CN104624184B - Mullite compound oxide catalyst for oxidizing nitric oxide - Google Patents
Mullite compound oxide catalyst for oxidizing nitric oxide Download PDFInfo
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Abstract
The invention discloses a catalyst for oxidizing nitric oxide. The catalyst is characterized by being a mullite compound oxide catalyst, the chemical formula of which is A(1-x)A'xB(2-y)B'yO5, wherein each of A and A' is independently one of rare earth metal elements or alkaline-earth metal elements, each of B and B' are independently one of transitional metal elements, and x is more than or equal to 0 but less than or equal to 1 and y is more than or equal to 0 but less than or equal to 2. According to the catalyst the nitric oxide can be efficiently oxidized to nitrogen dioxide in a relatively wide temperature range, the cost is low, the good heat stability is realized, a relatively high catalytic activity within a long time can be maintained, and the removal rate of oxynitride in automobile tail gas can be remarkably improved, and moreover, the catalyst is simple in preparation method, and easy to operate and is suitable for industrialized application on a large scale.
Description
Technical field
The present invention relates to a kind of catalyst for oxidation of nitric oxide, more particularly, to a kind of nitric oxide is used for
The mullite-type composite oxide catalysts of oxidation.
Background technology
As expanding economy, people's living standard are improved constantly, the environmental problem come therewith also increasingly causes
The concern of people, particularly closely bound up with human lives atmosphere polluting problem is needed badly and is resolved.Wherein, nitrogen oxides
（NOx）It is the very big first kinds of pollution matter of discharge capacity, acid rain and photochemical fog can be caused, also results in human breathing tract disease,
It is harmful to whole environmental and human health impacts.The nitrogen oxides discharged in vehicle exhaust account for very big ratio, with every country
Emission control to nitrogen oxides requires increasingly strictly, just to grow up for the tail gas disposal technique of nitrogen oxides.For example, nitrogen
Oxide storage reduction（NOxStorage and Reduction,NSR）Technology, the trapping of lean-burn nitrogen oxides（Lean NOx
Trap,LNT）The cyclic regeneration trapping that technology, nitrogen oxides and particulate matter are removed simultaneously（Continuously Regenerated
Trap,CRT）The SCR of technology, nitrogen oxides（Selective Catalytic Reduction,SCR）Technology
Deng.
NO2As the product after NO oxidations, because it is more easy in the above-described techniques store, trap and reduce compared with NO, effect is removed
Rate is higher.For example, in NSR technologies, NO must first be oxidized to NO2, could be in catalyst surface in the form of nitrate
Stored；In LNT technology, NO2Both it is more easy to be captured and be more easy to than NO to be reduced than NO；In CRT technologies, NO2Compare O2's
Oxidisability is higher, can react with carbon granule and be reduced to N2, while carbon granule is oxidized to into carbon dioxide, reach simultaneously
The effect of removal；In SCR technology, NO is oxidized to into NO2Afterwards again by NH3Reduction, can greatly improve removal efficiency, and work as NO
With NO2Mol ratio be 1:When 1, the utilization ratio and removal efficiency of reducing agent are attained by highest.Therefore, NO pre-oxidation is NO2
NO can be greatly improvedxPurification efficiency.
However, in existing automobile and exhaust gas from diesel vehicle, NO2Account for total NOxProportion very little, to obtain more NO2,
Must be by the catalyst for being capable of efficient oxidation NO.The NO oxidation catalysts for commonly using at present are mainly with Pt as active center
It is supported on Al2O3Deng on carrier, wherein, the load capacity of noble metal is 2-3%.The use cost of this catalyst is higher, and your gold
Category can occur to reunite and decline catalytic performance in high-temperature catalytic reaction, and these shortcomings significantly limit it in physical condition
Under application.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides it is a kind of for oxidation of nitric oxide not
Carry out stone-type composite oxide catalysts, can within the scope of wider temperature efficiently by nitric oxide catalysis oxidation be titanium dioxide
Nitrogen, the catalyst low cost, with good heat stability, can for a long time keep higher catalysis activity, hence it is evident that improve automobile
The removal efficiency of nitrogen oxide in tail gas, and the preparation method of the catalyst is simple, it is easy to operate, being adapted to heavy industrialization should
With.
