Method for degrading tetrabromobisphenol A through cooperation of oxidation reduction and electrocatalysis and application

Abstract

The invention belongs to the technical field of electrochemical catalytic degradation of organic pollutants, and particularly relates to a method for degrading tetrabromobisphenol A through redox and electrocatalysis and application of the method. The method comprises the following steps that an electrolyte is added into an electrolytic bath, and a cathode material and an anode material are put into the electrolytic bath for electrolysis; the tetrabromobisphenol A is subjected to an electroreduction debromination reaction at the cathode to be degraded into bisphenol A; then, the bisphenol A is further electrically oxidized into carbon dioxide and water at the anode, so that thorough degradation of the tetrabromobisphenol A is realized; the electrolyte comprises tetrabromobisphenol A, a surfactant and a supporting electrolyte, the concentration of the surfactant is 0.1-2 mmol / L, and the concentration of the supporting electrolyte is 0.1-1 mol / L; the cathode material is zinc, and the anode material is boron-doped diamond. According to the invention, reduction of tetrabromobisphenol A and oxidation of bisphenol A are synchronously realized in the same electrolytic bath by selecting a cathode material and an anode material.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochemical catalytic degradation of organic pollutants, and specifically relates to a method and application of redox-synergistic electrocatalytic degradation of tetrabromobisphenol A, which is used for treating a difficult-to-degrade wastewater system containing tetrabromobisphenol A. Background Art

[0002] Tetrabromobisphenol A (TBBPA), one of the world's most widely used brominated flame retardants, is widely used in electronic devices, plastics, and building materials. However, TBBPA is highly toxic, bioaccumulative, and environmentally persistent. Once it enters water bodies, it can accumulate through the food chain, disrupting the endocrine system and inducing carcinogenic and teratogenic risks. Furthermore, TBBPA is difficult to degrade under natural conditions, and its decomposition products (such as low-brominated bisphenol A and brominated dioxins) may be even more toxic, posing a long-term threat to the ecological environment and human health. Therefore, the development of efficient, economical, and environmentally friendly technologies for the complete degradation of TBBPA has become an urgent need in the field of environmental governance.

[0003] Current wastewater treatment technologies for TBBPA primarily include adsorption, biodegradation, and chemical oxidation. While adsorption methods (such as activated carbon and resin adsorption) can rapidly remove pollutants, they only transfer them between different phases, not completely eliminating them, posing a risk of secondary contamination. Due to TBBPA's strong resistance to biodegradation, biodegradation methods suffer from low efficiency and long treatment cycles, and are less adaptable to high-concentration wastewater. Chemical oxidation methods (such as the Fenton process and ozone oxidation) rely on strong oxidants (such as H2O2 and O3) and acidic conditions, resulting in high operating costs and the production of bromine-containing byproducts.

[0004] In recent years, TBBPA degradation technologies centered around electrochemical catalysis have garnered widespread attention due to their strong controllability and the absence of additional chemical reagents. Electrocatalytic advanced oxidation processes (EAOPs) typically utilize conventional electrode materials such as Pt and Ti / RuO2 as anodes. However, these processes often suffer from reduced current efficiency due to oxygen evolution side reactions and are susceptible to electrode passivation, making efficient debromination and deep mineralization of TBBPA difficult. Electrocatalytic reduction techniques can rapidly debrominate, but the degradation products are limited to varying degrees of low- or no-brominated bisphenol A, which cannot be further degraded to achieve deep mineralization of TBBPA. Furthermore, in the absence of an auxiliary oxidation system, some residual intermediates still possess endocrine-disrupting activity, posing potential environmental risks. Therefore, relying solely on electrocatalytic oxidation or reduction techniques cannot meet the demand for deep, harmless treatment of TBBPA. Summary of the Invention

[0005] In response to the deficiencies in the prior art, the present invention provides a method and application for the redox-synergistic electrocatalytic degradation of tetrabromobisphenol A, which is an efficient electrocatalytic degradation technology that can avoid the generation of toxic brominated intermediates and achieve complete mineralization of tetrabromobisphenol A.

[0006] The technical solution adopted in the present invention is described below.

