Method for degrading chlorobenzene pollutants based on reduction-oxidation coupling
By using a reduction-oxidation coupling method with modified biochar-supported nano-iron-palladium particles, the problem of secondary pollution from the degradation products of chlorobenzene pollutants was solved, achieving rapid mineralization and non-toxic treatment.
Patent Information
- Application Number
- CN202510913903.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-03
- Publication Date
- 2025-11-14
AI Technical Summary
Existing technologies are insufficient to effectively degrade chlorobenzene pollutants, and the degradation products are still toxic, leading to secondary pollution.
Modified biochar-supported nano-iron-palladium particles were used as the catalyst material, and a reduction-oxidation coupling method was adopted to mineralize chlorobenzene pollutants and their reduction products through a shaking reaction and hydrogen peroxide.
It achieves rapid mineralization of chlorobenzene pollutants, with short degradation time and low material consumption, and rapidly degrades highly toxic substances into non-toxic substances, making it suitable for the treatment of toxic and harmful chlorinated organic pollutants in groundwater.
Smart Images
Figure HDA0005480945030000011 
Figure HDA0005480945030000012 
Figure HDA0005480945030000021
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic pollutant degradation technology, and more specifically to a method for degrading chlorobenzene pollutants based on reduction-oxidation coupling. Background Technology
[0002] Chlorinated aromatic hydrocarbon pollutants contain stable aromatic rings and high-energy C-Cl bonds. The induced conjugation effect between the aromatic ring conjugated π bonds and chlorine atoms makes the C-Cl bond energy reach 340.2 kJ / mol, which is difficult to be attacked by nucleophiles or free radicals. In addition, they have low water solubility, high lipid solubility and high chemical stability, thus exhibiting strong persistence and bioaccumulation in the environment.
[0003] Advanced oxidation techniques can achieve dechlorination by breaking C-Cl bonds through the strong oxidizing power of hydroxyl radicals or sulfate radicals, such as persulfate activation technology under ultraviolet light or Fe... 2+ Catalysis increased the degradation rate of trichlorobenzene by 5 times compared to microbial cometabolism. The reduction system, on the other hand, utilizes the electron transfer properties of zero-valent iron (Fe0) to achieve dechlorination through hydrogenolysis.
[0004] However, the strong electron-withdrawing effect of the chlorine group weakens the electron density around the aromatic ring, hindering the electrophilic attack of ·OH. Furthermore, due to the high stability of the C-Cl bond, the oxidation process of ·OH typically leads to the breaking of the C-C bond, while the C-Cl bond remains intact. In reduction-only removal methods, although the chlorine group is easily attacked and dechlorinated by reducing species, the resulting dechlorination products cannot be further degraded and remain harmful to the environment and organisms.
[0005] Therefore, it is necessary to explore new methods for degrading chlorinated aromatic hydrocarbons in water. Summary of the Invention
[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for degrading chlorobenzene pollutants based on reduction-oxidation coupling. By using modified biochar-supported nano-iron-palladium particles as a catalyst and combining reduction-oxidation coupling, chlorobenzene pollutants and their reduction products are rapidly mineralized, thus solving the problem of secondary pollution caused by the degradation of chlorobenzene pollutants.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] A method for degrading chlorobenzene pollutants based on reduction-oxidation coupling includes the following steps:
[0009] Supported nano-iron palladium was added to the solution to be degraded, and the reaction was shaken until the chlorobenzene pollutants in the solution to be degraded were completely reduced.
[0010] Then, hydrogen peroxide was added under aerobic conditions, and the reaction was continued with shaking until the reduction products of chlorobenzene pollutants were completely mineralized.
[0011] The supported nano-iron palladium includes a support and nano-iron palladium particles supported on the support, wherein the support includes modified biochar.
[0012] As an optional implementation, the pH of the degradation solution is adjusted to 3-11.
[0013] As an optional implementation, the concentration of added hydrogen peroxide is 0.5–3 mmol / L.
[0014] As an optional implementation, the concentration of the added supported nano-iron palladium is 0.19–0.20 mg / mL.
[0015] As an optional implementation, the preparation process of the supported nano-iron palladium includes the following steps:
[0016] Iron salts and modified biochar were mixed in deionized water and stirred for adsorption. Then, an equal amount of ethanol as deionized water was added, and NaBH4 was slowly added under nitrogen purging. The reaction was continued with stirring. After the reaction was completed, the mixture was washed with water and anhydrous ethanol to obtain modified biochar-supported nano-zero valent iron.
