CN112774713A - Bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and preparation method and application thereof - Google Patents
Bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and preparation method and application thereof Download PDFInfo
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- CN112774713A CN112774713A CN202110094984.4A CN202110094984A CN112774713A CN 112774713 A CN112774713 A CN 112774713A CN 202110094984 A CN202110094984 A CN 202110094984A CN 112774713 A CN112774713 A CN 112774713A
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and a preparation method and application thereof; the bimetallic core-shell catalyst is MnFe formed by bimetallic polymerization of Mn and Fe3O4The nano-microsphere is prepared by mixing the following raw materials,as a core, the heteroatoms N, P and S are codoped to form a shell layer; the core-shell structure is formed by N and P source hexachlorocyclotriphosphazene, S source thioacetamide or thiourea and MnFe3O4The nano-microsphere is obtained by reaction after ultrasonic treatment in a solvent. The catalyst has excellent electrocatalysis performance and hydrogen production capacity, has excellent circulation stability, is not influenced by electrolyte property in the sewage treatment process as a compatible catalyst, and can be switched between the anode and the cathode at will. The catalyst of the invention has good electrocatalytic reaction and can be widely used for treating wastewater.
Description
Technical Field
The invention relates to a catalyst for sewage treatment, in particular to a bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and a preparation method and application thereof; the catalyst is a nano material, and belongs to the technical field of wastewater degradation.
Background
Widespread environmental damage has led researchers to focus on clean and efficient remediation to promote sustainable development in human society. Advanced Oxidation Process (AOP)S) The process of generating the activated oxidant is the most effective method for degrading the pollutants difficult to degrade in the wastewater. The activating oxidant comprises hydrogen peroxide (H)2O2) Peroxymonosulfate (PMS) and Peroxymonosulfate (PS). During these advanced oxidation processes, the redox potential of Reactive Oxygen Species (ROS) is higher than their parent oxidants. Therefore, how to activate the parent oxidant to generate active oxygen is a key issue. The ROS is produced by utilizing PMS and PS, and is widely applied due to the stable form and high ROS production amount. In addition, the reduction voltage of PS is higher (2.01vs 1.82V) and more stable than that of PMS, and is cheaper than PMS. The persulfate is usually activated by light, electricity, heat, ultrasound or metal ions, but the utilization efficiency of PS by a single physical or chemical method is not high, and the PS has disadvantages of high cost, secondary pollution, poor reusability and the like, so that the development of an excellent PS activation oxidation process is receiving attention.
Activation of PS with an oxygen reduction (ORR) catalyst is a cleaner and faster method of degrading contaminants in water. In recent years, among many Transition metals (e.g., Fe, Co, Ni, Cu, Mn, etc.), Fe-based Catalysts often exhibit ORR activity similar to Pt (Li X, Ao Z, Liu J, et al. porous Transformation of Metal-Organic Frameworks to Graphene-Encapsulated Transformation-Metal Nitrides as Efficient Fenton-like Catalysts [ J]ACS Nano,2016,10(12):11532-11540.DOI: 10.1021/acsnano.6b07522), such as graphene/Fe3O4、Fe/Fe3C or activated carbon aerogel/Fe3O4/Fe2O3Can be used as activation/generation H2O2The double active center of (1). However, Fe3O4Some of the disadvantages of matrix composites limit their practical applications, including: (1) high leaching of Fe from electrode surface under acidic condition2+/Fe3+Ions; (2) nanocarbon-Fe3O4Loosely bonded on the composite; (3) fe3O4Low conductivity, small specific surface area, and high aggregation due to anisotropic attraction, which greatly affect the stability and reusability of the electrode, ultimately resulting in a greatly reduced catalytic activity. These nanocarbon-Fe are often calcined at high temperatures or combined with conductive supports in order to improve stability and conductivity3O4The composite material is necessary. However, high temperature calcination may sacrifice the inherent ordered structure and molecular metal active centers, while bonding to the conductive support may hinder its inherent microporosity.
The core-shell composite material is a simpler and more effective catalyst. With Nanoparticles (NP)S) The core is coupled with various heteroatoms in the shell layer, and the hollow space of the core is enhanced to provide a large surface so as to generate enough active sites. Professor of the Onyang university of Tianjin, Gongjin, et al (Li A, Zhu W, Li C, et al]Chemical Society Reviews,2019,48(7):1874-1907.DOI:10.1039/C8CS 00711J) have studied the superiority of supported ZnO core-shell materials in improving photocatalytic performance, but the preparation process requires high temperature of 700 ℃ for high temperature reduction, which increases the difficulty of experiments. The inner layer and the outer layer of the obtained core-shell catalyst can provide charge separation and migration channels to promote charge utilization efficiency, but ultraviolet light is influenced by a wavelength range, and certain wastewater suspended matters and deeper chromaticity (such as printing and dyeing wastewater) are not beneficial to light transmission, so that the technology is not suitable for industrial wastewater treatment.
