CN115896862A - For electrosynthesis of H 2 O 2 Metal single-site catalytic material, preparation method and application thereof - Google Patents
For electrosynthesis of H 2 O 2 Metal single-site catalytic material, preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a method for electrosynthesis of H 2 O 2 Belonging to the technical field of electrocatalysis. The invention adopts an immersion method to prepare the catalyst with M-N 4 (M refers to metal, N refers to pyrrole nitrogen) characteristic structure metal phthalocyanine or porphyrin is loaded on the oxygen atom modified carbon carrier in a monomolecular isolated and dispersed mode to obtain the metal single-site material. The metal single-site material prepared by the method 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 to form a flow state three-phase reaction interface with an ultrathin catholyte fluid and a gas chamber, and a power supply is used for driving electro-catalysis O 2 Reduction synthesis of H 2 O 2 . The inventionThe preparation method is simple and easy to amplify, and expensive raw materials and equipment are not needed; the invention can realize the electrosynthesis of H with high current and high faradaic efficiency under the conditions of alkali, medium and acid 2 O 2 Performance and can continuously synthesize high-concentration H 2 O 2 And (3) solution.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a method for electrosynthesis of H 2 O 2 The metal single-site catalytic material and the preparation method and the application thereof.
Background
H 2 O 2 As an environment-friendly bulk chemical, the product is widely applied to the fields of chemical industry, medicine, new energy and the like, and has great economic and environmental benefits. The current industrial production of H 2 O 2 Mainly depends on the anthraquinone process and consumes a large amount of H 2 And heavy aromatic chemicals, and discharging organic wastes and acidic wastewater, and transporting and storing high-concentration H 2 O 2 The process is accompanied by the risk of corrosion, explosion. Based on the method, novel efficient, safe and environment-friendly in-situ H is researched and developed 2 O 2 The synthesis technology replaces the traditional process and promotes H 2 O 2 The development of the related chemical and environmental water treatment technology is an important way.
Electrocatalytic in situ production of H by oxygen cathodic reduction 2 O 2 Technology is receiving attention as an alternative to green cleaning. The technology can be carried out at normal temperature and normal pressure, organic reagents are not needed, controllability is strong, and reaction rate and product selectivity can be regulated and controlled by changing potential/current and electrode materials. The research shows that the modified carbon material, pd alloy, cobalt monoatomic catalyst and the like have nearly 100 percent of H in a rotating ring disc-disc test system 2 O 2 Alternatively, however, current electrolytic cell systems are ubiquitous with H 2 O 2 Low current distribution density and H 2 O 2 Low yield and concentration. The reasons for this are summarized as follows: microstructural properties of metal monoatomic species to electrocatalytic ORR to produce H 2 O 2 The performance regulation mechanism is not clear, and an optimal reaction path with high activity and high selectivity is difficult to realize; the monatomic material with specific active configuration is difficult to synthesize accurately, has insufficient active sites and is difficult to realize high H 2 O 2 The fractional current density.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for electrosynthesis of H 2 O 2 The metal single-site catalytic material and the preparation method and the application method thereof. Specifically provides a carbon load with M-N modified by oxygen atom 4 Preparation method of metal single-site catalytic material with key characteristics of isolated and dispersed metal phthalocyanine/porphyrin molecules with characteristic structures of (M refers to metal and N refers to pyrrole nitrogen), and method for improving H content by electrocatalytic oxygen reduction of gas diffusion type electrolytic cell with flowing state ultrathin fluid characteristics 2 O 2 Partial current density and product concentration. The electrode comprises a gas diffusion layer and a catalyst layer, wherein the active component of the catalyst layer is a carbon-supported metal single-site material modified by oxygen atoms, the metal monoatomic and coordination atom environment thereof is regulated and controlled by changing the metal species and modifying the surface chemical property of the carbon carrier, the adsorption energy of key reaction intermediate products is optimized, and the electrosynthesis H is improved together 2 O 2 Activity and selectivity of (a).
