CN107754826B - Hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide and preparation method thereof - Google Patents
Hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hollow nuclear shell structure Pd catalyst for directly synthesizing hydrogen peroxide and a preparation method thereof, the particle size distribution of the catalyst is uniform and is intensively distributed at 65-72nm, wherein, the thickness of shell layer carbon is intensively distributed at 7.18-7.9nm, and the particle size of nuclear layer Pd nanometer is intensively distributed at 7.6-8.6 nm; br element is deposited on the nuclear layer Pd; the pore diameter of the hollow core-shell structure Pd catalyst is concentrated at 12.62-18.89nm, and the BET specific surface area is 507-620m2Per g, pore volume of 1.6-2.3cm3(ii) in terms of/g. Pd @ SiO prepared by reversed micelle method2The method is characterized in that the seed solution is ultrasonically dispersed into a mixed solution of 70mL of deionized water and 28mL of ethanol, resorcinol and formaldehyde are added as carbon sources to react for 6 hours, and the seed solution is obtained through drying, nitrogen roasting, HF etching and reduction. The invention realizes H synthesis under normal pressure2O2High selectivity and yield, high catalyst activity and long service life, and synthesis of H2O2The stability is high.
Description
Technical Field
The invention belongs to the technical field of chemistry, and relates to a hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide, and a preparation method of the hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide.
Background
At present, H is at home and abroad2O2In the production method, the largest production method is an anthraquinone method, the method adopts two-step synthesis, and organic solvents are added in the production, so that the defects of complex production process, high energy consumption, serious environmental pollution and the like exist; compared with the prior art, the method for directly synthesizing the hydrogen peroxide by adopting the one-step method under the action of the catalyst from the hydrogen and the oxygen has the advantages of simple process, low operation cost, no pollution and the like, and becomes H2O2The research focus in the production field. The prior research reports prove that the Pd catalyst is directly synthesized into H by a one-step method2O2The catalyst with the best activity. At present, scholars at home and abroad in the field mainly carry out a great deal of research work on the preparation and modification of the supported Pd catalyst. Chinese patent publication No. CN104039441A discloses a catalyst for directly synthesizing hydrogen peroxide in No. 09/10 of 2014, a supported Pd catalyst based on tantalum oxide is prepared by an impregnation method, and H is obtained by reacting for 5 hours at a reaction pressure of 50bar and a reaction temperature of 5 DEG C2Has a conversion of 26.2%, H2O2The yield was 6659mol H2O2/(KgPd. h). However, the active component Pd of the supported Pd catalyst is easy to migrate and agglomerate in the high-temperature roasting process, and in the reaction, the Pd on the surface of the catalyst is easy to fall into a reaction medium due to strong mechanical stirring, so that H is caused2O2Decompose to thereby reduce H2O2Stability and catalyst life; in addition, such high pressures also increase reactant H2And O2The risk of explosion.
Chinese patent publication No. CN1880215A discloses "carrier metal catalyst, its preparation method and its use in directly preparing hydrogen peroxide" at 2006, 12/20, by reduction after impregnationPreparation of Pd-Pt/SiO2The catalyst reacts for 3 hours under the reaction pressure of 50bar and the reaction temperature of 20 ℃ to obtain H2Conversion of (3) is 42%, H2O2The concentration was 17.5%. However, since the supported catalyst is obtained by a reduction method after impregnation, the problem of chinese patent publication No. CN104039441A has not been solved.
In order to solve the problem of Pd loss from the carrier, Seo M et al recently synthesized a core-shell structure catalyst (Pd-nanocrystalline-graded SiO2 nano-beads [ J ] by coating a layer of shell on the outside of the traditional supported catalyst]Acs Catalysis, 2017, 7(4), which solved the problem of Pd loss from the support, Pd is prone to migration and agglomeration during high temperature calcination. Lee et al coated Pd on SiO2The inside of the shell layer is made into solid core-shell structure catalyst (Direct synthesis of hydrogen peroxide from hydrogen and oxygen over a Pd core-silica shell catalyst [ J]Catalysis communications 12 (2011) 968-971), which, although also solves the problem of Pd loss from the support, due to shell SiO2The Pd is completely solid, so that the active surface area of the Pd in the nuclear layer is reduced, and the mass transfer resistance of the reactants and the products in the shell layer is increased and the reaction rate and the yield are reduced because the reactants and the products enter and exit in the synonymous pore channels.
