A carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, its preparation method and application

Abstract

This invention provides a carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst, its preparation method, and its application, belonging to the field of photocatalytic materials technology. First, a carbon nitride precursor and a carboxylating agent are mixed in a solvent to undergo a carboxylation reaction, yielding carboxylated graphitic carbon nitride. Then, the carboxylated graphitic carbon nitride is mixed with a copper salt solution for a preliminary reaction, yielding copper-supported C3N4-C powder. Finally, the copper-supported C3N4-C powder and 1,3,5-pyromellitic acid are dispersed in a solvent for a hydrothermal reaction to obtain the carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst. This invention, through directional assembly and growth, ultimately obtains a composite photocatalyst with tight interfacial bonding, stable structure, and high photogenerated charge separation efficiency.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic materials technology, and in particular to a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, its preparation method, and its application. Background Technology

[0002] Graphitic carbon nitride (g-C3N4), as a non-metallic polymer semiconductor photocatalyst, has shown great potential in the field of photocatalytic water splitting for hydrogen production. However, its inherent disadvantages, such as small specific surface area, narrow visible light absorption range, and high recombination rate of photogenerated electron-hole pairs, severely limit its catalytic efficiency.

[0003] Metal-organic frameworks (MOFs) possess ultra-high specific surface areas, tunable pore structures, and functional groups; however, as photocatalysts, they often suffer from low photogenerated charge separation efficiency and poor stability. Constructing heterojunctions by combining g-C3N4 with MOFs is an effective strategy to improve photocatalytic performance. However, traditional physical mixing or disordered loading methods can easily lead to problems such as masking of MOF active sites, loose interfacial contacts, and impaired charge transport channels.

[0004] Therefore, it is of great significance to study a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst and its preparation method, and to use it for photocatalytic water splitting to produce hydrogen. Summary of the Invention

[0005] The purpose of this invention is to provide a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, its preparation method, and its application, in order to solve the problems of MOF active sites being masked, interfacial contact not being tight, and charge transport channels being blocked caused by physical mixing or disordered loading methods in the prior art.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, comprising the following steps: (1) The carbon nitride precursor and the carboxylating agent are mixed in a solvent to carry out a carboxylation reaction to obtain carboxylated graphitic carbon nitride; (2) Carboxyl graphitic carbon nitride and copper salt solution were mixed to carry out a preliminary reaction to obtain copper-loaded C3N4-C powder; (3) Copper-supported C3N4-C powder and 1,3,5-pyromellitic acid were dispersed in a solvent and subjected to hydrothermal reaction to obtain carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst.

[0007] Preferably, in step (1), the carbon nitride precursor comprises dicyandiamide and cyanuric chloride; and the carboxylating agent is 4-cyanobenzoic acid.

[0008] Preferably, the molar ratio of dicyandiamide, cyanuric chloride and 4-cyanobenzoic acid is 1:1~2:1~3.

[0009] Preferably, in step (2), the molar ratio of carboxylated graphitic carbon nitride to copper salt is 1:0.5~2.5; the temperature of the preliminary reaction is room temperature, and the time of the preliminary reaction is 20~40 min.

[0010] Preferably, the molar ratio of 1,3,5-pyromellitic acid to copper salt is 1:1.0~2.0.

[0011] Preferably, the hydrothermal reaction is carried out at a temperature of 90~120℃ for 8~12h.

[0012] The present invention also provides the above-described carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst.

[0013] This invention also provides an application of the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst described above in catalytic water splitting for hydrogen production. The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst is used as a photocatalyst, eosin Y is used as a photosensitizer, and triethanolamine is used as an electron donor to construct an aqueous photocatalytic reaction system.

[0014] Preferably, the specific steps for the hydrolysis hydrogen production are as follows: dispersing carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, eosin Y and triethanolamine in water, adjusting the pH value and then carrying out the reaction.

[0015] Preferably, the volume ratio of triethanolamine to water is 1:20~24; the amount of carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst added is 0.003~0.007 g / 50 mL; and the amount of eosin Y added is 0.005~0.01 g / 50 mL.

[0016] The beneficial effects of this invention are: This invention functionalizes g-C3N4 with carboxyl groups, utilizing the -COOH group as a strong electron donor and coordination site, and reacts with Cu. 2+ Ion coordination induces heterogeneous nucleation and directional growth of Cu-MOF crystals on the g-C3N4 surface, avoiding the disordered random growth of MOF and effectively exposing active sites.

