CN115845831A - Preparation method of fiber-reinforced porous titanium-based electro-catalytic filter material - Google Patents
Preparation method of fiber-reinforced porous titanium-based electro-catalytic filter material Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000010936 titanium Substances 0.000 title claims abstract description 129
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 92
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
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- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 40
- 238000000151 deposition Methods 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 230000008021 deposition Effects 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
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- 239000002253 acid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
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- 238000002791 soaking Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 8
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- 239000011800 void material Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
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- 229960000502 poloxamer Drugs 0.000 claims description 4
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- 239000002994 raw material Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention relates to the technical field of environmental treatment, in particular to a preparation method of a fiber reinforced porous titanium-based electro-catalytic filter material. The obtained electro-catalytic filter material comprises three functional layers, namely a fiber supporting layer, a nano intermediate layer and a catalytic layer active layer, so that the mechanical strength of the porous carbon matrix can be effectively increased, and the service life of the porous carbon-based electro-catalytic filter material is prolonged; the macroscopic color of the nanotube array is changed from blue to blue black, wherein the color of the nano middle layer is darker and darker as the filtering precision is increased (from 10 μm to 50 μm); after the catalyst layer is loaded, the whole macro morphology of the filter material is gray black, and a compact solid solution is formed with the nano intermediate layer, so that the binding force between the catalyst layer and the matrix and the electron transmission capability are enhanced; the material has the filtration and interception performances of a separation membrane, also has excellent electrocatalytic oxidation performance, can obviously improve the catalytic activity compared with the traditional coating titanium electrode mainly comprising flat titanium and porous titanium, and is not easy to passivate and inactivate.
Description
Technical Field
The invention relates to the technical field of environmental treatment, in particular to a preparation method of a fiber reinforced porous titanium-based electro-catalytic filter material.
Background
Electrochemical oxidation technology is a potential treatment for wastewater and waste gas treatment. The electrocatalytic oxidation method can generate a large amount of active substances (hydroxyl radicals, hydrogen peroxide and the like) on the surface of the electrode under the action of current, and has the unique advantages of mild reaction conditions, high degradation efficiency, no need of adding medicaments, simple operation and the like for the oxidative degradation of organic pollutants in water and air.
At present, a metal oxide coating electrode is one of the most widely used electrode materials in the field of electrocatalytic oxidation and has been widely applied to electrochemical oxidation wastewater treatment and various electrochemical industries, but at present, a carbon electrode which is mainly applied has a hydrophobic characteristic, so that the effective specific surface of the carbon electrode is possibly limited and the effective transmission of water-system electrolyte ions in nanopores of a carbon material is hindered. The porous titanium material has excellent performance of compact titanium material, not only has good corrosion resistance and mechanical property on the premise of light weight, but also has the excellent performance of small specific gravity, large specific surface area, good permeability and the like of porous metal material in the fields of catalyst carriers, biomedicine, electrode materials and the like. As the positive pole, compare with traditional graphite anode, performance is more excellent.
Therefore, the porous titanium filter material loaded with the metal oxide catalyst layer is applied to the field of environmental management, on one hand, nano-scale titanium nano materials (titanium nano tubes, titanium dioxide, lithium titanate and the like) can be introduced into the porous titanium substrate filter material by methods of coating, electrodeposition and the like, and the purpose is to improve the binding force between the catalytic active layer and the substrate and the electron transfer capability and enhance the stability of the catalytic active layer and the substrate; on the other hand, the mechanical strength of the raw materials can be enhanced by using the high-strength fiber material as the supporting layer substrate, so that the high-strength fiber material can meet higher operation requirements and prolong the service life.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention provides a preparation method of a fiber reinforced porous titanium-based electrocatalytic filter material.
