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. 2026 Mar 29;19(7):e70598. doi: 10.1002/cssc.70598

Boosting Methanol Electrooxidation on Pt/C with a Metal‐Free Nitrogen‐Doped Carbon Cocatalyst via the Ripple Effect

Jiawen Li 1, Lu Hao 1, Fangge Cheng 1, Mansor Hussain 1, Yuan Fu 1, Xinyi Ma 1, Jia Liu 1,✉
PMCID: PMC13449643  PMID: 41904957

Abstract

Platinum‐based catalysts are the core components for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). Although platinum catalysts on nitrogen‐doped carbon (NC) show promising MOR activity, the coupled variation between Pt and NC during synthesis obscures their individual contributions. Herein, a solid‐phase interface reaction (SIR) successfully decouples their interactions, clarifying the role of each component. We define the ripple effect as the long‐range electronic modulation induced by Pt–N coordination, which modulates the electronic state of Pt active sites in a long‐range manner and thus significantly accelerates MOR reaction kinetics. Based on this, a metal‐free catalytic promoter was developed. When combined with commercial 5 wt% Pt/C, the resulting Pt/C@NC‐6hr composite exhibits 1.67 times and twice the mass activity of 5 and 20 wt% Pt/C. Furthermore, statistical results indicate that the mass activity derived solely from the Pt on NC is 4.74 times higher than that of the original 5 wt% Pt/C catalyst, demonstrating a remarkably substantial activity enhancement. After 3600 s chronoamperometry at 0.75 V (vs. RHE), it maintains superior current density. This work elucidates the mechanism of microenvironment‐enhanced Pt catalysis via the ripple effect and offers a practical strategy for improving commercial Pt/C.

Keywords: commercial Pt/C catalysts, methanol oxidation reaction, nitrogen‐doped carbon material, ripple effect, solid‐phase interface reaction

Solid‐phase interface reaction triggers Pt nanoparticle migration, while the resulting Pt‐N coordination induces a a long‐range electronic modulation effect (ripple effect) that significantly accelerates methanol oxidation reaction kinetics.

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1. Introduction

Direct methanol fuel cells (DMFCs), with their advantages such as easy fuel sourcing, strong safety, compact size, and high theoretical energy density [1, 2, 3, 4, 5], hold promise as a clean and efficient energy conversion device to replace traditional fossil fuel‐based technologies [6, 7, 8, 9, 10, 11]. The overall reaction process of DMFCs involves 6 electron transfers, among which methanol oxidation reaction (MOR) is the most critical step, as it directly determines the operational efficiency of DMFCs [12]. Thus, enhancing MOR performance is essential for the advancement of DMFCs. Pt‐based catalysts are widely employed in MOR due to their superior catalytic activity [13, 14, 15]. As a commercially produced Pt‐based catalyst, Pt/C is widely used for MOR [16, 17]; among which 5 wt% Pt/C is the mainstream commercial grade for DMFC anodes due to its balanced Pt loading, cost‐effectiveness and industrial applicability, while 20 wt% Pt/C is a typical high‐loading commercial benchmark commonly used for MOR performance comparison. Unfortunately, 5 wt% Pt/C suffers from low mass activity and limited stability in practical application, which makes it the ideal research object for our modification strategy. Therefore, developing a simple and low‐cost method to improve the MOR performance of commercial 5 wt% Pt/C has become a promising yet challenging research direction in the field.

Extensive studies have demonstrated that regulating the coordination environment of Pt by doping with metals (e.g., Ni, Fe, Cu, Ru, etc.) [18, 19] or non‐metallic elements (e.g., N, S, P, etc.) [20, 21] can yield unexpected enhancements in the activity of Pt‐based catalysts. Among these, Pt/nitrogen‐doped carbon (Pt/NC) composites have emerged as a research hotspot in energy catalysis due to their excellent electrocatalytic activity and stability. Nitrogen atoms in NC can modulate the electronic structure of Pt through coordination interactions, even realizing long‐range electronic regulation of Pt active sites beyond the direct coordination interface, thereby reducing reaction energy barriers [22, 23]. Particularly in the MOR, nitrogen atoms can inhibit CO poisoning and enhance catalyst durability, while the strong Pt–NC interaction contributes to improved Pt dispersion and anti‐agglomeration capability [24, 25, 26].

However, critical challenges remain in this field [27, 28, 29]. The primary issue lies in the synchronous physicochemical changes between Pt nanoparticles and the substrate structure during synthesis, which makes it difficult to discern their individual contributions to MOR activity. This coupling effect not only increases uncertainty in the micro‐coordination environment of active sites but also poses significant challenges for establishing structure–activity relationships [30, 31]. Furthermore, conventional preparations of Pt/NC catalysts typically involve complex processes, limiting their large‐scale application. Therefore, developing scientific decoupling methods to separate the property variations of Pt from the substrate is crucial for investigating how the substrate microenvironment regulates Pt activity.

To address these challenges, this study proposes a modification strategy employing solid‐phase interface reactions (SIR) [32, 33]. This approach enables precise adjustment of the interfacial micro‐coordination environment while preserving the material's morphology and composition, successfully decoupling the properties of Pt nanoparticles from the substrate. Building on this foundation, we combined systematic experiments with theoretical calculations to investigate the MOR activity of Pt nanoparticles with identical properties across different substrate structures. This revealed the fundamental nature of Pt–substrate interactions and clarified the underlying mechanism behind the enhanced Pt catalytic performance through microenvironment modulation.

More significantly, a novel catalytic promoter for MOR has been developed based on these insights. By employing the SIR technology, it significantly boosts the MOR performance of existing commercial Pt/C. This approach is well‐suited for practical catalyst improvement, offering a simple and effective route to optimize the Pt–support interaction without the need for complex apparatus or severe conditions.

