CN116426970A - Polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere and preparation method and application thereof - Google Patents

Polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere and preparation method and application thereof Download PDF

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CN116426970A
CN116426970A CN202310333128.9A CN202310333128A CN116426970A CN 116426970 A CN116426970 A CN 116426970A CN 202310333128 A CN202310333128 A CN 202310333128A CN 116426970 A CN116426970 A CN 116426970A
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nhcss
phthalocyanine
polymetallic
porous hollow
electrode
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吕晓萌
龚善和
王文搏
王浩田
刘军
韩旭
陆润清
王雪学
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Jiangsu University
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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Abstract

The invention relates to a polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere, a preparation method and application thereof. The invention takes dopamine hydrochloride as nitrogen source, carbon source and SiO 2 The pellets are used as templates, and the physicochemical properties of NHCSs are regulated and controlled by optimizing the carbonization temperature, so that the activity of metal sites is optimized. The metal salt adopted by the invention is one of cobalt chloride, nickel chloride and ferric trichloride, and the specific M (M=Co, fe and Ni) PPc/NHCSs heterogeneous molecular catalyst material is obtained by regulating and controlling the precursor proportion and hydrothermal synthesis conditions, so that the electrocatalytic CO is realized 2 Converted into CO.

Description

Polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere and preparation method and application thereof
Technical Field
The present invention relates to a method for electrocatalytic reduction of CO 2 The technical field of preparation of catalytic materials for converting into CO, in particular to a polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere, a preparation method and application thereof in an anion membrane electrolytic cell for electrocatalytic CO under high current 2 The application of the catalyst in CO conversion.
Background
CO is converted from renewable energy sources into electric energy 2 Electrochemical reduction to carbon monoxide (CO), formic acid (HCOOH), methane (CH) 4 ) Equal C 1 Chemicals and fuels, thereby reducing greenhouse gas emissions. Among them, CO has proven to be a product with potential for industrialization as a product of simple double electron transfer, since it can be used directly, or reprocessed, and satisfactory productivity and low electric energy costs (adv. Mater.2021,33 (41): 2102212). At present, the reduction products correspond to large currents (> 100mA cm) –2 ) Is the occurrence of industrial CO 2 Electrocatalytic reduction (CO) 2 RR) indicates the direction (adv. Funct. Mater.2023,33 (4): 2208781). However, to realize CO 2 RR industrialization is still subject to CO with stable c=o bonds 2 High activation potential barrier of molecule (806 kJ mol) –1 Angew.chem.int.ed.2021, 60:2-24.) and CO 2 The effect of low solubility of the molecules in the aqueous electrolyte. In addition, competitive Hydrogen Evolution Reactions (HER) also present a significant challenge to increasing the Faraday Efficiency (FE) of the reduction product. Development of electrocatalytic CO with high activity, high selectivity and high stability 2 Reduced catalysts and electrolytic cells with industrial application prospects remain hot problems of recent research.
The existing commercial electrochemical technology is electrocatalytic CO 2 RR provides a blueprint. The anionic membrane electrolyzer is most similar to a water electrolyzer for producing hydrogen and oxygen, in terms of the electrocatalytic conversion principle or components of the electrolyzer, and is arranged between the cathode and the anodeZero gap, greatly reduces the ohmic resistance of the reaction and saves the energy consumption. Currently, companies such as Siemens, proton Onsite, teledyne, nel hydro gen and hydro genetics are selling commercial scale water baths. And electrocatalytic CO 2 RR products are already in many petrochemical supply chains, so chemical industry infrastructure is more readily adaptable to electrocatalytic CO 2 RR. Meanwhile, more mature electrocatalytic technologies in industry, such as chlor-alkali cells, hydrogen electrolysis cells and fuel cells, are CO 2 Electrochemical synthesis has provided examples and directions from laboratory to commercial scale. However, AEM may cause various problems in operation at high current densities resulting in reduced cell stability, most of which are below 10h (J.Am. Chem. Soc.2022,144:10446-10454,. Angew. Chem. Int. Ed.2022,61, e 202298. Energy)&Environmental Science, 2023). Development of electrocatalytic CO with high activity, high selectivity and high stability 2 The reduced catalyst is an important guarantee for realizing the high-current operation and stable operation of the catalyst.
