CN111589463B - Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof - Google Patents
Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01J35/23—
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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/22—Carbides
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a nanoparticle photo-thermal catalyst of iron carbide compounded titanium monoxide and a preparation method thereof, and the nanoparticle photo-thermal catalyst is prepared by firstly mixing and drying P25, PAN, DMF and ferric nitrate, calcining for 4 hours at 800-850 ℃ in an ammonia atmosphere, taking out a sample and grinding the sample into powder, so that the nanoparticle photo-thermal catalyst of iron carbide compounded titanium monoxide is obtained, and the nanoparticle photo-thermal catalyst has the characteristics of wide light absorption range, high methane yield, low resistivity, capability of quickly transferring carriers, high photo-generated carrier separation capability, low carrier recombination rate, good carbon dioxide reduction high cycle stability and the like, and can be used for photo-thermally catalyzing carbon dioxide to reduce methane, wherein the speed can reach 37.67 mu mol/g at most ‑1 ·h ‑1 . The preparation method has the advantages of simple operation, low cost, nontoxic raw materials and production according with the environmental protection concept.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide and a preparation method thereof.
Background
With the rapid development of the global population and the world economy, the demand of human beings for fossil energy is increasing.However, the increasing exhaustion of fossil fuels such as petroleum, coal, and natural gas, and the climate change caused by global greenhouse effect, the development of renewable clean energy is urgent. Chemical reduction is a key process of the earth's carbon cycle and is the developing direction of future solar energy capture and storage technologies. Photosynthesis converts carbon dioxide into carbohydrates, maintaining almost all of the life on earth. Inspired by this, researchers have attempted to develop photosynthetic simulation systems to reduce carbon dioxide to fuels and valuable chemical feedstocks. However, limiting the current stage of photocatalytic CO 2 Depending on three main factors: (1) the photocatalyst absorbs solar energy of a wider spectrum; (2) efficient separation and transfer of photogenerated carriers (electron-hole pairs); (3) the surface of the photocatalyst effectively catalyzes oxidation-reduction reaction. Ti-based materials are currently the most studied catalytic materials in the field of photocatalysis. Photocatalytic TiO was discovered since 1972 by Honda and Fujishima et al 2 After water is photolyzed by the single crystal electrode, a large number of Ti-based materials are widely studied. However, since conventional TiO2 photocatalysts cannot absorb visible light or even near infrared light, and since TiO 2 The conduction band potential of (C) is too low (-0.1eV vsNHE), and is far from satisfying CO 2 Reduction to CO (-0.52eV vs NHE) or CH 4 Potential of (-0.24eV vs NHE), and thus for the modified Ti-based materials for the reduction of CO 2 Is necessary. Generally, four typical strategies are employed to improve their catalytic capacity: (1) doping a semiconductor with a noble metal/non-noble metal; (2) compounding two different semiconductors to form a multi-band gap material; (3) the optimal crystal face of the catalytic reaction is exposed for improving the reaction efficiency; (4) oxygen vacancies are created by using low valence Ti oxides/nitrides to enhance photocatalytic performance.
However, the use of energy is very low because only the energy of light is used to excite the photo-generated electron-hole pairs, and most of the light energy is converted into heat energy during the whole process of illumination, and most of the heat energy is dissipated due to reaction, so that the overall utilization rate of sunlight is very low. Recently, a large number of researchers have started research on photothermal catalysis to achieve maximum utilization efficiency of sunlight. Fischer-tropsch synthesis (FTS) converts carbon monoxide from fossil fuels or biomass feedstocks into valuable hydrocarbons and oxygenates, and FTS has been used commercially for over 50 years. The most commonly used catalysts in FTS are the group VIIIB transition metals, especially iron, cobalt, nickel and ruthenium. These catalysts differ in CO hydrogenation activity and product selectivity, and several of these metals are often used together (in alloy form) to achieve high CO conversion or to enhance selectivity to a particular product or group of products. Iron-based catalysts exhibit good initial selectivity to light olefins during FTS. During FTS, metallic iron is gradually converted to iron carbide during the reaction (this is considered to be the true active phase of the iron-based FTS catalyst). Iron carbide has relatively mild hydrogenation capability and the ability to promote C-C coupling reactions.
