CN109999878A - For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof - Google Patents
For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109999878A CN109999878A CN201910299041.8A CN201910299041A CN109999878A CN 109999878 A CN109999878 A CN 109999878A CN 201910299041 A CN201910299041 A CN 201910299041A CN 109999878 A CN109999878 A CN 109999878A
- Authority
- CN
- China
- Prior art keywords
- ceo
- composite catalyst
- nonmetalloid
- catalytic reduction
- photo catalytic
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 75
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 103
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000002019 doping agent Substances 0.000 claims abstract description 21
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 35
- 229910001868 water Inorganic materials 0.000 description 32
- 238000000034 method Methods 0.000 description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- 238000002459 porosimetry Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/643—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
-
- 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
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
-
- 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
- C07C2527/24—Nitrogen compounds
Abstract
The present invention provides a kind of for photo catalytic reduction CO2Nonmetal doping Co3O4‑CeO2Composite catalyst and preparation method thereof, nonmetal doping Co3O4‑CeO2Composite catalyst is made of active component and dopant, and the active component is Co3O4‑CeO2, dopant is nonmetalloid.Its preparation process will the compound containing nonmetalloid and the metal nitrate containing cobalt, cerium slowly air-dried after stirring and dissolving again in deionized water, obtained solid powder high-temperature calcination under air atmosphere after air-drying, Temperature fall obtain nonmetal doping Co3O4‑CeO2Composite catalyst.The composite catalyst not only specific surface area with higher, nano-pore structure abundant, narrow band gap width and visible absorption performance, in photocatalytic conversion CO2Aspect shows very high activity and selectivity, and preparation method is also relatively easy, is easily enlarged.
Description
Technical field
The present invention relates to a kind of nonmetal doping composite catalysts, in particular to a kind of to be used for photo catalytic reduction CO2
Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof belongs to photochemical catalyst and its preparation technical field.
Background technique
With the rapid development of industry, the content of carbon dioxide is gradually increased in atmosphere, to natural environment and earth ecology
Influence be on the rise, thus reduce the discharge of carbon dioxide and selectivity is cut down the content of carbon dioxide in atmosphere and had become entirely
One of one big reality of ball economic development, new energy and the exploitation of high-tech environmental protection technology and strategic project.As Main Greenhouse gas
The CO of body2Carbon source abundant, have many advantages, such as it is cheap, stablize, do not burn, therefore by CO2Low energy consumption efficient is converted into
Useful chemical substance and product such as carbon monoxide, methane, methanol, ethyl alcohol, ethylene etc. can not only reduce CO in atmosphere2's
Content, but also global energy crisis can be alleviated, realize sustainable development.
At present by CO2It is converted into useful chemical substance, to realize CO2The research that renewable resources utilize has achieved centainly
Progress.The method of use mainly has bioanalysis, physical method, physical-chemical process and chemical method, and wherein chemical method is artificial a large amount of
Utilize CO2Main method.Chemically give CO2Adding hydrogen, there are mainly three types of modes: first is that CO2With H2Reaction generates equimolar
The C chemicals of amount；Second is that CO2With CH4Reaction generates synthesis gas and lower carbon number hydrocarbons etc.；Third is that CO2With H2O reaction generates hydrocarbon, alcohols has
Machine fuel.Although first two method technology is more mature, useful H is consumed2With CH4, it is not unusual economy；It is latter
Kind method raw material is the final product CO of fuel combustion2With water, cheap and easy to get, but also in exploring rank in theoretical and technology
Section, is the hot spot studied at present.Due to CO2It is the final oxidation product of organic compound, needs to be additionally provided a large amount of energy
Back reaction can just be made, therefore above-mentioned hydrogenation process there will be enough energy supplements.By CO2, water solar energy act on
Under be converted into the fuel gas such as carbon monoxide, methane, solar energy can be changed into chemical energy with lower cost, to obtain
Renewable, pollution-free organic-fuel forms the systemic circulation that renewable energy acts on lower carbon resource, finally realizes artificial photosynthesis
The rosy prospect of lower earth sustainable development.
