A triazole-based polymer colloid composite catalyst, its preparation method and application

Abstract

The present invention relates to a triazole-based polymer colloid composite catalyst, a preparation method thereof, and an application thereof. The composite catalyst is a metal nanoparticle supported by a 1,2,4-triazole-based polymer colloid. For the first time, the present invention successfully loads HEA-NPs at room temperature through the interaction between polycarbene sites and metals. The obtained catalyst system has good performance in stabilizing alloy metal nanoparticles and exhibits excellent catalytic performance in the dehydrogenation reaction of ammonia borane. The process adopted in the present invention is simple, the equipment is simple, the operation is simple, the conditions are mild, and the catalyst is easy to separate and recycle.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and particularly relates to a triazole-based polymer colloid composite catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] With the increasing energy demand and the increasingly serious environmental pollution, solving the energy and environmental problems has become one of the major challenges for countries around the world. Catalysis can not only promote the development and utilization of clean new energy (such as solar energy, hydrogen energy), realize the recycling of waste water, waste gas and waste, but also most of the reactions in the production process of chemical and chemical products are catalytic conversion reactions. It can be said that catalysis has become the key to the sustainable development of energy, chemical industry and environment, and the core of catalytic reaction is the catalyst. Therefore, it is crucial to develop green, efficient and stable catalysts.

[0003] However, at present, the production capacity, production quality and variety of catalysts in China cannot keep up with the demand gap. To meet the various demands of the industrial circle in China for the quality, performance, production capacity and variety of catalysts, and also to form the ability of import substitution, it is necessary to vigorously research and develop newer, more efficient and recyclable catalysts. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a triazole-based polymer colloid composite catalyst, a preparation method thereof, and an application thereof.

[0005] A triazole-based polymer colloid composite catalyst of the present invention, wherein the composite catalyst is a 1,2,4-triazole-based polymer colloid loaded with metal nanoparticles.

[0006] The structural formula of the 1,2,4-triazole-based polymer is where n = 50 - 150; the metal nanoparticles include one or several of Au, Pt, Re, Ir, Os, Pd, Rh nanoparticles, or include alloy nanoparticles of at least two of Au, Pt, Re, Ir, Os, Pd, Rh.

[0007] Preferably, the R is pentyl, heptyl or nonyl; the metal nanoparticles contain alloy nanoparticles of at least five of Re, Os, Ir, Pt, Au.

[0008] Furthermore, a 1,2,4-triazole-based polymer colloid room-temperature loaded high-entropy alloy nanoparticle (HEA-NPs) catalyst, wherein the 1,2,4-triazole-based polymer is poly(1-vinyl-4-pentyl-1,2,4-triazole) (Ptriaz-C5), and the metal composition of the HEA-NPs includes (Re, Os, Ir, Pt, Au).

[0009] Further preferably, the metal nanoparticles are Re, Os, Ir, Pt, Au five - element alloy nanoparticles (the mass ratio of Au, Pt, Re, Ir, Os is 2.5 - 5:0.84 - 3.35:1.25 - 5:1.25 - 5:0.65 - 2.5); Re, Os, Ir, Pt, Au, Pd six - element alloy nanoparticles (where the mass ratio of Au, Pt, Re, Ir, Os, Pd is 2.5 - 5:0.84 - 3.35:0.25 - 2.5:1.25 - 5:0.65 - 2.5:0.65 - 2.5) or Re, Os, Ir, Pt, Au, Rh six - element alloy nanoparticles (the mass ratio of Au, Pt, Re, Ir, Os, Rh is 2.5 - 5:0.84 - 3.35:0.25 - 2.5:1.25 - 5:0.65 - 2.5:0.65 - 2.5).

[0010] As described in 1, the structural formula of the HEA - NPs catalyst (HEA - NPs@Ptriaz - C5) supported by 1,2,4 - triazolyl polymer colloid is:

[0011]

[0012] The preparation method of the 1,2,4 - triazolyl polymer colloid includes: mixing 1 - vinyl - 4 - alkyl - 1,2,4 - triazolium ionic liquid, azobisisobutyronitrile AIBN, and a solvent under a protective gas condition, heating in an oil bath at 60 - 80 °C, stirring and reacting for 24 - 48 h, purifying, and drying.

