Dynamic Intermolecular Space for Reversible CO_(2)Capture and Release  

分子间动态空隙结构对CO_(2)的可逆捕获与释放

作　　者：Jin Zhou Yanan Wang Xiang Zhu Jin Zhao Hrvoje Petek Shijing Tan Bing Wang 周晋;王亚南;祝翔;赵瑾;Hrvoje Petek;谭世惊;王兵(中国科学技术大学合肥微尺度物质科学国家研究中心和新基石科学实验室,合肥230026;松山湖材料实验室,东莞523808;中国科学院物理研究所,北京100190;合肥国家实验室,合肥230088;美国匹兹堡大学物理与天文系,匹兹堡15260)

机构地区：[1]Hefei National Research Center for Physical Sciences at the Microscale and New Cornerstone Science Laboratory,University of Science and Technology of China,Hefei 230026,China [2]Songshan Lake Materials Laboratory,Dongguan 523808,China [3]Institute of Physics,Chinese Academy of Sciences,Beijing 100190,China [4]Hefei National Laboratory,University of Science and Technology of China,Hefei 230088,China [5]Department of Physics and Astronomy and the IQ Initiative,University of Pittsburgh,Pittsburgh 15260,USA

出　　处：《Chinese Journal of Chemical Physics》2025年第1期8-16,I0001-I0005,I0055,共15页化学物理学报(英文)

基　　金：supported by the Innovation Program for Quantum Science and Technology(2021ZD0303302);the CAS Project for Young Scientists in Basic Research(YSBR-054);the National Natural Science Foundation of China(Nos.22425206,21972129);NSF grant CHE-2303197;the New Cornerstone Science Foundation.

摘　　要：Molecular constructs define the elementary units in porous materials for efficient CO_(2)capture.The design of appro-priate interpore and intermolecular space is crucial to stabilize CO_(2)molecules and maximize the capacity.While the molecular construct usually has a fixed dimension,whether its inter-molecular space could be self-adjustable during CO_(2)capture and release,behaving as a balloon,has captured imagination.Here we report a flexible intermolecular space of the double chain structure of self-assembled 1,4-pheny-lene diisocyanide(PDI)molecules on Ag(110)surface,which dynamically broadens and recovers during the CO_(2)capture and release.The incipient PDI double chains organize along the[001]direction of Ag(110),in which individual PDI molecules stand up in a zigzag order with the interchain width defined by twice the Ag lattice distance along_([110])direction(2α_([110])).When CO_(2)molecules are introduced,they assemble to occupy the interchain spaces,expanding the interchain width to 3α_([110]),4α_([110])and 5α_([110]):Warming up the sample leads to the thermally-driven CO_(2)desorption that recovers the original interchain space.High-resolution scanning tunneling microscopy(STM)jointly with density functional theory(DFT)calculations determine the structural and electronic interactions of CO_(2)molecules with the dynamical PDI structures,providing a molecular-level perspective for the design of a self-adjustable metal-organic construct for reversible gas capture and release.高效的CO_(2)捕获依赖于材料结构的精确设计与调控:自适应的分子结构与孔隙尺寸,有益于增强CO_(2)分子的吸附稳定性并增大其吸附容量.如何实现分子间隙结构在CO_(2)捕获与释放过程中的自适应调节,引起了广泛的兴趣。本文报道了Ag(110)表面1,4-二异腈苯分子自组装双链结构的动态变化。这一动态变化使得分子间空隙结构在CO_(2)捕获与释放过程中能够自适应地拓宽与复原原始1,4-二异腈苯双链沿Ag(110)的[001]方向排列,其中1,4-二异腈苯分子之间形成Zigzag排列,链间宽度为Ag_([110])方向晶格常数的两倍(2α[100])当CO_(2)分子占据链间空间时,链可以向外侧移动,使双链间的宽度扩大到3α_([110]),4α_([110])或5α_([110]):样品升温会导致CO_(2)发生热驱动脱附,并导致双链恢复到2α_([110])宽度.通过高分辨率扫描隧道显微镜表征并结合密度泛函理论计算,确定了CO_(2)分子与1,4-二异腈苯双链结构之间的相互作用与电荷转移,为设计可逆气体捕获与释放的金属有机结构提供了分子水平的见解。

关 键 词：CO_(2)capture SELF-ASSEMBLY Intermolecular interactions Scanning tunneling microscopy 

分 类 号：X701[环境科学与工程—环境工程]