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[资源] ACCOUTS OF CHEMICAL RESEARCH:光催化分解水和光电催化分解水中助催化剂的作用已有1人参与

This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction
reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the
quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.

助催化剂通过提供氧化/还原活性位，降低反应活化能、捕捉电荷、抑制电荷复合来提高光催化剂的活性。还原型助催化剂有：贵金属、金属硫化物、仿生氢化酶；氧化型助催化剂有：IrOx、CoOx、Co3(PO4)2等。另外还有还原型和氧化型催化剂联用，通过协同作用能够更大幅度地提高光催化剂活性。当然，两者的接触在紧密反应中也显得非常重要。在硫化物光催化剂中，助催化剂还有另外一个小作用，那就是提高稳定性，降低光腐蚀。
对于助催化剂，如果其能级和电子结构与主体催化剂相匹配则会显示出更高的活性，这个是对于助催化剂的一点儿小要求。

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附件 1 : RolesofCocatalystsinPhotocatalysisandPhotoelectrocatalysisRolesofCocatalystsinPhotocatalysisandPhotoelectrocatalysis.pdf

2013-04-07 11:13:06, 2.14 M

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