CN114345422B - Preparation method of active carbon fiber porous material with continuous gradient nanoparticle catalyst distribution - Google Patents
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Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a preparation method of an active carbon fiber porous material with continuous gradient nanoparticle catalyst distribution, which combines a method of hydrophilic treatment and capillary seepage of the material for electrodeposition, and the catalyst loading capacity is gradually and continuously reduced along a direction. And immersing the hydrophilic treated active carbon fiber porous material part into electrolyte for electrodeposition, wherein capillary seepage of the electrolyte under the action of capillary force can wet the surface of the active carbon fiber porous material from bottom to top under the action of capillary force due to the reinforcement of the wetting characteristic of the hydrophilic treated active carbon fiber porous material. The active carbon fiber porous material loaded by the nanoparticle catalyst in a gradient manner is prepared by adopting an electrodeposition method, can be used for improving the reaction uniformity of volatile organic compounds adsorbed by the active carbon fiber for ozone catalytic degradation, improves the utilization efficiency of the catalyst, and simultaneously saves the amount of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of an activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution.
Background
Volatile organic compounds (Volatile Organic Compounds, VOCs for short) refer to organic compounds with a boiling point of 50-250 ℃ and a saturated vapor pressure of more than 13.33Pa at room temperature, and are easy to evaporate into the atmosphere. The sources of VOCs are very wide, the types of the VOCs are also many, and compounds such as phenols, aldehydes, esters, aromatic hydrocarbons and the like belong to the VOCs, and the VOCs can be released in the processes of pharmacy, organic synthetic materials, color printing, industrial cleaning and the like. These gases are toxic and harmful and can cause greenhouse effect and photochemical smog, severely threatening the earth environment. At the same time, these VOCs are flammable and explosive and often have off-flavors and malodors that are also a great hazard to human health. Therefore, the improvement of the atmospheric environment is urgent to effectively treat the industrial VOCs.
The treatment of VOCs at home and abroad generally adopts a recovery technology and a destruction technology. The recovery technology mainly comprises adsorption, absorption, condensation, membrane separation and the like; the destruction technique mainly comprises a direct combustion method, an ozone catalytic oxidation method, a catalytic combustion method, a photocatalytic degradation method, a biological degradation method, a plasma technique and the like. The ozone catalytic oxidation technology is widely applied and is an oxidative degradation technology, ozone is taken as a strong oxidant, and VOCs are oxidized and degraded into harmless inorganic matters at a certain temperature. The active carbon fiber porous material has the characteristics of developed pores, strong adsorption capacity and the like, can effectively adsorb VOCs, and can achieve better effect of ozone catalytic degradation of the VOCs by being matched with a supported catalyst.
The modified activated carbon fiber porous material loaded with the catalyst particles has been developed by relevant researchers, and experimental researches show that the modified activated carbon fiber porous material can improve the catalytic oxidation reaction efficiency of VOCs components and ozone under the catalytic action of the catalyst in the process of desorbing VOCs, so that organic pollutants are degraded into harmless substances such as carbon dioxide, moisture and the like, and the synergistic process of the regeneration of the activated carbon fiber porous material and the harmless treatment of the VOCs is completed. However, the traditional method for modifying the active carbon fiber porous material by using the impregnation method can cause the problems of difficult control of catalyst loading, easy agglomeration of particles, poor catalytic durability and the like, and greatly limits the development potential of the modified active carbon fiber porous material. In addition, as the adsorption capacity, desorption rate and ozone concentration of VOCs at different positions are different in the regeneration process of the active carbon fiber porous material, the degradation reaction rates of the VOCs at different positions are different, so that the non-uniform loading of the catalyst inside the active carbon fiber porous material is beneficial to improving the utilization efficiency of the catalyst and promoting the uniformity of the internal degradation reaction.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an active carbon fiber porous material with continuous gradient nanoparticle catalyst distribution aiming at the defects of the prior art. On the basis of hydrophilic treatment of the active carbon fiber porous material, the invention realizes a new continuous gradient loading way of the nanoparticle catalyst in the active carbon fiber porous material by utilizing a method that the active carbon fiber porous material is partially immersed in an electrolytic cell for electrodeposition, and provides a basis for the efficient collaborative regeneration process of the active carbon fiber porous material in the future. The preparation method disclosed by the invention is simple, the steps are easy to operate, the preparation method is especially suitable for industrial mass production, and the prepared gradient catalyst-loaded active carbon fiber porous material has both catalytic performance and economy.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method combines the hydrophilic treatment of the material and the electrodeposition method by utilizing capillary seepage, the prepared active carbon fiber porous material unevenly loads the nanoparticle catalyst, and the catalyst loading amount is gradually and continuously reduced along one direction.