Disclosure of Invention
One of the purposes of the invention is to solve the technical problems of poor photocatalytic carbon dioxide reduction performance caused by limited light absorption range, few surface active sites, easy recombination of photon-generated carriers, low conduction band position and the like of the traditional Ti-based material serving as a photocatalytic material, and provide the iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst which has the advantages of wide light absorption range, full light absorption range, difficult recombination of carriers and the like, and the catalyst has the advantages of wide light absorption range, full light spectrum, difficult recombination of carriers and the like at lambda>Under the irradiation of simulated sunlight with the wavelength of 420nm, the highest methane production rate can reach 37.67 mu mol.h -1 ·g -1 。
The invention also aims to provide the preparation method of the nanoparticle photo-thermal catalyst for compounding the iron carbide and the titanium monoxide.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide, which comprises the following steps:
(1) dissolving PAN in DMF solution, heating overnight, adding ferric nitrate nonahydrate, stirring uniformly to obtain orange yellow solution, adding titanium dioxide P25, stirring for reaction, and drying;
(2) putting the dried sample obtained in the step (1) into NH 3 And (3) heating and calcining under the atmosphere to obtain a blocky product, and grinding the blocky product into powder to obtain the target product.
Further, in the step (1), the ratio of the addition amounts of PAN, iron nitrate nonahydrate and titanium dioxide P25 was 0.8 g: (1-3) mmol: (0.03-0.05) g.
Further, in the step (1), the concentration of the DMF solution is 99.5% (mass fraction), and the ratio of the concentration to the addition amount of PAN is 10 mL: 0.8 g.
Further, in the step (1), the process conditions for heating overnight are as follows: heated in an oil bath at 60 ℃ overnight.
Further, in the step (1), the reaction time is 24 hours under stirring.
Further, in the step (1), the drying temperature is 60 ℃.
Further, the process conditions of temperature-rising calcination are as follows: heating to 800-850 ℃ at a heating rate of 2 ℃/min, and calcining for 3-4 h.
In the invention, the ternary carbon bridge chain Fe is synthesized by a one-step burning method 2 C/C/TiO complexes in NH 3 Calcination was carried out at 800 ℃ in an atmosphere. The prepared composite nano-fiber is a stable photo-thermal catalyst and can effectively realize CO 2 The photocatalytic reduction is suitable for the ultraviolet-near infrared spectrum of solar radiation.
The whole synthesis process is as follows:
p25 is nanometer level photosensitive titanium dioxide, and its tiny particle is favorable to produce titanium monoxide by combining reaction with ammonia gas;
② because the reaction for synthesizing titanium monoxide needs carbon to participate in P25 reduction, Fe can be combined with C to form Fe at the same time 2 C；
Thirdly, in the process of synthesis, because of the existence of PAN, Fe is burnt at high temperature 2 The carbon layer is formed on the C/TiO, so that the specific surface area of the catalyst is increased
The second technical scheme of the invention provides a nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide, which is prepared by the preparation method, and the particle size of the nanoparticle photo-thermal catalyst is 5-10 nm.
The prepared catalyst has four elements of Fe, C, Ti and O, wherein the iron carbide and the titanium monoxide are in nanoparticle structures, the particle size is 5-10nm, the molybdenum nitride nanoparticles are loaded on the surface of the carbon nitride nanosheet layer, and P25 and Fe (NO) are contained in the nanoparticle photo-thermal catalyst of iron carbide compounded with the titanium monoxide 3 ) 3 Amount of (b), as P25: fe (NO) 3 ) 3 The mass ratio of (1): 10-30 is preferably 1: and (5) calculating the proportion of 20. The absorption range of the catalyst is full-spectrum absorption, the catalyst is used for preparing methane by photo-thermal catalytic reduction of carbon dioxide, and the maximum methane production rate can reach 37.67 mu mol g under the irradiation of simulated sunlight with lambda more than 420nm -1 ·h -1 。
The iron carbide-titanium monoxide composite nanoparticle obtained by the invention is used as a novel photo-thermal catalyst, and has the following advantages in the application of photo-thermal catalytic carbon dioxide reduction:
due to the existence of the carbon substrate in the material, a larger specific surface area is provided, and the electron transmission rate is improved;
due to the small particle size of the material, more active sites are provided;
the titanium monoxide has stronger light absorption capacity as a novel titanium material;
the iron carbide as the transition metal carbide has high conductivity and is beneficial to the transmission of electrons, thereby promoting the generation of methane;
titanium monoxide has low resistance as a low-valence transition metal oxide, which is favorable for the transfer of current carriers, thereby promoting the generation of methane;
the titanium atom of titanium monoxide may serve as an active site for converting a proton into a methyl radical.