Disclosure of Invention
The invention relates to a method for electrocatalytic reduction of CO 2 Preparation method and application of catalytic material converted into CO, in particular to preparation Method of Polymetallic Phthalocyanine (MPPC) coated nitrogen doped porous hollow carbon spheres (NHCSs) and application of catalytic material in anion membrane electrolytic cell for high-current electrocatalytic CO 2 Application of CO.
The technical scheme provided by the invention is as follows:
the invention is used for high-current electrocatalytic CO 2 The preparation method of the poly-metal phthalocyanine material of CO comprises the following specific steps:
(1) Under alkaline condition, tetraethyl orthosilicate (TEOS) is utilized to generate silicon dioxide pellets (SiO 2 ) As a template. Dopamine hydrochloride (DA) is used as a precursor of the spherical shell, and under the alkaline condition, siO is used as a precursor of the spherical shell 2 The surface of the pellets grow in a polymerization way to form Polydopamine (PDA) @ SiO 2 Ball (SiO) 2 @PDA)，SiO 2 Calcining at high temperature under inert condition at the @ PDA, and treating with Hydrogen Fluoride (HF) to obtain the nitrogen-doped porous hollow carbon spheres (NHCSs).
(2) Adding NHCSs, metal salt and 1,2,4, 5-tetracyanobenzene into a solvent in sequence, and regulating and controlling the material ratio among the NHCSs, the metal salt and the 1,2,4, 5-tetracyanobenzene; under hydrothermal conditions, metal ions and 1,2,4, 5-tetracyanobenzene are subjected to polymerization reaction to generate polymetallic phthalocyanine on the surface of NHCSs, and the MPPC/NHCSs material is obtained after vacuum filtration, washing and drying. The structure of polymetallic phthalocyanine molecules and the polymeric structure thereof on the surface of NHCSs are optimized by regulating and controlling the solvent, the hydrothermal time and the temperature, so that the optimization of active sites is realized, the stability of central sites is improved, and the requirements of cathode catalyst materials for high-current long-acting stable operation of an anion membrane electrolytic cell are met.
The invention takes dopamine hydrochloride as nitrogen source, carbon source and SiO 2 The pellets are used as templates, and the physicochemical properties of NHCSs are regulated and controlled by optimizing the carbonization temperature, so that the activity of metal sites is optimized. The metal salt adopted by the invention is one of cobalt chloride, nickel chloride and ferric trichloride, and the specific M (M=Co, fe and Ni) PPc/NHCSs heterogeneous molecular catalyst material is obtained by regulating and controlling the precursor proportion and the hydrothermal synthesis condition.
Preferably, in step (1), siO 2 The size of (2) is controlled to be 200-500 nanometers (nm); the size of NHCSs is controlled to be 200-500 nm, and the surface mesoporous size is controlled to be 2-4 nm; the inert condition refers to the adoption of nitrogen, argon or helium as inert shielding gas.
Preferably, in step (2), the metal salt is: any one of cobalt chloride, nickel chloride and ferric chloride; the solvent is selected from any one of ethanol and water; NHCSs 50-150 mg, metal salt 10-40 mg,1,2,4, 5-tetracyanobenzene 56-225 mg. The hydrothermal time is 140-200℃, the time is 6-8 hours (h), and the solvent volume is 40-50 milliliters (mL).
The invention also provides a cathode catalytic material prepared by wrapping the polymetallic phthalocyanine with the nitrogen-doped porous hollow carbon spheres, which is used for electrocatalytic CO 2 Use for the reduction conversion to CO.
