CN115108626B - Application of rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment - Google Patents

Application of rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment Download PDF

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CN115108626B
CN115108626B CN202211055413.0A CN202211055413A CN115108626B CN 115108626 B CN115108626 B CN 115108626B CN 202211055413 A CN202211055413 A CN 202211055413A CN 115108626 B CN115108626 B CN 115108626B
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rhodium
michael
iron oxyhydroxide
bacterial cellulose
catalytic material
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CN115108626A (en
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陈世良
黄嘉驰
黄亦军
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Qianjiang College of Hangzhou Normal University
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Qianjiang College of Hangzhou Normal University
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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses an application of a rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment. The catalytic material is obtained by loading rhodium and iron oxyhydroxide on a Mike alkene-bacterial cellulose composite material. The method utilizes the bacterial cellulose to fix the michael in situ, and solves the problem that a large number of active sites cannot be exposed due to the agglomeration of the surfaces of molecules of the iron oxyhydroxide. Meanwhile, the existence of the bacterial cellulose enables the recycling of the catalytic material to be more convenient. In addition, the invention utilizes michael and rhodium to obviously enhance the reactivity of the iron oxyhydroxide: the mecamirene has an enrichment effect on pollutant molecules, and is beneficial to the subsequent catalytic reaction; the unique structure of the michael can enable the michael to generate interaction with the iron oxyhydroxide, and the electron transfer in the catalytic reaction process is more convenient, thereby achieving the purpose of improving the reaction efficiency of the catalyst.

Description

Application of rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment
Technical Field
The invention belongs to the technical field of industrial wastewater treatment; in particular to application of a rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment.
Background
With the development of industry, the treatment of organic pollution such as reactive dyes, phenols, nitrites and the like in industrial wastewater becomes a problem to be solved; in the prior art, ferric oxyhydroxide is used as an organic matter degradation catalyst; however, iron oxyhydroxide has a problem of low catalytic activity because it is easy for the iron oxyhydroxide to undergo surface agglomeration of molecules.
Maikolene (MXene) is a new two-dimensional graphene-like carbide/nitride nano-layered material that has received extensive and continuous attention from researchers since its discovery in 2011 by professor Gogotsi and professor barsum of daresel university, usa. Compared with graphene with a single-atom structure, the Mekko graphene contains transition metal elements and carbon/nitrogen elements simultaneously, so that the stability is better; meanwhile, michael contains mixed valence bonds such as covalent bonds, ionic bonds, and metallic bonds, as compared to single C — C atom bonds of graphene. These differences make michael have a much richer tunable potential than graphene.
The special structure of the mecamirene ensures that the mecamirene has excellent mechanical property, surface hydrophilicity, conductivity, electrochemistry and other properties, and has obvious application value in the fields of enhanced composite materials, energy storage, hydrogen storage, adsorption, catalysis and the like. For example, michael is widely reported as a reinforcing phase for polymer materials such as polyethylene, polydimethylsiloxane, polyvinyl alcohol, and the like, and the mechanical properties of the polymer materials can be remarkably enhanced by adding a small amount of michael. In particular, mecamirene is an ideal carrier material for functional molecules due to its unique two-dimensional layered structure and large specific surface area. Researchers have successfully realized the immobilization of small molecules such as carbon nanotubes, titanium dioxide and cuprous oxide on michaelis alkene, and the obtained composite material can be used in the fields of photocatalysis, lithium ion batteries, super capacitors and the like.
It is important to note that the particular two-dimensional layered structure of michaelene gives it a strong tendency to pack, which significantly affects the properties of the material. Therefore, in order to fully exhibit the excellent properties of the michael, it is necessary to ensure good dispersibility. In addition, when the functional material based on meckene is used in the field of environmental purification and the like, the recycling performance is one of the factors that must be considered.
Disclosure of Invention
The invention aims to provide application of a novel catalytic material in treatment of industrial wastewater such as reactive dyes, phenols and nitrites and a preparation method of the catalytic material, aiming at solving the problems that the existing iron oxyhydroxide catalyst is complex in preparation process, not ideal in catalytic efficiency, difficult to recycle and the like.
In a first aspect, the invention provides an application of a rhodium-containing iron oxyhydroxide-loaded mecamirene catalytic material in wastewater treatment; the process is that oxidant and rhodium-containing iron oxyhydroxide loaded mechine catalytic material are added into the treated wastewater. The rhodium-containing iron oxyhydroxide loaded Mekko alkene catalytic material is obtained by sequentially loading iron oxyhydroxide and rhodium on a Mekko alkene-bacterial cellulose composite material. The loading of the iron oxyhydroxide on the michaelis-bacterial cellulose composite material is realized by immersing the michaelis-bacterial cellulose composite material into an acidic ferric iron salt solution for heating reaction.
