CN112538003B - Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol - Google Patents

Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol Download PDF

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CN112538003B
CN112538003B CN202011462287.1A CN202011462287A CN112538003B CN 112538003 B CN112538003 B CN 112538003B CN 202011462287 A CN202011462287 A CN 202011462287A CN 112538003 B CN112538003 B CN 112538003B
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ethylene glycol
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sulfide
sulfide semiconductor
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CN112538003A (en
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谢顺吉
王力梅
张庆红
王野
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Xiamen University
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    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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Abstract

A method for preparing ethylene glycol directly by using sulfide semiconductor to catalyze methanol relates to the field of energy catalysis, wherein a photocatalyst is dispersed in a solution, oxygen in a reaction system is removed, and a light source is started to perform photocatalytic reaction to prepare ethylene glycol; wherein the solution is methanol or a methanol-water system; the photocatalyst is at least one of sulfide semiconductor photocatalyst and modified sulfide semiconductor photocatalyst; the structure of the sulfide semiconductor photocatalyst comprises at least one of a heterogeneous phase, a homogeneous phase and a twin crystal; the sulfide semiconductor photocatalyst contains at least one of a cubic phase and a hexagonal phase in a heterogeneous phase, a homogeneous phase and a twin crystal. Has the characteristics of greenness, high efficiency, mild reaction conditions and the like.

Description

Method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol
Technical Field
The invention relates to the field of energy catalysis, in particular to a method for directly preparing ethylene glycol by catalyzing methanol through sulfide semiconductor.
Background
Ethylene glycol, also known as glycol or ethylene glycol, is a colorless, odorless, slightly sweet, viscous liquid, and is the simplest glycol. It has the chemical formula of HOCH2CH2OH, English name is Ethylene glycol, abbreviated as EG. Ethylene glycol is an important basic chemical raw material, and the second major alcohol after methanol is used in alcohol substances in a large number of applications, and is mainly used for producing polyester fibers, coatings, unsaturated polyester resins and the like, and can also be used as an energy substance, such as an ethylene glycol fuel cell. The continuous demand of ethylene glycol forces people to develop different technologies to economically and environmentally prepare ethylene glycol. The photocatalysis technology is an advanced synthesis technology which is green, pollution-free and efficient. Therefore, the cheap and easily available methanol is prepared by adopting the photocatalysis technologyThe selective dehydrogenation and coupling are very significant for preparing the ethylene glycol.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol, which has the advantages of environmental friendliness, high efficiency, high ethylene glycol selectivity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol comprises dispersing a photocatalyst into a solution, removing oxygen in a reaction system, and starting a light source to perform photocatalytic reaction to obtain ethylene glycol; wherein the solution is methanol or a methanol-water system; the photocatalyst is at least one of sulfide semiconductor photocatalyst and modified sulfide semiconductor photocatalyst.
The sulfide semiconductor photocatalyst comprises at least one of a heterogeneous phase, a homojunction and a twin crystal in the structure.
The sulfide semiconductor photocatalyst contains at least one of a cubic phase and a hexagonal phase in a heterogeneous phase, a homogeneous phase and a twin crystal.
The sulfide semiconductor photocatalyst adopts a unitary metal sulfide or a binary metal sulfide, and the unitary metal sulfide can be selected from CdS, CuS and Cu2S、SnS、In2S3、Bi2S3、Ce2S3、GdS、NiS、MoS2At least one of FeS and the binary metal sulfide is selected from ZnxCdyS、CuxInyS、ZnxInyAt least one of S, wherein 0<x<1，0<y<1。
The modification method of the modified sulfide semiconductor photocatalyst comprises the steps of loading metal, loading metal oxide, loading metal sulfide, loading metal nitride and loading metal carbide.
The load amount is 0.01-20% of the sulfide semiconductor catalyst by mass percent.
The metal is at least one of Fe, Co, Ni, Cu, Cd, Pt, Rh, Pd and Mn.
The metal oxide is Fe2O3、Co2O3、Cr2O3、MoO2、WO3、ZnO、CuO、V2O5、MnO2At least one of; the metal sulfide is NiS, CoS and Cu2S、PdS、MoS2At least one of WS, CuS, PdS and FeS.
The metal carbide is Co2C. At least one of MoC and WC; the metal nitride is Ta3N5、Ti3N4And GaN.
The step of removing the oxygen in the reaction system is to perform ultrasonic degassing, vacuum exhaust and nitrogen introduction in sequence to keep inert atmosphere; the light source used in the photocatalytic reaction is one of a xenon lamp, an LED lamp, a mercury lamp, a halogen tungsten lamp and sunlight.
