JP6629018B2 - Method for producing metal-porous polymer-metal complex composite and metal-porous polymer-metal complex composite - Google Patents

Description

  The present invention relates to a method for producing a metal-porous polymer / metal complex composite material using a metal or a metal oxide, and a metal-porous polymer / metal complex composite material produced by the method.

  Porous polymer metal complex (PCP: Porous Coordination Polymer) is a crystalline solid composed of metal ions and organic ligands, and has various combinations of metal ions and organic ligands and a variety of skeleton structures. are doing. Since it is a porous body in which the pore size distribution and pore distribution of nano-sized pores are controlled with extremely high precision, application to gas separation / storage materials, sensors, catalysts, conductive materials, and the like is being studied. (Non-Patent Documents 1 to 4)

  Since the porous polymer metal complex is composed of a metal ion and an organic ligand, a substance capable of providing a metal salt containing a desired metal ion and an organic ligand (hereinafter, referred to as a “ligand substance”) "). This reaction can be carried out in a solution of the metal salt and the ligand substance or in a solid phase in which the metal salt and the ligand substance are mixed without using a solvent. An electrochemical synthesis method is also known in which a metal plate is used as an electrode instead of a metal salt, and a current is passed through the metal plate to react metal ions eluted from the metal plate with a ligand substance. Further, a technique has been proposed in which a metal oxide is reacted with a ligand substance at a high temperature to convert the metal oxide into a porous polymer metal complex.

  When formed into a film, the porous polymer metal complex has various advantages as follows. The technique of forming a porous polymer metal complex into a film is important. When the porous polymer metal complex is used as a catalyst, the effect of increasing the surface area to promote the reaction is obtained. Even when used as a sensor or a conductive material, the size of a device can be reduced by using a porous polymer metal complex as a film. It is also possible to perform gas separation using a porous polymer metal complex formed into a film.

PCP is a brittle material having poor elasticity unlike a resin or the like. Therefore, when the PCP is formed into a thin film, a porous polymer metal complex film is often formed on a certain substrate.
The following methods are known as such a method. (1) A method in which a substrate is immersed in a solution containing a metal salt and a ligand substance to form a porous polymer metal complex film on the substrate. (Non-Patent Document 8).
(2) A method of forming a porous polymer metal complex film on a substrate in a step-by-step manner by alternately immersing the substrate in a solution containing a metal salt and a solution containing a ligand substance ( Non-Patent Document 9).
(3) A method of using a high vacuum to deposit a porous polymer metal complex component on a substrate (Non-Patent Documents 5 and 6).
(4) The metal oxide surface is converted into a porous polymer metal complex film by immersing the metal oxide in the ligand substance solution and reacting at a high temperature, and as a result, the metal oxide surface has high porosity. A method of forming a molecular metal complex film (Non-Patent Document 10).
In addition, these methods are combined with a method of forming a thin layer of a carboxylic acid-containing functional group using a SAM (Self-Assembled Molecular) method in order to improve the familiarity between the substrate surface and the porous polymer metal complex. Used (Non-Patent Document 7).

JP 2010-059111 A

Susumu Kitagawa, Integrated Metal Complex, Kodansha Scientific, 2001, pp. 214-218 Hupp et al., Chem. Soc. Rev., (2009) 1450. James et al., Chem. Soc. Rev., (2003) 276. Zhou et al., Chem. Soc. Rev., (2009) 1477 Fischer et al., Angew. Chem. Int., Ed. (2004), 43, 2839 (synthesis using high vacuum). Fischer et al., Chem. Commun., (2009) 119 (synthesis using high vacuum). Fischer et al., Angew. Chem. Int., Ed. (2009), 48, 5038 (SAM based synthesis). Bein et al., J. Am. Chem. Soc., (2007) 129, 8054 (Thin film synthesis by general solution method). Kitagawa et al., J. AM. CHEM. SOC, 2008, 130, 15778 (Step-by-step method) Kitagawa et al., Nature Mat., (2012) 717 (High temperature reaction with metal oxides) Long et al., J. Am. Chem. Soc., (2014) 10752. Yahi et al., J. AM. CHEM. SOC., (2005) 1504. Cheetham et al., Dalton Trans., (2008) 2034 Tannenbaum et al., Eur. J. Inorg. Chem., 2009, 2338. Williams et al., Science, (1999) 283, 1148. Burrows et al., Dalton Trans., (2008) 6788 Dietzel et al., Angew. Chem. Int., Ed. (2005) 6354.

The existing method for producing a porous polymer metal complex has the following problems.
Since the metal ion and the ligand constitute the porous polymer metal complex, when a metal salt is used as the metal ion source, the counter ion is not taken into the formed porous polymer metal complex, It becomes a product. For example, in the reaction between copper nitrate and terephthalic acid, nitric acid is produced as a by-product.

  In the electrochemical synthesis method using a metal plate as an electrode, special equipment is required, and synthesis in a reaction vessel such as a general glass lining cannot be performed. In addition, a conductive additive, a sacrificial reducing agent, and the like for improving conductivity and preventing metal deposition at the counter electrode are required, which causes an increase in cost.

  Prior art methods using metal oxides are extremely limited, and the method described in Non-Patent Document 10 requires a high temperature, and is only performed with limited metal oxides and ligand substances. And lacks versatility.

  When the reaction between the metal oxide and the ligand substance is performed in a solution, a highly polar, high-boiling solvent such as dimethylformamide (DMF) is used to dissolve the metal ions and promote the reaction. Often used. Further, a base such as pyridine is often used as a reaction accelerator. However, these may be coordinated with the metal ions of the porous polymer metal complex in some cases, so that they remain in the pores of the porous polymer metal complex even after production, and the properties of the catalyst and gas adsorption storage In some cases, a treatment at a high temperature is required to reduce the amount of the compound or to remove the remaining reaction accelerator. The treatment at high temperature is complicated, and depending on the porous polymer metal complex, the properties may be deteriorated due to thermal deterioration. As a method of removing these without applying a high temperature, there is a method using supercritical carbon dioxide or the like, but a complicated process using a special device is required.

The existing film forming method has the following problems.
In the methods (1) and (2) for forming the porous polymer metal complex into a film, only a part of the metal ions and the ligand in the solution are deposited on the substrate, and the reaction efficiency is low.
The method (3) is a reaction using a special device, and lacks versatility.
As described above, the prior art of the method (4) is extremely limited, and the method of Non-Patent Document 10 requires a high temperature, and is performed only with a limited metal oxide and a ligand substance. And lacks versatility. In addition, when the obtained thin film of the porous polymer metal complex is used as a gas separation membrane or a conductive device, the denseness of the membrane is very important. It is difficult to say that the reaction of forming the porous polymer metal complex on the substrate could be strictly controlled, and as a result, it was difficult to obtain a dense film.

The present invention is a method for producing a metal-porous polymer-metal complex composite material by reacting a metal ion source providing a desired metal ion with a ligand substance in an alcohol-based solvent. The metal ion source used may be in the form of a powder or a plate or the like. The metal powder or metal plate serving as a metal ion source that can be used in the present invention includes pure metal, and, for example, metal compound powder or metal compound containing metal such as metal oxide, metal nitride, and metal sulfide. Including molded articles. Hereinafter, in the present specification, these are collectively referred to simply as “metal powder” or “metal plate” for convenience.

  When the reaction is sufficiently performed using the metal powder, all of the metal powder is converted into a porous polymer metal complex, so that powder particles of the porous polymer metal complex are obtained. When the reaction time is controlled using metal powder and a part of the metal powder particles are reacted, the metal powder particles are partially coated with the porous polymer metal complex, and the metal-porous polymer metal complex A composite powder is obtained.

  When the metal ion source is a plate-shaped metal molded body, the reaction time is controlled, and when a part of the metal is reacted, the porous polymer metal complex is deposited on the metal plate, that is, on the metal plate. A composite having the porous polymer metal complex film formed thereon is obtained. In the case where the reaction time is controlled and all of the metals are reacted in a molded product such as a metal plate, a plate-shaped porous polymer metal complex can be obtained in the same manner as when metal powder is used.

  These reactions can be carried out at a mild temperature in an alcoholic solvent in a short time, no post-treatment is required, there are no by-products derived from counter ions, and the reaction is extremely clean and easy. It can be implemented using. Since dimethylformamide and pyridine are not used as the reaction solvent and an alcoholic solvent having a low boiling point is used, dimethylformamide and pyridines remain in the pores after the reaction to deteriorate the properties of the porous polymer metal complex, There is no need to perform heat treatment to remove formamide and pyridines. Further, the characteristics of gas adsorption storage are not reduced.

  Using a metal plate as a metal ion source, a reaction is carried out in a solution containing a ligand substance A, and a porous polymer metal complex film comprising a metal ion and a ligand A (for convenience, PCP- A), the material is further reacted in a solution containing another ligand substance B, and a porous polymer metal complex film (PCP- It is possible to form a composite film in which A) and a porous polymer metal complex film (PCP-B) composed of ligand B are laminated. By combining two types of porous polymer metal complex films, it is possible to combine the functions of each porous polymer metal complex.

  In this case, when the diameter of the ligand B is smaller than the pore diameter of the porous polymer membrane (PCP-A), the ligand B passes through the pores of the porous polymer membrane (PCP-A). Since it reacts with metal A, the composition of the resulting material is metal A / PCP-B / PCP-A. On the other hand, when the diameter of the ligand B is larger than the pore diameter of the porous polymer membrane (PCP-A), the metal ions pass through the pores and react with the ligand B on the PCP-A membrane. Therefore, the composition of the obtained material is metal A / PCP-A / PCP-B. These configurations are not necessarily uniquely determined because they are affected not only by the pore diameter and the size of the ligand but also by reaction conditions such as a solvent.