Recently, a metal organic framework prepared by Li Jian Sheng and the like at Nanjing university of science and technology to wrap Co nanoparticles to form a nucleocapsid material can activate PMS in an electro-Fenton system to realize selective oxidation of pollutants, short-chain small-sized pollutants can be degraded and mineralized through a nucleocapsid pore channel, but the material is not friendly to degradation of large-sized humic acid, cannot degrade long-chain pollution and has no selectivity to mixed pollution in actual sewage. (Jie S, Lin X, Chen Q, et al, Montmorillonite-associated synthesis of cobalt-nitro-large carbon nano sheets for high-performance selection of alkyl aromatic [ J ]. Applied Surface Science,2018,456:951-958.DOI:10.1016/J. ap-susc.2018.06.109.
Preparation of Metal sulfide catalyst (MoS) by the Chengming Sun, university of eastern China2、WS2、Cr2S3、CoS2PbS or ZnS) can increase H in AOPs2O2Decomposition efficiency (Xing M, Xu W, Dong C, et al. Metal Sulfides as Excellent Co-catalysts for H2O2 Decomposition in Advanced Oxidation Processes[J]Chem,2018: S241929418301153), but Fe needs to be continuously added into the system2+The participation in the Fenton reaction brings process complexity and high treatment cost.
Core-shell material Fe @ Fe prepared by Wangli team of university of China2O3The tetrapolyphosphate exists in electro-Fenton reaction together with tetrapolyphosphate, and the complexation of the tetrapolyphosphate and ferrous ions not only ensures that the Fenton reaction has enough soluble Fe (II), but also provides another way for generating more OH in solution through a one-electron molecular oxygen reduction way (Wang L, Cao M, Ai Z, et al. Dramataily Enhanced Aerobic Atrazine depletion with Fe @)2O3Core–Shell Nanowires by Tetrapolyphosphate[J].Environmental Science&Technology, 2014.). But the reaction process is long in time, the activity of superoxide radicals generated by side reactions is weak, the treatment time is prolonged, and the mineralization efficiency is not high.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a high-catalytic and stable bimetallic core-shell catalyst for electrocatalytic synergetic hydrogen production and a preparation method thereof, wherein the high-catalytic and stable bimetallic core-shell catalyst can be obtained without high-temperature calcination.
The invention also aims to provide the application of the core-shell catalyst for electrocatalysis synergetic hydrogen production in sewage treatment.
The invention adopts cheap conventional metal to replace noble metal, prepares simple and effective core-shell composite catalyst, does not need high-temperature calcination in the whole process, and can increase the conductivity and catalytic stability of the metal active center by wrapping the outer layer with hetero atoms. The dissolution of metal ions is reduced, and the maximum release of the catalytic activity of the catalyst is ensured. And the electrons are shunted inside and outside the core shell, the electrons adsorbed on the surface of the shell can realize the targeted adsorption and removal of organic pollutants through a 2-electron ORR process, and small molecular organic substances entering the core can realize complete mineralization through a 1-electron reduction path and simultaneously reduce H through 1 electron2O coproduction of H2。
Firstly, adopting a solvothermal method to prepare MnFe with hydroxyl and carboxyl modified surfaces3O4The magnetic microsphere is used as a core to prepare a heterostructure containing sulfo modification by adopting polyatomic doping, the electrocatalytic activity of the heterostructure is improved by utilizing the polyatomic doping, a larger specific surface area is provided, and H can be effectively captured+Activating to generate active hydrogen, and uniformly distributing lone pair electrons P in MnFe3O4The surface of the nano-core microsphere can form a heterojunction with bimetal, and hydrogen is easily desorbed from the surface of the catalyst to generate due to strong mutual influence of the heterojunction, so that the nano-core microsphere is an ideal bifunctional electrocatalyst. The product is finally coated on carbon paper or carbon felt, sewage degradation is carried out under an electro-Fenton system, and degradation of pollutants can be realized without adjusting pH before and after reaction. The applicable pH range is extended from 2-4 to 2-8 compared to conventional electro-fenton. The pH value of the effluent is not required to be adjusted, and the addition of chemicals is reduced. Besides, the polyatomic coating structure can inhibit the shedding or agglomeration of the catalyst, accelerate the transmission of electrons to active sites, improve the conductivity of the catalyst, quickly capture/activate a target substrate, generate reaction free radicals on the catalytic sites and degrade target pollutants on the adsorption sites.
The purpose of the invention is realized by the following technical scheme:
a core-shell catalyst for electrocatalysis-synergetic hydrogen production is formed by bimetal polymerization of Mn and FeFormed MnFe3O4The nano-microsphere is used as a core, and hetero atoms N, P and S are co-doped to form a shell layer; the core-shell structure is formed by N and P source hexachlorocyclotriphosphazene, S source thioacetamide or thiourea and MnFe3O4The nano-microsphere is obtained by reaction after ultrasonic treatment in a solvent.
In order to further achieve the purpose of the invention, preferably, the diameter of the core-shell catalyst for electrocatalytic synergetic hydrogen production is 100-200nm, and the thickness of the shell layer is 20 +/-0.5 nm.
