Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(5)

Опубликована: Янв. 23, 2024

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present practical strategy to rationally design model catalyst with single zinc (Zn) atom coordinated nitrogen and sulfur atoms multilevel carbon matrix. The Zn site exhibits an atomic interface configuration ZnN 4 S 1 , where Zn's electron injection effect enables thermal-neutral hydrogen adsorption neighboring atoms, pushing the activity boundaries electrocatalysts toward electrochemical evolution unprecedented level. Experimental theoretical analyses confirm low-barrier Volmer–Tafel mechanism proton reduction, while multishell hollow structures facilitate even at high current intensities. This work provides for understanding actual active species during reaction paves way designing high-performance electrocatalysts.

Язык: Английский

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A molecular view of single-atom catalysis toward carbon dioxide conversion

Chemical Science, Год журнала: 2024, Номер 15(13), С. 4631 - 4708

Опубликована: Янв. 1, 2024

We present critical advances in single-atom catalysis toward CO 2 transformation and address crucial issues about SACs from a molecular point of view.

Язык: Английский

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Topological Conversion of Nickel Foams to Monolithic Single‐Atom Catalysts

Advanced Functional Materials, Год журнала: 2024, Номер 34(16)

Опубликована: Янв. 4, 2024

Abstract Single‐atom catalysts have emerged as a promising class of due to their tailored coordination environments on the support, which can improve variety catalytic reactions, making them highly desirable research subject in materials science with significant potential for industrial applications. However, traditional synthesis methods mainly obtain low‐yield powder without macroscopic mechanical strength, and also require tedious procedures, limiting practicability. Here, monolithic carbon fibers are prepared single atomic Ni sites directly from bulk metal. The synchronous support growth metal diffusion realizes effective atomization nickel foam, innovative strategy topological within confined space results robust tough monolith. application this single‐atom‐monolith is demonstrated free‐standing electrode efficient electrochemical CO 2 reduction. proposed allows feasible preparation functional single‐atom applications advantages using low‐cost raw materials, enabling large‐scale production, providing processable, moldable materials.

Язык: Английский

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Microenvironment Engineering of Heterogeneous Catalysts for Liquid-Phase Environmental Catalysis

Chemical Reviews, Год журнала: 2024, Номер 124(20), С. 11348 - 11434

Опубликована: Окт. 9, 2024

Environmental catalysis has emerged as a scientific frontier in mitigating water pollution and advancing circular chemistry reaction microenvironment significantly influences the catalytic performance efficiency. This review delves into engineering within liquid-phase environmental catalysis, categorizing microenvironments four scales: atom/molecule-level modulation, nano/microscale-confined structures, interface surface regulation, external field effects. Each category is analyzed for its unique characteristics merits, emphasizing potential to enhance efficiency selectivity. Following this overview, we introduced recent advancements advanced material system design promote (e.g., purification, transformation value-added products, green synthesis), leveraging state-of-the-art technologies. These discussions showcase was applied different reactions fine-tune regimes improve from both thermodynamics kinetics perspectives. Lastly, discussed challenges future directions engineering. underscores of intelligent materials drive development more effective sustainable solutions decontamination.

Язык: Английский

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Isolated FeN₃ sites anchored hierarchical porous carbon nanoboxes for hydrazine‐assisted rechargeable Zn‐CO₂ batteries with ultralow charge voltage

Carbon Energy, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 8, 2024

Abstract Zn‐CO 2 batteries (ZCBs) are promising for CO conversion and electric energy release. However, the ZCBs couple electrochemical reduction (ECO R) with oxygen evolution reaction competitive hydrogen reaction, which normally causes ultrahigh charge voltage efficiency attenuation, thereby resulting in ~90% total power consumption. Herein, isolated FeN 3 sites encapsulated hierarchical porous carbon nanoboxes (Fe‐HPCN, derived from thermal activation process of ferrocene polydopamine‐coated cubic ZIF‐8) were proposed hydrazine‐assisted rechargeable based on ECO R (discharging process: + 2H → H O) hydrazine oxidation (HzOR, charging N 4 4OH − 4H O 4e ). The endows HzOR a lower overpotential boosts 96% Faraday (FE Benefitting bifunctional catalytic activities, homemade assembled Fe‐HPCN air cathode exhibited an ultralow (decreasing by ~1.84 V), excellent selectivity close to 100%), high 89% efficiency. In situ infrared spectroscopy confirmed that can generate rate‐determining *N *CO intermediates during R. This paper proposes centers R/HzOR performance further presents pioneering achievements ZCBs.