Preferably, the industrial waste water contains several of reactive dyes (i.e., dyes containing reactive groups), phenols, and nitrites.
Preferably, the organic pollutant in the industrial wastewater is reactive red 2.
In a second aspect, the invention provides a rhodium-containing iron oxyhydroxide-loaded michael catalytic material, which is obtained by sequentially loading iron oxyhydroxide and rhodium on a michael-bacterial cellulose composite material. The loading of the iron oxyhydroxide on the michaelis-bacterial cellulose composite material is realized by immersing the michaelis-bacterial cellulose composite material into an acidic ferric iron salt solution for heating reaction.
Preferably, the michaelis-maiden-bacterial cellulose composite material is obtained by adding acetobacter into a bacterial cellulose culture solution containing michaelis and culturing.
Preferably, the ferric salt solution is ferric trichloride aqueous solution.
Preferably, the loading of rhodium on the michaelene-bacterial cellulose composite material is realized by adding the ferric hydroxide loaded michaelene catalytic material into a mixed solution of urea and rhodium salt.
In a third aspect, the invention provides a preparation method of the rhodium-containing iron oxyhydroxide-supported michael catalytic material, which comprises the following steps.
Step one, adding the michael dispersion liquid into a bacterial cellulose culture solution.
And step two, adding acetobacter into the mixed culture solution obtained in the step one, and culturing to obtain the Mike alkene-bacterial cellulose composite material.
And step three, preparing an iron trichloride aqueous solution.
And step four, immersing the mecamicene-bacterial cellulose composite material obtained in the step two into the ferric trichloride aqueous solution obtained in the step three, heating for reaction, and taking out the solid after the reaction is finished.
Step five, preparing the rhodium salt aqueous solution.
Step six, adding the rhodium salt aqueous solution obtained in the step five into the product obtained in the step four, heating for reaction, taking out the solid after the reaction is finished, and washing the solid with deionized water.
Preferably, in the first step, the concentration of the michael dispersion is 2.5mg/mL, and the diameter of the titanium carbide sheet is 2 to 5 μm. The bacterial cellulose culture solution contains glucose, peptone, yeast extract and disodium hydrogen phosphate; wherein the concentrations of glucose, peptone, yeast extract and disodium hydrogen phosphate are 2-10%, 0.2-1% and 0.02-0.1%, respectively.
Preferably, in the second step, the culture conditions are: the culture temperature is 30 ℃, and the culture time is 3-7 days.
Preferably, in the third step, the concentration of the ferric trichloride aqueous solution is 0.10mol/L, and the pH value of the ferric trichloride aqueous solution is adjusted to 2.5-3.5 by hydrochloric acid.
Preferably, in the fourth step, the temperature-rising reaction is carried out at a speed of 5 ℃/min from room temperature to 85 ℃, and then the isothermal reaction is carried out for 2-4h.
Preferably, in the fifth step, the rhodium salt aqueous solution is rhodium sulfate aqueous solution or rhodium nitrate aqueous solution, wherein the concentration of rhodium ions is 0.05mol/L; the solution contains urea with concentration 50-100 times of rhodium ion.
Preferably, in the sixth step, the temperature-raising reaction is carried out for 4-6h after raising the temperature of the solution to 90 ℃.
Compared with the prior art, the invention has the following beneficial effects.
1. The mecien is fixed in situ on the bacterial cellulose, so that the efficient dispersion of the mecien is conveniently realized, and meanwhile, the restacking among mecien molecules is avoided; in addition, the uniform loading of the iron oxyhydroxide is realized by utilizing the michael, and the problem that a large number of active sites cannot be exposed due to the agglomeration of the molecular surface of the iron oxyhydroxide, so that the catalytic activity is reduced is solved, thereby improving the treatment efficiency of the industrial wastewater. Meanwhile, the existence of the bacterial cellulose enables the recycling of the catalytic material to be more convenient.
