CN111790383B - Method for preparing CeO derived from Ce-BTC by in-situ reduction one-bath process 2 Method for loading Pd nano-catalyst - Google Patents
Method for preparing CeO derived from Ce-BTC by in-situ reduction one-bath process 2 Method for loading Pd nano-catalyst Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 35
- 230000009467 reduction Effects 0.000 title claims abstract description 20
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 13
- 238000011068 loading method Methods 0.000 title claims abstract description 12
- 230000008569 process Effects 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
Method for preparing Ce-BTC derived CeO by in-situ reduction one-bath process 2 A method for loading Pd nano-catalyst, belonging to the field of nano-material preparation. Firstly, dimethylformamide is added into a container, and then cerium nitrate, trimesic acid and PdCl are sequentially added 2 The solution is stirred for 1h, then heated to 100 ℃ and kept for 24h, and then cooled to 140 ℃ and kept for 6h, and stirring is kept during the process. The product obtained by centrifuging, washing and drying the solution is roasted at 500-800 ℃ in the atmosphere of air and nitrogen to obtain the final in-situ xPd-CeO 2 A catalyst. Compared with the traditional two-step supported catalyst, the sample has better CO catalytic oxidation performance. The material has the advantages of novel and simple preparation method, controllable process, high specific surface area, narrow particle size distribution of noble metal, excellent CO catalytic oxidation performance and the like.
Description
Technical Field
The invention relates to Ce-BTC derived CeO prepared by an in-situ reduction one-bath method 2 The Pd nano-catalyst is loaded, so that the high-efficiency catalytic oxidation of CO can be realized. In particular to a method adopting in-situ reduction and one bathSuccessfully prepares series in-situ xPd-CeO such as xPd-Ce-BTC-A500, xPd-Ce-BTC-A800, xPd-Ce-BTC-N500, xPd-Ce-BTC-N800 and the like 2 And (3) a nano catalyst. The performance of a sample calcined by reducing nitrogen in situ by a one-bath method for catalyzing CO oxidation is superior to that of a traditional two-step method supported catalyst, and belongs to the field of nano material preparation.
Background
CO is a gas which has wide source, is easy to generate in daily life and has larger harmfulness. It is colorless, odorless, non-irritating, and has blood and nerve toxicity. Any carbonaceous matter may produce CO when the combustion is insufficient, such as fuel combustion, thermal power generation, and the like, and trace CO is also commonly discharged from automobile exhaust. One of the most effective methods for eliminating CO exhaust gas is catalytic oxidation, and common catalysts include non-noble metal oxide catalysts and supported noble metal catalysts. CeO (CeO) 2 As a typical transition metal oxide, the catalyst has good catalytic performance, and has coordination with noble metals such as Au, pd and the like, so that the catalytic activity can be further improved. Ce-BTC is a very excellent cerium source as a cerium-based MOFs material, and CeO can be obtained by calcining it 2 . For Ce-BTC, a material, researchers have attempted to apply it to CO catalytic oxidation. Although previous research is available, on one hand, the process of loading the precious metal to the Ce-BTC is complex, and the metal particle size is large; on the other hand, the prepared catalyst has no high temperature resistance and is difficult to be applied to practical scenes such as automobile exhaust treatment and the like. Therefore, it is required to develop a simple method for preparing a Ce-BTC supported noble metal catalyst, and at the same time, the catalyst has good thermal stability and excellent catalytic CO oxidation performance through subsequent treatment. To our knowledge, no relevant report that the catalyst prepared by the in-situ reduction one-bath method has good performance of catalyzing and oxidizing CO at high temperature exists at present. In the invention, a precursor required by Ce-BTC and a precursor of Pd are mixed in dimethylformamide, the reduction rate of Pd and the self-assembly rate of Ce-BTC are controlled by temperature, the precursor of Pd is reduced in a Ce-BTC pore channel, fine particle size and high dispersion are kept under the action of pore channel confinement, the in-situ Pd-Ce-BTC catalyst is successfully prepared in situ by one bath, and the in-situ Pd-Ce-BTC catalyst is prepared at high temperatureUnder the condition, ce-BTC is pyrolyzed into CeO 2 But still keeps the porous structure, and the Pd particles are still limited in the pore channels, and still keeps the small particle size and the high dispersion state, which is beneficial to improving the thermal stability and the catalytic performance. Therefore, the in-situ reduction one-bath method is used for successfully preparing the in-situ xPd-CeO 2 (x is the mass ratio of Pd to Ce, and is about 1%), and has innovativeness; meanwhile, the catalytic activity of the sample roasted by nitrogen on CO oxidation is better.
Disclosure of Invention
The invention aims to provide a method for preparing CeO derived from Ce-BTC by an in-situ reduction one-bath process 2 Pd-loaded in-situ xPd-CeO 2 The method of the nano catalyst is characterized in that the specific catalyst is named as xPd-Ce-BTC (x is the mass ratio of Pd to Ce and is about 1 percent), and the catalyst calcined by the one-bath method in-situ reduction nitrogen shows excellent CO catalytic oxidation activity.
