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1.
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co‐TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co‐PB‐1(6) bearing six Co‐TPP subunits connected through twenty‐four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co‐rPB‐1(6). Both Co‐PB‐1(6) and Co‐rPB‐1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co‐TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.  相似文献   

2.
The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual-metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN6 moieties with double-N-bridged adjacent metal-N4 clusters decorated on a nitrogen-doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ gmetal−1 ⋅ h−1) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so-called formate pathway with the C−H dissociation of HCOO* as the rate-determining step. Theoretical calculations reveal that Cu in the CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d-band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.  相似文献   

3.
We present here the syntheses, crystal structures, and spin crossover (SCO) properties of a series of halogen-functionalized cobalt(II) complexes, [Co(Brphtpy)2](OTf)2 ⋅ DMF ⋅ 2H2O ( 1 ), [Co(Brphtpy)2](HBS)2 ⋅ H2O ( 2 ), [Co(Brphtpy)2](MQ)2 ⋅ 2MeCN ⋅ 3H2O ( 3 ) ( Brphtpy =4′–(4-Bromophenyl)–2,2′:6′,2′′-terpyridine; OTf=trifluoromethanesulfonate; HBS=hydroxybenzenesulfonate dihydrate; MQ=methyl orange). Variable-temperature single-crystal X-ray analyses revealed mononuclear compounds of 1 – 3 consisted of [Co(Brphtpy)2]2+ SCO active units and organosulfonate anions and no structural phase transformation happened in measured high-low temperature. The packing structures of these complexes were tuned by varying organosulfonates. However, no notable supramolecular interactions can be found, in turn leading to gradual, incomplete, and non-hysteretic SCO behaviors. Interestingly, the SCO behaviors of these three complexes were significantly modified after the removal of lattice solvents. Combined structural and magnetic investigations revealed the non-cooperative supramolecular packing structures, guest internal pressure, and the small structural distortions of the SCO units should be responsible for the worse SCO properties of 1 – 3 . The foregoing results show that to achieve high-performance Co2+ SCO, both the weak interactions, internal pressure, and structural distortion should be considered during the design and construction of SCO complexes.  相似文献   

4.
The complexes resulting from the interaction of a new Schiff base ligand derived from crosslinked polystyrene bound benzaldehyde and 2-aminobenzimidazole with a square planar complex [Co(TPP)] (where TPP = meso-tetraphenylporphyrin), and also with tetrahedral complexes [Co(BPBI)2X2] (where BPBI = 1-benzyl-2-phenylbenzimidazole, X = Cl, Br, or NCS) have been isolated and characterized. The percentages of cobalt and nitrogen in the complexes show that only one Schiff base unit is coordinated to cobalt. Infrared spectra suggest that the bonding of the polymer ligand to cobalt is through the N-3 atom of the benzimidazole moiety. The EPR spectra indicate that all the complexes are in the low-spin state and have a square pyramidal environment around cobalt(II). © 1992 John Wiley & Sons, Inc.  相似文献   

5.
Environmentally friendly metal–organic frameworks (MOFs) have gained considerable attention for their potential use as heterogeneous catalysts. Herein, two CuI-based MOFs, namely, [Cu4Cl4L] ⋅ CH3OH ⋅ 1.5 H2O ( 1-Cl ) and [Cu4Br4L] ⋅ DMF ⋅ 0.5 H2O ( 1-Br ), were assembled with new functionalized thiacalix[4]arenes (L) and halogen anions X (X=Cl and Br) under solvothermal conditions. Remarkably, catalysts 1-Cl and 1-Br exhibit great stability in aqueous solutions over a wide pH range. Significantly, MOFs 1-Cl and 1-Br , as recycled heterogeneous catalysts, are capable of highly efficient catalysis for click reactions in water. The MOF structures, especially the exposed active CuI sites and 1D channels, play a key role in the improved catalytic activities. In particular, their catalytic activities in water are greatly superior to those in organic solvents or even in mixed solvents. This work proposes an attractive route for the design and self-assembly of environmentally friendly MOFs with high catalytic activity and reusability in water.  相似文献   

6.
A new catalytic aziridination system that consists of cobalt(II) tetraphenylporphyrin [Co(TPP)] as the catalyst and diphenylphosphoryl azide (DPPA) as the nitrene source has been developed. The cobalt-based catalytic system allows direct synthesis of N-phosphorus-substituted aziridines from alkenes with dinitrogen as the byproduct. Cobalt ion seems essential to the catalytic aziridination with DPPA as no or only trace amounts of the desired products were observed with other metal complexes of tetraphenylporphyrin.  相似文献   