The preparation method comprises the steps of mixing and drying P25, PAN, DMF and ferric nitrate, calcining for 4 hours at 800 ℃ in an ammonia atmosphere, taking out a sample, grinding into powder to obtain the iron carbide-titanium monoxide composite nanoparticle photo-thermal catalyst, wherein the iron carbide-titanium monoxide composite nanoparticle photo-thermal catalyst has the advantages of wide light absorption range, high methane yield, low resistivity and rapid transfer of current-carryingThe catalyst has the characteristics of high carrier separating capability, low carrier recombination rate, good carbon dioxide reduction and high cycle stability, and the like, and can be used for reducing methane by photo-thermal catalytic carbon dioxide at the highest rate of 37.67 mu mol g -1 ·h -1 . The preparation method has the advantages of simple operation, low cost, nontoxic raw materials and production according with the environmental protection concept.
Compared with the prior art, the invention has the following advantages:
(1) because the iron carbide composite titanium monoxide nano particles are synthesized by adopting a one-step calcination method in the preparation process, compared with bulk phase materials, the ultra-large specific surface area can enable a large number of surface atoms to be used as active sites, and is used for improving the catalytic process and the catalytic activity and beneficial to constructing a clear atomic structure model.
(2) The titanium-based catalyst is combined with the traditional thermocatalytic material iron carbide, and the iron carbide composite titanium monoxide nano particles are obtained by an ammonia one-step calcination method, so that the full spectrum absorption and utilization are realized, the development of the photothermal catalyst is promoted, and the obvious practical application of more fully utilizing sunlight is realized.
(3) Compared with pure P25, the iron carbide and titanium monoxide compounded nanoparticle photocatalyst has the characteristics of wide light absorption range, high carbon dioxide reduction performance, low resistivity, capability of rapidly transferring self-current, high photogeneration carrier separation capability, low carrier recombination rate and good carbon dioxide reduction cycle stability.
(4) The invention takes carbon calcined by PAN as a basic framework, iron carbide and titanium monoxide nanoparticles are distributed on the base material, the morphological characteristics are uniformly and regularly distributed, high specific surface area is provided for the material to better absorb sunlight, the preparation process is very simple, the method is suitable for industrial mass production, and the method has high economic and practical values.
(5) Iron carbide is applied to the photo-thermal catalysis direction for the first time to synthesize the iron carbide/carbon/titanium monoxide sandwich structure, the material is a noble metal-free photo-thermal catalysis material absorbing the full spectrum, the addition of the iron carbide effectively promotes the C-C coupling of methyl free radicals, and the high efficiency is shownThe carbon dioxide has reduction performance, shows good photo-thermal catalytic activity in an ultraviolet-near infrared region, is used for photo-catalytically reducing carbon dioxide to generate methane under the irradiation of visible light, and has the highest methane generation rate of 37.67 mu mol g -1 ·h -1 。
(6) The catalyst has light absorption range of full spectrum, carrier recombination difficulty and lambda>Under the irradiation of simulated sunlight with the wavelength of 420nm, the highest methane production rate can reach 37.67 mu mol.h -1 ·g -1 . The preparation method of the catalyst has the advantages of low preparation cost, batch production and the like because the raw materials are easily obtained, the operation is simple, and the experimental conditions are easily achieved.
Drawings
FIG. 1 shows Fe obtained in example 1 2 X-ray electron diffraction pattern of C/C/TiO nanoparticle photo-thermal catalyst;
FIG. 2 shows Fe obtained in example 1 2 C/C/TiO nanoparticles, TiO/C UV-visible diffuse reflectance pattern prepared in comparative example 2;
FIG. 3 shows Fe obtained in example 1 2 C/C/TiO nanoparticles, Fe obtained in comparative example 1 2 A photocurrent performance diagram of the C/C nanoparticle photo-thermal catalyst when the bias voltage adopted by the photocurrent is 0V;
FIG. 4 shows Fe obtained in example 1 2 C/C/TiO nanoparticles, Fe obtained in comparative example 1 2 C/C, electrochemical impedance of TiO/C nanoparticle photothermal catalyst obtained in comparative example 2;
FIG. 5 shows Fe obtained in example 1 2 C/C/TiO nanoparticles, Fe obtained in comparative example 1 2 C/C, the methane yield of the TiO/C nanoparticle photo-thermal catalyst obtained in the comparative example 2 and the time;
fig. 6 is an X-ray electron diffraction pattern of the catalyst prepared in comparative example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The electrochemical workstation used for testing the electrochemical performance of the iron carbide composite titanium monoxide photothermal catalysis carbon dioxide reduction material with effective photon-generated carrier separation and transfer performance in the embodiment of the invention is an Aiwei electrochemical workstation with the model IviumStat.h. UV-visible diffuse reflectance passes the UV-2800 test; fluorescence spectra were measured by FLS 980; the carbon dioxide reduction performance test adopts Shimadzu GC2014 gas chromatography.
