CN111589463A - 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
- Publication number
- CN111589463A CN111589463A CN202010161661.8A CN202010161661A CN111589463A CN 111589463 A CN111589463 A CN 111589463A CN 202010161661 A CN202010161661 A CN 202010161661A CN 111589463 A CN111589463 A CN 111589463A
- Authority
- CN
- China
- Prior art keywords
- iron carbide
- photo
- titanium monoxide
- thermal catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910001567 cementite Inorganic materials 0.000 title claims abstract description 45
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 32
- 239000001569 carbon dioxide Substances 0.000 abstract description 26
- 230000009467 reduction Effects 0.000 abstract description 20
- 239000002131 composite material Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 229910017356 Fe2C Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 241000131832 Avicennia Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VKRWBTVMYISSEF-UHFFFAOYSA-N oxygen(2-);titanium(2+) Chemical compound [O-2].[Ti+2] VKRWBTVMYISSEF-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
-
- B01J35/23—
-
- B01J35/61—
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 composite titanium monoxide and a preparation method thereof, wherein P25, PAN, DMF and ferric nitrate are mixed and dried, calcined for 4 hours at 800-850 ℃ in an ammonia atmosphere, a sample is taken out and ground into powder to obtain the nanoparticle photo-thermal catalyst of iron carbide composite titanium monoxide, which 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 is used for photo-thermal catalysisThe methane is reduced by the thermal catalysis of the carbon dioxide, and 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 and 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 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 CO2Depending 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 has been discovered since 1972 by Honda and Fujishima et al2After 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 TiO2The conduction band potential of the carbon nanotube is too low (-0.1eVvsNHE), and the carbon nanotube is far from meeting the requirement of CO2Reduction to CO (-0.52eV vs NHE) or CH4Potential of (-0.24eV vs NHE), and thus for the modified Ti-based materials for the reduction of CO2Is highly desirable. Generally, four typical strategies are employed to improve their catalytic capacity: (1) Doping a semiconductor with 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. The CO hydrogenation activity and product selectivity of these catalysts vary, 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 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 NH3And (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 the PAN solution 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 method2C/C/TiO complexes in NH3Calcination was carried out at 800 ℃ in an atmosphere. The prepared composite nano-fiber is a stable photo-thermal catalyst and can effectively realize CO2By photocatalytic reduction of (D), is suitable forUltraviolet-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 since the reaction for synthesizing titanium monoxide needs carbon to participate in the process of reducing P25, the addition of Fe can combine Fe with C to form Fe2C；
③ in the course of synthesis, due to the presence of PAN, under high temperature ignition in Fe2The 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 has the particle size of 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 monoxide3)3Amount of (c), as P25: fe (NO)3)3The 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 methane production rate can reach 37.67 mu mol g at most under the irradiation of simulated sunlight with lambda being more than 420nm-1·h-1。
The iron carbide composite titanium monoxide nano-particles obtained by the invention are used as a novel photo-thermal catalyst, and have the following advantages in the application of photo-thermal catalytic carbon dioxide reduction:
the carbon substrate exists in the material, so that a larger specific surface area is provided, and the electron transmission rate is improved;
secondly, the material is beneficial to providing more active sites due to small particle size;
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 method comprises the steps of mixing and drying P25, PAN, DMF and ferric nitrate, calcining for 4 hours at 800 ℃ in the atmosphere of ammonia gas, taking out a sample, and grinding the sample into powder to obtain the iron carbide composite titanium monoxide nano-particle photo-thermal catalyst, wherein the iron carbide composite titanium monoxide nano-particle photo-thermal catalyst has the characteristics of wide light absorption range, high methane yield, low resistivity, rapid carrier transfer capability, 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 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, so that the catalytic process is improved, the catalytic activity is improved, and a clear atomic structure model is favorably constructed.
