Preparation method and application of ruthenium-embedded cobalt nitride-cobalt phosphide composite catalyst based on Ti3C2Tx

Abstract

The invention discloses a preparation method of a ruthenium-embedded cobalt nitride-cobalt phosphide composite catalyst based on Ti3C2Tx and catalytic application of ammonia borane to hydrogen release through hydrolysis. The method comprises the following steps: firstly, taking a Ti3C2Tx nanosheet as a carrier, mixing a Co < 2 + > salt solution, a Ru < 3 + > salt solution and urea, refluxing in N2 airflow at 100 DEG C for 5 hours, adsorbing ions on the carrier through electrostatic interaction, and growing into a RuCo-LDH / Ti3C2Tx precursor in situ; and then respectively placing NaH2PO2.H2O and the precursor in the upstream and downstream of a tubular furnace, and deriving the RuCo-LDH into the Ru / CoN-CoP / Ti3C2Tx composite catalyst through high temperature. The hydrogen evolution conversion frequency of the catalyst can reach 589.7 mol H2.mol Ru <-1 >. Min <-1 >, and 80% of initial activity is still kept after hydrolysis and hydrogen evolution are carried out five times at 298 K. The preparation process is simple, convenient and controllable, green and environment-friendly, does not need harsh conditions and complex equipment, is easy for large-scale mass production, provides technical and theoretical support for active site regulation and control and carrier collaborative optimization of heterogeneous catalysis, and has important academic value and industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a catalyst based on Ti3C2T x Preparation method and application of ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst. Background Technology

[0002] Among the catalyst systems to date, Rh, Pt, Ru-based noble metals or their alloys are ideal high-activity catalysts, but their high cost and scarcity limit their widespread use. Studies have shown that transition metal phosphides (TMPs) and transition metal nitrides (TMNs) exhibit excellent electron transport properties due to their high conductivity and noble metal-like characteristics, making them potential catalysts. However, they exhibit slow kinetics in catalytic reactions due to their low adsorption and dissociation efficiency for reactants and water, resulting in low intrinsic catalytic activity. Research indicates that adjusting their electronic configuration or coupling them with other active components to construct heterostructures can significantly improve catalytic performance. Furthermore, adjusting the chemical composition by doping with foreign elements to generate synergistic effects can further enhance catalytic performance.

[0003] Besides component regulation, microstructure regulation is also a common strategy to improve the catalytic activity and stability of catalysts. Generally, the large particle size of metal nanoparticles leads to a decrease in the utilization rate of active sites, and their high surface energy makes them prone to aggregation during catalysis. Recent studies have shown that using support materials to load metal nanoparticles can effectively inhibit the aggregation of active metals and also provide additional active sites. Since their discovery in 2011, MXenes have exhibited excellent conductivity, good structural stability, and abundant surface functional groups. These superior structural characteristics make MXenes promising for applications in electrocatalysis and energy storage. Research has found that Ti3C2T... x Interfacial coupling between MXenes and other active components can effectively leverage their synergistic effects, optimize electronic structure to promote the adsorption and desorption of intermediates, thereby kinetically promoting water dissociation.

[0004] Despite Ti3C2T x It provides an ideal support for active components such as TMPs and TMNs, and the composite system of the two shows certain potential in the field of electrocatalysis. However, for the hydrogen decomposition reaction of ammonia borane hydrolysis, the existing Ti3C2T x TMPs / TMNs composite catalysts still have many shortcomings, making it difficult to meet practical application requirements and achieve efficient replacement of precious metal catalysts. Existing systems mostly consist of a single TMPs or TMNs component combined with Ti3C2T. xThe current method lacks the synergistic construction of multiple active components and fails to achieve precise control of noble metal doping. It cannot optimize electronic configuration or lower reaction energy barriers through multi-component synergy, resulting in catalytic activity that still lags behind noble metal catalysts. Furthermore, existing preparation methods tend to cause the active components to remain in the Ti3C2T matrix. x Surface aggregation and poor dispersion, coupled with weak interfacial bonding, lead to the easy detachment and aggregation of active components in the hydrogen release cycle of ammonia borane hydrolysis. This results in a decline in catalyst cycle stability and repeatability, making it unsuitable for long-term reaction conditions. Furthermore, existing technologies for controlling composite systems are mostly limited to a single dimension, either optimizing component ratios or simply loading them onto a support surface. These limitations fail to achieve the multiple objectives of increasing the number of active sites, enhancing intrinsic catalytic activity, accelerating reaction kinetics, and optimizing cycle stability in Ti3C2T catalysts. x The core bottleneck in the large-scale application of TMPs / TMNs composite catalysts in the hydrogen dehydrogenation reaction of ammonia borane is the lack of TMPs / TMNs composite catalysts. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a Ti3C2T-based solution. x Preparation method and application of ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalysts, and the Ru / CoN-CoP / Ti3C2T catalyst prepared by this method. x It is used to catalyze the hydrogen release reaction of ammonia borane hydrolysis, and exhibits good stability and reproducibility.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method based on Ti3C2T x A method for preparing a ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, the method being as follows:

[0007] S1. Add Co(NO3)2·6H2O, RuCl3·nH2O and urea to deionized water, sonicate for 20-40 min and stir magnetically until completely dissolved to obtain solution A;

[0008] S2, Ti3C2T x The solution and the N-dimethylpyrrolidone solution were mixed at a volume ratio, and 3-5% by mass of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1-2 hours to obtain the dispersion-modified solution B.

[0009] S3. Under room temperature conditions, while stirring, solution A obtained in S1 is added dropwise to solution B obtained in S2. After the addition is complete, stirring is continued for 30 min. Then, the reaction is carried out under N2 atmosphere and oil bath at 100℃ with stirring for 5 h. After the reaction is completed, the mixture is naturally cooled to room temperature, washed with deionized water by centrifugation until the supernatant is neutral, and then washed 2-3 times by centrifugation with anhydrous ethanol. After vacuum drying at 60℃ for 12 h, the dried sample is immersed in a 0.1-0.5 mol / L dilute NaOH solution and stirred evenly. It is etched at room temperature for 5-10 min, filtered, washed with deionized water until neutral, and vacuum dried at 60℃ for 12 h to obtain RuCo-LDH / Ti3C2T. x Precursor.

