CN104549412A - Mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and preparation method - Google Patents
Mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and preparation method Download PDFInfo
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- CN104549412A CN104549412A CN201410847569.1A CN201410847569A CN104549412A CN 104549412 A CN104549412 A CN 104549412A CN 201410847569 A CN201410847569 A CN 201410847569A CN 104549412 A CN104549412 A CN 104549412A
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Abstract
The invention discloses a mesoporous metal oxide catalyst for photo-catalytic CO2 reduction and a preparation method. The mesoporous metal oxide catalyst for the photo-catalytic CO2 reduction consists of an active component and a doping agent, wherein the active component is mesoporous CeO2, and the doping agent is transition metal ions. In the preparation process, transition metal nitrate and cerium nitrate are dissolved into acetone, mesoporous silica materials are added into an obtained metal nitrate acetone solution and are uniformly mixed, the mixture is naturally dried to obtain first powder, the first powder is calcined in a muffle furnace to obtain second powder, the second powder is etched by using a sodium hydroxide aqueous solution to remove the mesoporous silica materials, and the second powder is washed by using pure water and then is dried to obtain the mesoporous metal oxide catalyst for the photo-catalytic CO2 reduction, which has higher specific surface area, larger aperture and a regular pore structure. The mesoporous metal oxide catalyst is high in activity and selectivity in terms of photo-catalytic CO2 conversion, and the preparation method is relatively simple, and easy to expand.
Description
Technical field
The invention belongs to photocatalyst and preparing technical field thereof, be specifically related to a kind of for photo catalytic reduction CO
2mesopore metal oxide catalyzer and preparation method.
Background technology
Along with the develop rapidly of industry, in air, the content of carbonic acid gas increases gradually, the impact of physical environment and earth ecology is on the rise, thus reduce the content that the discharge of carbonic acid gas and selectivity cut down carbonic acid gas in air and become global economic development, large one of a reality and strategic problem of new forms of energy and the exploitation of high-tech green technology.As the CO of main greenhouse gas
2be abundant carbon source, advantages such as having cheapness, stablize, do not burn, therefore by CO
2less energy-consumption, high efficiency useful chemical substance and the product of being converted into are as carbon monoxide, and methane, methyl alcohol, ethanol, ethene etc., not only can reduce CO in air
2content, but also can global energy crisis be alleviated, realize Sustainable development.
At present by CO
2be converted into useful chemical substance, to realize CO
2the research that renewable resources utilizes makes some progress.The method adopted mainly contains biological process, Physical, physico-chemical processes and chemical method, and wherein chemical method manually utilizes CO in a large number
2main method.Chemically give CO
2hydrogenation mainly contains three kinds of modes: one is CO
2with H
2reaction generates the C chemical of equimolar amount; Two is CO
2with CH
4reaction generates synthetic gas and lower carbon number hydrocarbons etc.; Three is CO
2with H
2o reaction generates hydrocarbon, alcohols organic-fuel.Although first two method technology is comparatively ripe, useful H be consumed
2with CH
4, be not economy very; Rear a kind of method raw material is the final product CO of fuel combustion
2with water, cheap and easy to get, but theoretical and be technically also in the exploratory stage, be the focus studied at present.Due to CO
2be the final oxidation products of organic compound, need additionally to provide a large amount of energy that reversed reaction just can be made to occur, therefore above-mentioned hydrogenation process all will have enough energy supplements.By CO
2, water is converted into the fuel gas such as carbon monoxide, methane under sun power effect, just can change sun power into chemical energy with lower cost, thus obtain renewable, pollution-free organic-fuel, form the systemic circulation of carbon resource under renewable energy source effect, finally realize the rosy prospect of earth Sustainable development under artificial photosynthesis.
Utilize semiconductor light-catalyst to implement CO
2react with the resource utilization of water and start from 1979, Inoue etc. utilize Powdered semi-conductor WO
3, TiO
2, ZnO, CdS, GaP and SiC etc. as photocatalyst, with xenon lamp or mercury lamp be light source, H
2o is as hydrogen source, photoreduction CO
2, produce formic acid (HCOOH), formaldehyde (HCHO), methyl alcohol (CH
3and trace amounts of methane (CH OH)
4), pull open conductor photocatalysis CO thus
2with H
2o reaction generates the prelude of hydrocarbon, the research of alcohols organic-fuel.2002, Tseng etc. by the method for sol-gel by Cu load at TiO
2cu/TiO is made on surface
2catalyzer also uses it for photo catalytic reduction CO
2the research of methyl alcohol processed, experimental result shows the TiO of Cu load
2catalyst activity will be better than the TiO of precious metal (as Pt, Ag etc.) load greatly
2catalyzer.Recently, Slamet etc. have synthesized different valence state copper species (Cu
0, Cu
+ 1, or Cu
+ 2) TiO that adulterates
2catalyzer, and system examines three kinds of catalyzer photo catalytic reduction CO
2with H
2o reacts the performance of methanol, finds CuO (i.e. Cu
+ 2species) TiO that adulterates
2it is active that catalyzer has the highest photo catalytic reduction.
