title: Modular and Stepwise Synthesis of a Hybrid Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution.
abstract: The paddle-wheel type cluster Co2(RCOO)4(LT)2(R = substituent group, LT= terminal ligand), possessing unusual metal coordination geometry compared with other cobalt compounds, may display high catalytic activity but is highly unstable especially in water. Here, we show that with judicious considerations of the host/guest geometries and modular synthetic strategies, the labile dicobalt clusters can be immobilized and stabilized in a metal-organic framework (MOF) as coordinative guests. The Fe(na)4(LT) fragment in the MOF [{Fe3(μ3-O)(bdc)3}4{Fe(na)4(LT)}3] (H2bdc = 1,4-benzenedicaboxylic acid, Hna = nicotinic acid) can be removed to give [{Fe3(μ3-O)(bdc)3}4] with a unique framework connectivity possessing suitable distribution of open metal sites for binding the dicobalt cluster in the form of Co2(na)4(LT)2. After two-step, single-crystal to single-crystal, postsynthetic modifications, a thermal-, water-, and alkaline-stable MOF [{Fe3(μ3-O)(bdc)3}4{Co2(na)4(LT)2}3] containing the desired dicobalt cluster was obtained, giving extraordinarily high electrocatalytic oxygen evolution activity in water at pH = 13 with overpotential as low as 225 mV at 10.0 mA cm-2.
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Jian-Qiang
authors.initials: JQ
authors.lastname: Shen
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Pei-Qin
authors.initials: PQ
authors.lastname: Liao
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Dong-Dong
authors.initials: DD
authors.lastname: Zhou
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Chun-Ting
authors.initials: CT
authors.lastname: He
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Jun-Xi
authors.initials: JX
authors.lastname: Wu
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Wei-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Jie-Peng
authors.identifier: 0000-0002-2614-2774
authors.initials: JP
authors.lastname: Zhang
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University , Guangzhou 510275, China.
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Chen