Preparation method and application of high-dispersion Ni delta < + >-based MOFs catalytic hydrogenation material
By synthesizing MOFs catalytic hydrogenation materials through bimetallic nodes and functionalized ligands, the problems of insufficient activity and uneven dispersion of metal catalytic materials are solved, and efficient and stable unsaturated olefin/alkyne fuel hydrogenation reactions are achieved with good cycle stability and low cost.
Patent Information
- Application Number
- CN202510746869.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-05
- Publication Date
- 2025-09-19
AI Technical Summary
In the hydrogenation reaction of unsaturated olefin/alkyne fuels, the existing catalysts have insufficient activity of metal catalytic materials, and the metal nanoparticles are unevenly dispersed and easily aggregated, resulting in poor cycle stability and recyclability.
Bimetallic nodes and functionalized ligands were used to synthesize MOFs catalytic hydrogenation materials. Solvothermal and impregnation methods were used to prepare highly crystalline Niδ+-based MOFs. SMSI was used to anchor highly dispersed Niδ+ to form a Ni@CeMIL-101-NH2 structure, ensuring that the active sites were not easily lost.
The catalytic hydrogenation material with highly dispersed Niδ+ achieves efficient hydrogenation at low temperature, has excellent cycle stability and recyclability, and has a simple preparation method and low cost.
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Figure CN120662383A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of MOFs anchored transition metal catalytic hydrogenation to prepare high-quality aviation fuel, and specifically relates to anchoring highly dispersed and highly active Ni on bimetallic MOFs (CeMIL-101-NH2). δ+ Preparation method and application of catalytic hydrogenation materials. Background Art
[0002] The catalytic hydrogenation of unsaturated olefin / alkyne fuels is a key catalytic reaction in the chemical industry, playing an important role in the production of various transportation fuels such as gasoline, diesel, and jet fuel. Catalyst design should consider ease of synthesis, recyclability, and cyclic stability. In particular, the activity of catalysts remains to be significantly improved using metal catalytic materials. The development of non-precious metal catalytic materials that can effectively activate HH and C=C / C≡C bonds and achieve the hydrogenation of unsaturated olefin / alkyne fuels remains a significant challenge.
[0003] Metal-organic frameworks (MOFs) hold great potential in catalytic hydrogenation due to their high surface area and well-defined pore structure. Due to their unique metal-support interactions, they are considered excellent candidates for stabilizing guest species (such as nanoparticles, NPs) and have demonstrated excellent catalytic performance towards unsaturated olefin / alkyne fuels in numerous studies. However, these NPs are typically located on the outer surface of MOFs, exhibiting uneven dispersion and, to a certain extent, prone to aggregation. In some reports, MOFs have been used as precursors for the preparation of metal oxide or carbon-based materials to support the conversion of unsaturated olefin / alkyne fuels with NPs. However, the permanent porosity and inherently high surface area of the pristine MOFs are sacrificed. Furthermore, although some NPs are encapsulated within the pores of MOFs, these metal atoms may leach out of the MOF framework due to a lack of strong binding interactions with the MOF. Importantly, metal oxide cluster design and ligand functional group modification can be used to anchor guest molecules as active sites, thereby introducing high metal dispersion to modulate strong interactions (SMSI) between NPs and MOFs. Current research requires the construction of a catalytic hydrogenation material that achieves high reaction efficiency, excellent cycle stability and recyclability. Summary of the Invention
[0004] The purpose of the present invention is to synthesize MOFs catalytic hydrogenation materials with a bimetallic node and functionalized ligands, and to use SMSI to anchor highly dispersed Ni δ+ , so that the catalytic hydrogenation material has high cycle stability, and at the same time provides a preparation method with simple process, mild conditions and low cost, so as to realize the catalytic hydrogenation material with efficient hydrogenation at low temperature and non-loss of active sites.
[0005] The technical solution of the present invention is as follows: 1) first, two soluble salts are selected as metal sources for synthesizing MOFs, and different functionalized ligands are selected. A certain amount of soluble base is added to the mixed solution of metal salts and organic ligands, and a bimetallic MOFs carrier with high crystallinity and high exposure of active sites is synthesized by a solvent thermal method to prepare MOFs carriers with different metal nodes and different functionalized ligands; 2) different types of MOFs carriers are dispersed in a methanol solution by an impregnation method, a certain amount of soluble nickel salt is added, and the mixture is stirred at a certain temperature, and then the mixture is centrifuged, washed and dried to obtain a highly dispersed Ni δ+ MOFs-based catalytic hydrogenation materials.