The electrochemical performance test method in each embodiment of the invention is as follows:
mixing 7.5mg of nanoparticle photocatalyst, 1mg of ethyl cellulose, 1mL of alpha-terpineol and 0.5mL of ethanol, and then carrying out ultrasonic treatment for 12h with the power of 60W and the frequency of 40KHz to obtain slurry;
coating the obtained slurry on FTO glass, controlling the coating thickness to be 0.5-1mm, drying in an oven at 60 ℃ to obtain an electrochemical testing working electrode, and then testing at an electrochemical workstation to carry out electrochemical performance.
In the following examples, unless otherwise specified, the starting materials or the treatment techniques are all conventional and commercially available materials or conventional treatment techniques in the art.
Example 1:
a nanoparticle photocatalyst of iron carbide and titanium monoxide is mainly prepared from four main elements of Fe, C, Ti and O by the following steps:
(1)Fe 2 preparation of C/C/TiO precursor
0.8g of PAN is dissolved in 10mL of DMF solution and heated in an oil bath at 60 ℃ overnight, then x mmol of iron nitrate nonahydrate (x ═ 1, 2, 3) is added, after the solution has stirred uniformly to give an orange-yellow solution, 0.04g of P25 is added, and after stirring for 24h, it is dried at 60 ℃.
(2)Fe 2 Preparation of C/C/TiO
Putting the dried sample into a crucible and then putting into NH 3 Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe 2 C/C/TiO bulk product, grinding into powder in a mortar,to obtain Fe 2 C/C/TiO powder.
Comparative example 1:
Fe 2 C/C preparation:
0.8g of PAN is dissolved in 10mL of DMF solution and heated in an oil bath at 60 ℃ overnight, then x mmol of iron nitrate nonahydrate (x ═ 1, 2, 3) is added, and after the solution is stirred well and becomes an orange-yellow solution, it is dried at 60 ℃. Putting the dried sample into a crucible and then putting into NH 3 Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe 2 C/C lump product, ground into powder in mortar to obtain Fe 2 C/C powder.
Comparative example 2:
preparation of TiO/C powder:
0.8g of PAN is dissolved in 10mL of DMF solution, heated in an oil bath at 60 ℃ overnight, and dried at 60 ℃ after the solution is stirred uniformly to form a transparent light yellow solution. Putting the dried sample into a crucible and then putting into NH 3 Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain a TiO/C blocky product, and grinding the blocky product into powder in a mortar to obtain TiO/C powder.
Comparative example 3:
preparation of TiO/C at 700 deg.C
0.8g of PAN is dissolved in 10mL of DMF solution, heated in an oil bath at 60 ℃ overnight, and dried at 60 ℃ after the solution is uniformly stirred to form a transparent light yellow solution. Putting the dried sample into a crucible and then putting into NH 3 Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 700 ℃ and calcining for 4h to obtain a TiO/C (700 ℃) blocky product, and grinding the blocky product into powder in a mortar to obtain TiO/C (700 ℃) powder.
Comparative example 4:
preparation of Fe by addition of 5mmol Fe 2 C/C/TiO-5：
0.8g of PAN was dissolved in 10mL of DMF solution and heated in an oil bath at 60 ℃ overnight, then 5mmol of ferric nitrate nonahydrate was added, 0.04g of P25 was added after the solution was stirred uniformly to give an orange-yellow solution, and after stirring for 24 hours, it was dried at 60 ℃.
Placing the dried sample into a crucible and then addingNH 3 Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe 2 The C/C/TiO-5 lumpy product was ground in a mortar to give Fe 2 C/C/TiO-5 powder.
