Revealing Correlation-driven Charge transfer and Electron Redistribution via strong metal-metal interactions in the Construction of High Stability Pt Catalysts

Revealing Correlation-driven Charge transfer and Electron Redistribution via strong metal-metal interactions in the Construction of High Stability Pt Catalysts | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 1 August 2025 V1 Latest version Share on Revealing Correlation-driven Charge transfer and Electron Redistribution via strong metal-metal interactions in the Construction of High Stability Pt Catalysts Authors : Yang Han , Fengqin Zhang , Tingquan Zhang , Chang Yang , and Qingmei Wang 0009-0008-7424-782X [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.175402084.43518578/v1 192 views 112 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Developing catalysts with high performance for the oxygen reduction reaction via a cost-effective methodology is the key to promoting the industrialization of fuel cells. Herein, we design and synthesize a Pt-Mo 2 C/NC dual-composite with a unique electronic coupling interface, where the electronic structure and surface property of Pt can be precisely controlled by using the macro-porous cross-linked anion exchange resin as a chelating agent via a facile “in-situ concurrent pyrolysis-reduction” route. The XAFS analysis reveals that each Pt atom in the Pt-Mo 2 C/NC dual-composite catalyst coordinates with ~1.29 N atoms, ~5.88 Pt atoms and ~1.81 Mo atoms, respectively. Moreover, DFT calculations further confirm the strong interfacial coupling effect between metal Pt and Mo 2 C support, resulting in the formation of electron-rich regions at the Pt-Mo interface, which can act as an “electronic reservoir” and optimize the adsorption energy of the ORR intermediate. Benefiting from the constructed electron-enriched region and the induced strong interfacial coupling effect, the obtained Pt-Mo 2 C/NC catalyst exhibits enhanced ORR electrocatalysis activity, with a mass activity and specific activity of 0.65 A/mg Pt and 1.16 mA/cm 2 . Such an efficient synthesis of high-performance Pt-Mo 2 C/NC nanocomposite with controlled particle size and composition is extremely desired in energy conversion materials. Cite this paper: Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX Revealing Correlation-driven Charge transfer and Electron Redistribution via strong metal-metal interactions in the Construction of High Stability Pt Catalysts Yang Han, Fengqin Zhang, Tingquan Zhang, Chang Yang, and Qingmei Wang * Guizhou University Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University Engineering Research Center of Efficient Utilization for Industrial Waste, School of Chemistry and Chemical Engineering, Guizhou University, Institute of Guizhou University Chemistry Experiment and Teaching Center, Guiyang, Guizhou, 550025, China. Phase Evolution | Interfacial Coupling Effect | Electron-adequate Interfacial | Platinum-based catalyst | Oxygen Reduction Reaction Comprehensive Summary Developing catalysts with high performance for the oxygen reduction reaction via a cost-effective methodology is the key to promoting the industrialization of fuel cells. Herein, we design and synthesize a Pt-Mo 2 C/NC dual-composite with a unique electronic coupling interface, where the electronic structure and surface property of Pt can be precisely controlled by using the macro-porous cross-linked anion exchange resin as a chelating agent via a facile “in-situ concurrent pyrolysis-reduction” route. The XAFS analysis reveals that each Pt atom in the Pt-Mo 2 C/NC dual-composite catalyst coordinates with ~1.29 N atoms, ~5.88 Pt atoms and ~1.81 Mo atoms, respectively. Moreover, DFT calculations further confirm the strong interfacial coupling effect between metal Pt and Mo 2 C support, resulting in the formation