CN112916027A - Method for preparing iron phosphide/carbon composite material by using yeast biomass - Google Patents
Method for preparing iron phosphide/carbon composite material by using yeast biomass Download PDFInfo
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- CN112916027A CN112916027A CN201911239216.2A CN201911239216A CN112916027A CN 112916027 A CN112916027 A CN 112916027A CN 201911239216 A CN201911239216 A CN 201911239216A CN 112916027 A CN112916027 A CN 112916027A
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- yeast
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
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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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
The invention discloses a method for preparing an iron phosphide/carbon composite material by using yeast, which comprises the following steps: bread yeast, ferric trichloride hexahydrate and ammonium bicarbonate are used as raw materials, a certain amount of iron oxyhydroxide is loaded on the surface of the bread yeast by a coprecipitation method, the produced yeast/iron oxyhydroxide compound is centrifugally washed, then is freeze-dried, and is frozen and dried in 700- oCCalcining under the protective atmosphere to obtain the iron phosphide/carbon material with the pore structure. The material can catalyze oxygen in an aqueous solution to generate an active oxygen component to degrade sulfamethoxazole. The invention not only recycles phosphorus resources in biomass, but also provides a preparation method of transition metal phosphide, and realizes the purpose of realizing water bodyHigh-efficiency removal of mesosulfamethoxazole.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a method for preparing an iron phosphide/carbon composite material by using yeast biomass.
Background
Advanced oxidation techniques (AOPs) have been investigated for the degradation treatment of organic pollutants because they generate some highly reactive oxidizing radicals. Generally, an additional oxidant such as ozone, hydrogen peroxide, persulfate and the like is required for obtaining the active oxygen free radical component. The expensive cost of raw materials or the difficulty of storage and transportation limit the wide application. In recent years, researchers have attracted extensive attention to the use of the electron transfer capability of low-valence iron ions (ferrous iron) to activate oxygen in an aqueous solution to generate an active oxygen component for treating groundwater organic pollutants, but iron ions have the disadvantages of difficult recovery, low activity and the like, and therefore, the development of a lower-valence active iron solid catalyst for catalyzing oxygen to generate active oxygen is of great practical significance.
The transition metal phosphide is an important compound formed by connecting a phosphorus atom and a transition metal through a covalent bond or a metal bond, and not only has the characteristics of high strength and high hardness of the metal, but also has good conductivity and stability. At present, transition metal phosphide is widely researched and used in the fields of catalytic hydrogenation in the petroleum industry, hydrogen evolution and oxygen evolution of electrochemistry and the like. Among them, iron phosphide is of great interest because of its rich iron resource and low valence state of iron, which is easy to generate electron transfer. The traditional phosphide synthesis needs toxic reagents such as red phosphorus and trioctylphosphine as phosphorus sources or needs complex processes such as hydrogen reduction and the like, and is difficult to popularize and apply, and considering that biomass not only contains rich carbon elements, but also contains phospholipid bilayers in cell membranes and ribonucleic acid also contains phosphorus elements. Therefore, the biomass can be used as a phosphorus source and a carbon source to synthesize the transition metal phosphide/carbon composite material. The invention utilizes high-temperature anoxic pyrolysis of yeast biomass loaded with hydroxyl ferric oxide to prepare an iron phosphide/carbon material which is used for catalyzing oxygen in an aqueous solution to generate active free radicals to remove sulfamethoxazole.
Disclosure of Invention
The invention aims to provide a method for preparing an iron phosphide/carbon composite material by using yeast biomass.
The purpose of the invention is realized by the following technical scheme.
A method for preparing an iron phosphide/carbon composite material by using yeast biomass comprises the following specific operations:
(1) uniformly dispersing a certain mass of baker's yeast in 100-500 mL of ethanol, adding ferric chloride hexahydrate according to a certain proportion under magnetic stirring, adding ammonium bicarbonate after uniform mixing, and continuously stirring for 6-12 h to obtain a yeast/hydroxyl iron oxide suspension;
(2) centrifugally washing the suspension obtained in the step (1), and then putting the suspension into a freeze dryer for drying to obtain a compound of the yeast and the hydroxyl ferric oxide;
(3) transferring the compound obtained in the step (2) into a corundum crucible, placing the corundum crucible into a tube furnace, and calcining the corundum crucible in an inert atmosphere at the calcining temperature of 700-oC, calcining for 2-6 h, and heating up at a rate of 5oC/min, obtaining black powder after the calcining procedure is finished;
(4) washing the black powder obtained in step (3) with deionized water, and drying in a vacuum drying oven 60oC, drying to obtain an iron phosphide/carbon material;
(5) preparing 20 mg/L sulfamethoxazole, taking the iron phosphide/carbon material obtained in the step (5) as a catalyst, adding a sulfamethoxazole-containing solution according to a certain proportion, and then placing the mixture in a constant-temperature shaking table for catalytic degradation.
