CN115970690A - Crystal boron modified copper oxide catalyst and preparation method and application thereof - Google Patents
Crystal boron modified copper oxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 31
- -1 boron modified copper oxide Chemical class 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 38
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 36
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229960001680 ibuprofen Drugs 0.000 claims abstract description 33
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- 230000003213 activating effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
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- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
A crystal boron modified copper oxide catalyst and a preparation method and application thereof comprise the following steps: 1) Dissolving copper nitrate trihydrate into an aqueous solution, wherein the mass ratio of the copper nitrate trihydrate to the aqueous solution is 1 (10-45); 2) Adding crystal boron (C-boron) into the solution obtained in the step 1), wherein the adding amount of the C-boron is 0.1-10 wt%, and adding alkali during stirring to form an alkaline environment; 3) Stirring for 5-10 min, and standing for 3-4 days; 4) And (4) drying the solution in vacuum and cooling to room temperature to obtain the crystal boron modified copper oxide catalyst. The application method of the C-boron-C-CuO material in degrading organic pollutants in water provided by the invention can effectively remove ibuprofen and benzoic acid, has high removal efficiency, can be used for purifying organic matters, and has application value in treating refractory organic matters, such as emergency treatment of water polluted by non-steroidal anti-inflammatory drugs.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a crystal boron modified copper oxide (C-boron-C-CuO) material, and a preparation method and application thereof.
Background
With the gradual progress of social economy and the continuous improvement of the level of science and technology, the requirements of people on the environment are increasingly improved, so that the problem of water environment pollution is more prominent. Among them, with the increasing development of industrialization and urbanization, the kinds and the amount of organic matters in the water environment are increased sharply. These organic pollutants can be discharged in large quantities from three sources, municipal, agricultural and industrial, into natural waters, presenting a series of problems to the water environment and human health. Antibiotics and Personal Care Products (d) are an emerging class of organic pollutants, including various antibiotics, hormones, nsaids, antiepileptic antibiotics, lipid regulators, beta blockers, contrast agents, cytostatics, and Personal Care Products such as antibacterial agents, synthetic musks, insect repellents, antiseptics, fragrances, sunscreens, and the like. The pollution of the organic pollutants to the environment has been concerned as early as the beginning of the 21 st century abroad, and most of refractory organic matters have strong polarity, high water solubility and certain bacteriostasis and biotoxicity, so that the PPCPs can be continuously existed in surface water, underground water, drinking water and sewage because the PPCPs are difficult to be removed by traditional water supply treatment methods such as coagulation, precipitation, filtration and the like and sewage treatment methods based on an activated sludge method. In addition, persistent organic pollutants enriched in aqueous environments can pose long-term potential hazards to human health and the ecosystem. The conventional PPCPs treatment technology includes three major types, i.e., biological treatment, physical treatment and chemical treatment. Biological treatment methodThe method is to remove organic wastewater by using artificially cultured activated sludge. PPCPs are typically removed during processing by either biological transfer or sludge adsorption. However, since PPCPs are of various types and have large differences in properties, the biological treatment method has significant differences in treatment effects for different PPCPs. The physical treatment method comprises flocculation, precipitation, adsorption, membrane treatment and the like. The conventional coagulation-precipitation-filtration-disinfection of the current waterworks has low removal efficiency on PPCPs. Physical treatment, which is primarily a transfer of contaminants from the aqueous phase to the solid phase, causes secondary treatment of the sludge/membrane to be problematic. The chemical treatment method mainly refers to Advanced Oxidation Processes (AOPs), which are characterized by generating highly active free radicals, degrading most organic substances and having a fast reaction rate. The PPCPs which are difficult to biodegrade are mainly oxidized and decomposed by active oxygen components generated in the advanced oxidation process or directly mineralized into inorganic matters, and common advanced oxidation technologies comprise an ozone oxidation method, an electrocatalytic oxidation method, a photocatalytic oxidation method, a Fenton/Fenton-like oxidation method and the like. The conventional advanced oxidation technology generally refers to the oxidative degradation of pollutants by taking OH & lt- & gt as a main active free radical, and the activated persulfate is SO 4 ·- Is an emerging advanced oxidation technology