CN115896862B - Be used for electrosynthesis H2O2Metal single-site catalytic material as well as preparation method and application thereof - Google Patents
Be used for electrosynthesis H2O2Metal single-site catalytic material as well as preparation method and application thereof Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
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Abstract
The invention discloses a metal single-site catalytic material for electrosynthesis of H 2O2, and a preparation method and application thereof, and belongs to the technical field of electrocatalysis. According to the invention, a dipping method is adopted to load metal phthalocyanine or porphyrin with a characteristic structure of M-N 4 (M refers to metal and N refers to pyrrole nitrogen) onto an oxygen atom modified carbon carrier in a single-molecule isolated and dispersed form to obtain a metal single-site material. The metal single-point material prepared by the invention is loaded on the surface of a hydrophobic, porous and conductive substrate by using an adhesive to prepare a gas diffusion electrode, the electrode is used as a cathode of an electrolytic cell, a flowing state three-phase reaction interface is formed by the electrode, an ultrathin catholyte fluid and an air chamber, and the H 2O2 is synthesized by using a power supply to drive electro-catalysis O 2 to reduce. The preparation method provided by the invention is simple and easy to amplify, and expensive raw materials and equipment are not needed; the invention can realize high-current and high Faraday-efficiency electrosynthesis H 2O2 performance under alkaline, medium and acidic conditions, and can continuously synthesize high-concentration H 2O2 solution.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a metal single-site catalytic material for electrosynthesis of H 2O2, and a preparation method and application thereof.
Background
H 2O2 is used as an environment-friendly bulk chemical, is widely applied to the fields of chemical industry, medicine, new energy and the like, and has huge economic benefit and environmental benefit. At present, the industrial production of H 2O2 mainly depends on an anthraquinone process, a large amount of H 2 and heavy aromatic chemicals are consumed, organic waste and acid wastewater are discharged, and the transportation and storage of high-concentration H 2O2 are accompanied with corrosion and explosion risks. Based on the method, the development of a novel in-situ H 2O2 synthesis technology which is efficient, safe and environment-friendly is an important way for replacing the traditional technology and promoting the development of chemical and environmental water treatment technology related to H 2O2.
The electrocatalytic in-situ H 2O2 production by oxygen cathodic reduction technology has been attracting attention as an alternative to green cleaning. The technology can be carried out at normal temperature and normal pressure, does not need organic reagents, has strong controllability, and can regulate and control the reaction rate and the product selectivity by changing the potential/current and the electrode material. The research shows that the catalysts such as modified carbon materials, pd alloy, cobalt monoatoms and the like have H 2O2 selectivity of nearly 100% in a rotating ring disk-disk test system, however, the current electrolytic cell system generally has the problems of low H 2O2 partial current density, low H 2O2 yield and low concentration. The reason for this is mainly summarized as follows: the microstructure of the metal monoatoms is not clear for the performance regulation mechanism of the H 2O2 produced by the electrocatalytic ORR, and the optimal reaction path with high activity and high selectivity is difficult to realize; the single-atom material with specific active configuration is difficult to accurately synthesize, the active site is insufficient, and high H 2O2 minute current density is difficult to realize.
Disclosure of Invention
In order to solve the technical problems, the invention provides a metal single-site catalytic material for electrosynthesis of H 2O2, and a preparation method and an application method thereof. In particular to a preparation method of a metal single-site catalytic material taking an oxygen atom modified carbon supported metal phthalocyanine/porphyrin molecule with an M-N 4 (M refers to metal and N refers to pyrrole nitrogen) characteristic structure as a key characteristic, and a method for improving H 2O2 partial current density and product concentration by electrocatalytic oxygen reduction of a gas diffusion type electrolytic cell with a flowing state ultrathin fluid characteristic. The electrode comprises a gas diffusion layer and a catalytic layer, wherein the active component of the catalytic layer is an oxygen atom modified carbon-supported metal single-site material, and the activity and the selectivity of the electrosynthesis H 2O2 are improved together by changing the metal type and the surface chemical property of the modified carbon carrier and simultaneously regulating and controlling the environment of metal single atoms and coordination atoms thereof, optimizing the adsorption energy of key reaction intermediate products.
