A supported copper nanoparticle photocatalyst, its preparation method and application

Abstract

This invention discloses a supported copper nanoparticle photocatalyst, its preparation method, and its application. The catalyst includes a support and an active component supported on the support, wherein the support is alumina nanosheets; and the active component is copper nanoparticles. The supported copper nanoparticle photocatalyst provided by this invention, when used in a photocatalytic water-gas shift reaction system, can achieve the photocatalytic water-gas shift reaction at low temperatures. Compared with the traditional high-temperature system of thermal catalytic water-gas shift reaction using non-precious metal catalysts, it effectively utilizes solar energy and reduces fossil fuel consumption and carbon emissions.

Description

Technical Field

[0001] This invention belongs to the field of photocatalysis technology, and more specifically, relates to a supported copper nanoparticle photocatalyst, its preparation method, and its application. Background Technology

[0002] The water gas shift process (SFS) is a process for producing hydrogen from water gas (a mixture of carbon monoxide and water vapor) under appropriate conditions and with the aid of a catalyst. Recent studies have shown that using noble metal-based catalysts can thermally drive the SFS reaction at lower temperatures and achieve relatively high hydrogen production rates. However, the high cost of noble metal-based catalysts hinders the practical application of this reaction. To reduce catalyst costs, non-noble metal-based catalysts, such as copper-based and iron-based catalysts, have been extensively studied. However, in many SFS reactions, non-noble metal-based catalysts still require reaction temperatures above 250°C, and their performance in low-temperature SFS needs further improvement. Furthermore, photothermal catalysis, utilizing the photothermal effect of materials, can effectively drive catalytic reactions and is an important direction for researching green SFS reactions that do not require external heat sources. Therefore, developing a photothermal catalyst capable of producing hydrogen from the SFS reaction under mild conditions (low temperatures, such as 200°C) can greatly meet the requirements of high economic efficiency and sustainable development.

[0003] In the study of traditional photothermal catalysts, copper-based semiconductor catalysts (CuO) x Copper-based semiconductor materials possess good light absorption properties, enabling them to effectively drive the water-gas shift reaction (SFR) under illumination. However, the SFR activity of copper-based semiconductor materials themselves is limited at low temperatures, resulting in a relatively high temperature range (minimum 285℃) for currently reported photocatalytic SFR studies. Therefore, designing a novel copper-based catalyst structure that enables the catalytically active sites to exhibit excellent SFR activity at low temperatures is a key factor in realizing the photocatalytic SFR under mild conditions and effectively improving the hydrogen production rate. Summary of the Invention

[0004] The first objective of this invention is to provide a supported copper nanoparticle photocatalyst. This photocatalyst exhibits excellent catalytic activity under low-temperature illumination conditions and is used in water-gas shift reactions to achieve a high hydrogen production rate.

[0005] The second objective of this invention is to provide a method for preparing a supported copper nanoparticle photocatalyst.

[0006] The third objective of this invention is to provide an application of a supported copper nanoparticle photocatalyst in a photocatalytic water-gas shift reaction.

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

[0008] In a first aspect, the present invention provides a supported copper nanoparticle photocatalyst, comprising a support and an active component supported on the support, wherein the support is alumina nanosheets and the active component is copper nanoparticles.

[0009] Furthermore, the loading of the copper nanoparticles is 30wt% to 80wt%; preferably 50wt% to 60wt%.

[0010] Furthermore, the particle size of the copper nanoparticles is 5nm to 15nm; preferably 5nm to 10nm.

[0011] Furthermore, the thickness of the alumina nanosheets is on the nanometer scale.

[0012] Secondly, the present invention provides a method for preparing the above-mentioned supported copper nanoparticle photocatalyst, comprising the following steps:

[0013] 1) Containing Cu 2+ And Al 3+ The mixed solution and precipitant were simultaneously added dropwise to the buffer solution, the pH value was adjusted to 9-10, and after thorough mixing, crystallization was performed to obtain the precursor hydrotalcite material.

[0014] 2) The precursor hydrotalcite material is calcined in air to obtain the intermediate metal oxide material;

[0015] 3) The intermediate metal oxide material is reduced in a hydrogen-argon mixed atmosphere to obtain the final product.