The preparation method of the polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere serving as a cathode catalytic material comprises the following steps: combining the MPPC/NHCSs material obtained by the previous step with a certain amount of ionomerAnd mixing with solvent to obtain electrode ink, coating on electrode carrier, and constructing cathode Gas Diffusion Electrode (GDE). First, the catalyst is used for an H-shaped electrolytic cell to electrically catalyze CO 2 And (3) reducing to prepare CO, and testing the electrocatalytic performance of the material. Specifically, a Pt electrode is used as a counter electrode, a cathode gas diffusion electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and CO 2 The saturated aqueous phase salt solution is used as electrolyte, the H-type electrolytic cell is connected with an electrochemical workstation (CHI 1140C) to perform electrocatalytic reduction of CO 2 The reaction was tested for conversion to CO, and the faraday efficiency of the electrochemical conversion was calculated by monitoring and analyzing the type and content of the product by on-line gas and liquid chromatography.
The design and optimization of the anion membrane electrolytic cell in the invention are based on the construction technology of the prior anion membrane electrolytic cell (metal aerogel catalytic material is used for preparing the electrocatalytic reduction CO of the anion membrane electrolytic cell) 2 Use of the reaction, application number: 202110759115.9). The size of the grinding tool is independently built and optimized to obtain the anion membrane electrolytic cell, and a specific model is shown in figure 1. The whole reaction volume of the electrolytic cell is controlled at 7cm multiplied by 5cm, and from left to right, the electrolytic cell is respectively a metal baffle plate (with the thickness of 1 cm), a cathode snake-shaped gas flow field plate (with the thickness of 1.5 cm), a silica gel sealing sheet, a cathode electrode gas diffusion electrode, an anion exchange membrane (AEM membrane), an anode electrode, a silica gel sealing sheet, an anode liquid flow field plate (with the thickness of 1.5 cm) and a metal baffle plate (with the thickness of 1 cm). The reaction area of the cathode is 1cm multiplied by 1cm, the control area of the serpentine gas flow field is 1cm multiplied by 1cm, and the depth is controlled to be 0.5cm. The principle of upper connection of air inlet and lower connection of air outlet is followed. The air port above the flow field is connected with humidified CO 2 The gas, the downside is the gas outlet, is used for the collection of product gas and online gas chromatography monitoring product. An anion exchange membrane (AEM membrane) was used as a separation membrane, 1.5cm by 1.5cm in size, placed between the cathode and anode electrodes. The back side of the cathode electrode (the side opposite to the side against the AEM film) is connected to a conductive copper foil, which serves as a current collector. The silica gel sealing sheet, the cathode electrode and the AEM film are sealed together by using a non-conductive adhesive tape, so that the cathode electrode is not damaged when the device is disassembled and the serpentine channel is washed. Based on Nickel Foam (NF), by conventional electrostatic deposition (Nature Communication)s6 (2015): 1-7) NiFe/LDH/NF electrodes were prepared for use as anodes in membrane cells. The upper end of the NiFe/LDH/NF is connected with copper foil, extends to the outside of the flow field and is used as a current collector. The assembly sequence of the anion membrane electrolytic cell is shown in figure 1. After the assembly of the anion membrane electrolytic cell is completed, the cathode is externally connected with humidified CO 2 The air outlet is connected with a liquid collecting bottle for collecting overflowed liquid. The flow rate at the gas outlet of the online gas chromatograph was tested to quantify the reducing gas component. And flowing electrolyte is externally added on the anode side, and a peristaltic pump is adopted to control the flow rate of the liquid. The electrochemical workstation of Shanghai Chenhua (CHI 1140C) is connected with an online gas chromatograph for testing, the working lines of a reference electrode and a counter electrode are connected with an anode, the working electrode is connected with a cathode, an MPPC/NHCSs/CC/FeNi/LDH/NF system is constructed, and the electrocatalytic reduction CO in an anion membrane electrolytic cell is tested 2 The reactivity and stability of CO.
Preferably, the cathode made of MPPC/NHCSs material has an electrode carrier made of one of carbon paper, carbon felt, carbon cloth and carbon fiber, and the preferred electrode carrier does not participate in electrocatalytic CO 2 The reduction reaction has good conductivity and satisfies the uniform dispersion of the catalyst material.
Preferably, the method of preparing the cathode from MPPC/NHCSs uses a commercial perfluorinated acid resin Nafion solution (5 wt%) as the ionomer to stabilize the catalyst on the surface of the electrode. Catalyst (2-4 mg) and Nafion solution (20-60 mu L) are added into ethanol (1-3 mL) solution, and the mixture is ultrasonically mixed for 1h, thus obtaining uniform electrode ink. And coating electrode ink on an electrode carrier, and drying to obtain the cathode.