The catalyst is in the shape of at least one of nanoparticles, nano squares, nano spheres, nano wires, nano rods, nano flowers and nano sheets.
The mass ratio of the sulfide-based semiconductor photocatalyst or modified sulfide-based semiconductor photocatalyst to the solvent is 0.001-2.
The sulfide-based semiconductor photocatalyst or the modified sulfide-based semiconductor photocatalyst can be prepared by a high-temperature solid-phase reaction method, a molten salt method, a hydrothermal method and a sol-gel method.
The sulfide-based semiconductor photocatalyst or the modified sulfide-based semiconductor photocatalyst is in the shape of at least one of nanoparticles, nano squares, nano spheres, nano wires, nano rods, nano flowers and nano sheets.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the invention takes a sulfide-based semiconductor with a special phase structure as a photocatalyst, and the sulfide-based semiconductor reacts for a period of time under the irradiation of light, so that methanol can be converted into glycol, and the reaction is carried out under the atmosphere of nitrogen, thus the invention has the characteristics of environmental protection, high efficiency, mild reaction conditions and the like. Compared with sulfides with a non-special phase structure, the sulfide-based semiconductor catalyst with a special phase structure has higher activity and higher selectivity, can realize the directional transfer of photo-generated electrons and holes by utilizing the energy level difference and the phase interface between phases, and can realize the modification of a cocatalyst at a specific position by utilizing the structural characteristic, thereby realizing the efficient separation and the directional transfer of the photo-generated electrons and the holes. On the other hand, the photocatalyst can selectively activate the carbon-hydrogen bond of the methanol, has weak adsorption on the methanol and a reaction intermediate, and is beneficial to desorption coupling of the intermediate to generate the ethylene glycol. In addition, the catalyst has better stability, and is a very potential photocatalyst for preparing ethylene glycol by photocatalytic methanol coupling.
Drawings
FIG. 1 is a transmission electron micrograph of a ZCS sulfide catalyst of example 1;
FIG. 2 is a high power transmission electron micrograph of the ZCS sulfide catalyst of FIG. 1 (ZB for cubic phase and WZ for hexagonal phase);
FIG. 3 is a high performance liquid chromatogram of the reaction product of example 6.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
A ZCS sulfide catalyst with a special phase structure is synthesized by a hydrothermal method. The process is as follows: 10 to 40mL of a catalyst containing 5 to 30mmol of Cd (CH)3COO)2And Zn (CH)3COO)2In the solution, 1-20 mL of Ethylenediamine (EN) and 5-40 mmol of Thioacetamide (TAA) are sequentially added, and the total reaction volume is controlled to be 50-250 mL by adding additional water. The whole process is carried out in stirring, after stirring for a period of time, the obtained reaction solution is moved into a 50-250 mL polytetrafluoroethylene lining closed reaction kettle, heated by an oven, and kept at about 150-250 ℃ for a period of time. After the reaction, the sample was separated by centrifugation and washed with water and ethanol, respectivelyCleaning for several times, and finally, keeping the centrifuged sample in a vacuum oven at the temperature of 60-80 ℃ for 2-5 hours to obtain dried powder, namely preparing ZnxCdyS catalyst, x: y is the molar ratio of Zn to Cd, and the obtained samples are respectively Zn0.1Cd0.9S(ZCS-1)、Zn0.3Cd0.7S(ZCS-2)、Zn0.5Cd0.5S(ZCS-3)、Zn0.7Cd0.3S(ZCS-4)、Zn0.9Cd0.1S (ZCS-5). FIG. 1 shows a transmission electron microscope image of a sulfide with a special phase structure. FIG. 2 is a high power transmission electron micrograph of the nanorod of FIG. 1, where distinct cubic (ZB) and hexagonal (WZ) phases are visible, with the two phases interleaved and a heterogeneous phase present.
And (3) respectively carrying out catalytic performance tests on the catalysts:
weighing 10mg of the prepared sulfide catalyst ZCS-1, ZCS-2, ZCS-3, ZCS-4 and ZCS-5 with the special phase structure, adding the sulfide catalyst into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, ultrasonically dispersing uniformly, extracting, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 1.1mmol g-1h-1、2.0mmol g-1h-1、4.0mmol g-1h-1、6.4mmol g-1h-1、2.2mmol g-1h-1(ii) a The corresponding selectivities were 54%, 62%, 71%, 75%, 65%, respectively. The catalyst has better activity of preparing the ethylene glycol by photocatalytic methanol coupling.
