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Results for “electrocatalytic oxidation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur (Li/S) cells. A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue. Herein, we employed in situ/operando X-ray absorption spectroscopy (XAS) to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces, respectively, in a real-time condition. After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix (BSOC), we found the Li/S cell showed greatly improved sulfur utilization and longer life span. The operando S K-edge XAS results revealed that the BSOC modification was bi-functional: trapping polysulfides and catalyzing conversion of sulfur species simultaneously. We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection. Finally, our results could offer potential stratagem for designing more advanced Li/S cells.

25 ENERGY STORAGE↗
DOE OSTI2024

Origins of enhanced oxygen reduction activity of transition metal nitrides

Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure–(re)activity relationships and rational catalyst design. Here, in this work, we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn 3 O 4 shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn 3 O 4 . The strained Mn 3 O 4 shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn 3 O 4 . A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure–reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.

electrocatalysis↗
DOE OSTI2020

Rapid Electrochemical Methane Functionalization Involves Pd–Pd Bonded Intermediates

High-valent Pd complexes are potent agents for the oxidative functionalization of inert C-H bonds, and it was previously shown that rapid electrocatalytic methane monofunctionalization could be achieved by electro-oxidation of Pd II to a critical dinuclear Pd III intermediate in concentrated or fuming sulfuric acid. However, the structure of this highly reactive, unisolable intermediate, as well as the structural basis for its mechanism of electrochemical formation, remained elusive. Herein, we use X-ray absorption and Raman spectroscopies to assemble a structural model of the potent methane-activating intermediate as a Pd III dimer with a Pd-Pd bond and a 5-fold O atom coordination by H x SO 4 (x-2) ligands at each Pd center. We further use EPR spectroscopy to identify a mixed-valent M-M bonded Pd 2 II,III species as a key intermediate during the Pd II -to-Pd III 2 oxidation. Combining EPR and electrochemical data, we quantify the free energy of Pd dimerization as <-4.5 kcal/mol for Pd 2 II,III and <-9.1 kcal/mol for Pd III 2 . The structural and thermochemical data suggest that the aggregate effect of metal-metal and axial metal-ligand bond formation drives the critical Pd dimerization reaction in between electrochemical oxidation steps. This work establishes a structural basis for the facile electrochemical oxidation of Pd II to a M-M bonded Pd III dimer and provides a foundation for understanding its rapid methane functionalization reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity

To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts are considered as potential candidates because of intrinsic redox attributes, but in-depth understanding and rational design of Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation of Ni-metalloids (NiP x , NiS x , and NiSe x ) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TO x ), among which NiOOH-PO x shows optimal local coordination environment and boosts electrocatalytic activity of Ni sites towards selective oxidation of methanol to formate. Experiments and theoretical results demonstrate that NiOOH-PO x possesses improved adsorption of OH* and methanol, and favors the formation of CH 3 O* intermediates. The coordinated phosphate oxyanions effectively tailor the d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study provides additional insights into modulation of active-center coordination environment via oxyanions for organic molecules transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

How Noninnocent Spectator Species Improve the Oxygen Reduction Activity of Single-Atom Catalysts: Microkinetic Models from First-Principles Calculations

Graphene-based single-atom catalysts are promising alternatives to platinum-based catalysts for fuel cell applications. Different transition metals have been screened using electronic structure methods by estimating onset potentials from the most endergonic elementary reaction step. Here, we calculate onset potentials for the oxygen reduction reaction on metal atoms embedded in N-substituted graphene di-vacancies by virtue of first-principles-informed microkinetic analysis. We find that for more oxophilic metals (Cr, Fe, Mn, and Ru), purely thermodynamic models systematically underestimate onset potentials. Furthermore, the oxophilic metals (Cr, Fe, Mn, and Ru) are oxidized under reaction conditions, leading to an increase in activity compared to their reduced state. Importantly, coadsorbed O m H n species actively participate in the reaction, which requires a dynamic treatment of spectator species. These findings highlight the limitations of thermodynamic analyses for electrocatalytic processes, which commonly assume the same oxidation state for each metal, and show that deviations between computational and experimental onset potentials cannot be solely attributed to the shortcomings of the electronic structure methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Intensified Catalytic Conversion of CO2 into High Value Chemicals

