A RuOx-Mo2C cluster-cluster heterostructure catalyst, its preparation method and its application

Abstract

This invention relates to a RuO x This paper describes the preparation method and application of Mo2C cluster-cluster heterostructure catalysts, belonging to the field of catalyst technology. Ammonium molybdate tetrahydrate is dissolved in water and stirred to form solution A; dopamine hydrochloride is dissolved in ethanol and stirred to form solution B. Solution B is slowly added dropwise to solution A, and after thorough mixing, a reddish-brown solution is obtained. Ammonia water is added and stirring continues. After stirring is complete, centrifugation is performed to obtain a reddish-brown precipitate, which is washed, dried, and then the Mo-PDA precursor is obtained. Calcination yields the Mo2C catalyst; RuO is prepared. x -Mo2C clusters-cluster heterostructure. The RuO of this invention... x -Mo2C cluster-cluster heterostructure catalysts, due to the high density of accessible active sites and efficient mass transport pathways provided by the strongly coupled cluster structure, allow hydrogen to migrate directionally and rapidly from Mo2C sites to RuO through a reverse hydrogen spillover effect. x The site can effectively induce a reverse hydrogen spillover effect.

Description

Technical Field

[0001] This invention relates to a RuO x -Mo2C cluster- Cluster heterostructure catalysts, preparation methods and applications belong to the field of catalyst technology. Background Technology

[0002] With the escalating global energy crisis, seeking sustainable green energy alternatives has become an urgent priority. Hydrogen (H2), with its excellent renewable energy storage and conversion capabilities and broad application prospects, has become an ideal green energy carrier. Utilizing renewable electricity from wind and solar power to drive water electrolysis for zero-emission hydrogen production is a key production route. The hydrogen evolution reaction in an alkaline system begins with the Vollmer step: H2O adsorbs on the electrode surface and dissociates, generating an adsorption intermediate (…). and However, the inherent scarcity of active sites, coupled with the hydrogen adsorption free energy (…), The deviation from the optimal range leads to sluggish water dissociation kinetics and insufficient proton supply within the system. Simultaneously, a large amount of... Strong adsorption occurs on the electrode surface, further crowding out active sites. These two factors ultimately significantly limit the entire HER process. Although platinum-based catalysts can achieve excellent performance by adjusting the hydrogen adsorption energy and accelerating the HER catalytic kinetics in water electrolysis, their limited reserves, scarcity, and high cost hinder the commercial application of ruthenium. Comparable to platinum, it meets the requirements of the hydrogen evolution reaction, and its cost is only one-third that of platinum, making it a high-performance and cost-effective candidate material for the next generation of hydrogen evolution reaction electrocatalysts.

[0003] Metal clusters typically consist of several to hundreds of atoms, exhibiting high active site exposure and atom utilization efficiency comparable to single-atom catalysts. Simultaneously, they effectively prevent single-atom aggregation induced by atom migration during the reaction, thus preventing a reduction in active sites. This structure allows electrolyte ions (such as H+) to... + OH - Rapid diffusion and timely desorption of product gases (H2, O2) enhance mass transport, thereby reducing surface clogging. However, single-component clusters, due to their monofunctional active sites, cannot meet the catalytic requirements of multi-step, multi-electron transfer reactions. To overcome this limitation, a cluster-cluster heterostructure catalyst was constructed. By utilizing the electron transfer effect between clusters, this catalyst synergistically modulates the electronic structure, thereby finely regulating the electron transfer. It also effectively inhibits the excessive accumulation of intermediates at individual active sites, preventing catalyst deactivation and ultimately achieving highly efficient HER.

