CN112658278A - Green preparation method and application of palladium-iron bimetallic nano material - Google Patents
Green preparation method and application of palladium-iron bimetallic nano material Download PDFInfo
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- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention is suitable for the technical field of preparation of palladium-iron bimetallic nano materials, and provides a green preparation method and application of a palladium-iron bimetallic nano material, which comprises the following steps: drying the cleaned pomegranate rind, grinding the dried pomegranate rind, and sieving the ground pomegranate rind with a 30-50-mesh sieve to obtain dried pomegranate rind powder; putting the pomegranate rind powder into a utensil, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and carrying out vacuum filtration to obtain a pomegranate rind extracting solution; taking the pomegranate rind extract liquid in a beaker, and sucking FeSO by using a syringe4Dropwise adding the solution into a flask, and stirring to obtain a zero-valent iron nano-material mixed solution; measuring a certain volume of potassium chloropalladate solution, adding the potassium chloropalladate solution into the zero-valent iron nano material mixed solutionIn the method, the Pd/Fe mass ratio wt% is 0.1% -1.0%, and the P-Pd/Fe nano material mixed liquor with different Pd loading amounts is prepared by stirring. Therefore, the P-Pd/Fe nano material can be prepared from the pomegranate rind.
Description
Technical Field
The invention relates to the technical field of preparation of palladium-iron bimetallic nano materials, in particular to a green preparation method of a palladium-iron bimetallic nano material.
Background
Polybrominated diphenyl ethers are a generic name of brominated flame retardants, and are widely added to plastic products, electronic components, textiles, furniture and building materials as flame retardant materials. The polybrominated diphenyl ether is a persistent organic pollutant, has stable chemical property, is difficult to degrade in natural environment, has long retention time, and has the characteristics of low water solubility, strong lipophilicity, high toxicity and the like. At present, polybrominated diphenyl ethers are widely detected in water, air, soil, sediments, animals, plants and human bodies in the global range, and become a global pollution problem. In the fourth contracting convention of stockholm convention, held in geneva, switzerland in 2009, commercially available pentabromodiphenyl ethers and octabromodiphenyl ethers were listed and regulated in POPs.
The palladium-iron bimetallic (Pd/Fe) nano material has large specific surface area, strong catalytic reduction capability and high reaction activity, is a good environment functional material, and can effectively remove polybrominated diphenyl ethers in polluted water bodies and soil. However, the traditional Pd/Fe nano material preparation method has some problems and defects: if the requirement of the equipment required by the physical method is high, the reducing agents (such as borohydride, hydrazine hydrate and the like) used in the chemical method have high toxicity, and the prepared Pd/Fe nano material is easy to agglomerate under the action of surface energy and magnetic force and is easy to oxidize in the air, so that the reaction activity is reduced. Therefore, the development of a method for preparing Pd/Fe nano-materials, which is environment-friendly, simple to operate and low in cost, is needed. Researches show that plant extract such as tea leaves, eucalyptus leaves and the like contains polyphenol, reducing sugar, protein and enzyme substances, and can be used as a reducing agent and a stabilizing agent to synthesize a green Pd/Fe nano material. Compared with the traditional method, the method is simple to operate, green and environment-friendly, and the synthesized nano material has good oxidation resistance and dispersibility, high reaction activity and large-scale application potential.
Pomegranate is deciduous tree or shrub, and is planted in north and south of China. The fruit is spherical, has multiple seeds and rich nutrition, and the content of vitamin C is higher than that of apples and pears. After eating, the pomegranate produces a large amount of waste peel, and direct discarding can cause resource waste and environmental pollution, so the pomegranate peel needs to be utilized, and waste recycling is realized. The pomegranate rind contains a large amount of plant polyphenol and reducing carbohydrate, and theoretically has the possibility of preparing green Pd/Fe nano materials. At present, no report is found about a method for preparing a Pd/Fe nano material in a green manner by using a pomegranate bark extracting solution and catalytically degrading typical polybrominated diphenyl ether (2,2 ', 4' -tetrabromobiphenyl ether (BDE47)) in water and an application.