The product shows Fe by X-ray crystal diffraction analysis (XRD)3P and Fe2P。
Optionally, in step (1), the transition metal used is iron.
Optionally, in step (1), the precipitant used is ammonium bicarbonate.
Optionally, in step (4), the protective atmosphere used for the calcination of the composite is nitrogen or argon.
Optionally, in step (5), the organic contaminant is selected from sulfamethoxazole solution.
The invention has the following innovation and beneficial effects:
(1) the invention firstly uses baker's yeast biomass as a phosphorus source and a carbon source, prepares the high-catalytic-activity ferric phosphide/carbon material by coprecipitation and high-temperature calcination, is used for catalyzing oxygen in aqueous solution to degrade organic pollutants in water, realizes high-value utilization of phosphorus in the biomass, simultaneously provides a preparation method of transition metal phosphide, and can realize high-efficiency degradation and removal of sulfamethoxazole in the water.
(2) The iron phosphide/carbon material prepared by the method does not need to be additionally added with an oxidant, and can directly catalyze oxygen in an aqueous solution to generate active oxygen so as to degrade organic matters.
Description of the drawings:
FIG. 1 is an X-ray crystal diffraction analysis chart of an iron phosphide/carbon material prepared in examples 1 to 3 of the present invention;
FIG. 2 is a schematic diagram of sulfamethoxazole degradation by different materials obtained in examples 1 to 3 of the present invention;
FIG. 3 is a graph showing a signal for detecting active oxygen generated in example 3 of the present invention.
The specific implementation mode is as follows:
for a better understanding of the invention, reference is made to the following detailed description of the invention in conjunction with the accompanying drawings. It should be specifically noted that the examples are provided only for the purpose of further illustrating the present invention, and the scope of the present invention as claimed should not be limited thereto.
Example 1 was carried out:
50 g of baker's yeast cells are evenly dispersed in 500 mL of ethanol, 2.41 g of ferric chloride hexahydrate is respectively added under magnetic stirring, then a certain amount of ammonium bicarbonate is added, continuous stirring is carried out for 6-12 h, and the obtained compound is dried in a freeze dryer after being centrifugally washed. Transferring the dried compound to a corundum crucible, placing the corundum crucible in a tubular furnace, and calcining the corundum crucible in a protective atmosphere at the calcining temperature of 900 DEG CoC, calcining for 2-6 h, and heating up at a rate of 5oC/min, cooling to room temperature and taking out. The resulting material was washed with deionized water in a vacuum drying oven 60oC, drying to obtain an iron phosphide/carbon material which is named1%-Fe。
Example 2 was carried out:
50 g of baker's yeast cells are evenly dispersed in 500 mL of ethanol, 7.24 g of ferric chloride hexahydrate is respectively added under magnetic stirring, then a certain amount of ammonium bicarbonate is added, continuous stirring is carried out for 6-12 h, and the obtained compound is dried in a freeze dryer after being centrifugally washed. Transferring the dried compound to a corundum crucible, placing the corundum crucible in a tubular furnace, and calcining the corundum crucible in a protective atmosphere at the calcining temperature of 900 DEG CoC, calciningThe time is 2-6 h, and the heating rate is 5oC/min, cooling to room temperature and taking out. The resulting material was washed with deionized water in a vacuum drying oven 60oC, drying to obtain an iron phosphide/carbon material which is named3%-Fe。
Example 3 of implementation:
50 g of baker's yeast cells are evenly dispersed in 500 mL of ethanol, 12.07 g of ferric chloride hexahydrate is respectively added under magnetic stirring, then a certain amount of ammonium bicarbonate is added, continuous stirring is carried out for 6-12 h, and the obtained compound is dried in a freeze dryer after being centrifugally washed. Transferring the dried compound to a corundum crucible, placing the corundum crucible in a tubular furnace, and calcining the corundum crucible in a protective atmosphere at the calcining temperature of 900 DEG CoC, calcining for 2-6 h, and heating up at a rate of 5oC/min, cooling to room temperature and taking out. The resulting material was washed with deionized water in a vacuum drying oven 60oC, drying to obtain an iron phosphide/carbon material which is named5%-Fe。
In order to examine the catalytic degradation performance of the iron phosphide/carbon material on sulfamethoxazole, 20 mg/L sulfamethoxazole solution is prepared, and 40 mg of sulfamethoxazole solution is subjected to shaking table rotation speed of 180 rpm at 30 DEG1%-Fe，3%-Fe， 5%- FeThe sample was added to 100 ml of sulfamethoxazole solution, and the sample was sampled at regular intervals to detect the concentration of the residual sulfamethoxazole solution by high performance liquid chromatography. According to the analysis result, within 30 min1%-Fe，3%-Fe，5%-FeThe degradation removal rate of the sample on sulfamethoxazole reaches 89.2 percent, 97.9 percent and 99.0 percent respectively. The comparative results of this experiment are shown in FIG. 2. The active oxygen component signal generated on the system is captured by an electron paramagnetic resonance spectrometer as shown in fig. 3.
