S-doped Ru2P / Ru difunctional electrocatalyst derived from cucurbituril [6] as well as preparation method and application of S-doped Ru2P / Ru difunctional electrocatalyst
By constructing an S-doped Ru2P/Ru bifunctional electrocatalyst on the surface of cucurbita[6], the problems of low reserves and high energy consumption of noble metal-based catalysts were solved, and low-cost and high-efficiency water electrolysis for hydrogen production was achieved. In particular, it showed excellent catalytic activity and stability in hydrazine oxidation-assisted hydrogen evolution.
Patent Information
- Application Number
- CN202511566347.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-30
- Publication Date
- 2026-01-30
AI Technical Summary
Existing precious metal-based catalysts suffer from low reserves and high prices in the process of hydrogen production by water electrolysis. Furthermore, the oxygen evolution reaction at the anode requires a high potential, resulting in high energy consumption and making it difficult to achieve efficient and low-cost hydrogen production.
A Ru2P/Ru-S-CBC catalyst derived from cucurbita[6] was used. By growing a poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) polymer coating on the surface of cucurbita[6], a Ru2P/Ru-S-CBC catalyst was formed. Combined with the synergistic effect of Ru nanoparticles, the catalytic activity was improved.
Under alkaline electrolyte conditions, the Ru2P/Ru-S-CBC catalyst exhibits excellent HER and HzOR performance, with low overpotentials. It requires only 9mV and -81mV when the current density reaches 10mA·cm-2, which significantly reduces the energy consumption for hydrogen production by water electrolysis.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of HER catalyst technology, specifically relating to a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst, its preparation method and application. Background Technology
[0002] As the global energy crisis intensifies, traditional fossil fuels are increasingly unable to meet the new demands of green and sustainable development. Meanwhile, hydrogen energy, as an ideal new energy source to replace fossil fuels, has attracted significant attention. Among these technologies, water electrolysis is a relatively green hydrogen production method, which uses an external voltage to crack the raw material into high-purity hydrogen gas without producing any carbon-containing substances. However, the HER reaction typically requires overcoming an overpotential far exceeding the theoretical potential. Noble metal-based catalysts exhibit a clear advantage in this process, but their limited reserves and high cost restrict their further application.
[0003] Furthermore, water electrolysis typically requires overcoming the high-potential oxygen evolution reaction at the anodic end (theoretical thermodynamic potential: 1.23V vs. RHE), which also increases energy consumption to some extent. Therefore, the HzOR reaction, with its green and safe products and lower theoretical thermodynamic potential (theoretical thermodynamic potential: -0.33V vs. RHE), has become an effective strategy to replace the oxygen evolution reaction for energy-saving hydrogen production. Therefore, to achieve the goal of efficient and low-cost hydrogen production through hydrazine-assisted water splitting, it is urgent to develop an efficient strategy to improve the hydrazine-assisted hydrogen evolution performance of noble metal-based electrocatalysts. Summary of the Invention
[0004] To address the aforementioned technical problems, the present invention aims to provide a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst, its preparation method, and its application. The bifunctional electrocatalyst of the present invention exhibits excellent HzOR and HER performance, while also possessing excellent stability.
[0005] To achieve the above-mentioned objectives, the technical solution adopted in this invention is as follows: a bifunctional electrocatalyst derived from cucurbita[6] and doped Ru2P / Ru is obtained by using cucurbita[6] (CB[6]) as a support, introducing RuCl3,4,4'-sulfonyl diphenol (BPS) and hexachlorocyclotriphosphazene (HCCP) as building units, growing a poly(cyclotriphosphazene-co-4,4'-sulfonyl diphenol) polymer (PZS) coating on the surface of CB[6] in situ, and then pyrolyzing it to obtain the bifunctional electrocatalyst Ru2P / Ru-S-CBC.
[0006] A method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst includes the following steps:
[0007] Step 1: Disperse cucurbituril[6] (CB[6]) and RuCl3 in methanol and sonicate to form a uniform dispersion; dissolve 4,4'-sulfonyldiphenol (BPS) and hexachlorocyclotriphosphazene (HCCP) in methanol and slowly pour them into the dispersion; stir evenly and slowly add triethylamine solution while stirring continuously at room temperature; finally, centrifuge and wash, and vacuum dry to obtain intermediate CB[6]@Ru-PZS;
[0008] Step 2: Pyrolyze the intermediate CB[6]@Ru-PZS under an inert gas and cool it naturally to room temperature to obtain the bifunctional electrocatalyst Ru2P / Ru-S-CBC.