The invention provides a preparation method and an application method of a metal single-site catalytic material for electrosynthesis of H 2O2. The metal single-site catalytic material is prepared by a one-step impregnation method by utilizing a carbon carrier modified by oxygen atoms and metal phthalocyanine or porphyrin molecules; the electrosynthesis H 2O2 is characterized in that an ultrathin flow dynamic gas-liquid-solid three-phase reaction interface is formed on a catalytic layer by a metal single-site electrode based on a gas diffusion function, and H 2O2 solution is continuously produced with high selectivity under the condition of high-current electrolysis.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a metal single-site catalytic material which takes a carbon material modified by oxygen atoms as a carrier to load isolated and dispersed metal phthalocyanine or metalloporphyrin molecules with a characteristic structure of M-N 4, wherein M is metal, and N is pyrrole nitrogen.
Further, in the above technical solution, the oxygen atom modified carbon material includes at least one of carbon nanotubes, graphene, porous carbon, or carbon black.
Further, the carbon black comprises at least one of Cabot VXC72, black pearl 2000, ketjenback ECP-600JD, kurary YP-80F.
Further, in the above technical solution, the isolated and dispersed metallophthalocyanine or metalloporphyrin molecule having the characteristic structure of M-N 4 includes at least one of manganese phthalocyanine, manganese porphyrin, cobalt phthalocyanine, cobalt porphyrin, nickel phthalocyanine, nickel porphyrin, copper phthalocyanine, copper porphyrin, metallophthalocyanine or derivatives of metalloporphyrin having the characteristic structure of M-N 4.
The invention also provides a preparation method of the metal single-site catalytic material, which comprises the following steps:
(1) Oxidizing the carbon material to obtain an oxygen atom modified carbon material carrier;
(2) Respectively dispersing oxygen atom modified carbon material carrier and metal phthalocyanine or metalloporphyrin in an organic solvent, adding the dispersion liquid of the metal phthalocyanine or metalloporphyrin into the dispersion liquid of the oxygen atom modified carbon material carrier, and continuously stirring to obtain the metal single-site catalytic material, wherein the mass ratio of the metal phthalocyanine or metalloporphyrin to the carbon material carrier is 1-20%.
Further, in the step (1), after the carbon material is subjected to oxidation treatment, the carbon material is washed and dried to obtain the carbon material carrier modified by oxygen atoms.
Further, in the step (2), after continuous stirring, the metal single-point catalytic material is obtained after suction filtration separation, cleaning and drying.
Further, in the above technical solution, the oxidation treatment method includes a concentrated oxidative acid heat treatment method, a high temperature carbonization method or a hydrothermal method;
the concentrated oxidative acid heat treatment process comprises: adding a carbon material carrier into concentrated oxidizing acid with the mass concentration of 37-100% for oxidation treatment, wherein the oxidation temperature is 110-140 ℃ and the oxidation time is 5-12 h; the oxidizing acid comprises sulfuric acid, nitric acid or perchloric acid;
The high temperature carbonization method comprises: uniformly mixing a carbon material carrier and polyethylene oxide in a mass ratio of 2:1-1:5, and calcining at 500-800 ℃ for 1-4 h in an N 2 or inert gas atmosphere;
the hydrothermal method comprises the following steps: dispersing the carbon material carrier in 7-10M KOH or NaOH solution, and preserving the temperature for 12-24 h at 150-200 ℃.
Further, in the above technical scheme, the organic solvent includes at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone and N-hexane.
The invention also provides an application of the metal single-site catalytic material or the metal single-site catalytic material prepared by the method, and the metal single-site catalytic material is used as a cathode catalyst of a gas diffusion type electrolytic cell for electrosynthesis of H 2O2.
Further, in the above technical solution, the method includes the following steps:
(1) Loading a metal unit material on the surface of a substrate to prepare an electrode with one side being a catalyst layer and the other side being a diffusion layer;
(2) The electrosynthesis H 2O2 electrolytic cell assembly mainly comprises: a cathode, an anode, a cathode chamber, an anode chamber, an ion exchange membrane and an air chamber;
The electrode prepared in the step (1) is used as a cathode, the electrode with electrocatalytic oxidation activity is used as an anode, a catalyst layer of the cathode is contacted with catholyte of a cathode chamber, a diffusion layer of the cathode is exposed to an air chamber, and a gas-liquid-solid three-phase reaction interface is formed on the surface of the catalyst; separating the cathode chamber and the anode chamber by an ion exchange membrane; the width of the catholyte has an adjusting range of 1-13 mm;
(3) And applying constant current or constant potential, and adopting a cathode-anode liquid flow dynamic electrolysis mode to electrolyze H 2O2.