The invention is realized by the following technical scheme:
the preparation method of the fiber reinforced porous titanium-based electrocatalytic filter material is characterized by comprising the following steps:
the method specifically comprises the following steps:
(1) Pretreatment of a titanium substrate:
soaking a titanium substrate in 39-41% sodium hydroxide solution, carrying out water bath at 75-85 ℃ for 9-11 min, then treating in a mixed solution consisting of 35-37% by mass of concentrated hydrochloric acid, 29-30% by mass of hydrogen peroxide and deionized water for 10-25 min, wherein the volume ratio of the concentrated hydrochloric acid to the hydrogen peroxide to the deionized water is 1;
alternately cleaning the titanium matrix with deionized water and absolute ethyl alcohol until the titanium matrix is neutral, and placing the titanium matrix in an oven for drying at a constant temperature of 90-105 ℃ to obtain a titanium matrix for later use;
(2) Preparing a fiber support layer:
blending the porous titanium matrix pretreated in the step (1) with 1-5 wt.% of a high polymer binder, putting the mixture into a die of a tablet press, taking a high-strength fiber substrate as a supporting layer, controlling the forming pressure at 50-100MPa and the pressure maintaining time at 10-30 min, pressing the titanium matrix into a flat laminated structure, and placing the flat laminated structure in a muffle furnace to be calcined at a high temperature of 300-400 ℃ for 1-2 h; the obtained porous titanium matrix with the fiber support layer;
(3) Preparing a nanometer middle layer;
loading the nano intermediate layer on the flat laminated structure in the step (2) by an impregnation method or an electrochemical deposition method;
wherein, the dipping method comprises the following steps: soaking the porous titanium material with the flat laminated structure in the step (2) in 0.1-0.5 wt.% of ammonium fluoride, 1-3 wt.% of poloxamer F27, 0.5-2mol/L of sodium perchlorate and the balance of H 2 Placing the solution system consisting of O into an oven at the temperature of 90-150 ℃ for drying for 5-10 min, and repeating the steps for 20-30 times until the load capacity of the titanium nano material is 0.3-0.4 g;
the electrochemical deposition method comprises the following steps: soaking the flat laminated porous titanium material in the step (2) in a solution of 0.1 to 0.5wt.% of ammonium fluoride, 1 to 3wt.% of ethylene glycol, 3 to 5wt.% of sodium perchlorate and the balance of H 2 O, taking a porous titanium material with a flat laminated structure as a working electrode, a platinum electrode as a counter electrode, setting the voltage within the range of 10-40V, and setting the deposition number of turns within the range of 10-30 turns until the load capacity of the titanium nano material is 0.65-0.8g;
(4) Preparing a catalytic active layer;
the loading of the catalytic layer active layer can be realized by one of sol-gel method or electrodeposition method;
wherein the sol-gel method comprises the following steps:
s1: preparing 2 to 5 metal salts containing transition metals, wherein the transition metals can be Sn, ru, ir, sb, bi or Ta;
s2: mixing a metal salt withAdding H into polycarboxylic acid with 2-5 carbon atoms 2 Mixing the metal salts in the O to form a first mixed solution which is uniformly dissolved, wherein the total molar concentration of the metal salts is 0.05-0.6 mol/L, and the molar concentration of the polycarboxylic acid is 1-3 mol/L;
s3: adding ethylene glycol or glycerol with the carbon number of 2-5 into the first mixed solution, and uniformly mixing to obtain a second mixed solution, wherein the ratio of the mole number of the polyhydric alcohol to the mole number of the polycarboxylic acid is 3-8: 1;
s4: heating the second mixed solution in a water bath at the temperature of 60-120 ℃ for reaction for 30-60 min to form an aging solution;
s5: soaking the titanium substrate loaded with the nano intermediate layer in the step (3) in an aging solution for 5 to 10 seconds, drying the titanium substrate in a constant-temperature oven at the temperature of 100 to 140 ℃, placing the titanium substrate in a muffle furnace heated to the temperature of 395 to 400 ℃ after drying, roasting for 9 to 111min, repeating the operation for 10 to 20 times, and finally placing the titanium substrate in the muffle furnace for roasting for 1 to 3 hours for the last time; the catalyst layer formed by the coating particles is uniformly covered on the surface of the nano intermediate layer in a stacked ball cluster shape, the grain diameter of the crystal is 80 to 100 nm, and the corresponding void surface areas are respectively 0.102 m 2 /g、0.030 m 2 G and 0.011 m 2 /g；
The electrodeposition method comprises the following steps:
s1: preparing a deposition solution A consisting of a first transition metal salt, acid and water, wherein the acid is hydrochloric acid, sulfuric acid or citric acid, the first metal in the first transition metal salt is Sn, ru, ir, sb, bi or Ta,