[0004] Zhang et al. (B. Zhang, J. Wang, G. Liu, CM Weiss, D. Liu, Y. Chen, L.Xia, P. Zhou, M. Gao, Y. Liu, Nat. Catal. 2024, 7 (441-451) A heterostructure catalyst composed of discrete Ru and CrOx clusters was constructed. The strong coupling between these clusters generated a unique interpenetrating interface, modulating the adsorption behavior on each cluster and providing key support for achieving high-performance hydrogen electrocatalysis in alkaline media. Hydrogen spillover (HS) has become an important research topic in the field of water electrolysis because it can effectively regulate the transport and distribution of hydrogen species in the catalytic system and significantly enhance the catalytic activity of bimetallic catalysts. Hydrogen spillover refers to the adsorption of... The process of hydrogen migrating from hydrogen-rich sites to hydrogen-poor sites. In two-component catalytic systems, this typically manifests as hydrogen migration from the metal active phase to the support phase, Ir / HfO2@C (W.Shao, Z. Xing, X. Xu, D. Ye, R. Yan, T. Ma, Y. Wang, Z. Zeng, B. Yin, C. Cheng, S. Li, J. Am. Chem. Soc. 2024, 146 , 27486-27498), Ru-WO3 (Y. Wang, H. Liu, Z. Lv, Y. Fan, G. Zhao, J. Xu, S. Tan, P. Tong, S. Wei, Z. Zhang, Angew. Chem., Int. Ed. 2025, 64 (e202512466) and Pt / WO3 (H. Tian, ​​X. Cui, L. Zeng, L. Su, Y. Song, J. Shi, J. Am. Chem. Soc. 2019, 7 The 6285-6293 system is a representative example. Reverse hydrogen overflow (RHS) is a variant of hydrogen overflow, referring to... However, catalysts that regulate the mechanism of reverse hydrogen spillover are also very rare, as they involve the migration from the support phase to the metal active phase. Summary of the Invention

[0005] To address the problems and shortcomings of the existing technology, this invention provides a RuO x -Mo2C cluster- Cluster heterostructure catalyst, preparation method and application. The RuO of this invention... x-Mo2C cluster-cluster heterostructure catalysts, due to the high density of accessible active sites and efficient mass transport pathways provided by the strongly coupled cluster structure, allow hydrogen to migrate directionally and rapidly from Mo2C sites to RuO through a reverse hydrogen spillover effect. x The site can effectively induce a reverse hydrogen spillover effect. This invention is achieved through the following technical solution.

[0006] A RuO x The preparation method of the -Mo2C cluster-cluster heterostructure catalyst includes the following steps: Step 1: Preparation of Mo2C catalyst: Ammonium molybdate tetrahydrate was dissolved in water and stirred to form solution A; dopamine hydrochloride was dissolved in ethanol and stirred to form solution B; solution B was slowly added dropwise to solution A and mixed evenly to obtain a reddish-brown solution; ammonia water was added and stirring was continued; after stirring was completed, centrifugation was performed to obtain a reddish-brown precipitate, which was washed and dried to obtain the Mo-PDA precursor. Under an argon / hydrogen mixed atmosphere, the temperature was raised to 400°C-800°C and held for 5-10 hours. After cooling to room temperature, the catalyst was ground to obtain the Mo2C catalyst. Step 2: Preparation of RuO x -Mo2C clusters-cluster heterostructure catalysts: Mo2C catalyst was added to water to obtain dispersion A; ruthenium acetylacetone was added to water to obtain dispersion B; dispersion B was slowly added to dispersion A, mixed evenly, and centrifuged after the reaction was completed to obtain the bottom precipitate; The bottom precipitate was washed, dried, calcined, cooled to room temperature, and then ground to obtain prepared RuO. x -Mo2C cluster-cluster heterostructure catalyst.

[0007] In step 1, the solid-liquid ratio of molybdic acid tetrahydrate to water is 120:32 mg / mL; the solid-liquid ratio of dopamine hydrochloride dissolution to ethanol is 120:64 mg / mL; the ammonia water is analytical grade ammonia water, and the volume of ammonia water to water is 0.6:32.

[0008] In step 1, the volume ratio of argon to hydrogen in the argon / hydrogen mixed atmosphere is 95:5.

[0009] The process involves purging the gas with a mixed argon / hydrogen atmosphere at room temperature for 20 minutes, then heating to 400°C at a rate of 5°C / min and holding for 2 hours; then heating to 800°C and holding for 3 hours.

[0010] In step 2, the solid-liquid ratio of Mo2C catalyst to water is 100:50 mg / mL; the solid-liquid ratio of ruthenium acetylacetone to water is 100:50 mg / mL.