[0017] The coordination bonding between the carboxyl group and the copper ion enables the π-π interaction between the g-C3N4 π-conjugated system and the benzene ring of the organic ligand in the MOF to form a strong chemical bond at the interface between the two, constructing an efficient electron transport "highway" that greatly promotes the separation and migration of photogenerated charges.

[0018] The carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst prepared in this invention combines the visible light response characteristics of g-C3N4 with the high specific surface area and porosity of MOF, achieving complementary advantages and significantly improving photocatalytic performance.

[0019] This invention achieves a composite photocatalyst with tight interfacial bonding, stable structure, and high photogenerated charge separation efficiency through directional assembly and growth.

[0020] The reaction conditions for preparing carboxyl-functionalized g-C3N4 supported Cu-MOF catalysts according to this invention are mild. By adjusting the proportion of raw materials and reaction conditions, the morphology, structure and composition of the catalyst can be effectively controlled. The catalyst exhibits good reproducibility and is suitable for large-scale production.

[0021] The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst prepared in this invention can be used in catalytic water electrolysis for hydrogen production. With adjustments to the reaction system and process parameters, the photocatalytic hydrogen evolution rate can reach [percentage missing] under visible light irradiation. It is far superior to the hydrogen production efficiency of pure g-C3N4, uncarboxylated C3N4-MOF and single Cu-MOF, and is 1.68 times the hydrogen production efficiency of uncarboxylated C3N4-MOF.

[0022] The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst prepared in this invention has the advantages of heterojunction synergistic catalysis, effectively suppressing the recombination of photogenerated electron-hole pairs and improving charge separation and transport efficiency.

[0023] The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst prepared by this invention has good cycling stability and can be recycled after simple washing and drying. After five cycles, there is no significant change in crystal structure and chemical functional groups, and the hydrogen production only decreases slightly, indicating that it has good structural stability and recycling performance, and can significantly reduce the cost of hydrogen production.

[0024] The photocatalytic hydrogen production method provided by this invention does not require complex equipment, has mild reaction conditions, readily available visible light sources, clear and highly controllable process steps, and is an aqueous system, making it environmentally friendly and suitable for large-scale industrial production. It provides a feasible technical solution for green hydrogen production.

[0025] Using eosin Y as a photosensitizer and triethanolamine as an electron donor, a highly efficient photocatalytic synergistic system is formed with a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst. Eosin Y can extend the visible light absorption range, and triethanolamine can capture photogenerated holes in time, further inhibiting charge recombination and improving the sustainability of the hydrogen production reaction. Attached Figure Description

[0026] Figure 1Transmission electron microscopy image of C3N4-C-MOF1.0 prepared in Example 1; Figure 2 Transmission electron microscopy image of C3N4-C-MOF2.0 prepared in Example 2. Detailed Implementation

[0027] This invention provides a method for preparing a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, comprising the following steps: (1) The carbon nitride precursor and the carboxylating agent are mixed in a solvent to carry out a carboxylation reaction to obtain carboxylated graphitic carbon nitride; (2) Carboxyl graphitic carbon nitride and copper salt solution were mixed to carry out a preliminary reaction to obtain copper-loaded C3N4-C powder; (3) Copper-supported C3N4-C powder and 1,3,5-pyromellitic acid were dispersed in a solvent and subjected to hydrothermal reaction to obtain carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst.

[0028] In this invention, in step (1), the carbon nitride precursor comprises dicyandiamide and cyanuric chloride; the carboxylating agent is 4-cyanobenzoic acid.

[0029] In this invention, the molar ratio of dicyandiamide, cyanuric chloride and 4-cyanobenzoic acid is 1:1~2:1~3, preferably 1:2:2.

[0030] In this invention, the solvent in step (1) is preferably acetonitrile; the molar volume ratio of the dicyandiamide to the solvent is 7.5 mmol: 60 mL.

[0031] In this invention, the temperature of the carboxylation reaction is 170~190℃, preferably 180℃; the time of the carboxylation reaction is 22~26h, preferably 23~25h, and more preferably 24h.

[0032] In this invention, in step (2), the molar ratio of carboxylated graphitic carbon nitride to copper salt is 1:0.5~2.5, preferably 1:1~2, and more preferably 1:2; the temperature of the preliminary reaction is room temperature, and the time of the preliminary reaction is 20~40 min, preferably 0.5 h.

[0033] In this invention, the molar ratio of 1,3,5-pyromellitic acid to copper salt is 1:1.0~2.0, preferably 1:1.2~1.8, and more preferably 1:1.4~1.6.

[0034] In this invention, in step (3), the solvent is a mixture of N,N-dimethylformamide (DMF) and anhydrous ethanol; the volume ratio of N,N-dimethylformamide (DMF) and anhydrous ethanol is 1:1.

