Modeling Operando Electrochemical CO2 Reduction DOI
Federico Dattila, Ranga Rohit Seemakurthi, Yecheng Zhou

et al.

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

Electrocatalysis for CO2conversion: from fundamentals to value-added products DOI

Genxiang Wang,

Junxiang Chen, Yichun Ding

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(8), P. 4993 - 5061

Published: Jan. 1, 2021

This timely and comprehensive review mainly summarizes advances in heterogeneous electroreduction of CO2: from fundamentals to value-added products.

Language: Английский

Citations

906
Strategies to suppress hydrogen evolution for highly selective electrocatalytic nitrogen reduction: challenges and perspectives DOI
Yongwen Ren,

Chang Yu,

Xinyi Tan

et al.

Energy & Environmental Science, Journal Year: 2021, Volume and Issue: 14(3), P. 1176 - 1193

Published: Jan. 1, 2021

This review underlines the strategies to suppress HER for selective NRR in view of proton-/electron-transfer kinetics, thermodynamics, and electrocatalyst design on basis deep understanding mechanisms.

Language: Английский

Citations

426
An industrial perspective on catalysts for low-temperature CO2 electrolysis DOI
Richard I. Masel, Zengcai Liu,

Hongzhou Yang

et al.

Nature Nanotechnology, Journal Year: 2021, Volume and Issue: 16(2), P. 118 - 128

Published: Jan. 11, 2021

Language: Английский

Citations

417
High carbon utilization in CO2 reduction to multi-carbon products in acidic media DOI
Yi Xie, Pengfei Ou, Xue Wang

et al.

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(6), P. 564 - 570

Published: June 9, 2022

Language: Английский

Citations

396
Impedance Analysis of Electrochemical Systems DOI
Vincent Vivier, Mark E. Orazem

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(12), P. 11131 - 11168

Published: June 10, 2022

Interpretation of impedance spectroscopy data requires both a description the chemistry and physics that govern system an assessment error structure measurement. The approach presented here includes use graphical methods to guide model development, measurement analysis assess presence stochastic bias errors, systematic development interpretation models in terms proposed reaction mechanism physical description. Application corrosion, batteries, biological systems is discussed, emerging trends implementation are presented.

Language: Английский

Citations

326
Efficiency and selectivity of CO2 reduction to CO on gold gas diffusion electrodes in acidic media DOI Creative Commons
Mariana C. O. Monteiro, Matthew F. Philips, Klaas Jan P. Schouten

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Aug. 16, 2021

Abstract The electrochemical reduction of CO 2 to is a promising technology for replacing production processes employing fossil fuels. Still, low energy efficiencies hinder the at commercial scale. electrolysis has mainly been performed in neutral or alkaline media, but recent fundamental work shows that high selectivities can also be achieved acidic media. Therefore, we investigate feasibility pH 2–4 indrustrially relevant conditions, using 10 cm gold gas diffusion electrodes. Operating current densities up 200 mA −2 , obtain faradaic between 80–90% sulfate electrolyte, with 30% improvement overall process efficiency, comparison Additionally, find weakly hydrated cations are crucial accomplishing reaction rates and enabling This study represents step towards application electrolyzers electroreduction.

Language: Английский

Citations

269
Electrocatalytic CO2-to-C2+ with Ampere-Level Current on Heteroatom-Engineered Copper via Tuning *CO Intermediate Coverage DOI
Min Zheng, Pengtang Wang, Xing Zhi

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14936 - 14944

Published: Aug. 4, 2022

An ampere-level current density of CO2 electrolysis is critical to realize the industrial production multicarbon (C2+) fuels. However, under such a large density, poor CO intermediate (*CO) coverage on catalyst surface induces competitive hydrogen evolution reaction, which hinders reduction reaction (CO2RR). Herein, we report reliable CO2-to-C2+ by heteroatom engineering Cu catalysts. The Cu-based compounds with (N, P, S, O) are electrochemically reduced heteroatom-derived significant structural reconstruction CO2RR conditions. It found that N-engineered (N-Cu) exhibits best productivity remarkable Faradaic efficiency 73.7% -1100 mA cm-2 and an energy 37.2% -900 cm-2. Particularly, it achieves C2+ partial -909 at -1.15 V versus reversible electrode, outperforms most reported In situ spectroscopy indicates adjusts *CO adsorption alters local H proton consumption in solution. Density functional theory studies confirm high strength N-Cu results from depressed HER promoted both bridge atop sites Cu, greatly reduces barrier for C-C coupling.