Further, in the above technical scheme, the loading amount of the metal unit material on the electrode is 0.25-1.0 mg cm -2.
Further, in the above technical solution, the anode includes a Pt electrode for water oxidation, a RuO 2 electrode, an IrO 2 electrode, or a Pt electrode for hydrogen oxidation.
Further, in the technical scheme, the current range is 0-1100 mA, and the current density range is 0-300 mA cm -2; the electrolyte of the cathode chamber and the anode chamber is 0.1-1.0M KOH or NaOH, 0.1-0.5M K 2SO4 or Na 2SO4、0.3M K2SO4 or Na 2SO4, and the pH value of the electrolyte is 1-11.
Further, in the above technical solution, the preparation method of the electrode in step (1) includes: taking a mixed solution of water and an organic solvent as a solvent, adding an adhesive, preparing the metal single-site catalytic material into catalyst slurry, uniformly loading the catalyst slurry onto the surface of a hydrophobic, porous and conductive substrate, and drying to prepare an electrode;
The organic solvent comprises an alcohol solution, and the alcohol solution comprises at least one of ethanol and isopropanol; the adhesive comprises at least one of Nafion film solution, polytetrafluoroethylene solution and perfluorinated sulfonic acid polymer; the catalyst loading method comprises a coating method, a spin coating method or a pressing method, and the hydrophobic, porous and conductive substrate comprises carbon paper, carbon cloth, carbon felt or metal mesh with or without a micropore filling layer.
The invention uses adhesive to load the metal unit material to the surface of hydrophobic, porous and conductive substrate to prepare gas diffusion electrode, uses the electrode as cathode of electrolytic cell, and forms flowing three-phase reaction interface with ultrathin catholyte fluid and air chamber, uses power supply to drive electro-catalysis O 2 to reduce H 2O2.
The electrolytic cell disclosed by the invention has the key that the width of the cathode and anode chamber is 1-13 mm, and is different from a runner with a conventional centimeter-level size, and the electrolytic cell disclosed by the invention can realize 1mm ultrathin catholyte fluid, so that the value transmission efficiency is greatly improved, the system resistance loss is reduced, and the energy consumption is reduced.
The catalytic active center configuration of the metal single-site catalytic material provided by the invention consists of M-N 4 (M refers to metal and N refers to pyrrole nitrogen) unique to metal phthalocyanine/porphyrin and oxygen groups existing on the surface of a carbon carrier in a C-O-C form, and the activity and the selectivity of electrocatalytic oxygen reduction synthesis H 2O2 can be improved jointly by changing the types of the metal phthalocyanine/porphyrin and the nature of the oxygen groups on the surface of the modified carbon carrier to regulate and control the metal single-site and the coordination atom environment thereof. The activity and the selectivity of the metal single-site catalyst with different metal centers show a volcanic curve law, the oxygen reduction activity of the manganese, iron, cobalt, nickel and copper single-site catalysts is sequentially reduced, the selectivity of H 2O2 is opposite, and the cobalt single-site catalyst has optimal activity and selectivity. The oxygen-containing groups on the surface of the concentrated oxidizing acid modified carbon support are mainly present in the form of C-O-C, with only a small amount of c=o. The C-O-C modified cobalt center can further increase H 2O2 selectivity compared to c=o or no O groups. In conclusion, the cobalt single-site catalytic material disclosed by the invention has the unique characteristics of cobalt Co-N 4 (N refers to pyrrole nitrogen) configuration and C-O-C modification, and the activity and selectivity of the electrocatalytic oxygen reduction product H 2O2 are positioned at the top of the volcanic diagram, so that the performance is optimal. Secondly, different from a cathode chamber flow channel with a common centimeter-level size, the electrolytic cell for electrosynthesis of H 2O2 can realize 1mm ultrathin catholyte fluid, greatly improve the value transmission efficiency, reduce the system resistance loss and reduce the energy consumption.
