CN115869934A - Metal/carbon nanofiber persulfate catalyst, preparation method and application - Google Patents
Metal/carbon nanofiber persulfate catalyst, preparation method and application Download PDFInfo
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 112
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
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- 238000005516 engineering process Methods 0.000 claims abstract description 15
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
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- 239000011701 zinc Substances 0.000 claims abstract description 7
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- 239000002121 nanofiber Substances 0.000 claims description 44
- 238000009987 spinning Methods 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
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- 238000006731 degradation reaction Methods 0.000 claims description 8
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- 239000000969 carrier Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 abstract description 38
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 abstract description 19
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 14
- 150000002772 monosaccharides Chemical class 0.000 abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 abstract description 10
- 150000003624 transition metals Chemical class 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 7
- 239000008103 glucose Substances 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 6
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- 150000002823 nitrates Chemical class 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 230000003213 activating effect Effects 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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Images
Abstract
The invention relates to a metal/carbon nanofiber persulfate catalyst, a preparation method and application, and belongs to the field of water treatment and environmental material functions. The invention takes carbon nano-fiber as a carrier, takes chlorides or nitrates of transition metals such as manganese, iron, cobalt, nickel, copper, zinc and the like as metal precursors, adopts an electrostatic spinning technology to prepare a composite catalyst, and is used for catalyzing and degrading viscose waste water by combining a persulfate advanced oxidation technology. The removal rate of monosaccharide (xylose and glucose) in the viscose wastewater by combining the metal/carbon nanofiber persulfate catalyst prepared by the invention with a persulfate technology is 28-60%. The catalyst prepared by the invention has the characteristics of recoverability, avoidance of secondary pollution of metal residual water body and the like, and is beneficial to popularization of persulfate advanced oxidation technology in industrial application of treating viscose waste water.
Description
Technical Field
The invention relates to a metal/carbon nanofiber persulfate catalyst, a preparation method and application thereof, which are suitable for catalyzing persulfate to oxidize viscose waste water and belong to the field of water treatment and environmental material functions.
Background
The viscose fiber is prepared by separating and regenerating natural cellulose in cheap cotton linters, bamboo, wood and the like through chemical reaction, has the characteristics of easy dyeing, strong air permeability, good antistatic performance and the like, and is widely applied to the fields of various textiles, clothing and the like. Under the condition that non-renewable resources such as petroleum are increasingly in short supply, the development of the process for preparing viscose fibers by using renewable resources as raw materials is more and more accepted by the industry, so the yield of the viscose fibers worldwide increases year by year. However, the environmental pressure caused by the scale-up will also increase, and the pollution situation is also becoming more severe. The viscose waste water has the characteristics of high COD content, high concentration of suspended matters, complex components, high chroma and the like. The viscose waste water is also a main source of acidic waste water and alkaline waste water in the textile industry, can cause obvious salinization of soil, has great damage to plants planted around, and finally has potential influence on human health. The method for treating the viscose waste water is mainly a large-scale process, such as: micro-electrolysis, catalytic oxidation, neutralization and precipitation, aerobic biochemical method and the like. This patent is studied the degradation of monosaccharide composition in the viscose waste water, mainly uses catalytic oxidation technique degradation monosaccharide. The possibility of degrading the viscose waste water by persulfate advanced oxidation technology is researched.
The double oxygen bond in persulfate can be broken to generate sulfate (& SO) with strong oxidizing property 4 - ) Free radicals, which play an important role in the degradation process of antibiotics. However, persulfate alone cannot rapidly generate a large amount of SO 4 - Free radicals, which need to be activated in order to increase the degradation rate of monosaccharides (xylose, glucose). The activation means of persulfate includes thermal activation, ultraviolet activation, ultrasonic activation, carbon activation, and transition metal activation. Among them, physical activation such as thermal activation, ultrasonic activation, and ultraviolet activation consumes a lot of energy, so chemical activation such as carbon activation and transition metal activation has attracted extensive attention of researchers. However, only the transition metal is activated, so that the problem of metal ion leaching is solved, and secondary pollution is caused; the effect of activating persulfate by carbon alone is not obvious. Therefore, a chemical activator having a good activating effect and no secondary pollution is needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a metal/Carbon Nanofiber (CNF) persulfate catalyst prepared by an electrostatic spinning technology and a preparation method thereof, which are used for treating refractory viscose waste water in persulfate advanced oxidation reaction. The carbon nanofiber is used as a metal carrier and is compounded with one or more of transition metals such as manganese, iron, cobalt, nickel, copper, zinc and the like to prepare the high-efficiency activated persulfate catalyst, so that the viscose wastewater can be treated in a persulfate oxidation reaction system.
One of the technical solutions of the present invention for solving the above technical problems is as follows: a preparation method of a metal/carbon nanofiber persulfate catalyst is characterized in that carbon nanofibers are used as carriers, a metal precursor is loaded into the carbon nanofibers by adopting an electrostatic spinning technology, and the metal/carbon nanofiber persulfate catalyst is obtained through pre-oxidation and carbonization processes.
The beneficial effects of the invention are: among many carbon materials, electrospun carbon nanofibers have been widely used in the field of environmental protection due to their advantages of high specific surface area, large porosity, good gas permeability, and the like. The invention can improve the catalytic performance of the carbon nanofiber on persulfate by loading transition metal on the carbon nanofiber, and the carbon nanofiber in the composite material is taken as a carrier to enrich monosaccharide (xylose and glucose) and persulfate in viscose wastewater and degrade the monosaccharide into H through redox reaction 2 O and CO 2 Thereby removing the organic matter.
The electrostatic spinning carbon nanofiber is used as a metal carrier and is compounded with one or more of manganese, iron, cobalt, nickel, copper, zinc and other metals, viscose wastewater is degraded in a persulfate catalytic oxidation system, metal ion leaching can be reduced, the catalytic performance of a carbon material can be improved, and the catalyst has the advantages of low cost, high activity, good stability, recyclability, reduction of metal leaching and the like.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the metal precursor is metal chloride or metal nitrate, and the metal element in the metal precursor is one or a mixture of manganese, iron, cobalt, nickel, copper and zinc.
The method has the advantages that the carbon nanofiber is used as a carrier, chlorides or nitrates of transition metals such as manganese, iron, cobalt, nickel, copper, zinc and the like are used as metal precursors, the electrostatic spinning technology is adopted to prepare the composite catalyst, and the composite catalyst is used for catalyzing and degrading the viscose waste water by combining the persulfate advanced oxidation technology. The metal/carbon nanofiber persulfate catalyst prepared by the method disclosed by the invention has the removal rate of monosaccharide (xylose and glucose) in high-concentration viscose wastewater of 28% -60% by combining the persulfate technology. The catalyst prepared by the invention has the characteristics of being recoverable, avoiding secondary pollution of metal residual water bodies and the like, and is beneficial to popularization of persulfate advanced oxidation technology in industrial application of treating viscose waste water.
Further, the metal element in the metal precursor is copper or cobalt which is attached to the surface of the fiber in a spherical structure, and the diameter of the obtained metal/carbon nanofiber persulfate catalyst is 100 nm-300 nm.
The further scheme has the beneficial effects that the shapes of the materials are different after different metals and carbon nano fibers are compounded, and the diameters of the fibers are changed. Wherein, when the copper and the cobalt are compounded with the carbon nano fiber, the two metals are attached to the surface of the fiber in a spherical structure, the diameter of the metal/carbon nano fiber persulfate catalyst is 100 nm-300 nm, and the diameter of the blank carbon nano fiber catalyst fiber is 100 nm-200 nm.
Further, in the metal/carbon nanofiber persulfate catalyst, the metal content is calculated according to atomic percent, and the atomic percent range is 1% -9%, and preferably 3% -7%.
Further, the method comprises the following steps: (1) Preparation of metal/Polyacrylonitrile (PAN) nanofibers: dissolving a metal precursor in N, N-Dimethylformamide (DMF), then adding polyacrylonitrile, stirring to obtain a uniformly dispersed spinning solution, and carrying out electrostatic spinning to obtain metal/polyacrylonitrile nano-fibers; (2) Preparation of metal/carbon nanofiber persulfate catalyst: pre-oxidizing the metal/polyacrylonitrile nano fiber in the step (1), and then carbonizing the obtained pre-oxidized fiber at high temperature under inert gas to obtain the metal/carbon nano fiber persulfate catalyst.
