Universal Mechanochemical One‐Pot Synthesis of Hybrid Two‐Dimensional Nanomaterials With Metal Nanoparticles

Abstract

A universal mechanochemical methodology is presented for the one‐pot synthesis of two‐dimensional hybrid nanomaterials. Exfoliation of bulk layered precursors and simultaneous formation of metallic nanoparticles anchored on their surfaces are achieved through ball milling. The process is operationally simple, solvent‐free, and environmentally friendly, enabling the scalable preparation of diverse 2D–nanoparticle hybrids from readily available starting materials.

1. Introduction

The discovery of few‐layer graphene (FLG) in 2004 was a significant boost to research activity in nanotechnology [1]. This was the beginning of the exploitation of new nanomaterials with new and intriguing properties such as semiconductors (transition‐metal dichalcogenides, TMDs with the general formula MX₂, MX or M₂X₃, such as MoS₂, WSe₂) [2, 3, 4], other nanomaterials with insulators properties (h‐BN) [5, 6], semi‐metallic (e.g., PtSe₂, TiS₂), metallic (e.g., NbSe₂), including superconducting (e.g., NbS₂), transition metal oxides and hydroxides [7], and metal carbides and nitrides [8, 9], among others.

Many of the nanomaterials mentioned before are vital to the future of many applications, including catalysis, sensing, bioimaging, and biological applications, solar cells, in the electronic area, etc [10]. With the emergence of these new nanomaterials, different synthesis methods emerged over the years, first for graphene and then extrapolated to other 2D nanomaterials. We can find two principal routes among these synthesis methodologies, the top‐down and bottom‐up techniques. Depending on the nanomaterial, some may be better than others, but if we look at the application, technically the same nanomaterials could be obtained using different methods, although the final properties would be different. It should also be noted that some of the most notable properties depend largely on the number of layers and the dispersion of the 2D nanomaterials [11].

In addition, the applications of 2D nanomaterials can be enhanced by adding nanoparticles to create 2D nanohybrids. Therefore, these hybrid nanomaterials are highly desirable for tuning surface morphology and other essential properties [12] such as enhanced capacitance, electron conductivity to increase the electrochemical activity [13], and catalytic potential [14]. All these properties depend on the size and crystallinity of nanoparticles avoiding at the same time the restacking of layers in the 2D nanomaterials [15]. The nanoparticles could act as a stabilizer of 2D nanomaterials [16], and the hydride provides new ways to improve energy storage reactions [17, 18] to enhance catalytic, magnetic, electrical, and optoelectronic properties [19], to expand photovoltaics, photocatalysis, biological applications, and more. These hybrid nanomaterials can be synthesized through two main methods: i) in situ (e.g., growing the nanoparticles on the 2D nanomaterial surface using techniques such as reduction, hydrothermal [20, 21, 22], and electrochemical deposition [23] and ii) ex‐situ (e.g., attaching premade nanoparticles on the 2D nanomaterial surface through covalent, noncovalent interactions, van der Waals interactions, hydrogen bonding, π–π stacking, or electrostatic interactions methods) [24, 25] using solution mixing [26], sol–gel processes [27, 28], self‐assembly [29], microwave irradiation [30]. However, all these methodologies suffer from some disadvantages such as the disruption of the 2D nanomaterials’ basal planes [31], the use of highly hazardous and non‐environmentally friendly reactants, complex and time‐consuming protocols with low yields [31, 32], and uneven formation and distribution of nanoparticles on the surfaces of the desired 2D nanomaterials [33, 34].