7.
The cobalt(II) coordination polymers{[Co(L1)(nda)] · 2H2O}n ( 1 ) and [Co(L2)2(nda)]n ( 2 ), [L1 = 1,2‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, L2 = 1,4‐bis(5,6‐dimethylbenzimidazol‐1‐ylmethyl)benzene, H2nda = 2,6‐naphthalenedicarboxylic acid] were hydrothermally synthesized by self‐assembly of cobalt chloride with H2nda and different semi‐rigid bis(benzimidazole) derivatives and characterized by IR spectroscopy, elemental analysis, and X‐ray single‐crystal diffraction. Complex 1 displays a 2D layer with (4,4) topology, complex 2 exhibits a 1D infinite chain structure, both complexes were further packed into 3D and 2D supramolecular architectures by weak hydrogen bonding. The catalytic activities of the complexes for degradation of Congo red in a Fenton‐like process are presented. In addition, the electrochemical and electrocatalytical behavior of CPEs modified with both cobalt complexes (Co‐CPE) were investigated in detail.  相似文献   

8.
Photocatalytic synthesis of hydrogen peroxide (H2O2) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co14(L−CH3)24 , is constructed by directly coordinating metal sites (Co sites) used for the O2 reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H2O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g−1 h−1 for H2O2 production under O2-saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host–guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H2O2 synthesis.  相似文献   

9.
The sole and unexpected products from the reactions of a variety of lead (II) and lead (IV) compounds with [Co2(CO)6(L)2] complexes (L = tertiary arsine, phosphine, or phosphite) in refluxing benzene solution are the blue, air-stable percobaltoplumbanes [Pb{Co(CO)3(L)}4]. These have also been obtained from the reaction of Na[Co(CO)3(L)] (L  PBu3n) with lead (II) acetate which with Na[Fe(CO)2(NO)(L)] forms the isoelectronic [Pb{Fe(CO)2(NO)(L)}4] [L  P(OPh)3]. The IR spectra of the complexes in the v(CO) and v(NO) regions are consistent with tetrahedral PbCo4 or PbFe4 fragments, trigonal bipyramidal coordination about the cobalt or iron atoms and linear PbCoAs, PbCoP, or PbFeP systems. Unlike [Pb{Co(CO)4}4], our complexes do not dissociate to [Co(CO)3(L)]? or [Fe(CO)2(NO)(L)]? ions when dissolved in donor solvents.  相似文献   

10.
A rational approach to modulating easy-axis magnetic anisotropy by varying the axial donor ligand in heptacoordinated FeII complexes has been explored. In this series of complexes with formulae of [Fe(H4L)(NCS)2] ⋅ 3 DMF ⋅ 0.5 H2O ( 1 ), [Fe(H4L)(NCSe)2] ⋅ 3 DMF ⋅ 0.5 H2O ( 2 ), and [Fe(H4L)(NCNCN)2] ⋅ DMF ⋅ H2O ( 3 ) [H4L=2,2′-{pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)}bis(N-phenylhydrazinecarboxamide)], the axial positions are successively occupied by different nitrogen-based π-donor ligands. Detailed dc and ac magnetic susceptibility measurements reveal the existence of easy-axis magnetic anisotropy for all of the complexes, with 1 [Ueff=21 K, τ0=1.72×10−6 s] and 2 [Ueff=25 K, τ0=2.25×10−6 s] showing field-induced slow magnetic relaxation behavior. However, both experimental studies and theoretical calculations indicate the magnitude of the D value of complex 3 to be larger than those of complexes 1 and 2 due to the axial bond angle being smaller than that for an ideal geometry. Detailed analysis of the field and temperature dependences of relaxation time for 1 and 2 has revealed that multiple relaxation processes (quantum tunneling of magnetization, direct, and Raman) are involved in slow magnetic relaxation for both of these complexes. Magnetic dilution experiments support the role of intermolecular short contacts.  相似文献   