for degrading pollutants by using main active substances. To generate SO 4 ·- Generally, the Peroxydisulfate (PDS) or Peroxymonosulfate (PMS) is deactivated by heat, alkali, ultraviolet (UV), ultrasonic waves, transition metals, etc. Transition metals are considered effective and viable activators due to their high catalytic efficiency, low energy consumption, and ease of handling, as compared to other processes. Generally, PMS is always more easily activated by transition metals than PDS due to its asymmetric structure. In addition, the PMS is solid at normal temperature, has stable property and is convenient to transport and store, thereby gradually arousing the attention of broad scholars. Among catalysts of PMS, copper-based catalysts have many advantages over iron-based catalysts, and are widely used in the field of environmental catalysis. The iron-based catalyst has more iron mud precipitates, the catalytic activity of copper oxide (CuO) on PMS is obviously higher than that of iron oxide, the utilization rate of the oxidant is high, and the dissolution of metal ions is low. But because the catalytic rate of the copper oxide to the PMS is still slower, cuO or PMS with higher concentration needs to be added to realize the catalytic reactionThe organic matters are removed efficiently. How to further modify materials and construct a more stable and efficient catalytic system is the key for further improving the removal level of the refractory pollutants in water by the advanced oxidation method based on PMS. The crystal boron modified copper oxide (C-boron-C-CuO) material has high-efficiency catalytic activity on PMS, is simple to prepare and good in stability, can be used for purifying organic matters in water, has an application value for emergently treating water bodies polluted by refractory organic matters, and is a brand-new breakthrough in the research field of controlling the pollution of the refractory organic pollutants in the water and ensuring the safety of drinking water.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems that the copper oxide material has low catalytic efficiency when being applied to the catalysis of PMS and high-efficiency removal of organic matters is realized by adding CuO or PMS with high concentration, the invention provides a crystal boron modified copper oxide (C-boron-C-CuO) catalyst, a preparation method and application thereof, and the catalytic efficiency of the CuO catalytic material in the process of catalyzing PMS is improved.
The technical scheme is as follows: a preparation method of a crystal boron modified copper oxide catalyst comprises the following steps: 1) Dissolving copper nitrate trihydrate into an aqueous solution, wherein the mass ratio of the copper nitrate trihydrate to the aqueous solution is 1 (10-45); 2) Adding crystal boron (C-boron) into the solution obtained in the step 1), wherein the adding amount of the C-boron is 0.1-10 wt%, and adding alkali during stirring to form an alkaline environment; 3) Stirring for 5-10 min, and standing for 3-4 days; 4) And (4) drying the solution in vacuum and cooling to room temperature to obtain the crystal boron modified copper oxide catalyst.
The alkaline environment in the step 2) means that the concentration of NaOH in the solution after the NaOH is added is 1-10 mol/L.
The stirring in the step 3) refers to stirring in a magnetic stirrer for 1 to 30 minutes.
The vacuum drying in the step 4) refers to drying for more than 12 hours in a vacuum drying oven at the temperature of more than 60 ℃.
The crystal boron modified copper oxide catalyst prepared by the method.
The crystal boron modified copper oxide catalyst is applied to degradation of organic pollutants in water.
The application steps are as follows: 1) Adding borate into the aqueous solution of the organic pollutant to be treated to adjust the pH = 6.5-7.5 of the solution; 2) Preparing a peroxymonosulfate solution in advance, adding the peroxymonosulfate solution into the pollutant solution in the step 1), and stirring to obtain a mixed solution; 3) Adding a crystal boron modified copper oxide material into the mixed solution obtained in the step 2) to start reaction.
The organic pollutants comprise Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA).
The concentration of the peroxymonosulfate solution is 100mM, and the concentration of the peroxymonosulfate is 0.1-1.2 mM after the peroxymonosulfate solution is mixed with the pollutant solution.
The concentration of the crystal boron modified copper oxide material in the step 3) in the solution is 0.096g/L.
Has the advantages that: 1. the C-boron-C-CuO provided by the invention has the advantages of simple preparation process, easily purchased raw materials, safe and mild preparation conditions and capability of batch production;
2. in the application method for degrading organic pollutants in water, provided by the invention, the C-boron-C-CuO improves the reaction speed of catalyzing PMS to degrade pollutants, reduces the addition amount of the catalyst and the cost, and the C-boron-C-CuO has good stability, is simple to operate and is easy to realize;
3. the application method of the C-boron-C-CuO material in degrading organic pollutants in water provided by the invention can effectively remove ibuprofen and benzoic acid, has high removal efficiency, can be used for purifying organic matters, and has application value in treating refractory organic matters, such as emergency treatment of water polluted by non-steroidal anti-inflammatory drugs.
