CuLi_1/3Ti_2/3O₂ (CLTO) is a visible-responsive photocatalyst, whose photo-response reaches up to 600 nm, for H₂ evolution using sacrificial electron donors such as methanol and S²⁻. In this study, utilization of CLTO in Z-scheme water splitting (Z-WS) was investigated. The photocatalytic performance of Cr₂O₃/M/CLTO as a H₂-evolving photocatalyst, which was prepared by sequential photodeposition of cocatalysts (M: Ru, Rh, Pd and Pt) and Cr₂O₃, was evaluated for Z-WS using BiVO₄, an O₂-evolving photocatalyst, and a Co(bpy)₃^3+/2+ redox shuttle under visible light. Among the examined samples, Cr₂O₃/Ru/CLTO produced both H₂ and O₂ with meaningful rates. Thus, CLTO was first utilized in a visible responsive Z-scheme system for water splitting. The Cr₂O₃ layer played a significant role in the suppression of backward reactions, such as reduction of Co(bpy)₃³⁺. The activity of Cr₂O₃/Ru/CLTO for Z-WS was remarkably affected by the deposition conditions of the Ru cocatalyst. The activity for Z-WS was remarkably improved when the photodeposition of the Ru cocatalyst was conducted in a methanol solution of RuCl₃. Unusually large plate Ru species with 100–200 nm sizes and about 30 nm thickness were present in the highly active sample. Characterization using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy indicated that the Ru cocatalyst was deposited as mainly the oxyhydroxide of Ru. Z-WS also proceeded in the absence of Co(bpy)₃^3+/2+ (the system based on interparticle electron transfer), however, the Z-scheme system using the Co(bpy)₃^3+/2+ electron shuttle showed 10 times higher activity than the interparticle electron transfer system. The external quantum yield and efficiency of solar energy conversion to hydrogen were determined to be 0.5% at 430 nm and 0.029%, respectively.

中文翻译：

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利用 CuLi1/3Ti2/3O2 作为析氢光催化剂进行 Z 型水分解，光响应高达 600 nm

CuLi _1/3 Ti _2/3 O ₂ (CLTO) 是一种可见光响应光催化剂，其光响应达到600 nm，用于使用牺牲电子供体（例如甲醇和S ^{2− ）析出H} ₂。在本研究中，研究了 CLTO 在 Z 型水分解 (Z-WS) 中的利用。_{通过连续光沉积助催化剂（M：Ru、Rh、Pd 和 Pt）和 Cr 2} O ₃制备的Cr ₂ O ₃ /M/CLTO 作为 H ₂析出光催化剂的光催化性能，以 Z- 进行评价。在可见光下使用BiVO ₄、O ₂演化光催化剂和Co(bpy) ₃ ^{3+/2+氧化还原梭进行WS​​。}在所检查的样品中，Cr ₂ O ₃ /Ru/CLTO 均以有意义的速率产生 H ₂和 O ₂。因此，CLTO 首先被用于水分解的可见响应 Z 方案系统中。Cr ₂ O ₃层在抑制逆向反应中发挥了重要作用，例如Co(bpy) ₃ ³⁺的还原。_{Cr 2} O ₃ /Ru/CLTO 对于 Z-WS的活性受到 Ru 助催化剂的沉积条件的显着影响。_{当Ru助催化剂在RuCl 3}的甲醇溶液中进行光沉积时，Z-WS的活性显着提高。高活性样品中存在异常大的板状钌物质，尺寸为 100-200 nm，厚度约为 30 nm。使用 X 射线光电子能谱和 X 射线吸收光谱进行表征表明，Ru 助催化剂主要以 Ru 的羟基氧化物形式沉积。Z-WS也在没有Co(bpy) ₃ ^{3+/2+ （基于粒子间电子转移的系统）的情况下进行，然而，使用Co(bpy)} ₃ ^3+/2+电子穿梭的Z-方案系统显示出比颗粒间电子转移系统高10倍的活性。430 nm 处的外部量子产率和太阳能转化为氢的效率分别为 0.5% 和 0.029%。