Search

This study introduces a promising technique to enhance the sensitivity of p-type semiconductors in gas-sensing applications. By utilizing a glycerate-templated synthesis approach, a unique hierarchical W-doped Co 3 O 4 yolk-shell sphere (YSS)-based sensor was developed, exhibiting exceptional sensitivity toward acetone gas. The synthesized YSSs feature a yolk-shell structure with a diameter of approximately 500 nm and a large surface area of 117.46 m 2 /g, which allows for efficient gas interaction and high sensitivity toward acetone gas. Furthermore, the incorporation of tungsten (W), a non-noble metal, as a dopant significantly enhances the surface activity of Co 3 O 4 , leading to a remarkably high response of 16.5 toward 5 ppm acetone, which is substantially higher than that of the pure Co 3 O 4 YSS (2.9). The W-doped Co 3 O 4 YSS also exhibits excellent selectivity to other interfering gases and the ability to detect ultralow concentrations of acetone as low as 10 ppb. The proposed non-noble metal doping strategy presents a practical solution for enhancing the sensitivity and selectivity of p-type semiconductor-based gas sensors. This approach holds great potential for practical gas-sensing applications due to their affordability and abundance, making them a cost-effective and versatile alternative to noble metal-catalyzed sensors.

The increase of surface area and the functionalization of catalyst are crucial to development of high-performance semiconductor metal oxide (SMO) based chemiresistive gas sensors. Herein, nanoscale catalyst loaded Co 3 O 4 hollow nanocages (HNCs) by using metal-organic framework (MOF) templates have been developed as a new sensing platform. Nanoscale Pd nanoparticles (NPs) were easily loaded on the cavity of Co based zeolite imidazole framework (ZIF-67). The porous structure of ZIF-67 can restrict the size of Pd NPs (2-3 nm) and separate Pd NPs from each other. Subsequently, the calcination of Pd loaded ZIF-67 produced the catalytic PdO NPs functionalized Co 3 O 4 HNCs (PdO-Co 3 O 4 HNCs). The ultrasmall PdO NPs (3-4 nm) are well-distributed in the wall of Co 3 O 4 HNCs, the unique structure of which can provide high surface area and high catalytic activity. As a result, the PdO-Co 3 O 4 HNCs exhibited improved acetone sensing response (R gas /R air = 2.51-5 ppm) compared to PdO-Co 3 O 4 powders (R gas /R air = 1.98), Co 3 O 4 HNCs (R gas /R air = 1.96), and Co 3 O 4 powders (R gas /R air = 1.45). In addition, the PdO-Co 3 O 4 HNCs showed high acetone selectivity against other interfering gases. Moreover, the sensor array clearly distinguished simulated exhaled breath of diabetics from healthy people's breath. These results confirmed the novel synthesis of MOF templated nanoscale catalyst loaded SMO HNCs for high performance gas sensors.

Bio-inspired Pt (∼2 nm) and Au (∼2.7 nm) catalysts encapsulated by a protein shell, i.e., Pt-apoferritin (Pt@AF) and Au-apoferriten (Au@AF), were synthesized via the hollow protein nanocage (apoferritin) templating route and directly functionalized on the interior and exterior walls of electrospun SnO2 nanotubes (NTs) during controlled single-nozzle electrospinning followed by high temperature calcination with heating rate control. Fast crystallization of the exterior shell and outward diffusion of the interior Sn precursors and crystallites result in the continued growth of a tubular wall, which is related to rapid heating driven Ostwald-ripening behavior. Very importantly, the Pt and Au nanoparticles (NPs) were immobilized onto thin-walled SnO2 NTs with a diameter of ∼350 nm and a shell thickness of ∼40 nm without any aggregation of catalysts due to high dispersibility, which originated from repulsive electrostatic (Coulombic) forces acting on the surface charged protein shells, leading to an enhanced catalytic effect and outstanding gas sensing properties. Pt-loaded SnO2 NTs exhibited superior acetone response (R(air)/R(gas) = 92 at 5 ppm) compared to pure SnO2 NFs (R(air)/R(gas) = 4.8 at 5 ppm) and SnO2 NTs (Rair/Rgas = 11 at 5 ppm) while Au-loaded SnO2 NTs showed a high response when exposed to hydrogen sulfide (R(air)/R(gas) = 34 at 5 ppm), offering selective gas detection with minimal cross-sensitivity against other interfering gases such as NH3, CO, NO, C6H5CH3, and C5H12. Our results provide a new insight into facile, cost-effective, and highly dispersible catalyst loading on the interior and exterior walls of hollow metal oxide NTs via simple electrospinning as a potential breath analyzer.