[0013] The alkyl group in the 1 - vinyl - 4 - alkyl - 1,2,4 - triazolium ionic liquid is pentyl, heptyl, or nonyl; the solvent is N,N - dimethylformamide DMF; the ratio of the 1 - vinyl - 4 - alkyl - 1,2,4 - triazolium ionic liquid, AIBN, and the solvent is 2.5 - 5 g:40 - 80 mg:25 - 50 mL.

[0014] The stirring is: magnetic stirring, and the stirring speed is 300 r / min - 400 r / min.

[0015] Further, the ratio of the 1 - vinyl - 4 - pentyl - 1,2,4 - triazolium ionic liquid, AIBN, and the solvent is 5 g:80 mg:50 mL.

[0016] The structural formula of the 1 - vinyl - 4 - pentyl - 1,2,4 - triazolium ionic liquid is:

[0017]

[0018] The purification is to place the free radical polymerization product in a dialysis bag, and place the dialysis bag containing the product in a container (>1L) filled with water. Change the water every 4 hours, and dialyze for 4 - 8 days according to this method, and then filter by suction with a water-based filter membrane.

[0019] The vacuum drying is specifically as follows: at a temperature of 40 °C, dry for 12 - 24 hours.

[0020] A preparation method of a triazole-based polymer colloid composite catalyst of the present invention includes:

[0021] Physically mix 1,2,4-triazole-based polymer colloid with a metal precursor, load the metal precursor mixture onto this colloid by physical impregnation method, and add NaBH4 for in-situ reduction to obtain it.

[0022] A preparation method of a triazole-based polymer colloid composite catalyst of the present invention includes:

[0023] Mix the metal precursor solution and 1,2,4-triazole-based polymer colloid solution, stir at room temperature, and then add NaBH4 for in-situ reduction to obtain a triazole-based polymer colloid composite catalyst.

[0024] The preferred manner of the above preparation method is as follows:

[0025] The metal precursor includes one or several of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, chloroiridic acid hydrate, potassium hexachloroiridate, palladium chloride, rhodium chloride; the solvent of the metal precursor solution is methanol, and the concentration is 10 mg / mL; the solvent of the 1,2,4-triazole-based polymer colloid solution is CHCl2 and CH3OH, where V CHCl2 :V CH3OH =2:1 - 4:1, and the addition amount of NaBH4 is 1 - 2 times the total mass of the added metals;

[0026] The stirring at room temperature is in a shaker, with a rotation speed of 300 r - 400 r / min and oscillation for 40 - 50 min; the in-situ reduction is specifically: in a shaker, oscillate at room temperature for 10 - 20 min, and the oscillation rate is 300 r - 400 r / min.

[0027] Preferably, the metal precursor is a five-element metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, chloroiridic acid hydrate and potassium hexachloroiridate, or a six-element metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, chloroiridic acid hydrate, potassium hexachloroiridate and palladium chloride; or a six-element metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, chloroiridic acid hydrate, potassium hexachloroiridate and rhodium chloride: or a seven-element metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, chloroiridic acid hydrate, potassium hexachloroiridate, palladium chloride and rhodium chloride;

[0028] Further preferably, the addition amount ratio of the quinary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridic acid hydrate and potassium hexachloroosmate to the 1,2,4-triazolyl polymer is: 250 - 500 μl (containing 2.5 - 5 mg of Au): 84 - 335 μl (containing 0.84 - 3.35 mg of Pt): 125 - 500 μl (containing 1.25 - 5 mg of Re): 125 - 500 μl (containing 1.25 - 5 mg of Ir): 65 - 500 μl (containing 0.65 mg - 2.5 mg of Os): 12.5 - 50 mg; the addition amount ratio of the hexary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridic acid hydrate, potassium hexachloroosmate and palladium chloride to the 1,2,4-triazolyl polymer is: 250 - 500 μl (containing 2.5 - 5 mg of Au): 84 - 335 μl (containing 0.84 - 3.35 mg of Pt): 25 - 250 μl (containing 0.25 - 2.5 mg of Re): 125 - 500 μl (containing 1.25 - 5 mg of Ir): 65 - 250 μl (containing 0.65 mg - 2.5 mg of Os): 65 - 250 μl (containing 0.65 - 2.5 mg of Pd): 12.5 - 50 mg; the addition amount ratio of the hexary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridic acid hydrate, potassium hexachloroosmate and rhodium chloride to the 1,2,4-triazolyl polymer is: 250 - 500 μl (containing 2.5 - 5 mg of Au): 84 - 335 μl (containing 0.84 - 3.35 mg of Pt): 25 - 250 μl (containing 0.25 - 2.5 mg of Re): 125 - 500 μl (containing 1.25 - 5 mg of Ir): 65 - 250 μl (containing 0.65 mg - 2.5 mg of Os): 65 - 250 μl (containing 0.65 - 2.5 mg of Rh): 12.5 - 50 mg.