In view of the above, the prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.
Disclosure of Invention
In view of the above-mentioned drawbacks, the present invention aims to provide a green preparation method of a pd-fe bimetallic nanomaterial, which can prepare the pd-fe bimetallic nanomaterial through pomegranate rind, and has a low cost.
In order to achieve the above object, the present invention provides a method for preparing a palladium-iron bimetallic nanomaterial, the method comprising:
the preparation method of the pomegranate bark extracting solution comprises the following steps:
placing the cleaned pomegranate rind in an environment of 60-80 ℃ for drying, grinding the dried pomegranate rind, and sieving the ground pomegranate rind by a sieve of 30-50 meshes to obtain dried pomegranate rind powder;
putting a predetermined amount of pomegranate bark powder into a device, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and performing vacuum filtration to obtain a pomegranate bark extracting solution;
the preparation method of the zero-valent iron nano material mixed solution comprises the following steps:
putting T ml of pomegranate peel extracting solution into a beaker, sucking 0.05-0.2 mol/L FeSO4 or FeCl3 solution of T/2ml by using an injector, dropwise adding the solution into the flask, and mechanically stirring for 5min to prepare a zero-valent iron nano material mixed solution;
the synthesis of the P-Pd/Fe nano material comprises the following steps:
measuring a certain volume of potassium chloropalladate or palladium acetate solution, adding the solution into the zero-valent iron nano-material mixed solution to ensure that the mass ratio wt% of Pd/Fe is 0.1-1.0%, and stirring for 5min to obtain the P-Pd/Fe nano-material mixed solution with different Pd loading amounts.
According to the preparation method of the palladium-iron bimetallic nanomaterial, the synthesis step of the P-Pd/Fe nanomaterial further comprises the following steps: and (3) carrying out vacuum filtration on the P-Pd/Fe nano material mixed solution, and then placing the P-Pd/Fe nano material mixed solution in a vacuum environment at the temperature of 60-80 ℃ to obtain P-Pd/Fe nano material solid powder.
According to the preparation method of the palladium-iron bimetallic nano material, the rotation speed of mechanical stirring in the steps of preparing the zero-valent iron nano material mixed solution and synthesizing the P-Pd/Fe nano material is 100-200 r/min.
According to the preparation method of the palladium-iron bimetallic nanomaterial, in the synthesis step of the P-Pd/Fe nanomaterial, the Pd/Fe mass ratio wt% is 0.5%.
According to the preparation method of the palladium-iron bimetallic nano material, the preparation step of the pomegranate bark extracting solution is as follows: the feed-liquid ratio in (1) is 10g/200 mL.
The invention also provides an application of the palladium-iron bimetallic nano material prepared by the method in degradation of polybrominated diphenyl ethers.
The invention is suitable for the technical field of preparation of palladium-iron bimetallic nano-materials, and provides a preparation method and application of a palladium-iron bimetallic nano-material, wherein the preparation method comprises the following steps: drying the cleaned pomegranate rind, grinding the dried pomegranate rind, and sieving the ground pomegranate rind with a 30-50-mesh sieve to obtain dried pomegranate rind powder; putting the pomegranate rind powder into a utensil, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and carrying out vacuum filtration to obtain a pomegranate rind extracting solution; taking the pomegranate rind extract liquid in a beaker, and sucking FeSO by using a syringe4Solutions or FeCl3Dropwise adding the solution into a flask, and stirring to obtain a zero-valent iron nano-material mixed solution; measuring a certain volume of potassium chloropalladate or palladium acetate solution, adding the solution into the zero-valent iron nano material mixed solution to ensure that the mass ratio wt% of Pd/Fe is 0.1-1.0%, and stirring to obtain the P-Pd/Fe nano material mixed solution with different Pd loading amounts. Therefore, the P-Pd/Fe nano material can be prepared from the pomegranate rind, and the cost is low.
