Thermochemical aerobic oxidation catalysis in water can be analysed as two coupled electrochemical half-reactions

Ryu, Jaeyune; Bregante, Daniel T.; Howland, William C.; Bisbey, Ryan P.; Kaminsky, Corey J.; Surendranath, Yogesh

doi:10.1038/s41929-021-00666-2

Cited by 56 publications

(69 citation statements)

References 62 publications

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“…The potential difference and current intensity are closely related to the catalytic activity of the alcohol aerobic oxidation reaction (Supplementary Fig. 21 ) 24 . H 2 O 2 was also detected in the process of Au-catalyzed oxidation of benzyl alcohol, while the content of produced H 2 O 2 was much lower than that for the single-atom catalyst, and no H 2 O 2 was observed in Pt/C-catalyzed oxidation of benzyl alcohol.…”

Section: Resultsmentioning

confidence: 99%

Kinetically restrained oxygen reduction to hydrogen peroxide with nearly 100% selectivity

Chen

Zheng

et al. 2022

Nat Commun

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Hydrogen peroxide has been synthesized mainly through the electrocatalytic and photocatalytic oxygen reduction reaction in recent years. Herein, we synthesize a single-atom rhodium catalyst (Rh1/NC) to mimic the properties of flavoenzymes for the synthesis of hydrogen peroxide under mild conditions. Rh1/NC dehydrogenates various substrates and catalyzes the reduction of oxygen to hydrogen peroxide. The maximum hydrogen peroxide production rate is 0.48 mol gcatalyst−1 h−1 in the phosphorous acid aerobic oxidation reaction. We find that the selectivity of oxygen reduction to hydrogen peroxide can reach 100%. This is because a single catalytic site of Rh1/NC can only catalyze the removal of two electrons per substrate molecule; thus, the subsequent oxygen can only obtain two electrons to reduce to hydrogen peroxide through the typical two-electron pathway. Similarly, due to the restriction of substrate dehydrogenation, the hydrogen peroxide selectivity in commercial Pt/C-catalyzed enzymatic reactions can be found to reach 75%, which is 30 times higher than that in electrocatalytic oxygen reduction reactions.

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Section: Resultsmentioning

confidence: 99%

Kinetically restrained oxygen reduction to hydrogen peroxide with nearly 100% selectivity

Chen

Zheng

et al. 2022

Nat Commun

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“…showed that aerobic formic acid oxidation reactions should be viewed as two electrochemical half reactions: 1) HCOOH → CO2 + 2H + + 2e -; 2) 0.5O2 + 2H + + 2e -→ H2O, in the same way as the electro-catalytic oxidation of formic acid. [18] These findings provide a quantitative and predictive link between thermo-and electro-catalytic aerobic oxidation. Validating whether such mechanisms are extendable to other important thermal catalytic reactions, e.g.…”

Section: Introductionmentioning

confidence: 86%

Electron transfer rather than direct hydrogen atom transfer can drive catalytic hydrogenation on supported metal catalysts

Yan

Sun

et al. 2022

Preprint

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Heterogeneous thermocatalytic hydrogenation is widely believed to occur via co-adsorption of H2 and other reactants. Herein, we test the hypothesis that hydrogenation over supported metal catalysts can proceed via two half reactions in water involving electron release from H2 and proton-electron addition to substrate. Using 4-nitrophenol as a model substrate, the core of our study is to conduct hydrogenation in an unbiased H-cell, where H2 and 4-nitrophenol are separately supplied into two electrically connected chambers separated by a proton exchange membrane. Based on the observation of the almost identical hydrogenation performance between a single cell, in which H2 and 4-nitrophenol are co-fed, and the H-cell, we conclude that co-adsorption of H2 and 4-nitrophenol is not a prerequisite for hydrogenation in aqueous phase in the tested pH range of 0-4.5. The isotope experiments, reaction rate-pH relationship, scavenger test and DFT calculations suggest that a coupled electrochemical half-reaction mechanism for 4-nitrophenol hydrogenation in acidic aqueous phase is not just possible but is predominant. H2 oxidation primarily occurs on metal sites, while 4-nitrophenol reduction occurs on both metal sites and conductive supports.

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“…In order to verify the hypothesis mentioned above, the activation of GLY and oxygen was studied by electrochemical measurements including two coupled electrochemical halfreactions of ORR and alcohol electro-oxidation. [34,44] Firstly, ORR was performed under O 2 saturated conditions via RDE polarization voltammetry and linear sweeping voltammetry curves (LSVs). As shown in Figure 3b, MnO 2 /CNT, and CNT exhibited poor activity for ORR.…”

Section: Chemcatchemmentioning

confidence: 99%

Chemoselective Oxidation of Glycerol over Platinum‐Based Catalysts: Toward the Role of Oxide Promoter

Yang

Song

et al. 2022

ChemCatChem

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The metal oxide promoters remarkably enhance the catalytic activity of supported Pt catalysts in the glycerol oxidation toward glyceric acid, whereas the primary factor that metal oxide promotes the reaction, as well as the kinetics relevant step remain indistinct. Herein, manganese dioxide (MnO2) is chosen as a model to uncover the role of promoter in the glycerol oxidation over Pt‐based catalyst in alkali‐free solution. The results prove that the superior catalytic performance is mainly attributed to the increased synergistic interaction between Pt particles and the metal oxides to boost the activation of oxygen (not glycerol), while the increased dispersion shows slight effect. Furthermore, the detailed kinetic studies reveal that MnO2 is prone to accelerate the awkward step of glyceraldehyde to glyceric acid, and the lattice oxygen of MnO2 also involves in this particular step.

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Thermochemical aerobic oxidation catalysis in water can be analysed as two coupled electrochemical half-reactions

Cited by 56 publications

References 62 publications

Kinetically restrained oxygen reduction to hydrogen peroxide with nearly 100% selectivity

Kinetically restrained oxygen reduction to hydrogen peroxide with nearly 100% selectivity

Electron transfer rather than direct hydrogen atom transfer can drive catalytic hydrogenation on supported metal catalysts

Chemoselective Oxidation of Glycerol over Platinum‐Based Catalysts: Toward the Role of Oxide Promoter

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