[0010] S4, The RuCo-LDH / Ti3C2T obtained from S3 is reacted with NaH2PO2·H2O. x The precursors were placed in the upstream phosphorus production zone and downstream reaction zone of the tubular furnace at a mass ratio of 1:(0.8~1.2). The thickness of the NaH2PO2·H2O layer was 1~2 mm, and the thickness of the precursor layer was controlled at 0.5~1 mm. The distance between the two zones was maintained at 3~5 cm. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 50~80 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2℃·min. –1 The temperature was increased to 300-400℃ at a rising rate and held for 2-3 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed to obtain a Ti3C2T-based product. x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, denoted as Ru / CoN-CoP / Ti3C2T x .

[0011] Preferably, the ratio of Co(NO3)2·6H2O, RuCl3·nH2O, urea and deionized water in S1 is 0.2 mmol:0.01 mmol:2 mmol:10 mL.

[0012] Preferably, the Ti3C2T in S2 x The volume ratio of the solution to the N-dimethylpyrrolidone solution is 5 mL:15 mL;

[0013] This invention also provides Ti3C2T based preparation method. x The application of ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalysts, the Ti3C2T-based catalysts... x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is used to catalyze the hydrogen release reaction of ammonia borane hydrolysis.

[0014] Preferably, the Ti3C2T-based x When the ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is used for the cyclic catalytic hydrogen release reaction of ammonia borane, it can still maintain 80% of the initial catalytic activity after 5 hydrogen release reactions.

[0015] Compared with the prior art, the present invention has the following advantages:

[0016] This invention utilizes a solution self-assembly method to form in-situ grown Ti3C2T x Layered double hydroxide (RuCo-LDH) nanosheet precursor (RuCo-LDH / Ti3C2T) x Then, through a one-step phosphating process, RuCo-LDH nanosheets are derivatized into Ru / CoN-CoP nanoparticles under high temperature conditions, and uniformly dispersed in Ti3C2T. x Nanosheets (Ru / CoN-CoP / Ti3C2T) x CoN coupled with CoP to construct heterostructures can significantly improve catalytic performance. Simultaneously, doping with Ru can modulate its local electronic environment, accelerating electron transfer rates and further enhancing catalytic activity. Furthermore, the support material Ti3C2T... x The interfacial modulation between the active metal and the nanoparticles can effectively exert a synergistic effect, which is beneficial to stabilizing the nanoparticles and further improving catalytic performance and cycle stability. The Ru / CoN-CoP / Ti3C2T nanoparticles prepared in this invention... x It is used to catalyze the hydrogen release reaction of ammonia borane hydrolysis, and exhibits good stability and reproducibility. Attached Figure Description

[0017] Figure 1 It is the Ru / CoN-CoP / Ti3C2T prepared in Example 1 of this invention. x A schematic diagram of catalyst preparation.

[0018] Figure 2 This is a SEM image of Embodiment 1 of the present invention, wherein (a) Ti3C2T x MXene; (b) RuCo-LDH / Ti3C2T x (cd) Ru / CoN-CoP / Ti3C2T at different magnifications x .

[0019] Figure 3 It is the Ru / CoN-CoP / Ti3C2T prepared in Example 1 of this invention. x (a) TEM image of the catalyst; (b) HRTEM image; (c) SAED image; (d) HAADF-STEM image and (e) EDS spectrum.

[0020] Figure 4 This is the XRD pattern of Embodiment 1 of the present invention, wherein (a): precursor RuCo-LDH, Co-LDH / Ti3C2T x and RuCo-LDH / Ti3C2T x (b): CoN-CoP / Ti3C2T x Ru / CoN / Ti3C2T x and Ru / CoN-CoP / Ti3C2T x .

[0021] Figure 5 It is the Ru / CoN-CoP / Ti3C2T prepared in Example 1 of this invention. x XPS spectra, of which (a) full spectrum; (b) high-resolution C 1s + Ru 3d spectrum; (c) high-resolution N 1s spectrum; (d) high-resolution O 1s spectrum; (e) high-resolution Ti 2p spectrum and (f) high-resolution P2p spectrum.

[0022] Figure 6 This is the CoN-CoP / Ti3C2T of Embodiment 1 of the present invention. x and Ru / CoN-CoP / Ti3C2T x XPS spectra of (a) Co 2p; (b) P 2p; Ru / CoN / Ti3C2T x and Ru / CoN-CoP / Ti3C2T x XPS spectra: (c) Co 2p; (d) Ru 3p + Ti 2p.

[0023] Figure 7 Examples 2 of this invention include (a) hydrogen release curves of ammonia borane hydrolysis catalyzed by different catalysts at 298 K and (b) histograms of corresponding conversion frequency (TOF) and hydrogen production rate (HGR); (c) hydrogen release curves of ammonia borane hydrolysis catalyzed by composite catalysts with different Ru doping amounts at 298 K and (d) histograms of corresponding conversion frequency (TOF) and hydrogen production rate (HGR).

[0024] Figure 8 This refers to Example 2 of the present invention, (a) Ru / CoN-CoP / Ti3C2T at different temperatures. x Catalytic hydrogen release curves of ammonia borane hydrolysis and (b) Arrhenius curves; (c) Ru / CoN-CoP / Ti3C2T at 298 K x Hydrogen release curves of catalytic ammonia borane hydrolysis cycle and the catalytic activity retention rate corresponding to (d).

