is to find a simple, efficient, green and environment-friendly preparation device and method.
Patent CN108067249B discloses highly dispersed SiO carrier for dehydrogenating isobutane 2 The method comprises the step of soaking a mixed solution of lanthanum nitrate, ferric nitrate, nickel nitrate and chloroplatinic acid in SiO subjected to high-temperature calcination treatment in equal volume 2 Then the sample is calcined and washed in H 2 -N 2 Fully reducing in the atmosphere to obtain the product. The method uses pretreatment steps of dipping, roasting, drying, tabletting, grinding and the like, has a plurality of devices, needs continuous operation, cannot realize large-scale production, and has unstable product quality of different batches. The present invention combines 3D movement with microchannel discharge,the device is flexible and controllable, energy consumption, reaction time and manual operation steps are greatly reduced, continuous production is realized by using the movable device, and the stability of product quality is ensured.
Patent CN105582913A discloses a Pt/SiO synthetic core-shell structure 2 The preparation method of the catalyst comprises the steps of obtaining Pt nano particles by a method of synthesis first and adsorption later, and taking inorganic and organic silicon sources as precursors. The method has complex process and large particle size of the product, and increases the cost of product preparation. The invention only needs chloroplatinic acid mixed with nano SiO 2 The solution is used as a precursor, high-energy electrons are used as a reducing agent, the preparation of the nano particles is realized by a one-step method, and the prepared product has small size, short synthetic process and environmental protection.
The atmospheric pressure-limited domain discharge technology is a technology for generating high-density excited species through inelastic collision of high-energy electrons so as to strengthen the chemical reaction. The one-step method for preparing Pt/SiO can be realized by applying the atmospheric pressure limited discharge technology to nano synthesis 2 And (3) nanoparticles. Through combining the atmospheric pressure limited discharge technology with the 3D printing technology, can break traditional limited discharge electric arc, realize the movable discharge, reach and print nanometer pattern or nanometer film that have high specific surface area nature and particle distribution are even in the region of large scale. Because the moving speed of the capillary electrode in the 3D printer is controllable, the thickness of the nanometer pattern or the film can be accurately controlled, and the method can be suitable for various production requirements. In addition, the microreactor has the characteristics of small size and excellent mass transfer and heat transfer performance, so that the preparation process is simple, efficient, accurate in regulation and control, green and safe.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant of the invention provides a method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology 2 An apparatus and method for compounding nanoparticles. The invention prints Pt/SiO with controllable thickness on the surface of a large-range substrate by a one-step method through a movable discharge technology and by utilizing a discharge arc generated by argon gas mixed with a liquid-phase precursor 2 And (3) nanoparticles. The method does not need chemical reducing agent or oxidizing agent, does not need high-temperature calcination process, and the printedThe nano particles are adsorbed on the substrate and are not easy to fall off. The equipment is safe in operation process, high in flexibility, strong in controllability, green, high-efficiency, high in practicability and adaptability.
The technical scheme of the invention is as follows:
Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 The device for preparing the nano particles comprises an injection pump 1, a computer 2, a shaft moving device 3, a three-way pipe 4, a 3D printer 5, a substrate 6, a capillary electrode 7, a mass flow controller 8, a direct current power supply 9, a voltage-stabilizing impedance 10 and an argon steel cylinder 11;
the injection pump 1 is connected with a first connector of a three-way pipe 4; the second interface of the three-way pipe 4 is connected with an argon gas steel cylinder 11, and the pipelines of the two are provided with a mass flow controller 8; a third interface of the three-way pipe 4 is connected with the upper end of the capillary electrode 7; the lower end of the capillary electrode 7 is close to the surface of the substrate 6; the 3D printer 5 includes a front-rear movement shaft, a left-right movement shaft, and an up-down movement shaft, and the capillary electrode 7 is fixed on the left-right movement shaft; one end of the shaft moving device 3 is connected with the computer 2, the other end of the shaft moving device is connected with three shafts of the 3D printer 5, and directional movement of the three shafts of the 3D printer 5 is controlled through instructions of the computer 2; the positive electrode of the direct current power supply 9 is connected with the upper end of the capillary electrode 7; the negative pole of the direct current power supply 9 is connected with the front and back movement shaft of the 3D printer 5 and is grounded, and a voltage stabilizing impedance 10 is arranged on the circuit of the direct current power supply and the back and forth movement shaft;
argon in the argon steel cylinder 11 enters the three-way pipe 4 under the regulation and control of the mass flow controller 8, and the reaction solution A enters the capillary electrode 7 after being doped in the three-way pipe 4 with the argon through the injection pump 1. The computer 2 controls a moving shaft of the 3D printer 5 and drives the capillary electrode 7 to move directionally; an arc is generated between the lower end of the capillary electrode 7 and the substrate 6.
