CN106492778A - A kind of doping vario-property nano Ce O2Rod catalyst and its application - Google Patents
A kind of doping vario-property nano Ce O2Rod catalyst and its application Download PDFInfo
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- CN106492778A CN106492778A CN201610969493.9A CN201610969493A CN106492778A CN 106492778 A CN106492778 A CN 106492778A CN 201610969493 A CN201610969493 A CN 201610969493A CN 106492778 A CN106492778 A CN 106492778A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
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Abstract
The invention discloses a kind of doping vario-property nano Ce O2Rod catalyst and its application, the modified metal adulterated thereon by ceria nanopowder rod and by a step Vacuum-assisted method is elementary composition, the ceria nanopowder rod exposes (110) and (100) crystal face, and the modified metal element is Zr, La, Y or Sr.Nano Ce O due to different-shape2Different crystal faces are exposed, completely different surface characteristic and catalysis characteristicses is shown, is wherein exposed the nano Ce O of (110) and (100) crystal face2The reverse water-gas-shift reaction performance of rod is optimal, and the present invention is with rod-like nano CeO2The catalytic action of catalyst can at utmost be played.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of doping vario-property nano Ce O2Rod catalyst and its should
With.
Background technology
At present in CO2Conversion and application in, reverse water-gas-shift reaction be using carbon dioxide generate carbon monoxide
One of effective ways, are also considered as one of most promising reaction.In the practical application of reverse water-gas-shift reaction,
Generally with CO2As carbon source, more valuable CO is generated by reverse water-gas-shift reaction, then using CO as intermedium, entered
Row next step synthesizes, and in the direct preparing low-carbon olefins technique of synthesis gas, the reverse water-gas-shift reaction under hot conditionss is to close
One step of key.
At present, multiple reverse water-gas-shift reaction catalyst have been developed by the effort of research worker, but has been existed stable
Property the defect such as poor, high temperature easy-sintering, easy in inactivation, such as copper-based catalysts easily sinter under the high temperature conditions and aoxidize, cause to be catalyzed
Agent is inactivated；Easily reduction is inactivated zinc-aluminium catalyst under the high temperature conditions；Platinum cerium catalyst is also easy to produce carbon distribution during the course of the reaction and leads
Cause inactivation.In addition, the conversion ratio and selectivity of many catalyst there is also shortcomings, thus research and development high activity is high steady
Qualitatively reverse water-gas-shift reaction catalyst has for the production of the recycling and Organic chemical products of carbon dioxide
Huge meaning.
Content of the invention
It is an object of the invention to overcoming prior art defect, there is provided a kind of doping vario-property nano Ce O2Rod catalyst.
Another object of the present invention is to providing above-mentioned doping vario-property nano Ce O2The preparation method of rod catalyst.
It is still another object of the present invention to provide above-mentioned doping vario-property nano Ce O2The application of rod catalyst.
Technical scheme is as follows：
A kind of doping vario-property nano Ce O2Rod catalyst, is adulterated by ceria nanopowder rod and by a step Vacuum-assisted method
Modified metal thereon is elementary composition, and the ceria nanopowder rod exposes (110) and (100) crystal face, the modified metal element be Zr,
La, Y or Sr.
Above-mentioned doping vario-property nano Ce O2The preparation method of rod catalyst, including：
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3·6H2O is dissolved in distilled water, is sufficiently stirred for
Obtain the first solution, nitrate of the modified metal elemental precursors for modified metal element；
(2) accurately weigh appropriate NaOH to be dissolved in distilled water, be sufficiently stirred for, obtain the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues to be sufficiently stirred for, obtain suspension；
(4) suspension is loaded PPL liners, is put in the Hydrothermal Synthesiss kettle of stainless steel, and then by the Hydrothermal Synthesiss
Kettle is put into 20～30h of heating in 95～105 DEG C of baking ovens, obtains the nano Ce O of doping vario-property2Rod；
(5) after Hydrothermal Synthesiss kettle natural cooling, wherein supernatant is removed, adds deionized water wash to precipitate 2～3 times,
It is centrifuged after supersound process, must precipitates, then precipitated with absolute ethanol washing, is centrifuged after continuing supersound process, obtains white precipitate；
(6) white precipitate is vacuum dried, vacuum drying temperature is 55～65 DEG C, and the time is 20～30h, obtains
Pale yellow powder；
(7) by above-mentioned pale yellow powder in N2380～420 DEG C of 3～5h of roasting under atmosphere, obtain final product the doping vario-property nanometer
CeO2Rod catalyst.