The beneficial effects of the invention are as follows: the preparation method of the metal single-site catalytic material is simple and easy to amplify, and expensive raw materials and equipment are not needed; the active center configuration of the metal single-site catalytic material can be regulated and controlled, and the activity and the selectivity of the electrosynthesis H 2O2 are directly determined; the gas diffusion type metal single-point electrode can realize high-current and high-Faraday-efficiency electrosynthesis H 2O2 performance under alkaline, medium and acidic conditions, and can continuously synthesize high-concentration H 2O2 solution. The flowing type in-situ electrosynthesis H 2O2 electrolytic cell can be used as a substitute process of the traditional anthraquinone method, and a novel water pollution control and restoration technology integrating multiple functions of toxic pollutant removal and sterilization is formed by the coupled Fenton technology.
Drawings
FIG. 1 is a high resolution X-ray photoelectron spectrum of oxygen atoms on the surface of a metal single site catalytic material prepared by the preparation method of the present invention.
FIG. 2 shows a K-side X-ray absorption near-side structure spectrum (a) and an R-space Fourier transform-expansion side X-ray absorption fine spectrum of Co element in a metal single-site catalytic material (Co-OCNT in the figure) prepared by the preparation method of the invention, and a fitting curve (b) thereof.
FIG. 3 is a schematic view and a physical diagram of a reaction principle, a reactor and a physical diagram of a flowing state electrolytic cell a and b with a gas diffusion type metal single-point electrode as a cathode prepared by the preparation method related to the invention.
Detailed Description
The invention will be described in further detail below in order to better understand the technical scheme of the invention. However, the following examples are merely illustrative examples of the present invention and are not limited to the following examples.
Embodiment one:
The embodiment provides a preparation method of a metal single-site catalytic material for electrosynthesis of H 2O2, which is implemented according to the following steps:
(1) And (3) oxidizing the carbon nano tube with the outer diameter of 10-20 nm by adopting 68wt% of concentrated nitric acid. Adding 3g of carbon nano tube powder and 150mL of concentrated nitric acid into a 250mL round bottom flask, magnetically stirring for 30min, carrying out ultrasonic oscillation for 30min to uniformly disperse the carbon nano tube powder, oxidizing the carbon nano tube at 140 ℃ for 14h by adopting heating jacket equipment, and adopting a condensation reflux method to avoid solution volatilization loss; after the oxidation treatment is finished, pouring out supernatant after the temperature is reduced to room temperature, and dispersing the bottom carbon nano tube in 500mL high-purity water; separating the carbon nanotubes by vacuum filtration, and continuously flushing with ultrapure water until the pH is near neutral; and drying the carbon nanotube material at 80 ℃ for 12 hours to obtain the carbon nanotube (OCNT) modified by oxygen atoms.
(2) The carbon nano tube supported metal single-site catalyst is prepared by adopting an impregnation method. 200mg of OCNT and 20mg of cobalt phthalocyanine reagent (CoPc) prepared in the step (1) were added to 100mL and 250mL of N, N-dimethylformamide solvent, respectively, and the mixture was sonicated for 1 hour, with stirring to accelerate dispersion. After OCNT and CoPc are completely and uniformly dispersed or dissolved, continuing to strongly stir, dripping the CoPc solution into the OCNT solution by using a peristaltic pump, wherein the flow rate is 2.5mL min -1, and continuously stirring for 20 hours; separating carbon nanotubes by vacuum filtration, sequentially washing with N, N-dimethylformamide, ethanol and ultrapure water, and freeze-drying to obtain the oxygen atom modified carbon-supported cobalt single-site catalyst (CoPc-OCNT).
FIG. 1 is a high resolution X-ray photoelectron spectrum of oxygen atoms on the surface of a metal single site catalytic material prepared in this example. The results show that 79% of the oxygen atoms on the surface of the metallic single-site catalytic material are present in the form of C-O-C, with a c=o group ratio of only 21%.
Fig. 2 shows a K-edge X-ray absorption near-edge structure spectrum (a) and an R-space fourier transform-expansion-edge X-ray absorption fine spectrum of Co element in a metal single-site catalytic material (labeled Co-OCNT in the figure) prepared in this example, and a fitted curve (b) thereof. The results in FIG. a show that the Co-OCNT catalytic material has a Co-N 4 structure similar to that of the CoPc molecule, and that the Co center is positively charged. The results of panel b further demonstrate that Co centers in Co-OCNT catalytic materials have Co-N coordination similar to that of CoPc molecules.