2. The invention utilizes the mecamirene and rhodium to obviously enhance the reaction activity of the iron oxyhydroxide: firstly, the mecamirene has an enrichment effect on pollutant molecules, and is beneficial to the subsequent catalytic reaction; secondly, the unique structure (planar structure and hydroxyl group and other groups) of the mecamirene can interact with the iron oxyhydroxide, and the electron transfer in the catalytic reaction process is more convenient, so that the catalytic activity of the iron oxyhydroxide is obviously improved; finally, the rhodium atom is introduced into the catalytic system, so that the oxidation of reactants in the catalytic process is promoted, and the catalytic efficiency of the catalyst is further improved. In addition, the rhodium atom and the iron atom generate chemical interaction, and the catalytic activity of the iron oxyhydroxide is further improved.
3. According to the preparation method provided by the invention, the mecamicene is added into the culture solution, so that the uniform loading of the mecamicene on the bacterial cellulose is realized while the acetobacter xylinum generates the bacterial cellulose; the preparation process is simplified, and simultaneously uniform loading of the michael on the inside and the outside of the bacterial cellulose can be realized. The whole process does not need to use organic solvent and harsh experimental conditions, and has the advantages of simple preparation method, mild conditions, green process, low cost and the like. In addition, the catalytic material prepared by the invention has excellent recycling performance.
Drawings
FIG. 1 is a field emission scanning electron microscope image of the Mike alkene-bacterial cellulose composite material prepared by the present invention.
FIG. 2 is a scanning electron microscope image of a field emission scanning electron microscope of a rhodium-containing iron oxyhydroxide-supported michael catalytic material.
FIG. 3 is a graph comparing the adsorption effect of the present invention and other substances on a reactive red 2 dye solution.
FIG. 4 shows the present invention and other materials in H 2 O 2 The catalytic degradation effect of the active red 2 active dye solution is compared with that of an oxidant.
FIG. 5 is a diagram showing the results of the cyclic catalytic degradation performance test of the rhodium-containing iron oxyhydroxide-supported michael catalytic material on phenol solution.
Detailed Description
The technical solutions in the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a rhodium-containing iron oxyhydroxide loaded michael catalytic material comprises the following steps.
(1) Weighing 4.00g of glucose, 0.40g of peptone, 0.40g of yeast extract and 0.04g of disodium hydrogen phosphate, and dissolving in 50mL of deionized water to prepare the bacterial cellulose culture solution. 5mL of Mekkenmethylene dispersion with an initial concentration of 2.50mg/mL was added to the bacterial cellulose culture solution to obtain a Mekkenmethylene-containing bacterial cellulose mixed culture solution. The Mekkoene dispersion liquid is a product of titanium carbide dispersed in water, is purchased from Beijing Huaweiruike chemical Co., ltd, has the concentration of 2.5mg/mL, and has the diameter of a titanium carbide sheet of 2-5 μm. The bacterial cellulose culture solution contains glucose, peptone, yeast extract and disodium hydrogen phosphate, wherein the concentrations of the glucose, the peptone, the yeast extract and the disodium hydrogen phosphate are respectively 2-10%, 0.2-1% and 0.02-0.1%.
(2) Adding acetobacter xylinum into the mixed culture solution obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the mecien-bacterial cellulose composite material, wherein the content of the mecien is 12wt%.
(3) 20mL of ferric trichloride aqueous solution with the concentration of 0.10mol/L is prepared, and the pH value of the ferric trichloride aqueous solution is adjusted to 3 by hydrochloric acid.
(4) And (3) soaking the mececene-bacterial cellulose composite material obtained in the step (2) into the ferric trichloride aqueous solution obtained in the step (3), heating the solution from room temperature to 85 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 4 hours. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the iron oxyhydroxide loaded maikoene catalytic material.
(5) 5mL of an aqueous rhodium sulfate solution having a rhodium ion concentration of 0.005mol/L was prepared, and urea was added thereto so that the concentration of urea in the aqueous solution was 0.4mol/L, thereby obtaining a rhodium salt aqueous solution.
(6) Adding the rhodium salt aqueous solution obtained in the step (5) into the product obtained in the step (4), heating to 90 ℃, and reacting for 6h at the temperature. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the rhodium-containing iron oxyhydroxide loaded maikoene catalytic material. In the obtained rhodium-containing iron oxyhydroxide-supported Michael alkene catalytic material, the content of iron oxyhydroxide is 28wt%, and the content of rhodium is 0.95wt%.
Fig. 1 is a field emission scanning electron microscope image of the mecamicene-bacterial cellulose composite material obtained in step (2), and it can be observed that mecamicene has adhered to the surface of the bacterial cellulose fiber.
