Red-Light-Driven Photocatalytic Reduction of CO2 using Os(II)-Re(I) Supramolecular Complexes
Red-Light-Driven Photocatalytic Reduction of CO2 using Os(II)-Re(I) Supramolecular Complexes
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DOI：
10.1021/ic4015543
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发表时间：
2013-10-21
影响因子：
4.6
通讯作者：
Ishitani, Osamu
中科院分区：
文献类型：
--
作者：
Tamaki, Yusuke;Koike, Kazuhide;Ishitani, Osamu
本文报道了由[Os（5DMB）（2）（BL）]（2+）型配合物组成的新型超分子配合物（5DMB = 5，5 '-二甲基-2，2'-联吡啶; BL = 1，2-双（4 ′-甲基-[2，2 ′-联吡啶]-4-基）乙烷）作为光敏剂和顺，反-[Re（BL）（CO）（2）{P合成了（p-X-C6 H4）（3）}（2）]（+）型配合物（X = F、Cl）作为催化剂。它们在红光照射（λ> 620 nm）下光催化选择性还原CO2为CO。Re单元上的膦配体对超分子的光催化性能有一定的影响，含P（p-Cl-C6 H4）（3）配体的超分子具有较好的光催化活性（Phi（CO）= 0.12，TONCO = 1138，TOFCO = 3.3min（-1））。详细的研究澄清了电子平衡和物质平衡;即，一个分子的牺牲电子供体（1，3-二甲基-2-苯基-2，3-二氢-1H-苯并[d]-咪唑（BIH））提供两个电子，一个分子的CO2接受这两个电子，另一个CO2分子充当“O2-”受体，以得到BIH、CO和HCO 3-的每个双电子氧化化合物分子。
The novel supramolecular complexes, which are composed of an [Os(5dmb)(2)(BL)](2+)-type complex (5dmb = 5,5'-dimethyl-2,2'-bipyridine; BL = 1,2-bis(4'-methyl-[2,2'-bipyridin]-4-yl)ethane) as a photosensitizer and cis,trans-[Re(BL)(CO)(2){P(p-X-C6H4)(3)}(2)](+)-type complexes (X = F, Cl) as a catalyst, have been synthesized. They photocatalyzed selective reduction of CO2 to CO under red-light irradiation (lambda > 620 nm). The photocatalytic abilities were affected by the phosphine ligands on the Re unit, and the supramolecule with P(p-Cl-C6H4)(3) ligands exhibited better photocatalysis (Phi(CO) = 0.12, TONCO = 1138, TOFCO = 3.3 min(-1)). The detailed studies clarified the electron balance and material balance; i.e., one molecule of the sacrificial electron donor (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]-imidazole (BIH)) donated two electrons, one molecule of CO2 accepted the two electrons, and another CO2 molecule served as an "O2-" acceptor to give each molecule of the two-electron oxidized compound of BIH, CO, and HCO3-.