First principles study of Rh-doped SnO2 for highly sensitive and selective hydrogen detection
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.
References (47)
- et al.
Ultra-high sensitive micro-chemo-mechanical hydrogen sensor integrated by palladium-based driver and high-performance piezoresistor
Int. J. Hydrog. Energy
(2021) - et al.
Theoretical investigations of hydrogen gas sensing and storage capacity of graphene-based materials: a review
Sens. Actuators A: Phys.
(2021) - et al.
Review on hydrogen safety issues: incident statistics, hydrogen diffusion, and detonation process
Int. J. Hydrog. Energy
(2021) - et al.
Performance tests of catalysts for the safe conversion of hydrogen inside the nuclear waste containers in Fukushima Daiichi
Int. J. Hydrog. Energy
(2021) - et al.
MEMS-based thermal conductivity sensor for hydrogen gas detection in automotive applications
Sens. Actuators A: Phys.
(2020) - et al.
Hydrogen sensing characteristics of Pd-decorated ultrathin ZnO nanosheets
Sens. Actuators B: Chem.
(2021) - et al.
Metal oxide semiconductors with highly concentrated oxygen vacancies for gas sensing materials: A review
Sens. Actuators A: Phys.
(2020) - et al.
Nanopillar ZnO gas sensor for hydrogen and ethanol
Sens. Actuators B: Chem.
(2007) - et al.
VO2 nanostructures based chemiresistors for low power energy consumption hydrogen sensing
Int. J. Hydrog. Energy
(2014) - et al.
Hydrogen gas sensing based on nanocrystalline SnO2 thin films operating at low temperatures
Int. J. Hydrog. Energy
(2020)
Interfacial micro-structure and properties of TiO 2 /SnO 2 heterostructures with rutile phase: A DFT calculation investigation
Appl. Surf. Sci.
Au doped ZnO/SnO2 composite nanofibers for enhanced H2S gas sensing performance
Sens. Actuators A: Phys.
Ultra-sensitive and highly selective H2 sensors based on FSP-made Rh-substituted SnO2 sensing films
Sens. Actuators B: Chem.
Adsorption and diffusion of oxygen on metal surfaces studied by first-principle study: A review
J. Mater. Sci. Technol.
Gas sensing properties of defective tellurene on the nitrogen oxides: A first-principles study
Sens. Actuators A: Phys.
Temperature-dependent gas sensing properties of porous silicon oxycarbide: Insight from first principles
Appl. Surf. Sci.
C2x: A tool for visualisation and input preparation for Castep and other electronic structure codes
Comput. Phys. Commun.
Ab initio DFT computation of SnO2 and WO3 slabs and gas–surface interactions
Sens. Actuators B: Chem.
The adsorptions of fixed groups −CN, −NH2, −SH, −OH and −COOH of dye molecules on stoichiometric, oxygen vacancy and Pt-doped SnO2 (110) surfaces
Appl. Surf. Sci.
Structural and electronic properties of Sb-doped SnO2 (110) surface: A first principles study
Appl. Surf. Sci.
Phosphorene: A promising candidate for H2 storage at room temperature
Int. J. Hydrog. Energy
Low-cost hydrogen sensor in the ppm range with purely optical readout
ACS Sens
Highly responsive room-temperature hydrogen sensing of alpha-MoO(3) nanoribbon membranes
ACS Appl. Mater. Interfaces
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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.
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.