CN108816289B - Preparation method and application of amino functionalized MOFs loaded CrPd nano-catalyst - Google Patents
Preparation method and application of amino functionalized MOFs loaded CrPd nano-catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method and application of amino functionalized MOFs loaded CrPd nano-catalyst, which comprises the following steps: preparing MIL-101 by a hydrothermal method; preparation of MIL-101-NH by post-modification2(ii) a CrPd/MIL-101-NH prepared by dipping-reduction method2And (3) a nano catalyst. The invention can be used as a novel, simple and efficient method to synthesize the supported palladium-based catalyst, and the synthesized catalyst can obtain very good catalytic activity when being applied to the hydrogen production reaction by Formic Acid (FA) decomposition, thereby providing a new way for developing safe and efficient solid catalysts and further promoting the application of FA as a hydrogen storage material in vehicle-mounted fuel cells.
Description
Technical Field
The invention relates to the field of sustainable development of catalysis and energy, in particular to a preparation method and application of amino functionalized MOFs loaded CrPd nano-catalyst.
Background
Energy is a key for human survival and development, and with the rapid development of society, the energy crisis caused by the continuous reduction of fossil fuels and the environmental pollution caused by combustion products of fossil fuels continuously present a serious challenge to the current energy system mainly based on fossil fuels. Development of novel regenerable detergentsClean energy is a necessary trend in the field of energy. Hydrogen energy is popular among people as an ideal clean, safe and efficient secondary energy source. The fuel cell taking hydrogen as a hydrogen source is widely applied to the fields of small portable products, fuel cell automobiles, aerospace and the like. However, low density hydrogen gas is inconvenient to store and transport, thereby restricting the development of fuel cells. Compared with the traditional high-pressure gaseous hydrogen storage and low-temperature liquid hydrogen storage, the hydrogen storage material realizes high storage density and high safety at the same time. Formic acid (HCOOH, FA) is used as a light-weight small-molecule chemical hydrogen storage material, has higher energy density, is stable liquid at room temperature, is easy to fill, and is considered as a chemical hydrogen storage material with huge application potential. Formic acid can generate the required hydrogen and carbon dioxide through dehydrogenation reaction under the action of a catalyst (HCOOH → H)2+CO2) (ii) a It is also possible to generate water and carbon monoxide by dehydration (HCOOH → H)2O + CO). Among them, the dehydrogenation reaction of formic acid is a desirable route, and since CO generated by the dehydration reaction of formic acid easily poisons and deactivates the catalyst, the occurrence of the dehydration reaction of formic acid must be strictly controlled.
At present, the catalysts used for the hydrogen production reaction by formic acid decomposition mainly include homogeneous catalysts and heterogeneous catalysts, wherein the heterogeneous catalysts are widely researched and used due to the advantages of easy control, convenient recovery and the like. In the formic acid dehydrogenation reaction, the noble metal (such as Pd and Au) nano material has higher catalytic activity on the hydrogen production reaction of FA, but the cost of the catalyst can be reduced by partially replacing the noble metal with non-noble metal in consideration of the limited resource and expensive price of the noble metal; meanwhile, the synergistic effect of two or three metals in the binary or ternary nano material catalyst can effectively improve the reaction activity. However, the catalytic performance of most of the prior non-noble metal-containing catalysts for FA hydrogen production still has a great promotion space and does not meet the requirements of practical application.
In addition, the catalytic performance of the metal nano material is closely related to the dispersion degree, the particle size, the specific surface area and the electronic characteristic of the metal nano material besides the element composition of the metal nano material. Because the nanometer metal particles with high surface energy are easy to agglomerate in the reaction process, the concentration of the reaction active site is reduced, and the catalytic performance of the nanometer metal particles is restricted to a great extent, so that the selection of a proper catalyst carrier becomes an effective method for obtaining the nanometer catalyst with uniform and fine particle size and high dispersibility. Compared with a plurality of carrier materials, the Metal Organic Frameworks (MOFs) as a porous coordination polymer has the advantages of high specific surface area, chemical compatibility and the like, and is easy to perform functional modification by post-treatment or ligand design and other methods. The modified MOFs can further improve the dispersibility of the metal nano-catalyst and simultaneously improve the electronic structure of the metal nano-catalyst through the interaction of the functional group and the metal nano-catalyst, thereby improving the catalytic performance of the functional MOFs-based compound.
