CN109529821B - Palladium-based catalyst for thermal catalysis of formaldehyde degradation - Google Patents
Palladium-based catalyst for thermal catalysis of formaldehyde degradation Download PDFInfo
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Abstract
The invention discloses a palladium-based catalyst for thermal catalysis of formaldehyde degradation. The Pd/TiO2The catalyst comprises, by weight, 100% of the catalyst, 0.1-0.4% of Pd by mass, and the preparation method comprises the following steps: 1) adding TiO into the mixture2Carrying out reduction treatment on the carrier; 2) adding a proper amount of TiO into the palladium nitrate solution2(ii) a 3) Adjusting the pH of the solution and reducing; 4) drying the obtained mixture to obtain the required Pd/TiO2A formaldehyde oxidation catalyst. The preparation method is simple, and the prepared Pd/TiO2The catalyst being Anatase (ATiO)2) Phase structure of Pd/TiO formed2Shows excellent formaldehyde oxidation catalytic performance.
Description
Technical Field
The invention relates to a palladium-based catalyst for thermal catalysis of formaldehyde degradation and a preparation method thereof, belonging to the technical field of thermal catalysis materials and environmental protection.
Background
Formaldehyde is a gas which has the greatest harm to human bodies in indoor environment, and designing and preparing a high-efficiency stable catalyst to realize catalytic oxidation of formaldehyde under mild conditions is one of important research contents in the field of environmental catalysis. However, in the existing catalysts used in the thermal catalytic reaction, the nonmetal-supported catalyst has poor catalytic effect, while the noble metal-supported catalyst has good effect, but has the problems of high noble metal consumption, poor noble metal dispersion, poor stability and the like.
TiO2As a thermal catalytic carrier, extensive studies have been made. For formaldehyde thermal catalytic degradation, Pt-supported TiO is reported more2The catalyst has better catalytic activity, and Pd/TiO2There are few reports. Huang et al (chem. Eng.J.,2013,230,73-79.) prepared Pd/TiO by impregnation and precipitation2Catalyst reported successful Pd loading on TiO by precipitation2In addition, the catalyst can efficiently and chemically adsorb oxygen, and the surface of the catalyst can well utilize hydroxyl groups, so that the catalyst has good activity of catalyzing and oxidizing formaldehyde. Zhang et al (environ. Sci. Techniol., 2014,48,5816-3And Pd (NO)3)2Coprecipitation supported on TiO2In the above, reports show that Na-Pd/TiO by coprecipitation of Na2The efficiency of the catalyst for catalyzing and degrading formaldehyde at normal temperature (30 ℃) is higher than that of Pd/TiO2A catalyst. Li et al (Catal. today,2017,281,412-3And Pd (NO)3)2Coprecipitation supported on TiO2In the above, the influence of different Na addition amounts on the catalytic activity is investigated, and reports indicate that the high activity of the catalyst is mainly due to the fact that the catalyst has abundant surface hydroxyl groups, so that the formaldehyde gas can be efficiently degraded.
However, Pd/TiO was prepared as described above2There are certain limitations, as the amount of Pd used is all large, 1 w.t.% Pd; in addition, high-temperature calcination is required in the preparation process.
Although the Pd/TiO2 catalyst prepared by the above method has good performance of catalyzing and explaining formaldehyde, it still faces some problems, such as high Pd content, addition of other auxiliary agents, high temperature calcination during preparation, etc., which makes the catalyst more expensive to manufacture, and this is limited in practical application.
Disclosure of Invention
In view of the above-mentioned research field of catalytic degradation of formaldehyde, in particular based on Pd/TiO2The invention provides a palladium-based catalyst for thermally catalyzing formaldehyde degradation, which solves the problems of the prior supported noble metal catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Pd-base catalyst for thermally catalyzing the degradation of formaldehyde is prepared from TiO2And Pd to form Pd/TiO2The catalyst is characterized in that the mass fraction of Pd is 0.1-0.4% based on 100% of the weight of the catalyst.
The preparation method of the palladium-based catalyst for thermally catalyzing formaldehyde degradation comprises the following steps:
(1) taking TiO2Placing the mixture in a fixed bed reduction reaction tube;
(2) raising the temperature to different temperatures at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature;
(3) sucking a palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring;
(4) adding reduced anatase into the solution of the three-neck flask under stirring, and stirring for reaction;
(5) subsequently, dropwise adding NaOH solution until the pH value of the solution is 10;
(6) weighing NaBH4Adding pure water to the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction;
(7) after the reaction was completed, the solution was centrifuged, washed with deionized water, and finally air-dried.
