Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, P.R. China.
Department of Chemistry, The University of Chicago, Chicago, IL, USA.
Nat Chem. 2021 Apr;13(4):358-366. doi: 10.1038/s41557-020-00635-5. Epub 2021 Feb 15.
Metal-organic frameworks (MOFs) have been studied extensively in the hydrogen evolution reaction (HER) and the water oxidation reaction (WOR) with sacrificial reagents, but overall photocatalytic water splitting using MOFs has remained challenging, principally because of the fast recombination of photo-generated electrons and holes. Here we have integrated HER- and WOR-MOF nanosheets into liposomal structures for separation of the generated charges. The HER-MOF nanosheets comprise light-harvesting Zn-porphyrin and catalytic Pt-porphyrin moieties, and are functionalized with hydrophobic groups to facilitate their incorporation into the hydrophobic lipid bilayer of the liposome. The WOR-MOF flakes consist of [Ru(2,2'-bipyridine)]-based photosensitizers and Ir-bipyridine catalytic centres, and are localized in the hydrophilic interior of the liposome. This liposome-MOF assembly achieves overall photocatalytic water splitting with an apparent quantum yield of (1.5 ± 1)% as a result of ultrafast electron transport from the antennae (Zn-porphyrin and [Ru(2,2'-bipyridine)]) to the reaction centres (Pt-porphyrin and Ir-bipyridine) in the MOFs and efficient charge separation in the lipid bilayers.
金属-有机骨架（MOFs）在牺牲试剂存在的情况下，在析氢反应（HER）和水氧化反应（WOR）中得到了广泛的研究，但总体而言，利用 MOFs 进行光催化水分解仍然具有挑战性，主要是因为光生电子和空穴的快速复合。在这里，我们将 HER 和 WOR-MOF 纳米片整合到脂质体结构中，以分离产生的电荷。HER-MOF 纳米片包含光捕获的 Zn-卟啉和催化 Pt-卟啉部分，并进行了疏水性基团的功能化，以方便它们掺入脂质体的疏水性脂质双层中。WOR-MOF 薄片由基于 [Ru(2,2'-联吡啶)] 的光敏剂和 Ir-联吡啶催化中心组成，并定位于脂质体的亲水性内部。由于天线（Zn-卟啉和 [Ru(2,2'-联吡啶)])到 MOFs 中的反应中心（Pt-卟啉和 Ir-联吡啶）的超快电子传输以及脂质双层中的有效电荷分离，这种脂质体-MOF 组装实现了总体光催化水分解，表观量子产率为 (1.5±1)%。