The pre-oxidation may be carried out in a muffle furnace and the high temperature carbonization may be carried out in a tube furnace. The step (2) is specifically operated as follows: and (2) placing the metal salt/polyacrylonitrile nano fiber obtained in the step (1) into a muffle furnace for pre-oxidation, placing the obtained pre-oxidized fiber into a tubular furnace, and carbonizing at high temperature under inert gas to obtain the metal/carbon nano fiber persulfate catalyst.
Furthermore, in the step (1), 0.8-1.2 g of polyacrylonitrile can be dissolved in every 10mL of N, N-dimethylformamide, the stirring temperature of the spinning solution is 60-80 ℃, the rotating speed is 100-200 r/min, and the time is 1-4 h.
Further, in the step (1), the mass ratio of the metal atoms in the metal precursor to the polyacrylonitrile is 1-9%.
The method has the advantages that the materials obtained by different metal ratios have different properties, and aiming at the purpose of degrading the viscose waste water in a persulfate catalytic oxidation system, the mass percent of metal atoms needs to be controlled to be 1-9%, the method is most suitable, the degradation efficiency of monosaccharide (xylose and glucose) is high, metal cannot be remained in a water body, and secondary pollution is avoided.
Further, in the step (1), the electrostatic spinning step specifically comprises: firstly setting the temperature of an electrostatic spinning instrument to be 15-40 ℃, the humidity to be 10-30%, the advancing speed to be 0.02-0.1 mm/min, the voltage to be 7.00-23.00 KV, the rotating speed of a receiver to be 140r/min and the receiving distance to be 15-25 cm, then injecting the spinning solution into an injector, and then selecting a needle head with a proper type, wherein the type of the needle head is 20-25 nm, and carrying out electrostatic spinning.
Further, in the step (2), the pre-oxidation specifically comprises: heating to 250-300 ℃ at the heating rate of 2-5 ℃/min, preserving the heat for 30-90 min, and cooling to room temperature; the high-temperature carbonization specifically comprises the following steps: heating to 700-1000 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 1-5 h, and then cooling to room temperature.
Another technical solution for solving the above technical problems of the present invention is as follows: the metal/carbon nanofiber persulfate catalyst is prepared by the preparation method.
Another technical solution of the present invention for solving the above technical problems is as follows: an application of the metal/carbon nanofiber persulfate catalyst is used for degrading viscose wastewater in a persulfate system.
The metal/carbon nanofiber persulfate catalyst and persulfate oxidation system are used for treating viscose wastewater, and the metal/carbon nanofiber catalyst has obviously better catalytic performance than a carbon nanofiber catalyst.
The invention has the advantages and beneficial effects that:
(1) Compared with a blank CNF, the metal/CNF persulfate catalyst has the advantages that the fiber appearance is changed, and the fiber diameters are different.
(2) The existence of the CNF in the metal/CNF persulfate catalyst prepared by the preparation method can reduce metal agglomeration, so that the composite catalyst has more catalytic active sites and adsorption sites than a blank CNF catalyst.
(3) In the prepared metal/CNF catalyst, chemical bond force exists between transition metal and CNF, so that the metal residual water body and secondary pollution to the water body can be avoided to a certain extent.
(4) The persulfate oxidation reaction catalyst prepared by the method has the characteristics of good dispersibility, high catalytic activity, strong stability, low equipment requirement and the like.
(5) Some metal/CNF persulfate catalysts prepared by the invention have magnetism, and the materials are easy to recycle.
Drawings
FIG. 1 is an XRD pattern of the Co/CNF persulfate catalyst prepared in example 1.
Fig. 2 is an XRD pattern of the catalysts of examples 2 to 4 and comparative example 1.
FIG. 3 is an SEM picture of the Co/CNF persulfate catalyst prepared in example 1.
FIG. 4 is an SEM picture of the Cu/CNF persulfate catalyst prepared in example 4.
Fig. 5 is an SEM picture of CNF prepared in comparative example 1.
FIG. 6 is a graph comparing the degradation curves of xylose by the catalysts prepared in examples 1-4 and comparative examples 1-2 in combination with the persulfate advanced oxidation technology.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. The mode for carrying out the present invention includes, but is not limited to, the following examples, which are provided for illustrating the present invention and are not intended to limit the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention discloses a composite material, namely a metal and carbon nanofiber composite material. Compared with carbon nanofibers, the morphology of most transition metal and carbon nanofiber composites is changed, wherein Cu in Cu/CNF is attached to the surface of the carbon nanofibers in a particle structure, and the diameter of the carbon nanofibers is 50-300 nm.
