CN114988534A - Cresol wastewater treatment method and composite catalytic electrode used in method - Google Patents
Cresol wastewater treatment method and composite catalytic electrode used in method Download PDFInfo
- Publication number
- CN114988534A CN114988534A CN202210851213.XA CN202210851213A CN114988534A CN 114988534 A CN114988534 A CN 114988534A CN 202210851213 A CN202210851213 A CN 202210851213A CN 114988534 A CN114988534 A CN 114988534A
- Authority
- CN
- China
- Prior art keywords
- metal
- ruthenium
- catalytic electrode
- cresol
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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 a cresol wastewater treatment method and a composite catalytic electrode used by the method. Cresol in the wastewater is converted into methylcyclohexanol by an electrocatalysis mode and is recycled; the cathode adopted in the electrocatalysis process is a nano-cellulose composite catalytic electrode which simultaneously loads metal phthalocyanine and metal ruthenium. Meanwhile, the nano-cellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium is obtained by depositing the metal phthalocyanine and the metal ruthenium on the nano-cellulose composite membrane. The nano-cellulose composite membrane is a nano-cellulose-graphene binary composite material. The invention can realize the electrocatalytic reduction of the cresol industrial wastewater, prepare and obtain the methylcyclohexanol, and solve the problems of complicated steps and the like of the existing industrial methylcyclohexanol preparation method. In addition, the metal phthalocyanine and the metal ruthenium in the composite catalytic electrode can generate obvious catalytic activity synergistic enhancement effect, so that the treatment efficiency of cresol wastewater and the synthesis rate of methylcyclohexanol are improved.
Description
Technical Field
The invention belongs to the technical field of industrial organic wastewater treatment; in particular to a cresol wastewater treatment method and a nanocellulose composite catalytic electrode which simultaneously loads metal phthalocyanine and metal ruthenium.
Background
Cresol wastewater is organic wastewater formed in industrial production of common petroleum, coal tar, petrochemical products, resin, paint and the like, and the direct discharge of the cresol wastewater causes serious harm to the environment and even human health. The prior cresol wastewater treatment method mainly comprises a physical method (such as an adsorption method, a membrane extraction method and the like), a chemical method (such as an ozone oxidation method, an advanced oxidation technology and the like) and a biological method (such as an activated sludge method, an enzyme catalysis method and the like). The physical method has the problems of unstable operation, high adsorbent regeneration cost, suitability for low-concentration wastewater and the like; the chemical method has the advantages that the cost of chemical reagents used is high, and the effect is influenced by factors such as the pH value of water, impurities and the like; the biological method has high requirements on the operation management of high-concentration wastewater, and the effluent quality and sanitary conditions are poor and are greatly limited by climatic conditions.
Methylcyclohexanol is an organic solvent commonly used in industrial production and an important organic intermediate in chemical production processes, and is widely used as a solvent for rubber, resins, cellulose derivatives, oil wax and the like, and is used as an essential base material in the synthesis processes of organic fine chemicals, medicines, perfumes and the like. In addition, the methyl cyclohexanol may be used as material for nitro lacquer, rubber compounding agent, fiber detergent, antioxidant for lubricating oil, pesticide, special soap, etc.
At present, the industrial preparation of methylcyclohexanol mainly uses toluene as raw material, and is prepared by two different ways: (1) after sulfonation, toluene is co-melted with sodium hydroxide to obtain sodium phenolate, and then the sodium phenolate is acidified and hydrogenated to obtain a final product; (2) toluene and propylene are catalyzed by aluminum trichloride to obtain isopropyltoluene, cresol is obtained through oxidation and acidification, and a final product is obtained through hydrogenation reaction. The methods have the disadvantages of complicated preparation steps, harsh synthesis process conditions, large amount of acid and alkali required in the production process, unsatisfactory economy and easy environmental pollution.
In view of the problems of the existing method, if the synthesis method can be designed scientifically, the production process is shortened, the operation steps are simplified, a new method is provided for the industrial production of the methylcyclohexanol while the cresol wastewater is treated, and the method has important values in the aspects of environment and economy.
Disclosure of Invention
The invention aims to solve the problems that the existing production method of methylcyclohexanol is complex in preparation steps, harsh in synthesis process conditions, large amount of acid and alkali are needed in the production process, the economy is not ideal enough, and environmental pollution is easily caused, and the like, and provides a method for treating cresol wastewater.
In a first aspect, the invention provides a cresol wastewater treatment method, which converts cresol in wastewater into methylcyclohexanol for recycling in an electrocatalysis mode; the cathode adopted in the electrocatalysis process is a nano-cellulose composite catalytic electrode which simultaneously loads metal phthalocyanine and metal ruthenium. Meanwhile, the nano-cellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium is obtained by depositing the metal phthalocyanine and the metal ruthenium on the nano-cellulose composite membrane. The nano-cellulose composite membrane is a nano-cellulose-graphene binary composite material.
Preferably, the anode used in the electrocatalytic process is platinum metal.
Preferably, the current magnitude in the electrocatalysis process is 100 mA-200 mA.
Preferably, the magnitude of the current in the electrocatalytic process is 150 mA.
Preferably, in the nanocellulose composite catalytic electrode simultaneously loading the metal phthalocyanine and the metal ruthenium, the mass ratio of the metal phthalocyanine to the metal ruthenium is 10: 1-1: 1.
