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尺寸选择合成铂钌纳米催化剂:反应与尺寸控制机制。

Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism.

作者信息

Bock Christina, Paquet Chantal, Couillard Martin, Botton Gianluigi A, MacDougall Barry R

机构信息

National Research Council of Canada, 1200 Montreal Road, Ottawa, Ontario, Canada, K1A 0R6.

出版信息

J Am Chem Soc. 2004 Jun 30;126(25):8028-37. doi: 10.1021/ja0495819.

Abstract

A rapid synthesis method for the preparation of PtRu colloids and their subsequent deposition on high surface area carbons is presented. The reaction mechanism is shown to involve the oxidation of the solvent, ethylene glycol, to mainly glycolic acid or, depending on the pH, its anion, glycolate, while the Pt(+IV) and Ru(+III) precursor salts are reduced. Glycolate acts as a stabilizer for the PtRu colloids and the glycolate concentration, and hence the size of the resulting noble metal colloids is controlled via the pH of the synthesis solution. Carbon-supported PtRu catalysts of controlled size can be prepared within the range of 0.7-4 nm. Slow scan X-ray diffraction and high-resolution transmission electron microscopy show the PtRu catalysts to be crystalline. The Ru is partly dissolved in the face-centered cubic Pt lattice, but the catalysts also consist of a separate, hexagonal Ru phase. The PtRu catalysts appear to be of the same composition independent of the catalyst size in the range of 1.2-4 nm. Particular PtRu catalysts prepared in this work display enhanced activities for the CH(3)OH electro-oxidation reaction when compared to two commercial catalysts.

摘要

本文介绍了一种快速合成方法,用于制备铂钌胶体及其随后在高比表面积碳上的沉积。结果表明,反应机理涉及溶剂乙二醇氧化生成主要产物乙醇酸,或者根据pH值生成其阴离子乙醇酸盐,同时铂(IV)和钌(III)前驱体盐被还原。乙醇酸盐作为铂钌胶体的稳定剂,通过合成溶液的pH值控制乙醇酸盐浓度,从而控制所得贵金属胶体的尺寸。在0.7-4nm范围内可以制备尺寸可控的碳载铂钌催化剂。慢扫描X射线衍射和高分辨率透射电子显微镜表明铂钌催化剂是晶体。钌部分溶解在面心立方铂晶格中,但催化剂也由单独的六方钌相组成。在1.2-4nm范围内,铂钌催化剂的组成似乎与催化剂尺寸无关。与两种商业催化剂相比,本文制备的特定铂钌催化剂对甲醇电氧化反应表现出更高的活性。

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