In a preferred embodiment of the invention, the time of the stirring of step (1), (2) and (3) is at least
30min.
In a preferred embodiment of the invention, step (4) are：Suspension is loaded PPL liners, is put into not
In the Hydrothermal Synthesiss kettle of rust steel matter, and then the Hydrothermal Synthesiss kettle is put into heating 24h in 100 DEG C of baking ovens, obtains doping vario-property
Nano Ce O2Rod.
In a preferred embodiment of the invention, the time of the supersound process of step (5) is 20min.
In a preferred embodiment of the invention, in step (6), vacuum drying temperature is 60 DEG C, and the time is
24h.
In a preferred embodiment of the invention, step (7) are：By above-mentioned pale yellow powder under N2 atmosphere
400 DEG C of roasting 4h, obtain final product the doping vario-property nano Ce O2Rod catalyst.
A kind of above-mentioned doping vario-property nano Ce O2Application of the rod catalyst in reverse water-gas-shift reaction.
Beneficial effects of the present invention：
(1) due to the nano Ce O of different-shape2Different crystal faces are exposed, completely different surface characteristic and catalysis is shown
Characteristic, wherein exposes the nano Ce O of (110) and (100) crystal face2The reverse water-gas-shift reaction performance of rod is optimal, the present invention with
Rod-like nano CeO2The catalytic action of catalyst can at utmost be played.
(2) present invention is with above-mentioned nano Ce O2Catalysis material of the rod as reverse water-gas-shift reaction, using a step hydro-thermal
The mode of method adds the auxiliary agents such as Zr, La, Y, Sr to nano Ce O2Rod is doped modification, the heat of raising catalyst easily and effectively
Stability and reverse water-gas-shift reaction performance, specifically, in nano Ce O2Doping Zr, La, Y, Sr etc. in the growth course of rod
Metallic element, the big Ce of substitution ion radius in hydro-thermal reaction4+, nano Ce O can be made2Rod into more defects and Lacking oxygen,
Increase nano Ce O2Barred body phase oxygen and the mobility of Surface Oxygen, reduce oxonium ion Diffusion Activation Energy, and can increase nano Ce O2
The structural stability of rod, improves its high-temperature stability.
Description of the drawings
Fig. 1 is the doping vario-property nano Ce O of the present invention2The preparation technology of rod catalyst and the flow chart of application.
Fig. 2 is doping vario-property nano Ce O obtained in various embodiments of the present invention2The FE-SEM figures of rod catalyst.
Specific embodiment
Accompanying drawing is combined below by way of specific embodiment to be further detailed technical scheme and describe.
In following embodiments, the preparation technology flow process and application flow of obtained catalyst is as shown in figure 1, obtained urge
The reverse water-gas-shift reaction performance test of agent is carried out in the miniature fixed-bed catalytic reactor that voluntarily builds.Concrete anti-
Should carry out in isothermal fixed bed continuously flows reaction system, quartz ampoule of the reactor for 8mm internal diameters is carried out under atmospheric pressure environment anti-
Should.Reaction temperature is provided by electric tube furnace, and beds insert the K-type thermocouple of a diameter of 1mm.Unstripped gas drying pipe and
After deoxidation pipe dries deoxidation, through mass flow controller controller flow.Take 100mg catalyst, in 1: 10 (g/g) ratio with
The quartz sand mix homogeneously of 100～200 mesh.Silica wool is filled in quartz tube reactor in advance, 60～100 mesh of 1g is recharged
Quartz sand, then load the catalyst of dilution.80%H before reaction at 400 DEG C with 60ml/min2/N2Gaseous mixture is reduced
60min.Unstripped gas is CO2And H2, reacted by beds under certain flow and certain air speed, reaction temperature model
Enclose for 400～800 DEG C, detect once per 50 DEG C.Unstripped gas and exhaust gas component are divided online using gas chromatogram (EChrom A90)
Analysis, TCD detectors are detected.
