Modulation of the selectivity of CO2 to CO electroreduction in palladium rich Palladium-Indium nanoparticles

Pavesi, Davide; Dattila, Federico; Poll, Rim C.J. van de; Anastasiadou, Dimitra; Garcı́a-Muelas, Rodrigo; Figueiredo, Margarida; Gruter, Gert Jan M.; López, Núria; Koper, Marc T. M.; Schouten, Klaas Jan P.

doi:10.1016/j.jcat.2021.08.021

Cited by 13 publications

(10 citation statements)

References 45 publications

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“…A similar weakening effect of polarized sites on binding energy was reported by Ismail et al , on a Au/Pb interface, where subsurface oxygens dopants hindered poisoning of the Pb surface, thus allowing formation of methane. An analogous electrostatic repulsion between positively charged surface atoms and adsorbates has been mentioned for a In–Pd solid solution, where In substituents weaken *H and *CO binding energy due to their partial positive charge, +0.64 |e – | estimated through Bader charge analysis. , Finally, similar tuning of eCO 2 R selectivity due to surface polarization were proposed for nickel oxygenates …”

Section: Modeling Reconstruction Under Electrochemical Conditionssupporting

confidence: 57%

“…An analogous electrostatic repulsion between positively charged surface atoms and adsorbates has been mentioned for a In−Pd solid solution, where In substituents weaken *H and *CO binding energy due to their partial positive charge, +0.64 |e − | estimated through Bader charge analysis. 311,312 Finally, similar tuning of eCO 2 R selectivity due to surface polarization were proposed for nickel oxygenates. 97 Recently, we have systematically assessed the influence of polarized sites on CO 2 reduction activity and selectivity on the AIMD-derived OD-Cu models discussed previously (Figure 9a, section 4.2).…”

Section: Surface Polarization Effectsmentioning

confidence: 63%

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Modeling Operando Electrochemical CO₂ Reduction

et al. 2022

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Since the seminal works on the application of density functional theory and the computational hydrogen electrode to electrochemical CO2 reduction (eCO2R) and hydrogen evolution (HER), the modeling of both reactions has quickly evolved for the last two decades. Formulation of thermodynamic and kinetic linear scaling relationships for key intermediates on crystalline materials have led to the definition of activity volcano plots, overpotential diagrams, and full exploitation of these theoretical outcomes at laboratory scale. However, recent studies hint at the role of morphological changes and short-lived intermediates in ruling the catalytic performance under operating conditions, further raising the bar for the modeling of electrocatalytic systems. Here, we highlight some novel methodological approaches employed to address eCO2R and HER reactions. Moving from the atomic scale to the bulk electrolyte, we first show how ab initio and machine learning methodologies can partially reproduce surface reconstruction under operation, thus identifying active sites and reaction mechanisms if coupled with microkinetic modeling. Later, we introduce the potential of density functional theory and machine learning to interpret data from Operando spectroelectrochemical techniques, such as Raman spectroscopy and extended X-ray absorption fine structure characterization. Next, we review the role of electrolyte and mass transport effects. Finally, we suggest further challenges for computational modeling in the near future as well as our perspective on the directions to follow.

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Section: Modeling Reconstruction Under Electrochemical Conditionssupporting

confidence: 57%

Section: Surface Polarization Effectsmentioning

confidence: 63%

Modeling Operando Electrochemical CO₂ Reduction

et al. 2022

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“…Similar effect of weaking of *CO and *H binding has been reported for positively polarized In sites. 43 It is likely that for the Ni 40 In 60 Ox mixed oxides presented here, the persistence of oxidized Ni and In sites at À0.8 V contribute to the weakening of *CO, facilitating its release as main product. and In(III) species as well as small Ni X In Y alloy crystallites in the form of amorphous oxide/alloy composite during the early stages of material transformation at low reductive bias (E $ À0.8 V).…”

Section: Oxide-derived Vs Alloy Catalystmentioning

confidence: 87%

Section: Oxide-derived Vs Alloy Catalystmentioning

confidence: 87%

CO₂ electroreduction activity and dynamic structural evolution of in situ reduced nickel-indium mixed oxides

et al. 2022

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“…Despite extensive efforts of the scientific community, achieving high selectivity at low overpotentials remains a significant challenge for the CO 2 RR. − One strategy to influence product selectivity is catalyst modification with organic additives such as poly(4-vinyl pyridine) (P4VP), N-substituted pyridinium, poly(acrylamide) (PAM), and N , N ′-ethylene-phenanthrolinium dibromide . Coating polycrystalline Cu electrodes with P4VP yields improved formic acid selectivity with maximum faradaic efficiency (FE) of ca.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Electrochemical CO₂ Reduction to Formate on Poly(4-vinylpyridine)-Modified Copper and Gold Electrodes

Raaijman

Rothenberg

et al. 2022

ACS Appl. Mater. Interfaces

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Developing active and selective catalysts that convert CO2 into valuable products remains a critical challenge for further application of the electrochemical CO2 reduction reaction (CO2RR). Catalytic tuning with organic additives/films has emerged as a promising strategy to tune CO2RR activity and selectivity. Herein, we report a facile method to significantly change CO2RR selectivity and activity of copper and gold electrodes. We found improved selectivity toward HCOOH at low overpotentials on both polycrystalline Cu and Au electrodes after chemical modification with a poly(4-vinylpyridine) (P4VP) layer. In situ attenuated total reflection surface-enhanced infrared reflection-adsorption spectroscopy and contact angle measurements indicate that the hydrophobic nature of the P4VP layer limits mass transport of HCO3 – and H2O, whereas it has little influence on CO2 mass transport. Moreover, the early onset of HCOOH formation and the enhanced formation of HCOOH over CO suggest that P4VP modification promotes a surface hydride mechanism for HCOOH formation on both electrodes.

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Modulation of the selectivity of CO2 to CO electroreduction in palladium rich Palladium-Indium nanoparticles

Cited by 13 publications

References 45 publications

Modeling Operando Electrochemical CO₂ Reduction

Modeling Operando Electrochemical CO₂ Reduction

CO₂ electroreduction activity and dynamic structural evolution of in situ reduced nickel-indium mixed oxides

Enhanced Electrochemical CO₂ Reduction to Formate on Poly(4-vinylpyridine)-Modified Copper and Gold Electrodes

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Modulation of the selectivity of CO2 to CO electroreduction in palladium rich Palladium-Indium nanoparticles

Cited by 13 publications

References 45 publications

Modeling Operando Electrochemical CO2 Reduction

Modeling Operando Electrochemical CO2 Reduction

CO2 electroreduction activity and dynamic structural evolution of in situ reduced nickel-indium mixed oxides

Enhanced Electrochemical CO2 Reduction to Formate on Poly(4-vinylpyridine)-Modified Copper and Gold Electrodes

Contact Info

Product

Resources

About

Modeling Operando Electrochemical CO₂ Reduction

Modeling Operando Electrochemical CO₂ Reduction

CO₂ electroreduction activity and dynamic structural evolution of in situ reduced nickel-indium mixed oxides

Enhanced Electrochemical CO₂ Reduction to Formate on Poly(4-vinylpyridine)-Modified Copper and Gold Electrodes