Preferably, in the test of the H-type electrolytic cell, the load capacity of the polymetallic phthalocyanine coated nitrogen-doped porous hollow carbon sphere material on the electrode carrier is 0.1-1 mg cm -2 。
Preferably, in the anion membrane electrolytic cell, the load of the polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere material on the electrode carrier is 0.1-2 mg cm -2 。
By adopting the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) Compared with the traditional non-covalent fixation technology, the polymetallic phthalocyanine coated nitrogen-doped porous hollow carbon sphere prepared by the invention optimizes the combination mode between the polymetallic phthalocyanine molecule catalytic site and the substrate, is beneficial to stabilizing the macrocyclic molecule on the surface of the substrate, and inhibits the polymetallic phthalocyanine molecule catalyst from electrocatalytic CO 2 The problem of precipitation in the process is solved, and the stability of the catalyst under high-current operation is improved.
(2) The polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere prepared by the invention is used for electrocatalytic CO 2 CO reaction. In the H-type electrolytic cell, the optimal components of the nitrogen-doped porous hollow carbon sphere wrapped by the polymetallic phthalocyanine molecular catalyst can realize the electrocatalytic CO 2 The high selectivity of CO (the highest Faraday efficiency of CO is more than 95%) and the uniform dispersion of the molecular active sites greatly improves the utilization rate of the catalyst and saves the cost. In the test of the anionic membrane electrolytic cell, the test current range is 20-150 mA cm -2 Electrocatalytic CO of optimal catalyst 2 The Faraday efficiency of CO is more than 95 percent; at constant current-100 mA cm -2 Under the test condition, the optimal catalyst can stably work for 110h, and the Faraday efficiency of CO is stabilized to be more than 80%.
Drawings
FIG. 1 is a schematic diagram of an anion membrane electrolytic cell.
FIG. 2 is an infrared spectrum of CoPPc in the material of example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph (left image) and a high angle annular dark field scan (HADDF-TEM, right image) of CoPPc/NHCSs in the material of example 1, with scales of 100nm and 50nm, respectively.
FIG. 4 is a photograph of a spherical aberration correcting transmission electron microscope (AC HADDF-TEM) of CoPPc/NHCSs of the material of example 1, scale 5nm.
FIG. 5 is a graph of synchrotron radiation data of the CoPPc/NHCSs and Co foil standards in the material of example 1.
FIG. 6 is a graph of test performance of CoPPc/NHCSs in an H-cell in the material of example 1.
FIG. 7 is a graph of the performance of the material of example 1 tested in a CoPPc/NHCSs anionic membrane cell.
FIG. 8 is a graph of test stability in an anionic membrane cell of CoPPc/NHCSs in the material of example 1.
FIG. 9 is a Scanning Electron Microscope (SEM) photograph of CoPPc/NHCSs-2 of the material of example 2, scale bar 1. Mu.m.
FIG. 10 is an SEM image of NiPPc/NHCSs of the material of example 3.
FIG. 11 is an SEM image of FePPc/NHCSs of the material of example 4.
FIG. 12 is a graph of the test performance of NiPPc/NHCSs in an H-cell in the material of example 3.
FIG. 13 is a graph of the test performance of FePPc/NHCSs in an H-cell in the material of example 4.