[0025] Figure 9 This is Ru / CoN-CoP / Ti3C2T from Embodiment 2 of the present invention. xAfter 5 cycles of hydrogen release reaction: (a) XRD pattern; (b) TEM (inset is particle size distribution). Detailed Implementation

[0026] The preparation methods of the substances involved in the following examples are as follows:

[0027] The preparation method of RuCo-LDH is as follows: Co(NO3)2·6H2O (0.2 mmol), RuCl3·nH2O (0.01 mmol) and urea (2 mmol) are added to a certain amount of deionized water (10 mL), sonicated for 30 min and magnetically stirred until completely dissolved to form a mixed solution. Then, the mixture is stirred and reacted for 5 h under N2 atmosphere and oil bath at 100℃. After the reaction is completed, it is naturally cooled to room temperature, washed with deionized water by centrifugation until the supernatant is neutral, and then washed three times by centrifugation with anhydrous ethanol. After vacuum drying at 60℃ for 12 h, the dried sample is immersed in 0.1 mol / L NaOH dilute solution and stirred evenly. It is etched at room temperature for 10 min, filtered, washed with deionized water until neutral, and vacuum dried at 60℃ for 12 h to obtain RuCo-LDH.

[0028] RuCo-LDH / Ti3C2T x The preparation method is as follows: Co(NO3)2·6H2O (0.2 mmol), RuCl3·nH2O (0.01 mmol) and urea (2 mmol) are added to a certain amount of deionized water (10 mL), sonicated for 30 min and magnetically stirred until completely dissolved to form mixed solution A; 5 mL of Ti3C2T x The solution was mixed with 15 mL of N-dimethylpyrrolidone solution, and 5% (w / w) of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1 h to obtain a dispersion-modified solution B. Under room temperature conditions, solution A was added dropwise to solution B while stirring. After the addition was complete, stirring was continued for 30 min. The mixture was then reacted at a constant temperature of 100℃ in an oil bath under N2 atmosphere for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, washed with deionized water by centrifugation until the supernatant was neutral, and then washed three times with anhydrous ethanol by centrifugation. The sample was then vacuum dried at 60℃ for 12 h. The dried sample was then immersed in a 0.1 mol / L dilute NaOH solution and stirred until homogeneous. Etching was performed at room temperature for 10 min. After filtration, the sample was washed with deionized water until neutral and then vacuum dried at 60℃ for 12 h to obtain RuCo-LDH / Ti3C2T. x ;

[0029] Co-LDH / Ti3C2T xThe preparation method is as follows: Co(NO3)2·6H2O (0.2 mmol) and urea (2 mmol) are added to a certain amount of deionized water (10 mL), sonicated for 30 min and magnetically stirred until completely dissolved to form mixed solution A; 5 mL of Ti3C2T x The solution was mixed with 15 mL of N-dimethylpyrrolidone solution, and 5% (w / w) of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1 h to obtain a dispersion-modified solution B. Under room temperature conditions, solution A was added dropwise to solution B while stirring. After the addition was complete, stirring was continued for 30 min. The reaction was then carried out under N2 atmosphere and an oil bath at 100 °C for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, washed with deionized water until the supernatant was neutral, and then washed three times with anhydrous ethanol. The sample was then vacuum dried at 60 °C for 12 h. The dried sample was then immersed in a 0.1 mol / L NaOH solution and stirred until homogeneous. Etching was performed at room temperature for 10 min. After filtration, the sample was washed with deionized water until neutral and then vacuum dried at 60 °C for 12 h to obtain Co-LDH / Ti3C2T. x ;

[0030] Ru / CoN-CoP / Ti3C2T x The preparation method is as follows: NaH2PO2·H2O and RuCo-LDH / Ti3C2T x The precursors were placed in the upstream phosphorus production zone and downstream reaction zone of the tubular furnace at a mass ratio of 1:1. The thickness of the NaH2PO2·H2O layer was 1 mm, and the thickness of the precursor layer was controlled at 1 mm, with a distance of 3 cm between the two zones. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 60 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C / min. –1 The temperature was increased to 380℃ at a rising rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed, yielding a Ti3C2T-based product. x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, denoted as Ru / CoN-CoP / Ti3C2T x ;

[0031] CoN-CoP / Ti3C2T x The preparation method is as follows: NaH2PO2·H2O and Co-LDH / Ti3C2T xThe precursors were placed in the upstream phosphorus production zone and the downstream reaction zone of the tubular furnace at a mass ratio of 1:1. The thickness of the NaH2PO2·H2O layer was 1 mm, and the thickness of the precursor layer was controlled at 1 mm, with a distance of 3 cm between the two zones. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 60 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C / min. –1 The temperature was increased to 380℃ at a rising rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed, yielding a Ti3C2T-based product. x The cobalt nitride-cobalt phosphide composite catalyst, denoted as CoN-CoP / Ti3C2T x ;

[0032] Ru / CoN / Ti3C2T x The preparation method is as follows: RuCo-LDH / Ti3C2T x Placed in a tube furnace, the thickness of the gas layer is controlled to be 1 mm; a hydrogen-argon mixture (5% H2 volume fraction, Ar as the balance gas) is introduced into the tube furnace at a flow rate of 60 mL / min. After purging the furnace for 30 min, the gas flow rate is increased to 2 °C / min. –1 The temperature was increased to 380℃ at a rising rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed, yielding a Ti3C2T-based product. x The ruthenium-intercalated cobalt nitride composite catalyst, denoted as Ru / CoN / Ti3C2T x ;

[0033] CoN / Ti3C2T x The preparation method is as follows: Co-LDH / Ti3C2T x Place the material in a tube furnace, with a thickness controlled at 1 mm; introduce a hydrogen-argon mixture (5% H2 volume fraction, Ar as balance gas) into the tube furnace, controlling the gas flow rate at 60 mL / min. After purging the furnace by first purging for 30 min, reduce the flow rate to 2 °C / min. –1 The temperature was increased to 380℃ at a rising rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed, yielding a Ti3C2T-based product. x The cobalt nitride composite catalyst, denoted as CoN / Ti3C2T x ;