2. Experimental Section

2.1. Chemicals

The commercially available Pt/C catalysts with 5 and 20 wt% Pt contents were both purchased from Energy Chemical (as revealed by the respective quality inspection reports, the Pt contents of the two products were determined to be 5% and 20%). Zinc nitrate hexahydrate (Zn(NO3)2·6H2O, ≥98%), 2‐methylimidazole (2‐MeMi, C4H6N2, ≥98%), potassium hydroxide (KOH, ≥95%) were purchased from Shanghai Aladdin Industrial. Anhydrous methanol (CH3OH, ≥98%), absolute ethanol (C2H5OH), ethylene glycol (EG), and isopropyl alcohol were supplied by Tianjin Damao Chemical Reagent Factory. Nafion (5 wt%) was procured from Sigma–Aldrich. All chemicals were used as received without further purification.

Declaration: No animal experiments were involved, and ethical approval was therefore not required.

2.2. Synthesis of ZIF‐8 Precursor

Solution A was prepared by dissolving 1.19 g of zinc nitrate hexahydrate in 50 mL of anhydrous methanol, and Solution B was obtained by dissolving 1.32 g of 2‐MeMi in 50 mL of anhydrous methanol. Under magnetic stirring, Solution A was added dropwise to Solution B at room temperature with a dripping rate of 10 mL/min, and the mixture was continuously stirred for 8 h. The resulting precipitate was centrifuged at 10,000 rpm for 6 min and washed three times with anhydrous methanol to obtain a white solid, which was identified as the ZIF‐8 precursor.

2.3. Preparation of NC Support

The as‐prepared ZIF‐8 precursor was pyrolyzed in a tube furnace under a nitrogen atmosphere. The pyrolysis process involved heating from room temperature to 950°C at a rate of 5°C/min, maintaining at 950°C for 2, and then naturally cooling to room temperature. During pyrolysis, Zn species in the rhombic dodecahedral structure of ZIF‐8 sublimated, forming abundant Zn vacancies. Notably, the nitrogen atoms retained in the carbon matrix serve as optimal anchoring sites for Pt nanoparticles. The resulting black powder was the NC support.

2.4. Modification of NC Support

10 mg of the NC support was dispersed in 20 mL of EG via ultrasonic treatment for 30 min to form a uniform suspension. After magnetic stirring for 10 min, the suspension was heated in an oil bath at 140°C for different durations (2, 4, 6, 8, or 10 h). These treatments yielded pre‐treated NC‐X h materials, where X represents the oil bath heating time.

2.5. Fabrication of Pt/C@NC‐X h Composite Catalyst

1 mg of 5 wt% Pt/C catalyst and 0.5 mg of the NC‐X h material (pretreated at 140°C for X hours) were mixed and manually ground in a quartz mortar for 20 min for the solid‐phase interface reaction (SIR) to ensure homogeneous dispersion. This process resulted in the Pt/C@NC‐X h composite catalyst, where the Pt/C nanoparticles were physically integrated with the NC support.

3. Results and Discussion

First, we screened the optimal conditions for synthesizing the composite catalyst, with commercial 5 wt% Pt/C (a practical mainstream DMFC catalyst) as the SIR starting material and 20 wt% Pt/C as the high‐loading reference catalyst for performance comparison. As reported by Li et al. [34] and Ni et al. [35], different nitrogen configurations in nitrogen‐doped carbon (NC) materials significantly influence the behavior of platinum. It has been demonstrated that modulating the nitrogen coordination environment around Pt centers enables flexible and directional regulation of the reaction pathways of Pt‐based catalysts. Inspired by these studies, we pretreated nitrogen‐doped carbon cocatalysts by oil bath heating at a constant temperature. The N configuration ratio was adjusted by varying the constant‐temperature heating time (heating at 140°C for 0, 2, 4, 6, 8, 10 h to obtain NC‐X h (X = 0, 2, 4, 6, 8, 10)). All commercial Pt/C catalysts used in this work were commercially available: 5 wt% Pt/C catalysts were used as part of the composite catalyst, and 20 wt% Pt/C catalysts were used as reference materials.

According to Figure S1a, the composite of NC support (heated at 140°C for 6 h) and 5 wt% Pt/C catalyst exhibited the best MOR activity, indicating that this NC sample (denoted as NC‐6h) had the optimal N configuration ratio. Subsequently, we optimized the mass ratio of 5 wt% Pt/C catalyst and NC cocatalyst using the SIR (Figure S1b). The composite catalyst with the highest MOR activity was obtained when the mass ratio was 1:0.5 (5 wt% Pt/C : NC‐6h). The composite catalyst with the best MOR activity was denoted as Pt/C@NC‐6h.

Furthermore, control experiments were conducted to rule out the potential influence of mechanical grinding (Figure S2) and to verify that direct contact between Pt/C and NC is required for the performance enhancement (Figure S3). Equivalent blank grinding control for 5 and 20 wt% Pt/C (20 min grinding without NC) was completed, and the results confirm that the mechanical grinding process itself has no effect on the MOR activity of Pt/C catalysts (Figure S2). Bare NC‐6h shows negligible intrinsic MOR activity (Figure S4). As shown in Figure S3, the five characteristic curves in the figure correspond to the following five test configurations: 1) pristine 5 wt% Pt/C catalyst; 2) 5 wt% Pt/C and NC‐6h drop‐cast separately on the working electrode surface, physically isolated by a Nafion membrane (ensuring no direct contact between Pt and NC); 3) 5 wt% Pt/C and NC‐6h directly co‐deposited on the working electrode surface (without a Nafion membrane, allowing contact); 4) a composite system where 5 wt% Pt/C and NC‐6h were mixed without grinding, but only ultrasonicated for 20 min; 5) the Pt/C@NC‐6h composite catalyst reported in this work. A clear conclusion can be drawn from the comparative analysis of the curves: When Pt and NC are prevented from direct contact (Configuration 2), the MOR activity of Pt/C was almost identical to that of the pristine catalyst (Configuration 1), with only peak broadening observed (attributed to increased electrode interfacial capacitance from NC). In contrast, as the extent of contact between Pt and NC increases (Configuration 3 → Configuration 4 → Configuration 5), the MOR activity gradually enhanced, with Pt/C@NC‐6h (Configuration 5) exhibiting the optimal catalytic performance.