Detailed Description
Example 1:
NHCSs sample preparation: to a 250mL single-necked flask, 35mL of deionized water, 5mL of aqueous ammonia (25 to 28 wt%) and 100mL of ethanol were added, and the mixture was stirred for 30 minutes to obtain a homogeneous solution. Next, 5mL of TEOS was added to the above mixed solution, and stirring was continued for 1h to obtain SiO 2 The pellet suspension was sonicated for 3min. Then 0.5 g of dopamine hydrochloride is added and stirring is continued for 12h. Under alkaline conditions, dopamine hydrochloride undergoes polymerization and grows on SiO 2 Is a surface of the substrate. Centrifuging at 7000 rpm for 3min, collecting samples, washing with water and alcohol respectively, and oven drying at 60deg.C to obtain SiO 2 Sample @ PDA. Immediately thereafter, siO 2 The @ PDA sample was carbonized at 400℃for 2 hours at a high temperature of 1℃per minute under an inert atmosphere of nitrogen, followed by 3 hours at 800℃with a heating program of 5℃per minute. The carbonized sample is treated by HF for 72 hours at a concentration of 4mol/L to remove SiO 2 And (5) a hard template. NHCSs samples were collected by vacuum filtration, rinsed 30 times with fresh water, then 3 times with ethanol for removal of residual acid, and finally dried at 60 ℃. The NHCSs are obtained with the size of 394+/-31 nm and the surface mesoporous size of 3.74nm.
Preparation of cathode catalytic material CoPPc/NHCSs: 100mg of NHCSs,16mg of cobalt chloride and 90mg of 1,2,4, 5-tetracyanobenzene are weighed, added into 50mL of ethanol solution, ultrasonically stirred for 30min, transferred into a 100mL hydrothermal kettle and hydrothermal for 8h at 180 ℃. Finally, the sample is washed by vacuum filtration and sequentially by 2mol/L hydrochloric acid and hot ethanol (60 ℃) solution, finally the sample is washed by deionized water and ethanol (normal temperature), and finally the porous hollow carbon spheres-CoPPc/NHCSs coated with nitrogen and wrapped by cobalt phthalocyanine are obtained by drying at 60 ℃.
H-cell performance test: 3mg of the resulting CoPPc/NHCSs sample was taken and 30. Mu.L of Nafion (5 wt%) ionomer and 3mL of ethanol were added and sonicated for 1h to give a catalyst ink. The ink obtained was applied to a commercial carbon paper of 3cm X1 cm in an area of 1cm 2 Catalyst loading was 0.45mg cm -2 And drying at normal temperature to obtain the working electrode. Together with an Ag/AgCl reference electrode and a Pt counter electrode, a three-electrode system was formed, and the potentials tested were all converted to Reversible Hydrogen Electrodes (RHEs). The linear sweep interval of volt-ampere is-0.2 to-1.16V vs. RHE, and the sweep speed is 5mV s -1 . The test potentials were-0.5, -0.6, -0.7, -0.75, -0.8, -0.85, -0.9 and-1.0 v vs. rhe, and the products were monitored by on-line gas chromatography. The potentiostatic test was set at-0.8 v vs. rhe, the electrolyte was changed every 20h, and the electrode surface was rinsed with deionized water.
Performance test of anionic membrane cell: 3mg of CoPPc/NHCSs catalyst was weighed, mixed with 3mL of ethanol containing 50. Mu.L of Nafion (5 wt%) solution, and sonicated for 1h to give a uniform catalyst ink. The Nafion with low content is used for stabilizing the catalyst on the surface of the electrode and has the conductive effect. Then spraying the catalytic ink onto commercial hydrophobic carbon paper (CC) as gas diffusion layer by using air brush, and oven drying at 50deg.C to obtain cathode gas diffusion electrode with catalyst loading of 2mg cm -2 . The NiFe/LDH/NF is adopted as the anode on one side of the anode, and Ni and Fe metal salts are deposited on commercial foam nickel by a traditional electrostatic deposition method (Nature Communications (2015): 1-7). Commercial nickel foam was pre-cut to a size of 1.5cm by 1.5cm and washed with 2mol/L hydrochloric acid and ethanol, respectively. The electrostatically deposited NiFe/LDH/NF sample was rinsed with deionized water and ethanol, and dried at room temperature to serve as an anion membraneAn anode of the electrolytic cell. Cathode external field humidifying CO 2 The flow rate of the flowing gas was controlled at 20sccm. The anode side was externally supplied with flowing electrolyte (1M KHCO 3 ) A peristaltic pump was used to control the gas flow rate to 20sccm. The test is carried out by using an electrochemical workstation of Shanghai Chenhua (CHI 1140C), the working lines of the reference electrode and the counter electrode are connected with an anode, and the working electrode is connected with a cathode. The test adopts a constant current test model, and the test current is as follows: 20. 50, 75, 90, 100, 125 and 150mA cm -2 The test duration was 1200s. The constant current test stability is 110h, and the solution is changed every 3-5 h in the test time period. Disassembling the anionic membrane electrolytic cell, flushing the serpentine gas channel with deionized water, removing salting out, assembling the electrode, and continuously applying 100mA cm -2 Is tested.