Drawings
FIG. 1 is a graph showing the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) as organic pollutants, which are anti-inflammatory and antibacterial drugs, with c-CuO activated potassium monopersulfate and c-CuO as catalysts at 25 ℃ in example 1, and the removal rate of the potassium monopersulfate and the Benzoic Acid (BA) as time-dependent parameters, wherein
Respectively represent organic pollutant nitratePhenylbenzene, benzoic acid, ibuprofen, an anti-inflammatory and antibacterial drug; working conditions are as follows: PMS =0.6mM; c-CuO =0.096g/L, [ polutants]=20 μ M, pH =7.5 (boric acid buffered 50 mM)
FIG. 2 is a graph showing the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) as anti-inflammatory antibacterial agents, activated by C-boron-C-CuO and potassium peroxymonosulfate, as a function of time at 25 ℃ in the presence of C-boron-C-CuO as a catalyst in example 2, and the graph shows
Respectively representing organic pollutants such as nitrobenzene, benzoic acid and ibuprofen serving as an anti-inflammatory and antibacterial medicament; working conditions are as follows: PMS =0.6mM; C-boron-C-CuO =0.096g/L, [ polutants]=20 μ M, pH =7.5 (boric acid buffered 50 mM).
FIG. 3 is a graph showing the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) which are anti-inflammatory and antibacterial drugs, by activating potassium monopersulfate with C-boron-C-CuO at 40 ℃ and under the condition that the catalyst is C-boron-C-CuO in example 3, and the removal rate is related to time.
FIG. 4 is a graph showing the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) which are anti-inflammatory and antibacterial drugs, by activating potassium monopersulfate with C-boron-C-CuO at 55 ℃ and under the condition that the catalyst is C-boron-C-CuO in example 3, and the removal rate is related to time.
FIG. 5 shows the k-value of the reaction of C-boron-C-CuO activating potassium peroxymonosulfate to remove Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) as anti-inflammatory and antibacterial drugs in example 3, wherein the catalyst is C-boron-C-CuO, the temperature is 25 ℃,40 ℃ and 55 ℃ respectively obs A numerical map.
FIG. 6 is a graph showing the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) which are anti-inflammatory antibacterial agents, as well as the removal rate of potassium hydrogen peroxymonosulfate activated by C-boron-C-CuO, and the removal rate of the Benzoic Acid (BA) in example 4, at a temperature of 25 ℃ and a catalyst of C-boron-C-CuO, wherein the concentrations of NOM are respectively 1mg/L and 20 mg/L.
FIG. 7 is a graph showing the relationship between the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) which are antibacterial agents for inflammation, and the removal rate of the Benzoic Acid (BA) and the time, wherein the C-boron-C-CuO material activates potassium hydrogen peroxymonosulfate under the condition that the temperature is 25 ℃ and the catalyst is the C-boron-C-CuO material recovered through one-time regeneration.
FIG. 8 is a graph showing the relationship between the removal rate of Ibuprofen (IBP), nitrobenzene (NB) and Benzoic Acid (BA) which are antibacterial agents for inflammation, and the removal rate of potassium hydrogen peroxymonosulfate for the C-boron-C-CuO material activated by the C-boron-C-CuO material under the condition that the temperature is 25 ℃ and the catalyst is the C-boron-C-CuO material recovered by secondary regeneration.
FIG. 9 is a graph showing the relationship between the removal rate of ibuprofen antibacterial agent IBP (IBP), organic pollutants Nitrobenzene (NB) and Benzoic Acid (BA) and time when potassium hydrogen peroxymonosulfate is activated by C-boron-C-CuO material recovered by three regeneration processes under the condition that the catalyst is at 25 ℃.
FIG. 10 is a Scanning Electron Microscope (SEM) image of catalysts c-CuO in example 1.
FIG. 11 is a Scanning Electron Microscope (SEM) image of the catalyst C-boron-C-CuO in example 2.
FIG. 12 is an energy spectrum obtained by scanning the catalyst C-boron-C-CuO in example 2 with an energy spectrometer (EDS).
