金属有机骨架（MOF）材料，特别是MOF-74，对于许多技术上重要的工艺具有有前途的性能。然而，它们在潮湿条件下的不稳定性严重限制了实际应用。我们表明，这种不稳定性和伴随的减少的CO $_2$吸收能力的MOF-74在潮湿的条件下起源于水的解离反应H $_2$ O $\rightarrow$ OH+H的金属中心。在这种解离之后，OH基团与金属中心配位，解释了MOF的CO $_2$吸收能力的降低。因此，这种还原强烈依赖于M0 F-74对水解离反应的催化活性。我们进一步表明，虽然水分子本身对MOF-74的晶体结构的影响可以忽略不计，但解离反应的OH和H产物显着削弱了MOF框架，并导致观察到的晶体结构破坏。有了这些知识，我们提出了一种抑制这种特殊反应的方法，通过修改MOF-74结构来增加水解离能垒，从而控制系统在潮湿条件下的稳定性。
英文摘要：
Metal organic framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technologically important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying reduction of the CO$_2$ uptake capacity of MOF-74 under humid conditions originate in the water dissociation reaction H$_2$O$\rightarrow$OH+H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOF's CO$_2$ uptake capacity. This reduction thus strongly depends on the catalytic activity of MOF-74 towards the water dissociation reaction. We further show that-while the water molecules themselves only have a negligible effect on the crystal structure of MOF-74-the OH and H products of the dissociation reaction significantly weaken the MOF framework and lead to the observed crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissociation energy barrier and thus control the stability of the system under humid conditions.
Cluster Assisted Water Dissociation Mechanism in MOF-74 and Controlling it Using Helium
我们表明，水的解离反应H $_2$ O $\rightarrow$ OH+H在有限的环境中的MOF-74通道可以精确地控制通过添加惰性气体He。用从头算方法和红外光谱（IR）阐明整个反应过程，我们证明了水分子之间的相互作用对水簇的形成至关重要，其使解离势垒降低高达37%，从而显着影响反应。我们的时间分辨红外测量证实，这些簇的形成可以通过引入He气体来抑制，从而提供对水解离速率的前所未有的控制。由于水解离反应是MOF-74在水存在下结构不稳定的原因，我们对反应机理的发现为设计水稳定的MOF-74版本以及一般理解MOF中与水相关的现象奠定了基础。
Facile and Fast Transformation of Non-Luminescent to Highly Luminescent MOFs: Acetone Sensing for Diabetes Diagnosis and Lead Capture from Polluted Water
Density Functional Theory Meta-GGA+U Study of Water Incorporation in the Metal Organic Framework Material Cu-BTC
利用密度泛函理论在meta-GGA +U水平上研究了金属有机骨架材料Cu-BTC的吸水性，最高可达3.5 H $_2$ O/Cu离子.水分子的稳定排列显示氢键水分子的链和在高浓度下形成封闭笼的趋势。水分子团簇主要通过水-水氢键和铜-水-氧相互作用的结合而稳定。通过范德华相互作用、水-水键合的电场增强以及水与骨架氧的氢键合进一步增强稳定性。我们假设形成这种稳定簇的趋势解释了水对Cu-BTC和具有暴露金属位点的相关MOF的特别强的亲和力。
System of Agentic AI for the Discovery of Metal-Organic Frameworks
University of California, Berkeley（加州大学伯克利分校）；Lawrence Berkeley National Laboratory（伯克利国家实验室）；Google DeepMind（谷歌DeepMind）；Kavli Energy NanoScience Institute（Kavli能源纳米科学研究所）