  When a metal plate is used as a metal ion source and a metal foil A is attached to a metal foil B, a reaction between the metal B and the ligand substance occurs first. A porous polymer metal complex film (for convenience, called B-PCP) formed from metal B and the ligand is formed. By allowing the reaction to proceed until all the metal B is consumed, a material having the metal A / B-PCP can be obtained. When the metal A / B-PCP is further reacted with the ligand substance after the metal A / B-PCP is formed, the metal A reacts with the coordinating substance to form a porous polymer film (referred to as A-PCP for convenience). The result is a metal A / PCP-B / PCP-A configuration. These configurations are not necessarily uniquely determined because they are affected by the reaction time, the relationship between the pore diameter and the size of the ligand, and the reaction conditions such as the solvent.

As described above, various composites can be prepared from a metal plate and a porous polymer metal complex film based on the present invention.
A porous polymer metal complex film (PCP-A) composed of ligand A and a porous polymer metal complex film (PCP-B) composed of ligand B were laminated on a substrate metal. In order to form a composite film, a composite material in which a porous polymer metal complex film (PCP-A) composed of a ligand A is formed on a substrate metal may be immersed in a solution of a ligand B. However, it is considered that the composite structure of the finally formed composite depends on the type of the metal used and the ligand substances A and B. When the ligand B is larger than the pore diameter of the formed PCP-A, a small amount of dissolved metal ions from the substrate metal diffuses in the pores of the PCP-A, reacts with the ligand B, and reacts with the PCP-A. Since the PCP-B layer is formed on the A layer, the finally formed composite material has a structure of substrate metal / PCP-A / PCP-B.

  On the other hand, when the ligand B is smaller than the pore diameter of PCP-A, the ligand B diffuses in the pores of PCP-A and reacts with the substrate metal. It has a metal / PCP-B / PCP-A configuration. However, when the interaction between PCP-A and ligand B is strong, the diffusion of ligand B into the pores of PCP-A is inhibited, so that the metal ions pass through the pores of PCP-A. Diffusion and reaction with ligand B take precedence, and as a result, a configuration of substrate metal / PCP-A / PCP-B may be obtained.

  The porous polymer metal complex membrane obtained by the method of the present invention is capable of forming a dense membrane because the reaction between the metal ion and the ligand substance is performed at a high degree of control. / It can be suitably used for separation materials, sensors, electronic devices and the like.

  An object of the present invention is to provide a metal-porous polymer metal complex film formed from a metal ion and a ligand, and a method for forming a powder thereof. Another object of the present invention is to provide an apparatus and devices using these powders and films.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result of reacting a metal ion source with a ligand substance using an alcohol-based solvent, a by-product is produced. It is found that a porous polymer metal complex can be obtained without any problem, and further, when the shape of the metal ion source is selected and the reaction is controlled, a composite material of a metal-porous polymer metal complex can be obtained. Was completed. Further, since the material of the present invention can be used for gas separation materials, electronic devices, and the like, the present invention has been completed.

(1) A plate-shaped compact selected from the group consisting of a pure metal plate, a metal oxide plate, and a metal nitride plate is prepared as a metal ion source, and the metal ion source is magnesium, calcium, iron, cobalt, nickel. , Copper, silver, one or two or more selected from the group consisting of any metal of metal and their metal oxides or metal nitrides,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the plate-shaped molded body in the solution,
The plate-like molded body reacts with the ligand substance, and the following formula (1) is formed on the plate-like molded body.
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
Forming a porous polymer metal complex film represented by
Including stopping the reaction before the plate-shaped molded body is completely consumed by the reaction,
A method for forming a composite having the porous polymer metal complex film on the plate-like molded body .
(2) The forming method according to (1), wherein the water content of the alcohol-based solvent is 0 to 12% by mass.
(3) The method according to (2), wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof.
(4) The method according to any one of (1) to (3), wherein the reaction is performed at a temperature of −20 to 150 ° C.
( 5 ) The method according to ( 1 ), wherein M is an ion of copper or silver or a mixed ion thereof.
(6) the metal ion source is a copper, any metal of silver, and a plate-shaped molded body comprising one or more members selected from the group consisting of metal oxide or metal nitride (1 ).
( 7 ) The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles or a mixture thereof The forming method according to any one of (1) to (4).

( 8 ) A plate-shaped molded body is prepared as a metal ion source , and the metal ion source is any one of magnesium, calcium, iron, cobalt, nickel, copper, silver, and zinc, and a metal oxide or metal thereof. One or more selected from the group consisting of nitrides,
Dissolving the first ligand substance in an alcohol-based solvent to prepare a first ligand substance solution;
A second ligand substance different from the first ligand substance is dissolved in an alcoholic solvent to prepare a second ligand substance solution,
Charging the plate-like molded body into the first ligand substance solution,
The plate-like molded body is reacted with the first ligand substance, and the following formula (1) is formed on the plate-like molded body.
[ML1 _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L1, yes capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value by which the positive charge of the metal ion M and the negative charge of the ligand L1 cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML1 _x ] are assembled. And n is 5 or more.)
Forming a first porous polymer metal complex film represented by
Stopping the reaction before the plate-like molded body is completely consumed by the reaction, and then washing the composite having the porous polymer metal complex film on the plate-like molded body ,
Charging the complex into the second ligand substance solution,
The plate-shaped body and the second ligand substance are reacted to form the following formula (2) on the plate-shaped body or the first porous polymer metal complex film.
[ML2 _x ] _n (2)
(Wherein, M and X are the same as in the case of the formula (1), and L2 is different from the above L1 and contains two or more functional groups capable of coordinating to M in its structure. A ligand capable of cross-linking with M is shown, and n represents a characteristic that a large number of constituent units composed of [ML2 _x ] are assembled, and n is 5 or more.)
Forming a second porous polymer metal complex film represented by
Stopping the reaction between the plate-shaped body and the second ligand substance before the plate-shaped body is completely consumed by the reaction;
A method for forming a composite having two different types of porous polymer metal complex films on the plate-like molded body .
( 9 ) The method according to ( 8 ), wherein the alcohol solvent has a water content of 0 to 12% by mass.
( 10 ) The forming method according to ( 9 ), wherein the alcohol solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof.
( 11 ) The formation method according to any one of ( 8 ) to ( 10 ), wherein each of the reactions is performed at a temperature of -20 to 150 ° C.
( 12 ) The method according to ( 8 ), wherein M is an ion of copper or silver or a mixed ion thereof.
(13) wherein the metal ion source, a plate-shaped molded body made of copper, any metal of silver, and one or more members selected from the group consisting of metal oxide or metal nitride (8 ).
( 14 ) The first and second ligand substances are terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalene 1 selected from dicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles The forming method according to any one of ( 8 ) to ( 11 ), which is a seed or a mixture thereof.

( 15 ) As a metal ion source, a laminate having a plate-shaped molded body A and a plate-shaped molded body B is prepared on a substrate, and the plate-shaped molded bodies A and B are a pure metal plate and a metal oxide, respectively. Plate, metal nitride plate, and the metal ion source is any one of magnesium, calcium, iron, cobalt, nickel, copper, silver, zinc, and a metal oxide or metal nitride thereof. One or more selected from the group consisting of
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the laminate into the ligand substance solution,
The plate-shaped molded body B is reacted with the ligand substance, and the following formula (1) is formed on the plate-shaped molded body A.
[M1L _x ] _n (1)
(Wherein, M1 represents a metallic ion from the plate-shaped molded product B, L is to contain functional groups capable of coordinating to M1 into two or more its structure crosslink with two M1 X represents a value obtained by canceling the positive charge of the metal ion M1 and the negative charge of the ligand L, and n represents a characteristic that a large number of constituent units composed of [M1L _x ] are aggregated. Where n is 5 or more.)
Forming a first porous polymer metal complex film represented by
Ensure that the plate-shaped molded product B is consumed by the reaction, then the plate-like molded product A is reacted with the ligand material, said plate-shaped molded product A or on the first porous On the polymer metal complex film, the following formula (2)
[M2L _x ] _n (2)
(Wherein, M2 represents a metallic ion from the plate-shaped molded body A, except M1 and M2 are different, X, L is the same as in formula (1), n, [M2L _x ], And n is 5 or more.)
Forming a second porous polymer metal complex film represented by
Stopping the reaction between the plate-shaped body A and the ligand substance before the plate-shaped body A is completely consumed by the reaction,
A method for forming a composite having two different types of porous polymer metal complex films on the plate-like molded body A, comprising:
( 16 ) The method according to ( 15 ), wherein the water content of the alcohol-based solvent is 0 to 12% by mass.
(17) the alcohol solvent is methanol, ethanol, 1-propanol, forming method according to a any one or a mixture of these 2-propanol (16).
( 18 ) The forming method according to any one of ( 15 ) to ( 17 ), wherein each of the reactions is performed at a temperature of -20 to 150 ° C.
( 19 ) The forming method according to ( 15 ), wherein M1 and M2 are either copper or silver ions or mixed ions thereof, but M1 and M2 are different.
( 20 ) The plate-shaped molded product A and the plate-shaped molded product B of the metal ion source are one or two selected from the group consisting of a metal of copper or silver and a metal oxide or metal nitride thereof. forming method according to is a plate-shaped molded body made of the seed above, except the plate-like molded body a and plate-shaped molded body B of a different metal (15).
( 21 ) The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles or a mixture thereof ( 15 ) The method according to any one of ( 15 ) to ( 18 ).

