Dai Yitao, Ren Pengju, Li Yaru, Lv Dongdong, Shen Yanbin, Li Yongwang, Niemantsverdriet Hans, Besenbacher Flemming, Xiang Hongwei, Hao Weichang, Lock Nina, Wen Xiaodong, Lewis James P, Su Ren
SynCat@Beijing, Synfuels China Technology Co. Ltd., Leyuan South Street II, No.1, Yanqi Economic Development Zone C#, Huairou District, Beijing, 101407, China.
Interdisciplinary Nanoscience Centre (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.
Angew Chem Int Ed Engl. 2019 May 6;58(19):6265-6270. doi: 10.1002/anie.201900773. Epub 2019 Feb 27.
The selective oxidation of primary alcohols to aldehydes by O instead of stoichiometric oxidants (for example, Mn , Cr , and Os ) is an important but challenging process. Most heterogeneous catalytic systems (thermal and photocatalysis) require noble metals or harsh reaction conditions. Here we show that the Bi O Br (OH) photocatalyst is very efficient in the selective oxidation of a series of aliphatic (carbon chain from C to C ) and aromatic alcohols to their corresponding aldehydes/ketones under visible-light irradiation in air at room temperature, which would be challenging for conventional thermal and light-driven processes. High quantum efficiencies (71 % and 55 % under 410 and 450 nm irradiation) are reached in a representative reaction, the oxidation of isopropanol. We propose that the outstanding performance of the Bi O Br (OH) photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo-oxidation of alcohols.
用氧气而非化学计量的氧化剂（例如锰、铬和锇）将伯醇选择性氧化为醛是一个重要但具有挑战性的过程。大多数多相催化体系（热催化和光催化）需要贵金属或苛刻的反应条件。在此我们表明，BiOBr(OH)光催化剂在室温下于空气中可见光照射下，能非常有效地将一系列脂肪族（碳链从C1到C6）和芳香族醇选择性氧化为其相应的醛/酮，这对于传统的热驱动和光驱动过程而言具有挑战性。在一个典型反应——异丙醇的氧化反应中，实现了高量子效率（在410和450 nm照射下分别为71%和55%）。我们提出，BiOBr(OH)光催化剂的优异性能与碱性表面位点和活性晶格氧有关，它们促进了醇光氧化过程中的脱氢步骤。