The preparation method of the active carbon fiber porous material with continuous gradient nanoparticle catalyst distribution comprises the following steps:
(1) Performing hydrophilic treatment on the activated carbon fiber porous material for later use;
(2) Preparing an electrolyte solution: preparing an electrolyte solution containing Mn, sn, ti or Ni ions for electrodeposition at a concentration of 0.1-1 mol/L;
(3) Loading a three-electrode system:
cutting the activated carbon fiber porous material subjected to hydrophilic treatment in the step (1), clamping the top end of the activated carbon fiber porous material by adopting an electrode clamp, immersing the activated carbon fiber porous material in the electrolyte solution in the step (2), and keeping the non-immersed part of the activated carbon fiber porous material with a proper length;
then, the saturated calomel electrode is used as a reference electrode, the platinum sheet is used as a counter electrode, and the activated carbon fiber porous material after hydrophilic treatment is used as a working electrode to form a three-electrode system;
(4) Electrodeposition of catalyst:
and (3) under the three-electrode system in the step (3), performing constant-voltage electrodeposition on the working electrode, cleaning the electrodeposited active carbon fiber porous material with ultrapure water, and drying to obtain the active carbon fiber porous material with continuous gradient metal oxide nanoparticle distribution.
In the step (1), the active carbon fiber porous material is at least one of active carbon cloth and active carbon felt.
In the step (1), the hydrophilic treatment of the activated carbon fiber porous material is at least one of heat treatment, acid treatment, alkali treatment, oxidant modification, nitrogen doping modification and biopolymer modification.
In the step (2), the electrolyte solution is one of acetate, chloride, nitrate or sulfate of Mn, sn, ti, ni;
in the step (3), the length ratio of the electrolyte solution immersed part to the non-immersed electrolyte solution part in the activated carbon fiber porous material is 1:10 to 1:1.
in the step (4), the drying temperature is 50-100 ℃ and the drying time is 6-12h; the metal oxide nano particles are MnO 2 、SnO 2 、TiO 2 Or NiO, the voltage ranges of the electrodeposition of the four metal oxide nanoparticles are respectively 0.5-1.0V, 0.2-0.7V, 0.9-1.4V and 0.9-1.2V, and the deposition time of the four metal oxide nanoparticles is 1-30min.
Compared with the prior art, the invention has the following advantages:
the invention provides a preparation method combining hydrophilic treatment and electro-deposition by capillary seepage, which develops a gradient supported nanoparticle catalyst of an active carbon fiber porous material. According to the invention, the hydrophilic treated active carbon fiber porous material is partially immersed in the electrolyte, and capillary seepage of the electrolyte under the action of capillary force can be enabled to soak the surface of the active carbon fiber porous material from bottom to top under the action of capillary force due to the reinforcing of the wetting characteristic of the hydrophilic treated active carbon fiber porous material, and then the active carbon fiber porous material loaded with the nanoparticle catalyst in a gradient manner is effectively prepared by adopting an electrodeposition method, so that the method can be used for improving the reaction uniformity of VOCs adsorbed by the ozone catalytic degradation active carbon fiber, improving the catalyst utilization efficiency and saving the amount of the required catalyst.
The invention aims to realize the combination of the catalytic performance and the economy of the VOCs catalyst with the lowest catalyst dosage.
Drawings
FIG. 1 is a schematic view of the loading and sampling positions of the activated carbon mat of example 1;
FIG. 2 is a schematic diagram of the oxidation-reduction potential of manganese ions under cyclic voltammetry;
FIG. 3 is a schematic representation of XRD characterization of an electrode after electrodeposition;
the morphology of the activated carbon mat samples at the different locations in FIG. 4 was characterized by 2cm (a), 6cm (b), 10cm (c), 14cm (d).