Drawings
FIG. 1 is a morphological feature of a P-Pd/Fe nano-material mixed solution prepared by the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) analysis diagram of the P-Pd/Fe nano material prepared by the invention;
FIG. 3 is an X-ray diffraction (XRD) analysis diagram of the P-Pd/Fe nano-material prepared by the present invention;
FIG. 4A is an X-ray photoelectron spectroscopy (XPS) analysis chart of P-Pd/Fe nano material prepared by the present invention;
FIG. 4B is an XPS analysis of Fe 2p of the present invention;
FIG. 4C is an XPS analysis of Pd 3p of the present invention;
FIG. 5 is a FT-IR spectrum of P-Pd/Fe nano-material prepared by the present invention;
FIG. 6 is a schematic diagram of the BDE47 removal rate according to one embodiment of the invention;
FIG. 7 is a graph of the effect of initial solution pH on BDE47 removal in accordance with an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The Pd/Fe nano material prepared by the pomegranate bark extracting solution is referred to as P-Pd/Fe nano material for short.
The invention provides a method for green synthesis of a palladium-iron bimetallic nano material by using pomegranate rind, which comprises the following steps:
the preparation method of the pomegranate bark extracting solution comprises the following steps:
placing the cleaned pomegranate rind in an environment of 60-80 ℃ for drying, grinding the dried pomegranate rind, and sieving the ground pomegranate rind by a sieve of 30-50 meshes to obtain dried pomegranate rind powder;
putting a predetermined amount of pomegranate bark powder into a device, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and carrying out vacuum filtration to obtain a pomegranate bark extracting solution. In the step, the material-liquid ratio of the pomegranate rind to tap water is 10g/200 mL.
The preparation method of the zero-valent iron nano material mixed solution comprises the following steps:
taking T ml of pomegranate peel extracting solution in a beaker, and sucking 0.05-0.2 mol/L FeSO of T/2ml by using an injector4Or FeCl3Dropwise adding the solution into a flask, and mechanically stirring for 5min to obtain a zero-valent iron nano-material mixed solution.
The synthesis of the P-Pd/Fe nano material comprises the following steps:
measuring a certain volume of potassium chloropalladate or palladium acetate solution, adding the solution into the zero-valent iron nano-material mixed solution to ensure that the mass ratio wt% of Pd/Fe is 0.1-1.0%, and stirring for 5min to obtain the P-Pd/Fe nano-material mixed solution with different Pd loading amounts.
In one embodiment of the invention, in the step of preparing the pomegranate bark extracting solution, 10g of dried pomegranate bark can be weighed and put into a triangular conical flask, 200mL of tap water is added, the mixture is heated at 60-80 ℃ for 2h, and vacuum filtration is carried out, so that the pomegranate bark extracting solution is obtained and is placed in a brown glass reagent bottle for later use.
In the preparation step of the zero-valent iron nano material mixed solution, 100mL of pomegranate peel extract is measured and put in a beaker, and 50mL of 0.05-0.2 mol/L FeSO is absorbed by an injector4Or FeCl3Dropwise adding the solution into a flask, and mechanically stirring for 5min (100-200 r/min), wherein Fe2+Or Fe3+Reducing Fe0 by the pomegranate peel extracting solution to obtain black zero-valent iron nano material mixed solution.
In the green synthesis step of the P-Pd/Fe nano material, potassium chloropalladate or palladium acetate solution with a certain volume is measured and added into the mixed solution of the zero-valent iron nano material to ensure that the mass ratio wt% of Pd/Fe (namely the load capacity of Pd) is 0.1-1.0%, and the Pd is mechanically stirred for 5min (100-200 r/min)2+Quilt Fe0And the pomegranate bark extract is reduced into Pd0Thus obtaining P-Pd/Fe nano material mixed liquor with different Pd loading capacity, and storing the P-Pd/Fe nano material mixed liquor in a refrigerator at 4 ℃ for later use. In the step, P-Pd/Fe nano-material solid powder can be obtained in a vacuum drying oven at 60-80 ℃ after vacuum filtration.
