The bismuth sulfide nanostructure has become a promising gas sensing material thanks to its exceptional intrinsic properties. However, pristine Bi
2S
3 as a room-temperature sensing material cannot achieve the highly sensitive detection of ppb-level NO
2 gas. Herein, 1D nanorods with
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The bismuth sulfide nanostructure has become a promising gas sensing material thanks to its exceptional intrinsic properties. However, pristine Bi
2S
3 as a room-temperature sensing material cannot achieve the highly sensitive detection of ppb-level NO
2 gas. Herein, 1D nanorods with self-assembled hierarchical Bi
2S
3 nanostructures were obtained via a simple hydrothermal process. The as-prepared hierarchical Bi
2S
3 nanostructures exhibited outstanding NO
2 sensing behaviors, such as a high response value (R
g/R
a = 5.8) and a short response/recovery time (τ
90 = 28/116 s) upon exposure to 1 ppm NO
2. The limit of detection of hierarchical Bi
2S
3 was down to 50 ppb. Meanwhile, the sensor exhibited excellent selectivity and humidity tolerance. The improved NO
2 sensing properties were associated with the self-assembled hierarchical nanostructures, which provided a rich sensing active surface and accelerated the diffusion and adsorption/desorption processes between NO
2 molecules and Bi
2S
3 materials. Additionally, the sensing response of hierarchical Bi
2S
3 nanostructures is much higher at 100% N
2 atmosphere, which is different from the chemisorption oxygen model.
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