The results indicate that the NC substrate itself possesses no intrinsic activity to boost catalysis, showing negligible activity toward methanol molecules, hydroxyl groups, or MOR intermediates. Combined with the blank grinding control result, mechanical grinding is also confirmed to have no effect on Pt/C performance, thus the significant enhancement in catalytic activity manifests only when Pt nanoparticles establish direct contact with the NC substrate, and this improvement can be solely attributed to the Pt‐N coordination and the subsequent ripple effect induced by NC introduction. The underlying reason is that the grinding process facilitates the maximal migration of Pt species from the Pt/C surface onto the NC support. Furthermore, under external mechanical force, the migrated Pt species can form stable coordinatively anchored structures with the N species in the NC. This Pt‐N coordination optimizes the electronic structure and surface distribution of Pt, ultimately leading to enhanced catalytic activity. Therefore, the Pt/C@NC‐6h catalyst with the highest MOR activity was selected for subsequent characterization and discussion.

As shown in Figure 1a, the commercially purchased 5 wt% Pt/C catalyst was mixed with the pretreated ZIF‐8‐derived NC material. Through SIR, the two were ground manually in a mortar for 20 min, which caused the Pt nanoparticles originally supported on the carbon matrix to migrate to the NC support and be anchored by N‐atoms. This preparation method is simple and suitable for large‐scale catalyst production.

FIGURE 1.

FIGURE 1

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(a) Schematic diagram for the synthesis of Pt/C@NC‐6h. (b) TEM image of 5 wt% Pt/C; inset: SEM image of 5 wt% Pt/C. (c) TEM image of NC; inset: SEM image of NC. (d,e) TEM images of Pt/C@NC‐6h. (f) HAADF–STEM image of Pt/C@NC‐6h. (g–i) EDS mappings of C, N, and Pt. (j) XRD patterns of NC, 5 wt% Pt/C, and Pt/C@NC‐6h.

The microstructure of the catalysts was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Figure 1b and its inset show that Pt nanoparticles in the 5 wt% Pt/C catalyst are uniformly dispersed on the carbon substrate. Figure 1c and its inset display that NC particles have a regular shape with a size of approximately 50 nm. Figure 1d,e reveal that NC particles are scattered in Pt/C in the Pt/C@NC‐6h sample, and Pt nanoparticles supported on NC particles can be observed. The particle size distribution analysis (Figure S5) shows that the average particle size of Pt in Pt/C@NC‐6h is 2.00 nm. This indicates that during the SIR process, a portion of Pt particles migrates from Pt/C to the NC material. The abundant nitrogen atoms in NC utilize their lone electron pairs to precisely capture Pt particles, thereby adjusting the interfacial micro‐coordination environment of Pt. Since this method avoids the potential dissolution of Pt particles that may occur in solvothermal reactions, the original morphologies of the composite's structural units (carbon support, NC, and Pt particles) were largely preserved. This preservation is crucial for investigating the structure–activity relationships. The HAADF–STEM image (Figure 1f) of the Pt/C@NC‐6h sample shows the Pt particle distribution, while Figure 1g–i show the uniform distribution of various elements in the Pt/C@NC‐6h catalyst, and Pt particles supported on NC particles can be clearly observed.

X‐ray diffraction (XRD) analysis (Figure 1j) shows that all samples exhibit a distinct diffraction peak at 26.50°, corresponding to the (002) crystal plane of graphitic carbon. For 5 wt% Pt/C and Pt/C@NC‐6h samples, three characteristic diffraction peaks are observed at 39.80°, 46.30°, and 67.50°, which correspond to the (111), (200), and (220) crystal planes of Pt (PDF # 04‐001−3301), respectively. This indicates that the migration of Pt from Pt/C to the NC support and its subsequent anchoring by nitrogen species do not alter the crystal structure of Pt. These results demonstrate that the SIR method has a significant advantage in preserving the original morphological and structural integrity of the materials. Additionally, the relative intensity of the Pt diffraction peaks in Pt/C@NC‐6h is lower than that in 5 wt% Pt/C, which is attributed to the incorporation of NC material.

X‐ray photoelectron spectroscopy (XPS) was used to investigate the chemical states of key elements in each sample, as coordination environment exerts indispensable influence on the electronic structure of key elements [36, 37, 38]. The full XPS spectrum results are consistent with the elemental mapping (Figure S6). As shown in Figures 2a and S7, the binding energies at approximately 284.80, 286.50, and 288.10 eV, corresponding to C=C, C=N/C=O, and C—C=O bonds, respectively. Among these, the proportion of the characteristic peak corresponding to C=N/C=O in the 5 wt% Pt/C material is very low, indicating a weak interaction between C and N/O in the 5 wt% Pt/C material.

FIGURE 2.