Pore-loaded WO3 nanofibers (NFs) functionalized with spherical catalyst films were achieved via electrospinning combined by the sacrificial templating route using layer-by-layer (LbL) catalyst assembled polystyrene (PS) colloids. The catalyst-loaded porous WO3 NFs exhibited significantly improved toluene and acetone detection capability for potential application in exhaled breath analysis.

Diagnostic sensing device using exhaled breath of human have critical advantages due to the noninvasive diagnosis and high potential for portable device with simple analysis process. Here, we report ultrafast as well as highly sensitive bumpy WO3 hemitube nanostructure assisted by O2 plasma surface modification with functionalization of graphene-based material for the detection of acetone (CH3COCH3) and hydrogen sulfide (H2S) which are biomarkers for the diagnosis of diabetes and halitosis, respectively. 0.1 wt % graphene oxide (GO)- and 0.1 wt % thin layered graphite (GR)- WO3 hemitube composites showed response times of 11.5 ± 2.5 s and 13.5 ± 3.4 s to 1 ppm acetone as well as 12.5 ± 1.9 s and 10.0 ± 1.6 s to 1 ppm of H2S, respectively. In addition, low limits of detection (LOD) of 100 ppb (Rair/Rgas = 1.7 for acetone and Rair/Rgas = 3.3 for H2S at 300 °C) were achieved. The superior sensing properties were ascribed to the electronic sensitization of graphene based materials by modulating space charged layers at the interfaces between n-type WO3 hemitubes and p-type graphene based materials, as identified by Kelvin Probe Force Microscopy (KPFM). Rapid response and superior sensitivity of the proposed sensing materials following cyclic thermal aging demonstrates good potential for real-time exhaled breath diagnosis of diseases.

Sensitive detection of acetone and hydrogen sulfide levels in exhaled human breath, serving as breath markers for some diseases such as diabetes and halitosis, may offer useful information for early diagnosis of these diseases. Exhaled breath analyzers using semiconductor metal oxide (SMO) gas sensors have attracted much attention because they offer low cost fabrication, miniaturization, and integration into portable devices for noninvasive medical diagnosis. However, SMO gas sensors often display cross sensitivity to interfering species. Therefore, selective real-time detection of specific disease markers is a major challenge that must be overcome to ensure reliable breath analysis. In this work, we report on highly sensitive and selective acetone and hydrogen sulfide detection achieved by sensitizing electrospun SnO2 nanofibers with reduced graphene oxide (RGO) nanosheets. SnO2 nanofibers mixed with a small amount (0.01 wt %) of RGO nanosheets exhibited sensitive response to hydrogen sulfide (Rair/Rgas = 34 at 5 ppm) at 200 °C, whereas sensitive acetone detection (Rair/Rgas = 10 at 5 ppm) was achieved by increasing the RGO loading to 5 wt % and raising the operation temperature to 350 °C. The detection limit of these sensors is predicted to be as low as 1 ppm for hydrogen sulfide and 100 ppb for acetone, respectively. These concentrations are much lower than in the exhaled breath of healthy people. This demonstrates that optimization of the RGO loading and the operation temperature of RGO-SnO2 nanocomposite gas sensors enables highly sensitive and selective detection of breath markers for the diagnosis of diabetes and halitosis.

Thin-walled WO(3) hemitubes and catalytic Pt-functionalized WO(3) hemitubes were synthesized via a polymeric fiber-templating route and used as exhaled breath sensing layers for potential diagnosis of halitosis and diabetes through the detection of H(2)S and CH(3)COCH(3), respectively. Pt-functionalized WO(3) hemitubes with wall thickness of 60 nm exhibited superior acetone sensitivity (R(air)/R(gas) = 4.11 at 2 ppm) with negligible H(2)S response, and pristine WO(3) hemitubes showed a 4.90-fold sensitivity toward H(2)S with minimal acetone-sensing characteristics. The detection limit (R(air)/R(gas)) of the fabricated sensors with Pt-functionalized WO(3) hemitubes was 1.31 for acetone of 120 ppb, and pristine WO(3) hemitubes showed a gas response of 1.23 at 120 ppb of H(2)S. Long-term stability tests revealed that the remarkable selectivity has been maintained after aging for 7 months in air. The superior cross-sensitivity and response to H(2)S and acetone gas offer a potential platform for application in diabetes and halitosis diagnosis.

Single‐atom catalysts (SACs) supported on inorganic materials have attracted much attention in numerous research fields for their high catalytic performance. However, such SACs have been limited by the low metal loading, especially on different types of inorganic supports. Herein, a general approach is presented for preparing SACs on metallic, metal oxide, and perovskite nanosheet (NS) supports to reach a high metal loading of up to 3.94 wt%, by utilizing N‐doped graphene as a sacrificial template that spatially confines the single atoms (SAs). Specifically, the target support material precursors are adsorbed onto the SAs‐stabilized sacrificial template, followed by subsequent heat treatment to transfer the SAs to the support material and to remove the graphene layer. Pt SAs on oxide support exhibits little to no aggregation throughout >10 000 min of annealing at 275 °C, demonstrating high thermal stability, as also supported by ex situ post‐anneal electron microscopy and X‐ray absorption fine structure studies. As a proof‐of‐concept, Pt SACs on SnO2 NSs exhibit high catalytic activity toward chemiresistive sensing of acetone gas (response = 95.4 at 10 ppm, 7.6‐fold enhancement compared with pristine SnO2 NSs) and unprecedented stability under highly humid conditions (27.4% response deterioration at 95% relative humidity). [ABSTRACT FROM AUTHOR]

Electrospinning–etching strategy was employed to synthesize Pt-loaded SnO 2 hollow microbelts (Pt_SnO 2 HBLs) based chemiresistive-type sensor demonstrating high sensitivity and selectivity toward acetone gas. This strategy overcomes a major hurdle toward achieving ubiquitous gas diffusion in electrospun structures, and provides highly porous thin-walled HBLs with large surface area and small crystallites. [Display omitted] • In situ templating of SnO 2 with SiO 2 was employed to form Pt-loaded SiO 2 @SnO 2 core–shell microbelts. • Etching away of SiO 2 in the Pt-loaded SiO 2 @SnO 2 microbelts yielded Pt-loaded SnO 2 hollow microbelts. • The Pt-loaded SnO 2 hollow microbelts exhibited good response (R a /R g = 93.5) and selectivity toward 2 ppm acetone at 350 °C. Challenges for ubiquitous diffusion of gas analytes into semiconducting metal oxides (SMOs) based sensing layers have necessitated the introduction of unprecedented synthesis techniques for thin, porous and high-performance gas sensing materials. In this work, electrospinning and calcination were employed to prepare unprecedented SiO 2 –SnO 2 core–shell microbelts (hereinafter referred to as SiO 2 @SnO 2 BLs) followed by etching away of SiO 2 in NaOH solution (pH 12) to achieve hollow SnO 2 BLs (hereinafter referred to as SnO 2 HBLs) with mean crystal size of 14.01 nm, large BET surface area (143.5 m2‧g–1), high porosity (mean pore size of 5.7 nm), and shell thickness of 58.3 ± 11.4 nm. Sensitization of SnO 2 HBLs with apoferritin-templated platinum nanoparticles (Pt NPs) enhanced their detection capability toward acetone. Response (defined as R a /R g , where R a and R g are sensor resistances in air and target gas, respectively) of Pt(0.12 %)_SnO 2 HBLs toward 2 ppm acetone was up to 7.8 times higher compared to that of pristine SnO 2 HBLs, and exhibited faster response (9.2 s). The Pt(0.12 %)_SnO 2 HBLs based sensor indicated a promising long-term stability, and outstanding repeatability of response (R a /R g = 93.7 ± 0.89) toward 25 cycles of 2 ppm acetone exposure in a humid environment of 90 % relative humidity. This performance could be attributed to the unique morphology of HBLs, sensitization effects of catalytic Pt NPs, and enlargement of the electron-depleted layer resulting from a Schottky barrier between Pt NPs and SnO 2 grains. [ABSTRACT FROM AUTHOR]

In this work, catalytic Rh 2 O 3 -functionalized WO 3 nanofibers (NFs) were synthesized via an electrospinning route and used as a highly selective acetone-sensing layer for potential diagnosis of diabetes. Catalytic rhodium nanoparticles (Rh NPs) with average diameters of 5.0 ± 0.52 nm, which were synthesized by the polyol process, were dispersed in water with W precursor and poly(vinylpyrrolidone) (PVP) for electrospinning. As-spun Rh NP-loaded W precursor/PVP composite NFs were calcined at 600 °C for 1 h in air atmosphere to achieve Rh 2 O 3 -decorated WO 3 NFs. Microstructure evolution and chemical composition of Rh 2 O 3 -decorated WO 3 NFs as a function of Rh-loading amounts, i.e., 0.01 wt%, 0.05 wt%, 0.10 wt%, and 0.15 wt%, were examined using energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The mean size (30 nm) of the WO 3 crystallites in Rh 2 O 3 -decorated WO 3 NFs was much smaller than that (60 nm) of the WO 3 crystallites in pristine WO 3 NFs. The Rh 2 O 3 -decorated WO 3 NFs showed outstanding acetone (CH 3 COCH 3 ) sensing response ( R air / R gas = 41.2 to 5 ppm), which was 4.6 times higher than the response ( R air / R gas = 9.0 to 5 ppm) of pristine WO 3 NFs at highly humid atmosphere (95% RH). In addition, superior acetone cross-sensitivity of the Rh 2 O 3 -decorated WO 3 NFs was observed in other interfering gases such as pentane ( n -C 5 H 12 ), ammonia (NH 3 ), toluene (C 6 H 5 CH 3 ), carbon monoxide (CO), and ethanol (C 2 H 5 OH) at 5 ppm. These results are highly promising for the accurate and selective detection of acetone in exhaled breath for potential diagnosis of diabetes. [ABSTRACT FROM AUTHOR]

Abstract: Chemoresistive H2S sensors using various oxide nanoparticles were prepared and heat-treated at 600°C in an effort to define halitosis in human breath. WO3, ZnO, and SnO2 were tested as sensing materials, among which WO3 showed the highest stability to H2S. XPS analysis showed a metal sulfate peak on the surface of ZnO and SnO2, which causes a recovery problem after 2ppm H2S exposure. On the contrary, the WO3 sensor showed a stable signal in long-term operation in the presence of H2S gas. WO3 gas sensors decorated with various catalytic metals were fabricated to investigate their sensing properties in the 0.2–5ppm H2S range with 80% relative humidity (RH). A 0.03wt% Au-doped WO3 sensor exhibited excellent H2S sensitivity (R air/R gas =12.40at 2ppm) toward H2S, whereas pure WO3 showed a sensitivity of 4.85 with negligible interference from the volatile organic compounds (VOCs). [Copyright &y& Elsevier]

• To control the porosity, the e-spraying and PS beads templating route are combined, resulting in highly porous structure. • Pt functionalized PH-SnO 2 spheres exhibited high response (R air /R gas = 44.83) toward 5 ppm of acetone. • Pt-PH-SnO 2 spheres exhibited exceptional selectivity toward acetone against interfering molecules. Tailoring of semiconducting metal oxides (SMOs) nanostructures with high porosity is of importance for enhanced gas sensing performance. Hierarchically-assembled SMOs possess high surface area but often suffer from low porosity. Here, bimodal pore-loaded hierarchical SnO 2 (PH-SnO 2) spheres were successfully synthesized via electrostatic spraying method (e-spraying) combined with colloidal templating route using polystyrene beads. The resulting porous PH-SnO 2 spheres were used as sensing layers for detection of acetone, which exhibited about 20 % enhanced response compared with hierarchical SnO 2 (H-SnO 2) spheres without pores. In addition, e-spraying is a fascinating technique for uniform catalytic functionalization through a simple dispersion of catalytic nanoparticle (NPs) in the e-spraying solution to improve the sensing performance. As a result, the Pt-functionalized PH-SnO 2 (Pt-PH-SnO 2) spheres showed dramatically improved acetone detection capability with a response (R air /R gas) of 44.83 at 5 ppm as compared to PH-SnO 2 spheres (R air /R gas = 6.61) as well as superior selectivity. In this work, the unique combination of e-spraying and PS templating route paves the way for robust and facile synthetic method for bimodal pore loaded 3D hierarchical SMOs, and demonstrates the feasibility for application in exhaled breath sensors. [ABSTRACT FROM AUTHOR]