Implement CO using semiconductor light-catalyst2Reacting with the recycling of water starts from 1979, and Inoue etc. utilizes powder
Shape semiconductor WO3、TiO2, ZnO, CdS, GaP and SiC etc. as photochemical catalyst, using xenon lamp or mercury lamp as light source, H2O is as hydrogen
Source, photo-reduction CO2, generate formic acid (HCOOH), formaldehyde (HCHO), methanol (CH3) and trace amounts of methane (CH OH4), thus pull open
Conductor photocatalysis CO2With H2O reaction generates the prelude of hydrocarbon, the research of alcohols organic-fuel.2002, Tseng etc. passed through sol-
Cu is supported on TiO by the method for gel2Cu/TiO is made in surface2Catalyst is simultaneously used for photo catalytic reduction CO2Methanol processed is ground
Study carefully, the experimental results showed that the TiO of Cu load2The TiO that catalyst activity will be loaded much better than noble metal (such as Pt, Ag)2Catalysis
Agent.Recently, Slamet etc. has synthesized different valence state copper species (Cu0, Cu+1, or Cu+2) doping TiO2Catalyst, and system
Examine three kinds of catalyst photo catalytic reduction CO2With H2O reaction generates the performance of methanol, finds CuO (i.e. Cu+2Species) doping
TiO2Catalyst has highest photo catalytic reduction activity.
However, up to the present there is not yet the composite semiconductor oxide material modified about nonmetal doping is urged for light
Change reduction CO2The related patents report that resourcable transformation utilizes.
Summary of the invention
An object of the present invention is to improve tradition CeO2Semiconductor catalyst is in photocatalytic conversion CO2And H2O reaction generates
Fuel activity and the not high technical problem of selectivity and the one kind provided are for photo catalytic reduction CO2Nonmetal doping
Co3O4-CeO2Composite catalyst, specific surface area with higher, nano-pore structure abundant, narrow band gap width and visible light
Absorbent properties have been greatly improved photo catalytic reduction CO2With H2O reaction generates fuel activity and selectivity.
The second object of the present invention is to provide above-mentioned one kind for photo catalytic reduction CO2Nonmetal doping
Co3O4-CeO2The preparation method of composite catalyst.
The technical solution adopted by the present invention to solve the technical problems is:
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, the composite catalyst
It is made of active component and dopant, the active component is Co3O4-CeO2, dopant is nonmetalloid；The Co3O4-
CeO2Co in active component3O4/CeO2Molar ratio is 0.1-2:1；The nonmetalloid be one of nitrogen, sulphur, boron, fluorine or
Two kinds of nonmetallic mixing.
Preferably, described be used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2The specific surface of composite catalyst
Product is 10-200m2/ g, aperture are 1-30 nm, and pore volume is 0.05-1.85 cm3/g。
Preferably, nonmetal doping agent and Co3O4-CeO2The molar ratio of active component is 1:11.1-22.5.
Photo catalytic reduction CO is used for described in a kind of2Nonmetal doping Co3O4-CeO2The preparation method of composite catalyst,
The preparation method comprises the following steps:
(1), the compound containing target nonmetalloid and the metal nitrate containing cobalt, cerium are dissolved in deionized water, are obtained
Precursor mixed solution is stirred 0.5-6h, then 30-100 DEG C at a temperature of air-dry, obtain the first powder；
The compound containing nonmetalloid is the mixing of one or both of urea, thiocarbamide, boric acid, ammonium fluoride
Object；
The compound containing nonmetalloid has both the function of pore creating material；
The metal nitrate containing cobalt is cobalt nitrate；The nitrate containing ce metal is cerous nitrate, one in ammonium ceric nitrate
Kind or two kinds of mixture；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing
The compound of nonmetalloid: the ratio that deionized water is 2-40mmol:20-300mmol:10-100ml calculates；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating of 1-20 DEG C/min under oxygen atmosphere
Rate, which heats up most 200-800 DEG C, carries out calcining 1-12h, and Temperature fall obtains photo catalytic reduction CO2Nonmetalloid mix
Miscellaneous Co3O4-CeO2Composite catalyst.
Preferably, air-dried temperature is 40-70 DEG C.
Preferably, calcination temperature is 400-550 DEG C.
Preferably, calcination time is 1-6 h.