Embodiment two:
The embodiment provides a preparation method of a metal single-site catalytic material for electrosynthesis of H 2O2, which is implemented according to the following steps:
(1) The oxidation treatment was carried out with 27wt% concentrated nitric acid and commercial Cabot VXC 72. Adding 1g of VXC72 powder, 90mL of ultrapure water and 60mL of concentrated nitric acid (27 wt%) into a 250mL round-bottom flask respectively, magnetically stirring for 30min, ultrasonically oscillating for 30min to uniformly disperse, oxidizing VXC72 at 110 ℃ for 5h by adopting heating jacket equipment, and adopting a condensation reflux method to avoid solution volatilization loss; after the oxidation treatment is finished, after the temperature is reduced to room temperature, pouring out supernatant, and dispersing the bottom VXC72 into 500mL high-purity water; separating VXC72 by vacuum filtration, and continuously flushing with ultrapure water until the pH is near neutral; the VXC72 material was dried at 80℃for 12h to give oxygen atom modified VXC72 (OVX).
(2) The OVX supported metal single-site catalyst is prepared by adopting an impregnation method. 200mg of the OVX prepared in the step (1) and 20mg of cobalt phthalocyanine agent (CoPc) were added to 100mL and 250mL of N, N-dimethylacetamide solvent, respectively, and the mixture was sonicated for 1 hour, while stirring was continued to accelerate the dispersion. After the OVX and the CoPc are completely and uniformly dispersed or dissolved, continuing to strongly stir, dripping the CoPc solution into the OVX solution by using a peristaltic pump, wherein the flow rate is 2.5mL min -1, and continuously stirring for 20 hours; and (3) separating the OVX by adopting a vacuum suction filtration method, washing the OVX by using N, N-dimethylacetamide, ethanol and ultrapure water in sequence, and freeze-drying the washed solution to obtain the carbon-supported cobalt single-site catalyst (CoPc-OVX) modified by oxygen atoms.
Embodiment III:
The embodiment provides a preparation method of a metal single-site catalytic material for electrosynthesis of H 2O2, which is implemented according to the following steps:
(1) And oxidizing the carbon nano tube with the outer diameter of 10-20 nm by adopting a high-temperature carbonization method. Uniformly mixing 1g of carbon nano tube powder with 2g of polyethylene oxide, and calcining at 700 ℃ for 2 hours in an Ar gas atmosphere. After natural cooling, washing with ultrapure water, separating the carbon nanotubes by a vacuum filtration method, and drying the carbon nanotube material at 80 ℃ for 12 hours to obtain the carbon nanotubes (OCNT-P) modified by oxygen atoms.
(2) The carbon nano tube supported metal single-site catalyst is prepared by adopting an impregnation method. 500mg of OCNT-P prepared in step (1) and 5mg of copper porphyrin reagent (CuTCPP) are added into 50mL and 500mL of acetone solvent respectively, and the mixture is subjected to ultrasonic oscillation for 1h, and the mixture is continuously stirred during the ultrasonic oscillation to accelerate dispersion. After OCNT-P and CuTCPP are completely and uniformly dispersed or dissolved, continuing to strongly stir, dropwise adding the CuTCPP solution into the OCNT-P solution by using a peristaltic pump, and continuously stirring for 12 hours at a flow rate of 3mL min -1; separating carbon nanotubes by vacuum filtration, sequentially washing with acetone and ultrapure water, and freeze-drying to obtain the carbon-supported copper single-site catalyst (CuTCPP-OCNT-P) modified by oxygen atoms.
Embodiment four:
The embodiment provides an application method of the metal single-site catalytic material prepared in the embodiment I in the electrosynthesis of H 2O2, which is implemented according to the following steps:
(1) The gas diffusion type cobalt single-point electrode is prepared by adopting a coating method. Using 0.8mL of ultrapure water, 0.2mL of isopropyl alcohol and 50 μ LNafion of a film solution as a solvent, 10mg of the CoPc-OCNT catalyst prepared in example one was added to the solvent, and the catalyst was uniformly dispersed by ultrasonic vibration, to obtain a catalyst slurry. Electrodes of two sizes were prepared: 50 and 200. Mu.L of the catalyst slurry were applied to the hydrophobic carbon paper side with areas of 1cm -2 and 4cm -2, respectively, and dried at 50℃with catalyst loadings of 0.53mg cm -2.