FIGURE 2

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XPS spectra: (a) C 1s spectra of NC‐6h, 5 wt% Pt/C, and Pt/C@NC‐6h. (b) O 1s spectra of NC‐6h, 5 wt% Pt/C, and Pt/C@NC‐6h. (c) N 1s spectra of NC‐6h and Pt/C@NC‐6h. (d) Pt 4f spectra of 5 wt% Pt/C and Pt/C@NC‐6h.

The O 1s spectra of the materials were analyzed and compared. Figures 2b and S8 reveal three distinct peaks, corresponding to oxygen strongly bound to Pt (OS, 530.30–530.80 eV), oxygen with moderate binding strength (O M , 531.80–532.50 eV), and weakly adsorbed oxygen (O ads, 533.30–533.80 eV), respectively. The differences in oxygen binding energy are attributed to variations in the interaction strength between oxygen and the active sites of the material [39, 40]. In the metal‐free nitrogen‐doped carbon support, the interaction between oxygen and the support is weak, dominated by adsorbed oxygen and oxygen vacancies. In the 5 wt% Pt/C material, the proportion of strongly bound oxygen species increases significantly. This is because the introduction of metallic Pt alters the chemical environment of oxygen through electron transfer effects: electrons from the d‐orbitals of metallic Pt can transfer to oxygen in the support, facilitating the formation of Pt—O bonds (evidenced by the enhanced peak intensity of O M ). Compared to the pure 5 wt% Pt/C material, the Pt/C@NC‐6h composite catalyst exhibits a decreased proportion of O S and a significant increase in O ads. This can be attributed to interfacial interactions: after the formation of an interface between NC‐6h and Pt/C, the Pt—N coordination modifies the electronic structure of Pt, promoting the transformation of originally stable Pt—O bonds into surface‐adsorbed states (shifting from low‐binding‐energy O S to high‐binding‐energy O ads). Meanwhile, the porous/defective structure of NC‐6h also enhances the physical adsorption of oxygen, further increasing the proportion of adsorbed oxygen.

To investigate the Pt—N coordination, the N 1s XPS spectra were deconvoluted into four distinct peaks: pyridinic‐N (≈398.5 eV), pyrrolic‐N (≈400.0 eV), graphitic‐N (≈401.0 eV), and oxidized‐N (≈405 eV). The results show that the initial NC material (Figure S9) has the highest content of pyridinic‐N (49.13%). In contrast, in the NC‐6h material pretreated by oil bath heating at 140°C for 6 h, although pyridinic‐N still dominates (45.77%), the proportion of pyrrolic‐N increases (Figure 2c) (from 15.56% to 18.20%), indicating that high‐temperature heating pretreatment can promote the formation of pyrrolic‐N. Furthermore, as shown in Figure 2c, in Pt/C@NC‐6h obtained by compositing NC materials with commercial Pt/C, the relative content of pyridinic‐N decreases compared with that in pure NC‐6h (from 45.77% to 39.23%), while the relative content of pyrrolic‐N increases significantly (from 18.20% to 23.36%). This result indicates that after contact, electrons shift from pyridinic N to Pt, thereby increasing the binding energy of N.

The analysis of the Pt 4f spectra of Pt‐containing samples (Figure 2d) identifies three different doublets: Pt0 (≈ 71.40 and 74.80 eV), Pt2+ (≈72.50 and 75.70 eV), and Pt4+ (≈75.90 and 78.90 eV). Notably, compared with 5 wt% Pt/C, the characteristic peaks of Pt 4f in Pt/C@NC‐6h shift to lower binding energies, indicating that the incorporation of the NC support effectively modulates the electronic structure of the catalyst and promotes electron transfer from N to Pt.

To investigate the reason for the excellent MOR performance of the Pt/C@NC‐6h catalyst, a series of MOR electrochemical characterizations were conducted on three materials (5 wt% Pt/C, Pt/C@NC‐6h, and 20 wt% Pt/C; these three materials are referred to as such throughout the following text) to study their intrinsic reaction mechanisms. The results of cyclic voltammetry (CV) for different catalysts shown in Figure 3a were obtained at room temperature in an Ar‐saturated 0.5 M KOH + 1.0 M CH3OH mixed solution. It can be observed that the CV curve of the NC material does not exhibit a characteristic peak for methanol oxidation, indicating that the NC material has no activity toward MOR. Among the three materials, Pt/C@NC‐6h catalyst exhibits the highest mass activity of 1.79 A mg−1 Pt, which is 1.67 times that of 5 wt% Pt/C (1.07 A mg−1 Pt) and twice that of 20 wt% Pt/C (0.89 A mg−1 Pt). More importantly, by counting the number of Pt nanoparticles successfully migrated from the Pt/C catalyst to the nitrogen‐doped carbon support (NC) (Figure S10, and Table S1), the enhancement effect of Pt—N coordination during the SIR process on the mass activity of the catalyst can be initially quantified: the mass activity of the migrated Pt solely on the NC support reaches 5.07 A mg−1 Pt, and this enhancement magnitude is equivalent to 4.74 times that of the original 5 wt% Pt/C catalyst. This finding demonstrates the authentic boost in catalytic performance conferred by Pt—N coordination.

FIGURE 3.

FIGURE 3

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Electrochemical performance of different catalysts: (a) Pt mass‐normalized MOR curves in 0.5 M KOH + 1.0 M CH3OH. (b) MA and SA of 5 wt% Pt/C, Pt/C@NC‐6h, 20 wt% Pt/C and theoretical Pt on NC. (c) ECSA measured in 0.5 M KOH. (d) Linear fitting curves of forward peak current density vs. square root of scan rate for MOR and diffusion coefficients of 5 wt% Pt/C, Pt/C@NC‐6h, and 20 wt% Pt/C. (e) CA tests of 5 wt% Pt/C, Pt/C@NC‐6h, and 20 wt% Pt/C for 3600 s. (f) 1000‐cycle accelerated durability tests of 5 wt% Pt/C, Pt/C@NC‐6h, and 20 wt% Pt/C at 0–1.2 V (vs. RHE).