As shown in FIG. 2, the characteristic infrared absorption spectrum of CoPPc in example 1 demonstrates that CoPPc has been successfully synthesized.
As shown in FIG. 3a, the CoPPc/NHCSs catalyst of example 1 has a uniform spherical structure. As shown in FIG. 3b, the spherical shell surface of CoPPc/NHCSs is rich in mesoporous structure.
The apparent bright spots are seen in fig. 4, demonstrating that the metal has reached an atomic scale distribution, demonstrating the formation of CoPPc monodisperse sites.
The a-plot in FIG. 5 is an X-ray absorption near side absorption spectrum plot of CoPPc/NHCSs and Co foil (Co foil), which can be seen to reveal a different pre-side structural information than Co foil. FIG. b is a Fourier transform expanded X-ray absorption structure diagram of CoPPc/NHCSs sample, and FIG. c is a fitting graph, and analysis of the graphs b and c shows that the coordination configuration of Co in CoPPc/NHCS is Co-N 4 Structure is as follows. And d, comparing a theoretical spectrogram with an experimental spectrogram, wherein an inserted chart shows the spatial configuration of the CoPc structure, and the characterization information fully shows that the CoPPc is successfully synthesized and is loaded on the surface of the NHCSs substrate.
FIG. 6 is a graph of test performance of CoPPc/NHCSs as cathode material in an "H" type cell. As shown in FIG. 6a, coPPc/NHCSs shows the response to CO 2 Specific electrocatalytic reduction properties. at-0.8V vs. RHE test potential, the overall current density reaches 45mA cm -2 . As shown in FIG. 6b, potentiostatic test data found that CoPPc/NHCSs electrocatalytic CO at-0.8V vs. RHE test potential 2 Faraday efficiency of reduction of CO (FE CO ) Maximum, 95.46%. At the same time, the partial current density of CO (j CO ) As shown in FIG. 6c, j is at-0.8V vs. RHE potential CO Has a value of 36.31mA cm -2 . The potentiostatic test of the CoPPc/NHCSs is shown in figure 6d, and the CoPPc/NHCSs is tested for 135h at the potentiostatic level of-0.8V vs. RHE, and the selectivity to CO is maintained above 80%, which shows that the CoPPc/NHCSs has excellent stability.
FIG. 7 is a graph showing constant current measurements of CoPPc/NHCSs as cathode material in an anionic membrane cell at 20, 50, 75, 90, 100, 125 and 150mA cm, respectively -2 . At a test current of 90mA cm -2 When the CO selectivity is up to 95.22%.
Constant current stability test As shown in FIG. 8, the final 100mA cm was achieved by replacing the electrolyte and flushing the electrodes -2 Under constant current density, the device stably works for 110h, and the Faraday efficiency of CO is stabilized to be more than 80%.
Example 2:
NHCSs samples were prepared as in example 1. 100mg of NHCSs,32mg of cobalt chloride and 180mg of 1,2,4, 5-tetracyanobenzene are weighed, added into 50mL of ethanol solution, ultrasonically stirred for 30min, transferred into a 100mL hydrothermal kettle and subjected to hydrothermal treatment at 180 ℃ for 8h. Finally, vacuum filtering, washing the sample by sequentially passing through 2mol/L hydrochloric acid and hot ethanol (60 ℃) solution, washing the sample by deionized water and ethanol (normal temperature), and drying at 60 ℃ to finally obtain the cobalt phthalocyanine coated porous nitrogen doped hollow carbon spheres-CoPPc/NHCSs-2.
And the morphology of the CoPPc/NHCSs-2 is characterized by a field emission scanning electron microscope.
As shown in FIG. 9, the CoPPc/NHCSs-2 catalyst of example 2 has a spherical structure, and the CoPPc polymer exists in the substrate.
