The role of oxygen-vacancy in bifunctional indium oxyhydroxide catalysts for electrochemical coupling of biomass valorization with CO2 conversion

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

Published: April 11, 2023

Electrochemical coupling of biomass valorization with carbon dioxide (CO2) conversion provides a promising approach to generate value-added chemicals on both sides the electrolyzer. Herein, oxygen-vacancy-rich indium oxyhydroxide (InOOH-OV) is developed as bifunctional catalyst for CO2 reduction formate and 5-hydroxymethylfurfural electrooxidation 2,5-furandicarboxylic acid faradaic efficiencies over 90.0% at optimized potentials. Atomic-scale electron microscopy images density functional theory calculations reveal that introduction oxygen vacancy sites causes lattice distortion charge redistribution. Operando Raman spectra indicate vacancies could protect InOOH-OV from being further reduced during increase adsorption competitiveness hydroxide ions in alkaline electrolytes, making main-group p-block metal oxide electrocatalyst activities. Based catalytic performance InOOH-OV, pH-asymmetric integrated cell fabricated by combining oxidation together single electrochemical produce high yields (both around 90.0%), providing valuable commodity simultaneously electrodes.

Language: Английский

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Atomically Dispersed Metal–Nitrogen–Carbon Catalysts with d-Orbital Electronic Configuration-Dependent Selectivity for Electrochemical CO₂-to-CO Reduction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2374 - 2385

Published: Feb. 1, 2023

A variety of atomically dispersed transition-metal-anchored nitrogen-doped carbon (M–N–C) electrocatalysts have shown encouraging electrochemical CO2 reduction reaction (CO2RR) performance, with the underlying fundamentals central transition-metal atom determined CO2RR activity and selectivity yet remaining unclear. Herein, a universal impregnation-acid leaching method was exploited to synthesize various M–N–C (M: Fe, Co, Ni, Cu) single-atom catalysts (SACs), which revealed d-orbital electronic configuration-dependent toward for CO production. Notably, Ni–N–C exhibits very high Faradaic efficiency (FE) 97% at −0.65 V versus RHE above 90% in potential range from −0.5 −0.9 RHE, much superior other Cu). With configurations metals SACs well elucidated by crystal-field theory, Dewar–Chatt–Duncanson (DCD) differential charge density analysis reveal that vacant outermost Ni2+ SAC would benefit electron transfer C atoms molecules Ni thus effectively activate surface-adsorbed molecules. However, Fe3+, Co2+, Cu2+ occupied unpaired electrons weaken electron-transfer process then impede activation. In situ spectral investigations demonstrate generation *COOH intermediates is favored over relatively low applied potentials, supporting its CO2-to-CO conversion performance. Gibbs free energy difference rate-limiting step hydrogen evolution (HER) reveals thermodynamically SAC, explaining performance as compared SACs. This work presents facile general strategy modulate perspective configuration

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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Membrane Electrode Assembly for Electrocatalytic CO₂ Reduction: Principle and Application

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: March 27, 2023

Abstract Electrocatalytic CO 2 reduction reaction (CO RR) in membrane electrode assembly (MEA) systems is a promising technology. Gaseous can be directly transported to the cathode catalyst layer, leading enhanced rate. Meanwhile, there no liquid electrolyte between and anode, which help improve energy efficiency of whole system. The remarkable progress achieved recently points out way realize industrially relevant performance. In this review, we focus on principles MEA for RR, focusing gas diffusion electrodes ion exchange membranes. Furthermore, anode processes beyond oxidation water are considered. Besides, voltage distribution scrutinized identify specific losses related individual components. We also summarize generation different reduced products together with corresponding catalysts. Finally, challenges opportunities highlighted future research.

Language: Английский

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Electrocatalytic CO₂ Reduction to C₂₊ Products in Flow Cells

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(5)

Published: Aug. 31, 2023

Abstract Electrocatalytic CO 2 reduction into value‐added fuels and chemicals by renewable electric energy is one of the important strategies to address global shortage carbon emission. Though classical H‐type electrolytic cell can quickly screen high‐efficiency catalysts, low current density limited mass transfer process essentially impede its industrial applications. The cells based on electrolyte flow system (flow cells) have shown great potential for devices, due higher density, improved local concentration, better efficiency. design optimization are significance further accelerate industrialization electrocatalytic reaction (CO RR). In this review, progress RR C 2+ products concerned. Firstly, main events in development outlined. Second, principles products, architectures, types summarized. Third, optimizing generate reviewed detail, including cathode, anode, ion exchange membrane, electrolyte. Finally, preliminary attempts, challenges, research prospects toward discussed.

Language: Английский

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CO₂ Electrolyzers

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(7), P. 3648 - 3693

Published: March 22, 2024

CO2 electrolyzers have progressed rapidly in energy efficiency and catalyst selectivity toward valuable chemical feedstocks fuels, such as syngas, ethylene, ethanol, methane. However, each component within these complex systems influences the overall performance, further advances needed to realize commercialization will require an approach that considers whole process, with electrochemical cell at center. Beyond boundaries, electrolyzer must integrate upstream feeds downstream separation processes a way minimizes product intensity presents viable use cases. Here we begin by describing sources, their intensities, impurities. We then focus on cell, most common system architectures, systems. evaluate savings feasibility of alternative approaches including integration capture, direct conversion flue gas two-step via carbon monoxide. pathways minimize separations produce concentrated streams compatible existing sectors. Applying this comprehensive upstream-to-downstream approach, highlight promising routes, outlook, for reduction.

Language: Английский

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Unusual double ligand holes as catalytic active sites in LiNiO2

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

Published: April 13, 2023

Abstract Designing efficient catalyst for the oxygen evolution reaction (OER) is of importance energy conversion devices. The anionic redox allows formation O-O bonds and offers higher OER activity than conventional metal sites. Here, we successfully prepare LiNiO 2 with a dominant 3 d 8 L configuration ( hole at O p ) under high pressure, achieve double ligand holes since one electron removal occurs orbitals Ni III oxides. exhibits super-efficient among LiMO , R MO (M = transition metal, rare earth) other unary 3d catalysts. Multiple in situ/operando spectroscopies reveal →Ni IV together Li-removal during OER. Our theory indicates that (3 leads to direct coupling between lattice *O intermediates accelerating activity. These findings highlight new way design enough created process.

Language: Английский

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The refinery of the future

Nature, Journal Year: 2024, Volume and Issue: 629(8011), P. 295 - 306

Published: May 8, 2024

Language: Английский

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Efficient strategies for promoting the electrochemical reduction of CO2 to C2+ products over Cu-based catalysts

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 48, P. 32 - 65

Published: May 1, 2023

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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