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Review

Recent Progress with Bismuth Sulfide for Room-Temperature Gas Sensing

by
Renping Ma
1,
Haoxin Lei
2,
Mingyang Han
2 and
Juanyuan Hao
2,*
1
Beijing Vocational College of Labour and Social Security, Beijing 100029, China
2
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
*
Author to whom correspondence should be addressed.
Chemosensors 2025, 13(4), 120; https://doi.org/10.3390/chemosensors13040120
Submission received: 18 February 2025 / Revised: 23 March 2025 / Accepted: 27 March 2025 / Published: 1 April 2025
(This article belongs to the Special Issue Chemical Sensors for Volatile Organic Compound Detection, 2nd Edition)
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Abstract

:
Monitoring hazardous gases is increasingly critical for environmental protection and human health. As a novel class of two-dimensional nanomaterials, layered metal chalcogenides have attracted substantial research attention in recent years. This is attributed to their unique physical and chemical characteristics, which endow them with remarkable potential for applications in gas sensing. In particular, bismuth sulfide (Bi2S3) has been extensively studied recently due to its cost-effectiveness, abundance, and eco-friendliness, aligning with the requirements of advanced sensing platforms. This article systematically summarizes recent advancements in gas sensors based on Bi2S3. Initially, the structural and functional properties of Bi2S3 are outlined, emphasizing its potential in detecting toxic gases. Subsequently, innovative methodologies aimed at enhancing room-temperature sensing efficiency are critically analyzed. The discussion concludes by addressing existing limitations and proposing future research directions to optimize Bi2S3 for practical applications. This review aims to systematically examine the design and optimization of next-generation gas detection nanomaterials, offering fundamental understanding of their performance enhancement mechanisms and exploring their potential implementation across multiple technological platforms.

1. Introduction

Gas sensors, designed for the detection of noxious and perilous gases, have been utilized in extensive applications across a wide range of domains, including agricultural and industrial manufacturing processes, food safety, and medical diagnosis procedures [1,2,3]. In the context of atmospheric surveillance, these gas sensors can quantify concentrations of nitrogen dioxide (NO2) [4,5,6,7,8,9], hydrogen sulfide (H2S) [10,11], and volatile organic compounds (VOCs) [12], thereby ensuring that environmental conditions remain conducive to human health and productivity [13,14,15]. In the context of hazard detection, gas sensors are of vital significance in the monitoring of combustible and explosive gases during industrial operations, thus mitigating the risk of injuries resulting from gas leaks [16]. Additionally, in the realm of medical diagnostics, non-invasive gas-sensing apparatuses are employed for the analysis of exhaled gases, which can indicate various pathological and metabolic states [17]. Studies have shown that the detection of acetone, ammonia (NH3), and H2S in breath samples can facilitate the preliminary diagnosis of conditions such as diabetes, kidney disease, and oral infections, respectively [18].
Currently, gas sensors demonstrate significant potential in applications such as intelligent home devices, advanced medical technology, and wearable devices [19,20]. Owing to the increase in the Internet of Things (IoT), the essential necessities for advanced gas sensor development predominantly encompass cost-effectiveness and minimal energy consumption characteristics, and straightforward operational conditions [20,21]. Gas-sensing devices can be systematically classified according to their operational mechanisms, encompassing five primary categories: electrochemical detection systems, resistance-based chemical sensors (chemoresistive sensors), photonic measurement platforms, acoustic wave transduction devices, and catalytic oxidation detectors [22]. Among these, chemoresistive gas sensors are particularly favored for their affordability, ease of fabrication, and compatibility with integrated circuits [14]. However, traditional gas detection systems utilizing metal oxide semiconductor materials often necessitate elevated operational temperatures for optimal performance (ranging from 200 to 600 °C), which undermines their advantages for low-power integrated applications [12,23]. As a result, an increasing tendency is emerging regarding the development of novel sensing materials aimed at producing gas sensors that function effectively at room temperature.
Inspired by advancements in graphene research, there has been a marked increase in scientific interest surrounding two-dimensional (2D) materials, including layered metal chalcogenides (LMCs) [24], phosphorene [25], and MXenes [26,27]. Phosphorene, a monolayer of black phosphorus, exhibits exceptional carrier mobility and tunable bandgaps, making it promising for optoelectronic and sensing applications [25]. However, its chemical instability under ambient conditions due to rapid oxidation and moisture sensitivity severely limits its practical utility in gas sensors [28]. Similarly, MXenes, a family of transition metal carbides/nitrides, demonstrate high electrical conductivity and surface functionality [26]. Despite these advantages, their synthesis often requires hazardous etching agents (e.g., HF), and their irreversible adsorption behavior toward analytes complicates recovery performance in sensing applications [26]. Within this category, LMCs have gained significant attention as potential materials for gas detection systems due to their exceptional physicochemical properties, including remarkably high surface-to-volume ratios, superior charge transport capabilities, and enhanced surface chemical activity [29], rendering them more viable for real-world gas-sensing devices. The crystal structures of 2D LMCs are mainly stacked in the forms MX2, MX, or M2X3, where M is a metallic element in the transition groups IVB-VIB (e.g., Mo, W, V, Nb, Zr, and Ta) or the main group IIIA-VA (e.g., Ga, In, Sn, Sb, and Bi), and X is a chalcogenide element (S, Se, or Te) [30,31]. The structural configuration of LMCs exhibits a distinctive anisotropic bonding arrangement, featuring robust covalent bonding within individual layers while demonstrating weak interlayer cohesion mediated by van der Waals forces. This architecture provides a substantial specific surface area, enhancing the adsorption kinetics and molecular diffusion dynamics of gaseous species [32]. Additionally, their superior electrical conductivity facilitates gas-sensing capabilities at low or room temperatures [33,34]. In comparison with graphene, phosphorene, and MXenes, LMCs exhibit remarkable sensitivity and selectivity in gas detection, enabling effective monitoring at parts per million or even parts per billion concentrations [35].
Among the family of LMCs, bismuth sulfide (Bi2S3) has garnered significant attention due to its abundance, non-toxicity, ease of surface modification, and low levels of heavy metals [36,37]. Bi2S3, a semiconductor material characterized by its narrow and adjustable bandgap ranging from 1.3 to 1.7 eV [38,39], exhibits exceptional performance in various applications, including optoelectronic apparatuses, electrocatalytic reduction processes, photocatalytic generation reactions, and especially gas-sensing applications [40,41,42,43,44,45], attributed to its unique structural characteristics.
However, pristine Bi2S3 is ineffective at room temperature due to its low inherent conductivity, leading to substantial energy consumption and complex equipment requirements, thus limiting its widespread adoption in state-of-the-art sensing platforms. Recently, significant research endeavors have been focused on enhancing the gas detection capabilities of Bi2S3 through the implementation of diverse material engineering approaches, including morphological design, defect engineering, heterostructure construction, and light irradiation.
This review provides an overview of established experimental and theoretical approaches related to Bi2S3-based gas-sensing materials. While previous reviews have covered preparation methods, performance evaluation parameters, and fundamental working principles of LMCs, this review comprehensively examines contemporary advancements in material engineering strategies specifically designed to enhance the ambient temperature gas detection performance of Bi2S3 nanostructures toward various toxic and hazardous gaseous compounds. Additionally, the primary challenges and prospects associated with Bi2S3-based gas sensors are outlined. It is anticipated that this article will contribute foundational insights to address the limitations of Bi2S3 and facilitate its broader application in the field.

2. Bi2S3: Rising Material for Gas-Sensing Applications

Bi2S3, as a newly-emerged constituent of LMCs, has attracted extensive attention due to its relatively low toxicity and eco-friendly characteristics. The crystal structure exerts a substantial influence on determining both the synthesis route and the characteristics of a material. Bi2S3 crystallizes in an orthorhombic structure, belonging to the space group Pbnm (62), with lattice constants of a = 1.114 nm, b = 1.130 nm, and c = 0.3981 nm [42,46]. Unlike typical van der Waals materials that possess a single distribution direction of van der Waals force, the crystal atoms of Bi2S3 are covalently bonded in just one direction, thereby forming long chains that are parallel to one another (Figure 1). Meanwhile, the adjacent two chains are joined via van der Waals forces along two separate directions [47].

2.1. Gas Sensors Constructed with Pristine Bi2S3

A room-temperature H2 sensor utilizing individual Bi2S3 nanowires was developed by Yao et al. [49]. This research represented a notable milestone in the field of Bi2S3-based gas sensing, achieving a detection sensitivity of 22% at a 10 ppm H2 concentration at room temperature. This pioneering work established a foundation for elucidating the intrinsic sensing characteristics of Bi2S3 and paved the way for subsequent explorations into its potential in gas-sensing applications. Yang et al. [50] synthesized high-quality Bi2S3 single-crystalline nanowires, which demonstrated superior gas-sensing properties, especially for ethanol, outperforming conventional powders in terms of elevated response, more rapid response and recovery intervals, and favorable selectivity. The experimental results demonstrate that Bi2S3 nanowire-based architectures exhibit promising characteristics as advanced sensing materials for ethanol detection at ambient temperatures, suggesting their potential utilization in diverse technological applications requiring gas-monitoring capabilities.
Kan et al. [51] made contributions to the development of Bi2S3-based gas sensors. The sensors fabricated from Bi2S3 nanobelts treated with Pb(NO3)2 demonstrated enhanced responsiveness and recovery at ambient temperature, achieving a response value of 58.8 when exposed to 5 ppm of NO2 (Figure 2). The incorporation of Pb(NO3)2 during ligand exchange eliminates insulating long-chain organic ligands (e.g., OLA and PVP) from Bi2S3 nanobelts, enabling the formation of a porous network. This process enhances gas adsorption and charge transfer by reducing surface insulation and optimizing interfacial interactions. The uniform Pb²⁺ distribution on nanobelt surfaces further modifies surface chemistry, contributing to structural refinement. The resulting interconnected nanobelt bundles exhibit a high specific surface area (13.59 m2/g) and facilitate rapid gas diffusion. These structural advantages—enhanced porosity, efficient gas accessibility, and improved charge dynamics—collectively enhance gas-sensing performance, establishing Bi2S3 nanobelts as a promising material for low-power, cost-effective sensors. It is worth highlighting that the presence of adsorbed OH- on the surface played a role in augmenting the sensors’ sensitivity to NO2. The ambient temperature response characteristics of Bi2S3 nanobelts, coupled with their outstanding solution process characteristics, render them highly promising in the development of economical gas sensors that consume less power.
Feng et al. [52] explored Bi2S3’s gas-sensing mechanisms using first-principles calculations. Their analysis covered adsorption, electronic properties, and gas diffusion on Bi2S3. Results highlighted Bi2S3’s strong NO2 selectivity, with high adsorption energy (−0.88 eV vs. −0.14 eV for CH4), reduced bandgap (ΔG = 1.42 eV), and low NO2 diffusion (9.09 × 10⁻⁴ cm2/s). Experimental studies [53] confirmed these findings: solvothermal Bi2S3 nanobelts achieved 17 ppb NO2 detection at room temperature, outperformed NH3/CO selectivity, and showed humidity-enhanced sensitivity (−1.01 eV adsorption energy). Theoretical bandgap narrowing matched experimental conductivity improvements. Low NO2 diffusion ensured stable adsorption, minimizing desorption. This computational–experimental synergy validates Bi2S3 as a high-performance NO2 sensor.
Despite the performance in gas sensing achieved with Bi2S3, the burgeoning field of pristine Bi2S3 still encounters several challenges. Pure Bi2S3 has some drawbacks as a gas-sensing material. Its high room-temperature resistance and low response value make signal acquisition difficult. The long recovery time of pure Bi2S3-based sensors also limits their practical application. Moreover, the presence of long-chain surfactants on the surface of solution-processed Bi2S3 nanobelts reduces gas molecule accessibility and inhibits carrier transport, resulting in poor gas-sensing performance. Additionally, the recovery time of pure Bi2S3-based sensors is relatively long, up to 106 s even after Pb(NO3)2 treatment, which is not ideal for real-time gas detection applications [51].
For instance, pure Bi2S3 as a gas sensor exhibits inferior recovery performance (prolonged recovery time of approximately 400 s upon exposure to 1 ppm NO2 [51]) and limited sensitivity to gases like NO2 at room temperature due to its intrinsic poor conductivity [54]. This slow recovery behavior means that the sensor requires about 400 s to return to its baseline state after exposure to the target gas, which fundamentally hinders its application in real-time monitoring systems.
Furthermore, previous studies have demonstrated that pristine Bi2S3-based gas sensors typically exhibit a relatively high limit of detection (LoD) at room temperature, making it difficult to detect trace amounts of gases, which is crucial for early warning systems and precise environmental monitoring [55]. For example, Yao et al. reported a Bi2S3 nanowire-based H2 sensor with an LoD of 10 ppm [49], while Yang et al. developed Bi2S3 nanowires for ethanol sensing, achieving a detectable concentration as low as 10 ppm [50]. However, unmodified Bi2S3 remains insufficient for trace-level NO2 detection (e.g., parts-per-billion, ppb), primarily due to its limited surface reactivity and adsorption capacity. Even with surface modification (e.g., Pb(NO3)2 treatment), the LoD of NO2 detection was only reduced to 500 ppb [51], which still fails to meet practical requirements for environmental monitoring. To address this limitation, strategies have been engineered to amplify sensing performance. Notably, hierarchical Bi2S3 architectures synthesized by Yang et al. [56] achieved an ultralow LoD of 50 ppb for NO2, underscoring the critical role of morphology optimization in improving gas adsorption kinetics and charge transfer efficiency.
Additionally, while Bi2S3 shows good selectivity towards NO2 in the presence of humidity [52], its overall performance is still not sufficient for reliable NO2 sensing under ambient conditions. The study was mainly based on first-principles calculations, which are theoretical in nature. In practical applications, the morphology and size of Bi2S3 nanomaterials play crucial roles, which can influence the adsorption and diffusion of NO2. Additionally, other factors such as surface defects and temperature fluctuations, which are common in real-world materials, can impact the sensing performance. Although Bi2S3 shows potential for selectively detecting NO2 in humid environments, more research is needed to address these issues and improve its overall performance for reliable sensing under ambient conditions. These limitations highlight the need for modifications or the development of composite materials to improve the gas-sensing capabilities of Bi2S3. To exploit the gas-sensing application of Bi2S3 at room temperature, specific structural modifications through functionalization strategies are essential to enhance its inherent properties.

2.2. Strategies for Enhancing Room-Temperature Sensing Performance

2.2.1. Morphological Design

Control over the morphology of materials is a highly efficacious strategy for modulating their properties, frequently employed in the synthesis of various compounds. By altering the synthesis methods or the precursors used, the morphology of materials can be readily manipulated. The characteristics of the configuration and architecture of gas-sensing materials are pivotal in the enhancement of their sensing performance, because these properties are contingent upon the dynamics of diffusion and the adsorption/desorption mechanisms involving the substances and the analyzed gases. Scientific investigations have focused on the optimization of morphological structures of Bi2S3, enhancing active sites and improving gas adsorption capabilities.
The synthesis of low-dimensional Bi2S3 nanostructures, such as nanowires [50], nanobelts [42,53], nanorods [57], and nanosheets [48], aims to enhance gas-sensing capabilities. However, the propensity of low-dimensional nanomaterials to undergo stacking and aggregation phenomena significantly compromises their functional effectiveness by reducing accessible active sites for gas adsorption, while simultaneously impeding molecular diffusion and adsorption-desorption kinetics, ultimately leading to the degradation of their inherent sensing capabilities [56,58]. Constructing hierarchical nanostructures offers a viable strategy to alleviate restacking and increase the active surface area, which enriches the sensing active sites and facilitates the diffusion and adsorption/desorption of gases on the nanomaterial surface [56]. In this regard, hierarchically structured Bi2S3 nanomaterials, characterized by their unique architecture and large surface area, emerge as highly promising candidates for sensing applications. As a result, extensive scientific investigations [39,56,59,60,61,62] have been focused on developing architecturally controlled Bi2S3 nanoarchitectures with enhanced surface-to-volume ratios through advanced synthesis methodologies.
Li et al. [62] pioneered the use of hydrothermal synthesis for creating hierarchical Bi2S3 nanostructures, showcasing their applicability in gas sensing, specifically focusing on methanol detection, as shown in Figure 3a,b. This work laid the groundwork for subsequent research into the gas-sensing capabilities of these complex architectures. The diversity in Bi2S3 nanomaterial morphologies, such as flower-like [44] and urchin-like [63], has been achieved through various synthesis techniques, aiming to augment their functional attributes. Notably, Fu and colleagues [61] prepared a 3D Bi2S3 nanowire network for NH3 sensing at room temperature which underscored the advantage of large surface areas in enhancing sensing properties, as shown in Figure 3c–e. This research contributes to the understanding that morphological design of Bi2S3 can effectively amplify the sensing capabilities of low-dimensional materials, offering a pathway for optimizing nanostructures in gas-sensing applications.
Yang et al. [56] synthesized one-dimensional nanorods featuring self-assembled hierarchical Bi2S3 nanostructures synthesized through a straightforward hydrothermal method (Figure 4a). By constructing hierarchical nanostructures, abundant sensing active sites can be provided and monitoring of gas diffusion and adsorption/desorption on nanomaterial surfaces can be promoted. The gas-sensing material based on Bi2S3 nanostructures for NO2 detection can work at room temperature. The hierarchical Bi2S3 nanostructures, composed of nanorods, exhibited exceptional NO2 sensing behavior, exhibiting a large response value and quick response/recovery intervals (Figure 4b). The sensor’s low limit of detection and excellent selectivity, along with its humidity tolerance (Figure 4c–e), were attributed to the rich active sensing surface and expedited diffusion as well as the processes of adsorption and desorption occurring between NO2 molecules and Bi2S3 materials.
The fabrication of hierarchical structures emerges as an optimal approach to mitigate the aggregation of low-dimensional nanomaterials, thereby enhancing their gas-sensing capabilities. Such structures not only expand the active surface area available for interaction with target gases but also expedite the processes of adsorption, diffusion, and desorption. In the case of Bi2S3, various hierarchical nanostructures, such as urchin-like microspheres (composed of radially aligned nanorods) [64], 3D nanowire networks (interconnected porous frameworks) [61], flower-like architectures (self-assembled from nanoplates or nanorods) [44,65], and sheaf-like bundles (aligned nanorod aggregates) [66], have been successfully synthesized. These diverse forms of Bi2S3 nanostructures highlight the versatility in fabrication methods and underscore the significance of developing appropriate hierarchical configurations to enhance gas sensor sensitivity. For instance, urchin-like structures provide a high surface-to-volume ratio for efficient gas adsorption, while 3D networks facilitate rapid gas diffusion and electron transport, collectively improving sensing performance.