Detailed Description
The invention discusses the mechanism and the efficiency of the PMS system activated by the copper oxide material, tries to degrade typical organic pollutants, and has important academic research and application values for the development of an advanced oxidation method based on potassium monopersulfate and the high-efficiency control of refractory organic pollutants in water. The invention is described in further detail below with reference to the following description of the drawings and the detailed description.
Example 1: effect of c-CuO material activating PMS for degrading typical organic pollutants in water body
1) IBP, NB and BA were dissolved in water at a concentration of 20. Mu.M, respectively. Adding boric acid to adjust the pH = 6.5-7.5 to obtain an aqueous solution containing organic pollutants;
2) Pre-preparing a potassium hydrogen peroxymonosulfate solution with the concentration of about 100mM, adding the potassium hydrogen peroxymonosulfate solution into the pollutant solution in the step 1), and stirring to obtain a mixed solution of potassium hydrogen peroxymonosulfate with the concentration of 0.55-0.65 mM;
3) Adding c-CuO material into the mixed solution in the step 2) to ensure that the concentration of the c-CuO material in the solution is about 0.096g/L, starting the reaction, and controlling the reaction temperature to be 25 ℃. Taking out a certain amount of samples at certain time intervals, filtering, and carrying out subsequent analysis on the filtrate. The removal effect is shown in fig. 1.
Example 2: effect of C-boron-C-CuO material activating PMS for degrading typical organic pollutants in water body
A crystal boron modified copper oxide material (C-boron-C-CuO) is prepared by the following steps:
1) Dissolving copper nitrate trihydrate into an aqueous solution;
2) Adding the purchased C-boron into the solution in the step 1), and quickly adding NaOH into the solution in the stirring process to form an alkaline environment;
3) Stirring for 5-10 min, standing for 3-4 days;
4) The solution was dried in vacuo and cooled to room temperature to give C-boron-C-CuO.
The subsequent other operation steps are the same as those in example 1, only the C-CuO added in step 3) in the application method of the C-CuO material in degrading typical organic pollutants in water is changed into C-boron-C-CuO, and the removal rate of the copper oxide catalyst on IBP, NB and BA in water is shown in figure 2. As can be seen from fig. 1 and 2, under the condition that other conditions are not changed, when the crystalline boron modified copper oxide is used as the catalyst, the removal rate of IBP and BA in water is significantly improved compared with when the copper oxide is used as the catalyst. The BA removal rate at 30 minutes was increased from 75.6% to 86.3%, and the IBP removal rate at 30 minutes was increased from 92.0% to 96.6%.
Example 3: influence of temperature on effect of C-boron-C-CuO material activated PMS in removing typical organic pollutants in water body
Example 5 is the same as example 2 except that the reaction temperature in step 3) is different, the predetermined temperature is 40 ℃ and 55 ℃, the removing effect at different reaction temperatures is shown in fig. 3 and 4, and k at different temperatures is shown in fig. 3 obs As shown in fig. 5. As can be seen from the graph, the removal rate of the contaminants at the 3 rd, 6 th and 10 th minutes is significantly increased as the temperature is increased. However, at 30 minutes, the removal rate of each contaminant was not significantIt is improved. It is shown that under the system, the removal rate of the pollutants (IBP, NB, BA) is obviously improved along with the increase of the temperature.
Example 4: influence of NOM concentration on effect of C-boron-C-CuO material activated PMS in removing typical organic pollutants in water body
Example 6 the same experimental procedure as in example 2, except that NOM was added in steps 1) at 1mg/L and 20mg/L, respectively, and the removal effect after adding NOM at different concentrations is shown in FIG. 6. As can be seen from the figure, the removal of contaminants (IBP, NB, BA) is significantly better at NOM =1mg/L than at NOM =20 mg/L.
Example 5: the C-boron-C-CuO material is used for activating PMS to remove the influence of typical organic pollutant effect in water body after being regenerated and recycled
The mixed solution obtained in experimental example 2 was filtered through a glass fiber membrane, washed with distilled water and ethanol and dried in a vacuum oven at 60 ℃ for 12 hours to obtain a regenerated C-boron-C-CuO material. The remaining operation steps are the same as example 2, only the C-boron-C-CuO material added in step 3 is replaced by the C-boron-C-CuO material recovered through the regeneration for one time, two times and three times, and the experimental result is shown in FIG. 7. As can be seen from the figure, the C-boron-C-CuO material has better stability, and after three times of regeneration and recycling, the C-boron-C-CuO material still has better activation effect in the degradation of typical organic pollutants in water by activating PMS.