But, up to the present there is not yet about rare earth semiconductor oxide compound CeO
2and the material of modification is used for photo catalytic reduction CO
2the Patents report that resourcable transformation utilizes.
Summary of the invention
An object of the present invention improves conventional Ti O
2catalyzer is at photocatalytic conversion CO
2and H
2o reaction generate fuel activity and selectivity not high-technology problem and the one that provides for photo catalytic reduction CO
2mesopore metal oxide catalyzer, this is used for photo catalytic reduction CO
2mesopore metal oxide catalyzer there is the pore passage structure of higher specific surface area, larger aperture Sum fanction, photo catalytic reduction CO can be substantially increased
2with H
2o reaction generates fuel activity and selectivity, and this catalyzer is photo catalytic reduction CO at 25 DEG C
2and H
2the productive rate that O reacts 7h generation carbon monoxide and methane is respectively 550-3900umol/g-cat. and 490-2600umol/g-cat..
Two of object of the present invention is to provide above-mentioned one for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer.
Technical scheme of the present invention
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), transition metal nitrate and cerous nitrate are dissolved in acetone, obtain metal nitrate acetone soln, then add meso pore silicon oxide material and be uniformly mixed 0.5-12h, then natural air drying, obtain the first powder;
Described transition metal nitrate is one or more the mixture in iron nitrate, chromium nitrate, nickelous nitrate, cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
Described Metaporous silicon dioxide material is one or more the mixture in hexagonal structure SBA-15, cubic structure KIT-6 and MCM-48;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17-19.8mmol:0.2-3mmol:1-3g:10-20ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 1-15 DEG C/min heat up most 200-1000 DEG C carry out calcining 1-12h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 1-6mol/L aqueous sodium hydroxide solution etching 10-15h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 50-100 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Described transition metal ion is the mixing of one or more metal ions in iron ion, chromium ion, nickel ion, cupric ion, cobalt ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5-99;
Gained for photo catalytic reduction CO
2the specific surface area of mesopore metal oxide catalyzer be 130.5-220m
2/ g, aperture is 2.9-5.5nm, and pore volume can reach 0.47-1.21cm
3/ g.
The photo catalytic reduction CO of above-mentioned gained
2mesopore metal oxide catalyzer not only there is the pore passage structure of higher specific surface area, larger aperture Sum fanction, and show good catalytic reduction CO
2and H
2the performance of O, this catalyzer is difference photo catalytic reduction CO at 25 DEG C
2and H
2o reacts 7h and generates carbon monoxide and methane, and its productive rate is respectively 550-3900umol/g-cat. and 490-2600umol/g-cat..
Of the present invention useful
effect
One provided by the invention is used for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be CeO
2for active ingredient, transition metal ion is doping agent, and special meso-hole structure makes catalyzer possess the single characteristic such as evenly of high specific surface area, larger pore volume and pore structure.With traditional conventional Ti O
2catalyzer is compared, and substantially increases photo catalytic reduction CO
2with H
2o reaction generates fuel activity and selectivity.
Of the present invention for photo catalytic reduction CO
2mesopore metal oxide catalyzer and traditional TiO
2with pure order mesoporous CeO
2catalyzer is compared, and not only has the pore passage structure of higher specific surface area, larger aperture Sum fanction, and shows higher catalytic reduction CO
2performance.
Further, of the present invention for photo catalytic reduction CO
2mesopore metal oxide method for preparing catalyst, being be template with Metaporous silicon dioxide material, take transition metal nitrate as the precursor of doping component, with Ce (NO
3)
3.9H
2o is the order mesoporous CeO of main active ingredient
2precursor.By SiO 2 mesoporous materials, doping component precursor and main active ingredient meso-pore Ce O in preparation process
2precursor air-dry after acetone soln stirs, the pressed powder of air-dry rear gained is calcined under air atmosphere, then soaks in sodium hydroxide solution, remove Metaporous silicon dioxide material, finally wash, filter, drying obtains for photo catalytic reduction CO
2mesopore metal oxide catalyzer, the features such as therefore its preparation method has simple to operate, and process is reproducible.