The beneficial effects of the present invention are: provided by the present invention for photo catalytic reduction CO2Nonmetal doping Co3O4-
CeO2Composite catalyst is with Co3O4-CeO2For active component, nonmetalloid is dopant.Especially during the preparation process
Compound containing nonmetalloid, which can be used as pore creating material, makes have the spies such as high specific surface area, nano-pore structure abundant
Property.With traditional N doping CeO2Catalyst is compared, and photo catalytic reduction CO is substantially increased2With H2O reaction generate fuel activity and
Selectivity.
Of the invention is used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst has higher
Specific surface area, nano-pore structure abundant, narrow band gap width and visible absorption performance, be greatly improved photocatalysis also
Former CO2With H2O reaction generates fuel activity and selectivity, catalyst photo catalytic reduction CO at 25 DEG C2And H2It is raw that O reacts 8h
Yield at carbon monoxide and methane is respectively 90-210umol/g-cat. and 60-140umol/g-cat..
Provided by the present invention for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and biography
Unite N doping CeO2Catalyst is compared, and not only has higher specific surface area, richer nano-pore structure, but also show
Higher catalysis restores CO2Performance.Further, provided by the present invention for photo catalytic reduction CO2Nonmetal doping
Co3O4-CeO2The preparation method of composite catalyst, using the compound containing nonmetalloid as pore creating material and nonmetalloid before
Body is driven, is metallic oxide precursor object containing cobalt, cerium nitrate, by the compound containing nonmetalloid and is contained in preparation process
Cobalt, cerium nitrate slowly air-dry after stirring and dissolving in deionized water, and obtained solid powder is in air atmosphere after air-drying
Lower high-temperature calcination, Temperature fall obtain nonmetal doping Co3O4-CeO2Composite catalyst, therefore preparation method has
It is easy to operate, the features such as process is reproducible.
Detailed description of the invention
Fig. 1 is 1 nonmetal doping Co of the embodiment of the present invention3O4-CeO2The transmission electron microscope photo of composite catalyst；
Fig. 2 is the nonmetallic nitrogen-doping Co of embodiment 13O4-CeO2Composite catalyst and traditional N doping CeO2Nano-catalytic
Agent photo catalytic reduction CO2With H2O generates CO (a) and CH after reacting 8h4(b) comparison diagram of yield.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair
Bright implementation is not limited by the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen
Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
Embodiment 1
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 10g containing nonmetalloid, 1.5 mmol cobalt nitrates and 5 mmol cerous nitrates be dissolved in 20ml go from
In sub- water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 40 DEG C, obtains the
One powder；
The compound containing nonmetalloid is urea；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by cerous nitrate: containing nonmetallic
The compound of element: deionized water is 6.5 mmol:166.7mmol:20ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating rate of 5 DEG C/min under oxygen atmosphere
Most 400 DEG C of heating carries out calcining 4h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is compound to urge
Agent.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 0.1:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 3:50；The nonmetalloid is nitrogen.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 90 m2/ g, aperture are
2.6nm, pore volume are 0.86 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 120 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 93 μm of ol/g.
Nonmetal doping Co prepared by embodiment 13O4-CeO2The transmission electron microscope photo of composite catalyst is shown in Fig. 1, from
It can be seen that the composite catalyst has sheet-like morphology and surface has the mesoporous of a large amount of rules in electromicroscopic photograph figure.
The nonmetallic nitrogen-doping Co of embodiment 13O4-CeO2Composite catalyst and traditional N doping CeO2Nano-catalytic
Agent photo catalytic reduction CO2With H2O generates CO (a) and CH after reacting 8h4(b) comparison diagram of yield is as shown in Fig. 2, can from figure
To find out nonmetallic nitrogen-doping Co3O4-CeO2Composite catalyst has higher photo catalytic reduction CO2With H2O reactivity,
General activity is than traditional N doping CeO2Nanocatalyst is 2-3 times high.
Embodiment 2
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 8g containing nonmetalloid, 7.5 mmol cobalt nitrates and 5 mmol cerous nitrates be dissolved in 25ml go from
In sub- water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 50 DEG C, obtains the
One powder；
The compound containing nonmetalloid is thiocarbamide；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing non-
The compound of metallic element: deionized water 12.5mmol:105.3mmol:25ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating speed of 15 DEG C/min under oxygen atmosphere
Rate heats up most 450 DEG C and carries out calcining 3h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is compound
Catalyst.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 0.5:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 2:45；
The nonmetalloid is element sulphur.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 76 m2/ g, aperture are
6.7nm, pore volume are 0.56 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 156 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 87 μm of ol/g.