Further, the lower end of the capillary electrode 7 is spaced from the substrate 6 by a distance of 2 to 3 mm.
Further, the substrate 6 has a length of 5 to 10cm and a width of 5 to 10cm.
Furthermore, the capillary electrode 7 has a tube length of 70-100 mm, a tube inner diameter of 0.5-1 mm, and a tube outer diameter of 1.5-2.5 mm.
Furthermore, the inner diameter of the three-way pipe 4 is 1.5-3.2 mm.
Furthermore, the substrate 6 is made of metal material, polymer, textile, silicon wafer, or the like.
Furthermore, the hose material adopted by the connecting part is polytetrafluoroethylene.
Further, the voltage stabilizing impedance 10 has a resistance of 10 to 20k Ω.
Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 The preparation method of the nano-particles comprises the following steps:
(1) Using deionized water as a solvent to prepare a Pt ion solution with the concentration of 0.5-1 mM and nano SiO with the concentration of 0.5-1 mg/mL 2 The solution is uniformly mixed to be used as a precursor solution, a Pt ion solution and nano SiO 2 The volume ratio of the solution is 1;
(2) Connecting a reaction device: the precursor solution is conveyed to the capillary electrode 7 through the injection pump 1, argon is conveyed to the capillary electrode 7 through the mass flow controller 8, and the computer 2 sends an instruction to the shaft moving device 3 so as to control the movement of the moving shaft of the 3D printer 5 and further control the movement of the capillary electrode 7;
(3) Applying direct current to the capillary electrode 7, and controlling the power of discharge to be kept between 10 and 30W so as to break down gas to generate discharge arc;
(4) After the electric arc is generated, the flow rate of the precursor solution is kept between 0.05 mL/min and 0.1mL/min by controlling the injection pump 1, the flow rate of argon is kept between 20 sccm and 50sccm by controlling the mass flow meter 8, and the precursor solution and the reaction gas form intermittent gas-liquid doping between the three-way pipe 4 and the capillary electrode 7;
(5) The generated nano particles are deposited on the substrate 6 through the movement of the 3D printer 5, so that nano patterns with uniform particle distribution are formed, and the processing time is 5-10 min.
Further, the noble metal precursor used may be chloroplatinic acid or sodium chloroplatinate.
Further, the precursor is reduced in the capillary electrode 7 to form Pt/SiO 2 Composite nanoparticles, carried by the arc, are deposited on the substrate 6.
Compared with the prior art, the invention has the following advantages:
(1) The invention utilizes the coupling of the 3D printing technology and the high-voltage discharge technology to solve the problem that the conventional limited-area discharge technology is too limited in action area and cannot process a large-area in a short time.
(2) The invention only needs Pt metal ion solution to dope nano SiO 2 The precursor is taken as, the high-energy electrons are taken as a reducing agent, no chemical reducing agent or oxidizing agent is used, no environmental pollution is caused, and the method is green and environment-friendly.