In an embodiment of the present invention, the P-Pd/Fe nanomaterial prepared by the above method has the characteristics shown in fig. 1 to 4C.
As shown in figure 1, the P-Pd/Fe nano material is uniformly dispersed into the solution and is black without layering and precipitation, which shows that the pomegranate bark extract is used for preparing Fe2+Or Fe3+Reduction to Fe0Meanwhile, the nano-material can be used as a stabilizer and a dispersant to uniformly disperse the nano-material into a solution system, so that the nano-material is reducedThe material is settled and layered due to agglomeration, and the mobility of the nano material is improved.
Referring to fig. 2 again, the vacuum dried Pd/Fe nano-material is mainly spherical or ellipsoidal particles, the particle size is 30-100 nm, and the particle size distribution is relatively uniform.
FIG. 3 shows that 2 θ is 240There is a broad diffraction peak in the vicinity, which is caused by the organic components in the pomegranate rind extract. 44.8 at 2 theta0With weak alpha-Fe0The characteristic diffraction peak of the green synthesized P-Pd/Fe nano material shows that zero-valent iron exists on the surface of the green synthesized P-Pd/Fe nano material, but the zero-valent iron content is low because the organic components in the pomegranate rind are wrapped on the surface of the material.
As shown in FIG. 4A, C, O, N, Fe is present on the surface of the Pd/Fe nano-material. FIG. 4B shows that characteristic peaks of Fe 2P3/2 and Fe 2P1/2 exist near the binding energies of 711.9 and 725.8eV, which indicates that Fe oxide or hydroxide exists on the surface of the P-Pd/Fe nano material; the existence of characteristic peak at 706.9eV shows that Fe exists on the surface of the material0. FIG. 4C shows that the characteristic peaks of Pd 3d3/2 and Pd 3d5/2 exist at the binding energies of 340.7 and 335.3eV, which indicates that Pd exists on the surface of the material0. The X-ray photoelectron spectrum shows that the Pd/Fe nano material is successfully prepared by the pomegranate bark extract.
The invention also uses the P-Pd/Fe nano material mixed solution prepared by the method for degrading the typical polybrominated diphenyl ether-BDE 47 in the wastewater. The main chemical reaction principle of the application is as follows:
(1)Fe0and H2Reaction of O to H2
Fe0+2H+→Fe2++H2(acid solution) (formula 1)
Fe0+2H2O→Fe2++H2+2OH-(neutral or alkaline solution) (formula 2)
(2) Generation of H2Adsorbed by metal Pd and embedded into crystal lattice to form strong reducing substance Pd.2H.
H2+ Pd → Pd.2H (formula 3)
(3) BDE47 (in RBr) in wastewater4Is expressed) is adsorbed by metal PdAttached to the bromine element and combined with the p electron pair to form a transition complex Pd & R & Br4。
RBr4+Pd→Pd…R…Br4(formula 4)
(4) Pd.2H and Pd.R.Br4Catalytic hydrogenation reaction is carried out, bromine atoms are removed from BDE47 to form Br-Into solution.
Pd·2H*+Pd…R…Br4→2Pd+RBr3+H++Br-(formula 5)
(5) Low bromination reaction product RBr3And then the diphenyl ether is finally generated by debrominating step by step through the same reaction.
In one embodiment, the P-Pd/Fe nano material mixed solution and the BDE 47-containing wastewater solution with different volumes are mixed in a flask, so that the addition amount of the P-Pd/Fe nano material in the mixed solution is 0.1-0.5 g.L-1The Pd loading was 0.3% and the initial concentration of BDE47 was 5 mg.L-1 Initial pH 4, shaking or stirring for 30min, sampling with a glass syringe, filtering the sample with 0.45 μm glass fiber membrane, and measuring the BDE47 concentration with high performance liquid chromatography. The results of the experiment are shown in FIG. 5. In FT-IR spectrogram of Pd/Fe nano material, 3395cm-1Near the vibration absorption peaks of O-H, 1698 and 1426cm-1Near C ═ C stretching vibration peak, 1063cm-1The vicinity of the peak is a symmetrical absorption peak of C-O-C, 2920cm-1Nearby is-CH2A stretching vibration peak. FT-IR spectrogram analysis shows that the organic components in the pomegranate bark extracting solution are coated on the surface of the P-Pd/Fe nano material.