[0034] Ru 0.5 / CoN-CoP / Ti3C2Tx The preparation method is as follows: Co(NO3)2·6H2O (0.2 mmol), RuCl3·nH2O (0.005 mmol) and urea (2 mmol) are added to a certain amount of deionized water (10 mL), sonicated for 30 min and magnetically stirred until completely dissolved to form mixed solution A; 5 mL of Ti3C2T x The solution was mixed with 15 mL of N-dimethylpyrrolidone solution, and 5% (w / w) of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1 h to obtain a dispersion-modified solution B. Under room temperature conditions, solution A was added dropwise to solution B while stirring. After the addition was complete, stirring continued for 30 min. The mixture was then reacted at a constant temperature of 100℃ in an oil bath under N2 atmosphere for 5 h. After the reaction, the mixture was naturally cooled to room temperature, washed with deionized water until the supernatant was neutral, and then washed three times with anhydrous ethanol. The sample was then vacuum-dried at 60℃ for 12 h. The dried sample was then immersed in a 0.1 mol / L dilute NaOH solution and stirred until homogeneous. Etching was performed at room temperature for 10 min. After filtration, the sample was washed with deionized water until neutral and then vacuum-dried at 60℃ for 12 h to obtain Ru. 0.5 Co-LDH / Ti3C2T x Subsequently, NaH2PO2·H2O and Ru 0.5 Co-LDH / Ti3C2T x The precursors were placed in the upstream phosphorus production zone and downstream reaction zone of the tubular furnace at a mass ratio of 1:1. The thickness of the NaH2PO2·H2O layer was 1 mm, and the thickness of the precursor layer was controlled at 1 mm, with a distance of 3 cm between the two zones. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 60 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C / min. –1 The temperature was increased to 380℃ at a constant heating rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. The gas flow was then stopped, and the product was removed to obtain Ru. 0.5 / CoN-CoP / Ti3C2T x ;

[0035] Ru2 / CoN-CoP / Ti3C2T x The preparation method is as follows: Co(NO3)2·6H2O (0.2 mmol), RuCl3·nH2O (0.02 mmol) and urea (2 mmol) are added to a certain amount of deionized water (10 mL), sonicated for 30 min and magnetically stirred until completely dissolved to form mixed solution A; 5 mL of Ti3C2T xThe solution was mixed with 15 mL of N-dimethylpyrrolidone solution, and 5% (w / w) of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1 h to obtain a dispersion-modified solution B. Under room temperature conditions, solution A was added dropwise to solution B while stirring. After the addition was complete, stirring was continued for 30 min. The mixture was then reacted at a constant temperature of 100℃ in an oil bath under N2 atmosphere for 5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, washed with deionized water until the supernatant was neutral, and then washed three times with anhydrous ethanol. The mixture was then vacuum dried at 60℃ for 12 h. The dried sample was then immersed in a 0.1 mol / L dilute NaOH solution and stirred until homogeneous. Etching was performed at room temperature for 10 min. After filtration, the sample was washed with deionized water until neutral and then vacuum dried at 60℃ for 12 h to obtain Ru2Co-LDH / Ti3C2T. x Subsequently, NaH2PO2·H2O and Ru2Co-LDH / Ti3C2T were added. x The precursors were placed in the upstream phosphorus production zone and downstream reaction zone of the tubular furnace at a mass ratio of 1:1. The thickness of the NaH2PO2·H2O layer was 1 mm, and the thickness of the precursor layer was controlled at 1 mm, with a distance of 3 cm between the two zones. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 60 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C / min. –1 The temperature was increased to 380℃ at a constant rate and held for 2 h, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed to obtain Ru2 / CoN-CoP / Ti3C2T. x ;

[0036] Example 1

[0037] This embodiment is based on Ti3C2T. x A method for preparing a ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, the method being as follows:

[0038] S1. Add 0.2 mmol Co(NO3)2·6H2O, 0.01 mmol RuCl3·nH2O and 2 mmol urea to 10 mL of deionized water, sonicate for 30 min and stir magnetically until completely dissolved to obtain mixed solution A;

[0039] The Co(NO3)2·6H2O, urea and RuCl3·nH2O were purchased commercially from Xilong Scientific Co., Ltd. and Aladdin Reagent Co., Ltd., respectively.

[0040] S2, Add 5 mL of Ti3C2T xThe solution was mixed with 15 mL of N-dimethylpyrrolidone solution, and 5% (w / w) of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1 h to obtain the dispersion-modified solution B.

[0041] The Ti3C2T x The solution was commercially available, with a concentration of 5 mg / mL, purchased from Jilin Yiyi Technology Co., Ltd. T x The symbols -OH, -F, and -O are indicated; N-dimethylpyrrolidone was purchased from Xilong Scientific Co., Ltd.

[0042] S3. Under room temperature conditions, solution A obtained in S1 was added dropwise to solution B obtained in S2 while stirring. After the addition was complete, stirring was continued for 30 min. Then, the reaction was carried out under N2 atmosphere and 100℃ oil bath conditions for 5 h. After the reaction was completed, the sample was naturally cooled to room temperature, washed with deionized water by centrifugation until the supernatant was neutral, and then washed three times with anhydrous ethanol by centrifugation. The sample was then vacuum dried at 60℃ for 12 h. The dried sample was then immersed in a 0.1 mol / L dilute NaOH solution and stirred until homogeneous. The sample was etched at room temperature for 10 min, filtered, washed with deionized water until neutral, and vacuum dried at 60℃ for 12 h to obtain RuCo-LDH / Ti3C2T. x ;

[0043] S4, The RuCo-LDH / Ti3C2T obtained from S3 is reacted with NaH2PO2·H2O. x The precursors were placed in the upstream phosphorus production zone and the downstream reaction zone of the tubular furnace at a mass ratio of 1:1. The thickness of the NaH2PO2·H2O layer was 1 mm, and the thickness of the precursor layer was controlled at 1 mm, with a distance of 3 cm between the two zones. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 60 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C / min. –1 The temperature was increased to 380℃ at a rising rate and held for 2 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed, yielding a Ti3C2T-based product. x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, denoted as Ru / CoN-CoP / Ti3C2T x .