(2) The electrosynthesis H 2O2 electrolytic cell assembly mainly comprises: cathode, anode, proton exchange membrane, cathode chamber, anode chamber, and air chamber. Taking a metal single-point catalytic electrode as a cathode, wherein one side of a supported catalytic layer is contacted with catholyte of a flowing cathode chamber, and the other side (a diffusion layer) is exposed to a gas chamber with a serpentine flow passage, so that a gas-liquid-solid three-phase reaction interface is formed on the surface of the catalytic layer; the anode electrode adopts a Pt electrode with electrocatalytic water oxidation oxygen evolution activity, and the cathode and anode chambers are separated by a proton exchange membrane Nafion 117. The embodiment provides two electrolytic cells with two sizes, wherein an electrolytic cell a is composed of four components (the structure of the electrolytic cell a is shown as a1-a4 in figure 3), namely an air chamber serpentine flow channel plate, a catholyte flow channel plate, an anolyte flow channel plate and an anode cover plate, wherein the widths of the anode flow channel plate and the cathode flow channel plate are 13mm, the distances between the anode and the cathode are 27mm, and the working areas of the anode and the cathode are 1cm -2; the electrolytic cell b is composed of two components (the structure of the electrolytic cell b is shown as b1-b4 in figure 3), namely an air chamber serpentine flow channel plate and an anode liquid serpentine flow channel plate, a catholyte inlet and outlet are integrated on one side of the air chamber serpentine flow channel plate, a rubber pad clung to the air chamber is used as the catholyte flow channel plate, the thickness of the catholyte is regulated by changing the thickness of the rubber pad, the thickness of the catholyte (cathode chamber) is 1mm at the minimum, the cathode-anode distance is 3.5mm (comprising a proton exchange membrane, the rubber pad, the cathode chamber and the anode chamber), and the working area of the cathode and the anode is 4cm -2.
(3) Constant current is applied through a direct current power supply, and peristaltic pumps are used for conveying electrolyte to form a flowing state electrolysis mode, so that electrosynthesis H 2O2 directly flows out of the cathode chamber.
(4) The performance of gas diffusion type cobalt single point electrode synthesis H 2O2 under different experimental conditions was tested by using an electrolytic cell a. Experimental conditions: 1.0M KOH catholyte at flow rate 5mL h -1 and oxygen at flow rate 20mL min -1; the anode electrode adopts Pt sheets as anode, is exposed to anolyte of 0.5M H 2SO4, has a working area of 1cm 2 and a flow rate of 33mL h -1, and the anolyte is recycled; the cathode and anode chambers are separated by a proton exchange membrane Nafion 117. Results 1: constant current 100mA cm -2, faraday efficiency of H 2O2 production of 98%, H 2O2 concentration of 376mM; results 2: constant current 200mA cm -2, H 2O2 Faraday efficiency 96%, H 2O2 concentration 719mM; results 3: constant current 300mA cm -2, H 2O2 Faraday efficiency 96%, H 2O2 concentration 1086mM.
(5) The performance of gas diffusion type cobalt single point electrode synthesis H 2O2 under different experimental conditions was tested by using an electrolytic cell b. The oxygen flow rates for the following experiments were all 30mL min -1. Condition 1: constant current 500mA, catholyte of 1.0M KOH, anolyte of 0.5M H 2SO4, liquid flow rate of 100mL H -1, H 2O2 Faraday efficiency 96% and H 2O2 concentration 90mM; condition 2: constant current 800mA, cathode-anode liquid of 1.0M KOH, flow rate of 82mL H -1, faraday efficiency of H 2O2 production of 100%, and H 2O2 concentration of 185mM; condition 3: constant current 400mA, cathode and anode liquid of 0.3M K 2SO4 (pH 7.2) and flow rate of 100mL H -1, faraday efficiency of H 2O2 is 93%, and H 2O2 concentration is 69mM; condition 4: constant current 500mA, cathode and anode liquid of 0.3M K 2SO4 (pH 1.5), flow rate 82mL H -1, faraday efficiency of H 2O2, and H 2O2 concentration of 106mM.