In view of the above, it is necessary to find a simple and effective method for synthesizing a supported heterogeneous catalyst with high efficiency, high selectivity, low cost and good dispersibility to improve the FA dehydrogenation reaction efficiency.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of an amino functionalized MOFs loaded CrPd nano-catalyst.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
the preparation method of the amino functionalized MOFs supported CrPd nano-catalyst comprises the following steps:
s1, preparing MIL-101 by a hydrothermal method;
s2 preparation of MIL-101-NH by post-modification using the MIL-101 obtained2;
S3, use of the MIL-101-NH thus obtained2CrPd/MIL-101-NH prepared by dipping-reduction method2And (3) a nano catalyst.
Further, the step S1 specifically includes:
s11, adding 0.3mL of HF with the weight percent of 40% into 28.8mL of deionized water, and uniformly stirring; c with a molar ratio of 1:18H6O4And Cr (NO)3)3·9H2O is uniformly dispersed in the solutionThen placing the mixture into a reaction kettle, heating the mixture for 8 hours at 473K, and naturally cooling the mixture to room temperature;
s12, washing the obtained product with ethanol for several times, and dissolving NH with the concentration of 1M4Soaking the mixture in an aqueous solution of F for 24 hours at 343K, repeatedly centrifuging and washing the soaked solution, and finally drying the soaked solution overnight in a vacuum environment at 423K to obtain green MIL-101.
Further, the step S2 specifically includes:
s21, first add 100mg MIL-101 to 5mL HNO3And 7mL of H2SO4Stirring the mixed solution for 5 hours in an ice bath, adding 50mL of ice blocks into the solution, and washing with water and ethanol for 2 times to obtain MIL-101-NO2;
S22, adding 3.26g SnCl2And 100mg of MIL-101-NO2Adding the mixture into 20mL of ethanol, stirring for 6h at 343K, adding solid powder obtained after centrifugation into HCl solution, performing ultrasonic treatment for 20-30 min, filtering, repeatedly washing with water and ethanol, and drying overnight in 423K vacuum environment to obtain yellowish green MIL-101-NH2。
Further, the step S3 specifically includes:
s31, mixing 40mg of MIL-101-NH2Dissolving in 10mL of deionized water, and performing ultrasonic treatment for 40min to obtain a solution A;
s32 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution; 0.06mmol of Na is taken2PdCl4Aqueous solution and 0.04mmol of Cr (NO)3)3·9H2Adding O into the solution A, and stirring for 2 hours at room temperature to obtain a mixed solution B;
s33, mixing 30-50 mg NaBH4Adding the reducing agent into the mixed solution B, and continuously stirring and reducing to obtain a mixed solution C;
s34, magnetically stirring and reducing the mixed solution C in the air at room temperature, centrifuging at 8000-12000 rpm for 3-10 min when no bubbles exist, and washing for 3 times to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
Further, NaBH is used in the S334The temperature for reduction is room temperature, and the reduction time is 10-30 min.
Further, CrPd/MIL-101-NH obtained in the step S342In the nano catalyst, binary alloy CrPd Nano Particles (NPs) are in MIL-101-NH2The particle size of the particles is 2.5-3.0 nm.
In addition, the application of the amino-functionalized MOFs-loaded CrPd nano-catalyst prepared by the invention is used for catalyzing FA solution to decompose and produce hydrogen, and specifically, CrPd/MIL-101-NH is adopted2Mixing the nano-catalyst and FA at a molar ratio of 0.02, wherein the FA solution has a concentration of 1M, and can generate 225mL of gas at 323K in 7.5 min, and the initial conversion frequency (TOF) isThe conversion rate is 100%; the hydrogen selectivity was 100%.