[0007] The method for efficiently degrading tetrabromobisphenol A by redox synergistic electrocatalysis of the present invention combines the high efficiency of electrochemical reduction debromination with the complete mineralization capability of electrochemical oxidation technology to construct a paired electrochemical system, achieving efficient and complete degradation of tetrabromobisphenol A through the following synergistic effects:

[0008] (1) The C-Br bond in the tetrabromobisphenol A molecule is preferentially reduced and broken on the Zn cathode to generate an easily oxidizable bisphenol A (BPA) intermediate, thereby reducing the electrochemical oxidation energy barrier;

[0009] (2) Electro-oxidation mineralization is carried out on the BDD anode to completely degrade BPA into CO2 and H2O, avoiding the risk of producing highly toxic brominated intermediates such as brominated dioxins and polybrominated diphenyl ethers during the direct electro-oxidation of TBBPA, fundamentally improving the environmental safety of the overall treatment;

[0010] (3) Reactions (1) and (2) proceed simultaneously in the same electrolytic cell, forming a synergistic degradation effect. The electrons released by the Zn cathode and the OH generated by the electrons obtained by the BDD anode form a paired electrochemical system, which optimizes the electrode reaction kinetics and improves the overall current efficiency and energy utilization.

[0011] Specifically, the present invention provides a method for redox-synergistic electrocatalytic degradation of TBBPA, which comprises the following steps in sequence:

[0012] The electrolyte is added to a single-chamber electrolytic cell, the cathode material and the anode material are placed in the electrolytic cell, and a regulated DC power supply is connected for electrolysis. TBBPA undergoes electroreduction and debromination reaction at the cathode and degrades into bisphenol A (BPA); subsequently, BPA is further electro-oxidized into carbon dioxide and water at the anode, thereby achieving complete degradation of TBBPA.

[0013] The electrolyte comprises TBBPA, a surfactant, and a supporting electrolyte, wherein the concentration of the surfactant is 0.1 mmol / L to 2 mmol / L, and the concentration of the supporting electrolyte is 0.1 mol / L to 1 mol / L;

[0014] The cathode material is zinc, and the anode material is boron-doped diamond.

[0015] During the electrolysis process, an appropriate amount of the reaction solution can be taken at regular intervals to detect the degradation effect of TBBPA using a high performance liquid chromatograph.

[0016] Boron-doped diamond (BDD) is considered an ideal anode material for electrocatalytic oxidation due to its high oxygen evolution overpotential, strong corrosion resistance, and wide potential window. It can efficiently generate hydroxyl radicals (·OH) to directly mineralize organic matter. However, electrolysis systems using only BDD for the treatment of high-concentration bromine-containing organic matter still have certain limitations. First, the stable C-Br bond and aromatic structure of the TBBPA molecule result in a high oxidation energy barrier, requiring higher energy consumption. Second, direct oxidation of TBBPA on the electrode surface tends to generate more toxic byproducts, and brominated intermediates tend to accumulate on the electrode surface, resulting in decreased electrode activity. Furthermore, existing technologies have largely focused on anodic oxidation, overlooking the synergistic potential of cathodic reduction reactions. For example, Zn, as a reducing material, releases electrons during electrolysis to promote dehalogenation reactions. However, the synergistic mechanism between BDD and BDD, the optimization of interfacial reaction kinetics, and the targeted degradation pathway for bromine-containing pollutants remain unclear.

[0017] The above-mentioned method of the present invention utilizes a new electrocatalytic system, through innovation of electrode materials and optimization of reaction mechanisms, to break through the bottlenecks of low debromination efficiency, incomplete mineralization and high risk of by-products in the degradation process of TBBPA, providing technical support for the green treatment of brominated persistent organic pollutants.

[0018] Preferably, the supporting electrolyte is NaOH or KOH, most preferably NaOH.

[0019] Preferably, the surfactant is cetyltrimethylammonium bromide (CTAB) or dodecyltrimethylammonium bromide (DTAB) or sodium dodecyl sulfate (SDS), and CTAB is most preferred.

[0020] Preferably, the concentration of the surfactant in the electrolyte is 1 mmol / L.

[0021] Preferably, in the electrolyte, the concentration of the supporting electrolyte is 0.1-0.3 mol / L, especially 0.1 mol / L.