[0009] Further, in step 1, the molar ratio is CB[6]:RuCl3=(3-8):1.
[0010] Further, in step 1, triethylamine solution is slowly added dropwise, and the mixture is continuously stirred at room temperature for 12-36 hours.
[0011] Furthermore, in step 1, the vacuum drying conditions are 60℃-80℃ for 10h-20h.
[0012] Furthermore, in step 2, the inert gas is argon.
[0013] Furthermore, in step 2, the pyrolysis conditions are: pyrolysis at 700℃-900℃ for 1-3 hours.
[0014] The present invention provides the application of a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst in hydrazine oxidation-assisted hydrogen evolution.
[0015] Furthermore, the application of S-doped Ru2P / Ru bifunctional electrocatalysts derived from cucurbituril [6] as HzOR catalysts in hydrazine oxidation-assisted hydrogen evolution.
[0016] Furthermore, the application of S-doped Ru2P / Ru bifunctional electrocatalysts derived from cucurbituril [6] as HER catalysts in hydrazine oxidation-assisted hydrogen evolution.
[0017] Compared with the prior art, the beneficial effects of the present invention are:
[0018] The bifunctional electrocatalyst Ru₂P / Ru-S-CBC provided by this invention exhibits excellent HER and HzOR performance in alkaline electrolytes, even at current densities reaching 10 mA·cm⁻¹. -2The overpotentials were 9 mV and -81 mV, respectively, which may be attributed to the synergistic effect between Ru₂P and Ru nanoparticles. S also played a moderating role in improving catalytic activity. A dual-electrode hydrazine decomposition electrolyzer was further assembled, and its overall hydrazine decomposition (OHzS) performance was tested. This electrolyzer requires only 0.029 V to reach 10 mA·cm⁻¹. -2 The current density is [not specified]. However, OHzS (Overall Water Splitting) requires an ultra-high voltage of 2.395V to achieve the same current density, confirming that OHzS can indeed achieve a significant voltage reduction. This invention provides a new approach for hydrazine-assisted hydrogen evolution catalysis based on nitrogen-doped carbon materials. Attached Figure Description
[0019] Figure 1 This is a synthetic route diagram for the bifunctional electrocatalyst Ru2P / Ru-S-CBC of the present invention.
[0020] Figure 2 The images show SEM (a) and TEM (b) images of Ru2P / Ru-S-CBC-0.08, which is used as a HER catalyst in this invention.
[0021] Figure 3 The images show SEM (a) and TEM (b) images of Ru2P / Ru-S-CBC-0.04, which is used as a HzOR catalyst in this invention.
[0022] Figure 4 PXRD plots for CBC, NPS-CBC, Ru2P / Ru-S-CBC-0.08, and Ru2P / Ru-S-CBC-0.04.
[0023] Figure 5 LSV curves (a), Tafel curves (b), and C values for different catalysts under alkaline conditions are shown. dl Double-layer capacitor (c); Comparison of LSV curves of Ru2P / Ru-S-CBC-0.08 before and after 5000 CV cycles (d).
[0024] Figure 6 Screening for the optimal hydrazine concentration of the bifunctional electrocatalyst Ru2P / Ru-S-CBC (a), LSV curve (b) and Tafel curve (c); LSV curve of Ru2P / Ru-S-CBC-0.04 before and after 1500 CV cycles (d).
[0025] Figure 7 This is a schematic diagram of the assembled dual-electrode OHzS electrolytic cell Ru2P / Ru-S-CBC-0.08||Ru2P / Ru-S-CBC-0.04.
