2016
DOI: 10.1039/c6ce00358c
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A stable and porous iridium(iii)-porphyrin metal–organic framework: synthesis, structure and catalysis

Abstract: Self-assembly of a new metalloporphyrin tetracarboxylic ligand Ir(TCPP)Cl (TCPP = tetrakisIJ4carboxyphenyl)porphyrin) with ZrCl 4 in the presence of benzoic acid leads to the formation of a threedimensional (3D) iridiumIJIII)-porphyrin metal-organic framework (Ir-PMOF) with the formula of [(Zr 6 (μ 3 -O) 8 (OH) 2 (H 2 O) 10 ) 2 (Ir(TCPP)Cl) 3 ]•solvents (Ir-PMOF-1(Zr)), which possesses square-shaped channels of 1.9 × 1.9 nm 2 (atom-to-atom distances across opposite Ir metal atoms) in three orthogonal directions … Show more

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Cited by 67 publications
(25 citation statements)
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“…Further valance state information was collected by XPS analysis (Figure S14), which revealed pure Ir 3+ species in Ir-SAC, resembling the valance state of Ir in homogeneous iridium porphyrins. [11] In contrast, both Ir 3+ and Ir 0 species were present in the Ir/N-C,a nd Ir/C samples, evidencing the copresence of single Ir atoms and metallic Ir clusters.These results strongly indicate the decreased electron density of Ir in the as-developed coordinative configuration, which is expected to weaken the intermediates adsorption energy on Ir-SACc ompared with its metallic crystalline counterpart and thereby improve ORR electrochemical kinetics by better facilitating the intermediate desorption.…”
Section: Resultsmentioning
confidence: 88%
“…Further valance state information was collected by XPS analysis (Figure S14), which revealed pure Ir 3+ species in Ir-SAC, resembling the valance state of Ir in homogeneous iridium porphyrins. [11] In contrast, both Ir 3+ and Ir 0 species were present in the Ir/N-C,a nd Ir/C samples, evidencing the copresence of single Ir atoms and metallic Ir clusters.These results strongly indicate the decreased electron density of Ir in the as-developed coordinative configuration, which is expected to weaken the intermediates adsorption energy on Ir-SACc ompared with its metallic crystalline counterpart and thereby improve ORR electrochemical kinetics by better facilitating the intermediate desorption.…”
Section: Resultsmentioning
confidence: 88%
“…[6,13] As expected, colorless crystals were obtained through solvothermal reaction of ZrCl 4 and H 2 L 1 in N,Ndimethylformamide (DMF) at 120 8 8C, giving LIFM-28 as an isostructure of PCN-700 with required network. [10] Thea sprepared LIFM-28 crystallizes in P4 2 /mmc group (Supporting Information, Table S1), possessing an eutral framework with most probably octahedral Zr 6 O 8 (H 2 O) 8 clusters [14] bridged by eight L 1 ligands while leaving four pairs of terminal H 2 O groups at equatorial plane appropriate for further modification (Scheme 1; Supporting Information, Figure S4). The crystal lattice presents two types of pores,s maller ones (atom-to-atom separation 713 and 76 2 )along the a-or b-axis (a-o rb-pores), and larger ones (17 17, 10 10 2 ) along the c-axis (c-pores).…”
mentioning
confidence: 99%
“…29 At this point, the structure of the material is considered as crucial for the catalytic activity, either because of the metal 32 . Since this is the first time we report on 1, it has been exhaustively characterized by means of single crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction and transmission electron microscopy (TEM).…”
Section: Introductionmentioning
confidence: 99%