KR20170109311A - Catalyst for preparing hydrogen peroxide having core-shell structure and method for preparing hydrogen peroxide using the same - Google Patents

Catalyst for preparing hydrogen peroxide having core-shell structure and method for preparing hydrogen peroxide using the same Download PDF

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KR20170109311A
KR20170109311A KR1020160033257A KR20160033257A KR20170109311A KR 20170109311 A KR20170109311 A KR 20170109311A KR 1020160033257 A KR1020160033257 A KR 1020160033257A KR 20160033257 A KR20160033257 A KR 20160033257A KR 20170109311 A KR20170109311 A KR 20170109311A
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hydrogen peroxide
core
nanoparticles
palladium
shell
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KR101825907B1 (en
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이관영
한상수
유태경
서명기
한근호
김인호
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고려대학교 산학협력단
한국과학기술연구원
경희대학교 산학협력단
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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
    • 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
    • B01J23/44—Palladium
    • 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
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/002—Catalysts characterised by their physical properties
    • B01J35/0046—Physical properties of the active metal ingredient
    • B01J35/006—Physical properties of the active metal ingredient metal crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/002—Catalysts characterised by their physical properties
    • B01J35/0073—Distribution of the active metal ingredient
    • B01J35/008—Distribution of the active metal ingredient egg-shell like
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/002—Catalysts characterised by their physical properties
    • B01J35/0073—Distribution of the active metal ingredient
    • B01J35/0086—Distribution of the active metal ingredient egg-yolk like
    • 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
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/029—Preparation from hydrogen and oxygen

Abstract

The present invention relates to a catalyst for the production of hydrogen peroxide having a core-shell structure and a process for producing hydrogen peroxide using the same. More particularly, the present invention relates to a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as a core and core-shell nanoparticles in which a noble metal surrounds the core, and a process for producing hydrogen peroxide using the same. The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an effect showing excellent hydrogen peroxide selectivity and production rate.

Description

[0001] The present invention relates to a catalyst for preparing hydrogen peroxide having a core-shell structure and a method for preparing hydrogen peroxide using the catalyst,

The present invention relates to a catalyst for the production of hydrogen peroxide having a core-shell structure and a process for producing hydrogen peroxide using the same. More particularly, the present invention relates to a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as a core and core-shell nanoparticles in which a noble metal surrounds the core, and a process for producing hydrogen peroxide using the same.

Hydrogen peroxide is used as a bleaching agent for pulp and fiber, disinfectant disinfectant, semiconductor cleaning liquid, oxidizer for water treatment process, and environmentally friendly oxidizer for chemical reaction (propylene oxide synthesis). As of 2009, 2.2 million tons of hydrogen peroxide are being produced annually, and the demand for hydrogen peroxide is expected to rise along with the increase in propylene oxide demand.

At present, hydrogen peroxide is generated through continuous oxidation and hydrogenation processes starting from anthraquinone-based compounds. In this case, a large amount of organic solvent is used and generated as waste. In addition, there is also a problem that the production of hydrogen peroxide requires a lot of energy consumption through a multi-stage continuous process and purification and concentration process after production.

Direct manufacturing process of synthesizing hydrogen peroxide by directly reacting hydrogen and oxygen has been attracting attention. This direct manufacturing process has been studied as an alternative process of commercial process because water is produced as a reaction by-product and use of organic solvent is low. The direct manufacturing process is simple in construction and can be manufactured where hydrogen peroxide is needed, thus greatly reducing the risk of explosion when storing and transporting hydrogen peroxide (Korean Patent Laid-Open Publication No. 2002-0032225).

In the direct production process of hydrogen peroxide, in the case of palladium catalyst, a halogen anion is added to the solvent to increase the selectivity of hydrogen peroxide. However, in the case of a halogen anion, it may not be necessary to add a halogen anion to the solvent since separation purification may be necessary later. In order to solve this problem, studies have been reported to increase the selectivity of hydrogen peroxide by using palladium-gold (Pd-Au) alloy as a catalyst.

