Hydrogenation as an instrument for modifying structures and properties of certain classes ofintermetallics and inorganic metal-rich compounds

氢化作为改变某些金属间化合物和富含无机金属化合物的结构和性能的工具

• 批准号: 448675425
• 负责人: Professor Dr. Holger Kohlmann
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/448675425?language=en
• 关键词: Hydrogenation; instrument; modifying; structures; properties

The project has the fundamental aim of further developing hydrogenation as an instrument for modifying structures and properties of intermetallics and inorganic metal-rich compounds, to investigate the fundamental principles of hydrogen insertion, and to establish structure-property relationships for such metal hydrides and chemical ways of their manipulation. Within the scope of the project we aim to synthesize new metal hydrides based on certain structural classes of intermetallics, as well as new intermetallics of said classes, to characterize their crystal structures, to establish structure-property relationships for the compounds in question, to characterize bonding in complex and intermetallic hydrides and the electronic state of hydrogen, to develop a working predictive approach to the reactivity of intermetallics towards hydrogen, to investigate the factors that favor hydrogenation of intermetallics (calculation of thermodynamics) and their possible connection to structure and bonding, and to formulate guidelines for potential applications of complex intermetallic-based systems for hydrogen storage, embrittlement, and catalysis. We are particularly interested in the bond systems based on d- and f-metals, since these offer a lot of possibilities for different kinds of element combinations and variations in bonding patterns, and are generally less well understood. We will study the influence of hydrogen insertion on structures and properties, focusing on several classes of compounds based on specific structure types and element ratios. These classes include binary intermetallics of the MNi3, MPd3, MPt3 and MLn3 types (M = main-group metal, Ln = lanthanide), of the MNi2 and MPd2 types (M = s, p, d, or f metal), and certain compounds of the MTX- (“111”) and ZrSiCuAs- (“1111”) types (M = alkaline earth or lanthanide; T = transition metal or Mg; X = Si, Ge, Sn). Characterization of the compounds will be based on X-ray single-crystal investigations, X-ray and neutron powder diffraction (including in situ studies), electron microscopy, microprobe analysis, thermal analysis, and galvanomagnetic measurements. Electronic structures will be studied based on DFT calculations and bonding analysis will be performed both in direct and orbital space. Joint research of the groups from Lomonosov Moscow State and Leipzig Univ. will make use of the complementarity of both sides regarding expertise and infrastructure, and will also offer an opportunity of regular researcher exchange in order to disseminate specific knowledge and expertise between both groups. As a result, we expect to gain new systematic knowledge about hydrogenation of intermetallics, the principles governing stability of the structures of hydrides, the structure-property relationships in complex inorganic hydrides and chemical ways of tuning said properties; we also aim to develop recommendations on the potential use of the compounds in question as the basis for new functional materials.

该项目的基本目标是进一步发展氢化作为一种改变金属间化合物和无机富金属化合物结构和性质的工具，研究氢插入的基本原理，并建立这类金属氢化物的结构-性质关系和化学操纵方法。在项目范围内，我们的目标是根据金属间化合物的某些结构类别合成新的金属氢化物，以及上述类别的新金属间化合物，表征它们的晶体结构，建立有关化合物的结构-性质关系，表征络合物和金属间氢化物中的键和氢的电子状态，开发金属间化合物对氢的反应性的实用预测方法，调查有利于金属间化合物氢化的因素(热力学计算)及其与结构和键的可能联系，并为复杂的金属间化合物体系在储氢、脆化和催化方面的潜在应用制定指南。我们对基于d-和f-金属的键系统特别感兴趣，因为这些系统为不同类型的元素组合和键模式的变化提供了许多可能性，而且通常不太被理解。我们将研究氢插入对结构和性能的影响，重点是几类基于特定结构类型和元素比例的化合物。这些类别包括MNi3、MPd3、MPt3和MLn3型(M=主族金属，Ln=稀土元素)的二元金属间化合物，MNi2和MPd2型(M=S、p、d或f金属)的二元金属间化合物，以及某些MTX-(111“)和ZrSiCuAs-(”1111“)型的化合物(M=碱土或稀土；T=过渡金属或镁；X=硅、锗、锡)。化合物的表征将基于X射线单晶研究、X射线和中子粉末衍射(包括现场研究)、电子显微镜、微探针分析、热分析和电磁场测量。电子结构的研究将基于密度泛函理论计算，成键分析将在直接空间和轨道空间进行。来自莫斯科洛蒙诺索夫大学和莱比锡大学的小组的联合研究。将利用双方在专门知识和基础设施方面的互补性，并将提供定期研究人员交流的机会，以便在两个小组之间传播具体知识和专门知识。因此，我们期望获得关于金属间化合物氢化的新的系统知识，控制氢化物结构稳定性的原理，复杂无机氢化物的结构-性质关系以及调整这些性质的化学方法；我们的目标也是开发有关化合物作为新功能材料基础的潜在用途的建议。