Fifth embodiment:
The embodiment provides an application method of the metal single-site catalytic material prepared in the embodiment II in the electrosynthesis of H 2O2, which is implemented according to the following steps:
(1) And preparing the gas diffusion type cobalt single-point electrode by adopting a spin coating method. Using 4mL of ultrapure water, 1mL of isopropyl alcohol and 250 μl of Nafion membrane solution as solvents, 50mg of the CoPc-OVX catalyst prepared in example two was added to the solvents, and the catalyst was uniformly dispersed by ultrasonic vibration; a50. Mu.L portion of the catalyst slurry was applied to one side of the hydrophobic carbon paper by spin coating, the area was 1cm -2, and the catalyst was dried at 50℃to give a catalyst loading of 0.53mg cm -2.
(2) Taking the gas diffusion type cobalt single-point electrode obtained by the preparation method as a cathode, wherein one side of a supported catalytic layer is contacted with 1.0M KOH catholyte at a flow rate of 5mL h -1, and the other side (diffusion layer) is exposed to an oxygen chamber with a serpentine flow passage at a flow rate of 20mL min -1; the anode electrode adopts Pt sheets as anode, is exposed to anolyte of 0.5M H 2SO4, has a working area of 1cm 2 and a flow rate of 33mL h -1, and the anolyte is recycled; the cathode and anode chambers are separated by a proton exchange membrane Nafion 117, and the width of each cathode and anode chamber is 13mm.
(3) The synthesized H 2O2 directly flows out of the cathode chamber by applying a constant current through the electrochemical workstation. Under the current condition of 100mA, the Faraday efficiency of H 2O2 is 92%, and the concentration of H 2O2 is 330mM; under the current condition of 150mA, the Faraday efficiency of H 2O2 is 98%, and the concentration of H 2O2 is 550mM.
Example six:
The embodiment provides an application method of the metal single-site catalytic material prepared in the third embodiment in electrosynthesis of H 2O2, and the specific method refers to an electrolytic cell a in the fourth embodiment. Results 1: constant current 100mA cm -2, H 2O2 Faraday efficiency 97%, H 2O2 concentration 372mM; results 2: constant current 150mA cm -2, faraday efficiency of H 2O2, and H 2O2 concentration of 415mM.
Embodiment seven:
The embodiment provides a practical application method for electrosynthesis of H 2O2 by using the electrolytic cell b in the fourth embodiment, which is implemented according to the following steps:
H 2O2 was synthesized by electrolysis at a constant current of 500mA and a flow rate of 82mL H -1 with a pH of 0.3M K 2SO4 (pH 1.5) in the anodic and cathodic solutions, and the concentration of the H 2O2 eluted was 106mM. Mixing the effluent H 2O2 with a solution containing 1mM Fe 2+ and 10mg L -1 phenol, levofloxacin, bisphenol A or secondary biochemical effluent of coking wastewater in a flowing state reaction tank, wherein the pollutant removal rate is 100%, the phenol and levofloxacin removal rate is 40-60% and the total organic carbon removal rate of the secondary biochemical effluent of the coking wastewater is 90% in the reaction time of 3 hours.
The examples described above represent only embodiments of the invention and are not to be understood as limiting the scope of the patent of the invention, it being pointed out that several variants and modifications may be made by those skilled in the art without departing from the concept of the invention, which fall within the scope of protection of the invention.
Claims (9)
1. A metal single-site catalytic material is characterized in that the metal single-site catalytic material is prepared by taking a carbon material modified by oxygen atoms as a carrier, and loading isolated and dispersed metal phthalocyanine or metalloporphyrin molecules with a characteristic structure of M-N 4, wherein M is metal, and N is pyrrole nitrogen;
The isolated and dispersed metallophthalocyanine or metalloporphyrin molecule with the characteristic structure of M-N 4 comprises at least one of manganese phthalocyanine, manganese porphyrin, cobalt phthalocyanine, cobalt porphyrin, nickel phthalocyanine, nickel porphyrin, copper phthalocyanine and copper porphyrin.
2. The metal single-site catalytic material of claim 1, wherein the oxygen atom modified carbon material comprises at least one of carbon nanotubes, graphene, porous carbon, or carbon black.
