Noble metal ruthenium monatomic supported catalyst and preparation method and application thereof
阅读说明：本技术 一种贵金属钌单原子负载型催化剂及其制备方法和应用 (Noble metal ruthenium monatomic supported catalyst and preparation method and application thereof ) 是由 贾宏鹏 蔡松财 于 2020-05-06 设计创作，主要内容包括：本发明公开了一种贵金属钌单原子负载型催化剂及其制备方法和应用。该催化剂包括硫化物载体和以单原子形式分散在其表面的钌,以钌基催化剂的质量计,钌单原子的占比为0.01-10％。本发明催化剂的CO-(2)吸附能力、光生电荷分离能力、光吸收能力、光热转换能力等方面的性质得到明显提升。其制备方法具有制备简单,快速,节约成本,可实现高比重的贵金属钌在硫化镉表面的单原子分散；采用该方法制备的单原子分散的钌贵金属催化剂在提高贵金属分散度降低贵金属使用成本的同时保证催化剂光热催化还原CO-(2)及高CH-(4)选择性。(The invention discloses a noble metal ruthenium single-atom supported catalyst, and a preparation method and application thereof. The catalyst comprises a sulfide carrier and ruthenium which is dispersed on the surface of the sulfide carrier in a single atom form, wherein the content of the single atom of the ruthenium is 0.01-10% by mass of the ruthenium-based catalyst. CO of the catalyst of the invention 2 The properties of the adsorption capacity, the photo-generated charge separation capacity, the light absorption capacity, the photo-thermal conversion capacity and the like are obviously improved. The preparation method has the advantages of simple and quick preparation, cost saving and capability of realizing the monoatomic dispersion of the noble metal ruthenium with high specific gravity on the surface of the cadmium sulfide; the monoatomic dispersion ruthenium noble metal catalyst prepared by the method can improve the dispersion degree of noble metals, reduce the use cost of the noble metals and ensure the photo-thermal catalytic reduction of CO by the catalyst 2 And high CH 4 And (4) selectivity.)
1. A ruthenium-based catalyst, characterized in that the catalyst comprises a support and ruthenium in a monoatomic form dispersed on the surface thereof;
the carrier is at least one of cadmium sulfide, molybdenum sulfide and zinc sulfide.
2. The ruthenium-based catalyst according to claim 1, wherein the ruthenium monoatomic ratio is 0.01 to 10% by mass of the ruthenium-based catalyst;
preferably, the ruthenium monoatomic group is uniformly dispersed on the support;
preferably, the support is any morphological support, preferably a nanorod.
3. A ruthenium-based catalyst according to claim 1 or 2, characterized in that the ruthenium-based catalyst is in a powder form;
preferably, the ruthenium-based catalyst has a particle size of 20 to 250 nm;
preferably, the ruthenium-based catalyst has a specific surface area of 10 to 150m2/g；
Preferably, the ruthenium-based catalyst is 0.1% Ru/CdS, 0.5% Ru/CdS, 1% Ru/CdS, 3% Ru/CdS.
4. A method for preparing a ruthenium-based catalyst according to any one of claims 1 to 3, comprising the steps of:
(1) dispersing a carrier and ammonium carbonate in deionized water to obtain a suspension;
(2) and dropwise adding a ruthenium salt aqueous solution into the suspension, stirring for reaction, and washing, drying and carrying out hydrogen reduction treatment on a reaction product to obtain the noble metal-based catalyst.
5. The method for preparing a ruthenium-based catalyst according to claim 4, wherein in step (1), the support has the meaning as defined in claim 1, preferably a CdS support;
preferably, the CdS carrier is prepared by a hydrothermal reaction;
preferably, the preparation process of the CdS carrier comprises the following steps: adding cadmium acetate dihydrate and L-cysteine into deionized water, continuously stirring until a milky solution is formed, adding ethanolamine into the solution, continuously stirring until a transparent solution is formed, carrying out hydrothermal reaction, and carrying out post-treatment on a reaction product to obtain the CdS carrier.
6. The preparation method of ruthenium-based catalyst according to claim 4 or 5 wherein in step (1), the ratio of the carrier, ammonium carbonate and deionized water is 1g (10-40) mmol (80-150) mL;
preferably, in the step (1), the carrier is firstly dispersed in deionized water, and then ammonium carbonate aqueous solution is added into the deionized water until the system is uniformly mixed;
preferably, the concentration of the ammonium carbonate aqueous solution is 0.5-2 mol/L;
preferably, the amount of the ammonium carbonate aqueous solution is 10-50 mL.
