Method for removing propranolol by activating calcium sulfite through bimetallic MOFs material

Abstract

The invention discloses a method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material, which comprises the following steps: dissolving ferrous chloride tetrahydrate, cobalt nitrate hexahydrate and terephthalic acid in a mixed solution of N, N-dimethylformamide, methanol and ultrapure water, magnetically stirring, carrying out hydrothermal reaction after stirring, centrifugally recovering to obtain a precipitate, and drying to obtain the propranolol. Washing and drying the precipitate to obtain MOF-(Fe, Co); and adding the MOF-(Fe, Co) and calcium sulfite into a water sample containing propranolol. According to the method, the limitations of low conductivity, single unsaturated metal type, easy inactivation in the reaction process and the like of a monometal MOFs material are overcome, the problem of reactive active species quenching caused by high solubility of Na2SO3 in water is solved, and efficient removal of propranolol in water is realized through the synergistic effect of the bimetal MOFs material and calcium sulfite.

Description

Technical Field

[0001] The invention belongs to the field of water treatment, and particularly relates to a method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material. Background Art

[0002] Pharmaceuticals and personal care products (PPCPs) are widely used in diverse sectors, including animal husbandry, medicine, aquaculture, personal hygiene products, and cosmetics. Due to their frequent detection in aquatic environments, PPCPs have become a new pollutant of widespread public concern. Cardiovascular drugs are common among PPCPs. Due to the high incidence of cardiovascular diseases, cardiovascular drugs account for a significant portion of commonly prescribed medications worldwide. Cardiovascular drugs can enter natural water bodies through various pathways, impacting the natural environment and human health and safety. Contamination from cardiovascular drugs and the associated risks are of significant concern. Beta-blockers are beta-adrenergic receptor antagonists commonly used to treat cardiovascular diseases such as hypertension, angina pectoris, and heart dysfunction. They are frequently detected in aquatic environments. Propranolol (PPL), a typical beta-blocker, is biotoxic, and its release and accumulation in aquatic environments pose a threat to the ecological environment and human health and safety. Conventional treatment technologies have certain limitations in removing cardiovascular drugs, and there is an urgent need to develop new and effective treatment methods to degrade cardiovascular drugs in water.

[0003] Advanced oxidation technologies (AOTs) have been a research hotspot in the field of emerging pollutant control in recent years. These technologies remove emerging pollutants by oxidizing them through the generation of reactive species using activated oxidants. Sulfate-based AOTs have been found to be an effective technology for removing emerging pollutants, offering enhanced oxidation and mineralization capabilities for organic matter and a wider pH range. Currently, persulfate is commonly used as a precursor for sulfate radical generation. However, persulfate is expensive, and its persistent stability may pose a risk of chronic toxicity. Sulfite is a byproduct of many industrial processes. Using sulfite as a precursor for sulfate radical generation can achieve a waste-to-waste solution. Furthermore, residual sulfite in water can be converted to non-toxic sulfate through aeration. Sodium sulfite (Na2SO3) can replace persulfate as a sulfate radical precursor. However, the high solubility of Na2SO3 in water may cause sulfite ions to quench reactive species, reducing degradation efficiency.

[0004] Transition metal ions are highly efficient homogeneous catalysts in advanced oxidation reactions, with high activation efficiencies. However, as homogeneous catalysts, transition metal ions are difficult to recycle and present a high risk of contamination. Metal-organic frameworks (MOFs) possess abundant active sites and can be used as heterogeneous catalysts. The catalytic materials can be recovered after the reaction, facilitating catalyst recycling. However, traditional monometallic MOFs have limitations in catalysis, including low electrical conductivity, a single type of unsaturated metal, and easy deactivation during the reaction.

[0005] Therefore, alleviating the quenching effect of sulfite on reactive species and improving the catalytic performance of metal-organic frameworks are crucial for enhancing the efficiency of advanced oxidation technologies in removing new pollutants. Furthermore, the combination of metal-organic frameworks and sulfite may have great potential in removing cardiovascular drug pollutants. Summary of the Invention

[0006] This invention provides a method for removing propranolol by activating calcium sulfite using a bimetallic MOF material. This method overcomes the limitations of monometallic MOFs, such as low conductivity, a single type of unsaturated metal, and easy deactivation during the reaction. It also addresses the quenching of reactive species caused by the high solubility of Na2SO3 in water. The synergistic effect of the bimetallic MOF material and calcium sulfite enables efficient removal of propranolol from water.

