Nickel-based metal organic framework material, plasmon nickel-based metal organic framework composite material, and synthesis method and application of nickel-based metal organic framework material and plasmon nickel-based metal organic framework composite material

Abstract

The invention belongs to the technical field of metal-organic framework functional materials, and particularly relates to a nickel-based metal-organic framework material, a plasmon nickel-based metal-organic framework composite material and a synthesis method and application of the nickel-based metal-organic framework material and the plasmon nickel-based metal-organic framework composite material. According to the invention, chloroauric acid is directly reduced into gold nanoparticles by using the reducibility of the nickel-based metal organic framework material, and the gold nanoparticles are loaded on the nickel-based metal organic framework material, so that uniform dispersion and firm loading of the gold nanoparticles on the nickel-based metal organic framework material are realized. The method has the advantages of simple synthesis method, convenience in operation and no need of additional reducing agent, is easy for large-scale preparation, and has better market application value and development prospect. The prepared plasmon nickel-based metal organic framework composite material is used as a photoelectrocatalytic reaction catalyst to be applied to photoelectrocatalytic reduction of nitrate to prepare ammonia, and the catalytic performance is excellent.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal organic framework functional materials, and in particular relates to a nickel-based metal organic framework material, a plasmonic nickel-based metal organic framework composite material, and a synthesis method and application thereof. Background Art

[0002] Ammonia is an important chemical raw material and an ideal energy carrier, with an annual global production of 180 million tons. The main method for synthesizing ammonia is the Haber process. However, the Haber process for ammonia production is a high-energy consumption process, accounting for about 1% of the world's total energy consumption each year, and one of the raw materials, hydrogen, comes from the methane steam reforming reaction, which releases a large amount of carbon dioxide and exacerbates the greenhouse effect. On the other hand, the widespread use of fertilizers and wastewater discharge from the steel industry in recent years have caused excessive nitrates in the environment and increased concentrations, which has led to eutrophication of water bodies and seriously affected the ecology and environment. If clean electricity / solar energy can be used to convert the ubiquitous nitrate ions in the environment into ammonia at room temperature and pressure, it can not only provide a green, sustainable, low-cost, and distributable way to produce ammonia, but also cope with the increasingly severe nitrogen pollution problem. The development of high-performance catalysts is the key to achieving efficient conversion of nitrate to ammonia.

[0003] Plasmonic metal-organic framework composite materials have both the excellent optical properties of plasmonic nanocrystals and the highly designable catalytic performance of metal-organic frameworks, and may bring about synergistic enhancement effects, and have shown great application prospects in the fields of catalysis and sensing. However, the current methods for preparing plasmonic metal-organic framework composites are usually cumbersome and require the addition of reducing agents, and the catalytic performance needs to be improved. Summary of the invention

[0004] Based on the above reasons, the first object of the present invention is to provide a nickel-based metal organic framework material with regular appearance, reducibility, and the ability to further load metals to improve catalytic performance.

[0005] The second purpose of the present invention is to provide a method for synthesizing a nickel-based metal organic framework material, which is rapidly synthesized by a solvent thermal method and is simple.

[0006] The third object of the present invention is to provide a plasmonic nickel-based metal organic framework composite material with a regular appearance, excellent reducibility, and good photoelectrocatalytic performance of nitrate reduction to produce ammonia.

[0007] The fourth object of the present invention is to provide a method for synthesizing a plasmonic nickel-based metal organic framework composite material. The synthesis method is simple, easy to operate, and does not require the addition of an external reducing agent.

[0008] The fifth object of the present invention is to provide a plasmonic nickel-based metal organic framework composite material for use as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0009] The first object of the present invention can be achieved by adopting the following technical solutions:

[0010] A nickel-based metal organic framework material, wherein an organic ligand having a structure shown in formula I is chelated and coordinated with a nickel salt to form a nickel-based metal organic framework material; the structure of SR in formula I is as shown in formula II;

[0011]

[0012] The second object of the present invention can be achieved by adopting the following technical solutions:

[0013] A method for synthesizing a nickel-based metal organic framework material comprises the following steps: adding an organic ligand having a structure shown in formula I and a nickel salt into an organic solvent for solvothermal reaction to synthesize the nickel-based metal organic framework material.