Example 6: C-CuO material and C-boron-C-CuO material by scanning electron microscope analysis
The C-CuO and C-boron-C-CuO samples were observed by Scanning Electron Microscopy (SEM). The SEM acceleration voltage was 10.0keV, the magnification was 5000X, and the working distance was 15.0mm. FIG. 8 is a SEM image of a C-CuO sample, and FIG. 9 is a SEM image of a C-boron-C-CuO sample. As can be seen from the comparison of FIGS. 3 and 4, the surface morphology of the alloy is greatly changed after the C-boron is added. As can be seen from FIG. 8, c-CuO is in the form of two-dimensional sheet and has a smooth surface. As can be seen from FIG. 9, C-boron-C-CuO is in the form of long rattan, rough surface and increased gaps. The C-boron-C-CuO has larger specific surface area and higher surface roughness than the C-CuO, provides more active sites and has better catalytic performance.
Example 7: C-CuO material and C-boron-C-CuO material energy spectrometer analysis
The C-boron-C-CuO samples were analyzed by energy spectrometer (EDS). As can be seen from fig. 10, cu element, O element, B element, and C element are present in the sample, and the ratio of the amount of Cu element and O element species is about 1, and the ratio of the amount of Cu element, O element, and B element species is about 3:2.EDS characterization results show that crystal boron is successfully supported on CuO, and C-boron-C-CuO is a main catalyst.
Claims (10)
1. A preparation method of a crystal boron modified copper oxide catalyst is characterized by comprising the following steps: 1) Dissolving copper nitrate trihydrate into an aqueous solution, wherein the mass ratio of the copper nitrate trihydrate to the aqueous solution is 1 (10-45); 2) Adding crystal boron (C-boron) into the solution obtained in the step 1), wherein the adding amount of the C-boron is 0.1-10 wt%, and adding alkali during stirring to form an alkaline environment; 3) Stirring for 5-10 min, and standing for 3-4 days; 4) And (4) drying the solution in vacuum and cooling to room temperature to obtain the crystal boron modified copper oxide catalyst.
2. The method for preparing the crystalline boron-modified copper oxide catalyst according to claim 1, wherein the alkaline environment in the step 2) is that the concentration of NaOH in a solution after NaOH is added is 1 to 10mol/L.
3. The method for preparing the crystalline boron-modified copper oxide catalyst according to claim 1, wherein the stirring in the step 3) is performed in a magnetic stirrer for 1 to 30 minutes.
4. The method for preparing the crystalline boron-modified copper oxide catalyst according to claim 1, wherein the vacuum drying in step 4) is performed by drying in a vacuum drying oven at a temperature of 60 ℃ or higher for 12h or higher.
5. A crystalline boron-modified copper oxide catalyst obtainable by the process of any one of claims 1 to 4.
6. Use of the crystalline boron-modified copper oxide catalyst of claim 5 for degrading organic contaminants in a body of water.
7. Use according to claim 6, characterized in that the steps are as follows: 1) Adding borate into the aqueous solution of the organic pollutant to be treated to adjust the pH = 6.5-7.5 of the solution; 2) Preparing a peroxymonosulfate solution in advance, adding the peroxymonosulfate solution into the pollutant solution in the step 1), and stirring to obtain a mixed solution; 3) Adding a crystal boron modified copper oxide material into the mixed solution obtained in the step 2) to start reaction.
8. Use according to claim 6, wherein the organic contaminants comprise the anti-inflammatory antibacterial drug Ibuprofen (IBP), the organic contaminants Nitrobenzene (NB) and Benzoic Acid (BA).
9. The use of claim 7, wherein the concentration of the peroxymonosulfate solution is 100mM, and the concentration of the peroxymonosulfate is 0.1 to 1.2mM after the peroxymonosulfate solution is mixed with the contaminant solution.
10. The use of claim 7 wherein the crystalline boron modified copper oxide material of step 3) has a concentration of 0.096g/L in solution.
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