The invention provides a method for electrosynthesis of H 2 O 2 The preparation method and the application method of the metal single-site catalytic material. The metal single-site catalytic material is prepared by utilizing a carbon carrier modified by oxygen atoms and metal phthalocyanine or porphyrin molecules through a one-step impregnation method; the electrosynthesis of H 2 O 2 The metal single-point electrode based on the gas diffusion function forms an ultrathin flowing state gas-liquid-solid three-phase reaction interface on a catalyst layer, and H is continuously produced with high selectivity under the condition of high-current electrolysis 2 O 2 And (3) solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a metal single-site catalytic material which is prepared by taking an oxygen atom modified carbon material as a carrier and loading M-N 4 The metal phthalocyanine or metalloporphyrin molecule with the characteristic structure in an isolated and dispersed mode, wherein M is metal, and N is pyrrole nitrogen.
Further, in the above technical solution, the carbon material modified by oxygen atoms includes at least one of carbon nanotubes, graphene, porous carbon, or carbon black.
Further, the carbon black includes at least one of Cabot VXC72, black pearl 2000, ketjenblack ECP-600JD and Kurary YP-80F.
Further, in the above technical solution, the organic electroluminescent device has M-N 4 The isolated and dispersed metal phthalocyanine or metalloporphyrin molecule with characteristic structure comprises manganese phthalocyanine, manganese porphyrin, cobalt phthalocyanine, cobalt porphyrin, nickel phthalocyanine, nickel porphyrin, copper phthalocyanine, copper porphyrin and compounds with M-N 4 At least one of metal phthalocyanine or metal porphyrin derivative with characteristic structure.
The invention also provides a preparation method of the metal single-site catalytic material, which comprises the following steps:
(1) Oxidizing a carbon material to obtain an oxygen atom modified carbon material carrier;
(2) Respectively dispersing the carbon material carrier modified by the oxygen atom 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 the oxygen atom, wherein the mass ratio of the metal phthalocyanine or metalloporphyrin to the carbon material carrier is 1-20%, and continuously stirring to obtain the metal single-site catalytic material.
Further, in the step (1), the carbon material is oxidized, washed and dried to obtain the carbon material carrier modified by the oxygen atom.
Further, in the step (2), after continuous stirring, carrying out suction filtration separation, cleaning and drying to obtain the metal single-site catalytic material.
Further, in the above technical solution, the oxidation treatment method includes a concentrated oxidation acid heat treatment method, a high temperature carbonization method, or a hydrothermal method;
the concentrated oxidizing 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 the following steps: mixing a carbon material carrier and polyethylene oxide at a mass ratio of 2Mixing uniformly at N 2 Or calcining for 1-4 h at 500-800 ℃ in an inert gas atmosphere;
the hydrothermal process comprises: dispersing the carbon material carrier in 7-10M KOH or NaOH solution, and maintaining at 150-200 deg.c for 12-24 hr.
Further, in the above technical solution, the organic solvent includes at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone, and N-hexane.
The invention also provides 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 electrolytic cell and is used for electrosynthesis of H 2 O 2 。
Further, in the above technical solution, the method includes the following steps:
(1) Loading a metal single-site material on the surface of a substrate to prepare an electrode with a catalyst layer on one side and a diffusion layer on the other side;
(2) Electrosynthesis of H 2 O 2 The electrolytic cell component mainly comprises: the device comprises a cathode, an anode, a cathode chamber, an anode chamber, an ion exchange membrane and a gas chamber;
taking the electrode prepared in the step (1) as a cathode, taking an electrode with electrocatalytic oxidation activity as an anode, wherein a catalyst layer of the cathode is in contact with catholyte in a cathode chamber, a diffusion layer of the cathode is exposed in a gas chamber, and a gas-liquid-solid three-phase reaction interface is formed on the surface of the catalyst; an ion exchange membrane is used for separating a cathode chamber and an anode chamber; the width of the catholyte is in an adjusting range of 1-13 mm;
(3) Applying constant current or constant potential, adopting cathode and anode flow dynamic electrolysis mode to synthesize H 2 O 2 。
Furthermore, in the above technical scheme, the loading amount of the metal unit site 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, ruO 2 Electrode, irO 2 Electrodes or hydrogen oxidized Pt electrodes.