Compared with the prior art, the invention firstly adopts the dipping-reduction method to successfully synthesize the amino-functionalized MIL-101-loaded CrPd NPs, can be completed at room temperature, has the advantages of rapid and efficient synthesis process, simple and convenient operation and the like, and obviously improves the stability of the CrPd NPs in the MIL-101-NH2Dispersion on the substrate and reduction of the particle size of the metallic NPs; the synthesized CrPd/MIL-101-NH2The nano catalyst is applied to catalyzing FA aqueous solution to decompose and prepare hydrogen, the catalyst still shows excellent catalytic performance under the condition of no existence of any additive, 225mL of gas can be generated within 7.5 minutes at 323K, and the initial conversion frequency (TOF) isThe conversion rate is 100%; the hydrogen selectivity was 100%. The amino functionalized MOFs is used as a substrate, so that on one hand, the agglomeration of a catalyst active component CrPd NPs is effectively inhibited, and uniform and fine metal NPs are obtained, thereby obtaining high-concentration reaction active sites; on the other hand a functional group-NH2The high concentration of pyridine N in the catalyst can provide more electrons for the active atoms of the catalyst, thereby obtaining high electricityThe active atoms of the catalyst with the sub-density further obviously improve the activity of the catalyst.
For review, the invention can be used as a novel, simple and efficient method to synthesize the supported palladium-based catalyst, and the synthesized catalyst can obtain very good catalytic activity when being applied to FA decomposition hydrogen production reaction, thereby providing a new way for developing safe and efficient solid catalysts and further promoting the application of FA as a hydrogen storage material in vehicle-mounted fuel cells.
Drawings
FIG. 1 shows CrPd/MIL-101-NH in example 12Transmission electron micrographs of the nanocatalyst at (a) low magnification and (b) high magnification, wherein: the inset is the particle size distribution histogram of the CrPd nanoparticles. (c) The CrPd/MIL-101 in comparative example 1 and the CrPd/MIL-101-NH in example 12X-ray diffraction pattern of (a);
FIG. 2(a) is CrPd/MIL-101-NH in example 12An X-ray photoelectron spectrum of N1 s of the catalyst; (b) the CrPd, CrPd/MIL-101 in comparative example 1 and CrPd/MIL-101-NH in example 12An X-ray photoelectron spectrum of Pd 3 d;
FIG. 3(a) is CrPd/MIL-101-NH in example 12And the hydrogen production curve of the CrPd and CrPd/MIL-101 catalysts in the comparative example 1 catalyzing FA aqueous solution at 323K, (b) the three catalysts of (a) correspond to the initial conversion frequency of the catalytic reaction, and (c) the CrPd/MIL-101-NH of the comparative example 22A hydrogen production curve diagram of the catalytic FA aqueous solution at different temperatures, and (d) is CrPd/MIL-101-NH obtained by fitting the data in (c)2An arrhenius curve of the reaction for catalyzing FA to decompose and produce hydrogen.