In a second aspect, the invention provides a nanocellulose composite catalytic electrode simultaneously loaded with metal phthalocyanine and metal ruthenium; the metal phthalocyanine and the metal ruthenium are deposited on the nano-cellulose composite membrane to obtain the nano-cellulose composite membrane. The nano-cellulose composite membrane is a nano-cellulose-graphene binary composite material. The graphene content in the nano-cellulose composite membrane is 5 wt% -30 wt%. In the composite catalytic electrode, the mass ratio of metal phthalocyanine to metal ruthenium is 10: 1-1: 1; the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium is used for treating the cresol wastewater through electrocatalysis.
Preferably, the nanocellulose composite catalytic electrode simultaneously loaded with metal phthalocyanine and metal ruthenium is obtained by placing the nanocellulose-graphene oxide binary composite material in a mixed solution of metal phthalocyanine and ruthenium ions and then carrying out reduction treatment. The conductivity of the composite catalytic electrode is 2500S/m-30000S/m.
Preferably, in the mixed solution of sulfonated cobalt phthalocyanine and ruthenium ions, the ruthenium ions are obtained by ionizing ruthenium trichloride, the mass concentration of the sulfonated cobalt phthalocyanine is 0.1g/mL, and the mass concentration of the ruthenium trichloride is 0.04 g/mL.
Preferably, the nanocellulose-graphene binary composite material is obtained by culturing acetobacter in a mixed culture medium containing graphene oxide and performing reduction treatment.
Preferably, the mixed culture medium containing graphene oxide is a mixed solution of graphene oxide, glucose, peptone, yeast extract, disodium hydrogen phosphate and ethanol. Wherein, the mass concentrations of the glucose, the peptone, the yeast extract, the disodium hydrogen phosphate and the ethanol in the mixed solution are respectively 2 to 12 percent, 0.2 to 1 percent, 0.02 to 0.1 percent and 0.02 to 0.1 percent; the mass concentration of the graphene oxide in the mixed solution is 0.05-4%.
Preferably, the Acetobacter is one or more of Acetobacter xylinum, Acetobacter Gluconacetobacter intermedius and Acetobacter Hansenii.
Preferably, the culture conditions are as follows: the culture temperature is 30 ℃, and the culture time is 3-7 d.
Preferably, the metal phthalocyanine is sulfonated cobalt phthalocyanine; the ruthenium ions are obtained by dissolving ruthenium trichloride in water and then ionizing; in the mixed solution of the metal phthalocyanine and the ruthenium ions, the concentrations of the metal phthalocyanine and the ruthenium ions are respectively 1-10% and 0.2-2%.
Preferably, the reducing agent used in the reduction treatment is sodium borohydride.
Preferably, the adding amount of the sodium borohydride is 0.05-0.5 g/L; the reaction conditions are as follows: the reaction temperature is 10-50 ℃, and the reaction time is 4-24 h.
Preferably, the nanocellulose composite catalytic electrode simultaneously loaded with metal phthalocyanine and metal ruthenium is cleaned after being formed; the cleaning process is to clean by hydrochloric acid solution, sodium hydroxide solution and ultrapure water in sequence. The concentration of the hydrochloric acid solution is 0.01-0.05 mol/L, and the concentration of the sodium hydroxide solution is 0.01-0.05 mol/L.
In a third aspect, the invention provides an application of the nanocellulose composite catalytic electrode simultaneously loaded with metal phthalocyanine and metal ruthenium in the electrocatalytic treatment of cresol wastewater.
Compared with the prior art, the invention has the following beneficial effects.
1. The invention uses the nano-cellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium simultaneously in the electrocatalytic treatment process of cresol wastewater, and can almost completely remove 1 multiplied by 10 within 40min under the current intensity of 150mA -3 Cresol in mol/L cresol wastewater; meanwhile, the electrocatalysis efficiency of the composite catalytic electrode loaded with the metal phthalocyanine and the metal ruthenium to the cresol is obviously higher than the sum of the electrocatalysis efficiencies of the composite catalytic electrode loaded with the metal phthalocyanine only and the composite catalytic electrode loaded with the metal ruthenium only to the cresol, so that the obvious electrocatalysis activity synergistic enhancement effect can be generated between the metal phthalocyanine and the metal ruthenium, and the treatment efficiency of cresol wastewater and the synthesis rate of methylcyclohexanol are greatly improved.
2. According to the invention, the nanocellulose-graphene binary composite material is selected as a carrier of the metal phthalocyanine and the metal ruthenium, and the uniform dispersion of the metal phthalocyanine and the metal ruthenium on the nanocellulose-graphene binary composite material is realized by utilizing the advantages of ultrahigh specific surface area of the nanocellulose, specific three-dimensional network, good graphene immobilization performance, high conductivity and the like, so that the nanocellulose composite catalytic electrode which is high in performance and simultaneously loads the metal phthalocyanine and the metal ruthenium is prepared. In addition, the nano-cellulose-graphene composite material can quickly enrich organic pollutants in a solution, and the deposition of the metal ruthenium obviously improves the conductivity of the composite catalytic electrode, thereby being beneficial to the improvement of the electrocatalysis efficiency.
3. According to the invention, the nanocellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium is utilized, the methyl cyclohexanol can be prepared from cresol wastewater through electrocatalysis, the conversion rate of cresol converted into methyl cyclohexanol is up to more than 99%, the methyl cyclohexanol is obtained while the industrial wastewater is efficiently treated, and the sustainable resource utilization of water is realized.
4. The nanocellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium provided by the invention can be repeatedly and circularly applied, the technique for synthesizing the methylcyclohexanol is reliable, the condition is mild, the problems that the preparation step of the methylcyclohexanol is complicated, the synthesis process condition is harsh, a large amount of acid and alkali are required in the production process, the economy is not ideal enough, the environmental pollution is easily caused and the like are solved, and the nanocellulose composite catalytic electrode has obvious environmental and economic values.