Further, in the above technical scheme, the current range is 0-1100 mA, and the current density range is 0-300 mA cm -2 (ii) a The electrolyte of the cathode chamber and the anode chamber is 0.1-1.0M KOH or NaOH, 0.1-0.5M K 2 SO 4 Or Na 2 SO 4 、0.3M K 2 SO 4 Or Na 2 SO 4 The pH of the electrolyte is 1 to 11.
Further, in the above technical solution, the method for preparing 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 on 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 membrane solution, polytetrafluoroethylene solution and perfluorinated sulfonic acid polymer; the catalyst supporting 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 net with or without a micropore filling layer.
The invention uses adhesive to load the metal single-point material prepared by the invention on the surface of a hydrophobic, porous and conductive substrate to prepare a gas diffusion electrode, the electrode is used as the cathode of an electrolytic cell to form a flowing state three-phase reaction interface with ultrathin catholyte fluid and a gas chamber, and a power supply is used for driving electro-catalysis O 2 Reduction synthesis of H 2 O 2 。
The key point of the electrolytic cell is that the width of the cathode chamber and the anode chamber has an adjusting range of 1-13 mm, which is different from the conventional centimeter-sized flow channel, the electrolytic cell can realize 1mm of ultrathin catholyte fluid, greatly improves the value transmission efficiency, reduces the system resistance loss and reduces the energy consumption.
The catalytic activity center configuration of the metal single-site catalytic material is unique M-N of metal phthalocyanine/porphyrin 4 (M means a metal, N means pyrrole nitrogen) with an oxygen group present in the form of C-O-C on the surface of a carbon support, by varyingThe properties of the metal phthalocyanine/porphyrin types and the oxygen groups on the surface of the modified carbon carrier regulate and control the metal unit sites and the coordination atom environment thereof, and the electrocatalytic oxygen reduction synthesis of H is improved together 2 O 2 Activity and selectivity of (a). The activity and selectivity of the metal single-site catalyst with different metal centers show a volcano-shaped curve rule, the oxygen reduction activity of the manganese, iron, cobalt, nickel and copper single-site catalyst is sequentially reduced, and H is 2 O 2 Selectivity is the opposite, with cobalt single-site catalysts having the optimum activity and selectivity. The oxygen-containing groups of the surface of the concentrated oxidizing acid-modified carbon support are present predominantly in the C-O-C form, with only a small amount of C = O. C-O-C modified cobalt centers can further increase H compared to C = O or no O groups 2 O 2 And (4) selectivity. In summary, the cobalt single-site catalytic material of the invention is characterized by cobalt Co-N 4 Unique characteristics of (N refers to pyrrole nitrogen) configuration and C-O-C modification, and electrocatalytic oxidation reduction of H 2 O 2 The activity and the selectivity of the volcanic are positioned at the vertex of the volcanic image, and the performance is optimal. Secondly, unlike the conventional centimeter-sized cathode chamber flow channel, the present invention electrosynthesis H 2 O 2 The electrolytic cell can realize 1mm of ultrathin catholyte fluid, greatly improves the value transmission efficiency, reduces the system resistance loss and reduces the energy consumption.
The invention has the beneficial effects that: 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 electrosynthesis H is directly determined 2 O 2 Activity and selectivity of (a); the gas diffusion type metal single-site electrode can realize electrosynthesis H with high current and high faradaic efficiency under the conditions of alkali, medium and acid 2 O 2 Performance and can continuously synthesize high-concentration H 2 O 2 And (3) solution. The flow type in-situ electrosynthesis of H 2 O 2 The electrolytic cell can be used as a substitute process of the traditional anthraquinone method and is coupled with the Fenton technology to form a new water pollution control and restoration technology integrating multiple effects of toxic pollutant removal and sterilization.
