CN112619681B - Nitrogen-doped carbonized bacterial cellulose supported palladium catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped carbonized bacterial cellulose supported palladium catalyst and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 191
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 19
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- 239000002243 precursor Substances 0.000 claims abstract description 9
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- 239000000243 solution Substances 0.000 claims description 16
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 13
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a nitrogen-doped carbonized bacterial cellulose supported catalyst and a preparation method and application thereof. The method comprises the steps of freeze-drying bacterial cellulose impregnated with diethylene triamino pentaacetic acid pentasodium salt and palladium salt to enable a nitrogen precursor and a palladium precursor to be uniformly distributed in a three-dimensional grid structure of the bacterial cellulose, and then calcining at a high temperature in a carbon dioxide atmosphere to realize conversion from nitrogen doping and the palladium precursor to palladium, so that the nitrogen-doped carbonized bacterial fiber supported nano-palladium catalyst with high dispersibility is prepared. The palladium nano particles in the nitrogen-doped carbonized bacterial fiber loaded nano palladium catalyst are uniformly distributed and have a stable structure, the catalyst can be used for removing hexavalent chromium ions in a water body by catalysis, the catalytic reduction rate of Cr (VI) can reach 99.9%, and the catalyst is suitable for the requirement of industrial mass production.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and relates to a nitrogen-doped carbonized bacterial cellulose supported catalyst, and a preparation method and application thereof.
Background
Because the chromium Cr (VI) has great harm to human bodies and the environment, the reduction of the Cr (VI) into trivalent chromium Cr (III) with lower toxicity and weak migration capability is an effective way for treating chromium pollution. The commonly used reduction methods include electrochemical reduction, photoelectrocatalytic reduction, microbial reduction, catalytic reduction and the like. Among them, the catalytic reduction method is the most commonly used method for industrially treating Cr (VI), and its principle is to reduce Cr (VI) to Cr (III) with a reducing agent such as formic acid under the action of a catalyst. Although the common palladium catalyst has the advantages of strong catalytic activity, good selectivity and the like, the homogeneous catalyst is difficult to separate and recover, and the residual palladium catalyst pollutes products, thereby limiting the application range of the catalyst.
The palladium catalyst can be supported to solve the separation and recovery problem. In the supported palladium metal nanoparticle catalyst, the carrier of the catalyst is usually an oxide, a carbon material, some special polymer materials and the like. Among them, porous carbon materials such as carbon fibers, carbon nanotubes, graphene, and the like are considered to be the most important catalyst carriers due to their advantages of large surface area, good electrical conductivity, high thermal/chemical stability, and the like. However, the pure porous carbon material has poor hydrophilicity and few active adsorption sites, and the application development of the pure porous carbon material is restricted. Research shows that the surface characteristics and the physicochemical properties of the carbon can be changed by performing functional modification on the carbon. If nitrogen is doped and introduced into the carbon structure, the nitrogen-containing functional group can cause dislocation, bending, dislocation and the like between graphite layers of the carbon layer, so that structural defects of the carbon material occur. Meanwhile, nitrogen can provide more electrons, and the conductivity and the electron transmission performance of the material are enhanced. Compared with a pure carbon material, the nitrogen-doped carbon material has higher activity, active metal is modified by taking the nitrogen-doped carbon material as a carrier, and the nitrogen can enhance the interaction between the metal and the carrier, so that the dispersion degree of the metal and the stability of the composite material are improved. Therefore, nitrogen-doped carbon materials are receiving more and more attention in the field of catalysis, such as catalytic reactions, hydrogenation reactions, selective reduction reactions, and the like.
At present, nitrogen-doped porous carbon materials are mainly synthesized by two ways. The first method is to treat the carbon material at high temperature in an atmosphere containing nitrogen elements, so that the obtained material has low nitrogen element content, is only distributed on the surface of the carbon material, and cannot change the state of a bulk phase. The second method is an in-situ doping method, nitrogen elements are doped in the synthesis process of the carbon material, and the obtained carbon material is uniform in nitrogen element distribution and controllable in chemical property.
The bacterial cellulose is cellulose synthesized by microorganisms, can be produced in large scale by industrialization, and is cheap and easy to obtain. The carbonized bacterial cellulose is a biomass carbon material obtained by pyrolyzing bacterial fibers under the condition of limited oxygen, and has a three-dimensional reticular nanofiber structure and excellent conductivity and chemical stability.
