Porous Calcium Manganese Oxide: Preparation and Electrocatalytic Activity of Oxygen Reduction Reaction

doi:10.15541/jim20160437

Abstract

Abstract:

Calcium-manganese oxides (Ca-Mn-O) of layer-pervoskite Ca₂MnO₄ was firstly prepared by using calcium alginate fiber as supporter and then investigated as electrocatalysts for oxygen reduction reaction (ORR), compared with post-spinel CaMn₃O₆. The results of XRD, FE-SEM, TEM and BET displayed the as-synthesized layer-pervoskite Ca₂MnO₄ displayed interconnected porous network structure and high special surface area. The catalyst demonstrates significant electrocatalytic activity towards ORR: a high limit current density, near an apparent quasi four electron oxygen reduction, and low yield of peroxide species in alkaline solutions, which suggestes the potential application of Ca₂MnO₄as cheap and abundant ORR catalysts. The catalytic activities of Ca-Mn-O oxides (onset potential, limiting current density and transferred electron number) depend strongly on the surface Mn oxidation state and the crystallographic structures. In addition, high specific surface area and porous network structure increase electrocatalytic activity sites of ORR, high concentration of oxygen vacancies favor process of ORR, appropriate crystallographic structures with open tunnels, facilitating oxygen chemisorption.

Key words: calcium alginate fibre, non-noble metal catalysts, Ca2MnO4 oxygen reduction, fuel cell

CLC Number:

TM912

CAO Zhao-Xia, DING Yan-Min, WANG Zhi-Chao, MAO Xin-Xin, YIN Yan-Hong, YANG Shu-Ting. Porous Calcium Manganese Oxide: Preparation and Electrocatalytic Activity of Oxygen Reduction Reaction[J]. Journal of Inorganic Materials, 2017, 32(5): 535-542.

Figures/Tables 10

Fig. 1 XRD patterns (a), adsorption-desorption isothermal and inset of pore size distribution curves (b) of Ca-Mn-O samples

Fig. 2 SEM images of calcium alginate fibre

Fig. 3 FE-SEM images of CMO-1 (a, b) and CMO-2 (c, d); EDS results of CMO-1 (e, f)

Fig. 4 TEM and HRTEM images of CMO-1(a-c) and CMO-2 (d-f)

Fig. 5 XPS spectra of Ca-Mn-O samples(a) CMO-1; (b) CMO-2

Fig. 6 CV curves of Ca-Mn-O samples in N2-saturated 0.1 mol/L KOH

Fig. 7 LSVs of Ca-Mn-O samples and Pt/C (a), percentage of peroxide and electron transfer number at different potentials (b)

Table 1 Summary of electrochemical results for the Ca-Mn-O series

Material	Crystallographic structures	E_onset/V	E_half/V	n	HO₂/%	I_s/(mA·cm^-2)(0.3 V)
CMO-1	Ca₂MnO₄	0.81	0.66	3.78	12-18	-6.03
CMO-2	CaMn₃O₆	0.86	0.68	3.84	9-15	-4.41
Pt/C	-	0.93	0.86	3.87	5-11	-6.38

Fig. 8 LSVs of Ca-Mn-O samples at various rotation rates

Fig. 9 Chronoamperometric curves of Ca-Mn-O samples and Pt/C

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