For achieving the above object, according to one aspect of the present invention, there is provided a kind of catalysis for oxidation of nitric oxide
Agent, it is characterised in that the catalyst is mullite-type composite oxides, and chemical general formula is A1-xA'xB2-yB'yO5, wherein, A and
A' be each independently rare earth metal or alkali earth metal in one kind, B and B' is each independently transiting group metal elements
In one kind, and 0≤x≤1,0≤y≤2.
Preferably, the thulium be La, Ce, Nd, Gd and Sm, the alkali earth metal be Mg, Ca, Sr and
Ba, the transiting group metal elements are Fe, Co, Mn, Ni, Ti and Cr.
Preferably, the chemical general formula of the catalyst is La1-xSmxMn2-yCoyO5。
Preferably, 0.3≤x≤1, y=0.
Preferably, 0.3≤x≤0.7, y=0.
It is another aspect of this invention to provide that there is provided a kind of preparation method of above-mentioned catalyst, it is characterised in that include as
Lower step：（1）According to the chemical formula for generating catalyst, soluble metallic salt is stoichiometrically dissolved in deionized water, is matched somebody with somebody
Make aqueous solution；（2）Organic complexing agent and mix homogeneously are added, stirring, evaporation at 80 DEG C forms gel, after gel drying
Form catalyst precursor；（3）By catalyst precursor at 600-800 DEG C roasting 5-10h, obtain described for nitric oxide
The catalyst of oxidation.
Preferably, the organic complexing agent is citric acid, ascorbic acid or ethylenediaminetetraacetic acid.
It is another aspect of this invention to provide that there is provided a kind of preparation method of above-mentioned catalyst, it is characterised in that include as
Lower step：（1）According to the chemical formula for generating catalyst, soluble metallic salt is stoichiometrically dissolved in deionized water, is matched somebody with somebody
Make aqueous solution；（2）Add precipitant to adjust pH value of solution to pH ﹥ 9.0, filter and obtain precipitate and dry, before making catalyst
Drive body；（3）By catalyst precursor at 500-800 DEG C roasting 5-10h, obtain the catalysis for oxidation of nitric oxide
Agent.
Preferably, the precipitant is ammonia or tetramethyl ammonium hydroxide solution.
It is another aspect of this invention to provide that providing a kind of oxidation of nitric oxide method, it is characterised in that urged using above-mentioned
Agent.
In general, by the contemplated above technical scheme of the present invention compared with prior art, with following beneficial effect
Really：
1st, rare earth metal, alkaline-earth metal and transiting group metal elements are mainly included, cost is relatively low.
2nd, it is mullite-type structure, Stability Analysis of Structures, is difficult phase transformation, higher exhaust temperature can be born, thus with excellent
Different heat stability, life-span length can for a long time keep higher catalysis activity.
3rd, Jing XRD spectrums are calculated, and the catalyst granules for obtaining is nano_scale particle, and mean diameter has in below 100nm
Higher oxidation of nitric oxide catalysis activity, generally can reach 80% conversion ratio at 300 DEG C.
Description of the drawings
Fig. 1 is the conversion of nitric oxide gas rate variation with temperature song for repeatedly measuring catalyst obtained in the embodiment of the present invention 1
Line；
Fig. 2 is La obtained in the embodiment of the present invention 20.5Sm0.5Mn2O5Mullite-type composite oxide catalysts XRD figure
Spectrum；
Fig. 3 is the conversion of nitric oxide gas rate comparison diagram of catalyst obtained in the embodiment of the present invention and comparative example.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Not constituting conflict each other just can be mutually combined.
The chemical general formula of the mullite-type composite oxide catalysts for oxidation of nitric oxide of the embodiment of the present invention is：
A1-xA'xB2-yB'yO5, wherein, A and A' is each independently the alkali such as the rare earth metals such as La, Ce, Nd, Gd, Sm or Mg, Ca, Sr, Ba
One kind in earth metal element, B and B' are each independently in the transiting group metal elements such as Fe, Co, Mn, Ni, Ti, Cr
Kind, and 0≤x≤1,0≤y≤2.