The metal/carbon nanofiber persulfate catalyst disclosed by the invention is applied to activating persulfate and degrading viscose waste water.
Stirring by a water bath heating method at the rotating speed of 100r/min.
And (3) preparing 0.012mol/L xylose solution as a target pollutant, and then performing research on treating viscose wastewater by using the modified carbon nanofiber activated persulfate.
The metal/CNF persulfate catalyst can be combined with a persulfate advanced oxidation technology to treat refractory viscose wastewater and improve the removal rate of monosaccharide (xylose and glucose), thereby promoting the wide application of the persulfate advanced oxidation technology.
The following compares the prior art with the present invention, and the results are as follows: a preparation method of PAN nanofiber catalyst (prior art) and metal/carbon nanofiber persulfate catalyst (the invention) comprises the following steps:
(1) Preparation of a PAN nanofiber precursor: 0.8-1.2 g of Polyacrylonitrile (PAN) is taken and slowly added into 10mL of N, N-Dimethylformamide (DMF), and the mixture is stirred for 1-4 hours at the temperature of 60-80 ℃ and the rotating speed of 100-200 r/min to obtain a blank spinning solution, wherein the color of the spinning solution is faint yellow.
(2) Transferring the spinning solution into an injector, selecting a needle with the model number of 20-25, placing the injector on an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared white PAN nano-fiber precursor by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 15-40 ℃, the humidity is 10-30%, the advancing speed is 0.02-0.1 mm/min, the voltage is 7.00-23.00 KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15-25 cm.
(3) Preparation of metal/PAN nanofiber precursor: weighing a certain amount of metal salt (metal chloride or metal nitrate) according to the mass ratio of metal atoms to PAN molecules of 1-9%, dissolving the metal salt in DMF, uniformly mixing, slowly pouring 0.8-1.2 g of Polyacrylonitrile (PAN), and performing subsequent operation according to the stirring conditions and spinning parameters in the step (2) to obtain the metal/PAN nanofiber precursor. Different from the nanofiber precursor obtained in the step (2), the metal/PAN nanofiber precursor added with the metal salt has a color generally similar to that of metal ions, and the color of the spun metal/PAN nanofiber is slightly lighter than that of the spinning solution.
(4) Preparation of PAN nanofiber pre-oxidized fiber and metal/PAN nanofiber pre-oxidized fiber: and (3) respectively putting the PAN nanofiber precursor and the metal/PAN nanofiber precursor obtained in the steps (2) and (3) into a muffle furnace to be oxidized for 30-90 min, and respectively obtaining the light brown PAN nanofiber pre-oxidized filaments and the metal/PAN nanofiber pre-oxidized filaments with other colors.
The oxidation condition in the step (4): the heating rate is 2-5 ℃/min, and the heat preservation temperature is 250-300 ℃.
(5) Preparing the PAN nano-fiber carbonized filament and the metal/PAN nano-fiber carbonized filament: and (5) respectively putting the blank PAN nano fiber pre-oxidized fiber and the metal/PAN nano fiber pre-oxidized fiber obtained in the step (4) into a tubular furnace to be calcined for 1-5 hours, so as to obtain the brown CNF and the metal/CNF catalyst with darker color.
The calcining condition in the step (5): introducing inert gas, heating up at a rate of 3-5 ℃/min, and keeping the temperature at 700-1000 ℃.
The metal salt in the step (2) comprises transition metal chlorides or nitrates of manganese, iron, cobalt, nickel, copper, zinc and the like. Finally, the catalysts such as Mn/CNF, fe/CNF, co/CNF, ni/CNF, cu/CNF, zn/CNF and the like can be obtained.
The catalyst has the following intermittent reaction conditions in the persulfate oxidation reaction treatment of the viscose wastewater: normal pressure, initial pH of wastewater: 3 to 11, the reaction temperature is 20 to 70 ℃, the rotating speed is 50 to 300r/min, and the adding amount of the catalyst is 0.05 to 5.0g/L.
The present invention will be described in detail below with reference to examples, comparative examples and the accompanying drawings.