3. The method for preparing a metal single-site catalytic material according to any one of claims 1-2, comprising the steps of:
(1) Oxidizing the carbon material to obtain an oxygen atom modified carbon material carrier;
(2) And respectively dispersing the carbon material carrier modified by oxygen atoms and the metal phthalocyanine or metalloporphyrin in an organic solvent, adding the dispersion liquid of the metal phthalocyanine or metalloporphyrin into the dispersion liquid of the carbon material carrier modified by oxygen atoms, and continuously stirring to obtain the metal single-site catalytic material, wherein the mass ratio of the metal phthalocyanine or metalloporphyrin to the carbon material carrier is 1-20%.
4. The method for preparing a metal single-site catalytic material according to claim 3, wherein the method for oxidizing treatment comprises a concentrated oxidative acid heat treatment method, a high temperature carbonization method or a hydrothermal method;
The concentrated oxidative acid heat treatment process comprises: adding a carbon material carrier into concentrated oxidizing acid with the mass concentration of 37-100% for oxidation treatment, wherein the oxidation temperature is 110-140 ℃ and the oxidation time is 5-12 hours; the oxidizing acid comprises sulfuric acid, nitric acid or perchloric acid;
The high temperature carbonization method comprises: uniformly mixing a carbon material carrier and polyethylene oxide in a mass ratio of 2:1-1:5, and calcining at 500-800 ℃ for 1-4 h in an N 2 or inert gas atmosphere;
the hydrothermal method comprises the following steps: dispersing the carbon material carrier in 7-10M KOH or NaOH solution, and preserving the temperature at 150-200 ℃ for 12-24 hours.
5. The method for preparing a metal single-site catalytic material according to claim 3, wherein the organic solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone and N-hexane.
6. Use of a metal single-site catalytic material according to any one of claims 1-2 or obtained by a preparation method according to any one of claims 3-5, characterized in that the metal single-site catalytic material is used as a cathode catalyst of a gas diffusion type electrolytic cell for electrosynthesis of H 2O2.
7. The use according to claim 6, characterized in that it comprises the steps of:
1) Loading a metal unit material on the surface of a substrate to prepare an electrode with one side being a catalyst layer and the other side being a diffusion layer;
2) The electrosynthesis H 2O2 electrolytic cell assembly mainly comprises: a cathode, an anode, a cathode chamber, an anode chamber, an ion exchange membrane and an air chamber;
The electrode prepared in the step 1) is used as a cathode, the electrode with electrocatalytic oxidation activity is used as an anode, a catalyst layer of the cathode is contacted with catholyte of a cathode chamber, a diffusion layer of the cathode is exposed to an air chamber, and a gas-liquid-solid three-phase reaction interface is formed on the surface of the catalyst; separating the cathode chamber and the anode chamber by an ion exchange membrane; the width and thickness of the catholyte are within an adjusting range of 1-13 mm;
3) And applying constant current or constant potential, and adopting a cathode-anode liquid flow dynamic electrolysis mode to electrolyze H 2O2.
8. The use according to claim 7, wherein the loading of the metal single-site material on the electrode is 0.25-1.0 mg cm -2; the anode comprises a Pt electrode for water oxidation, a RuO 2 electrode, an IrO 2 electrode or a Pt electrode for hydrogen oxidation,
The current range is 0-1100 mA, and the current density range is 0-300 mA cm -2; the electrolyte of the cathode chamber and the anode chamber is 0.1-1.0M KOH or NaOH, 0.1-0.5M K 2SO4 or Na 2SO4、0.3 M K2SO4 or Na 2SO4, and the pH of the electrolyte is 1-11.
9. The use according to claim 7, wherein the method of preparing the electrode of step 1) comprises: taking a mixed solution of water and an organic solvent as a solvent, adding an adhesive, preparing the metal single-site catalytic material into catalyst slurry, uniformly loading the catalyst slurry onto the surface of a hydrophobic, porous and conductive substrate, and drying to prepare an electrode;
The organic solvent comprises an alcohol solution, and the alcohol solution comprises at least one of ethanol and isopropanol; the adhesive comprises at least one of Nafion film solution, polytetrafluoroethylene solution and perfluorinated sulfonic acid polymer; the catalyst loading method comprises a coating method, a spin coating method or a pressing method, and the hydrophobic, porous and conductive substrate comprises carbon paper, carbon cloth, carbon felt or metal mesh with or without a micropore filling layer.
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