[0007] The present invention provides a method for removing propranolol by activating calcium sulfite using a bimetallic MOFs material, comprising: (1) dissolving ferrous chloride tetrahydrate, cobalt nitrate hexahydrate and terephthalic acid in a mixed solution of N,N-dimethylformamide, methanol and ultrapure water, stirring the mixture magnetically, performing a hydrothermal reaction after stirring, recovering the mixture by centrifugation to obtain a precipitate, and washing and drying the precipitate to obtain MOF-(Fe,Co); (2) The MOF-(Fe, Co) and calcium sulfite were added to a water sample containing propranolol.

[0008] The high solubility of Na2SO3 in water makes the concentration of sulfite ions in the system too high, which will quench the active species (SO4 - and OH), reducing pollutant degradation efficiency. The CaSO3 system proposed in this invention has the characteristic of slow release of sulfite ions in aqueous solution, effectively alleviating the problem of free radical quenching. Compared with the Na2SO3 system, in one embodiment, the 60-minute degradation rate of propranolol in the CaSO3 system was increased by 11.4%.

[0009] Compared with traditional single-metal MOFs catalysts, the catalytic performance of the bimetallic MOF-(Fe, Co) proposed in the present invention is effectively improved. The synergistic effect between Fe and Co accelerates the degradation of propranolol. In one embodiment, the degradation rate of propranolol in the MOF-(Fe, Co) system is 1.2 and 2.7 times that of the MOF-(Fe) and MOF-(Co) systems, respectively. At the same time, the synergistic effect between Fe and Co slows down the deactivation of the catalyst, and the service life of MOF-(Fe, Co) is effectively extended. In one embodiment, after 6 cycles, the degradation rate of propranolol can still reach 85.2%. The MOF-(Fe, Co) / CaSO3 system shows good efficiency in removing propranolol from actual water bodies. The degradation rates of propranolol in lake water, river water, and tap water reach 99.6%, 99.5%, and 99.4%, respectively. This system has strong application potential.

[0010] The present invention proposes the activation mechanism of bimetallic MOF-(Fe, Co) to activate CaSO3: in the initial stage of activation (Formula 1-7), the ≡Fe on MOF-(Fe4, Co1) 2+ / Co 2+ Instead of directly activating CaSO3, a complex ≡Fe(Ⅲ)- / ≡Co(Ⅲ)-SO3, a subsequent chain reaction occurs to produce active species, ≡Fe on the surface of MOF-(Fe,Co) 2+ Promoted ≡Co 2+ Regeneration (Formula 8).

[0011] (1) (2) (3) (4) (5) (6) (7) (8) Preferably, when the mass ratio of the MOF-(Fe, Co) to calcium sulfite is 1:6 to 5:3, within this range, the catalyst can provide sufficient reactive sites and generate sufficient active species to degrade propranolol.

[0012] Preferably, the total volume of the mixed solution of N,N-dimethylformamide, methanol and ultrapure water is 39 to 51 mL, and the volume ratio is 10:2:1 to 10:6:1. Within this range, N,N-dimethylformamide and methanol can weaken the oxidation of ferrous groups and increase the number of active sites of the prepared catalyst.

[0013] Preferably, the Fe:Co molar mass ratio of the ferrous chloride tetrahydrate and the cobalt nitrate hexahydrate is 1:1 to 8:1. Within this range, the synergistic effect between the iron and cobalt bimetallics can be exerted, the number of active sites is increased, and the activation efficiency is promoted.

[0014] Preferably, the molar mass ratio of the total molar mass of the ferrous chloride tetrahydrate and the cobalt nitrate hexahydrate to the molar mass of terephthalic acid is 1 to 2.5. Within this range, collisions between the organic ligand and the metal ion are likely to occur, which is conducive to the coordination of the two.

[0015] Preferably, the magnetic stirring time is 1 to 3 hours.

[0016] Preferably, the hydrothermal reaction temperature is 100°C to 160°C, and the reaction time is 12 to 48 hours.

[0017] Preferably, the precipitate is washed alternately with anhydrous ethanol and ultrapure water 2 to 6 times.

[0018] Preferably, the concentration of propranolol in the water sample containing propranolol is 0.5 mg / L to 4.0 mg / L.