(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, a 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) The 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, the high-efficiency carbon dioxide reduction performance is shown, the better photo-thermal catalysis activity is shown in an ultraviolet-near infrared region, under the irradiation of visible light, the material is used for photo-catalytically reducing carbon dioxide to generate methane, and the methane generation rate can reach 37.67 mu mol g at most-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 12X-ray electron diffraction pattern of C/C/TiO nanoparticle photo-thermal catalyst;
FIG. 2 shows Fe obtained in example 12C/TiO nanoparticles, TiO/C uv-visible diffuse reflectance pattern prepared in comparative example 2;
FIG. 3 shows Fe obtained in example 12C/C/TiO nanoparticles, Fe obtained in comparative example 12A 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 12C/C/TiO nanoparticles, Fe obtained in comparative example 12C/C, comparisonElectrochemical impedance of the TiO/C nanoparticle photothermal catalyst obtained in example 2;
FIG. 5 shows Fe obtained in example 12C/C/TiO nanoparticles, Fe obtained in comparative example 12C/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)Fe2preparation 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)Fe2C/C/TiO preparation
Putting the dried sample into a crucible and then putting into NH3Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe2The C/C/TiO lumpy product was ground in a mortar to give Fe2C/C/TiO powder.
Comparative example 1:
Fe2C/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 NH3Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe2C/C lump product, ground into powder in mortar to obtain Fe2C/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 NH3Controlling 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 PAN was dissolved in 10mL DMF and heated in an oil bath at 60 ℃ overnight to dissolveThe solution is evenly stirred to form a transparent light yellow solution and then is dried at the temperature of 60 ℃. Putting the dried sample into a crucible and then putting into NH3Controlling 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 Fe2C/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 ℃.
Putting the dried sample into a crucible and then putting into NH3Controlling the heating rate to be 2 ℃/min under the atmosphere, heating to 800 ℃ and calcining for 4h to obtain Fe2The C/C/TiO-5 lumpy product was ground in a mortar to give Fe2C/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 separately2Respectively 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, CH3Free 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 12C/C as control, Fe2The 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 42C/C/TiO-5 as control, Fe2The 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 mu mol 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 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)2The 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 12The C/C/TiO nanoparticle photo-thermal catalyst has TiO and Fe2Peak of C, thereby indicating TiO and Fe2C 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 corporation, Japan)2The UV-VISIBLE Diffuse reflectance patterns of the C/C/TiO nanoparticles and the TiO/C nanoparticle photothermal catalyst obtained in comparative example 2 are shown in FIG. 2, in which FIG. 2, the abscissa is the wavelength and the ordinate is the absorbance, and it can be seen from FIG. 2 that Fe is present2C/C/TiO nanoparticles, red-shifted absorption edge, from this tableIs clear of Fe2The 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)2C/C/TiO nanoparticles, Fe obtained in comparative example 12C/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.
Fe obtained in example 1 was subjected to electrochemical working station (model: IviumStat. h, manufacturer: Dutch Avicennia indica)2C/C/TiO nanoparticles, Fe obtained in comparative example 12C/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 column box temperature 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 by controlling the power to be 60W and the frequency to be 40KHz, then vacuum pumping is carried out by a vacuum pump, and when the pressure reaches 1.2kPa, CO of 80kPa is added2After 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. Extracting 0.6mL of gas from the reactor every 1h of illumination, and introducing into gas chromatography for measurement to obtain methane yieldAs shown in fig. 5, it can be seen from fig. 5 that the amount of hydrogen produced by the carbon nitride supported molybdenum nitride nanoparticle photocatalyst is significantly higher than that of carbon nitride, wherein the iron carbide composite titanium monoxide nanoparticle photothermal catalyst obtained in example 1 with the best performance is shown, thereby indicating that the addition of iron carbide greatly improves the performance of carbon dioxide reduction of titanium monoxide.