Embodiment
below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
Various raw materials used in various embodiments of the present invention are commercially available.
embodiment 1
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), 0.08g transition metal nitrate and 8.60g nine water cerous nitrate are dissolved in 10ml acetone, obtain metal nitrate acetone soln, then add 2g meso pore silicon oxide material and be uniformly mixed 2h, then the mixture of gained is proceeded in culture dish, natural air drying under room temperature condition, obtains the first powder;
Described transition metal nitrate is nine water iron nitrates;
Described Metaporous silicon dioxide material is hexagonal structure SBA-15;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 19.8mmol:0.2mmol:2g:10ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 2 DEG C/min heat up most 400 DEG C carry out calcining 4h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 2mol/L aqueous sodium hydroxide solution etching 10h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 50 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:99;
Described transition metal ion is iron ion.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 145.8m
2/ g, aperture is 3.8nm, and pore volume is 0.47cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o Reactive Synthesis carbon monoxide, the productive rate of final carbon monoxide is 550 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photo catalytic reduction CO
2with H
2o Reactive Synthesis methane, the productive rate of final methane is 490 μm of ol/g-cat..
embodiment 2
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.40g transition metal nitrate and 8.25g nine water cerous nitrate be dissolved in 12ml acetone, obtain metal nitrate acetone soln, then add 2.4g meso pore silicon oxide material and be uniformly mixed 4h, then natural air drying, obtain the first powder;
Described transition metal nitrate is nine water chromium nitrates;
Described Metaporous silicon dioxide material is cubic structure MCM-48;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 19mmol:1mmol:2.4g:12ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 5 DEG C/min heat up most 550 DEG C carry out calcining 6h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 4mol/L aqueous sodium hydroxide solution etching 15h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 60 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:19;
Described transition metal ion is chromium ion.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 130.5m
2/ g, aperture is 3.5nm, and pore volume is 0.49cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 2200 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 900 μm of ol/g-cat..
embodiment 3
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.80g transition metal nitrate and 7.81g cerous nitrate be dissolved in 20ml acetone, obtain metal nitrate acetone soln, then add 3g meso pore silicon oxide material and be uniformly mixed 6h, then natural air drying, obtain the first powder;
Described transition metal nitrate is nine water chromium nitrates;
Described Metaporous silicon dioxide material is hexagonal structure SBA-15, cubic structure MCM-48 is the mixture of 1:1 composition in mass ratio;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 18.2mmol:2mmol:3g:20ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 10 DEG C/min heat up most 650 DEG C carry out calcining 8h, obtain the second powder;
(3), by the second powder concentration of step (2) gained be 6mol/L aqueous sodium hydroxide solution etching 10h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 65 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:9.1;
Described transition metal ion is chromium ion.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 156m
2/ g, aperture is 4.3nm, and pore volume is 0.65cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 3000 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 1000 μm of ol/g-cat..
embodiment 4
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.8g transition metal nitrate and 7.81g cerous nitrate be dissolved in 16ml acetone, obtain metal nitrate acetone soln, then add 2.8g meso pore silicon oxide material and be uniformly mixed 6h, then natural air drying, obtain the first powder;
Described transition metal nitrate is the mixture of 0.40g nine water iron nitrate and 0.40g nine water chromium nitrate composition;
Described Metaporous silicon dioxide material is hexagonal structure SBA-15;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 18mmol:1.9mmol:2.8g:16ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 5 DEG C/min heat up most 550 DEG C carry out calcining 4h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 6mol/L aqueous sodium hydroxide solution etching 10h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 70 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:9.47;
Described transition metal ion is chromium ion and iron ion, calculates, the precursor of ferric oxide: the precursor of chromic oxide is 1:1 by precursor mass ratio.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 180m
2/ g, aperture is 4.6nm, and pore volume is 0.62cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 3000 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 1200 μm of ol/g-cat..
embodiment 5
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.98g transition metal nitrate and 7.38g nine water cerous nitrate be dissolved in 15ml acetone, obtain metal nitrate acetone soln, then add 1.5g meso pore silicon oxide material and be uniformly mixed 6h, then natural air drying, obtain the first powder;
Described transition metal nitrate is the mixture of 0.40g nine water iron nitrate and 0.58g cobalt nitrate hexahydrate composition;
Described Metaporous silicon dioxide material is cubic structure MCM-48;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17mmol:3mmol:1.5g:15ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 5 DEG C/min heat up most 550 DEG C carry out calcining 6h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 6mol/L aqueous sodium hydroxide solution etching 15h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 75 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5.67;
Described transition metal ion is iron ion and cobalt ion, calculates in molar ratio, iron: cobalt is 1:2.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 175m
2/ g, aperture is 4.5nm, and pore volume is 0.58cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 2800 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 1400 μm of ol/g-cat..