[0011] In step 2, the calcination is carried out under a protective atmosphere of N2, and then the temperature is increased to 300°C at a rate of 5°C per minute and maintained for 2 hours.

[0012] A RuO x -Mo2C cluster-cluster heterostructure catalyst, prepared by the above method, RuO x -Mo2C cluster- Cluster heterostructure catalysts exhibit a hierarchical structure, consisting of numerous micron-sized flower-like aggregates, each aggregate being assembled from finer nano-sized petal-shaped structural units, where x ranges from 1.9 to 4.4.

[0013] The RuO x -Mo2C cluster- Cluster heterostructure catalyst has a specific surface area of ​​84.1 m². 2 / g, moderate mesopore size of 8.145nm and higher pore volume of 0.212cm³ 3 / g.

[0014] A RuO x The application of -Mo2C cluster-cluster heterostructure catalysts as electrocatalysts for hydrogen evolution reaction effectively induces the reverse hydrogen spillover effect.

[0015] The beneficial effects of this invention are: (1) The RuO of the present invention x -Mo2C cluster-cluster heterostructure catalysts can effectively induce a reverse hydrogen spillover effect. This well-defined interfacial coupling and functional partitioning significantly reduces water dissociation. The combined energy barrier of transport and HH coupling significantly accelerates HER kinetics and exhibits excellent electrocatalytic activity for hydrogen evolution.

[0016] (2) The RuO of the present invention x -Mo2C cluster-cluster heterostructure catalyst, at 10 mA cm⁻¹ -2 It requires only 15mV overpotential at current density, exhibiting excellent electrocatalytic activity for hydrogen evolution.

[0017] (3) The RuO of the present invention x The -Mo2C cluster-cluster heterostructure catalyst can maintain stable performance for 1000 hours under continuous electrolysis conditions without significant degradation, exhibiting excellent structural and catalytic stability.

[0018] (4) The RuO of the present invention x -Mo2C cluster- Cluster heterostructure catalyst, when used as a cathode in an anion exchange membrane water electrolyzer, at 1.0 A cm⁻¹ -2The battery voltage is only 1.76V at the current density and can maintain long-term stability for more than 1500 hours, demonstrating excellent catalytic activity and broad prospects for industrial high-current applications. Attached Figure Description

[0019] Figure 1 The RuO prepared in Example 1 of this invention x -Mo2C cluster-XRD pattern of cluster heterostructure catalyst.

[0020] Figure 2 The RuO prepared in Example 1 of this invention x -Mo2C cluster- Cluster heterostructure catalyst synthesis process and structural characterization diagram, where (a) is a schematic diagram of the preparation, (b, c) are TEM images, (d) is an HRTEM image, (e, f) are AC-STE images, and (g) is a RuO2 cluster. x - Elemental mapping of Ru, O, Mo and C in Mo2C catalyst.

[0021] Figure 3 The RuO prepared in Example 1 of this invention x -Mo2C cluster-cluster heterostructure catalyst BET results diagram.

[0022] Figure 4 The RuO prepared in Example 1 of this invention x -Mo2C cluster-Cluster heterostructure catalyst surface characteristic analysis diagram, where RuO x High-resolution XPS spectra of (a) Ru 3p, (b) Mo 3d, and (c) O 1s for Mo2C and Mo2C. (d) Nitrogen adsorption-desorption isotherm. (e) Ru K-edge XANES spectrum, (f) FT-EXAFS spectrum, and (gi) WT-EXAFS signal for RuOx-Mo2C.

[0023] Figure 5 The RuO prepared in Example 1 of this invention x -Mo2C cluster- Cluster heterostructure catalyst HER activity performance diagram in alkaline medium, (a)RuO x (a) LSV curves of Mo2C and other electrocatalysts; (b) Tafel slope; (c) Comparison of HER catalytic performance of similar catalysts in alkaline solution; (d) EIS; (e) Cdl value; (f) Comparison of HER performance indicators; (g) RuO x LSV curves of Mo2C in three different solutions; (h) RuO x -Stability test of Mo2C under constant potential for 1000 hours.

[0024] Figure 6The RuO prepared in Example 1 of this invention x -Mo2C cluster-Cluster heterostructure catalyst catalytic mechanism performance diagram; (a) RuO before and after selective SCN-poisoned metal Ru site. x - LSV curve of Mo2C, with the inset showing the corresponding Tafel slope; (b) RuO x In-situ ATR-FTIR spectra of (c)Mo2C and (d, e)Mo2C at different applied potentials; RuO x -Mo2C and Mo2C catalysts in 1.0 MKOH, scan rate 20-100 mV s -1 The following CV; (f) RuO x - Schematic diagram of HER enhancement mechanism on Mo2C.

[0025] Figure 7 The RuO prepared in Example 1 of this invention x -Mo2C cluster- Cluster heterostructure catalyst as cathode in AEMWE system, schematic diagram of simulated water electrolysis; (a) Schematic diagram; (b) Polarization curve; (c) RuO in radar image x A comprehensive comparison of the AEMWE performance of Mo2C and Pt / C catalysts; (d)RuO x Stability curves of -Mo2C||NiFeO-CeO2; (e) AEMWE at 1.0 A cm⁻¹ using previously reported advanced catalysts. -2 A comparison of battery voltage and energy efficiency. Detailed Implementation

[0026] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0027] In the examples, ammonium molybdate tetrahydrate ((NH4)6Mo7O) 24 ·4H2O), dopamine hydrochloride (C8H) 11 NO2·HCl), ruthenium acetylacetonate (C 15 H 21 O6Ru), ammonia solution, and potassium hydroxide (KOH) were purchased from Aladdin. Pt / C (20 wt% Pt) and Nafion (5 wt%) were purchased from Alfa Aesar. All chemical reagents were used directly without further purification; all aqueous solutions were prepared using ultrapure water (>18.25 Ω cm) prepared using the Millipore system. Example 1

[0028] like Figure 2 As shown in (a), the RuO x The preparation method of the -Mo2C cluster-cluster heterostructure catalyst includes the following steps: (1) Preparation of Mo2C catalyst: (1.1) Dissolve 120 mg of ammonium molybdate tetrahydrate in 32 mL of water and stir for 30 min to form solution A; dissolve 120 mg of dopamine hydrochloride in 64 mL of ethanol and stir for 30 min to form solution B; slowly add solution B to solution A and mix well to obtain a reddish-brown solution; add ammonia water and continue stirring for 6 h; after stirring, centrifuge to obtain a reddish-brown precipitate; wash with deionized water and ethanol 3-5 times and dry to obtain Mo-PDA precursor; (1.2) Under an argon / hydrogen mixed atmosphere (argon to hydrogen volume ratio of 95:5), the mixture was purged for 20 min at room temperature, then heated to 400°C at a rate of 5°C / min and held for 2 h; the temperature was further increased to 800°C and held for 3 h, and after cooling to room temperature, the Mo2C catalyst was obtained by grinding. (2) Preparation of RuO x -Mo2C clusters-cluster heterostructure catalysts: (2.1) 100 mg of Mo2C catalyst was added to 50 mL of water and stirred continuously for 1 h to obtain dispersion A; 100 mg of ruthenium acetylacetonate was added to 50 mL of water and stirred continuously for 1 h to obtain dispersion B; dispersion B was slowly added to dispersion A and stirred continuously for 6 h to mix evenly. After the reaction was completed, the bottom precipitate was obtained by centrifugation. (2.2) The bottom precipitate was first washed with deionized water and then with ethanol, 3 to 5 times with each solvent. After drying at 60°C for 24 hours, N2 was introduced as a protective atmosphere, and then the temperature was increased to 300°C at a rate of 5°C per minute and maintained at this temperature for 2 hours. After cooling to room temperature, it was ground to obtain prepared RuO. x -Mo2C cluster-cluster heterostructure catalyst, where X is 1.9-4.4.

[0029] The RuO prepared in this embodiment x -Mo2C clusters-XRD pattern of cluster heterostructure catalyst as shown in the figure Figure 1 As shown, RuO x The peaks at 37.7°, 43.7°, 63.4°, and 75.7° observed in the Mo2C catalyst correspond to the (111), (200), (220), and (311) crystal planes of the Mo2C phase (PDF # 15-0457), respectively. No obvious RuO was observed in the XRD pattern. x The diffraction characteristics can be explained by the significant peak broadening due to its extremely small crystallite size (<5nm), rather than the complete absence of the phase.