[0022] Preferably, the reaction is carried out at a temperature of 20°C to 35°C, a rotation speed of 0 rpm to 1000 rpm, and a current density of 5 mA / cm 2 ~ 30 mA / cm 2 The electrolysis reaction temperature is preferably 25°C. The current density is preferably 10 mA / cm 2 ~ 25 mA / cm2 , and most preferably 20 mA / cm 2 The rotation speed is further preferably 100 rpm to 800 rpm, and most preferably 500 rpm.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] 1. The present invention achieves the simultaneous reduction of TBBPA and oxidation of BPA in the same electrolytic cell by selecting the cathode material and the anode material, providing a method for effectively controlling brominated flame retardants in the environment.

[0025] 2. The cathode and anode materials of the present invention do not require special modification and pretreatment, are cheap and readily available, and the reaction conditions are simple and easy to implement.

[0026] 3. The present invention has a high degradation efficiency for brominated flame retardants. When the concentration of TBBPA is not higher than 20 mmol / L, the degradation rate is greater than 99%. When the concentration of TBBPA is 5 mmol / L, the mineralization rate reaches over 98%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a gas chromatographic analysis chart of the degradation product obtained by the method of an embodiment of the present invention;

[0028] Figure 2 The figure is a mass spectrum of the main product of the method according to the embodiment of the present invention. DETAILED DESCRIPTION

[0029] In order to make those skilled in the art more clearly understand the purpose, technical solutions and advantages of the present invention, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0030] Example 1:

[0031] A method for redox-synergistic electrocatalytic degradation of TBBPA comprises the following steps:

[0032] Step 1: Dissolve TBBPA (0.1088 g, 10 mmol / L), NaOH (0.32 g, 0.4 mol / L), and CTAB (0.0073 g, 1 mmol / L) in 20 mL of alkaline solution (0.32 g NaOH dissolved in 20 mL of deionized water). Add the reaction solution to a 30 mL temperature-controlled single-chamber electrolytic cell with Zn as the cathode and BDD as the anode, and connect it to a DC regulated power supply.

[0033] Step 2: Connect the temperature control jacket of the single-chamber electrolytic cell to the thermostatic bath, set the temperature to 25°C, add a 6 mm × 10 mm stirring bar, set the magnetic stirring to 500 rpm, start the DC regulated power supply and control the current density to 6.25 mA / cm 2 A certain amount of reaction solution was taken at reaction times of 0 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, and 8 h and passed through a 0.22 µm microporous filter membrane. The obtained supernatant was used for reaction product analysis and detection.

[0034] Detection conditions for TBBPA degradation products: Waters 2695 high performance liquid chromatograph (HPLC), ODS-SP 5µm 4.6×250 mm (UP) as the separation column, 80 v / v% methanol and 20 v / v% formic acid (0.1 v / v%) in water as the mobile phase, detection wavelength at 230 nm, flow rate at 1 mL / min, and temperature at 35°C.

[0035] Testing showed that after 5 hours, the degradation rate of TBBPA exceeded 99%, and after 8 hours, the residual BPA content dropped to 0.1 mmol / L. The mineralization rate of TBBPA was 87.3%. Analysis by a Thermo TR gas chromatography-mass spectrometer (GC-MS) revealed that the main product was 4-isopropenylphenol.

[0036] Comparative Example 1:

[0037] Unlike Example 1, a carbon rod electrode was used as the anode. All other conditions remained the same. Testing showed that after 5 hours, the TBBPA degradation rate exceeded 99%, and after 8 hours, the BPA content was 7.44 mmol / L. This result is consistent with previous findings by the research group. Because the carbon rod electrode lacks oxidative activity, this electrolysis system can only reduce TBBPA to BPA and cannot achieve complete mineralization of TBBPA.

[0038] Comparative Example 2:

[0039] Unlike Example 1, a carbon rod electrode was used as the anode and an Fe electrode was used as the cathode. All other conditions were the same as in Example 1. Testing revealed that the TBBPA degradation rate was 0 after 8 h. However, the results showed that the carbon rod and Fe electrodes lacked electrocatalytic oxidation and reduction activity, and were unable to achieve TBBPA degradation and complete mineralization.

[0040] Comparative Example 3:

[0041] Unlike Example 1, the cathode was an Fe electrode. All other conditions were the same as in Example 1. Testing showed that the TBBPA degradation rate exceeded 99% after 8 h. No BPA was detected during the electrolysis process, and no other debrominated intermediates were produced. The mineralization rate of TBBPA was 36.7%. Compared to Example 1, the TBBPA mineralization rate was significantly lower. This is primarily due to the greater oxidation potential of TBBPA than that of BPA, making direct oxidation of TBBPA more difficult. Furthermore, the direct oxidation process is prone to the generation of highly toxic brominated intermediates such as brominated dioxins and polybrominated diphenyl ethers.