[0044] In this embodiment, steps S1-S3 synthesize RuCo-LDH / Ti3C2T via solution self-assembly. x Precursor, soon to be Ti3C2T x Nanosheets as a carrier, Co 2+ Salt solution, Ru 3+The salt solution and urea were mixed with stirring and then refluxed at 100°C for 5 h in a nitrogen stream. Positively charged Co... 2+ and Ru 3+ Ions are adsorbed onto Ti3C2T via electrostatic interactions. x The negatively charged -OH groups on the surface serve as the core in Ti3C2T x RuCo-LDH is grown in situ on the nanosheets; in step S4, RuCo-LDH is derivatized into Ru / CoN-CoP nanoparticles under high temperature conditions and uniformly dispersed on Ti3C2T x On nanosheets ( Figure 1 ).

[0045] The microstructure and structure of the samples were characterized by scanning electron microscopy (SEM). Figure 2 SEM images of Ti3C2T show that... x The nanosheets are relatively thin and have a relatively smooth surface. RuCo-LDH / Ti3C2T x The SEM images show that Ti3C2T x The smooth surface is covered with densely arranged RuCo-LDH nanosheets, forming a unique 3D network cross-linked structure. Figure 2 (b) indicates that RuCo-LDH / Ti3C2T was successfully prepared. x Precursor. This 3D structure is derived in situ into highly dispersed nanoclusters under high temperature conditions and is tightly anchored to Ti3C2T. x superior. Figure 2 cd represents Ru / CoN-CoP / Ti3C2T at different magnifications. x The SEM images show that RuCo-LDH nanosheets are degenerated in situ into nanoclusters after high-temperature carbonization. These nanoclusters are connected by many interconnected porous structures. This porous structure can provide transport channels for reactants to contact with active metals, thereby improving mass transfer efficiency.

[0046] The Ru / CoN-CoP / Ti3C2T structure was further characterized by transmission electron microscopy (TEM). x More detailed morphology and internal structure. TEM images show Ti3C2T x The RuCo-LDH nanosheets exhibited a sheet-like layered structure, but no RuCo-LDH nanosheet structure was observed, indicating that the RuCo-LDH nanosheets were derivatized into a large number of uniformly dispersed nanoclusters after high-temperature carbonization. Figure 3 a), consistent with SEM results. In high-resolution transmission electron microscopy (HRTEM) images ( Figure 3(b) The lattice fringe spacings shown are 0.189, 0.248, and 0.221 nm, corresponding to the CoP (211), CoN (111), and Ru (111) crystal planes, respectively, indicating that in Ti3C2T x Ru / CoN-CoP nanoclusters were successfully synthesized on the surface. Furthermore, CoN and CoP form a heterostructure, and because the bonding strength of Ru-Co is weaker than that of Ru-Ru, Ru is embedded in it in elemental form. Meanwhile, as... Figure 3 As shown in c, Ru / CoN-CoP / Ti3C2T x Selected area electron diffraction (SAED) of the sample exhibits distinct circular diffraction spots, indicating the polycrystalline structure of CoN. Notably, the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image (…) Figure 3 d) Confirmed that Ru / CoN-CoP nanoclusters were dispersed in Ti3C2T x In terms of layered structure, according to the X-ray energy dispersive spectroscopy (EDS) spectrum, C, N, O, Ru, Co, P, and Ti elements are present respectively. Figure 3 The presence of trace amounts of P indicates the successful introduction of P, while N originates from LDH nanosheets, and both are distributed in the same locations as Co.

[0047] X-ray diffraction (XRD) was used to analyze RuCo-LDH and Co-LDH / Ti3C2T. x and RuCo-LDH / Ti3C2T x The precursor (RuCo-LDH / Ti3C2T prepared in step S3 of this embodiment) x The crystal structure of the precursor was characterized. Figure 4 As can be seen from Figure a, the XRD patterns of the three materials match the RuCo-LDH diffraction peaks reported in previous literature (Yan L, Zhang B. Rose-like, ruthenium-modified cobalt nitride nanoflowers grown in situ on an MXene matrix for efficient and stable water electrolysis [J]. Journal of Materials Chemistry A, 2021, 9(36): 20758-20765.), proving the successful preparation of the LDH structure. RuCo-LDH / Ti3C2T x Compared to Co-LDH / Ti3C2T xThe increased intensity and angular shift of the diffraction peaks indicate the successful introduction of Ru. Furthermore, with the addition of Ru, RuCo-LDH / Ti3C2T... x The XRD pattern showed no significant change, indicating that the addition of Ru did not alter its crystal structure. It is noteworthy that, compared to the support material Ti3C2T... x Nanosheets, Ti3C2T x The disappearance of the (002) diffraction peak may be due to Co. 2+ and Ru 3+ The adsorption at the surface -OH sites and the in-situ growth of RuCo-LDH disrupted Ti3C2T x The ordered stacked layered structure. Furthermore, RuCo-LDH / Ti3C2T x The diffraction peak intensity of Ti3C2T is more prominent than that of RuCo-LDH, indicating that the former has a higher degree of crystallinity. This may be due to Ti3C2T x Surface -OH can induce Co 2+ and Ru 3 + The adsorption of [something] promotes the directional growth of LDH. Simultaneously, [something] was applied to CoN-CoP / Ti3C2T [something]. x Ru / CoN / Ti3C2T x and Ru / CoN-CoP / Ti3C2T x XRD characterization revealed diffraction peaks at 36.5°, 42.9°, and 61.4°, corresponding to the (111), (200), and (220) crystal planes of CoN (PDF#16-0116), respectively. Figure 4 (b) This demonstrates the successful preparation of CoN. Furthermore, the diffraction peaks at 25.4°, 31.7°, and 48.3° are attributed to the (101), (011), and (211) crystal planes of CoP (PDF#29-0497), respectively, indicating the successful preparation of CoP, consistent with the TEM results. Clearly, in Ru / CoN / Ti3C2T... x and Ru / CoN-CoP / Ti3C2T x No additional Ru-related characteristic peaks were observed in the XRD pattern, possibly due to the low Ru content. Furthermore, Ru / CoN-CoP / Ti3C2T x Compared to CoN-CoP / Ti3C2T x The increased peak intensity and slight shift of the diffraction peaks indicate that Ru doping modulates the crystal structure of CoN-CoP.