[0016] Furthermore, in the above method, the Cu 2+ And Al 3+ The molar concentration ratio is 1 to 3:1.

[0017] The chemical formula of the precursor hydrotalcite material is [Cu]. 2+ 1-n Al 3+ n (OH)2] n+ ·(A x- ) n / x ·yH₂O, where 0.25≤n≤0.5; x is the valence of the anion; y is the amount of water of crystallization, and the value of y ranges from 0.5 to 9; A x- It is NO3 - or CO3 2- .

[0018] In step 1), the crystallization is carried out at 50℃~70℃ for 8h~24h.

[0019] In step 2), the calcination specifically includes the following steps: at 5°C·min -1 ~10℃·min -1 The heating rate is set to 400℃~600℃ and maintained for 2h~5h.

[0020] In step 3), the reduction specifically includes the following steps: at 2℃·min -1 ~5℃·min -1 The heating rate is set to 200℃~300℃, held for 2h~5h, and then cooled to room temperature in a protective atmosphere.

[0021] Thirdly, the present invention provides an application of the above-mentioned supported copper nanoparticle photocatalyst in photocatalytic water-gas shift reaction.

[0022] Furthermore, the application includes the following steps:

[0023] The supported copper nanoparticle photocatalyst is placed in a light-transmitting sealed container, and a reaction gas and water are added. It is then irradiated under full-spectrum conditions. The reaction gas includes carbon monoxide.

[0024] Furthermore, the pressure inside the sealed container is 0.1 MPa to 0.5 MPa.

[0025] Furthermore, the temperature inside the sealed container is 150℃~250℃.

[0026] Furthermore, the reaction gas also includes a diluent gas.

[0027] Furthermore, the diluting gas includes argon, helium, or nitrogen.

[0028] Furthermore, the volume ratio of hydrogen to diluent gas is 1:0 to 9.

[0029] Furthermore, the molar ratio of carbon monoxide to water is 1:0.5 to 2.

[0030] Furthermore, unless otherwise specified, all raw materials used in this invention are commercially available. Any range described in this invention includes endpoints, any values ​​between endpoints, and any sub-ranges formed by endpoints or any values ​​between endpoints. Unless otherwise specified, all percentages are mass percentages, and all solutions are aqueous solutions.

[0031] The beneficial effects of this invention are as follows:

[0032] The supported copper nanoparticle photocatalyst provided by this invention can realize photocatalytic water-gas shift reaction under low temperature conditions. Compared with the traditional high-temperature system of thermal catalytic water-gas shift reaction using non-precious metal catalysts, it effectively utilizes solar energy and reduces fossil energy consumption and carbon emissions.

[0033] The supported copper nanoparticle photocatalyst provided by this invention can effectively improve the hydrogen yield in the photocatalytic water-gas shift reaction. Specifically, the mass activity of the catalyst for hydrogen production can reach as high as 114.35 μmol g under low temperature conditions (200℃). 催化剂 -1 s -1 .

[0034] The method for preparing supported copper nanoparticle photocatalysts provided by this invention is low in cost, simple to prepare, easy to process, and easy to mass-produce. Attached Figure Description

[0035] Figure 1 The XRD patterns of the hydrotalcite precursor material, intermediate metal oxide material, and supported copper nanoparticle photocatalyst prepared in Example 1 are shown. Curve a is the XRD pattern of the hydrotalcite precursor material prepared in Example 1; curve b is the XRD pattern of the intermediate metal oxide material prepared in Example 1; and curve c is the XRD pattern of the supported copper nanoparticle photocatalyst prepared in Example 1.

[0036] Figure 2A The transmission electron microscopy (TEM) elemental distribution diagram of the supported copper nanoparticle photocatalyst prepared in Example 1 is shown.

[0037] Figure 2B The image shown is a high-resolution transmission electron microscope (TEM) image of the supported copper nanoparticle photocatalyst prepared in Example 1.

[0038] Figure 3 The graph shows a performance comparison between Example 1 and Comparative Example 1 in water-gas shift reaction at different temperatures.

[0039] Figure 4 The graph shows a performance comparison of the supported copper nanoparticle photocatalysts prepared in Example 1 and Comparative Example 2 in the photocatalytic water-gas shift reaction at 200°C. Detailed Implementation

[0040] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0041] In a first aspect, the present invention provides a supported copper nanoparticle photocatalyst, comprising a support and an active component supported on the support, wherein the support is alumina nanosheets and the active component is copper nanoparticles.

