Introduction

The persistent quest for new advances in gas sensing and optoelectronics has led to significant research in terms of new materials and device architectures. This work explores fascinating properties of a SnO_x/GO heterostructure, highlighting its dual potential for highly sensitive and selective methane detection, as well as tunable light absorption for optoelectronic applications [1,2]. It is well known fact that methane (CH₄) is a powerful greenhouse gas with a much higher global warming potential than carbon dioxide, making it a serious threat to the environment. Its rising concentration in the atmosphere, mainly caused by human activities, highlights the need for reliable and sensitive detection methods for environmental monitoring, industrial safety, and climate change efforts [3,4]. Traditional methods of methane detection often suffer from disadvantages such as high-power consumption, bulky instrumentation, and limited sensitivity, which makes highly sensitive, selective, and energy-efficient methane sensors important [5].

There are several materials available for methane detection, but metal oxides stand out due to their low operating temperatures (ranges around 25°C – 250 °C), high sensitivity, and stability [6]. One of the key advantages of metal oxides is their ease of fabrication at low temperatures using well-established techniques such as sputtering, sol-gel, and metal-organic chemical vapor deposition (MOCVD), making them an ideal choice for sensor applications. In our study, we have selected metal oxide (SnO_x) for methane sensing in combination with graphene oxide, leading to the formation of the SnO_x/GO heterostructure. This heterostructure offers several advantages, including enhanced sensitivity, improved selectivity, reduced operating temperatures for methane detection, and tunable optoelectronic properties [7]. In comparison to pure SnO₂ or graphene-based sensors, the SnO_x/GO heterostructure offers several distinct advantages. The integration of SnO₂ with graphene oxide (GO) significantly enhances charge transfer and surface interactions, improving the overall sensitivity and selectivity of the sensor [2]. The heterostructure benefits from the high surface area of GO, which facilitates better adsorption of target molecules, while the semiconducting properties of SnO₂ provide a robust platform for gas detection. Additionally, the hybrid structure offers better stability, improved conductivity, and increased photocatalytic activity, which are advantageous for applications in methane sensing [8]. These combined properties make the SnO_x/GO heterostructure more more efficient in methane detection, compared to pure SnO₂ or graphene based sensors, which may not exhibit the same level of sensitivity and stability. The SnO_x, a well-known metal oxide, is renowned for its tunable bandgap and high stability, making it ideal for gas sensing and optoelectronic applications [9]. GO, on the other hand, is a two-dimensional material with remarkable surface area and tunable electronic properties [10], which enhances the performance of the composite when integrated with SnO_x. The combination of the optical and electronic properties of graphene oxide (GO) with the semiconducting nature of SnO_x-based composites establishes a robust and versatile platform for the development of optoelectronic devices. While this study is centered on theoretical investigations, it builds upon a strong foundation of experimentally validated synthesis methods for SnO_X/GO-based heterostructures, which are well-documented in existing literature. According to literature, SnO_X/GO nanocomposites have been effectively synthesized using straightforward and cost-efficient methods, including room-temperature solution-based approaches and hydrothermal techniques [2,11]. A single-step method employing a domestic pressure cooker has also been reported for the fabrication of reduced graphene oxide/SnO₂ (RGO/SnO₂) composites, demonstrating the feasibility of scalable synthesis [12] Furthermore, a combination of sol-gel and hydrothermal methods has been used to produce SnO₂/rGO composites with tunable dielectric properties, directly relevant to sensor applications [13].In terms of material stability, experimental evidence indicates that SnO₂/graphene-based sensors maintain excellent methane sensing performance and structural integrity over extended testing periods [14]. Regarding its stability, multiple studies have consistently demonstrated the robust and durable performance of SnO_X/GO-based materials when exposed to methane under ambient conditions. In a study, it is reported that GO-SnO₂ composites exhibits stable methane sensing responses without significant degradation, even after repeated testing and prolonged ambient storage [15]. Supporting this, an earlier study confirmed the long-term operational reliability of related nanocomposite systems, emphasizing their durability [16]. Furthermore, additional evidence proves that Pd-doped SnO₂/rGO nanocomposites maintained consistent sensing behavior over long periods at room temperature [17]. Collectively, these findings affirm the suitability of SnO_X/GO-based sensors for reliable and sustained methane detection in practical applications. Ultimately, this research aims to pave the way for the next generation of sensors and devices, offering improved performance and functionality by uncovering the core mechanisms behind the gas sensing and optoelectronic capabilities of SnO_x-GO heterostructure.

Design consideration

In this study, the CASTEP toolkit package of Material Studio (BIOVIA) was utilized to explore the tunable optical and electronic properties of the SnO_x/GO heterostructure. Additionally, the Adsorption Locator tool in Materials Studio was employed to analyze the energy distribution of various atmospheric gases, including CO₂, H₂O, and CH₄, adsorbed on the surface of the SnO_x/GO heterostructure. It may be mentioned here that the dimensions of the simulation cells for each configuration of SnO_x/GO heterostructure has an in-plane unit cell of approximately 15 Å × 15 Å with a vacuum layer of 20 Å along the z-axis. The calculations have been performed using generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) functional by norm-conserving pseudopotentials of Cambridge Sequential Total Energy Package code (CASTEP) tool kit of Material Studio. Specifically, norm-conserving pseudopotentials has been used for all elements and incorporated Grimme’s correction for van der Waals interactions in all calculations to account for long-range dispersion forces. Regarding k-point sampling, we set the grid to 2 × 2 × 2 for Brillouin zone integration in bulk systems, ensuring sufficient accuracy for the simulations while maintaining computational efficiency. The convergence tolerance parameters value was set to be as 830 eV as cutoff energy for the k-point with fine mesh, maximum force, maximum stress and maximum displacement were set to be 0.03 eV/A⁰, 0.05 GPa and 0.001 Å, respectively. The SCF tolerance value was considered to be fine, i.e., 10⁻⁹ eV/atom.

Fig 1 illustrates the molecular structure of SnO_x/GO with varying oxygen content (x) in SnO_x. The oxygen molecule content in SnO_x was systematically varied, and its corresponding optoelectronic properties were observed. In Fig 1a–d, Sn atoms are depicted in green, oxygen atoms in pink, and the graphene oxide layer, positioned over the SnO_x layer, is shown in gray. The bottom SnO_x layer exhibits a gradual decrease in oxygen mole fraction which is shown from Fig 1a–d. Fig 1a represents a relatively higher oxygen mole fraction in SnO_x, while Fig 1d illustrates the lowest oxygen mole fraction. Throughout these molecular arrangements, the top graphene oxide layer remains unchanged. We have performed Density Functional Theory (DFT) simulations to model SnO_X molecules with varying oxygen content (x). The non-stoichiometry of SnO_X was systematically adjusted by modifying the relative proportions of SnO and SnO₂ [18,19].

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 1. Representation of the SnO_x/GO heterostructure, showcasing varying oxygen mole fraction (x) in SnO_x layer while preserving the integrity of the graphene oxide layer.

https://doi.org/10.1371/journal.pone.0326657.g001

For each compositional ratio, we calculated the corresponding value of (x), representing the oxygen mole fraction or the average number of oxygen atoms per Sn atom. In this study, we have considered four different ratios of SnO₂ and SnO to systematically vary the oxygen content in SnO_X, resulting in compositions with (x)=1.5, (x)=1.33, (x)=1.25, and (x)=1.20. These non-stoichiometric compositions represent intermediate states between pure SnO₂ and SnO are categorized as follows: SnO₁.₅ (Type-A, oxygen-rich), SnO₁.₃₃ (Type-B), SnO₁.₂₅ (Type-C), and SnO₁.₂₀ (Type-D, oxygen-deficient). The SnO₁.₅ corresponds to a mixture of 1 mole of SnO and 1 mole of SnO₂, yielding an average oxygen-to-tin ratio (x)=1.5. The value of oxygen mole fraction (x) is calculated using the formula, (x) = (Number of O atoms in the composition/ Number of Sn atoms in the composition).

In this case, the total O atoms = 1 (from SnO) + 2 (from SnO₂) = 3 and the total Sn atoms = 1 (from SnO) + 1 (from SnO₂) = 2, yielding (x)=3/2 = 1.5. Similarly, a composition of SnO₁.₃₃ corresponds to a mixture of 1 mole of SnO₂ and 2 moles of SnO, yielding an average oxygen-to-tin ratio (x)=1.33. For SnO₁.₂₅, the mixture consists of 1 mole of SnO₂ and 3 moles of SnO, resulting in (x)=1.25. Likewise, SnO₁.₂₀ represents a composition with 1 mole of SnO₂ and 4 moles of SnO, giving an average value of (x)=1.20. Each of these compositions reflects a different ratio of SnO₂ to SnO and is used to model non-stoichiometric SnO_X phases by varying the oxygen content systematically.

Based upon an optimized SnO_x/GO heterostructure in terms of opto-electronic properties, we further examine the effect of varying concentrations of methane molecules adsorbed on its surface. This analysis enables the classification of four additional heterostructure types as shown in Fig 2a–d, i.e., Type-I to Type-IV, which are based on the adsorption of methane molecules (depicted in light green atop heterostructure) on the surface of an optimized SnO_x/GO heterostructure. Here, Type-I (Fig 2a) represents the lowest concentration of methane molecules adsorbed on the SnO_x/GO surface, and Type-IV (Fig 2d) corresponds to the highest concentration. The concentration of methane molecules was varied to study the resulting changes in optoelectronic properties of SnO_x/GO heterostructure. The methane molecule concentration atop the SnO_x/GO heterostructure was gradually increased, as illustrated in Fig 2a through Fig 2d. It may be mentioned here that Adsorption Locator tool that uses Monte Carlo calculation has been used to identify possible adsorption configurations of SnO_x/GO heterostructure. The Monte Carlo calculation parameters were set to standard ambient conditions, with a temperature of 298 K and a pressure of 1 atm. The simulation has been carried out using Universal Force Field with a cutoff radius of 3 Å applied for van der Waals interactions. Additionally, the number of simulation steps was set to 100,000, ensuring sufficient sampling for equilibrium and reliable results. These parameters were selected to provide a realistic assessment of gas–surface interactions [20].

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 2. Illustration of the SnO_x/GO molecular structure, highlighting variation of methane concentration atop the heterostructure.

https://doi.org/10.1371/journal.pone.0326657.g002

Results and discussion

First of all, the absorption coefficient of SnO_x/GO heterostructures as shown in Fig 1a–d were studied to understand their light-absorbing capabilities. It is worth noting that SnO_x/GO structures with comparatively higher oxygen mole fraction (x) are classified as Type-A SnO_x/GO heterostructures. In contrast, Type-B SnO_x/GO structures denote lower oxygen mole fractions than Type-A, Type-C structures have even lower fractions than Type-C, and finally, Type-D SnO_x/GO represents the lowest oxygen molecule fraction in SnO_x. Accordingly, the SnO_x/GO heterostructures have been categorized into four types, based on oxygen content in decreasing order. All of these four samples showed a sharp absorption peak close to 100 nm with characteristics of materials known for strong absorption in UV or visible light. Beyond this, however, they showed differences in absorption characteristics in the spectrum range as shown in Fig 3a–d, which indicated material properties or compositions were different. Strong UV and visible absorption may just mean that the materials are useful for blocking or absorbing UV illumination while weak infrared absorption would simply mean an appropriate level of transparency over the infrared region.

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 3. Absorption coefficient of SnO_x/GO heterostructure with variation of oxygen mole fraction in SnO_x.

https://doi.org/10.1371/journal.pone.0326657.g003

It has been observed that the absorption coefficient of the SnO_x/GO heterostructure increases with the oxygen content in SnO_x, progressing from Type-A to Type-C. However, in Type-D, which has the highest oxygen molecule fraction, the absorption coefficient decreases abruptly. Among all types, the Type-C SnO_x/GO heterostructure exhibits the highest absorption coefficient.

These computational results align with experimentally reported trends in the light-absorbing capabilities of SnO_x, where the absorption coefficient decreases at very high oxygen molecule fractions [21]. This theoretical analysis confirms that the Type-C SnO_x/GO heterostructure, with an intermediate oxygen content (lower than Type-D but higher than Type-A and Type-B SnO_x/GO heterostructure), demonstrates the highest absorption coefficient.

Furthermore, our data demonstrate that the adsorption of methane molecules on the surface significantly influences the optical and electronic properties of the SnO_x/GO heterostructure. As the concentration of methane on the surface of the SnO_x/GO heterostructure increases, notable changes are observed in the refractive index, extinction coefficient, and absorption coefficient. These changes result from the interaction between methane molecules and the SnO_x/GO surface, which alters the electronic properties of the SnO_x/GO structure. The SnO_x/GO heterostructure with varying methane concentrations exhibits wavelength-dependent absorption spectra and reflectivity across the spectral range of 100 nm to 3000 nm, as shown in the Fig 4. Each curve uniquely corresponds to a specific methane concentration adsorbed on the SnO_x/GO heterostructure.

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 4. Absorption coefficient and reflectivity of SnO_x/GO heterostructures exposed to different methane concentrations.

https://doi.org/10.1371/journal.pone.0326657.g004

Among these, Type-II exhibits the highest extinction coefficient, peaking above 8 around 1000 nm, with intense light absorption in the near-infrared region, particularly at longer wavelengths. Conversely, Type-IV shows the lowest light absorption across the entire spectrum. Type-I and Type-III display moderate absorption, with peaks at approximately 1200 nm and 1500 nm, respectively. Furthermore, the absorption coefficient varies as a function of wavelength, with higher absorption occurring at shorter wavelengths and a gradual decrease at longer wavelengths. Type-I has the highest initial absorption, peaking near 1.6 × 10⁵ cm^-1 around 400 nm before gradually declining and flattening in the infrared region beyond 1500 nm. Type-II exhibits a minimum around 1.4 × 10⁵ cm^-1 and maintains a high absorption coefficient even at longer wavelengths, as it has the least reflectance among all types when measured at longer wavelengths, as seen in Fig 4. Type-III and Type-IV show significantly different absorption patterns. Type-III demonstrates a substantial reduction in absorption compared to other types, falling to negligible levels beyond 1000 nm. Type-IV, with the highest methane concentration, exhibits the lowest overall absorption, peaking slightly above 8.0 × 10⁴ cm^-1 near 400 nm and steadily decreasing, with minimal absorption in the infrared region beyond 1500 nm.

However, the magnitude of reflectance for SnO_x/GO heterostructures with different adsorption concentration of methane, varies significantly among the samples (shown in Fig 4b). Type-IV shows the highest reflectance, peaking at around 0.85. In contrast, Type-I demonstrates a relatively moderate reflectance value of approximately 0.45. Type-II and Type-III fall in between, peaking at around 0.35 and 0.6, respectively. These variations in reflectance highlight specific characteristics of the materials or surface treatments, which are critical for applications in optics, material science, and remote sensing. At lower methane concentrations, reflectance is relatively minimal, accompanied by lower light absorption, as observed in the SnO_x/GrapheneOxide heterostructures [22]. Conversely, as the methane concentration increases, reflectance rises within the heterostructure, indicating a lower extinction coefficient. The phenomenon of increased reflectivity and decreased photo absorption caused by methane adsorption on the surface of graphene oxide can be primarily attributed to changes in charge density, density of states (DOS), and the dielectric constant. When methane molecules adsorb onto the graphene oxide surface, they induce a redistribution of electronic charge at the interface, altering the local charge density. This redistribution modifies the electronic environment, leading to subtle shifts in the DOS, particularly near the Fermi level, which affects the probability of electronic transitions under incident light [23]. As shown in the Density of states (DOS) plots in Fig 5, an increase in methane concentration (from Type-I to Type-IV) results in significant modifications in the electronic structure of the SnO_x/GO heterostructure.

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 5. Density of states (DOS) of the SnO_x/GO heterostructure with varying concentrations of methane molecules adsorbed on its surface.

https://doi.org/10.1371/journal.pone.0326657.g005

Specifically, with higher CH₄ adsorption, the density of states near the Fermi level becomes more pronounced, indicating stronger electronic interactions between methane molecules and the sensing surface. These changes can be attributed to enhanced charge transfer between methane and the SnO_x/GO system. At low concentrations, methane introduces only slight perturbations to the DOS, mostly due to weak physisorption. However, as concentration increases, stronger chemisorption occurs, leading to additional localized states within the bandgap and near the Fermi level. This results in a shift in the Fermi level results in an increased in charge redistribution and electronic coupling between adsorbed methane and surface atoms. These DOS changes directly impact the material’s photoabsorption and sensing behavior. The introduction of new states modifies the allowed optical transitions, increasing the absorption of visible and UV light. These findings are consistent with reported trends in literature, where increased DOS near the Fermi level upon gas adsorption correlates with improved sensing properties [24,25]. Furthermore, these electronic changes influence the material’s complex dielectric constant—specifically, the real part (ε₁)which governs reflectivity, and the imaginary part (ε₂), which determines absorption. Methane adsorption tends to reduce ε₂ resulting in lower optical absorption, while changes in ε₁ can enhance reflectivity [26]. These combined electronic and optical modifications explain the observed increase in reflectivity and decrease in absorption upon methane adsorption, without requiring any significant structural transformation of the graphene oxide substrate. There is possibility that the high absorption coefficient indeed raises concerns regarding thermal stability and durability [27]. High absorption may lead to an increase in the local temperature during operation, which could negatively impact the material’s stability, especially at elevated temperatures. Thermal degradation or material fatigue over prolonged use is a critical factor that must be thoroughly evaluated to ensure the material maintains its performance over time, particularly in environments with fluctuating temperatures [28].

