KR20170044456A - Polymer catalyst comprising PtO2 and method for preparing the same - Google Patents

Polymer catalyst comprising PtO2 and method for preparing the same Download PDF

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KR20170044456A
KR20170044456A KR1020150144186A KR20150144186A KR20170044456A KR 20170044456 A KR20170044456 A KR 20170044456A KR 1020150144186 A KR1020150144186 A KR 1020150144186A KR 20150144186 A KR20150144186 A KR 20150144186A KR 20170044456 A KR20170044456 A KR 20170044456A
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South Korea
Prior art keywords
pto
polymer
catalyst
polymer catalyst
resorcinol
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KR1020150144186A
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Korean (ko)
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KR101793642B1 (en
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유종성
박종덕
김정호
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재단법인대구경북과학기술원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation

Abstract

The present invention relates to an RF (resorcinol-formaldehyde) polymer catalyst comprising PtO 2 and a process for producing the same, and more particularly to a process for producing a polymer electrolyte membrane, which comprises a simple hydrothermal reaction at a relatively low temperature The present invention relates to a polymer catalyst containing a single-phase PtO 2 and a method for producing the same.

Description

[0001] The present invention relates to a polymer catalyst comprising PtO2 and a method for preparing the same,

The invention RF containing PtO 2 (resorcinol-formaldehyde) relates to a method for producing a polymer catalyst and the counter, even more particularly to a low temperature with a high yield in a short time compared to the conventional platinum catalyst, PtO 2 And a process for producing the same.

PtO 2 , commonly referred to as Adam's catalyst, is used as a very powerful catalyst for hydrogenation and hydrocracking reactions in organic synthesis. In 1922, Roger Adams synthesized PtO 2 by first mixing H 2 PtCl 6 and NaNO 3 and heating at 450 ° C. Recently, various methods of synthesizing PtO 2 in nanoparticle form have been suggested. In general, the catalytic effect of nanoparticle-type is more important than the non-nanoparticle-type catalyst, and it is a very important factor that the chemical reaction scale can be determined according to the nanoparticle size. In the Reetz and Koch groups (J. Am. Chem. Soc., 1999, 121, 7933), PtCl 4 and carbobetaine were mixed well in aqueous solution in the presence of excess NaOH and reacted at 50 ° C for 7 days to yield red -rown PtO 2 colloidal solution, and reported that PtO 2 nanoparticles having a size of about 1.8 nm were synthesized by this method. However, this method requires a considerable amount of reaction time, so we need a simpler and more time-saving method. As an alternative to this, He et al. (Journal of colloid and interface science, 308, 2007, 105) reported that PtO 2 was synthesized at a faster and lower temperature by controlling the ratio of starting materials and heating conditions. In this experiment, we have successfully controlled the PtO 2 nanoparticle size by controlling the ratio of stabilizer polyvinylpyrrolidone (PVP), pH control and sodium acetate. Recently, Gao et al. (Chem. Eur. J., 2012, 18, 8423-8429) mixed H 2 PtCl 6 in a water-based solvent and hydrothermally reacted at 180 ° C. for 24 hours to form PtO 2 nano Particles were synthesized. On the other hand, when synthesizing PtO 2 -based polymers or carbon catalysts, it is necessary to synthesize polymers and carbon carriers separately and to carry out the synthesis of PtO 2. However , in this study, Through hydrothermal reaction, it is possible to easily synthesize a PtO 2 -supported polymer catalyst having excellent activity in a single step.

Korean Patent Laid-Open No. 10-2007-0085541 also discloses a carbon-supported platinum alloy catalyst which can be obtained by simultaneous chemical reduction of platinum dioxide formed in situ on a carbon support and at least one transition metal hydratable oxide.

The present invention provides a polymer catalyst containing PtO 2 and a method for producing the same by a simple hydrothermal reaction in a short time in comparison with a conventional platinum catalyst even at a relatively low temperature.

In order to solve the above problems, the present invention proposes a polymer catalyst comprising PtO 2 and a resorcinol-formaldehyde complex and a process for producing the same, thereby providing a polymer catalyst which overcomes the limitations of conventional general platinum catalysts, .

The present invention can be synthesized in the form of an RF (resorcinol-formaldehyde) polymer catalyst containing PtO 2 through a simple hydrothermal reaction in a shorter time than a conventional platinum catalyst at a relatively low temperature.

