Precision Molecular Engineering of Carbon Nitride for Efficient and Selective Photoreduction of CO₂ to C₂H₆ in Pure Water

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Abstract Photocatalytic CO 2 reduction into high‐value C 2+ products such as H 6 is of great importance but challenging due to their multi‐electron steps and high energy barrier C─C coupling. Moreover, improving its solar‐to‐chemical (STC) conversion efficiency in pure water beyond the current 1% empirical value also a significant challenge. Herein, graphite carbon nitride (g‐C 3 N 4 ) nanosheets with controllable (C) doping nitrogen (N) vacancies (PCCN‐x) are designed through biochar‐tailored protocol for efficiently selectively photo‐converting . The optimal PCCN‐10 photocatalyst enables achievement an exceptional activity 99.14 µmol g −1 h selectivity 80.33% over 20 water. A record STC ≈1.13% solar fuel production from O vapor achieved without any other inputs. Outdoor tests demonstrated impressive ‐to‐C photo‐conversion rate 43.17 water, stable 50 period. Critically, experimental theoretical calculations further confirm pivotal role bridged sites activating molecules promoting formation coupling intermediate ( * OCCO), which very beneficial performance this work photocatalytic fuels paves way large‐scale broader sustainable applications.

Язык: Английский

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Fluorine Doping‐Assisted Reconstruction of Isolated Cu Sites for CO₂ Electroreduction Toward Multicarbon Products

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

Abstract The electrocatalytic synthesis of multicarbon compounds from CO 2 is a promising method for storing renewable electricity and addressing global issues. Single‐atom catalysts are candidates reduction, but producing high‐value (C 2+ ) products using single‐atom structure remains significant challenge. In this study, fluorine doping strategy proposed to facilitate the reconstruction isolated Cu atoms, promoting generation. in situ formed nanocrystals contain substantial amount stable + species, demonstrating remarkable activity −to‐multicarbon conversion. Notably, they achieve highest utilization, with C partial current density −2.01 A mg per −1 formation rate 7.03 mmol h at ≈−1 V versus RHE. Raman spectroscopy functional theory calculations confirm crucial role atoms structural evolution electrolysis.

Язык: Английский

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Adjacent Metal Atomic Pairs Within Atomically Dispersed Catalysts for Reaching a Synergistic Electrocatalytic CO₂ Reduction: A Review

Advanced Energy Materials, Год журнала: 2024, Номер 14(21)

Опубликована: Фев. 27, 2024

Abstract In response to the global climate change and energy crisis, electrocatalytic CO 2 reduction reaction (ECR) is regarded as one of potential ways simultaneously reach conversion obtain various value‐added products. Currently, several challenges remain for in‐depth understanding ECR from fundamentals, including ambiguous structure‐activity relationships, uncontrollable catalytic selectivity, complex mechanisms. Compared traditional metal nanoparticle‐based materials, atomically dispersed catalysts (ADCs) have aroused significant interest owing their maximal atomic utilization simplified site configuration, offering a superior platform discussing relationships during ECR. Especially, adjacent pairs (AAPs) within ADCs are gradually emphasized novel concept follow synergistic mechanisms Herein, first time broad AAPs analyzed how reached effect summarized. view varying on different supports, three types supports illustrated (containing graphene model, functional porous frameworks, metals oxides), aiming help scholars with more insights in broadening feasible ADCs.

Язык: Английский

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Electrode, Electrolyte, and Membrane Materials for Electrochemical CO₂ Capture

Advanced Energy Materials, Год журнала: 2024, Номер 14(24)

Опубликована: Апрель 23, 2024

Abstract One of the many possible ways to capture carbon dioxide (CO 2 ) is through electrochemical means. This an emerging approach with various merits. It energy efficient, utilizes renewable energy, operates under ambient conditions, provides ease for control reaction rates, and scalable. Additionally, it can be integrated as a plug‐and‐play module at scales, including large industrial sources or small scale, e.g., on vehicles, easily combine CO capture, storage, utilization into value‐added chemicals. Various “proof‐of‐concept” approaches have been demonstrated in recent past. These are made electro‐active materials that separate, concentrate form electrodes, electrolytes, membranes devices. Herein, these their working mechanisms identified reviewed devices where they utilized. Also, current challenges future research directions summarized give rational understanding guidance selecting designing use

Язык: Английский

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CO₂ Reduction by an Iron(I) Porphyrinate System: Effect of Hydrogen Bonding on the Second Coordination Sphere