[0006] A highly dispersed Ni δ+ The preparation method of MOFs-based catalytic hydrogenation material, the specific preparation steps are as follows:
[0007] 1) Preparation of MOFs carrier
[0008] Soluble metal salt, dicarboxylic acid organic ligand and NaOH are dissolved in ultrapure water with the molar ratio of each component being soluble metal salt: dicarboxylic acid organic ligand: NaOH: H2O = 1:1:1~2.5:1~15 to obtain a mixed solution, which is stirred at room temperature and then transferred to an autoclave for reaction at 150-200°C for 15-24h. The green crystalline powder is further purified, centrifuged and washed, and then vacuum dried. Subsequently, high-temperature activation is performed in a muffle furnace to obtain a highly crystalline MOFs support material with a large specific surface area.
[0009] 2) Highly dispersed Ni δ+ Preparation of MOFs-based catalytic hydrogenation materials
[0010] The activated MOFs support was uniformly dispersed in water at 6.5 mg / mL-30 mg / mL and ultrasonically treated until it was highly dispersed. Then, a 3-8 wt% NiCl2·6H2O aqueous solution was added, the two solutions were mixed and stirred, and then a 1.5-2.5 mmol NaBH4 aqueous solution was added and stirred. The solution was then washed with water and methanol by centrifugation and vacuum dried to obtain a highly dispersed Ni δ+ MOFs-based catalytic hydrogenation materials.
[0011] Furthermore, the dicarboxylic acid organic ligand in step 1) includes: H2BDC, BDC-NH2, and BDC-NO2.
[0012] Furthermore, the soluble metal salt described in step 1) is mainly composed of Cr(NO3)3·9H2O, and is configured with any one of Ce(NO3)3·6H2O, Eu(NO3)3·6H2O, Fe(NO3)3·9H2O, and La(NO3)3·6H2O, and the configuration ratio is based on the metal molar ratio Cr:M=2:1, where M is Ce, Eu, Fe, and La, to form a soluble metal salt.
[0013] Furthermore, the stirring time in step 1) is 20-40 minutes to ensure thorough mixing.
[0014] Furthermore, the purified green crystalline powder in step 1) is centrifuged and washed by adding 30-50 mL of N,N-dimethylformamide (DMF) and 30-50 mL of ethanol.
[0015] Furthermore, the vacuum drying in step 1) is carried out at a temperature of 60° C.-80° C. for 10-12 hours.
[0016] Furthermore, the high temperature activation in step 1) is performed by drying at a temperature of 180-220° C. for 5-15 hours.
[0017] Furthermore, in step 2), the stirring after adding NiCl2·6H2O is carried out at a temperature of 20-40°C for 7-9 hours, the stirring time after adding NaBH4 is 1-2 hours, and the vacuum drying is carried out at 60-80°C for 10-12 hours.
[0018] The highly dispersed Ni δ+ The MOFs-based catalytic hydrogenation material has a bimetallic node and a -NH2 functionalized ligand-coordinated MOFs-anchored highly dispersed Ni δ+ active site, named Ni@CeMIL-101-NH2.
[0019] A highly dispersed Ni δ+ Application of MOFs-based catalytic hydrogenation materials in the hydrogenation of unsaturated olefins / alkynes fuels.
[0020] Catalytic hydrogenation experiments were carried out in a stainless steel sealed autoclave. The reaction substrate, cyclohexane (solvent) and a certain amount of active catalyst were loaded into the autoclave. N2 entered the sealed autoclave and then released. This was repeated 2-4 times to remove the air in the reactor. H2 was introduced and the pressure was adjusted to 1-2 MPa. The reactor was stirred and heated to 40-120°C. The reaction time was set to 0.1-2 h and the rotation speed was set to 500-800 r / min.
[0021] Furthermore, the hydrogenation reaction substrate is one of dicyclopentadiene (DCPD), phenylacetylene, styrene, and cyclohexene.
