CN114345422A - Preparation method of activated 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 activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution, which combines a material hydrophilicity treatment and capillary seepage flow to carry out electrodeposition, wherein a nanoparticle catalyst is loaded in a non-uniform manner, and the loading capacity of the catalyst is gradually and continuously reduced along one direction. The activated carbon fiber porous material after hydrophilic treatment is partially immersed into electrolyte for electrodeposition, and due to the enhancement of the wetting characteristic of the activated carbon fiber porous material after hydrophilic treatment, the capillary seepage of the electrolyte can wet the surface of the activated carbon fiber porous material from bottom to top from the liquid level of the electrolyte under the action of capillary force. The active carbon fiber porous material loaded with the nano-particle catalyst in a gradient manner is prepared by an electrodeposition method, and can be used for improving the reaction uniformity of volatile organic compounds adsorbed by ozone catalytic degradation active carbon fibers, improving the utilization efficiency of the catalyst and saving the amount of the required 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 (VOCs) are Organic Compounds that have a boiling point of 50-250 deg.C, a saturated vapor pressure of greater than 13.33Pa at room temperature, and are readily evaporated into the atmosphere. The sources of VOCs are very wide and various, compounds such as phenols, aldehydes, esters and aromatic hydrocarbons belong to VOCs, and VOCs are 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, seriously threatening the global environment. Meanwhile, the VOCs are flammable and explosive, often have peculiar smell and stink, and are also very harmful to human health. Therefore, the method effectively treats the industrial VOCs and improves the atmospheric environment.
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 destroying technology mainly comprises a direct combustion method, an ozone catalytic oxidation method, a catalytic combustion method, a photocatalytic degradation method, a biodegradation method, a plasma technology and the like. The catalytic ozonation technology is widely applied to oxidative degradation, and takes ozone as a strong oxidant to oxidize and degrade VOCs into harmless inorganic matters at a certain temperature. The activated carbon fiber porous material has the characteristics of developed pores, strong adsorption capacity and the like, can effectively adsorb VOCs, and can achieve a better effect of catalyzing and degrading the VOCs by ozone by matching with a loaded catalyst.
Related research researchers have developed modified activated carbon fiber porous materials loaded with catalyst particles, and experimental studies have found that the modified activated carbon fiber porous materials can improve the catalytic oxidation reaction efficiency of VOCs components and ozone under the catalytic action of a catalyst in the process of desorbing VOCs to realize regeneration, so that organic pollutants are degraded into carbon dioxide, moisture and other harmless substances, and the synergistic process of activated carbon fiber porous material regeneration and VOCs harmless treatment is completed. However, the traditional method for modifying the porous material of the activated carbon fiber by using the impregnation method causes the problems of difficult control of the loading capacity of the catalyst, easy agglomeration of particles, poor catalytic durability and the like, and greatly limits the development potential of the modified porous material of the activated carbon fiber. In addition, as the adsorption quantity and desorption rate of VOCs at different positions and the ozone concentration are different in the regeneration process of the activated carbon fiber porous material, the degradation reaction rates of VOCs at different positions are different, so that the realization of the non-uniform loading of the catalyst in the activated 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 technical problem to be solved by the invention is to provide a preparation method of an activated 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 activated carbon fiber porous material, the method realizes a new way of continuously and gradiently loading the nanoparticle catalyst in the activated carbon fiber porous material by using a method of immersing the activated carbon fiber porous material into an electrolytic cell for electrodeposition, and provides a foundation for the efficient collaborative regeneration process of the activated carbon fiber porous material in the future. The preparation method is simple, the steps are easy to operate, the method is particularly suitable for industrial large-scale production, and the prepared activated carbon fiber porous material of the gradient supported catalyst has both catalytic performance and economical efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that: the preparation method combines the hydrophilic treatment of materials and a method for carrying out electrodeposition by utilizing capillary seepage flow, the prepared activated carbon fiber porous material is non-uniformly loaded with the nanoparticle catalyst, and the loading capacity of the catalyst is gradually and continuously reduced along one direction.
