CN115318324A - Application of porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol - Google Patents
Application of porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol Download PDFInfo
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012279 sodium borohydride Substances 0.000 description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 10
- 229910020676 Co—N Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000000527 sonication Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- -1 rainwater Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses an application of a porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol; the porous FeCo-N/C carbon nano material is obtained by loading bimetal Fe, co and a silicon dioxide shell on a ZIF matrix in a calcining mode and then forming a porous structure on the silicon dioxide shell in an acid etching mode. The porous FeCo-N/C catalyst can efficiently degrade p-nitrophenol in sewage together with a reducing agent at 30 ℃ to generate p-aminophenol, so that the toxicity of the sewage can be greatly reduced, and the generated PAP product can be used as a raw material for fine chemical engineering. In addition, the FeCo-N/C carbon nano material used by the invention has the characteristics of multiple catalytic active sites and long service life; in addition, the material uses transition metal to replace noble metal, thereby saving the loading amount of the noble metal and greatly reducing the cost for degrading the p-nitrophenol.
Description
Technical Field
The invention belongs to the technical field of organic sewage treatment; in particular to application of a porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol and a preparation method of the material.
Background
The p-nitrophenol (PNP) is a chemical raw material and a drug intermediate with wide application, and the production processes of medicines, dyes, pesticides, herbicides, bactericides and the like can not be separated. However, PNPs are highly water-soluble, and PNPs have been detected in agricultural soils, surface water, underground water, rainwater, air, activated sludge, and industrial wastewater. In addition, the PNP has a long half-life period in natural environment, poses a threat to ecological environment, is identified as an environmental endocrine disruptor, and is listed in a national priority control pollutant list. It is seen that the high toxicity and persistence of p-nitrophenol in the environment poses serious problems for waste management.
In the past, supercritical water oxidation (SCWO) has shown great potential in the clean and efficient purification of p-nitrophenol wastewater. However, supercritical water oxidation technology is very expensive due to the high temperature and pressure and the large amount of power required to pressurize the oxidant. To reduce these costs, catalysts that can operate at lower temperatures, pressures, and that can reduce the amount of oxidant used have attracted attention.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide an application of a porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol and a preparation method of the material.
In a first aspect, the invention provides an application of a porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol; the porous FeCo-N/C carbon nano material is obtained by loading bimetal Fe, co and a silicon dioxide shell on a ZIF matrix in a calcining mode and then forming a porous structure on the silicon dioxide shell in an acid etching mode.
Preferably, the mass percentages of Fe and Co in the porous FeCo-N/C carbon nanomaterial are 0.20% and 0.207%, respectively.
Preferably, the ZIF matrix adopts a ZIF-8 metal organic framework.
In a second aspect, the invention provides a preparation method of a porous FeCo-N/C carbon nano material, which comprises the following steps:
step one, completely mixing ferrous salt, a metal chelating agent, cobalt salt and an N/C precursor, and grinding to obtain a FeCo-N/C precursor material.
And step two, adding the FeCo-N/C precursor material into a mixed solution of water and methanol, adding hexadecyl trimethyl ammonium bromide and tetraethyl orthosilicate into the mixed solution, and uniformly mixing. Then, the mixed solution was centrifuged to obtain a precipitate.
And step three, calcining the precipitate obtained in the step two, and then performing acid etching to obtain the porous FeCo-N/C carbon nano material.
Preferably, in the first step, feSO is used as the ferrous salt 4 ·7H 2 O; the metal chelating agent adopts 1, 10-phenanthroline; the cobalt salt is Co (NO) 3 ) 2 ·6H 2 O。
Preferably, the molar ratio of ferrous ions in the ferrous salt to cobalt ions in the cobalt salt is 1.
Preferably, in the second step, the N/C precursor is a ZIF material; the amount of FeCo-N/C precursor material relative to the mixed solution of water and methanol was 2g/L. The volume ratio of water to methanol in the mixed solution of water and methanol was 10.
Preferably, in the second step, the dosage of the hexadecyl trimethyl ammonium bromide relative to the FeCo-N/C precursor material is 0.25g/g; the amount of tetraethyl orthosilicate used relative to FeCo-N/C precursor material was 2mL/g.
