Topochemical Synthesis of Ca3CrN3H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis
Topochemical Synthesis of Ca3CrN3H Involving a Rotational Structural Transformation for Catalytic Ammonia Synthesis
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DOI：
10.1002/anie.202209187
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发表时间：
2022-08-23
影响因子：
16.6
通讯作者：
Kageyama, Hiroshi
中科院分区：
文献类型：
--
作者：
Cao, Yu;Kirsanova, Maria A.;Kageyama, Hiroshi
拓扑化学反应在发现具有新的化学和物理性质的亚稳态化合物方面取得了很大进展。通过这些反应，主体材料的整体晶体结构通常得到保持。在这里，我们报告的拓扑化学合成的六方晶系氮化物氢化物，h-Ca 3CrN 3 H，通过加热正交氮化物，o-Ca 3CrN 3，在氢在673 K下，伴随着旋转结构的转变。氢嵌入修改的Ca-N岩盐样原子堆积在o-Ca 3CrN 3的面共享八面体链在h-Ca 3CrN 3 H，模仿“铰链镶嵌”运动。此外，h-Ca 3CrN 3 H在用作催化剂时表现出稳定的氨合成活性。
Topochemical reactions have led to great progress in the discovery of new metastable compounds with novel chemical and physical properties. With these reactions, the overall crystal structure of the host material is generally maintained. Here we report a topochemical synthesis of a hexagonal nitride hydride, h-Ca3CrN3H, by heating an orthorhombic nitride, o-Ca3CrN3, under hydrogen at 673 K, accompanied by a rotational structural transformation. The hydrogen intercalation modifies the Ca-N rock-salt-like atomic packing in o-Ca3CrN3 to a face-sharing octahedral chain in h-Ca3CrN3H, mimicking a "hinged tessellation" movement. In addition, the h-Ca3CrN3H exhibited stable ammonia synthesis activity when used as a catalyst.