Drawings
FIG. 1 is a graph showing the change of 4-cresol concentration with reaction time in the electrocatalytic process of example 1 of the present invention.
FIG. 2 is a graph showing the effect of the composite catalytic electrode on the cyclic treatment of a 4-cresol solution used in example 1 of the present invention.
FIG. 3 is a graph showing the comparison between the electrocatalytic degradation efficiency of 4-cresol and the amount of 4-methylcyclohexanol produced in example 1 and comparative examples 1 and 2 according to the present invention (example 1: use of a nanocellulose composite catalytic electrode supporting both metal phthalocyanine and metal ruthenium; comparative example 1: use of a nanocellulose composite catalytic electrode supporting only metal ruthenium; comparative example 2: use of a nanocellulose composite catalytic electrode supporting only metal phthalocyanine).
FIG. 4 is a graph showing the change of 4-cresol concentration with reaction time in the electrocatalytic process of example 2 of the present invention.
FIG. 5 is a graph showing the amount of 2-methylcyclohexanol produced within 40min as a function of the current intensity in the present invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood 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 method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time.
The preparation method of the nano-cellulose composite catalytic electrode simultaneously loaded with metal phthalocyanine and metal ruthenium comprises the following steps.
(1) 5.00 g of graphene oxide, 10.00 g of glucose, 0.8 g of peptone, 0.8 g of yeast extract, 0.05 g of disodium hydrogen phosphate and 0.05 g of ethanol are respectively weighed and dissolved in 100 mL of ultrapure water to prepare the mixed culture medium containing graphene oxide.
(2) And (2) adding acetobacter xylinum into the mixed culture medium containing graphene oxide obtained in the step (1), and culturing for 7 days at the temperature of 30 ℃ to obtain the nano cellulose-graphene oxide composite membrane.
(3) 10.00 g of sulfonated cobalt phthalocyanine and 4.00 g of ruthenium trichloride are respectively weighed and dissolved in 100 mL of ultrapure water to prepare a mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions.
(4) And (3) placing the nano-cellulose-graphene oxide composite membrane obtained in the step (2) into the mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions obtained in the step (3), adding 0.40 g/L of sodium borohydride, reacting for 12 hours at 25 ℃, reducing the graphene oxide into graphene, and realizing deposition of the sulfonated cobalt phthalocyanine and ruthenium metal on the nano-cellulose-graphene binary composite material.
(5) And (4) sequentially washing the product obtained in the step (4) with 0.05 mol/L hydrochloric acid, 0.05 mol/L sodium hydroxide and ultrapure water to obtain the nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and metal ruthenium. The conductivity of the composite catalytic electrode is 29000S/m; wherein the contents of the graphene, the sulfonated cobalt phthalocyanine and the metal ruthenium on the nano-cellulose composite catalytic electrode are respectively 25.38 wt%, 7.69 wt% and 1.88 wt%.
In order to prove the effect of the nanocellulose composite catalytic electrode on electrocatalytic treatment of cresol wastewater and synthesis of methylcyclohexanol, the following experiment is carried out.
5L of the mixture with the concentration of 1X 10 is prepared -3 4-cresol solution of mol/L is used for simulating industrial cresol wastewater. The composite catalytic electrode (with a mass of about 0.040 g) provided in this example was cut to 10 cm × 10 cm, and used as a cathode for electrocatalytic reaction; a10 cm × 10 cm platinum sheet was used as an anode. The electrode was inserted into the 4-cresol solution, and the current was turned on to 150mA, and the reaction temperature was controlled at 30 ℃. As shown in FIG. 1, the electrocatalytic effect for 40min reduced the 4-cresol concentration in the solution by 99.71%, indicating almost complete removal of 4-cresol.
Treating the reacted solution with a rotary evaporator for 15 min to obtain 4.983X 10 -3 The mol of 4-methylcyclohexanol proves that the technique provided by the invention can efficiently obtain the methylcyclohexanol while removing the cresol wastewater.
In order to examine the stability and the reusability of the composite catalytic electrode provided in this example, the nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium was taken out of the reaction solution, washed with ultrapure water and then used for 4-cresol wastewater treatment again, and the experimental conditions were kept unchanged. As shown in FIG. 2, after 10 times of recycling, the concentration of 4-cresol solution is reduced by 99.62%, and 4.976X 10 can be obtained -3 The conversion of mol of 4-methylcyclohexanol, 4-cresol into 4-methylcyclohexanol was 99.52%.
The composite catalytic electrode provided by the embodiment has excellent stability and reusability.
Comparative example 1
A method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nano-cellulose composite catalytic electrode only loading ruthenium metal. Compared with the composite catalytic electrode provided in example 1, the difference of the preparation process of the nano-cellulose composite catalytic electrode only loaded with metal ruthenium is that no sulfonated cobalt phthalocyanine is added in step (3), so that the finally obtained nano-cellulose composite catalytic electrode does not contain sulfonated cobalt phthalocyanine.
The conductivity of the nano-cellulose composite catalytic electrode only supporting metal ruthenium is 29000S/m. The obtained nano-cellulose composite catalytic electrode is used for electrocatalytic treatment of 4-cresol solution to synthesize methylcyclohexanol, and the experimental conditions are kept the same as those in example 1. As shown in FIG. 3, the concentration of 4-cresol in the solution decreased 54.68% after 40min of electrocatalysis. Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 2.233X 10 -3 The removal rate of 4-methylcyclohexanol by mol, 4-cresol and the amount of 4-methylcyclohexanol produced were all far lower than those in example 1. Also, the conversion of 4-cresol to 4-methylcyclohexanol in this comparative example was 81.68%, which is significantly lower than that of example 1.