The performance comparison between the modified 5 wt% Pt/C and commercial 20 wt% Pt/C fully reflects the practical optimization effect of our SIR strategy. As shown in Figure 3b, the mass activity of the Pt/C@NC‐6h is 1.67 times that of 5 wt% Pt/C and twice that of 20 wt% Pt/C. Furthermore, Pt/C@NC‐6h exhibits the highest specific activity (SA) of 2.68 mA cm−2. Compared with the pristine 5 wt% Pt/C catalyst (2.54 mA cm−2), it is enhanced by 1.06 times. Meanwhile, SA of Pt/C@NC‐6h is twice that of the 20 wt% Pt/C catalyst (1.34 mA cm−2), which are consistent with the typical values reported in relevant literatures [41, 42, 43]. This excellent performance can be attributed to the SIR, which facilitates the migration of partial Pt nanoparticles from the carbonaceous support to the nitrogen‐doped carbon support, leading to the formation of Pt‐N coordination structures. Consequently, the intrinsic MOR activity of the commercial Pt/C catalyst is significantly improved. Additionally, we calculated that the Pt transferred from the carbon support to the NC support exhibits a theoretical mass activity of 5.07 A mg−1 Pt and a SA of 56.08 mA cm−2, both significantly higher than those of Pt on the carbon support. This indicates that the migration of a portion of Pt nanoparticles from the carbon support to the NC support via the SIR strategy can effectively enhance the catalyst's activity toward the MOR. More importantly, the successful preparation of the Pt/C@NC‐6h catalyst simultaneously achieves the dual goals of low cost and high activity.

Figure 3c shows the CV curves obtained in an Ar‐saturated 0.5 M KOH solution. Based on the hydrogen adsorption area in the CV curves, the electrochemical active surface areas (ECSA) of 5 wt% Pt/C, Pt/C@NC‐6h, and 20 wt% Pt/C were calculated to be 42.16, 66.81, and 66.42 m2/gPt, respectively. It is worth noting that the electrochemically active surface area (ECSA) of Pt/C@NC‐6h is 1.01 times that of 20 wt% Pt/C, however, under the condition of the same material mass, the Pt content in 20 wt% Pt/C is approximately 6 times that of Pt/C@NC‐6h. This result indicates that 20 wt% Pt/C is not only costly but also difficult to achieve the same excellent MOR activity as Pt/C@NC‐6h under equivalent conditions. Meanwhile, the higher Pt content in 20 wt% Pt/C is the reason for its minimum electrochemical impedance (Figure S11). In addition, the ECSA of Pt/C@NC‐6h is 1.58 times that of 5 wt% Pt/C, with Pt/C@NC‐6h exhibiting the largest ECSA value. It should be noted that the SIR process employed in this study does not alter the nanoscale structure of the materials; based on this characteristic, it can be theoretically inferred that the structure of Pt nanoparticles in the composite material remains unchanged, and their geometric specific surface area should be consistent with that before compositing. Therefore, we have sufficient reason to believe that the increase in ECSA of Pt/C@NC‐6h essentially stems from the modified electronic structure of Pt via Pt‐N coordination, which enhances the accessibility of active sites and improves reaction kinetic efficiency, ultimately enabling Pt/C@NC‐6h to exhibit the optimal catalytic activity.

Furthermore, the 5 wt% Pt/C and Pt/C@NC‐6h catalysts do not exhibit characteristic peaks corresponding to Pt oxidation, indicating that Pt nanoparticles have stronger oxidation resistance when their content is low. This is one of the reasons why 5 wt% Pt/C and Pt/C@NC‐6h have better stability and durability than 20 wt% Pt/C.

Electrochemical kinetics is also one of the important indicators for evaluating the catalytic performance of materials [44]. By testing CV curves at different scan rates, the reaction diffusion kinetics and intrinsic chemical reaction kinetics of the three materials were studied (Figures S12–S14). As the scan rate increases from 20 to 100 mV s−1, the current density of all three materials increases accordingly. The peak current density (If) increases linearly with the square root of the scan rate (v 1/2) (Figure 3d), and Pt/C@NC‐6h shows the steepest slope. Combined with the D values calculated using the Randles‐Sevcik equation, the Pt/C@NC‐6h catalyst has a larger diffusion coefficient (D) than 5, and 20 wt% Pt/C, indicating the fastest diffusion rate and excellent reaction kinetics.

