An Yang, Liu Yuanyuan, Bian Hongtao, Wang Zeyan, Wang Peng, Zheng Zhaoke, Dai Ying, Whangbo Myung-Hwan, Huang Baibiao
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China; Institute for Innovative Materials and Energy, Yangzhou University, Yangzhou 225002, China.
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
Sci Bull (Beijing). 2019 Oct 30;64(20):1502-1509. doi: 10.1016/j.scib.2019.07.030. Epub 2019 Jul 29.
UiO-67 is a Zr-based metal-organic framework (MOF) containing an organic linker namely, the dianion of biphenyl-4,4'-dicarboxylic acid (bpdc). Ce metal ions (0.02 Ce to Zr atom ratio) were incorporated into UiO-67 via partially replacing bpdc with the dianion of 2,2'-bipyridine-5,5'-dicarboxylic acid (bpydc); thus, the latter forms a bpydc-Ce complex. The resulting product (i.e., UiO-67-Ce) demonstrated a photocatalytic hydrogen evolution rate that was over 10 times higher than that of UiO-67. Through this modification, a new energy transfer channel is opened up. The energy transfer between the bpdc and bpydc-Ce ligands (i.e., from excited bpdc to bpydc-Ce) weakened the recombination of the charge carriers, which was confirmed by photoluminescence, emission lifetime, and transient absorption measurements. This study presents a new way to construct highly efficient MOF photocatalysts.
UiO-67是一种基于锆的金属有机框架材料（MOF），其包含一种有机连接体，即联苯-4,4'-二羧酸（bpdc）的二价阴离子。通过用2,2'-联吡啶-5,5'-二羧酸（bpydc）的二价阴离子部分取代bpdc，将铈金属离子（铈与锆原子的比例为0.02）掺入UiO-67中；因此，后者形成了一种bpydc-Ce络合物。所得产物（即UiO-67-Ce）的光催化析氢速率比UiO-67高出10倍以上。通过这种改性，开辟了一条新的能量转移通道。bpdc与bpydc-Ce配体之间的能量转移（即从激发态的bpdc到bpydc-Ce）削弱了电荷载流子的复合，这通过光致发光、发射寿命和瞬态吸收测量得到了证实。本研究提出了一种构建高效MOF光催化剂的新方法。
