CO2 electro-reduction on Cu3P: Role of Cu(I) oxidation state and surface facet structure in C1-formate production and H2 selectivity

Laursen, Anders B.; Calvinho, Karin U. D.; Goetjen, Timothy A.; Yap, Kyra M. K.; Hwang, Shinjae; Yang, Hongbin; Garfunkel, Eric; Dismukes, G. Charles

doi:10.1016/j.electacta.2021.138889

Cited by 30 publications

(26 citation statements)

References 70 publications

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“…This pathway is calculated to have a barrier as high as 2.3 eV, which is inconsistent with the low experimentally applied potentials . In addition to nickel phosphides and FeP, other phosphides shown to catalyze CO 2 RR are MoP and Cu 3 P producing formic acid, BP producing methanol, and CuP 2 , which generates 1-butanol.…”

Section: Introductionmentioning

confidence: 78%

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

et al. 2021

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Development of efficient electrocatalysts for the CO2 reduction reaction (CO2RR) to multicarbon products has been constrained by high overpotentials and poor selectivity. Here, we introduce iron phosphide (Fe2P) as an earth-abundant catalyst for the CO2RR to mainly C2–C4 products with a total CO2RR Faradaic efficiency of 53% at 0 V vs RHE. Carbon product selectivity is tuned in favor of ethylene glycol formation with increasing negative bias at the expense of C3–C4 products. Both Grand Canonical-DFT (GC-DFT) calculations and experiments reveal that *formate, not *CO, is the initial intermediate formed from surface phosphino-hydrides and that the latter form ionic hydrides at both surface phosphorus atoms (H@Ps) and P-reconstructed Fe3 hollow sites (H@P*). Binding of these surface hydrides weakens with negative bias (reactivity increases), which accounts for both the shift to C2 products over higher C–C coupling products and the increase in the H2 evolution reaction (HER) rate. GC-DFT predicts that phosphino-hydrides convert *formate to *formaldehyde, the key intermediate for C–C coupling, whereas hydrogen atoms on Fe generate tightly bound *CO via sequential PCET reactions to H2O. GC-DFT predicts the peak in CO2RR current density near −0.1 V is due to a local maximum in the binding affinity of *formate and *formaldehyde at this bias, which together with the more labile C2 product affinity, accounts for the shift to ethylene glycol and away from C3–C4 products. Consistent with these predictions, addition of exogenous CO is shown to block all carbon product formation and lower the HER rate. These results demonstrate that the formation of ionic hydrides and their binding affinity, as modulated by the applied potential, controls the carbon product distribution. This knowledge provides new insight into the influence of hydride speciation and applied bias on the chemical reaction mechanism of CO2RR that is relevant to all transition metal phosphides.

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Section: Introductionmentioning

confidence: 78%

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

et al. 2021

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“…[31,32] In Figure 4b, the strong peaks centered at 932.5 eV in the Cu 2p 3/2 profile and the peak centered at 952.3 eV in the Cu 2p 1/2 profile can be attributed to Cu + of Cu 3 P or Cu 0 . [33][34][35] Oxidation occurs on the surface when the sample is exposed to air. Significant satellite peaks at 943.3 eV and 962.6 eV are attributed to Cu 2 + .…”

Section: Resultsmentioning

confidence: 99%

Cu/Cu₃P@CNT Flexible Film Electrode for Highly Efficient Electrocatalytic Hydrogen Evolution in Alkaline Solution

Zhang

Xia

et al. 2022

ChemElectroChem

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Global warming and the global energy crisis are worsening owing to the increasing consumption of fossil fuels; thus, there is a need to explore renewable and clean energy sources. The energy conversion efficiency of water electrolysis – an important and feasible means to obtain green hydrogen energy – can be improved by developing catalytic electrode materials with high activity and low overpotential. Herein, low‐temperature phosphating of copper deposited on flexible carbon nanotube (CNT) films was conducted to fabricate high‐performance Cu/Cu3P@CNT electrocatalysts for the hydrogen evolution reaction (HER). The optimal conditions for the preparation of catalytic electrodes were determined by adjusting the electrodeposition time. Owing to the porous CNT framework and the heterostructure of the Cu3P/Cu nanoparticles, the Cu/Cu3P@CNT exhibited long‐term stability and highly efficient catalytic HER in an alkaline electrolyte with an overpotential of only 77 mV at 10 mA cm−2. This study provided a facile strategy for designing inexpensive and efficient electrocatalytic HER systems using highly active transition metal phosphides heterostructures and CNT materials.