The utilization of CO2 produced from power generation plants as a feedstock for creating new valuable products offers a strategy to reduce GHG emissions, offset carbon capture costs, and facilitate the rebalancing of the carbon cycle. After considering the thermodynamic requirement of potential products from CO2 utilization and their market size, formic acid is a desirable target that offers widespread utility in industrial chemical production and chemical energy storage as a liquid fuel. To effectively utilize CO2 from power generation plants, UK proposes an enhanced bimetallic oxide carbon utilization process (EBOCU) that enables electrochemical CO2 conversion to formic acid. The UK intensified electrocatalytic process combines three main components: 1) a novel bimetallic oxide electrocatalyst; 2) a stable electrochemical reactor using robust electrodes; and 3) a pressurized electrochemical reactor. The output from this project showed the economic viability of producing high-value formic acid from CO2 to both offset the cost associated with post-combustion CCS and reduce GHG emissions. This project developed and screened a series engineered catalysts to selectively reduce CO2 directly to formic acid. The best performing catalyst based on formic acid production, stability, and Faradaic efficiency, was immobilized on carbon electrodes, and tested inside a flow through reactor. After lab-scale testing was completed, the experimental data was used to perform a Life-Cycle Analysis (LCA) and conduct an Initial Technical and Economic Feasibility Study. The LCA showed a pathway to a net negative CO2 utilization process with the incorporation of renewable energy, while the TEA showed the potential to produce formic acid below the current commercial price. The UK EBOCU process was successfully demonstrated at the TRL3 level and has a clear pathway to further development and contribution to the nation’s ambitious decarbonization goals.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

A single-Pt-atom-on-Ru-nanoparticle electrocatalyst for CO-resilient methanol oxidation

Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. In this report we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Construction of a Pt‐CeO x Interface for the Electrocatalytic Hydrogen Evolution Reaction

Abstract The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeO x that improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeO x interfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeO x nanosheets. This interface structure facilitates substantial electron transfer from Pt to CeO x , resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeO x interfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.

25 ENERGY STORAGE↗
DOE OSTI2021

Plasma-Initiated Graft Polymerization of Acrylic Acid onto Fluorine-Doped Tin Oxide as a Platform for Immobilization of Water-Oxidation Catalysts

The discovery of new and versatile strategies for the immobilization of molecular water-oxidation catalysts (WOCs) is crucial for developing clean energy conversion devices [e.g., (photo)electrocatalytic cells for water splitting]. The traditional approach for surface attachment to transparent conductive oxides [e.g., fluorine doped tin oxide (FTO)] is via synthetic modification of the ligand architecture to incorporate functional groups such as carboxylic acids (-COOH) or phosphonates (-PO 3 H 2 ) prior to immobilization. However, challenges arising from desorption and the cumbersome derivatizations steps have limited the scope and applications of surface-bound WOCs. Herein, we report the successful immobilization of underivatized Ru(II)-based WOCs (Ru–Cat1 = [Ru(tpy) (bpy) (H 2 O)] 2+ (tpy = 2,2':6'2"–terpyridine and bpy = 2,2;-bipyridine) and Ru–Cat2 = [Ru(Mebimpy) (bpy) (H 2 O)] 2+ (Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) pyridine)) and the Ru(II) polypyridyl chromophore Ru–C3 = [Ru(bpy) 3 ] 2+ onto a FTO plasma-grafted poly(acrylic acid) surface (PAA|FTO). Various characterization techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and cyclic voltammetry measurements provide evidence for the plasma-induced grafted PAA|FTO film and immobilization. Surface stability and electrocatalytic properties of these new hybrid composite films upon cycling were investigated at different pH values. Immobilized Ru–Cat1 and Ru–Cat2 onto PAA|FTO displayed pH-dependent (RuIII/RuII) couples and onset potentials indicative of PCET (proton-coupled electron transfer) reactions. Based on cyclic voltammetry results and spectroscopic monitoring, the immobilized WOCs Ru–Cat1 and Ru–Cat2 exhibited a higher surface stability in neutral aqueous solutions relative to Ru–C3 upon electrochemical oxidation. Furthermore, we attribute the surface PCET and stability to the presence of a water ligand in the coordination sphere of immobilized Ru–Cat1 and Ru–Cat2 which can H-bond with negatively charged carboxylate groups of the cross-linked PAA brushes. Our findings demonstrate that the plasma-grafted polymeric network onto FTO offers a versatile platform to directly anchor unmodified homogeneous WOCs or chromophores for potential applications in solar-to-fuel energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Anodic electrocatalytic conversion of carboxylic acids on thin films of RuO 2 , IrO 2 , and Pt