[0048] The Ru / CoN-CoP / Ti3C2T was analyzed using X-ray photoelectron spectroscopy (XPS). xx The surface chemical composition and chemical bonding characteristics of catalysts. For example... Figure 5 As shown in figure a, the XPS spectra confirm Ru / CoN-CoP / Ti3C2T x The coexistence of elements Co, Ru, N, P, O, Ti, and C is consistent with the EDS results. Figure 5 As shown in b, the high-resolution XPS overlap spectra of C 1s and Ru 3d are divided into five main peaks. The characteristic peaks at 277.4 and 283.8 eV are attributed to Ru 3d. 5 / 2 and Ru 3d 3 / 2 This proves Ru 0 The presence of [a specific element / value]. The remaining characteristic peaks at 281.9, 285, and 286.7 eV are attributed to Ti-C, C-C, and CO bonds, respectively. Figure 5 c shows the high-resolution N 1s fitting results, attributed to Co-N (397.8 eV) and NH (400.5 eV), respectively, confirming the successful introduction of nitrogen and its promotion of nitride formation. Different forms of nitrides exist, which can interact with H... + Interactions enhance catalytic activity. Furthermore, nitrogen doping provides good electrical conductivity and improves electron transfer rates. The high-resolution O 1s spectrum can be decomposed into four peaks at 527.7, 529.4, 530.7, and 532.1 eV. The three main peaks at 527.7, 529.4, and 532.1 eV correspond to Ti-O, Ti-CO, and Ti-OH bonds, respectively, indicating that Ti3C2T x The surface is rich in oxygen-containing functional groups; and the fitting peak at 530.7 eV is attributed to Ti-O-Co bonds, indicating that CoN reacts with Ti3C2T. x Covalent bonds were formed between them. Figure 5 d). Covalent bonds facilitate electron transport and maintain structural stability during catalysis, thereby improving catalytic performance. Figure 5 e is the high-resolution Ti 2p spectrum, where the peaks at 455.7 and 462.3 eV are attributed to Ti-C bonds, the characteristic peaks at 457.7 and 463.7 eV correspond to Ti-OH bonds, and the other two characteristic peaks at 458.7 and 464.8 eV correspond to Ti-O bonds. Figure 5 f shows the high-resolution P 2p fitting results, which can be decomposed into three peaks: PO (134.1 eV), PC (131.7 eV), and Co-P (129.3 eV), confirming the successful formation of the metal-P band after phosphating and the P doping of the carbon matrix. High-resolution Co 2p can be further divided into Co 2p... 3 / 2 and Co 2p 1 / 2 For Ru / CoN-CoP / Ti3C2T x In high-resolution Co 2p, the Co-Co bonds are located at 779.5 eV (Co 2p).3 / 2 ) and 794.4 eV (Co 2p 1 / 2 The peak at 777.7 eV corresponds to the Co-P bond, while the peaks at 781 and 796.3 eV correspond to the Co-N bond, confirming the formation of CoN after the nitriding process. The Co-O (782.7 eV) peak likely formed during catalyst storage, and the remaining peaks are satellite peaks. In summary, the XPS results confirm the formation of Ru / CoN-CoP / Ti3C2T x Successful preparation of catalytic materials.

[0049] according to Figure 6 ab, compared to CoN-CoP / Ti3C2T x Ru / CoN-CoP / Ti3C2T x The binding energy in the Co 2p spectrum shows a slight shift, as does the binding energy in the P 2p spectrum, indicating electron transfer between them. The incorporation of Ru can alter the electronic configuration of the CoN-CoP heterostructure, promoting the adsorption and desorption of reaction intermediates, thereby effectively improving catalytic performance. Similarly, compared to Ru / CoN / Ti3C2T... x Ru / CoN-CoP / Ti3C2T x The Co 2p and Ru 3p spectra also show a certain shift accordingly ( Figure 6 The presence of phosphorus (P) indicates that the introduction of P significantly alters the electron density of the d-band in CoN. Furthermore, the heterojunction formed by CoP and CoN modulates the local electronic environment, resulting in strong electronic synergy and interactions, which facilitates adsorption and desorption between reactants and products, thereby significantly enhancing the catalytic activity of ammonia borane hydrolysis.

[0050] Example 2

[0051] This embodiment is based on Ti3C2T prepared in Example 1. x Ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst (Ru / CoN-CoP / Ti3C2T) x The application of Ti3C2T x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is used to catalyze the hydrogen release reaction of ammonia borane hydrolysis. When this catalyst is used to cyclically catalyze the hydrogen release reaction of ammonia borane hydrolysis, it can still maintain 80% of the initial catalytic activity after the 5th hydrolysis reaction.

[0052] The Ru / CoN-CoP / Ti3C2T prepared in Example 1 x The catalyst was used to catalyze the hydrogen release reaction of ammonia borane at 298 K, and its performance was analyzed. Under the same conditions, the effects of different catalyst components on the hydrogen release reaction of ammonia borane were investigated. Figure 7As shown in ab, the carrier material is Ti3C2T x and RuCo-LDH / Ti3C2T x Precursor material (RuCo-LDH / Ti3C2T prepared in step S3 of Example 1) x The precursor's catalytic effect on hydrogen release from the hydrolysis of ammonia borane was unsatisfactory. (CoN / Ti3C2T) x CoN-CoP / Ti3C2T x The catalytic hydrogen release rate of ammonia borane hydrolysis was improved, but the overall rate remained low. Therefore, the introduction of Ru element improved the Ru / CoN-CoP / Ti3C2T... x The catalytic activity was significantly improved, with a conversion frequency (TOF) as high as 589.7 mol. H2 ·mol Ru –1 ·min –1 This indicates that Ru can effectively modulate the local electronic environment of CoN-CoP nanoparticles, thereby improving the catalytic effect. However, Ru / CoN / Ti3C2T without the introduction of P... x The catalytic activity of the catalyst for the hydrolysis of ammonia borane is compared with that of Ru / CoN-CoP / Ti3C2T x The catalyst was of poor quality, with a conversion frequency (TOF) of only 215 mol. H2 ·mol Ru –1 ·min –1 This indicates that the introduction of P element to form CoP and CoN heterostructures has synergistic and electronic effects, as well as Ru / CoN-CoP and Ti3C2T x Strong interfacial interactions throughout the structure can accelerate electron transport rates, thereby promoting the adsorption and dissociation of ammonia borane and water molecules.

