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

ACS Nano, Год журнала: 2024, Номер 18(14), С. 9823 - 9851

Опубликована: Март 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.

Язык: Английский

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Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction

Chemical Reviews, Год журнала: 2024, Номер 124(15), С. 9136 - 9223

Опубликована: Июль 22, 2024

The electrocatalytic oxygen evolution reaction (OER) supplies the protons and electrons needed to transform renewable electricity into chemicals fuels. However, OER is kinetically sluggish; it operates at significant rates only when applied potential far exceeds reversible voltage. origin of this overpotential hidden in a complex mechanism involving multiple electron transfers chemical bond making/breaking steps. Our desire improve catalytic performance has then made mechanistic studies an area major scientific inquiry, though complexity understanding difficult. While historically, have relied solely on experiment phenomenological models, over past twenty years

Язык: Английский

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Downsizing Porphyrin Covalent Organic Framework Particles Using Protected Precursors for Electrocatalytic CO₂ Reduction

Advanced Materials, Год журнала: 2024, Номер 36(19)

Опубликована: Фев. 1, 2024

Abstract Covalent organic frameworks (COFs) are promising electrocatalyst platforms owing to their designability, porosity, and stability. Recently, COFs with various chemical structures developed as efficient electrochemical CO 2 reduction catalysts. However, controlling the morphology of COF catalysts remains a challenge, which can limit electrocatalytic performance. Especially, while porphyrin show catalytic properties, particle size is mostly large uncontrolled because severe aggregation crystallites. In this work, new synthetic methodology for rationally downsized catalyst particles reported, where tritylated amine employed novel protected precursor synthesis. Trityl protection provides high solubility precursor, its deprotection proceeds in situ under typical synthesis conditions. Subsequent homogeneous nucleation colloidal growth yield smaller than conventional synthesis, suppressed crystallite aggregation. The exhibit superior performance reduction, higher production rate faradaic efficiency compared particles. improved attributed contact area conductive agent. This study reveals an important factor evaluation electrocatalysts strategy control it.

Язык: Английский

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Selective Electrosynthesis of Ethanol via Asymmetric C–C Coupling in Tandem CO₂ Reduction

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8776 - 8785

Опубликована: Май 21, 2024

Selective electroreduction of CO2 to ethanol has economic value and environmental significance. However, the activity selectivity reduction toward are still low due sluggish kinetics C–C coupling intense competition hydrocarbon production. Herein, we report a layered tandem catalyst consisting Cu nanosheets with Cu(111)-oriented surface Ag nanoparticles, which can effectively shift from hydrocarbons ethanol. The Faradaic efficiency was improved less than 30% on bare Cu(111) 56.5 ± 2.6% Cu/Ag catalysts, partial current density 356.7 9.5 mA cm–2. In situ Raman spectroscopy results functional theory calculations suggest that high be attributed asymmetric *CH2–CO mechanism, is facilitated by selective generation *CH2 species (111)-facet-exposed local CO concentration supplied catalyst.

Язык: Английский

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Preventing Salt Formation in Zero-Gap CO₂ Electrolyzers by Quantifying Cation Accumulation

ACS Energy Letters, Год журнала: 2025, Номер unknown, С. 807 - 814

Опубликована: Янв. 14, 2025

Язык: Английский

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Copper/metal oxide heterostructures for electrochemical carbon dioxide reduction

Rare Metals, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Язык: Английский

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Carbon Dioxide Valorization via Formate Electrosynthesis in a Wide Potential Window

Advanced Functional Materials, Год журнала: 2022, Номер 32(32)

Опубликована: Май 20, 2022

Abstract The electrochemical CO 2 reduction reaction (CO RR) is a promising strategy to convert carbon‐based fuels and simultaneously reduce the emission of greenhouse gases into atmosphere. In this work, bismuth subcarbonate nanoflowers (BOC NFs) are facilely prepared through one‐pot synthesis method for efficient formate electrosynthesis RR. Benefiting from crystal structure sheet‐stacked morphology, in situ measurements theoretical calculation results reveal self‐reinforced adsorption properties rapid adsorption–desorption kinetics on catalyst surface, which significantly facilitate RR process. As result, desirable Faradaic efficiencies over 90%, with maximum value 98.9%, toward formation, achieved wide potential window −0.8 −1.4 V an H‐type cell. Moreover, flow cell, superior intrinsic activity BOC NFs guarantees high throughput electrocatalytic performance FE 90% current density range as 1200 mV, demonstrating great practical applications. These underscore effectiveness designing electrocatalysts improve

Язык: Английский

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Tandem effect of Ag@C@Cu catalysts enhances ethanol selectivity for electrochemical CO2 reduction in flow reactors

Cell Reports Physical Science, Год журнала: 2022, Номер 3(7), С. 100949 - 100949

Опубликована: Июнь 17, 2022

CO-selective metals (e.g., Ag) on Cu catalysts improve the selectivity of multi-carbon (C2+) products in electrochemical CO2 reduction. However, origin improvement remains unclear due to convolution tandem and interface effects. Here, Ag@C@Cu core-shell were synthesized, which thin carbon interlayer inhibited direct interaction between Ag while still allowing reduction Ag, thus isolating effect from other This catalyst produced higher ratios ethanol ethylene relative monometallic catalyst, demonstrating that locally increased CO concentration promoted pathway over pathway. Further, was optimized by tuning thickness shell. work provides a rational approach design for understanding structure-performance relationships demonstrates key role C2+ products.

Язык: Английский

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Progress and Understanding of CO₂/CO Electroreduction in Flow Electrolyzers

ACS Catalysis, Год журнала: 2022, Номер 12(20), С. 12993 - 13020

Опубликована: Окт. 12, 2022

The electroreduction of CO2 and CO into valuable chemicals fuels powered by renewable electricity can tackle anthropogenic carbon emissions close the cycle. However, both have low solubility in aqueous electrolytes, affording their sluggish mass transport across electrolyte. CO2/CO a flow electrolyzer this problem directly delivering gaseous reactant to electrode surface. Significant progress has been made recently simultaneously obtaining high reaction rates product selectivity using cell configurations. This perspective highlights how different designs impact outlines potential strategies that may further improve performance. challenges opportunities related fundamental engineering aspects are also discussed.

Язык: Английский

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Chem-bio interface design for rapid conversion of CO2 to bioplastics in an integrated system

Chem, Год журнала: 2022, Номер 8(12), С. 3363 - 3381

Опубликована: Сен. 28, 2022

Integrating catalytic CO2 reduction with bioconversion could substantially advance carbon capture and utilization mitigate climate change. However, the state-of-the-arts are limited by inefficient electron mass transfers, unfavorable metabolic kinetics, inadequate molecular building blocks. We overcome these barriers systematic design of electrocatalysis, a chemical-biological (chem-bio) interface, microorganisms to enable efficient electro-microbial conversion C2 (EMC2) intermediates. The soluble intermediates can facilitate rapid transfer, readily enter primary metabolism, have less toxicity, carry more energy electrons, serve as better blocks for many microorganisms. multi-tier chem-bio interface delivered EMC2 system achieve 6 8 times increase microbial biomass productivity compared C1 intermediate hydrogen-driven routes, respectively. multi-module synthetic biology produced medium-chain-length polyhydroxyalkanoates (PHAs), biodegradable polymers, representing much higher chain length than platforms based on intermediates, hydrogen, or electrons.

Язык: Английский

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