Embodiment 3
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 10g containing nonmetalloid, 15 mmol cobalt nitrates and 5 mmol cerous nitrates be dissolved in 40ml go from
In sub- water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 60 DEG C, obtains the
One powder；
The compound containing nonmetalloid is urea and thiocarbamide, mass ratio 1:1；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing non-
The compound of metallic element: deionized water is 20 mmol:149.1mmol:40ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating speed of 10 DEG C/min under oxygen atmosphere
Rate heats up most 500 DEG C and carries out calcining 1.5h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is multiple
Close catalyst.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 1:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 3.5:51；
The nonmetalloid is nitrogen and element sulphur.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 101 m2/ g, aperture
For 4.2nm, pore volume is 0.77 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 149 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 66 μm of ol/g.
Embodiment 4
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 5g containing nonmetalloid, 13.5 mmol cobalt nitrates and 3 mmol cerous nitrates be dissolved in 15ml go from
In sub- water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 70 DEG C, obtains the
One powder；
The compound containing nonmetalloid is boric acid；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing non-
The compound of metallic element: deionized water 16.5mmol:80.6mmol:15ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating speed of 15 DEG C/min under oxygen atmosphere
Rate heats up most 400 DEG C and carries out calcining 5h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is compound
Catalyst.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 1.5:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 6:67；
The nonmetalloid is boron element.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 55 m2/ g, aperture are
15.8nm, pore volume are 0.44 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 187 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 132 μm of ol/g.
Embodiment 5
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 10g containing nonmetalloid, 15 mmol cobalt nitrates and 2.5 mmol ammonium ceric nitrates are dissolved in 70ml
In deionized water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 70 DEG C,
Obtain the first powder；
The compound containing nonmetalloid is ammonium fluoride；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing non-
The compound of metallic element: deionized water is 17.5 mmol:270.3mmol:70ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating speed of 10 DEG C/min under oxygen atmosphere
Rate heats up most 550 DEG C and carries out calcining 1h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is compound
Catalyst.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 2:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 2:37；
The nonmetalloid is fluorine element.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 77 m2/ g, aperture are
1.6nm, pore volume are 0.43 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 98 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 105 μm of ol/g.
Embodiment 6
One kind being used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Method for preparing composite catalyst, specific steps
It is:
(1), the compound by 10g containing nonmetalloid, 9 mmol cobalt nitrates and 3 mmol cerous nitrates are dissolved in 55ml deionization
In water, precursor mixed solution is obtained, then resulting mixture is transferred in culture dish, is air-dried under the conditions of 45 DEG C, obtains first
Powder；
The compound containing nonmetalloid is urea and ammonium fluoride；Its mass ratio is 1:1；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing non-
The compound of metallic element: deionized water 12mmol:218.8mmol:55ml；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating speed of 15 DEG C/min under oxygen atmosphere
Rate heats up most 400 DEG C and carries out calcining 6h, and the powder obtained after Temperature fall is nonmetal doping Co3O4-CeO2It is compound
Catalyst.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, by activity
Component and dopant composition, the active component are Co3O4-CeO2, dopant is nonmetalloid.
Active component Co3O4-CeO2Middle Co3O4/CeO2Molar ratio is 1:1；
Nonmetalloid: Co3O4-CeO2Molar ratio be 4.5:56；
The nonmetalloid is nitrogen and fluorine element.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is through detecting
(instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), specific surface area are 93 m2/ g, aperture are
9.2nm, pore volume are 0.77 cm3/g。
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photocatalysis CO down2With H2O reaction synthesis carbon monoxide, the carbon monoxide yield that reaction obtains after 8 hours is 201 μm of ol/g.
It is above-mentioned resulting for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst is at 25 DEG C
It is used for photo catalytic reduction CO down2With H2O reacts synthesizing methane, and the methane production that reaction obtains after 8 hours is 122 μm of ol/g.
