We show that synthetic [FeFe]‐hydrogenase mimics embedded within liposomes can be immobilized on high‐surface‐area carbon blacks for the construction of a three‐dimensional (3D) electrode for H₂ production in neutral aqueous media. In this design, the bilayer vesicles (liposomes) serve as a water‐insoluble electrocatalyst carrier, facilitating access of the embedded catalysts to aqueous solution. Fast electron‐transfer rates and low overpotentials are achieved compared to water‐soluble catalysts. The electron‐transfer rate constant between the embedded [(μ‐bdt)Fe₂(CO)₆] (bdt=1,2‐benzenedithiolate; 1) and the electrode is estimated to be 1.33±0.15 s⁻¹. Immobilized [(μ,κ²‐bdt‐Me)(μ‐PPh₂)Fe₂(CO)₅] (Me=methyl; 3) is able to catalyze H₂ production in Na₂SO_4(aq) solution (pH=7) at −1.06 V (vs. SHE) with an overpotential of approximately 400 mV. The reported general method for the construction of 3D electrodes paves the way to potential applications of molecular catalysts in energy devices.

中文翻译：

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双层囊泡作为中性水性介质中能量转化的电催化剂的非共价固定化平台

我们表明，嵌入脂质体中的合成[FeFe]-加氢酶模拟物可以固定在高表面积炭黑上，用于构建在中性水性介质中生产H ₂的三维（3D）电极。在这种设计中，双层囊泡（脂质体）充当了水不溶性电催化剂载体，促进了嵌入式催化剂与水溶液的接触。与水溶性催化剂相比，可实现更快的电子传输速率和较低的超电势。嵌入的[（μ-bdt）Fe ₂（CO）₆ ]（bdt = 1,2-苯二硫代酸盐；1）与电极之间的电子传递速率常数估计为1.33±0.15 s ^-1。固定化[（μ，κ ²-bdt-ME）（μ-PPH ₂）的Fe ₂（CO）₅ ]（Me =甲基; 3）是能够催化ħ ₂生产的Na ₂ SO _{4（水溶液）}溶液（pH = 7）在-1.06 V （相对于SHE）具有约400 mV的过电势。已报道的构建3D电极的通用方法为分子催化剂在能源设备中的潜在应用铺平了道路。