[0030] Scanning electron microscope (SEM) such as Figure 2 (b) and transmission electron microscopy (TEM) images as follows Figure 2 As shown in (c), it can be seen from the figure that RuO x The Mo2C catalyst exhibits a unique hierarchical structure composed of numerous micron-sized "flower-like" aggregates, each assembled from even finer nano-sized "petal" structural units. This hierarchical structure inherits and retains the basic microstructure of the Mo2C precursor, RuO. x The load did not change the main structural framework.

[0031] The RuO prepared in this embodiment x -Mo2C clusters- Cluster heterostructure catalysts high-resolution transmission electron microscopy such as Figure 2 As shown in (d), the morphology of the nanoclusters deposited on the carbon substrate can be seen, showing that the particle size is uniform and there is no obvious agglomeration.

[0032] Aberration-corrected scanning transmission electron microscope (AC-STEM) images as follows Figure 2 As shown in (e), it can be seen that RuO x Coexisting with Mo2C nanoclusters, the highly dispersed RuO is highlighted in red. x Nanoclusters, with Mo2C nanoclusters marked in blue. The two substances are in close nanoscale proximity on the nanosheet, forming RuO₂. x The formation of the -Mo2C cluster- provides direct evidence. This fully exposed cluster structure significantly increases the density of active sites and effectively promotes interfacial electron transport.

[0033] AC-STE images such as Figure 2 As shown in (f), a crystal plane spacing of 0.255 nm corresponds to RuO x (101) crystal plane, 0.238 nm corresponds to the Mo2C (111) crystal plane.

[0034] High-angle annular dark-field STEM (HAADF-STEM) Figure 2 As shown in (g), it can be seen that Ru, Mo, C and O are present in RuO x -Mo2C is uniformly distributed.

[0035] RuO x -Mo2C clusters- Cluster heterostructure catalyst BET results are shown in the figure. Figure 3 and Figure 4 As shown in (d), from Figure 3 As can be seen from this, compared with Mo2C, RuO x -Mo2C composite materials have a larger specific surface area (84.1 m²). 2 / g), moderate mesopore size (8.145nm), and higher pore volume (0.212cm³). 3 / g).

[0036] RuO x -Mo2C clusters- Cluster heterostructure catalysts high-resolution XPS spectra as follows Figure 4 As shown in (a), it can be seen that Ru 3pXPS fitting yields four characteristic peaks, which correspond to Ru respectively. 0 (462.57 eV and 484.76 eV) and Ru 4+ The 3p3 / 2 and 3p1 / 2 orbitals (465.11 eV and 487.02 eV) indicate that Ru... 0 and Ru 4+ A mixed oxidation state exists. Figure 4 (b) RuO x Both the -Mo2C and pure Mo2C catalysts showed three sets of diffraction peaks for Mo. For RuOx-Mo2C, these three sets of peaks corresponded to Mo, respectively. 4+ (229.05 eV and 232.13 eV), Mo 5+ (229.99 eV and 233.07 eV) and Mo 6+ (232.8 eV and 235.88 eV). The formation of high-valence Mo can be attributed to RuO. x -Surface oxidation of Mo2C.

[0037] like Figure 4 (c) As shown in the 1s XPS spectrum of O, RuO was observed. x -Mo2C and Mo2C share the same peaks, namely adsorbed H2O (~533.2 eV), O–C=O (~531.5 eV) and Mo–O (~530.5 eV).

[0038] like Figure 4 (e) It can be observed that RuO x The absorption edge of Ru in Mo2C is located on the Ru foil (corresponding to Ru). 0 ) and RuO2 (corresponding to Ru 4 + Between 0 and +4. Therefore, it can be inferred that Ru exists in valence states from 0 to +4. For example... Figure 4 (f) In the k3-weighted Ru FT-EXAFS spectrum, three distinct characteristic peaks appear at radial distances of 1.6 Å, 2.7 Å, and 3.1 Å. By associating the EXAFS peak positions with bond types, it can be confirmed that the 1.6 Å peak is attributed to the short-length Ru-O bond, the 2.7 Å peak corresponds to the Ru-Mo bond between Ru and metallic Mo, and the 3.1 Å peak is a Ru-O-Mo bridging oxygen bond formed by three atoms (Ru, O, and Mo).