Comparative example 2
A method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode only loaded with metal phthalocyanine. Compared with the composite catalytic electrode provided in example 1, the difference of the preparation process of the nanocellulose composite catalytic electrode only loading metal phthalocyanine is that no ruthenium trichloride is added in step (3), so that the nanocellulose composite catalytic electrode finally obtained does not contain metal ruthenium.
The conductivity of the nanocellulose composite catalytic electrode only supporting the metal phthalocyanine is 260S/m. The obtained nano-cellulose composite catalytic electrode is used for electrocatalytic treatment of 4-cresol solution to synthesize methylcyclohexanol, and the experimental conditions are kept the same as those in example 1. As shown in FIG. 3, the concentration of 4-cresol in the solution decreased by 23.85% by electrocatalysis for 40 min. Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 0.926X 10 -3 The mol of 4-methylcyclohexanol, the removal rate of 4-cresol and the synthesis amount of 4-methylcyclohexanol were much lower than those in example 1. Also, the conversion of 4-cresol to 4-methylcyclohexanol in this comparative example was 77.82%, which is significantly lower than that of example 1.
As can be seen from comparison of example 1 and comparative examples 1 and 2, under the same conditions, the nanocellulose composite catalytic electrode loaded with metal ruthenium (comparative example 1) and the nanocellulose composite catalytic electrode loaded with metal phthalocyanine (comparative example 2) can be used for synthesizing methylcyclohexanol, but the electrocatalytic efficiency is far lower than that of the nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time. And, even if the removal rates of 4-cresol of the nanocellulose composite catalytic electrode supporting only metallic ruthenium in comparative example 1 and the nanocellulose composite catalytic electrode supporting only metallic phthalocyanine in comparative example 2 were added (54.68% +23.85% = 78.53%), it was significantly lower than 99.71% in example 1. The metal ruthenium and the metal phthalocyanine in the composite catalyst generate obvious synergistic enhancement effect of catalytic activity.
Comparative example 3
A composite catalytic electrode which differs from that of example 1 only in that: graphene oxide is not added in the step (1) in the preparation process. In the finally obtained composite material, the contents of the graphene, the sulfonated cobalt phthalocyanine and the metal ruthenium on the nano-cellulose composite catalytic electrode are respectively 0 wt%, 0.95 wt% and 0.06 wt%, which are far lower than the corresponding contents in the embodiment 1.
Comparative example 4
A composite catalytic electrode which differs from the composite catalytic electrode of example 1 only in that: in the preparation process, the nano-cellulose culture medium is not added in the step (1). The nano cellulose film cannot be obtained in the step (2), and the subsequent steps cannot be carried out. It can be seen from comparative example 1 and comparative examples 3 and 4 that the nanocellulose-graphene binary composite material is a necessary carrier for the efficient immobilization of metal phthalocyanine and metal ruthenium.
Comparative example 5
A composite catalytic electrode which differs from the composite catalytic electrode of example 1 only in that: and (4) adding no sodium borohydride. The finally obtained nano-cellulose composite material is non-conductive, and no metal ruthenium is detected, which shows that the reduction of ruthenium trichloride into metal ruthenium is a necessary condition for realizing the immobilization of ruthenium on graphene.
Example 2
A method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time.
The preparation method of the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium comprises the following steps.
(1) 5.00 g of graphene oxide, 12.00 g of glucose, 1.00 g of peptone, 1.00 g of yeast extract, 0.10 g of disodium hydrogen phosphate and 0.10 g of ethanol are respectively weighed and dissolved in 100 mL of ultrapure water to prepare the mixed culture medium containing graphene oxide.
(2) And (2) adding acetobacter xylinum into the mixed culture medium containing graphene oxide obtained in the step (1), and culturing for 7 days at the temperature of 30 ℃ to obtain the nano cellulose-graphene oxide composite membrane.
(3) 5.00 g of sulfonated cobalt phthalocyanine and 4.00 g of ruthenium trichloride are respectively weighed and dissolved in 100 mL of ultrapure water to prepare a mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions.
(4) And (3) placing the nano-cellulose-graphene oxide composite membrane obtained in the step (2) into the mixed solution containing metal phthalocyanine and ruthenium ions obtained in the step (3), adding 0.30 g/L of sodium borohydride, reacting at 25 ℃ for 24 hours, reducing the graphene oxide into graphene, and realizing the deposition of sulfonated cobalt phthalocyanine and metal ruthenium on the nano-cellulose-graphene binary composite material.
(5) And (5) sequentially cleaning the product obtained in the step (4) with 0.05 mol/L hydrochloric acid, 0.05 mol/L sodium hydroxide and ultrapure water to obtain the nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and metal ruthenium, wherein the conductivity of the composite catalytic electrode is 30000S/m, and the contents of the graphene, the sulfonated cobalt phthalocyanine and the metal ruthenium on the nano-cellulose composite catalytic electrode are 27.88 wt%, 3.94 wt% and 1.96 wt% respectively.
In order to prove the effect of the nanocellulose composite catalytic electrode on electrocatalytic treatment of cresol wastewater and synthesis of methylcyclohexanol, a comparative experiment is carried out as follows.
Experimental groups: 5L of the mixture with the concentration of 1X 10 is prepared -3 The 2-cresol solution of mol/L is used for simulating industrial cresol wastewater. Shearing 10 cm × 10 cm to obtain nanocellulose composite catalytic electrode (mass about 0.040 g) loaded with metal phthalocyanine and metal ruthenium at the same timeAs a cathode for electrocatalytic reactions; a10 cm × 10 cm platinum sheet was used as an anode. The electrode was inserted into the 2-cresol solution, and the current was turned on to 150mA, and the reaction temperature was controlled at 30 ℃. As shown in FIG. 4, the 2-cresol concentration in the solution decreased by 99.85% over 40min electrocatalysis, indicating that the 2-cresol was almost completely removed.
Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 4.987X 10 -3 The mol of 2-methylcyclohexanol proves that the technique provided by the invention can efficiently obtain the methylcyclohexanol while removing the cresol wastewater.
Control group 1: the electrodes were inserted into the 2-cresol solution without electrical conduction as the experimental group maintained the other experimental conditions. After 40min, the concentration of 2-cresol in the solution is reduced by 8.76%, and meanwhile, 2-methylcyclohexanol is not detected in the reacted solution, which shows that the nanocellulose composite catalytic electrode in the non-electrified state only has a simple adsorption effect on 2-cresol, and the electrocatalytic reaction cannot occur.
Control group 2: and controlling the intensity of the electrified current to be 50mA as the other experimental conditions of the experimental group. Collecting by electrocatalysis for 40min to obtain 1.442 × 10 -3 mol of 2-methylcyclohexanol.
Control group 3: and controlling the intensity of the electrified current to be 100mA as the other experimental conditions of the experimental group. Collecting by electrocatalysis for 40min to obtain 4.094 × 10 -3 mol of 2-methylcyclohexanol.
Control group 4: and controlling the intensity of the electrified current to be 200mA as the same as the other experimental conditions of the experimental group. Collecting by electrocatalysis for 40min to obtain 4.972 × 10 -3 mol of 2-methylcyclohexanol.
As can be seen from the comparison of the experimental group and the control groups 1 to 4, the efficiency of the electrocatalytic reaction increases with increasing intensity of the applied current (see FIG. 5), and 150mA of the current intensity is sufficient to completely convert cresol into methylcyclohexanol within 40 min.
Example 3
A method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time.
The preparation method of the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium comprises the following steps.
(1) 5.00 g of graphene oxide, 12.00 g of glucose, 1.00 g of peptone, 1.00 g of yeast extract, 0.10 g of disodium hydrogen phosphate and 0.10 g of ethanol are respectively weighed and dissolved in 100 mL of ultrapure water to prepare the mixed culture medium containing graphene oxide.
(2) And (2) adding acetobacter xylinum into the mixed culture medium containing graphene oxide obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the nano-cellulose-graphene oxide composite membrane.
(3) 1.00 g of sulfonated cobalt phthalocyanine and 4.00 g of ruthenium trichloride are respectively weighed and dissolved in 100 mL of ultrapure water to prepare a mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions.
(4) And (3) placing the nano-cellulose-graphene oxide composite membrane obtained in the step (2) into the mixed solution containing metal phthalocyanine and ruthenium ions obtained in the step (3), adding 0.30 g/L of sodium borohydride, reacting at 25 ℃ for 24 hours, reducing the graphene oxide into graphene, and realizing the deposition of sulfonated cobalt phthalocyanine and metal ruthenium on the nano-cellulose-graphene binary composite material.
(5) And (3) sequentially cleaning the product obtained in the step (4) with 0.05 mol/L hydrochloric acid, 0.05 mol/L sodium hydroxide and ultrapure water to obtain the nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and ruthenium metal, wherein the conductivity of the composite catalytic electrode is 28700S/m, and the contents of the graphene, the sulfonated cobalt phthalocyanine and the ruthenium metal on the nano-cellulose composite catalytic electrode are respectively 28.22 wt%, 0.82 wt% and 2.05 wt%.
5L of the mixture with the concentration of 1X 10 is prepared -3 The 2-cresol solution of mol/L is used for simulating industrial cresol wastewater. Shearing a 10 cm multiplied by 10 cm nano cellulose composite catalytic electrode (the mass is about 0.040 g) which is simultaneously loaded with metal phthalocyanine and metal ruthenium, and taking the nano cellulose composite catalytic electrode as a cathode of an electrocatalytic reaction; a10 cm × 10 cm platinum sheet was used as an anode. Inserting the electrode into 2-cresol solution, electrifying to make the current intensityThe temperature was controlled at 150mA and 30 ℃. After 40min of electrocatalysis, the concentration of 2-cresol in the solution is reduced by 69.38%. After 60 min of electrocatalysis, the concentration of 2-cresol in the solution is reduced by 99.26%, which shows that 2-cresol is almost completely removed.
Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 4.912X 10 -3 The mol of 2-methylcyclohexanol proves that the technique provided by the invention can efficiently obtain the methylcyclohexanol while removing the cresol wastewater.
Example 4
A processing method of cresol wastewater is characterized in that cresol is converted into methylcyclohexanol through electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time.
The preparation method of the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium comprises the following steps.
(1) 5.00 g of graphene oxide, 12.00 g of glucose, 1.00 g of peptone, 1.00 g of yeast extract, 0.10 g of disodium hydrogen phosphate and 0.10 g of ethanol are respectively weighed and dissolved in 100 mL of ultrapure water to prepare the mixed culture medium containing graphene oxide.
(2) And (2) adding acetobacter xylinum into the mixed culture medium containing graphene oxide obtained in the step (1), and culturing at 30 ℃ for 7 days to obtain the nano-cellulose-graphene oxide composite membrane.
(3) 5.00 g of sulfonated cobalt phthalocyanine and 1.00 g of ruthenium trichloride are respectively weighed and dissolved in 100 mL of ultrapure water to prepare a mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions.
(4) And (3) placing the nano-cellulose-graphene oxide composite membrane obtained in the step (2) into the mixed solution containing metal phthalocyanine and ruthenium ions obtained in the step (3), adding 0.30 g/L of sodium borohydride, reacting at 25 ℃ for 24 hours, reducing the graphene oxide into graphene, and realizing the deposition of sulfonated cobalt phthalocyanine and metal ruthenium on the nano-cellulose-graphene binary composite material.
