Visible-Light-Responsive 2D Cadmium-Organic Framework Single Crystals with Dual Functions of Water Reduction and Oxidation
Visible-Light-Responsive 2D Cadmium-Organic Framework Single Crystals with Dual Functions of Water Reduction and Oxidation
复制标题
具有减水和氧化双重功能的可见光响应二维镉有机骨架单晶
DOI：
10.1002/adma.201803401
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发表时间：
2018
影响因子：
29.4
通讯作者：
Li Can
中科院分区：
文献类型：
--
作者：
Xiao Yejun;Qi Yu;Wang Xiuli;Wang Xiaoyu;Zhang Fuxiang;Li Can
在可见光照射下具有水还原和氧化双重功能的新型金属有机框架（MOFs）的开发对于有前景的太阳能水分解是非常可取的，但尚未报道。本文中，报道了通过采用1，3，6，8-四（对苯甲酸）芘（H4 TBAPy）作为有机连接剂的具有2D层状骨架的镉基MOF（表示为“Cd-TBAPy”）单晶，其表现出良好的可见光吸收，边缘为600 nm。Mott-Schottky（M-S）测量和UV-vis分析整体揭示了Cd-TBAPy是一种n型半导体，带隙为1.22eV，其导带和价带估计分别为-0.05和2.10 eV。与负载Pt或CoPi助催化剂一起，Cd-TBAPy在可见光照射下在清除剂存在下对水还原和氧化都具有活性。特别是，在420 nm处，O2释放的优化表观量子效率达到5.6%，远高于迄今为止报道的先前基于MOF的光催化剂。这被认为是第一个在可见光下作为水还原和氧化的光催化剂的MOF，展示了MOF材料在太阳能到化学能转换中的有趣未来。
The development of new metal–organic frameworks (MOFs) with dual functions of both water reduction and oxidation under visible‐light irradiation is highly desirable for promising solar water splitting, but is not yet reported. Herein, a cadmium‐based MOF (denoted as “Cd‐TBAPy”) single crystal with a 2D layered framework by employing 1,3,6,8‐tetrakis(p‐benzoic acid)pyrene (H4TBAPy) as an organic linker is reported, which exhibits good visible‐light absorption with edge of ≈600 nm. The Mott–Schottky (M–S) measurement and UV–vis analysis integrally reveal that the Cd‐TBAPy is an n‐type semiconductor with a bandgap of ≈2.15 eV whose conduction and valence band are estimated to be −0.05 and 2.10 eV, respectively. Together with loading of Pt or CoPi cocatalyst, the Cd‐TBAPy is active for both water reduction and oxidation in the presence of scavengers under visible‐light irradiation. Especially, the optimized apparent quantum efficiency for O2evolution reaches 5.6% at 420 nm, much higher than that of previous MOF‐based photocatalysts reported so far. This is thought to be the first MOF that functions as a photocatalyst for both water reduction and oxidation under visible light, demonstrating the intriguing future of MOF materials in solar‐to‐chemical energy conversion.