[0022] The advantages of the present invention are: (1) a new catalytic hydrogenation material is developed in which active Ni is anchored by a bimetallic node (CeCr2) and a ligand (BDC-NH2); electrons are transferred from Ce atoms to Ni atoms through bridging O, and -NH2 is an electron-donating group, which has a certain anchoring effect on Ni. The synergistic effect of the two makes the active site Ni have high dispersion; (2) SMSI between the active site Ni and the carrier CeMIL-101-NH2 makes Ni highly dispersed inside the pores, rather than on the surface of the carrier, and is not easily lost or sintered during the hydrogenation reaction, thereby achieving high cycle stability; (3) the raw materials provided by the method of the present invention are cheap and easy to obtain, the process is simple, the reaction conditions are mild, and the cost is low. The electronic and geometric structures of the active site Ni anchored on the bimetallic CeCr2 node and -NH2 are adjustable. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is the XRD pattern of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention.
[0024] Figure 2 This is the FTIR graph of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention.
[0025] Figure 3 This is the N2 adsorption-desorption curve of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention.
[0026] Figure 4 This is the pore structure distribution diagram of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention.
[0027] Figure 5 This is the SEM image of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention.
[0028] Figure 6 This is a performance comparison analysis chart of the DCPD hydrogenation of Ni@CeMIL-101-NH2 prepared in Example 2 of the present invention at 100°C and different reaction times.
[0029] Figure 7 This is a comparative analysis chart of the performance of Ni@CeMIL-101-NH2 prepared in Example 3 of the present invention after hydrogenation of DCPD at different reaction temperatures for 1.5 h.
[0030] Figure 8 This is a cyclic stability analysis diagram of Ni@CeMIL-101-NH2 hydrogenated DCPD prepared in Example 3 of the present invention.
[0031] Figure 9This is a performance analysis diagram of different reaction substrates for hydrogenation of Ni@CeMIL-101-NH2 prepared in Example 4 of the present invention.
[0032] Figure 10 This is a performance comparison chart of DCPD hydrogenation using a catalyst prepared in Comparative Example 1 of the present invention and doped with different metals into a bimetallic node.
[0033] Figure 11 This is a performance comparison chart of DCPD hydrogenation using a Ni-doped catalyst in the MIL-101 carrier prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION
[0034] The technical solution of the present invention is further described below in conjunction with specific implementation methods.
[0035] Example 1
[0036] Cr(NO₃)₃·9H₂O (532 mg, 1.33 mmol), Ce(NO₃)₃·6H₂O (291 mg, 0.67 mmol), BDC-NH₂ (360 mg, 2 mmol), and NaOH (200 mg, 5 mmol) were mixed in ultrapure water (15 mL). The mixture was stirred at room temperature for 20 min and then transferred to a 50 mL Teflon-lined stainless steel autoclave and reacted at 180°C for 20 h. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 8000 rpm for 3 min. This process was repeated three times to remove unreacted BDC-NH₂ from CeMIL-101-NH₂. The residue was then evacuated at 80°C for 12 h. The mixture was then activated at 200°C for 6 h. The activated CeMIL-101-NH2 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added and stirred at 40 ° C for 8 h; 57 mg (1.5 mmol) of NaBH4 aqueous solution (2.5 mL) was added and stirred for 1 h, washed with water and methanol, and centrifuged. Finally, it was dried in vacuum at 80 ° C for 10 h to obtain highly dispersed Ni δ+ MOFs-based catalytic hydrogenation materials.
[0037] DCPD hydrogenation was performed in a sealed 50mL stainless steel autoclave. 200µL of DCPD, 5mL of cyclohexane (solvent), and 20mg of the catalytic hydrogenation material prepared above were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating two to three times to remove air from the reactor. H2 was then introduced, the pressure raised to 2MPa, and the mixture was heated to 80°C with stirring for 1h at a speed of 600rpm. After the reaction, the product was analyzed by gas chromatography-mass spectrometry.
[0038] From Figure 1 It can be seen that the XRD peak of Ni@CeMIL-101-NH2 prepared in Example 1 of the present invention is retained. Figure 2 It can be seen that the highly dispersed Ni δ+ The MOFs-based catalytic hydrogenation materials maintain the coordination bonds of the original MOFs, indicating that the incorporation of Ni has no effect on the CeMIL-101-NH2 framework. Figure 3 It can be seen that Ni@CeMIL-101-NH2 MOFs has a porous structure. Figure 4 It can be seen that Ni@CeMIL-101-NH2 has a microporous structure of 1-2nm and a mesoporous structure of 3-5nm. Figure 5 It can be seen that the overall particle size distribution of Ni@CeMIL-101-NH2 is uniform.
