TW201121981A - Platinum complex and methods for making platinum complex and platinum catalyst therethrough - Google Patents

Abstract

A method for producing Pt complex is adding chloroplatinic acid (H2PtCl6) and a chelating agent into a solvent by continuous stirring so that [PtCl6]2- can decompose from chloroplatinic acid and then combines with the chelating agent to produce a Pt complex in a form, Pt[R]2+. The chelating agent can be selected from diethylenetriamine, triethylenetetraamine, ethylenediamine, 1, 10-phenanthroline, or 2, 2'-Bipyridine. A method for producing a Pt catalyst further includes a reduction step and a drying step. In the reduction step, Pt complex is reduced to Pt. In the drying step, the solvent is removed from Pt to get the Pt catalyst. A method for producing a Pt/C catalyst is mixing chloroplatinic acid, chelating agent and a support with a slovent to form a Pt complex on the support. Pt complex on the support is reduced to form a Pt/C. Following, the solvent is removed from Pt/C to get the Pt/C catalyst.

Description

201121981 VI. Description of the Invention: [Technical Field] The present invention relates to a complex compound and its use, and more particularly to a platinum complex, a method for producing the platinum complex, and the use of the platinum complex A method for producing a platinum catalyst, and a method for producing a platinum/support: a medium using the platinum complex. [Prior Art] Platinum does not react with strong acids or strong bases at room temperature, and does not combine with oxygen or sulfur-containing compounds in the air. Even under normal high-pass, the chemical properties remain stable. Currently, in the petrochemical and energy industries, it is mainly used as a catalyst (such as platinum catalyst). In the petrochemical industry, platinum catalysts can help increase oil production. Most refinery centers have a catalytic device coated with a molybdenum catalyst that is catalytically catalyzed by a platinum catalyst to convert the vaporized oil flowing through the catalytic converter into the desired form. In addition, most automotive exhaust gas purifiers convert carbon monoxide and unburned hydrogen barrier compounds into harmless carbon dioxide and water vapor by using a ceramic body coated with a palladium (Pd) alloy coating. In the energy industry, it is well known that there is a shortage of world oil sources. The development of fuel cells for commercial use has received widespread attention. Fuel cells are seen as the main source of green energy, with only roomless carbon dioxide, water and air. Among them, proton exchange membrane fuel cells (pEMFC, pr〇t〇n exchange membrane fuel cell) have been widely recognized as one of the key development technologies. The fuel cell's power generation is mainly through the input of hydrogen and oxygen from the outside world. In 201121981, the fuel (Fuels) is energy traced, and the material of the catalyst is added to the electrode of the battery to pass through the platinum catalyst. The reaction of the material is carried out to carry out the electrochemical reaction - the monthly b ^ electron reaction system decomposes the hydrogen of the anode into the Greek ion and combines the oxygen and hydrogen ions of the cathode with the electrons into two; ==Γ, the _ Catalytic ability, and the amount of hydrogen and oxygen in the area of the early rise, can also be increased simultaneously. however

The amount/in the self-feeding material 1 exists in the mass form, and the specific area of the granules in the pure shell is not in accordance with the requirements of the comparative surface area of the catalyst, so it is necessary to enter the step surface force m to obtain the catalyst of the nanoparticle. . In this way, the surface area of the medium can be improved, and the use of the medium can be reduced. The manufacturing method of the conventional touch medium is to use gas shop (chl〇r. careful coffee = 2PtCl6 · 6H20) as the main source of the nano level. The cuvuccinic acid is usually obtained by dissolving (iv) hydrochloric acid containing a large amount of Wei's aqua regia or excess chlorine gas, and the Kawasaki water is a mixture of U 3 nitric acid and concentrated hydrochloric acid. Wang Shui can dissolve the platinum system smoothly because the gas ions can induce the formation of a stable platinum complex ion [PtCl6]2-. The dissolution reaction was as follows: 3pt + 16 H+ + 4 NO3' + 18 Cl' -. 3 [PtCl6]2- + 4NO + 8 H2〇. Conventional platinum catalysts are generally produced by reacting a chloroplatinic acid-crossed ion [PtCl6]~ with sodium nitrate (NaN〇3) at a temperature of 500 ° C to obtain iridium oxide (PtO). Then, by a reduction step, ruthenium oxide is heated to 560 ° C to decompose to obtain a platinum catalyst. The above-mentioned conventional method for producing a catalyst is to directly convert a chloroformic acid into a wrong ion [Ptc! 6] 2 and a redox reaction with sodium nitrate to form an oxidized sub-201121981 platinum (Ρί〇). However, due to the aggregation and bonding of the +2 valence platinum ions of ruthenium oxide (ΡίΟ) Yin, the manufacturing method of the conventional media cannot effectively control the number of bonds between the turned ions, resulting in the completion of the Lai Cai The obtained catalyst particles are too large, and the distribution of the medium age range is too wide, so that the specific surface area and uniformity of the catalyst can not be effectively improved, thereby affecting the degree of the medium and the catalytic ability. & system, 1 to improve the above-mentioned conventional method of manufacturing the tactile medium, the conventional method of the kinematic medium of the carrier/supporting agent is attached to the carrier to the dragon body: the servant (four) points The conductive (four) body can enhance the force and stability of the sagittal catalyst' and can increase the contact area of the shop and the ability to withstand the pressure.曰目Do not use stone anti-black as the beginning of the carrier / carbon black catalyst C = many years ~ medium with better dispersion, particles: = cost her reading point, the current main test proton exchange membrane fuel ^ know uranium / carbon The black catalyst is produced by dissolving chlorine (tetra) and adding appropriate amount of carbon black as a support. After stirring uniformly, the solvent is used.

Then in a reduction step, the 藓-, L-carbon black catalyst is used. The material U is called a forming-turning/returning method, and the manufacturing method of the conventional turning/carboniferous black catalyst is carried out, so that the above-mentioned two: = valley easy random aggregation bonding, and the shaft made by the material is produced 0 r too wide 'capacity! agglomerate, make black black touch =::: even and then make 5 hp /% black catalyst specific surface area can not have the catalytic ability of the two platinum / carbon black catalyst. > 'Influence of the 201121981, the second method of manufacturing the carbon black catalyst, such as the manufacturing method of the Republic of China public 55547H tiger high performance platinum catalyst" 1 main material · body through the high heart ink, ^ It is attached to the treated carbon black and is dispersed like her carbon black catalyst. The detailed process is as follows: the chlorine fine 19 is solved in the water towel 7