11.
Wu B  Yuan D  Lou B  Han L  Liu C  Zhang C  Hong M 《Inorganic chemistry》2005,44(25):9175-9184
The reactions of cobalt(II) halides and flexible ligand L [L=1,3-bis(pyrid-4-ylthio)propan-2-one] under different conditions generated a series of complexes with various structural motifs ranging from tetragonal-prismatic cages to 1-3D coordination polymers. The layer diffusion of cobalt(II) chloride and L in methanol/acetone at 25 degrees C gave rise to a 3D polymer, [Co(L)2Cl2].Me2CO. At 30 degrees C, the slow diffusion of diethyl ether into the blue dimethylformamide (DMF) solution of complex 1 afforded a 1D polymer, Co(L)Cl2(DMF)2. However, at 10 degrees C, the diffusion of diethyl ether into the DMF solution of complex 1 produced a tetragonal-prismatic cage, [Co2(L)4Cl2]Cl2.Et2O.DMF.2MeOH.4H2O. The reaction of cobalt(II) bromide and L in DMF at 10 degrees C yielded a dimer, [Co2(L)4Br2]Br2.6DMF.2H2O, with a cage structure similar to. The preparation of the series of compounds indicates the subtle relationship between structures and tunable reaction conditions. It is also found that the structural motifs vary according to the ligand conformations and that the formation of tetragonal-prismatic cages and may be templated by anionic guests. Magnetic studies on complexes in a temperature range 4-300 K disclose that L is unfavorable for a long-range magnetic interaction; however, intramolecular spin-coupling constants of -19.6 and -21.5 cm-1 for and indicate rather strong magnetic superexchanges arising from the overlap of the dz2 orbitals of the cobalt(II) and pz orbitals of the encapsulated halide anions. Electron paramagnetic resonance (EPR) spectra of complexes 3 and 4 in solution and solid give information that both complexes are high-spin cobalt(II) compounds with a rhombic distortion of the axial zero-field splitting. Interestingly, the intramolecular magnetic-exchange coupling in 3 and 4 mediated by the encapsulated anion Cl- or Br- is also reflected by the EPR spectra.  相似文献   

12.
Highly efficient hydrogen evolution reaction (HER) electrocatalyst will determine the mass distributions of hydrogen-powered clean technologies, while still faces grand challenges. In this work, a synergistic ligand modulation plus Co doping strategy is applied to 1T−MoS2 catalyst via CoMo-metal-organic frameworks precursors, boosting the HER catalytic activity and durability of 1T−MoS2. Confirmed by Cs corrected transmission electron microscope and X-ray absorption spectroscopy, the polydentate 1,2-bis(4-pyridyl)ethane ligand can stably link with two-dimensional 1T−MoS2 layers through cobalt sites to expand interlayer spacing of MoS2 (Co−1T−MoS2-bpe), which promotes active site exposure, accelerates water dissociation, and optimizes the adsorption and desorption of H in alkaline HER processes. Theoretical calculations indicate the promotions in the electronic structure of 1T−MoS2 originate in the formation of three-dimensional metal-organic constructs by linking π-conjugated ligand, which weakens the hybridization between Mo-3d and S-2p orbitals, and in turn makes S-2p orbital more suitable for hybridization with H-1s orbital. Therefore, Co−1T−MoS2-bpe exhibits excellent stability and exceedingly low overpotential for alkaline HER (118 mV at 10 mA cm−2). In addition, integrated into an anion-exchange membrane water electrolyzer, Co−1T−MoS2-bpe is much superior to the Pt/C catalyst at the large current densities. This study provides a feasible ligand modulation strategy for designs of two-dimensional catalysts.  相似文献   

13.
A new hydrazone (LH2) derived from the condensation of 2‐(4‐fluorobenzamido)benzohydrazide with 3,5‐di‐tert‐butyl‐2‐hydroxybenzaldehyde was used to synthesize Co(III), Ni(II) and Cu(II) complexes. These were characterized using various physicochemical, thermal, spectroscopic and single‐crystal X‐ray diffraction techniques. All the complexes crystallize in a monoclinic crystal system with P21/n space group and Z = 4. Structural studies of [Co(L)(LH)]?H2O indicate the presence of both amido and imidol tautomeric forms of the ligand, resulting in a distorted octahedral geometry around the Co(III) ion. On the other hand, in the [Ni(L)(DMF)] and [Cu(L)(H2O)] complexes, the ligand coordinates to the metal through imidol form resulting in distorted square planar geometry, in which the fourth position is occupied by the oxygen of coordinated DMF in [Ni(L)(DMF)] and by a water molecule in [Cu(L)(H2O)]. Hirshfeld surface calculations were performed to explore hydrogen bonding and C―H???π interactions. Molecular docking studies were carried out to study the interaction between the synthesized compounds and proteins (cyclooxygenase‐2 and 5‐lipoxygenase). The complexes along with the parent ligand were screened for their in vivo anti‐inflammatory activity, using the carrageenan‐induced rat paw oedema method. The complexes show significant anti‐inflammatory potencies.  相似文献   

