Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization
Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization
复制标题
通过有机配体功能化稳定氢氧化亚铜纳米结构
DOI：
10.1002/adma.202208665
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发表时间：
2022
影响因子：
29.4
通讯作者：
Pan, Dingjie
中科院分区：
文献类型：
--
作者：
Liu, Qiming;Peng, Yi;Masood, Zaheer;DuBois, Davida;Tressel, John;Nichols, Forrest;Ashby, Paul;Mercado, Rene;Assafa, Tufa;Pan, Dingjie
铜化合物因其广泛的应用而被广泛研究。然而，由于结构的亚稳性，氢氧化亚铜(CuOH)的研究一直很少。在这里，报告了一种简便的湿化学方法，通过有意地与乙炔和硫醇衍生物等有机配体进行官能化来制备稳定的CuOH纳米结构。结果发现，所得到的纳米结构呈现出纳米带的形态，由嵌入在基本上无定形的纳米片状支架中的小纳米晶体组成。乙炔类化合物锚定在CuOH键上形成Cu--C-键，而Cu--S-界面键与巯基配体形成界面键。前者在配体-核心界面发生有效的电子耦合，而后者主要是非共轭界面键，如光谱测量所示，并在基于第一性原理计算的理论研究中得到证实。值得注意的是，乙炔封端的CuOH纳米结构在抑制细菌生长方面表现出显著增强的光动力学活性，这是因为乙炔封端的CuOH纳米结构的材料带隙减小，并且有效地光催化生成了活性氧物种。这项研究的结果表明，利用精心设计的有机配体进行结构工程是稳定和功能化CuOH纳米结构的有效策略，这是探索其多样化应用的关键第一步。
Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet‐chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet‐like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand‐core interface in the former, in contrast to mostly non‐conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene‐capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto‐capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.