Preparation method of reverse-phase CuO-Ce catalyst and application of reverse-phase CuO-Ce catalyst in catalytic decomposition of sulfur-containing VOCs (Volatile Organic Compounds)

Abstract

The invention discloses a preparation method of a reverse-phase CuO-Ce catalyst and application of the reverse-phase CuO-Ce catalyst in catalytic decomposition of sulfur-containing VOCs, and belongs to the technical field of organic sulfur pollutant treatment. The preparation method of the reverse-phase CuO-Ce catalyst comprises the following steps: (1) mixing a copper source with water to obtain a copper source solution, and then sequentially adding alkali liquor and a reducing agent for hydrothermal reaction to obtain Cu2O nanoparticles; and (2) dispersing the Cu2O nanoparticles in water, adding a cerium source solution and an alkali solution, carrying out a co-precipitation reaction, collecting a solid product after the co-precipitation reaction, and roasting to obtain the reverse-phase CuO-Ce catalyst. The prepared reverse-phase CuO-Ce catalyst has an obvious CeO2 nano island and a Ce-Ov-Cu interface structure, shows an outstanding capability of catalytically decomposing sulfur-containing VOCs pollutants at a low temperature, and has excellent stability and water resistance.

Description

Technical Field

[0001] This invention belongs to the field of organic sulfur pollutant treatment technology, and more specifically relates to a method for preparing a reverse CuO@Ce catalyst and its application in the catalytic decomposition of sulfur-containing VOCs. Background Technology

[0002] The extraction, processing, and utilization of coal, oil, and natural gas generate various sulfur-containing volatile organic compounds (S-VOCs), with methanethiol (CH3SH) being a typical example. Currently, the content of S-VOCs in natural gas and crude oil is approximately 0.03–6 wt%. Although the content is low, long-term untreated direct emission into the environment will have serious negative impacts on industrial production, human health, and the ecological environment. CH3SH is a colorless gas with a strong, pungent odor at room temperature, similar to rotting cabbage or onions, and has an extremely low odor threshold (0.4 ppb / v). In regulations concerning pollutant emissions, CH3SH is listed as a key controlled volatile organic sulfur compound (VOC). Furthermore, CH3SH is explicitly classified as a toxic substance, posing a serious threat to human health. Long-term exposure to methanethiol not only damages the respiratory and nervous systems but may also lead to acid rain, ecosystem destruction, and other environmental pollution problems. Therefore, developing an efficient technology for removing sulfur-containing odorous pollutants is of great significance to human health, industrial production, and the environment.

[0003] Currently, methods for treating volatile organic sulfur compounds include adsorption, absorption, biodegradation, combustion, catalytic oxidation, and catalytic decomposition. Adsorption equipment is simple and easy to operate, but it requires regular replacement or regeneration of the adsorbent, increasing operating costs. Absorption is highly efficient, technologically mature, and widely used, but it generates large amounts of wastewater, causing secondary pollution. Biodegradation is environmentally friendly and has low operating costs, but its reaction rate is slow and its treatment efficiency is relatively low. Combustion has high treatment efficiency and is suitable for high-concentration sulfur-containing pollutants, but it consumes a lot of energy and produces sulfur dioxide, which requires further treatment. Catalytic oxidation has mild reaction conditions and high treatment efficiency, and is suitable for a variety of sulfur-containing compounds, but the cost of oxidants is high, resulting in higher operating costs.

[0004] Catalytic decomposition is an ideal treatment technology due to its advantages such as high efficiency, energy saving, simple operation, no harmful byproducts, good economics, and wide application. The key lies in catalyst development. Currently, catalysts for the catalytic decomposition of sulfur-containing pollutants are mainly normal-phase supported catalysts such as rare-earth coupled molecular sieve catalysts (e.g., CeO2 / ZSM-5) and metal oxide supported catalysts (MoO3 / SiO2). While these catalysts have low operating costs, they face several challenges in practical applications. For example, the limited loading of active components leads to a low density of active sites; under high-temperature conditions, active components are prone to sintering, damaging the interfacial structure and causing deactivation. These problems result in relatively low catalytic activity (generally requiring temperatures above 400℃ for complete conversion), and it is difficult to simultaneously achieve good activity, stability, and adaptability to aqueous environments, severely restricting the application of traditional normal-phase catalysts in the removal of volatile organic sulfur compounds.