[0014] Further, the mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is (3-5):(0.5-1.5); and / or

[0015] The solvent thermal reaction conditions are: reacting at 100° C.-120° C. for 12 h-72 h.

[0016] Furthermore, nitrogen protection is introduced into the solvent thermal reaction, and sodium tert-butoxide and ethylenediamine are added into the reaction system;

[0017] The mass ratio of the sodium tert-butoxide, ethylenediamine and the organic ligand having the structure shown in formula I is 1:0.8:(4-7).

[0018] The third object of the present invention can be achieved by adopting the following technical solutions:

[0019] A plasmonic nickel-based metal organic framework composite material is prepared by reacting the above nickel-based metal organic framework material with chloroauric acid.

[0020] The fourth object of the present invention can be achieved by adopting the following technical solutions:

[0021] A method for synthesizing a plasmonic nickel-based metal-organic framework composite material comprises the following steps: dispersing the nickel-based metal-organic framework material in water to obtain a suspension, adding an aqueous solution of chloroauric acid to the suspension for reaction, centrifuging, washing with water and drying to synthesize the plasmonic nickel-based metal-organic framework composite material.

[0022] Furthermore, when the suspension is prepared by dispersion, the mass ratio of the nickel-based metal organic framework material to water is (3-6): (1-3); and / or

[0023] The dispersion method is ultrasonic dispersion, and the ultrasonic dispersion time is 5min-45min; and / or

[0024] Before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction using acetone; and / or the temperature of the Soxhlet extraction is 70° C.-90° C., and the time of the Soxhlet extraction is 20 h-30 h.

[0025] Among them, activating the nickel-based metal-organic framework material through Soxhlet extraction can remove the solvent inside the pores of the nickel-based metal-organic framework material, thereby ensuring its crystallinity for preparing plasmonic nickel-based metal-organic framework composite materials.

[0026] Further, the concentration of the chloroauric acid aqueous solution is 0.01mol / L-0.05mol / L;

[0027] The mass ratio of the nickel-based metal organic framework material to the aqueous solution of chloroauric acid is (5-50):1.

[0028] Furthermore, the reaction time is 10 min-45 min; and / or

[0029] The centrifugal speed is 1000rpm-15000rpm; and / or

[0030] The washing is performed with deionized water for 2-3 times; and / or

[0031] The drying is performed by vacuum drying, the vacuum drying temperature is 30° C.-80° C., the vacuum drying time is 15-45 min, and the vacuum degree is 0.04 MPa-0.08 MPa.

[0032] The fifth object of the present invention can be achieved by adopting the following technical solutions:

[0033] The plasmonic nickel-based metal organic framework composite material is used as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The nickel-based metal organic framework material of the present invention has a regular appearance, is reducible, and can further load metals to improve catalytic performance.

[0036] (2) The method for synthesizing a nickel-based metal organic framework material of the present invention can be rapidly synthesized through a solvent thermal reaction, has a simple synthesis process, and is easy to prepare on a large scale.

[0037] (3) A plasmonic nickel-based metal-organic framework composite material of the present invention is obtained by directly reacting a nickel-based metal-organic framework material with reduction activity with chloroauric acid, has a regular appearance, excellent reducibility, and can exhibit good photoelectrocatalytic performance of nitrate reduction to ammonia. Compared with the nickel-based metal-organic framework material, the plasmonic nickel-based metal-organic framework composite material has a 2.4-fold enhancement in the performance of photoelectrocatalytic nitrate reduction to ammonia.

[0038] (4) The synthesis method of a plasmonic nickel-based metal organic framework composite material of the present invention utilizes the reducing property of the nickel-based metal organic framework material itself to directly reduce chloroauric acid into gold nanoparticles, and loads the gold nanoparticles on the nickel-based metal organic framework material, thereby achieving uniform dispersion and firm loading of the gold nanoparticles on the nickel-based metal organic framework material. The method has the advantages of simple synthesis method, convenient operation, no need for external reducing agent, easy large-scale preparation, and good market application value and development prospects.

[0039] (5) The application of the plasmonic nickel-based metal organic framework composite material of the present invention as a catalyst for photoelectrocatalytic reaction in photoelectrocatalytic nitrate reduction to produce ammonia has excellent catalytic performance and good market application value and development prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a molecular structure diagram of a nickel-based metal organic framework material prepared in Example 4 of the present invention.