There are a few limited examples of alternative methods involving 2D‐TMDs and nanoparticles. For example, some researchers have explored the doping effect and gas sensing using MoS₂ and metallic nanoparticles (Au, Ag, Pd, Pt, Sc, and Y) [35]. In this process, the MoS₂ flakes were obtained via micromechanical exfoliation, and the metallic nanoparticles are incorporated by electron beam deposition. Another study has reported the synthesis of MoS₂ hybrid nanobelts using single‐ or few‐layer MoS₂ nanosheets as the precursor [36]. Here, benzyl alcohol acts as solvent and reductant and polyvinyl pyrrolidone as surfactant and complexing agent. Metal precursors (AgNO₃ and H₂PtCl₆) are rapidly reduced on the MoS₂ nanosheets, leading to the formation of metal MoS₂ hybrid nanobelts. A different study focuses on synthesizing gold nanoparticle‐decorated molybdenum sulfide (Au@MoS₂) through a redox reaction [37]. To create this hybrid nanomaterial, MoS₂ is exfoliated via sonication using a surfactant, followed by Au nanoparticle deposition through a spontaneous redox reaction with hexachloroauric acid. Lastly, another investigation examines various classes of 0D‐2D and 2D‐2D metal‐TMD hybrids (1T‐WS₂, 2H‐WS₂, 2H‐MoSe₂, 2H‐WSe₂, 1T’‐MoTe₂, and Td‐WTe₂) and elucidates the pathways by which Au and Ag grow on the different TMDs substrates. These were synthesized using hot‐injection reactions at ∼300°C in high‐boiling‐point organic solvents forming 2D nanosheets [38].

These methodologies have shown potential in producing high‐quality 2D nanomaterials with unique properties for diverse applications. They, along with other methods, will be vital in developing new materials with unprecedented properties and uses. However, all these methods typically involve two‐step procedures with some extreme reaction conditions (electron beam deposition, redox reactions, high boiling point condition, etc.…).

In this study, we present a groundbreaking advancement in the field of nanomaterials by introducing a novel, universal method for synthesizing hybrid nanomaterials. This approach is not only user‐friendly but also environmentally conscious, employing natural, nontoxic bulk materials as inexpensive and readily available precursors. To the best of our knowledge, this is the first methodology to develop a high‐yield procedure obtaining exfoliated TMDs anchorage with nanoparticles through an efficient, accessible, and eco‐friendly method in a single, straightforward step.

2. Results and Discussion

A key innovation of this method is the one‐pot synthesis for creating hybrid 2D nanomaterials, offering numerous benefits over traditional methods. These advantages include enhanced efficiency, scalability, reduced waste and production time, lower costs, and greater control over the size and morphology of the resulting nanomaterials. The hybrid 2D nanomaterials produced display unique properties that render them highly attractive for various applications, such as energy storage, catalysis, and electronic devices.

As milling parameters strongly influence both exfoliation efficiency and nanoparticle formation, this work refers to the optimization strategy previously reported. (FLG) [39, 40] Following that methodology, we systematically tuned rotational speed, milling time, and ball‐to‐material ratio. Higher speeds and longer times enhanced layer separation but eventually induced excessive defect formation beyond a threshold. A controlled ball‐to‐material ratio was therefore chosen to balance exfoliation with preservation of the crystalline network. Hardened steel milling jars and balls were employed to ensure effective energy transfer, and periodic cooling intervals were introduced to mitigate overheating. With these conditions, we achieved few‐layer materials bearing uniformly dispersed nanoparticles; full parameter ranges and screening data are provided in the Supporting Information. We added various metal precursors for the synthesis of nanoparticles, such as Fe₃O₄, Ni⁰, Ag⁰, CuO, Co⁰, and TiO₂, as well as glucose, which served as both an exfoliating agent and a nanoparticle reducer. Following the final dialysis, we analyzed and characterized the resulting hybrid nanomaterials.

Preliminary experiments in which the graphite‐to‐glucose ratio was varied showed that this parameter can influence the final metal loading; however, the magnitude and direction of this effect are strongly metal‐dependent, making it difficult to establish a universal trend. Likewise, extending milling duration can enhance defect formation and nanoparticle anchoring, but the associated changes are not systematic across different metal precursors. As the aim of the present work is to describe a general, operationally simple protocol, we report only the optimized conditions that reproducibly yield few‐layer flakes decorated with well‐dispersed nanoparticles. The procedural knowledge gained here has already been exploited to tailor loading and nanoparticle content for specific applications, which will be reported in separate publications.

To clarify the findings, the main text focuses on two representative examples of these nanoparticles (Ag and TiO₂) on FLG, as illustrated in Figure 1. The results for the remaining nanoparticles are provided in the supporting information (Fig. S1‐S6, Table S1‐S5).

FIGURE 1.

Characterization of FLG exfoliated and decorated with nanoparticles: a) XRD with their corresponding index peaks of each metallic nanoparticle, b) TGA of FLG and FLG exfoliated with metallic nanoparticles by ball milling, c,d) TEM images of FLG exfoliated and decorated with their corresponding metallic nanoparticles, e) TEM size distribution of nanoparticles on the FLG exfoliated materials, f) TEM size distribution of FLG exfoliated and decorated with their corresponding metallic nanoparticles, g) Raman spectra of FLG and FLG exfoliated with metallic nanoparticles by ball milling.