of electron-rich regions at the Pt-Mo interface, which can act as an “electronic reservoir” and optimize the adsorption energy of the ORR intermediate. Benefiting from the constructed electron-enriched region and the induced strong interfacial coupling effect, the obtained Pt-Mo 2 C/NC catalyst exhibits enhanced ORR electrocatalysis activity, with a mass activity and specific activity of 0.65 A/mg Pt and 1.16 mA/cm 2 . Such an efficient synthesis of high-performance Pt-Mo 2 C/NC nanocomposite with controlled particle size and composition is extremely desired in energy conversion materials. Background and Originality Content The oxygen reduction reaction (ORR) is a crucial electrochemical process that occurs in proton exchange membrane fuel cells (PEMFCs), which converts the chemical energy of oxygen into electrical energy [1-3] . As the most commonly used catalyst in ORR, carbon-supported platinum (Pt/C) still suffers from two main problems of the high cost of Pt and the weak adhesion between Pt and carbon, which makes the sluggish anode kinetics and the ponderous commercialization of PEMFCs [4,5] . Currently, diminishing the usage of Pt without sacrificing its activity and enhancing the interaction between metal and support remains a challenge [6,7] . Generally, engineering the electronic structure and surface properties of Pt would boost the interaction between Pt and carbon, preventing the exfoliation of Pt particles, while tailoring Nanostructures, sizes, and morphologies would further improve the electrocatalysis activity and stability [8-11] . Specifically, the support holds the role of dispersing and anchoring the active component, and the interaction force between different supports and the active component would vary, thus, the selection of support is extremely significant. Given this, geometrically stable molybdenum carbides (Mo x C) are attractive materials in the fields of electrocatalysis because of the hybridization of the d-orbital of Mo and s-/p- orbital of carbon, making them possess similar catalytic behavior of noble metal and represent one of the most promising candidates to replace carbon support known as the strong metal-support interaction (SMSI) [12-15] . Such SMSI effect in Pt-Mo x C phase can well-modulate the electronic structure of Pt via charge redistribution, and not necessarily the construction of alloy phase, which inevitably faces the problem of the dissolution of the less-noble-catalytic component [16,17] . Despite these advantages, however, the design techniques of Mo x C are severely limited by the harsh synthesis conditions, which involve multistep ammonification and carburization. Moreover, the conventional assembly high-temperature carburizing and wet-chemistry techniques cannot guarantee the uniform and considerable loading of noble metal due to the formation of surface carbon deposits [18-20] . Consequently, developing a constructive strategy that is available for the preparation of electrocatalysts with controllable crystal structure and composition that demonstrate well SMSI as well as optimized electron structure and surface property, is imperative. Herein, we design and synthesize a Pt-Mo 2 C/NC dual-composite with a unique electronic coupling interface, where the electronic structure and surface property of Pt can be precisely controlled by using the macro-porous cross-linked anion exchange resin as a chelating agent via a facile “in-situ concurrent pyrolysis-reduction” route. As shown in Figure 1, the resin skeleton is ”in-situ pyrolysis” to form the composite structure of nitrogen-doped carbon and the metal carbide during a high-temperature and inert atmosphere. Subsequently, the formed composite structure, in conjunction with the reduction atmosphere, drives the “in-situ reduction” of Pt precursor to form the Pt-Mo 2 C/NC dual-composite