CN112844436A - Catalyst for removing formaldehyde and carbon monoxide by catalysis and preparation method thereof - Google Patents
Catalyst for removing formaldehyde and carbon monoxide by catalysis and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for removing formaldehyde and carbon monoxide by catalysis and a preparation method thereof, wherein the general formula of the catalyst is A/Ce-TiO2(ii)/g-C3N 4; wherein A is one of Pt, Pd and Au, and A is a noble metal; wherein the loading amount of A is 0.1-1 wt%, and the balance is Ce-TiO2/g‑C3N4；Ce/TiO2The mass ratio of (A) to (B) is 0.3-3%; TiO 22The mass ratio of/g-C3N 4 is 0.1-2. The catalyst of the invention is Ce-TiO assisted by visible light2the/g-C3N 4 composite carrier has high photocatalytic efficiency, and the existence of proper amount of Ce obviously promotes double active sites to generate active oxygen species with high oxidizability for the oxidative decomposition of indoor formaldehyde and CO,thereby obtaining high formaldehyde and CO decomposition rate and high catalytic stability; the catalyst has extremely high catalytic efficiency even under the condition of high airflow speed.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a catalyst for catalytically removing formaldehyde and carbon monoxide and a preparation method thereof.
Background
Formaldehyde and carbon monoxide are both main indoor air pollutants and have serious harm to human bodies, the main harm of formaldehyde is represented by stimulation to skin mucosa, and when the formaldehyde reaches a certain concentration indoors, people feel uncomfortable and are more than 0.08mg/m3The formaldehyde concentration can cause redness, itching, discomfort or pain in the throat, hoarseness, sneezing, chest distress, asthma, dermatitis, etc.
Carbon monoxide is a pollutant with strong toxicity to blood and nervous system, and carbon monoxide in air enters human blood through respiratory system and combines with hemoglobin in blood to form reversible combination. The combination of carbon monoxide and hemoglobin not only reduces the oxygen carrying capacity of blood cells, but also inhibits and delays the resolution and release of oxyhemoglobin, so that body tissues are necrotized due to oxygen deficiency, and serious patients can endanger human life. One of the currently feasible methods for indoor formaldehyde and CO contaminant removal is to oxidize formaldehyde and CO to CO by room temperature catalytic oxidation2Thereby removing the contaminants.
One method for removing formaldehyde at present is to perform catalytic oxidation on formaldehyde through precious metals, and the decomposition mechanism of the formaldehyde through the catalytic oxidation at room temperature is as follows: firstly, formaldehyde is adsorbed on the surface sites of the catalyst, and then the noble metal activates O2Oxidation of formaldehyde into intermediates, e.g. formates, which are then further activated by O2Oxidation to CO and finally to CO2However, in this process there is a gradual accumulation of formate, which goes to CO2The conversion of (a) is a key step for determining the speed of the catalytic reaction, but the air not only contains formaldehyde,and CO with a certain concentration exists, and the adsorption capacity of the CO on the noble metal catalyst is very strong, so that the CO can gradually occupy activated oxygen sites of the noble metal, thereby forming poisoning, causing the reduction of the catalytic oxidation capacity of the catalyst on formaldehyde and CO, and influencing the catalytic efficiency and stability of the noble metal.
It follows that the removal of CO from air is very essential, since CO not only affects the air quality, causing CO poisoning in humans; and CO can also affect the catalytic oxidation of formaldehyde by precious metals.
In addition, to obtain indoor clean air quickly, high airflow rate is required to pass through the catalyst, and the catalytic efficiency and stability of the catalyst are affected under the condition of high airflow rate.
In order to solve the problems, the Chinese patent application with the patent number CN201911013173.6 (with the publication number CN110665531A) discloses' a Pt/g-C3N4/CeO2A composite photocatalyst is Pt/g-C3N4/CeO2The catalyst has response activity of a fluorescent lamp, and can remove formaldehyde gas pollutants at room temperature by utilizing visible light at room temperature. Although the catalyst utilizes CeO2g-C3N4 is compounded as a carrier to generate a heterojunction, thereby improving certain photocatalytic oxidation capacity, but g-C3N4/CeO2The carrier has a small specific surface area, and has a small dispersibility of Pt and a limited use of light efficiency.