embodiment 6
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.98g transition metal nitrate and 7.38g cerous nitrate be dissolved in 13ml acetone, obtain metal nitrate acetone soln, then add 2.6g meso pore silicon oxide material and be uniformly mixed 8h, then natural air drying, obtain the first powder;
Described transition metal nitrate is the mixture of 0.49g nine water chromium nitrate and 0.49g cobalt nitrate hexahydrate composition;
Described Metaporous silicon dioxide material is the mixture that hexagonal structure SBA-15 and cubic structure MCM-48 are calculated as 1:1 composition in mass ratio;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17mmol:2.4mmol:2.6g:13ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 10 DEG C/min heat up most 600 DEG C carry out calcining 6h, obtain the second powder;
(3), by the second powder concentration of step (2) gained be 6mol/L aqueous sodium hydroxide solution etching 10h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 80 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:7.5;
Described transition metal ion is chromium ion and cobalt ion, calculates by mol, chromium ion: cobalt ion is 1:1.37.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 220m
2/ g, aperture is 6.2nm, and pore volume is 0.87cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 3900 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 2600 μm of ol/g-cat..
embodiment 7
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.73g transition metal nitrate and 7.38g nine water cerous nitrate be dissolved in 12ml acetone, obtain metal nitrate acetone soln, then add 2g meso pore silicon oxide material and be uniformly mixed 4h, then natural air drying, obtain the first powder;
Described transition metal nitrate is nitrate trihydrate copper;
Described Metaporous silicon dioxide material is cubic structure KIT-6;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17mmol:3mmol:2g:12ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 2 DEG C/min heat up most 600 DEG C carry out calcining 4h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 2mol/L aqueous sodium hydroxide solution etching 12h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 100 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5.67;
Described transition metal ion is cupric ion.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 205m
2/ g, aperture is 2.9nm, and pore volume is 1.1cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 2760 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 1200 μm of ol/g-cat..
embodiment 8
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 1.16g transition metal nitrate and 7.38g cerous nitrate be dissolved in 19ml acetone, obtain metal nitrate acetone soln, then add 2.3g meso pore silicon oxide material and be uniformly mixed 4h, then natural air drying, obtain the first powder;
Described transition metal nitrate is six water nickelous nitrates;
Described Metaporous silicon dioxide material is cubic structure KIT-6;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17.6mmol:2.1mmol:2.3g:19ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 5 DEG C/min heat up most 600 DEG C carry out calcining 4h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be 2mol/L aqueous sodium hydroxide solution etching 15h after, to remove meso pore silicon oxide material, repeat this step 3 time, then wash with pure water, control temperature is 90 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:8.38;
Described transition metal ion is nickel ion.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 135m
2/ g, aperture is 5.5nm, and pore volume is 0.92cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 2700 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 1800 μm of ol/g-cat..
embodiment 9
A kind of for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, specifically comprise following steps:
(1), by 0.8g transition metal nitrate and 7.95g cerous nitrate be dissolved in 12ml acetone, obtain metal nitrate acetone soln, then add 1.6g meso pore silicon oxide material and be uniformly mixed 8h, then natural air drying, obtain the first powder;
Described transition metal nitrate is the mixture of 0.9g six water nickelous nitrate and 0.9g nitrate trihydrate copper composition;
Described Metaporous silicon dioxide material is cubic structure KIT-6;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 18.5mol:1.5mmol:1.6g:12ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 10 DEG C/min heat up most 650 DEG C carry out calcining 4h, obtain the second powder;
(3), by the second powder concentration of step (2) gained be 4mol/L aqueous sodium hydroxide solution etching 12
After h, to remove meso pore silicon oxide material, repeat this step 3 time, then with pure water washing, control temperature is 100 DEG C dries, and the powder obtained is photo catalytic reduction CO
2mesopore metal oxide catalyzer.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:12.3;
Described transition metal ion is nickel ion and cupric ion, calculates in molar ratio, nickel ion: cupric ion is 1:1.2.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer after testing (instrument: Bei Shide, 3H-2000PS4 type specific surface area and Porosimetry), its specific surface area is 215m
2/ g, aperture is 4.2nm, and pore volume is 1.21cm
3/ g.
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h and synthesizes carbon monoxide, and the productive rate of final carbon monoxide is 3500 μm of ol/g-cat..
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer at 25 DEG C for photochemical catalysis CO
2with H
2o reacts 7h synthesizing methane, and the productive rate of final methane is 2200 μm of ol/g-cat..
