吉林大学马琰铭团队报道了镓-氮体系中稳定的氮骨架阴离子。相关研究成果发表在2022年11月17日出版的国际知名学术期刊《美国化学会杂志》。

富氮化合物由于其适应多种氮键合模式的能力及其作为高能量密度材料的可行性，而引起了重大的基础和实际兴趣。

该文中，研究人员使用第一原理结构搜索和使用激光加热金刚石砧座电池的实验制备，来检查压缩Ga–N系统中的广泛化学成分。研究从理论上确定了三种热力学稳定的化学计量─GaN15、GaN10和GaN5─具有令人惊讶的多用途聚合物氮框架拓扑。引人注目的是，结果表明，在GaN10和GaN5中形成聚合氮相所需的合成压力远低于纯固体氮。

最后，研究人员评估了分解化合物所涉及的能量，并验证了它们是高能量密度材料的有前途的候选者。这些发现对设计和合成新的通过p电子元素与氮在适度压力下的反应的化合物，以及极端条件下的氮化学，具有广泛的意义。

附：英文原文

Title: Stabilized Nitrogen Framework Anions in the Ga–N System

Author: Hang Zhai, Rui Xu, Jianhong Dai, Xiaoli Ma, Xiaohui Yu, Quan Li, Yanming Ma

Issue&Volume: November 17, 2022

Abstract: Nitrogen-rich compounds have attracted significant fundamental and practical interest owing to their ability to accommodate diverse nitrogen-bonding patterns and their feasibility as high-energy-density materials. Herein, we examine a wide range of chemical compositions in the compressed Ga–N system using first-principles structural search and experimental preparation using a laser-heated diamond anvil cell. Our investigations have theoretically identified three thermodynamically stable stoichiometries─GaN15, GaN10, and GaN5─with surprisingly versatile polymeric nitrogen framework topologies. Strikingly, our results show that the required synthetic pressures for forming polymeric nitrogen phases in GaN10 and GaN5 are much lower than that for pure solid nitrogen. Finally, we evaluated the energy involved in decomposing the compounds and validated that they are promising candidates for high-energy-density materials. These findings have broad implications for designing and synthesizing novel nitrogen-rich compounds through the reaction between p electron elements and nitrogen at modest pressures and for nitrogen chemistry under extreme conditions.

DOI: 10.1021/jacs.2c09056

Source: https://pubs.acs.org/doi/10.1021/jacs.2c09056