CN112349943A - Humus-metal oxide composite modified electrode and preparation and application thereof - Google Patents
Humus-metal oxide composite modified electrode and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a humus-metal oxide composite modified electrode and preparation and application thereof. The preparation method comprises the following steps: 1) pretreating an electrode substrate; 2) preparing humus-metal salt colloid; 3) dipping: placing the pretreated electrode substrate in a humus-metal salt colloid for dipping, and drying at a certain temperature after dipping; 4) aging; 5) and roasting to finally prepare the humus-metal oxide composite modified electrode. According to the invention, humus and metal are organically combined and fixed on the electrode substrate, so that the problems of humus waste and pollution are solved, active groups on the electrode structure are added, the biocompatibility of the electrode is improved, electron transfer is promoted, the performance of a bioelectrochemical system is improved, and meanwhile, the modified electrode is simple in preparation process, low in cost and strong in practicability.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a humus-metal oxide composite modified electrode and preparation and application thereof.
Background
The bioelectrochemical technology is a resource technology of organic pollutants, and compared with the traditional biotechnology, the bioelectrochemical system utilizes microorganisms as a catalyst, can convert chemical energy into electric energy, and has high-efficiency treatment capacity on the organic pollutants in the environment, such as nitrobenzene, pentachlorophenol and the like. However, the bioelectrochemical system still has the problems of low electron transfer efficiency, slow degradation rate and the like.
In recent years, electron mediators rich in quinone groups have been widely used in bioelectrochemical systems, but the electron mediators are toxic and expensive. Humus is one of the main components of organic substances in the environment, and mainly comprises humic acid, fulvic acid and humins. Humus has attracted researchers' interest as a natural electron mediator. The humus has rich functional groups, mainly including phenolic hydroxyl, quinonyl, methoxyl and the like, and the active groups have decisive effect on the physicochemical properties of the humic acid. However, the application of humic substances directly to a bioelectrochemical system not only results in the waste of humic substances, but also in the contamination of humic substances resistant to biodegradation, and therefore is not feasible from the economic and environmental viewpoints.
The metal not only has conductive performance, but also can promote the transfer of electrons through the valence change of the metal. Meanwhile, the humus can be combined with metal through the actions of chelation, coordination and complexation and the like, and is fixed and polymerized on the electrode substrate, so that the problems of waste and pollution of the humus can be solved, the electron transfer is promoted, the biocompatibility of the electrode is improved, the performance of a bioelectrochemical system is enhanced, and the efficient degradation of organic pollutants in the environment is realized.
Disclosure of Invention
Based on the background technology, the invention provides the humus-metal oxide composite modified electrode and the preparation and application thereof, the humus-metal oxide composite modified electrode is applied to a bioelectrochemical system, the problems of humus waste and pollution are solved, and the performance of the bioelectrochemical system is further improved by the organic combination of humus and metal.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a humus-metal oxide composite modified electrode, which comprises the following steps:
1) pretreatment of an electrode substrate: cleaning the electrode substrate, and drying for later use;
2) preparation of humus-metal salt colloid: respectively taking a certain amount of nitrate and citric acid, and preparing a colloid by a sol-gel method; adding a certain amount of humus at the later stage of colloid formation, and stirring to finally prepare humus-metal salt colloid;
3) dipping: after the colloid is prepared, placing the pretreated electrode substrate in the colloid for dipping, and drying at a certain temperature after dipping;
4) aging: aging the dried electrode matrix loaded with the humus-metal salt colloid at room temperature;
5) roasting: and roasting the aged electrode substrate to finally prepare the humus-metal oxide composite modified electrode.
Each step is described in detail below.
1) Pretreatment of an electrode substrate: and cleaning the electrode substrate, and drying for later use.
Preferably, the electrode substrate is made of conductive materials such as carbon cloth, graphite rods, carbon felt or carbon brushes.
Preferably, the specific process of the electrode substrate pretreatment comprises the following steps: soaking the electrode substrate in acetone at room temperature, and then cleaning with ethanol and then deionized water; and after cleaning, drying for later use.
More preferably, the electrode substrate is soaked in acetone for 0.5-1h, and then washed with ethanol for 3-5 times and then with deionized water for 3-7 times; and after cleaning, drying at 60-80 ℃ for later use.
2) Preparation of humus-metal salt colloid: respectively taking a certain amount of nitrate and citric acid, and preparing a colloid by a sol-gel method; and adding a certain amount of humus at the later stage of colloid formation, and stirring to finally prepare the humus-metal salt colloid.