The preparation method of the core-shell catalyst for electrocatalysis synergetic hydrogen production comprises the following steps:
1)MnFe3O4preparing the nano microspheres: FeCl is added3·6H2O and MnCl2·4H2Adding a reducing agent into O for dispersing, stirring to be bright yellow, adding strong base and weak acid salt, uniformly stirring, adding organic base, reacting for 8-24h at the temperature of 120-200 ℃ in a reaction kettle, cooling, cleaning and drying to obtain MnFe3O4Nano-microspheres; the reducing agent is one or more of ethylene glycol, glycerol, propylene glycol and polyvinyl alcohol;
2) preparing a core-shell catalyst for electrocatalysis synergetic hydrogen production: according to parts by mass, 10-50 parts of N and P source hexachlorocyclotriphosphazene, 22.5-112.5 parts of S source thioacetamide or thiourea and 50-250 parts of MnFe3O4Adding the nano microspheres into a solvent, and performing ultrasonic treatment to realize dissolution and uniform dispersion; adding an acid-binding agent to form white emulsion; stirring for reaction for 8-12h, centrifuging, washing and drying; obtaining the core-shell catalyst for electrocatalysis and hydrogen production.
Preferably, the strong base weak acid salt is sodium acetate (NaAC) or potassium acetate (KAC), and the addition amount of the strong base weak acid salt is FeCl3·6H2The addition amount of O is 3-5 times; the FeCl3·6H2O and MnCl2·4H2The mass ratio of O is 1:8-8: 1; adding 0.125-0.5mmol FeCl into each milliliter of reducing agent3·6H2O。
Preferably, the organic base is ethylenediamine, ethylamine, trimethylamine or polyethylene glycol; the above-mentionedThe addition amount of the organic base is FeCl3·6H20.5-3 times of the mass of O.
Preferably, the solvent is a mixed solution of ethanol and tetrahydrofuran or ethanol and acetone; the mass ratio of the ethanol to the tetrahydrofuran or the ethanol to the acetone is 1:3-3: 1; the acid-binding agent is tertiary amine substance, and 0.15-0.5 ml of the acid-binding agent is added into each milligram of hexachlorocyclotriphosphazene.
Preferably, the tertiary amine is triethylamine, trimethylamine or tributylamine.
Preferably, in step 1), the washing and drying after cooling refers to washing with ethanol for multiple times after cooling, and drying by vacuum;
in the step 2), the washing and drying after centrifugation is repeatedly washing by using ethanol and deionized water after centrifugation, wherein the drying is carried out in a vacuum drying oven at 40-60 ℃.
The application of the core-shell catalyst for electrocatalysis synergetic hydrogen production in sewage treatment comprises the following steps: dispersing a core-shell catalyst for producing hydrogen by electrocatalysis in cooperation with hydrogen in a dispersing agent to obtain a mixed solution, performing ultrasonic treatment, uniformly dispersing, and uniformly coating the obtained mixture on carbon paper, using a carbon felt or a Ti plate as a modified cathode working electrode, using the carbon paper, the carbon felt or the Ti plate as an anode, connecting a cathode with a direct-current power supply cathode, connecting an anode with a positive level, connecting a power supply, building an electrocatalysis reaction device with the cathode and the anode in cooperation, and applying current to catalyze and degrade sewage.
Preferably, 5-20mg of the core-shell catalyst for electrocatalysis synergetic hydrogen production is dispersed in each 1-4mL of the dispersing agent; the dispersant is one or more of ethanol, methanol, acetone or water solution; the binder is a DuPont film or polytetrafluoroethylene; dispersing and adding 5-10 mu L of dispersant into 1-4mL of dispersant; coating 1.25-5mg of the mixture on each square centimeter of the modified cathode working electrode, wherein the thickness of the coating layer is kept 0.5-1 mm; the current is from a voltage-stabilizing direct-current power supply and is 5-100 mA; the sewage is municipal sewage, agricultural wastewater and medical wastewater.
Compared with the prior art, the invention has the following excellent effects:
firstly, the core-shell structure with the bimetallic active sites has a metal active center, and the electron/charge transfer between polyvalent metals has better catalytic performance than that of single metal dopants thereof;
secondly, heterojunction is formed in space by utilizing the core shell, active sites of oxidation-reduction reaction are separated, reverse reaction is inhibited, separation of electrocatalysis and hydrogen production active sites can be realized by the inner layer and the outer layer of the core shell, and a large amount of Reactive Oxygen Species (ROS) are generated.
Thirdly, the lone pair electron phosphorus can form an iron-phosphorus complex on the surface of Fe so as to adjust the electron transfer rate between metal particles and species on a particle-water interface and ensure more soluble Fe2+Take part in the reaction due to Fe2+Standard reduction potential lower than H (-0.44eV)+(0eV), H of the surface+Capable of capturing electrons to produce H2。
Fourthly, the bifunctional core-shell catalyst synthesized by the invention is simple to operate, does not need high-temperature calcination, does not damage the original structure and active center, keeps the inherent nano microsphere structure and provides a foundation for the electrocatalytic performance of subsequent catalysts.
Fifthly, the pH before and after the reaction is not required to be adjusted in the wastewater degradation process, the addition of chemicals is reduced, the method is more suitable for practical industrial application, and the reaction pH range is enlarged to 2-8 compared with the traditional electro-Fenton. The composite core-shell microsphere prepared by the invention has higher catalytic activity, can quickly degrade target pollutants, has a stable material structure and does not dissolve out metals.
Sixthly, the core-shell catalyst of the invention adopts a solvothermal method to prepare MnFe3O4The magnetic microsphere is used as a core, and a plurality of heteroatoms are wrapped on the surface of the core by a hydrothermal polycondensation method, so that the problem of secondary pollution caused by dissolution of the catalyst in the application process is avoided.
Drawings
FIG. 1 is a TEM image of a core-shell catalyst for electrocatalytic hydrogen co-production prepared in example 1;
fig. 2 is an EDS diagram of the core-shell catalyst for electrocatalytic co-production of hydrogen prepared in example 1.
FIG. 3 is a graph showing the degradation and mineralization of tetracycline by using the core-shell catalyst for electrocatalytic synergetic hydrogen production prepared in example 1 as a cathode.
FIG. 4 is a graph showing the tetracycline removal efficiency under different pH conditions using the core-shell catalyst for electrocatalytic coupled hydrogen production prepared in example 1 as a cathode;
FIG. 5 is a cyclic voltammogram of the core-shell material prepared in EXAMPLE 1;
FIG. 6 is a graph of the durability of core-shell materials at different current densities for the core-shell materials prepared in EXAMPLE 1;
FIG. 7 is a graph showing the effect of different shielding agents on tetracycline inhibition of the core-shell material prepared in EXAMPLE 1;
FIG. 8 is a TEM image of the core-shell material prepared in example 2.
Detailed Description
For a better understanding of the present invention, the following provides specific embodiments of the preparation of the bimetallic core-shell microspheres of the present invention and the use of the ORR catalyst thereof.
Example 1
A preparation method of a core-shell catalyst for electrocatalysis synergetic hydrogen production comprises the following steps:
1) 1.35g FeCl was added to a 50mL beaker3·6H2O、0.124MnCl2·4H2O and 40mL of glycol are vigorously stirred to be bright yellow, 3.6g of NaAC is added, 10mL of ethylenediamine is added after uniform stirring to obtain dark green solution, the dark green solution is poured into a 50mL of polytetrafluoroethylene reaction kettle to react for 12h at the temperature of 200 ℃, the solution is washed for 3 times by ethanol after cooling and then is dried in vacuum to obtain the bimetal MnFe3O4And (4) nano microspheres.
2) 10mg of hexachlorocyclotriphosphazene is used as an N source and a P source, 22.5mg of thioacetamide is used as an S source, and 50mg of bimetallic MnFe is added3O4Adding 15mL of ethanol and tetrahydrofuran which are in a mass ratio of 1:1 into the nano microspheres as a solvent, and carrying out ultrasonic treatment for 5min at an ultrasonic frequency of 50Hz until reactants are completely dissolved and uniformly dispersed. Then the mixture is sealed by a polyethylene film, and 1.5mL of triethylamine is quickly injected by an injector to be used as an acid-binding agent to form white emulsion. Then using magnetic forceStirring for continuous reaction for 8h, centrifuging at 8000rpm for 10min, washing with ethanol and deionized water for 2 times, and drying the final product in a vacuum drying oven at 40 deg.C to obtain the core-shell catalyst (MnFe) for electrocatalysis-assisted hydrogen production3O4@PZS)。
FIG. 1 is a core-shell catalyst (MnFe) for electrocatalytic hydrogen co-production prepared in example 13O4@ PZS), and fig. 1 shows the core-shell material core diameter is 100-200nm and the shell thickness is 20 ± 0.5 nm.
The core-shell material prepared in example 1 was subjected to composition analysis by combining a transmission electron microscope and utilizing the characteristic that the photon characteristic energies of different elements are different, to obtain an EDS diagram of the core-shell catalyst for electrocatalytic synergetic hydrogen production shown in FIG. 2, and it can be seen from FIG. 2 that the heteroatom N-P-S was also successfully doped in addition to the bimetallic Mn and Fe.
5.0mg of core-shell catalyst (MnFe) for electrocatalysis synergetic hydrogen production3O4@ PZS) sample, 1mL of ethanol and 10 μ L of a dupont membrane solution having a mass content of 10% were added, and subjected to ultrasonic treatment for 30min to be uniformly dispersed, to obtain a catalyst solution, which was uniformly coated on 2 × 2cm carbon paper to serve as a cathode (thickness of 0.4 cm). An electrocatalytic reaction apparatus was set up using 2X 2cm of blank carbon paper as anode (no catalyst coating) with a single treatment of 500mL containing 10mg L-1The electrolyte of the tetracycline waste water adopts 0.1M Na2SO4The container is internally inserted with a positive electrode and a negative electrode, the distance between the two electrodes is 5cm, the container is matched with a DC power supply of Meisheng MS-305D produced by Dongguan Meihao electronic technology limited company, the negative electrode is connected with the cathode, and the positive electrode is connected with the anode.
FIG. 3 is a graph showing the degradation and mineralization of tetracycline by using the core-shell catalyst for electrocatalytic synergetic hydrogen production prepared in example 1 as a cathode. The concentration of the target pollutant tetracycline is detected by utilizing high performance liquid chromatography, 1mL of water sample is taken at regular intervals to test the concentration of the target pollutant, 33% of acetonitrile and 67% of oxalic acid are adopted as mobile phases, the flow is 1uL/min, the absorbance is 320 to test the degradation concentration of the tetracycline, and as shown in figure 3 (left side coordinate), the tetracycline concentration is gradually reduced along with the increase of the reaction time and can be almost completely removed within 30 min. The total organic carbon detector TOC is utilized to test the mineralization efficiency of the tetracycline along with the reaction time, and as can be seen from figure 3 (right-side coordinate), the mineralization efficiency of the tetracycline within 50min of the reaction is as high as 74.5%.