Disclosure of Invention
The invention aims to provide a nitrogen-doped carbonized bacterial cellulose loaded nano palladium catalyst with better catalytic performance and stability, and a preparation method and application thereof. The method takes bacterial cellulose as a template and a carbon source, diethylene triamino pentaacetic acid pentasodium salt as a nitrogen source and palladium nitrate as a metal source, and completes the formation and nitrogen doping of a carbon nano material and the generation of metal palladium in one step by adopting a direct calcination mode. The active component palladium in the supported catalyst is uniformly distributed in a three-dimensional network structure of the nitrogen-doped carbonized bacterial cellulose, so that the utilization rate of the catalyst can be maximized. Meanwhile, the supported catalyst has good adsorbability, is beneficial to full contact between a substrate and the nano palladium and accelerates the catalytic reaction. The nitrogen-doped carbonized bacterial cellulose supported palladium catalyst prepared by the method can well catalyze formic acid to reduce hexavalent chromium. The catalyst has good stability, still maintains good catalytic activity after being recycled for eight times, and effectively reduces the cost of the catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst is formed by uniformly supporting palladium nano particles on nitrogen-doped carbonized bacterial cellulose with a three-dimensional grid structure, wherein the nitrogen content in the catalyst is 2.3-4.1 wt%, the palladium content is 0.9-1.9 wt%, the palladium nano particles are supported on the surface of the nitrogen-doped carbonized bacterial cellulose and in the three-dimensional grid, and the specific surface area is 413-560 m 2 The particle diameter of the palladium nano-particles is 8-22 nm.
The preparation method of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst comprises the following steps of firstly freezing and drying bacterial cellulose impregnated with diethylenetriaminepentaacetic acid pentasodium salt and palladium salt to uniformly distribute a nitrogen precursor and a palladium precursor in a three-dimensional grid structure of the bacterial cellulose, and finally calcining at high temperature in a carbon dioxide atmosphere to realize conversion of the nitrogen-doped and palladium precursor to palladium, so as to prepare the nitrogen-doped carbonized bacterial cellulose supported nano palladium catalyst with high dispersibility, wherein the preparation method specifically comprises the following steps:
soaking bacterial cellulose in 3.2-5.2 wt.% of diethylene triamino pentaacetic acid pentasodium salt solution, completely soaking, soaking the bacterial cellulose soaked with the sodium salt in 0.2-0.5 mg/L palladium nitrate solution, completely soaking, and freeze-drying to obtain a nitrogen-doped carbonized bacterial cellulose supported palladium catalyst precursor;
and 2, placing the precursor of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst in a tubular muffle furnace, carrying out carbonization treatment at 800 ℃ under the protection of carbon dioxide atmosphere, and cooling to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst with a three-dimensional network structure.
Preferably, in the step 1, the mass-to-volume ratio of the bacterial cellulose to the diethylene triamino pentaacetic acid pentasodium salt solution is 0.05-0.1: 100 to 200, g: mL; the volume ratio of the diethylene triaminopentaacetic acid pentasodium salt solution to the palladium nitrate solution is 1: 2-2: 1.
preferably, in the step 1, the dipping time is 24-48 h, and the dipping temperature is 0-40 ℃.
Preferably, in step 2, the temperature rise rate of carbonization is 1 to 4 ℃/min.
Preferably, in the step 2, the carbonization time is 1 to 3 hours.
The invention also provides application of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst in catalytic reduction of hexavalent chromium pollutants in water.
The bacterial cellulose has a fine three-dimensional grid structure and rich nano-pores, so that diethylenetriaminepentaacetic acid pentasodium salt and palladium nitrate can enter the bacterial cellulose quickly, and the bacterial cellulose has rich hydroxyl, so that a water-soluble complex formed by diethylenetriaminepentaacetic acid pentasodium salt and metal ion palladium can be anchored and uniformly distributed in the bacterial cellulose. The nitrogen-doped carbonized bacterial cellulose supported palladium catalyst precursor is subjected to high-temperature treatment in the atmosphere of carbon dioxide, the palladium precursor is subjected to in-situ reduction by carbon and carbon monoxide generated by the reaction of carbon and carbon dioxide to obtain palladium, the supported palladium is spaced by a net structure of carbonized bacterial cellulose, and a catalytic active component palladium is uniformly dispersed. The catalyst has large specific surface area and good hydrophilicity, can adsorb reactants to the periphery of the nano palladium, and has high catalytic activity. Meanwhile, the catalyst has good stability, and still maintains good catalytic activity after 8 times of cyclic utilization.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the diethylene triamino pentaacetic acid pentasodium salt solution is fully mixed with the bacterial cellulose, and the sodium salt is uniformly distributed in the bacterial cellulose by utilizing the rich hydroxyl of the bacterial cellulose. The coordination complexing action of the diethylene triamino pentaacetic acid pentasodium salt and metal ion palladium is utilized to combine the metal ion palladium and uniformly disperse the metal ion palladium in a three-dimensional network structure of the bacterial cellulose.