[0005] Based on this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a reversed-phase CuO@Ce catalyst and its application in the catalytic decomposition of sulfur-containing VOCs, thereby solving the problems existing in the prior art. The reversed-phase catalyst prepared by this invention, due to its unique nano-island and interface structure, can not only form reversed-phase interface active sites different from the normal phase interface, but also increase the number of interface active sites while maintaining the integrity of the interface structure, thus promoting the reaction. In other words, this invention develops a reversed-phase catalyst that can simultaneously achieve low-temperature activity, long-term desulfurization stability, and water resistance, and applies it to the field of volatile organic sulfur compound removal.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] One of the technical solutions of this invention is to provide a method for preparing a reverse-phase CuO@Ce catalyst, comprising the following steps:

[0009] (1) A copper source solution is obtained by mixing copper source with water, and then an alkaline solution and a reducing agent are added in sequence to carry out a hydrothermal reaction to obtain Cu2O nanoparticles.

[0010] (2) The Cu2O nanoparticles were dispersed in water, and a cerium source solution and an alkaline solution were added to carry out a coprecipitation reaction. After the coprecipitation reaction, the solid product was collected and calcined to obtain the reversed CuO@Ce catalyst.

[0011] Preferably, the copper source includes copper chloride; the concentration of the copper source solution is 0.007–0.01 mol / L.

[0012] Preferably, the alkaline solution independently includes sodium hydroxide solution or ammonia water; the concentration of the alkaline solution independently ranges from 0.133 to 2 mol / L.

[0013] Preferably, the reducing agent comprises an L-ascorbic acid solution; the concentration of the reducing agent is 0.3–0.6 mol / L.

[0014] Preferably, in step (1), the ratio of the amount of copper source, alkali solution and reducing agent is 0.01mol:60-120mL:120mL.

[0015] Preferably, the hydrothermal reaction is carried out at a temperature of 50–60°C for 1–3 hours.

[0016] Preferably, the cerium source solution is an aqueous solution of a cerium source; the concentration of the cerium source solution is 0.1 mol / L; and the cerium source includes cerium nitrate.

[0017] Preferably, in step (2), the volume ratio of the cerium source solution to the alkaline solution is 1.48–600:60–120. Preferably, the volume ratio of the copper source solution to the cerium source solution is 4.2:1.48–600.

[0018] Preferably, the temperature of the coprecipitation reaction is 50–80°C, and the time is 0–2 h, and not 0.

[0019] Preferably, the roasting temperature is 500°C and the time is 2 to 4 hours.

[0020] Furthermore, the hydrothermal reaction and the coprecipitation reaction are followed by separate steps of washing and drying the obtained solid product; the washing includes washing with water and ethanol at least once; the drying temperature is 60°C and the time is 2 to 12 hours.

[0021] This invention prepares a reverse-phase CuO@Ce catalyst with a reversed Cu-Ov-Ce interface and CeO2 nano-island structure by controlling the amount of cerium source solution. Adjusting the ratio of copper and cerium source solutions, using L-ascorbic acid solution as a reducing agent and ammonia as a co-precipitant, facilitates the control of CeO2 size to form nano-island structures and the formation and stabilization of the reversed Cu-Ov-Ce interface. Then, using the reversed CuO@Ce with the reversed Cu-Ov-Ce interface and CeO2 nano-island structure directly as a catalyst, it achieves a significant improvement in the degradation rate and efficiency of sulfur-containing VOCs pollutants at a low-temperature (180℃) degradation temperature. It also lowers the temperature at which the methanethiol degradation rate reaches 100%, increases the service life of the reversed CuO@Ce catalyst, breaks the inherent structural limitations of traditional supported catalysts, and enhances the catalyst's activity and stability.

[0022] The second technical solution of the present invention provides a reverse CuO@Ce catalyst prepared by the above preparation method, wherein the reverse CuO@Ce catalyst has a CeO2 nano-island structure and a reverse Cu-Ov-Ce interface.

[0023] The third technical solution of the present invention provides the application of the above-mentioned reversed CuO@Ce catalyst in the catalytic decomposition of sulfur-containing VOCs pollutants, wherein the sulfur-containing VOCs pollutants include methanethiol.