For example, the invention is also "a mixed crystal TiO", which is disclosed in the Chinese patent application with the patent number CN202010132068.0 (with the publication number CN111250139A)2a/g-C3N 4 nano hollow tube composite material and a preparation method thereof, wherein the catalyst only utilizes TiO2The photocatalytic oxidation of/g-C3N 4 degrades formaldehyde, and the catalytic capability is limited.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a catalyst for catalytically removing formaldehyde and carbon monoxide with high catalytic efficiency aiming at the current situation of the prior art.
The second technical problem to be solved by the present invention is to provide a method for preparing the above catalyst, aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a catalyst for the catalytic removal of formaldehyde and carbon monoxide, characterized by:
the general formula of the catalyst is A/Ce-TiO2/g-C3N4；
Wherein A is one of Pt, Pd and Au, and A is a noble metal;
wherein the loading amount of A is 0.1-1 wt%, and the balance is Ce-TiO2/g-C3N4；
Ce/TiO2The mass ratio of (A) to (B) is 0.3-3%;
TiO2the mass ratio of/g-C3N 4 is 0.1-2.
Preferably, A is Pt, and Pt has strong catalytic oxidation capability to formaldehyde.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the catalyst for catalytically removing formaldehyde and carbon monoxide is characterized by comprising the following steps of:
(1) dissolving a titanium source in absolute ethyl alcohol, adding g-C3N4, and uniformly mixing to obtain a solution B;
(2) dissolving a cerium source, acetic acid and deionized water in ethanol, and stirring to obtain a solution C;
(3) adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature to form gel, drying, and calcining at 300-500 ℃ under the condition of nitrogen to obtain Ce-TiO2a/g-C3N 4 sample;
(4) weighing the precursor solution of A, and adding Ce-TiO2Dispersing a/g-C3N 4 sample in the precursor solution, uniformly stirring, and then drying;
(5) calcining the dried sample in the step (4) at 200-450 ℃ under the nitrogen condition to obtain the catalyst A/Ce-TiO2/g-C3N4。
Preferably, the cerium source in step (2) is cerium nitrate.
Preferably, the titanium source in step (1) is tetrabutyl titanate.
Preferably, the precursor solution of a in the step (4) is hexahydroxyplatinic diethanol amine.
Preferably, the precursor solution of a in the step (4) is one of chloroplatinic acid, platinum nitrate and platinum tetraammine nitrate, and in the step (5), the dried sample is calcined at 200-450 ℃ under the nitrogen condition and then subjected to H2Reducing at 200-450 ℃ in the atmosphere to reduce the precursor solution of platinum into platinum, thereby obtaining the catalyst A/Ce-TiO2/g-C3N4。
Compared with the prior art, the invention has the advantages that: 1. in the aspects of promoting electron-hole separation and improving light efficiency: the support may be made of TiO2g-C3N4 heterojunction and proper amount of Ce doped TiO2A large number of oxygen vacancies are generated due to oxygen vacancies and TiO2The existence of the/g-C3N 4 heterojunction can effectively inhibit the recombination of electrons and holes and improve the catalytic efficiency, so that the reducing TiO2The composite g-C3N4 shows extremely strong visible light catalytic performance; 2. in terms of promoting the generation of free radicals and improving the oxidizing ability: Ce-TiO2the/g-C3N 4 carrier can generate a large amount of free electrons and holes under the irradiation of visible light, thereby generating active oxygen species with strong oxidizability, such as hydroxyl free radicals, superoxide free radicals, singlet oxygen and the like, and being capable of quickly oxidizing CO, formate and formaldehyde into CO2Thereby further assisting in improving the conversion rate of formaldehyde and CO, simultaneously weakening the catalyst deactivation problem caused by CO poisoning and formate accumulation and enhancing the stability of the catalyst; in addition, oxygen vacancies in the carrier cooperate with the Ce site to remarkably improve the oxygen storage capacity of the carrier, so that the oxygen is more favorable for capturing photo-generated electrons to generate more superoxide radicals; the composite carrier has more surface hydroxyl groups, so that the combined holes are effectively utilized to generate more hydroxyl radicals; 3. the proper amount of Ce is not only to make TiO2Generating a large number of oxygen vacancies and passing through CeO2The oxygen storage capacity of the carrier is combined with the cooperative oxygen storage capacity of the oxygen vacancy and a large number of surface hydroxyls in the carrier, so that the combination of oxygen and photo-generated electrons is obviously improved to generate active oxygen such as superoxide radical, hydroxyl free radical and the like, and the enhancement of noble metal A to O is facilitated2Activation efficiency ofThereby further improving the catalytic oxidation capability of the catalyst; 4. modified TiO of the invention2Base support (Ce-TiO)2/g-C3N4) has larger specific surface area and a large amount of surface hydroxyl, is more beneficial to the dispersion of the noble metal A and the improvement of the catalytic oxidation capability of Pt; 5. the invention has strong capability of catalyzing and oxidizing formaldehyde on one hand due to the existence of the noble metal A with good dispersity, and has stronger photocatalytic oxidation capability due to the existence of a large number of oxygen vacancies and Ce, thereby having stronger capability of oxidizing pollutants.