with a metal-support strong coupling interface. The construction of a coupling interface that acts as an “electronic reservoir” not only achieves the modification of the electronic structure but also avoids the key problem of the dissolution of the less-precious components. Moreover, the strong interaction between Pt and Mo 2 C can suppress the elimination and agglomeration of Pt nanoparticles and significantly alleviate the oxidation and corrosion of the carrier under the working conditions of the fuel cell. The technique of “in-situ concurrent pyrolysis-reduction” can greatly reduce the production cost of the catalyst, possessing enormous practical application prospects. Figure 1. Schematic abstract of the formation of typical Pt-Mo 2 C/NC and the illustration of the formed electron-enriched region. Results and Discussion Figure 2. (a) XRD types of Mo 2 C/NC, Pt/NC and Pt-Mo 2 C/NC catalyst; (b-d) TEM images of and Pt-Mo 2 C/NC (b) and Pt/NC (c), HRTEM images and the corresponding FFT images of selected typical NP (e-f), HADDF-STEM images (g) and elemental mappings (h-j) of the Pt-Mo 2 C/NC sample. (k, l) the AFM image and the corresponding height profiles of Pt-Mo 2 C/NC (k) and Pt-NC (l) nanoparticles. According to the feeding types of precursors (merely Mo, merely Pt, mixed Pt and Mo), the resultant samples were denoted and named Mo 2 C/NC, Pt/NC and Pt-Mo 2 C/NC, respectively. Powder X-ray diffraction (XRD) was first applied to inspect the crystal structure of the as-prepared Pt-Mo 2 C/NC, Pt/NC and Mo 2 C/NC materials. As shown in Figure 2a, the as-prepared Pt-Mo 2 C/NC sample simultaneously shows characteristic peaks of hexagonal closed-packed (hcp) β-Mo 2 C (PDF#35-0787) and face-centered cubic (fcc) Pt (PDF#04-0802). Such results preliminarily confirm that the successful formation of β-Mo 2 C in the pyrolysis process and the pre-adsorbed Pt precursor have been successfully reduced in the reduction procedure for the final constitution of Pt-Mo 2 C/NC composite [21] . To further explore the formation of the composite structure of Mo 2 C/NC during the ”in-situ pyrolysis” process, the in-situ XRD analysis and the corresponding contour map were applied. As shown in Figure 3a, the conversion of Mo 7 O 24 6- to MoO 3 and MoO 2 is observed at about 300 °C. Subsequently, MoO 3 and MoO 2 are step-by-step reduced into Mo 4 O 11 and C 6 MoO 6 after the temperature increases to about 550°C. Then carburization process of Mo 4 O 11 and C 6 MoO 6 occurred and rapidly transformed into Mo 2 C, corresponding to the β-Mo 2 C phase (PDF#35-0787) when the temperature was raised to 650 °C (Figure 3c). Such in-situ XRD result refers to evolution firmly proves the successful formation of β-Mo 2 C in the pyrolysis process. Transmission electron microscopy (TEM) images for the Pt-Mo 2 C/NC sample show that NPs are evenly dispersed on the Mo 2 C/NC support with a small particle size of ～2.8 nm (Figure 2b and Figure S2). For comparison, as observed in Figure 2c, the obtained Pt/NC catalyst exhibits serious nanoparticle agglomeration and sintering. Moreover, the atomic force microscopy (AFM) images also suggest that the obtained Pt-Mo 2 C/NC and Pt-NC catalysts possess smooth surfaces with particles of about 3.2nm and 10.4nm, respectively. Figure 3. (a) The dominant phases of Mo species at each stage, (b) the in-situ XRD patterns and (c) the contour map of Pt-Mo 2 C/NC during the high-temperature process in N 2 atmosphere. The standard diffraction peaks of β-Mo 2 C phases are shown on the top. These results imply that the aggregation of the NPs during the annealing procedure can be efficaciously avoided by the ”lattice confinement” originating from the pre-formed Mo 2 C/NC substrate. The high-resolution TEM (HRTEM) images and the fast Fourier transform (FFT) of selected core area analysis of