Adding sodium carbonate solution and sodium hydrogen sulfite solution to the human brix solution to form 冉 = adding sodium carbonate solution - Shen Dian 16 [Na6Pt(SQ3)4]::, then Na6Pt(S03)4 is dissolved in water and added to ion exchange In the resin, this = +2 price shop, after adding the carbon black treated by the person, after stirring evenly, adding hydrogen peroxide (H2〇2) as a reducing agent in the second reduction step, and then filtering and drying the precipitate by using the -^ step. Dry, and finally with a temperature of 2 〇〇 to 25 〇, hydrogen for reduction treatment. However, 'the other conventional platinum/carbon black catalyst manufacturing method still directly reacts with molybdic acid as a reactant', so that the above-mentioned platinum ions are easily bonded to each other, thereby causing turning/ The range of carbon black catalyst particles is less widely distributed, and it is easy to agglomerate, resulting in poor dispersibility, etc., which in turn affects the specific surface area of platinum/carbon black catalyst and reduces the catalytic ability; furthermore, it needs to add several solvents for reduction 'in the process It is also relatively complicated. Furthermore, it is known in the white/carbon black code medium manufacturing method to focus on the interaction between carbon black and turnover, because the interaction between carbon black and platinum is considered to affect the dispersion, growth and structure of platinum particles. The main key. In fact, how to effectively control the concentration of platinum particles is the effective way to increase the catalytic capacity of the carbon black catalyst and improve the current density and power of the fuel cell. For the above reasons, the present invention reacts with a platinum chelating acid and a chelating agent to form a platinum complex. The platinum complex is coated with platinum ions by the chelating agent 3 201121981 to bind the _ sub-interstitial, so 1 also. The lack of ^. The turning error is used as the side wheel (four) Xie, == [Summary of the Invention] The object of the present invention is to provide a uranium complex, which is formed by the scorpion, and is added to the law, and the manufacturing of the complex is free. Transferring the product to produce a regenerative binding reaction, the material is separated from the two == object 'to avoid the catalyst particle catalyst manufacturing method, _ _ the invention again - the purpose of the secret. The purpose of the catalytic activity. _Specific surface area, enhance the touch. The second objective of the present invention is to provide a method for the purpose of particle uniformity distribution of the surface/supporting catalyst particle size distribution. Increasing the uranium/support catalyst This rabbit is intended to provide the purpose of the particle dispersibility of the manufacturer of the surface/support catalyst (4).増 増 増 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / . For the purpose of the invention, the technical content of the present invention is as follows: A platinum complex having the formula Pt[R]2+' wherein R is diethylenetriamhie or triethylenetetraamine ), ethylenediamine, 1,]0-phenanthroline (1'10-phenanthroline) and 2,2,_0 is one of (2,2LBipyridine). A platinum complex The method comprises the steps of: mixing a gas platinum acid with a chelating agent in a solvent, so that a platinum complex ion [ptCl6]2- of chloroplatinic acid reacts with the chelating agent to form a first complex. The manufacturing method comprises the steps of: chelating a chloroplatinic acid and a chelating agent in a solvent to form a platinum complex solution, so that the platinum chloroplatinic acid in the ruthenium platinum complex solution is a platinum complex ion [ ptCl6] 2_ reacts with the chelating agent to form a platinum complex. In a reduction step, a reducing agent is added to the (tetra) compound to form a suspension, and the compound is reduced to platinum. The reduced platinum in the suspension is dried to obtain a uranium catalyst. & A uranium/support catalyst The method comprises the steps of: integrating the chloroplatinum, a chelating agent and a support into a solvent to form a uranium complex solution containing the support, such that the oxonic acid in the solution of the axial complex The tactile ionic ion -6f reacts with the chelating agent to form a complex compound and is attached to the support. The reduction step adds a reducing agent to the human body complex = liquid to form a suspension. The wrong person who is adsorbed on the support is moved into a seam. - Lin Noodle will dry the towel/load 仃 to obtain a platinum/support catalyst. 201121981 [Embodiment] The above and other objects, features and advantages of the present invention will become more apparent and obvious, and will be described in the following detailed description. The complex compound can be further applied to a platinum catalyst or a platinum/support catalyst production method. 1. The method for producing the complex of the present invention:

The method for producing a platinum complex of the present invention comprises a chelation step. The chelating step is carried out by placing chloroplatinic add (H2Pta6 · 6H, 0) and a chelating agent in a solvent to form a platinum complex solution, so that the platinum platinum complex ion [PtCy2· reacts with the chelating agent to cause platinum ions to be coated in the chelating agent to form a platinum complex. The solvent may be selected from the group consisting of water, ethanol, diethyl ether, acetone, and the like. For example, the solvent of the present invention is selected from water or an aqueous ethanol solution. The chelating agent of the present invention may be selected from the group consisting of diethylenetriamine (NH2CH2CH2NHCH2CH2NH2) (DETA), triethyltetramine (C6H18N4) (triethylenetetraamine, NH2CH2CH2NHCH2CH2NH 012012>^2), ethylenediamine b; 1^(^1^ this, >^2012(^2]^2), 1,10-phenanthroline (1,10-phenanthroline, C] 2H8N2), phenanthroline (C12H8N2), 2,2'·Tie ratio bite (2,2'-Bipyridine, C丨〇H8N2) or bipyridine (B)H8N2), etc. For the convenience of description, the following diethylenetriamine is abbreviated as "dien"; The triethylenetetraamine is abbreviated as "trien"; the ethylenediamine is abbreviated as "en"; the bipyridine is abbreviated as "bpy"; and the phenanthroline is abbreviated as "phen". 201121981 More specifically, the aforementioned method for producing a platinum complex of the present invention The chelating step S1 is preferably carried out by mixing the chelating agent with platinum in a molar ratio of 1:1 to 3: in the solvent, so that the chloroplatinic acid is dissociated in the solution by the platinum complex ion [Ptcy2 and The chelating agent undergoes a reaction to form a mask complex of the present invention. 'When the chelating agent is diethylenetriamine, the chelating agent and platinum have a molar ratio of preferably 1: 1 to 2: 1, a platinum complex formed by reacting with chloroic acid and the solvent. For Pt[dien]22+; when the chelation