Preferably, the preparation process of the ZIF material comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole are dissolved in the methanol solution and stirred. Centrifuging to obtain a precipitate; the resulting precipitate was washed with methanol, repeated three times and then dried.
Preferably, zn (NO) 3 ) 2 ·6H 2 The using amount of O relative to the methanol solution is 11.25g/L; the amount of 2-methylimidazole used was 25g/L relative to the methanol solution.
In a third aspect, a method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater specifically comprises the following steps:
step one, dissolving the porous FeCo-N/C carbon nano material prepared in the preparation method in water to obtain a catalyst solution.
And step two, adding the catalyst solution and the reducing agent into the treated p-nitrophenol wastewater, adjusting the pH value to 8.8-10.1, and reacting at the temperature of 10-40 ℃.
Preferably, the pH value of the treated p-nitrophenol wastewater is adjusted to 9.4.
Preferably, the temperature of the treated p-nitrophenol wastewater is adjusted to 30 ℃.
Preferably, the mass concentration of the catalyst solution is 1g/L; the volume ratio of the catalyst solution to the treated p-nitrophenol wastewater was 7.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the p-nitrophenol in the sewage is degraded by using the porous FeCo-N/C carbon nano material, and the p-nitrophenol in the sewage can be rapidly converted into the p-aminophenol, so that the subsequent recovery or further degradation is facilitated. In addition, the catalytic effect of the porous FeCo-N/C carbon nano material used by the invention is obviously better than that of an N/C material, a Co-N/C material and a Fe-N/C material, and the Co-N/C material and the Fe-N/C material are added at the same time.
2. The porous FeCo-N/C catalyst can react with a reducing agent (NaBH) at 30 DEG C 4 ) The p-nitrophenol in the sewage is efficiently degraded together to generate the p-aminophenol (PAP), so that the toxicity of the sewage is greatly reduced, and the generated PAP can be used as a raw material for fine chemical engineering.
3. The FeCo-N/C carbon nano material used by the invention has the characteristics of many catalytic active sites and long service life; in addition, the material uses transition metal to replace noble metal, thereby saving the loading amount of the noble metal and greatly reducing the cost for degrading the p-nitrophenol.
Drawings
FIG. 1 is a flow chart for preparing porous FeCo-N/C carbon nano-particles in example 1 of the present invention;
FIG. 2 is a TEM image of a porous FeCo-N/C carbon nanomaterial prepared in example 1 of the present invention;
FIG. 3 is a graph showing the degradation efficiency of p-nitrophenol according to the change of pH in example 2 of the present invention;
FIG. 4 is a graph comparing the degradation efficiency of p-nitrophenol with temperature in example 3 of the present invention;
FIG. 5 is a graph comparing example 2 of the present invention with comparative examples 1 to 4 under the same reaction conditions.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
As shown in FIG. 1, a method for preparing a porous FeCo-N/C carbon nano-material comprises the following specific steps:
step 1, preparation of an N/C precursor: 9g of Zn (NO) 3 ) 2 ·6H 2 O and 20g of 2-methylimidazole were dissolved in 800ml of a methanol solution and stirred slowly for 2 hours. Centrifuging the obtained solution for 5 minutes at the rotating speed of 14000r to obtain a precipitate; precipitating to obtain ZIF (N/C precursor). Washing the centrifuged ZIF precursor with methanol, repeating the washing for three times, smearing the ZIF precursor on the wall of a beaker, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
And 4, forming surface micropores: and (3) grinding and crushing the dried precipitate obtained in the step (3), calcining the crushed precipitate in a tubular furnace at 1000 ℃ for 2h in a nitrogen atmosphere, etching the calcined product by using 15wt% of HF solution, and forming holes on a silicon dioxide shell to obtain the porous FeCo-N/C carbon nano material. The mass percentages of Fe and Co in the porous FeCo-N/C carbon nano material are 0.20 percent and 0.207 percent respectively. A TEM image of the obtained porous FeCo-N/C carbon nano-material is shown in FIG. 2, and it can be seen that the FeCo-N/C carbon nano-material is a spherical porous particle with micropores on the surface.