[0029] Application of a triazolyl polymer colloid composite catalyst of the present invention in an alcoholysis reaction.

[0030] The 1,2,4-triazolyl polymer colloid described in the present invention is prepared by a simple radical polymerization reaction. Then, at room temperature, a method of physical impregnation and in-situ reduction with sodium borohydride (NaBH4) is adopted, and through the anchoring effect of the "polycarbene site", high-entropy alloy nanoparticles can be stably loaded on the 1,2,4-triazolyl polymer colloid, making it have good applications in the field of organic catalysis. For the first time in the present invention, HEA-NPs are successfully loaded at room temperature through the interaction between the polycarbene site and the metal. The obtained catalyst system has good performance in stabilizing alloy metal nanoparticles and exhibits excellent catalytic performance in the dehydrogenation reaction of ammonia borane. The process adopted in the present invention is simple in technology, simple in equipment, simple in operation, mild in conditions, and the catalyst is easy to separate and recycle.

[0031] The present invention provides a simple method for stably loading HEA-NPs at room temperature and atmospheric pressure with a 1,2,4-triazolyl polymer colloid as the carrier, overcoming the defects of complex operation and harsh preparation conditions (high temperature or high pressure) in the prior art for preparing HEA-NPs. The HEA-NPs catalyst prepared in the present invention has an ideal catalytic effect, good catalytic stability, and is easy to separate and recycle.

[0032] Beneficial effects

[0033] (1) For the first time in the present invention, HEA-NPs are successfully and stably loaded at room temperature and atmospheric pressure with a triazolyl polymer colloid as the carrier;

[0034] (2) The HEA-NPs catalyst prepared in the present invention has good catalytic activity for the dehydrogenation reaction of ammonia borane, which is at a relatively high level currently; and the catalyst can be separated and recycled by centrifugation;

[0035] (3) The preparation method in the present invention is simple, the preparation conditions are mild, the process is simple, the equipment is simple, and the operation is simple. Description of the Drawings

[0036] Figure 1 is the synthesis route diagram of HEA-NPs@Ptriaz;

[0037] Figure 2 is the comparison diagram of XPS (N 1s) curves of Ptriaz polymer colloid before and after loading metals;

[0038] Figure 3 The curves 1, 2, and 3 in represent the ultraviolet curves of Ptriaz colloid, Ptriaz colloid loaded with HEA metal precursor (Example 1), and Ptriaz polymer colloid loaded with HEA-NPs (Example 1), respectively;

[0039] Figure 4TEM and mapping diagrams of the HEA-NPs@Ptriaz catalyst (Example 1): (a) is the TEM diagram of HEA-NPs@Ptriaz, (b) is the distribution diagram of element I in Figure (a), (c) is the distribution diagram of element Re in Figure (a), (d) is the distribution diagram of element Os in Figure (a), (e) is the distribution diagram of element Ir in Figure (a), (f) is the distribution diagram of element Pt in Figure (a), and (g) is the distribution diagram of element Au in Figure (a);

[0040] Figure 5 XRD curve comparison diagram of HEA-NPs@Ptriaz (Example 1) and five single metals of Re, Os, Ir, Pt, and Au;

[0041] Figure 6 Hydrogen evolution amount versus time curves of the HEA catalyst (Example 1), single-metal Re catalyst (Example 2), single-metal Os catalyst (Example 3), single-metal Ir catalyst (Example 4), single-metal Pt catalyst (Example 5), and single-metal Au catalyst (Example 6) for the dehydrogenation of AB alcoholysis;

[0042] Figure 7 TOF (turnover frequency) comparison diagram of the HEA catalyst (Example 1), single-metal Re catalyst (Example 2), single-metal Os catalyst (Example 3), single-metal Ir catalyst (Example 4), single-metal Pt catalyst (Example 5), and single-metal Au catalyst (Example 6) for the dehydrogenation of AB alcoholysis.

[0043] Figure 8 Four-cycle experimental data diagram of the HEA-NPs@Ptriaz catalyst (Example 1) for the dehydrogenation reaction of AB alcoholysis: (a) is the curve diagram of the hydrogen evolution amount versus reaction time for four cycles; (b) is the TOF comparison diagram for four cycles.