[0017] A suspension of supported nano-iron palladium was added to a palladium acetate solution, ultrasonically dispersed, then washed with anhydrous ethanol and vacuum dried to obtain modified biochar-supported nano-iron palladium particles.
[0018] As an optional implementation, the modified biochar-supported iron-palladium nanoparticles contain 1% to 10% Pd / Fe by mass.
[0019] As an optional implementation, the iron salt includes divalent iron salt, with an iron ion concentration of 0.068–0.072 mol / L.
[0020] As an optional implementation, the concentration of NaBH4 is 0.475–0.5 mol / L.
[0021] As an optional implementation, the preparation process of the modified biochar includes:
[0022] The biomass raw material was crushed into powder, dried, carbonized, impregnated with hydrofluoric acid for 24 hours, and dried again to obtain the modified biochar.
[0023] As an optional implementation, the biomass raw materials used in the modified biochar include any one or more combinations of rice straw, wheat straw, and corn straw.
[0024] As can be seen from the above technical solutions of the present invention, the method for degrading chlorobenzene pollutants based on reduction-oxidation coupling proposed in this invention accelerates electron transfer in the electrochemical cell under specific pH conditions, promoting the generation of Fe from nano-zero valent iron. 2+ The reaction with H2 causes the C-Cl bond of 1,2,4-TCB to break and Ben to desorb, resulting in a higher reaction rate. Since the reduction process eliminates the obstacle of oxidative ring opening, it is more conducive to the attack of ·OH on dechlorination products. Therefore, the degradation time is short, the amount of material used is small, and it can rapidly degrade highly toxic substances into non-toxic substances. It is suitable for the treatment of toxic and harmful chlorinated organic pollutants in groundwater and has broad application prospects.
[0025] The method of this invention utilizes modified biochar-supported nano-iron palladium to remove organic pollutants such as chlorobenzene compounds from water. It is simple to operate; the material is directly added to the solution and mixed evenly to efficiently degrade organic pollutants. Moreover, this invention can be used over a wide pH range, greatly expanding its applicability.
[0026] The method of this invention provides a new approach and method for the degradation and removal of organic matter in water. It constructs a reduction and oxidation coupled degradation system based on modified biochar-supported nano-iron-palladium materials, which realizes the rapid mineralization of trichlorobenzene in water and has important theoretical and practical value. Attached Figure Description
[0027] Figure 1 These are scanning electron microscope images of different materials used in this invention.
[0028] Figure 2 These are X-ray diffraction patterns of different materials used in this invention.
[0029] Figure 3 The graph shows the removal efficiency of trichlorobenzene in solution by different materials of the present invention.
[0030] Figure 4 This is a graph showing the content of reduction products of trichlorobenzene degraded by the modified biochar-supported nano-iron-palladium material of the present invention.
[0031] Figure 5 The graph shows the removal efficiency of trichlorobenzene reduction products by the modified biochar-supported nano-iron-palladium material of the present invention.
[0032] Figure 6 This is a graph showing the change in chloride ion content in a trichlorobenzene solution during degradation by the modified biochar-supported nano-iron-palladium material of this invention.
[0033] Figure 7 The graph shows the removal efficiency of trichlorobenzene and its reduction products under different pH conditions according to the present invention.
[0034] Figure 8The graph shows the removal efficiency of trichlorobenzene reduction products by the modified biochar-supported nano-iron-palladium material of the present invention under different amounts of hydrogen peroxide. Detailed Implementation
[0035] To better understand the technical content of the present invention, specific embodiments are described below in conjunction with the accompanying drawings.
[0036] Various aspects of the invention are described in this disclosure with reference to the accompanying drawings, in which numerous illustrative embodiments are shown. The embodiments of this disclosure are not necessarily intended to encompass all aspects of the invention. It should be understood that the various concepts and embodiments described above, as well as those described below in more detail, can be implemented in any of a number of ways.
[0037] In an exemplary embodiment of the present invention, a method for degrading chlorobenzene pollutants based on reduction-oxidation coupling is provided, comprising the following steps:
[0038] Supported nano-iron palladium was added to the solution to be degraded, and the reaction was shaken until the chlorobenzene pollutants in the solution to be degraded were completely reduced.
[0039] Then, hydrogen peroxide was added under aerobic conditions, and the reaction was continued with shaking until the reduction products of chlorobenzene pollutants were completely mineralized.
[0040] The supported nano-iron palladium includes a support and nano-iron palladium particles supported on the support, wherein the support includes modified biochar.