Example 2
An ZIS sulfide catalyst with a special phase structure is synthesized by a hydrothermal method. The process is as follows: adding 20-50 mmol Thioacetamide (TAA) into a 250-500 mL three-necked flask, stirring and dropwise adding 30-50 mmol Zn (CH)3COO)2Solution and In (CH)3COO)2Continuously stirring the solution for 30-120 min, stirring the whole process, transferring the mixed solution into a high-pressure reaction kettle for constant-temperature reaction at 100-200 ℃ for 12-24 h after stirring for a period of time, naturally cooling to room temperature, precipitating with ethanol andwater was centrifuged alternately 5 times. The obtained samples are respectively Zn0.1In0.9S(ZiS-1)、Zn0.3In0.7S(ZIS-2)、Zn0.5In0.5S(ZIS-3)、Zn0.7In0.3S(ZIS-4)、Zn0.9In0.1S (ZIS-5). Weighing 10mg of ZIS-1, ZIS-2, ZIS-3, ZIS-4 and ZIS-5 sulfide catalyst with a special phase structure prepared above, adding into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, ultrasonically dispersing uniformly, extracting, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 0.3mmol g-1h-1、2.2mmol g-1h-1、3.6mmol g-1h-1、5.7mmol g-1h-1、3.1mmol g-1h-1(ii) a The corresponding selectivities were 87%, 77%, 68%, 78%, 76%, respectively. The catalyst has better activity of preparing the ethylene glycol by photocatalytic methanol coupling.
Example 3
The CdS sulfide catalyst with a special phase structure is synthesized by a hydrothermal method. The process is as follows: weighing 2-3 g of CdCl2·2.5H2O and 2-3 g Na2S·9H2The O powders were dissolved in water, respectively. Using a disposable dropper to mix with the prepared Na2The S solution is slowly added dropwise to CdCl under stirring2In (5), a yellow suspension was obtained. And transferring the yellow suspension after centrifugal washing to a reaction kettle with 50-150 mL of polytetrafluoroethylene, and adding 40-80 mL of deionized water. And after a hydrothermal kettle jacket is added, placing the hydrothermal kettle jacket in an oven for hydrothermal for 20-25 hours at the temperature of 150-250 ℃. Taking out the reaction kettle, cooling, performing centrifugal separation to obtain a sample, and washing with deionized water for 3 times. And finally, preserving the temperature of the centrifuged sample in a vacuum oven at 60-80 ℃ for 2-5 h to obtain dried powder, and grinding to obtain CdS sample powder. And (3) respectively carrying out catalytic performance tests on the catalysts: weighing 10mg of the prepared CdS sulfide catalyst with the special phase structure, adding the CdS sulfide catalyst into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, ultrasonically dispersing uniformly, exhausting, and introducingNitrogen gas. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 0.46mmol g-1h-1(ii) a The corresponding selectivities are 80% each.
Example 4
Weighing 10mg of ZCS-4 sulfide catalyst with a special phase structure prepared above, adding into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, and adding 100 μ L, 150 μ L, 200 μ L, 250 μ L, 300 μ L of LCoCl2(0.01M) solution, ultrasonic dispersing, pumping, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 6.3mmol g-1h-1、6.4mmol g-1h-1、6.8mmol g-1h-1、6.8mmol g-1h-1、6.3mmol g-1h-1(ii) a The corresponding selectivities were 73%, 75%, 73%, 78%, respectively.
Example 5
Weighing 10mg of ZCS-4 sulfide catalyst with a special phase structure prepared above, adding into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, and adding 100 μ L, 150 μ L, 200 μ L, 250 μ L and 300 μ L of LMnCl2(0.01M) solution, ultrasonic dispersing, pumping, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 6.7mmol g-1h-1、7.3mmol g-1h-1、16mmol g-1h-1、22mmol g-1h-1、13mmol g-1h-1(ii) a The corresponding selectivities were 72%, 74%, 73%, 75%, 77%, respectively.
Example 6
Weighing 10mg of a special phase prepared as described aboveThe ZCS-4 sulfide catalyst of structure was added to a reaction tube, 4.5mL of methanol and 0.5mL of water were added, and 100. mu.L, 150. mu.L, 200. mu.L, 250. mu.L, 300. mu.L of LiCl were added2(0.01M) solution, ultrasonic dispersing, pumping, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 6.7mmol g-1h-1、6.3mmol g-1h-1、6.4mmol g-1h-1、6.2mmol g-1h-1、63mmol g-1h-1(ii) a The corresponding selectivities were 75%, 77%, 71%, 73%, respectively. FIG. 3 shows a high performance liquid chromatogram of the reaction product.
