CN106492778B - A kind of doping vario-property nano Ce O2Stick catalyst and its application - Google Patents
A kind of doping vario-property nano Ce O2Stick catalyst and its application Download PDFInfo
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- CN106492778B CN106492778B CN201610969493.9A CN201610969493A CN106492778B CN 106492778 B CN106492778 B CN 106492778B CN 201610969493 A CN201610969493 A CN 201610969493A CN 106492778 B CN106492778 B CN 106492778B
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- 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
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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 O2Stick catalyst and its application, by ceria nanopowder stick and modified metal element thereon is adulterated by a step Vacuum-assisted method forms, the ceria nanopowder stick exposes (110) and (100) crystal face, which is Zr, La, Y or Sr.Due to the nano Ce O of different-shape2The different crystal faces of exposure, show completely different surface characteristic and catalysis characteristics, wherein the nano Ce O of exposure (110) and (100) crystal face2The reverse water-gas-shift reaction performance of stick is best, and the present invention is with rod-like nano CeO2The catalytic action of catalyst can utmostly be played.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of doping vario-property nano Ce O2It stick catalyst and its answers
With.
Background technique
At present in CO2Conversion and application in, reverse water-gas-shift reaction utilize carbon dioxide generate carbon monoxide
One of effective ways are also considered as most promising one of reaction.In the practical application of reverse water-gas-shift reaction,
Usually with CO2As carbon source, more valuable CO is generated by reverse water-gas-shift reaction, then using CO as intermediary, into
Row synthesizes in next step, and in the direct preparing low-carbon olefins technique of synthesis gas, the reverse water-gas-shift reaction under hot conditions is to close
One step of key.
Currently, having developed a variety of reverse water-gas-shift reaction catalyst by the effort of researcher, but exists and stablize
Property poor, high temperature easy-sintering, easy in inactivation the defects of, if copper-based catalysts are easy sintering and oxidation under the high temperature conditions, cause to be catalyzed
Agent inactivation；Zinc-aluminium catalyst is easy reduction inactivation under the high temperature conditions；Platinum cerium catalyst is also easy to produce carbon distribution during the reaction and leads
Cause inactivation.In addition, there is also shortcomings for the conversion ratio of many catalyst and selectivity, thus it is high steady to research and develop high activity
Qualitative reverse water-gas-shift reaction catalyst has the resource utilization of carbon dioxide and the production of Organic chemical products
Huge meaning.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of doping vario-property nano Ce O is provided2Stick catalyst.
Another object of the present invention is to provide above-mentioned doping vario-property nano Ce O2The preparation method of stick catalyst.
A further object of the present invention is to provide above-mentioned doping vario-property nano Ce O2The application of stick catalyst.
Technical scheme is as follows:
A kind of doping vario-property nano Ce O2Stick catalyst is adulterated by ceria nanopowder stick and by a step Vacuum-assisted method
Thereon modified metal element composition, the ceria nanopowder stick exposure (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 stick catalyst, comprising:
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3·6H2O is dissolved in distilled water, is sufficiently stirred
The first solution is obtained, modified metal elemental precursors are the nitrate of modified metal element；
(2) it accurately weighs appropriate NaOH to be dissolved in distilled water, be sufficiently stirred, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to be sufficiently stirred, obtains suspension；
(4) suspension is packed into PPL liner, be put into the hydrothermal synthesis kettle of stainless steel material, and then by the hydrothermal synthesis
Kettle is put into 20~30h of heating in 95~105 DEG C of baking ovens, obtains the nano Ce O of doping vario-property2Stick；
(5) after hydrothermal synthesis kettle natural cooling, wherein supernatant is removed, is added deionized water washing precipitating 2~3 times,
It is centrifuged, must precipitate after ultrasonic treatment, then wash precipitating with dehydrated alcohol, be centrifuged after continuing ultrasonic treatment, obtain white precipitate；
(6) white precipitate is dried in vacuo, vacuum drying temperature is 55~65 DEG C, and the time is 20~30h, is obtained
Pale yellow powder；
(7) by above-mentioned pale yellow powder in N2380~420 DEG C of 3~5h of roasting are under atmosphere to get the doping vario-property nanometer
CeO2Stick catalyst.