Thermogravimetric analysis (TGA) was conducted on all the various hybrid nanomaterials (Figure 1b and Figure S2A) under an air atmosphere. Among the FLG samples, the average weight loss at 400°C in most cases is around 20%, attributable to the pyrolysis of residual oxygen functional groups on the nanomaterials’ surface [41]. The thermal stability of all the different nanomaterials at 800°C can be found in the Table S2. FLG shows the nanoparticles of TiO₂ show a significant concentration with respect of graphene with a percentage about 50 wt%, while the sample with the least nanoparticle content on the graphene surface corresponds to Co nanoparticles. In all nanomaterials, weight loss is observed between 200°C and 400°C, which is consistent with the decomposition of oxygen functional groups such as carboxylate groups (RCOO–), carbonyl (CvO), and others [41]. The residual loss between 700°C and 800°C may be related to the percentage of metallic nanoparticles in each sample. The most significant drop, occurring around 700°C, was observed for FLG‐Cu nanoparticles and FLG‐Ag nanoparticles samples, which reflects the oxidation state and stability of the metal nanoparticles in the samples (Figures 1 and S2A). Overall, the extent and temperature range of the thermal degradation observed across all nanomaterials suggest that the TGA weight loss is directly associated with the formation of the most thermodynamically stable oxidized forms of the embedded nanoparticles.

Transmission electron microscopy (TEM) images (Figures 1c,1d, S3A) and their corresponding size distribution of nanoparticles and layers (Figures 1e, S4, Table S3) are shown for all the different nanomaterials FLG (Figures 1f, S5, Table S4). Additionally, representative SEM micrographs (Figures S3B–C) have now been included to assess the morphology and sample homogeneity at the micrometric scale for both FLG‐Fe and FLG‐Ni hybrids. These images confirm that, even in the powder state (Figure S3B), the materials do not exhibit large‐scale agglomerates and support the more localized nanoscale observations obtained by TEM (Figure S3C). TEM images reveal a uniform distribution of nanoparticles within the layers, exhibiting an average nanoparticle size ranging from 2 to 10 nm. A statistical analysis of FLG‐metal. samples (100–200 nm) indicates that the primary components are graphene flakes with varying size distributions, spanning from 100 to 200 nm, and exhibiting a reduced aggregation effect. The flake sizes remain relatively unchanged after hybridization with different nanoparticles.

X‐ray diffraction (XRD) analyses were conducted on the hybrid, exfoliated nanomaterials, and bulk materials (Figure 1a and Figure S1). In all cases, after the exfoliation process, a reduction in the number of counts was observed for the principal peak of FLG, which corresponds to the 002 peak in the diffraction pattern [42]. This can be noticed by comparing the results with those of the bulk material. To estimate the particle size for each nanomaterial, the Scherrer formula was employed based on the XRD data:

$$\mathit{D}=\frac{K\lambda }{\beta \cos \mathit{\theta }}$$

where K is the shape factor (usually 0.9), λ is 1.5406A°, β is the full width at half maximum, and θ is the Bragg diffraction angle. The crystallite sizes are shown in Table S1. By applying the Scherrer formula, we were able to determine the particle size decreases for all the different nanomaterials derived from the XRD results.

In the hybrid nanomaterials, in all the cases of the XRD data, it is possible to observe new peaks which correspond with the metallic nanoparticle of the hybrid nanomaterial, as it is clear for to observe the Ag and TiO₂ XRD new peaks corresponding to the anchored nanoparticles. However, Ni, Fe₃O₄, CuO, and Co are harder to visualize due to the overlap of the peaks and the principal peaks of the exfoliated nanomaterial. Although most FLG‐metal nanohybrids display XRD patterns dominated by the FLG (002) reflection, the successful formation of the composite materials is unequivocally demonstrated by complementary characterization techniques. TEM analysis confirms the presence of uniformly dispersed nanoparticles with diameters of 2–10 nm anchored on the FLG surface, while TGA reveals distinct residual mass contributions consistent with metal/metal–oxide loading. Collectively, the complementary characterization data confirm the successful synthesis of FLG‐based hybrids bearing Ni, Fe, Cu, and Co nanoparticles, even though their XRD signatures partially overlap with those of pristine FLG.