Preferably, the nitrate is manganese nitrate, iron nitrate or the like.
Preferably, the humus is humic acid, fulvic acid or humins and the like.
Preferably, the mass ratio of the nitrate to the citric acid is in the range of 1:6 to 2: 1. For example 1:6, 1:1 or 2:1 in the examples of the invention.
Preferably, the mass ratio of nitrate to humus is in the range of 1:2 to 5: 1. Such as 1:2, 1:1 or 5:1 in embodiments of the invention.
Preferably, the colloid forming temperature in the colloid preparation process is 60-80 ℃. For example 60 deg.C, 70 deg.C or 80 deg.C in the examples of the present invention.
Preferably, the humic substance is added 0.5h to 2h before the colloid is formed. For example 0.5h, 1.0h or 2.0h in the examples of the invention.
3) Dipping: and after the colloid is prepared, putting the pretreated electrode substrate into the colloid for dipping, and drying at a certain temperature after dipping.
Preferably, the electrode matrix is soaked in the colloid and then dried, and the drying is repeated for 1 to 3 times, wherein the drying temperature is 40 to 80 ℃. For example 40 deg.C, 60 deg.C or 80 deg.C in the examples of the present invention.
4) Aging: and (3) ageing the dried electrode matrix loaded with the humus-metal salt colloid at room temperature.
Preferably, the electrode matrix loaded with the humus-metal salt colloid is aged for 8-24h at room temperature. For example 8h, 16h or 24h in embodiments of the invention.
5) Roasting: and roasting the aged electrode substrate to finally prepare the humus-metal oxide composite modified electrode.
Preferably, the roasting temperature range of the aged electrode substrate is 160-240 ℃, and the roasting time range is 1-2 h. For example, in the present example, the calcination was carried out at 160 ℃ for 2 hours, at 200 ℃ for 1.5 hours, and at 240 ℃ for 1 hour.
The invention also provides the humus-metal oxide composite modified electrode prepared by the preparation method.
The invention further provides application of the humus-metal oxide composite modified electrode in a bioelectrochemical system.
The preparation method of the humus-metal oxide composite modified electrode provided by the invention has the following beneficial effects: the organic combination of humus and metal and the fixation of humus on the electrode substrate not only solves the problems of humus waste and pollution, but also increases active groups on the electrode structure, improves the biocompatibility of the electrode, promotes electron transfer, improves the performance of a bioelectrochemical system, and simultaneously, the modified electrode has simple preparation process, low cost and strong feasibility.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The invention provides a preparation method of a humus-metal oxide composite modified electrode, which comprises the following steps:
1) pretreatment of an electrode substrate: and cleaning the electrode substrate, and drying for later use.
In the following embodiments, the electrode substrate is made of conductive materials such as carbon cloth, graphite rod, carbon felt, or carbon brush.
In the following examples, the specific process of the electrode substrate pretreatment includes: soaking the electrode substrate in acetone at room temperature, and then cleaning with ethanol and then deionized water; and after cleaning, drying for later use.
In the following examples, the electrode substrate was soaked in acetone for 0.5-1h, then washed with ethanol 3-5 times, and then with deionized water 3-7 times; and after cleaning, drying at 60-80 ℃ for later use.
2) Preparation of humus-metal salt colloid: respectively taking a certain amount of nitrate and citric acid, and preparing a colloid by a sol-gel method; and adding a certain amount of humus at the later stage of colloid formation, and stirring to finally prepare the humus-metal salt colloid.
In the following examples, the nitrate is manganese nitrate, iron nitrate, or the like.
In the following examples, the humic substances are humic acid, fulvic acid or humins and the like.
In the following examples, the mass ratio of nitrate to citric acid ranges from 1:6 to 2: 1. For example 1:6, 1:1 or 2:1 in the examples of the invention.
In the following examples, the mass ratio of nitrate to humus ranged from 1:2 to 5: 1. Such as 1:2, 1:1 or 5:1 in embodiments of the invention.
In the following examples, the gelling temperature during the preparation of the colloid was 60-80 ℃. For example 60 deg.C, 70 deg.C or 80 deg.C in the examples of the present invention.
In the following examples, humus was added 0.5h to 2h before colloid formation. For example 0.5h, 1.0h or 2.0h in the examples of the invention.
3) Dipping: and after the colloid is prepared, putting the pretreated electrode substrate into the colloid for dipping, and drying at a certain temperature after dipping.