[0042] Comparative Example 4:

[0043] Unlike Example 1, a GF electrode was used as the anode. All other conditions were the same as in Example 1. Testing showed that after 5 hours, the TBBPA degradation rate exceeded 99%, and after 8 hours, the residual BPA content dropped to 0.1 mmol / L. The TBBPA mineralization rate was 47.4%. GC-MS and UPLC-QTOFMS analysis revealed 4-isopropenylphenol as a possible product.

[0044] Comparative Example 5:

[0045] The difference from Example 1 is that the anode is a DSA electrode, and the other conditions are the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 5 h, and the residual BPA content dropped to 0.1 mmol / L after 8 h. At the same time, the mineralization rate of TBBPA was 44.2%.

[0046] From Example 1 and Comparative Examples 5-6, it can be found that when BDD is used as the anode, the complete debromination and thorough mineralization of TBBPA are the best, and there is a significant difference between it and other anode electrodes. This is mainly attributed to the synergistic effect of TBBPA's debromination reduction at the cathode and the efficient generation of hydroxyl radicals (·OH) at the anode, which can directly achieve the mineralization of organic matter.

[0047] Comparative Example 6:

[0048] The difference from Example 1 is that the cathode is a GF electrode, and the other conditions are the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 8 h, no BPA was detected during the electrolysis process, and the mineralization rate of TBBPA was 70.9%.

[0049] As shown in Example 1, Comparative Examples 3, and 6, different cathode materials exhibit varying degrees of TBBPA debromination, which in turn affects the complete mineralization of TBBPA. Zn as the cathode achieves the best results in terms of complete debromination and mineralization of TBBPA, with significant differences compared to other cathode materials.

[0050] Comparative Example 7:

[0051] Unlike Example 1, CTAB was not added; all other conditions remained the same. Testing showed that after 8 hours, the degradation rate of TBBPA exceeded 99%. No BPA or other debromination intermediates were detected during the electrolysis process. The mineralization rate of TBBPA was 32.7%. Compared to Example 1, the TBBPA mineralization rate was significantly lower, primarily due to the absence of CTAB in the electrolyte. CTAB was unable to form a double-layer membrane on the electrode surface to adsorb TBBPA anions in the solution, preventing TBBPA from participating in the reduction reaction.

[0052] Comparative Example 8:

[0053] Unlike Example 1, the surfactant used was dodecyltrimethylammonium bromide (DTAB), and all other conditions were the same as in Example 1. Testing showed that after 5 hours, the degradation rate of TBBPA exceeded 99%, and after 8 hours, the residual BPA content dropped to 0.1 mmol / L. The mineralization rate of TBBPA was also 81.6%. Both DTAB and CTAB are cationic surfactants that adsorb on the electrode surface to form a double-layer membrane that absorbs TBBPA anions in the solution, thereby causing a reduction reaction of TBBPA to debrominate and produce BPA, thereby promoting oxidative degradation at the anode.

[0054] Comparative Example 9:

[0055] Unlike Example 1, the surfactant was an anionic surfactant, sodium dodecyl sulfate (SDS), and all other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA was 88% after 8 h, no BPA was detected during the electrolysis process, and no other debromination intermediates were found. The mineralization rate of TBBPA was 12%.

[0056] From Example 1 and Comparative Examples 7-9, it can be found that different surfactants have different degrees of debromination of TBBPA, which in turn affects the degree of complete mineralization of TBBPA. This further shows that the thorough mineralization effect of TBBPA is related to its complete debromination to BPA at the cathode. The paired electrochemical synergistic mechanism of debromination reduction at the cathode and oxidation at the anode is conducive to the harmless degradation of TBBPA.

[0057] Example 2:

[0058] Unlike Example 1, the NaOH concentration was 0.1 mol / L and was dissolved in 20 ml of deionized water. The other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 6 h, and almost no BPA remained after 8 h. At the same time, the mineralization rate of TBBPA reached 91.8%.