Example 1:
3% preparation of Co/CNF, procedure as follows:
(1) 0.1212g of CoCl was weighed out 2 ·6H 2 And dissolving O in DMF, mixing, slowly pouring 1.0g of PAN, and stirring at 70 ℃ and at the rotating speed of 200r/min for 1h to obtain the brown spinning solution.
(2) And transferring the spinning solution into a 10mL injector, selecting a needle with the model number of 23, placing the needle into an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared light brown Co/PAN nanofiber precursor with the metal atomic mass percentage of 3% by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 25 ℃, the humidity is 20%, the advancing speed is 0.07mm/min, the voltage is 10.00KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15cm.
(3) Oxidizing the Co/PAN nanofiber precursor obtained in step (2) 3% in a muffle furnace for 60min to obtain brown Co/PAN nanofiber pre-oxidized filaments.
The oxidation condition in the step (3): the temperature rise rate is 3 ℃/min, and the heat preservation temperature is 270 ℃.
(4) Putting the pre-oxidized filaments of Co/PAN nanofibers with the content of 3 percent obtained in the step (3) into a tube furnace to be calcined for 2 hours to obtain the reddish brown 3 percent Co/CNF composite catalyst. The SEM image is shown in FIG. 3.
The calcining condition in the step (4): introducing inert gas, heating up at a rate of 4 ℃/min, and keeping the temperature at 900 ℃.
(5) Persulfate oxidation reaction experimental conditions: 3% Co/CNF catalyst was added in an amount of 0.3g/L, potassium persulfate was added in an amount of 1g/L, the temperature was 25 ℃ and the initial pH was 7, and the xylose removal rate was 51.4% after the reaction for 60 min.
Example 2:
3% preparation of Cu/CNF, procedure as follows:
(1) 0.0966g of CuCl was weighed out 2 ·2H 2 And dissolving O in DMF, mixing, slowly pouring 1.2g of PAN, and stirring at 70 ℃ and at the rotating speed of 200r/min for 1h to obtain the blue-green spinning solution.
(2) Transferring the spinning solution into a 10mL injector, selecting a needle with the model number of 23, placing the needle in an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared light blue Cu/PAN nanofiber precursor with the metal atomic mass percentage of 3% by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 25 ℃, the humidity is 20%, the advancing speed is 0.07mm/min, the voltage is 10.00KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15cm.
(3) Oxidizing the 3% Cu/PAN nanofiber precursor obtained in step (2) in a muffle furnace for 60min to obtain a brownish-black 3% Cu/PAN nanofiber pre-oxidized fiber.
The oxidation condition in the step (3): the heating rate is 3 ℃/min, and the heat preservation temperature is 270 ℃.
(4) Putting the 3-percent Cu/PAN nanofiber pre-oxidized fiber obtained in the step (3) into a tube furnace to be calcined for 2 hours to obtain the black 3-percent Cu/CNF composite catalyst.
The calcining condition in the step (4): introducing inert gas, heating up at a rate of 4 ℃/min, and keeping the temperature at 900 ℃.
(5) Persulfate oxidation reaction experimental conditions: 3% the amount of Cu/CNF catalyst added was 0.3g/L, the amount of potassium persulfate added was 1g/L, the temperature was 25 ℃ and the initial pH was 7, and the xylose removal rate was 29.2% after 60min of the reaction.
Example 3:
5% preparation of Cu/CNF, procedure as follows:
(1) 0.1609g of CuCl is weighed out 2 ·2H 2 And dissolving O in DMF, uniformly mixing, slowly pouring 1.2g of PAN, and stirring at 70 ℃ and the rotating speed of 200r/min for 1h to obtain the blue spinning solution.
(2) And transferring the spinning solution into a 10mL injector, selecting a needle with the model number of 23, placing the needle into an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared blue Cu/PAN nanofiber precursor with the metal atomic mass percentage of 5% by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 25 ℃, the humidity is 20%, the advancing speed is 0.07mm/min, the voltage is 10.00KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15cm.
(3) Oxidizing the 5% Cu/PAN nanofiber precursor obtained in step (2) in a muffle furnace for 60min to obtain a brownish-black 5% Cu/PAN nanofiber pre-oxidized filament.