[0041] As an optional implementation, the pH of the degradation solution is adjusted to 3-11.
[0042] As an optional implementation, the concentration of added hydrogen peroxide is 0.5–3 mmol / L.
[0043] As an optional implementation, the concentration of the added supported nano-iron palladium is 0.19–0.20 mg / mL.
[0044] As an optional implementation, the preparation process of the supported nano-iron palladium includes the following steps:
[0045] Iron salts and modified biochar were mixed in deionized water and stirred for adsorption. Then, an equal amount of ethanol as deionized water was added, and NaBH4 was slowly added under nitrogen purging. The reaction was continued with stirring. After the reaction was completed, the mixture was washed with water and anhydrous ethanol to obtain modified biochar-supported nano-zero valent iron.
[0046] A suspension of supported nano-iron palladium was added to a palladium acetate solution, ultrasonically dispersed, then washed with anhydrous ethanol and vacuum dried to obtain modified biochar-supported nano-iron palladium particles.
[0047] As an optional implementation, the modified biochar-supported iron-palladium nanoparticles contain 1% to 10% Pd / Fe by mass.
[0048] As an optional implementation, the iron salt includes divalent iron salt, with an iron ion concentration of 0.068–0.072 mol / L.
[0049] As an optional implementation, the concentration of NaBH4 is 0.475–0.5 mol / L.
[0050] As an optional implementation, the preparation process of the modified biochar includes:
[0051] The biomass raw material was crushed into powder, dried, carbonized, impregnated with hydrofluoric acid for 24 hours, and dried again to obtain the modified biochar.
[0052] As an optional implementation, the biomass raw materials used in the modified biochar include any one or more combinations of rice straw, wheat straw, and corn straw.
[0053] To facilitate better understanding, the present invention will be further illustrated below with several specific examples, but the preparation process is not limited to these examples, and the content of the present invention is not limited to these examples.
[0054] Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.
[0055] Example 1
[0056] S1. Preparation of modified biochar: Rice straw powder was heated to 700°C in a tube furnace under a nitrogen atmosphere at a heating rate of 5°C per minute and held for 6 hours to obtain biochar. Subsequently, the biochar was shaken in 1M hydrofluoric acid solution at 150 rpm for 24 hours, then dried in an oven at 80°C and ground through a 100-mesh sieve.
[0057] Preparation of modified biochar-supported nano-iron-palladium materials: 2.5 g of ferrous sulfate heptahydrate and 125 mg of biochar prepared in S1 were dissolved in 100 mL of aqueous solution and stirred at room temperature for 24 hours. The solution was then transferred to a three-necked flask, followed by the addition of 100 mL of anhydrous ethanol, and purging with nitrogen for 30 minutes to remove oxygen. Next, 250 mL of freshly prepared 0.5 mol / L sodium borohydride solution was slowly added dropwise. The reaction was carried out in a three-necked flask for 80 minutes, with continuous nitrogen purging and vigorous stirring throughout. Finally, the product was washed three times each with deoxygenated deionized water and ethanol using magnetic separation. Then, 20 mL of an ethanol solution containing 26.25 mg of palladium acetate was added. Subsequently, the mixture was sonicated at 25 °C and 45 Hz for 10 minutes and dried in a vacuum drying oven at 60 °C for 24 hours. The resulting material was named Pd. 2.5 -nZVI / BC.
[0058] SEM image ( Figure 1 (ad) shows the surface morphology of Pd-nZVI and Pd-nZVI / BC. Pd-nZVI forms a chain-like structure, which tends to aggregate into large particles with diameters between 10 and 20 micrometers due to magnetic and van der Waals forces. Compared to Pd-nZVI, the porous structure of BC provides sufficient anchoring space and positioning points for good dispersion of nZVI particles, effectively inhibiting nanoparticle aggregation. The high dispersibility of Pd-nZVI creates favorable conditions for reducing contaminants.
[0059] like Figure 2 As shown, a new diffraction peak appears at 44.7° in nZVI / BC, corresponding to the (110) plane of α-Fe0. Furthermore, a characteristic peak can be observed in Pd-nZVI at 40.1°, corresponding to Pd... 0 The (111) plane. However, in Pd-nZVI / BC, due to the dispersion effect of BC, Pd 0 The peak did not appear.
[0060] The modified biochar / iron-palladium composite material prepared by the above method was added to a polluted water sample with a trichlorobenzene concentration of 10 mg / L at a dosage of 0.2 g / L and a wastewater pH of 6.5.