[0039] WT-EXAFS signal and wavelet transform analysis of RuOx-Mo2C, as follows: Figure 4 As shown in (g)-(i), the average coordination number of the Ru–O and Ru–Mo paths is displayed.

[0040] I. Regarding the RuO prepared in Example 1 x Experiments on hydrogen evolution reaction using Mo2C cluster-cluster heterostructure catalysts The electrocatalytic performance was evaluated by performing systematic electrochemical measurements in 1.0 M KOH using a standard three-electrode system.

[0041] like Figure 5 (a) RuO x The LSV curves of -Mo2C and other electrocatalysts are shown. Compared with Pt / C (35 mV), Ru / C (60 mV) and Mo2C (184 mV), RuO x -Mo2C exhibits excellent performance, reaching 10 mA cm⁻¹ -2 The overpotential is as low as 15 mV.

[0042] like Figure 5 (b) RuO x -Mo2C and other electrocatalysts, as shown by the Tafel slope, RuO x The Tafel slope of -Mo2C is only 29.1 mV dec -1 It is much smaller than that of traditional Pt / C catalysts (40.3 mV dec). -1 ), Ru / C (45.2 mV dec) -1 ) and Mo2C (106.4 mV dec -1 This clearly demonstrates that the reaction kinetics of the catalyst follow the Tafel process, further confirming its highly efficient catalytic performance.

[0043] RuO x -Mo2C and similar ruthenium-based catalysts reported in recent years exhibit HER activity such as Figure 5 (c), from Figure 5 (c) shows that RuO x -Mo2C exhibits superior HER activity compared to similar ruthenium-based catalysts reported in recent years, further highlighting its potential for hydrogen production through water electrolysis.

[0044] The variation of charge transfer resistance (Rct) was analyzed by electrochemical impedance spectroscopy. Figure 5 (d)). RuO x-Mo2C catalysts exhibit the smallest Rct, indicating more rapid charge transfer, which leads to a higher electron transfer rate per unit time, thus promoting faster HER. Electrochemical active surface area (ECSA) is a key indicator for evaluating HER performance and is directly related to the density of accessible active sites. It is usually estimated indirectly by characterization and calculation of the electrochemical double-layer capacitance (Cdl). RuO x The Cdl value of -Mo2C is 38.1 mF cm⁻¹. -2 It outperforms Mo2C and Ru / C catalysts, demonstrating that it has the largest electrochemical active surface area and excellent intrinsic activity. Figure 5 (e)).

[0045] HER performance metrics comparison Figure 5 As shown in (f), RuO x -Mo2C catalysts exhibit the highest conversion frequency (TOF) and mass activity (MA) under alkaline conditions, while RuO x -Mo₂C has a TOF value of 19.25 s at 100 mV. -1 It far surpasses Mo2C and Ru / C; MA is 3.5 times that of Pt / C catalysts, and RuO... x -Mo2C catalysts are superior to other catalysts in every respect, representing an advanced catalyst that combines high activity, excellent kinetics, and outstanding intrinsic catalytic efficiency.

[0046] The catalyst was tested in alkaline solution, simulated seawater (1.0 M KOH + 0.5 M NaCl) solution, and alkaline seawater (1.0 M KOH + seawater) solution, respectively. The test results are as follows: Figure 5 As shown in (g), in the two seawater systems, RuO x -Mo2C reaches 10 mA cm -2 With overpotentials of only 23mV and 31mV, it fully demonstrates excellent HER activity. Meanwhile, RuO x -Mo2C also exhibits excellent stability in alkaline seawater systems, and can operate stably for 200 hours.

[0047] RuO x -Mo₂C exhibits excellent structural and electrochemical stability in alkaline electrolytes. Polarization curves obtained from 10,000 CV cycles and continuous stability measurements over 1000 hours are shown in the figures. Figure 5 (h) can be seen that RuO x Mo2C exhibits excellent durability, with negligible current density fluctuations and no significant degradation. In contrast, Mo2C retains only 68% of its initial current density after just 90 hours.