1 shows an SEM image of a PtO 2 / RF polymer catalyst.
Figure 2 shows a TEM image of a PtO 2 / RF polymer catalyst.
FIG. 3 shows the X-ray diffraction analysis results of the PtO 2 / RF polymer catalyst and the Pt / RF polymer catalyst.
FIG. 4 shows the result of thermogravimetric analysis of the PtO 2 / RF polymer catalyst.
FIG. 5 shows the results of hydrogenation using PtO 2 / RF polymer catalysts at various temperatures and pressures.
FIG. 6 shows the hydrogenation reaction of dimethyl fumarate (DMF) using various catalysts in a PtO 2 / RF polymer catalyst.
FIG. 7 shows the results of hydrogenation using PtO 2 / RF polymer catalysts for various materials.

The present invention

PtO 2; And

Resorcinol-formaldehyde complex;

PtO 2 containing-catalyst provides a polymer.

In one embodiment of the present invention, the mass ratio of the PtO 2 and resorcinol-formaldehyde complex may be 0.1 to 3.0: 9 to 7.0, preferably 1: 9.

In one embodiment of the invention, the resorcinol-formaldehyde complex may be replaced by phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, or a combination of two or more thereof.

The present invention

1) mixing hexamethylenetetramine (HMTA), resorcinol and H 2 PtCl 6 in a solvent; And

2) heating the mixed solution;

(R) (regorcinol-formaldehyde) polymer catalyst comprising PtO 2 .

In one embodiment of the invention, the resorcinol-formaldehyde complex may be replaced by phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, or a combination of two or more thereof.

In one embodiment of the present invention, the solvent may be a mixed solution of distilled water and ethanol, and the mass ratio of the mixed solution may be 4 to 6: 4 to 2, preferably 5: 3.

In one embodiment of the present invention, the mass ratio of hexamethylenetetramine and resorcinol may be 2.5 to 3.5: 2.5 to 0.5, preferably 3: 1.

Hereinafter, preferred embodiments and the like are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Examples. PtO 2 Preparation of RF (resorcinol-formaldehyde) polymer catalyst comprising

The RF polymer catalyst containing PtO 2 is synthesized by hydrothermal synthesis. After mixing 100 ml of distilled water and 60 ml of ethanol, 0.3 g of hexamethylenetetramine (HMTA) and 0.1 g of resorcinol were added, and the mixture was stirred for about 30 minutes. Then, 3 ml of H 2 PtCl 6 was added to the solution. After stirring for about 30 minutes, the solution was transferred to a Teflon-coated stainless steel vessel and sealed, heated in an oven to 100 < 0 > C for about 10 hours and cooled at room temperature. The synthesized solution was filtered to separate the supernatant and the precipitate. The separated materials were dried in an oven at 70 ° C. Finally, the PtO 2 / RF polymer catalyst in the supernatant can be finally prepared.

In detail, when H 2 PtCl 6 , HMTA and resorcinol are added to distilled water and ethanol solution and hydrothermal reaction is carried out, HMTA is hydrolyzed with six molecules of formaldehyde and four molecules of ammonia, and formaldehyde is resorcinol And ammonia acts as a catalyst of the polymerization reaction to produce an RF polymer. At this time, the tetravalent Pt is supported on the RF polymer in oxide form, so that PtO 2 / RF polymer catalyst is formed in the supernatant.

Experimental Example 1. PtO 2 / SEM and TEM photograph of RF polymer catalyst

An SEM image of a PtO 2 / RF polymer catalyst prepared according to the above example is shown in FIG. 1, and a TEM image is shown in FIG. As shown in FIG. 1, the SEM image shows that spherical PtO 2 particles are embedded on the surface of the RF polymer catalyst. Also, as shown in FIG. 2, the TEM image shows that the PtO 2 particles are well dispersed in the thin polymer layer. When TEM images are compared with the SEM image of FIG. 1, it can be seen that these particles do not penetrate deeply into the polymer structure, but are dispersed relatively uniformly on the surface of the polymer. The structure of the RF polymer catalyst layer enclosing the PtO 2 nanoparticles can be confirmed. In addition, the PtO 2 nanoparticle size is about 14 nm, and it can be confirmed that particles are not agglomerated during the reaction because there is a polymer layer that can buffer the particle aggregation phenomenon which is the greatest disadvantage of the nanoparticle.