Example 3:
NHCSs samples were prepared as in example 1. 100mg of NHCSs,16mg of nickel chloride and 100mg of 1,2,4, 5-tetracyanobenzene are weighed, added into 50mL of ethanol solution, ultrasonically stirred for 30min, transferred into a 100mL hydrothermal kettle and subjected to hydrothermal treatment at 180 ℃ for 8h. Finally, the sample is washed by vacuum filtration and sequentially by 2mol/L hydrochloric acid and hot ethanol (60 ℃) solution, finally the sample is washed by deionized water and ethanol (normal temperature), and finally the porous hollow carbon sphere-NiPPc/NHCSs coated with the nickel phthalocyanine nitrogen is obtained by drying at 60 ℃.
H-cell performance test: 3mg of the resulting NiPPc/NHCSs sample was taken and 30. Mu.L of Nafion (5 wt%) ionomer and 3mL of ethanol were added and sonicated for 1h to give a catalyst ink. The ink obtained was applied to a commercial carbon paper of 3cm X1 cm in an area of 1cm 2 Catalyst loading was 0.45mg cm -2 And drying at normal temperature to obtain the working electrode. Together with an Ag/AgCl reference electrode and a Pt counter electrode, a three-electrode system was formed, and the potentials tested were all converted to Reversible Hydrogen Electrodes (RHEs). The linear sweep interval of volt-ampere is-0.2 to-1.2V vs. RHE, and the sweep speed is 5mV s -1 . The test potentials were-0.5, -0.6, -0.7, -0.75, -0.8, -0.85, -0.9 and-1.0 v vs. rhe, and the products were monitored by on-line gas chromatography.
Example 4:
NHCSs samples were prepared as in example 1. 100mg of NHCSs,33.40mg of ferric trichloride and 90mg of 1,2,4, 5-tetracyanobenzene are weighed, added into 50mL of ethanol solution, ultrasonically stirred for 30min, then transferred into a 100mL hydrothermal kettle, and hydrothermal for 8h at 180 ℃. Finally, the sample is washed by vacuum filtration and sequentially by 2mol/L hydrochloric acid and hot ethanol (60 ℃) solution, finally the sample is washed by deionized water and ethanol (normal temperature), and finally the porous hollow carbon spheres-FePPc/NHCSs coated with nitrogen and wrapped by the iron phthalocyanine are obtained by drying at 60 ℃.
H-cell performance test: 3mg of the resulting FePPc/NHCSs sample was taken and 30. Mu.L of Nafion (5 wt%) ionomer and 3mL of ethanol were added and sonicated for 1h to give a catalyst ink. The ink obtained was applied to a commercial carbon paper of 3cm X1 cm in an area of 1cm 2 Catalyst loading was 0.45mg cm -2 And drying at normal temperature to obtain the working electrode. Forms three electrodes together with Ag/AgCl reference electrode and Pt counter electrodeThe system, the potential tested was converted to a Reversible Hydrogen Electrode (RHE). The linear sweep interval of volt-ampere is-0.2 to-1.2V vs. RHE, and the sweep speed is 5mV s -1 . The test potentials were-0.5, -0.6, -0.7, -0.75, -0.8, -0.85, -0.9 and-1.0 v vs. rhe, and the products were monitored by on-line gas chromatography.
As shown in FIG. 10, the NiPPc/NHCSs catalyst of this example has a spherical structure.
As shown in FIG. 11, the FePPc/NHCSs catalyst of this example has a spherical structure.
As shown in FIG. 12a, niPPc/NHCSs prepared in example 3 showed a high potential for electrochemical CO at a test potential of-0.2 to-1.2V (vs. RHE) 2 Reducing obvious activity. As shown in FIG. 12b, the selectivity to CO reached a maximum of 98.7% at the applied-0.75V (vs. RHE) test potential. As shown in fig. 12c, j CO at-0.9V vs. RHE potential, a maximum of 27.82mA cm was reached -2 。
As shown in FIG. 13a, the FePPc/NHCSs prepared in example 4 showed significant electrocatalytic CO at a test potential of-0.2 to-1.2V (vs. RHE) 2 Activity of reduction. As shown in FIG. 13b, the selectivity to CO reaches a maximum of 85.38% and a maximum of j when a potential of-0.5V (vs. RHE) is applied CO 1.36mA cm -2 (shown in FIG. 13 c).
