Promises of MOF‐Based and MOF‐Derived Materials for Electrocatalytic CO₂ Reduction

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(39)

Published: July 29, 2024

Abstract Electrocatalytic CO 2 reduction (ECR) powered by renewable electricity is a promising technology to mitigate carbon emissions and lessen the dependence on fossil fuels toward carbon‐neutral energy cycle. Metal–organic frameworks (MOFs) their derivatives, due excellent intrinsic activity, have emerged as materials for ECR high‐demand products. However, challenges such unsatisfactory efficiency, selectivity, relatively low production rates hinder industrial scalability. Here, comprehensive critical review presented that summarizes state‐of‐the‐art progress in MOF‐based MOF‐derived electroreduction catalysts from design functionality perspectives. The fundamentals of reaction (CO RR) over heterogeneous catalysts, mechanisms, key faced are described first establish solid foundation forthcoming in‐depth analyses. MOF's building blocks, properties, shortcomings pertinent including conductivity stability, systematically discussed. Moreover, discussions provided design, fabrication, characterization, RR activity pinpoint intricate structure‐property‐performance relationship. Finally, recommendations put forward enhancing MOF electrocatalysts durability. This work may serve guideline developing high‐performance MOF‐related RR, benefiting researchers working this growing potentially game‐changing area.

Language: Английский

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Tailoring CO₂ Adsorption Configuration with Spatial Confinement Switches Electroreduction Product from Formate to Acetate

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Multi-proton-coupled electron transfer, multitudinous intermediates, and unavoidable competing hydrogen evolution reaction during CO2 electroreduction make it tricky to control high selectivity for specific products. Here, we present spatial confinement of Fe single atoms (FeN2S2) by adjacent FeS clusters (Fe4S4) orientate the transition adsorption configuration from C,O-side O-end, which triggers a shift activated first-step protonation C–C coupling, thus switching target product HCOOH in Faraday efficiency (FE: 90.6%) on FeN2S2 CH3COOH 82.3%) Fe4S4/FeN2S2. The strength *OCHO upon solitary site is linearly related coordination number Fe–S, with predominantly produced over single-atom (ortho-substituted S atoms). Fe4S4 cluster functions as switch reduction product, can not only optimize electronic structure neighboring but also impel complete hydrocarbon intermediate *CH3, followed coupling CO2* *CH3 via synergistic catalysis This strategy provides new avenue modulate reactant model desirable pathways, potential applications diverse multistep electrochemical processes controlled selectivity.

Language: Английский

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Enigma of Sustainable CO₂ Conversion to Renewable Fuels and Chemicals Through Photocatalysis, Electrocatalysis, and Photoelectrocatalysis: Design Strategies and Atomic Level Insights

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Growing global population, escalating energy consumption, and climate change threaten future security. Fossil fuel combustion, primarily coal, oil, natural gas, exacerbates the greenhouse effect driving warming through CO

Language: Английский

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Enhancing CO2 photoreduction on Au@CdZnS@MnO2 hollow nanospheres via electron configuration modulation

Journal of Material Science and Technology, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

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Solvent Mediated Interfacial Microenvironment Design for High‐Performance Electrochemical CO₂ Reduction to C₂₊ Products

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Electrochemical CO2 reduction (CO2RR) in membrane electrode assembly (MEA) represents a viable strategy for converting into value-added multi-carbon (C2+) compounds. Therefore, the microstructure of catalyst layer (CL) affects local gas transport, charge conduction, and proton supply at three-phase interfaces, which is significantly determined by solvent environment. However, microenvironment CLs mechanism effect on C2+ selectivity remains elusive. Herein, tailored interfacial structure designed introducing solvent-mediated catalyst-ionomer-solvent microenvironment. The acetone surface promotion beneficial unfolded ionomers to uniformly coat catalysts, contributes enhancing hydrophobicity inhibiting hydrogen evolution. Furthermore, molecular dynamics (MD) simulation situ ATR-SEIRAS are employed elucidate appropriate network with balanced distribution H2O. uniform continuous advantageous CO2-to-C2+. optimized favors production products Cu-based MEA, exhibiting high faradaic efficiency (FE) 80.27% 400 mA cm-2.