Example 7
Weighing 10mg of ZCS-4 sulfide catalyst with a special phase structure prepared above, adding into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, and adding 100 μ L, 150 μ L, 200 μ L, 250 μ L and 300 μ L H2PtCI6(0.01M) solution, ultrasonic dispersing, pumping, and introducing nitrogen. And starting a xenon lamp to carry out photocatalytic reaction for 12 h. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of ethylene glycol generated by coupling sulfide photocatalytic methanol with a special phase structure to generate ethylene glycol are respectively 11mmol g-1h-1、12mmol g-1h-1、8.1mmol g-1h-1、6.4mmol g-1h-1、5.4mmol g-1h-1(ii) a The corresponding selectivities were 68%, 71%, 73%, 79%, 78%, respectively.
Example 8
Weighing 10mg of ZCS-4 sulfide catalyst with a special phase structure prepared above, adding into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, and adding 100 μ L, 150 μ L, 200 μ L, 250 μ L and 300 μ L of CoCl2(0.01M) and 100. mu.L, 150. mu.L, 200. mu.L, 250. mu.L, 300. mu.L of mNCl2(0.01M) solution, ultrasonic dispersing, pumping, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After cooling the reaction, the liquid phase is usedThe product was analysed by chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 22mmol g-1h-1、22.6mmol g-1h-1、23.6mmol g-1h-1、24.4mmol g-1h-1、23.6mmol g-1h-1(ii) a The corresponding selectivities were 73%, 77%, 79%, 83%, 81%, respectively.
Example 9
10mg of ZCS-4 sulfide catalyst of a specific phase structure prepared as described above was weighed into a reaction tube, 4.5mL of methanol and 0.5mL of water were added, and 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt% of MoS was added2The solution is dispersed evenly by ultrasonic, air is extracted, and nitrogen is introduced. And starting a xenon lamp to perform photocatalytic reaction for 12 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 11mmol g-1h-1、13mmol g-1h-1、14mmol g-1h-1、8mmol g-1h-1、6mmol g-1h-1(ii) a The corresponding selectivities were 75%, 71%, 73%, 78%, 76%, respectively.
Example 10
Weighing 10mg of the ZCS-4 sulfide catalyst with the special phase structure prepared above, adding the ZCS-4 sulfide catalyst into a reaction tube, adding 4.5mL of methanol and 0.5mL of water, and then adding 50-250 mu LCoCl2(0.01M) and 50-250 mu LMnCl2(0.01M) solution, ultrasonic dispersing uniformly, pumping, and introducing nitrogen. And starting a xenon lamp to perform photocatalytic reaction for 60 hours. After the reaction was cooled, the product was analyzed by liquid chromatography. The liquid phase analysis result shows that the generation rates of the sulfide with a special phase structure for generating the ethylene glycol by photocatalytic methanol coupling are respectively 24.4mmol g-1h-1(ii) a The corresponding selectivity was 83%, the yield of ethylene glycol was 30%, and the quantum efficiency of ethylene glycol was 15%, respectively.
Comparative example 1
Hydrothermal synthesis of sulfide with non-specific phase structureA catalyst. The process is as follows: 10-40 mL of Cd (CH) with a certain molar ratio3COO)2And Zn (CH)3COO)21-20 mL of NaOH (0.01M) and 5-40 mmol of Thioacetamide (TAA) are sequentially added into the solution, and the total volume of the reaction is controlled to be 50-250 mL by adding additional water. The whole process is carried out in stirring, after stirring for a period of time, the obtained reaction solution is transferred into a 50-250 mL sealed reaction kettle with a polytetrafluoroethylene lining, heated by an oven, and kept at about 200 ℃ for a period of time. After the reaction, the sample was separated by centrifugation and washed with water and ethanol several times, respectively, and finally the centrifuged sample was kept at 80 ℃ for 5 hours in a vacuum oven to obtain dried powder. 10mg of catalyst was weighed into a reaction tube, and 4.5mL of methanol and 0.5mL of water were removed. Ultrasonic dispersing, pumping and introducing nitrogen. And turning on a light source to react for 12 h. After the reaction, the reaction mixture was filtered through a filter and subjected to liquid chromatography. The liquid phase result shows that the generation rate of the ethylene glycol is 0.3mmol g-1h-1The selectivity was 12% and the main product of the reaction was formaldehyde.
