Co_(12)C^(-)_(12)--metallo-carbospherenes:a new class of magic clusters for hydrogen storage  

Co^(-)_(12)C_(12)——metallo-carbospherenes:一类新型的具有储氢潜能的幻数团簇

作　　者：Lijun Geng Chaonan Cui Baoqi Yin Hanyu Zhang Yuhan Jia Zhixun Luo 耿丽君;崔超男;殷保祺;张含宇;贾钰涵;骆智训(Beijing National Laboratory for Molecular Sciences(BNLMS),State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;School of Chemical Sciences,University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]Beijing National Laboratory for Molecular Sciences(BNLMS),State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]School of Chemical Sciences,University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science Bulletin》2022年第22期2280-2284,共5页科学通报（英文版）

基　　金：supported by the National Key Research and Development Program of China(2020YFA0714602);the National Natural Science Foundation of China(21802146 and 21722308);National Project Development of Advanced Scientific Instruments Based on Deep Ultraviolet Laser Source(Y31M0112C1);CAS Key Research Project of Frontier Science(QYZDB-SSW-SLH024).

摘　　要：Metal carbides play significant roles in electronics and materials science due to their unique properties,high strength,and high melting points.Also,they are applied in various organometallic synthesis and catalytic reactions,such as in the Fischer-Tropsch process and olefin metathesis[1,2],and they are able to adsorb small gas molecules such as hydrogen showing promising application for the hydrogen storage[3].Hydrogen is known as a sustainable solution for rising energy demands and an environmentally friendly option to replace fossil fuels.Enormous efforts have been made to develop hydrogen storage materials[4],with the aim to facilitate the application of hydrogen energy for achieving the future carbon–neutral goal set by governments.It has been recognized that the removal of the metal-bound terminal ligands and the doping of transition metals(TMs)on carbon substrates can improve the capacity of hydrogen adsorption[5,6].早期研究发现前过渡金属(TM)可形成一类超稳定的M_(8)C_(12)金属碳化物Met-Cars;然而,尚不清楚后过渡金属是否也能形成类似的特殊物种.本文通过研究阴离子团簇Co_(n)-(n=7~33)与乙炔的反应,发现了Co_(12)C_(12)团簇异常的化学惰性,其突出的质谱丰度与其他纯金属簇及其碳化物形成鲜明对比.全局最低能量结构搜索和光电子能谱实验查证了该团簇具有高对称性的球状空心笼结构,且包含规则交替的C_(1)和C_(2)单元.相关实验和理论研究揭示了Ni~-团簇与乙炔的反应也生成稳定的Ni_(12)C_(12),且具有类似的笼状结构.进一步研究深入阐述了这一类新型“金属碳球烯”的稳定性机制和特殊极性键RC-CR的化学本质,并揭示了亚纳米Co_(12)C_(12)笼状团簇的储氢潜能.

关 键 词：金属碳化物 光电子能谱 化学惰性 笼状结构 超稳定 极性键 金属簇 

分 类 号：O641.4[理学—物理化学]