Language: Английский

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Recent Breakthroughs in Electrocatalytic Reduction of Nitrogen-Oxyanions for Environmentally Benign Ammonia Synthesis

Nano Energy, Journal Year: 2025, Volume and Issue: unknown, P. 110683 - 110683

Published: Jan. 1, 2025

Language: Английский

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Hydrophobic Ionic Liquid Engineering for Reversing CO Intermediate Configuration toward Ampere-Level CO₂ Electroreduction to C₂₊ Products

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7921 - 7931

Published: Feb. 24, 2025

Hydrophobic ionic liquid (HIL) engineering on the catalyst surface represents a simple yet potent direction for optimizing CO2 electroreduction performance. However, pivotal role of HIL at an industrial current density is still ambiguous due to limited and conflicting research findings. Herein, HIL-engineered oxide-derived Cu porous nanoparticles with electron-delocalized groups specific ultramicropore structure are first constructed facilitate CO2-to-C2+ ampere-level densities. The uniformly decorated innovatively demonstrated by positron annihilation lifetime spectroscopy, which offers unparalleled advantages in characterization. Bader charge-dependent performance analyses theoretical calculations disclose that N atoms lower adsorption energy CO atop site from -0.38 -1.42 eV through electron donation, inverts most stable favors energy-efficient dimerization atop-bound CO. Operando Raman spectra situ attenuated total reflection-surface enhanced infrared absorption spectroscopy indicate adhered increases *CO coverage alters configuration state abundant high-frequency band. Furthermore, staircase potential electrochemical impedance unravels arrangement enlarges charge about 1.5 times, thereby accelerating electroreduction. As result, achieve prominent C2+ productivity Faradaic efficiency 85.1% formation rate up 2512 μmol h-1 cm-2, outperforming reported Cu-based electrocatalysts.

Language: Английский

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Zinc Hollow-Fiber Penetration Electrode Promotes Ampere-Level CO₂ Electroreduction for Viable Applications

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4259 - 4269

Published: Feb. 25, 2025

Language: Английский

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Highly Dispersed Single Clusters Supported Porphyrinic Metal–Organic Frameworks for Synergetic CO₂ Electroreduction to CH₄

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The electrocatalytic CO2 reduction is a promising path toward the carbon-neutral goal but remains huge challenge due to high activation barrier for and poor selectivity. Herein, highly dispersed triruthenium single cluster (Ru3-SCs) confined into nanospace of pyrrole-3-carboxylic acid (PyrA)-modified nickel-porphyrin-based metal-organic framework (Ni-PCN-222-PyrA) form composite (Ru3-SCs@Ni-PCN-222-PyrA) through pre-coordination confinement strategy. prepared Ru3-SCs@Ni-PCN-222-PyrA can accelerate selective CH4 via electrocatalysis. Under -1.0 V versus reversible hydrogen electrode (RHE), affords electroreduction with selectivity 71.9% Faradaic efficiency. Mechanistic studies reveal that superior reactivity be attributed ensemble effect synergistic catalysis Ru3-SCs, in which one Ru atom responsible *CO another promotes water splitting generate *H, then two intermediates *H coupled key intermediate *CHO thermodynamically favorable way.

Language: Английский

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Progress in Cu‐Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Abstract The electrocatalytic conversion of CO 2 into valuable multi‐carbon (C 2+ ) products using Cu‐based catalysts has attracted significant attention. This review provides a comprehensive overview recent advances in catalyst design to improve C selectivity and operational stability. It begins with an analysis the fundamental reaction pathways for formation, encompassing both established emerging mechanisms, which offer critical insights design. In situ techniques, essential validating these by real‐time observation intermediates material evolution, are also introduced. A key focus this is placed on how enhance through manipulation, particularly emphasizing catalytic site construction promote C─C coupling via increasing * coverage optimizing protonation. Additionally, challenge maintaining activity under conditions discussed, highlighting reduction active charged Cu species materials reconstruction as major obstacles. To address these, describes strategies preserve sites control including novel utilization mitigation reconstruction. By presenting developments challenges ahead, aims guide future conversion.

Language: Английский

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