7. The preparation method of ruthenium-based catalyst according to any one of claims 4 to 6, wherein in the step (2), the ruthenium salt is selected from at least one of ruthenium chloride, ruthenium bromide, ruthenium nitrate, ruthenium nitrite, ruthenium sulfate and ruthenium acetate;
preferably, the mass ratio of the ruthenium salt to the support is 0.01 to 5 wt%;
preferably, the concentration of the ruthenium salt aqueous solution is 1-5 mg/mL;
preferably, the stirring reaction time is 10-36 h;
preferably, the reaction is carried out at room temperature;
preferably, the washing is alternately repeated washing by adopting absolute ethyl alcohol and deionized water;
preferably, the temperature of the hydrogen reduction treatment is 200-400 ℃, and the time of the hydrogen reduction treatment is 2-8 h.
8. The preparation method of ruthenium-based catalyst according to any one of claims 4 to 7, wherein the preparation method of ruthenium-based catalyst comprises the steps of:
(a) adding cadmium acetate dihydrate and L-cysteine into deionized water, continuously stirring until a milky solution is formed, adding ethanolamine into the solution, continuously stirring until a transparent solution is formed, carrying out hydrothermal reaction, and carrying out post-treatment on a reaction product to obtain a CdS carrier;
(b) dispersing the CdS carrier and ammonium carbonate in deionized water to obtain a mixture;
(c) and dropwise adding a ruthenium salt aqueous solution into the mixture, stirring for reaction, and washing, drying and carrying out hydrogen reduction treatment on a reaction product to obtain the ruthenium-based catalyst.
9. Ruthenium-based catalyst obtainable by a process according to any one of claims 4 to 8.
10. Ruthenium-based catalyst according to any of claims 1 to 3, 9 for the photothermal catalytic reduction of CO2The use of (1).
Technical Field
The invention belongs to CO2The technical field of reduction catalyst materials, in particular to a noble metal monatomic supported catalyst and a preparation method and application thereof.
Background
With followingThe rapid development of the industrial society and the increasing consumption of fossil energy not only cause CO2The discharge amount of the organic waste water is rapidly increased, a series of environmental problems such as greenhouse effect are caused, and the shortage of non-renewable resources is caused. Therefore, how to utilize CO2Changing waste into valuable has become one of the global hot topics.
Currently, CO is reduced by catalysis2The main methods of (1) are electrochemistry, bioelectrochemistry, thermocatalysis, photocatalysis and the like. Among them, the thermal catalysis method requires higher temperature for reaction, which increases energy consumption, causes sintering and deactivation of the catalyst, shortens the service life of the catalyst, and is a test for the high temperature stability of the catalyst; the electrochemical method is required to be completed in solution, and the hydrogen evolution reaction has great influence on the purity of the product; for the bioelectrochemical method, the living environment of the microorganism has a large influence on the reaction efficiency; and photocatalysis by utilizing solar energy for reaction is an environment-friendly means with wide prospect. But the photocatalyst has the problems of narrow absorption waveband, fast photo-generated charge recombination, low quantum efficiency, poor product selectivity and the like. Therefore, it is a significant work to develop photocatalysts with high catalytic activity and product selectivity.
Disclosure of Invention
In order to improve the above problems, the present invention provides a noble metal ruthenium-based catalyst comprising a sulfide support and a noble metal ruthenium monoatomic-dispersed on the surface of the support.
According to an embodiment of the present invention, the sulfide may be at least one of cadmium sulfide, molybdenum sulfide, zinc sulfide, and the like, and is preferably cadmium sulfide.
According to an embodiment of the invention, the proportion of ruthenium monoatomic atoms is 0.01 to 10%, for example 0.05 to 8%, exemplarily 0.1%, 0.2%, 0.3%, 0.5%, 1%, 1.5%, 3%, 4%, 5% by mass of the ruthenium-based catalyst.
According to an embodiment of the invention, the ruthenium monoatomic atom is uniformly dispersed on the support.