In addition, a certain volume of the P-Pd/Fe nano material mixed solution and the wastewater solution containing BDE47 are mixed in a flask, so that the addition amount of the P-Pd/Fe nano material in the mixed solution is 0.3 g.L < -1 >, the loading amount of Pd is 0.3 percent, and the initial concentration of BDE47 is 5 mg.L < -1 >-1Initial pH values of 4, 7 and 10, shaking or stirring for 30min, sampling by a glass syringe at a certain time point, filtering the sample by a 0.45 mu m glass fiber membrane, and measuring the BDE47 concentration by high performance liquid chromatography. The experimental results are shown in FIG. 6, and the removal effect of BDE47 is shown by different dosage of P-Pd/Fe nano materials. From the figure, it can be seen that the removal rate of BDE47 is dependent on the P-Pd/Fe nano-materialThe addition amount is increased when the addition amount of the P-Pd/Fe nano material is 0.3 g.L-1In the process, the removal rate of BDE47 in 30min is 95.6 percent, BDE47 in wastewater can be removed well, the addition amount of nano materials is increased, the removal rate of BDE47 is improved in a limited way, and therefore 0.3 g.L can be selected-1The removal experiment of BDE47 was carried out with the addition of P-Pd/Fe nanomaterial.
Referring to fig. 7, the removal rate of BDE47 decreased with increasing initial pH of the solution. When the initial pH value of the solution is 4, the removal rate of BDE47 in 30min is 95.6%, and when the initial pH value of the solution is increased to 7 and 10, the removal rate of BDE47 is respectively reduced to 86.8% and 78.5%, which shows that acidic conditions are more favorable for the removal of BDE47 by the P-Pd/Fe nano-material.
In summary, the invention is applicable to the technical field of preparation of palladium-iron bimetallic nano-materials, and provides a green preparation method and application of the palladium-iron bimetallic nano-material, which comprises the following steps: drying the cleaned pomegranate rind, grinding the dried pomegranate rind, and sieving the ground pomegranate rind with a 30-50-mesh sieve to obtain dried pomegranate rind powder; putting the pomegranate rind powder into a utensil, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and carrying out vacuum filtration to obtain a pomegranate rind extracting solution; putting the pomegranate peel extracting solution into a beaker, sucking FeSO4 or FeCl3 solution by using an injector, dropwise adding the solution into the flask, and stirring to prepare a zero-valent iron nano material mixed solution; measuring a certain volume of potassium chloropalladate or palladium acetate solution, adding the solution into the zero-valent iron nano material mixed solution to ensure that the mass ratio wt% of Pd/Fe is 0.1-1.0%, and stirring to obtain the P-Pd/Fe nano material mixed solution with different Pd loading amounts. Therefore, the P-Pd/Fe nano material can be prepared from the pomegranate rind, and the cost is low.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A green preparation method of a palladium-iron bimetallic nano material is characterized by comprising the following steps:
the preparation method of the pomegranate bark extracting solution comprises the following steps:
placing the cleaned pomegranate rind in an environment of 60-80 ℃ for drying, grinding the dried pomegranate rind, and sieving the ground pomegranate rind by a sieve of 30-50 meshes to obtain dried pomegranate rind powder;
putting a predetermined amount of pomegranate bark powder into a device, adding a proper amount of tap water according to a predetermined material-liquid ratio, heating at 60-80 ℃ for 2h, and performing vacuum filtration to obtain a pomegranate bark extracting solution;
the preparation method of the zero-valent iron nano material mixed solution comprises the following steps:
taking T ml of pomegranate peel extracting solution in a beaker, and sucking 0.05-0.2 mol/L FeSO of T/2ml by using an injector4Or FeCl3Dropwise adding the solution into a flask, and mechanically stirring for 5min to obtain a zero-valent iron nano-material mixed solution;
the synthesis of the P-Pd/Fe nano material comprises the following steps:
measuring a certain volume of potassium chloropalladate or palladium acetate solution, adding the solution into the zero-valent iron nano-material mixed solution to ensure that the mass ratio wt% of Pd/Fe is 0.1-1.0%, and stirring for 5min to obtain the P-Pd/Fe nano-material mixed solution with different Pd loading amounts.
