Liu Jiayi, Li Xuning, Liu Biao, Zhao Chunxiao, Kuang Zhichong, Hu Ruisheng, Liu Bin, Ao Zhimin, Wang Junhu
Mössbauer Effect Data Center , Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
ACS Appl Mater Interfaces. 2018 Nov 7;10(44):38051-38056. doi: 10.1021/acsami.8b12686. Epub 2018 Oct 23.
Controllable synthesis of metal-organic frameworks with well-defined morphology, composition, and size is of great importance toward understanding their structure-property relationship in various applications. Herein, we demonstrate a general strategy to modulate the relative growth rate of the secondary building units (SBUs) along different crystal facets for the synthesis of Fe-Co, MnFe-Co, and Mn-Co Prussian blue analogues (PBAs) with tunable morphologies. The same growth rate of SBUs along the {100}, {110}, and {111} surfaces at 0 °C results in the formation of spherical PBA particles, while the lowest growth rate of SBUs along the {100} surface resulting from the highest surface energy with increasing reaction temperature induces the formation of PBA cubes. Fenton reaction was used as the model reaction to probe the structure-catalytic activity relation for the as-synthesized catalysts. The cubic Fe-Co PBA was found to exhibit the best catalytic performance with reaction rate constant 6 times higher than that of the spherical counterpart. Via density functional theory calculations, the abundant enclosed {100} facets in cubic Fe-Co PBA were identified to have the highest surface energy and favor high Fenton reaction activity.
可控合成具有明确形态、组成和尺寸的金属有机框架对于理解其在各种应用中的结构-性能关系至关重要。在此，我们展示了一种通用策略，用于调节二级构建单元（SBU）沿不同晶面的相对生长速率，以合成具有可调形态的铁-钴、锰铁-钴和锰-钴普鲁士蓝类似物（PBA）。在0°C时，SBU沿{100}、{110}和{111}表面的相同生长速率导致形成球形PBA颗粒，而随着反应温度升高，{100}表面具有最高表面能，导致SBU沿该表面的生长速率最低，从而诱导形成PBA立方体。以芬顿反应作为模型反应来探究所合成催化剂的结构-催化活性关系。发现立方铁-钴PBA表现出最佳催化性能，反应速率常数比球形对应物高6倍。通过密度泛函理论计算，确定立方铁-钴PBA中丰富的封闭{100}面具有最高表面能，有利于高芬顿反应活性。