Stability and durability tests, including 3600 s chronoamperometry at 0.75 V (vs. RHE) (Figure 3e) and 1000‐cycle accelerated durability tests (ADT) at 0–1.2 V (vs. RHE) (Figure 3f), were performed to construct a comprehensive evaluation system (Figures S15–S17). The selection of 0.75 V (vs. RHE) as the chronoamperometry potential is based on two key practical considerations: first, this potential is close to the MOR forward peak current potential of the prepared catalysts, which well simulates the actual working potential of DMFC anodes in practical application scenarios—DMFCs typically operate at the potential region corresponding to the maximum MOR reaction rate to ensure high energy conversion efficiency, making this test condition more reflective of the catalyst's stability in real service environments; second, this potential avoids excessive oxidation of Pt active sites at ultrahigh anodic potentials, enabling accurate evaluation of the catalyst's stability dominated by intrinsic MOR factors (e.g., CO poisoning, reactant adsorption/desorption) rather than pure Pt structural degradation caused by high‐potential oxidation. Under this practical working potential, Pt/C@NC‐6h still exhibits the highest current density retention after 3600 s of continuous testing, far exceeding the commercial 5 and 20 wt% Pt/C. Moreover, the Pt/C@NC‐6h catalyst also maintains superior stability in the 1.0–1.2 V (vs. RHE) high‐potential ADT (Figures 3f and S15–S17), which is commonly used to examine catalyst tolerance in the high potential region: its catalytic activity retention after 1000 cycles is significantly higher than that of the commercial Pt/C catalysts. This dual‐potential stability test result fully demonstrates that the Pt/C@NC‐6h catalyst modified by the ripple effect has both excellent service stability under the actual DMFC operating conditions and strong tolerance to high anodic potential oxidation, which is attributed to the optimized electronic structure of Pt active sites induced by Pt—N coordination and the stable interfacial interaction between Pt nanoparticles and the NC support. Such a structural and electronic modulation effect effectively improves the anti‐degradation capability of the catalyst during the electrocatalytic process, thus endowing the Pt/C@NC‐6h composite with outstanding comprehensive stability for MOR. After the long‐term durability test, XPS characterization was performed on the after‐reaction Pt/C@NC‐6h catalyst. The N 1s and Pt 4f spectra of the after‐test sample (Figure S18) show no obvious differences from those of the fresh catalyst (Figure 2c,d), indicating that the Pt—N coordination environment and electronic structure are well maintained after the durability test, which contributes to the excellent structural stability of the catalyst.

To gain insight into the electrooxidation mechanism of methanol molecules in different catalysts, in situ Raman spectroscopy and 1H nuclear magnetic resonance (1H NMR) tests were conducted to study the reaction pathways of Pt/C@NC‐6h and 5 wt% Pt/C. In a 0.5 M KOH + 2.0 M CH3OH electrolyte, in situ Raman spectroscopy was used to capture the intermediate products generated during MOR over different catalysts under different potentials. In Figure 4a,b, characteristic peaks attributed to the C—O bond in CH3OH (approximately 1012 cm−1) and symmetric (v s (C—H)) and asymmetric (v as (C—H)) stretching vibrations of the C—H bond (approximately 2840 and 2950 cm−1) can be observed. In addition, peaks at approximately 1458 and 1632 cm−1 correspond to the D‐band and G‐band of graphitic carbon in the catalyst carbon support. The Raman results show that the intensity of these characteristic peaks does not change with the applied potential, indicating the excellent chemical stability of the catalyst.

FIGURE 4.

FIGURE 4

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In situ Raman spectra of (a) Pt/C@NC‐6h and (b) 5 wt% Pt/C. (c) CO‐stripping profiles of 5 wt% Pt/C and Pt/C@NC‐6h. (d) DOS of Pt nanoparticle, C‐PtIL, C‐PtIL‐PtML, CN‐PtIL, CN‐PtIL‐PtML.

A broad peak at roughly 2000 cm−1 matches the characteristic signal of CO intermediates during MOR. In Figure 4a, as the potential increases, a characteristic signal of COO— intermediates (≈1345 cm−1) shows up on the surface of the Pt/C@NC‐6h catalyst. Additionally, a comparison with the 1H NMR results of the electrolyte after 1000‐cycle ADT (Figures S19–S21) confirms the presence of formic acid as a reaction intermediate in both Pt/C@NC‐6h and 5 wt% Pt/C. Formic acid is clearly identified as a key intermediate over Pt/C@NC‐6h. These in situ Raman and 1H NMR results indicate that the direct reaction pathway (“non‐CO” pathway) is involved and may be favored in the Pt/C@NC‐6h catalyst, which can promote the conversion of related intermediates, thereby exhibiting better catalytic performance. In contrast, the results of Figures 4b and S21 suggest that the indirect reaction pathway (CO pathway) may be more involved in the 5 wt% Pt/C catalyst.

CO poisoning is a primary cause of activity loss in Pt‐based catalysts, as the adsorption of CO on the surface of Pt sites affects the kinetics of MOR [45]. Therefore, a CO‐stripping experiment (Figure 4c) was conducted to investigate this issue. First, the catalyst was placed in a 0.5 M Ar‐saturated KOH solution, and CO gas was continuously bubbled for 30 min to saturate the solution. Then, Ar was bubbled for 10 min to remove excess CO on the catalyst surface, achieving a CO monolayer adsorption state. Subsequent CV tests were performed, and the CV curves of two cycles were recorded. It can be observed in Figure 4c that an obvious CO oxidation peak appears in the first cycle, while this peak disappears significantly in the second cycle, indicating that CO can be completely oxidized after the first CV cycle and desorbed from the catalyst surface after the second cycle. The onset potentials of CO intermediate oxidation during MOR differ between the 5 wt% Pt/C and Pt/C@NC‐6h, which are 0.445 and 0.381 V, respectively. The lower onset potential of CO oxidation for the Pt/C@NC‐6h indicates that CO is more easily oxidized and desorbed on its surface, meaning that Pt/C@NC‐6h has stronger CO poisoning resistance at low potentials, leading to improved catalytic performance. Surprisingly, it can be observed that both catalysts exhibit Pt oxidation peaks in the first cycle, which is particularly obvious in Pt/C@NC‐6h. Compared with the disappeared Pt oxidation peak in the ECSA test curve (Figure 3c), this indicates that after Pt sites adsorb CO, the activity of Pt decreases and it is more easily oxidized, which also confirms that CO poisoning causes a reduction in catalyst activity.