the obtained Pt-Mo 2 C/NC sample demonstrated that the lattice fringe spacing matches well with the (111) lattice spacing of metal Pt (Figure 2e-f). As shown in Figure S3-4, owing to the ”carbon” in carbide and the ”carbon” in crystalline carbon being derived from resin decomposition, the Mo 2 C and graphite carbon in the sample are intertwined, and the lattice fringes of the two phases are closely combined. To further demonstrate the morphology and composition of the obtained materials, high-angle annular dark-field-scanning transmission electron microscopy (HAADF-STEM) as well as energy-dispersive X-ray spectroscopy (EDX) was conducted. As observed in Figure 2g-j, the HAADF-STEM and the EDX elemental mapping images of the Pt- Mo 2 C/NC sample illustrate that the Pt and Mo elements show an indistinguishable size as in the STEM image, demonstrating the successful reduction of adsorbed Pt (NH 3 ) 4 2+ and (MoO 4 ) 2+ precursor and the formation of the Pt-Mo 2 C/NC composite phase [22-24] . Figure 4. (a) Pt L 3 -edge XANES spectra of Pt-Mo 2 C/NC, PtO 2 and Pt foil. (b) k 2 -weighted χ(k) functions of the EXAFS spectra. Corresponding EXAFS fitting for Pt-Mo 2 C/NC in the k (c) and R (d) spaces. (e) WT for k 2 -weighted Pt L 3 -edge EXAFS signals in the Pt-Mo 2 C/NC and reference samples. (f)The top view and side view of the 3D charge density difference are surfaces of the Pt 4 -MoC (111) (in 0.004 e/bohr 3 , the yellow and blue surfaces represent charge accumulation and depletion, respectively). (g) The schematic of the Pt and Pt-Mo interface in the Pt 4 -MoC (111) model. (h) The schematic of charge transfer from Pt to Pt-Mo interface and the 2D charge density difference of the Pt-Mo interaction (the units for the color scale bar are e/bohr 3 ). We further used the X-ray absorption fine structure (XAFS) analysis to examine the coordination features and electron interaction effect of the Pt-Mo 2 C/NC catalyst. The X-ray absorption near-edge structure (XANES) spectra (Figure 4a) show that the white-line intensity of Pt-Mo 2 C/NC is similar to the shape of Pt foil, indicating that the valence state of Pt species is mostly zero valence. Moreover, the absorption edge in XANES spectra of the as-prepared Pt-Mo 2 C/NC catalyst is slightly positively shifted compared to the Pt foil, which demonstrates that Pt-Mo 2 C/NC possesses a higher Pt valence state than the Pt foil. Such a proposed statement was further confirmed by X-ray photoelectron spectroscopy (XPS) analysis (Figure S6). The Pt 4f binding energy of the obtained Pt-Mo 2 C/NC shows a 0.39 eV positive shift compared to commercial Pt/C, synchronously indicating the electron-donating behavior of Pt. Indeed, such charge transfer trend further confirms the successful construction of electron-rich regions and the establishment of a strong interfacial coupling effect between Pt and Mo 2 C. Ma Ding et al. have proven that the electron density at Pt sites can construct an electron-rich region on the Pt-Mo interface, leading to an enhancement of the ORR activity [25,26] . The Fourier transforms of the extended X-ray absorption fine structure (EXAFS) spectra (Figure 4b) demonstrate relatively prominent peaks at ~2.63 Å and Pt-Pt bond and Pt-Mo bond, further confirming the construction of the electron-rich regions on the Pt-Mo interface [27-29] . Moreover, the peak at (R-T effect). A comparison of the wavelet transforms (WT) analysis of Pt L 3 -edge EXAFS images of Pt-Mo 2 C/NC, PtO 2 and Pt foil was also shown in Figure 4e. The coordination environment of Pt was further revealed by the EXAFS fitting curves of the Pt-Mo 2 C/NC sample (Figure 4c and Figure 4d). The coordination number for Pt-Pt interactions (6.88) and the Pt-Mo coordination number (1.81) firmly further suggests the strong interplay between Pt and Mo 2 C. Specifically, the large