FIG. 4 is a graph showing the tetracycline removal efficiency under different pH conditions using the core-shell catalyst for electrocatalytic coupled hydrogen production prepared in example 1 as a cathode; the initial pH of the reaction solution was adjusted to test the tetracycline removal efficiency over time, and the degradation curves of tetracycline at different initial pH conditions were also tested using high performance liquid chromatography (the test conditions were the same as those described above), and FIG. 4 shows that pH exhibited the fastest degradation efficiency at neutral conditions (6-7). Under extreme conditions (extreme acid and extreme base), the removal rate can be slightly inhibited, but the tetracycline removal rate can still be kept to be more than 87% within 60 min. Compared with the traditional electro-Fenton, the pH value is expanded from 3 which is most suitable to 2-10. The protection of the shell layer enables more soluble Fe in the reaction2+So that iron mud (Fe) is not generated in the reaction process3+) This is significant for practical engineering applications. And testing the concentration of metal ions in the reacted solution by utilizing an atomic absorption spectrum, wherein Mn/Fe ions are detected, and the reaction solution is not dissolved out due to the protection of a shell layer.
5mg of MnFe in example 1 above was taken3O4Adding 1mL of ethanol into the sample, dispersing, dripping 10 microliters of ethanol into the center of a glassy carbon electrode to serve as a working electrode, establishing a three-electrode system by taking Pt as an auxiliary electrode and Hg/HgO as a reference electrode, and simultaneously inserting Na containing 0.1M2SO4The electrolytic solution was subjected to electrochemical testing. The electro-catalytic activity and the cycling stability of the catalyst are tested by adopting an electrochemical workstation (CHI-760E), and the electrolyte is O2Saturated 0.1MNa2SO4Solution and 1M KOH solution, scan rate 10mV s-1. Electrochemical tests are carried out to obtain a graph 5, and as can be seen from the graph 5, the core-shell catalyst has a pair of very symmetrical oxidation-reduction peaks (metal active centers), the upper half part of the graph is an oxidation peak participating in the reaction, the lower half part of the graph is a reduction peak participating in the reaction, and the limiting current density is as high as 0.4mA/cm2It can be shown that the catalyst has good ORR characteristics andand (4) cycling stability.
And testing the voltage curve of the core-shell catalyst along with the change of time by adopting an electrochemical workstation. The voltage change curves of different current densities are adjusted to obtain a graph 6, and the graph 6 shows that the voltage keeps stable and constant under different current densities, no attenuation trend exists, the voltage is increased along with the increase of the current density, but the voltage does not decay within a certain time when the same current density is small, so that the MnFe prepared by the invention can be well illustrated3O4The @ PZS core-shell catalyst has the advantages of good stability and durability under different current densities.
5.0mg of MnFe obtained in example 1 were weighed out3O4Adding 1mL of ethanol and 10 mu L of DuPont membrane solution with the mass content of 10% into a @ PZS sample, performing ultrasonic treatment for 30min to uniformly disperse the sample to obtain a catalyst solution, uniformly coating the catalyst solution on a 2 x 2cm Ti plate to form a 0.3cm film serving as a cathode, using a blank (not coated with any catalyst) Ti plate as an anode, and constructing an electrocatalytic reaction device, wherein the single treatment capacity is 500mL and the content of 10mg L-1The electrolyte of the tetracycline waste water adopts 0.1M Na2SO4The container is internally inserted with a positive electrode and a negative electrode, the distance between the two electrodes is 5cm, the container is matched with a DC power supply of Meisheng MS-305D produced by Dongguan Meihao electronic technology limited company, the negative electrode is connected with the cathode, and the positive electrode is connected with the anode. The main body of the sewage is mainly 10mg L-1Tetracycline waste water, in addition to the addition of different ROS shielding agents at the beginning of the reaction to investigate the active substances of the reaction system, wherein tert-butanol is used for shielding hydroxyl free radicals and atomic force H*Methanol is used for shielding sulfate radicals, benzoquinone is used for shielding superoxide radicals, furfural is used for shielding singlet oxygen, catalase is used for shielding hydrogen peroxide, shielding agents are respectively and independently added for exploring the influence of active components on the removal efficiency to obtain a figure 7, the figure 7 is an effect diagram of the core-shell material added with different shielding agents on the inhibition effect of tetracycline, the change curve of the influence of the core-shell material added with different shielding agents on the removal efficiency of tetracycline is tested by utilizing high performance liquid chromatography (the test conditions are consistent with the above conditions), and the fact that compared with a control group (no shielding agent is added), the added shielding agents are all used for shielding the tetracyclinesThe removal of the hormone has inhibitory action, and the inhibitory action is ranked from large to small: p-benzoquinone > furfural > methanol > catalase > tert-butanol, and the sequence of the active components contributing in the electrocatalysis system is as follows: superoxide radical > singlet oxygen > hydrogen peroxide > hydroxyl radical/atomic force H*。