[0024] Fourth technical solution of the present invention: A method for low-temperature degradation of sulfur-containing VOCs pollutants, comprising the following steps:

[0025] The above-mentioned reversed CuO@Ce catalyst was used to catalytically decompose sulfur-containing VOCs pollutants at 30–500 °C.

[0026] Preferably, the space velocity of the sulfur-containing VOCs pollutants is 9000–15000 mL / (g·h).

[0027] The present invention discloses the following technical effects:

[0028] The reversed CuO@Ce catalyst prepared by this invention possesses an abundant CeO2 nanoisland structure. Compared to conventional normal Ce / CuO catalysts, the CeO2 nanoislands form abundant reversed Cu-Ov-Ce interfacial active sites with CuO, directly increasing the contact area between sulfur-containing VOCs pollutants and the catalyst, and promoting the migration of Ov on the catalyst surface, allowing oxygen to participate in the reaction more effectively, thus facilitating the reaction. Simultaneously, the strong interaction between the CeO2 nanoislands and CuO increases the structural stability of the catalyst, preventing CuO agglomeration and sintering during the reaction, thereby improving the catalyst's lifespan.

[0029] The reversed-phase CuO@Ce catalyst prepared in this invention exhibits excellent low-temperature activity and stability in the catalytic decomposition of sulfur-containing VOCs pollutants. Methanethiol can be completely degraded at a low temperature of 180℃, while traditional zeolite molecular sieves (such as H-ZSM-5) and metal oxide supported catalysts still have an activity of less than 20% in decomposing sulfur-containing VOCs pollutants even at 250℃, and complete degradation of sulfur-containing VOCs pollutants usually requires temperatures above 400℃. Meanwhile, the reversed-phase CuO@Ce catalyst shows complete conversion lifetimes of up to 5 h for high concentration (5000 ppm) and 34.5 h for low concentration (500 ppm) of methanethiol at atmospheric pressure and 250℃, respectively, which are far superior to those of metal oxides reported in existing literature (whose lifetimes are generally 1–3 h). Furthermore, the reversed-phase CuO@Ce catalyst also exhibits excellent water resistance, with a complete conversion lifetime of up to 62.5 h for methanethiol in a water-containing environment.

[0030] The preparation method provided by this invention can obtain a reverse CuO@Ce catalyst with abundant CeO2 nano-island structure and unique reverse Cu-Ov-Ce interface. It exhibits excellent activity, stability and adaptability to water environment in the removal of sulfur-containing VOCs pollutants, and has practical application prospects in the field of environmental pollutant treatment. Attached Figure Description

[0031] Figure 1 is (a) CuO (23) @Ce (1) , (b) CuO, (c) CeO2, (d) IM-Cu (1) / CeO 2(23) TEM image of the catalyst;

[0032] Figure 2 CuO prepared in Example 1 (23) @Ce (1) HR-TEM image (a), HAADF-STEM image (b), (c), (e), line scan spectrum (d), and EDS elemental mapping image (f), (g), (k), (i) of the catalyst;

[0033] Figure 3 The results of the activity test (a), (b), and (c) and the results of the stability test (d) of the catalysts obtained in Examples 1-4 are shown.

[0034] Figure 4 The reversed CuO obtained in Example 1 (23) @Ce (1) Results of water resistance test on the catalyst. Detailed Implementation

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0037] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0038] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0039] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0040] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0041] Unless otherwise specified, all raw materials used in the following embodiments of the present invention are commercially available products, and the source of commercially available products does not affect the technical effect of the present invention.

[0042] Unless otherwise specified, the ambient temperature involved in this invention is 25±5℃.

[0043] Example 1

[0044] Preparation steps of reversed CuO@Ce catalyst:

[0045] S1. First, weigh 2g of CuCl2·2H2O and dissolve it in deionized water to prepare a CuCl2 solution (0.01mol / L). Then, add 120mL of NaOH solution (1.5mol / L), stir at room temperature for 30min, and then add 120mL of L-ascorbic acid solution (0.6mol / L). Heat to 55℃ and age for 3h. Centrifuge and wash, then vacuum dry at 60℃ for 5h to obtain Cu2O nanoparticles.