[0048] II. The RuO prepared in Example 1x -Mo2C clusters- Cluster heterostructure catalysts effectively induce reverse hydrogen spillover effect For RuO x -Mo2C cluster- Cluster heterostructure catalysts were subjected to thiocyanate (SCN-) poisoning experiments. SCN- exhibits high affinity and strong coordination ability to metal active sites, deactivating the catalytic metal center by forming stable coordination bonds with metal species, such as... Figure 6 As shown in the LSV curve in (a), after introducing SCN- into the electrolyte, RuO x The polarization potential of the Mo2C catalyst underwent a significant negative shift, while the LSV curve of Mo2C remained essentially unchanged. Further analysis of the Tafel slope indicated that SCN- poisoning caused RuO2 to... x The value of -Mo2C increased from 29.1 to 84.5 mV dec -1 This confirms that the Ru site is a key active site and positively regulates RuO2. x Electrocatalytic behavior of -Mo2C catalyst.

[0049] For RuO x In-situ ATR-FTIR tests were performed on the -Mo2C cluster-cluster heterostructure catalyst. Figure 6 (b) and 6(c)), as shown in the figure, the metal-hydrogen (M–H) bond is located at 1900–2100 cm⁻¹. -1 It exhibits its characteristic vibration signal within the range. In RuO x In the -Mo2C heterostructure, the Ru-H bond signal is significantly enhanced when the energy decreases from 0.3 eV to −0.4 eV, which directly proves... The accumulation at Ru sites confirms the reverse hydrogen overflow process. Efficient enrichment at Ru sites. In contrast, in Mo2C catalysts, the signal intensity of MH bonds hardly fluctuates with potential changes, indicating a lack of efficient enrichment. The migration channel did not experience reverse hydrogen overflow.

[0050] like Figure 6 As shown in (d), RuO was tested in 1 M KOH. x -CV curves of Mo2C and Mo2C at different potentials. RuO x The Mo2C heterostructure catalyst exhibited a clear hydrogen desorption peak at approximately 0.1 eV, and this peak showed a significant positive shift with increasing scan rate; for example... Figure 6 As shown in (e), no such characteristic peaks were observed on the Mo2C catalyst, and this difference directly confirms that the hydrogen desorption / intercalation behavior is RuO2. x -The characteristics unique to Mo2C catalysts reveal that their interfaces significantly promote... The overflow and enrichment from Mo sites to Ru sites produces characteristic hydrogen delocalization peaks. This is for RuO x - The reverse hydrogen spillover behavior within the Mo2C catalyst provides strong experimental support.

[0051] like Figure 6 As shown in (f), in RuO x In the Mo2C catalyst, the strong coupling of active sites achieved by the cluster-cluster structure establishes an efficient transport pathway for reverse hydrogen spillover. This enables... Capable of rapid migration from Mo2C to RuO x This improves the surface migration rate and It improves utilization efficiency. Simultaneously, it optimizes catalytic reaction kinetics, leading to a significant increase in HER activity.

[0052] III. RuO x Application of Mo2C in Industrial Water Electrolysis like Figure 7 As shown in (a), RuO x -Mo2C catalyst was used as the cathode in the AEMWE system, and NiFeO-CeO2 was used as the anode in the AEMWE system. From Figure 7 (b) RuO x The polarization curve of -Mo2C|| NiFeO-CeO2 is shown. When the current density reaches 1.0 Acm -2 At that time, the battery voltage was only 1.76 V, demonstrating excellent electrochemical performance. In contrast, from Figure 7 As can be seen in (c), the voltage of Pt / C||NiFeO-CeO2 is as high as 2.28V, which is significantly higher than that of the former; Figure 7 (d)RuO x The stability curve of -Mo2C||NiFeO-CeO2 shows that at 1.0 A cm⁻¹... -2 After continuous operation for over 1500 hours, the system activity showed no significant decline and maintained stable output. AEMWE using the previously reported advanced catalyst at 1.0 A cm⁻¹... -2 A comparison of battery voltage and energy efficiency under different conditions. Figure 7 As shown in (e), the RuO x -Mo2C catalyst at 1 A cm -2 The battery voltage of 1.76V is also superior to several similar catalysts reported in recent years.