Detailed Description
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are required for the embodiments will be briefly described, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
The technical scheme of the present invention will be further explained below in connection with specific examples.
Example 1
The active carbon fiber porous material used in the embodiment is an active carbon felt, and the supported catalyst is manganese dioxide nano particles. The instruments and reagents used are: CHI760 electrochemical workstation (Shanghai Chen Hua instruments Co., ltd.), saturated calomel electrode (Tianjin Aida Heng Cheng technology development Co., ltd.), platinum sheet (Tianjin Aida Heng Cheng technology development Co., ltd.), X-ray diffractometer (Bruker, germany), JSM-7800 scanning electron microscope (Japanese Hitachi Co.). Mn (CH) 3 COO) 2 (Chuandong chemical reagent plant), na 2 SO 4 (Chuandong chemical reagent plant), CH 3 COONH 4 Absolute ethyl alcohol (Chuandong chemical engineering reagent factory), all the above reagents are analytically pure.
The preparation method of the active carbon fiber porous material with continuous gradient nanoparticle catalyst distribution comprises the following steps:
(1) Hydrophilic treatment of the activated carbon felt: the activated carbon felt was ultrasonically cleaned in absolute ethanol for 10 minutes and with deionized water and dried at 70 ℃ for 6 hours. The activated carbon felt was placed in a muffle furnace and heat treated in an air atmosphere at 450 ℃ for 120min. And obtaining the activated carbon felt after hydrophilic treatment.
(2) Preparing an electrolyte solution: the electrolyte volume is 100ml, and the components comprise: 0.1mol/LMn (CH) 3 COO) 2 ，0.1mol/L Na 2 SO 4 ，0.1mol/L CH 3 COONH 4 。
(3) Loading a three-electrode system: a piece of hydrophilic activated carbon felt with the length of 15cm is prepared, the top end (approximately within one centimeter) of the activated carbon felt is clamped by an electrode clamp, and a working surface with the length of about 14 centimeters is reserved for electrodeposition treatment. Immersing 2cm of the bottom of the activated carbon felt in the electrolyte solution in the step (1). The loading position of the activated carbon felt is shown in figure 1. The saturated calomel electrode is used as a reference electrode, the platinum sheet is used as a counter electrode, and the activated carbon felt after hydrophilic treatment is used as a working electrode.
(4) Electrodeposition of catalyst: the cyclic voltammetry test is firstly carried out on the activated carbon felt under a three-electrode system, the high potential is set to be 1.0V, the low potential is set to be-0.2V, the scanning speed is set to be 0.01V/S, and the number of turns is set to be 5. The deposition potential of manganese dioxide was determined from the CV curve obtained from the test. And performing constant voltage electrodeposition on the electrode under a three-electrode system, wherein the voltage value is set to be 0.6V, and the deposition time is set to be 10min. And (3) cleaning the electrodeposited activated carbon felt with ultrapure water for three times, and drying at 70 ℃ for 6 hours to obtain the activated carbon felt with continuous gradient manganese dioxide nanoparticle distribution.
The electrochemical deposition method has the advantages of simplicity, reliability, accuracy, strong universality, low cost and the like, and has obvious effect in the aspect of changing the structure and electrochemical performance of the electrode material. The deposition parameters such as solution composition, temperature, anode overpotential and the like can influence the morphology of the active carbon felt surface sediment. The nucleation of manganese dioxide is controlled by controlling the deposition parameters, so that the catalytic activity of the activated carbon felt is improved.
The original activated carbon felt was subjected to cyclic voltammetry under a three electrode system, and the results are shown in fig. 2. The deposition potential of manganese dioxide was determined to be 0.6V with reference to the redox reaction potential of the different valence states of manganese ions. XRD characterization results of the deposited activated carbon felt are shown in figure 3. The peaks appearing at 42.5 °,54.8 °,67.3 ° in the spectrum by comparison with the standard card correspond to the crystal planes of nucleation of manganese dioxide, which indicates that corresponding manganese dioxide is formed on the surface of the activated carbon felt after the electrodeposition is completed.