[0046] S2. Disperse 0.6 g of Cu2O obtained in step S1 in 600 mL of deionized water, and add 1.48–593.17 mL of Ce(NO3)3 solution (0.1 mol / L, X is determined by the Ce loading). Heat to 60 °C, and slowly add 60 mL of NH3·H2O solution (0.1 mol / L) while stirring for 1 h. Centrifuge and wash, dry at 60 °C overnight, and calcine in a muffle furnace at 500 °C for 2 h to obtain a reversed CuO@Ce catalyst with Cu:Ce molar ratios of 23:1, 16:1, 13:1, 3:1, and 2:1, respectively, denoted as CuO. (23) @Ce (1) CuO (16) @Ce (1) CuO (13) @Ce (1) CuO (3) @Ce (1) CuO (2) @Ce (1) .

[0047] Example 2

[0048] Preparation steps of pure-phase CuO catalyst:

[0049] Compared with Example 1, the difference is that the Cu2O nanoparticles obtained in step S1 were directly calcined at 550°C for 2 hours to obtain a pure phase CuO catalyst.

[0050] Example 3

[0051] Preparation steps of pure-phase CeO2 catalyst:

[0052] 10 g of Ce(NO3)3·6H2O was dissolved in 600 mL of deionized water, and then 30 mL of NaOH solution (2 mol / L) was added. The mixture was stirred at 60 °C for 1 h. After centrifugation and washing, the mixture was dried at 60 °C overnight and calcined in a muffle furnace at 500 °C for 2 h to obtain a pure phase CeO2 catalyst.

[0053] Example 4

[0054] Preparation steps of normal phase IM-Cu / CeO2 catalyst:

[0055] Using the pure-phase CeO2 catalyst obtained in Example 3 as a support, 0.5721 g of Cu(NO3)2·3H2O was dissolved in deionized water, sonicated for 5 min until completely dissolved, and then 2 g of pure-phase CeO2 catalyst was added. The mixture was stirred for 15 min and impregnated overnight at room temperature, followed by drying at 80 °C overnight and calcination at 500 °C for 2 h to obtain a normal-phase IM-Cu / CeO2 catalyst, denoted as IM-Cu. (1) / CeO 2(23) .

[0056] Figure 1 is (a) CuO (23) @Ce (1) , (b) CuO, (c) CeO2, (d) IM-Cu (1) / CeO 2(23) TEM image of the catalyst. The image shows the reversed CuO phase. (23) @Ce (1) Similar in morphology to CuO catalysts, but CuO (23) @Ce (1) It exhibits a significantly increased surface roughness. Furthermore, CeO2 nanoparticles were observed to be uniformly dispersed on the CuO substrate. Normal-phase IM-Cu (1) / CeO 2(23) Similar in appearance to CeO2 catalyst, normal phase IM-Cu (1) / CeO 2(23) CuO nanoparticles were uniformly dispersed on a CeO2 substrate, indicating the successful preparation of four catalysts.

[0057] Figure 2 CuO prepared in Example 1 (23) @Ce (1) HR-TEM image (a), HAADF-STEM images (b), (c), (e), line scan spectrum (d), and EDS elemental mapping images (f), (g), (k), (i) of the catalyst. Figure 2 It can be seen that the obtained reversed CuO (23) @Ce (1) The catalyst formed distinct CeO2 nanoislands and Cu-Ov-Ce interface structures. The CeO2 nanoislands were approximately 4 nm in size, indicating a reverse-phase CuO... (23) @Ce (1) Successful preparation of the catalyst.

[0058] Figure 3 The results of the activity test (a), (b), and (c) and the results of the stability test (d) of the catalysts obtained in Examples 1 to 4 are shown.

[0059] Activity experiment:

[0060] A series of catalysts with different Ce loadings, including reversed-phase CuO@Ce, pure-phase CuO, pure-phase CeO2, and normal-phase IM-Cu / CeO2, were ground to a particle size of 40–60 mesh and packed into a fixed-bed reactor. The catalyst loading mass was 0.2 g. A single-component methanethiol gas with a concentration of 5000 ppm or 500 ppm was introduced into the fixed-bed reactor. The feed mass hourly space velocity was controlled at 9000 mL / (g·h), the reaction system pressure was atmospheric pressure, and the reaction temperature was 30–500 °C. Catalytic degradation catalytic activity evaluation experiments were conducted, and the results are as follows: Figure 3As shown in (a), (b) and (c).