Method for preparing CeO derived from Ce-BTC by in-situ reduction one-bath method for efficiently catalyzing and oxidizing CO 2 The method for supporting the Pd nano-catalyst is characterized by comprising the following steps of:
in-situ reduction one-bath method is adopted to prepare in-situ xPd-CeO 2 The catalyst, in general, is prepared by adding dimethylformamide to a vessel, followed by the sequential addition of cerium nitrate, trimesic acid and PdCl 2 Solution (corresponding to Pd load), wherein the solution is required to be uniformly dispersed before adding a new reactant every time, the solution is stirred for 1h, then heated to 90-120 ℃ and kept for at least 24h, then heated to 130-150 ℃ and kept for at least 6h, and stirring is kept during the period; centrifuging the solution, washing, drying, such as centrifuging at 1000r/min, washing the obtained product with methanol and deionized water, and oven drying at 60 deg.C; the obtained product is marked as in-situ xPd-Ce-BTC, is placed in a tube furnace, is heated to 500-800 ℃ under the atmosphere of air or nitrogen according to the heating rate of 2 ℃/min, and is roasted for 3h; finally obtaining the catalyst. According to different roasting atmospheres and temperatures, the catalyst is marked as xPd-Ce-BTC-A500, xPd-Ce-BTC-A800, xPd-Ce-BTC-N500 and xPd-Ce-BTC-N800, wherein the number in the catalyst represents the final roasting temperature, A represents air, N represents nitrogen, and x represents the mass ratio of Pd to Ce and is 0.5-1.2%.
The molar ratio of the cerium nitrate to the trimesic acid is preferably 10 (6-7).
Selecting CO as probe molecule for related catalyst evaluation, the composition of CO distribution is 1vol% CO +20vol% 2 +79vol％N 2 The space velocity was 100,000mL/(g h). The catalytic performance of the four catalysts with Ce-BTC as the carrier is superior to that of bulk CeO 2 A supported catalyst; in addition, the catalytic performance of the sample treated by nitrogen is better than that of the sample treated by air, and the catalytic performance of the sample subjected to in-situ reduction by the one-bath method is also better than that of the two-step supported catalyst treated by the same atmosphere. In consideration of the actual CO elimination environment of automobile exhaust and the like, the CO catalytic oxidation activity of the Pd-Ce-BTC series catalyst prepared by the in-situ reduction one-bath method with the most excellent performance after high-temperature treatment is further researched. Although the catalyst calcined at a high temperature of 800 ℃ for 3 hours showed a decrease in activity, it was heat-treated with CeO under the same conditions 2 Compared with the supported catalyst, the supported catalyst still has good CO oxidation catalytic activity, and the rule that the activity of a nitrogen treatment sample is superior to that of an air treatment sample is not changed.
The material of the invention has novel preparation method, simple preparation process, controllable process, high specific surface area and narrow noble metal particle size distribution. The sample roasted by reducing nitrogen in situ by the one-bath method shows the best CO catalytic oxidation performance and has very strong practical application value.
Drawings
FIG. 1 shows XRD patterns of Pd-Ce-BTC and Ce-BTC.
FIG. 2 is an XRD pattern of Pd-Ce-BTC and Pd/Ce-BTC series catalysts.
Fig. 3 is a TEM image and a Pd particle size distribution diagram of the prepared catalyst. Wherein panels (a, b, c) 0.93Pd-Ce-BTC-N500 and (e, f, g) 0.96Pd/Ce-BTC-N500 are TEM images; panel (d) 0.93Pd-Ce-BTC-N500 and panel (h) 0.96Pd/Ce-BTC-N500 are Pd particle size distribution plots.
Fig. 4 shows nitrogen adsorption-desorption curves (internal BET specific surface area) and pore size distribution curves of the catalysts prepared in the corresponding examples and comparative examples.
Fig. 5 is a graph showing the temperature-dependent change in the conversion of the catalyst for catalyzing CO oxidation according to the corresponding examples and comparative examples.
Fig. 6 is a graph showing the temperature-dependent change in the conversion rate of catalytic CO oxidation of samples calcined at different temperatures according to the corresponding examples and comparative examples.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples.
Comparative example 1: ce-BTC was synthesized according to the usual method. 60mL of dimethylformamide was added to the vessel, 10mmol of cerium nitrate was added thereto and stirred to disperse uniformly, 6.67mmol of trimesic acid was added thereto and stirred for 1 hour. After the vessel was sealed, it was heated and held at 100 ℃ for 24h while stirring was maintained. And then centrifuging the solution at the rotating speed of 10,000 r/min, fully washing the obtained product with methanol and deionized water, and drying in a drying oven at the temperature of 60 ℃ to obtain the Ce-BTC.