[0044] Figure 9 For Ptriaz-C5's 1 1H NMR spectrum;

[0045] Figure 10 Hydrogen evolution amount versus reaction time curve diagram in Example 7;

[0046] Figure 11 Hydrogen evolution amount versus reaction time curve diagram in Example 8. Detailed implementation method

[0047] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0048] Required materials and testing instruments:

[0049] 1-Vinyl-1,2,4-triazole was purchased from Santa Cruz Biotechnology, Inc. Iodopentane (98%), iodoheptane (98%), iodononane (98%) and sodium borohydride (98%) were purchased from Shanghai Titan Scientific Co., Ltd. N,N-Dimethylformamide (DMF, 99%) and diethyl ether (99.5%) were purchased from Sinopharm Chemical Reagent Co., Ltd. 2,2'-Azobis(2-methylpropionitrile) (98%), chloroiridic acid hydrate (Ir, 35%) and hexachloroplatinic acid hexahydrate (99.9%) were purchased from Beijing Innochem Science & Technology Co., Ltd. Potassium hexachloroosmate(IV) (Os, 38.7%) was purchased from Aladdin (Shanghai) Chemical Technology Co., Ltd. Rhenium(III) chloride (99.99%) and chloroauric acid (99%) were purchased from Shanghai Macklin Biochemical Co., Ltd. Palladium(II) chloride and rhodium(III) chloride were purchased from Shanghai J&K Chemical Co., Ltd. and Shanghai Macklin Biochemical Co., Ltd. respectively.

[0050] The XPS spectra were measured by an X-ray photoelectron spectrometer Escalab-250Xi; the UV spectra were measured by a UV-visible spectrophotometer UV-2600i; the content of each metal element in HEA-NPs was measured by an inductively coupled plasma atomic emission spectrometer (ICP); the TEM and mapping images were measured by a field emission transmission electron microscope; the XRD spectra were measured by an 18KW rotating anode X-ray diffractometer; 1 The 1H NMR spectra were measured by a Bruker Advance 600 (600 MHz) spectrometer.

[0051] Calculation formula for the TOF value of the dehydrogenation of ammonia borane (AB) by alcoholysis:

[0052]

[0053] Example 1

[0054] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the methanol solutions of five metal salts of Re, Os, Ir, Pt, and Au were mixed to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration in the five gold salt solutions was 10 mg / mL, and the addition amounts of each metal salt were Re: 165 μL, Os: 65 μL, Ir: 500 μL, Pt: 335 μL, Au: 500 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 32 mg of NaBH4 was added. The bottle was shaken manually and the lid was opened to release hydrogen. This was repeated several times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the HEA-NPs@Ptriaz-C5 catalyst.

[0055] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 1 (4 mL) was injected with a syringe. During the reaction, the flask was shaken manually, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve between the hydrogen evolution amount and the reaction time was obtained through data processing, and the hydrogen evolution TOF data graph was obtained through calculation.

[0056] The XPS (N1s) spectra of the HEA-NPs@Ptriaz catalyst and Ptriaz obtained in this example are as Figure 2 shown. After Ptriaz was loaded with HEA-NPs (HEA-NPs@Ptriaz), two characteristic peaks of N1s showed obvious shifts, which was consistent with the reported literature results, indicating that there was a strong interaction between HEA-NPs and Ptriaz, which was beneficial to its stable loading.

[0057] The UV spectra of the HEA-NPs@Ptriaz catalyst, Ptriaz loaded with five-metal salt precursor, and Ptriaz obtained in this example are as Figure 3 shown by Curve 3, Curve 2, and Curve 1. The positions of the UV absorption peaks of the three curves had obvious differences, which proved the existence of an interaction between Prtiaz and HEA-NPs.

[0058] The XRD spectrum of the HEA-NPs@Ptriaz catalyst obtained in this example is as Figure 4As shown, the XRD pattern of HEA-NPs@Ptriaz does not correspond one by one to the standard PDF cards of single metals Re, Os, Ir, Pt, and Au, indicating the formation of a new phase.