[0053] Catalysts with different Ru doping amounts (CoN-CoP / Ti3C2T) x Ru 0.5 / CoN-CoP / Ti3C2T x Ru / CoN-CoP / Ti3C2T x and Ru2 / CoN-CoP / Ti3C2T x The hydrogen release test of ammonia borane hydrolysis was performed at 298 K, and the results are as follows: Figure 7 As shown in cd. CoN-CoP / Ti3C2T xThe induction period for hydrogen release from the hydrolysis of ammonia borane is too long to be considered significant. However, the introduction of Ru significantly improves the catalytic activity, indicating that Ru can effectively modulate the local electronic environment of CoN-CoP nanoparticles, thereby improving the catalytic effect. As shown in the figure, when the Ru doping amount is 1.01 wt.% (as shown in Table 1), the Ru / CoN-CoP / Ti3C2T... x It exhibits optimal catalytic activity, with a corresponding conversion frequency (TOF) and hydrogen production rate (HGR) reaching 589.7 mol / L. H2 ·mol Ru –1 ·min –1 and 1.43 × 10 5 mL·min –1 ·g Ru –1 However, both excessively low and excessively high Ru doping levels can negatively impact catalytic activity. Lower Ru loading (0.78 wt.%) resulted in relatively poor local electronic environment modulation of the catalyst (conversion frequency of 67.2 mol / L). H2 ·mol Ru –1 ·min –1 The introduction of excess Ru (1.59 wt.%) may lead to its aggregation, resulting in a decrease in catalytic activity (conversion frequency of 170 mol). H2 ·mol Ru –1 ·min –1 ).

[0054] Table 1. Ru content in 10 mg catalyst determined by ICP-MS

[0055]

[0056] To investigate the effect of temperature on Ru / CoN-CoP / Ti3C2T x The dependence of catalyst activity on other experimental conditions was investigated by adjusting the water bath temperature sequentially to 298 K, 308 K, 318 K, and 328 K, while keeping other experimental conditions constant. Figure 8 It can be clearly seen that as the reaction temperature gradually increases, the time for complete hydrogen release from the hydrolysis of ammonia borane is significantly shortened. At 298 K, complete hydrogen release takes approximately 6.8 min, while at 328 K, the reaction time is reduced to about 1.5 min. The calculated conversion frequency (TOF) is 2474.9 mol / L. H2 ·mol Ru –1 ·min –1 This indicates that the catalytic activity is highly dependent on the reaction temperature. For example... Figure 8As shown in b, Ru / CoN-CoP / Ti3C2T is calculated using the Arrhenius formula. x Apparent activation energy (E) for catalytic hydrolysis of ammonia borane a It is approximately 26.3 kJ·mol. –1 This indicates that the catalyst can effectively promote the hydrogen release reaction of ammonia borane hydrolysis.

[0057] Stability and repeatability are also important indicators for evaluating catalyst performance. Further research was conducted on Ru / CoN-CoP / Ti3C2T under the same reaction conditions. x The effect of catalyst on the hydrogen release cycle stability of ammonia boron catalysis. Results are as follows: Figure 8 As shown in Figure 1, the hydrogen release reaction time of ammonia borane hydrolysis increases slightly with the increase of the number of cycles, and it still retains 80% of the initial catalytic activity after the 5th hydrolysis reaction. The results indicate that Ru / CoN-CoP / Ti3C2T x The catalyst exhibits excellent cycle stability.

[0058] XRD and TEM were used to analyze Ru / CoN-CoP / Ti3C2T after five hydrolysis reactions. x Catalysts were characterized, such as Figure 9 As shown in ab. By comparing Ru / CoN-CoP / Ti3C2T... x The XRD patterns of the catalyst before and after five reactions showed that its crystal phase structure remained unchanged during the reaction. Furthermore, TEM images revealed significant aggregation of the nanoparticles and an increased particle size, with an average diameter of approximately 10.76 nm. In summary, after five hydrolysis reactions, the Ru / CoN-CoP / Ti3C2T catalyst exhibited... x The main reasons for the decrease in catalytic activity are:

[0059] (1) As water is added to the solution during the reaction process, the entire reaction solution is continuously diluted;

[0060] (2) The reaction process produces byproducts (NH4BO2) which are adsorbed on the surface of active metal particles, leading to the "poisoning" and deactivation of the catalyst;

[0061] (3) The particle size of active metal nanoparticles is significantly increased, resulting in low metal utilization.

[0062] This invention successfully synthesized Ti3C2T using a solution self-assembly method. x RuCo-LDH nanosheets were grown in situ on the surface, and then Ti3C2T-based nanosheets were synthesized by a one-step phosphating method. x Ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst (Ru / CoN-CoP / Ti3C2T) xThe catalytic performance of this catalyst on the hydrolysis of ammonia borane was studied by adjusting different Ru doping amounts, catalyst compositions, and reaction temperatures. The mechanism by which its microstructure characteristics affect the hydrolysis of ammonia borane was also systematically investigated. The main conclusions are as follows:

[0063] (1) Catalyst morphology and structure: Ru / CoN-CoP nanoparticles derived in situ from precursor nanosheets after carbonization are uniformly dispersed in Ti3C2T x On nanosheets. Ru / CoN-CoP nanoparticles with Ti3C2T support. x The strong interfacial interactions throughout the structure can not only reduce the aggregation and shedding of nanoparticles during hydrolysis, but also accelerate the electron transport rate, thereby promoting the adsorption and dissociation of ammonia borane and water molecules.