A preparation method of an activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution comprises the following steps:
(1) carrying out hydrophilic treatment on the activated carbon fiber porous material for later use;
(2) preparing an electrolyte solution: preparing electrolyte solution containing Mn, Sn, Ti or Ni ions for electrodeposition with the 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 using an electrode clamp, and soaking part of the activated carbon fiber porous material in the electrolyte solution in the step (2) to keep the non-soaked part of the activated carbon fiber porous material with a proper length;
then, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the activated carbon fiber porous material subjected to hydrophilic treatment is used as a working electrode to form a three-electrode system;
(4) electro-deposition of the catalyst:
and (4) carrying out constant-pressure electrodeposition on the working electrode under the three-electrode system in the step (3), cleaning the electrodeposited activated carbon fiber porous material with ultrapure water, and drying to obtain the activated carbon fiber porous material with continuous gradient metal oxide nanoparticle distribution.
In the step (1), the activated carbon fiber porous material is at least one of activated carbon cloth and activated 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 and Ni;
in the step (3), the length ratio of the part, which is immersed in the electrolyte solution, of the activated carbon fiber porous material to the part, which is not immersed in the electrolyte solution, is 1: 10-1: 1.
in the step (4), the drying temperature is 50-100 ℃, and the drying time is 6-12 h; the metal oxide nanoparticles are MnO2、SnO2、TiO2Or NiO, the voltage ranges 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 for the four metal oxide nanoparticles is 1-30 min.
Compared with the prior art, the invention has the following advantages:
the invention provides a preparation method for carrying out electrodeposition by combining hydrophilic treatment and capillary seepage, and develops a gradient loaded nanoparticle catalyst of an activated carbon fiber porous material. The activated carbon fiber porous material after hydrophilic treatment is partially immersed into the electrolyte, and due to the enhancement of the wetting property of the activated carbon fiber porous material after hydrophilic treatment, the capillary seepage of the electrolyte can wet the surface of the activated carbon fiber porous material from bottom to top from the liquid level of the electrolyte under the action of capillary force, and then the activated carbon fiber porous material loaded with the nanoparticle catalyst in a gradient manner is effectively prepared by adopting an electrodeposition method, so that the activated carbon fiber porous material can be used for improving the reaction uniformity of VOCs adsorbed by the activated carbon fiber through catalytic degradation by ozone, improving the utilization efficiency of the catalyst and saving the amount of the required catalyst.
The invention aims to achieve the combination of the catalytic performance and the economical efficiency of the VOCs catalyst with the lowest catalyst dosage.
Drawings
FIG. 1 is a schematic view of the activated carbon mat loading and sampling position in example 1;
FIG. 2 is a graph showing the oxidation-reduction potential of manganese ions under cyclic voltammetry;
FIG. 3 is a schematic representation of XRD characterization of the electrode after electrodeposition;
FIG. 4 is a graph showing the morphology of activated carbon mat samples at different positions, 2cm (a),6cm (b),10cm (c), and 14cm (d).
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the drawings required to be used in the embodiments will be briefly described below, and it should be 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 solution of the present invention will be further explained with reference to specific examples.
Example 1
The activated carbon fiber porous material used in this example was activated carbon felt, and the supported catalyst was manganese dioxide nanoparticles. The instruments and reagents used were: a CHI760 type electrochemical workstation (shanghai chenhua instruments ltd), a saturated calomel electrode (tianjin aida cheng shi tech. development ltd), a platinum sheet (tianjin aida heng cheng shi tech. development ltd), an X-ray diffractometer (Bruker, germany), a JSM-7800 type scanning electron microscope (hitachi). Mn (CH)3COO)2(Chundong chemical reagent works), Na2SO4(Chuandong chemical reagent works), CH3COONH4(Chuandong chemical reagent factory), absolute ethyl alcohol (Chuandong chemical reagent factory), and the above reagents are analytically pure.
A preparation method of an activated 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 cleaned 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 120 min. And obtaining the activated carbon felt after hydrophilic treatment.
(2) Preparing an electrolyte solution: the electrolyte volume is 100ml, and the composition comprises the following components: 0.1mol/LMn (CH)3COO)2，0.1mol/L Na2SO4，0.1mol/L CH3COONH4。
(3) Loading a three-electrode system: a15 cm long activated carbon felt after hydrophilic treatment is prepared, the top end (within about 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. And (3) soaking the bottom 2cm of the activated carbon felt in the electrolyte solution in the step (1). The activated carbon mat is loaded in the position 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) Electro-deposition of the catalyst: firstly, performing cyclic voltammetry on the activated carbon felt under a three-electrode system, setting the high potential to be 1.0V, the low potential to be-0.2V, the scanning speed to be 0.01V/S and the number of turns to be 5. And determining the deposition potential of the manganese dioxide according to the CV curve obtained by the test. And carrying out constant-voltage electrodeposition on the electrodes in a three-electrode system, wherein the voltage value is set to be 0.6V, and the deposition time is set to be 10 min. And 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 on changing the structure and the electrochemical performance of the electrode material. The deposition parameters such as solution composition, temperature, anode overpotential, etc. can affect the surface deposit morphology of the activated carbon felt. The nucleation of manganese dioxide is controlled by controlling the deposition parameters, thereby improving the catalytic activity of the activated carbon felt.