In a preferred embodiment of the invention, the step (1), (2) and (3) time of stirring be at least
30min。
In a preferred embodiment of the invention, the step (4) are as follows: suspension is packed into PPL liner, is put into not
In the hydrothermal synthesis kettle for steel material of becoming rusty, and then the hydrothermal synthesis kettle is put into 100 DEG C of baking ovens and is heated for 24 hours, obtains doping vario-property
Nano Ce O2Stick.
In a preferred embodiment of the invention, the time of the ultrasonic treatment of the step (5) is 20min.
In a preferred embodiment of the invention, vacuum drying temperature is 60 DEG C in the step (6), and the time is
24h.
In a preferred embodiment of the invention, the step (7) are as follows: by above-mentioned pale yellow powder under N2 atmosphere
400 DEG C of roasting 4h are to get the doping vario-property nano Ce O2Stick catalyst.
A kind of above-mentioned doping vario-property nano Ce O2Application of the stick catalyst in reverse water-gas-shift reaction.
Beneficial effects of the present invention:
(1) due to the nano Ce O of different-shape2The different crystal faces of exposure, show completely different surface characteristic and catalysis
Characteristic, wherein the nano Ce O of exposure (110) and (100) crystal face2The reverse water-gas-shift reaction performance of stick is best, the present invention with
Rod-like nano CeO2The catalytic action of catalyst can utmostly be played.
(2) present invention is with above-mentioned nano Ce O2Catalysis material of the stick 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 O2Stick is doped modification, the heat of raising catalyst easily and effectively
Stability and reverse water-gas-shift reaction performance, specifically, in nano Ce O2Zr, La, Y, Sr etc. are adulterated in the growth course of stick
Metallic element, the big Ce of substitution ion radius in hydro-thermal reaction4+, nano Ce O can be made2Stick forms more defects and Lacking oxygen,
Increase nano Ce O2The mobility of barred body phase oxygen and Surface Oxygen reduces oxonium ion Diffusion Activation Energy, and can increase nano Ce O2
The structural stability of stick improves its high-temperature stability.
Detailed description of the invention
Fig. 1 is doping vario-property nano Ce O of the invention2The flow chart of the preparation process and application of stick catalyst.
Fig. 2 is doping vario-property nano Ce O made from various embodiments of the present invention2The FE-SEM of stick catalyst schemes.
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment combination attached drawing.
The preparation process flow and application flow of obtained catalyst are as shown in Figure 1, obtained urge in following embodiments
The reverse water-gas-shift reaction performance test of agent carries out in the miniature fixed-bed catalytic reactor voluntarily built.It is specific anti-
It should continuously flow in reaction system and carry out in isothermal fixed bed, reactor is the quartz ampoule of 8mm internal diameter, is carried out under atmospheric pressure environment anti-
It answers.Reaction temperature is provided by electric tube furnace, and catalyst bed is inserted into the K-type thermocouple that diameter is 1mm.Unstripped gas through drying tube and
After the dry deoxidation of deoxidation pipe, through mass flow controller controller flow.Take 100mg catalyst, in 1: 10 (g/g) ratio with
The quartz sand of 100~200 mesh is uniformly mixed.Silica wool is filled in quartz tube reactor in advance, recharges 60~100 mesh of 1g
Quartz sand, then load diluted catalyst.80% H of 60ml/min is used before reaction at 400 DEG C2/N2Gaseous mixture reduction
60min.Unstripped gas is CO2And H2, reacted under certain flow and certain air speed by catalyst bed, reaction temperature model
Enclosing is 400~800 DEG C, and every 50 DEG C of detections are primary.Unstripped gas and exhaust gas component are divided online using gas-chromatography (EChrom A90)
Analysis, the detection of TCD detector.