In the following examples, the electrode matrix is dipped in the colloid and then dried, and the drying is repeated for 1-3 times, wherein the drying temperature is 40-80 ℃. For example 40 deg.C, 60 deg.C or 80 deg.C in the examples of the present invention.
4) Aging: and (3) ageing the dried electrode matrix loaded with the humus-metal salt colloid at room temperature.
In the following examples, the electrode matrix loaded with the humic substance-metal salt colloid was aged at room temperature for 8 to 24 hours. For example 8h, 16h or 24h in embodiments of the invention.
5) Roasting: and roasting the aged electrode substrate to finally prepare the humus-metal oxide composite modified electrode.
In the following examples, the firing temperature range of the aged electrode substrate is 160-240 ℃, and the firing time range is 1-2 h. For example, in the present example, the calcination was carried out at 160 ℃ for 2 hours, at 200 ℃ for 1.5 hours, and at 240 ℃ for 1 hour.
Specific production examples are shown below for illustration.
Example 1
1.0g of manganese nitrate and 6.0g of citric acid are taken to be gelatinized by a sol-gel method, the gelatinization temperature is 60 ℃, 2.0g of humic acid is added and stirred uniformly 0.5h before colloid formation. After the colloid is formed, the pretreated carbon cloth is dipped and dried at 40 ℃, and the steps are repeated for 1 time. After completion of the impregnation, it was aged at room temperature for 8 hours, and then calcined at 160 ℃ for 2 hours. The prepared humic acid-manganese oxide based electrode is used in a bioelectrochemical system, polycyclic aromatic hydrocarbon phenanthrene is used as a probe, unmodified carbon cloth and single manganese oxide and humic acid modified carbon cloth are used as controls, and the performance of the modified electrode material is shown in the following table 1.
TABLE 1 Performance of different carbon cloth electrodes in bioelectrochemical systems
As can be seen from Table 1, the method has the advantages that the phenanthrene removal rate is highest, the power density of a bioelectrochemical system is highest, the coulombic efficiency is highest, and the biofilm formation time is shortest under the action of a humic acid-manganese oxide based electrode by using common carbon cloth as a matrix. The humic acid-manganese oxide can not only improve the performance of a bioelectrochemical system, but also promote the degradation of organic pollutant phenanthrene.
Example 2
2.0g of ferric nitrate and 2.0g of citric acid are taken to be gelatinized by a sol-gel method, the gelatinization temperature is 70 ℃, 1.0h before colloid formation, 2.0g of fulvic acid is added and stirred uniformly. After the colloid is formed, the pretreated graphite rod is dipped and dried at 60 ℃, and the steps are repeated for 2 times. After completion of the impregnation, it was aged at room temperature for 16 hours, and then calcined at 200 ℃ for 1.5 hours. The prepared fulvic acid-iron oxide-based electrode is used in a bioelectrochemical system, bisphenol A is used as a probe, an unmodified graphite rod and a graphite rod modified by iron oxide and fulvic acid alone are used as controls, and the performance of the modified electrode material is shown in the following table 2.
TABLE 2 Performance of different graphite rod electrodes in bioelectrochemical systems
As can be seen from Table 2, the common graphite rod is used as a substrate, and under the action of the fulvic acid-iron oxide-based electrode, the bisphenol A removal rate is highest, the power density of the bioelectrochemical system is highest, the coulombic efficiency is highest, and the biofilm formation time is shortest, wherein the removal rate is 86% and the biofilm formation time is 989mW/m213%, and 19 d. The fulvic acid-iron oxide can not only improve the performance of a bioelectrochemical system, but also promote the degradation of organic pollutant bisphenol A.
Example 3
Adding 0.4g of humin into 2.0g of ferric nitrate and 1.0g of citric acid, and uniformly stirring at 80 ℃ 2.0h before the colloid is formed. After the colloid is formed, the pretreated carbon felt is dipped and dried at 80 ℃, and the steps are repeated for 3 times. After completion of the impregnation, it was aged at room temperature for 24 hours, and then calcined at 240 ℃ for 1 hour. The prepared humin-iron oxide-based electrode is used in a bioelectrochemical system, phenol is used as a probe, an unmodified carbon felt and a single iron oxide and humin modified carbon felt are used as a reference, and the performances of the modified electrode material are as shown in the following table.