Language: Английский

Citations

269
The Role of Cation Acidity on the Competition between Hydrogen Evolution and CO2 Reduction on Gold Electrodes DOI Creative Commons
Mariana C. O. Monteiro, Federico Dattila, Núria López

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(4), P. 1589 - 1602

Published: Dec. 28, 2021

CO2 electroreduction (CO2RR) is a sustainable alternative for producing fuels and chemicals. Metal cations in the electrolyte have strong impact on reaction, but mainly alkali species been studied detail. In this work, we elucidate how multivalent (Li+, Cs+, Be2+, Mg2+, Ca2+, Ba2+, Al3+, Nd3+, Ce3+) affect CO2RR competing hydrogen evolution by studying these reactions polycrystalline gold at pH = 3. We observe that no effect proton reduction low overpotentials, alkaline surface acidic undergo hydrolysis, generating second regime. The activity onset water reaction correlate with cation acidity, weakly hydrated trivalent leading to highest activity. Acidic only favor overpotentials media. At high CO increases order Ca2+ < Li+ Ba2+ Cs+. To there must be an interplay between stabilization of *CO2- intermediate, accumulation outer Helmholtz plane (OHP), reduction. Ab initio molecular dynamics simulations explicit electric field show nonacidic lower repulsion interface, accumulating more OHP, thus triggering local promoting effects. Water dissociation kinetics increasingly promoted strongly (Nd3+, Al3+), agreement experimental evidence. Nd3+ coordinate adsorbed steadily; they enable barrierless protonation COOH further products.

Language: Английский

Citations

254
Electrolyte Effects on CO2 Electrochemical Reduction to CO DOI Creative Commons
Giulia Marcandalli, Mariana C. O. Monteiro, Akansha Goyal

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(14), P. 1900 - 1911

Published: June 30, 2022

ConspectusThe electrochemical reduction of CO2 (CO2RR) constitutes an alternative to fossil fuel-based technologies for the production fuels and commodity chemicals. Yet application CO2RR electrolyzers is hampered by low energy Faradaic efficiencies. Concomitant reactions, like hydrogen evolution (HER), lower selectivity, while conversion into (bi)carbonate through solution acid-base reactions induces additional concentration overpotential. During in aqueous media, local pH becomes more alkaline than bulk causing consumption homogeneous reactions. The latter effect, combination with solubility electrolytes (33 mM), leads a significant depletion at electrode surface.The nature electrolyte, terms cation identity, has recently emerged as important factor tune both efficiency. In this Account, we summarize recent advances understanding electrolyte effects on CO solutions, which first, crucial, step further reduced products. To compare literature findings meaningful way, focus results reported under well-defined mass transport conditions using online analytical techniques. discussion covers molecular-level proton donor, suppression gradient vs enhancement HER given rate cation, crucial enabling HER. These mechanistic insights are then translated possible implications industrially relevant cell geometries current densities.

Language: Английский

Citations

246
Suppression of Hydrogen Evolution in Acidic Electrolytes by Electrochemical CO2 Reduction DOI Creative Commons
Christoph J. Bondue, Matthias Graf, Akansha Goyal

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(1), P. 279 - 285

Published: Dec. 24, 2020

In this article we investigate the electrochemical reduction of CO2 at gold electrodes under mildly acidic conditions. Differential mass spectroscopy (DEMS) is used to quantify amounts formed hydrogen and carbon monoxide as well consumed amount CO2. We how Faradaic efficiency CO formation affected by partial pressure (0.1–0.5 bar) proton concentration (1–0.25 mM). Increasing former enhances rate suppresses evolution from reduction, leading efficiencies close 100%. Hydrogen suppressed all protons electrode surfaces are support water (CO2 + 2H+ 2e– → H2O). Under conditions slow transport, leaves no evolution. On basis our results, derive a general design principle for acid electrolyzers suppress reduction: CO/OH– must be high enough match/compensate transfer surface.

Language: Английский

Citations

244