FIG. 2 is a scanning electron microscope image of field emission scanning of the rhodium-containing iron oxyhydroxide-loaded Michael alkene catalytic material obtained in step (6), and it can be observed that the surface of the bacterial cellulose becomes denser due to the loading of the iron oxyhydroxide and rhodium; and no significant particle packing was observed in fig. 2, indicating that iron oxyhydroxide and rhodium have good dispersibility on the mecamirene-bacterial cellulose composite.
The rhodium-containing iron oxyhydroxide supported michaelolene catalytic material prepared in the example is applied to the catalytic degradation treatment of an active red 2 active dye solution (CAS number: 17804-49-8); the experimental conditions were as follows: the addition amount of the rhodium-containing iron oxyhydroxide-supported michael catalytic material is 7.5 multiplied by 10 -4 g; the concentration of the active red 2 solution is 1 x 10 -4 mol/L, the volume is 20mL, and the pH value is 3; h 2 O 2 The concentration of the oxidizing agent is 1X 10 -3 mol/L; the reaction temperature was 40 ℃. After 45min reaction, the concentration of the active red 2 solution is reduced by 96.34 percent.
In the embodiment, the mecene is fixed in situ by using bacterial cellulose, so that efficient dispersion of the mecene is conveniently realized, meanwhile, restack among mecene molecules is avoided, and meanwhile, recycling of the mecene is facilitated. On this basis, in the embodiment, the iron oxyhydroxide catalyst is directly loaded on mecien in the process of synthesizing the iron oxyhydroxide catalyst, so that the problem that a large number of active sites cannot be exposed due to the surface agglomeration of molecules, and the catalytic activity is reduced is solved, and the excellent electron transfer performance of the mecien can be utilized, so that the electron transfer in the catalytic reaction process is more convenient, and the purpose of improving the catalytic activity is achieved; meanwhile, due to the existence of bacterial cellulose, the recycling of the iron oxyhydroxide catalyst is indirectly and conveniently realized. In addition, in the embodiment, rhodium atoms are introduced into the catalytic system, so that the oxidation of reactants in the catalytic process is promoted, and the catalytic efficiency of the catalyst is further improved. Specifically, the rhodium atom and the iron atom are bonded together through an oxygen atom to form a rhodium-oxygen-iron structure; the system helps in catalyzing oxidation reactions; therefore, the rhodium-containing iron oxyhydroxide-loaded mecien catalytic material prepared by the embodiment can be used for efficiently catalyzing and degrading industrial wastewater such as active dye, phenols and nitrite.
Comparative example 1
A preparation method, the comparative example is different from the examples in that: step (1) does not add michael dispersion liquid; the final product was tested to be free of iron and rhodium, indicating that the mecamirene is essential for the loading of rhodium and iron oxyhydroxide.
Comparative example 2
A preparation method, the comparative example is different from the examples in that: and (4) omitting the step (3) and the step (4), and finally preparing the rhodium-maikeene-bacterial cellulose ternary composite material.
Comparative example 3
A preparation method, the comparative example is different from the examples in that: and (5) and (6) are omitted, and finally the rhodium-free iron oxyhydroxide supported michael catalytic material can be prepared.
To demonstrate the adsorption effect of the rhodium-containing iron oxyhydroxide-supported michael catalytic material prepared in example 1 on organic pollutants, a comparative experiment was performed. The results of the experiment are shown in FIG. 3.
Experimental groups 1-1: adding a rhodium-containing iron oxyhydroxide supported michaelis alkene catalytic materialWith no addition of H 2 O 2 The other experimental conditions remained the same as those for the treatment of the reactive red 2 reactive dye solution in example 1. After 45min, the concentration of the active red 2 solution is reduced by 17.77%, which shows that the obtained rhodium-containing iron oxyhydroxide loaded michael catalytic material has good adsorption and enrichment effects on the active dye.
Control group 1-1: the same other experimental conditions are kept as in experimental group 1-1, and bacterial cellulose is added but H is not added 2 O 2 After 45min, the concentration of the active red 2 solution is reduced by 2.64 percent.
Control groups 1-2: the same conditions as those in experiment group 1-1 were maintained, mekkoene was added but H was not added 2 O 2 After 45min, the concentration of the active red 2 solution is reduced by 14.08 percent.
Control groups 1-3: keeping the same other experimental conditions as those in experimental group 1-1, adding mecamirene-bacterial cellulose composite material but not adding H 2 O 2 After 45min, the concentration of the active red 2 solution is reduced by 19.92 percent.
The results of comparing the experimental group 1-1 with the control group 1-3 show that the adsorption of the active red 2 is mainly provided by mecamirene, and the bacterial cellulose can efficiently disperse mecamirene, thereby improving the adsorption performance of the bacterial cellulose on active dye molecules.