Pt-Mo coordination number is a result of the electron donation of Pt and Mo to generate a high density of electron-enriched interface for the interfacial coupling effect, while the Pt-Pt coordination environment is chiefly contributed by the highly dispersed Pt nanoparticles (in good agreement with our TEM observations). More data about the EXAFS fitting parameters at the Pt L3-edge for periodic density functional theory (DFT) calculations were per-formed to further reveal the electronic interactions in the Pt-Mo 2 C/NC cat alyst and the strong interfacial coupling effect between Pt and Mo 2 C. The Pt 4 -MoC (111) model is composed of Pt clusters containing 4 Pt atoms supported on MoC (111) plates, are shown in Figure 4f and 4g. We calculated the charge distribution in the model using DFT. As shown in Figure 4f, the Pt-Mo interface in Pt 4 -MoC (111) has obvious charge accumulation, indicating that the Pt cluster can effectively combine with MoC (111) support and has strong interaction with the MoC (111) surface, which can cause charge redistribution of the Pt cluster. Figure 4g and 4h show the schematic of electron transfer from Pt to Pt-Mo interface in the Pt 4 -MoC (111) model. Moreover, the 2D charge density difference images (Figure 4h) also show obvious charge accumulation in the Pt-Mo interface, demonstrating that charge transfer from the Pt atoms to the Pt-Mo interface. The DFT results confirmed the strong interfacial coupling effect between Pt and Mo 2 C in the Pt-Mo 2 C/NC catalyst, resulting in the formation of the Pt-Mo electron-rich region interface, which is consistent with the results of XANES and XPS. This Pt-Mo electron-rich structure in Pt/Mo 2 C/NC will facilitate the desorption of oxygenated intermediate species on Pt sites, thereby enabling high ORR performance can be expected. Figure S7 shows the XPS surveys and corresponding element content of the Mo 2 C/C, Pt-C and Pt-Mo 2 C/C catalysts, which certainly reveal that Pt-Mo 2 C/C catalysts contain C, N, Mo and Pt elements, the Mo 2 C/C contain C, N and Mo elements, the Pt-C catalysts contain C, N and Pt elements, respectively. As shown in Figure S8a, in an as-prepared catalyst, the N1s spectra can be deconvoluted into three peaks. The around 398.21 eV binding energy is attributed to the pyridinic-N, the approximately 400.54 eV binding energy is assigned to pyrrolic-N and the about 401.20 eV binding energy is classified as quaternary-N, respectively, indicating that the amino group in the functional group has been successfully transformed into N-doped carbon for forming Pt-N bonding after high-temperature annealing. Although there are still debates on what types of nitrogen configure ration contribute to the active sites for the ORR and MOR in acidic electrolytes, it is generally agreed that a larger proportion of the pyrrolic-N and pyridinic-N in N-doped carbon structure is highly favorable for the chemical and structural stability. As shown in Figure S8 and Figure S9, the Mo 3d spectra of the Pt-Mo 2 C/C and Mo 2 C/C exhibit two peaks that can be assigned to Mo 3d 7/2 and Mo 3d 5/2 and can be further divided into several doublets, which are associated with metallic Mo and Mo oxides. Meanwhile, the Pt4f spectra of Pt-Mo 2 C/C and Pt-C samples similarly show two peaks that can be attributed to Pt 4f 7/2 and Pt 4f 5/2 and can be further split into several doublets, associated with metallic Pt and Pt oxides. Recently published literature has shown that a greater proportion of the metallic state of Pt in the catalyst is beneficial to provide a more active site toward oxygen reduction. Figure 5. (a) CV curves of obtained Pt/NC, Pt-Mo 2 C/NC catalysts and commercial Pt/C conducted in N 2 -saturated 0.1 M HClO 4 solution. (b) ORR polarization curves of the obtained Pt/NC, Pt-Mo 2 C/NC catalysts and commercial Pt/C