Comparative example 2
A sulfide catalyst with a non-specific phase structure is synthesized by a hydrothermal method. The process is as follows: 10-40 mL of the catalyst contains Cd (CH) with a certain molar ratio3COO)2And Zn (CH)3COO)2In the solution, 5-40 mmol Thioacetamide (TAA) is added with additional water, and the total volume of the reaction is controlled to be 50-250 mL. The whole process is carried out in stirring, after stirring for a period of time, the obtained reaction solution is transferred into a 50-250 mL sealed reaction kettle with a polytetrafluoroethylene lining, heated by an oven, and kept at about 200 ℃ for a period of time. After the reaction, the sample was separated by centrifugation and washed with water and ethanol several times, respectively, and finally the centrifuged sample was kept at 80 ℃ for 5 hours in a vacuum oven to obtain dried powder. 10mg of the catalyst was weighed into a reaction tube, and 4.5mL of methanol and 0.5mL of water were removed. Ultrasonic dispersing, pumping air and introducing nitrogen. And turning on a light source to react for 12 h. After the reaction, the reaction mixture was filtered through a filter and subjected to liquid chromatography. The liquid phase result shows that the generation rate of the ethylene glycol is 0mmol g-1h-1The selectivity is 0, and the main product of the reaction is formaldehyde.
The invention takes a sulfide-based semiconductor with a special phase structure as a photocatalyst, and the sulfide-based semiconductor reacts for a period of time under the irradiation of light, so that methanol can be converted into glycol, and the reaction is carried out under the atmosphere of nitrogen, thus the invention has the characteristics of environmental protection, high efficiency, mild reaction conditions and the like. Compared with sulfides with a non-special phase structure, the sulfide-based semiconductor catalyst with the special phase structure has higher activity and higher selectivity. The highest generation rate of the ethylene glycol can reach 25mmol g-1h-1The yield can reach 30 percent, the quantum efficiency of the glycol can reach 15 percent, and the yield is obviously higher than that of the MoS with the best performance reported at present2A CdS catalyst.

Claims (7)

1. A method for directly preparing ethylene glycol from sulfide semiconductor photocatalytic methanol is characterized by comprising the following steps: dispersing the photocatalyst into the solution, removing oxygen in the reaction system, and starting a light source to perform photocatalytic reaction to obtain ethylene glycol; wherein the solution is methanol or a methanol-water system; the photocatalyst is ZnxCdyS and modified ZnxCdyAt least one of S, wherein, 0<x<1，0<y<1; said ZnxCdyThe structure of S comprises at least one of a heterogeneous phase, a homojunction and a twin crystal, wherein the heterogeneous phase, the homojunction and the twin crystal comprise at least one of a cubic phase and a hexagonal phase; said ZnxCdyThe preparation method of S comprises the following steps: adding Cd (CH) into a reaction kettle under the condition of stirring3COO)2、Zn(CH3COO)2The method comprises the following steps of adding extra water, controlling the total volume of the reaction to be matched with the volume of a reaction kettle, stirring, carrying out hydrothermal reaction, centrifuging, washing and drying.
2. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 1, wherein the method comprises the following steps: the modified ZnxCdyThe modification method of S comprises loading metal, loading metal oxide, loading metal sulfide, loading metal nitride and loading metal carbide.
3. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 2, wherein the method comprises the following steps: the load amount is 0.01-20% of the sulfide semiconductor catalyst by mass percent.
4. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 2, wherein the method comprises the following steps: the metal is at least one of Fe, Co, Ni, Cu, Cd, Pt, Rh, Pd and Mn.
5. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 2, wherein the method comprises the following steps: the metal oxide is Fe2O3、Co2O3、Cr2O3、MoO2、WO3、ZnO、CuO、V2O5、MnO2At least one of; the metal sulfide is NiS, CoS and Cu2S、PdS、MoS2、WS2At least one of CuS and FeS.
6. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 2, wherein the method comprises the following steps: the metal carbide is Co2C. At least one of MoC and WC; the metal nitride is Ta3N5、Ti3N4And GaN.
7. The method for preparing ethylene glycol directly from sulfide semiconductor photocatalytic methanol as claimed in claim 1, wherein the method comprises the following steps: the step of removing the oxygen in the reaction system is to perform ultrasonic degassing, vacuum exhaust and nitrogen introduction in sequence to keep inert atmosphere; the light source used in the photocatalytic reaction is one of a xenon lamp, an LED lamp, a mercury lamp, a halogen tungsten lamp and sunlight.
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