陳彬 張鐵銳 曾毅

摘要：氫是一種清潔高效的理想燃料。利用太陽能制氫是直接將太陽能高效轉(zhuǎn)化為化學(xué)能的有效方式。通過分子組裝構(gòu)筑了一系列高效太陽能光催化制氫的新體系，分子組裝體高效的能量傳遞、電子轉(zhuǎn)移和電荷分離過程顯著提高了催化體系的產(chǎn)氫效率和穩(wěn)定性。例如：采用低溫水熱方法制備的多級(jí)Sn2Nb2O7空心球可見光催化劑和采用多元醇熱注入法制備的由超薄納米片組裝而成的分等級(jí)花狀結(jié)構(gòu)ZnIn2S4亞微米球均表現(xiàn)出優(yōu)異的光解水產(chǎn)氫性能；利用樹枝狀聚合物、聚丙烯酸和殼聚糖開展對(duì)鐵氫化酶外圍保護(hù)蛋白的模擬和功能性研究，在國(guó)際上率先突破了鐵氫化酶模擬化合物穩(wěn)定性差、催化效率低的瓶頸，實(shí)現(xiàn)了太陽光驅(qū)動(dòng)鐵氫化酶模擬化合物的水相高效產(chǎn)氫。

關(guān)鍵詞：分子組裝體；光解水制氫；電子轉(zhuǎn)移

Molecular Assemblies Enhance the Performance of Photocatalytic Hydrogen Production

Abstract：Hydrogen is one of the most ideal clean fuels because of its high density of energy and environmentally benign combustion product （water）. Photocatalytic hydrogen production from water splitting has attracted much attention because it is promising for conversion of sustainable solar energy into chemical energy. In this project， we focus on the construction of a variety of molecular assemblies for hydrogen evolution under illumination of visible light. By modulating energy/electron transfer and long-lived charge separation， we are able to achieve photocatalytic hydrogen productive with higher efficiency and stability in the designed molecular assemblies. For example， hierarchical Sn2Nb2O7 hollow spheres were prepared for the first time via a facile hydrothermal route using bubbles generated in situ from the decomposition of urea as soft templates. Flower-like spherical ZnIn2S4 superstructures about 500 nm in diameter composed of ultrathin 2-3 nm thick mesoporous nanosheets were synthesized in several minutes by facile polyol-mediated hot-injection. These as-obtained hollow spheres and lower-like spherical ZnIn2S4 with a large specific surface area show improved visible-light-driven photocatalytic hydrogen production activity in aqueous solutions. Inspired by natural photosynthesis， a series of artificial [FeFe]-H2ase photocatalytic systems have been constructed using poly（aryl ether） dendrimers， poly（acrylic acid）， and chitosan with PS and Fe2S2 active site of [FeFe]-H2ase mimics. Irradiation of these systems with visible light results in the formation of long-lived reduced intermediates， and thus increasing the efficiency and durability of hydrogen photoproduction remarkably.

Keywords：molecular assemblies；photocatalytic hydrogen evolution；electron transfer；

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