KR Patent Publication No. 2002-0032225

The inventors of the present invention have found out that when using a catalyst for producing hydrogen peroxide in which a palladium (Pd) nanoparticle is used as a core and a noble metal includes core-shell nanoparticles surrounding the core, hydrogen and oxygen The present inventors confirmed that the hydrogen peroxide was excellent in hydrogen peroxide selectivity and production rate without adding a halogen anion to the solvent in the production of hydrogen peroxide.

Accordingly, the present invention provides a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as core and core-shell nanoparticles in which a noble metal surrounds the core, and a method for producing the same.

Accordingly, the present invention provides a process for producing hydrogen peroxide, which comprises reacting and supplying hydrogen and oxygen to a reactor comprising the catalyst for the production of hydrogen peroxide and a solvent.

In order to achieve the above object,

The present invention

There is provided a catalyst for producing hydrogen peroxide comprising palladium (Pd) nanoparticles as cores and noble metals as core-shell nanoparticles surrounding the cores.

In addition,

(1) preparing a core of palladium (Pd) nanoparticles;

(2) preparing a core (palladium) -shell (noble metal) nanoparticle by coating a noble metal on the nanoparticle core; And

(3) preparing a core (palladium) -shell (noble metal) nanoparticle supported on silica by binding the core (palladium) -shell (precious metal) nanoparticles with silica to produce a catalyst for producing hydrogen peroxide .

In addition,

And supplying hydrogen and oxygen to the reactor containing the catalyst for the production of hydrogen peroxide and the solvent to react them.

Hereinafter, the present invention will be described in detail.

The present invention

There is provided a catalyst for producing hydrogen peroxide comprising palladium (Pd) nanoparticles as cores and noble metals as core-shell nanoparticles surrounding the cores.

The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is superior to conventional palladium nanoparticles or alloy nanoparticles of palladium and gold in that hydrogen peroxide is produced from hydrogen peroxide without adding a halogen anion to the solvent, Selectivity and production rate.

The palladium (Pd) nanoparticles may have an average size of 1 to 30 nm, and preferably 2 to 20 nm.

The weight ratio of the palladium to the noble metal may be 1: 0.05 to 1: 1, and preferably 1: 0.1 to 1: 0.5. When the weight ratio of palladium to noble metal (Pd / noble metal) is less than 1, the characteristics of noble metal are strongly expressed on the core-shell surface and the selectivity of hydrogen peroxide is not high. .

The noble metal may be gold (Au), silver (Ag), platinum (Pt), or gold (Au).

The core-shell nanoparticles may be controlled in size and shape, and the shape thereof may be in the shape of a cube, an octahedron, or a dodecahedron.

The core-shell nanoparticles may be supported on a support. The support and the like, silica, alumina, titania, zirconia, it is preferable that the silica (SiO 2).

The hydrogen peroxide may be prepared by direct reaction of hydrogen and oxygen.

The present invention also relates to a method for preparing a palladium (Pd) nanoparticle comprising: (1) preparing a core of palladium (Pd) nanoparticles; (2) preparing a core (palladium) -shell (noble metal) nanoparticle by coating a noble metal on the nanoparticle core; And (3) preparing core (palladium) -chelled (noble metal) nanoparticles supported on silica by bonding the core (palladium) -shell (precious metal) nanoparticles with silica to produce a catalyst for the production of hydrogen peroxide. ≪ / RTI >

The present invention also provides a method for producing hydrogen peroxide, comprising supplying hydrogen and oxygen to a reactor containing the catalyst for producing hydrogen peroxide and a solvent and reacting the hydrogen peroxide.

The solvent may be one or more solvents selected from the group consisting of methanol, ethanol and water. Specifically, it may be methanol, ethanol or a mixture of water and alcohol, preferably a mixture of ethanol and water.

