Promotion of H2O2 decomposition activity over β-MnO2 nanorod catalysts

doi:10.1016/j.colsurfa.2007.04.022

Colloids and Surfaces A: Physicochemical and Engineering Aspects

Volume 304, Issues 1–3, 1 September 2007, Pages 60-66

https://doi.org/10.1016/j.colsurfa.2007.04.022 Get rights and content

Abstract

The relationship among the β-MnO₂ nanorod preparation conditions, morphology and catalytic performance on H₂O₂ decomposition has been investigated in the work. β-MnO₂ nanorod catalysts were prepared by heating different γ-MnOOH nanorod precursors at 250–450 °C. They were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen adsorption. The experimental results indicate that γ-MnOOH nanorod precursors prepared at higher hydrothermal temperature make final β-MnO₂ nanorods uniform. The catalytic performance on H₂O₂ decomposition shows that β-MnO₂ nanorod catalysts have excellent catalytic activity on the decomposition of H₂O₂, which has not been reported to our knowledge. β-MnO₂ nanorods which were prepared by calcining γ-MnOOH precursors at 250 °C have higher catalytic activity than those at higher calcination temperatures. The reaction of H₂O₂ decomposition over β-MnO₂ nanorod catalysts was found to follow first-order kinetics.

Introduction

Decomposition of H₂O₂ has been a subject of long-standing interest. It has been used as a source of power for rocket [1], [2], robot [3], [4] and a source of the hydroxyl radical ( radical dot OH) as oxidant for the removal of toxic pollutants from water [5], [6], [7], [8], [9], [10]. The catalytic decomposition of H₂O₂ has been performed both in homogeneous [11], [12], [13] and heterogeneous [13], [14], [15], [16], [17], [18], [19] media. Homogeneous catalysts are very efficient, but their recovery from the treated effluents is difficult and brings about additional costs. This problem can be overcome by using heterogeneous catalysts.

Transition metal oxides have been used as catalysts for decomposition of H₂O₂ [14], [15], [16], [17], [18], [19], [20] because of their significant activities. It was reported that pure and mixed manganese oxides have good activity for decomposition of H₂O₂ [16], [17], [18], [19], [20], [21], [22].

Nanomaterials have received great attention because of their unique properties caused by very small physical dimensions. The high volume fraction of atoms located both on the surface and interfaces results in an increasing surface energy, which may make the catalytic activity improved greatly. The electroanalytical methods for detecting H₂O₂ using MnO₂ nanoparticles [23] have been investigated and it was found that the activity of the MnO₂ nanoparticles was much higher than that of the MnO₂ powders. The carbon paste electrode modified with the nanostructured cryptomelane-type manganese oxides exhibits significant electrocatalytic activity [24].

Recently, nanoscaled one-dimensional structures attract much attention due to their low dimensionalities. Such 1D nanostructures have potential applications in wide-ranging sectors including catalysis, sensing, electronics, and photonics, with performances that are anticipated to be superior to those of their bulk counterparts [25]. Kawi et al. [26] reported a high catalytic activity of nanorods of Zn–Al oxides for the reduction of nitrogen oxides NOx in the presence of excess oxygen. Li et al. [27] reported that the CeO₂ nanorods had higher catalytic activity for CO oxidation than CeO₂ nanoparticles.

In this manuscript, we report a different manganese oxide catalyst—β-MnO₂ nanorods, which shows excellent catalytic activity on the decomposition of H₂O₂. To our knowledge, decomposition of H₂O₂ over the β-MnO₂ nanorods has not been reported. The β-MnO₂ nanorods were prepared by calcining γ-MnOOH nanorods, which were prepared through hydrothermal method. The effects of hydrothermal and calcination temperatures on catalyst activity for decomposition of H₂O₂ have been investigated. The kinetics of H₂O₂ decomposition over different β-MnO₂ nanorod catalysts was studied as well. The relationship among the β-MnO₂ nanorod preparation conditions, morphology and catalytic performance on H₂O₂ decomposition has been investigated in the work.

Section snippets

Reagents

All reagents were analytical grade and used without further purification. Distilled water was used in the preparation. The initial concentration of H₂O₂ (30%, w/w) was determined by titration with a 0.1 M solution of KMnO₄. The commercial β-MnO₂ was obtained from the Shanghai Chemicals Company.

Catalysts

γ-MnOOH nanorods were prepared through a hydrothermal method, which was reported in our previous paper [28], [29]. Four grams of KMnO₄, 4 mL of CH₃CH₂OH and 400 mL of distilled water were put in a stainless

Structures of catalysts

Fig. 2A–C shows XRD patterns of the precursors for preparing the β-MnO₂ catalysts including MnOOH{100}, MnOOH{150} and MnOOH{190}, which were prepared at 100, 150 and 190 °C for 24 h by the hydrothermal method. All the samples can be indexed to monoclinic γ-MnOOH (JCPDS 41-1379). When the hydrothermal temperature was increased to 200 °C, the XRD pattern (Fig. 2D) of the sample MnOOH{200} has Mn₃O₄ phase as impurity besides γ-MnOOH.

Fig. 3A–C shows XRD patterns of the catalysts including MnO₂

Conclusions

The work has revealed the relationships among the β-MnO₂ nanorod preparation conditions, morphology and catalytic performance on H₂O₂ decomposition. β-MnO₂ nanorods with diameters of 50–150 nm and lengths of 5–10 μm were prepared by a hydrothermal method. The β-MnO₂ nanorod catalysts converted from the MnOOH prepared at higher hydrothermal temperature have more uniform morphology. All β-MnO₂ nanorod catalysts have higher activity on H₂O₂ decomposition than commercial β-MnO₂ and known manganese

Acknowledgements

The project was financially supported by the National Natural Science Foundation of China (NSFC 20576024), Anhui Provincial Natural Science Foundation (070414165) and the Excellent Young Teachers Program of the Ministry of Education of China.

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Promotion of H2O2 decomposition activity over β-MnO2 nanorod catalysts

Abstract

Introduction

Section snippets

Reagents

Catalysts

Structures of catalysts

Conclusions

Acknowledgements

Appl. Catal. A

Compos. Struct.

Sensor. Actuators A

Water Res.

Aquaculture Eng.

Chemosphere

Chemosphere

Colloid Surf. A

Mater. Lett.

Mater. Lett.

J. Catal.

Appl. Catal. A

Thermochim. Acta

Appl. Catal. A

J. Colloid Interf. Sci.

Promotion of H₂O₂ decomposition activity over β-MnO₂ nanorod catalysts