JP4911593B2 - Spherical porous alloy, method for producing spherical porous alloy composite - Google Patents

Description

The present invention relates to the production how palladium-silver alloy spherical porous body with a controlled mixing ratio, more particularly, the spherical chelating resin was produced using a template, the compounding ratio of the palladium and silver controlled in any ratio, but relates to the production how spherical palladium-silver porous alloy which is held. The present invention produces a spherical porous palladium / silver alloy in which the alloying ratio of palladium and silver, the form and size of the alloy, etc. are controlled with high precision, thereby producing a hydrogenation catalyst, a hydrogen storage metal, and a hydrogen permeable membrane. The present invention provides a new spherical porous alloy material that expresses a unique function not found in conventional materials.

  Conventionally, polymer ions such as polymer resin, ion exchange resin, dextran, etc. are mixed with metal ions or metal nanoparticles, impregnated or adsorbed, and baked at a high temperature to remove the polymer on the support. And the method of producing a metal porous body is known (nonpatent literatures 1 and 2). At this time, since the support serves as a template, the form of the original support remains, and the organic component burns to obtain a porous metal in the form of the support. Further, it has been reported that by firing a similar metal-holding polymer resin in an inert gas atmosphere, the organic component is carbonized and porous carbon in which the metal is dispersed and supported can be obtained (Non-Patent Document 3, 4).

  However, in these conventional methods, metal ions and metal nanoparticles are held by a weak bond such as mixing, impregnation, or electrostatic interaction on the support surface with the polymer support. Insufficient retention of nanoparticles on the support, mainly supported by a single metal, and there is no easy way to produce an alloy with a high control of the compounding ratio of multiple metals. It has been difficult to produce such an alloy.

Walsh, L. Arcell, T. Inomata, J. Tanaka, S. Mann, Nature Mater., 2, 386 (2003) H. Zhang, A. I. Cooper, J. Mater. Chem., 15, 2157 (2005) H. Konno, R. Matsuura, M. Yamasaki, H. Habazaki, Syn. Met., 125, 167 (2002) H. Nakagawa, K. Watanabe, Y. Harada, K. Miura, Carbon, 37, 1455 (1999)

In such a situation, in view of the prior art, the present inventors can solve the problems of the prior art, and control the blending ratio and form with high accuracy, As a result of intensive research aimed at developing a new palladium-silver alloy that enables the development of unique functions that cannot be expected from conventional materials, palladium and silver can be used in any ratio using chelate resin as a mold. It has been found that the intended purpose can be achieved by adopting the holding method, and the present invention has been completed. The present invention aims to provide a manufacturing how palladium-silver alloy spherical porous body to allow the expression of specific functional unprecedented material by controlling the mixing ratio.

The present invention for solving the above-described problems comprises the following technical means.
( 1 ) A method for producing a spherical porous alloy comprising an alloy in which the ratio of palladium and silver is controlled, wherein a polymer having a chelate-forming group is added to an aqueous solution containing a palladium salt and a silver salt in an arbitrary ratio. Then, a metal-supported chelate resin in which palladium ions and silver ions are held in an arbitrary ratio by complex formation is prepared, and this is baked in the presence of oxygen to burn off organic components, and then baked in a hydrogen atmosphere. And producing a spherical porous alloy by reducing the alloy components.
( 2 ) A method for producing a spherical porous alloy composite in which alloy nanoparticles in which the ratio of palladium to silver is controlled is uniformly supported on a carbonized product, and includes a palladium salt and a silver salt in an arbitrary ratio A metal-supported chelate resin is prepared by adding a polymer having a chelate-forming group to an aqueous solution and holding palladium ions and silver ions in an arbitrary ratio by complex formation, and this is baked in an inert gas atmosphere and organically prepared. Spherical porous alloy composite in which alloy nanoparticles are uniformly supported on carbonized material by carbonizing the components and then reducing the alloy components by firing in a hydrogen atmosphere Of producing a high alloy composite.
( 3 ) The method according to ( 1 ) or ( 2 ) above, wherein the polymer having a chelate-forming group is a spherical chelate resin.
( 4 ) The method according to ( 3 ) above, wherein an amine, aminocarboxylic acid, aminothiol, aminoalcohol, or thiol is used as the chelating group of the chelating resin.
( 5 ) The method according to ( 3 ), wherein the matrix polymer of the chelate resin is a spherical resin of a crosslinked polystyrene resin, a crosslinked polyacrylic resin, or a crosslinked polyacrylamide.