According to above embodiments it is found that the resulting photo catalytic reduction CO of the present invention2Nonmetal doping Co3O4-CeO2
Composite catalyst not only specific surface area with higher, nano-pore structure abundant, narrow band gap width and vis-absorbing
Can, and show catalysis reduction CO well2And H2The performance of O, catalyst photo catalytic reduction CO at 25 DEG C2And H2O
Reacting 8h to generate carbon monoxide and the yield of methane is respectively 90-210umol/g-cat. and 60-140umol/g-cat..
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (7)
1. one kind is used for photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst, it is characterised in that described
Composite catalyst be made of active component and dopant, the active component be Co3O4-CeO2, dopant is nonmetallic member
Element；
The Co3O4-CeO2Co in active component3O4/CeO2Molar ratio is 0.1-2:1；
The nonmetalloid is the nonmetallic mixing of one or both of nitrogen, sulphur, boron, fluorine.
2. nonmetal doping Co according to claim 13O4-CeO2Composite catalyst, it is characterised in that: the use
In photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2The specific surface area of composite catalyst is 10-200m2/ g, aperture 1-
30 nm, pore volume are 0.05-1.85 cm3/g。
3. nonmetal doping Co according to claim 13O4-CeO2Composite catalyst, it is characterised in that: nonmetallic
Elemental dopant and Co3O4-CeO2The molar ratio of active component is 1:11.1-22.5.
4. a kind of be used for photo catalytic reduction CO as described in claim 12Nonmetal doping Co3O4-CeO2Composite catalyst
Preparation method, it is characterised in that the preparation method comprises the following steps:
(1), the compound containing target nonmetalloid and the metal nitrate containing cobalt, cerium are dissolved in deionized water, are obtained
Precursor mixed solution is stirred 0.5-6h, then 30-100 DEG C at a temperature of air-dry, obtain the first powder；
The compound containing nonmetalloid is the mixing of one or both of urea, thiocarbamide, boric acid, ammonium fluoride
Object；
The compound containing nonmetalloid has both the function of pore creating material；
The metal nitrate containing cobalt is cobalt nitrate；The nitrate containing ce metal is cerous nitrate, one in ammonium ceric nitrate
Kind or two kinds of mixture；
The amount of the above-mentioned compound containing nonmetalloid used, metal nitrate and deionized water, by metal nitrate: containing
The compound of nonmetalloid: the ratio that deionized water is 2-40mmol:20-300mmol:10-100ml calculates；
(2), the first powder obtained in step (1) is placed in Muffle furnace, with the heating of 1-20 DEG C/min under oxygen atmosphere
Rate, which heats up most 200-800 DEG C, carries out calcining 1-12h, and Temperature fall obtains photo catalytic reduction CO2Nonmetalloid mix
Miscellaneous Co3O4-CeO2Composite catalyst.
5. the preparation method according to claim 4, it is characterised in that: air-dried temperature is 40-70 DEG C.
6. the preparation method according to claim 4, it is characterised in that: calcination temperature is 400-550 DEG C.
7. the preparation method according to claim 4, it is characterised in that: calcination time is 1-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910299041.8A CN109999878A (en) | 2019-04-15 | 2019-04-15 | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910299041.8A CN109999878A (en) | 2019-04-15 | 2019-04-15 | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109999878A true CN109999878A (en) | 2019-07-12 |
Family
ID=67171859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910299041.8A Pending CN109999878A (en) | 2019-04-15 | 2019-04-15 | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109999878A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110665519A (en) * | 2019-09-25 | 2020-01-10 | 盐城师范学院 | CeO for activating potassium peroxymonosulfate composite salt under drive of visible light2/Co3O4Method for preparing photocatalyst |
| CN114345345A (en) * | 2021-12-02 | 2022-04-15 | 江苏大学 | Preparation method and application of metal oxide heterojunction photocatalyst with high-speed electron transmission channel |
| CN114768804A (en) * | 2022-04-10 | 2022-07-22 | 南京大学 | Preparation method and application of solid solution photo-thermal catalytic material |
| CN115178277A (en) * | 2022-08-03 | 2022-10-14 | 安徽大学 | Doped Co 3 O 4 Nano material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549412A (en) * | 2014-12-29 | 2015-04-29 | 上海理工大学 | Mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and preparation method |