Experimental Example 2. PtO 2 / X-ray diffraction (XRD) analysis of RF polymer catalysts

The results of X-ray diffraction analysis of PtO 2 / RF polymer catalyst and Pt / RF polymer catalyst prepared according to the above examples are shown in FIG. As shown in FIG. 3, this shows a completely different result from the XRD pattern of the pure platinum catalyst. Compared with the JCPDS (Joint Committee on Powder Diffraction Standards) file, the XRD pattern of the PtO 2 / RF polymer catalyst is the most similar XRD pattern to α-PtO 2 . Also, it can be seen that the black spot shown in the TEM image of FIG. 2 is PtO 2 nanoparticles.

Experimental Example 3 PtO 2 / Thermogravimetric analysis (TGA) analysis of RF polymer catalysts

The results of thermogravimetric analysis (oxygen condition) of the PtO 2 / RF polymer catalyst prepared according to the above Example are shown in FIG. As shown in FIG. 4, when the temperature is increased, the weight dropped by about 10% at about 100 ° C. means that moisture adsorbed in the sample is removed. In addition, at 200 ° C, the weight drops sharply to 8.3% because the RF polymer carrying the PtO 2 material is removed, resulting in a rapid mass reduction. This means that PtO 2, which is equivalent to about 8.3% of the RF polymer is supported on a polymer.

Experimental Example 4: PtO at various temperatures and pressures 2 / Hydrogenation of Organic Compounds Using RF Polymer Catalysts

The hydrogenation reaction of dimethyl fumarate (DMF) using PtO 2 / RF polymer catalysts at various temperatures and pressures is shown in FIG. As shown in FIG. 5, it was confirmed that the PtO 2 / RF polymer catalyst exhibited excellent catalytic activity at about 60 ° C., and the catalytic activity was also excellent when compared with the Adams catalyst used for commercial purposes under the same conditions .

Experimental Example 5: PtO in various solvents 2 / Hydrogenation of Organic Compounds Using RF Polymer Catalysts

The hydrogenation reaction of dimethyl fumarate (DMF) using PtO 2 / RF polymer catalyst in various solvents is shown in FIG. As shown in FIG. 6, it was confirmed that the PtO 2 / RF polymer catalyst was actively catalyzed mainly in an alcohol solvent. It was also confirmed that the PtO 2 / RF polymer catalyst exhibited excellent catalytic activity as compared with the Adams catalyst. In addition, it can be confirmed that the PtO 2 / RF polymer catalyst exhibits a catalytic activity reaction at a relatively low temperature in a short time.

Experimental Example 5: PtO for various materials 2 / Hydrogenation of Organic Compounds Using RF Polymer Catalysts

The results of the hydrogenation reaction using various catalysts such as PtO 2 / RF polymer catalyst in an ethanol solvent are shown in FIG. As shown in FIG. 7, it can be confirmed that the hydrogenation reaction was successfully performed using PtO 2 / RF polymer catalyst for most of the materials. This can also prove that the PtO 2 / RF polymer catalyst has performed well as a catalyst. In addition, it can be confirmed that the PtO 2 / RF polymer catalyst exhibits a catalytic activity reaction at a relatively low temperature in a short time.

Claims (6)

PtO 2; And
A resorcinol-formaldehyde complex; and a PtO 2 -modified catalyst comprising a resorcinol-formaldehyde complex. 2. The method of claim 1, wherein PtO 2 dae resorcinol-formaldehyde weight ratio of 0.1 to 3.0 complex: - 7.0 - polymer catalyst PtO 2, characterized in that 9.0 a. 1) mixing hexamethylenetetramine, resorcinol and H 2 PtCl 6 in a solvent; And
2) heating the mixture; PtO 2 comprising a method of preparing the polymer catalyst. 4. The method of claim 3 wherein the solvent is distilled water for the ethanol, 4 ~ 6: PtO 2, characterized in that a solution mixed at a mass ratio of 2-4-production method of the polymer catalyst. The method of claim 3 wherein the mass ratio of the hexamethylenetetramine for resorcinol 2.5 ~ 3.5: PtO 2, characterized in that 0.5 to 2.5 The method of the polymer catalyst. A process for reducing an organic compound using the catalyst of any one of claims 1 and 2.
KR1020150144186A 2015-10-15 2015-10-15 Polymer catalyst comprising PtO2 and method for preparing the same KR101793642B1 (en)

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