The oxidation condition in the step (3): the heating rate is 3 ℃/min, and the heat preservation temperature is 270 ℃.
(4) Placing the 5% Cu/PAN nanofiber pre-oxidized fiber obtained in the step (3) into a tube furnace to be calcined for 2h to obtain a black 5% Cu/CNF composite catalyst.
The calcining condition in the step (4): introducing inert gas, heating up at a rate of 4 ℃/min, and keeping the temperature at 900 ℃.
(5) Persulfate oxidation reaction experimental conditions: 5% the amount of Cu/CNF catalyst added was 0.3g/L, the amount of potassium persulfate added was 1g/L, the temperature was 25 ℃ and the initial pH was 7, and the xylose removal rate was 33.8% after 60min of the reaction.
Example 4:
7% preparation of Cu/CNF by the following procedure:
(1) 0.2254g of CuCl is weighed out 2 ·2H 2 And dissolving O in DMF, uniformly mixing, slowly adding 1.2g of PAN, and stirring at 70 ℃ and the rotating speed of 200r/min for 1h to obtain the dark blue spinning solution.
(2) And transferring the spinning solution into a 10mL injector, selecting a needle with the model number of 23, placing the needle into an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared blue Cu/PAN nanofiber precursor with the metal atomic mass percent of 7% by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 25 ℃, the humidity is 20%, the advancing speed is 0.07mm/min, the voltage is 10.00KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15cm.
(3) Putting the 7-percent Cu/PAN nanofiber precursor obtained in the step (2) into a muffle furnace to be oxidized for 60min to obtain the brownish-black 7-percent Cu/PAN nanofiber pre-oxidized fiber.
The oxidation condition in the step (3): the heating rate is 3 ℃/min, and the heat preservation temperature is 270 ℃.
(4) Calcining the 7% Cu/PAN nanofibrous pre-oxidized fiber obtained in step (3) in a tubular furnace for 2h to obtain black 7% Cu/CNF composite catalyst. The SEM image is shown in FIG. 4.
The calcining condition in the step (4): introducing inert gas, heating up at a rate of 4 ℃/min, and keeping the temperature at 900 ℃.
(5) Persulfate oxidation reaction experimental conditions: 7% the amount of Cu/CNF catalyst added was 0.3g/L, the amount of potassium persulfate added was 1g/L, the temperature was 25 ℃ and the initial pH was 7, and the xylose removal rate was 38.6% after 60min of the reaction.
In the invention, when 1% or 9% of Cu/CNF is used for preparing electrospinning, cu salt with different proportions is added, and an electrostatic spinning instrument cannot spin normal yarns under the voltage of 10.00KV, so that 1% or 9% of Cu/CNF is not available; while other transition metals exemplified above as modifiers may be present at 1% and 9% of the success of spinning, the resulting metal/CNF catalysts have similar catalytic effects, with xylose removal rates greater than 25%. Furthermore, the use of 3% Co/CNF complex catalyst indicates that metals other than Cu can also be complexed with CNF to give a highly active persulfate catalyst.
In addition, it should be noted that, the applicant also carries out relevant comparative experiments aiming at other relevant technical parameters in the preparation method within the range defined above, and can normally spin and obtain the metal/CNF catalyst with similar technical effect, and the description thereof is omitted here.
Comparative example 1:
preparation of blank CNF, procedure was as follows:
(1) 1.2g PAN is poured into 10mL DMF, and the mixture is stirred for 1h at 70 ℃ and 200r/min rotation speed to obtain light yellow spinning solution.
(2) Transferring the spinning solution into a 10mL injector, selecting a needle with the model number of 23, placing the needle in an electrostatic spinning instrument for high-voltage electrostatic spinning, and collecting the prepared white PAN nanofiber precursor by using aluminum foil paper.
Setting spinning parameters in the step (2): the temperature of the electrostatic spinning instrument is 25 ℃, the humidity is 20%, the advancing speed is 0.07mm/min, the voltage is 10.00KV, the rotating speed of the receiver is 140r/min, and the receiving distance is 15cm.
(3) And (3) putting the PAN nanofiber precursor obtained in the step (2) into a muffle furnace to oxidize for 60min to obtain the light brown PAN nanofiber pre-oxidized fiber.
The pre-oxidation condition in the step (3): the temperature rise rate is 3 ℃/min, and the heat preservation temperature is 270 ℃.