( 22 ) A powder selected from the group consisting of a pure metal, a metal oxide, and a metal nitride is prepared as a metal ion source, and the metal ion source is magnesium, calcium, iron, cobalt, nickel, copper, silver, zinc. And one or more selected from the group consisting of metal oxides and metal nitrides thereof,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the powder into the solution, stir,
Reacting the powder with the ligand substance,
Continue the reaction until all of the powder is consumed,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
A method for forming a porous polymer metal complex powder represented by the formula:
( 23 ) The formation method according to ( 22 ), wherein the water content of the alcohol-based solvent is 0 to 12% by mass.
(24) the alcohol solvent is methanol, ethanol, 1-propanol, forming method according to a any one or a mixture of these 2-propanol (23).
( 25 ) The formation method according to any one of ( 22 ) to ( 24 ), wherein the reaction is performed at a temperature of −20 to 150 ° C.
( 26 ) The method according to ( 22 ), wherein M is an ion of copper or silver or a mixed ion thereof.
( 27 ) The formation method according to ( 22 ), wherein the metal ion source is one or more selected from the group consisting of a metal of copper and silver and a metal oxide or metal nitride thereof. .
( 28 ) The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles or a mixture thereof The formation method according to any one of ( 22 ) to ( 25 ), wherein

( 29 ) A powder selected from the group consisting of a pure metal, a metal oxide, and a metal nitride is prepared as a metal ion source, and the metal ion source is magnesium, calcium, iron, cobalt, nickel, copper, silver, zinc. And one or more selected from the group consisting of metal oxides and metal nitrides thereof,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the powder into the solution, stir,
Reacting the powder with the ligand substance,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
To form a porous polymer metal complex represented by
Stopping the reaction before the powder has been completely consumed by the reaction.
A method for forming core-shell type composite particles having the porous polymer metal complex around the powder particles.
( 30 ) The forming method according to ( 29 ), wherein the water content of the alcohol-based solvent is 0 to 12% by mass.
( 31 ) The method according to ( 30 ), wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof.
( 32 ) The formation method according to any one of ( 29 ) to ( 31 ), wherein the reaction is performed at a temperature of -20 to 150 ° C.
( 33 ) The method according to ( 29 ), wherein M is an ion of copper or silver or a mixed ion thereof.
(34) wherein the metal ion source, copper, any metal silver, and methods formed according to at least one selected from the group consisting of metal oxide or metal nitride (29) .
( 35 ) The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles or a mixture thereof ( 29 ) The method according to any one of ( 29 ) to ( 32 ).

(36) pure metal plate, a metal oxide plate, complex consisting of a porous polymer metal complex layer located on one or both sides of the plate-shaped molded body and said plate-shaped molded product selected from the group consisting of metal nitride plate Wherein the plate-like formed body is one selected from the group consisting of magnesium, calcium, iron, cobalt, nickel, copper, silver, and zinc, and metal oxides or metal nitrides thereof. Or consist of two or more,
The porous polymer metal complex film,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the plate-shaped molded product, L is capable of cross-linking and two M contain a functional group capable of coordinating to M into two or more within its structure X represents a ligand, X represents a value by which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
Represented by
The plate-shaped molded body is a metal of the metal ion M of the porous polymer metal complex,
The root-mean- square roughness Rq (RMS) of the porous polymer metal complex film is less than 25% with respect to the film thickness, and the breakdown voltage is 0.1 V or more.
Complex.
( 37 ) The complex according to ( 36 ), wherein M is an ion of either copper or silver or a mixed ion thereof.
( 38 ) The ligand is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles or a mixture thereof The complex according to any one of ( 36 ) to ( 37 ), which is derived.

  According to the method of the present invention, a porous polymer metal complex can be formed, and a porous polymer metal complex powder, particles of a composite of a metal and a porous polymer metal complex, and a plate-like material can be produced. Can be. The powder of the porous polymer metal complex, the particles of the metal and the composite of the porous polymer metal complex, and the plate-like material produced by the present method can be used as a sensor, a conductive material, and the like.

  The powder of the porous polymer metal complex produced by the method of the present invention can remove the solvent remaining in the pores without performing a pretreatment at a high temperature. Deterioration is less likely to occur, and it exhibits excellent properties as a gas storage, separation material, catalyst and the like.

  The composite of the porous polymer metal complex and the metal plate produced by the method of the present invention is used when used as a gas separation storage material, an electronic device, a catalyst, etc., because the porous polymer metal complex membrane is dense. Express excellent characteristics.

4 is a graph showing the relationship between time and film thickness when forming a porous polymer metal complex film by the method for forming a porous polymer metal complex of the present invention. 2 is an SEM photograph showing the surface and cross section of the PCP thin film formed in Example 1.

The porous polymer metal complex obtained by the method of the present invention has the following formula (1)
[ML _x ] _n (1)
(In the formula, M represents a metal ion selected from Groups 2A to 3B of the periodic table of the elements, and L represents two or more M groups containing two or more functional groups capable of coordinating with M in the structure. X represents a ligand which can be cross-linked, X is a value by which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n is that many constituent units composed of [ML _x ] are assembled. It shows characteristics, and n is 5 or more.)
Is represented by

Since the porous polymer metal complex of the present invention is a porous body, when it comes into contact with water, an organic molecule such as alcohol or alcohol, it contains water or an organic solvent in the pores.
[ML _x ] _n (G) _y (2)
(In the formula, M represents a metal ion selected from Groups 2A to 3B of the periodic table of the elements, and L represents two or more M groups containing two or more functional groups capable of coordinating with M in the structure. X represents a ligand which can be cross-linked, X is a value by which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n is that many constituent units composed of [ML _x ] are assembled. N is 5 or more, G is a molecule such as water or alcohol, and y is 0.01 to 8).

  However, the guest molecule represented by G in these composite materials is only weakly bound to the porous polymer metal complex, and is easily removed by drying under reduced pressure or the like, and the original formula (1) Return to the material represented. Therefore, even the form represented by the formula (2) can be regarded as essentially the same as the porous polymer metal complex of the present invention (1). When G is an amount and substance that does not affect the physical properties of the target material, it can be used while containing G.

  The metal ion source used in the method of the present invention can provide a metal ion selected from Groups 2 to 15 of the periodic table of elements, a pure metal or a metal compound such as a metal oxide, a metal nitride, a metal sulfide. Things. Magnesium, potassium, manganese, iron, cobalt, nickel, copper, zinc, rare earth, and silver are preferred because they easily form a porous polymer metal complex. Iron, cobalt, nickel, copper, zinc, and silver are preferable in that a porous polymer metal complex having high adhesion to a substrate is easily formed. Copper and silver are preferred in terms of high smoothness, and copper is more preferred in terms of high film density. Since a metal having a high ionization tendency is easily ionized, a porous polymer metal complex film can be easily formed, but the obtained film tends to be coarse. A metal having a low ionization tendency can be formed into a film having better film roughness and density. In particular, metals having a lower ionization tendency than H, such as copper and silver, give excellent films.

  The metal oxide that can be a metal ion source used in the method of the present invention is an oxide of a metal selected from Groups 2 to 15 of the periodic table of the elements. Magnesium, potassium, manganese, iron, cobalt, nickel, copper, zinc, rare earth, and silver oxides are preferred because they easily form a porous polymer metal complex. Oxides of iron, cobalt, nickel, copper, zinc and silver are preferred in that a high-purity porous polymer metal complex is easily formed. Copper and silver oxides are preferred in terms of high smoothness, and copper oxides are more preferred in terms of high film density. Also, metal nitride can be a metal ion source. The metal nitride that can be used is a metal nitride selected from Groups 2 to 15 of the periodic table of the elements. Metal nitrides are more resistant to corrosion and oxidation than metals. Therefore, it is suitable for use as an electric electrode and is stable for a long time. In addition, it has a property of higher hardness than metal. For this reason, mechanically strong strength can be obtained. As examples of the metal nitride, nickel nitride and copper nitride are preferable.

  The metal that can be a metal ion source may be an alloy. In this case, a porous polymer metal complex containing a plurality of types of metal ions is formed. An alloy containing magnesium, potassium, manganese, iron, cobalt, nickel, copper, zinc, and a rare earth element with a purity of 50% or more is preferable because a porous polymer metal complex is easily formed. An alloy containing iron, cobalt, nickel, copper, and zinc at a purity of 50% or more is preferable because a high-purity porous polymer metal complex is easily formed. More preferably, it is an alloy containing 50% or more of copper. It is also possible to use a two-metal-laminated plate.

  When a powdery porous polymer metal complex is produced, it is preferable to use a metal powder or a metal foil as a metal ion source. The average particle size of the metal powder is 50 nm to 2 mm. If it is 50 nm or less, it is difficult to handle, and if it is 2 mm or more, the reaction is slow. A particle size of 100 nm or more and 1 mm or less is preferable in that a high-purity porous polymer metal complex can be obtained. When using a metal foil, the thickness of the metal foil is 2 nm or more and 1 mm or less. When producing composite particles of metal particles and a porous polymer metal complex, the size of the metal particles can be selected according to the target particle size.

  When a film-shaped porous polymer metal complex is produced, a metal plate may be used as a metal ion source. The thickness of the metal plate can be selected according to the purpose.