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 ℃.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. 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 NH3And (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 nanoparticle photo-thermal catalyst of iron carbide compounded with titanium monoxide as claimed in 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 temperature-rising calcination process conditions 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010161661.8A CN111589463B (en) | 2020-03-10 | 2020-03-10 | Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010161661.8A CN111589463B (en) | 2020-03-10 | 2020-03-10 | Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111589463A true CN111589463A (en) | 2020-08-28 |
| CN111589463B CN111589463B (en) | 2022-08-23 |
Family
ID=72180252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010161661.8A Active CN111589463B (en) | 2020-03-10 | 2020-03-10 | Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111589463B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131465A2 (en) * | 1983-07-07 | 1985-01-16 | Exxon Research And Engineering Company | Iron on titania catalyst and its use for hydrocarbon synthesis |
| US4608359A (en) * | 1984-06-29 | 1986-08-26 | Exxon Research And Engineering Co. | Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts |
| CN1867404A (en) * | 2003-08-14 | 2006-11-22 | 孟山都技术公司 | Transition metal-carbide and nitride containing catalysts, their preparation and use as oxidation and dehydrogenation catalysts |
| WO2011097441A1 (en) * | 2010-02-04 | 2011-08-11 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Carbon nanotube fibers/filaments formulated from metal nanoparticle catalyst and carbon source |
| CN106378134A (en) * | 2016-08-15 | 2017-02-08 | 青岛科技大学 | Nanometer porous spherical titanium dioxide powder with iron carbide or iron oxide codeposited surface, and preparation method and application thereof |
-
2020
- 2020-03-10 CN CN202010161661.8A patent/CN111589463B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131465A2 (en) * | 1983-07-07 | 1985-01-16 | Exxon Research And Engineering Company | Iron on titania catalyst and its use for hydrocarbon synthesis |
| US4608359A (en) * | 1984-06-29 | 1986-08-26 | Exxon Research And Engineering Co. | Iron carbide on titania surface modified with group VA oxides as Fischer-Tropsch catalysts |
| CN1867404A (en) * | 2003-08-14 | 2006-11-22 | 孟山都技术公司 | Transition metal-carbide and nitride containing catalysts, their preparation and use as oxidation and dehydrogenation catalysts |
| WO2011097441A1 (en) * | 2010-02-04 | 2011-08-11 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Carbon nanotube fibers/filaments formulated from metal nanoparticle catalyst and carbon source |
| CN106378134A (en) * | 2016-08-15 | 2017-02-08 | 青岛科技大学 | Nanometer porous spherical titanium dioxide powder with iron carbide or iron oxide codeposited surface, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ROBERT B. SANDBERG: "Strongly Modified Scaling of CO Hydrogenation in Metal Supported", 《ACS CATALYSIS》 * |
| 杜瑛等: "二氧化碳催化加氢催化剂研究进展", 《化工生产与技术》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111589463B (en) | 2022-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Ni, Co-based selenide anchored g-C3N4 for boosting photocatalytic hydrogen evolution | |
| US20220042184A1 (en) | Preparation Method and Application of Non-noble Metal Single Atom Catalyst | |
| Wang et al. | Fabrication of Bi4Ti3O12/ZnIn2S4 S-scheme heterojunction for achieving efficient photocatalytic hydrogen production | |
| Zhang et al. | NiSe2/Cd0. 5Zn0. 5S as a type-II heterojunction photocatalyst for enhanced photocatalytic hydrogen evolution | |
| CN111545235A (en) | 2D/2Dg-C3N4CoAl-LDH hydrogen-production heterojunction material and preparation method and application thereof | |
| CN107649150A (en) | A kind of preparation method and applications of the Cd/CdS hetero-junctions visible light catalysts rich in sulphur room | |
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN108671955B (en) | Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN112774692B (en) | Ru @ Ni2V2O7Efficient photo-thermal synergistic catalyst and preparation method and application thereof | |
| Gao et al. | Construction of heterostructured g-C3N4@ TiATA/Pt composites for efficacious photocatalytic hydrogen evolution | |
| CN113680372B (en) | Heat-assisted preparation method and application of graphite-phase carbon nitride nanosheets | |
| Xia et al. | Metal–organic framework with atomically dispersed Ni–N4 sites for greatly-raised visible-light photocatalytic H2 production | |
| CN111617790B (en) | Nitrogen-doped carbon layer-coated cobalt manganese carbide composite material and application thereof | |
| Liu et al. | CoNi bimetallic alloy cocatalyst-modified TiO2 nanoflowers with enhanced photocatalytic hydrogen evolution | |
| CN108927197B (en) | g-C with high catalytic performance3N4Preparation method and use of | |
| Su et al. | Oxygen-deficient MoO 3− x evoked synergistic photo-thermal catalytic CO 2 reduction over gC 3 N 4 | |
| CN114308079A (en) | Cadmium sulfide-double-cocatalyst composite photocatalytic material and preparation method and application thereof | |
| Qian et al. | Ultrathin Pd metallenes as novel co-catalysts for efficient photocatalytic hydrogen production | |
| CN105312090B (en) | One kind (C5H5)Ru/TiO2Organic inorganic hybridization photochemical catalyst | |
| CN112892607A (en) | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof | |
| Li et al. | Phosphating MIL-53 (Fe) as cocatalyst modified porous NiTiO3 for photocatalytic hydrogen production | |
| CN112495411A (en) | Carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst and preparation and application thereof | |
| CN111589463B (en) | Iron carbide and titanium monoxide compounded nanoparticle photo-thermal catalyst and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |