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卤化镍氨合物对氨的轻松吸收与释放

Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

作者信息

Breternitz Joachim, Vilk Yury E, Giraud Elsa, Reardon Hazel, Hoang Tuan K A, Godula-Jopek Agata, Gregory Duncan H

机构信息

WestCHEM, School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK.

Department of Chemistry, Ludwig-Maximilians Universität München, Butenandtstraße 5-13, 81377, Munich, Germany.

出版信息

ChemSusChem. 2016 Jun 8;9(11):1312-21. doi: 10.1002/cssc.201600140. Epub 2016 May 3.

Abstract

Although major difficulties are experienced for hydrogen- storage materials to meet performance requirements for mobile applications, alternative fuel cell feedstocks such as ammonia can be stored in the solid state safely at high capacity. We herein describe the NiX2 -NH3 (X=Cl, Br, I) systems and demonstrate their exceptional suitability for NH3 storage (up to 43 wt % NH3 with desorption that begins at 400 K). The structural effects that result from the uptake of NH3 were studied by powder X-ray diffraction (PXD), FTIR spectroscopy and SEM. NH3 release at elevated temperatures was followed by in situ PXD. The cycling capabilities and air stability of the systems were also explored. NH3 is released from the hexaammines in a three-step process to yield the diammine, monoammine and NiX2 dihalides respectively and (re)ammoniation occurs readily at room temperature. The hexaammines do not react with air after several hours of exposure.

摘要

尽管储氢材料在满足移动应用的性能要求方面面临重大困难,但诸如氨之类的替代燃料电池原料可以高容量安全地以固态形式储存。我们在此描述了NiX₂-NH₃(X = Cl、Br、I)体系,并证明了它们在氨储存方面具有卓越的适用性(氨储存量高达43 wt%,脱附起始温度为400 K)。通过粉末X射线衍射(PXD)、傅里叶变换红外光谱(FTIR)和扫描电子显微镜(SEM)研究了氨吸收所导致的结构效应。通过原位PXD跟踪高温下氨的释放情况。还探究了该体系的循环性能和空气稳定性。氨从六氨合物中以三步过程释放,分别生成二氨合物、单氨合物和NiX₂二卤化物,并且在室温下很容易发生(再)氨化反应。六氨合物在暴露于空气中数小时后不发生反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fba7/5084821/60d649ceac5c/CSSC-9-1312-g001.jpg

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