In conclusion, the invention efficiently decomposes formaldehyde and CO at room temperature by a photo-assisted catalytic oxidation method, and a very small amount of noble metal A is loaded on Ce-TiO2g-C3N4 composite carrier to obtain catalyst with double catalytic oxidation active sites, and Ce-TiO is added with the aid of visible light2the/g-C3N 4 composite carrier has high photocatalytic efficiency, and the existence of proper amount of Ce remarkably promotes double active sites to generate active oxygen species with high oxidizability for the oxidative decomposition of indoor formaldehyde and CO, thereby obtaining high formaldehyde and CO decomposition rate and high catalytic stability; the catalyst of the present invention has very high catalytic efficiency and stability even under high air flow rate conditions.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following tetrabutyl titanate is selected from chemical reagents of national medicine group, cerium nitrate (available from chemical reagents of national medicine group, Ltd.), diethanolamine hexahydroxyplatinate (refer to the university of Yunnan, Nature's edition): 2017, 39 (2): 283-287 platinum-carrying catalytic precursor (MEA)2Pt(OH)6Preparation of and performance studies of the same).
Example 1
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, Pt as active component, Ce-TiO2the/g-C3N 4 is used as a carrier, and the carrier is Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 1.5 wt%, TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 (purchased from national medicine group chemical reagent Co., Ltd.) in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing diethanolamine hexahydroxy platinate solution, and mixing with Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) for 2 hours at 400 ℃ under the nitrogen condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
When the precursor of platinum adopts hexahydroxy platinic acid diethanol amine, the precursor solution can be decomposed into a metal state at 200-450 ℃ under the condition of nitrogen without H2The reducing agent reduction step can achieve better reduction activity without introducing impurities. Of course, it is also possible to calcine under nitrogen and then reduce under hydrogen to achieve better reduction activity.
Example 2
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 1.5 wt%, TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing a certain amount of chloroplatinic acid (purchased from chemical reagents of national medicine group, Ltd.), adding a proper amount of sodium nitrate, and adding Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) at 400 ℃ for 2 hours under the nitrogen condition, and then H2Reducing for 1h at 300 ℃ under the condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 3
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 1.5 wt%, TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing a certain amount of chloroplatinic acid (purchased from chemical reagents of national medicine group, Ltd.), adding a proper amount of sodium nitrate, and adding Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) at 400 ℃ for 2 hours under the nitrogen condition, and then H2Reducing for 1h at 450 ℃ under the condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 4
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 1.5 wt%, TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing a certain amount of chloroplatinumAdding appropriate amount of sodium nitrate into acid (purchased from national chemical reagent group, Inc.) source solution, and adding Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) at 400 ℃ for 2 hours under the nitrogen condition, and then H2Reducing for 1h at 200 ℃ under the condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 5
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 0.3 wt% of TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing diethanolamine hexahydroxy platinate solution, and mixing with Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) for 2 hours at 400 ℃ under the nitrogen condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 6
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 0.6 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2Ce/TiO in/g-C3N 42Is 3.0 wt%, TiO2The mass ratio of/g-C3N 4 was 0.3.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing diethanolamine hexahydroxy platinate solution, and mixing with Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) for 2 hours at 400 ℃ under the nitrogen condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 7
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the load amount of Pt is 0.1 wt%, and the rest is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 3.0 wt%, TiO2The mass ratio of/g-C3N 4 was 0.1.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing diethanolamine hexahydroxy platinate solution, and mixing with Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) for 2 hours at 400 ℃ under the nitrogen condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Example 8
The catalyst of this example was Pt/Ce-TiO2g-C3N4, i.e. Pt-supported Ce-TiO2g-C3N4, support Ce-TiO2the/g-C3N 4 is Ce doped TiO2And compounded in g-C3N 4. Wherein the loading amount of Pt is 1 wt%, and the balance is carrier Ce-TiO2/g-C3N4；Ce-TiO2in/g-C3N 4: Ce/TiO 22Is 0.3 wt% of TiO2The mass ratio of/g-C3N 4 is 2.