[0061] like Figure 3As shown, nZVI / BC can remove a certain proportion of 1,2,4-TCB through adsorption; however, the removal efficiency is very limited, with a removal rate of only 22.95%. The loading of Pd has a crucial impact on the removal efficiency of 1,2,4-TCB, as it is the active center of the dechlorination reaction. Clearly, the removal efficiency of 1,2,4-TCB is significantly improved after loading Pd, which is attributed to the high activity of Pd nanoparticles, which generate a large amount of atomic hydrogen to accelerate the reaction. In samples with Pd loadings of 2.5%, 5%, and 10%, 1,2,4-TCB can be completely removed. Interestingly, when the Pd loading increases to 10%, the reaction rate decreases. This is because, at high Pd loadings, Pd reduction tends to occur in the Fe0-rich region, leading to rapid Fe substitution in the core region, hindering H2 production, and ultimately resulting in a lower reaction rate. Comparative experiments with Pd-nZVI were also conducted to investigate the effect of BC on the removal of 1,2,4-TCB. The results showed that without BC as a carrier, the removal rate of 1,2,4-TCB by Pd-nZVI was only 67.39%.
[0062] Due to the competitive adsorption of 1,2,4-TCB, no reduction products of 1,2,4-TCB were detected in the solid phase, consistent with previous studies. Figure 4 As shown, the main reduction product detected was benzene (Ben), followed by 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB), and trace amounts of chlorobenzene (MCB). Throughout the reaction, 1,2-DCB and 1,3-DCB showed a trend of first increasing and then decreasing. In contrast, benzene showed a slow increasing trend. After the reaction reached equilibrium, the concentration of benzene was 0.67 mg / L. In summary, Pd... 2.5 -nZVI / BC can provide sufficient Pd sites and H* to break the C-Cl bond and desorb Ben from 1,2,4-TCB, thus resulting in a higher reaction rate.
[0063] Since Pd-nZVI / BC completely removed 1,2,4-TCB during the reduction phase, the oxidative degradation of Ben, the main reduction product of 1,2,4-TBB, under aerobic conditions was further investigated. The results showed that Ben was completely eliminated within 3.5 hours after the addition of H₂O₂. Conversely, under anaerobic conditions, the Ben content did not decrease further, indicating that O₂ and H₂O₂ are crucial for the degradation of Ben. Figure 5 ).
[0064] Example 2
[0065] The basic content of this embodiment is the same as that of Embodiment 1, except that the specific preparation steps in this embodiment are as follows:
[0066] Biochar prepared by dissolving 2.5 g of ferrous sulfate heptahydrate and 125 mg of S1 in 100 mL of aqueous solution was stirred at room temperature for 24 hours. The solution was then transferred to a three-necked flask, followed by the addition of 100 mL of anhydrous ethanol, and purging with nitrogen for 30 minutes to remove oxygen. Next, 250 mL of freshly prepared 0.5 mol / L sodium borohydride solution was slowly added dropwise. The reaction was carried out in the three-necked flask for 80 minutes, with continuous nitrogen purging and vigorous stirring throughout. Finally, the product was washed three times each with deoxygenated deionized water and ethanol using magnetic separation. Then, 20 mL of an ethanol solution containing 10.55 mg of palladium acetate was added. Subsequently, the mixture was sonicated at 25 °C and 45 Hz for 10 minutes and dried in a vacuum drying oven at 60 °C for 24 hours. The resulting material was named Pd. 1.0 -nZVI / BC.
[0067] The modified biochar / iron-palladium composite material prepared by the above method was added to a polluted water sample with a trichlorobenzene concentration of 10 mg / L at a dosage of 0.2 g / L. The pH of the wastewater was 6.5. Figure 3 As shown, when the reaction time is 12-24 h, the modified biochar-supported nano-iron-palladium material can completely degrade 10 mg / L of trichlorobenzene.
[0068] Example 3
[0069] The basic content of this embodiment is the same as that of Embodiment 1, except that the specific preparation steps in this embodiment are as follows:
[0070] Biochar prepared from 2.5 g of ferrous sulfate heptahydrate and 125 mg of S1 was dissolved in 100 mL of aqueous solution and stirred at room temperature for 24 hours. The solution was then transferred to a three-necked flask, followed by the addition of 100 mL of anhydrous ethanol, and purged with nitrogen for 30 minutes to remove oxygen. Next, 250 mL of freshly prepared 0.5 mol / L sodium borohydride solution was slowly added dropwise. The reaction was carried out in the three-necked flask for 80 minutes, with continuous nitrogen purging and vigorous stirring throughout. Finally, the product was washed three times each with deoxygenated deionized water and ethanol using magnetic separation. Then, 20 mL of an ethanol solution containing 52.5 mg of palladium acetate was added. Subsequently, the mixture was sonicated at 25 °C and 45 Hz for 10 minutes and dried in a vacuum drying oven at 60 °C for 24 hours. The resulting material was named Pd. 5.0 -nZVI / BC.
