Breaking New Ground: MBene Route toward Selective Vinyl Double Bond Hydrogenation in Nitroarenes
Breaking New Ground: MBene Route toward Selective Vinyl Double Bond Hydrogenation in Nitroarenes
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DOI：
10.1021/jacs.3c08642
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发表时间：
2023-12-07
影响因子：
15
通讯作者：
Zaikina，Julia V.
中科院分区：
文献类型：
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作者：
Bhaskar，Gourab;Behera，Ranjan K.;Zaikina，Julia V.
掺杂，或一种元素对另一种元素的增量取代，是调整化合物结构及其物理和化学性质的有效方法。在本文中，我们在层状LiNiB化合物家族的成员中用Co取代了高达30%的Ni，稳定了LiNiB的高温多晶型物，而室温多晶型物不形成。通过原位高温粉末衍射研究这种层状硼化物，我们获得了LiNi 0.7Co 0.3B的变形变体，其特征在于[Ni 0.7Co 0.3B]层彼此顶部的完美层间放置─ ─这是以前在其他硼化物中没有看到的结构图案。由于Co掺杂，LiNi 0.7Co 0.3B可以在环境条件下经历几乎完全的局部化学Li脱嵌，从而产生具有式Li 0.04Ni 0.7Co 0.3B的亚稳态硼化物。在厌氧条件下加热Li 0.04 Ni 0.7 Co 0.3 B导致另一种亚稳硼化物Li 0.01 Ni 0.7 Co 0.3 B，其具有CoB型晶体结构，该结构不能通过Ni、Co和B的简单退火获得。没有显着的磁性能的变化后，检测到Co掺杂的温度无关的顺磁体LiNi 0.7Co 0.3B或其锂脱嵌对应物。最后，Li0.01Ni0.7Co0.3B脱颖而出，作为一个特殊的催化剂的选择性氢化的乙烯基C-3C键在3-硝基苯乙烯，即使在存在其他竞争的官能团。这项研究展示了一种创新的方法，通过精心合成亚稳化合物的非均相催化剂设计。
Doping, or incremental substitution of one element for another, is an effective way to tailor a compound’s structure as well as its physical and chemical properties. Herein, we replaced up to 30% of Ni with Co in members of the family of layered LiNiB compounds, stabilizing the high-temperature polymorph of LiNiB while the room-temperature polymorph does not form. By studying this layered boride with in situ high-temperature powder diffraction, we obtained a distorted variant of LiNi0.7Co0.3B featuring a perfect interlayer placement of [Ni0.7Co0.3B] layers on top of each other─a structural motif not seen before in other borides. Because of the Co doping, LiNi0.7Co0.3B can undergo a nearly complete topochemical Li deintercalation under ambient conditions, resulting in a metastable boride with the formula Li0.04Ni0.7Co0.3B. Heating of Li0.04Ni0.7Co0.3B in anaerobic conditions led to yet another metastable boride, Li0.01Ni0.7Co0.3B, with a CoB-type crystal structure that cannot be obtained by simple annealing of Ni, Co, and B. No significant alterations of magnetic properties were detected upon Co-doping in the temperature-independent paramagnet LiNi0.7Co0.3B or its Li-deintercalated counterparts. Finally, Li0.01Ni0.7Co0.3B stands out as an exceptional catalyst for the selective hydrogenation of the vinyl C═C bond in 3-nitrostyrene, even in the presence of other competing functional groups. This research showcases an innovative approach to heterogeneous catalyst design by meticulously synthesizing metastable compounds.