Mesoporous TiO2 as the Anode Catalyst Support for Solid Polymer Electrolyte Water Electrolysis†

doi:10.7503/cjcu20150442

Abstract

Abstract:

TiO₂ support was prepared through evaporation-induced self-assembly(EISA) by using butyl titanate as starting material. Three TiO₂ samples were calcined at different temperatures and then IrO₂ was loaded on them with a mass ratio of IrO₂/TiO₂ of 2/3 by a modified Adams fusion method. The samples were characterized by X-ray diffraction(XRD), specific surface area measurement, thermogravimetric and differential scanning calorimetry analysis(TGA-DSC), transmission electron microscopy(TEM) and electrochemical testing. The electrochemical activity of the catalysts was investigated in a single cell proton exchange membrane(PEM) electrolyzer consisting of a Pt/C cathode and a Nafion117 membrane. The results suggested that as the calcination temperature increased, the mesoporous structure of TiO₂ was destroyed, the pore size increased and the pore volume reduced, and the phase of TiO₂ transferred from anatase to rutile structure. Utilization of the TiO₂ support resulted in a reduction in the size of the IrO₂ crystallites and improved the distribution of catalyst. It was found that the lower the specific surface area of the support was, the higher the electrochemical activity of the catalyst was. This is most likely due to the formation of a conductive IrO₂ film on the surface of non-conductive supports with 40%(mass fraction) loading of IrO₂. The IrO₂, 40%IrO₂/TiO₂-2 and 40%IrO₂/TiO₂-3 catalysts showed a polarization potential of 2.024, 2.426 and 2.064 V, respectively, under a current density of 1.0 A/cm². These results suggest that the surface structure of the support has a great influence on the catalytic activity of IrO₂.

Key words: Hydrogen, Water electrolysis, Electrocatalyst support, IrO2, Proton exchange membrane electrolyzer

CLC Number:

O643

TrendMD:

CHEN Gang, MI Cangen, LÜ Hong, HAO Chuanpu, HUANG Yu, SONG Yukun. Mesoporous TiO₂ as the Anode Catalyst Support for Solid Polymer Electrolyte Water Electrolysis^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 126.

Figures/Tables 12

Fig.1 Structure of the SPE electrolyzer

Fig.2 TGA(a) and DSC(b) curves of TiO2 before calcination

Table 1 BET parameters of calcined TiO2 samples

Sample	Calcination temperature/℃	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	Pore diameter/nm
TiO₂-1	300	172	0.040	5.2
TiO₂-2	350	126	0.026	6.8
TiO₂-3	450	36	0.004	13.4

Fig.3 XRD patterns of TiO2 samples calcined at different temperatures

Fig.4 XRD patterns of pure IrO2(a) and 40%IrO2/TiO2-1(b), 40%IrO2/TiO2-2(c) and 40%IrO2/TiO2-3(d) catalysts

Fig.5 TEM images of TiO2 supports calcined at different temperatures^ (A1), (A2) TiO2-1; (B1), (B2) TiO2-2; (C1), (C2) TiO2-3.

Fig.6 TEM images of pure IrO2 and 40% IrO2/TiO2 catalysts^(A1, A2) IrO2; (B1, B2) 40%IrO2/TiO2-1; (C1, C2) 40%IrO2/TiO2-2; (D1, D2) 40%IrO2/TiO2-3.

Fig.7 Particles size distribution of pure IrO2 catalyst(A) and IrO2 particles size distribution of 40%IrO2/TiO2-2(B)

Fig.8 CV curves of catalyst samples in N2-satura-ted 0.5 mol/L H2SO4 solution at room temperature(scan rate: 50 mV/s)^a. IrO2; b. 40%IrO2/TiO2-1; c. 40%IrO2/TiO2-2; d. 40%IrO2/TiO2-3.

Fig.9 Polarization curves of catalysts at 80 ℃ for the single cell PEM electrolyzer^a. Pure-IrO2; b. 40%IrO2/TiO2-2; c. 40%IrO2/TiO2-3.

Fig.10 Nyquist diagram of catalyst samples in the PEM single cell^ a. IrO2 fit result; b. 40%IrO2/TiO2-2 fit result; c. 40%IrO2/TiO2-3 fit result.

Table 2 Impendence parameters obtained from fitting the experimental data to the RΩ(RctCPE) circuit measured at 0.1 A/cm2*

Sample	R_Ω/(Ω·cm²)	CPE/(mF·cm^-2)	R_ct/(Ω·cm²)	n
IrO₂	0.40	143	0.240	0.926
40%IrO₂/TiO₂-2	0.74	102	0.400	0.814
40%IrO₂/TiO₂-3	0.57	117	0.385	0.883

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Mesoporous TiO₂ as the Anode Catalyst Support for Solid Polymer Electrolyte Water Electrolysis^†

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