[0026] Figure 8Comparison of LSVs for assembled dual-electrode OHzS and OWS. Detailed Implementation
[0027] Example 1: Bifunctional electrocatalyst Ru2P / Ru-S-CBC
[0028] (a) Preparation of Ru2P / Ru-S-CBC-0.08
[0029] Synthetic routes such as Figure 1 The method includes the following steps:
[0030] 1. Synthesis of CB[6]@Ru-PZS
[0031] CB[6] (300.0 mg, 0.3 mmol) and RuCl3 (16.5 mg, 0.08 mmol) were dispersed in 32 mL of methanol and sonicated for 20 min to form a uniform dispersion. BPS (270.2 mg) and HCCP (125.2 mg) were added to 40 mL of methanol and sonicated for 10 min to dissolve them completely. The solution was then slowly poured into the dispersion of CB[6] and RuCl3 and stirred for 20 min. Triethylamine (400 µL) was then slowly added dropwise and stirred for 24 h at room temperature. The resulting precipitate was centrifuged and washed three times with methanol. It was then vacuum dried at 80°C for 12 h to obtain CB[6]@Ru-PZS.
[0032] 2. Synthesis of Ru2P / Ru-S-CBC-0.08
[0033] CB[6]@Ru-PZS was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1 The temperature was increased to 800℃ at a rising rate, and pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the bifunctional electrocatalyst Ru2P / Ru-S-CBC, labeled as Ru2P / Ru-S-CBC-0.08.
[0034] (II) Preparation of Ru2P / Ru-S-CBC-0.04
[0035] Synthetic routes such as Figure 1 The method includes the following steps:
[0036] 1. Synthesis of CB[6]@Ru-PZS
[0037] CB[6] (300.0 mg, 0.3 mmol) and RuCl3 (8.2 mg, 0.04 mmol) were dispersed in 32 mL of methanol and sonicated for 20 min to form a uniform dispersion. BPS (270.2 mg) and HCCP (125.2 mg) were added to 40 mL of methanol and sonicated for 10 min to dissolve them completely. The solution was then slowly poured into the dispersion of CB[6] and RuCl3 and stirred for 20 min. Triethylamine (400 µL) was then slowly added dropwise and stirred for 24 h at room temperature. The resulting precipitate was centrifuged and washed three times with methanol. It was then vacuum dried at 80°C for 12 h to obtain CB[6]@Ru-PZS.
[0038] 2. Synthesis of Ru2P / Ru-S-CBC-0.04
[0039] CB[6]@Ru-PZS was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1 The temperature was increased to 800℃ at a rising rate, and pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the bifunctional electrocatalyst Ru2P / Ru-S-CBC, labeled as Ru2P / Ru-S-CBC-0.04.
[0040] (III) Preparation of Comparative CBC
[0041] CB[6] was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1 The temperature was increased to 800℃ at a certain rate, and the sample was pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the electrocatalyst CBC.
[0042] (iv) Preparation of comparative NPS-CBC
[0043] 1. Synthesis of CB[6]@PZS
[0044] CB[6] (300.0 mg, 0.3 mmol) was dispersed in 32 mL of methanol and sonicated for 20 min to form a uniform dispersion. BPS (270.2 mg) and HCCP (125.2 mg) were added to 40 mL of methanol and sonicated for 10 min to dissolve them completely. The mixture was then slowly poured into the CB[6] dispersion and stirred for 20 min. Triethylamine (400 µL) was then slowly added dropwise and stirred for 24 h at room temperature. The resulting precipitate was centrifuged and washed three times with methanol. It was then vacuum dried at 80°C for 12 h to obtain CB[6]@PZS.
[0045] 2. Synthesis of NPS-CBC
[0046] CB[6]@PZS was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1The temperature was increased to 800℃ at a certain rate, and the sample was pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the electrocatalyst NPS-CBC.
[0047] (v) Preparation of comparative example Ru2P / Ru-CBC-0.08
[0048] 1. Synthesis of CB[6]@Ru-PZH
[0049] CB[6] (300.0 mg, 0.3 mmol) and RuCl3 (16.5 mg, 0.08 mmol) were dispersed in 32 mL of methanol and sonicated for 20 min to form a uniform dispersion. 4,4'-dihydroxybiphenyl (PPDP) (270.2 mg) and HCCP (125.2 mg) were added to 40 mL of methanol and sonicated for 10 min to dissolve them completely. The solution was then slowly poured into the dispersion of CB[6] and RuCl3 and stirred for 20 min. Triethylamine (400 µL) was then slowly added dropwise and stirring was continued for 24 h at room temperature. The resulting precipitate was centrifuged and washed three times with methanol. It was then vacuum dried at 80°C for 12 h to obtain CB[6]@Ru-PZH.