It can be seen that the core-shell material can promote the system to generate conventional free radicals of hydroxyl free radical (tert-butyl alcohol) and sulfate free radical (methanol), and can also generate non-free radical superoxide free radical (benzoquinone), singlet oxygen (furfural) and atomic force H*(tert-butyl alcohol) multiple ROS, the core-shell catalyst can realize the coupling of free radicals and non-free radicals to generate multiple ROS, and the multiple ROS can synergistically and rapidly degrade pollutants in the wastewater. The p-benzoquinone has the greatest influence on the removal of tetracycline, the superoxide radical is the main ROS, a reduction channel for activating molecular oxygen by a single electron is provided, and the conventional free radicals (hydroxyl free radicals and sulfate free radicals) can be generated only through a 2-electron reduction process with other common electrocatalytic systems*) Because the survival time of free radicals in water is extremely short, long-term existing non-free radicals have higher oxidative degradation efficiency on pollutants in water, the invention can couple the free radicals with the non-free radicals to have longer-acting degradation efficiency, can finish the degradation of tetracycline within 30min, has the removal efficiency of more than 99 percent and the mineralization efficiency of 74.5 percent, can react under wider pH conditions, does not need to adjust the pH of effluent before and after the reaction, saves the addition of chemical agents, and is more suitable for industrial application. And a large amount of bubble formation was observed on the cathode throughout the process, water was also able to generate H on the cathode by 1-electron activation2。
Example 2
A preparation method of a core-shell catalyst for electrocatalysis synergetic hydrogen production comprises the following steps:
1) 0.628g FeCl was added to a 50mL beaker3·6H2O,1.0g MnCl2·4H2O and40mL of ethylene glycol is vigorously stirred to be bright yellow, 3.6g of NaAC is added, 10mL of ethylene glycol is added after uniform stirring to obtain dark green solution, the dark green solution is poured into a 50mL of polytetrafluoroethylene reaction kettle at the temperature of 200 ℃ for 12h, the solution is cooled and then is washed by ethanol for 3 times and then is dried in vacuum to obtain bimetal MnFe3O4And (4) nano microspheres.
2) 20mg of hexachlorocyclotriphosphazene serving as an N source and a P source and 45mg of thiourea serving as an S source are adopted as a heteroatom shell layer, and 50mg of the bimetallic MnFe3O4And (3) completely dissolving and uniformly dispersing the nano microspheres in 15mL of ethanol and tetrahydrofuran which are in a mass ratio of 1:1 as solvents by ultrasonic waves (50Hz) for 5 min. Then the mixture is sealed by a polyethylene film, and 3mL of triethylamine is quickly injected by an injector to be used as an acid-binding agent to form white emulsion. Then continuously reacting for 8h by magnetic stirring, finally centrifuging for 10min at 8000rpm, washing with ethanol and deionized water for 2 times respectively, and drying the final product in a vacuum drying oven at 40 ℃. Obtaining the bimetallic core-shell catalyst (MnFe)3O4@PZS)。
FIG. 8 shows MnFe core-shell catalyst for electrocatalytic hydrogen production prepared in example 23O4TEM image of @ PZS. The core diameter of the core-shell material is 200 +/-20 nm, and the shell thickness is 20 +/-0.5 nm. Successfully synthesizes the nuclear shell microsphere MnFe on the surface3O4@PZS。
And (3) taking 10mg of the obtained sample, adding 1mL of ethanol and 10 mu L of Nafion solution with the mass fraction of 10%, performing ultrasonic treatment to uniformly disperse the sample, taking 10 mu L of the obtained catalyst solution, dripping the catalyst solution on a glassy carbon electrode, and testing the electrochemical property of the glassy carbon electrode by adopting cyclic voltammetry, wherein the core-shell catalyst can be seen to keep good redox characteristics and has good reversibility in fig. 8. And found a large amount of bubbles generated at the cathode, and also generated H at the cathode2。
Example 3
A preparation method of a multi-element heterojunction core-shell catalyst suitable for electro-Fenton comprises the following steps:
1) 0.675g FeCl was added to a 50mL beaker3·6H2O，0.248g MnCl2·4H2O and 40mL of polyvinyl alcohol, stirring vigorously to give a bright yellow color, adding 3.6g of KAC, stirring, adding 10mL of ethylenediamine to obtain a dark green solution, and adding 50mL of polyvinyl alcoholReacting the tetrafluoroethylene in a tetrafluoroethylene reaction kettle for 24 hours at the temperature of 200 ℃, cooling, washing with ethanol for 3 times, and drying in vacuum to obtain a metal microsphere core (MnFe)3O4)。