Based on the conclusions from in situ Raman and CO stripping experiments, we explore how the NC substrate impacts Pt nanoparticles via density functional theory (DFT) calculations. To probe the electronic properties of the Pt active sites, five structural models were constructed and their projected density of states (PDOS, Figure 4d) was computed. These models include a pure Pt nanoparticle (Pt); inner‐layer Pt atoms in direct contact with a carbon support (C‐PtIL); middle‐layer Pt atoms adjacent to the inner‐layer Pt but not contacting the carbon support (C‐PtIL‐PtML); inner‐layer Pt atoms directly bound to the NC support (CN‐PtIL); and middle‐layer Pt atoms adjacent to the inner‐layer Pt but not in direct contact with the NC support (CN‐PtIL‐PtML). It is revealed by the findings that the modification in the electronic structure of the middle‐layer Pt atoms in the last model is the reason for the enhanced MOR activity. We refer to this long‐range electronic structure influence exerted on the sub‐adjacent sites after Pt‐N coordination as the ripple effect, which is defined as the long‐range electronic modulation induced by Pt—N coordination in the Abstract.

To provide direct experimental verification for the “ripple effect” and correlate it with the electronic structure changes observed in DFT, in situ FT‐IR spectroscopy with CO as a probe molecule was performed on 5 wt% Pt/C and Pt/C@NC‐6h (Figure S22). As shown in Figure 4d, the DFT results indicate that the middle‐layer Pt atoms (CN‐PtIL‐PtML) experience a moderate electronic effect, leading to a slight upshift of the d‐band center away from the Fermi level compared to pure Pt. This subtle downshift in electron density at the Fermi level weakens the interaction between Pt and adsorbed species. Experimentally, distinct CO adsorption peaks were observed on both samples, and the CO peak of Pt/C@NC‐6h showed an obvious positive shift toward higher wavenumber relative to 5 wt% Pt/C. This positive shift in the FT‐IR spectrum directly reflects a reduction in the Pt—CO bond strength, which is a direct spectroscopic manifestation of the d‐band center modulation observed in the PDOS analysis. The correlation between the FT‐IR peak shift and the PDOS features confirms that the Pt—N coordination at the interface (CN‐PtIL‐PtML) exerts a long‐range electronic influence (the ‘ripple effect’) on the neighboring Pt atoms, thereby tuning the electronic structure of the active sites to optimize adsorption energy. These combined DFT and FT‐IR results provide solid evidence supporting the existence and propagation of the “ripple effect” in Pt/C@NC‐6h.

Previous studies have confirmed that Pt single atoms directly anchored by N on the N‐doped carbon support exhibit poor MOR catalytic activity [46, 47, 48]. Analyzing from the perspective of electronic structure modulation, a comparison of the d‐orbital electronic structures of the five models in Figure 4d reveals the following: the d‐band of the pure Pt nanoparticle is closer to the Fermi level, resulting in the strongest CO adsorption and consequently raising the energy barrier for carboxyl (—COOH) formation, which hinders the catalytic reaction process. In Pt nanoparticle supported on the carbonaceous support (Models 2 and 3), the interaction between both the inner‐ and middle‐layer Pt atoms and the carbon support is weak, and their d‐band electronic structures show almost no difference from that of the pure Pt nanoparticle. In the Pt nanoparticle supported on the NC support, electrons transfer from N to Pt for the inner‐layer Pt atoms (Model 4) due to the difference in work function between Pt and N, causing splitting of its d‐band and a shift further away from the Fermi level—this indicates that the strong direct Pt—N interaction is conversely detrimental to the catalytic activity of Pt. Notably, the middle‐layer Pt atoms (Model 5), through a moderate electronic effect, can precisely tune their d‐band center to an optimal position near the Fermi level. On one hand, this significantly enhances their adsorption capacity for reaction species, promoting the dehydrogenation step following CH3OH molecule adsorption. On the other hand, it accelerates the generation of abundant OH*, which can further oxidize COads on the Pt surface to CO2, thereby alleviating the CO poisoning effect, consistent with the results verified in Figure 4c. Simultaneously, from the perspective of steric hindrance, the inner‐layer Pt atoms adjacent to the NC support (Model 4) are located at the bottom of the cluster, where excessive steric hindrance makes it difficult for them to interact with reaction species such as CH3OH and OH*, thus preventing their effective participation in the catalytic process. In contrast, the catalytic advantage of the middle‐layer Pt atoms (Model 5) can be analyzed from two aspects: Regarding steric hindrance, the middle‐layer Pt atoms experience less steric hindrance, allowing CH3OH molecules and OH* intermediates to readily approach from the periphery of the Pt nanoparticle and initiate subsequent reactions by adsorbing onto these intermediate‐layer Pt sites. These findings fully highlight the crucial regulatory role of moderate Pt–N interaction in enhancing the Pt‐based catalysts’ MOR catalytic activity.

Finally, the reasons for the decrease in catalyst activity were explored. In addition to the poisoning effect caused by the blockage of active sites by COads mentioned above, the agglomeration, dissolution, and detachment of metallic Pt during the reaction process also serve as a primary cause of catalyst activity decay. Combined with Figure S23, it can be observed that the Pt nanoparticles undergo obvious agglomeration, with the particle diameter increasing from the initial 2.00 nm (Figure S5) to 4.84 nm (Figure S24). The agglomeration of Pt nanoparticles also brings a notable decline in the catalytic activity of the catalyst.