(3) The device is flexible and controllable, a three-dimensional moving path can be set through a computer, and the nano film or the nano array can be deposited on the substrates with various sizes, so that the production continuity and automation can be realized.
(4) The precursor solution is reacted in the microchannel in the whole process, and complex pretreatment, high-temperature calcination and post-treatment processes are not needed. And the micro-reactor has the characteristics of micro-scale and excellent mass and heat transfer performance, so that the heat of the system is not accumulated, the particle size of the nano material is controllable, and the particle aggregation is low.
(5) The long-range coulomb force exists in the plasma, so that the Pt nano particles can be charged, and the electrostatic repulsion between the Pt nano particles further inhibits the agglomeration of the Pt nano particles, so that the product has better catalytic performance.
Drawings
FIG. 1 shows a method for preparing Pt/SiO by coupling 3D printing and limited-area discharging technology 2 A schematic of the structure of a nanoparticle device;
FIG. 2 shows Pt/SiO solid particles obtained in example 1 of the present invention 2 SEM morphology of nanoparticles;
FIG. 3 shows Pt/SiO solid particles obtained in example 2 of the present invention 2 SEM morphology of nanoparticles;
FIG. 4 shows Pt/SiO solid particles obtained in example 3 of the present invention 2 SEM morphology of nanoparticles;
FIG. 5 shows Pt/SiO solid particles obtained in example 1 of the present invention 2 TEM morphology of nanoparticles;
FIG. 6 shows Pt/SiO solid particles obtained in example 2 of the present invention 2 TEM morphology of nanoparticles;
FIG. 7 shows example 3 of the present inventionPreparing Pt/SiO 2 TEM morphology of nanoparticles;
in the figure: the device comprises a syringe pump 1, a computer 2, a 3-axis moving device, a three-way pipe 4, a 53D printer, a base plate 6, a capillary electrode 7, a mass flow controller 8, a direct current power supply 9, a voltage stabilizing impedance 10 and an argon gas steel cylinder 11.
Detailed Description
The device comprises an injection pump, a computer, a shaft moving device, a three-way pipe, a 3D printer, a base plate, a capillary electrode, a mass flow controller, a direct current power supply, a voltage-stabilizing impedance and an argon steel cylinder (as shown in figure 1).
The invention is described in detail below with reference to the figures and examples.
The front and back moving shaft of the 3D printer 5 is powered by stepping motors on two sides of the bottom plane, and the plane is driven by a synchronizing wheel between the bottom plane and the stepping motors to move back and forth; the left and right moving shafts are powered by a stepping motor to directly connected left and right gears, and the gears rotate to drive the synchronous belt to stir, so that the capillary tube electrode 7 fixed on the synchronous belt is further controlled to move left and right; the up-and-down moving shaft is powered by a stepping motor positioned on the base, and the effect of controlling the capillary electrode 7 to move up and down is achieved by driving the screw rod to rotate; the boundaries of the three moving shafts are provided with limit switches for limiting the moving range of each shaft, and the stepping motors are connected with the shaft moving device.
The substrate (6) is 5cm long and 5cm wide.
The capillary electrode (7) has a tube length of 80mm, a tube inner diameter of 0.5mm and a tube outer diameter of 1.5mm.
The inner diameter of the three-way pipe (4) is 2mm.
The voltage-stabilizing impedance (10) is 20k omega in resistance.