[0041] Figure 2 It is a molecular structure diagram of the plasmonic nickel-based metal organic framework composite material prepared in Example 8 of the present invention.

[0042] Figure 3 This is an electron microscope image of the plasmonic nickel-based metal organic framework composite material prepared in Example 8 of the present invention.

[0043] Figure 4 The powder diffraction pattern of the plasmonic nickel-based metal organic framework composite material prepared in Example 8 of the present invention is

[0044] Figure 5 This is the absorption spectrum of the plasmonic nickel-based metal organic framework composite material prepared in Example 8 of the present invention

[0045] Figure 6 This is a performance comparison chart of the plasmonic nickel-based metal organic framework composite material prepared in Example 8 of the present invention for nitrate reduction of ammonia under electrocatalytic and photoelectrocatalytic conditions. DETAILED DESCRIPTION

[0046] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only partial embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0047] Wherein, HTHATN-Ni in the present invention refers to a nickel-based metal organic framework material.

[0048] Wherein, Au-HTHATN-Ni in the present invention refers to a plasmonic nickel-based metal organic framework composite material.

[0049] In an embodiment of the present invention, a nickel-based metal organic framework material is provided, wherein an organic ligand having a structure shown in Formula I is chelated and coordinated with a nickel salt to form a nickel-based metal organic framework material; the structure of SR in Formula I is as shown in Formula II;

[0050]

[0051] In an embodiment of the present invention, a method for synthesizing a nickel-based metal organic framework material comprises the following steps: adding an organic ligand having a structure shown in Formula I and a nickel salt into an organic solvent for a solvothermal reaction to synthesize the nickel-based metal organic framework material.

[0052] As one embodiment, the mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is (3-5):(0.5-1.5); and / or

[0053] The solvent thermal reaction conditions are: reacting at 100° C.-120° C. for 12 h-72 h.

[0054] As one embodiment, nitrogen protection is introduced into the solvent thermal reaction, and sodium tert-butoxide and ethylenediamine are added to the reaction system;

[0055] The mass ratio of the sodium tert-butoxide, ethylenediamine and the organic ligand having the structure shown in formula I is 1:0.8:(4-7).

[0056] In an embodiment of the present invention, a plasmonic nickel-based metal-organic framework composite material is prepared by reacting the above-mentioned nickel-based metal-organic framework material with chloroauric acid.

[0057] In an embodiment of the present invention, a method for synthesizing a plasmonic nickel-based metal-organic framework composite material comprises the following steps: dispersing the above-mentioned nickel-based metal-organic framework material in water to obtain a suspension, adding an aqueous solution of chloroauric acid to the suspension for reaction, centrifuging, washing with water and drying, and synthesizing the plasmonic nickel-based metal-organic framework composite material.

[0058] As one embodiment, when the suspension is prepared by dispersion, the mass ratio of the nickel-based metal organic framework material to water is (3-6): (1-3); and / or

[0059] The dispersion method is ultrasonic dispersion, and the ultrasonic dispersion time is 5min-45min; and / or

[0060] Before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction using acetone; and / or the temperature of the Soxhlet extraction is 70° C.-90° C., and the time of the Soxhlet extraction is 20 h-30 h.

[0061] Among them, activating the nickel-based metal-organic framework material through Soxhlet extraction can remove the solvent inside the pores of the nickel-based metal-organic framework material, thereby ensuring its crystallinity for preparing plasmonic nickel-based metal-organic framework composite materials.

[0062] As one embodiment, the concentration of the chloroauric acid aqueous solution is 0.01 mol / L-0.05 mol / L;

[0063] The mass ratio of the nickel-based metal organic framework material to the aqueous solution of chloroauric acid is (5-50):1.

[0064] As one embodiment, the reaction time is 10 min-45 min; and / or

[0065] The centrifugal speed is 1000rpm-15000rpm; and / or

[0066] The washing is performed with deionized water for 2-3 times; and / or

[0067] The drying is performed by vacuum drying, the vacuum drying temperature is 30° C.-80° C., the vacuum drying time is 15-45 min, and the vacuum degree is 0.04 MPa-0.08 MPa.