(5) And (5) sequentially cleaning the product obtained in the step (4) with 0.05 mol/L hydrochloric acid, 0.05 mol/L sodium hydroxide and ultrapure water to obtain the nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and metal ruthenium, wherein the conductivity of the composite catalytic electrode is 9500S/m, and the contents of the graphene, the sulfonated cobalt phthalocyanine and the metal ruthenium on the nano-cellulose composite catalytic electrode are respectively 28.72 wt%, 4.29 wt% and 0.56 wt%.
Preparation of 5L of 1X 10 -3 The mol/L3-cresol solution is used for simulating industrial cresol wastewater. Shearing a 10 cm multiplied by 10 cm nano cellulose composite catalytic electrode (the mass is about 0.040 g) which is simultaneously loaded with metal phthalocyanine and metal ruthenium, and taking the nano cellulose composite catalytic electrode as a cathode of an electrocatalytic reaction; a10 cm × 10 cm platinum sheet was used as an anode. The electrode was inserted into the 3-cresol solution, and the current was turned on to 150mA, and the reaction temperature was controlled at 30 ℃. After 40min of electrocatalysis, the concentration of 3-cresol in the solution is reduced by 50.66%. After 75 min electrocatalysis, the concentration of 3-cresol in the solution is reduced by 99.52 percent. Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 4.956X 10 -3 The mol 3-methylcyclohexanol proves that the technique provided by the invention can efficiently obtain the methylcyclohexanol while removing the cresol wastewater.
Example 5
A method for treating cresol wastewater comprises converting cresol into methylcyclohexanol by electrocatalytic oxidation; the cathode adopted in the electrocatalytic oxidation process is a nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium at the same time.
The preparation method of the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium comprises the following steps.
(1) 5.00 g of graphene oxide, 10.00 g of glucose, 0.8 g of peptone, 0.8 g of yeast extract, 0.05 g of disodium hydrogen phosphate and 0.05 g of ethanol are respectively weighed and dissolved in 100 mL of ultrapure water to prepare the mixed culture medium containing graphene oxide.
(2) And (2) adding acetobacter xylinum into the mixed culture medium containing graphene oxide obtained in the step (1), and culturing for 7 days at the temperature of 30 ℃ to obtain the nano cellulose-graphene oxide composite membrane.
(3) 8.00 g of sulfonated cobalt phthalocyanine and 3.50 g of ruthenium trichloride are respectively weighed and dissolved in 100 mL of ultrapure water to prepare a mixed solution containing sulfonated cobalt phthalocyanine and ruthenium ions.
(4) And (3) placing the nano-cellulose-graphene oxide composite membrane obtained in the step (2) into the mixed solution containing metal phthalocyanine and ruthenium ions obtained in the step (3), adding 0.40 g/L of sodium borohydride, reacting for 12 hours at 25 ℃, reducing the graphene oxide into graphene, and realizing deposition of sulfonated cobalt phthalocyanine and metal ruthenium on the nano-cellulose-graphene binary composite material.
(5) And (3) sequentially washing the product obtained in the step (4) with 0.05 mol/L hydrochloric acid, 0.05 mol/L sodium hydroxide and ultrapure water to obtain the nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and ruthenium metal, wherein the conductivity of the composite catalytic electrode is 27800S/m, and the contents of graphene, sulfonated cobalt phthalocyanine and ruthenium metal on the nano-cellulose composite catalytic electrode are respectively 26.33 wt%, 6.55 wt% and 1.59 wt%.
The obtained nano-cellulose composite catalytic electrode simultaneously loaded with sulfonated cobalt phthalocyanine and ruthenium metal can be used for synthesizing methyl cyclohexanol through electrocatalysis; in order to prove that the nano-cellulose composite catalytic electrode simultaneously loading the sulfonated cobalt phthalocyanine and the metal ruthenium can be used for synthesizing the methylcyclohexanol under electrocatalysis, the following experiment is carried out.
5L of the mixture with the concentration of 1X 10 is prepared -3 The mol/L3-cresol solution is used for simulating industrial cresol wastewater. Shearing a 10 cm multiplied by 10 cm nano cellulose composite catalytic electrode (the mass is about 0.040 g) which is simultaneously loaded with metal phthalocyanine and metal ruthenium, and taking the nano cellulose composite catalytic electrode as a cathode of an electrocatalytic reaction; a10 cm × 10 cm platinum sheet was used as the anode. The electrode was inserted into the 4-cresol solution, and the current was turned on to 150mA, and the reaction temperature was controlled at 30 ℃. After 45 min of electrocatalysis, the concentration of 3-cresol in the solution is reduced by 99.37 percent, which shows that 3-cresol is almost completely removed.
Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 4.931X 10 -3 mol 3-methyl cyclohexanol proves that the methyl cyclohexanol can be efficiently obtained while cresol wastewater is removed by the technology provided by the invention.
Taking 5L of the extract with the concentration of 1.165X 10 -3 And (3) carrying out electrocatalysis reaction treatment on the actual industrial wastewater of the mol/L3-cresol by using the nano-cellulose composite catalytic electrode, wherein the experimental conditions are kept unchanged. After 45 min of electrocatalysis, the concentration of 3-cresol is reduced by 99.11 percent, which shows that the 3-cresol in the wastewater is almost completely removed.
Treating the reacted solution with a rotary evaporator, collecting the solution after 15 min to obtain 5.694X 10 -3 The mol of 3-methylcyclohexanol proves that the technology provided by the invention can be applied to actual cresol wastewater.