Example 1
Weighing appropriate amount of sodium chloroplatinate and nano SiO 2 Adding the powder into deionized water, and uniformly stirring to prepare 1mM sodium chloroplatinate solution and 1mg/mL nano SiO 2 Taking sodium chloroplatinate solution and nano SiO 2 Solution 1. Applying to capillary electrodes in 3D printersAnd applying direct current negative bias to ensure that the discharge power is 20W to break down argon to generate a discharge arc, wherein the capillary electrode is arranged at the position 2mm away from the upper end of the copper substrate at the bottom, and the lower end of the copper substrate is connected to the grounding electrode. The flow rate of the precursor solution is kept at 0.1mL/min by controlling the injection pump, the solution is slowly pushed to the capillary electrode, then argon gas of 40sccm is continuously introduced into the system, and gas-liquid type intermingling of 'one section of gas and one section of liquid' is formed in a pipeline between the three-way pipe and the capillary electrode by the gas phase and the liquid phase. The moving path of the discharge arc generated at the lower end of the capillary is set by a computer to just cover the whole copper substrate, so that the deposited Pt/SiO is ensured 2 The nano particles just cover the copper substrate, the copper substrate is treated for 10min under the action of high-voltage electric arc, and the substrate is taken out to obtain a finished product.
Example 2
The preparation method is the same as that of example 1, except that: sodium chloroplatinate solution and nano SiO 2 The solutions were mixed in a volume ratio of 1.
Example 3
The preparation method is the same as that of example 1, except that: sodium chloroplatinate solution and nano SiO 2 The solutions were mixed in a volume ratio of 1.
1-3 examples Pt/SiO of different ratios 2 The SEM morphology characterization of the nanoparticles is shown in fig. 2 to 4, and it can be seen from the corresponding figures that the prepared nanoparticles are uniformly covered on the substrate, and present a close layered distribution. FIGS. 5 to 7 show Pt/SiO solutions of different ratios 2 TEM morphology characterization of nanoparticles, from which it can be seen that Pt is in nano SiO 2 The outer layer forms a distinct supported structure and a reduction in the stoichiometry results in a reduction in Pt loading.
The above examples are only for the purpose of clearly illustrating the process flow of the present invention. However, the present invention is not limited to the above embodiment. Any modifications, equivalent substitutions, improvements and the like which may occur to those skilled in the art without departing from the principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A kind of couplerPt/SiO prepared by combining 3D printing and limited-area discharging technology 2 The device for the nanoparticles is characterized by comprising a syringe pump (1), a computer (2), a shaft moving device (3), a three-way pipe (4), a 3D printer (5), a substrate (6), a capillary electrode (7), a mass flow controller (8), a direct-current power supply (9), a voltage-stabilizing impedance (10) and an argon steel cylinder (11);
the injection pump (1) is connected with a first connector of the three-way pipe (4); the second interface of the three-way pipe (4) is connected with an argon steel cylinder (11), and the pipelines of the two are provided with a mass flow controller (8); a third interface of the three-way pipe (4) is connected with the upper end of the capillary electrode (7); the lower end of the capillary electrode (7) is close to the surface of the substrate (6); the 3D printer (5) comprises a front-back moving shaft, a left-right moving shaft and a vertical moving shaft, and the capillary electrode (7) is fixed on the left-right moving shaft; one end of the shaft moving device (3) is connected with the computer (2), the other end of the shaft moving device is connected with three shafts of the 3D printer (5), and directional movement of the three shafts of the 3D printer (5) is controlled through instructions of the computer (2); the positive electrode of the direct current power supply (9) is connected with the upper end of the capillary electrode (7); the negative pole of the direct current power supply (9) is connected with a front-back moving shaft of the 3D printer (5) and is grounded, and a voltage stabilizing impedance (10) is arranged on the circuit of the direct current power supply and the front-back moving shaft;
argon in the argon steel cylinder (11) enters the three-way pipe (4) through the regulation and control of the mass flow controller (8), and the reaction solution A enters the capillary electrode (7) after being doped in the three-way pipe (4) with the argon through the injection pump (1); the computer (2) controls a moving shaft of the 3D printer (5) and drives the capillary electrode (7) to move directionally; an arc is generated between the lower end of the capillary electrode (7) and the substrate (6).
2. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 A nanoparticle device, characterized in that the lower end of the capillary electrode (7) is kept at a distance of 2 to 3mm from the substrate (6).
3. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 A device of nanoparticles, characterized in that the substrate (6) has a length of 5-10 cm and a width of 5-10 cm.
4. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 The device for preparing the nano particles is characterized in that the tube length of the capillary electrode (7) is 70-100 mm, the inner diameter of the tube is 0.5-1 mm, and the outer diameter of the tube is 1.5-2.5 mm.
5. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 The nanoparticle device is characterized in that the inner diameter of the three-way pipe (4) is 1.5-3.2 mm.
6. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 The device for preparing the nano particles is characterized in that the substrate (6) is made of a metal material, a polymer, a textile or a silicon wafer; the hose material adopted by the connecting part is polytetrafluoroethylene.
7. The method for preparing Pt/SiO by coupling 3D printing and limited-area discharge technology according to claim 1 2 Nanoparticle device, characterized in that the stabilizing impedance (10) has a resistance of 10-20 k omega.
8. Preparation of Pt/SiO by a coupled 3D printing and confined discharge technique according to any of claims 1 to 7 2 Device for preparing Pt/SiO by nano particles 2 A method of preparing nanoparticles, comprising the steps of:
(1) Using deionized water as a solvent to prepare a Pt ion solution with the concentration of 0.5-1 mM and nano SiO with the concentration of 0.5-1 mg/mL 2 The solution is uniformly mixed to be used as a precursor solution, a Pt ion solution and nano SiO 2 The addition volume ratio of the solution is 1;
(2) Connecting a reaction device: the precursor solution is conveyed to the capillary electrode (7) through the injection pump (1), argon is conveyed to the capillary electrode (7) through the mass flow controller (8), a computer (2) sends an instruction to the shaft moving device (3) so as to control the movement of a moving shaft of the 3D printer (5), and the movement of the capillary electrode (7) is further controlled;
(3) Applying direct current on the capillary electrode (7), and controlling the power of discharge to be kept between 10 and 30W so as to break down gas to generate discharge arc;
(4) After the electric arc is generated, the flow rate of the precursor solution is kept between 0.05 and 0.1mL/min by controlling the injection pump (1), the flow rate of argon is kept between 20 and 50sccm by controlling the mass flow meter (8), and the precursor solution and the reaction gas form discontinuous gas-liquid doping between the three-way pipe (4) and the capillary electrode (7);
(5) The generated nano particles are deposited on a substrate (6) through the movement of a 3D printer (5), so that a nano pattern with uniform particle distribution is formed, and the processing time is 5-10 min.
9. The method as claimed in claim 8, wherein the noble metal precursor is chloroplatinic acid or sodium chloroplatinate.
10. A method according to claim 8, characterized in that the reduction of the precursor to Pt/SiO takes place in the capillary electrode (7) 2 Composite nanoparticles carried by the arc are deposited on the substrate (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211138766.7A CN115533117A (en) | 2022-09-19 | 2022-09-19 | Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211138766.7A CN115533117A (en) | 2022-09-19 | 2022-09-19 | Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115533117A true CN115533117A (en) | 2022-12-30 |
Family
ID=84727126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211138766.7A Pending CN115533117A (en) | 2022-09-19 | 2022-09-19 | Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115533117A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008095163A (en) * | 2006-10-16 | 2008-04-24 | Osaka Univ | Method of forming nanometal particle and method of forming nanometal thin film, and method of controlling size of nanometal particle |
| JP2008308735A (en) * | 2007-06-15 | 2008-12-25 | Ulvac Japan Ltd | Method for carrying nanoparticles using coaxial type vacuum-arc vapor deposition source |
| CN103359734A (en) * | 2013-08-07 | 2013-10-23 | 常熟苏大低碳应用技术研究院有限公司 | Method for preparing metal carbide film and metal carbide composite film |