Four different activated carbon felt samples were taken at different locations (2 cm, 6cm, 10cm, 14 cm) against the activated carbon felt standard in fig. 1 for morphology characterization. As a result, as shown in fig. 4, the activated carbon felt at different locations exhibited different degrees of electrodeposition of manganese dioxide. The wettability of the activated carbon felt after hydrophilic treatment is improved, and the electrolyte can completely wet the surface of the activated carbon felt under the action of capillary force. In the electro-deposition process, the electrolyte of the activated carbon felt near the electrolyte pool is fully supplemented, and the deposition amount of manganese dioxide on the surface is obviously increased. In the part of the activated carbon felt far away from the electrolyte liquid pool, electrolyte can slowly reach the part in a long capillary seepage mode, so that electrolyte for deposition is slowly supplemented, and only trace manganese dioxide deposition is observed. So the deposition amount of the surface of the activated carbon felt near the electrolyte is obviously increased, especially the agglomeration phenomenon of manganese dioxide is aggravated at the position of 2cm, and the surface of the activated carbon felt is surrounded by a thicker manganese dioxide shell layer. At a position far from the liquid surface, such as 14cm, only a trace amount of manganese dioxide deposition is observed, and non-uniform loading of manganese dioxide nanoparticles is achieved. Therefore, the hydrophilic treatment and the capillary percolation electro-deposition method are combined to effectively prepare the active carbon fiber porous material loaded by the nanoparticle catalyst in a gradient way, so that the method can be used for improving the reaction uniformity of the ozone catalytic degradation of VOCs adsorbed by the active carbon fiber and improving the utilization efficiency of the catalyst.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the present invention still fall within the scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution is characterized by comprising the following steps:
(1) Performing hydrophilic treatment on the active carbon fiber porous material for later use;
the hydrophilic treatment is at least one of heat treatment, acid treatment, alkali treatment, oxidant modification, nitrogen doping modification and biopolymer modification;
(2) Preparing an electrolyte solution containing Mn, sn, ti or Ni ions for electrodeposition at a concentration of 0.1-1 mol/L;
(3) Loading a three-electrode system:
cutting the activated carbon fiber porous material subjected to hydrophilic treatment in the step (1), clamping the top end of the activated carbon fiber porous material by adopting an electrode clamp, immersing the activated carbon fiber porous material in the electrolyte solution in the step (2), and keeping the non-immersed part of the activated carbon fiber porous material with a proper length, wherein the length ratio of the part of the activated carbon fiber porous material immersed in the electrolyte solution to the part of the non-immersed electrolyte solution is 1:10 to 1:1, a step of;
then, the saturated calomel electrode is used as a reference electrode, the platinum sheet is used as a counter electrode, and the activated carbon fiber porous material after hydrophilic treatment is used as a working electrode to form a three-electrode system;
(4) Electrodeposition of catalyst:
and (3) under the three-electrode system in the step (3), performing constant-voltage electrodeposition on the working electrode, cleaning the electrodeposited active carbon fiber porous material with ultrapure water, and drying to obtain the active carbon fiber porous material with continuous gradient metal oxide nanoparticle distribution.
2. The method according to claim 1, wherein in the step (1), the activated carbon fiber porous material is at least one of activated carbon cloth and activated carbon felt.
3. The method of claim 1, wherein in step (2), the electrolyte solution is one of acetate, chloride, nitrate or sulfate of Mn, sn, ti, ni.
4. The method according to claim 1, wherein in the step (4), the drying temperature is 50 to 100 ℃ and the drying time is 6 to 12 hours.
5. The method according to claim 1, wherein in the step (4), the metal oxide nanoparticles are MnO 2 、SnO 2 、TiO 2 Or one of NiO, the voltage ranges of electrodeposition of the four metal oxide nanoparticles are respectively 0.5-1.0V, 0.2-0.7V, 0.9-1.4V and 0.9-1.2V, and the deposition time of the four metal oxide nanoparticles is 1-30min.
6. An activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution, which is characterized in that the activated carbon fiber porous material is prepared by the preparation method of any one of claims 1 to 5, the nanoparticle catalyst is unevenly loaded by the activated carbon fiber porous material, and the catalyst loading is gradually and continuously reduced along one direction.
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| US8211593B2 (en) * | 2003-09-08 | 2012-07-03 | Intematix Corporation | Low platinum fuel cells, catalysts, and method for preparing the same |
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