Example 2
A method for selectively reducing p-nitrophenol and preparing p-aminophenol comprises the following steps:
a. preparing a required catalyst solution: 1mg of FeCo-N/C carbon nanomaterial powder prepared in example 1 was weighed and dissolved in 1mL of deionized water under ultrasonic conditions.
And (b) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown as the step b:
b. preparation of 1L of a 3.5 mmol.L -1 P-nitrophenol solution. To five groups of beakers were added 108mL of deionized water and 4mL of p-nitrophenol solution, respectively, at 28 ℃. To the above solution, 140. Mu.L of a catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction was started, sampling was performed every 30 seconds using a timer and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated.
The pH values of the solutions in the five sets of beakers were adjusted to 8.8, 9.4, 10.1, and 10.4 respectively by boric acid solution and sodium hydroxide for reaction, so as to determine the influence of the pH values on the degradation effect, and the results are shown in FIG. 1.
As can be seen from FIG. 1, when the pH value is 9.4, the removal rate of p-nitrophenol is the highest, and the removal rate of nitrophenol in the solution is obviously better than that of other pH values by removing more than 90% of nitrophenol in the solution within 1.5 min.
Example 3
A method for preparing p-aminophenol by selectively reducing p-nitrophenol comprises the following steps:
a. preparing a required catalyst solution: 1mg of FeCo-N/C carbon nanomaterial powder prepared in example 1 was weighed and dissolved in 1mL of deionized water under ultrasonic conditions.
And (c) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown in the step b:
b. preparation 1L of 3.5 mmol. Multidot.L -1 P-nitrophenol solution of (1). At a constant pH of 9.4, 108mL of deionized water and 4mL of p-nitrophenol solution were added to the five sets of beakers, respectively. To the above solution, 140 μ L of the catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction started, sampling was performed every 30 seconds using a timer, and the concentration of p-nitrophenol at each time point was estimated by measuring the sample in an ultraviolet spectrophotometer.
The reaction is carried out in a constant-temperature water bath; the temperature of the solution in five groups of beakers was stabilized at 10 ℃, 20 ℃, 30 ℃ and 40 ℃ respectively, and the effect of temperature on the degradation effect was determined, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the removal rate of p-nitrophenol is the highest at 30 ℃, and the removal rate of nitrophenol in the solution is obviously better than that at other temperatures by removing more than 90% of nitrophenol in the solution within 0.5 min.
Comparative example 1
A method for selectively reducing p-nitrophenol and preparing p-aminophenol comprises the following steps:
a. preparing a required catalyst solution: 1mg of Co-N/C powder (the preparation differs from example 1 only in that no FeSO was added in step 2) 4 ·7H 2 O) was placed in a sample tube and dissolved in 1mL of deionized water for sonication.
And (c) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown in the step b:
b. preparation of 1L of a 3.5 mmol.L -1 P-nitrophenol solution. At a temperature of 28 ℃ and a pH of 9.4, 108mL of deionized water and 4mL of a p-nitrophenol solution were added to the beaker. To the above solution, 140. Mu.L of a catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction was started, sampling was performed every 30 seconds using a timer and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the solution is stabilized at 25 ℃ before the reaction is started.
Comparative example 2
A method for selectively reducing p-nitrophenol and preparing p-aminophenol comprises the following steps:
a. preparing a required catalyst solution: 1mg of Fe-N/C powder (the preparation process differs from example 1 only in that Co (NO) is not added in step 2) 3 ) 2 ·6H 2 O) was placed in a sample tube, which was dissolved in 1mL of deionized water and sonicated.
And (c) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown in the step b:
b. preparation 1L of 3.5 mmol. Multidot.L -1 P-nitrophenol solution of (1). 108mL of deionized water and 4mL of p-nitrophenol solution were added to the beaker. To the above solution, 140. Mu.L of a catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction was started, sampling was performed every 30 seconds using a timer and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant temperature water bath, and the solution is stabilized at 25 ℃ before the reaction is started.