In the direct production process of hydrogen peroxide, in the case of palladium catalyst, a halogen anion is added to the solvent to increase the selectivity of hydrogen peroxide. However, in the case of a halogen anion, it may not be necessary to add a halogen anion to the solvent since separation purification may be necessary later. Therefore, the solvent does not include a halogen element, and may further include an acid. When an acid is included, the hydrogen peroxide yield can be largely increased by suppressing the decomposition of the produced hydrogen peroxide. The acid may be sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ) and the like, preferably phosphoric acid.

The concentration of the acid in the solvent may be 0 to 1 M, preferably 0.01 to 0.05 M.

The reactants, hydrogen and oxygen, may be in a gaseous form and may be preferably fed directly to the solvent using a Dip Tube which may be contained in a solvent to improve the solubility in the solvent. The hydrogen gas may be flowed at a flow rate of 1 to 4 mL / min, and the oxygen gas may be flowed at a flow rate of 10 to 40 mL / min. More preferably, the hydrogen gas may be maintained at 1.5 to 2.5 ml / min, and the oxygen gas may be maintained at 15 to 25 ml / min, and the hydrogen to oxygen molar ratio may be 1: 5 to 1:15. If the ratio of oxygen to hydrogen is 1: 1, but the ratio of hydrogen to oxygen is lower than 1: 5, there is a risk of explosion. If oxygen is more than 1:15, The range of the hydrogen: oxygen molar ratio is preferable.

Preferably, the reactor is further reacted by supplying nitrogen as a reactant. When using nitrogen, it is possible to deviate from the explosion range even if the ratio of hydrogen to oxygen is set to 1: 1, and there is an advantage that it can be used without additional nitrogen separation when using oxygen in the air in the future.

While the hydrogen gas and the oxygen gas are flowed at a constant flow rate, the entire reaction pressure is regulated using a BPR (Back Pressure Regulator), and the reaction pressure can be measured through a pressure gauge connected to the reactor. The reaction pressure is preferably maintained at 1 to 40 atm, preferably at normal pressure, and it may be preferable to conduct the reaction while maintaining the reaction temperature at 10 to 30 ° C.

The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an advantage of showing excellent hydrogen peroxide selectivity and production rate.

The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an effect showing excellent hydrogen peroxide selectivity and production rate.

1 is a TEM (Transmission Electron Microscope) image of (a) silica (SiO 2 ) nanoparticles, (b) palladium (Pd) nanoparticles, and (c) core (Pd) Fig.
2 is a scanning transmission electron microscope (STEM) image showing the distribution of Pd and Au in core (Pd) @ shell (Au) nanoparticles according to Example 1. FIG.
FIG. 3 is a diagram showing a high-angle annular dark-field transmission electron microscope (HAADF-STEM) image showing the distribution of Pd and Au in core (Pd) @ shell (Au) nanoparticles according to Example 1. FIG.
4 shows Pd nanoparticles supported on silica, (b) Pd-Au alloy nanoparticles supported on silica, and (c) core supported on silica (Pd) according to Example 1 and Comparative Examples 1 and 2, ≪ RTI ID = 0.0 > (TEM) < / RTI > image of @ shell (Au) nanoparticles.
5 is a graph showing hydrogen conversion and hydrogen peroxide selectivity when hydrogen peroxide is directly produced from hydrogen and oxygen according to Example 2 and Comparative Examples 3 and 4. FIG.
FIG. 6 is a graph showing the rate of generation of hydrogen peroxide when hydrogen peroxide is directly produced from hydrogen and oxygen according to Example 2 and Comparative Examples 3 and 4. FIG.

Hereinafter, preferred embodiments of the present invention will be described in order 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.