According to an embodiment of the present invention, the ruthenium-based catalyst is in a powder form. For example, the rutheniumThe particle size of the base catalyst is in the range 20 to 250nm, for example 30 to 200nm, with 50nm being exemplary. For example, the ruthenium-based catalyst has a specific surface area of 10 to 150m2Per g, e.g. 20 to 100m2G, exemplary 34m2/g。
According to an embodiment of the present invention, the sulfide support is any morphology of sulfide support, preferably nanorod-shaped, exemplified by cadmium sulfide nanorod.
According to an embodiment of the present invention, the ruthenium-based catalyst may be 0.1% Ru/CdS, 0.5% Ru/CdS, 1% Ru/CdS, 3% Ru/CdS.
The invention provides a preparation method of the ruthenium-based catalyst, which comprises the following steps:
(1) dispersing a carrier and ammonium carbonate in deionized water to obtain a suspension;
(2) and dropwise adding a ruthenium salt aqueous solution into the suspension, stirring for reaction, and washing, drying and carrying out hydrogen reduction treatment on a reaction product to obtain the noble metal-based catalyst.
According to an embodiment of the invention, in step (1), the support has the meaning as described above, preferably CdS. Wherein the CdS carrier can be prepared by a hydrothermal reaction. For example, the preparation process of the CdS carrier includes: adding cadmium acetate dihydrate and L-cysteine into deionized water, continuously stirring until a milky solution is formed, adding ethanolamine into the solution, continuously stirring until a transparent solution is formed, carrying out hydrothermal reaction, and carrying out post-treatment on a reaction product to obtain the CdS carrier. For example, the molar ratio of cadmium acetate dihydrate, L-cysteine, and ethanolamine may be 1 (1.2-4) to (40-80), illustratively 1:2: 67. For example, the molar volume ratio of the cadmium acetate dihydrate to the deionized water is 1 (20-50) mol/L, and the exemplary ratio is 1:36 mol/L. For example, the temperature of the hydrothermal reaction is 160-200 ℃, and 180 ℃ is exemplary; the hydrothermal reaction time is 10-40h, and 24h is exemplified. For example, the post-treatment includes washing and drying the reaction product.
According to an embodiment of the invention, in step (1), the ratio of the carrier, ammonium carbonate and deionized water is 1g (10-40) mmol, for example 1g (15-35) mmol, (90-130) mL, exemplary 1g:25mmol:125 mL.
According to an embodiment of the present invention, in step (1), the carrier may be dispersed in deionized water, and then an aqueous solution of ammonium carbonate may be added thereto until the system is uniformly mixed. Wherein the dispersion may be by means of dispersion known in the art, such as ultrasound and/or stirring. Wherein the concentration of the ammonium carbonate aqueous solution is 0.5-2mol/L, such as 0.8-1.5mol/L, and is exemplary 1 mol/L. The amount of the ammonium carbonate aqueous solution may be 10-50mL, for example, 15-40mL, and exemplary 25 mL. The addition of ammonium carbonate facilitates the dispersion of the noble metal on the surface of the carrier.
According to an embodiment of the present invention, in the step (2), the ruthenium salt may be selected from at least one of ruthenium chloride, ruthenium bromide, ruthenium nitrate, ruthenium nitrite, ruthenium sulfate, ruthenium acetate, and the like, for example, at least one selected from ruthenium chloride, ruthenium bromide, and ruthenium nitrate, and exemplified by ruthenium chloride.
According to an embodiment of the invention, in step (2), the mass ratio of the ruthenium salt to the support is 0.01 to 5 wt%, for example 0.05 to 4.5 wt%, illustratively 0.1 to 3 wt%.
According to an embodiment of the present invention, in step (2), the concentration of the aqueous ruthenium salt solution can be 1-5mg/mL, such as 1.5-4.5mg/mL, with 2.58mg/mL being exemplary.
According to an embodiment of the invention, in step (2), the stirring reaction time is 10 to 36h, such as 12 to 24h, exemplary 12h, 15h, 20 h.
According to an embodiment of the invention, in step (2), the reaction is carried out at room temperature, for example at room temperature of 15-40 ℃, such as 20-30 ℃.
According to an embodiment of the present invention, in the step (2), the washing may be alternately performed a plurality of times by using absolute ethanol and deionized water.
According to an embodiment of the invention, in step (2), the temperature of the drying is 70-90 ℃, such as 75-85 ℃, exemplary 80 ℃. Wherein the drying time is 2-8h, such as 3-7h, and exemplary is 4h, 5h, 6 h.