[0068] In an embodiment of the present invention, the plasmonic nickel-based metal organic framework composite material is used as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0069] The following is a further description with reference to specific embodiments.

[0070] Example 1

[0071]

[0072]

[0073] A method for synthesizing a nickel-based metal organic framework material comprises the following steps: adding an organic ligand having a structure shown in formula I and a nickel salt into an organic solvent for solvothermal reaction, introducing nitrogen protection during the reaction, and adding sodium tert-butoxide and ethylenediamine into the reaction system to synthesize the nickel-based metal organic framework material.

[0074] In this embodiment, the mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is 4:1; the conditions of the solvent thermal reaction are to react at 110° C. for 24 hours; the mass ratio of sodium tert-butoxide, ethylenediamine and the organic ligand of the structure shown in Formula I is 1:0.8:5.

[0075] Example 2

[0076] A method for synthesizing a nickel-based metal organic framework material comprises the following steps: adding an organic ligand having a structure shown in formula I and a nickel salt into an organic solvent for solvothermal reaction, introducing nitrogen protection during the reaction, and adding sodium tert-butoxide and ethylenediamine into the reaction system to synthesize the nickel-based metal organic framework material.

[0077] In this embodiment, the mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is 3:0.5; the conditions of the solvent thermal reaction are to react at 100° C. for 72 hours; the mass ratio of sodium tert-butoxide, ethylenediamine and the organic ligand of the structure shown in Formula I is 1:0.8:4.

[0078] Example 3

[0079] A method for synthesizing a nickel-based metal organic framework material comprises the following steps: adding an organic ligand having a structure shown in formula I and a nickel salt into an organic solvent for solvothermal reaction, introducing nitrogen protection during the reaction, and adding sodium tert-butoxide and ethylenediamine into the reaction system to synthesize the nickel-based metal organic framework material.

[0080] In this embodiment, the mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is 5:1.5; the conditions of the solvent thermal reaction are to react at 120° C. for 12 hours; the mass ratio of sodium tert-butoxide, ethylenediamine and the organic ligand of the structure shown in Formula I is 1:0.8:7.

[0081] Example 4

[0082] A method for synthesizing a nickel-based metal organic framework material comprises the following steps: weighing an organic ligand with a structure shown in formula I, adding it into a 25 mL reaction bottle equipped with a rotor, repeatedly evacuating the vacuum several times, passing N2 to maintain an oxygen-free state; bubbling 3 mL of DMA (dimethyl adipate) solution for 5 minutes and then adding it into the reaction bottle; weighing sodium tert-butoxide, adding it into the reaction bottle, and stirring it in an oil bath at 110°C for 8 minutes; weighing nickel acetate tetrahydrate into a centrifuge tube, and adding 3 mL of DMA and ethylenediamine respectively, ultrasonicating until nickel acetate tetrahydrate is completely dissolved and the solution is pink, bubbling the solution for 5 minutes and then adding it into the reaction bottle, and the solution changes from orange to dark green; placing the reaction bottle in an oil bath at 110°C for stirring and reaction for two days.

[0083] The molecular structure of the nickel-based metal organic framework material prepared in this embodiment is as follows: Figure 1 shown.

[0084] Example 5

[0085] A method for synthesizing a plasmonic nickel-based metal-organic framework composite material comprises the following steps: ultrasonically dispersing the nickel-based metal-organic framework material obtained in Example 4 in water for 30 minutes to obtain a suspension, adding a 0.03 mol / L aqueous solution of chloroauric acid to the suspension to react for 35 minutes, centrifuging at 13000 rpm, washing twice with deionized water, and vacuum drying at 50°C and 0.06 MPa for 30 minutes to synthesize a plasmonic nickel-based metal-organic framework composite material.

[0086] In this embodiment, when the suspension is prepared by dispersion, the mass ratio of the nickel-based metal organic framework material to water is 5:2; before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction at 80°C for 25 hours using acetone.

[0087] In this embodiment, the mass ratio of the nickel-based metal organic framework material to the chloroauric acid aqueous solution is 30:1.