Therefore, the prepared hollow core-shell structure catalyst can not only prevent Pd from migrating and agglomerating in the high-temperature roasting process, solve the problem that Pd is easy to lose in the reaction process, but also solve the problem that mass transfer resistance of reactants and products in a shell layer is large. The designed hollow structure core-shell Pd catalyst not only can ensure that the volume of a larger hollow internal cavity is beneficial to the enrichment of reactant molecules and the reaction rate is improved, but also the Pd core in the cavity can provide more active surfaces for the adsorption and reaction of the reactant molecules. In addition, potassium bromide is added as a functional molecule to be adsorbed on unsaturated coordination active sites on the surface of a Pd core, so that the H content of the catalyst can be remarkably increased2O2Selectivity and yield. Thus, a direct synthesis was studiedThe preparation method of the hollow nuclear shell structure Pd catalyst for hydrogen oxide is of great significance.
Disclosure of Invention
The invention aims to overcome the defects and provide a method for synthesizing H under normal pressure2O2High selectivity and yield, high catalyst activity and long service life, and synthesis of H2O2The hollow nuclear shell structure Pd catalyst for directly synthesizing hydrogen peroxide has high stability.
The invention also aims to provide a preparation method of the hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide.
The object of the invention is achieved by the following method:
the hollow nuclear shell structure Pd catalyst for directly synthesizing hydrogen peroxide has uniform particle size distribution of 65-72nm, wherein the thickness of shell layer carbon is intensively distributed at 7.18-7.9nm, and the particle size of nuclear layer Pd nanometer is intensively distributed at 7.6-8.6 nm; br element is deposited on the nuclear layer Pd and can effectively reduce the reactant O adsorbed on the surface of the Pd2Molecule and product H2O2Dissociation activation energy of O-O bond in molecule. The pore diameter of the hollow core-shell structure Pd catalyst is concentrated between 12.62 and 18.89nm, and the BET specific surface area is 507-620m2Per g, pore volume of 1.6-2.3cm3/g。
The invention relates to a preparation method of a hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide, which comprises the following steps:
(1) weighing 6-10 g of polyethylene glycol monocetyl ether, adding the polyethylene glycol monocetyl ether into 40mL of mixed solution of cyclohexane and 10mL of n-octanol, stirring and dissolving the mixture in water bath at 35 ℃, weighing 0-0.05 g of potassium bromide, adding the potassium bromide into 1mL of 0.075M chloropalladite (H)2PdCl4) Adding the solution into the mixed solution after stirring and dissolving, and adding 300 mu L of sodium borohydride solution (NaBH) after stirring for 1h4) (wt 10%) and 2mL of ethyl orthosilicate for 6h to obtain a seed solution Pd @ SiO2；
(2) The obtained Pd @ SiO2Ultrasonically dispersing the seed solution into 100mL of mixed solution of deionized water and ethanol (the volume ratio is 3: 1), and adding Pd @ SiO into the seed solution2Adding resorcinol 0.35g, hexaalkyl ammonium bromide (CTAB) 2.3g, ammonia water 0.2mL and formaldehyde 0.5mL, reacting at 30-60 deg.C for 6h, centrifuging, washing three times, and standing at 80 deg.CoC, drying for 12 hours;
(3) the above-mentioned dried material is placed in a temperature of 450-600 deg.C N2Roasting for 2H under atmosphere, HF etching for 12H, roasting and oxidizing for 2H at 150-300 ℃ in air at 250 ℃ H2Reducing for 2.5h under the atmosphere to obtain the product.
Compared with the prior art, the invention has obvious beneficial effects, and can be known from the following technical scheme: the catalyst is Pd @ SiO prepared by a reversed-phase micelle method2The method is characterized in that the seed solution is ultrasonically dispersed into a mixed solution of 70mL of deionized water and 28mL of ethanol, resorcinol and formaldehyde are added as carbon sources to react for 6 hours, and the seed solution is obtained through drying, nitrogen roasting, HF etching, air roasting and hydrogen reduction. The obtained hydrogen and oxygen are directly synthesized into H2O2The catalyst is used, active component Pd nano particles are used as a core, and a porous inert material C is used as a shell, so that the loss of the active component Pd under mechanical stirring can be effectively prevented, the size of the active component Pd nano particles can be effectively controlled, and the migration and agglomeration of the active component Pd nano particles in the roasting and reaction processes can be prevented. The mesoporous aperture in the hollow core-shell structure can reduce the reactant H2And O2And product H2O2Mass transfer resistance diffused in the material pore channel of the shell layer ensures that reactants and products quickly enter and exit the shell layer; the larger volume of the hollow internal cavity is beneficial to the enrichment of reactant molecules, and the reaction rate is improved; the Pd core in the cavity provides more active surface for adsorption and reaction of reactant molecules. In addition, potassium bromide is added as a functional molecule to be adsorbed on unsaturated coordination active sites on the surface of a Pd core, so that the H content of the catalyst can be remarkably increased2O2Selectivity and yield.
Drawings
FIG. 1 is a TEM image of Pd @ HCS;
FIG. 2 is PdKBrThe TEM image of @ HCS.