  When a pure metal or a metal compound is used as the metal ion source, the metal ion is generated by being dissolved by the proton of the acidic ligand. In general, silver or copper, whose ionization tendency is smaller than H, is difficult to dissolve in protonic acid, but dissolution phenomenon occurs in the presence of oxygen. Therefore, this reaction should be used as a raw material for preparing a porous polymer metal complex. Is possible.

  In the method for forming a porous polymer metal complex of the present invention, it is essential to use an acidic ligand. As used herein, the term “acid ligand” refers to an organic ligand derived from an aliphatic or aromatic compound containing at least two of one or more of a carboxyl group, a sulfonic group, and a phosphate group. That means. Specifically, examples of the aliphatic ligand include 1,4-butanedicarboxylic acid, 1,6-hexanedicarboxylic acid, citric acid, fumaric acid, tartaric acid, 1,3,5-cyclohexanetricarboxylic acid, decahydro-1, Examples thereof include 4-naphthalenedicarboxylic acid and succinic acid. Citric acid and fumaric acid are preferred.

  Examples of the aromatic ring contained in the ligand derived from an aromatic compound include a benzene ring, a naphthalene ring, anthracene, and biphenyl. Specific examples include substituted or unsubstituted terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and anthracenedicarboxylic acid. More specifically, terephthalic acids and isophthalic acids in which one or two hydroxyl groups, amino groups, dialkylamino groups, alkyl groups, amide groups, alkoxy groups, halogens, and fluoroalkyl groups are substituted with one or two. Among them, terephthalic acid substituted at the 2-position or 2-position at the 5-position and isophthalic acid substituted at the 5-position are particularly preferable.

  Other preferred aromatic compounds from which organic ligands can be obtained are substituted and unsubstituted trimesic acid, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-tris (4'- Carboxy [1,1′-biphenyl] -4-yl) benzene, biphenyl-3,3 ′, 5,5′-tetracarboxylic acid, 9,10-anthracenedicarboxylic acid, 3,3 ′, 5,5′- Tetracarboxydiphenylmethane, 2,6-naphthalenedicarboxylic acid, dimethyl 2,7-naphthalenedicarboxylate, 1,4-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, pyromellitic acid (1,2,4,5- Tetracarboxylic acid, melitic acid (benzenehexacarboxylic acid), 1,3,5-tris (4′-carboxy [1,1′-biphenyl] -4-yl) benzene 1,3,5-triscarboxyphenylethynylbenzene, 3,3 ′, 5,5′-tetracarboxydiphenylmethane, [1,1 ′: 4 ′, 1 ″] tetraphenyl-3,3 ″, 5 5 ″ -tetracarboxylic acid, 9,10-anthracene dicarboxylic acid, biphenyl-3,3 ′, 5,5′-tetracarboxylic acid 3,4-propylenedioxythiophene-2,5-dicarboxylic acid, 1,2 , 4,5-Tetrakis (4-carboxyphenyl) benzene, 4,4 ', 4 "-s-triazine-2,4,6-triyl-tribenzoic acid, 1,4,5,8-naphthalenetetracarboxylic acid Acid, benzophenone-4,4'-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4'-oxybis (benzoic acid), 4,4'-sulfoni Dibenzoic acid, 3,5-pyrazoledicarboxylic acid, pyrimidine-5-carboxylic acid, 5-methylpyrazine-2-carboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, 2,3 -Pyrazine dicarboxylic acid.

  These ligand substances can be used as a mixture of plural kinds. The use ratio can be determined according to the ratio of the ligand contained in the target porous polymer metal complex.

  In addition to the above acidic ligands, basic ligands can be mixed and used. As used herein, the term "basic ligand" refers to a ligand derived from an organic compound containing an aromatic nitrogen atom such as a pyridyl group or an imidazolyl group, and specifically, substituted or unsubstituted 4,4. Examples thereof include 4′-bipyridines, substituted or unsubstituted imidazoles, and various ligands derived from organic compounds containing a pyridyl group or an imidazolyl group. Specific compounds include 2,4,6-tri (4-pyridyl) -1,3,5-triazine, 1,2-bis (4-pyridyl) ethane, trans-1,2-bis (4-pyridyl) ) -Ethylene, 1,3-di (4-pyridyl) propane, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 2,2′-dipyridylamine (dpa), zinc 5 , 10,15,20-Tetra (4-pyridyl) -21H, 23H-porphine, 1,10-phenanthroline, 1,3,5-triazine, 4,4'-bipyridyl, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] Octane (dabco), pyrazine.

  In the method for forming a porous polymer metal complex of the present invention, the solvent is a monohydric to trihydric alcohol. Since alcohols have polarity, they are excellent in solubility of a ligand substance containing a hetero atom. In addition, the metal ion source is excellent in solubility. Dimethylformamide, dimethylsulfoxide, water and the like also have a high metal ion source dissolving power, but the use of a solvent having excessive solubility promotes the formation of a porous polymer metal complex excessively, and the resulting membrane has a smoothness. And the film density is undesirably reduced.

  Examples of the monohydric alcohol include methanol, ethanol, and 1-propanol. Examples of the dihydric alcohol include ethylene glycol and diethylene glycol. Glycerin is mentioned as a trihydric alcohol. Methanol and ethanol are preferred in that the yield of the porous polymer metal complex is high. Ethanol is particularly preferred in that the purity of the obtained porous polymer metal complex is high. These solvents can be used as a mixture. The obtained porous polymer metal complex preferably contains ethanol at 70% or more in view of high purity.

  Solvents other than alcohols can be mixed with the above-mentioned alcohols and used. Examples of solvents that can be used in combination include alkanes such as hexane, aromatics such as benzene, ethers such as diethyl ether, and esters such as ethyl acetate. Examples include formamides such as dimethylformamide, and sulfoxides such as dimethylsulfoxide. The mixing ratio of solvents other than alcohols is preferably less than 50% by volume.

  As described above, the presence of excessive water is not preferred because it causes a reduction in the smoothness of the obtained film and a reduction in the film density. The water content of the total solvent is 0 to 12% by mass, 0.00001 to 7% by mass from the viewpoint of increasing smoothness, 0.001 to 4% by mass from the viewpoint of increasing the film density, and the viewpoint of improving the electrical characteristics. From 0.05 to 1% by mass.

  The reaction temperature during the reaction between the metal ion source and the ligand substance is preferably from -20C to 150C. 0 ° C to 140 ° C is preferred from the viewpoint that the reaction proceeds promptly. The temperature is more preferably from 20C to 120C from the viewpoint of improving the smoothness of the film. The temperature is more preferably 40 ° C to 90 ° C from the viewpoint of improving the denseness of the film. If the temperature is too high, the growth of the porous polymer metal complex is excessively promoted, and the crystal grain size becomes coarse, so that the resulting film loses smoothness. When the temperature is low, the number of crystal growth points decreases, the density of the film decreases, and this causes cracks and the like.

  The concentration of the ligand substance used in the reaction ranges from 0.001 mM in terms of the provided ligand to a saturated concentration of the ligand. From the viewpoint that the reaction proceeds rapidly, a concentration of 0.01 mM to a saturation concentration is preferable.

  Since the reaction time between the metal ion source and the ligand substance varies depending on the particle size and plate thickness of the metal powder and metal plate used, and the amount (thickness) of the desired porous polymer metal complex, Although it cannot be decided, it is 1 second to 180 hours. By increasing the time, the metal ion source as a raw material can be consumed more, and the amount (thickness in the case of a membrane) of the porous polymer metal complex can be increased.

  When metal powder is used as a metal ion source, a core-shell in which a porous polymer metal complex serving as a shell is formed around metal particles serving as a core by stopping the reaction before all the metal is consumed. It is possible to form type composite particles. The metal particle diameter and the thickness of the porous polymer metal complex of the obtained composite material can be controlled by the metal particle diameter to be used and the reaction time according to the purpose. By reacting for a long time, the size of the metal particles serving as the core is reduced, and the thickness of the porous polymer metal complex serving as the shell is increased.

  A metal / porous polymer metal complex (A) / porous polymer metal complex (B) type composite can be formed. The core-shell composite particles formed by the above method are further immersed in a solvent containing another kind of ligand, and re-reacted, thereby forming a porous layer formed from another kind of ligand on the composite particle. It is possible to form a polymer metal complex (B) layer.

  A porous polymer metal complex film can be formed on a metal plate serving as a metal ion source. When reacting a metal plate with a ligand, it is possible to form a layer of a porous polymer metal complex on the metal plate by stopping the reaction before the metal plate is completely consumed. . The thickness of the metal plate and the thickness of the porous polymer metal complex of the obtained composite can be set by controlling the thickness of the metal plate to be used and the reaction time.

  A plurality of types of porous polymer metal complex films can be formed on a metal plate serving as a metal ion source. By immersing the composite material in which the layer of the porous polymer metal complex is formed on the above-mentioned metal plate in a solution containing another kind of ligand substance, the porosity of another kind of ligand is further increased. It is possible to stack layers of a polymer metal complex.

  When a plated metal plate is used as a metal plate serving as a metal ion source, for example, when a plate in which zinc plating is formed on a copper plate is used, a laminate of a copper / zinc / zinc-containing porous polymer metal complex is formed. It is possible to form.

  Further, in the above method, by continuing the reaction even after zinc is consumed, a laminate of a copper / zinc / zinc-containing porous polymer metal complex / a copper-containing porous polymer metal complex composite material is formed. Is possible.

  Based on the same principle that a porous polymer metal complex can be formed on a plate using a plate as a metal ion source, using a linear A composite material coated with a porous polymer metal complex can be prepared. Further, by using a honeycomb structure used as a carrier of an exhaust gas purifying catalyst as a metal ion source, a composite material in which a porous polymer metal complex is coated on the honeycomb structure can be prepared. The shape of the material used as the metal ion source may be selected appropriately depending on the purpose.

A circuit can be formed using the method for forming a porous polymer metal complex of the present invention. The porous polymer metal complex is masked with a resin or the like so that the metal does not react with the metal on the metal plate serving as the metal ion source, and the material is reacted with the ligand to form a porous metal complex on the metal plate. It is possible to form a circuit of a molecular metal complex or the like.
As another method, a circuit is formed in advance on a metal that does not react with the ligand (for example, platinum) with a metal (for example, copper) that reacts with the ligand, and the material is used for the reaction with the ligand. As a result, it is possible to form a circuit of the porous polymer metal complex.

  In the prior art method for forming a porous polymer metal complex film, the mainstream was to immerse the substrate in a solution containing both the ligand and the metal ion. However, in this method, when the raw material concentration is low, the formation of the porous polymer metal complex is unlikely to occur, and the number of occurrence points of the porous polymer metal complex on the substrate is small. Since the complex film grows, there is a disadvantage that the film tends to be rough. On the other hand, when the concentration is high, the number of generation points increases, but the growth rate of the porous polymer metal complex increases, the particle size increases, and flatness is lost. In any case, there is an essential drawback that concentration control is difficult because both raw materials are dissolved in the solution.

  As an improvement of the above conventional method, a step-by-step method of alternately immersing a substrate in a metal salt solution and a ligand solution has been proposed. According to this method, the above-mentioned problem of the concentration control is solved. However, since one set (one each of the metal salt solution and the ligand solution) is immersed, only a film of one molecule grows. 100 sets of immersion are required to form a film (about 100 nano ultra-thin), which is extremely complicated.

The reason why a dense and smooth film is formed by the present invention can be estimated as follows. In other words, metal ions are gradually supplied to the surface of the porous polymer metal complex film through the nano-level pores of the porous polymer metal complex, and react with the ligand in the solution on the surface of the porous polymer metal complex film. By doing so, it is possible to control the production of the porous polymer metal complex with extremely high precision. FIG. 1 shows the relationship between time and film thickness when a reaction was performed using copper as a metal. d = log _n (t + 1) + fT (where d represents film thickness, t is reaction time (h), f represents a function of T, and T is temperature (K)) It can be seen that a thin film is growing. This is because ionized Cu diffuses in the pores of the porous polymer metal complex [dM / dt = αe-d (the number of metal ions contained in the thin film M∝d)], and the porous polymer metal complex / solvent The arrival at the interface means that the growth of the porous polymer metal complex proceeds. That is, since the metal ions slowly released through the pores react only on the surface of the membrane, a dense and flat membrane is formed. Since it is a dense film, when it is used for a gas separation film or an electronic device, a material having excellent characteristics with few leak paths can be obtained. Because of its high smoothness, when used for electronic devices, it is possible to suppress performance variations due to material uniformity, and when used for catalysts, it is possible to suppress side reactions and the like due to uneven surfaces.

  In some cases, instead of metal ions diffusing in the pores, the ligand diffuses in the pores and reacts with the metal ions on the substrate surface to form a porous polymer metal complex. Also in this case, the supply of the ligand, which is a raw material, is controlled by the pores, so that it is dense and smooth, compared to the case where both the metal ion and the ligand are present in the solution and a reaction occurs on the substrate. A film is easily obtained. This theory is speculation, and does not limit the content of the present invention.

  The formation reaction of the porous polymer metal complex can be terminated by removing the porous polymer metal complex from the reaction solution. When the porous polymer metal complex is a thin film formed on a substrate, the substrate may be taken out of the reaction solution, and when the porous polymer metal complex is a powder, the solution is filtered, centrifuged, or the like. What is necessary is just to separate a powder. When the concentration of the ligand substance is low, the sensor, the conductive material, It can be used as a gas separation material. If it is necessary to remove trace amounts of metal ions or ligand substances remaining in the porous polymer metal complex, the porous polymer metal complex film or powder was washed using an alcohol-based solvent or the like. Thereafter, it may be dried as described above.

  As described above, the formation reaction of the porous polymer metal complex can be terminated by removing the porous polymer metal complex from the reaction solution. Can be controlled by time. Increasing the concentration of the ligand substance in the reaction solution accelerates the reaction and increases the film thickness, or vice versa, and increases the reaction temperature to accelerate the reaction and increase the film thickness It is also possible to make the film thinner, or vice versa, but also in these cases, the film thickness can be controlled by the reaction time. The thickness of the porous polymer metal complex film that can be produced by this method is 2Å to 100 microns. Although a thinner film can be formed, the number of defects increases. Although a thicker film can be formed, the denseness is reduced.

<Analysis of PCP>
For the X-ray powder diffraction measurement, an X-ray diffractometer SmartLab (trade name) manufactured by Rigaku Corporation was used. For TG (Thermo Gravimetry) measurement, a differential thermal balance analyzer TG8120 (trade name) manufactured by Rigaku Corporation was used. For evaluation of gas adsorption characteristics, Bell Soap Mini II manufactured by Microtrack Bell was used. SEM (scanning electron microscope) was used to observe the thickness and formation of the metal plate and the porous polymer metal complex. For composition analysis of the porous polymer metal complex film, grazing incidence X-ray diffraction measurement (2θ measurement) was performed. As the apparatus, an X-ray diffractometer SmartLab (trade name) manufactured by Rigaku Corporation is used, and the measurement condition is an X-ray incident angle ω = 1.0.

  The smoothness of the porous polymer metal complex film was measured using AFM (atomic force microscope). The denseness was evaluated using the dielectric breakdown voltage of the porous polymer metal complex film. The confirmation of the porosity was evaluated using a commercially available gas adsorption device, Bellsorb Mini II, a gas adsorption evaluation device manufactured by Microtrac Bell.

Since the smoothness of the porous polymer metal complex film greatly depends on the film thickness to be formed, the value of the root mean square roughness Rq (RMS) representing the smoothness of the thin film thickness and the smoothness of the thick film thickness are determined. The values of the root mean square roughness Rq (RMS) cannot be compared in the same column. Therefore, the evaluation of the smoothness of the porous polymer metal complex film was performed by defining the ratio (%) of the root mean square roughness Rq (RMS) to the film thickness as an index of the smoothness, and evaluated as follows. An arbitrary part on the surface of the formed porous polymer metal complex film was subjected to AFM ((SII Nanotechnology Co., Ltd., SPI3800N / SPA400, probe SI-DF3-R (100) (tip diameter 100 nm)) to give a rough surface. The value of the roughness Rq (RMS) was read, and evaluated using the ratio of the obtained value of the root mean square roughness Rq (RMS) to the film thickness according to the following criteria.

Evaluation of smoothness (◎, ○, Δ were determined to be effective).

：: Ratio (%) of Rq (RMS) to film thickness: less than 10% ：: 10% or more and less than 18% △: 18% or more to less than 25% ×: 25% or more

  The denseness of the metal complex film was evaluated using the dielectric breakdown voltage of the porous polymer metal complex film. Since a high value is obtained when a more uniform and strong film is formed, the dielectric breakdown voltage was used as an index of the denseness of the obtained porous polymer metal complex film. It can be said that the higher the value, the denser the film is formed. This index was measured by voltage sweep-current measurement. A semiconductor parameter analyzer (Agilent Technology Co., Ltd., Agilent 4155C) was used for evaluation of the examples and the comparative examples.

(A, B, and B were determined to be effective).
The density of the metal complex film was evaluated from the obtained dielectric breakdown voltage value according to the following criteria.
◎: Dielectric breakdown voltage 10 V or more ○: Dielectric breakdown voltage 0.1 V or more and less than 10 V △: Dielectric breakdown voltage 0.1 V or more and less than 1 V ×: Dielectric breakdown voltage less than 0.1 V or insulating No (current leak state)

  As a solvent, methanol, ethanol, dimethylformamide, and N-methylpyrrolidinone used a dehydration grade manufactured by Kanto Chemical Co., Ltd. in each example. The water content of dehydrated methanol is less than 0.025% (catalog value), the water content of dehydrated ethanol is less than 0.005%, the water content of dehydrated dimethylformamide is less than 0.001%, and the water content of N-methylpyrrolidinone is 0.005. %. The ligand substance used in each example was purchased from Tokyo Chemical Industry Co., Ltd. and used without purification. Copper powder having a particle size of 75 μm to 150 μm manufactured by Kanto Chemical Co., Ltd. was used. As the copper oxide powder, a 3.3 μm particle size manufactured by Kanto Chemical Co., Ltd. was used. As the zinc powder, a special grade manufactured by Kanto Chemical Co., Ltd. was used. The cobalt powder used had a particle size of 3 μm to 7 μm manufactured by Kanto Chemical Co., Ltd. Copper nitrate, zinc nitrate, cobalt nitrate, and copper (II) hydroxide all used special grade products manufactured by Kanto Chemical Co., Ltd.

