Complexes of Nickel(II)with a Cyclic Tetradentate Secondary Amine

Bosnich, B.; Tobe, M. L.; Webb, G. A.

doi:10.1021/ic50030a004

Cited by 190 publications

(92 citation statements)

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“…(2016) or ethanol and the product separated by addition of ether. 16,17 Our approach affords a precipitated product in nearly quantitative yields.…”

Section: Methodsmentioning

confidence: 92%

Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Qin

Maza

Stratakes

et al. 2016

J. Electrochem. Soc.

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Hydrogen production in microbial electrolysis cells (MECs) is a promising approach for energy harvesting from wastewater. The kinetic barriers toward proton reduction necessitate the use of catalysts to drive hydrogen formation at appreciable rates and low applied potentials. Towards this end, cost effective alternatives to platinum catalysts are of paramount interest. In this study, Ni(OH) 2 films were synthesized by electrophoretic deposition from a Ni(II)cyclam precursor solution at varying concentrations (6 mM, 15 mM, and 23 mM). The films were characterized by scanning electron microscopy and X-ray photo-electron spectroscopy to confirm the deposition of Ni(OH) 2 . The Ni(OH) 2 -modified electrodes were then examined by both traditional electrochemical measurements and in an MEC for hydrogen production. Tafel analysis indicates an exchange current density of ∼0.36 mA cm −2 with a Tafel slope of ∼120 mV decade −1 consistent with a rate determining proton adsoprtion step. The hydrogen production rates increased with increasing Ni(II)cyclam concentration in the precursor solution, with the 23 mM-derived film exhibiting a rate comparable to that of a Pt-based catalyst in MEC tests. Hydrogen is considered to be one of the most promising energy carriers as an alternative fuel because of its high energy density and availability from renewable sources. Over 90% of hydrogen gas is produced by steam reforming and coal gasification, both of which are highly energy-consuming processes.1 Among the newly developed technologies for hydrogen production, microbial electrolysis cells (MECs) are of special interest as a new approach for hydrogen production from organic matter in wastewater and other organic waste. 2,3 In an MEC, organic compounds are degraded by exoelectrogens (electrochemically-active microorganisms), and as a result, electrons are passed to an anode electrode. Hydrogen gas can be formed at the cathode (−0.414 V vs. SHE, standard hydrogen electrode) by reducing protons. This process must be aided by an additional voltage (0.114 V in theory) as a result of the insufficiency of the anode potential (e.g., −0.300 V vs. SHE when acetate is used as an anode substrate) to drive proton reduction. In reality, an external voltage of more than 0.2 V is required to overcome the additional kinetic barriers imposed by the hydrogen formation reaction. 4 This additional voltage is substantially lower than that needed for electrochemical water splitting (theoretically 1.23 V vs. SHE 5 ) making hydrogen production energetically more cost efficient. In addition, recovery of valuable energy content from wastewater/waste also results in environmental benefits.Catalysts are indispensable in accomplishing the hydrogen evolution reaction (HER). Most MEC studies have used platinum-based catalysts for HER catalysis. Platinum is a highly efficient catalyst for HER, but its high cost obstructs its application in MECs, especially for large scale systems that are designed for wastewater treatment. 4,6 Thus, alternative catalysts have bee...

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“…(2016) or ethanol and the product separated by addition of ether. 16,17 Our approach affords a precipitated product in nearly quantitative yields.…”

Section: Methodsmentioning

confidence: 92%

Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Qin

Maza

Stratakes

et al. 2016

J. Electrochem. Soc.

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“…Optimization of the geometries leads to nearly the same configuration but the total energy of cyclam-Cu with Cu-Cl complex is lower than in the case of nickel based complexes. Alternatively, bonding of the central nickel with two chlorines seems more stable from the total energy criterion and can be compared to experimental reports based on X-ray diffraction [54]. The nickel-chlorine bonds were fond anomalously longer than usually shown for undistorted octahedral complexes.…”

Section: Geometry Of the Cyclam-metal Complexesmentioning

confidence: 90%

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Makowska‐Janusik

Kassiba

Errien

et al. 2010

J Inorg Organomet Polym

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Mesoporous silica functionalized by cyclammetal molecules were investigated by spectroscopic methods including Raman, IR, UV-VIS absorption and EPR technique. To analyse quantitatively the physical features, numerical models were developed using the density functional theory method. Thus, the construction of molecular geometries and their optimisation analysis were achieved on the cyclam-metal molecules in vacuum as well as constrained by the host mesoporous silica matrixes. In this context and with regard to the paramagnetic nature of the metals chelated by cyclam molecules, EPR technique allows probing the metal environments which can be compared to theoretical results inferred from numerical models. The vibrational and optical properties were exhaustively investigated and the assignment of the main features was quantitatively discussed thanks to the carried out numerical analyses. The developed approach point out the possibility to define a targeted application of such functional materials based on the possibility to fine tune the absorption features in a wide wavelength range by stabilizing defined configurations of the cyclam-metal groups.