Additionally, while scalability is a key aspect for the practical application of any novel material, fabrication challenges for SnO_x/GO heterostructures could arise during the scaling-up process. Achieving consistent quality and uniformity of the heterojunction in large-scale production may require careful optimization of synthesis methods and conditions. Material processing techniques, such as controlled deposition or layer-by-layer assembly, need to be evaluated for their ability to produce SnO_x/GO heterostructures on a larger scale without compromising performance [29].

Furthermore, the distinct optical properties exhibited by different SnO_x/GO heterostructure types, specifically, the high absorption coefficient of Type-C (~1.8 × 10⁵ cm ⁻ ¹ at ~100 nm) and the high extinction coefficient of Type-II (~8.0 near 1000 nm), highlight the critical role of oxygen content in tuning the material’s optoelectronic response. These two features correspond to different spectral regions and mechanisms of interaction: the absorption coefficient signify how strongly the material absorbs photons (useful for UV or high-energy applications), whereas the extinction coefficient encapsulates both absorption and scattering effects, more relevant for visible to near-infrared applications such as photodetection and gas sensing.

The potential to synergistically optimize these properties lies in the tunable composition of SnO_x. As SnO_x is a mixed-phase oxide comprising varying ratios of SnO (narrower bandgap) and SnO₂ (wider bandgap), adjusting the oxygen molar fraction effectively alters the electronic band structure, density of states, and optical transitions. For instance, Type-C SnO_X/GO having SnO-rich compositions (relatively having lower bandgap), tend to show enhanced absorption (~1.8 × 10⁵ cm ⁻ ¹ at ~100 nm) in the UV region. This is primarily due to lower energy electronic transitions and stronger localized electron interactions. In contrast, the Type-II SnO_X/GO heterostructure, when exposed to a relatively higher concentration of methane molecules, exhibits significant charge density redistribution and modifications in the density of states. These changes enhance charge separation and dielectric behavior, resulting in a pronounced increase in extinction in the near-infrared (NIR) region. Additionally, methane adsorption plays a significant role in altering the charge distribution, local electronic states, and dielectric properties at the interface of the heterostructure. According to our DFT simulations, the adsorption of methane leads to shifts in the Fermi level, changes in the local charge density, and slight modifications in the optical response due to perturbations in the electronic structure. This suggests that by controlling the exposure to methane, the optical behavior of the material could be dynamically tuned, offering a secondary mechanism for adjusting its properties in response to varying environmental conditions.

In addition, Fig 6 illustrates the wavelength dependent refractive index (n) and extinction coefficient (k), the SnO_x/GO heterostructure is highly sensitive to variations in methane concentration, allowing the detection of methane concentrations even below the ppm range. Trace amounts of methane can be effectively determined by analyzing and tracking these coefficients, making this technique highly effective for low-concentration detection. The graph illustrates the reflectance of the four types of structures, Type-I, Type-II, Type-III, and Type-IV, corresponding to one, two, three, and four methane molecules absorbed on the surface of SnO_x/GO heterostructure, respectively, as a function of wavelength ranging from 200 nm to 3000 nm. Four distinct samples—Type-I through Type-IV exhibit unique trends for the refractive index and extinction coefficient across the 100 nm to 3000 nm wavelength range.

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 6. Wavelength dependent refractive and extinction coefficient of SnO_x/GO heterostructure exposed to different methane concentrations.

https://doi.org/10.1371/journal.pone.0326657.g006

The refractive index of the SnO_x/Graphene Oxide heterostructures varies significantly across the four types. Type-I shows a gradual increase in refractive index, starting at approximately 2 in the 200–300 nm range and plateauing near 4 beyond 2000 nm. Type-II exhibits the most pronounced change, with a dramatic rebound from around 2 at shorter wavelengths to a peak exceeding 8 at the longer wavelength end, indicating a strong refractive response in the near-infrared region. Type-III follows a trend similar to Type-I but with a sharper rise, reaching a peak of about 6 at 2000 nm and continuing to increase thereafter. In contrast, Type-IV displays a smooth increase from about 2 at shorter wavelengths to approximately 5, with much less variation compared to Type-II and Type-III.

Finally, Fig 7 illustrates the energy distribution of various atmospheric gases, including methane (CH₄), carbon dioxide (CO₂), and water (H₂O), on the surface of the SnO_X/GO heterostructure. The horizontal axis represents the adsorption energy (E_ads) in kcal/mol, while the vertical axis indicates the probability density of energy, P(E), describing the likelihood of the system having a specific energy [30].

Download:

• PPT
  PowerPoint slide
• PNG
  larger image
• TIFF
  original image

Fig 7. Energy distribution of SnO_x/GO heterostructure for various molecules including carbon dioxide, water and methane, adsorbed atop the heterostructure.

https://doi.org/10.1371/journal.pone.0326657.g007

Specifically, we have evaluated the adsorption energies of methane (CH₄), carbon dioxide (CO₂), and water (H₂O) on the SnO_X/GO surface. Our simulation results indicate that methane exhibits a significantly higher adsorption energy of approximately −78.35 kcal/mol, compared to −42.75 kcal/mol for H₂O and −39.65 kcal/mol for CO₂. These results suggest that CH₄ interacts more strongly with the sensing surface than the potential interfering gases, supporting the material’s preferential affinity for methane. Therefore, under typical environmental conditions, the likelihood of interference from ambient CO₂ and H₂O is minimal. This computational validation reinforces the sensor’s selectivity and supports its suitability for practical methane detection applications. Moreover, these energy distributions provide important insight into the stability and effectiveness of the sensor. The discrete energy states correspond to different adsorption sites or surface configurations of the SnO_x/GO heterojunction [31]. Specifically, a more negative adsorption energy (such as −78.35 kcal/mol) indicates stronger affinity of methane molecules to the surface of SnO_x/GO heterostructure, which is typically associated with higher sensing sensitivity and better charge transfer efficiency [32]. This enhanced interaction can influence the local electronic structure, leading to measurable changes in optical properties such as the refractive index and extinction coefficient are key indicators in optical methane sensing. The energy states observed in the system (−78.35, −42.75, and −39.65 kcal/mol) are indeed crucial for understanding the adsorption stability and charge transfer mechanisms of the SnO_x/GO heterojunction in methane sensing or photoabsorption processes. Charge transfer between methane molecules and the surface could lead to changes in the electronic properties of the material, impacting its photoabsorption and methane sensing capabilities [33].

The lower energy state (such as −78.35 kcal/mol) typically corresponds to a more stable adsorption configuration, indicating stronger interactions between methane and the SnO_x/GO surface. This stronger interaction is likely due to enhanced adsorption strength, which can influence the methane sensing performance by improving the sensitivity of the material to trace amounts of methane [34]. Stronger adsorption generally implies that the material can detect and adsorb methane molecules more effectively, leading to better sensitivity and response. Therefore, this lower energy state could enhance the material’s ability to detect even low concentrations of methane, potentially lowering the limit of detection (LOD) and improving overall sensor performance [35].

In summary, SnO_X/GO heterojunctions represent a promising class of materials for photoelectrochemical applications, particularly in solar energy conversion systems such as water splitting and CO₂ reduction. The heterostructure take advantage of its high surface area and electronic properties of graphene oxide (GO), combined with the semiconducting characteristics of tin oxide (SnO_X), making them highly efficient in converting light energy into chemical energy. The integration of these two components creates a material with excellent charge separation, enhanced conductivity, and increased photocatalytic activity, making it suitable for use as photoanodes or catalysts in photoelectrochemical cells.

While this study focuses on theoretical investigations, existing experimental research provides a solid foundation that aligns with our theoretical findings. Several studies in the literature have demonstrated practical implementation strategies for SnO₂/GO heterojunctions in photoelectrochemical (PEC) applications. These experimental works offer valuable insights into synthesis techniques, device fabrication, and performance characteristics, supporting the potential integration of SnO₂/GO heterostructures into real-world PEC systems. For instance, earlier studies have shown that hydrothermal processing is a widely used method for synthesizing SnO₂/GO nanocomposites, which significantly enhance photocatalytic and electronic performance. Also, it has been shown that SnO₂/GO composites synthesized via this method exhibited improved photocatalytic activity due to enhanced light absorption and charge separation efficiency [2].

Additionally, the sol-gel method has been employed for precise morphological control, which is crucial for tuning the heterojunction’s properties. This approach has been used to fabricate SnO₂/GO heterostructure which are capable of visible-light-driven photocatalytic degradation, highlighting their potential in environmental remediation and solar-driven chemical reactions. Similarly, chemical vapor deposition (CVD) has been successfully used to grow high-quality SnO₂ thin films on GO substrates for optoelectronic applications, demonstrating the scalability and compatibility of CVD for device fabrication [2].

In terms of device integration, a self-powered UV photodetector based on SnO₂ nanorods combined with Ag/reduced graphene oxide (rGO) has been developed, showcasing the potential of SnO_X/GO-based structures in advanced optoelectronic devices [36]. Furthermore, it has been demonstrated that rGO-SnO₂ nanocomposites exhibited strong photocatalytic degradation of methylene blue under both UV and natural sunlight, suggesting their application in waste water treatment and other environmental technologies [37]. Moreover, there is often a significant gap between theoretical simulation results and actual sensing performance. Theoretical studies, such as those based on Density Functional Theory (DFT), are typically conducted under idealized and highly controlled conditions, assuming perfect crystalline structures, isolated gas molecules, and a vacuum environment. These simulations offer valuable insights into fundamental interactions, such as adsorption energies and charge transfer mechanisms. However, simulations often neglect dynamic effects like adsorption/desorption kinetics, response and recovery times, and long-term material degradation. Even if a material demonstrates strong gas interaction theoretically, practical performance may be hindered by challenges in device fabrication, signal transduction, and reproducibility. Therefore, while theoretical models are essential for guiding material design and predicting potential sensing behavior, experimental validation is crucial to confirm these predictions and assess the material’s reliability and efficiency in practical applications.

Conclusion

This study offers a comprehensive insight into the optical and electronic properties of SnO_x/GO heterostructures, highlighting its tunable light-absorbing capabilities along with its sensitivity and selectivity towards methane. The classification of SnO_x/GO heterostructures into four types based on oxygen mole fraction revealed distinct light absorption characteristics. Among these, Type-C heterostructures with intermediate oxygen content demonstrated the highest absorption coefficient, peaking at approximately 1.8 × 10⁵ cm ⁻ ¹ near 100 nm wavelength. This observation aligns with experimental values reported in literature and reinforces the suitability of Type-C heterostructures for UV and visible light absorption. Furthermore, methane adsorption on the surface of SnO_x/GO heterostructure was investigated, revealing enhanced tunability through variations in the refractive index, extinction coefficient, and absorption spectra. Notably, Type-II heterostructures demonstrate the highest extinction coefficient, exceeding 8.0 near 1000 nm, along with strong near-infrared absorption. Additionally, Type-IV structures, with the highest methane concentration, show the lowest absorption, peaking at 8.0 × 10⁴ cm ⁻ ¹ near 400 nm, and the highest reflectance (0.85), suggesting saturation effects at elevated gas concentrations. Additionally, energy distribution analysis of various atmospheric gases, such as CH₄, H₂O, and CO₂ on the surface of SnO_x/GO heterostructure, reveals that methane (CH₄) possesses the most negative energy state, indicating greater stability and a stronger adsorption affinity on the sensor surface. This makes the proposed heterostructure particularly effective for selective methane detection in the presence of other atmospheric gases. Energy distribution analysis reveals that the system stabilizes in discrete energy states, with the most probable state at −8.3 kcal/mol, followed by secondary states at −8.8 kcal/mol and −9.4 kcal/mol. This stabilization underscores the material’s interaction dynamics, contributing to its versatility in applications such as UV absorption, infrared transparency, and trace methane detection. These findings highlight the potential of SnO_x/GO heterostructures, particularly the Type-C variant with optimum amount of oxygen mole fraction, as promising candidates for advanced optical and sensing technologies.

Supporting information