[0061] Depend on Figure 3 As can be seen from (a), among the reverse CuO@Ce catalysts with different Ce loadings prepared in this invention, the low-load CuO (23) @Ce (1) The catalyst performed optimally, achieving complete conversion of methanethiol not only at a relatively low temperature of 180℃ but also maintaining stable and complete conversion at higher temperatures. With increasing Ce loading, the catalyst's activity significantly deteriorated, and CuO... (16) @Ce (1) The catalyst could not completely convert methanethiol at 400℃. CuO had the highest Ce loading. (2) @Ce (1) The inability to completely degrade methanethiol at temperatures above 180℃ indicates a low CuO loading. (23) @Ce (1) The catalyst exhibits excellent structural stability.

[0062] Depend on Figure 3 As shown in (b), pure phase CuO, CeO2 and normal phase IM-Cu (1) / CeO 2(23) The catalysts completely degraded methanethiol at temperatures of 300°C, 400°C, and 400°C, respectively, while the reverse-phase CuO prepared in this invention... (23) @Ce (1) The catalyst significantly reduces the temperature at which methanethiol is completely degraded, down to 180°C, demonstrating excellent low-temperature activity for methanethiol degradation.

[0063] Depend on Figure 3 As can be seen from (c), the reverse-phase CuO prepared in this invention (23) @Ce (1) The catalyst exhibits excellent low-temperature activity for both high concentrations (5000 ppm) and low concentrations (500 ppm) of methanethiol. It can completely degrade high concentrations (5000 ppm) of methanethiol at 180°C, while it can degrade low concentrations (500 ppm) of methanethiol at near 100% at room temperature.

[0064] Stability test:

[0065] reversed CuO (23) @Ce (1) Pure-phase CuO, pure-phase CeO2, and normal-phase IM-Cu / CeO2 catalysts were ground to a particle size of 40–60 mesh and packed into a fixed-bed reactor. The catalyst loading mass was 0.2 g, the methanethiol concentration was 5000 ppm, the temperature was 250 °C, the feed mass hourly space velocity was controlled at 9000 mL / (g·h), and the reaction system pressure was atmospheric pressure. Catalyst stability (lifetime) experiments were conducted, and the results are as follows: Figure 3 As shown in (d).

[0066] As shown in the figure, there are pure phase CuO, CeO2, and normal phase IM-Cu. (1) / CeO 2(23) The catalyst cannot completely convert methanethiol at 250℃, and its stability decreases with increasing time. However, the reverse-phase CuO prepared in this invention... (23) @Ce (1) The catalyst exhibits excellent stability in the complete degradation of methanethiol (5000 ppm) for up to 5 hours.

[0067] Water resistance test:

[0068] reversed CuO (23) @Ce (1) The catalyst was ground to a particle size of 40–60 mesh and packed into a fixed-bed reactor. The catalyst loading mass was 0.2 g. The gas concentration was 500 ppm methanethiol and 10% H₂O (v / v). The temperature was 250 °C. The feed space velocity was controlled at 9000 mL / (g·h) and 15000 mL / (g·h) (9000 mL / (g·h) for the first 2 hours, then increased to 15000 mL / (g·h)). The reaction system pressure was atmospheric pressure. The catalyst's water resistance stability (lifetime) was tested, and the results are as follows: Figure 4 As shown.

[0069] Figure 4 The reversed CuO obtained in Example 1 (23) @Ce (1) Results of water resistance test on the catalyst.

[0070] Depend on Figure 4 It can be seen that the reverse CuO (23) @Ce (1) The catalyst achieved 100% conversion in both aqueous (CH3SH+10%H2O) and anhydrous (CH3SH+0%H2O) environments for the first 2 hours. There was no difference after increasing the space velocity from 9000 mL / (g·h) to 15000 mL / (g·h), indicating that the catalyst has excellent space velocity adaptability.

[0071] Under anhydrous (CH3SH+0%) conditions, reverse-phase CuO (23) @Ce (1) The catalyst began to deactivate after 34.5 hours, and the activity retention rate was only 25.83% after 62.5 hours, indicating insufficient stability under normal operating conditions. Under aqueous conditions (CH3SH + 10% H2O), the reverse-phase CuO... (23) @Ce (1)The catalyst showed signs of deactivation after 62.5 hours, with an activity retention rate as high as 93.2%. Under the same operating time (62.5 hours), the activity retention rate of the aqueous system was 3.6 times higher than that of the anhydrous system (93.2% vs. 25.83%), demonstrating that CuO… (23) @Ce (1) It has excellent hydrothermal stability.