In sum, of the present invention for photo catalytic reduction CO
2mesopore metal oxide catalyzer respectively photo catalytic reduction CO at 25 DEG C
2and H
2o reacts 7h and generates carbon monoxide and methane, and its productive rate is respectively 550-3900umol/g-cat. and 490-2600umol/g-cat..
Be compared to traditional TiO
2with pure order mesoporous CeO
2catalyzer, of the present invention for photo catalytic reduction CO
2mesopore metal oxide catalyzer not only there is the pore passage structure of higher specific surface area, larger aperture Sum fanction, and show higher catalytic reduction CO
2and H
2the performance of O.
The above is only the citing of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (11)
1. one kind for photo catalytic reduction CO
2the preparation method of mesopore metal oxide catalyzer, it is characterized in that specifically comprising following steps:
(1), transition metal nitrate and cerous nitrate are dissolved in acetone, obtain metal nitrate acetone soln, then add meso pore silicon oxide material and be uniformly mixed 0.5-12h, then natural air drying, obtain the first powder;
Described transition metal nitrate is one or more the mixture in iron nitrate, chromium nitrate, nickelous nitrate, cupric nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
Described Metaporous silicon dioxide material is one or more the mixture in hexagonal structure SBA-15, cubic structure KIT-6 and MCM-48;
The amount of above-mentioned transition metal nitrate used, cerous nitrate, meso pore silicon oxide material and acetone, in cerous nitrate: transition metal nitrate: meso pore silicon oxide material: acetone is that the ratio of 17-19.8mmol:0.2-3mmol:1-3g:10-20ml calculates;
(2), by the first powder obtained in step (1) be placed in retort furnace, under oxygen atmosphere with the temperature rise rate of 1-15 DEG C/min heat up most 200-1000 DEG C carry out calcining 1-12h, obtain the second powder;
(3), by the second powder volumetric molar concentration of step (2) gained be after the aqueous sodium hydroxide solution etching 5-30h of 1-6mol/L, to remove meso pore silicon oxide material, then with pure water washing, dry, the powder obtained is for photo catalytic reduction CO
2mesopore metal oxide catalyzer.
2. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5.67-99;
The transition metal ion of gained is the mixing of one or more metal ions in iron ion, chromium ion, nickel ion, cupric ion, cobalt ion;
Gained is used for photo catalytic reduction CO
2the specific surface area of mesopore metal oxide catalyzer be 130.5-220m
2/ g, aperture is 2.9-5.5nm, and pore volume can reach 0.47-1.21cm
3/ g.
3. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:99;
Transition metal ion is iron ion;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 145.8m
2/ g, aperture is 3.8nm, and pore volume is 0.47cm
3/ g.
4. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:19;
Described transition metal ion is chromium ion;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 130.5m
2/ g, aperture is 3.5nm, and pore volume is 0.49cm
3/ g.
5. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:9.1;
Transition metal ion is chromium ion;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 156m
2/ g, aperture is 4.3nm, and pore volume is 0.65cm
3/ g.
6. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:9.47;
Transition metal ion is chromium ion and iron ion, calculates, the precursor of ferric oxide: the precursor of chromic oxide is 1:1 by precursor mass ratio;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 180m
2/ g, aperture is 4.6nm, and pore volume is 0.62cm
3/ g.
7. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5.67;
Transition metal ion is iron ion and cobalt ion, calculates in molar ratio, iron: cobalt is 1:2;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 175m
2/ g, aperture is 4.5nm, and pore volume is 0.58cm
3/ g.
8. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:7.5;
Transition metal ion is chromium ion and cobalt ion, calculates by mol, chromium ion: cobalt ion is 1:1.37;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 220m
2/ g, aperture is 6.2nm, and pore volume is 0.87cm
3/ g.
9. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:5.67;
Transition metal ion is cupric ion;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 205m
2/ g, aperture is 2.9nm, and pore volume is 1.1cm
3/ g.
10. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:8.38;
Transition metal ion is nickel ion;
Gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 135m
2/ g, aperture is 5.5nm, and pore volume is 0.92cm
3/ g.
11. as claimed in claim 1 preparation method's gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, it is characterized in that gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, be made up of active ingredient and doping agent, described active ingredient is meso-pore Ce O
2, doping agent is transition metal ion;
Transition metal ion: meso-pore Ce O
2mol ratio be 1:12.3;
Transition metal ion is nickel ion and cupric ion, calculates in molar ratio, nickel ion: cupric ion is 1:1.2;
Above-mentioned gained for photo catalytic reduction CO
2mesopore metal oxide catalyzer, its specific surface area is 215m
2/ g, aperture is 4.2nm, and pore volume is 1.21cm
3/ g.
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