Next, the present invention will be described in more detail.
The target product obtained in the present invention is a spherical porous alloy in which the ratio of palladium to silver is controlled, is spherical and porous, and the weight ratio of palladium after firing is 1 to 95%. The elements are uniformly dispersed up to the inside and have a diameter of 20 μm or more. In addition, the object obtained by the present invention is a spherical porous alloy composite, and the spherical porous alloy composed of alloy nanoparticles with a controlled ratio of palladium and silver is uniformly supported on the carbonized product. It is characterized by being.

  The present invention also provides a method for producing a spherical porous alloy comprising alloy nanoparticles with a controlled ratio of palladium to silver, wherein a chelate-forming group is added to an aqueous solution containing a palladium salt and a silver salt in an arbitrary ratio. After adding a polymer having, preparing a metal-supported chelate resin in which palladium ions and silver ions are held in an arbitrary ratio by complex formation, and firing this in the presence of oxygen to burn and remove organic components, A spherical porous alloy is produced by firing in a hydrogen atmosphere.

  Furthermore, the present invention is a method for producing a spherical porous alloy composite in which alloy nanoparticles with a controlled ratio of palladium and silver supported on a carbonized product, and an aqueous solution containing a palladium salt and a silver salt in an arbitrary ratio A metal-supported chelate resin in which palladium ions and silver ions are held in an arbitrary ratio by complex formation is prepared by adding a polymer having a chelate-forming group, and calcined in an inert gas atmosphere. A spherical porous alloy composite is produced by firing in an atmosphere.

  The present invention uses a chelate resin particle capable of firmly holding metal ions with a chelate bond as a precursor for producing an alloy, whereby the metal holding ratio can be controlled, and a spherical porous body can be obtained. It is characterized by. In the present invention, in particular, palladium and silver are arbitrarily mixed to form an alloy. Therefore, by controlling the holding amount of two kinds of metals in the chelate resin with high accuracy, the porosity of the alloy at an arbitrary ratio after firing is obtained. The body is obtained. In the present invention, a porous carbonized product in which the organic component of the chelate resin is carbonized and the alloy is highly dispersed can be obtained by firing in an atmosphere of an inert gas such as nitrogen.

  In the method of the present invention, a spherical chelate resin having a chelate group that strongly binds metal ions is used as a template, palladium and silver are held in an arbitrary ratio, and then fired in an oxygen atmosphere, and then a hydrogen atmosphere By reducing under, an organic component is burned and removed, and a palladium / silver porous alloy retaining the original form as a mold is obtained. In addition, a similar porous operation is performed in an inert gas atmosphere and then reduced with hydrogen to obtain a spherical porous carbonized material carrying alloy particles.

  In the present invention, a polymer resin having a large number of chelate groups in the molecule forming a stable complex with palladium and silver (hereinafter referred to as chelate resin) is used as a support for firmly binding metal ions and metal nanoparticles. ) Is used. Specifically, polymer resins having amine, aminocarboxylic acid, aminothiol, aminoalcohol, thiol and the like as the chelate group are exemplified.

  Prepare an aqueous solution containing palladium and silver in any ratio using palladium salt, silver salt, or these nanoparticles, add chelate resin to this, add these metal ions or nanoparticles to chelate resin by complex formation. After that, the metal-holding chelate resin is baked, and the organic component is baked and removed or carbonized to disperse and carry the porous palladium / silver alloy or alloy that maintains the original resin form in the carbide. A spherical porous carbonized product can be obtained.

  As described above, the present invention uses a spherical chelate resin having a chelate group that strongly binds metal ions as a template, holds palladium and silver in an arbitrary ratio, and then calcines in a hydrogen atmosphere. An organic component is removed to obtain a porous palladium / silver alloy. By chelate formation, palladium and silver ions or their nanoparticles are firmly held and their bonds are strong, so that metal ions are not eluted.

  As the chelate group of the polymer having a chelate-forming group, amine, aminocarboxylic acid, aminothiol, aminoalcohol, thiol and the like are used, and among these, in particular, palladium and silver can be firmly bonded together. , Iminodiacetic acid, EDTA type aminocarboxylic acid, and amines such as diamine and triamine are most preferable.