Embodiment 1:
(1) 0.0172g Zr (NO is weighed3)4·5H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
30min is stirred, the first solution is obtained；
(2) it accurately weighs 19.200g NaOH to be dissolved in 10ml distilled water, stirs 30min, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to stir 30min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
The nano Ce O for obtaining Zr doping vario-property for 24 hours is heated in 100 DEG C of baking ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 20
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 20min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 60 DEG C, and the time is for 24 hours, to obtain yellowish toner
End；
(7) by gained pale yellow powder under N2 atmosphere 400 DEG C of roasting 4h, obtain 1%Zr-CeO2Catalyst (such as Fig. 2
(b) shown in).
By 1%Zr-CeO2Catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, and reaction temperature is
At 600 DEG C, 30h, CO are reacted2Conversion ratio is always in 12.5% or more, CO yield up to 7.4%, CO selectivity 100%, no pair
Product methane generates.
Embodiment 2:
(1) 0.0173g La (NO is weighed3)3·6H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
30min is stirred, the first solution is obtained；
(2) it accurately weighs 19.200g NaOH to be dissolved in 10ml distilled water, stirs 30min, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to stir 30min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
The nano Ce O for obtaining Zr doping vario-property for 24 hours is heated in 100 DEG C of baking ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 20
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 20min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 60 DEG C, and the time is for 24 hours, to obtain yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roastings 4h of atmosphere, obtains 1%La-CeO2Catalyst.
By 1%La-CeO2Catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, and reaction temperature is
At 600 DEG C, 30h, CO are reacted2Conversion ratio is always in 11.0% or more, CO yield up to 6.6%, CO selectivity 100%, no pair
Product methane generates.
Embodiment 3:
(1) 1.736g Ce (NO is weighed3)3·6H2O is dissolved in 70ml distilled water, is stirred 30min, is obtained the first solution；
(2) it accurately weighs 19.200g NaOH to be dissolved in 10ml distilled water, stirs 30min, obtain the second solution；
(3) the first solution is added drop-wise in second dropwise, continues to stir 30min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
The nano Ce O for obtaining Zr doping vario-property for 24 hours is heated in 100 DEG C of baking ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 20
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 20min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 60 DEG C, and the time is for 24 hours, to obtain yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roastings 4h of atmosphere, obtains CeO2Stick catalyst is (such as Fig. 2 (a) institute
Show).
By CeO2Stick catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, reaction temperature 600
DEG C when, react 30h, CO2Conversion ratio is always in 8.5% or more, CO yield up to 4.8%, CO selectivity 100%, no coupling product
Methane generates.
Embodiment 4:
(1) 0.0516g Zr (NO is weighed3)4·5H2O and 1.736g Ce (NO3)3·6H2O is dissolved in 70ml distilled water,
30min is stirred, the first solution is obtained；
(2) it accurately weighs 19.200g NaOH to be dissolved in 10ml distilled water, stirs 30min, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to stir 30min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
The nano Ce O for obtaining Zr doping vario-property for 24 hours is heated in 100 DEG C of baking ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 20
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 20min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 60 DEG C, and the time is for 24 hours, to obtain yellowish toner
End；
(7) by gained pale yellow powder under N2 atmosphere 400 DEG C of roasting 4h, obtain 3%Zr-CeO2Catalyst (such as Fig. 2
(c) shown in).
By 3%Zr-CeO2Catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, and reaction temperature is
At 600 DEG C, 30h, CO are reacted2Conversion ratio is always in 15.9% or more, CO yield up to 9.6%, CO selectivity 100%, no pair
Product methane generates.