In the above preparation method: the different temperature ranges in the step (1) are 300-500 ℃; in the step (3), the concentration of the palladium nitrate solution is 10 mg/ml; in the step (5), the concentration of NaOH is 1mol/L, and in the step (6), NaBH4In a molar ratio of NaBH4Pd is 10; the centrifugation parameters were: 8000 rpm for 5 min; the washing conditions were: washing with deionized water for 3-5 times; the drying temperature is 105 ℃, and the drying time is 6-10 h.
The method for catalyzing and degrading formaldehyde by using the palladium-based catalyst has the catalysis conditions that: the concentration of formaldehyde is 50ppm, and the airspeed is 30000h-1The reaction temperature was 30 ℃.
The Pd/TiO2 catalyst provided by the invention is applied to the field of normal-temperature thermal catalysis. The catalyst has certain catalytic efficiency on monomer micromolecular organic matters, and can be used for degrading common organic pollutants in the air.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lowest load of Pd can reach 0.1 w.t.%, so that the load of Pd is greatly reduced;
(2) the TiO2 is rich in surface oxygen vacancy through pre-reduction treatment, so that the oxygen adsorption capacity of the TiO2 is improved, and the oxygen vacancy is favorable for the dispersion of the noble metal Pd.
(3) The catalyst has the advantages of low preparation cost, mild preparation conditions, convenient operation and convenient large-scale production in industry.
Drawings
FIG. 1 is the 0.2 wt.% Pd/TiO prepared in example 12TEM image and element mapping image of (a).
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1:
a preparation method of a palladium-based catalyst for thermal catalysis formaldehyde degradation comprises the following steps: (1) take 0.5g TiO2Placing the mixture in a fixed bed reduction reaction tube; (2) raising the temperature to 300 ℃ at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction for 3h at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature; (3) sucking 0.4ml of 10mg/ml palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring; (4) adding reduced anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (5) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (6) 0.0071g of NaBH was weighed4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (7) after the reaction was completed, the solution was centrifuged at 8000 rpm for 5min, washed with deionized water, the centrifugation and water washing processes were repeated 3 times, and finally air-dried.
Example 2:
a preparation method of a palladium-based catalyst for thermal catalysis formaldehyde degradation comprises the following steps: (1) take 0.5g TiO2Placing the mixture in a fixed bed reduction reaction tube; (2) raising the temperature to 400 ℃ at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction for 3h at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature; (3) sucking 0.4ml of 10mg/ml palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring; (4) adding reduced anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (5) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (6) 0.0071g of NaBH was weighed4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (7) after the reaction was completed, 8000 rotations of the solution were carried outCentrifuging for 5min, washing with deionized water, repeating centrifuging and washing for 3 times, and air drying.
Example 3:
a preparation method of a palladium-based catalyst for thermal catalysis formaldehyde degradation comprises the following steps: (1) take 0.5g TiO2Placing the mixture in a fixed bed reduction reaction tube; (2) raising the temperature to 500 ℃ at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction for 3h at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature; (3) sucking 0.2ml of 10mg/ml palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring; (4) adding reduced anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (5) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (6) 0.0071g of NaBH was weighed4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (7) after the reaction was completed, the solution was centrifuged at 8000 rpm for 5min, washed with deionized water, the centrifugation and water washing processes were repeated 3 times, and finally air-dried.
Example 4:
a preparation method of a palladium-based catalyst for thermal catalysis formaldehyde degradation comprises the following steps: (1) take 0.5g TiO2Placing the mixture in a fixed bed reduction reaction tube; (2) raising the temperature to 300 ℃ at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction for 3h at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature; (3) sucking 0.2ml of 10mg/ml palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring; (4) adding reduced anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (5) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (6) 0.0035g of NaBH was weighed4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (7) after the reaction was completed, the solution was centrifuged at 8000 rpm for 5min, washed with deionized water, the centrifugation and water washing processes were repeated 3 times, and finally air-dried.
Example 5:
palladium base for thermal catalysis of formaldehyde degradationThe preparation method of the catalyst comprises the following steps: (1) take 0.5g TiO2Placing the mixture in a fixed bed reduction reaction tube; (2) raising the temperature to 300 ℃ at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction for 3h at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature; (3) sucking 0.1ml of 10mg/ml palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring; (4) adding reduced anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (5) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (6) weighing 0.0018g NaBH4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (7) after the reaction was completed, the solution was centrifuged at 8000 rpm for 5min, washed with deionized water, the centrifugation and water washing processes were repeated 3 times, and finally air-dried.