[0042] This invention discovers a supported catalyst using copper nanoparticles as the active component and alumina nanosheets as the support, which, compared to traditional copper-based semiconductors (CuO), provides a more efficient and effective catalyst. x As an active component, the catalyst can more effectively reduce the reaction temperature, realize the photocatalytic water-gas shift reaction under mild conditions, and effectively increase the hydrogen production rate in the water-gas shift reaction.

[0043] Furthermore, the loading of the copper nanoparticles is 30wt% to 80wt%; preferably 50wt% to 60wt%. It can be understood that the loading refers to the mass of the copper nanoparticles relative to the photocatalyst.

[0044] Furthermore, the particle size of the copper nanoparticles is 5 nm to 15 nm; preferably 5 nm to 10 nm. The copper nanoparticles with a particle size within the range of this invention exhibit higher catalytic activity.

[0045] Furthermore, the thickness of the alumina nanosheets is in the nanometer range, such as 1nm~1000nm, 1nm~500nm, 1nm~200nm, 1nm~100nm, 1nm~50nm, 10nm~50nm, etc.

[0046] Secondly, the present invention provides a method for preparing the above-mentioned supported copper nanoparticle photocatalyst, comprising the following steps:

[0047] 1) Containing Cu 2+ And Al 3+ The mixed solution and precipitant were simultaneously added dropwise to the buffer solution, the pH value was adjusted to 9-10, and after thorough mixing, crystallization was performed to obtain the precursor hydrotalcite material.

[0048] 2) The precursor hydrotalcite material is calcined in air to obtain the intermediate metal oxide material;

[0049] 3) The intermediate metal oxide material is reduced in a hydrogen-argon mixed atmosphere to obtain the final product.

[0050] Hydrotalcite is a unique type of layered anionic compound. Its main lamellar structure is similar to brucite (Mg(OH)2), with octahedral MO6 lamellars sharing common edges. Metal ions occupy the centers of the octahedrons, and the elemental composition of the main lamellar structure and the interlayer guests can be controlled. This invention utilizes a hydrothermal reaction to transform Cu... 2+ And Al 3+The composite crystallization process forms a precursor hydrotalcite material. At this stage, Cu and Al elements together constitute a layered hydrotalcite precursor material. Then, air calcination and hydrogen reduction are used to transform Cu... 2+ It is reduced to an element, forming uniformly dispersed metallic copper nanoparticles on the carrier.

[0051] Furthermore, the hydrotalcite precursor can only be synthesized within the pH range specified in this invention. Preferably, the pH value is 9.2 to 9.8.

[0052] Furthermore, in the above method, the Cu 2+ And Al 3+ The molar concentration ratio is 1–3:1. The loading of copper nanoparticles can be controlled by adjusting the molar ratio of each metal ion.

[0053] The Cu 2+ The concentration is 0.01 mol·L⁻¹ -1 ~0.1mol·L -1 Among them, Cu in this concentration range 2+ It is possible to synthesize precursor hydrotalcite materials with better structure.

[0054] In step 2), the calcination specifically includes the following steps: at 5°C·min -1 ~10℃·min -1 The heating rate was adjusted to 400℃~600℃ and held for 2h~5h. The calcination conditions could affect the final structure of the photocatalyst.

[0055] In step 3), the reduction specifically includes the following steps: at 2℃·min -1 ~5℃·min -1 The heating rate is set to 200℃~300℃, held for 2h~5h, and then cooled to room temperature in a protective atmosphere.

[0056] For example, Cu 2+ The source can be cobalt nitrate, cobalt chloride, or cobalt sulfate; Al 3+ The source can be aluminum nitrate, aluminum chloride, or aluminum sulfate, etc.

[0057] For example, the amount of precipitant added is 0.1 mol·L⁻¹. -1 ~0.3 mol·L -1 For example, the precipitant is sodium hydroxide. Sodium hydroxide can more effectively synthesize the precursor hydrotalcite material.

[0058] For example, the amount of buffer added is 0.01 mol·L⁻¹. -1 ~0.1mol·L -1 .