According to the embodiment of the present invention, in the step (2), the temperature of the hydrogen reduction treatment is 200-. Wherein the hydrogen reduction treatment time is 2-8h, such as 3-7h, exemplary 4h, 5h, 6 h. Wherein the atmosphere of the hydrogen reduction treatment is ultrapure hydrogen.
According to an embodiment of the present invention, the preparation method of the ruthenium-based catalyst includes the steps of:
(a) adding cadmium acetate dihydrate and L-cysteine into deionized water, continuously stirring until a milky solution is formed, adding ethanolamine into the solution, continuously stirring until a transparent solution is formed, carrying out hydrothermal reaction, and carrying out post-treatment on a reaction product to obtain a CdS carrier;
(b) dispersing the CdS carrier and ammonium carbonate in deionized water to obtain a mixture;
(c) and dropwise adding a ruthenium salt aqueous solution into the mixture, stirring for reaction, and washing, drying and carrying out hydrogen reduction treatment on a reaction product to obtain the ruthenium-based catalyst.
The invention also provides the ruthenium-based catalyst prepared by the method. Preferably, the ruthenium-based catalyst has the meaning as described above.
The invention also provides the application of the ruthenium-based catalyst in photo-thermal catalytic reduction of CO2The use of (1).
The invention has the beneficial effects that:
the invention provides a method for CO-catalyzing CO by photo-thermal2Reduction and high CH4A selective noble metal-based catalyst, a preparation method and application thereof, in particular to a high-dispersion noble metal ruthenium monatomic loaded cadmium sulfide catalyst, wherein ruthenium monatomic is tightly combined with a catalyst carrier. Firstly, ruthenium monoatomic atom is used as an electron acceptor to promote the separation of photo-generated charges generated by cadmium sulfide to reach high CH4Selectivity; secondly, the ruthenium monoatomic atom provides more CO2Adsorption and activation sites are favorable for improving the catalytic activity; meanwhile, as a dark material, the material has good absorption and photo-thermal conversion capability on full spectrum, promotes charge transfer, and efficiently reduces CO by photo-thermal catalysis2Selective generation of CH4Thereby improving the catalytic activityAnd (4) sex.
For example, the catalyst synthesized by the present invention is at 0.71W/cm2After 4h of full spectrum irradiation, CO2+H2The photo-thermal catalytic activity of O reaches rCH4Not more than 8.11. mu. mol/g, CH thereof4The selectivity is as high as 97.6%.
The catalyst promotes photoproduction charge transfer and product adsorption and desorption by virtue of the photo-thermal effect, improves the catalytic activity and improves the CO resistance of the catalyst2Adsorption capacity of gas molecules to promote CO2Selective reduction to CH4. The supported ruthenium-based catalyst can regulate and control CO2Reduced CH4Selectivity and catalytic activity is improved by photo-thermal synergistic effect.
The preparation method has the advantages of easily available raw materials, simple and quick process, cost saving and easy industrialization, and can realize the monoatomic dispersion of the noble metal ruthenium with high specific gravity on the surface of the cadmium sulfide; the monoatomic dispersion ruthenium noble metal catalyst prepared by the method can improve the dispersion degree of noble metals, reduce the use cost of the noble metals and ensure the photo-thermal catalytic reduction of CO by the catalyst2And high CH4And (4) selecting.
Drawings
FIG. 1 is a HAADF-Cs-STEM test chart of the catalyst prepared in example 4 of the present invention;
FIG. 2 is a HRTEM test chart of the catalyst prepared in comparative example 1 of the present invention;
FIG. 3 is a graph comparing UV-visible diffuse reflectance spectra of catalysts prepared in examples 1,2,3,4,5 of the present invention and comparative example 1;
FIG. 4 shows the light intensity of 0.71W/cm for the catalysts prepared in examples 1,2,3,4,5 of the present invention and comparative example 12Under the irradiation of a full-spectrum xenon lamp, CO is reduced2A comparative plot of catalytic activity of (a);
FIG. 5 shows the reduction of CO in the catalyst prepared in example 1 of the present invention under different reaction conditions2A comparative plot of catalytic activity of (a);
FIG. 6 shows the reduction of CO in the catalyst prepared in example 4 of the present invention under different reaction conditions2A comparative plot of catalytic activity of (a);
FIG. 7 shows the photo-induced degradation of catalysts prepared according to examples 1,2,3,4,5 of the present invention and comparative example 1Luminescence spectrum and CO2-TPD curve.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
Weighing 3mmol of cadmium acetate dihydrate and 6mmol of L-cysteine, adding the cadmium acetate dihydrate and the 6mmol of L-cysteine into 108mL of deionized water, continuously stirring for 30min to form a milky white solution, adding 12mL of ethanolamine, continuously stirring for 30min to form a transparent solution, carrying out hydrothermal reaction at 180 ℃ for 24h, washing the solution for multiple times by using absolute ethyl alcohol and deionized water, and drying the solution at 80 ℃ overnight to obtain yellow pure CdS.