[0059] Example 3:

[0060] Unlike Example 1, the NaOH concentration was 0.2 mol / L and was dissolved in 20 ml of deionized water. All other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 8 h, and the residual BPA content dropped to 0.05 mmol / L after 8 h. The mineralization rate of TBBPA was 88.8%.

[0061] Example 4:

[0062] Unlike Example 1, the NaOH concentration was 0.3 mol / L and was dissolved in 20 ml of deionized water. All other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 8 h, the residual BPA content dropped to 0.16 mmol / L after 8 h, and the mineralization rate of TBBPA was 87.1%.

[0063] Example 5:

[0064] The difference from Example 1 was that the supporting electrolyte concentration was 0.5 mmol / L, and the other conditions were the same as Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 8 h, the residual BPA content was 0.34 mmol / L after 8 h, and the mineralization rate of TBBPA was 75.3%.

[0065] Example 6:

[0066] The difference from Example 1 was that the supporting electrolyte concentration was 0.7 mmol / L, and the other conditions were the same as Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 8 h, the residual BPA content was 0.92 mmol / L after 8 h, and the mineralization rate of TBBPA was 62.1%.

[0067] Examples 1, 2–6 show that appropriately reducing the NaOH concentration is beneficial for improving the mineralization rate of TBBPA. However, when the NaOH concentration is between 0.1 and 0.4 mol / L, the degradation rate of TBBPA is minimal. Furthermore, when the NaOH concentration is increased to 0.5 mol / L and above, the electrolysis reaction still proceeds, but the mineralization rate drops significantly to 62.1%, indicating that excessively high NaOH concentrations are detrimental to the complete mineralization of TBBPA.

[0068] Example 7:

[0069] The difference from Example 1 was that the concentration of TBBPA in the reaction solution was 5 mmol / L, and the other conditions were the same as Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 3 h, and almost no BPA remained after 8 h. At the same time, the TBBPA mineralization rate reached 92.9%.

[0070] Example 8:

[0071] The difference from Example 1 was that the TBBPA concentration in the reaction solution was 15 mmol / L, and the other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 5 h, and the residual BPA content dropped to 0.6 mmol / L after 8 h. The TBBPA mineralization rate was 67.6%.

[0072] Example 9:

[0073] Unlike Example 1, the TBBPA concentration in the reaction solution was 20 mmol / L, and the other conditions were the same as in Example 1. Testing showed that the degradation rate of TBBPA exceeded 99% after 6 h, and the residual BPA content dropped to 2.83 mmol / L after 8 h. The TBBPA mineralization rate was 66.8%.

[0074] From Examples 1 and 7-9, it can be seen that the increase in TBBPA concentration has little effect on the degradation of TBBPA. Properly extending the time can achieve complete degradation of TBBPA. However, it has a greater impact on the mineralization of TBBPA. As the TBBPA concentration increases, the complete mineralization rate of TBBPA gradually decreases.

[0075] Example 10:

[0076] The difference from Example 1 is that during electrolysis, the DC regulated power supply controls the current density to 5 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 6 h, the residual BPA content dropped to 2.49 mmol / L after 8 h, and the TBBPA mineralization rate was 75.3%.

[0077] Example 11:

[0078] The difference from Example 1 is that during electrolysis, the DC regulated power supply controls the current density to be 10 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 4 h, and there was almost no BPA residue after 8 h. At the same time, the mineralization rate of TBBPA reached 91.9%.

[0079] Example 12:

[0080] The difference from Example 1 is that during electrolysis, the DC regulated power supply controls the current density to be 15 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 4 h, and there was almost no BPA residue after 8 h. At the same time, the mineralization rate of TBBPA reached 95.8%.

[0081] Example 13:

[0082] The difference from Example 1 is that during electrolysis, the DC regulated power supply controls the current density to 20 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 4 h, and there was almost no BPA residue after 8 h. At the same time, the mineralization rate of TBBPA reached 97.4%.

[0083] Example 14:

[0084] The difference from Example 1 is that during electrolysis, the DC regulated power supply controls the current density to 25 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 3 h, and almost no BPA remained after 8 h. At the same time, the mineralization rate of TBBPA reached 95.8%.

[0085] Example 15:

[0086] The difference from Example 1 is that during electrolysis, the concentration of TBBPA in the reaction solution is 5 mmol / L, and the DC regulated power supply controls the current density to 20 mA / cm 2 , and the other conditions were the same as in Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 3 h, and there was almost no BPA residue after 8 h. At the same time, the mineralization rate of TBBPA reached 98.7%.