2) 50mg of hexachlorocyclotriphosphazene is used as a N source and a P source, 112.5mg of sulfuryl diphenol is used as an S source, 250mg of metal microsphere core with the diameter of 50x50 +/-10 nm prepared by the solvothermal method and 30mL of ethanol and tetrahydrofuran with the mass ratio of 1:1 are used as solvents, and the materials are completely dissolved and uniformly dispersed by ultrasound (100Hz) for 5 min. Then sealing the mouth with a preservative film, and quickly injecting 2mL of trimethylamine as an acid-binding agent by using an injector to form white emulsion. Then continuously reacting for 15h by magnetic stirring, finally centrifuging at 8000rpm for 10min, washing with ethanol and deionized water for 2 times, and drying the final product in a vacuum drying oven at 40 ℃ to obtain the core-shell catalyst MnFe for electrocatalysis-synergetic hydrogen production3O4@PZS。
The catalyst obtained in example 3 was subjected to the same degradation test as in example 1, and 5.0mg of a core-shell catalyst (MnFe) for electrocatalytic hydrogen co-production was used3O4@ PZS) sample, 1mL of ethanol and 10 μ L of a dupont membrane solution having a mass content of 10% were added, and subjected to ultrasonic treatment for 30min to be uniformly dispersed, to obtain a catalyst solution, which was uniformly coated on 4 × 4cm carbon paper to serve as a cathode (thickness of 0.2 cm). An electrocatalytic reaction apparatus was set up under laboratory conditions using 2X 2cm of blank carbon paper as anode (no catalyst coating) with a single treatment of 500mL containing 10mg L-1The electrolyte of the tetracycline waste water adopts 0.1M Na2SO4The container is internally inserted with a positive electrode and a negative electrode, the distance between the two electrodes is 5cm, the container is matched with a DC power supply of Meisheng MS-305D produced by Dongguan Meihao electronic technology limited company, the negative electrode is connected with the cathode, and the positive electrode is connected with the anode. The concentration of the target pollutant tetracycline is detected by using high performance liquid chromatography, a water sample in a 1mL container is taken at regular intervals to test the concentration of the target pollutant, 33% of acetonitrile and 67% of oxalic acid are adopted as a mobile phase, the flow is 1uL/min, the absorbance is 320 to test the degradation concentration of the tetracycline, and the tetracycline can still be completely removed within 30 min.
The embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. The core-shell catalyst for electrocatalysis synergetic hydrogen production is characterized in that MnFe formed by bimetal polymerization of Mn and Fe3O4The nano-microsphere is used as a core, and hetero atoms N, P and S are co-doped to form a shell layer; the core-shell structure is formed by N and P source hexachlorocyclotriphosphazene, S source thioacetamide or thiourea and MnFe3O4The nano-microsphere is obtained by reaction after ultrasonic treatment in a solvent.
2. The core-shell catalyst for electrocatalytic hydrogen production as set forth in claim 1, wherein the diameter of the core-shell catalyst for electrocatalytic hydrogen production is 100-200nm, and the thickness of the shell layer is 20 ± 0.5 nm.
3. The preparation method of the core-shell catalyst for electrocatalytic synergetic hydrogen production as recited in claim 1, characterized by comprising the steps of:
1)MnFe3O4preparing the nano microspheres: FeCl is added3·6H2O and MnCl2·4H2Adding a reducing agent into O for dispersing, stirring to be bright yellow, adding strong base and weak acid salt, uniformly stirring, adding organic base, reacting for 8-24h at the temperature of 120-200 ℃ in a reaction kettle, cooling, cleaning and drying to obtain MnFe3O4Nano-microspheres; the reducing agent is one or more of ethylene glycol, glycerol, propylene glycol and polyvinyl alcohol;
2) preparing a core-shell catalyst for electrocatalysis synergetic hydrogen production: according to parts by mass, 10-50 parts of N and P source hexachlorocyclotriphosphazene, 22.5-112.5 parts of S source thioacetamide or thiourea and 50-250 parts of MnFe3O4Adding the nano microspheres into a solvent, and performing ultrasonic treatment to realize dissolution and uniform dispersion; adding an acid-binding agent to form white emulsion; stirring for reaction for 8-12h, centrifuging, washing and drying; to obtain a solution for electrocatalysisA core-shell catalyst for producing hydrogen by chemical synergy.
4. The method for preparing the core-shell catalyst for electrocatalytic synergetic hydrogen production as recited in claim 3, wherein the strong and weak acid salt is sodium acetate (NaAC) or potassium acetate (KAC), and the amount of the strong and weak acid salt added is FeCl3·6H2The addition amount of O is 3-5 times; the FeCl3·6H2O and MnCl2·4H2The mass ratio of O is 1:8-8: 1; adding 0.125-0.5mmol FeCl into each milliliter of reducing agent3·6H2O。
5. The preparation method of the core-shell catalyst for electrocatalytic synergetic hydrogen production according to claim 3, wherein the organic base is ethylenediamine, ethylamine, trimethylamine or polyethylene glycol; the addition amount of the organic base is FeCl3·6H20.5-3 times of the mass of O.
6. The preparation method of the core-shell catalyst for electrocatalytic synergetic hydrogen production according to claim 3, wherein the solvent is a mixed solution of ethanol and tetrahydrofuran or ethanol and acetone; the mass ratio of the ethanol to the tetrahydrofuran or the ethanol to the acetone is 1:3-3: 1; the acid-binding agent is tertiary amine substance, and 0.15-0.5 ml of the acid-binding agent is added into each milligram of hexachlorocyclotriphosphazene.
7. The preparation method of the core-shell catalyst for electrocatalytic synergetic hydrogen production according to claim 6, wherein the tertiary amine is triethylamine, trimethylamine or tributylamine.