[0064] (2) Catalyst composition: After introducing phosphorus (P), CoN and CoP form a heterostructure. The synergistic effect between CoN and CoP and between CoN and the support can optimize the electronic structure, promote the adsorption and desorption of intermediates, and thus promote the hydrolysis of ammonia borane kinetically. Introducing a small amount of Ru can optimize the surface electronic environment of the CoN-CoP heterostructure, thereby reducing the reaction barrier and improving the catalytic activity.

[0065] (3) The effects of different Ru doping amounts, catalyst compositions, and reaction temperatures on the hydrogen release performance of ammonia borane hydrolysis were investigated: The catalytic hydrogen release results showed that, under 298 K conditions, Ru / CoN-CoP / Ti3C2T x The catalyst achieved a conversion frequency (TOF) and hydrogen production rate (HGR) of 589.7 mol / L for the hydrogen release reaction of ammonia borane hydrolysis. H2 ·mol Ru –1 ·min –1 and 1.43 × 10 5 mL·min –1 ·g Ru –1 Apparent activation energy (E) a The value is 26.3 kJ·mol⁻¹ –1 After five hydrolysis hydrogen release reactions, it still retains 80% of its initial catalytic activity, which is superior to most of the catalysts reported in the literature for hydrolysis hydrogen release of ammonia borane.

[0066] (4) Deactivation mechanism of catalyst: The morphology and structure of the catalyst after the cyclic hydrolysis reaction were analyzed by SEM and XRD. It was found that its crystal phase structure remained unchanged during the reaction, but the active metals were slightly aggregated. The reason for the decrease in catalyst activity may be the generation of byproducts (NH4BO2) and their adsorption on the surface of active metal particles, which leads to catalytic deactivation.

[0067] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the inventive essence shall still fall within the protection scope of the present invention.

Claims

1. A Ti3C2T-based x The method for preparing a ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is characterized by, The method is as follows: S1. Add Co(NO3)2·6H2O, RuCl3·nH2O and urea to deionized water, sonicate for 20~40 min and stir magnetically until completely dissolved to obtain solution A; S2, Ti3C2T x The solution and the N-dimethylpyrrolidone solution were mixed at a volume ratio, and 3-5% by mass of polyethylene glycol 2000 was added as a dispersant. The mixture was stirred at room temperature for 1-2 hours to obtain the dispersion-modified solution B. S3. Under room temperature conditions, while stirring, solution A obtained in S1 is added dropwise to solution B obtained in S2. After the addition is complete, stirring is continued for 30 min. Then, the reaction is carried out under N2 atmosphere and oil bath at 100℃ with stirring for 5 h. After the reaction is completed, the mixture is naturally cooled to room temperature, washed with deionized water by centrifugation until the supernatant is neutral, and then washed 2-3 times by centrifugation with anhydrous ethanol. After vacuum drying at 60℃ for 12 h, the dried sample is immersed in a 0.1-0.5 mol / L dilute NaOH solution and stirred evenly. It is etched at room temperature for 5-10 min, filtered, washed with deionized water until neutral, and vacuum dried at 60℃ for 12 h to obtain RuCo-LDH / Ti3C2T. x Precursor; S4, the RuCo-LDH / Ti3C2T obtained from S3 is reacted with NaH2PO2·H2O. x The precursors were placed in the upstream phosphorus production zone and downstream reaction zone of the tubular furnace at a mass ratio of 1:(0.8~1.2). The NaH2PO2·H2O layer was 1~2 mm thick, and the precursor layer was 0.5~1 mm thick. The distance between the two zones was 3~5 cm. A hydrogen-argon mixture (5% H2 volume fraction, Ar as the equilibrium gas) was introduced into the tubular furnace at a flow rate of 50~80 mL / min. After purging the furnace air for 30 min, the flow rate was increased to 2 °C·min. –1 The temperature was increased to 300-400℃ at a rising rate and held for 2-3 hours, with a continuous hydrogen-argon mixed gas flow during the holding period. After the reaction was completed, the gas flow was kept constant, and the mixture was allowed to cool naturally to room temperature. Then, the gas flow was stopped, and the product was removed to obtain a Ti3C2T-based product. x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst, denoted as Ru / CoN-CoP / Ti3C2T x .

2. A Ti3C2T based method according to claim 1 x The method for preparing a ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is characterized by, The ratio of Co(NO3)2·6H2O, RuCl3·nH2O, urea and deionized water used in S1 is 0.2 mmol:0.01 mmol:2 mmol:10 mL.

3. A Ti3C2T based method according to claim 1 x The method for preparing a ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is characterized by, The Ti3C2T mentioned in S2 x The volume ratio of the solution to the N-dimethylpyrrolidone solution is 5 mL:15 mL.

4. A Ti3C2T based preparation method according to any one of claims 1-3 x The application of the ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is characterized by, The Ti3C2T-based x The ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is used to catalyze the hydrogen release reaction of ammonia borane hydrolysis.

5. The application according to claim 4, characterized in that, The Ti3C2T-based x The effects of different Ru doping amounts, catalyst compositions, and reaction temperatures on the hydrogen release performance of ammonia borane were investigated when a Ru / CoN-CoP / Ti3C2T composite catalyst was used to catalyze the hydrogen release reaction of ammonia borane. The catalytic hydrogen release results showed that, under 298 K conditions, the Ru / CoN-CoP / Ti3C2T catalyst exhibited the best performance. x The catalyst can achieve a conversion frequency (TOF) of up to 589.7 mol / L for the hydrogen release reaction of ammonia borane hydrolysis. H2 ·mol Ru –1 ·min –1 .

6. The application according to claim 4, characterized in that, The Ti3C2T-based x When the ruthenium-intercalated cobalt nitride-cobalt phosphide composite catalyst is used for the cyclic catalytic hydrogen release reaction of ammonia borane, it can still retain 80% of the initial catalytic activity after 5 hydrogen release reactions.

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