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“…Transition-metal phosphides (TMPs), for example, are structurally complex materials that exhibit unique chemical, physical, and electronic properties due to the metal–phosphorus interactions in the crystal lattice. , These M–P interactions offer a route to precisely tune the properties of TMPs for diverse catalytic applications. TMPs are known to be highly active hydroprocessing catalysts , and, more recently, have generated significant interest as electrocatalysts due to their inherent electrical conductivity and stability. − Specifically, inexpensive and earth-abundant compositions have demonstrated activity for the hydrogen evolution reaction (HER) comparable to that of noble metal catalysts, , as well as the reduction of CO 2 to oxygenated single- and multi-carbon products. − …”

Section: Introductionmentioning

confidence: 99%

“…The composition and structure of TMPs have distinct effects on the electrocatalytic performance. ,− The introduction of a second metal to form ternary compositions (M x M y P z ), in particular, has led to catalytic performances that can exceed that of the binary parent phase. This enhancement in catalytic performance has been attributed to electronic and geometric effects that strongly influence the properties of the active sites.…”

Section: Introductionmentioning

confidence: 99%

Controlled Synthesis of Transition Metal Phosphide Nanoparticles to Establish Composition-Dependent Trends in Electrocatalytic Activity

et al. 2022

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Transition-metal phosphides (TMPs) are versatile materials with tunable electronic and structural properties that have led to exceptional catalytic performances for important energy applications. Identifying predictive relationships between the catalytic performance and key features such as the composition, morphology, and crystalline structure hinges on the ability to independently tune these variables within a TMP system. Here, we have developed a versatile, low-temperature solution synthesis route to alloyed nickel phosphide (Ni 1.6 M 0.4 P, where M = Co, Cu, Mo, Pd, Rh, or Ru) nanoparticles (NPs) that retains the structure of the parent Ni 2 P NPs, allowing investigation of compositional effects on activity without convoluting factors from differences in morphology and crystalline phase. As a measure of the controlled changes introduced within the isostructural series by the second metal, the binary and alloyed ternary TMP NPs supported on carbon at a nominal 5% weight loading were studied as electrocatalysts for the hydrogen evolution reaction (HER). The resultant activity of the electrocatalyst series spanned a 125 mV range in overpotential, and composition-dependent trends were investigated using density functional theory calculations on flat (0001) and corrugated (101̅ 0) Ni 1.67 M 0.33 P surfaces. Applying the adsorption free energy of atomic H (G H ) as a descriptor for HER activity revealed a facet-dependent volcano-shaped correlation between the overpotential and G H , with the activity trend well represented by the corrugated (101̅ 0) surfaces on which metal−metal bridge sites are available for H adsorption but not the flat (0001) surfaces. The versatility of the rational synthetic methodology allows for the preparation of a wide range of compositionally diverse TMP NPs, enabling the investigation of critical composition−performance relationships for energy applications.

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CO2 electro-reduction on Cu3P: Role of Cu(I) oxidation state and surface facet structure in C1-formate production and H2 selectivity

Cited by 30 publications

References 70 publications

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Cu/Cu₃P@CNT Flexible Film Electrode for Highly Efficient Electrocatalytic Hydrogen Evolution in Alkaline Solution

Controlled Synthesis of Transition Metal Phosphide Nanoparticles to Establish Composition-Dependent Trends in Electrocatalytic Activity

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CO2 electro-reduction on Cu3P: Role of Cu(I) oxidation state and surface facet structure in C1-formate production and H2 selectivity

Cited by 30 publications

References 70 publications

Surface Hydrides on Fe2P Electrocatalyst Reduce CO2 at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe2P Electrocatalyst Reduce CO2 at Low Overpotential: Steering Selectivity to Ethylene Glycol

Cu/Cu3P@CNT Flexible Film Electrode for Highly Efficient Electrocatalytic Hydrogen Evolution in Alkaline Solution

Controlled Synthesis of Transition Metal Phosphide Nanoparticles to Establish Composition-Dependent Trends in Electrocatalytic Activity

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Product

Resources

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Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Surface Hydrides on Fe₂P Electrocatalyst Reduce CO₂ at Low Overpotential: Steering Selectivity to Ethylene Glycol

Cu/Cu₃P@CNT Flexible Film Electrode for Highly Efficient Electrocatalytic Hydrogen Evolution in Alkaline Solution