The following two types were used as metal copper plates.
Metallic copper plate A: A copper-based film (size 10 × 15 mm) formed by a reactive sputtering method on a SiO ₂ —Si substrate (a 6-inch thermally oxidized film 1000Å film-formed product) of Shin-Etsu Semiconductor Co., Ltd. The sputtering conditions at this time are: Cu target purity 4N, sputtering output 800W, film forming temperature: room temperature, ultimate vacuum pressure 1 × 10 ⁻⁴ Pa, sputtering vacuum pressure 0.40 Pa, Ar flow rate 800 sccm, and film forming time 600 s.
Metallic copper plate B: CU-113513 manufactured by Nilaco Co., Ltd. (about 1.0 × 10 × 10 mm, purity 99.99%)

The following two types of copper oxide plates were used, in which the degree of oxidation was controlled by controlling the amount of oxygen introduced during sputtering.
Copper oxide plate A: CuO film formed by reactive sputtering on the above-mentioned SiO ₂ —Si substrate. The sputtering conditions at this time are: 4N Cu target purity, 800 W sputter output, film formation temperature: room temperature, ultimate vacuum pressure 1 × 10 ⁻⁴ Pa, sputtering vacuum pressure 0.25 Pa, Ar flow rate 900 sccm, and film formation time 600 s.
Copper oxide plate B: a film of Cu ₂ O formed on the above-mentioned SiO ₂ —Si substrate by a reactive sputtering method. The sputtering conditions at this time were as follows: Cu target purity: 4N, sputtering output: 800 W, film forming temperature: room temperature, ultimate vacuum pressure: 1 × 10 ⁻⁴ Pa, sputtering vacuum pressure: 0.25 Pa, Ar flow rate: 400 sccm, O ₂ flow rate: 800 sccm, film formation The time is 600 s.

  When the reaction was carried out at a temperature lower than the boiling point of the solvent, the reaction vessel was closed with a plastic paraffin film (trade name, parafilm), a glass stopcock, or the like to prevent water from entering, using a flask, a beaker, or the like. When the reaction was carried out at a temperature higher than the boiling point, an autoclave was used.

<Synthesis of thin film PCP>
Example 1
The metal copper plate A is immersed in 50 mL of a 0.1 mM concentration of trimesic acid ethanol solution, which is a ligand substance solution, and reacted at 20 ° C. for 2 hours. Then, the copper plate is taken out of the solution with tweezers, and placed three times in an anhydrous ethanol solution. After immersion and washing for 10 seconds each, and drying under reduced pressure at room temperature, the surface and cross section were observed by SEM. FIG. 2 shows a photograph of the cross-section observation. The left side is the surface, and the right side is the cross section. A beautiful film is obtained.

Example 2-30
The same operation as in Example 1 was performed using the metal plate and the ligand shown in Table 1 to cause the two to react, and the resulting composite having the porous polymer metal complex film was analyzed.

Comparative Examples 1 to 20
Using a solvent other than the alcohol-based solvent as the ligand substance solution, an experiment was performed by performing the same operation as in Example 1 using the metal plate and the ligand substance shown in Table 2. When water was not contained, the film forming reaction did not proceed. When water was included, the surface and cross section were observed by SEM. As a result, only a film having low smoothness and low denseness was obtained.

<Synthesis of powdered PCP>
Example 31
0.6 mMol of copper powder and 0.6 mMol of terephthalic acid were dispersed in 20 mL of dehydrated ethanol, and reacted at 50 ° C for 3 days with stirring using a magnetic stirrer. The obtained powder was centrifuged, the precipitated powder was dispersed in ethanol, centrifuged again, the ethanol was removed by decantation, and the obtained powder was vacuum-dried at room temperature. The obtained powder was analyzed with a powder X-ray structure diffractometer, and described as a compound described in Non-patent Document 14 (Cu (tpa) · (dmf) composed of Cu 2+ ion, terephthalic acid, and DMF of a guest molecule). Porous polymer metal complex). After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Example 32
As in Example 31, the reaction was carried out using trimesic acid instead of terephthalic acid.
The obtained powder was analyzed with a powder X-ray diffractometer, and the compound described in Non-Patent Document 15 (Cu ₃ (TMA) ₂ (H ₂ ) composed of Cu ²⁺ ion, trimesic acid, and water of a guest molecule was used. O) ₃ ] n).
After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Example 33
As in Example 31, the reaction was carried out using isophthalic acid instead of terephthalic acid.
The obtained powder was analyzed with a powder X-ray structure diffractometer, and the compound described in Non-Patent Document 16 (Cu ²⁺ ion and Cu (1,3-bdc) composed of isophthalic acid) and a porous material having a high porosity. Molecular metal complex).
After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Example 34
In the same manner as in Example 31, the reaction was carried out using zinc powder and using 2,5-dihydroxyterephthalic acid instead of terephthalic acid. The obtained powder was analyzed with a powder X-ray structure diffractometer, and the obtained compound was obtained from the compounds described in Non-patent Document 11 and Non-patent Document 12 (from Zn ²⁺ ion and 2,5-dihydroxyterephthalic acid). (MOF-74)). After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Example 35
The reaction was carried out in the same manner as in Example 31 using cobalt powder and using 2,5-dihydroxyterephthalic acid instead of terephthalic acid.
The obtained powder was analyzed with a powder X-ray structure diffractometer, and the obtained compound was described in Non-patent Document 11 and Non-Patent Document 17 (Co ²⁺ ion, 2,5-dihydroxyterephthalic acid, guest [Co ₂ (C ₈ H ₂ O ₆ ) (H ₂ O) ₂ ] .8H ₂ O (porous polymer metal complex) composed of water. After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Example 36
As in Example 31, a reaction was performed using copper powder, isophthalic acid and 4,4′-bipyridyl instead of terephthalic acid. The obtained powder was analyzed by a powder X-ray structure diffractometer, and the compound IV described in Non-patent Document 13 (Cu (HIP) ₂ (bipy) composed of Cu ²⁺ ion, isophthalic acid, and 4,4′-bipyridyl) (Porous polymer metal complex represented by the following formula). After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

Comparative Example 21
A powder sample was obtained by the method described in Non-Patent Document 14 using copper (II) nitrate trihydrate as a metal ion source, terephthalic acid as a ligand substance, and DMF as a solvent. The obtained powder was analyzed with a powder X-ray diffractometer, and the compound (Cu (tpa) · (dmf) composed of Cu ²⁺ ion, terephthalic acid and guest molecule DMF) described in the above-mentioned literature was described. Porous polymer metal complex).
The amount of gas adsorption of 30 mg of the powder was evaluated by using a gas adsorption evaluation device Bell Soap Mini II manufactured by Microtrack Bell. The solvent removal characteristics were confirmed by TG measurement. Compared with Example 31, by TG evaluation, weight loss at 140 ° C. was observed, DMF (N, N-dimethylformamide) used as a solvent was confirmed to remain, and the solvent could not be removed up to 100 ° C. Was confirmed. Nitrogen gas adsorption at 77K was smaller than that in Example 31, which is considered to be the effect of the remaining DMF.

Comparative Example 22
A powder sample was obtained by the method described in Non-Patent Document 15 using copper (II) nitrate trihydrate as a metal ion source, trimesic acid as a ligand substance, and water-DMF as a solvent. The obtained powder was analyzed with a powder X-ray structure diffractometer, and the compound (Cu ₃ (TMA) ₂ (H ₂ O) composed of a compound (Cu ²⁺ ion, trimesic acid, and guest molecule water) described in the above literature was used. ₃ ] a porous polymer metal complex represented by n). The amount of gas adsorption of 30 mg of the powder was evaluated by using a gas adsorption evaluation device Bell Soap Mini II manufactured by Microtrack Bell. The solvent removal characteristics were confirmed by TG measurement. Compared with Example 31, TG evaluation showed a weight loss at 140 ° C., and confirmed that DMF used as a solvent remained, and that the solvent could not be removed up to 100 ° C. Nitrogen gas adsorption at 77K was smaller than that in Example 32, which is considered to be due to the effect of remaining DMF.

Comparative Example 23
A powder sample was obtained by the method described in Non-Patent Document 16 using copper hydroxide as a metal ion source, isophthalic acid as a ligand substance, and water as a solvent. The obtained powder was analyzed by a powder X-ray structure diffractometer, and a porous polymer metal described as Cu (1,3-bdc) composed of a compound (Cu ²⁺ ion and isophthalic acid) described in the above-mentioned literature was used. Complex). The amount of gas adsorption of 30 mg of the powder was evaluated by using a gas adsorption evaluation device Bell Soap Mini II manufactured by Microtrack Bell. The solvent removal characteristics were confirmed by TG measurement. Compared with Example 33, the TG evaluation showed a weight loss at 110 ° C., the remaining water used as an additive was confirmed, and it was confirmed that the solvent could not be removed up to 100 ° C. Nitrogen gas adsorption at 77K was smaller than that in Example 33, which is considered to be the effect of remaining water.

Comparative Example 24
Compounds described in Non-Patent Document 11 and Non-Patent Document 12 using zinc (II) nitrate hexahydrate as a metal ion source, 2,5-dihydroxyterephthalic acid as a ligand substance, and DMF as a solvent (MOF -74) was synthesized by the method of the paper. The obtained powder was analyzed with a powder X-ray diffractometer, and was analyzed using a porous polymer metal complex “MOF-74” composed of the compound Zn ²⁺ ion and 2,5-dihydroxyterephthalic acid described in the above document. I confirmed that there is. Compared with Example 34, the TG evaluation showed a weight loss at 140 ° C., confirmed that DMF used as a solvent remained, and that the solvent could not be removed up to 100 ° C. Nitrogen gas adsorption at 77K was smaller than that in Example 34, which is considered to be due to the effect of remaining DMF.