The catalyst of this example was prepared as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving cerous nitrate, acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B under stirring, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hr to obtain gel, drying the obtained gel at 120 deg.C for 4 hr, and finally under nitrogen conditionCalcining at 400 ℃ for 2 hours to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing diethanolamine hexahydroxy platinate solution, and mixing with Ce-TiO2Dispersing a/g-C3N 4 sample in the hexahydroxy platinic acid diethanol amine source liquid, uniformly stirring, and then drying for 4 hours at 120 ℃;
(5) calcining the sample finally dried in the step (4) for 2 hours at 400 ℃ under the nitrogen condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Comparative example 1
The catalyst of this comparative example was Pt/TiO2g-C3N4, i.e. Pt-supported TiO2The carrier is TiO, wherein the carrier is Pt-C3N 4 as an active component2(ii)/g-C3N 4, wherein the loading of Pt is 0.6 wt%, and the balance is carrier TiO2/g-C3N4；TiO2The mass ratio of/g-C3N 4 was 0.3.
The preparation method of the catalyst of this comparative example is as follows:
(1) dissolving tetrabutyl titanate in absolute ethyl alcohol, stirring at room temperature until the tetrabutyl titanate is dissolved, then ultrasonically dispersing g-C3N4 in the solution, and uniformly mixing to obtain a solution B;
(2) dissolving acetic acid and deionized water in ethanol, and uniformly stirring to obtain a solution C;
(3) dropwise adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature for 24 hours to obtain gel, drying the obtained gel at 120 ℃ for 4 hours, and finally calcining the gel at 400 ℃ for 2 hours under the nitrogen condition to obtain Ce-TiO2a/g-C3N 4 sample;
(4) preparing a certain amount of chloroplatinic acid source liquid, adding a proper amount of sodium nitrate, and adding Ce-TiO2Dispersing the C3N 4/g sample in chloroplatinic acid solution, stirring uniformly, drying at 120 deg.C for 4 hr, calcining at 400 deg.C under nitrogen for 2 hr, and calcining at 300 deg.C for H2Reducing for 1h under the condition to obtain the catalyst Pt/Ce-TiO2/g-C3N4。
Comparative example 2
The catalyst of the present comparative example was prepared as nano TiO2Taking Pt as an active component as a carrier, and obtaining Pt/TiO, wherein the loading amount of Pt is 0.6 wt%2CatalysisAnd (3) preparing.
The preparation method of the catalyst comprises the following steps: preparing chloroplatinic acid source liquid, and then adding nano TiO2Dispersing in chloroplatinic acid source liquid, stirring for a period of time, drying at 120 deg.C for 4 hr, calcining at 400 deg.C for 2 hr in air, and calcining at 300 deg.C for H2Reducing for 1h under the condition to obtain the catalyst.
The following table shows activity data of the catalysts prepared in the above examples and comparative examples;
the above activity test conditions were: the composition of the reaction gas was 10ppm CO, 5ppm HCHO, 20% O2，N2The reaction gas is equilibrium gas, the relative humidity is 40%, the room temperature, the total flow of the reaction gas is 3L/min, the dosage of the catalyst is 0.1g, and an LED visible light source (30W) is adopted.
The catalyst provided by the embodiment 1-6 is used for simultaneously and efficiently catalyzing and oxidizing formaldehyde and CO under the conditions of room temperature and high air flow velocity, and simultaneously generates a large amount of active oxygen through visible light assisted catalysis, so that the capability of the catalyst for catalyzing and oxidizing formaldehyde and CO is further improved, the problem that the stability of the catalyst is poor due to the accumulation of key intermediate formate generated by CO poisoning and formaldehyde decomposition is solved, the pollution to the environment is avoided, the environment benefit is obvious, the use amount of noble metals can be reduced to a certain degree, and the cost is reduced.
Claims (7)
1. A catalyst for the catalytic removal of formaldehyde and carbon monoxide, characterized by:
the general formula of the catalyst is A/Ce-TiO2/g-C3N4；
Wherein A is one of Pt, Pd and Au,
wherein the loading amount of A is 0.1-1 wt%, and the balance is Ce-TiO2/g-C3N4；
Ce/TiO2The mass ratio of (A) is 0.3-3 wt%;
TiO2the mass ratio of/g-C3N 4 is 0.1-2.