Comparative example 3
A method for selectively reducing p-nitrophenol and preparing p-aminophenol comprises the following steps:
a. preparing a required catalyst solution: 1mg of pure N/C powder were weighed out (the preparation process differs from example 1 only in that no FeSO was added in step 2) 4 ·7H 2 O and Co (NO) 3 ) 2 ·6H 2 O) was placed in a sample tube and dissolved in 1mL of deionized water for sonication.
And (b) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown as the step b:
b. preparation 1L of 3.5 mmol. Multidot.L -1 P-nitrophenol solution. At a temperature of 28 ℃ and a pH of 9.4, 108mL of deionized water and 4mL of a p-nitrophenol solution were added to the beaker. To the above solution, 140. Mu.L of a catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction was started, sampling was performed every 30 seconds using a timer and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the solution is stabilized at 25 ℃ before the reaction is started.
Comparative example 4
A method for preparing p-aminophenol by selectively reducing p-nitrophenol comprises the following steps:
a. preparing a required catalyst solution: 0.05mg of Co-N/C powder (prepared in the same manner as the Co-N/C powder used in comparative example 1, co (NO) 3 ) 2 ·6H 2 Doubling the amount of O) and 0.05mg of Fe-N/C powder (same procedure as used for the preparation of Co-N/C powder in comparative example 1, feSO 4 ·7H 2 Double the amount of O) were loaded in sample tubes and they were dissolved in 1mL of deionized water for sonication. The Co content in 0.05mg of Co-N/C was equal to that in 0.1mg of FeCo-N/C carbon nanomaterial prepared in example 1. The content of Fe in 0.05mg of Fe-N/C was equal to that in 0.1mg of FeCo-N/C carbon nanomaterial prepared in example 1.
And (b) using the prepared catalyst solution as a catalyst, and using sodium borohydride to catalyze and reduce p-nitrophenol, wherein the process is shown as the step b:
b. preparation of 1L of a 3.5 mmol.L -1 Para nitro of (1)Phenol solution. At a temperature of 28 ℃ and a pH of 9.4, 108mL of deionized water and 4mL of a p-nitrophenol solution were added to the beaker. To the above solution, 140. Mu.L of a catalyst solution and 106.4mg of sodium borohydride were added simultaneously, and after the reaction was started, sampling was performed every 30 seconds using a timer and the sample was measured in an ultraviolet spectrophotometer, whereby the concentration of p-nitrophenol at each time point was estimated. The reaction is carried out in a constant-temperature water bath, and the solution is stabilized at 25 ℃ before the reaction is started.
Comparing the effect of example 2 (experimental group with pH 9.4) and comparative examples 1-4 on selective reduction of p-nitrophenol, the comparative examples 3 and 1-4 on selective reduction of p-nitrophenol are shown in FIG. 5, in which it can be seen that example 3 reduces p-nitrophenol significantly faster than each comparative example, in case that the conditions are controlled the same except for the catalyst added and the amount of Fe and Co added in the comparative examples is the same as the amount of FeCo-N/C material in example 1.
Example 3 removed over 98% of the p-nitrophenol within 2min, whereas the best comparative example 4 of each comparison achieved the removal over 2min of example 3 only after 10 min. It can be seen that the degradation effect of the FeCo-N/C material prepared in example 1 is better than that of the pure N/C structure, fe-N/C and Co-N/C, and is also better than that of the simple mixing of Fe-N/C and Co-N/C, thereby being sufficient to verify that the excellent catalytic performance of FeCo-N/C is derived from the combination effect of the bimetal and the N/C material.
Claims (10)
1. An application of a porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol is characterized in that: the porous FeCo-N/C carbon nano material is obtained by loading bimetal Fe, co and a silicon dioxide shell on an N/C precursor in a calcining mode and then forming a porous structure on the silicon dioxide shell in an acid etching mode.
2. Use according to claim 1, characterized in that: the mass percentages of Fe and Co in the porous FeCo-N/C carbon nano material are 0.20 percent and 0.207 percent respectively.
