Synthesis of active, robust and cationic Au<sub>25</sub> cluster catalysts on double metal hydroxide by long-term oxidative aging of Au<sub>25</sub>(SR)<sub>18</sub>
Synthesis of active, robust and cationic Au<sub>25</sub> cluster catalysts on double metal hydroxide by long-term oxidative aging of Au<sub>25</sub>(SR)<sub>18</sub>
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Au<sub>25</sub>(SR)<sub>18</sub>长期氧化老化在双金属氢氧化物上合成活性强的阳离子Au<sub>25</sub>簇催化剂
DOI：
10.1039/d1nr07493h
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发表时间：
2022
期刊：
影响因子：
6.7
通讯作者：
Tsukuda Tatsuya
中科院分区：
文献类型：
--
作者：
Masuda Shinya;Takano Shinjiro;Yamazoe Seiji;Tsukuda Tatsuya
以Au_（25）（BaET）_（18）（BaET-H = 2-（Boc-氨基）乙硫醇）为催化剂，在不同的双金属氢氧化物（DMH）载体上，通过长期低温老化，合成了原子级精确的Au_（25）簇催化剂。X射线吸收精细结构分析表明，通过在空气中150 °C氧化老化>12 h，在含Co和Ce（Co 3Ce）的DMH上成功地生成了高负载量（1 wt%）的裸Au 25团簇。X射线吸收近边结构和X射线光电子能谱分析表明，Co 3Ce表面的Au 25团簇带正电荷。由此合成的Au 25/Co 3 Ce催化剂在环境条件下（TOF = 1097 h-1，对苯甲酸的选择性>97%）在苯甲醇的有氧氧化中表现出优异的催化性能（上级），并且由于强的锚定效应而表现出高的耐久性。在动力学实验的基础上，提出Au_（25）从苄醇的α-碳上夺取氢化物是Au_（25）/Co_（3Ce）催化氧化苄醇的速率控制步骤。
Synthesis of an atomically precise Au25 cluster catalyst was attempted by long-term, low-temperature aging of Au25(BaET)18 (BaET-H = 2-(Boc-amino)ethanethiol) on various double metal hydroxide (DMH) supports. X-ray absorption fine structure analysis revealed that bare Au25 clusters with high loading (1 wt%) were successfully generated on the DMH containing Co and Ce (Co3Ce) by oxidative aging in air at 150 °C for >12 h. X-ray absorption near-edge structure and X-ray photoelectron spectroscopies showed that the Au25 clusters on Co3Ce were positively charged. The Au25/Co3Ce catalyst thus synthesized exhibited superior catalytic performance in the aerobic oxidation of benzyl alcohol under ambient conditions (TOF = 1097 h−1 with >97% selectivity to benzoic acid) and high durability owing to a strong anchoring effect. Based on kinetic experiments, we propose that abstraction of hydride from α-carbon of benzyl alkoxide by Au25 is the rate-determining step of benzyl alcohol oxidation by Au25/Co3Ce.