When the agent is triethylenetetraamine, the chelating agent is preferably 1:1 to 1.5:1, and the platinum complex formed by the reaction is Pt[trien]2+; The chelating agent is ethylenediamine, and the chain complex formed by the reaction is pt[en]2+; when the chelating agent is 2,2, _ %ρϋ, 2,2-bipyridine, The platinum complex formed by reacting with chlorinic acid and the solvent is Pt[bpy]22+; when the chelating agent is uo-phenanthroline (l,10-phenanthiOlme), reacting with chloroplatinic acid and the solvent The resulting complex compound S Pt[Phen] produces 'where the chelating agent is ethylenediamine, 2,21-bipyrene D疋 and UG-Hi ''g mixture is more suitable for 2: 3 1 Thus, the face complex of the present invention can be prepared. In the method for producing a ten-clamp compound, in order to make the gas mixture = more uniform to be mixed with the chelating agent, the chlorinating acid disk = chelating agent is preferably mixed in a stirring manner in the chelating step S1, wherein the solvent is held讳ir City mix 'and then mix the chlorine _ with the mixture in the solvent, the car I = magnets ordered to hold. Then, the chlorine is rubbed into the solution with the chelating agent, and the ultrasonic wave is shocked to mix the chlorine bribe with the chelating agent in the solution, and the ultrasonic wave is applied for 4 to 6 hours, more preferably = 201121981 The manufacturing method is not in accordance with the composition. Since the _ sub-self is easy to restore, the number of combinations between each other is different. While the present invention: = agent = pin complex solution, the process of the present invention can be completed to form the complex of the present invention. ^ The method of manufacturing the enamel ion-like complex is based on a ten-centered chelating system with a metal atom or a cation two = its empty orbital domain with a lone pair of electrons (1_" charged anion or polarity The combination of molecules forms a complex sub-bonded two-week sub-group. The ligand is defined as a central metal atom or a cationic molecule knife or ion. The ligands can be mainly divided into three categories: (1) neutral H2〇1|±y knife and Unbonded electron pairs, for example: nh3, milk + outer 'Γ anion: all can be used as ligands (3) cations: all can not be used as ligands. The ligands can be divided into single dentate, multidentate two = medium: Jinxin metal 扃 early New 1, C0, CN, H20, etc. There is more than one combination of multi-dental and neutral- or 1% ionic. The multi-dentate metal is the complex formed by ί_Γ. Compound (Kailing, "chelating,", the meaning of two bismuth. The first condition for the formation of a sound compound is that the integrator must have s, two, two: a coordinating atom that can provide an electron pair (mainly Ν '〇, ', the double base of the base of the base: can provide two pairs of l〇nepair and medium - 12 — 201121981 heart atom Combine 'for example, C2〇4"_(oxalate), ethylenediamine (H2NCH2CH2NH2, abbreviated as en), carbonate (CO32-), tartrate (c4h4o62·), sulfate (so/-). Six teeth base: can provide six pairs of lone pair combined with the central atom (ie, there are six places in the junction with the central atom) 'such as ethylenediaminetetraacetate (^11) '161^(^!1111^©1^3 61 & 16, abbreviated EDTA. The second condition for the formation of a chelate is that every two coordinating atoms that provide an electron pair must be separated by two or three other atoms to form a stable five-atom ring. Or a six-atom ring. The coordination number is defined as the number of unshared electron pairs attracted by the central atom or the total number of atoms at the center atom and the ligand. The same metal atom or ion may form a different kind of complex, so The coordination number is not fixed. Therefore, a chelating agent which satisfies the above conditions for forming a complex (chelate) can be used in the method for producing a platinum complex of the present invention. 2. The platinum complex of the present invention The formula of the complex which is obtained by the above-described method for producing a complex of the present invention is Pt[R ]2+, wherein R is diethyltriamine-^(ethylenediaminehlJ^ah^pJ'-BipyridinejAl'lO- phenanthroline (l,10-phenanthiOline) to form Pt[dien]2' Pt [trien, Pt[en, [Pt(bpy)2, and [pt(phen)2]2+). Thus, the complex of the present invention has a uniform dispersion in a solution. Therefore, it can be further applied to a gas turbine converter, etc. Since the dispersion uniformity of the turned-over complex obtained by the above-described method for producing a complex compound is good, it can be further applied to the production of a platinum catalyst. In order to improve the dispersion uniformity of the platinum catalyst. 13 201121981 3. Method for producing platinum catalyst of the present invention: The eye is shown in Fig. 1. The method for producing a platinum catalyst of the present invention comprises a chelation step S], a reduction step S2 and a drying step S3. To obtain a platinum catalyst. & In step S1, a gas acid (chl〇roplatinic acid H2PtCl6 6H2O) and a cheilating agent are placed in a solvent to form a platinum complex solution, so that the platinum platinum complex ion [ PtCU]2· reacts with the chelating agent to form a platinum complex. The chelation step S1 of the method for producing the platinum catalyst of the present invention is the same as the above, and will not be re-stated here. The reduction step S2 of the method for producing a pin catalyst of the present invention combines a reduction = addition into the solution of the compound to form a suspension to reduce the foreign matter into a non-rice particle. More specifically, the reducing agent is acid, and the molar ratio of the formic acid to the gas is preferably 20:], in order to reduce the composition of the solution in the money complex solution to the 〆 two-ear ratio system. Affecting the reducing power and the too many two agents of the nano-particles of the nano-particles will lead to less easy to re-granulate. When the chelating agent is too small, the ignorance is not between the water particles. The Wudou number is better than 1:; 3:1 In addition, because platinum ion is preferred in the solution, it is soluble in the test solution: the reduction ability of the 1 towel is more uniform than the acidity. Therefore, the reduction step s can make the reduction medium nai granules more The solution is slowly added to the === mouth after the reducing agent, the test value reaches pH value greater than 7, the core / "until the acidity of the suspension" "--(Na〇H) 14 ~ 201121981 Solution 'and I Hai job shy child ^ Ming better acid test value M gamma _ solution concentration is preferably 〇.5 Μ. The present hair as before · whole is 12 to 14, better ρ Η value is 14. _ 兮 兮 芯 core liquid pH to ΡΗ value greater than 7, after the Μ Μ Μ 进行 进行 进行 进行 进行 进行 进行 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超 超More uniform, . The 曰1 is preferably 〇. 2 to 5 hours, more preferably 30 minutes; the Xuan reducing agent is added to the county by the microwave method, and the sputum is cooled to another 30 minutes. Private; liquid heating, microwave heating time is preferably 3 . The present invention transmits the microwave power through the clock to be a biliary dispersion and a conversion effect. 4 for rapid high temperature, so that the tumbling particles are more evenly temperature =:=!: After the heat, the better suspension of the suspension is placed in the chamber, and the initial n 21 original arsenic rice is more difficult to be more consistent with the platinum angle: dry ^Step S3 ' is to carry out the reduced uranium n # :=. More specifically, in this embodiment, after the county is obtained -,), the sinking substance is placed in the c material (also = the temperature range is preferably observed; drying is performed, and at 373 K, it remains between 423 K). When the drying temperature is low, the solvent having a drying temperature higher than 423 will be less volatile. Further, it will be decomposed and disappeared. The drying time is higher than that of the reduction of the pin 4, and the platinum catalyst is present and the brewing time is small. After drying, it can be preferably formed into a ball 1 = catalyst. The method of making the platinum catalyst of the present invention is also completed. Please refer to, 筮 筮 β β 所 所 所 所 所 所 所 所Catalyst manufacturer 201121981 ^ After the reduction step S2 is completed, it is preferred to carry out the separation step and then to the drying step, step S3. The separation step S21 is to separate the white liquid from the liquid towel. Thereafter, the drying step s3 is performed. Further, the sheep 1::2 embodiment is performed by centrifuging the suspension to make the reduced molybdenum: , 'separated from δ. ten liquid. Preferably, the mixture is further ethanol and Deionized aquatic product 2: precipitate (reduced platinum). Thus, the reduced platinum can be made in the suspension; 'more complete in the night The method for producing a surface catalyst according to the present invention is characterized in that the chelating agent (iv) in the chelation step s] is ion-coated on the chelate to form a heterocompound, so that the core complex The mutual binding ability is lowered, so that the compounding compound can be uniformly dispersed in the solvent towel, and by reducing the center plane of each (10) compound, the bonding force between the members is effective to control the number of bonds between the seeds. The fine (tetra) nanoparticle can be uniformly grown by improving the dispersibility of the fN self-catalytic nanoparticle. In addition, in order to increase the dispersibility of the platinum catalyst and enhance the catalytic activity and stability of the platinum catalyst, platinum can be attached to A platinum/support catalyst is formed on a support, and the platinum/support catalyst is used to increase the contact area of the catalyst and increase the pressure resistance. Therefore, the platinum complex of the present invention can be further applied to platinum. / Preparation of carrier catalyst. 4. Method for producing platinum/support catalyst of the present invention: Referring to Fig. 3, the platinum/support catalyst production method of the present invention comprises a chelation step S. 〖, a reduction step S2, and a drying step S3, ' to prepare a platinum / support The chelating step S1 of the method for producing a platinum/support catalyst of the present invention comprises mixing chloroplatinic acid, a chelating agent and a support into a solvent to form a platinum containing a body. The complex solution is such that the platinum is misaligned from the heart (4) ===acid_' the chelating agent and the solvent; and the non-status; wherein the carrier is preferably selected from the porous year; It is a low-porosity support and a porous support H sub-body such as • pumice, heart ==, etc.