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 related to the invention.
Fig. 2 shows a K-edge X-ray absorption near-edge structure spectrum (a) and an R-space fourier transform-extended-edge X-ray absorption fine spectrum of a Co element in a metal single-site catalytic material (marked as Co-OCNT in the figure) prepared by the preparation method according to the present invention, and a fitting curve (b) thereof.
FIG. 3 is a schematic diagram and a physical diagram of the reaction principle, the reactor and the material of a flow dynamic electrolytic cell a and b with a gas diffusion type metal single-site electrode as a cathode prepared by the preparation method of the invention.
Detailed Description
In order to better understand the technical solution of the present invention, the present invention is further described in detail below. However, the following examples are merely illustrative examples of the present invention and are not intended to limit the scope of the present invention.
The first embodiment is as follows:
this example provides a method for electrosynthesis of H 2 O 2 The preparation method of the metal single-site catalytic material is implemented according to the following steps:
(1) 68wt% concentrated nitric acid is adopted to carry out oxidation treatment on the carbon nano tube with the outer diameter of 10-20 nm. Adding 3g of carbon nanotube powder and 150mL of concentrated nitric acid into a 250mL round-bottom flask, magnetically stirring for 30min, ultrasonically oscillating for 30min to uniformly disperse the carbon nanotube, oxidizing the carbon nanotube at 140 ℃ for 14h by using heating sleeve equipment, and avoiding the volatilization loss of the solution by using a condensation reflux method; after the oxidation treatment is finished, after the temperature is reduced to the room temperature, pouring out the supernatant, and dispersing the bottom carbon nano tube in 500mL of high-purity water; separating the carbon nano tube by a vacuum filtration method, and continuously washing the carbon nano tube by ultrapure water until the pH value is nearly neutral; and drying the carbon nanotube material at 80 ℃ for 12h to obtain the oxygen atom modified carbon nanotube (OCNT).
(2) The carbon nano tube metal-loaded single-site catalyst is prepared by adopting an impregnation method. 200mg of OCNT prepared in the step (1) and 20mg of cobalt phthalocyanine reagent (CoPc) are respectively added into 100mL and 250mL of N, N-dimethylformamide solvent, and ultrasonic oscillation is carried out for 1h, during which stirring is continuously carried out to accelerate dispersion. Until the OCNT and CoPc are completely dispersed uniformly orAfter dissolution, the mixture was stirred vigorously, and the CoPc solution was added dropwise to the OCNT solution by means of a peristaltic pump at a flow rate of 2.5mL min -1 Continuously stirring for 20 hours; separating the carbon nano tube by adopting a vacuum filtration method, sequentially washing the carbon nano tube by using 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 the metal single-site catalytic material prepared in this example. The results show that 79% of the oxygen atoms on the surface of the metal single-site catalytic material are present in the form of C-O-C, with a proportion of C = O groups of only 21%.
Fig. 2 shows a K-edge X-ray absorption near-edge structure spectrum (a) and an R-space fourier transform-extended-edge X-ray absorption fine spectrum of Co element in the metal single-site catalytic material (labeled as Co-OCNT in the figure) prepared in this example and a fitting curve (b) thereof. The results of panel a show that the Co-OCNT catalytic material has Co-N similar to CoPc molecule 4 Structure, and the Co center is positively charged. The results in panel b further verify that the Co center in the Co-OCNT catalytic material has a Co-N coordination similar to the CoPc molecule.
Example two:
this example provides a method for electrosynthesis of H 2 O 2 The preparation method of the metal single-site catalytic material is implemented according to the following steps:
(1) Commercial Cabot VXC72 was subjected to oxidation treatment with 27wt% concentrated nitric acid. 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 the VXC72, oxidizing the VXC72 at 110 ℃ for 5h by using a heating jacket device, and avoiding the volatilization loss of the solution by using a condensation reflux method; after the oxidation treatment is finished, after the temperature is reduced to the room temperature, pouring out the supernatant, and dispersing the VXC72 at the bottom in 500mL of high-purity water; separating VXC72 by a vacuum filtration method, and continuously washing with ultrapure water until the pH value is nearly neutral; the VXC72 material was dried at 80 ℃ for 12h to give oxygen atom modified VXC72 (OVX).