Embodiment 5
(1) 0.140g Y (NO is 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) it accurately weighs 38.400g NaOH to be dissolved in 20ml distilled water, stirs 30min, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to stir 60min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
Heating reaction for 24 hours, obtains the nano Ce O of Y doping vario-property in 100 DEG C of constant temperature ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 30
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 30min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 55 DEG C, and time 12h obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roastings 4h of atmosphere, obtains 1%Y-CeO2Catalyst is (such as figure (e)
It is shown).
By 1%Y-CeO2Catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, and reaction temperature is
At 750 DEG C, 1h, CO are reacted2Conversion ratio is in 40% or so, CO yield up to 22%, CO selectivity 100%, no coupling product methane
It generates.
Embodiment 6
(1) 0.143g anhydrous strontium nitrate and 1.500g Ce (NO are weighed3)3·6H2O is dissolved in 70ml distilled water, stirring
60min obtains the first solution；
(2) it accurately weighs 19.200g NaOH to be dissolved in 20ml distilled water, stirs 60min, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to stir 30min, obtains suspension；
(4) suspension is packed into 100ml PPL liner, is put into stainless steel water thermal synthesis kettle, which is put into
Heating reaction 18h, obtains the nano Ce O of Sr doping vario-property in 100 DEG C of constant temperature ovens2Stick；
(5) after water heating kettle temperature natural cooling, supernatant is removed, deionized water washing precipitating is added twice, ultrasound 30
It is centrifuged after min, then washs precipitating with dehydrated alcohol, be centrifuged after ultrasonic 30min, obtain white precipitate；
(6) white precipitate is put into vacuum oven, vacuum drying temperature is 65 DEG C, and time 12h obtains yellowish toner
End；
(7) by gained pale yellow powder in N2The lower 400 DEG C of roastings 3h of atmosphere, obtains 1%Sr-CeO2Catalyst is (such as figure (f)
It is shown).
By 1%Sr-CeO2Catalyst, which is placed in fixed-bed micro-devices, carries out reverse water-gas-shift reaction, and reaction temperature is
At 800 DEG C, 1h, CO are reacted2Conversion ratio is in 47% or so, CO yield up to 24%, CO selectivity 100%, no coupling product methane
It generates.
Those of ordinary skill in the art still are able to it is found that when technical solution of the present invention changes in following ranges
To same as the previously described embodiments or similar technical solution, protection scope of the present invention is still fallen within:
A kind of doping vario-property nano Ce O2Stick catalyst is adulterated by ceria nanopowder stick and by a step Vacuum-assisted method
Thereon modified metal element composition, the ceria nanopowder stick exposure (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 stick catalyst, comprising:
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3·6H2O is dissolved in distilled water, is sufficiently stirred
The first solution is obtained, modified metal elemental precursors are the nitrate of modified metal element；
(2) it accurately weighs appropriate NaOH to be dissolved in distilled water, be sufficiently stirred, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to be sufficiently stirred, obtains suspension；
(4) suspension is packed into PPL liner, be put into the hydrothermal synthesis kettle of stainless steel material, and then by the hydrothermal synthesis
Kettle is put into 20~30h of heating in 95~105 DEG C of baking ovens, obtains the nano Ce O of doping vario-property2Stick；
(5) after hydrothermal synthesis kettle natural cooling, wherein supernatant is removed, is added deionized water washing precipitating 2~3 times,
It is centrifuged, must precipitate after ultrasonic treatment, then wash precipitating with dehydrated alcohol, be centrifuged after continuing ultrasonic treatment, obtain white precipitate；
(6) white precipitate is dried in vacuo, vacuum drying temperature is 55~65 DEG C, and the time is 20~30h, is obtained
Pale yellow powder；
(7) by above-mentioned pale yellow powder in N2380~420 DEG C of 3~5h of roasting are under atmosphere to get the doping vario-property nanometer
CeO2Stick catalyst.
