Predictive control of selective secondary alcohol oxidation of glycerol on NiOOH

Goetz, McKenna K.; Bender, Michael; Choi, Kyoung‐Shin

doi:10.1038/s41467-022-33637-7

Cited by 67 publications

(73 citation statements)

References 46 publications

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“…Another more recently proposed mechanism is the potential-dependent (PD) mechanism, where at higher potentials, alcohols can be directly oxidized on the Ni 4+ surface without regenerating Ni(OH) 2 or NiOOH. 10,15 Other work on similar systems has shown the importance of catalyst support and composition, 16−18 size and morphology, 19,20 electrolyte pH, 21−23 and reactants (organic substrates) 16,21,24 on the catalytic mechanism. Unraveling the convoluted mechanistic web would enable the development of high-performance alcohol oxidation catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…This energy descriptor can then be found out from either the Pourbaix diagram or via cyclic voltammetry in an alcohol-free electrolyte, from which the electrochemical potential (labeled as E 0 ) required to form the M(OH) 2 /MOOH redox feature is determined. Another more recently proposed mechanism is the potential-dependent (PD) mechanism, where at higher potentials, alcohols can be directly oxidized on the Ni 4+ surface without regenerating Ni(OH) 2 or NiOOH. , Other work on similar systems has shown the importance of catalyst support and composition, − size and morphology, , electrolyte pH, − and reactants (organic substrates) ,, on the catalytic mechanism. Unraveling the convoluted mechanistic web would enable the development of high-performance alcohol oxidation catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes

et al. 2023

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The electrochemical oxidation of bio-derived molecules has recently garnered interest for its potential in opening electrified synthetic pathways toward value-added products. Herein, we investigate the electrochemical conversion of benzyl alcohol (BA) to benzaldehyde and benzoate on nickel–iron (Fe ∼ 7–18%) electrodes as a model system to understand reaction mechanisms and environmental conditions that can transform these molecules. Our results indicate a strong correlation between benzyl alcohol oxidation (BAO) onset potentials and Ni(II/III) redox peak positions, highlighting the potential role that lower oxidation states of nickel, i.e., Ni3+, can play in BAO catalysis. Our work on the Ni2+/3+ system complements mechanisms that involve higher oxidation states of Ni as reported by others. We note that the Ni redox position and thus BAO onset is impacted by Fe incorporation during electrochemistry from unpurified electrolytes, which can resemble standard reactor operating conditions. We perform a systematic computational investigation into BAO and provide density functional theory (DFT) insights into how the redox mechanism has been such a prominent focus of alcohol oxidations. This includes the mode of BA adsorption and the nature of the adsorption site; upon conversion of the Ni2+ surface to active Ni3+ via hydroxyl deprotonation, BAO is thermodynamically downhill. Our DFT study also introduces the possibility of a vacancy-driven mechanism, though expected to be less prevalent during catalysis than the redox mechanism for a Ni3+ surface. Through the systematic investigation of experimental reaction conditions and computational free energy thermodynamics, we have gained valuable insights into BAO reaction mechanisms that inform catalytic activity. Our study opens avenues for further design and development of catalyst active sites for the oxidation of related organic molecules.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes

et al. 2023

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“…The latter is responsible for the C-C cleavage with growing positive potential. [55] Pei et al observed that the glycerol concentration in the electrolyte during anodic oxidation influences the system's performance as the electrolyte's resistance increased over 0.2 mol L −1 , due to the large viscosity and the associated weakened convective mass transfer. [56] These findings underline the complexity and multitude of influential factors when tuning the selectivity and activity toward a desired product.…”

Section: Selectivity Activity and Stability In Hybrid Water Electrolysismentioning

confidence: 99%

Challenges for Hybrid Water Electrolysis to Replace the Oxygen Evolution Reaction on an Industrial Scale

Kahlstorf,

Hausmann,

Sontheimer

et al. 2023

Global Challenges

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To enable a future society based on sun and wind energy, transforming electricity into chemical energy in the form of fuels is crucial. This transformation can be achieved in an electrolyzer performing water splitting, where at the anode, water is oxidized to oxygen—oxygen evolution reaction (OER)—to produce protons and electrons that can be combined at the cathode to form hydrogen—hydrogen evolution reaction (HER). While hydrogen is a desired fuel, the obtained oxygen has no economic value. A techno‐economically more suitable alternative is hybrid water electrolysis, where value‐added oxidation reactions of abundant organic feedstocks replace the OER. However, tremendous challenges remain for the industrial‐scale application of hybrid water electrolysis. Herein, these challenges, including the higher kinetic overpotentials of organic oxidation reactions compared to the OER, the small feedstock availably and product demand of these processes compared to the HER (and carbon dioxide reduction), additional purifications costs, and electrocatalytic challenges to meet the industrially required activities, selectivities, and especially long‐term stabilities are critically discussed. It is anticipated that this perspective helps the academic research community to identify industrially relevant research questions concerning hybrid water electrolysis.

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“…The former could be attributed to the instability of the products in the high pH electrolyte, as previously reported for glycerol derived products. 56 The electrochemical reactions consumed the charge, and therefore further limited the glucose conversion.…”

Section: Electrooxidation Of Fructose and Gluconatementioning

confidence: 99%

Electrification of glucose valorization over NiO/Ni foam

Sanghez de Luna,

Tabanelli,

Velasco-Vélez

et al. 2023

Sustainable Energy Fuels

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Predictive control of selective secondary alcohol oxidation of glycerol on NiOOH

Cited by 67 publications

References 46 publications

Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes

Insights into Active Sites and Mechanisms of Benzyl Alcohol Oxidation on Nickel–Iron Oxyhydroxide Electrodes

Challenges for Hybrid Water Electrolysis to Replace the Oxygen Evolution Reaction on an Industrial Scale

Electrification of glucose valorization over NiO/Ni foam

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