(4) And (4) putting the blank PAN nano fiber pre-oxidized fiber obtained in the step (3) into a tubular furnace to calcine for 2 hours to obtain a brown CNF catalyst. The SEM image is shown in FIG. 5.
The calcining condition in the step (4): introducing inert gas, heating up at a rate of 4 ℃/min, and keeping the temperature at 900 ℃.
(5) Persulfate oxidation reaction experimental conditions: the adding amount of the CNF catalyst is 0.3g/L, the adding amount of the potassium persulfate is 1g/L, the temperature is 25 ℃, the initial pH value is 7, and the xylose removal rate is 24.2% after the reaction is carried out for 60 min.
Comparative example 2:
persulfate oxidation alone reaction experimental conditions: the adding amount of potassium persulfate is 1g/L, the temperature is 25 ℃, the initial pH value is 7, and the xylose removal rate is 5.95 percent after the reaction is carried out for 60 min.
And (4) analyzing results: as can be seen from fig. 1 and 2, the metal and CNF are successfully combined together, and the metal atom exists in the composite material in the form of simple substance.
As can be seen from FIG. 6, the degradation rate of xylose by the metal/CNF composite material activated PDS is higher than that by CNF.3% Co/CNF-activated PDS was able to achieve 51.4% removal of xylose, which is 27.2% higher than when CNF was used as catalyst, due to the addition of new active sites to the metal/CNF, which is better able to activate PDS. The Cu/CNF can also achieve at least 28% removal rate, which is higher than that of blank CNF.
Furthermore, as can be seen from FIG. 6, the Cu/CNF catalytic performance was improved as the proportion of Cu atoms increased, and the removal rate when 7% Cu/CNF-activated PDS degrades xylose was higher than that when 3% and 5% Cu/CNF were used as catalysts, because increasing the proportion of metal atoms corresponds to increasing the number of new active sites when the PAN proportion was unchanged, and the catalytic effect on PDS was better.
Therefore, compared with the common carbon nanofiber material, the metal/carbon nanofiber composite material provided by the invention is more suitable for catalyzing persulfate to oxidize viscose wastewater, and has higher removal rate of monosaccharide (xylose and glucose) in high-concentration viscose wastewater.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. All the changes made on the basis of the technical scheme according to the technical idea provided by the invention fall within the protection scope of the claims of the invention.
Claims (10)
1. A preparation method of a metal/carbon nanofiber persulfate catalyst is characterized in that carbon nanofibers are used as carriers, a metal precursor is loaded into the carbon nanofibers by adopting an electrostatic spinning technology, and the metal/carbon nanofiber persulfate catalyst is obtained through pre-oxidation and carbonization processes.
2. The method for preparing the metal/carbon nanofiber persulfate catalyst according to claim 1, wherein the metal precursor is a metal chloride or a metal nitrate, and the metal element in the metal precursor is one or more of manganese, iron, cobalt, nickel, copper and zinc.
3. The method for preparing the metal/carbon nanofiber persulfate catalyst according to claim 2, wherein the metal element in the metal precursor is copper or cobalt, which is attached to the surface of the fiber in a spherical structure, and the diameter of the obtained metal/carbon nanofiber persulfate catalyst is 100nm to 300nm.
4. The method for preparing the metal/carbon nanofiber persulfate catalyst according to any of claims 1 to 3, comprising the steps of: (1) preparing metal/polyacrylonitrile nano-fiber: dissolving a metal precursor in N, N-dimethylformamide, then adding polyacrylonitrile, stirring to obtain a uniformly dispersed spinning solution, and carrying out electrostatic spinning to obtain metal/polyacrylonitrile nano-fibers; (2) Preparation of metal/carbon nanofiber persulfate catalyst: and (2) pre-oxidizing the metal/polyacrylonitrile nano fiber in the step (1), and then carrying out high-temperature carbonization on the obtained pre-oxidized fiber under inert gas to obtain the metal/carbon nano fiber persulfate catalyst.
5. The method for preparing the metal/carbon nanofiber persulfate catalyst according to claim 4, wherein 0.8-1.2 g of polyacrylonitrile can be dissolved in every 10mL of N, N-dimethylformamide in the step (1), the stirring temperature of the spinning solution is 60-80 ℃, the rotation speed is 100-200 r/min, and the time is 1-4 h.