It is preferably carbon black and a dioxide material. The invention is more face 2 temple. The carrier of the present invention is used to increase the specific surface area of the turning and to increase the turning amount. As the white carbon, the carrier can reduce the subsequent use of the catalyst to be used for _, and also the amount of use is low. The invention is optional _: the meal mixture is added with the solvent, and then the support is added, of course, the body is added to the solvent, and then the gas acid and the chelating agent are added, or the acid, the chelating agent and the support _ Add people to dissolve money. Thus, the gas surface ==$ion _6]2· reacts with the chelating agent to form the cleavage compound, which can be adsorbed on the surface of the support, and uniformly dispersed, and further increased. Subtraction of the compound. Alternatively, the support may be subjected to a reaction S 2 0. Alternatively, the support is preferably hydrochloric acid (hc the support) to impregnate the metal impurities on the support, and then to wash with deionized water. The carrier is used to remove the impurities in the cage, so that the reduction is dispersed on the carrier, thereby preventing the chloride from binding to the size of the nanoparticle. Furthermore, the dispersion is more uniformly dispersed in the nanoparticle. The solvent is not agglomerated. Before the solvent is added to the support, the body is uniformly mixed with anhydrous alcohol to form a -support solution, and then the support solution is added to the solvent 201121981 to make the subsequent reduction奈 验 分布 分布 _ 体 体 体 。 。 。 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺 勺After the solvent is placed in the carrier, the mixture is mixed in a super-sequence, and the super-mixing agent and the carrier are further in the solvent. (The wave is between 4 and 6 hours, more preferably 4 small 3) As shown in the figure, the manufacturing method of the present invention is the same as:: two: the step S2' is to add - the reducing agent plus eight of the compound dissolved = (four). More;;:! The ship is attached to the support and the money complex is reduced to 妒; more 砰", the deactivating agent is the same as the above selection, and this is not the case == the reducing agent makes the solution in the solution The opening object f, the fine trace and the object carrier will scream in the suspension. The drying step can be directly performed by the picker. Preferably, the step: S2' is preferably adjusted to adjust the suspension. The steps of the acid value of the ultrasonic vibration method and the natural cooling of the night at room temperature are the same as the above, and the drying step of the method for producing the surface/supporting catalyst of the present invention is not the same. The platinum/support reduced by 5 liters is dried to obtain the platinum/support catalyst. More specifically, in this embodiment, the precipitate in the suspension (reduced platinum/support ° is taken out) After the 'thinking matter is placed in a vacuum supply box for drying, the drying and production range and time are as described above. After drying, the shaft/supporting medium can be obtained. The molybdenum/supporting catalyst manufacturing method of the invention is obtained. The cut carrier catalyst is preferably *~ 18 — 201121981 spherical. At this point, the date of the hair is completed. / The carrier catalyst nanoparticle is divided into two parts: the medium medium nanometer has a narrow distribution range and the particle size is consistent. The monthly text 'and the flipping = outside, please refer to the fourth step, the step of the invention S2l, % $, 乂1, the other knows to carry out a sub-system to reduce the scale of the reduction ^ the drying step Λ S3, the separation step 'S1', step S3,., more detailed after separation from the suspension The drying is further carried out so that the embodiment of the shoulder is centrifuged and separated. It is expected that the (four) material is completely washed by the water in the liquid. The original flip/support can be more completely divided into the suspension. The detailed method of the method for manufacturing the support catalyst is as follows: The method for manufacturing the flip/support of the lying household Hr embodiment For the preparation of the fine carbon black for the sake of convenience, in order to facilitate the description of the convenience, the stone is black as the support - the medium is abbreviated as Pi / C_x / the carrier catalyst f = 2, 3 or 4, etc. In the preparation method of the present invention, different distillate, (4) synonymous surface and coordination number can be used for chelation = __ medium, in the mixture, water is used as diethylenetriamine (diethylenetriamine) As a chelate as a carrier. The solution is prepared by dissolving 450 mg of Vulcan xc-72 carbon black as the solvent, and then imparting the 'chlorinic acid and the conjugate to the chelating agent::' The external network 2+, the inside is W house grams, and the amount of gas platinum acid is 26.lml. The —19 — 201121981 Hydrochloric acid (HC1) and water remove the side material on the carbon black _ into: the starting complex solution, so that carbon black is included. .2 _] = two gas, the chelating agent and carbon black are more fully mixed by the ultrasonic shock box complex solution forming - paste, two: set percentage is about 5%, compared The carbon black and the (tetra) compound are sufficient, and the reduction step S2 is followed by the reduction of the amount of the (a) reduction, preferably 5.2 ml, and the concentration: into the second paste to form a Suspension, a pair of acid-packed molybdenum 20 . 1, then adjust the pH value, 25m, alum, ',, the solution is slowly added to the order, emulsified _a 〇 H) until the acid test of the liquid The value reaches... The receiver must use the ultrasonic wave to shake it for 3 minutes, then put the county into the microwave oven to 7 times the power of the microwave for 6 minutes, then the county; = naturally cool at room temperature, so that it is adsorbed On the carrier, the body is mixed with the mother == and in the suspension. Then, after performing the second surface::, the separation support is separated from the surface liquid by the separation step S21. The surface/support is preferably washed with ethanol and deionized. Finally, the drying step S3 is carried out, and the crucible is placed in a vacuum oven having a temperature of about 373 K to 423 K to dry, thereby obtaining a carrier catalyst (abbreviated as Pt/C catalyst). The hair of the Japanese biliary carrier, the nanoparticle, is preferably formed into a one-sided cubic (fcc) crystal structure. Please refer to Figure 5 for the relationship between nanometer 粑 and 3.7_ made by Sit' average particle size of 25nm, standard = .5_. The conjugated nanoparticle of the present invention has a concentrated range and good chemistry. In addition, please refer to the gamma to _, from the different magnification concept - 20 - 201121981, it can be seen that the 纟 米 颗粒 granules are all self-distributed in the carrier carbon black. The particle distribution is obtained by measuring the random area. And use s as the equation to calculate the average particle size. In the method for producing a platinum/support catalyst according to the second embodiment of the present invention, the manufacturing method is the same as that of the first embodiment, except that the chelation step, s], = triethylenetetraamine is used as Integration should be formed to form a bribe and turn ηεηΓ, its _ (4) grams and the amount of gas is 26.1ml. For the rest of the steps, please refer to Lin: The application method is to describe the manufacturing method, and here is no longer the face (::6: ΓThe second embodiment of the invention is made by: pt/c-tnen) The nanoparticle range is from u to 2.5·, the average particle size is 2.7, and the standard deviation is 0.3. The range of the catalyst of the present invention is concentrated and the dispersion is good. Please refer to paragraphs (1) to ...^. It can be seen from different magnification TEM images that the nano-particles are consistent (4) in the carbon black of the support. The knife is horrible, and the method of manufacturing the third-phase of the invention is The method is the same as that of the first embodiment except that the chelation step is:; ethy] en2e+diamme acts as an integrator to react with chloropropanoic acid to form a complex Ct[en]2, wherein the amount of the chelating agent is 2〇mg, and the amount of chloroplatinic acid is 26. (5). For the rest of the steps, please refer to the first embodiment, and no further re-stated here. The invention of the third embodiment of the invention is shown in the following: Consumption: between ^ and ^ Cong 'average particle size is - two:, 〇 3 faces. The platinum / support catalyst nanoparticle range of the present invention is in the market and is good in bulk. In addition, please refer to In Figures I2a to 12c, it can be seen from different magnifications that the nanoparticles are uniformly and evenly distributed in the carbon black of the 201121981. _Table-, nano-particles of different pin/support catalysts (Pt/c) Size, particle size, and uranium content are related to each other. mi ^ 〇 in the white complex of the initial / carrier touch particle size standard deviation of the particle range in the white content medium (Pt / Cx) (nm) (nm) (nm) ( Wt.%) Pt[dien]2+ Pt/C-dien 2.5 ------- A r 1.5-3.7 12.6 U. D Pt[trien]2+ Pt/C-trien 1.7 0.3 1·]~2.5 9.8 Pt[en]22+ Pt/C-en 2 0.3 1.1-2.5 8 — Pt/C-ETEK 2.6 — 1.2 ～4.3 20 ...from the table – and the results of the 5th to 7th ® The average nanoparticle size of the catalyst is in the order of Pt/C_ETEK (--------- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Pt/C-en>Pt/C-trien. Among them, the platinum/support catalyst (pt/c_trien) has a relatively narrow particle size distribution and smaller particles than platinum/support catalysts (pt/c_dien and Pt/C-en). The average nanoparticle size is related to the nitrogen coordination number in the chelating agent. The platinum complex contains one or more penta atom rings or a six atom ring, and thus has a high formation constant (f〇rmati〇n constant), and the resulting complex is relatively stable. Platinum complexes Pt[trien]2+ is formed by bonding a central platinum ion to three five-atom rings and four nitrogen atoms. The platinum complex Pt[dien]2+ is bonded by a central platinum ion to two five-atom rings and three nitrogen atoms. The thermodynamic stability of Pt[trien]2+ is about 103 times higher than that of Pt[dien]2+. Thermodynamic stability affects the rate of reduction, which in turn affects particle size and particle distribution. The Pt[trien]2+ reduction rate is slower than Pt[dien]2+, so the formed platinum nanoparticles and particle distribution are smaller than Pt[dien]2+. Among them, the platinum content in the platinum/support catalyst is measured by inductively coupled plasma spectrometry (Inductively-Coupled — 22 — 201121981