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (8)

1. The preparation method of the polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere is characterized by comprising the following specific steps of:
(1) Generating silica pellets as templates by using tetraethyl orthosilicate under alkaline conditions; dopamine hydrochloride is used as a precursor of a spherical shell, and under an alkaline condition, siO is used as a precursor of the spherical shell 2 The surface of the pellets grow in a polymerization way to form Polydopamine (PDA) @ SiO 2 Ball (SiO) 2 @PDA)，SiO 2 PDA is calcined under inert conditions at high temperature and Hydrogen Fluoride (HF)Obtaining nitrogen doped porous hollow carbon spheres (NHCSs) after treatment;
(2) Adding NHCSs, metal salt and 1,2,4, 5-tetracyanobenzene into a solvent in sequence, and regulating and controlling the material ratio among the NHCSs, the metal salt and the 1,2,4, 5-tetracyanobenzene; under hydrothermal conditions, metal ions and 1,2,4, 5-tetracyanobenzene are subjected to polymerization reaction to generate polymetallic phthalocyanine on the surface of NHCSs, and the polymetallic phthalocyanine is subjected to vacuum filtration, washing and drying to obtain an MPPC/NHCSs material; the structure of polymetallic phthalocyanine molecules and the polymeric structure thereof on the surface of NHCSs are optimized by regulating and controlling the solvent, the hydrothermal time and the temperature, so that the optimization of active sites is realized, the stability of central sites is improved, and the requirements of cathode catalyst materials for high-current long-acting stable operation of an anion membrane electrolytic cell are met.
2. The method for preparing the polymetal phthalocyanine coated nitrogen-doped porous hollow carbon sphere according to claim 1, wherein in the step (1), siO 2 The size of (2) is controlled to be 200-500 nm; the size of NHCSs is controlled to be 200-500 nm, and the surface mesoporous size is controlled to be 2-4 nm; the inert condition refers to the adoption of nitrogen, argon or helium as inert shielding gas.
3. The method for preparing the polymetal phthalocyanine coated nitrogen-doped porous hollow carbon sphere according to claim 1, wherein in the step (2), the metal salt is: any one of cobalt chloride, nickel chloride and ferric chloride; the solvent is selected from any one of ethanol and water; 50-150 mg of NHCSs, 10-40 mg of metal salt and 56-225 mg of 1,2,4, 5-tetracyanobenzene; the hydrothermal time is 140-200 ℃, the time is 6-8 h, and the solvent volume is 40-50 mL.
4. The preparation method of the polymetallic phthalocyanine coated nitrogen-doped porous hollow carbon sphere serving as a cathode catalytic material prepared by the preparation method as claimed in claim 1 is characterized by comprising the following steps of: the MPPC/NHCSs material is mixed with a certain amount of ionomer and solvent to prepare electrode ink, and the electrode ink is coated on an electrode carrier to construct the cathode gas diffusion electrode.
5. The method of claim 4, wherein the electrode carrier is one of carbon paper, carbon felt, carbon cloth and carbon fiber.
6. The method of claim 4, wherein the ionomer is a 5wt% Nafion solution of perfluorinated acid resin; the solvent adopts ethanol solution; MPPC/NHCSs 2-4 mg, nafion solution 20-60 mu L, ethanol solution 1-3 mL, and ultrasonic mixing for 1h.
7. The method of claim 4, wherein the MPPC/NHCSs material is supported on the electrode carrier at a loading of 0.1-1 mg cm in the H-cell test -2 。
8. The preparation method according to claim 4, wherein the loading of MPPC/NHCSs material on the electrode carrier in the anionic membrane electrolytic cell is 0.1-2 mg cm -2 。
CN202310333128.9A 2023-03-30 2023-03-30 Polymetallic phthalocyanine coated nitrogen doped porous hollow carbon sphere and preparation method and application thereof Pending CN116426970A (en)

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