Example  1. Silica ( SiO 2 )on Supported  core( Pd ) @ Shell ( Au ) Preparation of nanoparticles

1-1. Palladium ( Pd) Of nanoparticles  Produce

105 mg of polyvinylpyrrolidone (PVP), 60 mg of L-ascorbic acid, 185 mg of potassium bromide (KBr) and 5 mg of potassium chloride (KCl) were dissolved in 8 mL of distilled water, Lt; / RTI > Then, a solution of 57 mg of disodium tetrachloropalladate (Na 2 PdCl 4 ) dissolved in 3 mL of distilled water was added to the mixture, followed by stirring at 80 rpm for 3 hours at 800 rpm. After completion of the reaction, the reaction solution and acetone were mixed at a ratio of 1:10, the nanoparticles were collected through a centrifuge (3500 rpm, 10 minutes), washed with distilled water, and the palladium (Pd) The nanocube particles were redispersed in 8 mL of distilled water.

1-2. core( Pd ) @ Shell ( Au ) Of nanoparticles  Produce

1 mL of Pd nanoparticles dispersed in distilled water according to Example 1-1 and 3 mg of L-ascorbic acid were dissolved in 8 mL of distilled water and then preheated at 95 DEG C for 30 minutes. Thereafter, a solution of 0.82 mg of gold (III) chloride hydrate (HAuCl 4 ) dissolved in 2 mL of distilled water was added to the mixture, and the mixture was stirred at 95 rpm for 15 minutes at 800 rpm. After completion of the reaction, the reaction solution and acetone were mixed at a ratio of 1:10, the nanoparticles produced through a centrifuge (3500 rpm, 10 minutes) were collected, washed with distilled water, @ Shell (Au) nanocube particles were redispersed in 8 mL of distilled water.

1-3. Amine group  The treated silica ( SiO 2 ) Preparation of nanoparticles

First, 10 mL of distilled water and 3.15 mL of ammonia water were mixed with 74 mL of ethanol, 6 mL of a silica precursor (tetraethyl orthosilicate, Si (OC 2 H 5 ) 4 ) was added, and the mixture was stirred for 12 hours to prepare silica nanoparticles. The prepared silica nanoparticles were washed with distilled water and propanol, and dispersed in 320 mL of propanol. The dispersed solution was preheated to 80 DEG C and amine groups were treated on the silica surface by adding 3-aminopropyltriethoxysilane (ATPS). Thereafter, the mixture was stirred at 80 DEG C for 2 hours, collected by a centrifuge, and dispersed in ethanol.

1-4. Silica ( SiO 2 )on Supported  core( Pd ) @ Shell ( Au ) Preparation of nanoparticles

The dispersion solution of the core (Pd) @ shell (Au) nanocube according to the above Example 1-2 was mixed with the silica (SiO 2 ) dispersion solution according to Example 1-3 and stirred for 2 hours. Thereafter, core (Pd) @ shell (Au) nanocube particles supported on silica (SiO 2 ) produced through a centrifugal separator were recovered and dried to be used as a catalyst.

Comparative Example  1. Silica ( SiO 2 )on Supported  Palladium ( Pd ) Preparation of nanoparticles

A support to the above-described embodiment in the first core (Pd) @ shell (Au) nanoparticles instead of palladium (Pd) in the same manner as in the method described in Example 1, except that nanoparticles of silica (SiO 2) palladium ( Pd) nanocube particles were prepared.

Comparative Example  2. Silica ( SiO 2 )on Supported  Palladium and gold alloys ( Pd - Au ) Preparation of nanoparticles

First, silica (SiO 2 ) nanoparticles were prepared in the same manner as in Example 1-3. Thereafter, the silica nanoparticles were mixed with Na 2 PdCl 4 and AuCl 3 dissolved in distilled water and coprecipitated. The prepared product was recovered, heat-treated at 500 ° C for 6 hours, and then reduced at 350 ° C in a hydrogen atmosphere to prepare palladium-gold (Pd-Au) alloy nanoparticles supported on silica.

Example  2. On silica Supported  core( Pd ) @ Shell ( Au Production of hydrogen peroxide using nanoparticles

A double jacketed reactor was charged with 0.2 g of core (Pd) @ shell (Au) nanoparticles supported on the silica according to Example 1 and 30 ml of a reaction solvent (distilled water, 120 ml; ethanol) containing no halogen anion; Phosphoric acid (H 3 PO 4 ) 0.03 M) was added thereto, and the reaction was carried out for 3 hours. The reaction temperature was maintained at 20 ° C and the pressure was maintained at 1 atm. The reaction gas (H 2 / O 2 = 1/10) was flowed constantly at 22 mL per minute. Then, hydrogen peroxide produced after the reaction was collected.

