Solar‐driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi‐electron transfer. Single‐cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells‐Dawson‐ and Keggin‐type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single‐cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M = Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface‐hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2‐1 exhibits the highest electron consumption rate of 1260 µmol g−1 for CO2‐to‐CH3OH conversion with H2O as the electron source, which is 11 times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single‐dispersion of molecular cluster to enrich surface‐reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction.

中文翻译：

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单簇功能化 TiO2 纳米管阵列促进水氧化和 CO2 光还原为 CH3OH

太阳能驱动的二氧化碳还原和水氧化成液体燃料是缓解能源危机和气候问题的一种有前景的解决方案，但对于以多电子转移为主的生成CH3OH和CH3CH2OH仍然是一个巨大的挑战。单簇催化剂具有超强的电子接受能力、精确的分子结构、可定制的电子结构和多个吸附位点，在催化各种具有挑战性的反应方面具有更大的潜力。然而，准确控制功能支撑上团簇的数量和排列仍然面临着巨大的挑战。在此，我们开发了一种简便的电合成方法，将 Wells-Dawson 型和 Keggin 型多金属氧酸盐均匀分散在 TiO2 纳米管阵列上，产生一系列单簇功能化催化剂 P2M18O62@TiO2 和 PM12O40@TiO2（M = Mo 或 W）。单个多金属氧酸盐簇可以被清楚地识别，并作为电子海绵接受来自激发的TiO2的电子，以提高表面空穴浓度并促进水氧化。在这些样品中，P2Mo18O62@TiO2-1以H2O为电子源将CO2转化为CH3OH时表现出最高的电子消耗率为1260 µmol g−1，比孤立的TiO2纳米管阵列高11倍。这项工作提供了一种简单的合成方法来实现分子簇的单分散，以丰富TiO2表面到达的空穴，从而促进水氧化和CO2还原。