TABLE 3 Performance of different carbon felt electrodes in bioelectrochemical systems
As can be seen from Table 3, the removal rate of phenol is the highest, the power density of the bioelectrochemical system is the highest, the coulombic efficiency is the highest, and the biofilm formation time is the shortest, respectively 92% and 1123mW/m, under the action of the humin-iron oxide-based electrode with the common carbon felt as the matrix218% and 15 d. The humin-iron oxide can not only improve the performance of a bioelectrochemical system, but also promote the degradation of organic pollutant phenol.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (15)
1. A preparation method of a humus-metal oxide composite modified electrode is characterized by comprising the following steps:
1) pretreatment of an electrode substrate: cleaning the electrode substrate, and drying for later use;
2) preparation of humus-metal salt colloid: respectively taking a certain amount of nitrate and citric acid, and preparing a colloid by a sol-gel method; adding a certain amount of humus at the later stage of colloid formation, and stirring to finally prepare humus-metal salt colloid;
3) dipping: after the colloid is prepared, placing the pretreated electrode substrate in the colloid for dipping, and drying at a certain temperature after dipping;
4) aging: aging the dried electrode matrix loaded with the humus-metal salt colloid at room temperature;
5) roasting: and roasting the aged electrode substrate to finally prepare the humus-metal oxide composite modified electrode.
2. The method according to claim 1, wherein the electrode substrate is a carbon cloth, a graphite rod, a carbon felt, or a carbon brush.
3. The preparation method according to claim 1, wherein in the step 1), the specific process of the electrode substrate pretreatment comprises: soaking the electrode substrate in acetone at room temperature, and then cleaning with ethanol and then deionized water; and after cleaning, drying for later use.
4. The preparation method of claim 3, wherein the electrode substrate is soaked in acetone for 0.5-1h, and then washed with ethanol for 3-5 times, and then with deionized water for 3-7 times; and after cleaning, drying at 60-80 ℃ for later use.
5. The method according to claim 1, wherein the nitrate is manganese nitrate or iron nitrate.
6. The method according to claim 1, wherein the humic substance is humic acid, fulvic acid or humins.
7. The preparation method according to claim 1, wherein in the step 2), the mass ratio of the nitrate to the citric acid is in the range of 1:6 to 2: 1.
8. The method according to claim 1, wherein the mass ratio of the nitrate to the humus in step 2) is in the range of 1:2 to 5: 1.
9. The method according to claim 1, wherein the colloid forming temperature in the colloid preparing process in step 2) is 60-80 ℃.
10. The method according to claim 1, wherein in step 2), the humic substance is added 0.5 to 2 hours before the colloid is formed.
11. The preparation method according to claim 1, wherein in the step 3), the electrode substrate is dipped in the colloid and then dried, and the drying is repeated for 1 to 3 times, wherein the drying temperature is 40 to 80 ℃.
12. The preparation method according to claim 1, wherein in the step 4), the electrode substrate loaded with the humus-metal salt colloid is aged at room temperature for 8-24 h.
13. The method as claimed in claim 1, wherein the step 5) comprises a step of calcining the aged electrode substrate at a temperature of 160-240 ℃ for a time of 1-2 h.
14. A humus-metal oxide composite modified electrode prepared by the preparation method of any one of claims 1 to 13.
15. Use of the humus-metal oxide composite modified electrode of claim 14 in a bioelectrochemical system.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101532147A (en) * | 2009-02-26 | 2009-09-16 | 中国船舶重工集团公司第七二五研究所 | Nanocrystal metal oxide composite electrode and method for preparing same |
| KR20090108964A (en) * | 2008-04-14 | 2009-10-19 | 한국기초과학지원연구원 | Manufacturing method of active electrode materials nano carbon coated with humic acid for lithium batteries |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| US20180019070A1 (en) * | 2016-07-15 | 2018-01-18 | Nanotek Instruments, Inc. | Humic Acid-Based Supercapacitors |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090108964A (en) * | 2008-04-14 | 2009-10-19 | 한국기초과학지원연구원 | Manufacturing method of active electrode materials nano carbon coated with humic acid for lithium batteries |
| CN101532147A (en) * | 2009-02-26 | 2009-09-16 | 中国船舶重工集团公司第七二五研究所 | Nanocrystal metal oxide composite electrode and method for preparing same |
| CN105489908A (en) * | 2016-01-13 | 2016-04-13 | 中国科学院广州能源研究所 | Application of humic acid composite biochar in microbial fuel cell and preparation method of humic acid composite biochar |
| US20180019070A1 (en) * | 2016-07-15 | 2018-01-18 | Nanotek Instruments, Inc. | Humic Acid-Based Supercapacitors |
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