Fig. 4 is a transmission electron micrograph of the catalyst prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to specific examples, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
The preparation method of the amino functionalized MOFs supported CrPd nano-catalyst comprises the following steps:
s1, preparing MIL-101 by a hydrothermal method:
s11, adding 0.3mL of HF with the weight percent of 40% into 28.8mL of deionized water, and uniformly stirring; c with a molar ratio of 1:18H6O4And Cr (NO)3)3·9H2Uniformly dispersing O in the solution, putting the solution into a reaction kettle, heating the solution for 8 hours at 473K, and naturally cooling the solution to room temperature;
s12, washing the obtained product with ethanol for several times, and dissolving NH with the concentration of 1M4Soaking the mixture in an F aqueous solution for 24 hours at 343K, repeatedly centrifuging and washing the soaked solution, and finally drying the soaked solution overnight in a vacuum environment at 423K to obtain green MIL-101;
s2 preparation of MIL-101-NH by post-modification using the MIL-101 obtained2:
S21, first add 100mg MIL-101 to 5mL HNO3And 7mL of H2SO4Stirring the mixed solution for 5 hours in an ice bath, adding 50mL of ice blocks into the solution, and washing with water and ethanol for 2 times to obtain MIL-101-NO2;
S22, adding 3.26g SnCl2And 100mg of MIL-101-NO2Adding into 20mL ethanol, stirring for 6h at 343K, centrifuging to obtain solid powder, adding into HCl solution, ultrasonic treating for 20min, filtering, repeatedly washing with water and ethanol, and drying overnight at 423K under vacuum to obtain yellow-green MIL-101-NH2;
S3, use of the MIL-101-NH thus obtained2CrPd/MIL-101-NH prepared by dipping-reduction method2Nano-catalyst:
s31, mixing 40mg of MIL-101-NH2Dissolving in 10mL of deionized water, and performing ultrasonic treatment for 40min to obtain a solution A;
s32 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution; 0.06mmol of Na is taken2PdCl4Aqueous solution and 0.04mmol of Cr (NO)3)3·9H2Adding of OAdding the mixture into the solution A, and stirring for 2 hours at room temperature to obtain a mixed solution B;
s33, mixing 50mg NaBH4Adding the reducing agent into the mixed solution B, and continuously stirring at room temperature to obtain a mixed solution C;
s34, magnetically stirring and reducing the mixed solution C in the air at room temperature, centrifuging at 8000rpm for 3min when no air bubbles exist, and washing with water for 3 times to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
Example 2
The preparation method of the amino functionalized MOFs supported CrPd nano-catalyst comprises the following steps:
s1, preparing MIL-101 by a hydrothermal method:
s11, adding 0.3mL of HF with the weight percent of 40% into 28.8mL of deionized water, and uniformly stirring; c with a molar ratio of 1:18H6O4And Cr (NO)3)3·9H2Uniformly dispersing O in the solution, putting the solution into a reaction kettle, heating the solution for 8 hours at 473K, and naturally cooling the solution to room temperature;
s12, washing the obtained product with ethanol for several times, and dissolving NH with the concentration of 1M4Soaking the mixture in an F aqueous solution for 24 hours at 343K, repeatedly centrifuging and washing the soaked solution, and finally drying the soaked solution overnight in a vacuum environment at 423K to obtain green MIL-101;
s2 preparation of MIL-101-NH by post-modification using the MIL-101 obtained2:
S21, first add 100mg MIL-101 to 5mL HNO3And 7mL of H2SO4Stirring the mixed solution for 5 hours in an ice bath, adding 50mL of ice blocks into the solution, and washing with water and ethanol for 2 times to obtain MIL-101-NO2;
S22, adding 3.26g SnCl2And 100mg of MIL-101-NO2Adding into 20mL ethanol, stirring for 6h at 343K, centrifuging to obtain solid powder, adding into HCl solution, ultrasonic treating for 30min, filtering, repeatedly washing with water and ethanol, and drying overnight at 423K under vacuum to obtain yellow-green MIL-101-NH2;
S3, use of the MIL-101-NH thus obtained2CrPd/MIL-101-NH prepared by dipping-reduction method2Nano-catalyst:
s31, mixing 40mg of MIL-101-NH2Dissolving in 10mL of deionized water, and performing ultrasonic treatment for 40min to obtain a solution A;