Comparative Example 25
Compounds described in Non-Patent Document 11 and Non-Patent Document 17 using cobalt nitrate hexahydrate as a metal ion source, 2,5-dihydroxyterephthalic acid as a ligand substance, and THF (tetrahydrofuran) as a solvent (Co) A porous polymer metal described as [Co ₂ (C ₈ H ₂ O ₆ ) (H ₂ O) ₂ ] · 8H ₂ O composed of ²⁺ ions, 2,5-dihydroxyterephthalic acid, and water as a guest Complex) was synthesized according to the method described in the paper, and the obtained powder was analyzed with a powder X-ray structure diffractometer to confirm that it was the compound described in the above-mentioned literature. Compared with Example 35, by TG evaluation, a weight loss at 100 ° C. was observed, THF used as a solvent was confirmed to remain, and it was confirmed that the solvent could not be completely removed up to 100 ° C. Nitrogen gas adsorption at 77K was smaller than that in Example 35, which is considered to be the effect of remaining THF.

Comparative Example 26
Dissertation on the compound (described as IV) described in Non-Patent Document 13 using copper (II) nitrate trihydrate as a metal ion source, isophthalic acid and 4,4'-bipyridine as ligand substances, and water as a solvent. And the obtained powder was analyzed by a powder X-ray diffractometer, and the compound (Cu (HIP) ₂ composed of Cu ²⁺ ion, isophthalic acid and 4,4′-bipyridyl) described in the above-mentioned literature was analyzed. In comparison with Example 36, the TG evaluation showed a weight loss at 100 ° C., the remaining water used as a solvent was confirmed, and the solvent was removed up to 100 ° C. It was confirmed that nitrogen gas adsorption at 77 K was smaller than that in Example 36, which is considered to be the effect of remaining water.

  Tables 3 and 4 show the gas adsorption amounts of Examples 31 to 36 and Comparative Examples 21 to 26.

<Formation of core-shell type composite particles>
Example 37
While the copper powder (0.6 mMol) and terephthalic acid (0.6 mMol) were dispersed in dehydrated ethanol (20 mL) and stirred at 50 ° C. using a magnetic stirrer, the reaction time of Example 31 was 72 hours, whereas that of Example 31 was 12 hours. I let it. The obtained powder was centrifuged, the precipitated powder was dispersed in ethanol, centrifuged again, the ethanol was removed by decantation, and the obtained powder was vacuum-dried at room temperature. The obtained powder was analyzed with a powder X-ray structural diffractometer and described as a compound described in Non-Patent Document 14 (Cu (tpa) · (dmf) composed of Cu ²⁺ ion, terephthalic acid, and DMF of a guest molecule). Porous polymer metal complex). In addition, microscopic observation confirmed that the powder obtained by this method was sky blue, and that the brown copper color was not exposed to the outside of the particles. After this powder was dispersed in 50 mL of concentrated ammonia water, the solution was filtered, and it was confirmed that copper powder remained on the filter paper. That is, it was confirmed that this powder was a composite particle in which the copper powder was the core and the porous polymer metal complex was the shell. After 30 mg of this powder was subjected to vacuum pretreatment under reduced pressure at 100 ° C. for 3 hours using a gas adsorption evaluation apparatus Bellsorp mini II manufactured by Microtrac Bell Co., the nitrogen gas adsorption at 77K was evaluated. In addition, the solvent removal characteristics were confirmed by TG measurement, and it was confirmed that the solvent ethanol could be removed up to 100 ° C.

<Formation of Composite Composed of Metal Plate / PCP-B Film / PCP-A Film>
Example 38
A metal plate (size 10 × 15 mm) on which a copper film was formed by a reactive sputtering method on a SiO ₂ —Si substrate of Shin-Etsu Semiconductor Co., Ltd. The ligand substance solution A was immersed in 50 mL of a 0.1 mM ethanol solution of trimesic acid and reacted at 20 ° C. for 1 hour. Thereafter, the copper plate was removed from the solution with tweezers, and immersed in an anhydrous ethanol solution three times for 10 seconds each and washed. Next, this material was immersed in 50 mL of a 0.1 mM ethanol solution of terephthalic acid as a second ligand substance solution B, and reacted at 20 ° C. for 4 hours. Thereafter, the copper plate was removed from the solution with tweezers, immersed in an anhydrous ethanol solution three times for 10 seconds each, washed, and dried at room temperature under reduced pressure. Since the reaction time was as short as 1 hour and 4 hours, respectively, the copper plate remained as a support.

  The surface and cross section of the obtained copper plate were observed by SEM. The outermost layer had a crystal structure obtained when immersed in an ethanol trimesic acid solution, and a crystal structure obtained thereunder between the copper plate and the copper plate was obtained when immersed in an ethanol terephthalate solution. Also, by powder X-ray, the outermost layer was formed of a porous polymer metal complex crystal obtained when immersed in an ethanol solution of trimesic acid, and between the lower part and the copper plate was obtained when immersed in an ethanol solution of terephthalic acid. It was confirmed that crystals of the resulting porous polymer metal complex had been formed. That is, in this material, a porous polymer metal complex film (PCP-B) made of terephthalic acid and a porous polymer metal complex film (PCP-A) made of trimesic acid were further formed on a copper plate. It was confirmed that it was a composite material.

  In this example, the obtained composite having two kinds of different porous polymer metal complex films is a porous polymer metal complex film (PCP-) made of terephthalic acid derived from a second ligand substance solution on a copper plate. B) is formed, and a porous polymer metal complex film (PCP-A) made of trimesic acid derived from the first ligand substance solution is formed on the uppermost layer. The reason for this is that the pore size of PCP-A created first is larger than the size of ligand B derived from terephthalic acid, so that ligand B passes through the pores of PCP-A and forms a copper plate. Above, it is considered that the eluted copper ion reacted with the ligand B derived from terephthalic acid to form a PCP-B film under the PCP-A film.

  With respect to the composite composed of the copper plate / PCP-B film / PCP-A film, the smoothness of the uppermost PCP-A film and the densities of the PCP-B film and the PCP-A film were evaluated based on the above-described criteria.

<Formation of Composite Composed of Metal Plate A / A-PCP Film / B-PCP Film>
Example 39
On the SEH _SiO 2 -Si substrate Ltd. (6 inches thermal oxide film 1000Å casting workpiece), by reactive sputtering, copper (metal plate A) is formed and further thereon, the A zinc film (metal plate B) was formed by the method. This multilayer metal plate (size 10 × 15 mm) was immersed in 50 mL of a 0.1 mM ethanol solution of trimesic acid and reacted at 20 ° C. for 24 hours. Thereafter, the complex was removed from the solution with tweezers, and immersed in an absolute ethanol solution three times for 10 seconds each and washed.

  The surface and cross section of the obtained composite were observed by SEM. A porous polymer metal complex film (B-PCP) obtained from trimesic acid and zinc is formed on the outermost layer, and a porous polymer metal complex film (A-PCP) obtained from copper and trimesic acid is formed thereunder. Confirmed that it had been. That is, this material is a composite material in which a porous polymer metal complex film composed of copper and trimesic acid is formed on a copper plate, and a porous polymer metal complex film composed of zinc and trimesic acid is further formed thereon. confirmed.

  The reason that such a complex was formed is that the zinc plate (metal B) of the multilayer metal plate reacts with trimesic acid to form a porous polymer metal complex film (B-PCP). After the zinc plate (metal B) has been consumed by the above, the copper plate (metal A) reacts with trimesic acid. The reaction between the copper plate (Metal A) and trimesic acid proceeds under the already formed porous polymer metal complex film (B-PCP) to form the porous polymer metal complex film (A-PCP). It is considered that a composite composed of a copper plate A / A-PCP film / B-PCP film was formed.

  With respect to the composite composed of the copper plate A / A-PCP film / B-PCP film, the smoothness of the topmost B-PCP film and the densities of the B-PCP film and the A-PCP film were evaluated based on the above-described criteria. .

  The porous polymer metal complex film of the composite having the porous polymer metal complex film obtained by the method of the present invention is smooth because the reaction between the metal ion and the ligand substance is highly controlled. A dense film having high properties is formed. The composite can be suitably used for catalysts, gas storage / separation materials, sensors, electronic devices, and the like.