[0059] For example, the buffer is sodium carbonate. Sodium carbonate can be used to synthesize the precursor hydrotalcite material more effectively.

[0060] For example, the volume fraction of hydrogen in the hydrogen-argon mixture is 10%.

[0061] For example, the protective atmosphere includes a nitrogen atmosphere, a hydrogen atmosphere, an argon atmosphere, and a helium atmosphere. The function of the protective atmosphere is to prevent the product from being oxidized under high-temperature conditions.

[0062] Exemplarily, the method further includes washing and drying the precursor hydrotalcite material.

[0063] For example, the washing method is to wash with deionized water 2 to 5 times, the drying temperature is 50℃ to 80℃, and the drying time is 6h to 20h.

[0064] Thirdly, the present invention provides an application of the above-mentioned supported copper nanoparticle photocatalyst in photocatalytic water-gas shift reaction.

[0065] Furthermore, the application includes the following steps:

[0066] The supported copper nanoparticle photocatalyst is placed in a light-transmitting sealed container, and a reaction gas and water are added. It is then irradiated under full-spectrum conditions. The reaction gas includes carbon monoxide.

[0067] Adding water to carbon monoxide is more conducive to the formation of hydrogen gas, and the conversion rate of carbon monoxide is not too low. The water can be in gaseous or liquid state, preferably distilled water.

[0068] Furthermore, the reaction gas also includes a diluent gas; the diluent gas includes argon, helium, or nitrogen. The diluent gas can prevent the reaction from becoming too violent and causing danger.

[0069] Example 1

[0070] (I) A supported copper nanoparticle photocatalyst and its preparation method are provided, the preparation method comprising the following steps:

[0071] 1) Dissolve 0.01 mol copper nitrate hexahydrate and 0.01 mol aluminum nitrate nonahydrate in 18 mL of deionized water to prepare solution A. Dissolve 0.045 mol sodium hydroxide in 30 mL of deionized water to prepare solution B. Dissolve 0.01 mol sodium carbonate in 180 mL of deionized water to prepare solution C. Add solutions A and B dropwise to solution C simultaneously, maintaining the pH of solution C at 9.5 by controlling the rate of addition. After all solution A has been added to solution C and the pH remains at 9.5, react at 60 °C for 12 h to obtain the hydrotalcite precursor material. Wash the precursor material three times with deionized water by centrifugation, and then dry it in a 60 °C oven for 12 h.

[0072] 2) The hydrotalcite precursor material obtained above was subjected to an air atmosphere at 5℃·min -1 The temperature is increased to 500℃ at a heating rate and maintained at that temperature for 4 hours, after which it is allowed to cool naturally to room temperature. This yields the intermediate metal oxide material.

[0073] 3) The intermediate metal oxide material obtained above was subjected to a hydrogen-argon mixed atmosphere (10% H2, v / v) at 5 °C·min. -1 The temperature was increased to 200℃ and maintained at this temperature for 5 hours. After that, the atmosphere was switched to N2 and the temperature was allowed to cool naturally to room temperature. The supported copper nanoparticle photocatalyst, denoted as LD-Cu, was obtained. The loading of copper nanoparticles was 55.7 wt.%, and the thickness of the alumina nanosheets was 10 nm to 50 nm.

[0074] (II) An application of the above-prepared supported copper nanoparticle photocatalyst in photocatalytic water-gas shift reaction is provided, comprising the following steps:

[0075] 20 mg of the above catalyst and 0.1 mL of deionized water were added to a 50 mL reactor. Pure CO was introduced and the pressure inside the reactor was 0.2 MPa (the molar ratio of CO to water was approximately 4.5:5.5). Full-spectrum illumination was used to raise the catalyst surface to the specified temperature. During the illumination process, the temperature change of the catalyst surface with the illumination time was detected in situ using an internal thermocouple (the reaction temperature was controlled by the light intensity). Illumination was stopped after 0.5 h. After the reactor cooled to room temperature, the hydrogen products were detected by gas chromatography (the results are shown in Table 1).

[0076] Table 1. Photothermal catalytic performance of LD-Cu

[0077]

[0078] As shown in Table 1, the catalyst prepared in this example achieves high hydrogen production activity at low temperatures in the photocatalytic water-gas shift reaction, with a hydrogen production rate of 114.35 μmol g under photothermal conditions at 200℃. 催化剂 -1 s -1 .