[0050] 2. Synthesis of Ru2P / Ru-CBC-0.08
[0051] CB[6]@Ru-PZH was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1 The temperature was increased to 800℃ at a rising rate, and pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the electrocatalyst Ru2P / Ru-CBC, labeled as Ru2P / Ru-CBC-0.08.
[0052] (vi) Preparation of comparative example Ru2P / Ru-CBC-0.04
[0053] 1. Synthesis of CB[6]@Ru-PZH
[0054] CB[6] (300.0 mg, 0.3 mmol) and RuCl3 (8.2 mg, 0.04 mmol) were dispersed in 32 mL of methanol and sonicated for 20 min to form a uniform dispersion. PPDP (270.2 mg) and HCCP (125.2 mg) were added to 40 mL of methanol and sonicated for 10 min to dissolve them completely. The dissolved PPDP and HCCP were then slowly poured into the dispersion of CB[6] and RuCl3 and stirred for 20 min. Triethylamine (400 µL) was then slowly added dropwise, and stirring was continued for 24 h at room temperature. The resulting precipitate was centrifuged and washed three times with methanol. It was then vacuum dried at 80°C for 12 h to obtain CB[6]@Ru-PZH.
[0055] 2. Synthesis of Ru2P / Ru-CBC-0.04
[0056] CB[6]@Ru-PZH was placed in a magnetic boat and heated at 5℃·min under a flowing argon atmosphere. -1 The temperature was increased to 800℃ at a rising rate, and pyrolyzed at 800℃ for 2 hours. After naturally cooling to room temperature, the sample was ground to obtain the electrocatalyst Ru2P / Ru-CBC, labeled as Ru2P / Ru-CBC-0.04.
[0057] (vii) Characterization
[0058] Figure 2 SEM (a) and TEM (b) images of Ru2P / Ru-S-CBC-0.08. Figure 2 It can be seen that the Ru2P / Ru-S-CBC-0.08 catalyst exhibits an uneven blocky structure morphology and a relatively rough surface. Figure 3 SEM (a) and TEM (b) images of Ru2P / Ru-S-CBC-0.04. Figure 3 It can be seen that the Ru2P / Ru-S-CBC-0.04 catalyst exhibits an uneven blocky structure morphology and a relatively rough surface. Figure 2 and Figure 3 This demonstrates that changes in Ru doping do not affect the microstructure of the material.
[0059] Figure 4 PXRD patterns of CBC, NPS-CBC, Ru2P / Ru-S-CBC-0.08, and Ru2P / Ru-S-CBC-0.04 are shown. The PXRD patterns reveal two broad peaks at 26.5° and 44.6° after pyrolysis in CBC and NPS-CBC, corresponding to the (002) and (101) crystal planes of graphitic carbon (PDF#99-0057), respectively, confirming the formation of the graphitic carbon structure. After Ru doping, the catalyst formed two phases on the original basis. Characteristic diffraction peaks of Ru2P (PDF#89-3031) were observed at positions of 30.5°, 38.1°, 40.6°, 47.0°, and 53.6°, belonging to the (111), (112), (211), (020), and (302) crystal planes, respectively. Furthermore, the characteristic diffraction peaks of Ru (PDF#06-0663) appeared at 38.4°, 42.1°, and 44.0°, corresponding to its (100), (002), and (101) crystal planes, respectively. Therefore, the PXRD results strongly confirm the successful construction of the dual catalytic active sites in the catalyst. Compared to the single-component catalyst, this Ru₂P / Ru binary catalyst exhibits a synergistic effect, significantly enhancing the catalytic activity.
[0060] Example 2: HER catalytic activity test of Ru2P / Ru-S-CBC-0.08 catalyst under alkaline conditions.
[0061] Methods: The Ru2P / Ru-S-CBC-0.08 catalyst (5 mg) prepared in Example 1 was mixed with ethanol (250 µL), water (935 µL), and Nafion (65 µL) to prepare an ink, which was then drop-coated onto a glassy carbon electrode as the working electrode. A saturated calomel electrode was used as the reference electrode, and a carbon rod was used as the counter electrode. The HER activity of Ru2P / Ru-S-CBC-0.08 was tested using a three-electrode system in 1.0 M KOH electrolyte.