[0053] The specific embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A RuO x The method for preparing a -Mo2C cluster-cluster heterostructure catalyst is characterized by: Includes the following steps: Step 1: Preparation of Mo2C catalyst: Dissolve ammonium molybdate tetrahydrate in water and stir to form solution A; Dopamine hydrochloride was dissolved in ethanol and stirred to form solution B. Solution B was slowly added dropwise to solution A and mixed evenly to obtain a reddish-brown solution. Ammonia water was added and stirring was continued. After stirring was completed, centrifugation was performed to obtain a reddish-brown precipitate. After washing and drying, the Mo-PDA precursor was obtained. Under an argon / hydrogen mixed atmosphere, the temperature was raised to 400°C-800°C and held for 5-10 hours. After cooling to room temperature, the catalyst was ground to obtain the Mo2C catalyst. Step 2: Preparation of RuO x -Mo2C clusters-cluster heterostructure catalysts: Mo2C catalyst was added to water to obtain dispersion A; ruthenium acetylacetone was added to water to obtain dispersion B; dispersion B was slowly added to dispersion A, mixed evenly, and centrifuged after the reaction was completed to obtain the bottom precipitate; The bottom precipitate was washed, dried, calcined, cooled to room temperature, and then ground to obtain prepared RuO. x -Mo2C cluster-cluster heterostructure catalyst.

2. The RuO according to claim 1 x The method for preparing a Mo2C cluster-cluster heterostructure catalyst is characterized by: In step 1, the solid-liquid ratio of molybdic acid tetrahydrate to water is 120:32 mg / mL; the solid-liquid ratio of dopamine hydrochloride dissolution to ethanol is 120:64 mg / mL; the ammonia water is analytical grade ammonia water, and the volume of ammonia water to water is 0.6:

32.

3. The RuO according to claim 1 x The method for preparing a Mo2C cluster-cluster heterostructure catalyst is characterized by: In step 1, the volume ratio of argon to hydrogen in the argon / hydrogen mixed atmosphere is 95:

5.

4. The RuO according to claim 1 x The method for preparing a Mo2C cluster-cluster heterostructure catalyst is characterized by: The process involves purging with the mixed gas for 20 minutes at room temperature under an argon / hydrogen mixed atmosphere, followed by heating to 400°C at a rate of 5°C / min and holding at that temperature for 2 hours. Continue heating to 800°C and hold for 3 hours.

5. The RuO according to claim 1 x The method for preparing a Mo2C cluster-cluster heterostructure catalyst is characterized by: In step 2, the solid-liquid ratio of Mo2C catalyst to water is 100:50 mg / mL; the solid-liquid ratio of ruthenium acetylacetone to water is 100:50 mg / mL.

6. The RuO according to claim 1 x The method for preparing a Mo2C cluster-cluster heterostructure catalyst is characterized by: In step 2, the calcination is carried out under a protective atmosphere of N2, and then the temperature is increased to 300°C at a rate of 5°C per minute and maintained for 2 hours.

7. A RuO x -Mo2C cluster-cluster heterostructure catalyst, characterized in that: RuO was prepared by the preparation method according to any one of claims 1 to 6. x -Mo2C cluster- Cluster heterostructure catalysts exhibit a hierarchical structure, consisting of numerous micron-sized flower-like aggregates, each aggregate being assembled from finer nano-sized petal-shaped structural units, where x ranges from 1.9 to 4.

4.

8. The RuO according to claim 7 x -Mo2C cluster-cluster heterostructure catalyst, characterized in that: The RuO x -Mo2C cluster- Cluster heterostructure catalyst has a specific surface area of ​​84.1 m². 2 / g, moderate mesopore size of 8.145nm and higher pore volume of 0.212cm³ 3 / g.

9. A RuO according to claim 7 or 8 x The application of -Mo2C cluster-cluster heterostructure catalysts as electrocatalysts for hydrogen evolution reaction effectively induces the reverse hydrogen spillover effect.

Images