Cyclic voltammetry tests were performed on the original activated carbon felt 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 manganese ion in its different valence states. The XRD characterization results of the deposited activated carbon felt are shown in fig. 3. By comparing peaks appearing at 42.5 °, 54.8 °, and 67.3 ° with those of the standard card, the crystal planes of the manganese dioxide nuclei are aligned, which indicates that corresponding manganese dioxide is generated on the surface of the activated carbon felt after the electrodeposition is finished.
Four different samples of activated carbon felt were taken at different positions (2cm, 6cm, 10cm, 14cm) with respect to the activated carbon felt reference in fig. 1 for topographical characterization. As a result, as shown in fig. 4, the activated carbon felt at different positions showed different degrees of electrodeposition of manganese dioxide. The wetting ability 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 process of electrodeposition, the electrolyte of the activated carbon felt close to the electrolyte liquid pool is fully supplemented, and the deposition amount of manganese dioxide on the surface is obviously increased. And in the part of the activated carbon felt far away from the electrolyte liquid pool, the electrolyte can slowly reach by a long capillary seepage mode, so that the electrolyte for deposition is slowly supplemented, and only trace manganese dioxide deposition is observed. Therefore, the deposition amount of the surface of the activated carbon felt close to the electrolyte is obviously increased, particularly the manganese dioxide agglomeration phenomenon is intensified 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, for example, 14cm, only a slight amount of manganese dioxide deposition was observed, and the non-uniform loading of manganese dioxide nanoparticles was achieved. Therefore, the active carbon fiber porous material loaded with the nano-particle catalyst in a gradient manner can be effectively prepared by combining hydrophilic treatment and the capillary infiltration 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 and improving the utilization efficiency of the catalyst.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the principles of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of an activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution is characterized by comprising the following steps:
(1) carrying out hydrophilic treatment on the activated carbon fiber porous material for later use;
(2) preparing electrolyte solution containing Mn, Sn, Ti or Ni ions for electrodeposition with the 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 using an electrode clamp, and soaking part of the activated carbon fiber porous material in the electrolyte solution in the step (2) to keep the non-soaked part of the activated carbon fiber porous material with a proper length;
then, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the activated carbon fiber porous material subjected to hydrophilic treatment is used as a working electrode to form a three-electrode system;
(4) electro-deposition of the catalyst:
and (4) carrying out constant-pressure electrodeposition on the working electrode under the three-electrode system in the step (3), cleaning the electrodeposited activated carbon fiber porous material with ultrapure water, and drying to obtain the activated carbon fiber porous material with continuous gradient metal oxide nanoparticle distribution.
2. The preparation 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 preparation method according to claim 1, wherein 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.
4. The method according to claim 1, wherein in the step (2), the electrolyte solution is one of acetate, chloride, nitrate or sulfate of Mn, Sn, Ti, Ni.
5. The production method according to claim 1, wherein in the step (3), the length ratio of the portion of the activated carbon fiber porous material immersed in the electrolyte solution to the portion not immersed in the electrolyte solution is 1: 10-1: 1.
6. 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.
7. The production method according to claim 1, wherein in the step (4), the metal oxide nanoparticles are MnO2、SnO2、TiO2Or NiO, the voltage ranges of the four metal oxide nano-particles are respectively 0.5-1.0V, 0.2-0.7V, 0.9-1.4V and 0.9-1.2V, and the four metal oxide nano-particles are depositedThe time is 1-30 min.
8. An activated carbon fiber porous material with continuous gradient nanoparticle catalyst distribution is characterized by being prepared by the preparation method of any one of claims 1 to 7, wherein the activated carbon fiber porous material is loaded with the nanoparticle catalyst in a non-uniform manner, and the loading amount of the catalyst is gradually and continuously reduced along one direction.
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