[0062] Meanwhile, working electrodes were prepared by replacing Ru2P / Ru-S-CBC-0.08 with CBC, NPS-CBC, Ru2P / Ru-CBC-0.08, and Pt / C for comparison.
[0063] from Figure 5 In the LSV curve of a, it can be observed that at 10 mA·cm -2 At current densities of 9 mV, both Ru2P / Ru-S-CBC-0.08 and Ru2P / Ru-CBC-0.08 exhibited overpotentials superior to commercial Pt / C (20 mV). However, with further increases in current density, Ru2P / Ru-S-CBC-0.08 showed a significant advantage, indicating that S plays a crucial role in enhancing catalytic activity. Furthermore, neither CBC nor NPS-CBC exhibited HER activity, further demonstrating that Ru2P and Ru are active sites for the catalyst. To verify their superior reaction kinetics, this invention also fitted the Tafel slope (… Figure 5 (b) It can be observed that Ru2P / Ru-S-CBC-0.08 has a low Tafel slope (20.37 mV·dec). -1 ), far lower than Ru2P / Ru-CBC-0.08 (82.63 mV·dec) -1 ) and Pt / C (44.28mV·dec -1 To investigate the intrinsic catalytic activity of different catalysts, C was also calculated. dl Value. C of Ru2P / Ru-S-CBC-0.08 dl The value is 98.27 mF·cm -2 Its value is much larger than that of other catalytic materials, which proves that it has the largest electrochemical active surface area and more active sites, which is beneficial to improving the HER catalytic activity. Finally, the stability of the catalyst was verified by comparing the LSV curves before and after 5000 CV cycles. Figure 5(d). It can be observed that the LSV curves before and after the cycle are almost completely overlapped, which also indicates that Ru2P / Ru-S-CBC-0.08 has excellent stability in the HER catalytic reaction.
[0064] Example 3: HzOR catalytic activity test of Ru2P / Ru-S-CBC-0.04 catalyst in hydrazine-containing alkaline electrolyte.
[0065] Methods: The Ru2P / Ru-S-CBC-0.04 catalyst (5 mg) prepared in Example 1 was mixed with ethanol (250 µL), water (935 µL), and Nafion (65 µL) to prepare an ink, which was then drop-coated onto a glassy carbon electrode as the working electrode. A saturated calomel electrode was used as the reference electrode, and a carbon rod was used as the counter electrode. The HzOR activity of Ru2P / Ru-S-CBC-0.04 was tested using a three-electrode system in 1.0 M KOH and 0.1 M–1.0 M N2H4 electrolytes.
[0066] Meanwhile, working electrodes were prepared by replacing Ru2P / Ru-S-CBC-0.04 with CBC, NPS-CBC, Ru2P / Ru-CBC-0.04, and Pt / C for comparison.
[0067] First, the optimal hydrazine concentration for the HzOR reaction was screened. It was observed that the overpotential gradually decreased as the hydrazine (N2H4) concentration increased from 0.1M to 1.0M. Therefore, this invention selected 1.0M N2H4 as the optimal concentration for subsequent experiments. Figure 6 (a) By observing the LSV curve comparison graph, it can be found that Ru2P / Ru-S-CBC-0.04 at current densities of 10 mA·cm⁻¹ -2 and 100mA·cm -2 At these times, the overpotentials were -81 mV and -3 mV, respectively, which were far superior to those of commercial Pt / C (98 mV and 150 mV) and Ru2P / Ru-CBC-0.04 (-4 mV and 1070 mV), confirming the excellent HzOR catalytic activity of Ru2P / Ru-S-CBC-0.04. Figure 6 (b) The Tafel slope value is only 10.36 mV·dec. -1 It is significantly lower than Ru2P / Ru-CBC-0.04 (65.46 mV·dec) -1 ) and Pt / C (28.47mV·dec) -1 () Figure 6(c). This performance is also significantly better than most Ru-based catalysts reported in recent years. The catalyst's performance was also verified by CV cycling; after 1500 CV cycles, the LSV polarization curve did not change significantly, indicating that Ru2P / Ru-S-CBC-0.04 has good stability. Figure 6 (d).