Claims (6)
1. A method for preparing an iron phosphide/carbon composite material by using yeast biomass is characterized by comprising the following steps:
(1) uniformly dispersing certain mass of baker's yeast cells in 100-500 mL of ethanol, adding ferric chloride hexahydrate according to a certain proportion under magnetic stirring, adding ammonium bicarbonate after uniform mixing, and continuously stirring for 6-12 h to obtain a yeast/iron oxyhydroxide suspension;
(2) centrifugally washing the suspension obtained in the step (1), and then putting the suspension into a freeze dryer for drying to obtain a compound of the yeast and the hydroxyl ferric oxide;
(3) transferring the compound obtained in the step (2) into a corundum crucible, placing the corundum crucible into a tube furnace, and calcining the corundum crucible in a protective atmosphere at the calcining temperature of 700-oC, calcining for 2-6 h, and heating up at a rate of 5oC/min, obtaining black powder after the calcining procedure is finished;
(4) washing the black powder obtained in step (3) with deionized water, and drying in a vacuum drying oven 60oC, drying to obtain an iron phosphide/carbon material;
(5) preparing 20 mg/L sulfamethoxazole, taking the iron phosphide/carbon material obtained in the step (5) as a catalyst, adding a sulfamethoxazole-containing solution according to a certain proportion, and then placing the mixture in a constant-temperature shaking table for catalytic degradation.
2. The method for preparing iron phosphide/carbon composite material by using yeast biomass as claimed in claim 1, wherein the transition metal in step (1) is iron, but not limited to iron, and other transition metals such as cobalt, nickel and the like are also suitable for synthesizing the transition metal phosphide by the method.
3. The method for preparing iron phosphide/carbon composite material by using yeast biomass as claimed in claim 1, wherein the precipitation reagent in step (1) is ammonium bicarbonate, but the precipitation reagent is not limited to ammonium bicarbonate, and other alkaline reagents such as ammonia water, sodium hydroxide and the like are also suitable for the method.
4. The method for preparing iron phosphide/carbon composite material by using yeast biomass as claimed in claim 1, wherein the biomass in step (1) is baker's yeast, but not limited to baker's yeast, other phosphorus-containing biomass such as candida utilis, chlorella and the like are also applicable to the method.
5. The method for preparing iron phosphide/carbon composite material by using yeast biomass as claimed in claim 1, wherein the atmosphere for protection used in the calcination in the step (3) is nitrogen or argon.
6. The method for preparing iron phosphide/carbon composite material by using yeast biomass as claimed in claim 1, wherein the organic pollutant used in step (5) is sulfamethoxazole, but is not limited to sulfamethoxazole, and any environmental organic pollutant existing in water body and capable of being degraded by the material catalysis should be included, such as sulfanilamide, sulfathiazole, dye, etc.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064717A (en) * | 2022-07-12 | 2022-09-16 | 郑州大学 | ORR-OER catalyst for zinc-air battery anode and preparation method thereof |
| CN116873886A (en) * | 2023-05-15 | 2023-10-13 | 同济大学 | Yeast-derived metal phosphide electrode material and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064717A (en) * | 2022-07-12 | 2022-09-16 | 郑州大学 | ORR-OER catalyst for zinc-air battery anode and preparation method thereof |
| CN116873886A (en) * | 2023-05-15 | 2023-10-13 | 同济大学 | Yeast-derived metal phosphide electrode material and preparation method and application thereof |
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