wherein the molar concentration of the first transition metal salt solution is 0.05-0.6 mol/L, and the molar concentration of the acid is 1.25-3 mol/L;
s2: preparing a deposition solution B consisting of a second transition metal salt, an acid and water, wherein the acid is hydrochloric acid, sulfuric acid or citric acid, the second metal in the second transition metal salt is Sn, ru, ir, sb, bi or Ta, the molar concentration of the second transition metal salt solution is 0.05-0.6 mol/L, and the molar concentration of the acid is 1.25-3 mol/L;
s3: taking the titanium substrate loaded with the nano intermediate layer in the step (3) as a working cathode, taking a platinum electrode as a counter electrode, firstly depositing in a deposition liquid A for 5-20min, wherein the current density is 5-10mA/cm & lt 2 & gt, then depositing in a deposition liquid B for 20-60 s, wherein the current density is 2-5mA/cm & lt 2 & gt, repeatedly depositing for 2-5 times, and after the deposition is finished, placing in a muffle furnace at 350-400 ℃ for roasting for 1-3 h;
the filter material prepared by the method sequentially comprises a fiber supporting layer, a porous titanium matrix, a nano intermediate layer and a catalyst layer active layer;
the fiber support layer is one of titanium alloy fiber, titanium boride fiber, titanium carbide fiber, aluminum-titanium fiber, graphene fiber or titanium nitride fiber;
the porous titanium matrix can be synthesized or formed by selecting precursor titanium raw materials such as titanium powder, titanium hydride powder, titanium alloy, ammonium fluotitanate and the like, and the porous titanium matrix comprises microporous titanium with the titanium category of less than 2nm, mesoporous titanium with the titanium category of 2nm to 50nm or macroporous titanium with the titanium category of more than 50 nm;
the nano-interlayer is a titanium nanotube, titanium dioxide and lithium titanate coated or deposited on the porous titanium matrix;
the catalytic layer active layer is composed of a transition metal oxide or a composite metal oxide composed of metal oxides.
Further, the transition metal oxide of the catalytic layer active layer is one or two of PbO2, snO2, ruO2, mnO2, irO2, sb2O3, sb2O5, or Bi2O 3.
The invention has the following beneficial technical effects:
(1) The preparation method of the fiber-reinforced porous titanium-based electro-catalytic filter material comprises the steps of sequentially preparing an electro-catalytic filter material, wherein the electro-catalytic filter material comprises a fiber supporting layer, a porous titanium substrate, a nano intermediate layer and a catalytic layer active layer;
the added fiber support layer, the nanometer intermediate layer and the catalyst layer active layer can effectively increase the mechanical strength of the porous carbon matrix, the tensile strength of the porous carbon matrix is as high as 1.5 MPa, and the service life of the porous carbon matrix electro-catalysis filter material is prolonged;
the macroscopic color of the nanotube array is changed from blue to blue black, wherein the color of the nano middle layer is darker and darker as the filtering precision is increased (from 10 μm to 50 μm);
after the catalyst layer is loaded, the whole macro morphology of the filter material is gray black and is in the middle of nanometerThe interlayer forms a compact solid solution, the bonding force between the electro-catalytic layer and the matrix and the electron transmission capability are enhanced, the current efficiency can reach 69 percent, and the accelerated service life of the porous titanium-based electro-catalytic filter material is prolonged to 1.83 years; the void surface areas of the porous titanium-based electrocatalytic filter materials are respectively 0.102 m 2 The macroscopic surface area of the flat electrode with the same specification is only 2.36 to 2.54 cm 2 The concentration is increased by 402 to 433 times;
the electrocatalytic filter material has the filtration and interception performances of the separation membrane, also has excellent electrocatalytic oxidation performance, is not easy to passivate and inactivate, and has high efficiency, low cost and stable performance.
(2) The preparation method of the fiber-reinforced porous titanium-based electro-catalytic filter material can remove organic pollutants, has excellent electro-catalytic oxidation performance and has the current density of 20mA/cm 2 The removal rate of COD can reach 70 to 80 percent; compared with the traditional titanium electrode with a coating mainly comprising flat titanium and porous titanium, the unit mass load of the metal oxide is as high as 58.06 mg/g, the catalytic activity can be obviously improved, passivation and inactivation are not easy to occur, and the fiber-reinforced porous titanium-based electrofiltration material has the advantages of high efficiency, low cost, stable performance and wide application prospect in the field of wastewater and waste gas treatment.
Drawings
FIG. 1 is a schematic diagram of a functional layer of the fiber-reinforced porous titanium-based electrocatalytic filter of the present invention.