[0035] In this invention, the molar volume ratio of 1,3,5-pyromellitic acid to solvent is 7.5 mmol: 60 mL.

[0036] In this invention, the temperature of the hydrothermal reaction is 90~120℃, preferably 100~110℃; the time is 8~12h, preferably 9~11h, and more preferably 10h.

[0037] The present invention also provides the above-described carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst.

[0038] In this invention, the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst is a mesoporous material with an average pore size of 4~5 nm.

[0039] This invention also provides an application of the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst described above in catalytic water splitting for hydrogen production. The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst is used as a photocatalyst, eosin Y is used as a photosensitizer, and triethanolamine is used as an electron donor to construct an aqueous photocatalytic reaction system.

[0040] In this invention, the specific steps for hydrogen production by hydrolysis are as follows: carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, eosin Y and triethanolamine are dispersed in water, and the pH value is adjusted before the reaction is carried out.

[0041] In this invention, the volume ratio of triethanolamine to water is 1:20~24, preferably 1:21~24, and more preferably 1:22~24; the amount of carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst added is 0.003~0.007 g / 50 mL, preferably 0.004~0.006 g / 50 mL, and more preferably 0.005 g / 50 mL; the amount of eosin Y added is 0.005~0.01 g / 50 mL, preferably 0.006~0.009 g / 50 mL, and more preferably 0.0075~0.008 g / 50 mL.

[0042] In this invention, the adjusted pH value is 8-9; the reaction is carried out under vacuum conditions and irradiated with a visible light source; the reaction temperature is 5-10°C, preferably 6-8°C; the reaction time is 1-4 hours, preferably 2-4 hours, and more preferably 3-4 hours.

[0043] In this invention, the wavelength of the visible light source is 420 nm.

[0044] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0045] In this invention, the photocatalytic evaluation system used in the application examples and comparative application examples is the CEL-PAEM-D8Pro model (Beijing Zhongjiao Jinyuan), the gas chromatograph is the GC-2014C model (Shimadzu), and the xenon lamp is 300W equipped with a 420nm long-pass filter.

[0046] Example 1 7.5 mmol of dicyandiamide (C2H4N4) and 15 mmol of cyanuric chloride (C3Cl3N3) were mixed in 60 mL of acetonitrile and stirred for 1 h until completely dissolved. Then, 4-cyanobenzoic acid was added (the molar ratio of dicyandiamide, cyanuric chloride and 4-cyanobenzoic acid was 1:2:2), and stirring was continued for 1 h to obtain a mixed solution. The above mixed solution was reacted at 180 °C for 24 h, then cooled to room temperature, and after centrifugation, washing, drying and grinding, carboxylated graphitic carbon nitride, denoted as C3N4-C, was obtained.

[0047] Cu(NO3)2·3H2O was dissolved in deionized water to prepare a copper salt solution. C3N4-C was dispersed in the copper salt solution (the molar ratio of C3N4-C to Cu(NO3)2·3H2O was 1:1), and the mixture was sonicated for 0.5 h to carry out a preliminary reaction. Then, it was dried at 90 °C for 8 h. Finally, it was washed with deionized water to remove the physically adsorbed but not firmly bound copper ions, and dried again to obtain copper-loaded C3N4-C powder.

[0048] Copper-supported C3N4-C powder and 7.5 mmol of 1,3,5-pyromellitic acid (the molar ratio of 1,3,5-pyromellitic acid to Cu(NO3)2·3H2O was 1:1.6) were dispersed in 60 mL of a mixed solvent (where the volume ratio of N,N-dimethylformamide to ethanol was 1:1). The mixture was magnetically stirred for 30 min and then transferred to a polytetrafluoroethylene-lined high-pressure reactor. The reaction was carried out at 100 °C for 10 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and centrifuged to collect the product. The product was washed three times with N,N-dimethylformamide and ethanol to remove unreacted ligands and solvent. Finally, the product was vacuum dried at 80 °C for 12 h to obtain the carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst, denoted as C3N4-C-MOF1.0.

[0049] Example 2 The difference from Example 1 is that the molar ratio of C3N4-C to Cu(NO3)2·3H2O is 1:2, and all other conditions are the same, to prepare a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, denoted as C3N4-C-MOF2.0, with an average pore size of 4~5nm and a specific surface area of ​​20.37m² / g.