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, and all equivalent changes and modifications made within the spirit and scope of the present invention should be included in the present invention.
Claims (10)
1. A cresol wastewater treatment method is characterized in that: cresol in the wastewater is converted into methylcyclohexanol by an electrocatalysis mode and is recycled; the cathode adopted in the electrocatalysis process is a nanocellulose composite catalytic electrode which simultaneously loads metal phthalocyanine and metal ruthenium; meanwhile, the nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium is obtained by depositing the metal phthalocyanine and the metal ruthenium on a nanocellulose composite membrane; the nano-cellulose composite membrane is a nano-cellulose-graphene binary composite material.
2. The method for treating cresol-based wastewater as set forth in claim 1, wherein: the anode used in the electrocatalysis process is metal platinum.
3. The method for treating cresol-containing wastewater as claimed in claim 1, wherein the method comprises the following steps: the current in the electrocatalysis process is 100 mA-200 mA.
4. The method for treating cresol-based wastewater as set forth in claim 1, wherein: in the nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium, the mass ratio of the metal phthalocyanine to the metal ruthenium is 10: 1-1: 1.
5. A nanometer cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium is characterized in that: the metal phthalocyanine and the metal ruthenium are deposited on the nano-cellulose composite membrane to obtain the nano-cellulose composite membrane; the nano-cellulose composite membrane is a nano-cellulose-graphene binary composite material; the content of graphene in the nano-cellulose composite membrane is 5 wt% -30 wt%; in the composite catalytic electrode, the mass ratio of metal phthalocyanine to metal ruthenium is 10: 1-1: 1; the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium is obtained by placing a nano-cellulose-graphene oxide binary composite material in a mixed solution of metal phthalocyanine and ruthenium ions and then carrying out reduction treatment; the conductivity of the composite catalytic electrode is 2500S/m-30000S/m; the nano-cellulose composite catalytic electrode simultaneously loading metal phthalocyanine and metal ruthenium is used for treating the cresol wastewater through electrocatalysis.
6. The nanocellulose composite catalytic electrode simultaneously supporting metal phthalocyanine and metal ruthenium according to claim 5, wherein: the nano-cellulose-graphene binary composite material is obtained by culturing acetobacter in a mixed culture medium containing graphene oxide and performing reduction treatment; the mixed culture medium containing graphene oxide is a mixed solution of graphene oxide, glucose, peptone, yeast extract, disodium hydrogen phosphate and ethanol; wherein, the mass concentrations of the glucose, the peptone, the yeast extract, the disodium hydrogen phosphate and the ethanol in the mixed solution are respectively 2 to 12 percent, 0.2 to 1 percent, 0.02 to 0.1 percent and 0.02 to 0.1 percent; the mass concentration of the graphene oxide in the mixed solution is 0.05-4%.
7. The nanocellulose composite catalytic electrode simultaneously supporting metal phthalocyanine and metal ruthenium according to claim 5, wherein: the metal phthalocyanine is sulfonated cobalt phthalocyanine; the ruthenium ions are obtained by ionization of ruthenium trichloride after the ruthenium trichloride is dissolved in water.
8. The nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium simultaneously according to claim 5, wherein: in the mixed solution of the metal phthalocyanine and the ruthenium ions, the concentrations of the metal phthalocyanine and the ruthenium ions are respectively 1-10% and 0.2-2%.
9. The nanocellulose composite catalytic electrode simultaneously supporting metal phthalocyanine and metal ruthenium according to claim 5, wherein: the reducing agent adopted in the reduction treatment is sodium borohydride; the adding amount of sodium borohydride is 0.05-0.5 g/L; the reaction conditions are as follows: the reaction temperature is 10-50 ℃, and the reaction time is 4-24 h.
10. The application of the nanocellulose composite catalytic electrode loaded with metal phthalocyanine and metal ruthenium according to any one of claims 5 to 9 in electrocatalytic treatment of cresol wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210851213.XA CN114988534B (en) | 2022-07-20 | 2022-07-20 | Cresol wastewater treatment method and composite catalytic electrode used in method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210851213.XA CN114988534B (en) | 2022-07-20 | 2022-07-20 | Cresol wastewater treatment method and composite catalytic electrode used in method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114988534A true CN114988534A (en) | 2022-09-02 |
| CN114988534B CN114988534B (en) | 2022-10-28 |
Family
ID=83022249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210851213.XA Active CN114988534B (en) | 2022-07-20 | 2022-07-20 | Cresol wastewater treatment method and composite catalytic electrode used in method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114988534B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650372A (en) * | 2022-12-27 | 2023-01-31 | 杭州师范大学钱江学院 | Method for treating antibiotic wastewater and composite material used by same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4690741A (en) * | 1984-10-12 | 1987-09-01 | Cape Cod Research, Inc. | Electrolytic reactor and method for treating fluids |
| CA2268694A1 (en) * | 1998-04-15 | 1999-10-15 | Degussa-Huls Aktiengesellschaft | Fuel cell anode for the oxidation of methanol |
| CN1614084A (en) * | 2004-12-02 | 2005-05-11 | 同济大学 | One-dimensional phthalocyanine compound nanometer thin film and preparation thereof |