Embodiment 1：
(1) 0.0172g Zr (NO are weighed3)4·5H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
Stirring 30min, obtains the first solution；
(2) 19.200g NaOH are accurately weighed to be dissolved in 10ml distilled water, 30min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues stirring 30min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
24h is heated in 100 DEG C of baking ovens, the nano Ce O of Zr doping vario-properties is obtained2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 20min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 20min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 60 DEG C, and the time is 24h, obtains yellowish toner
End；
(7) by gained pale yellow powder under N2 atmosphere 400 DEG C of roasting 4h, obtain 1%Zr-CeO2Catalyst is (such as Fig. 2
Shown in (b)).
By 1%Zr-CeO2Catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is
When 600 DEG C, 30h, CO is reacted2Conversion ratio all the time more than 12.5%, CO yields up to 7.4%, CO selectivitys 100%, without pair
Product methane is generated.
Embodiment 2：
(1) 0.0173g La (NO are weighed3)3·6H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
Stirring 30min, obtains the first solution；
(2) 19.200g NaOH are accurately weighed to be dissolved in 10ml distilled water, 30min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues stirring 30min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
24h is heated in 100 DEG C of baking ovens, the nano Ce O of Zr doping vario-properties is obtained2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 20min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 20min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 60 DEG C, and the time is 24h, obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roasting 4h of atmosphere, obtain 1%La-CeO2Catalyst.
By 1%La-CeO2Catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is
When 600 DEG C, 30h, CO is reacted2Conversion ratio all the time more than 11.0%, CO yields up to 6.6%, CO selectivitys 100%, without pair
Product methane is generated.
Embodiment 3：
(1) 1.736g Ce (NO are weighed3)3·6H2O is dissolved in 70ml distilled water, is stirred 30min, is obtained the first solution；
(2) 19.200g NaOH are accurately weighed to be dissolved in 10ml distilled water, 30min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in second, continues stirring 30min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
24h is heated in 100 DEG C of baking ovens, the nano Ce O of Zr doping vario-properties is obtained2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 20min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 20min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 60 DEG C, and the time is 24h, obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roasting 4h of atmosphere, obtain CeO2Rod catalyst is (such as Fig. 2 (a) institutes
Show).
By CeO2Rod catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is 600
DEG C when, react 30h, CO2, all the time more than 8.5%, CO yields are up to 4.8%, CO selectivitys 100%, no coupling product for conversion ratio
Methane is generated.
Embodiment 4：
(1) 0.0516g Zr (NO are weighed3)4·5H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
Stirring 30min, obtains the first solution；
(2) 19.200g NaOH are accurately weighed to be dissolved in 10ml distilled water, 30min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues stirring 30min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
24h is heated in 100 DEG C of baking ovens, the nano Ce O of Zr doping vario-properties is obtained2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 20min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 20min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 60 DEG C, and the time is 24h, obtains yellowish toner
End；
(7) by gained pale yellow powder under N2 atmosphere 400 DEG C of roasting 4h, obtain 3%Zr-CeO2Catalyst is (such as Fig. 2
Shown in (c)).
By 3%Zr-CeO2Catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is
When 600 DEG C, 30h, CO is reacted2Conversion ratio all the time more than 15.9%, CO yields up to 9.6%, CO selectivitys 100%, without pair
Product methane is generated.
Embodiment 5
(1) 0.140g Y (NO are weighed3)3·6H2O and 2.000g Ce (NO3)3·6H2O is dissolved in 70ml distilled water, is stirred
60min is mixed, the first solution is obtained；
(2) 38.400g NaOH are accurately weighed to be dissolved in 20ml distilled water, 30min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues stirring 60min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
Reacting by heating 24h in 100 DEG C of constant temperature ovens, obtains the nano Ce O of Y doping vario-properties2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 30min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 30min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 55 DEG C, and the time is 12h, obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roasting 4h of atmosphere, obtain 1%Y-CeO2Catalyst is (as schemed (e) institute
Show).