[0050] Comparative Example 1 7.5 mmol of dicyandiamide (C2H4N4) and 15 mmol of cyanuric chloride (C3Cl3N3) were mixed in 60 mL of acetonitrile and stirred for 1 h until completely dissolved. The mixture was then transferred to a high-pressure reactor lined with polytetrafluoroethylene and reacted at 180 °C for 24 h. After the reaction was completed, the mixture was allowed to cool to room temperature and centrifuged to obtain a pale yellow precipitate. The precipitate was washed three times with deionized water and anhydrous ethanol, and finally dried under vacuum at 80 °C for 12 h. The precipitate was then ground to obtain spherical graphitic carbon nitride powder, denoted as C3N4.

[0051] A copper salt solution was prepared by dissolving Cu(NO3)2·3H2O in deionized water. The above-mentioned C3N4 was dispersed in the copper salt solution (the molar ratio of C3N4 to Cu(NO3)2·3H2O was 1:1). The mixture was sonicated for 0.5 h to carry out a preliminary reaction. Then it was dried at 90 °C for 8 h. Finally, it was washed with deionized water to remove the physically adsorbed but not firmly bound copper ions. After drying again, copper-loaded g-C3N4 powder was obtained.

[0052] Copper-supported g-C3N4 powder and 7.5 mmol of 1,3,5-pyromellitic acid (the molar ratio of 1,3,5-pyromellitic acid to Cu(NO3)2·3H2O was 1:1.6) were dispersed in 60 mL of a mixed solvent (where the volume ratio of N,N-dimethylformamide to ethanol was 1:1). The mixture was magnetically stirred for 30 min and then transferred to a polytetrafluoroethylene-lined high-pressure reactor. The reaction was carried out at 100 °C for 10 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and centrifuged to collect the product. The product was washed three times with N,N-dimethylformamide and ethanol to remove unreacted ligands and solvent. Finally, the product was vacuum dried at 80 °C for 12 h to obtain the g-C3N4-supported Cu-MOF catalyst, denoted as C3N4-MOF1.0.

[0053] Comparative Example 2 The difference from Comparative Example 1 is that the molar ratio of C3N4 to Cu(NO3)2·3H2O is 1:2, and all other conditions are the same, to prepare g-C3N4 supported Cu-MOF catalyst, denoted as C3N4-MOF2.0.

[0054] Application Example 1 The C3N4-C-MOF2.0 from Example 2 was ground to 150 mesh, dried at 60°C for 12 hours, and then placed in a desiccator for later use.

[0055] In a 50 mL photocatalytic reactor, 48 mL of deionized water and 2 mL of triethanolamine were added, followed by 0.005 g of pretreated C3N4-C-MOF2.0 and 0.0075 g of eosin Y. The mixture was ultrasonically dispersed for 25 min to form a uniform suspension. The pH of the suspension was adjusted to 9.0 using dilute sodium hydroxide solution. The reactor was then sealed, and a vacuum pump was turned on to evacuate the system for 10 min to maintain the vacuum environment. The reactor was placed in the photocatalytic activity evaluation system, and the cooling circulation device was activated to control the temperature of the reaction system at 6 °C. A 300 W xenon lamp (420 nm long-pass filter) was turned on, with the distance between the light source and the reactor controlled at 12 cm. The stirring speed was adjusted to 400 rpm, and the reaction was irradiated for 3 h. The hydrogen production was monitored in real time using an online gas chromatograph (nitrogen as carrier gas), and the hydrogen evolution rate was measured to be [missing value]. .

[0056] After the reaction, the catalyst was collected by centrifugation, washed four times each with ethanol and deionized water, and then dried under vacuum at 60°C. The above catalytic hydrolysis hydrogen production steps were repeated, and after five cycles, the hydrogen evolution rate remained at [value missing]. The structure of the catalyst remained unchanged.

[0057] Application Example 2 The C3N4-C-MOF2.0 from Example 2 was ground to 150 mesh, dried at 60°C for 12 hours, and then placed in a desiccator for later use.

[0058] In a 50 mL photocatalytic reactor, 48 mL of deionized water and 2 mL of triethanolamine were added, followed by 0.005 g of pretreated C3N4-C-MOF2.0 and 0.0075 g of eosin Y. The mixture was ultrasonically dispersed for 20 min to form a uniform suspension. The pH of the suspension was adjusted to 8.5 using dilute sodium hydroxide solution. The reactor was then sealed, and a vacuum pump was turned on to evacuate the system for 10 min. The reactor was then placed in the photocatalytic activity evaluation system, and the cooling circulation device was activated to maintain the reaction system temperature at 6 °C. A 300 W xenon lamp (420 nm long-pass filter) was turned on, with the distance between the light source and the reactor controlled at 10 cm. The stirring speed was adjusted to 300 rpm, and the reaction was irradiated for 3 h. The hydrogen production was monitored in real time using an online gas chromatograph (nitrogen as carrier gas), and the hydrogen evolution rate was measured to be [missing value]. .