[0088] The plasmonic nickel-based metal organic framework composite material synthesized in this example is used as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0089] Example 6

[0090] A method for synthesizing a plasmonic nickel-based metal-organic framework composite material comprises the following steps: ultrasonically dispersing the nickel-based metal-organic framework material obtained in Example 4 in water for 5 minutes to obtain a suspension, adding a 0.01 mol / L aqueous solution of chloroauric acid to the suspension to react for 45 minutes, centrifuging at 1000 rpm, washing with deionized water for 3 times, and vacuum drying at 30° C. and 0.04 MPa for 15 minutes to synthesize a plasmonic nickel-based metal-organic framework composite material.

[0091] In this embodiment, when the suspension is prepared by dispersion, the mass ratio of the nickel-based metal organic framework material to water is 3:1; before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction at 70°C for 30 hours using acetone.

[0092] In this embodiment, the mass ratio of the nickel-based metal organic framework material to the chloroauric acid aqueous solution is 5:1.

[0093] The plasmonic nickel-based metal organic framework composite material synthesized in this example is used as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0094] Example 7

[0095] A method for synthesizing a plasmonic nickel-based metal-organic framework composite material comprises the following steps: ultrasonically dispersing the nickel-based metal-organic framework material obtained in Example 4 in water for 45 minutes to obtain a suspension, adding a 0.05 mol / L aqueous solution of chloroauric acid to the suspension to react for 10 minutes, centrifuging at 15000 rpm, washing twice with deionized water, and vacuum drying at 80°C and 0.08 MPa for 45 minutes to synthesize the plasmonic nickel-based metal-organic framework composite material.

[0096] In this embodiment, when the suspension is prepared by dispersion, the mass ratio of the nickel-based metal organic framework material to water is 6:3; before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction at 90° C. for 20 hours using acetone.

[0097] In this embodiment, the mass ratio of the nickel-based metal organic framework material to the chloroauric acid aqueous solution is 50:1.

[0098] The plasmonic nickel-based metal organic framework composite material synthesized in this example is used as a photoelectrocatalytic reaction catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

[0099] Example 8

[0100] A method for synthesizing a plasmonic nickel-based metal organic framework composite material comprises the following steps: 5 mg of HTHATN-Ni is added to a 10 mL glass bottle, 2 mL of deionized water is added, and the bottle is sealed and placed in an ultrasonic instrument for ultrasonication for 20-30 minutes to ensure that the HTHATN-Ni is uniformly dispersed in the water. Under the condition of a stirring speed of 800-1200 rpm, 10 μL of chloroauric acid aqueous solution (0.05 mol / L) is added, and after reacting for 20 minutes, the mixture is transferred to a 10 mL centrifuge tube, centrifuged at a speed of 5000-7000 rpm for 3 minutes, the supernatant is removed, the bottom precipitate is collected, and the precipitate is washed 2-3 times with deionized water. The washed precipitate is placed in a vacuum drying oven and dried at a temperature of 60° C. for 20-30 minutes and a vacuum degree of 0.06-0.08 MPa. 5.0 mg of synthesized Au-HTHATN-Ni and 5.0 mg of acetylene black were ultrasonically dispersed in 1 mL of a mixed solvent of water, isopropanol, and Nafion (volume ratio 8:12:1) to prepare a catalyst slurry. 40 μL of the catalyst slurry was evenly coated on a 0.5 cm 2 On carbon paper, then dried at room temperature and used as working electrode, carbon rod and Ag / AgCl were selected as counter electrode and reference electrode respectively. The electrolyte was an aqueous solution containing KNO3 and K2SO4, with concentrations of 0.1 and 0.05M respectively. Before the nitrate reduction ammonia test, Ar was introduced into the electrolytic cell for 20min, and the reaction was carried out at a voltage of -1.5V vs.Ag / AgCl for half an hour, then the electrolyte was replaced and the xenon lamp (255mW / cm 2 ), react for half an hour under the same conditions. Finally, the ammonia content in the electrolyte was quantified using the indoxyl blue colorimetric method.

[0101] Among them, the plasmonic nickel-based metal organic framework composite material prepared in this embodiment is as follows Figure 2 shown.

[0102] Among them, the electron microscope image of the plasmonic nickel-based metal organic framework composite material prepared in this embodiment is as follows: Figure 3 As shown. Figure 3 It can be seen that gold nanoparticles are successfully loaded on the nickel-based metal-organic framework material and are evenly distributed.