Example 1: in-situ reduction one-bath method is adopted to prepare in-situ xPd-CeO 2 A catalyst. In general, 60mL of dimethylformamide was placed in a vessel, followed by the addition of 10mmol of cerium nitrate, 6.67mmol of trimesic acid and the appropriate amount of PdCl in that order 2 Solution (corresponding to Pd loading) was uniformly dispersed before adding fresh reactant. The solution was stirred for 1h, heated to 100 ℃ and held for 24h, then raised to 140 ℃ and held for 6h, while stirring was maintained. Then the solution is centrifuged at the rotating speed of 1000r/min, the obtained product is fully washed by methanol and deionized water and dried in a drying box at the temperature of 60 ℃. The obtained product is marked as in-situ xPd-Ce-BTC, and is divided into two groups which are respectively placed in a tube furnace, respectively heated to 500/800 ℃ under the atmosphere of air and nitrogen at the heating rate of 2 ℃/min, and roasted for 3h. The finally obtained catalysts are marked as xPd-Ce-BTC-A500, xPd-Ce-BTC-A800, xPd-Ce-BTC-N500 and xPd-Ce-BTC-N800 according to different roasting atmospheres and temperatures. According to the test results of ICP, the actual Pd loading amounts of the catalysts were 0.97wt%, 1.02wt%, 0.53wt%, 0.83wt%, in this order, and the mass ratios (x) of Pd to Ce were 1.01%, 1.02%, 0.93%, 0.95% in this order.
Comparative example 2: the common stepwise synthesis strategy is adopted to synthesize the yPd/CeO 2 Catalyst as a control. In accordance withAfter Ce-BTC was synthesized according to the method of example 1, it was uniformly dispersed in 60mL dimethylformamide, and then appropriate amount of PdCl was added 2 Solution (corresponding to Pd loading). The solution was heated to 140 ℃ and held for 6h while maintaining stirring. Then the solution is centrifuged at the rotating speed of 1000r/min, the obtained product is fully washed by methanol and deionized water, and is dried in a drying oven at the temperature of 60 ℃. The obtained product is marked as yPd/Ce-BTC, and is divided into two groups which are respectively placed in a tube furnace, are respectively roasted to 500/800 ℃ under the atmosphere of air and nitrogen according to the heating rate of 2 ℃/min, and are kept for 3h. The finally obtained catalysts are recorded as yPd/Ce-BTC-A500, yPd/Ce-BTC-A800, yPd/Ce-BTC-N500 and yPd/Ce-BTC-N800 according to different roasting atmospheres and temperatures. According to the results of the ICP test, the actual Pd loading amounts of the catalysts were 0.95wt%, 0.98wt%, 0.57wt%, 0.87wt% in this order, and the mass ratios (y) of Pd to Ce were 0.96%, 0.98%, 0.97%, 0.96% in this order.
Comparative example 3: in addition, ceO in bulk phase is prepared 2 Pd/CeO as carrier 2 The catalyst was used as a control and is designated as Pd/CeO 2 A500, the supporting method is the same as above, and the heat treatment condition is roasting in air at 500 ℃.
Claims (6)
1. In-situ reduction one-bath method for preparing Ce-BTC derived CeO by efficiently catalyzing and oxidizing CO 2 The method for supporting the Pd nano-catalyst is characterized by comprising the following steps of:
in-situ reduction one-bath method is adopted to prepare in-situ xPd-CeO 2 Adding dimethyl formamide into a container, and then sequentially adding cerium nitrate, trimesic acid and PdCl 2 Solution, wherein the solution is required to be uniformly dispersed before adding a new reactant every time, the solution is stirred for 1h, then heated to 90-120 ℃ and kept for at least 24h, then heated to 130-150 ℃ and kept for at least 6h, and stirring is kept during the period; then centrifuging, washing and drying the solution, recording the obtained product as in-situ xPd-Ce-BTC, placing the in-situ xPd-Ce-BTC in a tube furnace, raising the temperature to 500-800 ℃ at the heating rate of 2 ℃/min in the air or nitrogen atmosphere, and roasting for 3h; finally obtaining the catalyst.
2.The in-situ reduction one-bath method for preparing Ce-BTC derived CeO by efficiently catalyzing and oxidizing CO according to claim 1 2 The method for loading the Pd nano-catalyst is characterized by comprising the following steps of centrifuging, washing and drying: centrifuging at 1000r/min, washing the obtained product with methanol and deionized water, and drying in a drying oven at 60 deg.C.
3. The in-situ reduction one-bath method for preparing Ce-BTC derived CeO by efficiently catalyzing and oxidizing CO according to claim 1 2 The method for loading the Pd nano-catalyst is characterized in that the mass ratio of Pd to Ce is 0.5-1.2%.
4. The in-situ reduction one-bath method for preparing Ce-BTC derived CeO by efficiently catalyzing and oxidizing CO according to claim 1 2 The method for loading the Pd nano-catalyst is characterized in that the molar ratio of cerium nitrate to trimesic acid is 10 (6-7).
5. Ce-BTC derived CeO prepared according to any one of claims 1 to 4 2 And loading Pd nano-catalyst.
6. Ce-BTC derived CeO prepared according to any one of claims 1 to 4 2 Use of Pd supported nanocatalyst, characterized in that the catalyst is used for the catalytic oxidation of CO, the composition of CO distribution is 1vol% CO +20vol% 2 +79vol％N 2 The space velocity was 100,000mL/(g.h).
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