Milligan Griffin M, Singsen Sirisak, To Sydney, Aoki Toshihiro, Zhi Brian Y, Collins Cameron J, Ogura Kaleolani S, Lee Elizabeth M Y, Arguilla Maxx Q
Department of Chemistry, University of California Irvine, Irvine, CA, 92697, USA.
Department of Materials Science and Engineering, University of California Irvine, Irvine, CA, 92697, USA.
Adv Mater. 2025 Jul;37(28):e2502213. doi: 10.1002/adma.202502213. Epub 2025 May 2.
The discovery and synthesis of atomically precise low-dimensional inorganic materials have led to numerous unusual structural motifs and nascent physical properties. However, access to low-dimensional van der Waals (vdW)-bound analogs of bulk crystals is often limited by chemical considerations arising from structural factors like atomic radii, bonding or coordination, and electronegativity. Using single-walled carbon nanotubes (SWCNTs) as confinement templates, we demonstrate the synthesis of a short-wave infrared-absorbing quasi-1D (q-1D) chain polymorph of SbTe ([SbTe]) that is structurally and electronically distinct from its 2D counterpart. It is found that the q-1D chain polymorph has both three- and five-coordinate Sb atoms covalently bonded to Te and is thermodynamically stabilized by the electrostatic interaction between the encapsulated chain and the model SWCNT. The complementary experimental and computational results demonstrate the synthetic advantage of vdW nanotube confinement in the discovery of low-dimensional polytypes with drastically altered physical properties and potential applications in energy conversion processes.
原子精确的低维无机材料的发现与合成已带来众多不同寻常的结构基序和新出现的物理性质。然而，获得块状晶体的低维范德华（vdW）键合类似物往往受到诸如原子半径、键合或配位以及电负性等结构因素所产生的化学因素限制。我们以单壁碳纳米管（SWCNT）作为限域模板，展示了一种SbTe的短波红外吸收准一维（q-1D）链多晶型物（[SbTe]）的合成，其在结构和电子性质上与其二维对应物不同。研究发现，q-1D链多晶型物具有与Te共价键合的三配位和五配位Sb原子，并且通过被封装链与模型SWCNT之间的静电相互作用在热力学上得以稳定。互补的实验和计算结果证明了vdW纳米管限域在发现具有大幅改变的物理性质的低维多型体以及在能量转换过程中的潜在应用方面的合成优势。