[0039] Example 2
[0040] Cr(NO₃)₃·9H₂O (532 mg, 1.33 mmol), Ce(NO₃)₃·6H₂O (291 mg, 0.67 mmol), BDC-NH₂ (360 mg, 2 mmol), and NaOH (200 mg, 5 mmol) were mixed in ultrapure water (15 mL). The mixture was stirred at room temperature for 30 min and then transferred to a 50 mL Teflon-lined stainless steel autoclave. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 8000 rpm for 3 min. This process was repeated three times to remove unreacted BDC-NH₂ from CeMIL-101-NH₂, and the residue was evacuated at 60°C for 12 h. The mixture was then activated at 180°C for 8 h. Activated CeMIL-101-NH2 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added. The mixture was stirred at 30°C for 8 h. 76 mg (2 mmol) of NaBH4 aqueous solution (2.5 mL) was then added and stirred for 2 h. The product was extracted by centrifugation, washed with water and methanol, and finally dried in vacuo at 100°C.
[0041] DCPD hydrogenation was performed in a sealed 50mL stainless steel autoclave. 200µL of DCPD, 5mL of cyclohexane (solvent), and 20mg of active catalyst were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating two to three times to remove air from the reactor. H2 was then introduced, the pressure raised to 2MPa, and the reaction mixture was heated to 100°C with stirring. The reaction times were set at 0.5, 1, and 1.5 hours, and the speed was set at 600 rpm. After completion of the reaction, the product was analyzed by gas chromatography-mass spectrometry.
[0042] from Figure 6 It can be seen that the DCPD hydrogenation performance of Ni@CeMIL-101-NH2 at different reaction times can reach 99.9% DCPD conversion and 100% tetrahydrodicyclopentadiene (THDCPD) selectivity when the reaction time is 1.5h.
[0043] Example 3
[0044] Cr(NO₃)₃·9H₂O (1064 mg, 2.66 mmol), Ce(NO₃)₃·6H₂O (582 mg, 1.34 mmol), BDC-NH₂ (720 mg, 4 mmol), and NaOH (400 mg, 10 mmol) were mixed in ultrapure water (30 mL). The mixture was stirred at room temperature for 30 min and then transferred to a 100 mL Teflon-lined stainless steel autoclave. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 9000 rpm for 3 min. This process was repeated three times to remove unreacted BDC-NH₂ from CeMIL-101-NH₂, and the residue was evacuated at 80°C for 24 h. The mixture was then activated at 200°C for 6 h. Activated CeMIL-101-NH2 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added. The mixture was stirred at 20°C for 10 h. 76 mg (2 mmol) of NaBH4 aqueous solution (2.5 mL) was then added and stirred for 2 h. The product was extracted by centrifugation, washed with water and methanol, and finally dried in vacuo at 100°C.
[0045] DCPD hydrogenation was carried out in a 50mL stainless steel sealed autoclave. 200uL DCPD, 5mL cyclohexane (solvent), and 20mg of active catalyst were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating 2-3 times to remove air from the reactor. H2 was then introduced, the pressure was adjusted to 2MPa, and the mixture was stirred and heated to 60, 80, and 100°C for 1.5h at a speed of 600r / min. After the reaction, the product was analyzed by gas chromatography-mass spectrometry. Cyclic stability test: After the cyclic reaction, the reactants and catalyst were added to an ethanol solution and centrifuged. The mixture was then dried under vacuum at 80°C overnight before the next reaction.
[0046] from Figure 7 It can be seen that the hydrogenation DCPD performance of Ni@CeMIL-101-NH2 at different reaction temperatures is as follows: when the reaction temperature is 100℃, 99.9% DCPD conversion and THDCPD selection are achieved. Figure 8It can be seen that the cycling stability of Ni@CeMIL-101-NH2 hydrogenation of DCPD and the cycling performance of Ni@CeMIL-101-NH2 catalytic hydrogenation are excellent.
[0047] Example 4
[0048] Cr(NO₃)₃·9H₂O (532 mg, 1.33 mmol), Ce(NO₃)₃·6H₂O (291 mg, 0.67 mmol), H₂BDC-NH₂ (360 mg, 2 mmol), and NaOH (200 mg, 5 mmol) were mixed in ultrapure water (15 mL). The mixture was stirred at room temperature for 30 min and then transferred to a 50 mL Teflon-lined stainless steel autoclave. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 8000 rpm for 3 min. This process was repeated three times to remove unreacted H₂BDC from CeMIL-101-NH₂, and the residue was evacuated at 60°C for 12 h. The mixture was then activated at 200°C for 6 h. Activated CeMIL-101-NH2 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added. The mixture was stirred at 40°C for 8 h. 57 mg (1.5 mmol) of NaBH4 aqueous solution (2.5 mL) was then added and stirred for 1 h. The product was extracted by centrifugation, washed with water and methanol, and finally dried in vacuo at 100°C.