s32 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution; 0.06mmol of Na is taken2PdCl4Aqueous solution and 0.04mmol of Cr (NO)3)3·9H2Adding O into the solution A, and stirring for 2 hours at room temperature to obtain a mixed solution B;
s33, mixing 50mg NaBH4Adding the reducing agent into the mixed solution B, and continuously stirring at room temperature to obtain a mixed solution C;
s34, magnetically stirring and reducing the mixed solution C in the air at room temperature, centrifuging at 12000rpm for 10min when no air bubbles exist, and washing with water for 3 times to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
Example 3
The preparation method of the amino functionalized MOFs supported CrPd nano-catalyst comprises the following steps:
s1, preparing MIL-101 by a hydrothermal method:
s11, adding 0.3mL of HF with the weight percent of 40% into 28.8mL of deionized water, and uniformly stirring; c with a molar ratio of 1:18H6O4And Cr (NO)3)3·9H2Uniformly dispersing O in the solution, putting the solution into a reaction kettle, heating the solution for 8 hours at 473K, and naturally cooling the solution to room temperature;
s12, washing the obtained product with ethanol for several times, and dissolving NH with the concentration of 1M4Soaking the mixture in an F aqueous solution for 24 hours at 343K, repeatedly centrifuging and washing the soaked solution, and finally drying the soaked solution overnight in a vacuum environment at 423K to obtain green MIL-101;
s2 preparation of MIL-101-NH by post-modification using the MIL-101 obtained2:
S21, first, 100mg of MIL-101 to 5mL of HNO3And 7mL of H2SO4Stirring the mixed solution for 5 hours in an ice bath, adding 50mL of ice blocks into the solution, and washing with water and ethanol for 2 times to obtain MIL-101-NO2;
S22, adding 3.26g SnCl2And 100mg of MIL-101-NO2Adding into 20mL ethanol, stirring for 6h at 343K, centrifuging to obtain solid powder, adding into HCl solution, ultrasonic treating for 25min, filtering, repeatedly washing with water and ethanol, and drying overnight at 423K under vacuum to obtain yellow-green MIL-101-NH2;
S3, use of the MIL-101-NH thus obtained2CrPd/MIL-101-NH prepared by dipping-reduction method2Nano-catalyst:
s31, mixing 40mg of MIL-101-NH2Dissolving in 10mL of deionized water, and performing ultrasonic treatment for 40min to obtain a solution A;
s32 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution; 0.06mmol of Na is taken2PdCl4Aqueous solution and 0.04mmol of Cr (NO)3)3·9H2Adding O into the solution A, and stirring for 2 hours at room temperature to obtain a mixed solution B;
s33, mixing 40mg NaBH4Adding the reducing agent into the mixed solution B, and continuously stirring at room temperature to obtain a mixed solution C;
s34, magnetically stirring and reducing the mixed solution C in the air at room temperature, centrifuging at 10000rpm for 8min when no air bubbles exist, and washing with water for 3 times to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
Sample detection
CrPd/MIL-101-NH prepared in example 12Dissolving the nano catalyst into a proper amount of deionized water for dilution, uniformly dispersing by ultrasonic, dripping 1-2 drops of the diluted solution onto a copper net, and carrying out observation and analysis by a Transmission Electron Microscope (TEM). Then the prepared CrPd/MIL-101-NH is added2The catalyst was dried in vacuum and subjected to X-ray powder diffraction (XRD) analysis, and referring to fig. 1, the analysis results showed that,the experimental method successfully synthesizes MIL-101-NH2The supported CrPd binary alloy catalyst has CrPd NPs uniformly dispersed in MIL-101-NH2The size of the particle diameter in the framework is about 2.5-3.0 nm. In addition, the CrPd/MIL-101-NH prepared in example 1 was used2Vacuum drying the nano-catalyst, taking appropriate amount of dried powder to perform X-ray photoelectron spectroscopy (XPS) detection, referring to FIG. 2, and the detection result shows that CrPd/MIL-101-NH2Pyridine N on the surface of the sample accounts for 72.93 percent of N element; compared with CrPd and CrPd/MIL-101, the functional group is-NH2Resulting in an increase in the electron density of Pd.
