Charge, adsorption, water stability and bandgap tuning of an anionic Cd(ii) porphyrinic metal-organic framework
Li, Q (Li, Qi)[ 1 ] ; Luo, YP (Luo, Yanping)[ 1,4 ] ; Ding, Y (Ding, Yue)[ 1 ] ; Wang, YN (Wang, Yina)[ 1 ] ; Wang, YX (Wang, Yuxin)[ 1 ] ; Du, HB (Du, Hongbin)[ 2 ] ; Yuan, RX (Yuan, Rongxin)[ 3 ] ; Bao, JC (Bao, Jianchun)[ 4 ] ; Fang, M (Fang, Min)[ 1,2 ]*（方敏）; Wu, Y (Wu, Yong)[ 1 ]*（吴勇）

[ 1 ] Nanjing Normal Univ, Jiangsu Key Lab New Power Batteries, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Sch Chem & Mat Sci, Nanjing 210023, Jiangsu, Peoples R China
[ 2 ] Nanjing Univ, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China
[ 3 ] Changshu Inst Technol, Sch Chem & Mat Engn, Changshu 215500, Jiangsu, Peoples R China
[ 4 ] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiansu Key Lab Biofunct Mat, Nanjing 210023, Jiangsu, Peoples R China

DALTON TRANSACTIONS,201906,48(24),8678-8692

Due to the designability of metal-organic frameworks (MOFs), semiconductor MOFs have become the focus of research as photocatalysts of useful chemical processes utilizing clean solar energy. In this work, we developed a method of tuning the framework charge of MOF materials and determined how the framework charge can affect the band edge positions and bandgaps of the novel anionic Cd(ii) porphyrinic metal-organic framework (PMOF) 1 ([Cd-3.2(H2TCPP)(2)][(CH3)(2)NH2](1.6)). It was constructed from H2TCPP4- (H6TCPP = tetrakis(4-carboxyphenyl)-porphyrin) and Cd(ii), forming a tube-like structure, and shown to have a negatively charged framework with a 60% occupancy of one type of Cd(ii) ion. By increasing the reaction time and the amount of Cd(ii) ions in the reactants, the nearly neutral counterpart of PMOF 1 was also obtained. The [(CH3)(2)NH2](+) counterions of PMOF 1 were also exchanged with Li+. Although the surface area of PMOF 1 and its derived PMOFs were only 407-672 m(2) g(-1), the CO2 and CH4 uptakes reached, respectively, 44-65 ml g(-1) (8.7-12.7%) and 22-26 ml g(-1) (1.6-1.8%) each at 1.0 atom and 273 K; at 9.0 atm these values nearly tripled. Li+-exchanged 1 favoured N-2, CO2 and CH4 adsorption, especially at 9 atm and a relatively low temperature (273 K). PMOF 1 subjected to a solvent exchange process showed an unstable structure in water, while PMOF 1 not subjected to this process was found to be stable in water. Thus, a method for making water-stable divalent-metal carboxylate MOFs was proposed. The counter ion type showed little effect on the band-edge positions and bandgaps, but the framework charge did show effects. Under visible light and with tris(2,2 '-bipyridine)dichlororuthenium(ii) (Ru(bpy)(3)Cl-2) as the co-catalyst and triethylamine (TEA) as the sacrificial agent, the efficiency of CO production resulting from CO2 reduction using 1-DMF reached 56 mu mol g(-1) h(-1), about 5 times greater than that for the system without using Ru(bpy)(3)Cl-2.

文章链接：
https://pubs.rsc.org/en/content/articlelanding/2019/DT/C9DT00478E#!divAbstract

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