Carbon dioxide reduction Performance test
5mg of TiO/C obtained in comparative example 2 and Fe obtained in comparative example 1 were weighed out separately 2 Respectively putting the iron carbide and titanium monoxide composite nano-particle photocatalyst finally obtained in the example 1 into a reactor, respectively adding 10mL of triethanolamine aqueous solution (the triethanolamine aqueous solution is calculated according to the volume ratio, wherein the ratio of triethanolamine to water is 1:4), then controlling the power to be 60W and the frequency to be 40KHz, carrying out ultrasonic treatment for 10min, vacuumizing by using a vacuum pump, pumping 80kPa CO2 when the pressure reaches 1.2kPa, and placing the reactor under the irradiation of a 300W xenon lamp (with a 420nm cut-off filter) to carry out a carbon dioxide reduction test after the pressure is maintained at about 50 kPa. Wherein the triethanolamine acts as a sacrificial agent for sacrificing holes, thereby facilitating the combination of electrons and CO2 to form CO, CH 3 Free radicals, etc.
The nano-particle photo-thermal catalyst compounded by iron carbide and titanium monoxide is used for preparing methane by photo-thermal catalytic reduction of carbon dioxide, the dosage of the catalyst is 5mg, the 2-hour yield of the methane prepared by catalytic reduction of carbon dioxide is 75.34 mu mol, and the methane production rate is 37.67 mu mol g -1 ·h -1 ；
Fe obtained in comparative example 1 2 C/C as control, Fe 2 The dosage of C/C as the catalyst is 5mg, the 2h yield of the methane prepared by catalyzing the reduction of carbon dioxide is 12.42 mu mol, and the methane production rate is 7.72 mu mol g -1 ·h -1 。
The TiO/C obtained in comparative example 2 is used as a control, the dosage of the TiO/C used as a catalyst is 5mg, the 2h yield of the methane prepared by catalyzing carbon dioxide reduction is 12.68 mu mol, and the methane production rate is 6.34 mu mol g -1 ·h -1
Fe obtained in comparative example 4 2 C/C/TiO-5 as control, Fe 2 The dosage of C/C/TiO-5 as a catalyst is 5mg, the 2h yield of the methane prepared by catalyzing the reduction of carbon dioxide is 12.84 mu mol, and the methane production rate is 6.42 mumol·g -1 ·h -1
The above results indicate that the carbon dioxide reduction performance of the loaded iron carbide/carbon/titanium monoxide composite is much higher than that of iron carbide and titanium monoxide, probably due to the simultaneous utilization of the heat generated by the composite for photons and light.
The Fe obtained in example 1 was subjected to X-ray diffractometry (model: Burker-AXS D8, manufacturer: Bruker, Germany) 2 The XRD pattern obtained from the C/C/TiO nanoparticles is shown in FIG. 1, the abscissa is 2 θ angle, the ordinate is diffraction peak intensity, and Fe obtained in example 1 2 The C/C/TiO nanoparticle photo-thermal catalyst has TiO and Fe 2 Peak of C, thereby indicating TiO and Fe 2 C forms a composite material. The XRD pattern obtained for TiO/C (700 ℃ C.) obtained in comparative example 3 is shown in FIG. 6, and does not allow complete conversion of P25 to TiO at 700 ℃ indicating that the temperature needs to be between 800 ℃ and 850 ℃.
Fe obtained in example 1 was subjected to UV-visible spectrophotometer (model: UV-2401PC, manufacturer: Shimadzu, Japan) 2 The ultraviolet-visible diffuse reflection patterns of the C/C/TiO nanoparticles and the TiO/C nanoparticle photothermal catalyst obtained in comparative example 2 are shown in FIG. 2, the abscissa is the wavelength and the ordinate is the absorption rate, and it can be seen from FIG. 2 that Fe is 2 C/C/TiO nanoparticles, red-shifted absorption edge, thus indicating Fe 2 The light absorption range of the C/C/TiO nano particle composite material is widened.
Fe obtained in example 1 was subjected to electrochemical working station (model: IviumStat. h, manufacturer: Dutch Avicennia indica) 2 C/C/TiO nanoparticles, Fe obtained in comparative example 1 2 C/C and TiO/C obtained in comparative example 2 were measured, respectively, and the obtained photocurrent was measured with a bias voltage of 0V, and the photocurrent performance graph is shown in fig. 3, in which the abscissa is time and the ordinate is photocurrent, and it can be seen from fig. 3 that no current was generated when the lamp was turned off and photocurrent was generated when the lamp was turned on, thus indicating that photo-generated electron-hole pairs were separated under the excitation of light, resulting in the generation of current.