Detailed Description
Example 1
A preparation method of a hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide comprises the following steps:
(1) 8.7g of polyethylene glycol monocetyl ether was weighed into a mixed solution of 40mL of cyclohexane and 10mL of n-octanol, and dissolved by stirring in a water bath at 35 ℃. A further 1mL, 0.075M H was measured2PdCl4The solution was added to the above mixed solution. Stirring for 1h, adding sodium borohydride and ethyl orthosilicate, and reacting for 6h to obtain seed solution Pd @ SiO2。
(2) The obtained Pd @ SiO2Ultrasonically dispersing the seed solution into 100mL of mixed solution of deionized water and ethanol, adding 0.35g of resorcinol, 2.3g of CTAB, 0.2mL of ammonia water and 0.5mL of formaldehyde into the seed solution, reacting for 6h at 30-60 ℃, centrifuging, washing for three times, and performing ultrasonic wave washing on the mixture at 80 DEG CoC, drying for 12 hours;
(3) drying the above extract at 600 deg.CoC N2Roasting for 2H under atmosphere, etching with HF for 12H, roasting at 250 deg.C in air for 2H, and oxidizing at 250 deg.C in H2Reducing for 2.5h under the atmosphere to obtain the product.
Catalyst activity evaluation experiment:
marking the obtained catalyst as Pd @ HCS, and using the catalyst for directly synthesizing H by hydrogen and oxygen2O2And (4) reacting.
The reaction is carried out in a self-made jacketed glass reactor, the reaction temperature is 0 ℃, the reaction pressure is normal, and H in feed gas is2And O2The ratio was 1/2, the reaction medium was 80mL of methanol and 1mL of concentrated H2SO4The amount of the catalyst used was 0.15 g.
Taking reaction for 1H under the reaction condition as an activity evaluation point, and taking H2Conversion, H2O2Selectivity, H2O2Yield and H2O2The yield was used as an evaluation index. Wherein H in the liquid phase medium is determined by iodometry2O2Concentration; measuring total flow of gas in and out of the reactor by soap film flowmeter, and analyzing H in and out of the reactor by gas chromatography2、O2And then calculating H2Conversion, H2O2Yield H2O2Selectivity and H2O2The yield is specifically calculated by the following formula:
the Pd @ HCS catalyst obtained above was used for activity evaluation by the method described above. Evaluation results were as follows: h2Conversion, H2O2Yield H2O2Selectivity is respectively30%，22%，72%，H2O2The yield was 1711mmol.gPd -1.h-1. The resulting catalyst had a pore diameter of 18.89nm and a BET specific surface area of 620m2Per g, pore volume of 2.3cm3(ii) in terms of/g. As can be seen from a TEM image (figure 1) of the Pd @ HCS catalyst, the prepared catalyst is of a hollow core-shell structure, and the average particle size of the catalyst is 72.46 +/-9.84 nm, wherein the thickness of shell layer carbon is intensively distributed at 7.90 +/-1.31 nm, and the particle size of core layer Pd nanometer is intensively distributed at 7.6 nm.
Example 2
The only difference between the method and example 1 is that 0.03g of potassium bromide is added as a functional molecule and the catalyst obtained is labeled as PdKBr@HCS。
Catalyst activity evaluation experiment:
the evaluation results were obtained in the activity evaluation manner in example 1: h2Conversion, H2O2Yield H2O2Selectivity is respectively36%，31%，86%，H2O2The yield was 2014mmol.gPd -1.h-1. The resulting catalyst had a pore diameter of 12.62nm and a BET specific surface area of 507m2G, pore volume of 1.6cm3(ii) in terms of/g. By addition of BrPd prepared for functional moleculesKBrTEM image (FIG. 2) of @ HCS catalyst shows that the catalyst structure is a hollow core-shell structure with an average particle size of 65.70. + -. 9.22 nm. Wherein, the thickness of the shell layer carbon is intensively distributed at 7.18 +/-0.96 nm, and the grain diameter of the nuclear layer Pd nano-particles is 7.6 nm.
Example 3
The only difference between the method and example 2 is that 0.05g of potassium bromide is added as a functional molecule and the catalyst is PdKBr-5@HCS。
Catalyst activity evaluation experiment:
the evaluation results were obtained in the activity evaluation manner in example 1: h2Conversion, H2O2Yield H2O2Selectivity is respectively30%，26%，81%，H2O2The yield was 1816mmol.gPd -1.h-1. The catalyst obtained had an average pore diameter of 12.02nm and a BET specific surface area of 495m2G, pore volume of 1.56cm3(ii) in terms of/g. The pore structure parameters of the obtained catalyst are similar to those of example 2.