  As the base material of the chelate resin having the chelate-forming group, a copolymer such as polystyrene, polyacrylic acid or polyacrylamide which is insolubilized by partial cross-linking with divinylbenzene or the like is usually used as a bead-shaped spherical resin. . Further, as a copolymer such as polystyrene, polyacrylic acid, polyacrylamide, etc., any of non-porous gel type and porous macroporous type can be used. The size of the resin beads varies depending on the application, but when used for production of a catalyst or an electrode, 50-400 mesh is preferable, and 100-200 mesh is particularly preferable.

  Palladium ions and silver ions are supported on the chelate resin by adding chelate resin beads to an aqueous solution or an organic solvent solution containing both metal ions, and stirring or shaking. The metal salt to be used is not particularly limited as long as it is soluble in water or an organic solvent, and an appropriate metal salt can be used. Specifically, palladium acetate, palladium chloride, and palladium complex are suitably used as palladium, and silver nitrate and silver complex are suitably used as silver. Moreover, it is also possible to use a metal nanoparticle dispersion instead of the metal salt solution.

  The chelate resin holding palladium and silver is washed with water, heated and baked in an electric furnace in an oxygen atmosphere, the organic components are burned and removed, and further reduced in a hydrogen atmosphere, so that the metal part becomes an alloy porous body. Remains as. Since the two types of metal ions are uniformly dispersed in the chelate resin, alloying easily proceeds by heating in a hydrogen atmosphere. By adjusting the ratio of metal ions held in the chelate resin in advance, an alloy having an arbitrary ratio can be obtained.

  On the other hand, the chelate resin holding palladium and silver is washed with water and then heated and baked in an electric furnace under an inert gas atmosphere such as nitrogen, so that the organic component remains as carbon, and further in a hydrogen atmosphere. By reducing, carbon particles in which alloy particles of palladium and silver are dispersed are obtained.

  The firing temperature of the chelate resin carrying a metal is desirably 500 ° C. or higher, and 600 to 800 ° C. is favorably applied to the combustion removal of organic components in an oxygen atmosphere. Moreover, in order to carbonize an organic component in an inert gas atmosphere and to alloy it simultaneously, 700-1200 degreeC is applied and 960 or more of melting | fusing point of silver is preferable. At a temperature lower than this, there is a problem that it takes a long time for alloying. The firing time is preferably 5 hours or longer, although it depends on the firing temperature. In order to reduce the metal, the firing atmosphere is carried out under a hydrogen stream, and preferably a hydrogen pressure of 20 to 400 kPa is applied.

  Palladium and palladium / silver alloy, for example, have a remarkable effect as a hydrogenation catalyst, a hydrogen storage metal, a hydrogen permeable membrane material, and as a hydrogen diffusion electrode. In the present invention, palladium is in any ratio with silver. The solubility and diffusion coefficient of hydrogen change depending on the alloying ratio with silver, and the expression and control of unique hydrogen permeability and catalytic function can be expected. Palladium has the disadvantage of hydrogen embrittlement, but it is significantly relaxed by alloying with silver. Further, by making the alloy spherical and porous, the surface area is increased, and when used as a catalyst or an electrode material, the reaction activity is remarkably improved. By using a polymer resin as a mold, the form is reflected even after firing, and a porous alloy material having a desired size and shape suitable for the above-described application can be produced.

The spherical porous alloy composite obtained in the present invention is spherical and porous, the weight ratio of palladium after firing is 1 to 95%, both elements are dispersed almost uniformly to the inside, and the alloy nanoparticles are Having a palladium / silver alloy spherical porous body characterized by being an alloy fine particle of 20 nm or less and having a specific surface area by nitrogen adsorption method of at least 50 m ² / g, it has characteristics not found in conventional materials. .