CrPd/MIL-101-NH prepared in example 12The nano catalyst is used for catalyzing FA solution to decompose and produce hydrogen: CrPd/MIL-101-NH2The catalyst and FA were mixed at a molar ratio of 0.02, wherein the concentration of FA solution was 1M, and the produced gas was measured by a gas burette at 323K, CrPd/MIL-101-NH2The gas production (mL) and time (min) of the process for producing hydrogen by catalyzing FA aqueous solution by the nano catalyst are shown in (a) in fig. 3, the gas production (225 mL) in 7.5 minutes can be achieved by catalyzing FA to decompose and produce hydrogen, and the initial conversion frequency (TOF) is(as shown in fig. 3 b), the conversion rate reaches 100%.
Comparative example 1
Preparing MIL-101 by hydrothermal method, adding 0.04mmol Cr (NO)3)3And 0.06mmol of Na2PdCl4Dissolving in aqueous solution containing 40mg of MIL-101, and stirring; 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing with water, and obtaining the CrPd/MIL-101 nano catalyst. Adding 0.04mmol of Cr (NO)3)3And 0.06mmol of Na2PdCl4Dissolved in an appropriate amount of deionized water, 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing with water, and obtaining the CrPd catalyst.
Dispersing the CrPd/MIL-101 nano catalyst and the CrPd catalyst into water, and then adding 5mmol of FA and the amount of gas produced was measured by a gas burette. At 323K, the gas production (mL) and time (min) of the hydrogen production process by catalyzing FA with the CrPd/MIL-101 nano catalyst and the CrPd catalyst are shown in (a) in figure 3, and the initial conversion frequency (TOF) of hydrogen production by catalyzing FA hydrolysis is respectively (as shown in fig. 3 b).
Comparative example 2
Preparing MIL-101 by hydrothermal method, and preparing MIL-101-NH by post-modification method20.04mmol of Cr (NO)3)3And 0.06mmol of Na2PdCl4Dissolving in solution containing 40mg of MIL-101-NH2Stirring the mixture evenly in the aqueous solution of (1); 40mg of NaBH4Adding into the above solution, and magnetically stirring at 25 deg.C to completely reduce; centrifuging, washing to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
CrPd/MIL-101-NH2The nanocatalyst was dispersed in water, 5mmol of formic acid was added, and the hydrogen produced was measured by a gas burette. The reaction temperature was varied and the CrPd/MIL-101-NH at 303, 313, 323 and 333K was recorded2The relationship between the gas production (mL) and the time (min) in the FA hydrogen production process catalyzed by the nano catalyst is drawn as shown in (c) in figure 3, and the data in figure 3c are fitted to obtain CrPd/MIL-101-NH2The activation energy of the catalytic FA decomposition hydrogen production reaction was 43.5kJ/mol (as shown in FIG. 3 d).
FIG. 4 is TEM photographs of CrPd/MIL-101 and CrPd nanocatalyst prepared in comparative example 1, (a) CrPd/MIL-101, and (b) CrPd. As can be seen from the figure, CrPdNPs in the CrPd/MIL-101 nano catalyst are uniformly distributed on the MIL-101 carrier, the average particle size is about 9.5-10nm, and the particle distribution is sparser; and obvious agglomeration phenomenon appears in CrPd NPs.