Finally, Raman spectroscopy is a useful experimental tool for determining and analyzing nanomaterials, especially to distinguish between the ordered and disordered regions in graphenic nanomaterials. It is possible to analyze the different characteristic bands present in carbon nanomaterials (D at 1347 cm⁻¹, G at 1590 cm⁻¹, and 2D at 2700 cm⁻¹) [43, 44]. The detailed results are listed in Figure 1g and Fig. S6 and Table S5. We analyzed the ratio between the D and G bands (I_D/I_G) or both FLG without and with nanoparticles (FLG‐nanoparticles). A higher ratio was observed when nanoparticles were incorporated into the hybrid nanomaterials, with a value of 0.56 for FLG and ranging from 0.47 to 0.88 for FLG‐nanoparticles, depending on the degree of nanoparticle anchorage. This demonstrates a direct relationship between nanoparticle anchorage and the nanohybrid system. The most notable shift was observed in FLG‐Fe nanoparticles and FLG‐Cu nanoparticles cases, indicating an increase in the vibrational energy of in‐plane stretching of sp²‐bonded carbon due to the anchorage of metal nanoparticles. The shift for Fe₃O₄ and CuO nanoparticles in the D position may be attributed to the more significant distortion generated by atom occupation. These shifts can be directly related to the changes and effects on the carbon nanomaterial resulting from the presence of metal nanoparticles in the sp³‐bonded carbon, shown in Figure S6. This shift indicates a strong interaction between graphene and all the nanoparticles, suggesting a change in the electronic structure of graphene. In addition to these analyses, high‐resolution X‐ray photoelectron spectroscopy (XPS) further corroborates the surface chemistry and low extent of unintended oxidation in the composites. As presented in the SI (Figure S7), the C 1s spectra of the FLG‐Ni and FLG‐Co nanomaterials are dominated by a graphenic sp² component at ∼284.5 eV, with only minor higher‐binding‐energy contributions (∼285.8–286.0 eV) attributable to C—O and/or C—N environments at defect sites or adventitious species. The O1s region exhibits low overall intensity, consistent with only background levels of oxygen species rather than intrinsic oxidation introduced during mechanochemical processing. Core‐level spectra of the metal species show signals consistent with their presence in the hybrid materials without dominant highly oxidized states. These XPS results corroborate that the mechanochemical synthesis yields FLG‐based hybrids with preserved graphenic carbon frameworks and incorporated metal species, further supporting the conclusions drawn from Raman, XRD, TEM/SEM, and TGA characterizations.

Beyond the structural and spectroscopic evolution observed upon milling, these results suggest a cooperative mechanism underpinning nanoparticle nucleation and anchoring. Mechanical shear with glucose during ball milling exfoliates the nanomaterials, as we have previously demonstrated in previous works [40], but also likely generates defect sites, and edge terminations that act as anchoring points. In parallel, glucose contributes as a mild solid‐state reducing agent, enabling in situ formation of metal species from their precursors. The close spatial confinement within the milling jar favors rapid nucleation and immobilization of nanoparticles on exfoliated surfaces, preventing extensive growth or phase segregation. Although the relative contribution of mechanochemical activation versus glucose‐mediated reduction may depend on the metal precursor, the evidence supports a synergistic mechanism in which mechanical energy facilitates both exfoliation and nanoparticle deposition with high surface coverage.

Building on our success in synthesizing hybrid FLG with nanoparticle anchorage, we extended our research to include other 2D nanomaterials, specifically TMDs. To accomplish this, we prepared MoS₂ and WS₂ TMDs for anchoring with different nanoparticles. By optimizing our method and parameters, we achieved TMDs with excellent quality and reproducibility. We employed a similar synthesis approach as for FLG but adjusted the experimental conditions for MoS₂ and WS₂ nanomaterials. Characterization of the samples was conducted using XRD, TGA, TEM, SEM, and Raman spectroscopy to evaluate the distribution and functionalization of the TMDs.