The mullite-type composite oxide catalysts for oxidation of nitric oxide of the embodiment of the present invention can by colloidal sol-
Prepared by gel method or coprecipitation, while can be by adjusting specific preparation technology to obtain highly active oxidation of nitric oxide
Catalyst.
Sol-gel process specifically includes following steps：First, according to the chemical formula for generating catalyst, by soluble metal
Salt is stoichiometrically dissolved in deionized water, is configured to aqueous solution；Then, add appropriate organic complexing agent and mix equal
Even, stirring, evaporation at 80 DEG C forms gel, and after gel drying catalyst precursor is formed；Finally, by catalyst precursor
The roasting 5-10h at 600-800 DEG C, obtains the mullite-type composite oxide catalysts of the embodiment of the present invention.
Specifically, organic complexing agent is citric acid, ascorbic acid or ethylenediaminetetraacetic acid（EDTA）Deng.
Coprecipitation specifically includes following steps：First, according to the chemical formula for generating catalyst, soluble metallic salt is pressed
Stoichiometric proportion is dissolved in deionized water, is configured to aqueous solution；Then, add precipitant to adjust pH value of solution to pH ﹥ 9.0, filter
Obtain precipitate and dry, make catalyst precursor；Finally, by catalyst precursor at 500-800 DEG C roasting 5-10h,
Obtain the mullite-type composite oxide catalysts of the embodiment of the present invention.
Specifically, precipitant is ammonia or Tetramethylammonium hydroxide（TMAH）Solution etc..
In above-mentioned sol-gel process and coprecipitation, specifically, soluble metallic salt is nitrate or chlorate etc..
To make those skilled in the art more fully understand the present invention, with reference to specific embodiment, to co-precipitation legal system
The method of the mullite-type composite oxide catalysts for oxidation of nitric oxide of the standby present invention is described in detail.
In following examples, the chemical structure of general formula of obtained mullite-type composite oxide catalysts is La1- xSmxMn2-yCoyO5, wherein, A is La, and A' is Sm, and B is Mn, and B' is Co.
Embodiment 1
Chemical formula is prepared for La0.7Sm0.3Mn2O5（X=0.3, y=0）The mullite-type composite oxygen for oxidation of nitric oxide
Compound catalyst.Weigh samaric nitrate [Sm (NO3)3·6H2O]1.33g（0.003mol）, Lanthanum (III) nitrate [La (NO3)3·6H2O]
3.04g（0.007mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution 7.16g（0.02mol）With blocked polyethers
（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring dissolves it；Add that appropriate mass fraction is 25% four
Ammonium hydroxide（TMAH）Solution makes pH between 9-10；It is added dropwise over the H that mass fraction is 30%2O2Solution 3g, is instilling
During add TMAH solution make pH be maintained at more than 9, while instill 1-2 drop capryl alcohol as defoaming agent；By the solution in room temperature
Lower stirring 2h, filters and obtains tan precipitate composition granule, and granule is dried into 12h in 100 DEG C of baking ovens, obtains catalyst precursor powder
Body；It is polished, the roasting 8h at 500 DEG C, then the roasting 8h at 800 DEG C, obtains sepia powder sample.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly La0.7Sm0.3Mn2O5Mullite-type be combined
Metal-oxide.
Obtained catalyst is taken into 50mg, being placed in U-shaped microreactor carries out respectively catalyst activity evaluation test, passes through
Nitrogen-oxide analyzer,（CLD822Mh ECO Physics）NO, NO2 and NO under record corresponding temperaturexContent, so as to calculate
Go out the conversion ratio of NO.Specific experiment condition is as follows：Volume is constituted：Oxygen：10%；Nitric oxide：400ppm；Nitrogen：Total flow is
150ml/min, as Balance Air.Temperature setting：400 DEG C are risen to the speed of 2 DEG C/min from room temperature.