By 1%Y-CeO2Catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is
When 750 DEG C, 1h, CO is reacted2Conversion ratio is in 40% or so, CO yields up to 22%, CO selectivitys 100%, no coupling product methane
Generate.
Embodiment 6
(1) 0.143g anhydrous strontium nitrates and 1.500g Ce (NO are weighed3)3·6H2O is dissolved in 70ml distilled water, stirring
60min, obtains the first solution；
(2) 19.200g NaOH are accurately weighed to be dissolved in 20ml distilled water, 60min is stirred, is obtained the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues stirring 30min, obtain suspension；
(4) suspension is loaded 100ml PPL liners, is put into stainless steel water thermal synthesis kettle, the Hydrothermal Synthesiss kettle is put into
Reacting by heating 18h in 100 DEG C of constant temperature ovens, obtains the nano Ce O of Sr doping vario-properties2Rod；
(5) after water heating kettle temperature natural cooling, supernatant is removed, adds deionized water wash to precipitate twice, ultrasound
It is centrifuged after 30min, is then precipitated with absolute ethanol washing, is centrifuged after ultrasonic 30min, obtains white precipitate；
(6) white precipitate is put into vacuum drying oven, vacuum drying temperature is 65 DEG C, and the time is 12h, obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roasting 3h of atmosphere, obtain 1%Sr-CeO2Catalyst is (such as figure (f)
Shown).
By 1%Sr-CeO2Catalyst is placed in fixed-bed micro-devices carries out reverse water-gas-shift reaction, and reaction temperature is
When 800 DEG C, 1h, CO is reacted2Conversion ratio is in 47% or so, CO yields up to 24%, CO selectivitys 100%, no coupling product methane
Generate.
Those of ordinary skill in the art understand, when technical scheme changes in the following ranges, remain able to
To same as the previously described embodiments or close technical scheme, protection scope of the present invention is still fallen within：
A kind of doping vario-property nano Ce O2Rod catalyst, is adulterated by ceria nanopowder rod and by a step Vacuum-assisted method
Modified metal thereon is elementary composition, and the ceria nanopowder rod exposes (110) and (100) crystal face, the modified metal element be Zr,
La, Y or Sr.
Above-mentioned doping vario-property nano Ce O2The preparation method of rod catalyst, including：
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3·6H2O is dissolved in distilled water, is sufficiently stirred for
Obtain the first solution, nitrate of the modified metal elemental precursors for modified metal element；
(2) accurately weigh appropriate NaOH to be dissolved in distilled water, be sufficiently stirred for, obtain the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues to be sufficiently stirred for, obtain suspension；
(4) suspension is loaded PPL liners, is put in the Hydrothermal Synthesiss kettle of stainless steel, and then by the Hydrothermal Synthesiss
Kettle is put into 20～30h of heating in 95～105 DEG C of baking ovens, obtains the nano Ce O of doping vario-property2Rod；
(5) after Hydrothermal Synthesiss kettle natural cooling, wherein supernatant is removed, adds deionized water wash to precipitate 2～3 times,
It is centrifuged after supersound process, must precipitates, then precipitated with absolute ethanol washing, is centrifuged after continuing supersound process, obtains white precipitate；
(6) white precipitate is vacuum dried, vacuum drying temperature is 55～65 DEG C, and the time is 20～30h, obtains
Pale yellow powder；
(7) by above-mentioned pale yellow powder in N2380～420 DEG C of 3～5h of roasting under atmosphere, obtain final product the doping vario-property nanometer
CeO2Rod catalyst.
The above, only presently preferred embodiments of the present invention, therefore the scope of present invention enforcement can not be limited according to this, i.e.,
The equivalence changes that is made according to the scope of the claims of the present invention and description and modification, all still should belong in the range of the present invention covers.
Claims (8)
1. a kind of doping vario-property nano Ce O2Rod catalyst, it is characterised in that：Close by ceria nanopowder rod and by a step Situ Hydrothermal
Into and the modified metal thereon of adulterating is elementary composition, the ceria nanopowder rod exposes (110) and (100) crystal face, the modified metal
Element is Zr, La, Y or Sr.