Example 2
Taking 1g of the dry pure CdS powder prepared in the example 1, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment and stirring for 15min, adding 25mL of 1mol/L ammonium carbonate solution, continuing stirring for 15min, and taking 0.388mL of RuCl with the concentration of 2.58mg/mL3Dispersing the aqueous solution in 50mL of deionized water, dropwise adding, stirring overnight, washing with absolute ethyl alcohol and deionized water for several times, drying at 80 ℃ for 4h, and treating at 200 ℃ for 4h in a pure hydrogen atmosphere to obtain CdS-loaded Ru, wherein the Ru accounts for 0.1% of the total mass, namely 0.1% of Ru/CdS.
Example 3
Taking 1g of the dry pure CdS powder prepared in the example 1, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment and stirring for 15min, adding 25mL of 1mol/L ammonium carbonate solution, continuing stirring for 15min, and taking 1.948mL of RuCl with the concentration of 2.58mg/mL3Dispersing the aqueous solution in 50mL deionized water, dropwise adding, stirring overnight, washing with anhydrous ethanol and deionized water for several times, drying at 80 deg.C for 4h, treating at 200 deg.C in pure hydrogen atmosphere for 4h to obtain CdS loaded Ru with Ru content of 0.5% by total mass, i.e. 0.5%Ru/CdS。
Example 4
Taking 1g of the dry pure CdS powder prepared in the example 1, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment and stirring for 15min, adding 25mL of 1mol/L ammonium carbonate solution, continuing stirring for 15min, and taking 3.915mL of RuCl with the concentration of 2.58mg/mL3Dispersing the aqueous solution in 50mL of deionized water, dropwise adding, stirring overnight, washing with absolute ethyl alcohol and deionized water for several times, drying at 80 ℃ for 4h, and treating at 200 ℃ for 4h in a pure hydrogen atmosphere to obtain CdS loaded Ru, wherein the Ru accounts for 1% of the total mass, namely 1% of Ru/CdS.
The HAADF-Cs-STEM test pattern for catalyst 1% Ru/CdS shown in FIG. 1 shows that: the bright spot is noble metal ruthenium which is highly dispersed on the surface of cadmium sulfide, and the ruthenium belongs to a single atom by analyzing the particle size.
Example 5
Taking 1g of the dry pure CdS powder prepared in the example 1, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment and stirring for 15min, adding 25mL of 1mol/L ammonium carbonate solution, continuing stirring for 15min, and taking 11.988mL of RuCl with the concentration of 2.58mg/mL3Dispersing the aqueous solution in 50mL of deionized water, dropwise adding, stirring overnight, washing with absolute ethyl alcohol and deionized water for several times, drying at 80 ℃ for 4h, and treating at 200 ℃ for 4h in a pure hydrogen atmosphere to obtain CdS loaded Ru, wherein the Ru accounts for 3% of the total mass, namely 3% of Ru/CdS.
Comparative example 1
Taking 1g of the dry pure CdS powder prepared in the example 1, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment and stirring for 15min, and taking 3.915mL of RuCl with the concentration of 2.58mg/mL3Dispersing the aqueous solution in 50mL of deionized water, dropwise adding, stirring overnight, washing with absolute ethyl alcohol and deionized water for several times, drying at 80 ℃ for 4h, and treating at 200 ℃ for 4h in a pure hydrogen atmosphere to obtain CdS-loaded Ru, wherein the total mass of the obtained CdS-loaded Ru is 1%, namely 1% Ru/CdS-C.
As shown in FIG. 2, ruthenium in the 1% Ru/CdS-C catalyst was dispersed in the form of nanoparticles (particle size 1.07nm) on a CdS support.