It is repeated 3 times and tests nitric oxide production conversion ratio variation with temperature under the catalyst action, test result such as Fig. 1 institutes
Show, three suite lines are almost completely superposed, illustrate that the catalyst has excellent heat stability, can use for a long time.
Embodiment 2
Chemical formula is prepared for La0.5Sm0.5Mn2O5（X=0.5, y=0）The mullite-type composite oxygen for oxidation of nitric oxide
Compound catalyst.Weigh samaric nitrate [Sm (NO3)3·6H2O]2.22g（0.005mol）, Lanthanum (III) nitrate [La (NO3)3·6H2O]
2.17g（0.005mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution 7.16g（0.02mol）With blocked polyethers
（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring dissolves it, according to method system same as Example 1
Obtain sepia powder sample.
As shown in Fig. 2 Jing x-ray diffractogram of powder Analysis and Identification is obtained, the powder body is mainly La0.5Sm0.5Mn2O5Not
Carry out stone-type metal composite oxide.With nitric oxide production turn under method repeated measure catalyst action same as Example 1
Rate variation with temperature, as a result shows that the catalyst has excellent heat stability.
Embodiment 3
Chemical formula is prepared for LaMn2O5（X=0, y=0）The mullite-type composite oxide catalytic for oxidation of nitric oxide
Agent.Weigh Lanthanum (III) nitrate [La (NO3)3·6H2O]4.34g（0.01mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution
7.16g（0.02mol）With blocked polyethers（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring makes its molten
Solution, according to method same as Example 1 sepia powder sample is obtained.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly LaMn2O5Mullite-type composition metal oxygen
Compound.With nitric oxide production conversion ratio variation with temperature under method repeated measure catalyst action same as Example 1,
As a result show that the catalyst has excellent heat stability.
Embodiment 4
Chemical formula is prepared for La0.3Sm0.7Mn2O5（X=0.7, y=0）The mullite-type composite oxygen for oxidation of nitric oxide
Compound catalyst.Weigh samaric nitrate [Sm (NO3)3·6H2O]3.11g（0.007mol）, Lanthanum (III) nitrate [La (NO3)3·6H2O]1.3g
（0.003mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution 7.16g（0.02mol）With blocked polyethers
（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring dissolves it, according to method system same as Example 1
Obtain sepia powder sample.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly La0.3Sm0.7Mn2O5Mullite-type be combined
Metal-oxide.With nitric oxide production conversion ratio under method repeated measure catalyst action same as Example 1 with temperature
Change, as a result show that the catalyst has excellent heat stability.
Embodiment 5
Chemical formula is prepared for SmMn2O5（X=1, y=0）The mullite-type composite oxide catalytic for oxidation of nitric oxide
Agent.Weigh samaric nitrate [Sm (NO3)3·6H2O]4.44g（0.01mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution
7.16g（0.02mol）With blocked polyethers（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring makes its molten
Solution, according to method same as Example 1 sepia powder sample is obtained.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly SmMn2O5Mullite-type composition metal oxygen
Compound.With nitric oxide production conversion ratio variation with temperature under method repeated measure catalyst action same as Example 1,
As a result show that the catalyst has excellent heat stability.
Embodiment 6
Chemical formula is prepared for SmMnCoO5（X=1, y=1）The mullite-type composite oxides for oxidation of nitric oxide urge
Agent.Weigh samaric nitrate [Sm (NO3)3·6H2O]4.44g（0.01mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）It is molten
Liquid 3.58g（0.01mol）, cobalt nitrate（Co(NO3)2·6H2O）2.91g（0.01mol）With blocked polyethers（Pluronic
F127）0.2g, in adding 40ml deionized waters, stirring dissolves it, and brown toner is obtained according to method same as Example 1
Body sample.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly SmMnCoO5Mullite-type composition metal
Oxide.With nitric oxide production conversion ratio under method repeated measure catalyst action same as Example 1 with temperature change
Change, as a result show that the catalyst has excellent heat stability.