In summary, the invention adopts the dipping-reduction method to successfully synthesize the amino-functionalized MIL-101 loaded CrPdNPs, can be completed at room temperature, and has the advantages of rapid synthesis processHigh efficiency, simple operation and the like, and obviously improves the CrPd NPs in MIL-101-NH2Dispersion on the substrate and reduction of the particle size of the metallic NPs; the synthesized CrPd/MIL-101-NH2The nano catalyst is applied to catalyzing FA aqueous solution to decompose and prepare hydrogen, the catalyst still shows excellent catalytic performance under the condition of no existence of any additive, 225mL of gas can be generated within 7.5 minutes at 323K, and the initial conversion frequency (TOF) is The conversion rate is 100%; the hydrogen selectivity was 100%. The amino functionalized MOFs is used as a substrate, so that on one hand, the agglomeration of a catalyst active component CrPd NPs is effectively inhibited, and uniform and fine metal NPs are obtained, thereby obtaining high-concentration reaction active sites; on the other hand a functional group-NH2The high-concentration pyridine N contained in the catalyst can provide more electrons for the active atoms of the catalyst, so that the active atoms of the catalyst with high electron density are obtained, and the activity of the catalyst is obviously improved.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (5)
1. The preparation method of the amino functionalized MOFs supported CrPd nano-catalyst is characterized by comprising the following steps:
s1, preparing MIL-101 by a hydrothermal method;
s11, adding 0.3mL of HF with the weight percent of 40% into 28.8mL of deionized water, and uniformly stirring to form a solution; c with a molar ratio of 1:18H6O4And Cr (NO)3)3·9H2Uniformly dispersing O into the solution, putting into a reaction kettle, heating at 473K for 8h, and naturally cooling to room temperature;
s12, washing the obtained product with ethanol for several times, and dissolving the product into the solution with the concentration of 1NH of M4Soaking the mixture in an F aqueous solution for 24 hours at 343K, repeatedly centrifuging and washing the soaked solution, and finally drying the soaked solution overnight in a vacuum environment at 423K to obtain green MIL-101;
s2 preparation of MIL-101-NH by post-modification using the MIL-101 obtained2;
S21, first add 100mg MIL-101 to 5mL HNO3And 7mL of H2SO4Stirring the mixed solution for 5 hours in an ice bath, adding 50mL of ice blocks into the solution, and washing with water and ethanol for 2 times to obtain MIL-101-NO2;
S22, adding 3.26g SnCl2And 100mg of MIL-101-NO2Adding the mixture into 20mL of ethanol, stirring for 6h at 343K, adding solid powder obtained after centrifugation into HCl solution, performing ultrasonic treatment for 20-30 min, filtering, repeatedly washing with water and ethanol, and drying overnight in 423K vacuum environment to obtain yellowish green MIL-101-NH2;
S3, use of the MIL-101-NH thus obtained2CrPd/MIL-101-NH prepared by dipping-reduction method2A nano-catalyst;
s31, mixing 40mg of MIL-101-NH2Dissolving in 10mL of deionized water, and performing ultrasonic treatment for 40min to obtain a solution A;
s32 PdCl with the molar ratio of 1:22Dissolving NaCl in distilled water, and stirring to obtain brown yellow Na with concentration of 0.025M2PdCl4An aqueous solution; 0.06mmol of Na is taken2PdCl4Aqueous solution and 0.04mmol of Cr (NO)3)3·9H2Adding O into the solution A, and stirring for 2 hours at room temperature to obtain a mixed solution B;
s33, mixing 30-50 mg NaBH4Adding the reducing agent into the mixed solution B, and continuously stirring and reducing to obtain a mixed solution C;
s34, magnetically stirring and reducing the mixed solution C in the air at room temperature, centrifuging at 8000-12000 rpm for 3-10 min when no bubbles exist, and washing for 3 times to obtain CrPd/MIL-101-NH2And (3) a nano catalyst.
2. The process for the preparation of amino functionalized MOFs supported CrPd nanocatalysts according to claim 1, characterized in that: NaBH is used in the S334The temperature for reduction is room temperature, and the reduction time is 10-30 min.
3. The process for the preparation of amino functionalized MOFs supported CrPd nanocatalysts according to claim 1, characterized in that: CrPd/MIL-101-NH obtained in S342In the nano catalyst, binary alloy CrPd Nano Particles (NPs) are in MIL-101-NH2The particle size of the particles is 2.5-3.0 nm.
4. Use of amino functionalized MOFs-supported CrPd nanocatalysts according to any of claims 1 to 3, characterized in that: used for catalyzing FA solution to decompose and produce hydrogen.
5. The application of amino functionalized MOFs supported CrPd nanocatalyst according to claim 4, which is characterized by comprising the following specific steps: according to CrPd/MIL-101-NH2The nanocatalyst and FA were mixed at a molar ratio of 0.02, wherein the concentration of the FA solution was 1M.
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