2. The green preparation method of the palladium-iron bimetallic nanomaterial as in claim 1, wherein the synthesis step of the P-Pd/Fe nanomaterial further comprises: and (3) carrying out vacuum filtration on the P-Pd/Fe nano material mixed solution, and then placing the P-Pd/Fe nano material mixed solution in a vacuum environment at the temperature of 60-80 ℃ to obtain P-Pd/Fe nano material solid powder.
3. The preparation method of the Pd-Fe bimetallic nano-material as in claim 1, wherein the rotation speed of mechanical stirring in the steps of preparing the zero-valent Fe nano-material and synthesizing the P-Pd/Fe nano-material is 100-200 r/min.
4. The green preparation method of the Pd-Fe bimetallic nano-material as in claim 1, wherein in the synthesis step of the P-Pd/Fe nano-material, the Pd/Fe mass ratio wt% is 0.5%.
5. The preparation method of the palladium-iron bimetallic nanomaterial as claimed in claim 1, characterized in that the preparation step of the pomegranate bark extract liquid is as follows: the feed-liquid ratio in (1) is 10g/200 mL.
6. The application of the palladium-iron bimetallic nano material prepared in the claim 1 in degradation of polybrominated diphenyl ethers.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100721A (en) * | 2013-01-23 | 2013-05-15 | 昆明理工大学 | Method for preparing modified nanometer-palladium/iron duplex-metal particles |
| CN105750562A (en) * | 2016-04-21 | 2016-07-13 | 太原理工大学 | Method for green synthesis of nanometer zero-valent iron suspension liquid with peels or seed kernels |
| CN106186163A (en) * | 2016-08-15 | 2016-12-07 | 华南师范大学 | A kind of preparation method and application of PBDE pollution waters restoration material |
| WO2017063558A1 (en) * | 2015-10-13 | 2017-04-20 | 吴倍任 | Composite material in catalytic hydrogenolysis and preparation method and use thereof |
| CN109847774A (en) * | 2019-03-16 | 2019-06-07 | 泉州师范学院 | It is a kind of for removing the preparation method and application of p-nitrophenol material |
-
2020
- 2020-12-18 CN CN202011508944.1A patent/CN112658278A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100721A (en) * | 2013-01-23 | 2013-05-15 | 昆明理工大学 | Method for preparing modified nanometer-palladium/iron duplex-metal particles |
| WO2017063558A1 (en) * | 2015-10-13 | 2017-04-20 | 吴倍任 | Composite material in catalytic hydrogenolysis and preparation method and use thereof |
| CN105750562A (en) * | 2016-04-21 | 2016-07-13 | 太原理工大学 | Method for green synthesis of nanometer zero-valent iron suspension liquid with peels or seed kernels |
| CN106186163A (en) * | 2016-08-15 | 2016-12-07 | 华南师范大学 | A kind of preparation method and application of PBDE pollution waters restoration material |
| CN109847774A (en) * | 2019-03-16 | 2019-06-07 | 泉州师范学院 | It is a kind of for removing the preparation method and application of p-nitrophenol material |
Non-Patent Citations (1)
| Title |
|---|
| 李长芳等: "纳米Pd /Fe 催化甲醇/水中2，2"，4，4"-四溴联苯醚( BDE-47) 还原脱溴", 《环境科学学报》 * |
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