(2) The porous carbon composite material is prepared by in-situ reduction of a nitrogen-doped carbonized bacterial cellulose supported palladium catalyst precursor. The three-dimensional network structure of the carbonized bacterial cellulose is bound, so that the aggregation of palladium in the reduction process is effectively avoided, and metal ion palladium forms metal clusters after being reduced and is dispersed in the three-dimensional network structure of the carbonized bacterial cellulose, so that active ingredients are uniformly distributed on the carbonized bacterial cellulose and are firmly combined. The prepared nitrogen-doped carbonized bacterial cellulose supported palladium catalyst has large specific surface area and a large number of catalytic active sites.
(3) The nitrogen-doped carbonized bacterial cellulose load palladium prepared by the method has a core-shell structure. The carbon-coated nano palladium structure slows down the inactivation and leaching of the palladium active component, and can accelerate the electron transfer between the metal particles and the carrier, thereby improving the catalytic performance of the catalyst. The nitrogen doping can increase the active sites of the catalyst, improve the conductivity of the catalyst, and further improve the catalytic activity of the material by combining the catalytic advantages of the nano metal. The nitrogen-doped carbonized bacterial cellulose supported palladium catalyst has better hydrophilicity and large surface area, can adsorb reactants around the nano palladium, and is beneficial to the catalytic reduction reaction.
Drawings
Fig. 1 is an SEM image of bacterial cellulose (a), an SEM image of a nitrogen-doped carbonized bacterial cellulose-supported palladium catalyst (b) and a TEM image of the bacterial cellulose prepared in example 1.
Fig. 2X-ray electron energy spectrum (XPS) of the nitrogen-doped bacterial cellulose supported palladium catalyst prepared in example 1.
FIG. 3 is a graph showing the results of performance tests on the palladium-catalyzed reduction of Cr (VI) with formic acid prepared in example 1 and comparative examples 1 to 3.
Fig. 4 is a graph showing the result of the recycling performance test of the nitrogen-doped carbonized bacterial cellulose supported palladium prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating speed of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 1h, then cooling to 600 ℃ at a temperature of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst CBC/N/Pd (1).
Fig. 1 is a Scanning Electron Microscope (SEM) image of bacterial cellulose, an SEM image of a nitrogen-doped carbonized bacterial cellulose-supported palladium catalyst (b) prepared in example 1, and a Transmission Electron Microscope (TEM) image (c). As can be seen from the SEM image, the bacterial cellulose is a three-dimensional network structure formed by interweaving nano fibers. The nano palladium particles generated after carbonization are uniformly dispersed in the three-dimensional network structure of the nitrogen-doped carbonized bacterial cellulose. As can be seen from the TEM image, the palladium nanoparticles were successfully coated with the carbon layer to form a core-shell structure in which the palladium particles are a core and the carbon is a shell. In the catalyst obtained in this example, the supported amount of palladium was 1.1% by weight, the particle size of palladium was 12nm, the content of nitrogen was 2.7% by weight, and the specific surface area was up to 482m 2 (iv) g. Fig. 2X-ray electron energy spectrum (XPS) of the nitrogen-doped bacterial cellulose supported palladium catalyst prepared in example 1. The XPS graph can analyze that the material contains nitrogen, palladium, oxygen and carbon elements.
Example 2
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating rate of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 3h, then cooling to 600 ℃ at a heating rate of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst.
In the catalyst obtained in the embodiment, palladium particles are uniformly distributed in a three-dimensional grid of carbonized bacterial cellulose, the loading amount of palladium is 1.9wt%, the size of the palladium particles is 21nm, the content of nitrogen element is 4.1wt%, and the specific surface area can reach 426m 2 /g。
Example 3
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating rate of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 3h, then cooling to 600 ℃ at a heating rate of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst.
In the catalyst obtained in the embodiment, palladium particles are uniformly distributed in a three-dimensional grid of carbonized bacterial cellulose, the loading amount of palladium is 1.5wt%, the size of the palladium particles is 18nm, the content of nitrogen is 3.6wt%, and the specific surface area can reach 457m 2 /g。
Example 4
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating rate of 1 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 1h, then cooling to 600 ℃ at a temperature of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst.
In the catalyst obtained in the embodiment, palladium particles are uniformly distributed in a three-dimensional grid of carbonized bacterial cellulose, the loading amount of palladium is 0.9wt%, the size of the palladium particles is 10nm, the content of nitrogen is 2.3wt%, and the specific surface area can reach 553m 2 /g。
Comparative example 1
The procedure is as in example 1 except that the nitrogen precursor, diethylenetriaminepentaacetic acid pentasodium salt, is not added.
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating speed of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 1h, then cooling to 600 ℃ at a temperature of 2 ℃/min, and finally naturally cooling to room temperature to obtain the carbonized bacterial cellulose supported palladium catalyst CBC/Pd.
Comparative example 2
The procedure was as in example 1 except that the nitrogen precursor, diethylene triaminopentaacetic acid pentasodium salt, was changed to ethylenediamine.