The electrocatalytic upgrading of carboxylic acids, abundant biomass-derived molecules, remains a challenging task. In this paper, we report an electrocatalytic decarboxylation (ECDX) approach for the conversion of carboxylic acids into paraffins, olefins, and alcohols via (non-)Kolbe electrolysis on thin films (TFs). The ECDX rate, product selectivity, and current efficiency were potential and electrode dependent. For example, the ECDX activity of RuO 2 -TF was similar to that of Pt foil, but the selectivity to Kolbe products was lower on the former. RuO 2 -TF showed about five times higher rates for the oxygen evolution reaction than Pt foil, which resulted in lower current efficiency. The ECDX and O 2 evolution activities of IrO 2 -TF were potential dependent, but this electrode was selective to non-Kolbe products with low current efficiency (<10 %). This work highlights the performance of thin films as an alternative to bulk metals as anodes for oxidative upgrading of carboxylic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Catalytic and electrocatalytic performance of Sr(Ti 0.3 Fe 0.7 Ru 0.07 )O 3-δ for applications in solid oxide fuel cells supplied with ethanol steam reforming mixtures

We discuss how direct utilization of alcohols in Solid Oxide Fuel Cells (SOFCs) can improve the conversion efficiency by using excess heat for internal reforming and simplify the system balance of plant. Thanks to their scarce carbon- formation tendency, perovskite oxide anodes are promising alternatives to Ni-based cermets. Here we show that Sr(Ti 0.3 Fe 0.7 Ru 0.07 )O 3-δ (STF-Ru) exsolution anodes provide both catalytic reforming activity and electro- chemical activity with steam/ethanol (S/E) mixtures at 3:1 and 2:1 M ratio between 700 and 800 °C. Electrolyte- supported scandia stabilized zirconia SOFCs with STF-Ru anodes and Sr 0.95 Ti 0.3 Fe 0.7 O 3-δ (STF) cathodes are reasonably stable in the 3:1 S/E mixture over 20 h at 800 °C, with maximum power density of 195 mW/cm 2 and 140 mW/cm 2 at 0.7 V. Deactivation instead occurs with the 2:1 S/E mixture. Comparatively, cells with Ni-YSZ anodes rapidly coke and fail under the same conditions. Ethanol steam reforming experiments in a fixed bed powder reactor reveal that, above 650 °C, gas phase reactions convert ethanol to CO, hydrogen, acetaldehyde and ethylene, while STF-Ru catalyzes steam reforming. Thermogravimetric and Raman characterizations show that a moderate amount of carbon is deposited on the STF-Ru surface, which is more amorphous than the disruptive carbon which degrades Ni-YSZ.

09 BIOMASS FUELS↗
DOE OSTI2023

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction

In this study, we have investigated a hierarchical CuO-derived inverse opal (CuO-IO) catalyst with high CO selectivity up to 80–90% and minimal H 2 evolution at moderate potentials for CO 2 electroreduction. The three-dimensionally (3D) structured, porous catalyst was composed of small CuO nanoparticles and exhibited a peak CO faradaic efficiency (FE) of 72.5% (±1.8), complete suppression of H 2 formation, and good stability over 24 hours operation at –0.6 V versus the reversible hydrogen electrode (RHE). In situ Raman, X-ray absorption spectroscopy and X-ray diffraction measurements indicated reduction of the catalyst into metallic Cu0 oxidation state with dominant Cu(111) orientation under electrocatalytic conditions. We suggest that rapid depletion of CO 2 and protons at the highly roughened catalyst surface likely increased the local pH during the electrolysis. The combination of C 1 favoring Cu(111) surfaces and reduced local proton/CO 2 availability facilitated selective conversion of CO 2 into CO and reduced H 2 and C 2 products. Our work provides additional understanding of the structure–property relationships of 3D porous electrocatalysts for CO 2 reduction applications by evaluating the crystallographic orientation, oxidation state, and crystallite size of a CO-selective CuO-IO catalyst under realistic working conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Redox-stable symmetrical solid oxide fuel cells with exceptionally high performance enabled by electrode/electrolyte diffuse interface