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (7)
1. a kind of doping vario-property nano Ce O2Stick catalyst, it is characterised in that: closed by ceria nanopowder stick and by a step Situ Hydrothermal
At and adulterate thereon modified metal element composition, the ceria nanopowder stick exposure (110) and (100) crystal face, the modified metal
Element is Zr, La or Y；
Preparation method includes:
(1) appropriate modified metal elemental precursors and appropriate Ce (NO are weighed3)3∙6H2O is dissolved in distilled water, be sufficiently stirred
One solution, modified metal elemental precursors are the nitrate of modified metal element；
(2) it accurately weighs appropriate NaOH to be dissolved in distilled water, be sufficiently stirred, obtain the second solution；
(3) the first solution is added drop-wise to dropwise in the second solution, continues to be sufficiently stirred, obtains suspension；
(4) suspension is packed into PPL liner, be put into the hydrothermal synthesis kettle of stainless steel material, and then the hydrothermal synthesis kettle is put
Enter 20 ~ 30 h of heating in 95 ~ 105 DEG C of baking ovens, obtains the nano Ce O of doping vario-property2Stick；
(5) after hydrothermal synthesis kettle natural cooling, wherein supernatant is removed, is added deionized water washing precipitating 2 ~ 3 times, at ultrasound
It is centrifuged, must precipitate after reason, then wash precipitating with dehydrated alcohol, be centrifuged after continuing ultrasonic treatment, obtain white precipitate；
(6) white precipitate is dried in vacuo, vacuum drying temperature is 55 ~ 65 DEG C, and the time is 20 ~ 30 h, is obtained yellowish
Color powder；
(7) by above-mentioned pale yellow powder in N2380 ~ 420 DEG C of 3 ~ 5 h of roasting are under atmosphere to get the doping vario-property nano Ce O2
Stick catalyst.
2. a kind of doping vario-property nano Ce O as described in claim 12Stick catalyst, it is characterised in that: the step (1), (2)
(3) time of stirring is at least 30min.
3. a kind of doping vario-property nano Ce O as described in claim 12Stick catalyst, it is characterised in that: the step (4) are as follows:
Suspension is packed into PPL liner, is put into the hydrothermal synthesis kettle of stainless steel material, and then the hydrothermal synthesis kettle is put into 100 DEG C
The nano Ce O for obtaining doping vario-property for 24 hours is heated in baking oven2Stick.
4. a kind of doping vario-property nano Ce O as described in claim 12Stick catalyst, it is characterised in that: the step (5) surpasses
The time of sonication is 20min.
5. a kind of doping vario-property nano Ce O as described in claim 12Stick catalyst, it is characterised in that: true in the step (6)
The dry temperature of sky is 60 DEG C, and the time is 24 h.
6. a kind of doping vario-property nano Ce O as described in claim 12Stick catalyst, it is characterised in that: the step (7) are as follows:
By above-mentioned pale yellow powder in N2The lower 400 DEG C of roasting 4h of atmosphere are to get the doping vario-property nano Ce O2Stick catalyst.
7. doping vario-property nano Ce O described in any claim in a kind of claim 1 to 62Stick catalyst becomes in coal gas against the current
Change the application in reaction.
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| CN111770793A (en) * | 2018-05-29 | 2020-10-13 | 积水化学工业株式会社 | Catalyst, carbon dioxide reduction method, and carbon dioxide reduction device |
| CN109589962B (en) * | 2018-12-25 | 2020-05-08 | 江南大学 | High-sulfur-resistance rare earth cerium-based low-temperature denitration catalyst and preparation method thereof |
| CN110127746B (en) * | 2019-06-11 | 2020-10-13 | 北京科技大学 | Method for regulating and controlling concentration of oxygen vacancy of monocrystalline cerium dioxide |
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| CN103183346A (en) * | 2012-12-13 | 2013-07-03 | 浙江海洋学院 | Method of reverse water gas shift reaction for reverse water gas shift catalyst |
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| CN103183346A (en) * | 2012-12-13 | 2013-07-03 | 浙江海洋学院 | Method of reverse water gas shift reaction for reverse water gas shift catalyst |
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