baseline catalysts were conducted in O 2 -saturated 0.1 M HClO 4 solution with a rotation rate of 1600 rpm. (c) Tafel plots of Pt/NC, Pt-Mo 2 C/NC and commercial Pt/C catalysts. (d) mass activity of obtained Pt/NC, Pt-Mo 2 C/NC catalysts and commercial Pt/C baseline at 0.9 V versus RHE. CV curves (e and g) and ORR polarization curves (f and h) of the aged Pt-Mo 2 C/NC and commercial Pt/C catalysts and (i) corresponding specific activity and mass activity before and after 20,000 potential cycles between 0.6 and 1.1 V versus RHE. The electrocatalytic performances for ORR of the obtained Pt/NC and Pt-Mo 2 C/NC samples and reference commercial JM Pt/C were characterized by the electroanalysis of cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Figure 5a shows the CV curves of the Pt/NC, Pt-Mo 2 C/NC and commercial Pt/C catalysts at a scan rate of 50 mV/s in N 2 -saturated 0.1 M HClO 4 solution. Figure 5b exhibits the ORR polarization curves for the Pt/NC and Pt-Mo 2 C/NC and commercial Pt/C catalysts after being normalized by the 0.196 cm 2 glassy carbon area. The most positive half-wave potential (E 1/2 ) occurred in the Pt-Mo 2 C/NC (0.928 V) catalyst, and such E 1/2 values were notably greater than the as-prepared Pt/NC (0.711V) and the reference Pt/C catalyst (0.887 V). Moreover, Figure 5c shows that the Tafel slope fit of Pt-Mo 2 C/NC is 67.56 mV dec -1 , smaller than Pt/NC (322.37 mV dec -1 ) and Pt/C (99.81 mV dec -1 ), revealing fine ORR kinetics for Pt-Mo 2 C/NC. Utilizing the integrated charge from CO stripping and the exchange current density (j k @ 0.9V), the calculated electrochemical surface area (ECSA) is shown in Table S1. The value of the ECSA for the Pt-Mo 2 C/NC catalyst based on the Pt mass exhibits 56 m 2 /g, which is lower than the commercial Pt/C catalyst (69 m 2 /g) and higher than the as-prepared Pt/NC sample (5.7 m 2 /g), indicating that such small-sized Pt NP loaded on the support could further increase the exposure of the Pt active site. To further explore the activity of as-prepared Pt/NC and Pt-Mo 2 C/NC catalysts, we have normalized the kinetic currents with respect to the loading amount of Pt and the ECSA. The mass activities (Figure 5d) of the Pt-Mo 2 C/NC were valued to be 0.65 A/mg Pt , which is 4.82 and 8.67 times greater than the commercial Pt/C (0.135 A/mg Pt ) and Pt/NC (0.075 A/mg Pt ) samples. This enhancement towards ORR activity can be attributed to the strong electron transfer interaction between Pt and Mo 2 C and the Mo 2 C-induced interfacial coupling effect. The accelerated durability test (ADT) was employed to further assess the ORR stability of the Pt-Mo 2 C/NC and the commercial JM Pt/C for 20,000 CV cycles between 0.6 and 1.1 V in O 2 -purged solution at a scan rate of 50 mV/s. For the commercial JM Pt/C (Figure 5e-f), the ADT cycling causes a significant decrease in E 1/2 and spe- cific surface area owing to the ripening of NP or leaching of Pt during potential cycling. Contrarily, no obvious ECSA and E 1/2 potential loss was observed for the Pt-Mo 2 C/NC catalyst (Figure 5g-h), preliminarily indicating that the obtained Pt-Mo 2 C/NC catalysts were more stable than the commercial Pt/C. To further get insight into the durability of catalysts, the activity loss before and after ADT was further assessed. As shown in Figure 5i, the specific activity of the commercial JM Pt/C catalyst shows a reduced percentage of only 34.07% and 33.16% from the initial mass activity and specific activity. As observed in Figure 5i, owing to the ECSA of the Pt-Mo 2 C/NC catalysts being largely unchanging after the ADT potential cycling, the Pt-Mo 2 C/NC catalysts only show a decrease of 10.77% and 8.62% from the initial mass activity and specific activity, respectively. These results further confirmed that the as-prepared Pt-Mo 2 C/NC catalyst possesses