摘要：Molecular constructs define the elementary units in porous materials for efficient CO_(2)*** design of appro-priate interpore and intermolecular space is crucial to stabilize CO_(2)molecules and maximize the *** 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 *** 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 *** 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 ***-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.

摘要：Developing highly active alloy catalysts that surpass the performance of platinum group metals in the oxygen reduction reaction(ORR)is critical in ***-based single-atom alloy(AuSAA)clusters are gaining recognition as promising alternatives due to their potential for high ***,enhancing its activity of AuSAA clusters remains challenging due to limited insights into its actual active site in alkaline ***,we studied a variety of Au_(54)M_(1) SAA cluster catalysts and revealed the operando formed MO_(x)(OH)_(y) complex acts as the crucial active site for catalyzing the ORR under the basic solution *** observed volcano plot indicates that Au_(54)Co_(1),Au_(54)M_(1),and Au_(54)Ru_(1) clusters can be the optimal Au_(54)M_(1) SAA cluster catalysts for the *** findings offer new insights into the actual active sites of AuSAA cluster catalysts,which will inform rational catalyst design in experimental settings.

摘要：传统工业上,合成氨反应往往在高温高压下进行,造成了大量的能源消耗.因此,有必要发展绿色可持续的新方法,从而在温和条件下实现氨气的高效合成.从原子分子层面上理解合成氨的微观反应过程有利于高效高选择性催化剂的开发.本文系统探究了在金红石TiO_(2)(110)模型体系表面氨气生成的微观反应过程.利用程序升温脱附谱技术,发现了在金红石TiO_(2)(110)表面共吸附氮原子和水分子之后,在升温过程中,氨气可以生成并在400 K左右从五配位Ti^(4+)位(Ti_(5c))上脱附出去,这表明在金红石TiO_(2)(110)表面氨气的确可以在低温下生成.结果表明,桥氧列上的羟基和Ti_(5c)位上的水分子均可以提供氨气生成所需的氢原子.氢原子在金红石TiO_(2)(110)表面的迁移在氨气的生成过程中扮演了重要作用,通过改变水分子的覆盖度,氢原子的迁移方式会随着水分子覆盖度的改变而发生变化.当水分子的覆盖度较低时,氢键网络在金红石TiO_(2)(110)表面上尚未建立,氢原子主要以直接跃迁的方式迁移侄氮原子附近,其对应的扩散能垒约为1 eV:随着水分子覆盖度的逐渐增加,氢键网络在金红石TiO_(2)(110)表面逐步建立起来,此时氢原子更倾向于在氢键网络的辅助下迁移至氮原子附近,其对应的扩散能垒仅为0.2~0.3 eV.此外,吸附在氮原子附近的水分子也有可能直接与氮原子发生反应生成氨气.因此,在金红石TiO_(2)(110)表面,氮原子可能存在三种不同的加氢过程.实验结果不仅有助于深入理解合成氨反应中的加氢过程,同时也对催化剂的设计和优化提供了一种新思路.

摘要：The achievement of electrical spin control is highly *** promising strategy involves electrically mod-ulating the Rashba spin orbital coupling effect in materials.A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors,which is crucial for preserving spin coherence and enhancing integration ***,two-dimensional(2D)Rashba semiconductors with large Rashba constants and significant electric field responses are highly ***,by employing first-principles calculations,we design a thermodynamically stable 2D Rashba semiconductor,YSbTe_(3),which possesses an indirect band gap of 1.04 eV,a large Rashba constant of 1.54 eV·Åand a strong electric field response of up to 4.80 e·Å^(2).In particular,the Rashba constant dependence on the electric field shows an unusual nonlinear *** the same time,YSbTe_(3)has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier(~0.33 eV per formula).By changing the electric polarization direction,the Rashba spin texture of YSbTe_(3)can be *** out-standing properties make the ferroelectric Rashba semiconductor YSbTe_(3)quite promising for spintronic applications.