Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF
Heterogenization of a [NiFe] Hydrogenase Mimic through Simple and Efficient Encapsulation into a Mesoporous MOF
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DOI：
10.1021/acs.inorgchem.7b01824
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发表时间：
2017-12-18
影响因子：
4.6
通讯作者：
Gennari, Marcello
中科院分区：
文献类型：
--
作者：
Balestri, Davide;Roux, Yoann;Gennari, Marcello
在寻求新的，有效的，不含贵金属的H-2-释放催化剂的过程中，氢化酶是灵感的来源。在这里，我们描述了一种新的混合材料的基础上的结构和功能[NiFe]-氢化酶模型复合物（NiFe）纳入锆基MOF PCN-777的发展。通过简单封装合成块状NiFe@PCN-777材料。通过固态NMR和IR光谱、SEM-EDX、ICP-OES和气体吸附的表征证实了客体的存在。FTO支撑的NiFe@PCN-777复合物的薄膜通过本体材料的电泳沉积获得，并通过SEM-EDX、ICP-OES和循环伏安法表征。发现膜中电活性NiFe催化剂的平均表面浓度类似于9.6 × 10（-10）mol cm（-2），这意味着结合在MOF中的NiFe单元的令人惊讶的高分数（37%）是电活性的。通过循环伏安法，我们表明，NiFe保持其电催化能力的H+还原内的MOF腔，即使在控制电位电解条件下的活性的NiFe不能从自由的PCN-777和FTO辨别。
In the quest for new, efficient, and noble-metal free H-2-evolution catalysts, hydrogenase enzymes are a source of inspiration. Here, we describe the development of a new hybrid material based on a structural and functional [NiFe]-hydrogenase model complex (NiFe) incorporated into the Zr-based MOF PCN-777. The bulk NiFe@PCN-777 material was synthesized by simple encapsulation. Characterization by solid-state NMR and IR spectroscopy, SEM-EDX, ICP-OES, and gas adsorption confirmed the inclusion of the guest. FTO-supported thin films of the NiFe@PCN-777 composite were obtained by electrophoretic deposition of the bulk material and characterized by SEM-EDX, ICP-OES, and cyclic voltammetry. The average surface concentration of electroactive NiFe catalyst in the film was found to be similar to 9.6 x 10(-10) mol cm(-2), implying that a surprisingly high fraction (37%) of NiFe units incorporated in the MOF are electroactive. By cyclic voltammetry, we showed that NiFe maintains its electrocatalytic capabilities for H+ reduction inside the MOF cavities, even if under controlled-potential electrolysis conditions the activity of NiFe cannot be discerned from that of free PCN-777 and FTO.