[0072] Inverse CuO (23) @Ce (1) The catalyst's resistance to water lies in the fact that CeO2 nanoislands can capture H2O molecules through oxygen vacancies. The Ce-O-Cu interface promotes hydroxylation of H2O molecules, accelerating the desorption of sulfur species and preventing CuO from being deeply sulfided by sulfur species, thus avoiding poisoning of the active sites at the Ce-O-Cu interface and delaying the rate of deactivation due to poisoning. Moisture inhibits the sulfidation reaction, maintains the stability of the active phase, and reduces the formation of sulfides.

[0073] Combination Figure 3 (d) and Figure 4 It was found that the reversed CuO@Ce catalyst exhibited complete conversion lifetimes of up to 5 h for high concentration (5000 ppm) and 34.5 h for low concentration (500 ppm) of sulfur-containing VOCs (methanethiol) at atmospheric pressure and 250 °C. Furthermore, the reversed CuO@Ce catalyst also demonstrated excellent water resistance, with a complete conversion lifetime of up to 62.5 h for methanethiol under aqueous conditions.

[0074] In summary, the reverse CuO@Ce catalyst prepared by this invention has obvious CeO2 nano-islands and Ce-Ov-Cu interface structures, exhibiting outstanding ability to catalytically decompose sulfur-containing VOCs pollutants at low temperatures, and possessing excellent stability and water resistance.

[0075] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0076] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A preparation method of a reverse phase CuO@Ce catalyst, characterized in that, The method comprises the following steps: (1) mixing a copper source with water to obtain a copper source solution, and then adding a lye and a reducing agent to perform a hydrothermal reaction to obtain Cu2O nanoparticles; (2) dispersing the Cu2O nanoparticles in water, adding a cerium source solution and a lye to perform a co-precipitation reaction, collecting a solid product after the co-precipitation reaction, and calcining to obtain the reverse CuO@Ce catalyst.

2. The production method according to claim 1, characterized by, The copper source comprises copper chloride; and the concentration of the copper source solution is 0.007-0.01 mol / L.

3. The preparation method according to claim 1, characterized in that, The lye independently comprises a sodium hydroxide solution or ammonia water; the concentration of the lye is independently 0.133-2 mol / L; and / or, the reducing agent comprises an L-ascorbic acid solution; the concentration of the reducing agent is 0.3-0.6 mol / L; and / or, in step (1), the use amount ratio of the copper source, the lye and the reducing agent is 0.01 mol: 60-120 mL: 120 mL.

4. The production method according to claim 1, characterized by, The hydrothermal reaction is performed at a temperature of 50-60 ℃ for 1-3 h.

5. The preparation method according to claim 1, characterized in that, The cerium source solution is an aqueous solution of a cerium source; the concentration of the cerium source solution is 0.1 mol / L; the cerium source comprises cerium nitrate; and / or, in step (2), the volume ratio of the cerium source solution and the lye is 1.48-600: 60; and / or, the volume ratio of the copper source solution and the cerium source solution is 4.2: 1.48-600.

6. The method of claim 1, wherein, The co-precipitation reaction is performed at a temperature of 50-80 ℃ for 0-2 h, and the time is not 0; and / or, the calcination is performed at a temperature of 500 ℃ for 2-4 h.

7. The reverse CuO@Ce catalyst prepared by the preparation method according to any one of claims 1-6, characterized in that, The reverse CuO@Ce catalyst has a CeO2 nanoparticle island structure and a reverse Cu-Ov-Ce interface.

8. Use of the inverse CuO@Ce catalyst according to claim 7 for catalytic decomposition of sulphur-containing VOCs pollutants, characterized by, The sulfur-containing VOCs pollutants comprise methyl mercaptan.

9. A method of cryogenic degradation of sulfur-containing VOCs pollutants, characterized in that, The method comprises the following steps: The reverse CuO@Ce catalyst of claim 7 is used to catalytically decompose the sulfur-containing VOCs pollutants at 30-500 ℃.

10. The method of claim 9, wherein, The space velocity of the sulfur-containing VOCs pollutants is 9000-15000 mL / (g·h).

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