(2) An OVX-supported metal single-site catalyst is prepared by adopting an impregnation method. Mixing 200mg of OVX prepared in step (1) with 20mg of cobaltThe phthalocyanine reagent (CoPc) is added into 100mL and 250mL of N, N-dimethylacetamide solvent respectively, and the mixture is subjected to ultrasonic oscillation for 1h, during which the mixture is continuously stirred to accelerate the dispersion. After OVX and CoPc are completely dispersed or dissolved, strong stirring is continued, and CoPc solution is dropwise added into the OVX solution by using a peristaltic pump at the flow rate of 2.5mL min -1 Continuously stirring for 20 hours; separating OVX by vacuum filtration, washing with N, N-dimethylacetamide, ethanol and ultrapure water in sequence, and freeze-drying to obtain the oxygen atom modified carbon-supported cobalt single-site catalyst (CoPc-OVX).
Example three:
this example provides a method for electrosynthesis of H 2 O 2 The preparation method of the metal single-site catalytic material is implemented according to the following steps:
(1) The carbon nano tube with the outer diameter of 10-20 nm is oxidized by adopting a high-temperature carbonization method. 1g of carbon nanotube powder and 2g of polyethylene oxide are uniformly mixed and calcined for 2 hours at 700 ℃ in Ar gas atmosphere. And after natural cooling, washing with ultrapure water, separating the carbon nanotube by a vacuum filtration method, and drying the carbon nanotube material at 80 ℃ for 12 hours to obtain the oxygen atom modified carbon nanotube (OCNT-P).
(2) The carbon nano tube metal-loaded 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) were added to 50mL and 500mL of acetone solvent, respectively, and the mixture was ultrasonically shaken for 1 hour while stirring continuously to accelerate dispersion. After the OCNT-P and the CuTCPP are completely dispersed and uniformly or dissolved, strong stirring is continued, and the CuTCPP solution is dripped into the OCNT-P solution by using a peristaltic pump at the flow rate of 3mL min -1 Continuously stirring for 12 hours; separating the carbon nano tube by adopting a vacuum filtration method, sequentially washing with acetone and ultrapure water, and freeze-drying to obtain the oxygen atom modified copper-on-carbon single-site catalyst (CuTCPP-OCNT-P).
Example four:
this example provides the electrosynthesis of H from the metal single-site catalytic material prepared in example one 2 O 2 The application method specifically comprises the following steps:
(1) Preparation of gas diffusion type cobalt single-site electrode by coating methodAnd (4) a pole. A solvent was prepared using 0.8mL of ultrapure water, 0.2mL of isopropanol, and 50. Mu.L of a membrane solution, 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. Two sizes of electrodes were prepared: the catalyst slurry was applied to an area of 1cm in 50. Mu.L and 200. Mu.L, respectively -2 And 4cm -2 Drying one side of the hydrophobic carbon paper at 50 ℃, wherein the loading capacity of the catalyst is 0.53mg cm -2 。
(2) Electrosynthesis of H 2 O 2 The electrolytic cell component mainly comprises: cathode, anode, proton exchange membrane, cathode chamber, anode chamber, gas chamber. Taking a metal single-site catalytic electrode as a cathode, wherein one side of a supported catalytic layer is in contact with catholyte of a flowing cathode chamber, the other side (a diffusion layer) is exposed in a gas chamber with a serpentine flow channel, and 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 chamber and the anode chamber are separated by a proton exchange membrane Nafion 117. This embodiment provides electrolytic cell of two kinds of sizes, and electrolytic cell a comprises four block assembly (electrolytic cell a's structure is as a1-a4 in fig. 3), is air chamber snakelike runner plate, negative pole liquid runner plate, positive pole apron respectively, and negative and positive pole runner plate width is 13mm, and the interpolar distance is 27mm, and negative and positive pole working area is 1cm -2 (ii) a Electrolytic cell b comprises two subassemblies (electrolytic cell b's structure is as b1-b4 in figure 3), be air chamber snakelike flow path board and anolyte snakelike flow path board respectively, import and export integrated air chamber snakelike flow path board one side with catholyte to utilize the rubber pad of hugging closely in the air chamber as catholyte flow path board, adjust catholyte thickness through changing rubber pad thickness, catholyte (cathode chamber) thickness is 1mm at minimum, the anodal interval is 3.5mm (including proton exchange membrane, rubber pad, cathode chamber and anode chamber), the anodal active area of negative pole is 4cm -2 。
(3) Applying constant current by a direct current power supply, conveying electrolyte by a peristaltic pump to form a flow state electrolysis mode, and electrosynthesizing H 2 O 2 Directly flows out of the cathode chamber.
