Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment with Polymer Binders

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(9)

Published: Jan. 5, 2022

Abstract The activity and selectivity of the electrochemical CO 2 reduction reaction (CO RR) are often hindered by limited access to catalyst surface overtaken competing hydrogen evolution reaction. Herein, it is revealed that polymers used as binders can effectively modulate accessibility relative H O at vicinity thus performance RR. Three with different hydrophilicities (i.e., polyacrylic acid (PAA), Nafion, fluorinated ethylene propylene (FEP)) selected for Cu catalysts. At a thickness only ≈1.2 nm, these strongly affect toward multi‐carbon (C 2+ ) products. FEP coated exhibits C partial current density over 600 mA cm −2 ≈77% faradaic efficiency −0.76 V versus RHE. This high attributed hydrophobic (aerophilic) properties FEP, which reduces local concentration enhances reactant intermediates CO). These findings suggest tuning hydrophobicity electrocatalysts polymer be promising way regulate reactions involving gas–solid–liquid interfaces.

Language: Английский

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Engineering the NiNC Catalyst Microenvironment Enabling CO₂ Electroreduction with Nearly 100% CO Selectivity in Acid

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(38)

Published: July 28, 2022

CO2 electrolysis in acid has emerged as a promising route to achieve high utilization due the inhibition of undesired carbonate formation that generally occurs alkaline or neutral conditions. However, efficiency and stability this system need be further improved through tailoring electrocatalyst its working environment. Here, microenvironment structurally engineered NiNC catalyst for acidic is probed optimized by adding hydrophobic poly(tetrafluoroethylene) (PTFE) nanoparticles catalytic layer gas-diffusion electrodes. The PTFE-modified electrode delivers nearly 100% CO Faradaic at an industry-relevant current density 250 mA cm-2 , single-pass 75.7% 200 under 20 sccm gas flow rate. Moreover, compared conventional without added PTFE, exhibits substantially enhanced water-flooding-resistant ability. Mechanistic investigations reveal moderate PTFE modification can optimize local /H2 O ratio layer, favoring reduction diffusion thickness highly active stable solid-liquid-gas interfacial microenvironment.

Language: Английский

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A unifying mechanism for cation effect modulating C1 and C2 productions from CO2 electroreduction

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 19, 2022

Abstract Electrocatalysis, whose reaction venue locates at the catalyst–electrolyte interface, is controlled by electron transfer across electric double layer, envisaging a mechanistic link between rate and layer structure. A fine example in CO 2 reduction reaction, of which shows strong dependence on alkali metal cation (M + ) identity, but there yet to be unified molecular picture for that. Using quantum-mechanics-based atom-scale simulation, we herein scrutinize M -coupling capability possible intermediates, establish H - -associated ET mechanisms CH 4 CO/C formations, respectively. These theoretical scenarios are successfully underpinned Nernstian shifts polarization curves with or concentrations first-order kinetics formation electrode surface charge density. Our finding further rationalizes merit using Nafion-coated enhanced C2 production terms

Language: Английский

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Microenvironment Engineering for the Electrocatalytic CO₂ Reduction Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: July 12, 2022

Abstract Rather than just focusing on the catalyst itself in electrocatalytic CO 2 reduction reaction (eCO RR), as previously reviewed elsewhere, we herein extend discussion to special topic of microenvironment around center and present a comprehensive overview recent research progress. We categorize based components relevant active sites, i.e., surface, substrate, co‐reactants, electrolyte, membrane, reactor. Supported by most reported articles, factors affecting catalytic performance eCO RR are then discussed detail, existing challenges potential solutions mentioned. Perspectives for future RR, including integration different factors, extension industrial application coupling with carbon capture conversion, separation products, also discussed.

Language: Английский

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Selective CO2 electrolysis to CO using isolated antimony alloyed copper

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 20, 2023

Abstract Renewable electricity-powered CO evolution from 2 emissions is a promising first step in the sustainable production of commodity chemicals, but performing electrochemical reduction economically at scale challenging since only noble metals, for example, gold and silver, have shown high performance -to-CO. Cu potential catalyst to achieve industrial scale, C-C coupling process on significantly depletes CO* intermediates, thus limiting rate producing many hydrocarbon oxygenate mixtures. Herein, we tune selectivity by alloying second metal Sb into Cu, report an antimony-copper single-atom alloy (Sb 1 Cu) isolated Sb-Cu interfaces that catalyzes efficient conversion -to-CO with Faradaic efficiency over 95%. The partial current density reaches 452 mA cm −2 approximately 91% efficiency, negligible C 2+ products are observed. In situ spectroscopic measurements theoretical simulations reason atomic interface promotes adsorption/activation weakens binding strength CO*, which ends up enhanced rates.

Language: Английский

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Tailoring acidic microenvironments for carbon-efficient CO₂electrolysis over a Ni–N–C catalyst in a membrane electrode assembly electrolyzer

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(4), P. 1502 - 1510

Published: Jan. 1, 2023

By tailoring the microenvironments of a Ni–N–C catalyst in an acidic MEA electrolyzer, we achieve CO faradaic efficiency 95% at 500 mA cm −2 , and 2 loss is reduced by 86% 300 pH 0.5, compared to alkaline electrolysis.

Language: Английский

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Modeling Operando Electrochemical CO₂ Reduction

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(12), P. 11085 - 11130

Published: April 27, 2022

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

Language: Английский

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Energy- and carbon-efficient CO2/CO electrolysis to multicarbon products via asymmetric ion migration–adsorption

Nature Energy, Journal Year: 2023, Volume and Issue: 8(2), P. 179 - 190

Published: Jan. 12, 2023

Language: Английский

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Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 3, 2023

Electrochemical conversion of CO2 to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it still difficult achieve high production at wide voltage intervals and industrial current densities because Bi are often poisoned by oxygenated species. Herein, we report a Bi3S2 nanowire-ascorbic hybrid catalyst that simultaneously improves selectivity, activity, stability applied voltages. Specifically, more than 95% faraday efficiency was achieved formate formation over potential range above 1.0 V ampere-level densities. The observed excellent catalytic performance attributable unique reconstruction mechanism form defective sites while ascorbic layer further stabilized trapping poisoning hydroxyl groups. When used in an all-solid-state reactor system, newly developed efficient pure 120 hours 50 mA cm-2 (200 cell current).

Language: Английский

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Continuum Modeling of Porous Electrodes for Electrochemical Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(12), P. 11022 - 11084

Published: May 4, 2022

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources power the conversion of abundant feedstocks value-added commodity chemicals and fuels. Of potential system architectures for these processes, only systems employing 3-D structured porous electrodes have capacity achieve high rates necessary industrial scale. However, phenomena environments in are not well understood challenging probe experimentally. Fortunately, continuum modeling is well-suited rationalize observed behavior electrochemical synthesis, as ultimately provide recommendations guiding design next-generation devices components. In this review, we begin by presenting an historical review electrode systems, with aim showing how past knowledge macroscale can contribute rising challenge synthesis. We then present a detailed overview governing physics assumptions required simulate Leveraging developed understanding porous-electrode theory, survey discuss literature reports on simulating multiscale order demonstrate their relevance improving performance Lastly, our perspectives regarding future directions development models that most accurately describe predict such best applications models.

Language: Английский

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