[0019] Compared with the prior art, the present invention has the following beneficial effects: The present invention constructs a MOF-(Fe, Co) / CaSO3 system for the degradation of propranolol in water. The combination of two different metals in the bimetallic MOF-(Fe, Co) can increase the number of active sites in the MOFs material and promote electron transfer. Redox reactions may also occur between different metal sites, exerting a synergistic effect, thereby improving the catalytic performance of the material.

[0020] The present invention uses CaSO3 as a precursor to generate sulfate radicals instead of persulfate. The solubility of CaSO3 (0.007 g / 100 g H2O) in water is lower than that of Na2SO3 (30.7 g / 100 g H2O), so that CaSO3 can slowly release sulfite ions. The concentration of the slowly released sulfite ions can react to generate active substances without quenching the active species, effectively alleviating the problem of quenching the reactive species by high concentrations of sulfite.

[0021] Furthermore, due to its low solubility, CaSO3 releases sulfite ions in proportion to the consumption of metal active sites, resulting in higher active site utilization, extended catalyst life, longer cycle times, and improved stability. Furthermore, CaSO3 is a common byproduct in the flue gas desulfurization process, and using CaSO3 as a sulfite source allows for resource recycling. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a SEM photograph of MOF-(Fe4,Co1) prepared in Example 2; Figure 2 is an SEM photograph of MOF-(Fe) prepared in Comparative Example 2; Figure 3 is an SEM photograph of MOF-(Co) prepared in Comparative Example 3; Figure 4 FTIR spectra of MOF-(Fe4,Co1), MOF-(Fe), and MOF-(Co) prepared in Example 2, Comparative Example 2, and Comparative Example 3; Figure 5 The effect of the metal ratio on the degradation of PPL by CaSO3 activated by MOF-(Fe, Co) in Example 1; Figure 6 Comparison of the effects of CaSO3 and Na2SO3 activated by MOF-(Fe4, Co1) prepared in Example 2 and Comparative Example 1 on the degradation of PPL; Figure 7 This is a comparison of the effects of MOF-(Fe4, Co1), MOF-(Fe), and MOF-(Co) activated with CaSO3 to degrade PPL prepared in Example 2, Comparative Example 2, and Comparative Example 3; Figure 8 The effect of MOF-(Fe4, Co1) prepared in Example 3 on the activation of CaSO3 to degrade different new pollutants; Figure 9 This is the effect of the MOF-(Fe4, Co1) prepared in Example 4 on the degradation of PPL by cyclic activation of CaSO3. DETAILED DESCRIPTION

[0023] The present invention will be further analyzed and explained below in conjunction with specific embodiments. It is necessary to point out that this embodiment is only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments based on the content of the above invention.

[0024] Example 1 (1) Ferrous chloride tetrahydrate, cobalt nitrate hexahydrate (Fe: Co = 8:1 ~ 1:1), and 3.6 mmol of terephthalic acid were dissolved in a mixed solution of N,N-dimethylformamide, methanol, and ultrapure water (v:v:v = 10:2:1) and magnetically stirred for 2 h.

[0025] (2) The mixed solution was poured into a stainless steel autoclave lined with polytetrafluoroethylene and the reaction was maintained at a hydrothermal temperature of 160 °C for 24 h. The resulting precipitate was then recovered by centrifugation, washed alternately with anhydrous ethanol and ultrapure water several times, and vacuum dried to obtain MOF-(Fe,Co).

[0026] (3) Prepare a water sample containing 1 mg / L propranolol, add the MOFs and CaSO3 obtained in step (2) to the water sample at dosages of 50 mg / L and 60 mg / L, respectively, take samples at specific times, and measure the concentration of residual propranolol.

[0027] Figure 5 The study shows the influence of the bimetallic ratio during the preparation process on the activation performance of MOF-(Fe,Co). As the Fe:Co ratio decreases from 8:1 to 4:1, the degradation rate of PPL increases from 73.0% to 92.9%. When the Fe:Co ratio decreases further from 4:1 to 1:1, the degradation rate of PPL only increases by 2.2%. Cobalt doping in MOF-(Fe) increases the number of active sites in the catalyst, but an excessive number of active sites can cause a quenching effect, resulting in reduced activation efficiency.

[0028] Example 2 (1) Ferrous chloride tetrahydrate, cobalt nitrate hexahydrate (Fe: Co = 4:1), and 3.6 mmol of terephthalic acid were dissolved in a mixture of N,N-dimethylformamide, methanol, and ultrapure water (v:v:v = 10:2:1) and magnetically stirred for 2 h.