Plasma spectrometer, ICp_A: ES). Among them, commercially available solid chloroplatinic acid (i.g. parent 3<:}11〇1, such as 1^&(^,}1:^(:16,99.995%) is added to 1〇〇宅升The chloroplatinic acid solution obtained by diluting the deionized water, the platinum content of the chloroplatinic acid solution is 431.7 mg as measured by ICP. In the method for producing a platinum/support catalyst according to the fourth embodiment of the present invention, the manufacturing method and the Consistently the same application 'with 450 mg of Vulcan XC-72 carbon black as the support. The only difference lies in the chelation step S1, in which ethyiene (jiamine • (ΝϋΑ^ΟΗζΝΗ2) is used as a chelating agent, the chelating agent and gas The platinum acid is placed in an aqueous solution of ethanol to form a platinum complex Pt[en]2+, wherein the platinum is 〇33 mmol, 0.67 mmol, 1 mm〇i, respectively, relative to the ruthenium containing the stone. The ratio of the chelating agent to the platinum is 2: 1. The ratio of ethanol to water in the aqueous ethanol solution is preferably 1:4, and the rest of the steps are referred to the first embodiment, and the description is not repeated here. Chelating agent, the effect of different platinum content on the catalyst particles. According to the ratio of platinum to carbon black molars, 铂.%, 〇.67, 1 mmol, obtained platinum/support The media are represented by pt/c_ei>1 platinum/support catalyst, Pt/C-en-2 platinum/support catalyst and Pt/C_en_3 platinum/support catalyst. Pt/C-ETEK is a general commercial touch. The platinum/support catalyst prepared by the method for producing platinum/support catalyst of the present invention has better particle size or particle range than commercial catalyst. Further, the platinum/support catalyst of the present invention is utilized. The platinum/support catalyst obtained by the production method can obtain a platinum/support catalyst which is uniformly distributed and does not agglomerate even if the platinum content is increased. Please refer to the particle distribution map and Table 2 as shown in Fig. 7a-c. The platinum/support catalyst (Pt/C-en-1, Pt/C-en-2, Pt/C-en-3) nanoparticle prepared by the fourth embodiment of the present invention has a concentrated concentration and good dispersion. Table 1. Under the same chelating agent (ethylenediamine), according to the surface content, it is not 201121981.

Pt/C-en-l Pt/C-en-2 Pt/C-en-3 Pt/C-ETEK 1.9 2.0 2.2 2.6 7.6 17.8 30.2 20 52 79 99 1-2~3.0 1.3 ~2.7 】·6~3.0 1.2 to 4.3 The catalyst method of the fifth embodiment of the present invention and the first embodiment _ are only for the (4) step S1, = 2, 2. As a chelating agent, it is reacted with valproic acid to form a compound Ctp[bpy, wherein the chelating agent is used in an amount of 52: ^ and the initial acid is 1 in 2.6 ml. For the rest of the steps, please refer to the manufacturing method of the first ship/support catalyst, which will not be repeated here. Please refer to the figure. The platinum/support catalyst CbPy obtained in the fifth embodiment of the present invention has an average particle size of (9) Cong, and the standard deviation is 〇.4 nm. Please refer to the figures 13a to 13c for different The magnification TEM image shows that the surface particles are uniformly and uniformly distributed in the carbon black of the support. In the method of manufacturing the touch-sensitive contact of the sixth embodiment of the present invention, the method of making, reporting, and the same is the same as the chelation step S1, ^ 1 ' 1 〇 # - 菲 ( (1,1 〇 _ phenanthiO (4) reacts with chloropropanoic acid as a chelating agent, and forms a uranium complex Pt [punching <, wherein the chelating agent is used in an amount of 60 mg' and the amount of gas-surface acid is 261. For the remaining steps, please refer to the first embodiment of the present invention. = /#_ 叙 制作 制作 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the method for producing a platinum/support catalyst according to the seventh embodiment of the present invention, the manufacturing method is the same as the first embodiment, and the difference is only in the chelation step si, in which UO-phenamhroline is used. The chelating agent reacts with chloroplatinic acid to form a platinum complex pt[Phen]22+, wherein the content of platinum relative to carbon black is 〇33 mmol, (K67mni〇b1mmol, the remaining steps, please refer to the first embodiment) For example, it will not be repeated here. According to the ratio of surface to carbon black, Ο·%, 0.67, 1 mmol ' The platinum/support catalysts are represented by Pt/C-phen-2 and Pt/C-phen-3, respectively. Please refer to Table 3 and Figures 9a and 9b for the seventh embodiment of the present invention. Platinum/support catalyst, regardless of the platinum content of 21.4% or 30%, can obtain platinum/support catalyst with concentrated nanoparticle range and good dispersibility. The platinum/support catalyst of the present invention is transmitted by transmission. The electron microscope (transmission electron microscope) was observed to be dispersed in the support and to measure the size of the platinum particles. Please refer to the 14th to 14k graphs for platinum/support catalysts in different regions with a platinum content of 21.4%. TEM schematic diagram. In addition, please refer to the TEM diagram of platinum/support catalyst in different regions with a platinum content of 30% as shown in Figures 15a to 1.5k. It can be seen from the figure that even if the content of the element is increased, the particles can be evenly distributed and not The agglomerated platinum/support catalyst is uniformly dispersed in the carbon black of the support. Table 3. Under the same chelating agent (l, 10-phenanthroline), the platinum/support catalyst nanoparticle according to the platinum content Size, particle range and yield relative relationship.'

S in the white complex platinum / carrier touch particle size standard deviation particle range in white content - J ^ (Pt / Cx) (nm) (nm) (nm) (wt.%) 1.6 0.2 1 '1 ~ 2.5 - ----- 7.5 Pt[phen]22+ Pt/C-phen 1.63 0.2 1 ~2.6 21.4 •—— --——., 1.82 0.3 1-2.8 "--- 30.0 1------ In a method for producing a platinum/support catalyst according to an eighth embodiment of the present invention, the manufacturing method is the same as that of the first embodiment, except that the chelation step s], wherein tnethylenetetraamine is used as a chelating agent and chlorine The acid reacts to form a complex Pt[trien]f. The content of ' _ for carbon black is 〇·33 mm G G.67 mm. 1 mmd, the rest of the steps, please refer to the first embodiment, and will not be repeated here. Please refer to the 16a-i圊, which is a schematic diagram of the catalyst in different regions of platinum content and 55%. In addition, please refer to the diagram called 'Fig. ’ for the different area of the tumbling/supporting catalyst T£M. As shown in the figure, 'Whether the content of the mark is 15.5% or 骂, the transferable catalyst nano-particles are evenly distributed. The age range is wide and the dispersion is good. Even if the turbidity is increased, the particles are evenly distributed and distributed. As shown in Table 4, the non-caking uranium/supported body can be obtained under the control of the amount of platinum/support catalyst with narrow distribution and small particle size. Table 4, Platinum/support catalyst (pt/c) of different platinum content, nano granules, large il, and platinum content; relative open 俜〇4 white complex platinum/supporting particle size standard deviation granules Range Platinum Content Medium (Pt/CX) — 'One (nm) (nm) (nm) (wt.%') 1.7 0.3 1.1 ~2.5 9.80 Pt[trien]2+ Pt/C- trien 2.08 0.3 1.2-3.0 15.5 2.48 0.3 1.6 to 3.2 30.0 In the method for producing a platinum/support catalyst according to the ninth embodiment of the present invention, the production method is the same as that of the first embodiment, and the difference is 45 gram of Vulcan XC_72 carbon black as a support. In step S1, 2'2-b]pyridme(C]GH8N2) is used as a chelating agent, and the chelating agent and gas platinum acid are placed in an aqueous solution of ethanol to form a platinum complex [pt(bpy)2]2. +. Among them, platinum - 26 - 201121981 is 0.33 mm relative to the content of carbon black. Bu 0.67 face. The ratio of 1 mmol to 4 and 5 to 5 is 2: 丨. Preferably, the water in the water solution is ethanol: water is 4: the rest of the steps are referred to the first embodiment and will not be repeated here. According to the age I black mole ratio, 〇_33, 〇·67, 1 mm〇1' obtained the flip/support catalysts were Pt/C-bpy-1 Pt/C-bpy-2, and pt/ respectively. C_bpy_3 indicates. Please refer to Table 5 for use.