[0059] The TEM and mapping images of the HEA-NPs@Ptriaz catalyst obtained in this example are shown as Figure 5 shown. The lattice fringes can be clearly seen through the TEM image. By measuring the lattice fringe spacing and performing Fourier transform, the crystal plane indices can be obtained. The analysis results are consistent with the XRD results. From the mapping image, it can be seen that the five metals in HEA-NPs are uniformly and randomly mixed, proving that the HEA-NPs we obtained are a single-phase structure with uniform mixing of various metals;

[0060] The ICP data of the HEA-NPs@Ptriaz catalyst obtained in this example are shown in Table 1, where the molar ratios of various metals are between 5% and 35%, meeting the current requirements for the composition ratio of HEA.

[0061] The relationship curve between the hydrogen evolution amount and reaction time of the HEA-NPs@Ptriaz catalyst obtained in this example for the dehydrogenation of AB alcohol is shown as Figure 6 shown, TOF = 361.5 min -1 ( Figure 7 HEA bar chart), which is at a quite ideal level in the dehydrogenation reaction of AB alcohol, and is much greater than the TOF (Re: 294 min -1 , Os: 207 min -1 , Ir: 141.6 min -1 , Pt: 307.5 min -1 , Au: 211.8 min -1 ) of the single-metal catalysts in Examples 2 - 6 under the same conditions. This fully demonstrates the synergistic catalytic effect of the five metals in the HEA-NPs@Ptriaz catalyst in Example 1, which benefits from the single-phase structure with uniform mixing of the high-entropy alloy.

[0062] The cyclic stability test of the HEA-NPs@Ptriaz catalyst obtained in this example for the dehydrogenation of AB alcohol is shown as Figure 8 shown. After 4 cycles, it still has high catalytic activity, proving that the HEA-NPs@Ptriaz catalyst obtained in Example 1 has excellent cyclic stability.

[0063] Table 1

[0064] Element Re Os <![CDATA h > Pt Au Molar ratio / % 22.4 8.2 34.7 6.1 28.6

[0065] Example 2

[0066] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. The mixture was shaken at room temperature (300 r / min) for 15 min to dissolve and mix it thoroughly. The Re metal salt was mixed with methanol to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the Re metal precursor solution was 10 mg / mL, and its addition amount was 1565 μL. Then, it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 32 mg of NaBH4 was added. The bottle was shaken manually and the lid was opened to release hydrogen. This was repeated several times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the Re@Ptriaz-C5 catalyst.

[0067] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 2 (4 mL) was injected with a syringe. During the reaction process, the flask was shaken manually, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve graph of the hydrogen evolution amount and reaction time of this example ([ Figure 6 Re curve) was obtained through data processing. Through calculation, the hydrogen evolution TOF of this example was 426.7 min -1 ( Figure 7 Re bar graph).

[0068] Example 3

[0069] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. The mixture was shaken at room temperature (300 r / min) for 15 min to dissolve and mix it thoroughly. The Os metal salt was mixed with methanol to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the Os metal precursor solution was 10 mg / mL, and its addition amount was 1565 μL. Then, it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 32 mg of NaBH4 was added. The bottle was shaken manually and the lid was opened to release hydrogen. This was repeated several times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the Os@Ptriaz-C5 catalyst.

[0070] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 3 (4 mL) was injected with a syringe. During the reaction process, the flask was manually shaken. The reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve of the hydrogen evolution amount and reaction time in this example was obtained through data processing ( Figure 6 Os curve), and the hydrogen evolution TOF of this example was calculated to be 339.7 min -1 ( Figure 7 Os bar chart).

[0071] Example 4

[0072] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the Ir metal salt was mixed with methanol to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the Ir metal precursor solution was 10 mg / mL, and its addition amount was 1565 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, then 32 mg of NaBH4 was added, the bottle was manually shaken and the cap was opened to release hydrogen. This was repeated multiple times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the Ir@Ptriaz-C5 catalyst.

[0073] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 4 (4 mL) was injected with a syringe. During the reaction process, the flask was manually shaken. The reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve of the hydrogen evolution amount and reaction time in this example was obtained through data processing ( Figure 6 Ir curve), and the hydrogen evolution TOF of this example was calculated to be Ir: 395 min -1 ( Figure 7 Ir bar chart).

[0074] Example 5

[0075] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the Pt metal salt was mixed with methanol to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the Pt metal salt solution was 10 mg / mL, and its addition amount was 1565 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 32 mg of NaBH4 was added. The bottle was shaken manually and the cap was opened to release hydrogen. This was repeated multiple times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the Pt@Ptriaz-C5 catalyst.