[0079] Depend on Figure 1 As can be seen from curve a, the precursor material prepared in this example has characteristic peaks of the (003), (006) and (009) crystal plane structures of hydrotalcite, and there are no impurity peaks between the characteristic peaks of the (003) and (006) crystal planes, indicating that the precursor hydrotalcite material prepared in this example is a pure phase.

[0080] Depend on Figure 1 As can be seen from curve b, the intermediate metal oxide material prepared in this example is in an amorphous state.

[0081] Depend on Figure 1 As can be seen from curve c, copper exists in the form of a metallic element in the supported copper nanoparticle photocatalyst prepared in this example.

[0082] Depend on Figure 2A It can be seen that in the supported copper nanoparticle photocatalyst prepared in this example, copper is uniformly dispersed on alumina nanosheets in the form of nanoparticles.

[0083] Depend on Figure 2B It can be seen that in the supported copper nanoparticle photocatalyst prepared in this example, the spacing between the exposed crystal planes of the nanoparticles is 0.21 nm, which is the (111) crystal plane of copper, and the particle size of the copper nanoparticles is about 7.1 nm.

[0084] Comparative Example 1

[0085] The application of the supported copper nanoparticle photocatalyst prepared in Example 1 in the thermocatalytic water-gas shift reaction is provided, including the following steps:

[0086] 20 mg of the photocatalyst prepared in Example 1 and 0.1 mL of deionized water were added to a 50 mL light-proof reactor. Pure CO was introduced, and the pressure inside the reactor was 0.2 MPa. The catalyst was heated to a specified temperature using an external heat source. During heating, the temperature change of the catalyst surface with reaction time was monitored in situ using an internal thermocouple (the reaction temperature was controlled by the heating power of the external heat source). Heating was stopped after 0.5 h, and the hydrogen products were detected by gas chromatography after the reactor cooled to room temperature (results are shown in Table 2). The results were compared with those of the photocatalytic water-gas shift reaction in Example 1. Figure 3 As shown.

[0087] Table 2. Thermocatalytic performance of LD-Cu

[0088]

[0089] From Table 2 and Figure 3 It can be seen that the catalyst in this example, when used in the thermocatalytic water-gas shift reaction, exhibits catalytic activity at low temperatures, but its hydrogen production performance at the same reaction temperature is not as good as that of photothermal catalysis. This indicates that light irradiation has a significant effect on improving the activity of the catalyst prepared in this example.

[0090] Comparative Example 2

[0091] The preparation and application methods of the catalyst are the same as in Example 1, except that the precursor hydrotalcite material is not subjected to the calcination process in step 2) of the preparation method. Instead, the precursor hydrotalcite material obtained in step 1) is directly reduced in step 3) to obtain the supported copper nanoparticle photocatalyst, denoted as CuAl-200R. During application, the reaction temperature under photothermal conditions is 200℃. The results are shown in Table 3, and a comparison with the thermocatalytic performance of the photocatalyst in Example 1 is shown in the table. Figure 4 As shown.

[0092] Table 3 Comparison of photothermal catalytic performance between LD-Cu and CuAl-200R

[0093]

[0094] From Table 3 and Figure 4 It can be seen that the catalyst used in this example, when applied to the photothermal catalytic water-gas transformation reaction, achieves a hydrogen production rate of only 95.19 μmol g under photothermal conditions at 200℃. 催化剂 -1 s -1 It differs significantly from the LD-Cu catalyst in Example 1.

[0095] Summary: By comparing the results of Example 1, Comparative Examples 1 and 2, it can be found that the lack of light conditions, or the absence of the synthesis method of first calcining the precursor hydrotalcite material to the intermediate metal oxide material and then reducing it to the supported copper nanoparticle photocatalyst, will reduce the hydrogen generation rate.

[0096] Experimental Example 1: Investigating the effect of the amount of raw material metal salt added for the synthesis of hydrotalcite precursor materials on the catalytic performance of the catalyst.