In the case of XRD characterization for MoS₂ (Figure 2), various peaks and planes can be identified, such as 14° (002), 33° (100), 40° (103), 50° (105), and 59° (110), corresponding to the hexagonal phase of MoS2 (JCPDS card file No. 37‐1492). In all cases, no significant shifts in the 2θ peak bands were observed for exfoliated MoS₂ or exfoliated MoS₂ with nanoparticle anchorage, although there was a decrease in the intensity of the main peaks (002), indicating nanomaterial exfoliation [45, 46].

FIGURE 2.

XRD pattern of MoS₂ exfoliation and MoS₂ exfoliated decorated with nanoparticles, with their corresponding index peaks of each metallic nanoparticle.

In the case of XRD characterization for MoS₂ (Figure 2), various peaks and planes can be identified, such as 14° (002), 33° (100), 40° (103), 50° (105), and 59° (110), corresponding to the hexagonal phase of MoS₂ (JCPDS card file No. 37–1492). In all cases, no significant shifts in the 2θ peak bands were observed for exfoliated MoS₂ with nanoparticle anchorage, although there was a decrease in the intensity of the main peaks (002), indicating nanomaterial exfoliation [45, 46].

Similar behavior was observed in the WS₂ nanomaterials (Figure 3), with the primary peaks and planes at 14.3° (002), 28.9° (004), 43.9° (006), and 60° (008), corresponding to PDF#08−0237, respectively. Distinct diffraction peaks were observed that were absent in the pristine supports, allowing clear identification of the nanoparticle phases. Peaks at 2θ ≈ 38.1° and 44.3° were assigned to metallic silver (Ag⁰), while reflections at ∼43.3° and ∼51.8° matched the face‐centered cubic structure of metallic nickel (Ni⁰). The characteristic peaks at ∼35.5° and 38.7° indicated the presence of monoclinic copper(II) oxide (CuO), and the strong reflection at ∼25.3° confirmed the anatase phase of titanium dioxide (TiO₂). Signals at 30.1°, 35.5°, and 62.6° corresponded to the spinel structure of magnetite (Fe₃O₄), and additional reflections at ∼44.2° and ∼51.5° were attributed to metallic cobalt (Co⁰). To facilitate phase identification, the diffraction peaks of the metallic and metal–oxide nanoparticles have been indexed in Figures 2 and 3, and the corresponding reference patterns (JCPDS/PDF numbers) are Ag⁰ (PDF #04‐0783), Ni⁰ (PDF #04‐0850), CuO (PDF #48‐1548), TiO₂‐anatase (PDF #21‐1272), Fe₃O₄ (PDF #19‐0629), and Co⁰ (PDF #15‐0806). These results collectively validate the presence of both metallic and metal oxide nanoparticles dispersed over the layered supports. Table S6 displays the crystallite sizes of all the TMDs and their corresponding nanoparticles.

FIGURE 3.

XRD pattern of WS₂ exfoliation and WS₂ exfoliated decorated with nanoparticles, with their corresponding index peaks of each metallic nanoparticle.

Regarding MoS₂ and WS₂ nanomaterials generally exhibit superior thermal stability compared to graphenic nanomaterials, as observed in Figure 4. For instance, graphene can degrade at temperatures as low as 700°C in an air atmosphere [47], while MoS₂ and WS₂ can withstand temperatures up to 900°C‐1000°C [48]. The multistep mass‐loss behavior observed in Figure 4 is characteristic of 2D–nanoparticle hybrids and reflects sequential thermal events. The initial weight loss below ∼150°C is attributed to desorption of physiosorbed water. The second step, typically between 200 and 400°C, corresponds to the decomposition of oxygen‐containing surface groups and residual glucose‐derived species. At higher temperatures, sulfur‐containing species and carbon frameworks progressively oxidize, leaving metal or metal–oxide residues. For MoS₂‐ and WS₂‐based hybrids, additional contributions from sulfur oxidation processes are expected in the 400–600°C range. Although overlap among curves arises naturally from similar decomposition pathways among supports, quantitative comparison is enabled by the residual mass above ∼750–800°C, which reflects the relative metal/metal–oxide loading. These residual percentages are provided in Tables in the supporting info (Table S7) and allow direct comparison of nanoparticle content between samples.

FIGURE 4.

TGA for a) MoS₂ exfoliated and MoS₂ exfoliated and functionalized with metallic nanoparticles and b) WS₂ exfoliated and WS₂ exfoliated and functionalized with metallic nanoparticles by ball milling.