| CN111618313A (en) * | 2020-05-14 | 2020-09-04 | 西安石油大学 | Method for preparing silver nanoparticles based on microfluidic technology |
| CN111940757A (en) * | 2020-08-14 | 2020-11-17 | 江南大学 | Device and method for continuously preparing noble metal and alloy nanoparticles thereof |
| US20210380405A1 (en) * | 2020-06-04 | 2021-12-09 | Savannah River Nuclear Solutions, Llc | Systems and Methods for Manufacturing Nano-Scale Materials |
-
2022
- 2022-09-19 CN CN202211138766.7A patent/CN115533117A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008095163A (en) * | 2006-10-16 | 2008-04-24 | Osaka Univ | Method of forming nanometal particle and method of forming nanometal thin film, and method of controlling size of nanometal particle |
| JP2008308735A (en) * | 2007-06-15 | 2008-12-25 | Ulvac Japan Ltd | Method for carrying nanoparticles using coaxial type vacuum-arc vapor deposition source |
| CN103359734A (en) * | 2013-08-07 | 2013-10-23 | 常熟苏大低碳应用技术研究院有限公司 | Method for preparing metal carbide film and metal carbide composite film |
| CN111618313A (en) * | 2020-05-14 | 2020-09-04 | 西安石油大学 | Method for preparing silver nanoparticles based on microfluidic technology |
| US20210380405A1 (en) * | 2020-06-04 | 2021-12-09 | Savannah River Nuclear Solutions, Llc | Systems and Methods for Manufacturing Nano-Scale Materials |
| CN111940757A (en) * | 2020-08-14 | 2020-11-17 | 江南大学 | Device and method for continuously preparing noble metal and alloy nanoparticles thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111940757B (en) | Device and method for continuously preparing noble metal and alloy nanoparticles thereof | |
| Kong et al. | Bridging the gap between reality and ideality of graphdiyne: the advances of synthetic methodology | |
| JP5309317B2 (en) | Method and apparatus for producing carbon nanostructure | |
| CA2560263A1 (en) | Modified carbon products and their applications | |
| WO2012028695A2 (en) | Method for depositing nanoparticles on substrates | |
| WO2003008331A1 (en) | Preparation of carbon nanotubes | |
| EP2714590A1 (en) | Installation and method for the functionalization of particulate and powdered products | |
| CN107651708A (en) | A kind of method that microwave hydrothermal prepares 1T@2H MoS2 | |
| Sui et al. | Plasmas for additive manufacturing | |
| CN103882412A (en) | Method of preparing high-barrier film by adopting plasma jet | |
| JP2023549718A (en) | Powder processing and ball milling production equipment and method using continuous low-temperature plasma | |
| CN115533117A (en) | Pt/SiO prepared by coupling 3D printing and limited-area discharging technology 2 Nanoparticle devices and methods | |
| CN111687425B (en) | Core-shell structure nano material and preparation method thereof | |
| US20050281944A1 (en) | Fluid-assisted self-assembly of meso-scale particles | |
| CN113237867B (en) | Device and method for preparing surface enhanced Raman substrate by coupling micro-fluidic technology and plasma technology | |
| KR101501164B1 (en) | Platinum-based bimetallic catalyst using successive solution plasma process and device for manufacturing and synthesis method thereof | |
| CN108249429B (en) | Method for modifying nano or micro particles continuously by plasma | |
| CN107952433B (en) | Preparation method and device of nano metal/carbon nano tube/titanium dioxide catalyst | |
| CN115845752A (en) | Device and method for continuously preparing core-shell structure composite nanoparticles | |
| WO2018182995A1 (en) | Methods of making metal particles | |
| CN211828678U (en) | Plasma reaction equipment | |
| CN116575018A (en) | Device for preparing InAs nanowire array in positioning mode and preparation method | |
| CN109499565B (en) | Method for preparing carbon-loaded platinum nanoparticles by one-step method | |
| TWI250685B (en) | Fuel cell, method of manufacturing the same, electronic apparatus and vehicle | |
| CN110499497B (en) | Preparation method of titanium dioxide nano film and titanium dioxide nano film |
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 |