An electrochemical workstation (model: IviumStat. h, manufacturer: Netherlands) is usedEverlasting fern) to Fe obtained in example 1 2 C/C/TiO nanoparticles, Fe obtained in comparative example 1 2 C/C and TiO/C obtained in comparative example 2 respectively, and the alternating current impedance diagram obtained at the frequency of 1000000-0.01Hz is shown in FIG. 4, the abscissa is real part impedance, and the ordinate is imaginary part impedance, and it can be seen from FIG. 4 that the radius of the Quite spectrum semicircle of the iron carbide/titanium monoxide composite material is smaller than that of a pure sample, thereby showing that the impedance of the iron carbide/titanium monoxide composite material is smaller, and the photon-generated carrier transfer is facilitated.
5mg of TiO/C obtained in the comparative example 2, Fe2/C obtained in the comparative example 1 and the iron carbide composite titanium monoxide nano-particle photocatalyst finally obtained in the example 1 are respectively weighed in a reactor by adopting a gas chromatography (model: GC2014, manufacturer: Shimadzu) under the conditions that the temperature of a column box is 55 ℃ and the FID temperature is 380 ℃, 10mL of triethanolamine aqueous solution (the volume ratio of the triethanolamine aqueous solution is 1:4) is respectively added, then ultrasonic treatment is carried out for 10min under the conditions that the power is controlled to be 60W and the frequency is 40KHz, a vacuum pump is used for vacuumizing, and when the pressure reaches 1.2kPa, CO of 80kPa is added 2 After the pressure was maintained at about 50kPa, the sample was placed under a 300W xenon lamp (with a 420nm cut-off filter) to conduct a carbon dioxide reduction test. 0.6mL of gas is extracted from the reactor every 1h of illumination and is pumped into a gas chromatography for measurement, the obtained methane yield is shown in figure 5, and from figure 5, the hydrogen yield of the carbon nitride supported molybdenum nitride nanoparticle photocatalyst is obviously higher than that of carbon nitride, wherein the iron carbide composite titanium monoxide nanoparticle photo-thermal catalyst obtained in example 1 with the best performance is shown, so that the performance of carbon dioxide reduction of the titanium monoxide is greatly improved by adding the iron carbide.
In conclusion, the nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide has excellent electrochemical performance, and when the nanoparticle photo-thermal catalyst is applied to photo-thermal catalytic carbon dioxide reduction, the maximum methane production rate can reach 37.67 mu mol g -1 ·h -1 . And the preparation method has the characteristics of simple operation and low production cost.
In the above examples, P25 used may be adjusted to 0.03g or 0.05g as necessary, and the calcination temperature may be adjusted to 825 ℃ or 850 ℃ or the like.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of a nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide is characterized by comprising the following steps:
(1) dissolving PAN in a DMF solution, heating overnight, adding ferric nitrate nonahydrate, stirring uniformly to obtain an orange yellow solution, adding titanium dioxide P25, stirring for reaction, and drying;
(2) putting the dried sample obtained in the step (1) into NH 3 And (3) heating and calcining under the atmosphere to obtain a blocky product, and grinding the blocky product into powder to obtain the target product.
2. The method for preparing nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide as claimed in claim 1, wherein in the step (1), the addition ratio of PAN, ferric nitrate nonahydrate and titanium dioxide P25 is 0.8 g: (1-3) mmol: (0.03-0.05) g.
3. The method for preparing nanoparticle photo-thermal catalyst of iron carbide and titanium monoxide as claimed in claim 1, wherein in step (1), the concentration of DMF solution is 99.5%, and the ratio of DMF solution to PAN addition is 10 mL: 0.8 g.
4. The method for preparing nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide as claimed in claim 1, wherein in the step (1), the overnight heating process conditions are as follows: heated in an oil bath at 60 ℃ overnight.
5. The method for preparing the nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide according to claim 1, wherein in the step (1), the stirring reaction time is 24 h.
6. The method for preparing nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide as claimed in claim 1, wherein the drying temperature in step (1) is 60 ℃.
7. The preparation method of the nanoparticle photo-thermal catalyst of iron carbide and titanium monoxide as claimed in claim 1, wherein the process conditions of temperature-rising calcination are as follows: heating to 800-850 ℃ at a heating rate of 2 ℃/min, and calcining for 3-4 h.
8. A nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide, which is prepared by the preparation method of any one of claims 1 to 7, and has a particle size of 5 to 10 nm.
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