[0029] (2) The mixed solution was poured into a stainless steel autoclave lined with polytetrafluoroethylene and the reaction was maintained at a hydrothermal temperature of 160 °C for 24 h. The resulting precipitate was then recovered by centrifugation, washed alternately with anhydrous ethanol and ultrapure water several times, and vacuum dried to obtain MOF-(Fe4,Co1).

[0030] (3) Prepare a water sample containing 1 mg / L propranolol, add the MOF-(Fe4, Co1) and CaSO3 obtained in step (2) to the water sample at dosages of 50 mg / L and 60 mg / L, respectively, take samples at specific times, and determine the concentration of remaining propranolol.

[0031] like Figure 1As shown in the figure, MOF-(Fe4,Co1) appears nano-spherical, which may be due to the low amount of cobalt doping in MOF-(Fe4,Co1).

[0032] like Figure 6 As shown in the figure, the efficiency of propranolol degradation by MOF-(Fe4,Co1) activated CaSO3 was 92.9% within 60 min.

[0033] Example 3 Steps (1) and (2) of this embodiment are the same as those of embodiment 2, except that: (3) Prepare water samples containing different new pollutants (bezafibrate, diclofenac sodium, carbamazepine, ibuprofen, and moxifloxacin), add the MOF-(Fe4, Co1) and CaSO3 obtained in step (2) to the water samples at dosages of 50 mg / L and 60 mg / L, respectively. Take samples at specific times and measure the concentrations of the remaining new pollutants.

[0034] Figure 8 The results demonstrate the effectiveness of MOF-(Fe4,Co1)-activated CaSO3 in degrading various emerging pollutants. The MOF-(Fe4,Co1) / CaSO3 system achieved degradation rates of 99.5% for bezafibrate, 95.1% for diclofenac sodium, 93.1% for carbamazepine, 82.8% for ibuprofen, and 67.3% for moxifloxacin, respectively. The MOF-(Fe4,Co1) / CaSO3 system is capable of effectively degrading a wide range of emerging pollutants.

[0035] Example 4 Steps (1), (2) and (3) of this embodiment are the same as those of embodiment 2, except that: (4) The used MOF-(Fe4,Co1) was filtered, centrifuged, and vacuum-dried. The recovered MOF-(Fe4,Co1) and CaSO3 were then added to a water sample containing 1 mg / L propranolol at dosages of 50 mg / L and 60 mg / L, respectively. Samples were taken at specific times to determine the concentration of residual propranolol. This method was used to repeat the MOF-(Fe4,Co1) experiment six times.

[0036] Figure 9 This image shows the performance of recycled MOF-(Fe4,Co1) when reused. After six cycles, the degradation of PPL still reached 85.2%, demonstrating the excellent recyclability of MOF-(Fe4,Co1).

[0037] Comparative Example 1 (1) Ferrous chloride tetrahydrate, cobalt nitrate hexahydrate (Fe: Co = 4:1), and 3.6 mmol of terephthalic acid were dissolved in a mixture of N,N-dimethylformamide, methanol, and ultrapure water (v:v:v = 10:2:1) and magnetically stirred for 2 h.

[0038] (2) The mixed solution was poured into a stainless steel autoclave lined with polytetrafluoroethylene and the reaction was maintained at a hydrothermal temperature of 160 °C for 24 h. The resulting precipitate was then recovered by centrifugation, washed alternately with anhydrous ethanol and ultrapure water several times, and vacuum dried to obtain MOF-(Fe4,Co1).

[0039] (3) Prepare a water sample containing 1 mg / L propranolol, add the MOF-(Fe4, Co1) and Na2SO3 obtained in step (2) to the water sample at dosages of 50 mg / L and 60 mg / L, respectively. Take samples at specific times and measure the concentration of residual propranolol.

[0040] like Figure 6 As shown in the figure, the efficiency of propranolol degradation by MOF-(Fe4,Co1) activated by Na2SO3 was 81.5% within 60 min, which was lower than the efficiency of propranolol degradation by MOF-(Fe4,Co1) activated by CaSO3 (92.9%).

[0041] Comparative Example 2 (1) Dissolve 9 mmol of ferrous chloride tetrahydrate and 3.6 mmol of terephthalic acid in a mixture of N,N-dimethylformamide, methanol, and ultrapure water (v:v:v = 10:2:1) and stir magnetically for 2 h.