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating speed of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 1h, then cooling to 600 ℃ at a temperature of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst CBC/N/Pd (2).
Comparative example 3
The procedure was as in example 1 except that the mass fraction of pentasodium diethylenetriaminopentaacetic acid was increased to 8.9%.
And 2, putting the carbonized bacterial cellulose supported palladium catalyst precursor obtained in the step 1 into a tubular muffle furnace, heating to 800 ℃ at a heating speed of 2 ℃/min under the protection of carbon dioxide atmosphere, preserving heat for 1h, then cooling to 600 ℃ at a temperature of 2 ℃/min, and finally naturally cooling to room temperature to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst CBC/N/Pd (3).
Example 5
The catalysts obtained in comparative examples 1 to 3 and examples 1 to 4 were used for the experiments on the catalytic reduction of Cr (VI) in water. The dosage of the catalyst is 0.2g/L, the content of Cr (VI) in water is 60mg/L, the molar ratio of HCOOH to Cr (VI) is 40, the stirring speed is 500r/min, and the pH value of the solution is 2. The catalytic reduction kinetics curves are shown in FIG. 3. The catalytic reduction rate of the catalyst CBC/Pd on Cr (VI) is only 79.1 percent and is obviously less than the catalytic reduction rate (99.7 percent) of the catalyst CBC/N/Pd (1) on Cr (VI) because nitrogen is not introduced. Indicating that nitrogen doping is important to improve the catalytic performance of the catalyst. The catalytic reduction rate of CBC/N/Pd (2) to Cr (VI) is 87.3%, which is lower than the catalytic performance of CBC/N/Pd (1), and shows that the selection of a nitrogen precursor is very important, and the higher catalytic performance can be achieved by using diethylene triamino pentaacetic acid pentasodium salt as the nitrogen precursor. The catalytic reduction rate of Cr (VI) corresponding to CBC/N/Pd (3) is 93.1 percent, which is lower than the catalytic performance of CBC/N/Pd (1), and the nitrogen precursor can enable the prepared catalyst to have higher catalytic performance within a proper concentration range.
The above catalytic reduction experiments measured that the catalytic reduction rates of Cr (VI) for example 2, example 3, and example 4 were 99.5%, 99.9%, and 99.2%, respectively.
Example 6
The catalyst after the reaction of example 1 was filtered, washed three times with deionized water, and the experiment in example 5 was repeated. The recycling performance of the catalyst is shown in figure 4, and the nitrogen-doped carbon bacterial cellulose supported palladium catalyst can still keep good activity after being repeatedly used for eight times.
Claims (9)
1. The preparation method of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst is characterized by comprising the following steps of:
step 1, preparing a nitrogen-doped carbonized bacterial cellulose supported palladium catalyst precursor:
soaking bacterial cellulose in 3.2-5.2 wt.% of diethylene triamino pentaacetic acid pentasodium salt solution, completely soaking, soaking the bacterial cellulose soaked with the sodium salt in 0.2-0.5 mg/L palladium nitrate solution, completely soaking, and freeze-drying to obtain a nitrogen-doped carbonized bacterial cellulose supported palladium catalyst precursor;
and 2, placing the precursor of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst in a tubular muffle furnace, carrying out carbonization treatment at 800 ℃ under the protection of carbon dioxide atmosphere, and cooling to obtain the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst with a three-dimensional network structure.
2. The method according to claim 1, wherein in step 1, the mass-to-volume ratio of the bacterial cellulose to the solution of pentasodium diethylenetriaminopentaacetic acid is 0.05 to 0.1:100 to 200,g: and (mL).
3. The method according to claim 1, wherein in step 1, the volume ratio of the solution of pentasodium diethylenetriaminopentaacetic acid to the solution of palladium nitrate is 1: 2-2: 1.
4. the method according to claim 1, wherein the dipping time is 24 to 48 hours and the dipping temperature is 0 to 40 ℃ in the step 1.
5. The method according to claim 1, wherein the temperature increase rate of the carbonization in the step 2 is 1 to 4 ℃/min.
6. The method according to claim 1, wherein the carbonization time in step 2 is 1 to 3 hours.
7. The nitrogen-doped carbonized bacterial cellulose supported palladium catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The nitrogen-doped carbonized bacterial cellulose supported palladium catalyst as claimed in claim 7, wherein the nitrogen content in the catalyst is 2.3-4.1 wt%, the palladium content is 0.9-1.9 wt%, palladium nanoparticles are supported on the surface and in the three-dimensional grid of the nitrogen-doped carbonized bacterial cellulose, and the specific surface area is 413-560 m 2 The particle diameter of the palladium nano-particles is 8-22 nm.
9. The use of the nitrogen-doped carbonized bacterial cellulose supported palladium catalyst of claim 8 in the catalytic reduction of hexavalent chromium contaminants in water.
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