Fig. 2 is an SEM picture of the catalytic layer active layer of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Pretreatment of the porous titanium-based material: carbonizing a titanium substrate (selected from titanium hydride powder) at a high temperature of 400 ℃ in a tubular muffle furnace under the protection of nitrogen for 1h, soaking the titanium substrate in a mixed solution consisting of concentrated hydrochloric acid, 30% hydrogen peroxide and deionized water (the volume ratio is 1; after the surface of the titanium substrate is modified by inorganic acid, the metal film layer on the surface of the substrate is removed, the color becomes dark, the surface is rough, the surface area is increased, and the stress of the interface between the titanium substrate and the metal is reduced;
(2) Putting the porous titanium-based material pretreated in the step (1) into a die of a tablet press, selecting a high-strength titanium fiber substrate as a supporting layer, performing compression molding, adding 1-5 wt.% of polyvinyl alcohol binder, controlling the molding pressure at 50MPa and the pressure maintaining time at 20min, pressing the titanium substrate into a flat laminated structure, and calcining the flat laminated structure at the high temperature of 400 ℃ in a muffle furnace for 1h; the supporting layer is of a laminated structure, so that the mechanical strength of the matrix is greatly improved;
(3) Soaking the porous titanium material with the flat laminated structure in the step (2) in 0.1-0.5 wt.% of ammonium fluoride, 1-3 wt.% of poloxamer F27, 0.5-2mol/L of sodium perchlorate and the balance of H 2 Drying in a solution system composed of O in an oven at 150 ℃ for 10min, and repeating the steps for 20 times;
(4) Preparing ethylene glycol: citric acid: snCl 4 ·5H 2 O：SbCl 3 Heating and reacting a mixed solution of a 130-30 molar ratio;
soaking the material in the step (3) in a sol solution for 5s, drying in a constant-temperature oven at 140 ℃, taking out a sample, placing the sample in a muffle furnace heated to 400 ℃ for roasting for 10min, repeating the operation for 10 times, and placing the sample in the muffle furnace for roasting for 2h for the last time;
the catalyst layer formed by the coating particles is uniformly covered on the surface of the nano intermediate layer in a stacked ball cluster shape, the crystal grain diameter is about 80 to 100 nm, the specific surface area is obviously increased, and the corresponding void surface areas are respectively 0.102 m 2 /g、0.030 m 2 G and 0.011 m 2 The macroscopic surface area of the flat filter material with the same specification is only 2.54 cm 2 The concentration is increased by 48 to 433 times, and more active sites are provided.
Example 2
(1) Pretreatment of the porous titanium-based material: carbonizing a titanium substrate at a high temperature of 400 ℃ in a tubular muffle furnace under the protection of nitrogen for 1h, soaking the substrate in a mixed solution consisting of concentrated hydrochloric acid, 30% hydrogen peroxide and deionized water (the volume ratio is 1.
(2) And (2) putting the porous titanium-based material pretreated in the step (1) into a die of a tablet press (a high-strength carbon fiber substrate is selected as a supporting layer) for compression molding, adding 1-5 wt.% of polyvinyl alcohol binder, controlling the molding pressure at 50MPa and the pressure maintaining time at 20min, pressing the carbon substrate into a flat laminated structure, and placing the flat laminated structure in a muffle furnace for high-temperature calcination at 400 ℃ for 1h.
(3) Soaking the porous titanium material with the flat laminated structure in the step (2) in 0.1-0.5 wt.% of ammonium fluoride, 1-3 wt.% of poloxamer F27, 0.5-2mol/L of sodium perchlorate and the balance of H 2 O, drying in an oven at 150 ℃ for 10min, and repeating the steps for 20 times.
(4) Preparing a deposition solution A: the molar concentration of SbCl is 0.01 mol/L 3 0.05mol/L citric acid mixed solution; deposition solution B: the molar concentration is 0.01 mol/L SnCl 4 ·5H 2 O and 0.05mol/L HCl. Depositing the porous carbon-based material in the step (3) as a working cathode and the platinum electrode as a counter electrode in the deposition solution A for 20min (with the current density of 5 mA/cm) 2 ) Then depositing for 40s (the current density is 5 mA/cm) in the deposition liquid B 2 ) And repeating the deposition for 2 times, and after the deposition is finished, placing the obtained product in a muffle furnace heated to 400 ℃ for roasting for 3 hours.