^Inventive 1 The method of manufacturing a stomach-physical catalyst is a platinum-supporting catalyst which has a uniform particle distribution and does not agglomerate even if it is made of platinum. Yinshenzhi, 18a-j U, is a schematic diagram of the catalyst chamber in different regions with a content of 18.7%. In addition, please refer to the figure 丨9a-i for the different area/support _ ΤΕΜ diagram of the age of 30β2%. As shown in the figure, the 18.7 % or 3G.2% 'molybdenum/support catalyst nanoparticles can evenly distribute the granules and the dispersion is good. Even if the age is increased, the particles can be obtained evenly. Cloth and not agglomerated | self / carrier catalyst. Table 5, the same chelating agent (2,2'-biPyridine), according to the uranium content and the relative size of the paving catalyst nanoparticle size, particle range and yield

Pt/C-bpy-2 Pt/C-bpy-3 Pt/C-ETEK 1.9 2.0 2.6 1.0 to 3.0 1'3 to 2.9 1.2-4.3 18.7 30.2 20 96 99 In addition, the platinum/support catalyst of the present invention is The proton-parent replacement membrane fuel cell (pEMF〇', ..., is used to combine the platinum/support catalyst with the Nafion8212 fuel cell membrane to form the fuel cell membrane electrode assembly (Membrane electrode assembly, MEA) 'Detailed, in order to put the P t / C catalyst prepared by the present invention into a solvent such as ethanol or isopropanol and a Nafion® solution (5 wt.%) purchased by DuPont to form a uniform sentence The mixed solution is sprayed onto the carbon cloth substrate by spraying, and the worn/c catalyst of the present invention can be applied only to the single electrode or the anode and the cathode at the same time. The Pt/c catalyst of the present invention is coated on two carbon cloth substrates respectively, and the DuPont product Nafion® 212 fuel cell film is placed between two carbon cloth substrates, and then the carbon is heated by a conventional hot pressing method. The cloth substrate is combined with the Nafion82l2i battery film... It can be used for 90 seconds under the temperature pit and the Fortune%(8)(10)2. 6. Select the regional electron diffraction pattern (SeIec Ted _ dectr〇n(1) is similar to patterns, SADP) Please refer to the pt/c catalysts of different chelating agents as pt/c_dien, as shown in the drawings, Ud, 12d and 13d, respectively.

Electron diffraction analysis was performed on Pt/C-en and Pt/C_bpy, showing a silk-faceted cubic structure and high crystallization. 7-X-ray ^^^^(X-ray diffractometer, XRD) In addition, the flip/support catalyst of the present invention is subjected to a diffraction test, and the particle size of the flat sentence is calculated by using the Debye_Seh_r equation. Special U peak (1 1 1). Please refer to the second () to 22, for the Pt / C catalyst prepared by different chelating agents for the haze diffraction analysis test. From the test results, the diffraction characteristic peak at 25 is (4) 2), the carbon black of the present invention (111^^(:72) is a hexagonal structure, and the surface diffraction characteristic peaks are respectively shown in 6, 66 and 81 respectively. 1 1 1), (2 0 0), (2 2 0), and (3 - 28 - 201121981 I)), the Pt/c catalyst obtained by the present invention is a face-centered cubic structure (fee). .cv (Wei voltain surface) curve electrical test: Pt / C catalyst of the present invention and the conventional commercial Pt / C-ETEK (DeNora) touch car and 'test sample manufacturing method is to first touch the female , egg ethanol mixed with 2〇μ1 5% by weight of Nafion solution (DuPont) 5 and ultrasonically oscillated for about 30 minutes to obtain a slurry solution, about 25μ1 of the slurry solution was applied to a carbon On the material electrode (area about cm66cm2), it is dried in the chamber to form a film on the surface of the electrode, that is, the step of coating the catalyst on the electrode. The commercial Pt/C_ETEK catalyst test sample is manufactured as described above. The electrical test was carried out under 8〇1111 and 〇.5]^ sulfuric acid at a temperature of 25 C. The nitrogen was used to activate the electrode activity before the electrical test. The voltage was 〇~1. In the range of 2 V, a cV (cyciic v〇ltamm〇gram) curve was obtained, and Ag/AgCl was used as a control electrode. The chelating agents used in the examples of the present invention were diethylenetriamine 'triethylenetetraamine 'ethylenediamine ' lJO-phenanthroline and 2, 2'- The platinum complexes obtained by Bipyridine are Pt[dien]]2+, Pt[ti,ien]2+, and Pt[en]22+, [Pt(phen)2]2+ and [Pt(bpy)2, respectively. 2+, the formed platinum/support catalysts were named Pt/C-dien, Pt/C-trien, Pt/C-en, Pt/C-phen and Pt/C-bpy. As can be seen from the CV diagram of Fig. 23, the Pt/C-dien, Pt/C-tri.en and Pt/C-en catalysts prepared by diethylenetriamine, triethylenetetraamine and ethylenediamine as chelating agents are more commercial than commercial Pt/C. -ETEK Catalyst electrical performance is better. The active specific surface area is Pt/C-trien>Pt/C-en > Pt/C-dien. In addition, the CV diagrams of Figs. 24 and 25 respectively show that the present invention uses 2,2'-Bipyi'idine and l,l〇-phenanthiOline as a chelating agent to obtain a Pt/C catalyst. Commercial Pt/C-ETEK catalysts perform better, and the active specific surface area is larger than commercial Pt/C-ETEK, indicating that the platinum/support catalyst catalytic ability of the present invention is better than that of commercial Pt/C-ETEK. 9. Single cell test: In order to measure the MEA performance, the single cell operates the MEA at a voltage of 〇5V. Under 24-hour fuel cell conditions, a stable current density and polarization curves are obtained. The results are shown in Figures 26 to 28. As can be seen from the figure, the pt/c catalyst of the present invention performs better than the commercial Pt/C_ETEK catalyst. When the platinum weight accounts for only 12% of the weight of the support, the current density has been Two-quarters of commercially available Pt/C_ETEK catalysts with a platinum content of 40% can be achieved: See also Figures 29 to 31, which show that the platinum/support of the present invention has good electrical stability. Please refer to s._, l for more relevant experimental data.

Lm, C, H. Huang, C, K. Huang, W, S. Hwang, Chem. Comm. (2009), et al. 10. The effect achieved by the present invention: The complexing compound of the present invention is formed by coating a turning ion with a sounding agent, and achieving the function of increasing the stability of the complex.妓 _ 错 错 错 错 错 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , According to the manufacturing method of the medium of the present invention, the manufacturing method of the uranium catalyst is effectively controlled to control the particle size of the uranium catalyst, and the catalyst particle size range is small and the dispersion uniformity is achieved. Good effect. The method for manufacturing the stalk of the stalk, by the chelating step, so that the surface of the invention can be made by the sensation of the nano-particles of the invention. The work of S _ specific surface area and lifting surface catalyst induces the development of the flip/support catalyst of the present invention:: = :::: The distribution of the catalyst particles is small.

The method for manufacturing the surface/supporting catalyst of the present invention is coated in the chelating agent by the integration step, so that the heterogeneous method of the method of the invention is not easy to be combined, and has a high content. Ming's face complex can also be evenly dispersed in the support to achieve the effect of lifting the dispersion of the self-supporting catalyst particles. In the method for producing a guer/support catalyst of the present invention, the method for producing a platinum/support catalyst of the present invention is obtained by the chelating step si'', and the starting point of the particle range distribution is obtained. Granules, which increase the specific surface area of the platinum/support catalyst and enhance the catalytic ability. The present invention has been disclosed in the above-described preferred embodiments, and it is not intended to limit the invention. It is intended that the present invention may be practiced without departing from the spirit and scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims. 31 201121981 [Simplified description of the drawings] Fig.: A flow chart of a manufacturing method of a pure embodiment of the present invention. The figure is a flow chart of a method for manufacturing a separation medium with a separation step. Fig. 3 is a flow chart showing the manufacturing method of the carrier catalyst according to the preferred embodiment of the present invention. The third embodiment of the present invention has a flow chart of the method for manufacturing the separation/support catalyst. Ten maps of this study, the surface of the embodiment of the car / the carrier catalyst (Pt / C-en-1) particle distribution map, in which uranium accounted for # m心 (four) Lai Π — π π 黑 black molar ratio is 0.33 mmol. Brother 7b: The platinum/support catalyst (Pt/C-en-2) particle of the invention is more than the target of 籾 占 佑 θ 铋仏 铋仏 , , , , , , · Peng!. Brother, the uranium/support catalyst (pt/C-en-3) particle distribution map of Ben Maoming's parent example, in which the surface accounts for carbon (W) (3) 3) Figure 8: Good, 歹, is 1 mm〇1. Particle distribution map. Pt/C-bpy particles of the perforated example. Figure 9a: The age of the invention, - (4) Particle distribution map 21% of the steroid catalyst 201121981 Figure 9b · The preferred embodiment of the present invention has a surface content of 3 〇 0 /. Pt / C-phen particle distribution map. = Dan" Figure 10a: The present invention In a preferred embodiment, the diethylenetdamine is used as a chelating agent, and the platinum/support catalyst is at a low magnification. Fig. 10b is a schematic view showing a preferred embodiment of the present invention in which a diethylenetriamine is used as a chelating agent and a platinum/support catalyst.

Figure 10c: A preferred embodiment of the invention, using diethyknetriamine as a chelating agent, a high magnification of platinum/support catalyst. The preferred embodiment of the invention uses diethyldiamine _hyl-(iv) as a chelating agent, molybdenum/support catalyst diffraction pattern (SADP). A

Low magnification TEM with triethyltetramine catalyst Figure 11a: A preferred embodiment of the invention (triethyleneteti'aamine) as a chelating agent, a flip/support schematic.

For example, a triethyltetramine catalyst is used as a chelating agent, and a triethylenetetraamine is used as a chelating agent.

High-magnification TEM with triethyltetramine medium Figure 11c: Preferred embodiment of the invention, (triethylenetetraamine) is a schematic diagram of a chelating agent, a flip/support. Selected region of triethyltetramine medium. Figure 11d: preferred embodiment of the invention, (triethylenetetraamine) when a chelating agent, platinum/support, touches the 201121981 sub-diffraction pattern (SADP). Fig. 2a is a schematic view showing a low-magnification TEM of a platinum/support catalyst as a chelating agent for ethylenediamine. 1st - b Q A preferred embodiment of the present invention is a schematic TEM diagram of the ratio of ethylene diamine ((4) 1 (3) ediamine) hm ′ #/support catalyst. Figure 12c is a schematic illustration of a high magnification TEM of ethylene chelate (dhyi(3) ediamjne) as a chelating agent' The preferred embodiment of the present invention is a selective area electron diffraction pattern (SADp) of ethylenediamine as a chelating agent. Fig. % is a schematic representation of a preferred embodiment of the invention by using 2,2,-bipyridine as a chelating agent, a low ratio of platinum/support catalyst. Figure 13b. A preferred embodiment of the invention, wherein 2,2-Bipyridine is used as a chelating agent in the platinum/support catalyst. Figure 13c. A preferred embodiment of the present invention, using 2,2,-bipyridyl (2,2, Na (4) as a chelating agent, a high-power TEM schematic of the pin/support catalyst. Figure 13d. In a preferred embodiment, a selective region electron diffraction pattern (SADP) is used as a chelating agent, a face/support catalyst, in the form of a chelating agent. 14a_k ® . Illustrative TEM diagram of uranium/support catalyst in different regions with 1,10-phenanthroline (1,1 〇-caine brain as 〇1). K-picture: a preferred embodiment of the present invention, which is a schematic diagram of the TEM of the support catalyst of m• phenanthroline 34 _ 201121981 (= _anthl. (4) when S mixture, uranium content ^. ^ A platinum / (6)-i A preferred embodiment of the present invention, wherein the ti'iethylenetetraamine is used as a chewing man-made system, and the different content of the surface content is 15.5%. Figure 18a-j: The present invention is more than η 〇1 Ό. . ^ ^ soil ~ case, with 2, 2 '- outer 匕 (2, 2-Bipyndme) as a chelating agent, platinum b ^ body catalyst TEM Schematic. In different areas of the .. / 〇 / / 19a-i diagram: the present invention Good every, (2, 2, Royal}, secret) When the chelating agent, turn the second: 歹 1 'to, - 17 17 ° ° fixed catalyst TEM diagram. ' £ 0 · 2 / 〇 different areas of molybdenum / 弟弟20图 · The present invention is preferred for each comparison. Κ & dicing carrier XRD test Figure 21: Comparison of each (Pt / C-bpy) XRD test of the present invention. /Supporting body brother 22 diagram · The invention of the light society ~ (Pt / C-phen) XRD test comparison chart again. Soil only% of the example of platinum / carrier catalyst Figure 23: the preferred comparison of the present invention Example of the flip / support catalyst CV curve measured 图 24 map. The present invention is more smashed ~

Curve test comparison chart. ^Example of molybdenum / support catalyst (Pt / C-bPy) CV brother 25 map. This day on the day ^ ^ car and good examples of platinum / support catalyst 35 -- 201121981 (.Pt / C-phen ) CV curve test comparison chart. The surface/support catalyst voltage power measurement of the preferred embodiment of the present invention is s. t L· *""",] 11 ^ ^(pt/c-bpy) electric two == preferred embodiment, body "(·ρ_第30图. The present invention is better for each place VII ^ Qualitative test chart. "Example of flip / support catalyst (Pt / C-en) steady 31: preferred stability test chart of the present invention. u case / carrier catalyst (pt / C_phen) [Main component symbol description] # *»>

Claims (1)