Inorganic Chemistry, Год журнала: 2024, Номер 63(10), С. 4474 - 4481

Опубликована: Фев. 26, 2024

Transforming CO2 into valuable materials is an important reaction in catalysis, especially because concentrations the atmosphere have been growing steadily due to extensive fossil fuel usage. From environmental perspective, reduction of should be catalyzed by environmentally benign catalyst and avoid use heavy transition-metal ions. In this work, we present a computational study novel iron(I) porphyrin for reduction, namely, with tetraphenylporphyrin ligand analogues. particular, investigated one meso-phenyl groups substituted o-urea, p-urea, or o-2-amide groups. These substituents can provide hydrogen-bonding interactions second coordination sphere bound ligands assist proton relay. Furthermore, our studies bicarbonate phenol as stabilizers donors mechanism. Potential energy landscapes double protonation porphyrinate are reported. The work shows that bridges urea/amide iron center provides tight bonding pattern strong facilitates easy delivery CO2. Specifically, low-energy shuttle mechanism form CO water efficiently. o-urea group locks orientation helps ideal transfer, while there more mobility lesser stability o-amide position instead. Our calculations show leads proton-transfer barriers, line experimental observation. We then applied electric-field-effect estimate effects on two steps reaction. describe perturbations enhance driving forces used make predictions about how catalysts further engineered enhanced processes.

Язык: Английский

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Construction of Cobalt Porphyrin‐Modified Cu₂O Nanowire Array as a Tandem Electrocatalyst for Enhanced CO₂ Reduction to C₂ Products

Small, Год журнала: 2024, Номер 20(32)

Опубликована: Март 19, 2024

Abstract Here, the molecule‐modified Cu‐based array is first constructed as self‐supporting tandem catalyst for electrocatalytic CO 2 reduction reaction (CO RR) to C products. The modification of cuprous oxide nanowire on copper mesh (Cu O@CM) with cobalt(II) tetraphenylporphyrin (CoTPP) molecules achieved via a simple liquid phase method. systematical characterizations confirm that formation axial coordinated Co‐O‐Cu bond between Cu O and CoTPP can significantly promote dispersion electrical properties CoTPP‐Cu O@CM heterojunction array. Consequently, compared array, optimized sample electrocatalyst realize 2.08‐fold Faraday efficiency (73.2% vs 35.2%) 2.54‐fold current density (‒52.9 ‒20.8 mA cm –2 ) at ‒1.1 V versus RHE in an H‐cell. comprehensive performance superior most reported materials Further study reveals adsorption restrain hydrogen evolution reaction, improve coverage * intermediate, maintain existence Cu(I) low potential.

Язык: Английский

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Progress of photocatalytic CO2 reduction toward multi-carbon products

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 8, 2024

Язык: Английский

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Metal‐Organic Frameworks‐Based Copper Catalysts for CO₂ Electroreduction Toward Multicarbon Products

Exploration, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

ABSTRACT Copper (Cu) is the most promising catalyst for electrochemical CO 2 ‐to‐C 2+ conversion, whereas performance remains below practical thresholds due to high energy barrier of C−C coupling and lack effective approaches steer reaction pathway. Recent advances show that metal‐organic frameworks (MOF) could be a platform as support, pre‐catalyst, co‐catalyst modify electronic structure local environment Cu catalysts promoting reduction by virtue their great tunability over compositions pore architectures. In this review, we discussed general design principles, catalytic mechanisms, achievements MOF‐based catalysts, aiming boost refinement steering pathway C products. The fundamentals challenges are first introduced. Then, summarized conceptions from three aspects: engineering properties Cu, regulating environment, managing site exposure mass transport. Further, latest progress products namely Cu‐based MOF, MOF‐derived Cu@MOF hybrid discussed. Finally, future research opportunities strategies suggested innovate rational advanced electrifying transformation.

Язык: Английский

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Advances in CO₂ Electroreduction over Hollow Fiber Gas Diffusion Electrodes

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Апрель 2, 2024

Abstract CO 2 electroreduction (CO RR) to high‐value chemicals by renewable energy is a promising route for achieving carbon cycling. Traditional two‐dimensional planar electrodes applied in RR are faced with problems of high mass transfer resistance, carbonate precipitation, flooding, and complicated structures, seriously limiting their efficiency application. Three‐dimensional hollow fiber gas diffusion (HFGDEs) candidates due rich specific surface area, low simplified component, no flooding trouble, which beneficial current density as well efficiency. In this review, we provide inspirations positive paradigms the rational design HFGDE toward following part: 1. The mechanism RR. 2. classification typical metal‐based catalysts. 3. preparation process HFGDEs. 4. Recent advanced studies 5. Challenges at stage future development HFGDEs towards accelerating application industrial reduction electrolyzers.

Язык: Английский

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Synthesizing nickel single atom catalyst via SiO2 protection strategy for efficient CO2 electroreduction to CO in a wide potential range

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 675, С. 207 - 217

Опубликована: Июль 2, 2024

Язык: Английский

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