2. The catalyst of claim 1, wherein: the A is Pt.
3. A method for preparing a catalyst for the catalytic removal of formaldehyde and carbon monoxide according to claim 1 or 2, characterized by comprising the steps of:
(1) dissolving a titanium source in absolute ethyl alcohol, adding g-C3N4, and uniformly mixing to obtain a solution B;
(2) dissolving a cerium source, acetic acid and deionized water in ethanol, and stirring to obtain a solution C;
(3) adding the solution C into the solution B in a stirring state, continuously stirring until sol is formed, standing the obtained sol at room temperature to form gel, drying, and calcining at 300-500 ℃ under the condition of nitrogen to obtain Ce-TiO2a/g-C3N 4 sample;
(4) weighing the precursor solution of A, and adding Ce-TiO2Dispersing a/g-C3N 4 sample in the precursor solution, uniformly stirring, and then drying;
(5) calcining the dried sample in the step (4) at 200-450 ℃ under the nitrogen condition to obtain the catalyst A/Ce-TiO2/g-C3N4。
4. The production method according to claim 3, characterized in that: the cerium source in the step (2) is cerium nitrate.
5. The production method according to claim 3, characterized in that: the titanium source in the step (1) is tetrabutyl titanate.
6. The production method according to claim 3, characterized in that: the precursor solution of A in the step (4) is a hexahydroxyplatinic diethanol amine solution.
7. The production method according to claim 3, characterized in that: the precursor solution of A in the step (4) is at least one of chloroplatinic acid, platinum nitrate and tetrammine platinum nitrate, and in the step (5), the dried sample is calcined at 200-450 ℃ under the nitrogen condition and then subjected to H2Reducing at 200-450 ℃ in the atmosphere to obtain the catalyst A/Ce-TiO2/g-C3N4。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471146A (en) * | 2022-02-10 | 2022-05-13 | 杭州妙蓝环保科技有限公司 | Green odorless formaldehyde scavenger and preparation method thereof |
| CN114832848A (en) * | 2022-04-27 | 2022-08-02 | 中山市洁鼎过滤制品有限公司 | Catalyst and preparation method and application thereof |
| CN115090323A (en) * | 2022-06-30 | 2022-09-23 | 宁波方太厨具有限公司 | Catalyst for purifying air, preparation method and purification assembly |
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004074069A (en) * | 2002-08-21 | 2004-03-11 | National Institute Of Advanced Industrial & Technology | Formaldehyde oxidation removal method |
| CN101045203A (en) * | 2007-04-29 | 2007-10-03 | 华南农业大学 | Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method |
| JP2012200698A (en) * | 2011-03-28 | 2012-10-22 | Daicel Corp | Photocatalyst and oxidation method for organic compound using the same |
| CN103230808A (en) * | 2013-05-25 | 2013-08-07 | 南昌航空大学 | Method for preparing Pt-C3N4-TiO2 three-component visible light photocatalyst |
| CN104307552A (en) * | 2014-11-06 | 2015-01-28 | 江苏理工学院 | TiO2/g-C3N4Preparation method of composite visible light catalyst |
| CN104907069A (en) * | 2015-04-22 | 2015-09-16 | 中国科学院生态环境研究中心 | Catalyst for room temperature formaldehyde purification, and use thereof |
| CN105606655A (en) * | 2016-02-25 | 2016-05-25 | 济南大学 | Palladium-supported acetone gas sensor manufacturing method based on two-dimensional porous nano composite material and application |
| US20170354962A1 (en) * | 2014-12-01 | 2017-12-14 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| CN108906043A (en) * | 2018-08-02 | 2018-11-30 | 广州大学 | A kind of alloy catalyst of degradation of formaldehyde and its preparation method and application |
| WO2019021189A1 (en) * | 2017-07-27 | 2019-01-31 | Sabic Global Technologies B.V. | Methods of producing a nanocomposite heterojunction photocatalyst |
| CN109985625A (en) * | 2017-11-02 | 2019-07-09 | 北京懂爱科技发展有限公司 | A kind of load type nano gold photochemical catalyst and preparation method thereof |
| US20190381490A1 (en) * | 2016-11-07 | 2019-12-19 | Hangzhou Tong-King Enviro-Tech Co., Ltd | Composite photocatalysts, method for making the same and application thereof |