Figure 5 displays the Raman spectra of MoS₂ and WS₂ exhibiting similar patterns. These nanomaterials possess two primary Raman modes: an in‐plane mode for S bond $E_{2g}^1$ and an out‐of‐plane mode A_1g. For MoS₂, these appear around 380 and 405 cm⁻¹ and 350 and 415 cm⁻¹ for WS₂ [49]. [46] A blueshift in the A_1g mode for MoS₂ and a redshift for WS₂ were observed in the exfoliated materials, indicating a decrease in the number of layers in the exfoliated nanomaterials (Table S8 and S9). The $E_{2g}^1$ and A_1g bands of MoS₂ nanomaterials are located between 378.00 and 387.58 cm⁻¹ and 404.04 and 413.33 cm⁻¹, respectively. The energy difference between $E_{2g}^1$ and A_1g is used to characterize the number of MoS₂ layers; in our case, it ranges from 25.75 to 26.21 cm⁻¹, corresponding to two or three layers [50]. As mentioned previously, the most significant shifts in these two materials (MoS₂ and WS₂) were observed in the samples containing Fe₃O₄ and CuO nanoparticles. A similar shift is observed in FLG for all different particles, as discussed before. The change in the $E_{2g}^1$ is related to the atomic radius of each nanoparticle. The separation between the $E_{2g}^1$ and the A_1g mode for WS₂ nanomaterials ranges from 66.63 to 68.36 cm⁻¹.

FIGURE 5.

Raman spectra for a) MoS₂ exfoliated and MoS₂ exfoliated and functionalized with metallic nanoparticles and b) WS₂ exfoliated and WS₂ exfoliated and functionalized with metallic nanoparticles by ball milling.

Additional TEM data for the MoS₂ samples (Figures 6, S8 and S9) and WS₂ (Figures 7, S10 and S11) are included in the SI (Supporting Information). The average size of each nanoparticle for all the different hybrid nanomaterials are showed in Table S10 and for average layers are in Table S11. The size of the layers of the nanomaterials consistently remains in the range of 100–300 nm and does not significantly change after hybridization with different nanoparticles. Moreover, TEM analysis reveals that the nanoparticles are homogeneously distributed on the surface of the exfoliated MoS₂ and WS₂ flakes. Some degree of nanoparticle agglomeration is observed in several samples (e.g., Figure 6b,f and Figure 7a,d). This behavior is expected for materials produced under mechanochemical conditions. The absence of stabilizing organic species promotes direct metal–metal interactions, favoring partial coalescence during nucleation and growth. In addition, local defects and heterogeneous surface energies at the exfoliated 2D interfaces can serve as preferential anchoring domains, leading to clustered deposition rather than perfectly uniform decoration. Under these mechanochemical conditions, MoS₂ and WS₂ similarly undergo defect generation and edge‐site exposure during exfoliation, and these defect‐rich regions act as effective anchoring points for nanoparticle nucleation, analogous to the mechanism described for FLG. In systems with higher intrinsic reduction kinetics (e.g., Cu and Fe) [51, 52], nucleation may occur faster than anchoring, favoring short‐range aggregation. Importantly, despite these agglomeration features, nanoparticles remain anchored at the nanosheet surfaces and maintain lateral sizes in the 2–10 nm range, as supported by TEM analysis. Notably, no significant variation in nanoparticle size is observed between different supports, suggesting that the ball milling process enables reproducible nanoparticle formation across various 2D substrates. This uniform decoration of the 2D flakes further confirms the effectiveness of the one‐pot mechanochemical route for producing stable, well‐dispersed 2D–0D hybrid nanomaterials with potential for scalable applications.

FIGURE 6.

TEM images of MoS₂ anchorage with different metallic nanoparticles.

FIGURE 7.

TEM images of WS₂ anchorage with different metallic nanoparticles.

3. Conclusion

In this work, we have demonstrated a universal and operationally simple mechanochemical strategy for the one‐pot synthesis of 2D hybrid nanomaterials based on FLG, MoS₂, and WS₂ decorated with a broad range of metallic and metal–oxide nanoparticles. By combining exfoliation and nanoparticle formation in a single solvent‐free step, this approach overcomes several limitations of conventional multistep routes, including the need for hazardous reagents, complex processing, and poor scalability.

