Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: Feb. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Language: Английский

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Boosting Electroreduction of CO₂over Cationic Covalent Organic Frameworks: Hydrogen Bonding Effects of Halogen Ions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(7)

Published: Nov. 25, 2022

We present the first example of charged imidazolium functionalized porphyrin-based covalent organic framework (Co-iBFBim-COF-X) for electrocatalytic CO2 reduction reaction, where free anions (e.g., F- , Cl- Br- and I- ) ions nearby active Co sites can stabilize key intermediate *COOH inhibit hydrogen evolution reaction. Thus, Co-iBFBim-COF-X exhibits higher activity than neutral Co-BFBim-COF, following trend

Language: Английский

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Vanadium as Auxiliary for Fe–V Dual-Atom Electrocatalyst in Lithium–Sulfur Batteries: “3D in 2D” Morphology Inducer and Coordination Structure Regulator

ACS Nano, Journal Year: 2023, Volume and Issue: 17(17), P. 17405 - 17416

Published: Aug. 25, 2023

The undesirable shuttling behavior, the sluggish redox kinetics of liquid-solid transformation, and large energy barrier for decomposition Li2S have been recognized problems impeding practical application lithium-sulfur batteries. Herein, inspired by spectacular catalytic activity Fe/V center in bioenzyme nitrogen/sulfur fixation, we design an integrated electrocatalyst comprising N-bridged Fe-V dual-atom active sites (Fe/V-N7) dispersed on ingenious "3D 2D" carbon nanosheets (denoted as DAC), which vanadium induces laminar structure regulates coordination configuration centers simultaneously, realizing redistribution 3d-orbital electrons Fe centers. high coupling/conjunction between 3d S 2p shows strong affinity enhanced reactivity DAC-Li2Sn (1 ≤ n 8) systems. Thus, DAC presents strengthened chemisorption ability toward polysulfides significantly boosts bidirectional sulfur reaction kinetics, evidenced theoretically experimentally. Besides, well-designed morphology enables uniform distribution, facilitated electron transfer, abundant exposure. Therefore, assembled Li-S cells present outstanding cycling stability (637.3 mAh g-1 after 1000 cycles at 1 C) rate capability (711 4 under content (70 wt %).

Language: Английский

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Ligand-Bound CO₂ as a Nonclassical Route toward Efficient Photocatalytic CO₂ Reduction with a Ni N-Confused Porphyrin

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10550 - 10558

Published: April 8, 2024

Implementing the synergistic effects between metal and ligand has successfully streamlined energetics for CO2 activation gained high catalytic activities, establishing important breakthroughs in photocatalytic reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N–H group. It is readily deprotonated exists anion form during catalysis. Owing to this functional site, NiNCP gave rise outstanding turnover number (TON) as 217,000 with 98% selectivity reduction CO, while parent (NiTPP) was found be nearly inactive. Our mechanistic analysis revealed nonclassical reaction pattern where effectively activated via attack of Lewis-basic ligand. The resulting ligand-bound adduct could further reduced produce CO. This new metal–ligand effect anticipated inspire design highly active catalysts small molecule activations.

Language: Английский

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Metalloporphyrins in Bio-Inspired Photocatalytic Conversions

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Recent developments in porphyrin-based artificial photosynthetic assemblies are highlighted, emphasizing biomimetic photocatalytic processes, namely water splitting, CO 2 reduction and alcohol oxidation, with high energetic environmental impact.

Language: Английский

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Porosity as a Design Element for Developing Catalytic Molecular Materials for Electrochemical and Photochemical Carbon Dioxide Reduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(40)

Published: May 5, 2023

Abstract The catalytic reduction of carbon dioxide (CO 2 ) using sustainable energy inputs is a promising strategy for upcycling atmospheric into value‐added chemical products. This goal has inspired the development catalysts selective and efficient CO conversion electrochemical photochemical methods. Among diverse array catalyst systems designed this purpose, 2D 3D platforms that feature porosity offer potential to combine capture conversion. Included are covalent organic frameworks (COFs), metal–organic (MOFs), porous molecular cages, other hybrid materials developed increase active site exposure, stability, water compatibility while maintaining precise tunability. mini‐review showcases reaction RR) incorporate well‐defined elements integrated structures. Selected examples provide insights how different approaches overall design can augment their electrocatalytic and/or photocatalytic activity.

Language: Английский

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Engineering an Oxygen‐Binding Protein for Photocatalytic CO₂Reductions in Water

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 14, 2023

Abstract While native CO 2 ‐reducing enzymes display remarkable catalytic efficiency and product selectivity, few artificial biocatalysts have been engineered to allow understanding how the work. To address this issue, we report cobalt porphyrin substituted myoglobin (CoMb) as a homogeneous catalyst for photo‐driven conversion in water. The activity selectivity were optimized by varying pH concentrations of enzyme photosensitizer. Up 2000 TON(CO) was attained at low with (15 %), while 74 % reached increasing loading but compromised TON(CO). generation overall further improved introducing positively charged residues (Lys or Arg) near active stie CoMb, which demonstrates value tuning secondary coordination sphere enhance performance protein‐based photocatalytic system.

Language: Английский

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Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO₂Reduction**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(5)

Published: Dec. 20, 2022

We present a supramolecular approach to catalyzing photochemical CO

Language: Английский

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Redox-Active Ligand Assisted Multielectron Catalysis: A Case of Electrocatalyzed CO₂-to-CO Conversion

ACS Organic & Inorganic Au, Journal Year: 2023, Volume and Issue: 3(6), P. 384 - 392

Published: Aug. 22, 2023

The selective reduction of carbon dioxide remains a significant challenge due to the complex multielectron/proton transfer process, which results in high kinetic barrier and production diverse products. Inspired by electrostatic H-bonding interactions observed second sphere [NiFe]-CODH enzyme, researchers have extensively explored these regulate proton transfer, stabilize intermediates, ultimately improve performance catalytic CO2 reduction. In this work, series cobalt(II) tetraphenylporphyrins with varying numbers redox-active nitro groups were synthesized evaluated as electrocatalysts. Analyses redox properties complexes revealed consistent relationship between number corresponding accepted electron ligand at −1.59 V vs. Fc+/0. Among catalysts tested, TNPPCo four exhibited most efficient activity turnover frequency 4.9 × 104 s–1 onset potential 820 mV more positive than that parent TPPCo. Furthermore, frequencies increased higher groups. These demonstrate promising design strategy incorporating multielectron ligands into enhance performance.

Language: Английский

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Porphyrin Atropisomerism as a Molecular Engineering Tool in Medicinal Chemistry, Molecular Recognition, Supramolecular Assembly, and Catalysis

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 24, 2024

Porphyrin atropisomerism, which arises from restricted σ-bond rotation between the macrocycle and a sufficiently bulky substituent, was identified in 1969 by Gottwald Ullman 5,10,15,20-tetrakis(o-hydroxyphenyl)porphyrins. Henceforth, an entirely new field has emerged utilizing this transformative tool. This review strives to explain consequences of atropisomerism porphyrins, methods have been developed for their separation analysis present diverse array applications. Porphyrins alone possess intriguing properties structure can be easily decorated molded specific function. Therefore, serves as tool, making it possible obtain even molecular shape. Atropisomerism thoroughly exploited catalysis recognition yet presents both challenges opportunities medicinal chemistry.

Language: Английский

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