[0042] (2) The mixed solution was poured into a stainless steel autoclave lined with polytetrafluoroethylene and the reaction was maintained at a hydrothermal temperature of 160 °C for 24 h. The resulting precipitate was then recovered by centrifugation, washed alternately with anhydrous ethanol and ultrapure water several times, and vacuum dried to obtain MOF-(Fe).

[0043] (3) Prepare a water sample containing 1 mg / L propranolol, add the MOF-(Fe) and CaSO3 obtained in step (2) to the water sample at dosages of 50 mg / L and 60 mg / L, respectively, take samples at specific times, and determine the concentration of remaining propranolol.

[0044] like Figure 2 As shown, MOF-(Fe) has a nano-spherical structure.

[0045] like Figure 7As shown in the figure, the efficiency of propranolol degradation by MOF-(Fe) activated CaSO3 was 34.7% within 60 min, which was lower than the efficiency of propranolol degradation by MOF-(Fe4,Co1) activated CaSO3 (92.9%).

[0046] Comparative Example 3 (1) 9 mmol of cobalt nitrate hexahydrate and 3.6 mmol of terephthalic acid were dissolved in a mixture of N,N-dimethylformamide, methanol, and ultrapure water (v:v:v = 10:2:1) and magnetically stirred for 2 h.

[0047] (2) The mixed solution was poured into a stainless steel autoclave lined with polytetrafluoroethylene and the reaction was maintained at a hydrothermal temperature of 160 °C for 24 h. The resulting precipitate was then recovered by centrifugation, washed alternately with anhydrous ethanol and ultrapure water several times, and vacuum dried to obtain MOF-(Co).

[0048] (3) Prepare a water sample containing 1 mg / L propranolol, add the MOF-(Co) and CaSO3 obtained in step (2) to the water sample at dosages of 50 mg / L and 60 mg / L, respectively, take samples at specific times, and determine the concentration of remaining propranolol.

[0049] like Figure 3 As shown, MOF-(Co) has a layered structure.

[0050] like Figure 4 As shown, 467 cm -1 and 547 cm -1 The peaks at 745 cm-1 and 750 cm-2 correspond to the vibration of metal oxygen. -1 and 809 cm -1 1015, 1102 and 1146 cm -1 The peak at 1388cm may be the bending vibration of the metal hydroxyl group. -1 and 1586 cm -1 The peaks at 1499 cm correspond to the asymmetric and symmetric stretching vibrations of -COOH. The C=C bond vibration appears at 1499 cm -1 Place.

[0051] like Figure 7 As shown in the figure, the efficiency of propranolol degradation by MOF-(Co) activated CaSO3 was 80.9% within 60 min, which was lower than the efficiency of propranolol degradation by MOF-(Fe4,Co1) activated CaSO3 (92.9%).

Claims

1. A method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material, characterized in that: include: (1) dissolving ferrous chloride tetrahydrate, cobalt nitrate hexahydrate and terephthalic acid in a mixed solution of N,N-dimethylformamide, methanol and ultrapure water, stirring the mixture magnetically, performing a hydrothermal reaction after stirring, recovering the mixture by centrifugation to obtain a precipitate, and washing and drying the precipitate to obtain MOF-(Fe,Co); (2) The MOF-(Fe, Co) and calcium sulfite were added to a water sample containing propranolol.

2. The method for removing propranolol by activating calcium sulfite using a bimetallic MOFs material according to claim 1, wherein: The mass ratio of the MOF-(Fe, Co) to calcium sulfite is 1:6 to 5:

3.

3. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The total volume of the mixed solution of N,N-dimethylformamide, methanol and ultrapure water is 39 to 51 mL, and the volume ratio is 10:2:1 to 10:6:

1.

4. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The Fe:Co molar mass ratio is 1:1 ~ 8:

1.

5. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The molar mass ratio of the total molar mass of the ferrous chloride tetrahydrate and the cobalt nitrate hexahydrate to the molar mass of terephthalic acid is 1 to 2.

5.

6. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The magnetic stirring time is 1 to 3 h.

7. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The temperature of the hydrothermal reaction is 100°C to 160°C, and the reaction time is 12 to 48 hours.

8. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The precipitate was washed alternately with anhydrous ethanol and ultrapure water 2 to 6 times.

9. The method for removing propranolol by activating calcium sulfite with a bimetallic MOFs material according to claim 1, characterized in that: The concentration of propranolol in the water sample containing propranolol is 0.5 mg / L to 4.0 mg / L.

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