Язык: Английский

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Regulating Spin Polarization via Axial Nitrogen Traction at Fe‐N5 Sites Enhanced Electrocatalytic CO2 Reduction for Zn‐CO2 Batteries

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июль 18, 2024

Abstract Single Fe sites have been explored as promising catalysts for the CO 2 reduction reaction to value‐added CO. Herein, we introduce a novel molten salt synthesis strategy developing axial nitrogen‐coordinated Fe‐N 5 on ultrathin defect‐rich carbon nanosheets, aiming modulate pathway precisely. This distinctive architecture weakens spin polarization at sites, promoting dynamic equilibrium of activated intermediates and facilitating balance between *COOH formation *CO desorption active site. Notably, synthesized FeN , supported in nitrogen‐doped (FeN @DNC), exhibits superior performance RR, achieving Faraday efficiency 99 % production (−0.4 V vs. RHE) an H‐cell, maintaining 98 current density 270 mA cm −2 (−1.0 flow cell. Furthermore, @DNC catalyst is assembled reversible Zn−CO battery with cycle durability 24 hours. In situ IR spectroscopy functional theory (DFT) calculations reveal that N coordination traction induces transformation crystal field local symmetry, therefore weakening central atom lowering energy barrier desorption.

Язык: Английский

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Single‐Atom Long‐Range Interaction: Basic Principles and Applications

Advanced Sustainable Systems, Год журнала: 2024, Номер 8(7)

Опубликована: Июнь 6, 2024

Abstract Single‐atom catalysis involves loading the active metal onto carrier's surface as a single‐atom. This atom is primarily bonded to carrier through hetero‐atom bonding. It important note that coordination environment of atoms may not be same when each dispersed has an identical on surface. The utilization single‐atom catalysts (SACs) doesn't strictly imply solitary with zero valency functions core. Singular can also engage in distant interactions other or clusters substrate, like electron transfer, and frequently demonstrate specific charges. main reason for high activity catalyst remote (i.e., long‐range) interaction surrounding atoms. For this reason, study mechanism long‐range between multiple sites atomic cluster become urgent task design regulation performance.

Язык: Английский

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Remote p–d orbital hybridization via first/second-layer coordination of Fe single atoms with heteroatoms for enhanced electrochemical CO₂-to-CO reduction

Journal of Materials Chemistry A, Год журнала: 2024, Номер 12(15), С. 8991 - 9001

Опубликована: Янв. 1, 2024

d–p orbital hybridization induced by S/N in the coordination layer of pyrrole-type Fe–N 4 can modulate electronic structure Fe single atoms, enabling *COOH adsorption and *CO desorption to exclusively furnish CO but suppressing H 2 formation.

Язык: Английский

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Hierarchically Ordered Pore Engineering of Carbon Supports with High‐Density Edge‐Type Single‐Atom Sites to Boost Electrochemical CO₂ Reduction

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 3, 2024

Abstract Metal sites at the edge of carbon matrix possess unique geometric and electronic structures, exhibiting higher intrinsic activity than in‐plane sites. However, creating single‐atom catalysts with high‐density remains challenging. Herein, hierarchically ordered pore engineering metal–organic framework‐based materials to construct edge‐type single‐atomic Ni for electrochemical CO 2 reduction reaction (CO RR) is reported. The created macroporous structure can expose enriched edges, further increased by hollowing walls, which overcomes low percentage in traditional microporous substrates. prepared on ultra‐thin hollow walls (Ni/H‐OMC) exhibit Faraday efficiencies above 90% an ultra‐wide potential window 600 mV a turnover frequency 3.4 × 10 4 h −1 , much superior that material dominant plane‐type Theory calculations reveal NiN edges have significantly disrupted charge distribution, forming electron‐rich centers enhanced adsorption ability * COOH, thereby boosting RR efficiency. Furthermore, Zn–CO battery using Ni/H‐OMC cathode shows unprecedentedly high power density 15.9 mW cm −2 maintains exceptionally stable charge–discharge performance over 100 h.

Язык: Английский

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Relationships between structural design and synthesis engineering of Cu-based catalysts for CO2 to C2 electroreduction

Chemical Engineering Journal, Год журнала: 2023, Номер 479, С. 147606 - 147606

Опубликована: Ноя. 23, 2023

Язык: Английский

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