3. A porous FeCo-N/C carbon nano material is characterized in that: the method is used for selectively reducing p-nitrophenol and is prepared by the following steps;
step one, completely mixing ferrous salt, a metal chelating agent, cobalt salt and an N/C precursor, and then grinding to obtain a FeCo-N/C precursor material;
step two, adding the FeCo-N/C precursor material into a mixed solution of water and methanol, adding hexadecyl trimethyl ammonium bromide and tetraethyl orthosilicate into the mixed solution, and uniformly mixing; then, centrifuging the mixed solution to obtain a precipitate;
and step three, calcining the precipitate obtained in the step two, and then performing acid etching to obtain the porous FeCo-N/C carbon nano material.
4. The porous FeCo-N/C carbon nanomaterial according to claim 3, wherein: in the step one, feSO is adopted as ferrous salt 4 ·7H 2 O; the metal chelating agent is 1, 10-phenanthroline.
5. A porous FeCo-N/C carbon nanomaterial according to claim 3, characterized in that: in the second step, the N/C precursor adopts a ZIF material; the dosage of FeCo-N/C precursor material relative to the mixed solution of water and methanol is 2g/L; the volume ratio of water to methanol in the mixed solution of water and methanol is 10; the dosage of the hexadecyl trimethyl ammonium bromide relative to the FeCo-N/C precursor material is 0.25g/g; the amount of tetraethyl orthosilicate relative to FeCo-N/C precursor material was 2mL/g.
6. A porous FeCo-N/C carbon nanomaterial according to claim 3, characterized in that: the preparation process of the ZIF material comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 Dissolving O and 2-methylimidazole in the methanol solution and stirring; centrifuging to obtain a precipitate; the resulting precipitate was washed with methanol, repeated three times and then dried.
7. The porous FeCo-N/C carbon nanomaterial according to claim 6, wherein: zn (NO) 3 ) 2 ·6H 2 The using amount of O relative to the methanol solution is 11.25g/L; the amount of 2-methylimidazole used was 25g/L relative to the methanol solution.
8. A method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater is characterized by comprising the following steps: the method comprises the following steps:
step one, dissolving the porous FeCo-N/C carbon nano material as defined in any one of claims 3 to 7 in water to obtain a catalyst solution;
and step two, adding the catalyst solution and the reducing agent into the treated p-nitrophenol wastewater, adjusting the pH value to 8.8-10.1, and reacting at the temperature of 10-40 ℃.
9. The method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater according to claim 8, wherein: the pH value of the treated p-nitrophenol wastewater is adjusted to 9.4.
10. The method for preparing p-aminophenol by selectively reducing p-nitrophenol wastewater according to claim 8, wherein: the temperature of the treated p-nitrophenol wastewater is adjusted to 30 ℃.
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| CN109126809A (en) * | 2018-10-09 | 2019-01-04 | 沈阳工业大学 | A kind of catalyst and the preparation method and application thereof of efficient catalytic reduction nitrophenol |
| CN109928898A (en) * | 2019-04-09 | 2019-06-25 | 武汉工程大学 | A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green |
| CN113437310A (en) * | 2021-05-17 | 2021-09-24 | 上海大学 | Mesoporous silica shell-coated metal-N co-doped/porous carbon composite material, and preparation method and application thereof |
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| CN109126809A (en) * | 2018-10-09 | 2019-01-04 | 沈阳工业大学 | A kind of catalyst and the preparation method and application thereof of efficient catalytic reduction nitrophenol |
| CN109928898A (en) * | 2019-04-09 | 2019-06-25 | 武汉工程大学 | A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green |
| CN113437310A (en) * | 2021-05-17 | 2021-09-24 | 上海大学 | Mesoporous silica shell-coated metal-N co-doped/porous carbon composite material, and preparation method and application thereof |
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| WENLING HE, ET AL: "Structural Evolution and Compositional Modulation of ZIF-8- Derived Hybrids Comprised of Metallic Ni Nanoparticles and Silica as Interlayer", INORG. CHEM., vol. 58, 16 May 2019 (2019-05-16), pages 7255 - 7266 * |
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