Pyridine Complexes of Cobalt(II) and Nickel(II) Nitrates

Biagetti, Richard V.; Haendler, Helmut M.

doi:10.1021/ic50037a012

Cited by 29 publications

(16 citation statements)

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“…The spectrum of the solid complex shows the following absorption bands (cm -1 , v -very strong, s -strong, m -medium, sh -shoulder): 1470 sh,s, 1430 s, 1380 vs, 1310 s and 1280 ms. These bands are indicative of the existence of mono-and bidentate nitrato groups in the complex [5,6]. In fact these absorption bands are very similar to corresponding bands reported for [Cu(NO3)2(N3)2(3-picoline)4(H2O)] complex containing both monodentate and bridging bidentate nitrato groups as established by its X-ray crystal structure analysis [7].…”

Section: Electronic and Infrared Spectrasupporting

confidence: 79%

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

et al. 1994

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Section: Electronic and Infrared Spectrasupporting

confidence: 79%

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

et al. 1994

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“…As‐prepared P10, which contains residual palladium (0.33 wt %) originating from the polymer synthesis, gave a lower but measurable oxygen evolution rate of 1.20 μmol h −1 under broadband irradiation (full arc, 300 W Xe light source) and 0.95 μmol h −1 under visible light irradiation ( λ >420 nm, 300 W Xe light source). Sulfones as well as pyridines can act as ligands for cobalt, which might also impact the photocatalytic performance of the materials in this study. X‐Ray absorption spectroscopy of P10/Co (Supporting Information, Figure S27) indicates that cobalt is, similar to other reports, present as CoO x , which is believed to be the active species for water oxidation.…”

Section: Resultsmentioning

confidence: 99%

Water Oxidation with Cobalt‐Loaded Linear Conjugated Polymer Photocatalysts

et al. 2020

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The first examples of linear conjugated organic polymer photocatalysts that produce oxygen from water after loading with cobalt and in the presence of an electron scavenger are reported. The oxygen evolution rates,w hich are higher than for related organic materials,c an be rationalized by acombination of the thermodynamic driving force for water oxidation,t he light absorption of the polymer,a nd the aqueous dispersibility of the relatively hydrophilic polymer particles.W ea lso used transient absorption spectroscopyt o study the best performing system and we found that fast oxidative quenchingofthe exciton occurs (picoseconds) in the presence of an electron scavenger,minimizing recombination.

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“…The optimization of the catalyst and assembly displayed remarkable performance of FE, EE, and current density with the nafion‐based MEA and promising durability performance. We believe that the efficacy of this catalyst is made possible by creating metal‐nitrogen interactions in the precursor solution, [ 64 ] followed by low‐temperature processing conditions to maintain the integrity of the nanoscale Co‐pyridine coordination. These results are central to further developments of electrochemical CO 2 RR and will accelerate advances in CO 2 utilization.…”

Section: Figurementioning

confidence: 99%

Highly Efficient Electrochemical CO₂ Reduction Reaction to CO with One‐Pot Synthesized Co‐Pyridine‐Derived Catalyst Incorporated in a Nafion‐Based Membrane Electrode Assembly

Fujinuma

Ikoma

Lofland

2020

Advanced Energy Materials

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hindered because the corresponding reaction requires only two electrons and two protons, making it a promising initial feedstock. [19] Recent studies have described high (>90%) Faradaic efficiency (FE) for CO 2 RR to CO at high current density (>50 mA cm −2) for several different catalysts. [20-23] Among catalysts, metaldoped carbon materials have emerged at the intersection between heterogeneous carbon and metal microcycles, showing high selectivity toward CO 2 RR to CO. [23-38] Despite the wide variety of structural designs, most catalysts were shown to promote CO 2 RR only in CO 2-saturated basic or neutral aqueous solution to suppress the competing hydrogen evolution reaction (HER). Another underlying challenge is that the synthetic procedures often require relatively complicated steps such as templating. Such constraints impose practical difficulties and additional costs for operation. As seen in fuel-cell technology, a membrane electrode assembly (MEA) offers technical advantages in terms of scalability, design flexibility, and ease of operation. [39] However, only a few studies have demonstrated CO 2 RR with MEAs with either cation-exchange [25,36,40,41] or anion-exchange membranes. [37,42,43] While cation-exchange based MEAs face a fundamental challenge due to the competing HER because of the acidic environment, they have great potential for commercialization because of their highly durable and widely available components. [44] Herein, we describe a straightforward one-pot synthesis of cobalt and organic [poly-4-vinylpyridine (P4VP)] precursors with carbon supports to form the cathode of a highly effective nafion-based MEA, using the synergy between the reduced cobalt and pyridine moieties to drive the CO 2 RR. Studies indicate that the catalyst performed CO 2 RR predominantly over HER across a wide range of pH. Optimization of the catalyst components led to CO production with 92% FE and 58% EE at 85 mA cm −2 , and preliminary durability tests showed stable FE for 20 h of operation. Metal-pyridine derived carbon catalysts were synthesized according to the reported pyrolysis method as illustrated in Figure 1a. [25,36] Metal (Co, Fe, and Ni) nitrate and pyridine derivatives [4-ethylpyridine (EPy), 4-aminopyridine (APy), poly-4-vinylpyridine (P4VP), and poly-2-vinylpyridine (P2VP)], There is great need for the development of an electrochemical CO 2 reduction reaction (CO 2 RR) process with high Faraday efficiency (FE), energy efficiency (EE), and current density for practical utilization of CO 2. Here, a facile one-pot synthesis of a catalyst is reported that is based on cobalt and poly-4-vinylpyridine that can perform CO 2 RR to CO predominantly with respect to the hydrogen evolution reaction in a nafion-based membrane electrode assembly and can work in pH ranging from 2 to 7. Cell optimization results in CO 2 RR to CO with 92% FE and 58% EE at 85 mA cm −2 , while showing no noticeable degradation in FE at 20 h. These characteristics are attributed to synthesis and processing conditions which promote nearly...

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Pyridine Complexes of Cobalt(II) and Nickel(II) Nitrates

Cited by 29 publications

References 0 publications

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

Water Oxidation with Cobalt‐Loaded Linear Conjugated Polymer Photocatalysts

Highly Efficient Electrochemical CO₂ Reduction Reaction to CO with One‐Pot Synthesized Co‐Pyridine‐Derived Catalyst Incorporated in a Nafion‐Based Membrane Electrode Assembly

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Pyridine Complexes of Cobalt(II) and Nickel(II) Nitrates

Cited by 29 publications

References 0 publications

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)3(NO3)2

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)3(NO3)2

Water Oxidation with Cobalt‐Loaded Linear Conjugated Polymer Photocatalysts

Highly Efficient Electrochemical CO2 Reduction Reaction to CO with One‐Pot Synthesized Co‐Pyridine‐Derived Catalyst Incorporated in a Nafion‐Based Membrane Electrode Assembly

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EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

EPR and Spectral Studies of a Molecular and Crystal Structure of Cu (3,5-dimethylpyridine)₃(NO₃)₂

Highly Efficient Electrochemical CO₂ Reduction Reaction to CO with One‐Pot Synthesized Co‐Pyridine‐Derived Catalyst Incorporated in a Nafion‐Based Membrane Electrode Assembly