2. a kind of doping vario-property nano Ce O as claimed in claim 12The preparation method of rod catalyst, it is characterised in that：Including：
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3·6H2O is dissolved in distilled water, be sufficiently stirred for
One solution, nitrate of the modified metal elemental precursors for modified metal element；
(2) accurately weigh appropriate NaOH to be dissolved in distilled water, be sufficiently stirred for, obtain the second solution；
(3) the first solution is dropwise added drop-wise in the second solution, continues to be sufficiently stirred for, obtain suspension；
(4) suspension is loaded PPL liners, is put in the Hydrothermal Synthesiss kettle of stainless steel, and then the Hydrothermal Synthesiss kettle is put
Enter 20～30h of heating in 95～105 DEG C of baking ovens, obtain the nano Ce O of doping vario-property2Rod；
(5) after Hydrothermal Synthesiss kettle natural cooling, wherein supernatant is removed, adds deionized water wash to precipitate 2～3 times, ultrasound
It is centrifuged after process, must precipitates, then precipitated with absolute ethanol washing, is centrifuged after continuing supersound process, obtains white precipitate；
(6) white precipitate is vacuum dried, vacuum drying temperature is 55～65 DEG C, and the time is 20～30h, obtains yellowish
Color powder；
(7) by above-mentioned pale yellow powder in N2380～420 DEG C of 3～5h of roasting under atmosphere, obtain final product the doping vario-property nano Ce O2
Rod catalyst.
3. preparation method as claimed in claim 2, it is characterised in that：The time of the stirring of step (1), (2) and (3) is extremely
It is 30min less.
4. preparation method as claimed in claim 2, it is characterised in that：Step (4) are：Suspension is loaded PPL liners,
It is put in the Hydrothermal Synthesiss kettle of stainless steel, and then the Hydrothermal Synthesiss kettle is put into heating 24h in 100 DEG C of baking ovens, is mixed
Miscellaneous modified nano Ce O2Rod.
5. preparation method as claimed in claim 2, it is characterised in that：The time of the supersound process of step (5) is
20min.
6. preparation method as claimed in claim 2, it is characterised in that：In step (6), vacuum drying temperature is 60 DEG C,
Time is 24h.
7. preparation method as claimed in claim 2, it is characterised in that：Step (7) are：By above-mentioned pale yellow powder in N2
The lower 400 DEG C of roasting 4h of atmosphere, obtain final product the doping vario-property nano Ce O2Rod catalyst.
8. the doping vario-property nano Ce O described in a kind of claim 12Application of the rod catalyst in reverse water-gas-shift reaction.
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| CN106984320A (en) * | 2017-04-24 | 2017-07-28 | 北京化工大学 | A kind of high-dispersion loading type metallic catalyst and preparation method thereof |
| WO2019230853A1 (en) * | 2018-05-29 | 2019-12-05 | 積水化学工業株式会社 | Catalyst mixture, method for producing reduced product, and device for producing reduced product |
| WO2019230855A1 (en) * | 2018-05-29 | 2019-12-05 | 積水化学工業株式会社 | Catalyst, method for reducing carbon dioxide, and apparatus for reducing carbon dioxide |
| JPWO2019230855A1 (en) * | 2018-05-29 | 2021-07-08 | 積水化学工業株式会社 | Catalysts, carbon dioxide reduction methods, and carbon dioxide reduction devices |
| US11305261B2 (en) | 2018-05-29 | 2022-04-19 | Sekisui Chemical Co., Ltd. | Catalyst, carbon dioxide reducing method, and apparatus for reducing carbon dioxide |
| JP7305633B2 (en) | 2018-05-29 | 2023-07-10 | 積水化学工業株式会社 | Catalyst, carbon dioxide reduction method, and carbon dioxide reduction device |
| CN109589962A (en) * | 2018-12-25 | 2019-04-09 | 江南大学 | A kind of high resistance to SO_2 cerium based low-temperature denitration catalyst and preparation method thereof |
| CN110127746A (en) * | 2019-06-11 | 2019-08-16 | 北京科技大学 | A kind of regulation method of monocrystalline state ceria oxygen vacancy concentration |
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