| CN108314214A (en) * | 2018-02-26 | 2018-07-24 | 彭波涛 | A kind of technique of heterogeneous ozone catalytic degradation dyeing waste water |
-
2019
- 2019-04-15 CN CN201910299041.8A patent/CN109999878A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549412A (en) * | 2014-12-29 | 2015-04-29 | 上海理工大学 | Mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and preparation method |
| CN108314214A (en) * | 2018-02-26 | 2018-07-24 | 彭波涛 | A kind of technique of heterogeneous ozone catalytic degradation dyeing waste water |
Non-Patent Citations (1)
| Title |
|---|
| 张国芳等: "纳米Ｃｅ1-ｘＣｏｘＯ2-δ固溶体的水热合成及表征", 《高等学校化学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110665519A (en) * | 2019-09-25 | 2020-01-10 | 盐城师范学院 | CeO for activating potassium peroxymonosulfate composite salt under drive of visible light2/Co3O4Method for preparing photocatalyst |
| CN114345345A (en) * | 2021-12-02 | 2022-04-15 | 江苏大学 | Preparation method and application of metal oxide heterojunction photocatalyst with high-speed electron transmission channel |
| CN114768804A (en) * | 2022-04-10 | 2022-07-22 | 南京大学 | Preparation method and application of solid solution photo-thermal catalytic material |
| CN114768804B (en) * | 2022-04-10 | 2023-11-10 | 南京大学 | Solid solution photo-thermal catalysis CO 2 Application of conversion reaction |
| CN115178277A (en) * | 2022-08-03 | 2022-10-14 | 安徽大学 | Doped Co 3 O 4 Nano material and application thereof |
| CN115178277B (en) * | 2022-08-03 | 2024-04-05 | 安徽大学 | Doped Co 3 O 4 Nanomaterial and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109999878A (en) | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof | |
| CN104549412A (en) | Mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and preparation method | |
| CN112174764B (en) | Application of iron-based catalyst in catalyzing carbon dioxide hydrogenation to synthesize low-carbon olefin | |
| Liu et al. | Recent advances in thermal catalytic CO2 methanation on hydrotalcite-derived catalysts | |
| CN109569695B (en) | Preparation method and use method of core-shell structure catalyst for carbon dioxide hydrogenation | |
| CN103272604A (en) | Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst | |
| WO2021042874A1 (en) | Nickel-based catalyst for carbon dioxide methanation, preparation method therefor and application thereof | |
| CN114272950A (en) | CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof | |
| CN110721690B (en) | Ni-Fe bimetal multifunctional catalyst for biological oil steam reforming hydrogen production | |
| CN114160143B (en) | CO (carbon monoxide) 2 Catalyst for preparing methanol by hydrogenation and preparation method and application thereof | |
| CN103816913A (en) | Catalyst for preparing synthetic gas by reforming of methane and carbon dioxide as well as preparation method and application of catalyst | |
| CN111841530A (en) | Catalyst for promoting water photolysis to produce hydrogen and preparation method thereof | |
| CN101733089A (en) | Catalyst for preparing hydrogen gas, method for preparing same and application thereof | |
| CN105498780B (en) | A kind of Cu/ZnO catalyst and preparation method thereof and in CO2Application in chemical conversion | |
| CN105170156B (en) | The preparation method of the Ni-based methane dry reforming catalyst of aerogel-like structure | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| JP5897722B2 (en) | Method for preparing carbon dioxide methanation catalyst | |
| KR20230034166A (en) | METHOD FOR SYNTHESIS Ni/AlMaOx CATALYSTS FOR AMMONIA DECOMPOSITION USING CATION ANION DOUBLE HYDROLYSIS | |
| CN113101946B (en) | NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof | |
| TWI551542B (en) | Photocatalysis induced partial oxidation of methanol reaction for producing hydrogen and photocatalyst thereof | |
| CN113952956B (en) | Preparation method of methane dry reforming catalyst, methane dry reforming catalyst and application thereof | |
| CN114029048A (en) | Preparation method and application of tungsten oxide catalyst coated by porous carbon | |
| CN113522293A (en) | Preparation method and application of catalyst for hydrogen production by dry reforming of methane and carbon dioxide | |
| KR101988370B1 (en) | Catalysts for methanation of carbon dioxide and the manufacturing method of the same | |
| CN112619644A (en) | Ru-based catalyst with tetragonal barium titanate as carrier and preparation and application 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190712 |