201121981 VII. Patent application scope: 1. A platinum complex with the formula Pt[R]2+, wherein R is diethylenetriamine, ti'iethylenetetraamine, B One of ethylenediamine, 1,10-phenanthroline, and 2,2'-Bipyridine. 2. A method for producing a platinum complex by mixing chloroplatinic acid with a chelating agent in a solvent, and reacting the platinum-plated ion of the platinum-platinic acid [PtCl6]2 with the chelating agent to form a fault. Compound. 3. The method for producing a platinum complex according to claim 2, wherein the chelating agent is preselected from diethylenetriamine, triethyl ethane before the chelating agent is placed in the solvent. One of triethylenetetraamine, ethylenediamine, 1,10-phenanthroline, and 2,2'-bi ratio (2,2'-Bipyridine) . 4. A method of producing a platinum complex according to claim 2, wherein the gas platinum acid and the chelating agent are placed in the solvent and the mixture is contained in the mixing process, and the solvent is continuously stirred. 5. A method of producing a platinum complex according to claim 2 or 3, wherein after the gas is placed in the solvent with the platinum acid and the chelating agent, the solvent is further ultrasonically oscillated. 6. The method for producing a platinum complex according to claim 5, wherein the time for performing the ultrasonic oscillation is 4 to 6 hours. 7. The molar ratio of the platinum complex according to the scope of claim 2 or 3 of the patent application is 37 - 201121981 8 10 , and the molar ratio of the mixture (4) is between the cores. To: Range? The manufacturing method of the three-components, the molar number thereof: two "pre-first" to:: diethyltriamine, the manufacturing method of the chelated fine substance complex compound 'its', taken from the second The base tetraamine, the ratio of the chelating agent to the platinum ratio is 1:1 to 】.5:]. = 4 patent scope, the third item, the chelating agent, the apricot search & a clothing, ',, first , taken from ethylenediamine, 2,2,-bipyridyl or],]〇_ 】. Yifei's '3 hai chelating agent and turned Moir ratio is 2:1 to 3: 】, a platinum touch The preparation method of the medium comprises: a chelation step of placing a chlorine_and a chelating agent in a solvent-mixing solution to form a solution of the complex solution, so that the surface of the gas complex in the solution of the complex is wrong And a mixture of the same as the mixture of the hexanyl complex; a reduction step of adding a reducing agent to the platinum complex solution to form a suspension, the platinum complex Reducing to platinum; and a drying step of drying the reduced platinum in the suspension to obtain a platinum catalyst. 12. A method for producing a platinum catalyst according to the scope of claim 5, wherein Chelated Before the mixture is placed in the solvent, the chelating agent is preselected from diethylenetriamine, triethylenetetraamine, ethylenediamine, 1,10-phenanthroline (l , 10-phenanthroline) and 2,2'-linked "Bite-38-201121981 PJ'-Bipyridine". 13. According to the patent application scope of the patent application of the 11th or 12th article of the platinum catalyst, The chloro-acid is placed in the solvent and mixed with the chelating agent, and the solvent is continuously stirred during the mixing process. 14. The manufacturer of the platinum catalyst according to the scope of claim 11 or 2* a method in which the chloroplatinic acid and the chelating agent are placed in the solvent, and the solvent is further ultrasonically oscillated. 15. The method for producing a platinum catalyst according to claim 14 of the patent application, wherein the ultrasonic wave is performed The oscillating time is 4 to 6 hours. 16. The method for producing a platinum catalyst according to claim 11 or 12, wherein the reducing agent is pre-added before the reducing agent is added to the solution of the complex solution. Choose to furfural. 17. According to the application The method for producing a platinum catalyst according to Item 16, wherein the molar ratio of furfural to chloroplatinic acid is 20: 1. 18. The method for producing a platinum catalyst according to claim 11 or 12, In the reduction step, after the reducing agent is added to the platinum complex solution solution to form the suspension, the method further comprises: adding an alkaline solution to adjust the pH value of the suspension to a pH greater than 7. 19. The method for producing a platinum catalyst according to claim 18, wherein adjusting the pH of the suspension to a pH greater than 7 comprises adjusting the pH of the suspension to a pH of 12 To 14. 20. The method of producing a platinum catalyst according to claim 18, wherein the test solution is preselected as sodium hydroxide (NaOH) before the test solution is added to the suspension. 21. The method for producing a platinum catalyst according to item 18 of the patent application scope, wherein the liquid material is tilted, such as a supersonic wave. 22. Z. The patent application method described in item 2], the method of manufacturing the medium, the time of the shock of the ultrasound is Q2 to 5 hours. According to the application scope of the patent scope 】]*] 2, the manufacturer of the medium ^ (4) restores the step, and dissolves the solution in the le man system; the other suspension is heated, and then the Dry step township. The method of manufacturing the medium described in claim 23, wherein the heating of the pot suspension comprises heating the suspended crucible by microwave. According to the method for manufacturing the medium according to the scope of patent application No. 23, after the bath is heated, the suspension is cooled, and then the suspension is cooled, and the drying is carried out according to the scope of the patent application. After the completion of the reduction step, a separate separation step is performed to separate the reduction from the suspension, and then the method according to claim 12, wherein the chelating agent is The molar ratio is between: 1 and 3. According to the 12th article of the patent application scope, :::::: pre-selected from the second amine, the ratio of the ear = 1 : 1 To 2: 1. According to the scope of claim 12, the self-catalyst dream == pre-selected from triethyltetramine, the ratio of the acoustic agent to the = hopper is 1: 1 to 15 : i乂In accordance with the manufacturer of the catalyst at the beginning of the patent application, the manufacturer of the catalyst is used in its 23 24 25 26 27 28 29 30 201121981. The Haisheng mixture is pre-selected from ethylenediamine, 2, 2, _. Nitrogen phenanthrene - the molar ratio of the meal mixture oil is "to -1 ° 31, according to the manufacturing method of the medium described in Item 11 of the patent application scope, A temperature of the drying step is performed is 373K to 493K. 32. A method for producing a platinum/support catalyst, comprising: a one-chelating step of placing a chlorine fine I-chelating agent and a carrier in a solvent: mixing to form a carrier-containing compound a solution such that the platinum complex ion [ptC16]2 of the chloroplatinic acid in the solution is reacted with the chelating agent to form a platinum complex and adsorbed on the support; the reduction step is a Adding a reducing agent to the solution of the complex solution to form a % float, reducing the platinum complex adsorbed on the support to a platinum/support; and a drying step of reducing the suspension in the suspension The platinum/support is dried to obtain a platinum/support catalyst. 33. The method for producing a platinum/support catalyst according to claim 32, wherein the chelating agent is preselected from diethylenetriamine, before the chelating agent is placed in the solvent. Triethylenetetraamine, ethylenediamine, 1,10-phenanthroline (1,1'-bianthin) and 2,2'-bipyridine (2,2'-Bipyridine) one. 34. The method for producing a tumbling/supporting catalyst according to claim 32, wherein chloroplatinic acid, the chelating agent and the support are placed in the solvent to form the platinum-containing complex of the support. The solution comprises: dissolving chloroplatinic acid, the chelating agent and the support which is a porous material in the solvent, and forming the solution of the initial complex containing the support. 35. The method for producing a platinum/support catalyst according to claim 32, wherein the chloroplatinic acid, the chelating agent and the support are contained in the solvent, and the mixture is included in the mixing process. The solvent was continuously stirred. 36. A method of producing a platinum/support catalyst according to claim 32 or 33, wherein the solvent is oscillated by ultrasonic waves after the chloroic acid, the chelating agent and the support are placed in the solvent. 37. A method of producing a platinum/support catalyst according to claim 36, wherein the time for performing the ultrasonic oscillation is 4 to 6 hours. 38. A method of producing a platinum/support catalyst according to claim 32 or 33, wherein the reducing agent is preselected as furfural before the reducing agent is added to the platinum complex solution. 39. A method for producing a platinum/support catalyst according to claim 38, wherein the molar ratio of furfural to chloroplatinic acid is 20:1. 40. The method for producing a platinum/support catalyst according to claim 32 or 33, wherein in the reducing step, after the reducing agent is added to the platinum complex solution, the method further comprises: adding an assay solution The acid value of the suspension was adjusted to a pH greater than 7. 41. A method for producing a platinum/support catalyst according to claim 40, wherein adjusting the pH of the suspension to a pH greater than 7 comprises adjusting the acid value of the suspension to a pH value 12 to 14. 42. A method of producing a platinum/support catalyst according to claim 40, wherein the test solution is preselected as sodium hydroxide (NaOH) before the test solution is added to the suspension. 43. Manufacturer of platinum/support catalyst according to item 40 of the patent application scope. 42-201121981 Method: After adjusting the pH value of the suspension, the suspension is further ultrasonically oscillated. The method of manufacturing the transfer catalyst according to item 43 of the patent application scope: wherein the time for performing the ultrasonic oscillation is 〇2 to 5. Health's application. In the reduction step, in the reduction step, in the reduction step, after the reducing agent is added to the pin wrong substance, the liquid is heated separately, and the operation is performed. Applying the butterfly catalyst described in item 45 of the patent;; heating the liquid suspension to include microwave-based _float: according to the formula 1 = profit range, item 45, the manufacture of the body catalyst, the heat of the suspension After the liquid, the suspension is further cooled, and then the sputum is dried. I Dan Yan • In accordance with the scope of the patent application, the original method of the reduced smoke is completed. (6) The carrier is separated from the suspension, and then torn = 乞 according to the patent application scope, the method is: Or between 33 of the _ body catalysts. The molar ratio of the mixture to the Ming is between 3:150, according to the patent application method, and the platinum/support catalyst is used to make the chelating agent preselected from the second The ratio of one s/(four) square to platinum molar ratio is 】··] to 2 .] soil-amine, the chelating agent 51'H, please patent the range % method, shoot the f mixture system _ 0 / limb touch The manufacturer of the media pre-existed with triethyltetramine, 44 45 46 47 48 49 201121981 The molar ratio of platinum to platinum was 1:] to 1.5:1. 52. A method of producing a platinum/support catalyst according to claim 33, wherein the chelating agent is preselected from ethylenediamine and 2,2'-linked. The molar ratio of the chelating agent to platinum is from 2:1 to 3:1, in the case of pyridinium or one of 1,10-phenanthroline. 53. A method of producing a platinum/support catalyst according to claim 32 or 33, wherein the drying step is carried out at a temperature of from 373 K to 423 K. 54. The method for producing a platinum/support catalyst according to claim 32 or 33, wherein in the chelating step, the chloroplatinic acid and the chelating agent are added to the solvent, and then the tar is added. body. 55. The method for producing a platinum/support catalyst according to claim 32 or 33, wherein in the chelation step, the support is added to the solvent, and then the gas is added and the chelate is added. mixture. 56. A method of producing a platinum/support catalyst according to claim 32 or 33, wherein in the chelating step, the support is first mixed with an anhydrous alcohol and then added to the solvent. —44 —