Comparative example 1:
a preparation method of a palladium-based catalyst for thermal catalytic formaldehyde degradation comprises (1) sucking 0.2ml of 10mg/ml palladium nitrate solution, adding into a three-neck flask, adding pure water, and continuously stirring; (2) adding anatase (TiO) into the three-neck flask solution under stirring2) Stirring the solid to react for 1 h; (3) then dropwise adding 1mol/L NaOH solution until the pH value of the solution is 10; (4) 0.0071g of NaBH was weighed4Adding 10ml of pure water into the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction for 2 hours; (5) after the reaction was completed, the solution was centrifuged at 8000 rpm for 5min, washed with deionized water, the centrifugation and water washing processes were repeated 3 times, and finally air-dried.
TABLE 1 Pd/TiO2Evaluation of catalyst Activity
Description of the attached tables:
examples all use TiO2Method for preparing Pd/TiO by carrier prereduction2While the comparative example did not go through TiO2And (3) pre-reducing the carrier. As can be seen from Table 1, although the comparative example had a Pd content exceeding that ofThe Pd content of the examples is higher than that of the catalysts in the prior art, but the conversion rate of the catalysts catalyzing formaldehyde under the same conditions is lower than that of the catalysts in the prior examples; this indicates that TiO is used2Pd/TiO prepared by carrier prereduction method2Can strengthen the catalytic activity of the catalyst. Furthermore, a high catalytic activity is still achieved at a noble metal content of 0.2 wt.%. Therefore, the invention is a thermal catalyst with excellent activity.
Claims (2)
1. A Pd-base catalyst for thermally catalyzing the degradation of formaldehyde is prepared from TiO2And Pd to form Pd/TiO2The catalyst is characterized in that the mass fraction of Pd is 0.1-0.4% based on 100% of the weight of the catalyst.
The preparation method comprises the following steps:
(1) taking TiO2Placing the mixture in a fixed bed reduction reaction tube;
(2) raising the temperature to different temperatures at normal temperature under the condition of the heating rate of 10 ℃/min, carrying out hydrogen reduction at different temperatures, and then continuously introducing hydrogen to naturally cool to the room temperature;
(3) sucking a palladium nitrate solution, adding the solution into a three-neck flask, adding pure water, and continuously stirring;
(4) adding reduced anatase into the solution of the three-neck flask under stirring, and stirring for reaction;
(5) subsequently, dropwise adding NaOH solution until the pH value of the solution is 10;
(6) weighing NaBH4Adding pure water to the solid to prepare NaBH4Dropwise adding the solution into the solution, and continuously stirring for reaction;
(7) after the reaction was completed, the solution was centrifuged, washed with deionized water, and finally air-dried.
2. The palladium-based catalyst according to claim 1, characterized in that: the different temperature range in the step (2) is 300-; in the step (3), the concentration of the palladium nitrate solution is 10 mg/ml; in the step (5), the concentration of NaOH is 1 mol/L; NaBH in step (6)4In a molar ratio of NaBH4Pd = 10; the centrifugation parameters were: 8000 revolutions per minute, time5 min; the washing conditions were: washing with deionized water for 3-5 times; the drying temperature is 105 ℃, and the drying time is 6-10 h.
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| CN111517278A (en) * | 2020-03-24 | 2020-08-11 | 中南大学 | Ti3C2TxApplication of MXenes non-noble metal heterogeneous catalyst in formic acid dehydrogenation |
| CN113941327B (en) * | 2021-11-23 | 2024-03-19 | 江苏科技大学 | Palladium-based catalyst and preparation method and application thereof |
| CN114797845A (en) * | 2022-05-18 | 2022-07-29 | 北京化工大学 | Pd catalyst for carbon-carbon triple bond selective hydrogenation reaction and preparation method thereof |
| CN115212872B (en) * | 2022-08-03 | 2023-08-15 | 中山大学 | Monoatomic alloy catalyst for directly synthesizing high-concentration hydrogen peroxide by using hydrogen and oxygen and preparation method thereof |
| CN115212874A (en) * | 2022-08-16 | 2022-10-21 | 深圳市康弘智能健康科技股份有限公司 | Preparation method of improved photocatalytic material for catalytic purification of formaldehyde by visible light |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1795970A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院生态环境研究中心 | High performance catalyst for catalyzing formaldehyde to complete oxidation under room temperature temperature |
| CN103736484A (en) * | 2014-01-13 | 2014-04-23 | 中山大学 | Supported integrated catalyst for formaldehyde purification and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795970A (en) * | 2004-12-28 | 2006-07-05 | 中国科学院生态环境研究中心 | High performance catalyst for catalyzing formaldehyde to complete oxidation under room temperature temperature |
| CN103736484A (en) * | 2014-01-13 | 2014-04-23 | 中山大学 | Supported integrated catalyst for formaldehyde purification and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Synergetic effect of oxygen vacancy and Pd site on the interaction between Pd/Anatase TiO2(101) and formaldehyde: A density functional theory study;Xuyu Wang等;《Catalysis Today》;20170630;第297卷;第151-158页 * |
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