Department of Chemical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda 151 001, India.
Dalton Trans. 2019 Mar 12;48(11):3531-3538. doi: 10.1039/c8dt04639e.
Hydrogen is seen as an increasingly important clean and sustainable energy source going into the future. There are a host of materials being investigated for the storage of hydrogen. In this frontier, we provide an overview of hydride clusters derived from Earth-abundant copper being used for the storage and conversion of hydrides into hydrogen, and the reaction of CO2 with hydride sources to produce the formic acid/formate pairing, which are considered excellent hydrogen carriers. We summarize the main synthesis methods to stabilize high-nuclearity hydride clusters with phosphine, N-heterocyclic carbene, and in particular phosphor-1,1-dithiolate ligands. Unprecedented structures and hydride geometries have been revealed through both X-ray and neutron single crystal analyses. We point to the release of hydrogen in such hydride clusters through solar irradiation, thermolysis and acid treatments. Finally, we show the facile formation of rhombic nanoparticle copper morphologies derived from accurately determined high-nuclearity clusters and suggest that this could provide a mechanism that links molecular structures with bulk microstructures of materials.
氢被视为未来越来越重要的清洁和可持续能源。有许多材料正在被研究用于储氢。在这个前沿领域，我们提供了一个综述，介绍了源自地球丰富的铜的氢化物簇被用于储氢和将氢化物转化为氢，以及氢化物与二氧化碳反应生成甲酸/甲酸盐对，它们被认为是优秀的储氢载体。我们总结了主要的合成方法，用膦、N-杂环卡宾和特别是磷-1,1-二硫代羧酸酯配体稳定高核氢化物簇。通过 X 射线和中子单晶分析揭示了前所未有的结构和氢化物几何形状。我们指出通过太阳能辐射、热解和酸处理在这些氢化物簇中释放氢。最后，我们展示了通过精确确定的高核簇形成的菱形纳米粒子铜形态的容易形成，并表明这可能提供了一种将分子结构与材料的体微结构联系起来的机制。