[0068] Example 4: Overall Hydrazine Decomposition (OHzS) Performance Test of a Two-Electrode System
[0069] Methods: A two-electrode electrolyzer was assembled using Ru₂P / Ru-S-CBC-0.08 and Ru₂P / Ru-S-CBC-0.04. The electrolyte was 1.0 M KOH + 1.0 M N₂H₄. The mechanism was as follows: Figure 7 As shown. The electrode reactions are as follows:
[0070] Cathodic reaction (HER): 4H₂O + 4e - →4OH - +2H2;
[0071] Anodic reaction (HzOR): N₂H₄ + 4OH⁻ - →N2 + 4H2O + 4e - ;
[0072] Overall reaction: N2H4 → N2 + 2H2;
[0073] Given its excellent HER and HzOR bifunctional activity, a dual-electrode electrolyzer was further assembled using Ru2P / Ru-S-CBC-0.08 and Ru2P / Ru-S-CBC-0.04 as the cathode and anode, respectively, and its OHzS performance was tested. The test results show that this electrolyzer requires only 0.029V, 0.065V, 0.180V, and 0.380V to achieve 10, 20, 50, and 100 mA·cm⁻¹, respectively. -2 The current density was measured. To demonstrate the potential advantage of hydrazine-assisted hydrogen evolution, the OWS performance (electrolyte: 1.0 M KOH) was also tested using the same electrolyzer. The test results showed that the electrolyzer required ultra-high voltages of 2.395 V, 2.556 V, 2.779 V, and 2.971 V to achieve the corresponding current densities. This also verifies the initial experimental objective of this invention: OHzS can indeed achieve a significant voltage reduction, thereby reducing energy consumption. Figure 8 These results demonstrate that the Ru2P / Ru-S-CBC-0.08 and Ru2P / Ru-S-CBC-0.04 catalysts exhibit excellent HER and HzOR catalytic activities.
Claims
1. A cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst, characterized in that, A bifunctional electrocatalyst Ru2P / Ru-S-CBC is prepared by using cucurbituril [6] as a carrier, introducing RuCl3, 4,4'-sulfonated phenol and hexachlorocyclotriphosphazene as building units, growing a poly(cyclotriphosphazene-co-4,4'-sulfonated phenol) polymer coating on the surface of cucurbituril [6] in situ, and pyrolyzing the polymer coating.
2. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 1, characterized in that, The preparation method comprises the following steps: Step 1: cucurbituril [6] and RuCl3 are dispersed in methanol to form a uniform dispersion liquid by ultrasonic treatment; 4,4'-sulfonated phenol and hexachlorocyclotriphosphazene are dissolved in methanol and then slowly poured into the dispersion liquid; after uniform stirring, triethylamine solution is slowly added dropwise, and continuous stirring is carried out at room temperature; finally, centrifugal washing and vacuum drying are carried out to obtain an intermediate CB[6]@Ru-PZS; Step 2: the intermediate CB[6]@Ru-PZS is pyrolyzed under inert gas, and the bifunctional electrocatalyst Ru2P / Ru-S-CBC is obtained after natural cooling to room temperature.
3. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 2, characterized in that, In step 1, the molar ratio of cucurbituril [6] to RuCl3 is (3-8):
1.
4. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 2, characterized in that, In step 1, the triethylamine solution is slowly added dropwise, and continuous stirring is carried out at room temperature for 12-36 hours.
5. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 2, characterized in that, In step 1, the vacuum drying conditions are 60-80℃ for 10-20 hours.
6. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 2, characterized in that, In step 2, the inert gas is argon.
7. The method for preparing a cucurbituril[6]-derived S-doped Ru2P / Ru bifunctional electrocatalyst according to claim 2, characterized in that, In step 2, the pyrolysis conditions are 700-900℃ for 1-3 hours.
8. The use of the cucurbituril [6] derivative S-doped Ru2P / Ru bifunctional electrocatalyst in hydrazine oxidation assisted hydrogen evolution.
9. Use according to claim 8, characterized in that, The use of the cucurbituril [6] derivative S-doped Ru2P / Ru bifunctional electrocatalyst as a HzOR catalyst in hydrazine oxidation assisted hydrogen evolution.
10. Use according to claim 8, characterized in that, The use of the cucurbituril [6] derivative S-doped Ru2P / Ru bifunctional electrocatalyst as a HER catalyst in hydrazine oxidation assisted hydrogen evolution.