2.2.2. Defect Engineering

Defect engineering has emerged as a potent strategy to enhance the sensing performance of gas sensors, particularly those based on 2D metal sulfides. This approach involves regulating the kinetics of charge transport and introducing additional active sites to bolster the overall sensing capabilities of the materials. Considerable efforts have been directed towards engineering defects in Bi2S3 nanomaterials, leveraging their inherent properties to improve sensing performance.
Bi2S3 nanomaterials are particularly amenable to the formation of sulfur vacancies due to their low defect formation energy, which positions them as ideal candidates for defect engineering [57,67]. The incorporation of defects into Bi2S3 has been employed to enhance its photocatalysis, photothermal therapy, and photovoltaic applications, demonstrating the versatility of these materials in various fields [57,67,68]. The incorporation of defects into Bi2S3 has been extensively studied for enhancing its gas-sensing performance, particularly for room-temperature NO2 detection. Unlike applications in photocatalysis or photovoltaics, where defects primarily improve charge carrier separation or light absorption, sulfur vacancies in Bi2S3 significantly amplify surface reactivity and electron depletion layer modulation, directly boosting gas adsorption and charge transfer kinetics [63,69]. In a recent study, Chen et al. [69] demonstrated a high-efficiency sensor motivated by neuronal conduction mechanisms, which led to significant advancements achieved in the sensitivity and selectivity features of gas-sensing materials. The strategic incorporation of sulfur vacancy defects through Au quantum dot modification resulted in enhanced sensor performance, demonstrating rapid response characteristics, exceptional sensitivity with ultra-low detection thresholds, and remarkable mechanical durability under repeated deformation cycles. These findings provide compelling evidence for the critical function of sulfur vacancies in achieving highly selective and ultrasensitive NO2 detection capabilities.
In a study by Yang et al. [63], urchin-like Bi2S3 nanostructures with an abundance of sulfur vacancies were fabricated via the hydrothermal method (Figure 5a), enabling the detection of NO2 at the ppb level at room temperature. Gas sensors with an urchin-like morphology (Figure 5b–e) facilitate gas adsorption, diffusion, and desorption. These sensors demonstrate high sensitivity, rapid response and recovery times, and the ability to detect NO2 at the ppb level at room temperature (Figure 5f–h). The results suggest that urchin-like Bi2S3 nanostructures, rich in sulfur vacancies, show significant potential for the evolution of sophisticated gas-sensing devices.
Kan and colleagues [55] utilized a hot-injection synthesis approach to engineer Bi2S3 nanorod structures, which were subsequently used to create sensor devices via spin-coating onto Al2O3 ceramic substrates. These strategies enable the accurate regulation of both the aspect ratio of the nanorods and the concentration of sulfur vacancies. These modifications significantly enhanced electron transfer within the film and augmented the number of active sites on the Bi2S3 nanorods. This work reveals that a gas sensor constructed with Bi2S3 nanorods with Bi/S = 4:1 displays exceptional sensitivity to NO2 at room temperature, accompanied by rapid response and recovery kinetics.
In conclusion, defect engineering in Bi2S3 gas sensors holds great promise for improving sensing performance. The strategic introduction of sulfur vacancies and the integration of heterostructures have been shown to significantly enhance the detection of NO2. To elucidate the correlation between the defect density and gas-sensing performance, further investigations are indispensable, which could offer valuable insights for the design of innovative sensing materials. These advancements underscore the importance of defect engineering in the development of next-generation gas sensors with improved sensitivity, selectivity, and stability.

2.2.3. Heterostructures Construction

The fabrication of heterogeneous architectures has turned out to be a promising strategy for improving gas detection capabilities, primarily through facilitating effective charge carrier separation, modulating carrier concentration, and generating additional active sites at interfacial regions [29,70,71]. The integration of Bi2S3 with various materials to form heterojunction structures has emerged as a promising approach in enhancing gas-sensing capabilities, particularly for the detection of NO2 and other gases [52,72]. This section summarizes the recent advancements in Bi2S3 heterojunction-based gas sensors, highlighting their improved sensing performance and potential applications.
Chen et al. [73] developed a gas detection mechanism utilizing CuS quantum dot-decorated Bi2S3 nanosheet heterostructures, inspired by artificial neural networks, which achieved high-sensitivity NO2 sensing. The incorporation of CuS quantum dots significantly improved NO2 detection sensitivity, attributed to their high density of active sites and pronounced quantum confinement effects, while the Bi2S3 nanosheets served as an efficient charge transfer network channel. This neuron-like sensor showed a markedly improved response value, outstanding responsiveness, rapid recovery rate, a low theoretical detection threshold, and exceptional selectivity towards NO2. The wearable device developed could visualize NO2 detection through real-time signal changes. Chen et al. [73] investigated the synergistic NO2-sensing mechanisms of CuS quantum dots (QDs) and Bi2S3 nanosheets (NSs) using density functional theory (DFT) and experimental validation. DFT calculations revealed that NO2 preferentially adsorbs on CuS QDs via N-Cu bonding (binding energy: 2.25 eV), with significant charge transfer (3.371 e) confirmed by charge density difference analysis (Figure 6a,b). Bi2S3 NSs, while exhibiting minimal direct NO2 adsorption, functioned as a high-mobility charge transport network. The CuS/Bi2S3 heterojunction formed a built-in electric field due to interfacial electron transfer, amplifying resistance changes during gas exposure (Figure 6c). Further analysis of the type-II band alignment (Bi2S3 CB: −4.37 eV; CuS: −4.79 eV) demonstrated band bending at the interface, creating electron-depleted Bi2S3 and hole-rich CuS layers. This alignment optimized charge separation and enabled ultrafast response (18 s) and high sensitivity (response: 3.4 to 10 ppm NO2). The study highlights how DFT-guided heterojunction design overcomes the limitations of individual materials, achieving biomimetic NO2 sensing at room temperature.
Pei et al. [74] fabricated Bi2S3/Bi2MoO6 nanocomposites featuring a heterogeneous cookie-shaped structure. The research team also explored the gas-sensing characteristics of the Bi2S3/Bi2MoO6 nanocomposite in response to alcohol and n-hexane. The Bi2S3/Bi2MoO6 nanocomposite exhibited superior gas-sensing properties compared to pure Bi2MoO6, further enhancing its potential for application as a gas sensor. The Bi2S3/Bi2MoO6 nanocomposite forms a type-II heterojunction due to the alignment of their energy bands, which facilitates efficient charge separation. The heterojunction interface significantly amplifies gas-sensing performance through increased active sites and catalytic activation. What is more, synergistic surface chemistry at the heterojunction accelerates redox reactions.
Zhao et al. [75] synthesized MoS2-modified Bi2S3 heterojunctions which displayed ultrafast NO2 response at 200 °C, underscoring the significance of extra active sites in the heterojunctions. Despite these improvements, there is a consensus that further enhancements in sensitivity, recovery, and ppb-level detection at room temperature are necessary. Expanding on this, the synthesis of Bi2S3/MoS2 hybrid aerogels, featuring a distinctive parallel heterojunction structure with MoS2 nanoflakes layered on Bi2S3 nanorods, was achieved by Liu et al. This particular Bi2S3/MoS2-2 configuration demonstrated superior sensing capabilities when compared to sensors based solely on Bi2S3 or MoS2 [40]. The enhanced performance of this composite sensor provides significant insights for the development and engineering of room-temperature sensors that leverage the properties of both Bi2S3 and MoS2.
The integration of Bi2S3 with Ti3C2Tx nanosheets yielded composite nanomaterials with enhanced gas-sensing properties. The Ti3C3Tx MXene/Bi2S3 woven nanomesh structures, synthesized by a hydrothermal method, exhibited an excellent response and fast response/recovery at room temperature upon exposure to 1 ppm NO2 [26]. The smart wearable wireless NO2 monitoring system developed is capable of transmitting signals to be displayed in smartphone apps in real time, offering a new approach to improve the comprehensive performance of gas sensors and promote the application of composites in flexible gas sensors.
Lately, Bi2S3/Ti3C2Tₓ nanomaterials were successfully synthesized and demonstrated enhanced responsiveness in real-time NH3 monitoring as humidity levels rose [76]. Specifically, under 90% relative humidity, the response value increased to 1.32 times that under normal humidity conditions. This remarkable moisture resistance enables the sensor to maintain stability and performance in challenging environments.
The synthesis of hierarchical structures combined with heterojunction effects offers a prospective approach for enhancing the sensing performance. For instance, the integration of hierarchical nanoheterojunctions, such as those reported by Hao et al. [77] with SnS2/SnO2, has demonstrated ultrasensitive detection of NO2 due to an increased number of active sites. For instance, Yang et al. [54] fabricated materials for room-temperature NO2 detection with high sensitivity. These materials, consisting of Bi2S3 nanoflowers and reduced graphene oxide (rGO), were synthesized via an in situ hydrothermal approach (Figure 7a–d). The rGO/Bi2S3 sensor demonstrates a high response of 9.8 and a fast response time of 22 s when exposed to 1 ppm NO2 at room temperature. Additionally, the sensor exhibits excellent humidity independence, selectivity, and stability (Figure 7e–g). The enhanced NO2 detection performance primarily originates from synergistic heterointerface effects and hybrid structural advantages, which facilitate optimized charge transfer kinetics at the interface between NO2 molecules and the rGO/Bi2S3 composite surface. This research provides valuable insights for enhancing the NO2 sensing performance of metal chalcogenides.
Yang et al. [78] strategically integrated vacancy defect modulation with heterostructure engineering to develop BiOCl/Bi2S3−x heterojunctions with controlled sulfur vacancies, demonstrating enhanced NO2 detection capabilities. The BiOCl/Bi2S3−x heterostructures featuring abundant S vacancies were fabricated through a straightforward one-step hydrothermal approach (Figure 8a–d). The optimized sensor, constructed on the S-vacancy-rich BiOCl/Bi2S3−x heterostructure, displayed a high response value (Rg/Ra = 29.1) to 1 ppm of NO2 at room temperature, roughly 17-fold higher than that of pure Bi2S3. Furthermore, the developed sensor demonstrated superior performance metrics, featuring rapid response kinetics, ultra-low theoretical detection limits, excellent operational stability, outstanding selectivity, and mechanical flexibility (Figure 8e–g). This investigation provides a strategic methodology for synergistic defect engineering and heterostructure design to achieve advanced room-temperature gas detection capabilities.
Hu et al. [79] achieved the successful synthesis of high-quality Bi2S3/CuO heterostructures (Figure 9a–d). The Bi2S3/CuO-based sensor exhibited a response value of 31.2 to 1 ppm of H2S, which was five-fold higher than that of pure Bi2S3. The enhanced detection capabilities primarily originate from synergistic heterojunction effects and increased surface chemisorption of oxygen at interfacial regions. Additionally, the sensor manifested a remarkably short response time, notable selectivity, dependable repeatability, outstanding moisture resistance, favorable long-term stability, and an exceedingly low detection limit of 25 ppb for H2S (Figure 9e–g). This study emphasizes the viability of Bi2S3/CuO as an effective sensing material for H2S gas detection at room temperature, providing valuable perspectives for the development of heterojunction sensors.
In conclusion, the development of Bi2S3 heterojunction structures has significantly advanced the field of gas sensing, offering a range of innovative solutions for improving sensor performance. These advancements not only enhance the detection capabilities for specific gases but also pave the way for the creation of smart, flexible, and reliable gas-sensing technologies.

2.2.4. Light Irradiation

Beyond optimizing the intrinsic structure of sensing materials, external auxiliary strategies have proven to be effective in enhancing sensing performance [80]. Among these, light-activated gas sensors have attracted substantial interest owing to their outstanding potential for gas sensing at room temperature [81]. Light activation enables the generation of energetic charge carriers, thereby modifying surface electronic characteristics and facilitating enhanced gas–solid interactions. Consequently, light irradiation serves as an effective strategy for simultaneously improving sensor response magnitude and accelerating reaction kinetics during both gas adsorption and desorption processes [82].
Wang et al. [41] presented a novel strategy for developing bifunctional gas sensors using Bi2S3/SnS2 heterostructures, which exhibit enhanced sensitivity and selectivity for detecting NO2 and H2S at room temperature. The Bi2S3/SnS2 heterostructures were fabricated via a two-step solvothermal approach. The Bi2S3/SnS2 heterostructures possessed flower-like morphology, and the Bi2S3 nanoparticles were homogeneously adhered to the surface of hierarchical SnS2 (Figure 10a–c). This work demonstrated that pristine SnS2 can detect NO2 solely under illumination owing to its low conductivity at room temperature. Bi2S3 showed weak responses to NO2 and H2S, with light having a minor modulating effect. In contrast, the Bi2S3/SnS2 (BS-2) heterostructure exhibited ultrahigh sensitivity to NO2 under light and high selectivity to H2S in the dark (Figure 10d). The study demonstrates that the sensor’s performance is significantly modulated by visible light, achieving ultrahigh response values of 14.0 (Rg/Ra) for 500 ppb NO2 under light irradiation and 12.3 (Ra/Rg) for 500 ppb H2S in the dark.
The bifunctional sensing mechanism of the Bi2S3/SnS2 heterostructure originates from the synergy between heterojunction-induced charge modulation and photoactivation. The n-n heterojunction, formed due to the work function mismatch (Bi2S3: 4.65 eV; SnS2: 5.05 eV), facilitates electron transfer from Bi2S3 to SnS2, equilibrating Fermi levels and boosting SnS2 conductivity. This interfacial charge redistribution creates depletion/accumulation layers, expanding reactive sites as reflected by the increased specific surface area (24.3 vs. 17.6 m²/g for pure SnS2). Visible-light irradiation generates electron–hole pairs that desorb pre-adsorbed oxygen (O2⁻), evidenced by in situ XPS revealing a decrease in surface oxygen from 22.7% to 19.1% (Figure 10e). The selectivity arises from distinct sensing models: H2S detection follows an oxygen-mediated redox mechanism, while NO2 sensing relies on physisorption-driven electron trapping. Light-activated oxygen desorption dynamically modulates active site availability (Figure 10f), achieving dual functionality: enhanced NO2 response under illumination and optimized H2S sensitivity in the dark.
The Bi2S3/SnS2 sensor also demonstrates swift response–recovery kinetics, remarkable repeatability, and dependable stability towards ppb-level target gases. This work highlights the potential of visible light modulation in designing multifunctional gas sensors and suggests that Bi2S3/SnS2 heterostructures could be promising material platforms for next-generation detection systems in IoT-enabled smart technologies.
Inspired by bifunctional gas sensors for detecting NO2 and H2S, researchers discovered that Bi2S3 can also be utilized for the detection of H2S. In the process of H2S sensing, a specific concentration of oxygen is beneficial [83]. In the dark, the existence of a greater amount of surface-adsorbed oxygen can lead to a more pronounced H2S sensing response [41]. The Bi2S3/ZnS heterostructures displayed a substantial response to H2S in the dark, approximately four-fold higher than that of pure Bi2S3 under indoor light [84]. Furthermore, the Bi2S3/ZnS-based sensor demonstrated exceptional operational characteristics, including superior gas selectivity, excellent reproducibility, remarkable long-term stability, and robust resistance to humidity variations (Figure 11a).
The sensing mechanism of Bi2S3/ZnS heterostructures toward H2S is illustrated in Figure 11b, based on the oxygen adsorbate-mediated model. When exposed to air, these heterostructures adsorb oxygen to form O2⁻(ads), which reacts with H2S, causing sensor resistance changes. The enhanced gas-sensing performance of Bi2S3/ZnS heterostructures in the dark is attributed to two main factors. First, the n-n heterojunction formed between ZnS nanoparticles and Bi2S3 nanowires improves the sensing response. Surface potential measurements show Bi2S3 and ZnS have work functions of 4.83 and 4.97 eV, respectively. Electron diffusion from Bi2S3 to ZnS increases the resistance of the heterostructures, aiding in effective electron–hole pair separation and enhancing sensor response. Under visible light, electron transfer forms a depletion layer at the Bi2S3 interface and an accumulation layer at the ZnS interface, providing more active sites for gas adsorption (Figure 11b i and ii). Consequently, Bi2S3/ZnS heterostructures exhibit an enhanced gas-sensing performance compared to pristine Bi2S3 and ZnS. Second, increased oxygen adsorption on the material surface in the dark boosts the sensor’s response to H2S. Under light, photo-excitation generates electron–hole pairs, with holes reacting with O2⁻(ads) to form oxygen molecules. Thus, as illustrated in Figure 11b (iii and iv), the depletion layer on the material surface becomes thicker, as well as the concentration of electrons being lower in the dark compared with that under visible light illumination. Based on the aforementioned reasons, the n-n heterostructure and light modulation contribute to the superior sensitivity and selectivity of Bi2S3/ZnS heterostructures toward H2S.
Bi2S3/Sb2S3 heterostructures generate photoinduced oxygen anions under visible-light exposure, leading to an enhanced H2S sensing ability [10]. The Bi2S3/Sb2S3 heterostructure sensor (Figure 12a) exhibited a notable rise in the sensing response to H2S under indoor lighting compared to its performance in the dark. The enhanced H2S sensing performance of the Bi2S3/Sb2S3 heterostructure under light irradiation results from the synergistic heterojunction and photoinduced effects (Figure 12b). The n-n heterojunction optimizes electronic properties, with electron transfer from Sb2S3 to Bi2S3 forming depletion and accumulation layers, providing additional gas adsorption sites and enhancing charge transfer. Under illumination, photoexcitation generates electron–hole pairs, whose separation is enhanced by the built-in electric field, increasing adsorbed oxygen ions that react more readily with H2S. However, excessive light intensities can reduce sensitivity by decreasing O2⁻ content. Overall, the combined heterojunction and photoinduced effects elevate O2⁻ levels on the sensor surface, enabling sensitive H2S detection under room-temperature illumination.
One-dimensional Bi2S3 nanorods are composited with 2D vanadium-based MXene nanosheets to construct Schottky heterojunctions as NO2 room-temperature sensing materials [85]. Such a composite sensor demonstrates a substantial response (~190%) to 20 ppm of NO2. Aided by UV illumination during the recovery process and the synergistic effect of the heterojunction, the composite sensor can fully recover to the baseline with a much shorter recovery time (103 s). Furthermore, the results demonstrate that the composite sensor achieves a reversible NO2 detection of 0.25−40 ppm, as well as excellent stability and selectivity to NO2.

3. Conclusions and Outlook

The recent advances in Bi2S3-based gas sensing have demonstrated the potential of structural design and material engineering to significantly enhance sensor performance. Morphological design, defect engineering, heterostructure construction and light irradiation have all contributed to improvements in sensitivity, selectivity, response time, and stability.
A considerable portion of the reported Bi2S3-based gas sensors has been used for detecting NO2, which suggests that Bi2S3-based gas sensors have a good response capability to NO2. However, Bi2S3 exhibits good responsiveness to NO2 and high selectivity towards H2S. If the response ratio of Bi2S3-based gas sensors to NO2 and H2S under the same conditions is not significantly different, it would lead to poor selectivity of the Bi2S3-based gas sensors. This would prevent them from accurately determining whether the gas present in the environment is specifically NO2 or H2S, and also from conducting quantitative gas analysis. Consequently, this would render the sensor unsuitable for environments with complex gas mixtures, resulting in inferior sensor performance. Future research should focus on elucidating the factors that account for these differences in selectivity.
Investigations into the selectivity of Bi2S3 towards various gases can bolster its utility in practical applications. Enhancing the selectivity of Bi2S3-based gas sensors would facilitate the precise detection and quantification of specific gases within complex settings, a capability essential for environmental monitoring, industrial safety, and healthcare applications. Improved selectivity would mitigate the risk of false positives and enhance the reliability of gas detection, positioning Bi2S3 as a more valuable material in the realm of gas-sensing technologies.

Funding

This work was financially supported by the National Natural Science Foundation of China (No. 52272147).

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. The crystal structure of Bi2S3 viewed from three axes: (a) b-c planes, (b) a-c planes, (c) a-b planes. Reproduced with permission from [48].
Figure 1. The crystal structure of Bi2S3 viewed from three axes: (a) b-c planes, (b) a-c planes, (c) a-b planes. Reproduced with permission from [48].
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Figure 2. Structural and gas-sensing characterization of Bi2S3 nanowires and nanobelts. (a) SEM image of an individual Bi2S3 nanowire connected to Pt electrodes. (b) Hydrogen sensing response of Bi2S3 nanowires at 0.5 V bias under 10–1000 ppm H2 in N2, showing a sensitivity of 22% at 10 ppm. Reproduced with permission from [49]. (c) SEM image of Bi2S3 nanobelt film showing a porous network morphology (inset shows the corresponding high-magnification SEM image). (d) Sensing response of Pb(NO3)2-treated Bi2S3 nanobelts at room temperature under 0.5–5 ppm NO2, demonstrating a response value of 58.8 at 5 ppm. Reproduced with permission from [51].
Figure 2. Structural and gas-sensing characterization of Bi2S3 nanowires and nanobelts. (a) SEM image of an individual Bi2S3 nanowire connected to Pt electrodes. (b) Hydrogen sensing response of Bi2S3 nanowires at 0.5 V bias under 10–1000 ppm H2 in N2, showing a sensitivity of 22% at 10 ppm. Reproduced with permission from [49]. (c) SEM image of Bi2S3 nanobelt film showing a porous network morphology (inset shows the corresponding high-magnification SEM image). (d) Sensing response of Pb(NO3)2-treated Bi2S3 nanobelts at room temperature under 0.5–5 ppm NO2, demonstrating a response value of 58.8 at 5 ppm. Reproduced with permission from [51].
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Figure 3. (a) SEM image of hierarchical Bi2S3 nanostructures. (b) Temporal variation of the current in the gas sensor based on hierarchical Bi2S3 nanostructures under a 0.5 V bias [62]. (c) Proposed self-assembly mechanism of Bi2S3 nanowires and their network. Response features of the 3D Bi2S3 nanowire networks sensor at 30 °C. (d) Responses to 360 ppm of different gases at 5 V. (e) Response transients for NH3 at 5 V. Reproduced with permission from [61].
Figure 3. (a) SEM image of hierarchical Bi2S3 nanostructures. (b) Temporal variation of the current in the gas sensor based on hierarchical Bi2S3 nanostructures under a 0.5 V bias [62]. (c) Proposed self-assembly mechanism of Bi2S3 nanowires and their network. Response features of the 3D Bi2S3 nanowire networks sensor at 30 °C. (d) Responses to 360 ppm of different gases at 5 V. (e) Response transients for NH3 at 5 V. Reproduced with permission from [61].
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Figure 4. (a) Schematic illustration of the formation process, (b) SEM image of hierarchical Bi2S3 nanomaterials. The RT NO2 sensing properties test of the samples: (c) Selectivity measurement toward interfering gases. (d) Baseline resistance and sensitivity to 1 ppm NO2 under different humidity environments. (e) Long-term stability. Reproduced with permission from [56].
Figure 4. (a) Schematic illustration of the formation process, (b) SEM image of hierarchical Bi2S3 nanomaterials. The RT NO2 sensing properties test of the samples: (c) Selectivity measurement toward interfering gases. (d) Baseline resistance and sensitivity to 1 ppm NO2 under different humidity environments. (e) Long-term stability. Reproduced with permission from [56].
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Figure 5. (a) Schematic representation of the preparation procedure for urchin-like Vs-Bi2S3. (b) SEM, (c) TEM, (d) HRTEM and (e) false-color images of the BS-4 sample. (f) Six consecutive sensing cycles for 1 ppm NO2. (g) Long-term stability toward 1 ppm NO2 for 30 days. (h) Selective response toward different gases. Reproduced with permission from [63].
Figure 5. (a) Schematic representation of the preparation procedure for urchin-like Vs-Bi2S3. (b) SEM, (c) TEM, (d) HRTEM and (e) false-color images of the BS-4 sample. (f) Six consecutive sensing cycles for 1 ppm NO2. (g) Long-term stability toward 1 ppm NO2 for 30 days. (h) Selective response toward different gases. Reproduced with permission from [63].
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Figure 6. (a,b) Diagrams of charge density difference of NO2 on CuS-Bi2S3 with n2 and n4 binding structure for side and top view, where the charge density isosurfaces of blue and yellow are 0.0015 and −0.0015 e Å−3, respectively. (c) Charge distribution at the interface of CuS QDs and Bi2S3 NSs calculated by density functional theory. Reproduced with permission from [73].
Figure 6. (a,b) Diagrams of charge density difference of NO2 on CuS-Bi2S3 with n2 and n4 binding structure for side and top view, where the charge density isosurfaces of blue and yellow are 0.0015 and −0.0015 e Å−3, respectively. (c) Charge distribution at the interface of CuS QDs and Bi2S3 NSs calculated by density functional theory. Reproduced with permission from [73].
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Figure 7. (a) Schematic representation of the synthesis of the rGO/Bi2S3 heterostructures. (b) SEM, (c) TEM, (d) HRTEM images. (e) Selectivity assessment against interfering gases. (f) Responsivity evaluation during six consecutive response–recovery cycles to 1 ppm NO2. (g) Long-term stability examination upon exposure to 1 ppm NO2. Reproduced with permission from [54].
Figure 7. (a) Schematic representation of the synthesis of the rGO/Bi2S3 heterostructures. (b) SEM, (c) TEM, (d) HRTEM images. (e) Selectivity assessment against interfering gases. (f) Responsivity evaluation during six consecutive response–recovery cycles to 1 ppm NO2. (g) Long-term stability examination upon exposure to 1 ppm NO2. Reproduced with permission from [54].
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Figure 8. (a) Schematic representation of the synthesis process of BiOCl/ Bi2S3−x heterostructures, (b) SEM image, (c) TEM images, (d) HRTEM image. (e) Repeatability assessment over five consecutive cycles. (f) Long-term stability evaluation for 40 days against 1 ppm NO2. (g) Selectivity test for NO2, NH3, SO2, H2S, H2, and CO. Reproduced with permission from [78].
Figure 8. (a) Schematic representation of the synthesis process of BiOCl/ Bi2S3−x heterostructures, (b) SEM image, (c) TEM images, (d) HRTEM image. (e) Repeatability assessment over five consecutive cycles. (f) Long-term stability evaluation for 40 days against 1 ppm NO2. (g) Selectivity test for NO2, NH3, SO2, H2S, H2, and CO. Reproduced with permission from [78].
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Figure 9. (a) Synthetic process, (b) SEM, (c) TEM and (d) HRTEM images of Bi2S3/CuO heterostructures. (e) Dynamic response–recovery curve of Bi2S3/CuO-2 to 25–1000 ppb H2S. (f) Assessment of the selectivity of the Bi2S3/CuO-2 sensor for H2S gas in comparison with other gases. (g) Repeatability test of Bi2S3/CuO-2 for 1 ppm H2S with five continuous cycles. Reproduced with permission from [79].
Figure 9. (a) Synthetic process, (b) SEM, (c) TEM and (d) HRTEM images of Bi2S3/CuO heterostructures. (e) Dynamic response–recovery curve of Bi2S3/CuO-2 to 25–1000 ppb H2S. (f) Assessment of the selectivity of the Bi2S3/CuO-2 sensor for H2S gas in comparison with other gases. (g) Repeatability test of Bi2S3/CuO-2 for 1 ppm H2S with five continuous cycles. Reproduced with permission from [79].
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Figure 10. (a–c) SEM and HRTEM images of the synthetic process of the Bi2S3/SnS2 heterostructures. (d) Summarized sensing responses of the SnS2, Bi2S3, and BS-2 sensor to 500 ppb NO2 and H2S in the dark and under light illumination. (e) The in situ O 1s XPS spectra of Bi2S3/SnS2 heterostructure in the dark and under 525 nm light illumination. (f) Schematic of the bifunctional H2S and NO2 sensing process of Bi2S3/SnS2 heterostructures under dark and light conditions. Reproduced with permission from [41].
Figure 10. (a–c) SEM and HRTEM images of the synthetic process of the Bi2S3/SnS2 heterostructures. (d) Summarized sensing responses of the SnS2, Bi2S3, and BS-2 sensor to 500 ppb NO2 and H2S in the dark and under light illumination. (e) The in situ O 1s XPS spectra of Bi2S3/SnS2 heterostructure in the dark and under 525 nm light illumination. (f) Schematic of the bifunctional H2S and NO2 sensing process of Bi2S3/SnS2 heterostructures under dark and light conditions. Reproduced with permission from [41].
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Figure 11. (a) HRTEM images of Bi2S3/ZnS heterostructures, repeatability and stability measurement of the Bi2S3/ZnS sensor to 500 ppb H2S in the dark. (b) Schematic of the H2S sensing process under (i,ii) light and (iii,iv) dark conditions for Bi2S3/ZnS heterostructures. Reproduced with permission from [84].
Figure 11. (a) HRTEM images of Bi2S3/ZnS heterostructures, repeatability and stability measurement of the Bi2S3/ZnS sensor to 500 ppb H2S in the dark. (b) Schematic of the H2S sensing process under (i,ii) light and (iii,iv) dark conditions for Bi2S3/ZnS heterostructures. Reproduced with permission from [84].
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Figure 12. (a) HRTEM images, repeatability and selectivity measurement of the Bi2S3/Sb2S3 heterostructure. (b) Schematic of the H2S sensing process under (i) dark and (ii) light conditions for Bi2S3/Sb2S3 heterostructures. Reproduced with permission from [10].
Figure 12. (a) HRTEM images, repeatability and selectivity measurement of the Bi2S3/Sb2S3 heterostructure. (b) Schematic of the H2S sensing process under (i) dark and (ii) light conditions for Bi2S3/Sb2S3 heterostructures. Reproduced with permission from [10].
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Ma, R.; Lei, H.; Han, M.; Hao, J. Recent Progress with Bismuth Sulfide for Room-Temperature Gas Sensing. Chemosensors 2025, 13, 120. https://doi.org/10.3390/chemosensors13040120

AMA Style

Ma R, Lei H, Han M, Hao J. Recent Progress with Bismuth Sulfide for Room-Temperature Gas Sensing. Chemosensors. 2025; 13(4):120. https://doi.org/10.3390/chemosensors13040120

Chicago/Turabian Style

Ma, Renping, Haoxin Lei, Mingyang Han, and Juanyuan Hao. 2025. "Recent Progress with Bismuth Sulfide for Room-Temperature Gas Sensing" Chemosensors 13, no. 4: 120. https://doi.org/10.3390/chemosensors13040120

APA Style

Ma, R., Lei, H., Han, M., & Hao, J. (2025). Recent Progress with Bismuth Sulfide for Room-Temperature Gas Sensing. Chemosensors, 13(4), 120. https://doi.org/10.3390/chemosensors13040120

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