Zhong Ziyun, Fu Hao, Wang Siyuan, Duan Yingnan, Wang Qinglun, Yan Chun-Hua, Du Yaping
Tianjin Key Lab for Rare Earth Materials and Applications, Center for Rare Earth and Inorganic Functional Materials, Smart Sensing Interdisciplinary Science Center, Haihe Laboratory of Sustainable Chemical Transformations, School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin, 300350, P. R. China.
College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Nankai University, Tianjin, 300071, P. R. China.
Small. 2023 Aug;19(33):e2301392. doi: 10.1002/smll.202301392. Epub 2023 Apr 22.
As an important lanthanide (Ln)-based functional materials, the Ln chalcogenides possess unique properties and various applications. However, the controllable synthesis of Ln chalcogenide nanocrystals still faces great challenges because of the rather poor affinity between Ln and chalcogenide ions (S, Se, Te) as well as strong preference of combination with existed oxygen. Herein, a facile but general heterogeneous nucleation synthetic strategy is established toward a series of colloidal ternary Cu Ln sulfides nanocrystals using the Ln dithiocarbamates and CuI as precursors. To extend this synthetic protocol, similar strategy is used to prepare six kinds of high quality CuLnS nanocrystals, while the bulk ones are only obtained by the traditional solid-state reaction at rigorous condition. Importantly, high-entropy nanocrystals CuLnS and CuEu Ln S which contain six Ln elements (Nd, Sm, Gd, Tb, Dy) are readily obtained by the co-decomposed process attributed to their similar diffusion speed. As a proof-of-concept application, CuEu S nanocrystals showed efficient photocatalytic hydrogen production properties.
作为一类重要的基于镧系元素（Ln）的功能材料，镧系硫属化物具有独特的性能和广泛的应用。然而，由于镧系元素与硫属化物离子（S、Se、Te）之间的亲和力较差，以及它们对与已存在的氧结合的强烈偏好，镧系硫属化物纳米晶体的可控合成仍然面临巨大挑战。在此，我们以二硫代氨基甲酸盐镧系化合物和碘化亚铜为前驱体，建立了一种简便通用的非均相成核合成策略，用于制备一系列胶体三元铜镧硫化物纳米晶体。为了扩展这种合成方法，我们采用类似的策略制备了六种高质量的铜镧硫纳米晶体，而块体材料只能通过传统的固态反应在苛刻条件下获得。重要的是，通过共分解过程，由于其相似的扩散速度，很容易获得包含六种镧系元素（Nd、Sm、Gd、Tb、Dy）的高熵纳米晶体CuLnS和CuEuLnS。作为概念验证应用，CuEuS纳米晶体表现出高效的光催化产氢性能。