[0103] The powder diffraction pattern of the plasmonic nickel-based metal organic framework composite material prepared in this embodiment is as follows: Figure 4 As shown. Figure 4 It can be seen that the powder diffraction pattern can simultaneously measure the diffraction peaks of nickel-based metal-organic framework materials and gold nanoparticles.

[0104] The absorption spectrum of the plasmonic nickel-based metal organic framework composite material prepared in this embodiment is as follows: Figure 5 As shown. Figure 5It can be seen that nickel-based metal-organic framework materials have absorption in a wide wavelength range.

[0105] Among them, the performance comparison chart of the plasmonic nickel-based metal organic framework composite material prepared in this embodiment for nitrate reduction of ammonia under electrocatalytic and photoelectrocatalytic conditions is as follows: Figure 6 As shown. Figure 6 It can be seen that the performance of nitrate reduction to ammonia by photoelectrocatalysis is significantly improved compared with that by electrocatalysis.

[0106] Example 9

[0107] A method for synthesizing a plasmonic nickel-based metal organic framework composite material comprises the following steps: 5 mg of HTHATN-Ni is added to a 10 mL glass bottle, 2 mL of deionized water is added, and the bottle is sealed and placed in an ultrasonic instrument for ultrasonication for 20-30 minutes to ensure that the HTHATN-Ni is uniformly dispersed in the water. Under the condition of a stirring speed of 800-1200 rpm, 20 μL of chloroauric acid aqueous solution (0.05 mol / L) is added, and after reacting for 20 minutes, the mixture is transferred to a 10 mL centrifuge tube, centrifuged at a speed of 5000-7000 rpm for 3 minutes, the supernatant is removed, the bottom precipitate is collected, and the mixture is washed 2-3 times with deionized water. The washed precipitate is placed in a vacuum drying oven and dried at a temperature of 60° C. for 20-30 minutes and a vacuum degree of 0.06-0.08 MPa. 5.0 mg of synthesized Au-HTHATN-Ni and 5.0 mg of acetylene black were ultrasonically dispersed in a mixed solvent of 1 mL of water, isopropanol, and Nafion (volume ratio 8:12:1) to prepare a catalyst slurry. 40 μL of the catalyst slurry was evenly coated on 0.5 cm2 carbon paper and then dried at room temperature and used as a working electrode. Carbon rods and Ag / AgCl were selected as counter electrodes and reference electrodes, respectively. The electrolyte was an aqueous solution containing KNO3 and K2SO4, with concentrations of 0.1 and 0.05 M, respectively. Before the nitrate reduction test of ammonia, 20 min of Ar was passed into the electrolytic cell, and the reaction was carried out at a voltage of -1.5 V vs. Ag / AgCl for half an hour. Then the electrolyte was replaced and the xenon lamp (255 mW / cm2) was turned on, and the reaction was carried out under the same conditions for half an hour. Finally, the indoxyl blue colorimetric method was used to quantify the ammonia content in the electrolyte.

[0108] Example 10

[0109] A method for synthesizing a plasmonic nickel-based metal organic framework composite material comprises the following steps: 5 mg of HTHATN-Ni is added to a 10 mL glass bottle, 2 mL of deionized water is added, and the bottle is sealed and placed in an ultrasonic instrument for ultrasonication for 20-30 minutes to ensure that the HTHATN-Ni is uniformly dispersed in the water. Under the condition of a stirring speed of 800-1200 rpm, 30 μL of chloroauric acid aqueous solution (0.05 mol / L) is added, and after reacting for 20 minutes, the mixture is transferred to a 10 mL centrifuge tube, centrifuged at a speed of 5000-7000 rpm for 3 minutes, the supernatant is removed, the bottom precipitate is collected, and the precipitate is washed 2-3 times with deionized water. The washed precipitate is placed in a vacuum drying oven and dried at a temperature of 60° C. for 20-30 minutes and a vacuum degree of 0.06-0.08 MPa. 5.0 mg of synthesized Au-HTHATN-Ni and 5.0 mg of acetylene black were ultrasonically dispersed in a mixed solvent of 1 mL of water, isopropanol, and Nafion (volume ratio 8:12:1) to prepare a catalyst slurry. 40 μL of the catalyst slurry was evenly coated on 0.5 cm2 carbon paper and then dried at room temperature and used as a working electrode. Carbon rods and Ag / AgCl were selected as counter electrodes and reference electrodes, respectively. The electrolyte was an aqueous solution containing KNO3 and K2SO4, with concentrations of 0.1 and 0.05 M, respectively. Before the nitrate reduction test of ammonia, 20 min of Ar was passed into the electrolytic cell, and the reaction was carried out at a voltage of -1.5 V vs. Ag / AgCl for half an hour. Then the electrolyte was replaced and the xenon lamp (255 mW / cm2) was turned on, and the reaction was carried out under the same conditions for half an hour. Finally, the indoxyl blue colorimetric method was used to quantify the ammonia content in the electrolyte.