6. The preparation method of the metal/carbon nanofiber persulfate catalyst according to claim 4, wherein in the step (1), the mass ratio of metal atoms in the metal precursor to polyacrylonitrile is 1% to 9%.
7. The method for preparing the persulfate catalyst for metal/carbon nanofibers according to claim 4, wherein in the step (1), the step of electrospinning specifically comprises: firstly setting the temperature of an electrostatic spinning instrument to be 15-40 ℃, the humidity to be 10-30%, the advancing speed to be 0.02-0.1 mm/min, the voltage to be 7.00-23.00 KV, the rotating speed of a receiver to be 140r/min and the receiving distance to be 15-25 cm, then injecting the spinning solution into an injector, and then selecting a needle head with a proper type, wherein the type of the needle head is 20-25 nm, and carrying out electrostatic spinning.
8. The method for preparing the metal/carbon nanofiber persulfate catalyst according to claim 4, wherein in the step (2), the pre-oxidation is specifically as follows: heating to 250-300 ℃ at the heating rate of 2-5 ℃/min, preserving the heat for 30-90 min, and cooling to room temperature; the high-temperature carbonization specifically comprises the following steps: heating to 700-1000 ℃ at the heating rate of 3-5 ℃/min, preserving the heat for 1-5 h, and then cooling to room temperature.
9. A metal/carbon nanofiber persulfate catalyst, characterized by being prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the metal/carbon nanofiber persulfate catalyst according to claim 9 in the degradation of viscose waste water in persulfate systems.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214738A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the wet dip preparation method of a kind of efficient carbon nanofiber |
| CN105214668A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the blending preparation method of a kind of efficient carbon nanofiber |
| CN106835364A (en) * | 2017-01-19 | 2017-06-13 | 南京理工大学 | A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ |
| CN108786814A (en) * | 2018-06-06 | 2018-11-13 | 武汉工程大学 | A kind of copper cobalt dual-metal/porous carbon nanofiber composite material and preparation method and application |
| CN109950562A (en) * | 2019-04-08 | 2019-06-28 | 上海电力学院 | A kind of preparation method and application of nickel, cobalt, nitrogen co-doped nano-fiber catalyst |
| CN112501791A (en) * | 2020-12-02 | 2021-03-16 | 新乡学院 | Cobalt-loaded hollow carbon fiber film for efficiently removing 4-nitrophenol and preparation method thereof |
| US20210245142A1 (en) * | 2020-02-10 | 2021-08-12 | Uif (University Industry Foundation), Yonsei University | Method for producing hollow activated carbon nanofiber for activating peroxymonosulfate, catalyst for purifying water, and method for purifying water |
| CN115106091A (en) * | 2022-07-01 | 2022-09-27 | 长春理工大学 | Method for preparing perovskite persulfate catalyst by electrostatic spinning process |
-
2022
- 2022-10-31 CN CN202211347261.1A patent/CN115869934A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214738A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the wet dip preparation method of a kind of efficient carbon nanofiber |
| CN105214668A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the blending preparation method of a kind of efficient carbon nanofiber |
| CN106835364A (en) * | 2017-01-19 | 2017-06-13 | 南京理工大学 | A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ |
| CN108786814A (en) * | 2018-06-06 | 2018-11-13 | 武汉工程大学 | A kind of copper cobalt dual-metal/porous carbon nanofiber composite material and preparation method and application |
| CN109950562A (en) * | 2019-04-08 | 2019-06-28 | 上海电力学院 | A kind of preparation method and application of nickel, cobalt, nitrogen co-doped nano-fiber catalyst |
| US20210245142A1 (en) * | 2020-02-10 | 2021-08-12 | Uif (University Industry Foundation), Yonsei University | Method for producing hollow activated carbon nanofiber for activating peroxymonosulfate, catalyst for purifying water, and method for purifying water |
| CN112501791A (en) * | 2020-12-02 | 2021-03-16 | 新乡学院 | Cobalt-loaded hollow carbon fiber film for efficiently removing 4-nitrophenol and preparation method thereof |
| CN115106091A (en) * | 2022-07-01 | 2022-09-27 | 长春理工大学 | Method for preparing perovskite persulfate catalyst by electrostatic spinning process |
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