improved stability for ORR because of the induced strong interfacial coupling effect and the formed N-doped carbon. Figure 6. (a) Schematic illustration of the Pt (111), MoC (111) and Pt 4 /MoC (111) models. Schematic diagram of the ORR process of Pt sites on the (b) Pt 4 /MoC (111) and (c) Pt (111) models. (d) Free energy plots of ORR intermediate for Pt 4 /MoC (111) and (c) Pt (111) models at U=0 V and U=1.23 V. Projected density of state of Pt on (e) Pt (111) and (f) Pt 4 /MoC (111) models. Further DFT calculations were performed to understand the effect of the Pt-Mo 2 C/NC interface electronic structure on catalytic ORR. We constructed three computational models, including Pt (111), MoC (111) and Pt 4 /MoC (111) models are shown in Figure 6a, in which Pt 4 /MoC (111) is composed of Pt clusters containing four Pt atoms supported on MoC (111) plates. Figure 6b and 6c illustrate the ORR process of Pt sites on the Pt 4 /MoC (111) and Pt (111) models, respectively. The free energies of the ORR intermediate at U = 0 V and 1.23 V were calculated for the Pt 4 /MoC (111) and Pt (111) models, respectively, as shown in Figure 6d. The ORR rate determination step (RDS) is *O converse to*OH step for Pt (111) model, while it changes to *OH transform to H 2 O step for Pt 4 /MoC (111) model. Compared with the Pt (111) model, the Pt 4 /MoC (111) can enhance the *OOH and *OH adsorption while weakening the *O adsorption, which effectively reduces the free energy change of the *O and *OH formation step change of the *O and *OH formation step while making the H 2 O formation step is more energetic. And the free energy of 0.90 eV and 0.69 eV or overpotential of 0.90 V and 0.69 V are needed under electrode potential of 1.23 V to make the ORR proceed spontaneously on Pt (111) and Pt 4 /MoC (111) respectively, denoting that Pt 4 /MoC (111) have higher ORR activity than Pt (111). The improved ORR activity of Pt 4 /MoC (111) can be attributed to the special interface electronic structure of the Pt4 cluster on MoC (111). The electron-rich interface between Pt-Mo in the Pt 4 /MoC (111) model has been confirmed in the previously mentioned Figure 3f-3h. Meanwhile, as shown in Figure 6e and 6f, the d band center (ε d =-1.91 mV) of top most Pt atom (Pt top ) of Pt 4 /MoC (111) is much closer to the Fermi level, while that of the interface Pt atom (Pt int , ε d =-1.91 mV) of Pt 4 /MoC (111) slightly moves far away to Fermi level when compared with ε d (-2.61 mV) of surface Pt on Pt (111). The downshifting of ε d of Pt int plays a major role in weakening the *O adsorption due to *O bonds with more Pt int on Pt 4 /MoC (111). While the upshift of ε d of Pt top greatly enhances the *OOH and *OH adsorption, owing to *OOH and *OH mainly bonding with Pt top . Thus, theoretical calculation confirmed the special electronic structure of the Pt cluster on MoC (111) results in different alterations on the adsorption of *OOH, *OH and *O, enabling reduced free energy change of ORR RDS , thus enhancing ORR activity. Conclusions In conclusion, we have successfully synthesized layered Pt nanoparticles on a molybdenum carbide (MoC) substrate to create an interfacial catalyst system for the oxygen reduction reaction. Meanwhile, the interplay between Pt and Mo 2 C/NC substrate has an unparalleled role in oxygen reduction. The specific activity and mass activity of the obtained Pt-Mo 2 C/NC at 0.9 V reach 1.16 mA. cm −2 and 0.65 A.mg −1 Pt , respectively, which are much higher than the baseline commercial Pt catalyst (0.196 mA cm −2 and 0.135 A.mg −1 Pt ). In our research system, when Pt is incorporated onto the surface of Mo 2 C, XANES and XPS analysis, as well as DFT calculations reveal that the electron density of Pt reduces greatly, while the Pt-Mo interface forms electron-enriched district, which optimized the adsorption energy