Here, in this study, we report a high performance and redox-stable symmetrical solid oxide fuel cell (SOFC) based on (Ba 0.5 Sr 0.5 ) (Mo 0.1 Fe 0.9 )O 3-δ (BSMF) electrode and La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) electrolyte. BSMF is able to operate both as anode and cathode. Excellent electrocatalytic activity has been achieved on BSMF towards hydrogen oxidation and oxygen reduction. Due to its closely matched lattice parameter to LSGM electrolyte, a unique diffuse interface is formed between BSMF and LSGM. Compared to a clean interface, e.g. BSMF/gadolinium doped ceria interface, this diffuse interface promotes the performance of BSMF electrode 1–1.8 times in 600–800 °C. Polarization resistance of the BSMF/LSGM specimen is as low as 0.047 and 0.007 Ωcm 2 in humidified H 2 and in air at 800 °C, respectively. On the BSMF/LSGM/BSMF symmetrical cell, a maximum power density of 2.28 W/cm 2 is achieved at 800 °C, the highest among with redox-stable ceramic electrodes to the best of our knowledge. Redox stability of this cell is confirmed. The role of anode and cathode is reversed back and forth in different operation modes. No apparent degradation is observed through 4 cycles within a 110 h operation period. These findings demonstrate that (Ba 0.5 Sr 0.5 ) (M o0.1 Fe 0.9 )O 3-δ coupled with LSGM electrolyte is an excellent choice to build a high performance, redox-stable SOFC.

25 ENERGY STORAGE↗
DOE OSTI2021

Elucidating the Role of Single-Atom Pd for Electrocatalytic Hydrodechlorination

In this study, we loaded Pd catalysts onto a reduced graphene oxide (rGO) support in an atomically dispersed fashion [i.e., Pd single-atom catalysts (SACs) on rGO or Pd 1 /rGO] via a facile and scalable synthesis based on anchor-site and photoreduction techniques. The as-synthesized Pd 1 /rGO significantly outperformed the Pd nanoparticle (Pdnano) counterparts in the electrocatalytic hydrodechlorination of chlorinated phenols. Downsizing Pd nano to Pd 1 leads to a substantially higher Pd atomic efficiency (14 times that of Pdnano), remarkably reducing the cost for practical applications. The unique single-atom architecture of Pd 1 additionally affects the desorption energy of the intermediate, suppressing the catalyst poisoning by Cl – , which is a prevalent challenge with Pdnano. Characterization and experimental results demonstrate that the superior performance of Pd 1 /rGO originates from (1) enhanced interfacial electron transfer through Pd–O bonds due to the electronic metal–support interaction and (2) increased atomic H (H*) utilization efficiency by inhibiting H 2 evolution on Pd 1 . Furthermore, this work presents an important example of how the unique geometric and electronic structure of SACs can tune their catalytic performance toward beneficial use in environmental remediation applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tuning the Co/Fe ratio in BaCo x Fe 0.8– x Zr 0.1 Y 0.1 O 3– δ , a promising triple ionic and electronic conducting oxide, to boost electrolysis and fuel cell performance

The triple conducting oxide BaCo 0.4 Fe 0.4 Zr 0.1 Y0.1O 3–δ (BCFZY4411), which accommodates simultaneous transport of protons, oxygen ions, and p-type electronic carriers, has been intensively investigated in recent years as a high-performance positive electrode material for fuel cell and electrolysis applications. The heavy Co and Fe-based transition metal doping in BCFZY4411 ensures adequate electrical conductivity while the multiple oxidation states of Co and Fe assist the electrocatalytic and redox ability. Despite the considerable role of Co and Fe transition metal doping in controlling electrochemical activity, however, the study of alternative BCFZY compositions with varying Co/Fe ratios has not yet been pursued. Here, we evaluate the electrochemical performance of a series of BaCo x Fe 0.8–x Zr 0.1 Y0.1O 3–δ compositions with varying Co/Fe ratio (x = 0.1, 0.2, 0.4, 0.6, 0.7) and use oxygen ion tracer diffusion and in situ high-temperature X-ray diffraction to investigate the effect of Co/Fe ratio on electrocatalytic activity, electronic conductivity, oxygen ion incorporation and transport kinetics, and thermomechanical behavior. We find that Co-rich BCFZY7111 yields the highest performance due to exceptionally high oxygen vacancy diffusion and shows a lower and more linear thermal expansion behavior compared to Fe-rich compositions. A protonic ceramic button cell incorporating a BCFZY7111 positive electrode yields a peak power density of 695 mW cm –2 under fuel cell mode and an electrolysis current density of 1976 mA cm –2 at 1.4 V at 600 °C, underscoring the promise of this new BCFZY electrode composition.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage

Abstract C−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C 3 H 2 * was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.

Chemistry↗