SGER: Chemical Frustration and the Design of New Hydrogen Storage Materials

储氢的挑战，以及大规模制氢中同样引人注目的问题，阻碍了这种引人注目的能源载体的广泛商业化。现有的存储技术不仅不能满足容量、成本和可逆性方面的要求，而且从已知系统到完全实用的机载存储系统也没有明确的优化路径。在这项研究中，PI将进行为期两年的理论材料设计研究，使用强大的第一性原理方法，并利用氢-基质相互作用中的几个新概念，目标是发现一个或多个新的氢吸附剂家族。它将利用电子挫折的概念，其中内在的或几何诱导的电子缺陷产生新的多中心电子配置，不寻常的电荷转移状态，或极大的局部领域，增强氢结合。在为期两年的研究工作中，这些计算将通过凸壳相稳定性和动力学障碍的研究，确定进一步研究和优化氢容量和可合成性的目标。硼-氢分子具有令人惊讶的丰富和高度非常规的化学性质，这是由于在s-p壳层中只有三个价电子而产生的固有电子挫折。PI将研究几种具有多中心氢键结合内置位点的新型硼基框架，并将使用掺杂来调节框架的总体电荷状态，以获得最大框架稳定性，最佳氢键结合能量学，动力学和相对相稳定性热力学约束内的可逆性。电子阻挫也将在几何学上被诱导，通过拓扑和地形约束来防止具有众所周知的原子成分的系统达到其传统的基态结构。拓扑障碍和地形的限制将有助于诱导新的电子状态的前景，以展示新的模式结合到封闭的壳层物种，如分子氢。氢储存挑战的解决方案将对整个社会产生变革性影响，从环境问题到能源安全，国家安全和交通运输。拟议的研究将教育一个跨学科的计算材料研究的研究生。电子结构理论的学生培训依赖于凝聚态理论的坚实基础，但也需要化学和材料科学的重要概念，并自然地培养学生对大规模并行计算机上的大规模高性能计算的熟悉程度。这种以应用为导向的项目的综合多学科培训将拓宽学生的知识和经验，从而为跨学科的职业生涯做好准备。学生将有机会在研究场所和公众中交流他们的成果。

CBET-0844720ZhangThe hydrogen storage challenge, and equally compelling issues in large-scale hydrogen generation, impedes the broad commercialization of this otherwise compelling energy carrier. Not only do existing storage technologies fail to meet requirements in capacity, cost and reversibility, but there are no clear optimization paths from known systems to fully practical on-board storage systems. In this research, the PI will perform an intense two-year theoretical materials design search, using powerful first-principles methods and exploiting several new concepts in hydrogen-substrate interaction, with the goal of discovering one or more new families of hydrogen sorbents. It will exploit the concept of electronic frustration, wherein intrinsic or geometrically-induced electron deficiency generates novel multi-center electronic configurations, unusual charge-transfer states, or anomalously large local fields that enhance hydrogen binding. Over the course of the two-year research effort, these calculations will identify targets for further investigation and optimization of hydrogen capacity and synthesizability, through studies of convex-hull phase stability and kinetic barriers. Boron-hydrogen molecules have a surprisingly rich and highly unconventional chemistry arising from an intrinsic electronic frustration associated with having just three valence electrons in the s-p shell. The PI will investigate several novel boron-based frameworks with build-in sites for multicenter hydrogen binding and will use doping to modulate the overall charge state of the framework to attain maximal framework stability, optimal hydrogen binding energetics, kinetics and reversibility within thermodynamic constraints on relative phase stability. Electronic frustration will also be induced geometrically, by means of topological and topographical constraints that prevent systems with well-known atomic constituents from attaining their traditional ground state structures. Topological barriers and topographical constraints will help induce novel electronic states with prospects to demonstrate new modes of binding to close-shell species such as molecular hydrogen. A solution to the hydrogen storage challenge would have a transformative impact throughout society, from environment issues to energy security, national security and transportation. The proposed research will educate one graduate student in interdisciplinary computational materials research. Student training in electronic structure theory relies upon a solid grounding in condensed matter theory, yet also requires important concepts from chemistry and materials science and naturally develops in students a strong familiarity with large-scale high-performance computation on massively parallel computers. This integrated multidisciplinary training on an application-oriented project will broaden the student's knowledge and experience and thereby prepare them for careers that span disciplines. Students will have opportunity to communicate their results both at research venues and to the general public.