8. The preparation method of the core-shell catalyst for electrocatalysis synergetic hydrogen production according to claim 1, wherein in the step 1), the cleaning and drying after cooling means cleaning with ethanol for a plurality of times after cooling, and drying in vacuum;
in the step 2), the washing and drying after centrifugation is repeatedly washing by using ethanol and deionized water after centrifugation, wherein the drying is carried out in a vacuum drying oven at 40-60 ℃.
9. The application of the core-shell catalyst for electrocatalytic synergetic hydrogen production in sewage treatment as recited in claim 1 or 2, wherein: dispersing a core-shell catalyst for producing hydrogen by electrocatalysis in cooperation with hydrogen in a dispersing agent to obtain a mixed solution, performing ultrasonic treatment, uniformly dispersing, and uniformly coating the obtained mixture on carbon paper, using a carbon felt or a Ti plate as a modified cathode working electrode, using the carbon paper, the carbon felt or the Ti plate as an anode, connecting a cathode with a direct-current power supply cathode, connecting an anode with a positive level, connecting a power supply, building an electrocatalysis reaction device with the cathode and the anode in cooperation, and applying current to catalyze and degrade sewage.
10. The application of the core-shell catalyst for electrocatalysis synergetic hydrogen production in sewage treatment as recited in claim 9, which is characterized in that: 5-20mg of core-shell catalyst for electrocatalysis and hydrogen generation is dispersed in each 1-4mL of dispersant; the dispersant is one or more of ethanol, methanol, acetone or water solution; the binder is a DuPont film or polytetrafluoroethylene; dispersing and adding 5-10 mu L of dispersant into 1-4mL of dispersant; coating 1.25-5mg of the mixture on each square centimeter of the modified cathode working electrode, wherein the thickness of the coating layer is kept 0.5-1 mm; the current is from a voltage-stabilizing direct-current power supply and is 5-100 mA; the sewage is municipal sewage, agricultural wastewater and medical wastewater.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818796A (en) * | 2023-01-10 | 2023-03-21 | 东莞理工学院 | Zr metal atom doped Ti 4 O 7 Preparation of composite electrode and method of use thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070027028A1 (en) * | 2003-08-14 | 2007-02-01 | Pears David A | Microencapsulated catalyst-ligand system, methods of preparation and methods of use thereof |
| CN101070389A (en) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | Hollow micro-ball containing phosphazene and preparing method |
| CN107039660A (en) * | 2017-06-07 | 2017-08-11 | 北京化工大学常州先进材料研究院 | The preparation of the porous carbon microsphere of Fe NPS codopes and its it is used as the application of ORR catalyst |
| CN107126974A (en) * | 2017-06-07 | 2017-09-05 | 北京化工大学常州先进材料研究院 | ZIF 67 modifies Fe3O4The preparation and its application of ORR catalyst of@PZS core-shell particles |
| CN108479724A (en) * | 2018-01-30 | 2018-09-04 | 郑州大学 | A kind of preparation method with high magnetic responsiveness iron-iron oxide@polyphosphazene magnetic nano chains |
| CN108704621A (en) * | 2018-06-05 | 2018-10-26 | 东华理工大学 | A kind of amidoxime group core-shell structure magnetic poly phosphazene nanoparticle and its preparation and the application as uranium absorption agent |
| CN109705329A (en) * | 2018-12-28 | 2019-05-03 | 广东工业大学 | A kind of ring opening catalyst and its preparation method and application that can be recycled |
-
2021
- 2021-01-25 CN CN202110094984.4A patent/CN112774713A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070027028A1 (en) * | 2003-08-14 | 2007-02-01 | Pears David A | Microencapsulated catalyst-ligand system, methods of preparation and methods of use thereof |
| CN101070389A (en) * | 2007-06-21 | 2007-11-14 | 上海交通大学 | Hollow micro-ball containing phosphazene and preparing method |
| CN107039660A (en) * | 2017-06-07 | 2017-08-11 | 北京化工大学常州先进材料研究院 | The preparation of the porous carbon microsphere of Fe NPS codopes and its it is used as the application of ORR catalyst |
| CN107126974A (en) * | 2017-06-07 | 2017-09-05 | 北京化工大学常州先进材料研究院 | ZIF 67 modifies Fe3O4The preparation and its application of ORR catalyst of@PZS core-shell particles |
| CN108479724A (en) * | 2018-01-30 | 2018-09-04 | 郑州大学 | A kind of preparation method with high magnetic responsiveness iron-iron oxide@polyphosphazene magnetic nano chains |
| CN108704621A (en) * | 2018-06-05 | 2018-10-26 | 东华理工大学 | A kind of amidoxime group core-shell structure magnetic poly phosphazene nanoparticle and its preparation and the application as uranium absorption agent |
| CN109705329A (en) * | 2018-12-28 | 2019-05-03 | 广东工业大学 | A kind of ring opening catalyst and its preparation method and application that can be recycled |
Non-Patent Citations (8)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115818796A (en) * | 2023-01-10 | 2023-03-21 | 东莞理工学院 | Zr metal atom doped Ti 4 O 7 Preparation of composite electrode and method of use thereof |
| CN115818796B (en) * | 2023-01-10 | 2024-05-24 | 东莞理工学院 | Zr metal atom doped Ti4O7Preparation and application methods of composite electrode |
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