(4) The electrolytic cell a is used for testing gas diffusion type cobalt under different experimental conditionsSingle site electrode Synthesis H 2 O 2 The performance of (c). The experimental conditions are as follows: 1.0M KOH catholyte, flow rate 5mL h -1 Oxygen flow rate of 20mL min -1 (ii) a The anode electrode adopts a Pt sheet as an anode and is exposed to 0.5 MH of anolyte 2 SO 4 Working area is 1cm 2 Flow rate of 33mL h -1 The anolyte is recycled; the anode and cathode chambers are separated by a proton exchange membrane Nafion 117. Results 1: constant current 100mA cm -2 Produce H 2 O 2 Faraday efficiency 98%, H 2 O 2 The concentration is 376mM; results 2: constant current of 200mA cm -2 Produce H 2 O 2 Faraday efficiency 96%, H 2 O 2 The concentration is 719mM; results 3: constant current 300mA cm -2 Produce H 2 O 2 Faraday efficiency 96%, H 2 O 2 The concentration was 1086mM.
(5) Electrolytic cell b was used to test gas diffusion type cobalt single site electrode synthesis H under different experimental conditions 2 O 2 The performance of (c). The oxygen flow rate in the following experiment was 30mL min -1 . Condition 1: constant current 500mA, catholyte of 1.0M KOH and anolyte of 0.5M H 2 SO 4 Liquid flow rate 100mL h -1 Produce H 2 O 2 Faraday efficiency 96%, H 2 O 2 The concentration is 90mM; condition 2: constant current of 800mA, 1.0M KOH for both cathode and anode solutions, flow rate of 82mL h -1 Produce H 2 O 2 Faraday efficiency of 100% H 2 O 2 The concentration was 185mM; condition 3: constant current 400mA, and cathode and anode liquid are all 0.3M K 2 SO 4 (pH 7.2) flow rate 100mL h -1 Produce H 2 O 2 Faraday efficiency 93%, H 2 O 2 The concentration was 69mM; condition 4: constant current 500mA, and cathode and anode liquid are all 0.3M K 2 SO 4 (pH 1.5) flow Rate 82mL h -1 Produce H 2 O 2 Faraday efficiency 93%, H 2 O 2 The concentration was 106mM.