[0059] After the reaction, the catalyst was collected by centrifugation, washed four times each with ethanol and deionized water, and then dried under vacuum at 60°C. The above catalytic hydrolysis hydrogen production steps were repeated, and after five cycles, the hydrogen evolution rate remained at [value missing]. The structure of the catalyst remained unchanged.

[0060] Comparative Application Example 1 The difference from Application Example 1 is that the C3N4-C-MOF2.0 of Example 2 was replaced with C3N4 prepared in Comparative Example 1, while all other conditions remained the same. The measured hydrogen evolution rate was [missing value]. .

[0061] Comparative Application Example 2 The difference from Application Example 1 is that the C3N4-C-MOF2.0 prepared in Comparative Example 2 was used instead of the C3N4-C-MOF2.0 in Example 2. All other conditions were the same, and the measured hydrogen evolution rate was [missing value]. This represents 59.4% of the hydrogen production efficiency of Application Example 1.

[0062] Comparative Application Example 3 The difference from Application Example 1 is that the reaction was irradiated for 2 hours, while all other conditions were the same, and the measured hydrogen evolution rate was [missing value]. This indicates that the reaction time was insufficient, the catalyst performance was not fully utilized, and the hydrogen production efficiency decreased significantly.

[0063] Comparative Application Example 4 The difference from Application Example 1 is that the pH value was adjusted to 7.0, while all other conditions remained the same, and the measured hydrogen evolution rate was [missing value]. This indicates that a pH of 7.0 in the reaction system is unfavorable for the photocatalytic hydrogen production reaction, resulting in reduced charge separation efficiency.

[0064] The above application examples and comparative examples demonstrate that the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst prepared in this invention can significantly improve the efficiency of hydrogen production through water splitting under visible light and exhibits good cycle stability. Optimizing the reaction pH and reaction time can maximize the hydrogen production efficiency.

[0065] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, characterized in that, Includes the following steps: (1) The carbon nitride precursor and the carboxylating agent are mixed in a solvent to carry out a carboxylation reaction to obtain carboxylated graphitic carbon nitride; (2) Carboxyl graphitic carbon nitride and copper salt solution were mixed to carry out a preliminary reaction to obtain copper-loaded C3N4-C powder; (3) Copper-supported C3N4-C powder and 1,3,5-pyromellitic acid were dispersed in a solvent and subjected to hydrothermal reaction to obtain carboxyl-functionalized g-C3N4-supported Cu-MOF catalyst.

2. The method for preparing the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 1, characterized in that, In step (1), the carbon nitride precursor contains dicyandiamide and cyanuric chloride; the carboxylating agent is 4-cyanobenzoic acid.

3. The method for preparing the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 2, characterized in that, The molar ratio of dicyandiamide, cyanuric chloride, and 4-cyanobenzoic acid is 1:1~2:1~3.

4. The method for preparing the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to any one of claims 1 to 3, characterized in that, In step (2), the molar ratio of carboxylated graphitic carbon nitride to copper salt is 1:0.5~2.5; the temperature of the preliminary reaction is room temperature, and the time of the preliminary reaction is 20~40 min.

5. The method for preparing the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 4, characterized in that, The molar ratio of 1,3,5-pyromellitic acid to copper salt is 1:1.0~2.

0.

6. The method for preparing the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 2, 3, or 5, characterized in that, The hydrothermal reaction is carried out at a temperature of 90~120℃ for 8~12 hours.

7. The carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst prepared by the method according to any one of claims 1 to 6.

8. The application of the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 7 in catalytic hydrolysis for hydrogen production, characterized in that, An aqueous photocatalytic reaction system was constructed using a carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst as a photocatalyst, eosin Y as a photosensitizer, and triethanolamine as an electron donor.

9. The application of the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 8 in catalytic hydrolysis for hydrogen production, characterized in that, The specific steps for hydrogen production by hydrolysis are as follows: carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst, eosin Y and triethanolamine are dispersed in water, and the pH value is adjusted before the reaction is carried out.

10. The application of the carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst according to claim 9 in catalytic hydrolysis for hydrogen production, characterized in that, The volume ratio of triethanolamine to water is 1:20~24; the amount of carboxyl-functionalized g-C3N4 supported Cu-MOF catalyst added is 0.003~0.007 g / 50 mL; and the amount of eosin Y added is 0.005~0.01 g / 50 mL.

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