[0076] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 5 (4 mL) was injected with a syringe. During the reaction process, the flask was shaken manually, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve between the hydrogen evolution amount and the reaction time of this example was obtained through data processing ( Figure 6 Pt curve), and the hydrogen evolution TOF of this example was calculated to be Pt: 474.1 min -1 ( Figure 7 Pt bar chart).

[0077] Example 6

[0078] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the Au metal salt was mixed with methanol to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the Au metal precursor solution was 10 mg / mL, and its addition amount was 1565 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 32 mg of NaBH4 was added. The bottle was shaken manually and the cap was opened to release hydrogen. This was repeated multiple times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain the Au@Ptriaz-C5 catalyst.

[0079] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 6 (4 mL) was injected with a syringe. During the reaction process, the flask was manually shaken, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve of the hydrogen evolution amount and reaction time in this example was obtained through data processing ( Figure 6 Au curve), and the hydrogen evolution TOF of this example was calculated to be Au: 395 min -1 ( Figure 7 Au bar chart).

[0080] Example 7

[0081] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the methanol solutions of six metal salts of Re, Os, Ir, Pt, Au, and Pd were mixed to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentrations of the six metal salt solutions were all 10 mg / mL, and their addition ratios were 130 μL: 80 μL: 300 μL: 250 μL: 400 μL: 125 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 28 mg of NaBH4 was added. The bottle was manually shaken and the lid was opened to release hydrogen. This was repeated multiple times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain a six-component alloy nanoparticle catalyst (ReOsIrPtAuPd@Ptriaz).

[0082] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 6 (4 mL) was injected with a syringe. During the reaction process, the flask was manually shaken, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve of the hydrogen evolution amount and reaction time in this example was obtained through data processing (as Figure 10 shown).

[0083] Example 8

[0084] 25 mg of Ptriaz-C5 (Example 9) was added to a 20 mL vial, and a mixed solvent of 6 mL of dichloromethane and 3 mL of methanol was added. It was shaken at room temperature (300 r / min) in a shaker for 15 min to fully dissolve and mix; the methanol solutions of six metal salts of Re, Os, Ir, Pt, Au, and Rh were mixed to form a metal precursor solution, and this precursor solution was added to the above mixed system. Among them, the metal concentration of the seven metal salt solutions was 10 mg / mL, and the addition ratio was 130 μL:80 μL:300 μL:250 μL:400 μL:125 μL. Then it was shaken at room temperature (300 r / min) in a shaker for 50 min, and then 30 mg of NaBH4 was added. The bottle was shaken manually and the lid was opened to release hydrogen. This was repeated several times until no gas was released. Finally, it was shaken at room temperature (300 r / min) in a shaker for 10 min to obtain a six-component alloy nanoparticle catalyst (ReOsIrPtAuRh@Ptriaz).

[0085] Hydrogen evolution performance test of catalytic ammonia borane (AB) alcoholysis at room temperature: 1 mmol of AB (30.8 mg) was fully dissolved and mixed with 1 mL of methanol to obtain a mixed solution. This mixed solution was placed in a reaction flask, and then the reaction flask was sealed. The catalyst prepared in Example 6 (4 mL) was injected with a syringe. During the reaction process, the flask was shaken manually, and the reaction stopped when no more hydrogen was released. The hydrogen evolution amount and hydrogen evolution rate were recorded by the water displacement method. The relationship curve of the hydrogen evolution amount and reaction time in this example was obtained through data processing ( Figure 11 ).

[0086] Example 9

[0087] 1-Vinyl-4-pentyl-1,2,4-triazole iodide monomer (5 g, 0.017 mol), azobisisobutyronitrile AIBN (80 mg, 1 - 1.5 mol%), and DMF (50 mL) were added to a 150 mL Schlenk flask respectively. Three vacuum-N2 filling cycles were carried out. The reaction mixture was heated to 70 °C under magnetic stirring and kept at this temperature for 24 h. Then, the reaction solution was dialyzed with deionized water (dialysis membrane specifications: MW: 3500, flattened width: 55 mm, diameter: 35 mm). The dialyzed liquid was vacuum filtered and placed in an oven at 40 °C for vacuum drying for 24 h to obtain a light yellow solid Ptriaz-C5.

[0088] All the catalysts prepared in the examples used the Ptriaz-C5 support, and its 1H NMR spectrum is as Figure 9 shown. The H atoms in various chemical environments in the structure are marked in the figure, and the results are consistent with those reported in the literature.