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“…6H2O and then allowed to dry. This method differs slightly from typical synthetic approaches in which equimolar amounts of Ni(II)Cl2 and the tetraazacyclotetradecane are dissolved in methanol or ethanol and the product separated by addition of ether (Bosnich et al 1965, Voelcker et al 2008. Our approach affords a precipitated product in nearly quantitative yields.…”

Section: Methodsmentioning

confidence: 97%

Resource recovery by osmotic bioelectrochemical systems towards sustainable wastewater treatment

Qin

2017

Environ. Sci.: Water Res. Technol.

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(academic)Recovering valuable resources from wastewater will transform wastewater management from a treatment focused to sustainability focused strategy, and creates the need for new technology development. An innovative treatment concept -osmotic bioelectrochemical system (OsBES), which is based on cooperation between bioelectrochemical systems (BES) and forward osmosis (FO), has been introduced and studied in the past few years. An OsBES can accomplish simultaneous treatment of wastewater and recovery of resources such as nutrient, energy, and water (NEW). The cooperation can be accomplished in either an integrated (osmotic microbial fuel cells, OsMFC) or coupled (microbial electrolysis cell-forward osmosis system, MEC-FO) configuration.In OsMFC, higher current generation than regular microbial fuel cell (MFC) was observed, resulting from the lower resistance of FO membrane. The electricity generation in OsMFC could greatly inhibit the reverse salt flux. Besides, ammonium removal was successfully demonstrated in OsMFC, making OsMFCs a promising technology for "NEW recovery" (NEW: nutrient, energy and water). For the coupled OsBES, an MEC-FO system was developed. The MEC produced an ammonium bicarbonate draw solute via recovering ammonia from synthetic organic solution, which was then applied in the FO for extracting water from the MEC anode effluent. The system has been advanced with treating landfill leachate. A mathematical model developed for ammonia removal/recovery in BES quantitatively confirmed that the NH4 + ions serve as effective proton shuttles across cation exchange membrane (CEM). Resource Recovery by Osmotic Bioelectrochemical Systems towards Sustainable Wastewater TreatmentMohan Qin Abstract (general audience)Nowadays, wastewater is no longer considered as waste. Instead, it is a pool for different kinds of resources, such as nutrient, energy, and water (NEW). Various technologies were developed to achieve NEW recovery from wastewater. A novel concept, osmotic bioelectrochemical system (OsBES) has been introduced and studied in the past few years. OsBES is based on two technologies: bioelectrochemical systems (BES) and forward osmosis (FO); and the corporation between these two technologies could accomplish simultaneous wastewater treatment and resource recovery. We investigated two kinds of OsBES: one is osmotic microbial fuel cells (OsMFC), and the other is microbial electrolysis cell-forward osmosis system (MEC-FO). For OsMFC, a mathematical model was built to understand the internal resistance, which will affect the current generation according to Om's law (I=U/R). The salt transport across the cation exchange membrane (CEM) is related to the current generation. The ion transport, especially ammonium/ammonia transport, across CEM membrane in BES was modelled, which will help the BES design and operation for ammonia recovery systems. The system performance for wastewater treatment and resource recovery in MEC-FO was fully investigated with both synthetic wastewater and landfill leach...

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Complexes of Nickel(II)with a Cyclic Tetradentate Secondary Amine

Cited by 190 publications

References 1 publication

Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Resource recovery by osmotic bioelectrochemical systems towards sustainable wastewater treatment

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Complexes of Nickel(II)with a Cyclic Tetradentate Secondary Amine

Cited by 190 publications

References 1 publication

Nanoparticulate Ni(OH)2Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Nanoparticulate Ni(OH)2Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Resource recovery by osmotic bioelectrochemical systems towards sustainable wastewater treatment

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Product

Resources

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Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells

Nanoparticulate Ni(OH)₂Films Synthesized from Macrocyclic Nickel(II) Cyclam for Hydrogen Production in Microbial Electrolysis Cells