4. Conclusion

In summary, this study successfully designed a low‐Pt‐content Pt/C@NC‐6h catalyst through the solid‐phase interface reaction (SIR) strategy, where the introduction of the NC support effectively modulates the surface micro‐coordination environment. The optimized catalyst demonstrates significantly enhanced methanol oxidation reaction performance, achieving a mass activity of 1.79 A mg‐1Pt, which is 1.67 times and twice that of commercial 5 and 20 wt% Pt/C catalysts, respectively. Furthermore, the mass activity enhancement induced by the Pt on NC is 4.74 times that of the pristine 5 wt% Pt/C catalyst, indicating that the Pt—N interaction can significantly boost the catalytic activity. More importantly, this research system clearly reveals the respective contributions of N‐species and Pt nanoparticles, and for the first time defines and elucidates the ripple effect (the long‐range electronic modulation induced by Pt—N coordination) generated by Pt—N coordination, which provides crucial theoretical insights into the long‐range electronic regulation mechanism of Pt active sites. In situ Raman and 1H NMR characterization qualitatively reveals the involvement of formic acid intermediates and the preference for non‐CO pathway over Pt/C@NC‐6h, supporting the improved reaction kinetics. Furthermore, the exclusive presence of Pt nanoparticles without interference from Pt single atoms in the Pt/C@NC‐6h catalyst enables unambiguous assessment of active sites. This not only establishes a clean platform for mechanistic studies of MOR but also opens new perspectives for the rational design of advanced electrocatalysts.

Supporting Information

Additional supporting information can be found online in the Supporting Information section. The authors have cited additional references within the Supporting Information [41, 42, 43]. Supporting Fig. S1: The optimization conditions for preparing the composite catalyst were screened. (a) The isothermal holding time for the oil‐bath heating pretreatment of the NC support. (b) The optimal mass ratio between 5 wt% Pt/C and the NC‐X h support. Supporting Fig. S2: CV curves of pristine and blank ground (20 min without NC) 5 wt% Pt/C and 20 wt% Pt/C in 0.5 M KOH and 1.0 M CH3OH solution. Supporting Fig. S3: Control experiments to exclude the intrinsic activity of the NC material (Black curve: 5 wt% Pt/C catalyst; Purple curve: 5 wt% Pt/C and NC‐6h drop‐cast separately on the working electrode and isolated by a Nafion membrane; Blue curve: 5 wt% Pt/C and NC‐6h directly co‐deposited on the working electrode; Green curve: a composite of 5 wt% Pt/C and NC‐6h mixed without grinding and subjected to 20 min ultrasonication; Red curve: Pt/C@NC‐6h). Supporting Fig. S4: (a) CV curves of bare NC‐6h recorded in 0.5 M KOH and 1.0 M CH3OH solution. (b) Chronoamperometric (i–t) curve of bare NC‐6h tested in 0.5 M KOH + 1.0 M CH3OH solution. Supporting Fig. S5: Particle size statistical histogram of Pt nanoparticles supported on Pt/C@NC‐6 h. Supporting Fig. S6: XPS full spectrum of Pt/C@NC‐6 h. Supporting Fig. S7: XPS spectra: C 1s spectra of NC support. Supporting Fig. S8: XPS spectra: O 1s spectra of NC support. Supporting Fig. S9: XPS spectra: N 1s spectra of NC support. Supporting Fig. S10: TEM images of Pt/C@NC‐6 h. The red circle in the figures shows a fraction of Pt nanoparticles migrated from C to NC. Supporting Fig. S11: EIS curves of 5 wt% Pt/C, Pt/C@NC‐6 h, and 20 wt% Pt/C. Supporting Fig. S12: CV curves at different scan rates ranging from 20 to 100 mV s−1 of 5 wt% Pt/C. Supporting Fig. S13: CV curves at different scan rates ranging from 20 to 100 mV s−1 of Pt/C@NC‐6 h. Supporting Fig. S14: CV curves at different scan rates ranging from 20 to 100 mV s−1 of 20 wt% Pt/C. Supporting Fig. S15: 1000‐cycles of ADT for 5 wt% Pt/C at 0–1.2 V (vs. RHE). Supporting Fig. S16: 1000‐cycles of ADT for Pt/C@NC‐6 h at 0–1.2 V (vs. RHE). Supporting Fig. S17: 1000‐cycles of ADT for 20 wt% Pt/C at 0–1.2 V (vs. RHE). Supporting Fig. S18: (a) N 1s and (b) Pt 4f XPS spectra of after‐reaction Pt/C@NC‐6h. Supporting Fig. S19: 1H nuclear magnetic resonance (1H NMR) tests of initial electrolyte (0.5 M KOH + 1.0 M CH3OH electrolyte). Supporting Fig. S20: 1H nuclear magnetic resonance (1H NMR) tests of Pt/C@NC‐6 h. Supporting Fig. S21: 1H nuclear magnetic resonance (1H NMR) tests of 5 wt% Pt/C. Supporting Fig. S22: In‐situ FT‐IR spectra with CO probe molecules on 5 wt% Pt/C and Pt/C@NC‐6h. Supporting Fig. S23: (a) and (b)TEM images of Pt/C@NC‐6h after 1000‐cycles of ADT. Supporting Fig. S24: Particle size statistics histogram of Pt nanoparticles on Pt/C@NC‐6 h after 1000‐cycles of ADT. Supporting Table S1: Statistics on the number of Pt nanoparticles (Pt NPs) migrated from Pt/C (C) to the nitrogen‐doped carbon support (NC). Supporting Table S2: Electrochemical performance for MOR of different catalysts.

Funding

This study was supported by Grant YLU‐DNL Fund (2021004), TJU Independent Innovation Fund (0903064050).

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

Supplementary Material

CSSC-19-e70598-s001.pdf (2.4MB, pdf)

Acknowledgments

The authors are grateful to the Grant YLU‐DNL Fund2021004. We also thank TJU Independent Innovation Fund (0903064050). We gratefully acknowledge the technical support from the Analysis and Testing Center, Tianjin University, for their provision of high‐performance characterization services.

Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Supplementary Material

CSSC-19-e70598-s001.pdf (2.4MB, pdf)

Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

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