[0049] The reaction was carried out in a sealed 50mL stainless steel autoclave. Phenylacetylene (165µL), styrene (172.5µL), cyclohexene (250µL), 5mL of cyclohexane, and 20mg of the active catalyst were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating two to three times to remove air from the reactor. H2 was then introduced, the pressure raised to 2MPa, and the reaction was heated to 100°C with stirring for 1.5-4h at a speed of 600rpm. After the reaction, the product was analyzed by gas chromatography-mass spectrometry.
[0050] from Figure 9 It can be seen that Ni@CeMIL-101-NH2 has good hydrogenation performance for different reaction substrates.
[0051] Comparative Example 1
[0052] Cr(NO₃)₃·9H₂O (800 mg, 2 mmol), BDC (332 mg, 2 mmol), and NaOH (200 mg, 5 mmol) were mixed in ultrapure water (15 mL). The mixture was stirred at room temperature for 30 min and then transferred to a 50 mL Teflon-lined stainless steel autoclave. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 8000 rpm for 3 min. This process was repeated three times to remove unreacted H₂BDC from MIL-101, and the residue was evacuated at 60°C for 12 h. The mixture was then activated at 200°C for 6 h. Activated MIL-101 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added. The mixture was stirred at 40°C for 8 h. 57 mg (1.5 mmol) of NaBH4 aqueous solution (2.5 mL) was then added and stirred for 1 h. The product was extracted by centrifugation, washed with water and methanol, and finally dried in vacuo at 100°C.
[0053] DCPD hydrogenation was performed in a 50mL sealed stainless steel autoclave. 200µL of DCPD, 5mL of cyclohexane, and 20mg of active catalyst were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating two to three times to remove air from the reactor. H2 was then introduced, and the pressure was raised to 2MPa. The reaction was heated to 100°C with stirring for 1.5 hours at a speed of 600 rpm. After completion of the reaction, the product was analyzed by gas chromatography-mass spectrometry.
[0054] like Figure 11 This is a performance comparison analysis diagram of the single metal Cr-MIL-101-BDC carrier prepared in Comparative Example 1 and then doped with Ni for hydrogenation of DCPD. It can be seen that the catalyst Ni@CeMIL-101-NH2, which is a mixed metal Cr2Ce and has a terephthalic acid ligand of -NH2, can achieve the best performance in catalytic hydrogenation of DCPD.
[0055] Comparative Example 2
[0056] Cr(NO₃)₃·9H₂O (800 mg, 2 mmol), BDC-NH₂ (360 mg, 2 mmol), and NaOH (200 mg, 5 mmol) were mixed in ultrapure water (15 mL). The mixture was stirred at room temperature for 30 min and then transferred to a 50 mL Teflon-lined stainless steel autoclave. The green crystalline powder was further purified by washing with DMF and ethanol, followed by centrifugation at 8000 rpm for 3 min. This process was repeated three times to remove unreacted BDC-NH₂ from MIL-101-NH₂. The residue was then evacuated at 60°C for 12 h. The mixture was then activated at 200°C for 6 h. Activated MIL-101-NH2 (100 mg) was suspended in water (10 mL), and then 22 mg (0.09 mmol) of NiCl2·6H2O aqueous solution (0.5 mL) was added. The mixture was stirred at 40°C for 8 h. 57 mg (1.5 mmol) of NaBH4 aqueous solution (2.5 mL) was then added and stirred for 1 h. The product was extracted by centrifugation, washed with water and methanol, and finally dried in vacuo at 100°C.
[0057] DCPD hydrogenation was performed in a 50mL sealed stainless steel autoclave. 200µL of DCPD, 5mL of cyclohexane, and 20mg of active catalyst were placed in the autoclave. N2 was introduced into the sealed autoclave and then released, repeating two to three times to remove air from the reactor. H2 was then introduced, and the pressure was raised to 2MPa. The reaction was heated to 100°C with stirring for 1.5 hours at a speed of 600 rpm. After completion of the reaction, the product was analyzed by gas chromatography-mass spectrometry.