FIG. 3 is a graph comparing UV-visible diffuse reflectance spectra of catalysts prepared in examples 1,2,3,4,5 of the present invention and comparative example 1. Therefore, all samples have characteristic absorption peaks at the wavelength of less than 580nm and belong to the inherent band gap absorption of cadmium sulfide; the noble metal ruthenium-loaded catalyst sample has strong absorption in visible light and near infrared light regions, and is derived from the light scattering principle of the noble metal ruthenium.
Example 6
By testing the sample for CO2The activity was evaluated by the yield of reduction and the product selectivity, and the reactor used was a quartz reactor having a volume of 227 mL. Before the experiment, 50mg of catalyst sample (the catalyst prepared in examples 1-5 and comparative example 1) is weighed and mixed with 2-30mL of absolute ethyl alcohol, the mixture is uniformly dispersed by ultrasonic, and the mixture is uniformly coated on a glass fiber membrane by adopting a sand core filtering methodDrying at 40 deg.C, placing in a reactor, and continuously introducing high-purity CO2And after 1h, the gas mixture of the water vapor and the steam (the volume ratio of the water vapor is about 5 vol.%), closing the gas to ensure the static reaction. During the reaction, a PLS-SXE300 xenon lamp produced by Beijing Pochle technology ltd is used for providing a full spectrum light source, and an IR375CH IR2 infrared lamp produced by PHILIPS provides infrared light. After 4h of reaction, 1mL of gas was withdrawn and CO was analyzed on-line by gas chromatography equipped with FID and a nickel reformer in the atmosphere2、CH4And the concentration of CO.
FIG. 4 shows the light intensity of 0.71W/cm for the catalysts prepared in examples 1,2,3,4,5 of the present invention and comparative example 12Under the irradiation of a full-spectrum xenon lamp, CO is reduced2Comparative catalytic activity of (c). It can be seen that the product selectivity of the pure cadmium sulfide of example 1 is biased towards the more readily produced CO, whereas the product selectivity of the noble metal ruthenium monatomic supported catalysts of examples 2-5 is gradually biased towards CH as the loading is increased41% CH of Ru/CdS4The selectivity is as high as 97.6%. In addition, the comparative example 1 catalyst sample supporting noble metal ruthenium nanoparticles was biased toward CH in spite of the product selectivity4But not high catalytic activity.
FIG. 5 shows the reduction of CO in the catalyst prepared in example 1 of the present invention under different reaction conditions2Comparative catalytic activity of (c). It can be seen thatUnder the full-spectrum irradiation of different light intensities, the product selectivity of the pure cadmium sulfide is biased to CO, and the experiment of illumination heating and control (85 ℃) and the experiment of infrared illumination (85 ℃) show that the traditional photocatalysis exists; higher light intensity has higher temperature, and the catalytic activity is improved.
FIG. 6 shows the reduction of CO in the catalyst prepared in example 4 of the present invention under different reaction conditions2Comparative catalytic activity of (c). It can be seen that under the full spectrum irradiation of different light intensities, the product selectivity of 1% Ru/CdS is biased to CH4The experiment of illumination heating temperature control (110 ℃) and the experiment of infrared illumination (110 ℃) indicate the existence of the traditional photocatalysis; higher light intensity has higher temperature, and the catalytic activity is improved.
FIG. 7 is a photoluminescence spectrum and CO of catalysts prepared in examples 1,2,3,4,5 and comparative example 1 of the present invention2-TPD curve. Therefore, the photoluminescence intensity of the noble metal ruthenium-loaded catalyst is lower, which shows that the noble metal ruthenium-loaded catalyst is beneficial to the separation of photo-generated charges generated by cadmium sulfide; load noble metal ruthenium single atom catalyst pair CO2The adsorption amount of (2) is larger, and the adsorption amount is increased along with the increase of the loading amount, which shows that the noble metal ruthenium monoatomic atom is taken as CO2Adsorption sites and reaction sites, and supported noble metal ruthenium nanoparticle catalyst for CO2The amount of adsorption of (a) is not so much increased.
And sulfide carriers similar to cadmium sulfide, such as molybdenum sulfide, zinc sulfide and the like, are adopted for replacement, so that the noble metal ruthenium monatomic supported catalyst with similar performance can be obtained.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.