Embodiment 7
Chemical formula is prepared for SmCo2O5（X=1, y=2）The mullite-type composite oxide catalytic for oxidation of nitric oxide
Agent.Weigh samaric nitrate [Sm (NO3)3·6H2O]4.44g（0.01mol）, cobalt nitrate（Co(NO3)2·6H2O）5.82g
（0.01mol）With blocked polyethers（Pluronic F127）0.2g, in adding 40ml deionized waters, stirring dissolves it, according to
Method same as Example 1 is obtained sepia powder sample.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly SmCo2O5Mullite-type composition metal oxygen
Compound.With nitric oxide production conversion ratio variation with temperature under method repeated measure catalyst action same as Example 1,
As a result show that the catalyst has excellent heat stability.
Embodiment 8
Chemical formula is prepared for La0.5Sm0.5MnCoO5（X=0.5, y=1）The mullite-type for oxidation of nitric oxide be combined
Oxide catalyst.Weigh samaric nitrate [Sm (NO3)3·6H2O]2.22g（0.005mol）, Lanthanum (III) nitrate [La (NO3)3·6H2O]
2.17g（0.005mol）, the manganese nitrate that mass fraction is 50%（Mn(NO3)2）Solution 3.58g（0.01mol）, cobalt nitrate（Co
(NO3)2·6H2O）2.91g（0.01mol）With blocked polyethers（Pluronic F127）0.2g, in adding 40ml deionized waters,
Stirring dissolves it, and sepia powder sample is obtained according to method same as Example 1.
Jing x-ray diffractogram of powder Analysis and Identification is obtained, and the powder body is mainly La0.5Sm0.5MnCoO5Mullite-type answer
Close metal-oxide.With nitric oxide production conversion ratio under method repeated measure catalyst action same as Example 1 with temperature
The change of degree, as a result shows that the catalyst has excellent heat stability.
Comparative example
Take 5 grams of γ-Al2O3Powder is soaked in certain density platinum nitrate solution, stirs 0.5h, the mistake in 100 DEG C of baking ovens
Night is dried, in air atmosphere at 500 DEG C roasting 2h, be down to room temperature, then 72h is incubated at 750 DEG C, obtain the load of platinum component
Measure as the noble metal carrier catalyst of mass fraction 2.0%.Measured under the catalyst action with method same as Example 1
Nitric oxide production conversion ratio variation with temperature.
Due to the various embodiments described above prepare catalyst multiple catalytic performance test result closely, from it is above-mentioned each
Respectively choose 1 group of test result in embodiment to be compared with the noble metal carrier catalyst of comparative example, as a result as shown in figure 3,
Specific catalytic performance parameter is shown in Table 1.
The catalytic performance parameter of catalyst obtained in the embodiment of the present invention of table 1 and comparative example
As it can be seen from table 1 mullite-type composite oxide catalysts obtained in the embodiment of the present invention and comparative example are urged
Agent is compared, and nitric oxide production conversion ratio is significantly improved, and corresponding catalytic reaction temperature is generally reduced.Further, when 0.3
≤ x≤1, during y=0, catalyst obtained in the embodiment of the present invention has more preferably catalytic performance, that is, be obtained in that a higher oxygen
Change conversion rate of nitrogen and lower catalytic reaction temperature；When 0.3≤x≤0.7, y=0, catalyst tool obtained in the embodiment of the present invention
There is optimal catalytic performance.
La prepared by above-described embodiment1-xSmxMn2-yCoyO5Be merely illustrative, the present invention for nitric oxide oxygen
The mullite-type composite oxide catalysts A of change1-xA'xB2-yB'yO5Above-described embodiment is not limited to, specifically, A not offices
It is limited to La, A' is not limited to Sm, and B is not limited to Mn, and B' is not limited to Co.More generally, A and A' are each independently
One kind in the alkali earth metal such as the rare earth metals such as La, Ce, Nd, Gd, Sm or Mg, Ca, Sr, Ba, B and B' is each independently
One kind in the transiting group metal elements such as Fe, Co, Mn, Ni, Ti, Cr.The value of x, y is not limited to above-described embodiment, and more one
As, x can be any value between 0～1, and y can be any value between 0～2.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. are limited, all should be included
Within protection scope of the present invention.