Comparative Example  3. To silica Supported  Palladium ( Pd Production of hydrogen peroxide using nanoparticles

Hydrogen peroxide was collected in the same manner as in Example 2, except that palladium (Pd) nanoparticles were used in place of the core (Pd) @ shell (Au) nanoparticles in Example 2. [

Comparative Example  4. To silica Supported  Palladium and gold alloys ( Pd - Au Production of hydrogen peroxide using nanoparticles

Hydrogen peroxide was collected in the same manner as described in Example 2, except that palladium and gold alloy (Pd-Au) alloy nanoparticles were used in place of the core (Pd) @ shell (Au) .

Experimental Example  1. Electron microscopic observation

Each catalyst prepared according to Example 1 and Comparative Examples 1 and 2 was observed using an electron microscope.

(TEM) image of (a) silica (SiO 2 ) nanoparticles, (b) palladium (Pd) nanoparticles and (c) core (Pd) @ shell (Au) nanoparticles according to Example 1 1, scanning electron microscopy (STEM) and high-angle annular dark-field transmission electron microscope (HAADF-STEM) images showing the distribution of Pd and Au in Pd @ Au nanoparticles are shown in FIG. 2 and FIG.

As shown in FIG. 1, the silica (SiO 2 ) nanoparticles showed a spherical shape having a diameter of about 200 to 300 nm, and the palladium (Pd) nanoparticles showed a cube shape having a size of 5 to 10 nm . In addition, core (Pd) @ shell (Au) nanoparticles have a size of 20 to 30 nm and are similar to palladium (Pd) nanoparticles.

As shown in FIG. 2, it can be seen that palladium (Pd) and gold (Au) form a core (Pd) @ shell (Au) structure.

As shown in FIG. 3, it can be seen that palladium (Pd) and gold (Au) are evenly distributed. The red dot indicates the point where more than a certain amount of palladium (Pd) is detected, and the green dot indicates the point where more than a certain amount of gold (Au) is detected.

Pd nanoparticles supported on silica, (b) Pd-Au alloy nanoparticles supported on silica, and (c) Pd supported on silica (shell) according to Example 1 and Comparative Examples 1 and 2 Transmission electron microscopy (TEM) images of Au nanoparticles are shown in FIG.

As shown in FIG. 4, it can be confirmed that the Pd nanoparticles and the core (Pd) @ shell (Au) nanoparticles are uniformly distributed and supported on the silica.

Since Pd nanoparticles and core (Pd) @ shell (Au) nanoparticles are chemically reduced, they can be synthesized without heat treatment, so that the size of the nanoparticles is small and uniform. However, in the case of Pd-Au nanoparticles, And it is possible to confirm that the particle size is irregular by the TEM image.

Experimental Example  2. Inductively coupled plasma An atomic emission spectrometer (ICP-AES)  Used palladium ( Pd ) And gold Au ) Content measurement

Palladium (Pd) and gold (Au) contents were measured by ICP-AES analysis for each catalyst prepared according to Example 1 and Comparative Examples 1 and 2, and the results are shown in Table 1.

division ICP-AES (% by weight) Pd Au Example 1 Pd @ Au supported on silica 0.64 0.09 Comparative Example 1 Pd supported on silica 1.13 - Comparative Example 2 Pd-Au alloy supported on silica 0.63 0.10

As shown in Table 1, Pd and Au in the core (Pd) @ shell (Au) nanoparticles were contained in 0.64 wt% and 0.09 wt%, respectively, and Pd-Au alloy showed similar contents .

Experimental Example  3. Production of hydrogen peroxide

The concentration of hydrogen peroxide collected in Example 2 and Comparative Examples 3 and 4 was measured by the following Equation 1 using iodometric titration. The amount of hydrogen peroxide produced was calculated by the following equation (2).