[0071] The modified biochar / iron-palladium composite material prepared by the above method was added to a polluted water sample with a trichlorobenzene concentration of 10 mg / L at a dosage of 0.2 g / L. The pH of the wastewater was 6.5. Figure 3As shown, when the reaction time is 12-24 h, the modified biochar-supported nano-iron-palladium material can completely degrade 10 mg / L of trichlorobenzene.
[0072] Example 4
[0073] Biochar prepared by dissolving 2.5 g of ferrous sulfate heptahydrate and 125 mg of S1 in 100 mL of aqueous solution was stirred at room temperature for 24 hours. The solution was then transferred to a three-necked flask, followed by the addition of 100 mL of anhydrous ethanol, and purging with nitrogen for 30 minutes to remove oxygen. Next, 250 mL of freshly prepared 0.5 mol / L sodium borohydride solution was slowly added dropwise. The reaction was carried out in the three-necked flask for 80 minutes, with continuous nitrogen purging and vigorous stirring throughout. Finally, the product was washed three times each with deoxygenated deionized water and ethanol using magnetic separation. Then, 20 mL of an ethanol solution containing 105 mg of palladium acetate was added. Subsequently, the mixture was sonicated at 25 °C and 45 Hz for 10 minutes and dried in a vacuum drying oven at 60 °C for 24 hours. The resulting material was named Pd. 10 -nZVI / BC.
[0074] The modified biochar / iron-palladium composite material prepared by the above method was added to a polluted water sample with a trichlorobenzene concentration of 10 mg / L at a dosage of 0.2 g / L. The pH of the wastewater was 6.5. Figure 3 As shown, when the reaction time is 12-24 h, the modified biochar-supported nano-iron-palladium material can completely degrade 10 mg / L of trichlorobenzene.
[0075] Example 5
[0076] The basic content of this embodiment is the same as that of Embodiment 1, except that the modified biochar / iron-palladium composite material is added to wastewater with a trichlorobenzene concentration of 10 mg / L, wherein the mass percentage of Pd / Fe is 2.5%. The dosage of the material is 0.2 g / L, and the pH of the polluted water sample is set to 3-11. The removal rate of trichlorobenzene reduction products can reach 100%.
[0077] The effects of initial pH on the reductive degradation of 1,2,4-TCB and the oxidative degradation of Ben were investigated within a pH range of 3–11. Figure 7 (ab). The results showed that the reaction rate of Pd-nZVI / BC for 1,2,4-TCB was high under neutral and acidic conditions; however, the reaction rate decreased significantly under alkaline conditions. Similarly, in the oxidation phase, Ben produced was almost completely degraded at all pH values except pH 11, with higher reaction rates observed in acidic and neutral environments. Lower pH values can accelerate electron transfer in the electrochemical cell and promote the production of Fe from nZVI. 2+H2 and promote the rapid corrosion of iron oxide deposited on the Pd-nZVI / BC surface. In contrast, at higher pH values, the significant decrease in H+ concentration in the solution leads to the formation of flocculants on the Pd-nZVI / BC surface, which hinders the adsorption of pollutants and the generation of free radicals at active sites, thereby reducing the reaction rate.
[0078] Example 6
[0079] The basic content of this embodiment is the same as that of Embodiment 1, except that the modified biochar / iron-palladium composite material is added to wastewater with a trichlorobenzene concentration of 10 mg / L, wherein the mass percentage of Pd / Fe is 2.5%. The dosage of the material is 0.2 g / L, the pH of the wastewater is 6.5, and the added hydrogen peroxide concentrations are 1, 2, and 3 mM, respectively. The removal rate of trichlorobenzene reduction products can reach 100%.
[0080] The effects of different hydrogen peroxide concentrations (0.5, 1, 2, and 3 mM) on the degradation kinetics of the oxidation phase are as follows: Figure 8 As shown in the figure, the concentration of H2O2 significantly affects the degradation efficiency of Ben. Both the degradation rate and extent increase with increasing H2O2 concentration. Specifically, when the hydrogen peroxide concentration exceeds 1 mM, Ben is completely degraded within 3 hours. Notably, at a concentration of 3 mM, Ben is almost completely removed within 30 minutes.