Example 3
(1) Pretreatment of the porous titanium-based material: carbonizing a titanium substrate (selected from titanium hydride powder) at a high temperature of 400 ℃ in a tubular muffle furnace under the protection of nitrogen for 1h, soaking the titanium substrate in a mixed solution consisting of concentrated hydrochloric acid, 30% hydrogen peroxide and deionized water (the volume ratio is 1.
(2) And (2) putting the porous titanium-based material pretreated in the step (1) into a die of a tablet press (a high-strength carbon fiber substrate is selected as a support layer) for compression molding, adding 1-5wt.% of polyvinyl alcohol binder, controlling the molding pressure at 50MPa and the pressure maintaining time at 20min, pressing the carbon substrate into a flat laminated structure, and calcining the flat laminated structure in a muffle furnace at a high temperature of 400 ℃ for 1h.
(3) Soaking the flat laminated porous titanium material in the step (2) in a solution of 0.1 to 0.5wt.% of ammonium fluoride, 1 to 3wt.% of ethylene glycol, 3 to 5wt.% of sodium perchlorate and the balance of H 2 And O, taking a porous titanium material with a flat laminated structure as a working electrode, taking a platinum electrode as a counter electrode, setting the voltage within the range of 30V, and setting the number of deposition turns to be 20.
(4) Preparing a deposition solution A: the molar concentration of SbCl is 0.01 mol/L 3 0.05mol/L citric acid mixed solution; deposition solution B: the molar concentration is 0.01 mol/L SnCl 4 ·5H 2 O and 0.05mol/L HCl. Depositing the porous carbon-based material in the step (3) as a working cathode and the platinum electrode as a counter electrode in the deposition solution A for 20min (with the current density of 5 mA/cm) 2 ) Then depositing for 40s (the current density is 5 mA/cm) in the deposition liquid B 2 ) And repeating the deposition for 2 times, and after the deposition is finished, placing the obtained product in a muffle furnace heated to 400 ℃ for roasting for 3 hours.
Example 4
(1) Pretreatment of the porous titanium-based material: carbonizing a titanium substrate (selected from titanium hydride powder) at a high temperature of 400 ℃ in a tubular muffle furnace under the protection of nitrogen for 1h, soaking the titanium substrate in a mixed solution consisting of concentrated hydrochloric acid, 30% hydrogen peroxide and deionized water (the volume ratio is 1.
(2) And (2) putting the porous titanium-based material pretreated in the step (1) into a die of a tablet press (a high-strength carbon fiber substrate is selected as a supporting layer) for compression molding, adding 1-5 wt.% of polyvinyl alcohol binder, controlling the molding pressure at 50MPa and the pressure maintaining time at 20min, pressing the carbon substrate into a flat laminated structure, and placing the flat laminated structure in a muffle furnace for high-temperature calcination at 400 ℃ for 1h.
(3) Soaking the flat laminated porous titanium material in the step (2) in a solution of 0.1 to 0.5wt.% of ammonium fluoride, 1 to 3wt.% of ethylene glycol, 3 to 5wt.% of sodium perchlorate and the balance of H 2 And O, taking a porous titanium material with a flat laminated structure as a working electrode, taking a platinum electrode as a counter electrode, setting the voltage within the range of 30V, and setting the number of deposition turns to be 20.
(4) Preparing ethylene glycol: and (3) citric acid: snCl 4 ·5H 2 O：SbCl 3 Heating and reacting a mixed solution of a 130-30 molar ratio;
and (3) soaking the material in the step (3) in the sol solution for 5s, drying in a constant-temperature oven at 140 ℃, taking out the sample, placing the sample in a muffle furnace heated to 400 ℃ for roasting for 10min, repeating the operation for 10 times, and finally placing the sample in the muffle furnace for roasting for 2h.
Referring to fig. 1, the filter material prepared by the method sequentially comprises a fiber support layer, a porous titanium matrix, a nano intermediate layer and a catalytic layer active layer;
the fiber supporting layer is one of titanium alloy fiber, titanium boride fiber, titanium carbide fiber, aluminum-titanium fiber, graphene fiber or titanium nitride fiber;
the porous titanium matrix can be synthesized or formed by selecting precursor titanium raw materials such as titanium powder, titanium hydride powder, titanium alloy, ammonium fluotitanate and the like, and the porous titanium matrix comprises microporous titanium with the titanium category of less than 2nm, mesoporous titanium with the titanium category of 2nm to 50nm or macroporous titanium with the titanium category of more than 50 nm;
the nano-interlayer is a titanium nanotube, titanium dioxide and lithium titanate coated or deposited on the porous titanium matrix;
the catalytic layer active layer is composed of a transition metal oxide or a composite metal oxide composed of metal oxides.
