Probing the Critical Metal Node and Ligand Concentrations for MOF Nucleation on a Substrate

IF 9.6 1区化学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

ACS Materials Letters Pub Date : 2025-03-24 DOI:10.1021/acsmaterialslett.5c0036110.1021/acsmaterialslett.5c00361

Sijie Xie, Xiaoyu Tan*, Xuan Zhang* and Jan Fransaer*,

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Abstract

Determining the critical concentrations of metal nodes and ligands required for metal–organic framework (MOF) nucleation on a substrate remains a fundamental challenge. Here we propose an electrochemical method to address this issue by integrating in situ surface mass change analysis with in situ surface pH measurement during a cathodic deposition process. Taking UTSA-280 ([Ca(C₄O₄)]_n) as an example, the critical metal ion (c(Ca²⁺)) and deprotonated ligand (c(C₄O₄^2–)) concentrations for UTSA-280 nucleation on a gold substrate are determined. It is found that the values of c(Ca²⁺) × c(C₄O₄^2–) in different electrolytes with varied bulk Ca²⁺ concentrations are similar, which can be seen as an analogue of the solubility product of UTSA-280 considering its chemical formula. Also, a simple yet previously overlooked strategy to shorten the incubation time for MOF nucleation in cathodic deposition is proposed and verified. The presented method can be applied to other MOFs.

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探测基体上MOF成核的关键金属节点和配体浓度

确定金属-有机骨架（MOF）在底物上成核所需的金属节点和配体的临界浓度仍然是一个根本性的挑战。在这里，我们提出了一种电化学方法，通过在阴极沉积过程中结合原位表面质量变化分析和原位表面pH测量来解决这个问题。以UTSA-280 （[Ca(C4O4)]n）为例，测定了UTSA-280在金底物上成核的临界金属离子（c(Ca2+)）和去质子配体（c(C4O42 -)）浓度。发现c（Ca2+） × c（C4O42 -）在不同体积Ca2+浓度的电解质中的值相似，考虑其化学式，这可以看作是UTSA-280溶解度产物的类似物。此外，提出并验证了一种简单但以前被忽视的策略，以缩短阴极沉积中MOF成核的孵育时间。该方法可应用于其他mof。

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

ACS Materials Letters MATERIALS SCIENCE, MULTIDISCIPLINARY-

CiteScore

14.60

自引率

3.50%

发文量

261

期刊介绍： ACS Materials Letters is a journal that publishes high-quality and urgent papers at the forefront of fundamental and applied research in the field of materials science. It aims to bridge the gap between materials and other disciplines such as chemistry, engineering, and biology. The journal encourages multidisciplinary and innovative research that addresses global challenges. Papers submitted to ACS Materials Letters should clearly demonstrate the need for rapid disclosure of key results. The journal is interested in various areas including the design, synthesis, characterization, and evaluation of emerging materials, understanding the relationships between structure, property, and performance, as well as developing materials for applications in energy, environment, biomedical, electronics, and catalysis. The journal has a 2-year impact factor of 11.4 and is dedicated to publishing transformative materials research with fast processing times. The editors and staff of ACS Materials Letters actively participate in major scientific conferences and engage closely with readers and authors. The journal also maintains an active presence on social media to provide authors with greater visibility.