To demonstrate the superiority of the catalytic degradation of the rhodium-containing iron oxyhydroxide-supported mecamirene catalytic material prepared in example 1, a comparative experiment was carried out. The results of the experiment are shown in FIG. 4.
Experimental group 2-1: the conditions for treating the reactive red 2 reactive dye solution as in example 1 remained the same.
Control group 2-1: addition of H only 2 O 2 (i.e., no rhodium-containing iron oxyhydroxide-loaded michael catalytic material was added), and other experimental conditions were kept the same as those in experimental group 2-1.
Control group 2-2: the rhodium-containing iron oxyhydroxide-loaded michael catalytic material is replaced by bacterial cellulose, and other experimental conditions are kept the same as those of the experimental group 2-1.
Control groups 2-3: the rhodium-containing iron oxyhydroxide-loaded mecienene catalytic material is replaced by mecienene, and other experimental conditions are kept the same as those of experimental group 2-1.
Control groups 2-4: the rhodium-containing iron oxyhydroxide-supported michael catalytic material was replaced with the michael-bacterial cellulose composite material prepared in example 2, and the other experimental conditions were kept the same as those in experimental group 2-1.
Control groups 2-5: the rhodium-containing iron oxyhydroxide loaded michael catalytic material is replaced by a rhodium-michael-bacterial cellulose ternary composite material, and other experimental conditions are kept the same as those of the experimental group 2-1.
Control groups 2-6: the rhodium-containing iron oxyhydroxide-supported michael catalytic material was replaced with iron oxyhydroxide, and other experimental conditions were kept the same as those of experimental group 2-1.
Control groups 2-7: the rhodium-containing iron oxyhydroxide-supported michael catalytic material was replaced with the iron oxyhydroxide-supported michael catalytic material of comparative example 3, and the other experimental conditions were kept the same as in experimental group 2-1.
As can be seen from FIG. 4, only H was added 2 O 2 There was little change in the concentration of the reactive dye solution, indicating H 2 O 2 Active red 2 cannot be oxidized by itself; the bacterial cellulose can only adsorb a small amount of active red 2 molecules, but can not catalyze H 2 O 2 Degrading the reactive dye; under defined experimental conditions, meconene + H 2 O 2 The reaction system reduces the concentration of the reactive dye solution by about 25%. Compared with the adsorption result of the mecamirene, the mecamirene has certain catalytic degradation capability on the reactive dye solution; the catalytic degradation activity of the mecamirene-bacterial cellulose composite material and the rhodium-mecamirene-bacterial cellulose composite material on the active dye solution is basically the same as that of mecamirene; under the same experimental conditions, the content of the iron oxyhydroxide (the dosage of the iron oxyhydroxide is the same as the content of the iron oxyhydroxide in the rhodium-containing iron oxyhydroxide-loaded michaelis alkene catalytic material) + H 2 O 2 The reaction system can reduce the concentration of the reactive dye solution by about 50 percent, which shows that the iron oxyhydroxide has good catalytic performance; in contrast, the iron oxyhydroxide-supported michaene catalytic material and the rhodium-containing iron oxyhydroxide-supported michaene catalytic material were able to reduce the concentration of the reactive dye solution by about 84% and 96%, respectively. From the above results canIt is known that the mecamirene has obvious enhancement effect on the catalytic activity of the iron oxyhydroxide, and the introduction of a small amount of rhodium can further improve the catalytic reaction efficiency of the catalytic material.
Example 2
A preparation method of a rhodium-containing iron oxyhydroxide loaded michaelis alkene catalytic material comprises the following steps.
(1) 4.00g of glucose, 0.40g of peptone, 0.40g of yeast extract and 0.04g of disodium hydrogen phosphate are weighed and dissolved in 50mL of deionized water to obtain a bacterial cellulose culture solution. 2.50mL of Mekkien dispersion with an initial concentration of 2.50mg/mL was added to the bacterial cellulose culture solution to obtain a Mekkien-containing bacterial cellulose mixed culture solution.
(2) Adding acetobacter xylinum into the mixed culture solution obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the mecien-bacterial cellulose composite material, wherein the content of the mecien is 6.05wt%.
(3) 20mL of ferric trichloride aqueous solution with the concentration of 0.10mol/L is prepared, and the pH value of the ferric trichloride aqueous solution is adjusted to 3 by hydrochloric acid.
