Molecular solid solution of lanthanide-titanium-oxo clusters with enhanced photocatalytic hydrogen evolution

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2023-12-19 DOI:10.1007/s11426-023-1847-x

Rong Chen, Chao-Long Chen, Hui Zhang, Zi-Han Wang, Fu-Li Sun, Ming-Hao Du, Gui-Lin Zhuang, Cheng Wang, La-Sheng Long, Lan-Sun Zheng, Xiang-Jian Kong

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引用次数: 0

Abstract

Molecular solid solutions of metal clusters containing different metal centers with well-defined structures can accurately regulate the HOMO-LUMO gap, but are rarely available. Herein, a series of colorless lanthanide-titanium-oxo clusters Ln₂Ti₄(μ₂-O)₂(μ₃-O)₄(Piv)₁₀(THF)₂ (Ln₂Ti₄, Ln = Eu, Gd, Tb, and Ce, HPiv = pivalic acid) were synthesized by the reaction of pivalic acid with Ln(Ac)₃ and titanium isopropoxide. The light yellow crystal of cluster solid solutions Eu₂Ti_4−xCd_x, containing a mixture of Eu₂Ti₄ and Eu₂Ti₃Cd, was obtained by in situ doping Cd²⁺ and S²⁻. Eu₂Ti_3.92Cd_0.08 displays efficient photocatalytic hydrogen evolution activity without a co-catalyst, which is up to 2.6 times that of Eu₂Ti₄. Femtosecond time-resolved transient absorption spectroscopy and spin-polarized density functional calculations showed that the enhanced photocatalytic performance of Eu₂Ti_4−xCd_x can be attributed to the narrower HOMO-LUMO gap and lower LUMO position than that of Eu₂Ti₄. This studyprovides an in situ doping method to realize the simple preparation of cluster solid solution.

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具有增强光催化氢进化能力的镧钛氧团簇分子固溶体

含有不同金属中心、结构明确的金属簇分子固溶体可以精确调节 HOMO-LUMO 间隙，但这种固溶体很少见。本文通过新戊酸与 Ln(Ac)3 和异丙醇钛反应，合成了一系列无色镧钛氧簇合物 Ln2Ti4(μ2-O)2(μ3-O)4(Piv)10(THF)2 （Ln2Ti4，Ln = Eu、Gd、Tb 和 Ce，HPiv = 新戊酸）。通过原位掺杂 Cd2+ 和 S2-，得到了含有 Eu2Ti4 和 Eu2Ti3Cd 混合物的浅黄色晶体 Eu2Ti4-xCdx 团簇固溶体。Eu2Ti3.92Cd0.08 在不使用辅助催化剂的情况下显示出高效的光催化氢气进化活性，其活性是 Eu2Ti4 的 2.6 倍。飞秒时间分辨瞬态吸收光谱和自旋极化密度泛函计算表明，Eu2Ti4-xCdx 的光催化性能之所以增强，是因为其 HOMO-LUMO 间隙比 Eu2Ti4 窄，LUMO 位置比 Eu2Ti4 低。该研究提供了一种原位掺杂方法，实现了团簇固溶体的简单制备。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.