[0058] like Figure 11 This is a performance comparison analysis diagram of the single metal Cr-MIL-101-NH2 carrier prepared in Comparative Example 2 and then doped with Ni for hydrogenation of DCPD. It can be seen that the mixed metal Cr2Ce catalyst Ni@CeMIL-101-NH2 can achieve the best performance in catalytic hydrogenation of DCPD.
Claims
1. A highly dispersed Ni δ+ A method for preparing a MOFs-based catalytic hydrogenation material, characterized in that: The specific preparation steps are as follows: 1) Preparation of MOFs carrier A soluble metal salt, a dicarboxylic acid organic ligand, and NaOH are dissolved in ultrapure water in a molar ratio of soluble metal salt: dicarboxylic acid organic ligand: NaOH: H2O = 1:1:1-2.5:1-15 to obtain a mixed solution, which is stirred at room temperature and then transferred to an autoclave for reaction at 150-200°C for 15-24 hours. The green crystalline powder is further purified, washed by centrifugation, and then vacuum-dried. Subsequently, the powder is activated at high temperature in a muffle furnace to obtain a highly crystalline MOFs support material with a large specific surface area. 2) Highly dispersed Ni δ+ Preparation of MOFs-based catalytic hydrogenation materials The activated MOFs support was uniformly dispersed in water at 6.5 mg / mL-30 mg / mL and ultrasonically treated until it was highly dispersed. Then, a 3-8 wt% NiCl2·6H2O aqueous solution was added, the two solutions were mixed and stirred, and then a 1.5-2.5 mmol NaBH4 aqueous solution was added and stirred. The solution was then washed with water and methanol by centrifugation and vacuum dried to obtain a highly dispersed Ni δ+ MOFs-based catalytic hydrogenation materials.
2. The preparation method according to claim 1, wherein The dicarboxylic acid organic ligands described in step 1) include: H2BDC, BDC-NH2, and BDC-NO2.
3. The preparation method according to claim 1, wherein The soluble metal salt described in step 1) is mainly composed of Cr(NO3)3·9H2O, and is configured with any one of Ce(NO3)3·6H2O, Eu(NO3)3·6H2O, Fe(NO3)3·9H2O, and La(NO3)3·6H2O, and the configuration ratio is based on the metal molar ratio of Cr:M=2:1, where M is Ce, Eu, Fe, and La.
4. The preparation method according to claim 1, wherein The stirring time in step 1) is 20-40 minutes to ensure that the mixture is fully mixed.
5. The preparation method according to claim 1, wherein The purified green crystalline powder in step 1) is centrifuged and washed by adding 30-50 mL of N,N-dimethylformamide (DMF) and 30-50 mL of ethanol.
6. The preparation method according to claim 1, wherein The vacuum drying in step 1) is carried out at a temperature of 60° C. to 80° C. for 10 to 12 hours.
7. The preparation method according to claim 1, wherein The high temperature activation in step 1) is performed by drying at a temperature of 180-220° C. for 5-15 hours.
8. The preparation method according to claim 1, wherein The stirring after adding NiCl2·6H2O in step 2) is carried out at a temperature of 20-40°C for 7-9 hours, the stirring time after adding NaBH4 is 1-2 hours, and the vacuum drying is carried out at 60-80°C for 10-12 hours.
9. The method according to any one of claims 1 to 8 for obtaining highly dispersed Ni δ+ MOFs-based catalytic hydrogenation material, characterized in that Highly dispersed Ni δ+ The MOFs-based catalytic hydrogenation material has a bimetallic node and a -NH2 functionalized ligand-coordinated MOFs-anchored highly dispersed Ni δ+ active site, named Ni@CeMIL-101-NH2.
10. A highly dispersed Ni δ+ The application of MOFs-based catalytic hydrogenation materials in the hydrogenation of unsaturated olefins / alkynes fuels is characterized in that: A catalytic hydrogenation experiment was carried out in a stainless steel sealed autoclave. The reaction substrate, cyclohexane solvent and a certain amount of active catalyst were loaded into the autoclave. N2 entered the sealed autoclave and then released, repeating 2-4 times to remove air from the reactor. H2 was introduced and the pressure was regulated to 1-2 MPa. The mixture was stirred and heated to 40-120°C. The reaction time was set to 0.1-2 hours and the rotation speed was set to 500-800 r / min. The hydrogenation reaction substrate was one of dicyclopentadiene DCPD, phenylacetylene, styrene, and cyclohexene.