Beyond the structural characterization, the results consistently show that the mechanochemical process enables effective nanoparticle anchoring, controlled nanoparticle sizes in the few‐nanometre range, and homogeneous distribution across different 2D supports. The robustness of the method across multiple metals and layered materials highlights its generality and reproducibility, rather than being restricted to a specific composition or system. Importantly, the use of benign solid precursors and glucose as a multifunctional exfoliating and reducing agent underscores the sustainability of the approach and aligns with current demands for greener nanomaterial synthesis.

From a broader perspective, this work establishes a versatile platform for the scalable preparation of 2D–0D hybrid nanomaterials with tunable structural features. While application testing is beyond the scope of the present study, the demonstrated control over exfoliation, nanoparticle size, and anchoring suggests clear potential for future application‐oriented developments in areas such as catalysis, energy storage, sensing, and functional composites. As such, the methodology presented here provides a general foundation for the rational design of advanced hybrid nanomaterials using mechanochemistry as a sustainable and adaptable synthetic tool.

Supporting Information

Additional supporting information can be found online in the Supporting Information section. The data that support the findings of this study are available from the corresponding author upon reasonable request. Supporting Fig. S1: XRD pattern of FLG exfoliated and decorated with nanoparticles, with their corresponding index peaks of each metallic nanoparticle. Supporting Fig . S2A: TGA of FLG and FLG exfoliated with metallic nanoparticles by ball milling. Supporting Fig . S2B: Expanded TGA of graphite at 900°C. Supporting Fig . S3A: TEM images of FLG exfoliated and decorated with their corresponding metallic nanoparticles. Supporting Fig . S3B: HRSEM of the Ni‐FLG sample from 5Kx magnification to 100KX, showing the FLG‐Ni sheet. Supporting Fig . S3C: SEM image on the distribution of FLG layers decorated with iron nanoparticles as sample. Supporting Fig . S4: TEM size distribution of FLG exfoliated and decorated with their corresponding metallic nanoparticles. Supporting Fig . S5: TEM size distribution of nanoparticles on the FLG exfoliated materials. Supporting Fig . S6: Raman spectra of FLG and FLG exfoliated with metallic nanoparticles by ball milling. Supporting Fig . S7: Full XPS spectra and C1s deconvolution from our synthesize materials FLG‐Ni and FLG‐Co. Supporting Fig . S8: TEM size distribution of MoS2 exfoliation and MoS2 exfoliated decorated with their corresponding metallic nanoparticles. Supporting Fig . S9: TEM size distribution of MoS2 layers exfoliation and MoS2 exfoliated decorated with their corresponding metallic nanoparticles. Supporting Fig . S10: TEM size distribution of WS2 exfoliation and WS2 exfoliated decorated with their corresponding metallic nanoparticles. Supporting Fig . S11: TEM size distribution of WS2 layers exfoliation and WS2 exfoliated decorated with their corresponding metallic nanoparticles. Supporting Table . S1: The crystallite sized for the different nanomaterials. Supporting Table . S2: TGA data of loss weight at 800°C of the FLG, MoS2 and WS2 nanomaterials exfoliated and anchorage with metallic nanomaterials under air atmosphere. Supporting Table . S3: Average size of nanoparticle (NP) for all the different hybrid nanomaterials. Supporting Table . S4: Average size of layers for all the different hybrid nanomaterials. Supporting Table . S5: Raman data for FLG exfoliated and anchorage with metallic nanomaterials. Supporting Table . S6: The crystallite sized for the different nanomaterials. Supporting Table . S7: TGA data of loss weight at 800°C of the FLG, MoS2 and WS2 nanomaterials exfoliated and anchorage with metallic nanomaterials under air atmosphere. Supporting Table . S8: Raman data for the MoS2 nanomaterials exfoliated and anchorage with metallic nanomaterials. Supporting Table . S9: Raman data for the WS2 nanomaterials exfoliated and anchorage with metallic nanomaterials. Supporting Table . S10: Average size of nanoparticle for all the different hybrid nanomaterials. Supporting Table . S11: Average size of layers for all the different hybrid nanomaterials.

Author Contributions

V.J.G.V. and A.M.R.G. performed the experimental work and material characterization. V.J.G.V. and A.M.R.G. wrote the manuscript with input from all authors. A.M.R.G. and E.V. obtained funding, contributed to the experimental design, and supervised the research. All authors discussed the results and approved the final manuscript.

Supporting information

Supplementary Material