[0097] The preparation and application methods of the catalyst are the same as in Example 1, except that the amount of metal salt (Cu) added in step 1) of the preparation method is changed. 2+ With Al 3+ The ratio remained 1:1, and the reaction temperature under photothermal conditions was 200℃. The results are shown in Table 4.

[0098] Table 4 Catalytic results of different catalysts

[0099]

[0100] As shown in Table 4, the amount of metal salt added to the precursor hydrotalcite material does not have a significant impact on the hydrogen production rate in the final photocatalytic water-gas shift reaction.

[0101] Experimental Example 2: Investigating the effect of synthesis time of the precursor hydrotalcite material on the catalytic performance of the catalyst.

[0102] The preparation and application methods of the catalyst are the same as in Example 1, except that the hydrothermal reaction time in step 1) of the preparation method is changed (i.e., the reaction time at 60°C). The results are shown in Table 5.

[0103] Table 5 Catalytic results of different catalysts

[0104]

[0105] As shown in Table 5, the synthesis time of the precursor hydrotalcite material does not have a significant impact on the hydrogen production rate in the final photocatalytic water-gas shift reaction.

[0106] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. The application of a supported copper nanoparticle photocatalyst in photocatalytic water-gas shift reaction, wherein the supported copper nanoparticle photocatalyst comprises a support and an active component supported on the support, characterized in that, The carrier is alumina nanosheets; the active component is metallic copper nanoparticles. The preparation method of the supported copper nanoparticle photocatalyst includes the following steps: 1) Containing Cu 2+ And Al 3+ The mixed solution and precipitant were simultaneously added dropwise to a buffer solution, the pH was adjusted to 9-10, and after thorough mixing, crystallization was performed to obtain the precursor hydrotalcite material; the Cu... 2+ The concentration is 0.01-0.1 mol / L. -1 The Cu 2+ And Al 3+ The molar concentration ratio is 1~3:1; the chemical formula of the precursor hydrotalcite material is [Cu 2+ 1-n Al 3+ n (OH)2] n+ ·(A x- ) n / x ·yH₂O, where 0.25≤n≤0.5; x is the valence of the anion; y is the amount of water of crystallization, and the value of y ranges from 0.5 to 9; A x- It is NO3 - or CO3 2- The crystallization was carried out at 50 ℃ to 70 ℃ for 8 h to 24 h. 2) The precursor hydrotalcite material is calcined in air to obtain the intermediate metal oxide material; the calcination specifically includes the following steps: at 5 °C·min -1 ~10 ℃·min -1 The heating rate was increased to 400 ℃~600 ℃ and held for 2 h~5 h; 3) The intermediate metal oxide material is reduced in a hydrogen-argon mixed atmosphere to obtain the final product; the reduction specifically includes the following steps: at 2 °C·min -1 ~5 ℃·min -1 The heating rate was increased to 200 ℃~300 ℃, held for 2 h~5 h, and then cooled to room temperature in a protective atmosphere.

2. The application according to claim 1, characterized in that, The loading of the copper nanoparticles is 30 wt% to 80 wt%, where the loading refers to the percentage of copper nanoparticles by mass in the photocatalyst.

3. The application according to claim 1, characterized in that, The loading of the copper nanoparticles is 50 wt% to 60 wt%, where the loading refers to the percentage of the copper nanoparticles by mass in the photocatalyst.

4. The application according to claim 1, characterized in that, The copper nanoparticles have a particle size of 5 nm to 15 nm.

5. The application according to claim 1, characterized in that, The copper nanoparticles have a particle size of 5 nm to 10 nm.

6. The application according to claim 1, characterized in that, The thickness of the alumina nanosheets is in the nanometer range.

7. The application according to claim 1, characterized in that, The application includes the following steps: The supported copper nanoparticle photocatalyst is placed in a light-transmitting sealed container, and a reaction gas and water are added. It is then irradiated under full-spectrum conditions. The reaction gas includes carbon monoxide.

8. The application according to claim 7, characterized in that, The pressure inside the sealed container is 0.1 MPa to 0.5 MPa; The temperature inside the sealed container is 150 ℃~250 ℃; The reaction gas also includes a diluent gas; the diluent gas is selected from argon, helium, or nitrogen. The volume ratio of carbon monoxide to diluent gas is 1:0~9; The molar ratio of carbon monoxide to water is 1:0.5~2.

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