[0081] Comparative Example 1
[0082] The basic content of this comparative example is the same as that of Example 1, except that the specific preparation method is as follows:
[0083] 2.5 g of ferrous sulfate heptahydrate was dissolved in 100 mL of aqueous solution and stirred at room temperature for 24 hours. The solution was then transferred to a three-necked flask, followed by the addition of 100 mL of anhydrous ethanol, and purging with nitrogen for 30 minutes to remove oxygen. Next, 250 mL of freshly prepared 0.5 mol / L sodium borohydride solution was slowly added dropwise. The reaction was carried out in the three-necked flask for 80 minutes, with continuous nitrogen purging and vigorous stirring throughout. Finally, the product was washed three times each with deoxygenated deionized water and ethanol using magnetic separation. Then, 20 mL of an ethanol solution containing 105 mg of palladium acetate was added. Subsequently, the mixture was sonicated at 25 °C and 45 Hz for 10 minutes and dried in a vacuum drying oven at 60 °C for 24 hours. The resulting material was named Pd-nZVI.
[0084] Comparative Example 2
[0085] The basic content of this comparative example is the same as that of Example 1, except that the specific degradation method is as follows:
[0086] Modified biochar / iron-palladium composite material was added to oxygenated wastewater with a trichlorobenzene concentration of 10 mg / L, wherein the mass percentage of Pd / Fe was 2.5%. The dosage of the material was 0.2 g / L, the pH of the wastewater was 6.5, and the concentration of added hydrogen peroxide was 0.5 mM.
[0087] The Cl- concentration increased to 95 μM in the reduction-oxidation coupling process, while it was only 63 μM in the direct oxidation process. Figure 6 These findings suggest that the reduction-oxidation coupling process can significantly reduce the formation of chlorinated hydrocarbon byproducts and improve the mineralization efficiency of 1,2,4-TCB.
[0088] While the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention shall be determined by the claims.
Claims
1. A method for degrading chlorobenzene pollutants based on reduction-oxidation coupling, characterized in that, Includes the following steps: Supported nano-iron palladium was added to the solution to be degraded, and the reaction was shaken until the chlorobenzene pollutants in the solution to be degraded were completely reduced. Then, hydrogen peroxide was added under aerobic conditions, and the reaction was continued with shaking until the reduction products of chlorobenzene pollutants were completely mineralized. The supported nano-iron palladium includes a support and nano-iron palladium particles supported on the support, wherein the support includes modified biochar.
2. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 1, characterized in that, The pH of the degradation solution was adjusted to 3–11.
3. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 1, characterized in that, The concentration of added hydrogen peroxide is 0.5–3 mmol / L.
4. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 1, characterized in that, The concentration of the added supported nano-iron palladium was 0.19–0.20 mg / mL.
5. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 1, characterized in that, The preparation process of the supported nano-iron palladium includes the following steps: Iron salts and modified biochar were mixed in deionized water and stirred for adsorption. Then, an equal amount of ethanol as deionized water was added, and NaBH4 was slowly added under nitrogen purging. The reaction was continued with stirring. After the reaction was completed, the mixture was washed with water and anhydrous ethanol to obtain modified biochar-supported nano-zero valent iron. A suspension of supported iron-palladium nanoparticles was added to a palladium acetate solution, ultrasonically dispersed, washed with anhydrous ethanol, and vacuum dried to obtain modified biochar-supported iron-palladium nanoparticles (Pd-nZVI / BC).
6. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 5, characterized in that, The modified biochar-supported iron-palladium nanoparticles contain Pd / Fe at a mass percentage of 1% to 10%.
7. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 5, characterized in that, The iron salt includes divalent iron salts with an iron ion concentration of 0.068–0.072 mol / L.
8. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 5, characterized in that, The concentration of NaBH4 is 0.475–0.5 mol / L.
9. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to any one of claims 1-8, characterized in that, The preparation process of the modified biochar includes: The biomass raw material was crushed into powder, dried, carbonized, impregnated with hydrofluoric acid for 24 hours, and dried again to obtain the modified biochar.
10. The method for degrading chlorobenzene pollutants based on reduction-oxidation coupling according to claim 9, characterized in that, The modified biochar uses biomass raw materials including any one or more combinations of rice straw, wheat straw, and corn straw.