Example five:
this example provides the electrosynthesis of H from the metal single-site catalytic material prepared in example two 2 O 2 The application method in (1) is implemented according to the following steps:
(1) And preparing the gas diffusion type cobalt single-site electrode by adopting a spin-coating method. Preparing a solvent by using 4mL of ultrapure water, 1mL of isopropanol and 250 mu L of Nafion membrane solution, adding 50mg of the CoPc-OVX catalyst prepared in the second embodiment into the solvent, and uniformly dispersing the catalyst by ultrasonic vibration; applying 50 μ L of the catalyst slurry to one side of hydrophobic carbon paper by spin coating, the area of the catalyst slurry is 1cm -2 Oven drying at 50 deg.C with catalyst loading of 0.53mg cm -2 。
(2) The gas diffusion type cobalt single-site electrode obtained by the preparation method is used as a cathode, one side of the supported catalyst layer is contacted with 1.0M KOH catholyte, and the flow rate is 5mL h -1 The other side (diffusion layer) was exposed to an oxygen chamber with serpentine flow channels at an oxygen flow rate of 20mL min -1 (ii) a The anode electrode adopts a Pt sheet as an anode and is exposed to 0.5 MH of anolyte 2 SO 4 Working area is 1cm 2 Flow rate of 33mL h -1 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) Application of constant Current through electrochemical workstation, synthesis of H 2 O 2 Directly flows out of the cathode chamber. H is produced under the condition of 100mA current 2 O 2 Faraday efficiency 92%, H 2 O 2 The concentration is 330mM; h is produced under the condition of 150mA current 2 O 2 Faraday efficiency 98%, H 2 O 2 The concentration was 550mM.
Example six:
this example provides the electrosynthesis of H for the metallic single-site catalytic material prepared in example III 2 O 2 The specific method refers to the electrolytic cell a in the fourth embodiment. Results 1: constant current 100mA cm -2 Produce H 2 O 2 Faraday efficiency 97%, H 2 O 2 The concentration is 372mM; results 2: constant current 150mA cm -2 Produce H 2 O 2 Faraday efficiency 74%, H 2 O 2 The concentration was 415mM.
Example seven:
this example provides the electrosynthesis of H in cell b of example four 2 O 2 The practical application method is implemented according to the following steps:
under the conditions of constant current of 500mA and 0.3M K of cathode and anode liquid 2 SO 4 (pH 1.5) flow Rate 82mL h -1 Electrosynthesis of H under conditions 2 O 2 Out of H 2 O 2 The concentration was 106mM. H to be flowed out 2 O 2 And containing 1mM Fe 2+ And 10mg L of -1 The solution of the secondary biochemical effluent of phenol, levofloxacin, bisphenol A or coking wastewater is mixed in a flow dynamic reaction tank, the removal rate of pollutants is 100 percent within 3 hours of reaction time, the removal rate of phenol, levofloxacin, bisphenol A is 40-60 percent, and the removal rate of the total organic carbon in the secondary biochemical effluent of coking wastewater is 90 percent.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (10)
1. The metal single-site catalytic material is characterized in that the metal single-site catalytic material is a carbon material modified by oxygen atoms and loaded with M-N 4 The metal phthalocyanine or metalloporphyrin molecule with the characteristic structure in an isolated and dispersed mode, wherein M is metal, and N is pyrrole nitrogen.
2. The metallic 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 metallic single site catalytic material of claim 1, having M-N 4 The isolated and dispersed metal phthalocyanine or metalloporphyrin molecule with characteristic structure comprises manganese phthalocyanine, manganese porphyrin and cobalt phthalocyanineCobalt porphyrin, nickel phthalocyanine, nickel porphyrin, copper phthalocyanine, copper porphyrin, having M-N 4 At least one of metal phthalocyanine or metal porphyrin derivative with characteristic structure.
4. A method of preparing a metallic single site catalytic material as claimed in any of claims 1 to 3, comprising the steps of:
(1) Oxidizing the carbon material to obtain an oxygen atom modified carbon material carrier;
(2) Respectively dispersing the carbon material carrier modified by the 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 the oxygen atoms, wherein the mass ratio of the metal phthalocyanine or metalloporphyrin to the carbon material carrier is 1-20%, and continuously stirring to obtain the metal single-site catalytic material.
5. The method of claim 4, wherein the oxidation treatment comprises a concentrated oxidative acid heat treatment, a high temperature carbonization, or a hydrothermal method;
the concentrated oxidizing 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 the following steps: uniformly mixing a carbon material carrier and polyethylene oxide in a mass ratio of 2 2 Or calcining for 1-4 h at 500-800 ℃ in an inert gas atmosphere;
the hydrothermal process comprises: dispersing the carbon material carrier in 7-10M KOH or NaOH solution, and maintaining at 150-200 deg.c for 12-24 hr.
