Abstract:The heterometallic optical complexes [Cu2Co(S,S(+)cpse)3(H2O)3]·4H2O (1) and [Cu2Ni(S,S(+)cpse)3(H2O)3]·10H2O (2) were obtained from the mononuclear copper(II) compound by the addition of nickel(II) or cobalt(II) chlorides, where (H2cpse) is the acetyl amino alcohol derivative N-[2-hydroxy-1(R)-methyl-2(R)-phenylethyl]-N-methylglycine. In comparison with the homotrinuclear copper(II) compound [Cu3(S,S(+)cpse)3(H2O)3]·8H2O reported previously, the substitution of a copper(II) atom by one cobalt(II) ion gave pla… Show more
“…For ZIOS-Cu, the Cu 2 p spectrum exhibits peaks at 952.78 and 932.98 eV characteristic of Cu + (2 p 1/2 and 2 p 3/2 , respectively), in addition to weaker features at 954.48 and 934.78 eV that can be ascribed to Cu 2+ (2 p 1/2 and 2 p 3/2 , respectively). The copper(I) peaks could indicate the presence of a five-coordinate Cu + diamagnetic adduct or a four-coordinate Cu + complex with nitrogen macrocyclic ligands, while the copper(II) peaks are indicative of a heteronuclear Cu 2+ Zn 2+ complex 37 . Fig.…”
Herein, we present a scalable approach for the synthesis of a hydrogen-bonded organic–inorganic framework via coordination-driven supramolecular chemistry, for efficient remediation of trace heavy metal ions from water. In particular, using copper as our model ion of interest and inspired by nature’s use of histidine residues within the active sites of various copper binding proteins, we design a framework featuring pendant imidazole rings and copper-chelating salicylaldoxime, known as zinc imidazole salicylaldoxime supramolecule. This material is water-stable and exhibits unprecedented adsorption kinetics, up to 50 times faster than state-of-the-art materials for selective copper ion capture from water. Furthermore, selective copper removal is achieved using this material in a pH range that was proven ineffective with previously reported metal–organic frameworks. Molecular dynamics simulations show that this supramolecule can reversibly breathe water through lattice expansion and contraction, and that water is initially transported into the lattice through hopping between hydrogen-bond sites.
“…For ZIOS-Cu, the Cu 2 p spectrum exhibits peaks at 952.78 and 932.98 eV characteristic of Cu + (2 p 1/2 and 2 p 3/2 , respectively), in addition to weaker features at 954.48 and 934.78 eV that can be ascribed to Cu 2+ (2 p 1/2 and 2 p 3/2 , respectively). The copper(I) peaks could indicate the presence of a five-coordinate Cu + diamagnetic adduct or a four-coordinate Cu + complex with nitrogen macrocyclic ligands, while the copper(II) peaks are indicative of a heteronuclear Cu 2+ Zn 2+ complex 37 . Fig.…”
Herein, we present a scalable approach for the synthesis of a hydrogen-bonded organic–inorganic framework via coordination-driven supramolecular chemistry, for efficient remediation of trace heavy metal ions from water. In particular, using copper as our model ion of interest and inspired by nature’s use of histidine residues within the active sites of various copper binding proteins, we design a framework featuring pendant imidazole rings and copper-chelating salicylaldoxime, known as zinc imidazole salicylaldoxime supramolecule. This material is water-stable and exhibits unprecedented adsorption kinetics, up to 50 times faster than state-of-the-art materials for selective copper ion capture from water. Furthermore, selective copper removal is achieved using this material in a pH range that was proven ineffective with previously reported metal–organic frameworks. Molecular dynamics simulations show that this supramolecule can reversibly breathe water through lattice expansion and contraction, and that water is initially transported into the lattice through hopping between hydrogen-bond sites.
“…As for the O 1s spectrum (Figure b), apart from the peak at 530.1 eV assigned to the Ti−O bonds of TiO 2 , the peak at 531.8 eV corresponds to the C−O bonds formed between TiO 2 and the nanoplated carbon layer . Besides, the small peak at 533.4 eV is assigned to the formation of additional Co−O bonds, confirming the coordination between cobalt and oxygen . Figure c shows the Co 2p spectrum, which is spin‐orbit split into Co 2p 1/2 and Co 2p 3/2 components with identical chemical information.…”
Developing noble‐metal‐free electrocatalysts is important to industrially viable ammonia synthesis through the nitrogen reduction reaction (NRR). However, the present transition‐metal electrocatalysts still suffer from low activity and Faradaic efficiency due to poor interfacial reaction kinetics. Herein, an interface‐engineered heterojunction, composed of CoS nanosheets anchored on a TiO2 nanofibrous membrane, is developed. The TiO2 nanofibrous membrane can uniformly confine the CoS nanosheets against agglomeration, and contribute substantially to the NRR performance. The intimate coupling between CoS and TiO2 enables easy charge transfer, resulting in fast reaction kinetics at the heterointerface. The conductivity and structural integrity of the heterojunction are further enhanced by carbon nanoplating. The resulting C@CoS@TiO2 electrocatalyst achieves a high ammonia yield (8.09×10−10 mol s−1 cm−2) and Faradaic efficiency (28.6 %), as well as long‐term durability.
“…Baker) were used without further purification. The synthesis of the ligands N -[2-hydroxy-1( R )-methyl-2( R )-phenylethyl]- N -methylglycine (R,R(−) H 2 cpse and N -[2-hydroxy-1( S )-methyl-2( S )-phenylethyl]- N -methylglycine ( S , S (+)H 2 cpse) was carried out as previously described; [8].…”
Section: Experimental Design Materials and Methodsmentioning
confidence: 99%
“…IR (KBrν/cm −1 ): 1569 (ν as COO − ) and 1443 (ν s COO − ) Δν (as-s) = 126 cm-1. These methodology has been used by Barba- Behrens and et-al for tridentate ligands derivate of N - Acetyl pseudoephedrine, [[8], [9], [10]].…”
Section: Experimental Design Materials and Methodsmentioning
Dinuclear manganese (II– III) compounds, which are potential models of the active center of catalase, were synthetized. This type of metalloenzymes presents biological importance due to three factors: they are redox catalyst centres, they are able to carry out hydrolytic reactions and they participate in activated processes via Lewis acids. Structurally, their active centre is composed by dinuclear manganese compounds, linked to nitrogen and oxygen donor atoms. An octahedral geometry around the metal ions were found, with acetate, hydroxy and aquo ligands; which can work as molecule bridges between them. The acid medium favours the electronic transfer between Mn3+ - Mn2+ as redox centre at 1.559 V and the consequent oxidation of hydrogen peroxide or organic molecules. The work also reports the data of two chiral novel compounds, [Mn2(S,S(+)Hcpse)4(NaClO4)2(NaOH)(CH4O)]n·[(C2H6O)2]n·[(CH4O)2]n and its respective enantioisomer, in which μ-oxo being as bridge metal centre. The X-ray structural was obtained as well as the optical and magnetic properties using Circular Dichroism, Electronic Paramagnetic Resonance, Magnetic Susceptibility and X-ray photoelectron spectroscopy.
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