Claims (8)
1. a kind of catalyst for oxidation of nitric oxide, it is characterised in that the catalyst is mullite-type composite oxides,
Chemical general formula is A1-xA'xB2-yB'yO5, wherein, A and A' is each independently rare earth metal, and B and B' are each independently transition
One kind in race metallic element Co or Mn, and 0.3≤x≤0.7, y=0.
2. the as claimed in claim 1 catalyst for being used for oxidation of nitric oxide, it is characterised in that the thulium is
La, Ce, Nd, Gd or Sm.
3. the catalyst of oxidation of nitric oxide is used for as claimed in claim 2, it is characterised in that the chemistry of the catalyst leads to
Formula is La1-xSmxMn2-yCoyO5。
4. the preparation method of the catalyst of oxidation of nitric oxide is used for as claimed any one in claims 1 to 3, and its feature exists
In comprising the steps：
(1) according to the chemical formula for generating catalyst, soluble metallic salt is stoichiometrically dissolved in deionized water, is configured to
Aqueous solution；
(2) organic complexing agent and mix homogeneously are added, stirring, evaporation at 80 DEG C forms gel, is formed after gel drying and is urged
Agent presoma；
(3) by catalyst precursor at 600-800 DEG C roasting 5-10h, obtain the catalyst for oxidation of nitric oxide.
5. preparation method as claimed in claim 4, it is characterised in that the organic complexing agent be citric acid, ascorbic acid or
Ethylenediaminetetraacetic acid.
6. the preparation method of the catalyst of oxidation of nitric oxide is used for as claimed any one in claims 1 to 3, and its feature exists
In comprising the steps：
(1) according to the chemical formula for generating catalyst, soluble metallic salt is stoichiometrically dissolved in deionized water, is configured to
Aqueous solution；
(2) add precipitant to adjust pH value of solution to pH ﹥ 9.0, filter and obtain precipitate and dry, make catalyst precursor；
(3) by catalyst precursor at 500-800 DEG C roasting 5-10h, obtain the catalyst for oxidation of nitric oxide.
7. preparation method as claimed in claim 6, it is characterised in that the precipitant is that ammonia or Tetramethylammonium hydroxide are molten
Liquid.
8. a kind of oxidation of nitric oxide method, it is characterised in that usage right requires the catalyst any one of 1 to 3.
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| CN110013849B (en) * | 2019-05-13 | 2021-05-14 | 清华大学 | Ag-silver-doped modified manganese-based mullite oxidation catalyst and preparation and application thereof |
| CN110433794B (en) * | 2019-08-15 | 2020-10-30 | 南开大学 | General formula AM2O5-xApplication of compound as catalyst for catalyzing VOC combustion |
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| CN112439407B (en) * | 2019-09-04 | 2022-05-10 | 有研稀土新材料股份有限公司 | Core-shell structure rare earth manganese/cerium zirconium composite compound, preparation method and catalyst |
| CN110605114B (en) * | 2019-10-15 | 2022-04-01 | 南开大学 | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration |
| CN110833831B (en) * | 2019-11-07 | 2022-11-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of chromium-cobalt-based nitric oxide normal-temperature normal-pressure catalyst, product and application thereof |
| CN111889101B (en) * | 2020-08-13 | 2021-10-12 | 清华大学 | Modified composite oxide catalyst for synergistic purification of VOCs and NO and preparation method thereof |
| CN112774665B (en) * | 2021-01-29 | 2022-02-15 | 华中科技大学 | Mullite catalyst for improving ammonia selectivity and preparation method and application thereof |
| CN113559850B (en) * | 2021-07-13 | 2022-07-08 | 清华大学 | Manganese-based composite oxide catalyst and preparation method and application thereof |
| CN115739106B (en) * | 2022-11-10 | 2024-05-21 | 南开大学 | Preparation method and application of composite oxide |
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