The present invention has the following effects.
(1) According to the present invention, it is possible to synthesize and provide a palladium / silver alloy spherical porous body whose blending ratio is controlled with high accuracy.
(2) It is also possible to synthesize a spherical porous carbonized product in which alloy nanoparticles with a controlled ratio of palladium to silver are uniformly dispersed and supported.
(3) upper Symbol palladium-silver alloy spherical porous body and the porous carbonized material, because express specific hydrogen permeability and catalytic function, the hydrogen storage alloy, a hydrogenation catalyst, is useful as a hydrogen permeable membrane material and the like.
(4) Moreover, these can be suitably utilized as a catalyst or electrode material with significantly improved reaction activity.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

  1 g of spherical polystyrene resin (100-200 mesh size) having diethylenetriamine-N, N, N ′, N′-tetraacetic acid as a chelating group shown in FIG. 1 and silver nitrate and tetraammine palladium in water at a ratio of 60:40. The solution was added to 250 ml of an aqueous solution having a pH of 5.5 and shaken for 12 hours. The total concentration of palladium and silver was 0.05M. The chelate resin was filtered, washed with water and dried, then placed in an electric furnace, calcined at 600 ° C. for 6 hours in an oxygen atmosphere, and then calcined at 600 ° C. for 3 hours in a hydrogen atmosphere.

  An electron microscope (SEM) photograph of the fired body obtained is shown in FIG. It is recognized that the fired body is spherical and porous. The metal ratio after firing by ICP emission spectroscopic analysis was 64:36. FIG. 3 shows an X-ray diffraction pattern after firing. A peak of an alloy of palladium and silver is observed at 2θ = 39.92 °.

  5 g of spherical polystyrene resin (100-200 mesh size) having diethylenetriamine-N, N, N ′, N′-tetraacetic acid as a chelating group is added to an aqueous solution in which silver nitrate and tetraammine palladium are dissolved in water at a ratio of 40:60. And shaken for 12 hours. In the same manner as in Example 1, the chelate resin was filtered, washed with water, dried, put into an electric furnace, baked in an oxygen atmosphere at 600 ° C. for 6 hours, then baked in a hydrogen atmosphere at 600 ° C. for 3 hours, and porous. A quality alloy was obtained. The metal ratio after firing by ICP emission spectroscopic analysis was 42:58.

  5 g of spherical polystyrene resin (100-200 mesh size) having diethylenetriamine-N, N, N ′, N′-tetraacetic acid as a chelating group is added to an aqueous solution in which silver nitrate and tetraammine palladium are dissolved in water at a ratio of 20:80. And shaken for 12 hours. In the same manner as in Example 1, the chelate resin was filtered, washed with water, dried, put into an electric furnace, baked in an oxygen atmosphere at 600 ° C. for 6 hours, then baked in a hydrogen atmosphere at 600 ° C. for 3 hours, and porous. A quality alloy was obtained. The metal ratio after firing by ICP emission spectroscopic analysis was 20:80.

  5 g of spherical polystyrene resin (100-200 mesh size) having diethylenetriamine-N, N, N ′, N′-tetraacetic acid as a chelating group is added to an aqueous solution in which silver nitrate and tetraammine palladium are dissolved in water at a ratio of 80:20. And shaken for 12 hours. In the same manner as in Example 1, the chelate resin was filtered, washed with water, dried, put into an electric furnace, baked in an oxygen atmosphere at 600 ° C. for 6 hours, then baked in a hydrogen atmosphere at 600 ° C. for 3 hours, and porous. A quality alloy was obtained. The metal ratio after firing by ICP emission spectroscopic analysis was 78:22. FIG. 4 shows changes in the alloy composition and the X-ray peak position of Examples 1, 2, 3, and 4.

  5 g of spherical polystyrene resin (100-200 mesh size) having diethylenetriamine-N, N, N ′, N′-tetraacetic acid as a chelating group is added to an aqueous solution in which silver nitrate and tetraammine palladium are dissolved in water at a ratio of 20:80. And shake for 18 hours. The mixture was fired at 900 ° C. in an electric furnace in an inert gas atmosphere, and then reduced at 1050 ° C. in a hydrogen atmosphere to obtain composite particles of an alloy and a carbonized product.

The specific surface area of the composite particles by the nitrogen adsorption method was 220 m ² per gram. An electron microscope (SEM) photograph of the fired body is shown in FIG. It can be seen that the alloy and carbon composite particles are spherical and dense. The cross section of the composite particle was analyzed by the EDX method. The result of analyzing palladium and silver is shown in FIG. It can be seen that both elements are uniformly distributed to the inside. Moreover, the result of TEM observation of a thin piece is shown in FIG. It can be seen that alloy fine particles of 10 nm or less are distributed.