[Equation 1]

Figure pat00001

&Quot; (2) "

Figure pat00002

Hydrogen conversion and hydrogen peroxide selectivity when hydrogen peroxide was directly produced from hydrogen and oxygen are shown in FIG. 5 and the production rate of hydrogen peroxide is shown in FIG.

As shown in FIG. 5, when the core (Pd) @ shell (Au) nanoparticle catalyst was used, the hydrogen peroxide selectivity was much higher than that in the case of using the palladium (Pd) nanoparticles and the Pd-Au alloy nanoparticle catalyst Can be confirmed. It has been known that the selectivity of hydrogen peroxide greatly increases when Pd-Au alloy nanoparticles are used. However, when the core (Pd) @ shell (Au) nanoparticles of the present invention are used, hydrogen peroxide selectivity is further increased .

Further, as shown in FIG. 6, the hydrogen peroxide production rate also increased correspondingly to the increase of the hydrogen peroxide selectivity. That is, from the above results, it can be seen that when the core (Pd) @ shell (Au) nanoparticles are used in the direct hydrogen peroxide production reaction, the selectivity of hydrogen peroxide is greatly increased and the hydrogen peroxide production rate can be greatly increased.

Claims (13)

A catalyst for the production of hydrogen peroxide, comprising palladium (Pd) nanoparticles as the core and a noble metal surrounding the core. The method according to claim 1,
Wherein the palladium (Pd) nanoparticles have an average size of 1 to 30 nm. The method of claim 1, wherein
Wherein the weight ratio of palladium to noble metal is 1: 0.05 to 1: 1. The method of claim 1, wherein
Wherein the noble metal is gold (Au), silver (Ag), or platinum (Pt). The method of claim 1, wherein
Wherein the core-shell nanoparticles are controlled in size and shape, and the shape thereof is in the shape of a cube, an octahedron, or a dodecahedron. The method of claim 1, wherein
The core-shell nanoparticles, catalyst for hydrogen peroxide, characterized in that the support for the silica (SiO 2). The method according to claim 1,
Characterized in that the hydrogen peroxide is produced by direct reaction of hydrogen and oxygen. (1) preparing a palladium (Pd) nanoparticle core;
(2) preparing a core (palladium) -shell (noble metal) nanoparticle by coating a noble metal on the nanoparticle core; And
(3) preparing a core (palladium) -shell (noble metal) nanoparticle supported on silica by binding the core (palladium) -shell (precious metal) nanoparticles with silica to produce a catalyst for producing hydrogen peroxide . A method for producing hydrogen peroxide comprising the steps of: supplying hydrogen and oxygen to a reactor comprising the catalyst for producing hydrogen peroxide of claim 1 and a solvent and reacting. 10. The method of claim 9,
Wherein the solvent is at least one solvent selected from the group consisting of methanol, ethanol and water. 10. The method of claim 9,
Wherein the solvent does not contain a halogen element and further comprises at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid. 10. The method of claim 9,
Wherein the hydrogen and oxygen molar ratio is between 1: 5 and 1:15. 10. The method of claim 9,
Wherein the reaction is carried out at a pressure of from 1 to 40 atm and at a temperature of from 10 to 30 < 0 > C.
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KR20210041452A (en) * 2019-10-07 2021-04-15 한국과학기술연구원 Pd-Pt Core-shell Catalyst, Preparing Method thereof, and Synthesis of Hydrogen Peroxide using the same
KR20210127515A (en) * 2020-04-14 2021-10-22 경희대학교 산학협력단 A manufacturing method of a palladium-noble metal core-shell nanoparticles and a catalyst for synthesis of hydrogen peroxide

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KR20210127515A (en) * 2020-04-14 2021-10-22 경희대학교 산학협력단 A manufacturing method of a palladium-noble metal core-shell nanoparticles and a catalyst for synthesis of hydrogen peroxide

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