6. The method of claim 4, wherein the organic solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone, and N-hexane.
7. Use of a metal single-site catalytic material according to any one of claims 1 to 3 or obtained by a process according to any one of claims 4 to 6, as a cathode catalyst in a gas diffusion-type electrolytic cell for the electrosynthesis of H 2 O 2 。
8. Use according to claim 7, characterized in that it comprises the following steps:
(1) Loading a metal single-site material on the surface of a substrate to prepare an electrode with a catalyst layer on one side and a diffusion layer on the other side;
(2) Electrosynthesis of H 2 O 2 The electrolytic cell component mainly comprises: the cathode, the anode, the cathode chamber, the anode chamber, the ion exchange membrane and the gas chamber;
taking the electrode prepared in the step (1) as a cathode, taking an electrode with electrocatalytic oxidation activity as an anode, wherein a catalyst layer of the cathode is in contact with catholyte in a cathode chamber, a diffusion layer of the cathode is exposed in a gas chamber, and a gas-liquid-solid three-phase reaction interface is formed on the surface of the catalyst; an ion exchange membrane is used for separating a cathode chamber and an anode chamber; the width and thickness of the catholyte have an adjusting range of 1-13 mm;
(3) Applying constant current or constant potential, adopting cathode and anode liquid flow dynamic electrolysis mode to synthesize H 2 O 2 。
9. Use according to claim 8, wherein the loading of metal single site material on the electrode is 0.25-1.0 mg cm -2 (ii) a The anode comprises a Pt electrode for water oxidation, ruO 2 Electrode, irO 2 Electrodes or hydrogen oxidized Pt electrodes.
The current range is 0-1100 mA, and the current density range is 0-300 mA cm -2 (ii) a The electrolyte of the cathode chamber and the anode chamber is 0.1-1.0M KOH or NaOH, 0.1-0.5M K 2 SO 4 Or Na 2 SO 4 、0.3M K 2 SO 4 Or Na 2 SO 4 The pH of the electrolyte is 1 to 11.
10. The use of claim 8, wherein the preparation method of the electrode in 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 on the surface of a hydrophobic, porous and conductive substrate, and drying to prepare an electrode;
the organic solvent comprises an alcoholic solution, and the alcoholic solution comprises at least one of ethanol and isopropanol; the adhesive comprises at least one of Nafion membrane solution, polytetrafluoroethylene solution and perfluorinated sulfonic acid polymer; the catalyst supporting 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 net with or without a micropore flat layer.
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| CN116514291A (en) * | 2023-05-19 | 2023-08-01 | 深水海纳水务集团股份有限公司 | Preparation method of microbial carrier filler, microbial carrier filler and moving bed biomembrane reactor |
Citations (1)
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|---|---|---|---|---|
| CN110911694A (en) * | 2019-11-27 | 2020-03-24 | 南方科技大学 | Method for preparing heterogeneous monomolecular electrocatalyst by using metal phthalocyanine molecule-nano carbon and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| PEIKE CAO ET AL.: "Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents", 《NATURE COMMUNICATION》, 12 January 2023 (2023-01-12), pages 1 - 12 * |
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| CN116514291A (en) * | 2023-05-19 | 2023-08-01 | 深水海纳水务集团股份有限公司 | Preparation method of microbial carrier filler, microbial carrier filler and moving bed biomembrane reactor |
| CN116514291B (en) * | 2023-05-19 | 2023-11-17 | 深水海纳水务集团股份有限公司 | Preparation method of microbial carrier filler, microbial carrier filler and moving bed biomembrane reactor |
| CN116514234A (en) * | 2023-06-28 | 2023-08-01 | 广东工业大学 | Stack type electrochemical ammonia recovery device and method loaded with pulsed electric field |
| CN116514234B (en) * | 2023-06-28 | 2023-09-01 | 广东工业大学 | Stack type electrochemical ammonia recovery device and method loaded with pulsed electric field |
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