[0110] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A nickel-based metal organic framework material, characterized in that: The organic ligand of the structure shown in Formula I is chelated and coordinated with the nickel salt to form a nickel-based metal organic framework material; the structure of SR in Formula I is the structure shown in Formula II; 2. A method for synthesizing the nickel-based metal organic framework material according to claim 1, characterized in that: The method comprises the following steps: adding an organic ligand having a structure shown in formula I and a nickel salt into an organic solvent for a solvothermal reaction to synthesize the nickel-based metal organic framework material.

3. The method for synthesizing a nickel-based metal organic framework material according to claim 2, characterized in that: The mass ratio of the organic ligand of the structure shown in Formula I to the nickel salt is (3-5):(0.5-1.5); and / or The solvent thermal reaction conditions are: reacting at 100° C.-120° C. for 12 h-72 h.

4. The method for synthesizing a nickel-based metal organic framework material according to claim 2, characterized in that: Nitrogen protection is introduced into the solvent thermal reaction, and sodium tert-butoxide and ethylenediamine are added into the reaction system; The mass ratio of the sodium tert-butoxide, ethylenediamine and the organic ligand having the structure shown in formula I is 1:0.8:(4-7).

5. A plasmonic nickel-based metal organic framework composite material, characterized in that: The nickel-based metal organic framework material according to claim 1 is prepared by reacting with chloroauric acid.

6. A method for synthesizing the plasmonic nickel-based metal organic framework composite material according to claim 5, characterized in that: The steps include: The nickel-based metal organic framework material according to claim 1 is dispersed in water to obtain a suspension, an aqueous solution of chloroauric acid is added to the suspension to react, and the suspension is centrifuged, washed with water and dried to synthesize the plasmonic nickel-based metal organic framework composite material.

7. The method for synthesizing the plasmonic nickel-based metal organic framework composite material according to claim 6, characterized in that: When dispersing to prepare the suspension, the mass ratio of the nickel-based metal organic framework material to water is (3-6): (1-3); and / or The dispersion method is ultrasonic dispersion, and the ultrasonic dispersion time is 5min-45min; and / or Before the nickel-based metal organic framework material is dispersed in water, the nickel-based metal organic framework material is first subjected to Soxhlet extraction using acetone; and / or the temperature of the Soxhlet extraction is 70° C.-90° C., and the time of the Soxhlet extraction is 20 h-30 h.

8. The method for synthesizing the plasmonic nickel-based metal organic framework composite material according to claim 6, characterized in that: The concentration of the chloroauric acid aqueous solution is 0.01 mol / L-0.05 mol / L; The mass ratio of the nickel-based metal organic framework material to the aqueous solution of chloroauric acid is (5-50):

1.

9. The method for synthesizing the plasmonic nickel-based metal organic framework composite material according to claim 6, characterized in that: The reaction time is 10 min-45 min; and / or The centrifugal speed is 1000rpm-15000rpm; and / or The washing is performed with deionized water for 2-3 times; and / or The drying is performed by vacuum drying, the vacuum drying temperature is 30° C.-80° C., the vacuum drying time is 15-45 min, and the vacuum degree is 0.04 MPa-0.08 MPa.

10. Use of the plasmonic nickel-based metal organic framework composite material according to any one of claims 5 to 9 as a photoelectrocatalytic catalyst in photoelectrocatalytic nitrate reduction to produce ammonia.

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