Example 4
The process is as in example 2, the only difference being the H work-up of the catalyst2Before reduction, adding one-step oxidation treatment, wherein the oxidation temperature is 150 DEGoC。
Catalyst activity evaluation experiment:
the evaluation results were obtained in the activity evaluation manner in example 1: h2Conversion, H2O2Yield H2O2Selectivity is respectively23%，21%，90%，H2O2The yield was 1343mmol.gPd -1.h-1. The pore structure parameters of the obtained catalyst are similar to those of example 2.
Example 5
The process is as in example 2, the only difference being the H work-up of the catalyst2Before reduction, adding a step of oxidation treatment, wherein the oxidation temperature is 200 DEGoC。
Catalyst activity evaluation experiment:
by means ofEvaluation manner of activity in example 1, evaluation result: h2Conversion, H2O2Yield H2O2Selectivity is respectively24%，24%，87%，H2O2The yield was 1552mmol.gPd -1.h-1. The pore structure parameters of the obtained catalyst are similar to those of example 2.
Example 6
The only difference between the method and example 2 is that before the catalyst is subjected to H2 reduction, a step of oxidation treatment is added, and the oxidation temperature is 300 DEGoC。
Catalyst activity evaluation experiment:
the evaluation results were obtained in the activity evaluation manner in example 1: h2Conversion, H2O2Yield H2O2Selectivity is respectively28%，28%，81%，H2O2The yield was 1678mmol.gPd -1.h-1. The pore structure parameters of the obtained catalyst are similar to those of example 2.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the present invention without departing from the technical spirit of the present invention.
Claims (1)
1. A hollow core-shell structure Pd catalyst for directly synthesizing hydrogen peroxide is characterized in that: taking a porous inert material C as a shell, and taking a Pd core in a cavity; the particle size distribution is uniform and is intensively distributed at 65-72nm, wherein the thickness of the shell layer carbon is intensively distributed at 7.18-7.9nm, and the particle size of the nuclear layer Pd nano-particles is intensively distributed at 7.6-8.6 nm; br element is deposited on the nuclear layer Pd; the pore diameter of the hollow core-shell structure Pd catalyst is concentrated at 12.62-18.89nm, and the BET specific surface area is 507-620m2Per g, pore volume of 1.6-2.3cm3/g；
The hollow core-shell structure Pd catalyst is prepared by the following method:
(1) weigh 6-10 g of polyAdding ethylene glycol monohexadecane into a mixed solution of 40mL of cyclohexane and 10mL of n-octanol, stirring and dissolving the mixture in a water bath at 35 ℃, weighing 0-0.05 g of potassium bromide, adding the potassium bromide into a 1mL of 0.075M chloropalladate solution, stirring and dissolving the potassium bromide, adding the potassium bromide into the mixed solution, stirring the solution for 1h, adding 300 mu L of 10 wt% sodium borohydride solution and 2mL of ethyl orthosilicate, and reacting the mixture for 6h to obtain a seed solution Pd @ SiO2；
(2) The seed solution Pd @ SiO obtained above2Ultrasonically dispersing into 100mL of deionized water and ethanol mixed solution with the volume ratio of 3:1, and adding the Pd @ SiO of the seed solution2Adding resorcinol 0.35g, CTAB 2.3g, ammonia water 0.2mL and formaldehyde 0.5mL, reacting at 30-60 deg.C for 6h, centrifuging, washing three times, and standing at 80 deg.CoC, drying for 12 hours;
(3) drying the above mixture at 600 deg.C N2Roasting for 2H under atmosphere, HF etching for 12H, roasting and oxidizing for 2H at 150-300 ℃ in air at 250 ℃ H2Reducing for 2.5h under the atmosphere to obtain the product.
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| CN110064387A (en) * | 2019-03-19 | 2019-07-30 | 贵州大学 | A method of oxidation restores the catalyst that preparation surface Pd and PdO coexist |
| CN109985643A (en) * | 2019-03-19 | 2019-07-09 | 贵州大学 | A kind of add in-place bromine preparation small size PdKBrThe method of@HSC |
| CN110102320A (en) * | 2019-03-21 | 2019-08-09 | 贵州大学 | A kind of hydrogen peroxide catalyzed dose of hollow palladium base of preparation method |
| CN109999798A (en) * | 2019-05-08 | 2019-07-12 | 贵州大学 | A kind of preparation method of one shell yolk shell catalyst Pd@HCS of a core |
| CN110124665A (en) * | 2019-05-08 | 2019-08-16 | 贵州大学 | A kind of preparation method of shell multicore yolk shell catalyst Pd@HCS |
| CN114534721B (en) * | 2022-02-24 | 2023-10-17 | 河南科技大学 | Preparation method and application of Au@Pd core-shell structure super-long nanowire in water phase |
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