Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000,Energy & Fuels

当前位置： X-MOL 学术 › Energy Fuels › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000
Energy & Fuels ( IF 5.2 ) Pub Date : 2021-09-20 , DOI: 10.1021/acs.energyfuels.1c02623
Boris V. Kramar ₁ , Brian T. Phelan ₂ , Emily A. Sprague-Klein ₂ , Benjamin T. Diroll ₂ , Sungsik Lee ₃ , Ken-ichi Otake ₁ , Rebecca Palmer ₁ , Michael W. Mara _{1,

3} , Omar K. Farha ₁ , Joseph T. Hupp ₁ , Lin X. Chen _{1,

2}

Affiliation

Solvothermal deposition in metal–organic frameworks (MOFs) can be used to mount single-metal-atom catalytic species at chemically reactive sites on hexa-Zr(IV)–oxy(oxo,hydroxo,aqua) nodes in nanoscale crystallites of the MOF NDC–NU-1000 in a self-limiting fashion. Upon photoexcitation of the 1,3,6,8-tetrakis(p-benzoato)pyrene chromophores of the parent framework, charge transfer may occur between the chromophores and the installed heterometal sites. Extended X-ray absorption fine structure studies revealed the single-atom nature of the installed species. A combination of steady-state and ultrafast optical spectroscopy was used to uncover evidence of a charge-separated (CS) state arising in the metalated samples. The relevant dynamics were characterized with transient photoluminescence and femtosecond transient absorption spectroscopy. We find that a titanium–oxy single-atom site gives rise to the longest lived CS species compared to cobalt and nickel in a similar arrangement. This study provides guidance in designing MOF-based catalytic systems for photocatalysis and solar fuel production.

中文翻译：

单原子金属氧化物位点作为锆基金属-有机骨架 NDC-NU-1000 中电荷分离的陷阱

金属-有机框架 (MOF) 中的溶剂热沉积可用于在 MOF NDC 纳米级微晶的六-Zr(IV)-氧（氧、羟基、水）节点上的化学反应位点安装单金属原子催化物种– NU-1000 以自我限制的方式。在 1,3,6,8-tetrakis( p-苯并)芘发色团，在发色团和安装的异金属位点之间可能发生电荷转移。扩展的 X 射线吸收精细结构研究揭示了已安装物种的单原子性质。稳态和超快光谱的组合用于揭示金属化样品中出现电荷分离 (CS) 状态的证据。相关动力学通过瞬态光致发光和飞秒瞬态吸收光谱进行表征。我们发现，与类似排列的钴和镍相比，钛氧单原子位点产生寿命最长的 CS 物种。该研究为设计用于光催化和太阳能燃料生产的基于 MOF 的催化系统提供了指导。

更新日期：2021-09-20

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11