First principles study of Rh-doped SnO2 for highly sensitive and selective hydrogen detection

doi:10.1016/j.sna.2022.113788

Sensors and Actuators A: Physical

Volume 345, 1 October 2022, 113788

https://doi.org/10.1016/j.sna.2022.113788 Get rights and content

Highlights

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For the first time, atomic-scale gases sensing mechanism of Rh-SnO₂ is studied.
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Predicted gases sensing behaviours of Rh-SnO₂ consist with experiments.
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Detection of H₂ is related to the chemical adsorption between H₂ and Rh-SnO₂.
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Our work provides an approach for designing SnO₂-based gas sensor.

Abstract

Tin dioxide is a low-cost and efficient material with large potential in applications of hydrogen detection. Doping metals in SnO₂ is a solution to further improve its electrical performance, however, atomic-scale understanding of detection mechanism of doped SnO₂ is very limited. In this work, first principles and molecular dynamics method are applied to investigate adsorption properties and diffusion effects of CH₄, CO₂, H₂, N₂ on Rh-doped SnO₂. By calculating adsorption energy, adsorption distance, charge density difference, density of states, it is concluded that Rh-SnO₂ shows a strong sensing characteristics towards H₂, which is consistent with experiment result. After adsorption of H₂, the main energy bands of DOS shift to a lower level of energy, and the Fermi level move to higher level of energy. H₂ shows a strong chemical adsorption effect on Rh-SnO₂, while CH₄, CO₂ and N₂ only present weak physical adsorption on Rh-SnO₂. Furthermore, the diffusion of H₂ in Rh-SnO₂ is easier than those of other gases. Our study provides a fundamental and new perspective for designing highly sensitive hydrogen gas sensor from atomic and electronic level.

Graphical Abstract

Introduction

Hydrogen (H₂) gas is wildly used in many fields such as energy storage, aerospace area, fossil industrial and reducing agent in chemical reaction because of its renewable, rich in content and clean in the world [1], [2], [3]. However, the detection of H₂ is challenging due to colorlessness and explosion, which may cause potential safety hazards in some cases [4], [5], [6]. Thus, it is critical to develop high performance sensor for detecting hydrogen gas, in particular, from the mixture of gases [7], [8]. In recent years, there are many kinds of hydrogen sensors were developed, such as ZnO [9], MoO₃ [10], VO₂ [11] and SnO₂ [12]. The successful preparation of these hydrogen sensors has strongly aroused interest in new sensing materials. From these dazzling arrays of sensors, SnO₂ is a widely used material due to its unique rutile phase structure and interface characteristics [13], [14], [15], [16]. SnO₂ nanowires synthesized through thermal evaporation of tin oxide and activated carbon powders showed good performance in sensing hydrogen within 10–1000 ppm [17]. The most of the metal oxides for detection of hydrogen are limited by environmental conditions such as temperature and humidity, doping of metals in rutile phase SnO₂ is a solution to improve electrical performance of SnO₂ [18], [19]. SnO₂ nanoparticles doped with Rh were synthesized by flame spray pyrolyzation and exhibited excellent response to H₂, which was faster than the undoped one at the same temperature [20]. However, there is still a lack of in-depth theoretical investigation of the detection mechanism of these materials.

Density functional theory (DFT) is widely used to research the structure and electronic properties of sensing materials at atomic level [21], [22], [23], [24]. These methods were successfully used in simulations of gas adsorption and the validity was demonstrated [25], [26], [27]. DFT calculations indicate strong adsorption effect of Ag-MoS₂ towards CO, C₂H₄ and C₂H₂, which provides guidance for sensing performance of Ag-MoS₂ materials [28]. Adsorption of SO₂ gas on Ni, Pd doped graphene was studied by DFT, and the results indicated that the doping of Ni, Pd can obviously enhanced the adsorption mechanism towards SO₂ [29]. The adsorption properties of CO on Sb and S doped SnO₂ were explored by DFT, and it was concluded that Sb, S-SnO₂ shows greater sensitivity to CO than undoped one [30]. However, the atomic-scale sensing mechanisms of Rh-SnO₂ towards CH₄, H₂, CO₂ and N₂ were not investigated.

In this work, the adsorption characteristics of CH₄, H₂, CO₂ and N₂ on Rh-SnO₂ are studied by first principles, and the diffusion of CH₄, CO₂, H₂ and N₂ in Rh-SnO₂ are studied further. The gases sensing performance includes sensitivity and response speed are discussed and related to the calculated adsorption and diffusion properties.

Section snippets

Computational methods

The calculations were performed by CASTEP module in Materials Studio [31]. The GGA and PBE functional was applied for describing electron correlation [32]. DFT+U method was implemented to deal with the underestimation of band gap caused by the choice of functional, the values of U for Sn and O were 3 eV and 10 eV, which were closed to the values of 3.5 eV and 9.6 eV in pervious works [33], [34], [35]. The on-the-fly generated (OTFG) ultra-soft pseudo-potentials and Monk-horst-Pack grid were

Model construction

The optimized 2 × 2 × 1 supercell structure of SnO₂ and the band structure corrected by DFT+U are shown in Fig. 1. DFT+U method is usually used to correct underestimation of band gaps [30], [39]. As shown in Fig. 1(a), the supercell structure contains 8 Sn atoms and 16 O atoms, and the rutile SnO₂ cell belongs to the space group of P42/MNM. The lattice parameters of optimized initial unit cell of SnO₂ are a=b= 4.82325 Å, c= 3.234094 Å, α = β = γ = 90°, which are consistent with available

Conclusion

In this work, atomic-scale calculations are applied to investigate the adsorption and diffusion of CH₄, CO₂, H₂ and N₂ gases on Rh-SnO₂ surface. Based on adsorption energy, Mulliken charge transfer and adsorption distance, a strong sensing characteristic of Rh-SnO₂ towards H₂ can be concluded, being consistent with experimental results. After adsorption of hydrogen, the main bands of DOS shift significantly and the energy density presents a tendency of descending, indicating a strong chemical

CRediT authorship contribution statement

Qinkai Feng: Investigation, Software, Visualization, Writing - original draft, Xiuhuai Xie: Investigation, Miao Zhang: Writing - review & editing, Ningbo Liao: Methodology, Supervision, Writing - review & editing, Funding acquisition.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors would like to acknowledge the support of the Natural Science Foundation of Zhejiang province (LZ21E050001).

Qinkai Feng primarily works in first-principles calculations and sensors. His main research areas include first-principles calculations, nano-sensors, first-principles calculations and all-solid-state lithium-ion battery.

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Xiuhuai Xie primarily works in sensors and thin films mechanics. His main research areas include nano-sensors, first-principles calculations, lithium-ion battery and multi-scale mechanics.

Miao Zhang is a full professor of College of Mechanical & Electrical Engineering in Wenzhou university and primarily works in sensors and micro/nano systems. His main research areas include sensors, micromechatronics, materials mechanics and flowmeter.

Ningbo Liao is a full professor and the director of Multi-Scale Structure & Material Reliability Lab in Wenzhou university and primarily works in multi-scale computational materials and mechanics with an emphasis in nano-materials and nano-structures. His main research areas include multi-scale computations for micro/nano systems & materials, micromechatronics, electronic packaging and lithium-ion batteries.

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