(4) And (3) soaking the michaelidae alkene-bacterial cellulose composite material obtained in the step (2) into the ferric trichloride aqueous solution obtained in the step (3), heating the solution from room temperature to 85 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 4 hours. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the iron oxyhydroxide loaded maikoene catalytic material.
(5) 5mL of an aqueous rhodium sulfate solution having a rhodium ion concentration of 0.005mol/L was prepared, and urea was added so that the concentration of urea in the aqueous solution was 0.4mol/L.
(6) Adding the rhodium salt aqueous solution obtained in the step (5) into the product obtained in the step (4), heating to 90 ℃, and reacting for 6h at the temperature. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the rhodium-containing iron oxyhydroxide loaded maikoene catalytic material. In the obtained rhodium-containing iron oxyhydroxide-loaded michael catalytic material, the content of iron oxyhydroxide is 26.34wt%, and the content of rhodium is 0.89wt%.
Take 7.5X 10 -4 g the obtained rhodium-containing iron oxyhydroxide loaded Michael alkene catalystThe material is applied to the catalytic degradation treatment of phenol solution (CAS number: 108-95-2), and the experimental conditions are as follows: phenol solution concentration 1X 10 -4 mol/L, volume of solution 20mL 2 O 2 Oxidant concentration 1X 10 -3 mol/L, reaction temperature 50 ℃. After 30min reaction, the concentration of the phenol solution is reduced by 99.32%.
In order to examine the cyclic catalytic degradation performance of the obtained rhodium-containing iron oxyhydroxide supported michael catalytic material, the rhodium-containing iron oxyhydroxide supported michael catalytic material is taken out of a reaction solution, washed by ultrapure water and used for the catalytic degradation of a phenol solution again, and the experimental conditions are kept unchanged. As shown in FIG. 5, after 10 times of repeated use, the concentration of the phenol solution can still be reduced by 97.86% by the catalytic material, which shows that the obtained rhodium-containing iron oxyhydroxide-loaded michael catalytic material has excellent stability and cyclic catalytic degradation performance.
Example 3
A preparation method of a rhodium-containing iron oxyhydroxide loaded michaelis alkene catalytic material comprises the following steps.
(1) 4.00g of glucose, 0.40g of peptone, 0.40g of yeast extract and 0.04g of disodium hydrogen phosphate are weighed and dissolved in 50mL of deionized water to prepare a bacterial cellulose culture solution. 5mL of michael dispersion with an initial concentration of 2.50mg/mL was added to the bacterial cellulose culture solution to obtain a michael-containing bacterial cellulose mixed culture solution.
(2) Adding acetobacter xylinum into the mixed culture solution obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the mecien-bacterial cellulose composite material, wherein the content of the mecien is 12wt%.
(3) 10mL of ferric trichloride aqueous solution with the concentration of 0.10mol/L is prepared, and the pH value of the ferric trichloride aqueous solution is adjusted to 3 by hydrochloric acid.
(4) And (3) soaking the mececene-bacterial cellulose composite material obtained in the step (2) into the ferric trichloride aqueous solution obtained in the step (3), heating the solution from room temperature to 85 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 4 hours. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the iron oxyhydroxide loaded michael catalytic material.
(5) 2.50mL of rhodium sulfate aqueous solution with rhodium ion concentration of 0.005mol/L was prepared, and urea was added to make the concentration of urea in the aqueous solution 0.2mol/L.
(6) Adding the rhodium salt aqueous solution obtained in the step (5) into the product obtained in the step (4), heating to 90 ℃, and reacting for 6h at the temperature. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the rhodium-containing iron oxyhydroxide loaded maikoene catalytic material. In the obtained rhodium-containing iron oxyhydroxide-loaded michaelis catalytic material, the content of iron oxyhydroxide is 14.77wt%, and the content of rhodium is 0.47wt%.
Take 7.5X 10 -4 g, applying the obtained rhodium-containing iron oxyhydroxide loaded mecamirene catalytic material to the catalytic degradation treatment of sodium nitrite solution (CAS No. 7632-00-0), wherein the experimental conditions are as follows: sodium nitrite solution concentration 1X 10 - 3 mol/L, solution volume 50mL, H 2 O 2 Oxidant concentration 2.5X 10 -3 mol/L, reaction temperature 25 ℃. After 45min reaction, the concentration of the sodium nitrite solution is reduced by 99.81 percent.
Example 4
A preparation method of a rhodium-containing iron oxyhydroxide loaded michaelis alkene catalytic material comprises the following steps.