| JP2008178768A (en) * | 2007-01-23 | 2008-08-07 | Osaka Gas Co Ltd | Waste water treatment method |
| JP2014091061A (en) * | 2012-10-31 | 2014-05-19 | Kumamoto Univ | Iron phthalocyanine/graphene nanocomposite, iron phthalocyanine/graphene nanocomposite carried electrode, and manufacturing method thereof |
| CN105206431A (en) * | 2015-10-12 | 2015-12-30 | 中国林业科学研究院木材工业研究所 | Electrode material preparing method and electrode material prepared through same |
| CN105513834A (en) * | 2015-12-25 | 2016-04-20 | 哈尔滨工业大学 | Preparation method and application of bacterial cellulose graphene paper load cobaltosic oxide flexible electrode material |
| CN108660479A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that lignin-base phenolic compound electrocatalytic hydrogenation produces KA oil and its derivative |
| CN113603191A (en) * | 2021-08-23 | 2021-11-05 | 中国科学院生态环境研究中心 | Metal ruthenium-based electrode and preparation method and application thereof |
-
2022
- 2022-07-20 CN CN202210851213.XA patent/CN114988534B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4690741A (en) * | 1984-10-12 | 1987-09-01 | Cape Cod Research, Inc. | Electrolytic reactor and method for treating fluids |
| CA2268694A1 (en) * | 1998-04-15 | 1999-10-15 | Degussa-Huls Aktiengesellschaft | Fuel cell anode for the oxidation of methanol |
| CN1614084A (en) * | 2004-12-02 | 2005-05-11 | 同济大学 | One-dimensional phthalocyanine compound nanometer thin film and preparation thereof |
| JP2008178768A (en) * | 2007-01-23 | 2008-08-07 | Osaka Gas Co Ltd | Waste water treatment method |
| JP2014091061A (en) * | 2012-10-31 | 2014-05-19 | Kumamoto Univ | Iron phthalocyanine/graphene nanocomposite, iron phthalocyanine/graphene nanocomposite carried electrode, and manufacturing method thereof |
| CN105206431A (en) * | 2015-10-12 | 2015-12-30 | 中国林业科学研究院木材工业研究所 | Electrode material preparing method and electrode material prepared through same |
| CN105513834A (en) * | 2015-12-25 | 2016-04-20 | 哈尔滨工业大学 | Preparation method and application of bacterial cellulose graphene paper load cobaltosic oxide flexible electrode material |
| CN108660479A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that lignin-base phenolic compound electrocatalytic hydrogenation produces KA oil and its derivative |
| CN113603191A (en) * | 2021-08-23 | 2021-11-05 | 中国科学院生态环境研究中心 | Metal ruthenium-based electrode and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周明华等: "含酚模拟废水的电催化降解", 《化工学报》 * |
| 郭必泛等: "石墨烯/细菌纤维素复合材料的原位生物合成", 《杭州师范大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650372A (en) * | 2022-12-27 | 2023-01-31 | 杭州师范大学钱江学院 | Method for treating antibiotic wastewater and composite material used by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114988534B (en) | 2022-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Electrochemical conversion of corn stover lignin to biomass-based chemicals between Cu/NiMoCo cathode and Pb/PbO2 anode in alkali solution | |
| Wang et al. | Electro-reforming polyethylene terephthalate plastic to co-produce valued chemicals and green hydrogen | |
| Tian et al. | Mo 2 C-induced hydrogen production enhances microbial electrosynthesis of acetate from CO 2 reduction | |
| CN107364934B (en) | Electrocatalytic reduction composite electrode, preparation method and application thereof | |
| Aiswaria et al. | A review on graphene/graphene oxide supported electrodes for microbial fuel cell applications: Challenges and prospects | |
| CN114988534B (en) | Cresol wastewater treatment method and composite catalytic electrode used in method | |
| Ren et al. | Sustainable ammonia electrosynthesis from nitrate wastewater coupled to electrocatalytic upcycling of polyethylene terephthalate plastic waste | |
| CN110042424B (en) | Composite catalyst MXene/CNTs and preparation method and application thereof | |
| Weber et al. | Electrochemical oxidation of lignin and waste plastic | |
| Liang et al. | One-step synthesis of Cu (OH) 2-Cu/Ni foam cathode for electrochemical reduction of nitrate | |
| Jack et al. | Anode co-valorization for scalable and sustainable electrolysis | |
| Ren et al. | Electrochemical co-production of ammonia and biodegradable polymer monomer glycolic acid via the co-electrolysis of nitrate wastewater and waste plastic | |
| CN107512760B (en) | Electrolytic cell device for synchronously generating ozone and hydrogen peroxide through electricity, and preparation method and application thereof | |
| CN111825168B (en) | Copper-modified carbon fiber electrode and preparation method and application thereof | |
| Kim et al. | Unbiased photoelectrode interfaces for solar coupling of lignin oxidation with biocatalytic C═ C bond hydrogenation | |
| Dai et al. | A vertically configured photocatalytic-microbial fuel cell for electricity generation and gaseous toluene degradation | |
| CN110713233B (en) | Pd/MnO2-Ni electrode and preparation method and application thereof | |
| CN101811755B (en) | Method for preparing sodium dodecyl benzene sulfonate doped titanium catalyzed electrode | |
| CN106587282B (en) | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof | |
| Obasanjo et al. | Progress and perspectives of pulse electrolysis for stable electrochemical carbon dioxide reduction | |
| Pei et al. | Thermo-Electrochemically Induced Dynamic Snδ+/Sn Interface for Direct Bicarbonate Reduction to Formate | |
| CN112675879A (en) | Molybdenum disulfide nanosheet, preparation method and application thereof, and method for degrading halogenated antibiotics through electrochemical reduction | |
| Dimitriadis et al. | Pt-based electro-catalytic materials derived from biosorption processes and their exploitation in fuel cell technology | |
| CN108439546A (en) | Auto-dope TiO2Nanotube electrode, preparation method and applications | |
| Prajapati et al. | Microbial fuel cell‐assisted Congo red dye decolorization using biowaste‐derived anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |