Interconnected graphene scaffolds for functional gas sensors with tunable sensitivity

doi:10.1016/j.jmst.2020.03.055

Abstract

Abstract:

In this work, the interconnected graphene scaffolds are prepared by three-dimensional (3D) printing for multifunctional gas detection with tunable sensitivity. The scaffolds with regularly aligned graphene conductive networks exhibit significant mechanical strength and high electrical stability to multi-direction deformation, which can be attributed to the typical core-shell structure of graphene and PVP. The resistance of the free-standing scaffolds can realize the real-time response to H₂O and NO₂, and the relative resistance change to 100 ppm H₂O and 100 ppm NO₂ can reach 2% and 2.5 %, respectively. The charge doping of the oxidizing gases is considered to be the main reason for various response sensitivities of the scaffolds with different orthogonal layers, in which the interconnected conductive network can generate a large specific surface area and significantly improving the adsorption of the target gases and the transfer of charge. The controllable fabrication of regular structure has appropriately great potential for further optimizations and applications in gas detection.

Key words: Graphene scaffolds, Interconnected network, 3D printing, Gas sensors, Multifunctional gas detection

Xiao You, Jinshan Yang, Mengmeng Wang, Hongda Wang, Le Gao, Shaoming Dong. Interconnected graphene scaffolds for functional gas sensors with tunable sensitivity[J]. J. Mater. Sci. Technol., 2020, 58: 16-23.

Figures/Tables 8

Fig. 1. Schematic of the fabrication process of 3D scaffolds. The arrows represent that the graphene and PVP were homogenously dispersed to prepare graphene dispersion by ultrasonic. The paste-like graphene-based ink was obtained with the evaporation of ethanol accompany by continuous stirring. The ink was extruded from the nozzle to prepare a single layer. 3D scaffold was obtained by repeated U-shaped-layer printing with 90° horizontal rotations by the layer by layer integration.

Fig. 2. Log-log plots of (a) apparent viscosity as a function of shear rate and (b) shear storage and loss modulus as a function of shear stress for graphene-based inks with varying graphene contents.

Fig. 3. FESEM images of the prepared graphene-based scaffold: (a) diagram of the printed 3D scaffold; (b) exterior surface view and (c) the corresponding magnified image. The graphene sheets are immersed in PVP and distributed parallel to the surface; (d) fracture surface view and (e, f) the corresponding magnified images. The graphene sheets are distributed perpendicular to the cross-section and generated an interconnected conductive network.

Fig. 4. (a) TGA curves of the graphene-based scaffolds with varying graphene contents. (b) Exterior surface view of the annealed graphene scaffold and (c) corresponding magnified image. The graphene sheets generate an interconnected conductive network, which is distributed perpendicular to the radial direction. (d) Compressive strength and (e) compressive modulus of the printed graphene scaffolds with different ribbon diameters and graphene contents. (f) Typical stress-strain curves of the printed scaffolds with a ribbon diameter of 0.5 mm.

Fig. 5. (a) I-V characteristics of the 25 wt% graphene-based scaffold with a ribbon diameter of 0.5 mm in transvers and longitudinal directions. The applied voltage ranged from -1.0 to +1.0 V in 10 mV/s. The inset shows the different arrays of transverse and longitudinal to determine the electrical connection. Relative resistance change of the prepared 25 wt% scaffolds under compressing in (b) transverse and (c) longitudinal, in which the compressive stress is range from 0 to 15 MPa. (d) Relative resistance change of the sample as a function of compressive cycles for a compressive stress of 10 MPa.

Fig. 6. Relative resistance change (response) of the graphene scaffold assembled by different orthogonal layers exposed to relative humidity of 60 % from the vacuum chamber: (a) 25 wt% and (b) 66.7 wt%. Relative resistance change (response) of 25 wt% printed scaffolds and annealed scaffolds with three orthogonal layers under (c) 100 ppm H2O exposure and (d) 100 ppm NO2 exposure.

Fig. 7. (a) Relative resistance change (response) of 66.7 wt% scaffold with three orthogonal layers after thermal treatment under increasing NO2 exposure. (b) Schematic for mechanism of NO2 sensing of 3D graphene-based scaffold. The inset shows the periodic structure of graphene-based scaffold.

Table 1 Comparison of the gas-sensing performance of graphene-based gas sensors.

Materials	Target Gases	Sensitivity	LOD	Refs.
Graphene (CVD grown)	SO₂	5.88 × 10^-6 ppt^-1	67.4 ppt	[49]
Porous Graphene	NO₂	0.0432 ppm^-1	15 ppb	[50]
Graphene/Pd	H₂	1.532 × 10^-2 ppm^-1	20 ppm	[51]
Graphene/SnO₂	H₂S	2.1 ppm^-1	6 ppm	[52]
Graphene/Cu₂O	NO₂	0.35 ppm^-1	64 ppb	[47]
Graphene/PPy	NH₃	0.075 ppm^-1	5 ppm	[53]
Graphene scaffold	NO₂	1.46 × 10^-3 ppm^-1	3 ppm	This work

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