Referring to fig. 2, the catalytic layer formed by the coating particles is uniformly covered on the nano intermediate layer surface in a stacked ball cluster shapeThe grain diameter of the crystal is about 80 to 100 nm, the specific surface area is obviously increased, and the corresponding void surface areas are respectively 0.102 m 2 /g、0.030 m 2 G and 0.011 m 2 The macroscopic surface area of the flat filter material with the same specification is only 2.54 cm 2 The concentration is increased by 48 to 433 times, and more active sites are provided.
The filter material prepared by the method comprises three functional layers, namely a fiber supporting layer, a nanometer intermediate layer and a catalyst layer active layer, so that the mechanical strength of the porous carbon matrix can be effectively increased, and the service life of the porous carbon-based electro-catalytic filter material is prolonged; the macroscopic color of the nanotube array is changed from blue to blue black, wherein the color of the nano middle layer is darker and darker as the filtering precision is increased (from 10 μm to 50 μm); after the catalyst layer is loaded, the whole macro morphology of the filter material is gray black, and a compact solid solution is formed with the nano intermediate layer, so that the binding force between the catalyst layer and the matrix and the electron transmission capability are enhanced; the material has the filtration and interception performances of a separation membrane, also has excellent electrocatalytic oxidation performance, is not easy to passivate and inactivate, and has high efficiency, low cost and stable performance.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (2)
1. The preparation method of the fiber reinforced porous titanium-based electrocatalytic filter material is characterized by comprising the following steps:
the method specifically comprises the following steps:
(1) Pretreatment of a titanium substrate:
soaking a titanium substrate in 39-41% sodium hydroxide solution, carrying out water bath at 75-85 ℃ for 9-11 min, then treating in a mixed solution consisting of 35-37% by mass of concentrated hydrochloric acid, 29-30% by mass of hydrogen peroxide and deionized water for 10-25 min, wherein the volume ratio of the concentrated hydrochloric acid to the hydrogen peroxide to the deionized water is 1; alternately cleaning the titanium matrix with deionized water and absolute ethyl alcohol until the titanium matrix is neutral, and placing the titanium matrix in an oven for drying at a constant temperature of 90-105 ℃ to obtain a titanium matrix for later use;
(2) Preparing a fiber support layer:
blending the porous titanium matrix pretreated in the step (1) with 1-5 wt.% of a high polymer binder, putting the mixture into a die of a tablet press, taking a high-strength fiber substrate as a supporting layer, controlling the forming pressure at 50-100MPa and the pressure maintaining time at 10-30 min, pressing the titanium matrix into a flat laminated structure, and placing the flat laminated structure in a muffle furnace to be calcined at a high temperature of 300-400 ℃ for 1-2 h; the obtained porous titanium matrix with the fiber support layer;
(3) Preparing a nanometer middle layer;
loading the nano intermediate layer on the flat laminated structure in the step (2) by an impregnation method or an electrochemical deposition method;
wherein, the dipping method comprises the following steps: soaking the porous titanium material with the flat laminated structure in the step (2) in 0.1-0.5 wt.% of ammonium fluoride, 1-3 wt.% of poloxamer F27, 0.5-2mol/L of sodium perchlorate and the balance of H 2 Placing the solution system consisting of O into an oven at the temperature of 90-150 ℃ for drying for 5-10 min, and repeating the steps for 20-30 times until the load capacity of the titanium nano material is 0.3-0.4 g;
the electrochemical deposition method comprises the following steps: soaking the flat laminated porous titanium material in the step (2) in a solution of 0.1 to 0.5wt.% of ammonium fluoride, 1 to 3wt.% of ethylene glycol, 3 to 5wt.% of sodium perchlorate and the balance of H 2 O, taking a porous titanium material with a flat laminated structure as a working electrode, a platinum electrode as a counter electrode, setting the voltage within the range of 10-40V, and setting the deposition number of turns within the range of 10-30 turns until the load capacity of the titanium nano material is 0.65-0.8g;
(4) Preparing a catalytic active layer;