Claims

1. A triazole-based polymer colloid composite catalyst, characterized in that, The composite catalyst is a metal nanoparticle supported on a 1,2,4-triazolyl polymer colloid; The structural formula of the 1, 2, 4-triazolyl polymer is as follows where n = 50 - 150; the metal nanoparticles include nanoparticles of one or several of Au, Pt, Re, Ir, Os, Pd, Rh, or alloy nanoparticles of at least two of Au, Pt, Re, Ir, Os, Pd, Rh; and R is pentyl, heptyl or nonyl.

2. The catalyst according to claim 1, wherein, The metal nanoparticles are Re, Os, Ir, Pt, Au quinary alloy nanoparticles, Re, Os, Ir, Pt, Au, Pd hexary alloy nanoparticles, Re, Os, Ir, Pt, Au, Rh hexary alloy nanoparticles, or Re, Os, Ir, Pt, Au, Pd, Rh heptary alloy nanoparticles.

3. The catalyst according to claim 1, wherein The preparation method of the 1,2,4-triazolyl polymer colloid includes: mixing 1-vinyl-4-alkyl-1,2,4-triazolium ionic liquid, azobisisobutyronitrile AIBN, and a solvent under a protective gas condition, heating in an oil bath at 60-80 °C, stirring and reacting for 24-48 h, purifying, and drying; wherein the alkyl group in the 1-vinyl-4-alkyl-1,2,4-triazolium ionic liquid is pentyl, heptyl, or nonyl.

4. The catalyst according to claim 3, characterized in that, The solvent is N,N-dimethylformamide DMF; the ratio of the 1-vinyl-4-alkyl-1,2,4-triazolium ionic liquid, AIBN, and the solvent is 2.5-5 g: 40-80 mg: 25-50 mL.

5. A preparation method of the triazolyl polymer colloid composite catalyst according to any one of claims 1-4, comprising: Mixing a metal precursor solution and a 1,2,4-triazolyl polymer colloid solution, stirring at room temperature, and then adding NaBH4 for in-situ reduction to obtain a triazolyl polymer colloid composite catalyst.

6. The preparation method according to claim 5, characterized in that, The metal precursor includes one or more of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridium chloride hydrate, potassium hexachloroosmate, palladium chloride, and rhodium chloride; the solvent of the metal precursor solution is methanol; the solvent of the 1,2,4-triazolyl polymer colloidal solution is CH2Cl2 and CH3OH, where V CH2Cl2 :V CH3OH = 2:1 to 4:1, and the addition amount of NaBH4 is 1 to 2 times the mass of the metal added; The stirring at room temperature is carried out in a shaker at a rotation speed of 300-400 r / min for 50-100 min; the in-situ reduction specifically is: oscillating at room temperature in a shaker for 10-30 min at an oscillation rate of 300-400 r / min.

7. The preparation method according to claim 5, wherein, The metal precursor is a quinary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridium chloride hydrate, and potassium hexachloroosmate, or a hexary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridium chloride hydrate, potassium hexachloroosmate, and palladium chloride; or a hexary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridium chloride hydrate, potassium hexachloroosmate, and rhodium chloride: or a heptary metal salt mixture of chloroauric acid, chloroplatinic acid hexahydrate, rhenium trichloride, iridium chloride hydrate, potassium hexachloroosmate, palladium chloride, and rhodium chloride; The addition mass ratio of Au, Pt, Re, Ir, Os in the metal precursor to the 1,2,4-triazolyl polymer is: 2.5 - 5: 0.84 - 3.35: 1.25 - 5: 1.25 - 5: 0.65 - 2.5: 12.5 - 50; the addition mass ratio of Au, Pt, Re, Ir, Os, Pd to the 1,2,4-triazolyl polymer is: 2.5 - 5: 0.84 - 3.35: 0.25 - 2.5: 1.25 - 5: 0.65 - 2.5: 0.65 - 2.5: 12.5 - 50; the addition mass ratio of Au, Pt, Re, Ir, Os, Rh to the 1,2,4-triazolyl polymer is: 2.5 - 5: 0.84 - 3.35: 0.25 - 2.5: 1.25 - 5: 0.65 - 2.5: 0.65 - 2.5: 12.5 - 50.

8. Application of the triazolyl polymer colloid composite catalyst described in claim 1 in the alcoholysis reaction of ammonia borane.

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