[0087] From Examples 1 and 10-15, it can be seen that the increase of current density is beneficial to the mineralization of TBBPA. 2 When , the mineralization rate of TBBPA is the highest, and under the optimal conditions, the mineralization rate of TBBPA can reach 98.7%.

[0088] Example 16:

[0089] The difference from Example 1 was that the temperature was controlled at 35°C, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 7 hours, the residual BPA content was 3.01 mmol / L after 8 hours, and the mineralization rate of TBBPA was 69.9%.

[0090] Comparative Example 10:

[0091] The difference from Example 1 was that the temperature was controlled at 50°C, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 5 h, and the residual BPA content was 5.94 mmol / L after 8 h, but TBBPA could not be mineralized.

[0092] Comparative Example 11:

[0093] The difference from Example 1 is that the temperature was controlled at 45°C, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99% after 5 h, and the residual BPA content was 5.76 mmol / L after 8 h, but TBBPA could not be mineralized.

[0094] As shown in Examples 1 and 16, and Comparative Examples 10-11, within a certain temperature range, temperature has little effect on the degradation rate of TBBPA. Rapid debromination and degradation can still be achieved at higher temperatures, such as 35°C. However, the mineralization rate decreases with increasing temperature, and TBBPA cannot be mineralized at temperatures of 45°C or above.

[0095] Example 17:

[0096] The difference from Example 1 was that the electrolysis time was 2 h, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA was 75.6%, the mineralization rate was 42.4%, and the residual BPA content was 0.7 mmol / L.

[0097] Example 18:

[0098] The difference from Example 1 was that the electrolysis time was 4 h, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99%, the mineralization rate was 69.2%, and the residual BPA content was 0.57 mmol / L.

[0099] Example 19:

[0100] The difference from Example 1 was that the electrolysis time was 6 h, and the other conditions were the same as Example 1. After testing, the degradation rate of TBBPA exceeded 99%, the mineralization rate was 81.5%, and the residual BPA content was 0.26 mmol / L.

[0101] As shown in Examples 1 and 17-19, the degradation rate of TBBPA continued to increase with increasing electrolysis time, with complete degradation occurring after 6 h of electrolysis. The mineralization rate of TBBPA also continued to rise, reaching 87.3% after 8 h.

[0102] It will be easily understood by those skilled in the art that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for degradation of tetrabromobisphenol A by redox synergistic electrocatalysis, characterized in that: The following steps are involved: The electrolyte is added to a single-chamber electrolytic cell, cathode materials and anode materials are placed in the electrolytic cell, and a regulated DC power supply is connected for electrolysis. Tetrabromobisphenol A undergoes an electroreduction debromination reaction at the cathode, degrading it into bisphenol A. Subsequently, bisphenol A is further electrooxidized into carbon dioxide and water at the anode, thereby achieving complete degradation of tetrabromobisphenol A. The electrolyte comprises tetrabromobisphenol A, a surfactant and a supporting electrolyte, wherein the concentration of the surfactant is 0.1 mmol / L to 2 mmol / L, and the concentration of the supporting electrolyte is 0.1 mol / L to 1 mol / L; The cathode material is zinc, and the anode material is boron-doped diamond.

2. The method according to claim 1, characterized in that The supporting electrolyte is NaOH or KOH.

3. The method according to claim 1, characterized in that The supporting electrolyte is NaOH with a concentration of 0.1-0.3 mol / L.

4. The method according to claim 1, wherein The surfactant is hexadecyltrimethylammonium bromide or dodecyltrimethylammonium bromide or sodium lauryl sulfate.

5. The method according to claim 1, wherein The surfactant is cetyltrimethylammonium bromide.

6. The method according to claim 1, characterized in that In the electrolyte, the concentration of the surfactant is 1 mmol / L.

7. The method according to claim 1, characterized in that The reaction temperature in the electrolytic cell is 20°C to 35°C.

8. The method according to claim 1, characterized in that The current density of electrolysis was 5 mA / cm 2 ~ 30 mA / cm 2 .

9. The method according to claim 1, characterized in that The current density of electrolysis was 20 mA / cm 2 .

10. The method according to claim 1, characterized in that During the electrolysis process, the electrolyte was stirred at a speed of 100 rpm to 800 rpm.

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