Claims (38)

As a metal ion source, a plate-shaped compact selected from the group consisting of a pure metal plate, a metal oxide plate, and a metal nitride plate is prepared, and the metal ion source is magnesium, calcium, iron, cobalt, nickel, copper, Silver, one of two or more metals selected from the group consisting of a metal of zinc and a metal oxide or metal nitride thereof,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the plate-shaped molded body in the solution,
The plate-like molded body reacts with the ligand substance, and the following formula (1) is formed on the plate-like molded body.
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
Forming a porous polymer metal complex film represented by
Including stopping the reaction before the plate-shaped molded body is completely consumed by the reaction,
A method for forming a composite having the porous polymer metal complex film on the plate-like molded body .   The method according to claim 1, wherein the water content of the alcohol solvent is 0 to 12% by mass.   The method according to claim 2, wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof.   The method according to claim 1, wherein the reaction is performed at a temperature of −20 to 150 ° C. 5. The method according to claim 1 , wherein M is an ion of copper or silver or a mixed ion thereof. Wherein the metal ion source, copper, any metal silver, and claim 1 is one or plate-shaped molded body made of two or more selected from the group consisting of metal oxide or metal nitride Formation method.   The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,2 It is one selected from 7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles, or a mixture thereof. Item 5. The forming method according to any one of Items 1 to 4. As a metal ion source, a plate-shaped compact selected from the group consisting of a pure metal plate, a metal oxide plate, and a metal nitride plate is prepared, and the metal ion source is magnesium, calcium, iron, cobalt, nickel, copper, Silver, one of two or more metals selected from the group consisting of a metal of zinc and a metal oxide or metal nitride thereof,
Dissolving the first ligand substance in an alcohol-based solvent to prepare a first ligand substance solution;
A second ligand substance different from the first ligand substance is dissolved in an alcoholic solvent to prepare a second ligand substance solution,
Charging the plate-like molded body into the first ligand substance solution,
The plate-like molded body is reacted with the first ligand substance, and the following formula (1) is formed on the plate-like molded body.
[ML1 _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L1, yes capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value by which the positive charge of the metal ion M and the negative charge of the ligand L1 cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML1 _x ] are assembled. And n is 5 or more.)
Forming a first porous polymer metal complex film represented by
Stopping the reaction before the plate-like molded body is completely consumed by the reaction, and then washing the composite having the porous polymer metal complex film on the plate-like molded body ,
Charging the complex into the second ligand substance solution,
The plate-shaped body and the second ligand substance are reacted to form the following formula (2) on the plate-shaped body or the first porous polymer metal complex film.
[ML2 _x ] _n (2)
(Wherein, M and X are the same as in the case of the formula (1), and L2 is different from the above L1 and contains two or more functional groups capable of coordinating to M in its structure. A ligand capable of cross-linking with M is shown, and n represents a characteristic that a large number of constituent units composed of [ML2 _x ] are assembled, and n is 5 or more.)
Forming a second porous polymer metal complex film represented by
Stopping the reaction between the plate-shaped body and the second ligand substance before the plate-shaped body is completely consumed by the reaction;
A method for forming a composite having two different types of porous polymer metal complex films on the plate-like molded body . The method according to claim 8 , wherein the water content of the alcohol solvent is 0 to 12% by mass. The method according to claim 9 , wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof. Wherein each reaction, forming method according to any one of claims 8 to 10 carried out at a temperature -20 to 150 ° C.. 9. The method according to claim 8 , wherein M is an ion of copper or silver or a mixed ion thereof. Wherein the metal ion source, copper, any metal silver, and claim 8 is one or plate-shaped molded body made of two or more selected from the group consisting of metal oxide or metal nitride Formation method. The first and second ligand substances are terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, One or more selected from unsubstituted 2,7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles The formation method according to any one of claims 8 to 11 , which is a mixture of: As a metal ion source on a substrate, a laminate having a plate-shaped molded body A and a plate-shaped molded body B in order is prepared, and the plate-shaped molded bodies A and B are respectively a pure metal plate, a metal oxide plate, Selected from the group consisting of metal nitride plates, wherein the metal ion source is made of any one of magnesium, calcium, iron, cobalt, nickel, copper, silver, zinc, and a metal oxide or metal nitride thereof. One or more selected from the group,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the laminate into the ligand substance solution,
The plate-shaped molded body B is reacted with the ligand substance, and the following formula (1) is formed on the plate-shaped molded body A.
[M1L _x ] _n (1)
(Wherein, M1 represents a metallic ion from the plate-shaped molded product B, L is to contain functional groups capable of coordinating to M1 into two or more its structure crosslink with two M1 X represents a value obtained by canceling the positive charge of the metal ion M1 and the negative charge of the ligand L, and n represents a characteristic that a large number of constituent units composed of [M1L _x ] are aggregated. Where n is 5 or more.)
Forming a first porous polymer metal complex film represented by
Ensure that the plate-shaped molded product B is consumed by the reaction, then the plate-like molded product A is reacted with the ligand material, said plate-shaped molded product A or on the first porous On the polymer metal complex film, the following formula (2)
[M2L _x ] _n (2)
(Wherein, M2 represents a metallic ion from the plate-shaped molded body A, except M1 and M2 are different, X, L is the same as in formula (1), n, [M2L _x ], And n is 5 or more.)
Forming a second porous polymer metal complex film represented by
Stopping the reaction between the plate-shaped body A and the ligand substance before the plate-shaped body A is completely consumed by the reaction,
A method for forming a composite having two different types of porous polymer metal complex films on the plate-like molded body A, comprising: The forming method according to claim 15 , wherein the water content of the alcohol-based solvent is 0 to 12% by mass. 17. The forming method according to claim 16 , wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof. The method according to any one of claims 15 to 17 , wherein each of the reactions is performed at a temperature of -20 to 150 ° C. 16. The method of claim 15 , wherein M1 and M2 are either copper or silver ions or mixed ions thereof, provided that M1 and M2 are different. The plate-shaped compact A and the plate-shaped compact B of the metal ion source are made of one or more selected from the group consisting of copper, silver, and their metal oxides or metal nitrides. a method according to claim 15 is a plate-shaped molded body, except the plate-shaped molded body a and plate-shaped molded body B are different metals made. The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,2 It is one selected from 7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles, or a mixture thereof. Item 19. The forming method according to any one of Items 15 to 18 . As a metal ion source, a powder selected from the group consisting of a pure metal, a metal oxide, and a metal nitride is prepared, and the metal ion source is any one of magnesium, calcium, iron, cobalt, nickel, copper, silver, and zinc. Consisting of one or more selected from the group consisting of metals and their metal oxides or metal nitrides,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the powder into the solution, stir,
Reacting the powder with the ligand substance,
Continue the reaction until all of the powder is consumed,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
A method for forming a porous polymer metal complex powder represented by the formula: The method according to claim 22 , wherein the water content of the alcohol-based solvent is 0 to 12% by mass. The method according to claim 23 , wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof. The forming method according to any one of claims 22 to 24 , wherein the reaction is performed at a temperature of -20 to 150 ° C. 23. The forming method according to claim 22 , wherein M is an ion of copper or silver or a mixed ion thereof. 23. The forming method according to claim 22 , wherein the metal ion source is at least one selected from the group consisting of a metal of copper or silver and a metal oxide or metal nitride thereof. The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,2 It is one selected from 7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles, or a mixture thereof. Item 26. The forming method according to any one of Items 22 to 25 . As a metal ion source, a powder selected from the group consisting of a pure metal, a metal oxide, and a metal nitride is prepared, and the metal ion source is any one of magnesium, calcium, iron, cobalt, nickel, copper, silver, and zinc. Consisting of one or more selected from the group consisting of metals and their metal oxides or metal nitrides,
Dissolve the ligand substance in an alcoholic solvent to prepare a ligand substance solution,
Put the powder into the solution, stir,
Reacting the powder with the ligand substance,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the metal ion source, L is distribution capable of crosslinking with two M contain a functional group capable of coordinating to M into two or more within its structure X represents a value at which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more.)
To form a porous polymer metal complex represented by
Stopping the reaction before the powder has been completely consumed by the reaction.
A method for forming core-shell type composite particles having the porous polymer metal complex around the powder particles. 30. The forming method according to claim 29 , wherein the water content of the alcohol-based solvent is 0 to 12% by mass. 31. The forming method according to claim 30 , wherein the alcohol-based solvent is any one of methanol, ethanol, 1-propanol, and 2-propanol, or a mixed solvent thereof. The forming method according to any one of claims 29 to 31 , wherein the reaction is performed at a temperature of -20 to 150 ° C. 30. The forming method according to claim 29 , wherein M is an ion of copper or silver or a mixed ion thereof. 30. The forming method according to claim 29 , wherein the metal ion source is one or two or more selected from the group consisting of a metal of copper or silver and a metal oxide or metal nitride thereof. The ligand substance is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,2 It is one selected from 7-naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4′-bipyridine, substituted 4,4′-bipyridine, substituted and unsubstituted imidazoles, or a mixture thereof. Item 33. The forming method according to any one of Items 29 to 32 . Pure metal plate, a metal oxide plate, a composite body comprising a porous polymer metal complex layer located on one or both sides of the plate-shaped body selected from the group consisting of metal nitride plate and the plate-shaped molded body And the plate-like formed body is one or two selected from the group consisting of magnesium, calcium, iron, cobalt, nickel, copper, silver, and zinc, and metal oxides or metal nitrides thereof. Consisting of the above,
The porous polymer metal complex film,
The following equation (1)
[ML _x ] _n (1)
(Wherein, M represents a metallic ion from the plate-shaped molded product, L is capable of cross-linking and two M contain a functional group capable of coordinating to M into two or more within its structure X represents a ligand, X represents a value by which the positive charge of the metal ion M and the negative charge of the ligand L cancel each other, and n represents a characteristic that a large number of constituent units composed of [ML _x ] are assembled. And n is 5 or more and 5 or more.)
Represented by
The plate-shaped molded body is a metal of the metal ion M of the porous polymer metal complex,
The root-mean- square roughness Rq (RMS) of the porous polymer metal complex film is less than 25% with respect to the film thickness, and the breakdown voltage is 0.1 V or more.
Complex. 37. The composite according to claim 36 , wherein M is an ion of either copper or silver or a mixed ion thereof. The ligand is terephthalic acid, substituted terephthalic acids, isophthalic acid, substituted isophthalic acids, trimesic acid, substituted trimesic acid, biphenylcarboxylic acid, substituted biphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, unsubstituted 2,7 -Claims derived from one or a mixture of naphthalenedicarboxylic acid, fumaric acid, substituted fumaric acid, citric acid, 4,4'-bipyridine, substituted 4,4'-bipyridine, substituted and unsubstituted imidazoles Item 38. The complex according to Item 36 or 37 .