of the reaction intermediates and resulted in enhanced ORR intrinsic activity. The approach proposed here for the structural evolution from single-phase solid resin to a Pt-Mo 2 C/NC nanocomposite with small-sized NP, proper composition, and optimal electron structure can be promptly employed for the formation of other metal-supported catalyst electrocatalysts. Experimental Chemicals: Chloroplatinic acid hexahydrate (H 2 PtCl 6 ·6H 2 O, 19.75mg Pt /ml), Styrene series anion exchange resin (AER), Hexaammonium molybdate ((NH 4 ) 6 Mo 7 O 24 ), hydrochloric acid (0.1 M HCl), JM Pt/C (20%) and sodium hydroxide (0.1 M NaOH) were obtained from Macklin. Preparation of AER powder: Take 10 g of AER and place it in a beaker, then wash it four times in sequence with 50 mL of 1 M HCl solution, ultrapure water, 1M NaOH solution, and ultrapure water. Subsequently, the AER was filtered and vacuum-dried at 60°C for 24 hours. Crush the dried AER in a high-speed ball mill at a speed of 600 rpm for 2 hours to obtain AER powder. Preparation of Pt-Mo 2 C/NC samples: Typically, 2 ml of H 2 PtCl 6 ·6 H 2 O and 0.243 g of (NH 4 ) 6 Mo 7 O 24 are added and mixed in a beaker containing 20 ml of ultrapure water and 1 g of AER powder. Subsequently, the obtained mixture was stirred at room temperature for 12 hours. Then, the mixed solution was washed with water and ethanol, and the AER powder with adsorbed metal precursors was collected by centrifugation and dried in air at 60 ℃ for 12 hours. Then, the dried AER powder adsorbed with metal precursors was put into a tube furnace and heated to 300°C at a heating rate of 10°C/min and kept for half an hour, and then heated to 700°C at a heating rate of 5°C/min, maintaining an Ar atmosphere during the pyrolysis. Subsequently, the previous atmosphere was immediately replaced with an atmosphere of 5% H 2 and 95% Ar, and then the sample was heated from 700°C to 800°C at a heating rate of 5°C/min and kept for 2h. Pt-Mo 2 C/NC samples were obtained after Free cooling to room temperature. Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202400xxx. 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Energy Mater . 2017 , 8, 1701601. 29. Xiong, K.; Li, L.; Zhang, L.; Ding, W.; Peng, L.; Wang, Y.; Chen, S.; Tan, S.; Wei, Z. Ni-doped Mo2C nanowires supported on Ni foam as a binder-free electrode for enhancing the hydrogen evolution performance. J. Mater. Chem. A . 2015 , 3, 1863. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 Left to Right: Yang Han, Fengqin Zhang, Tingquan Zhang, Chang Yang, and Qingmei Wang Entry for the Table of Contents Constructing of an electron-rich regions and the induced strong interfacial coupling effect, can act as “electronic reservoir” and optimize the adsorption energy of the intermediate, achieving efficient and stable electrocatalysis. Information & Authors Information Version history V1 Version 1 01 August 2025 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords electron-adequate interfacial interfacial coupling effect oxygen reduction reaction phase evolution Authors Affiliations Yang Han Guizhou University View all articles by this author Fengqin Zhang Guizhou University View all articles by this author Tingquan Zhang Guizhou University View all articles by this author Chang Yang Guizhou University View all articles by this author Qingmei Wang 0009-0008-7424-782X [email protected] Guizhou University View all articles by this author Metrics & Citations Metrics Article Usage 192 views 112 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Yang Han, Fengqin Zhang, Tingquan Zhang, et al. Revealing Correlation-driven Charge transfer and Electron Redistribution via strong metal-metal interactions in the Construction of High Stability Pt Catalysts. Authorea . 01 August 2025. 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