(1) Weighing 4.00g of glucose, 0.40g of peptone, 0.40g of yeast extract and 0.04g of disodium hydrogen phosphate, and dissolving in 50mL of deionized water to prepare the bacterial cellulose culture solution. 7.50mL of michael dispersion with initial concentration of 2.50mg/mL is added into the bacterial cellulose culture solution to obtain a bacterial cellulose mixed culture solution containing michael.
(2) Adding acetobacter xylinum into the mixed culture solution obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the michael-bacterial cellulose composite material, wherein the content of michael is 17.36wt%.
(3) 20mL of ferric trichloride aqueous solution with the concentration of 0.10mol/L is prepared, and the pH value of the ferric trichloride aqueous solution is adjusted to 3 by hydrochloric acid.
(4) And (3) soaking the mececene-bacterial cellulose composite material obtained in the step (2) into the ferric trichloride aqueous solution obtained in the step (3), heating the solution from room temperature to 85 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 4 hours. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the iron oxyhydroxide loaded maikoene catalytic material.
(5) 5mL of rhodium sulfate aqueous solution with rhodium ion concentration of 0.005mol/L was prepared, and urea was added to make the concentration of urea in the aqueous solution 0.4mol/L.
(6) Adding the rhodium salt aqueous solution obtained in the step (5) into the product obtained in the step (4), heating to 90 ℃, and reacting for 6h at the temperature. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the rhodium-containing iron oxyhydroxide loaded maikoene catalytic material. In the obtained rhodium-containing iron oxyhydroxide-loaded michaelis catalytic material, the content of iron oxyhydroxide is 27.89wt%, and the content of rhodium is 0.94wt%.
Take 7.5X 10 -4 And g, applying the rhodium-containing iron oxyhydroxide supported michael catalytic material to the catalytic degradation treatment of an active red 2 active dye solution, wherein the specific experimental conditions are the same as those described in the example 1. After 35min reaction, the concentration of the reactive dye solution is reduced to 95.96%. After 45min reaction, the concentration of the reactive dye solution is reduced to 99.67%.
Example 5
A preparation method of a rhodium-containing iron oxyhydroxide loaded michaelis alkene catalytic material comprises the following steps.
(1) Weighing 4.00g of glucose, 0.40g of peptone, 0.40g of yeast extract and 0.04g of disodium hydrogen phosphate, and dissolving in 50mL of deionized water to prepare the bacterial cellulose culture solution. 7.50mL of Mekkien dispersion with an initial concentration of 2.50mg/mL was added to the bacterial cellulose culture solution to obtain a Mekkien-containing bacterial cellulose mixed culture solution.
(2) Adding acetobacter xylinum into the mixed culture solution obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the michael-bacterial cellulose composite material, wherein the content of michael is 17.36wt%.
(3) 20mL of ferric trichloride aqueous solution with the concentration of 0.10mol/L is prepared, and the pH value of the ferric trichloride aqueous solution is adjusted to 3 by hydrochloric acid.
(4) And (3) soaking the mececene-bacterial cellulose composite material obtained in the step (2) into the ferric trichloride aqueous solution obtained in the step (3), heating the solution from room temperature to 85 ℃ at the speed of 5 ℃/min, and reacting at constant temperature for 4 hours. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the iron oxyhydroxide loaded maikoene catalytic material.
(5) 7.50mL of rhodium sulfate aqueous solution with rhodium ion concentration of 0.005mol/L was prepared, and urea was added to make the concentration of urea in the aqueous solution 0.4mol/L.
(6) Adding the rhodium salt aqueous solution obtained in the step (5) into the product obtained in the step (4), heating to 90 ℃, and reacting for 6h at the temperature. And (3) taking out the solid after the reaction is finished, and washing the solid with deionized water to obtain the rhodium-containing iron oxyhydroxide loaded michael catalytic material. In the obtained rhodium-containing iron oxyhydroxide-supported michaelis catalytic material, the content of iron oxyhydroxide is 26.38wt%, and the content of rhodium is 1.49wt%.
Take 7.5X 10 -4 And g, applying the rhodium-containing iron oxyhydroxide loaded michael catalytic material to catalytic degradation treatment of an active red 2 active dye solution, wherein the specific experimental conditions are the same as those described in the example 1. After 35min reaction, the concentration of the reactive dye solution is reduced to 98.59 percent. It can be seen from comparison of examples 1, 4 and 5 that the increase of the michael content and the rhodium content is beneficial to improving the catalytic reaction efficiency of the catalytic material.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents and modifications.