| CN110665531A (en) * | 2019-10-23 | 2020-01-10 | 江汉大学 | Pt/g-C3N4/CeO2Composite photocatalyst and preparation method and application thereof |
| CN110860286A (en) * | 2019-11-11 | 2020-03-06 | 元林(上海)新材料科技有限公司 | Preparation method of high visible light response aqueous high-dispersion titanium dioxide |
| US20200239311A1 (en) * | 2020-01-14 | 2020-07-30 | Qatar University | Porous one-dimensional polymeric graphitic carbon nitride-based nanosystems for catalytic conversion of carbon monoxide and carbon dioxide under ambient conditions |
-
2021
- 2021-01-27 CN CN202110106991.1A patent/CN112844436B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004074069A (en) * | 2002-08-21 | 2004-03-11 | National Institute Of Advanced Industrial & Technology | Formaldehyde oxidation removal method |
| CN101045203A (en) * | 2007-04-29 | 2007-10-03 | 华南农业大学 | Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method |
| JP2012200698A (en) * | 2011-03-28 | 2012-10-22 | Daicel Corp | Photocatalyst and oxidation method for organic compound using the same |
| CN103230808A (en) * | 2013-05-25 | 2013-08-07 | 南昌航空大学 | Method for preparing Pt-C3N4-TiO2 three-component visible light photocatalyst |
| CN104307552A (en) * | 2014-11-06 | 2015-01-28 | 江苏理工学院 | TiO2/g-C3N4Preparation method of composite visible light catalyst |
| US20170354962A1 (en) * | 2014-12-01 | 2017-12-14 | Sabic Global Technologies B.V. | Synthesis of trimetallic nanoparticles by homogeneous deposition precipitation, and application of the supported catalyst for carbon dioxide reforming of methane |
| CN104907069A (en) * | 2015-04-22 | 2015-09-16 | 中国科学院生态环境研究中心 | Catalyst for room temperature formaldehyde purification, and use thereof |
| CN105606655A (en) * | 2016-02-25 | 2016-05-25 | 济南大学 | Palladium-supported acetone gas sensor manufacturing method based on two-dimensional porous nano composite material and application |
| US20190381490A1 (en) * | 2016-11-07 | 2019-12-19 | Hangzhou Tong-King Enviro-Tech Co., Ltd | Composite photocatalysts, method for making the same and application thereof |
| WO2019021189A1 (en) * | 2017-07-27 | 2019-01-31 | Sabic Global Technologies B.V. | Methods of producing a nanocomposite heterojunction photocatalyst |
| CN109985625A (en) * | 2017-11-02 | 2019-07-09 | 北京懂爱科技发展有限公司 | A kind of load type nano gold photochemical catalyst and preparation method thereof |
| CN108906043A (en) * | 2018-08-02 | 2018-11-30 | 广州大学 | A kind of alloy catalyst of degradation of formaldehyde and its preparation method and application |
| CN110665531A (en) * | 2019-10-23 | 2020-01-10 | 江汉大学 | Pt/g-C3N4/CeO2Composite photocatalyst and preparation method and application thereof |
| CN110860286A (en) * | 2019-11-11 | 2020-03-06 | 元林(上海)新材料科技有限公司 | Preparation method of high visible light response aqueous high-dispersion titanium dioxide |
| US20200239311A1 (en) * | 2020-01-14 | 2020-07-30 | Qatar University | Porous one-dimensional polymeric graphitic carbon nitride-based nanosystems for catalytic conversion of carbon monoxide and carbon dioxide under ambient conditions |
Non-Patent Citations (2)
| Title |
|---|
| MARIO J. MUNOZ-BATISTA ET AL.: "Promotion of CeO2–TiO2 photoactivity by g-C3N4: Ultraviolet and visible light elimination of toluene", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 姚仲鹏: "《空气净化原理、设计与应用》", 30 September 2014, 中国科学技术出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471146A (en) * | 2022-02-10 | 2022-05-13 | 杭州妙蓝环保科技有限公司 | Green odorless formaldehyde scavenger and preparation method thereof |
| CN114832848A (en) * | 2022-04-27 | 2022-08-02 | 中山市洁鼎过滤制品有限公司 | Catalyst and preparation method and application thereof |
| CN114832848B (en) * | 2022-04-27 | 2024-03-26 | 中山市洁鼎过滤制品有限公司 | Catalyst and preparation method and application thereof |
| CN115090323A (en) * | 2022-06-30 | 2022-09-23 | 宁波方太厨具有限公司 | Catalyst for purifying air, preparation method and purification assembly |
| CN115090323B (en) * | 2022-06-30 | 2024-01-16 | 宁波方太厨具有限公司 | Catalyst for purifying air, preparation method and purifying assembly |
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