Application example 1
The carbon composite in which the alloy nanoparticles prepared in Example 4 were dispersed and polytetrafluoroethylene (PTFE) were kneaded at 9: 1 and pressed into a silver wire netting, which was used as an electrode. The electrode was inserted into a Teflon (registered trademark) holder to supply hydrogen, and an electrochemical polarization measurement as a hydrogen diffusion electrode was performed using a 1 M sulfuric acid aqueous solution at 35 ° C. as an electrolyte. FIG. 8 shows the relationship between the alloy composition and the exchange current density. It can be seen that the activity is extremely high when the solid solution amount of silver is 40 mol%. This is presumably because the solubility and diffusibility of hydrogen and the conductivity change due to solid solution of silver.

As described above in detail, the present invention according to the manufacturing how palladium-silver alloy spherical porous body with a controlled mixing ratio, the present invention, a palladium-silver alloy spherical porous body with controlled mixing ratio Can be synthesized. Further, it is possible to synthesize a spherical porous carbonized product in which alloy nanoparticles with a controlled ratio of palladium to silver are uniformly dispersed and supported. Further, the palladium / silver alloy spherical porous body and porous carbonized product obtained in the present invention are useful as a hydrogen storage alloy, a hydrogen permeable membrane material and the like that exhibit unique hydrogen permeability and catalytic function. Furthermore, they can be suitably used as a catalyst or electrode material with significantly improved reaction characteristics. INDUSTRIAL APPLICABILITY The present invention is useful for providing a palladium / silver alloy that enables the expression and control of specific hydrogen permeability and catalytic function by controlling the alloying ratio of palladium and silver with high accuracy.

The metal capture group of the chelate resin used in Example 1 is shown. The electron microscope (SEM) image of an alloy porous body is shown. The X-ray diffraction pattern of an alloy porous body is shown. X-ray peaks of alloys having different ratios of palladium and silver (change due to alloying of 2θ = 40 ° peak of pure palladium) are shown. The vertical axis represents the value of 2θ, and the horizontal axis represents the silver content (% by weight). The electron microscope (SEM) image of a carbonized material is shown. The SDX image of a carbonized substance cross section and the EDX pattern which shows the presence state of palladium and silver are shown. The transmission electron microscope (TEM) image of the Pd-Ag alloy nanoparticle disperse | distributed inside carbonized material is shown. The relationship between the alloy composition of the electrode produced from carbonized material and the generated current density is shown. The vertical axis represents current density, and the horizontal axis represents the silver content (% by weight) in the alloy.

Claims (5)

  A method for producing a spherical porous alloy comprising an alloy in which the ratio of palladium and silver is controlled, wherein a polymer having a chelate-forming group is added to an aqueous solution containing a palladium salt and a silver salt in an arbitrary ratio, and palladium is added. A metal-supported chelate resin in which ions and silver ions are held in an arbitrary ratio by complex formation is prepared, and this is fired in the presence of oxygen to burn off organic components, and then fired in a hydrogen atmosphere to form an alloy. A method for producing a spherical porous alloy, comprising producing a spherical porous alloy by reducing components.   A method for producing a spherical porous alloy composite in which alloy nanoparticles with a controlled ratio of palladium and silver are uniformly supported on a carbonized product, and chelated in an aqueous solution containing a palladium salt and a silver salt in an arbitrary ratio A polymer having a forming group is added to prepare a metal-supported chelate resin in which palladium ions and silver ions are held in an arbitrary ratio by complex formation, and this is baked in an inert gas atmosphere to convert the organic component to carbon. And then producing a spherical porous alloy composite in which the alloy nanoparticles are uniformly supported on the carbonized product by reducing the alloy components by firing in a hydrogen atmosphere. Body manufacturing method. The method according to claim 1 or 2 , wherein the polymer having a chelate-forming group is a spherical chelate resin. The method according to claim 3 , wherein an amine, aminocarboxylic acid, aminothiol, aminoalcohol, or thiol is used as the chelating group of the chelating resin. The method according to claim 3 , wherein the matrix polymer of the chelate resin is a cross-linked polystyrene resin, a cross-linked polyacrylic resin, or a cross-linked polyacrylamide spherical resin.