14.
Novel 4,4′‐dichloro‐2,2′‐[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L) and its complexes [CuL] and {[CoL(THF)]2(OAc)2Co} have been synthesized and characterized by elemental analyses, IR, 1H‐NMR and X‐ray crystallography. [CuL] forms a mononuclear structure which may be stabilized by the intermolecular contacts between copper atom (Cu) and oxygen atom (O3) to form a head‐to‐tail dimer. In {[CoL(THF)]2(OAc)2Co}, two acetates coordinate to three cobalt ions through Co? O? C? O? Co bridges and four µ‐phenoxo oxygen atoms from two [CoL(THF)] units also coordinate to cobalt ions. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

15.
Detecting and measuring the concentration of ammonia is of interest in many scientific and technological areas. A porphyrin based cobalt(II) complex with a dansyl fluorophore has been synthesized and investigated as a ‘turn-on’ fluorescent ammonia sensor. Over sixfold increase in fluorescence emission occurs upon the treatment of NH3 to [Co(TPP)(Ds-pip)] sensor solution, resulting from NH3-induced displacement of the axially coordinated fluorophore.  相似文献   

16.
A covalently‐linked salen–C60 (H2L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C60 cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen–C60 introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal–salen–C60 complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene‐containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single‐, double‐ and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen–C60 complexes in heterogeneous catalysis.  相似文献   

17.
The metalloradical activation of o-aryl aldehydes with tosylhydrazide and a cobalt(II) porphyrin catalyst produces cobalt(III)-carbene radical intermediates, providing a new and powerful strategy for the synthesis of medium-sized ring structures. Herein we make use of the intrinsic radical-type reactivity of cobalt(III)-carbene radical intermediates in the [CoII(TPP)]-catalyzed (TPP=tetraphenylporphyrin) synthesis of two types of 8-membered ring compounds; novel dibenzocyclooctenes and unprecedented monobenzocyclooctadienes. The method was successfully applied to afford a variety of 8-membered ring compounds in good yields and with excellent substituent tolerance. Density functional theory (DFT) calculations and experimental results suggest that the reactions proceed via hydrogen atom transfer from the bis-allylic/benzallylic C−H bond to the carbene radical, followed by two divergent processes for ring-closure to the two different types of 8-membered ring products. While the dibenzocyclooctenes are most likely formed by dissociation of o-quinodimethanes (o-QDMs) which undergo a non-catalyzed 8π-cyclization, DFT calculations suggest that ring-closure to the monobenzocyclooctadienes involves a radical-rebound step in the coordination sphere of cobalt. The latter mechanism implies that unprecedented enantioselective ring-closure reactions to chiral monobenzocyclooctadienes should be possible, as was confirmed for reactions mediated by a chiral cobalt-porphyrin catalyst.  相似文献   

18.
Developing cost-effective and sustainable acidic water oxidation catalysts requires significant advances in material design and in-depth mechanism understanding for proton exchange membrane water electrolysis. Herein, we developed a single atom regulatory strategy to construct Co−Co dinuclear active sites (DASs) catalysts that atomically dispersed zirconium doped Co9S8/Co3O4 heterostructure. The X-ray absorption fine structure elucidated the incorporation of Zr greatly facilitated the generation of Co−Co DASs layer with stretching of cobalt oxygen bond and S−Co−O heterogeneous grain boundaries interfaces, engineering attractive activity of significantly reduced overpotential of 75 mV at 10 mA cm−2, a breakthrough of 500 mA cm−2 high current density, and water splitting stability of 500 hours in acid, making it one of the best-performing acid-stable OER non-noble metal materials. The optimized catalyst with interatomic Co−Co distance (ca. 2.80 Å) followed oxo-oxo coupling mechanism that involved obvious oxygen bridges on dinuclear Co sites (1,090 cm−1), confirmed by in situ SR-FTIR, XAFS and theoretical simulations. Furthermore, a major breakthrough of 120,000 mA g−1 high mass current density using the first reported noble metal-free cobalt anode catalyst of Co−Co DASs/ZCC in PEM-WE at 2.14 V was recorded.  相似文献   

19.
Photothermal CO2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K+−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K+−Co−C catalyst shows a record-high photothermal CO2 hydrogenation rate of 758 mmol gcat−1 h−1 (2871 mmol gCo−1 h−1) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO2 reduction reactions. We further demonstrate with this catalyst effective CO2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.  相似文献   

20.
The present investigation describes synthesis of a good range of henna‐based compounds in the presence of novel nano cobalt phthalocyanine like molten salt (tetra‐2,3‐pyridiniumporphyrazinato cobalt tribromomethanide) [Co (TPPABr)]CBr3 as an efficient, recyclable and thermally stable heterogeneous catalyst.  相似文献   

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