the loading of the catalytic layer active layer can be realized by one of a sol-gel method or an electrodeposition method respectively;
wherein the sol-gel method comprises the following steps:
s1: preparing 2 to 5 metal salts containing transition metals, wherein the transition metals can be Sn, ru, ir, sb, bi or Ta;
s2: adding metal salt and C2-5 polycarboxylic acid into H 2 Mixing the metal salts in the O to form a first mixed solution which is uniformly dissolved, wherein the total molar concentration of the metal salts is 0.05-0.6 mol/L, and the molar concentration of the polycarboxylic acid is 1-3 mol/L;
s3: adding ethylene glycol or glycerol with the carbon number of 2-5 into the first mixed solution, and uniformly mixing to obtain a second mixed solution, wherein the ratio of the mole number of the polyhydric alcohol to the mole number of the polycarboxylic acid is 3-8: 1;
s4: heating the second mixed solution in a water bath at the temperature of 60-120 ℃ for reaction for 30-60 min to form an aging solution;
s5: soaking the titanium substrate loaded with the nano intermediate layer in the step (3) in an aging solution for 5 to 10 s, drying the titanium substrate in a constant-temperature oven at the temperature of 100 to 140 ℃, placing the titanium substrate in a muffle furnace heated to the temperature of 395 to 400 ℃ after drying, roasting for 9 to 111min, repeating the operation for 10 to 20 times, and finally placing the titanium substrate in the muffle furnace for roasting for 1 to 3 hours; a catalyst layer formed by the coating particles is uniformly covered on the surface of the nanometer intermediate layer in a stacked ball cluster shape, the grain diameter of the crystal is 80 to 100 nm, and the corresponding void surface areas are respectively 0.102 m 2 /g、0.030 m 2 G and 0.011 m 2 /g；
The electrodeposition method comprises the following steps:
s1: preparing a deposition solution A consisting of a first transition metal salt, acid and water, wherein the acid is hydrochloric acid, sulfuric acid or citric acid, the first metal in the first transition metal salt is Sn, ru, ir, sb, bi or Ta,
wherein the molar concentration of the first transition metal salt solution is 0.05-0.6 mol/L, and the molar concentration of the acid is 1.25-3 mol/L;
s2: preparing a deposition solution B consisting of a second transition metal salt, an acid and water, wherein the acid is hydrochloric acid, sulfuric acid or citric acid, the second metal in the second transition metal salt is Sn, ru, ir, sb, bi or Ta, the molar concentration of the second transition metal salt solution is 0.05-0.6 mol/L, and the molar concentration of the acid is 1.25-3 mol/L;
s3: taking the titanium substrate loaded with the nano intermediate layer in the step (3) as a working cathode, taking a platinum electrode as a counter electrode, firstly depositing in a deposition liquid A for 5-20min, wherein the current density is 5-10mA/cm & lt 2 & gt, then depositing in a deposition liquid B for 20-60 s, wherein the current density is 2-5mA/cm & lt 2 & gt, repeatedly depositing for 2-5 times, and after the deposition is finished, placing in a muffle furnace at 350-400 ℃ for roasting for 1-3 h;
the filter material prepared by the method sequentially comprises a fiber supporting layer, a porous titanium matrix, a nano intermediate layer and a catalyst layer active layer;
the fiber supporting layer is one of titanium alloy fiber, titanium boride fiber, titanium carbide fiber, aluminum-titanium fiber, graphene fiber or titanium nitride fiber;
the porous titanium matrix can be synthesized or formed by selecting precursor titanium raw materials such as titanium powder, titanium hydride powder, titanium alloy, ammonium fluotitanate and the like, and the porous titanium matrix comprises microporous titanium with the titanium category of less than 2nm, mesoporous titanium with the titanium category of 2nm to 50nm or macroporous titanium with the titanium category of more than 50 nm;
the nano-interlayer is a titanium nanotube, titanium dioxide and lithium titanate coated or deposited on the porous titanium matrix;
the catalytic layer active layer is composed of a transition metal oxide or a composite metal oxide composed of metal oxides.
2. The fiber-reinforced porous titanium-based electrocatalytic filter material as recited in claim 1, wherein:
the transition metal oxide of the catalytic layer active layer is one or two of PbO2, snO2, ruO2, mnO2, irO2, sb2O3, sb2O5 or Bi2O 3.
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