Claims (9)

1. The application of the rhodium-containing iron oxyhydroxide loaded michael catalytic material in wastewater treatment is characterized in that: adding an oxidant and a rhodium-containing iron oxyhydroxide-loaded michael catalytic material into the treated wastewater; the rhodium-containing iron oxyhydroxide loaded michael catalytic material is obtained by sequentially loading iron oxyhydroxide and rhodium on a michael-bacterial cellulose composite material; the Mekkaiene-bacterial cellulose composite material is obtained by adding acetobacter into a bacterial cellulose culture solution containing Mekkaiene and culturing; the loading of the iron oxyhydroxide on the michael-bacterial cellulose composite material is realized by immersing the michael-bacterial cellulose composite material into a ferric iron salt solution which is adjusted to be acidic and then heating and reacting.
2. Use according to claim 1, characterized in that: the treated wastewater contains several of reactive dyes, phenols and nitrites.
3. A rhodium-containing iron oxyhydroxide supported michael catalytic material is characterized in that: the material is obtained by sequentially loading ferric hydroxide and rhodium on a michaelis alkene-bacterial cellulose composite material; the Mexican alkene-bacterial cellulose composite material is obtained by adding acetobacter into a bacterial cellulose culture solution containing Mexican alkene and culturing; the loading of iron oxyhydroxide on the michael-bacterial cellulose composite material is realized by immersing the michael-bacterial cellulose composite material into an acidic ferric salt solution and heating.
4. The rhodium-containing iron oxyhydroxide-supported michael catalytic material as claimed in claim 3, wherein: the ferric iron salt solution is ferric trichloride aqueous solution; the loading of rhodium on the michael-bacterial cellulose composite material is realized by adding ferric hydroxide loaded michael catalytic material into a mixed solution of urea and rhodium salt.
5. A preparation method of a rhodium-containing iron oxyhydroxide loaded michael catalytic material is characterized by comprising the following steps: the method comprises the following steps:
step one, adding the michaelolidone dispersion liquid into a bacterial cellulose culture solution;
step two, adding acetobacter into the mixed culture solution obtained in the step one, and culturing to obtain a Mike alkene-bacterial cellulose composite material;
step three, preparing an iron trichloride aqueous solution;
step four, immersing the mecamicene-bacterial cellulose composite material obtained in the step two into the ferric trichloride aqueous solution obtained in the step three, heating for reaction, and taking out a solid after the reaction is finished;
step five, preparing rhodium salt aqueous solution;
and step six, adding the rhodium salt aqueous solution obtained in the step five into the product obtained in the step four, heating for reaction, taking out the solid after the reaction is finished, and washing the solid with deionized water.
6. The method for preparing the rhodium-containing iron oxyhydroxide supported mecamirene catalytic material according to claim 5, wherein the method comprises the following steps: in the first step, the concentration of the michael alkene dispersion liquid is 2.5mg/mL, and the diameter of a titanium carbide sheet is 2-5 μm; the bacterial cellulose culture solution contains glucose, peptone, yeast extract and disodium hydrogen phosphate; wherein the concentrations of glucose, peptone, yeast extract and disodium hydrogen phosphate are respectively 2-10%, 0.2-1% and 0.02-0.1%; in the second step, the culture conditions are as follows: the culture temperature is 30 ℃, and the culture time is 3-7 days.
7. The method for preparing the rhodium-containing iron oxyhydroxide supported mecamirene catalytic material according to claim 5, wherein the method comprises the following steps: in the third step, the concentration of the ferric trichloride aqueous solution is 0.10mol/L, and the pH value of the ferric trichloride aqueous solution is adjusted to 2.5-3.5 by hydrochloric acid.
8. The method for preparing the rhodium-containing iron oxyhydroxide supported mecamirene catalytic material according to claim 5, wherein the method comprises the following steps: in the fourth step, the temperature rise reaction is carried out at the speed of 5 ℃/min from room temperature to 85 ℃, and then the constant temperature reaction is carried out for 2-4 h; in the sixth step, the temperature-raising reaction is to raise the temperature of the solution to 90 ℃ and then carry out constant-temperature reaction for 4-6h.
9. The method for preparing the rhodium-containing iron oxyhydroxide supported mecamirene catalytic material according to claim 5, wherein the method comprises the following steps: in the fifth step, the rhodium salt aqueous solution is rhodium sulfate aqueous solution or rhodium nitrate aqueous solution, wherein the concentration of rhodium ions is 0.05mol/L; the solution contains urea with concentration 50-100 times of rhodium ion.
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