Tetraphenylporphyrin‐based Chelating Ligand Additive as a Molecular Sieving Interfacial Barrier toward Durable Aqueous Zinc Metal Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

The sustained water consumption and uncontrollable dendrite growth strongly hamper the practical applications of rechargeable zinc (Zn) metal batteries (ZMBs). Herein, for first time, we demonstrate that trace amount chelate ligand additive can serve as a "molecular sieve-like" interfacial barrier achieve highly efficient Zn plating/stripping. As verified by theoretical modeling experimental investigations, benzenesulfonic acid groups on molecular not only facilitates its solubility selective adsorption anode, but also effectively accelerates de-solvation kinetics Zn2+ . Meanwhile, central porphyrin ring expels free molecules from via chemical binding against hydrogen evolution, reversibly releases captured to endow dendrite-free deposition. By virtue this non-consumable additive, high average plating/stripping efficiency 99.7 % over 2100 cycles together with extended lifespan suppressed decomposition in Zn||MnO2 full battery were achieved, thus opening new avenue developing durable ZMBs.

Language: Английский

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Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni‐Porphyrin to Facilitate CO₂ Photocatalytic Reduction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(25)

Published: Feb. 10, 2024

Abstract Adapting the coordination environment to influence electronic configuration of active sites represents an efficient approach for improving photocatalytic performance CO 2 reduction reaction (CO RR) but how execute it precisely remains challenging. Herein, heteroatom‐substitution in Ni‐porphyrin break symmetry Ni center is proposed be effective solution. Based on this, two symmetry‐breaking Ni‐porphyrins, namely Ni(Cl)ON 3 Por and Ni(Cl)SN , are designed successfully prepared. By theoretical calculation, found that efficiently regulates d orbital energy levels center. Furthermore, experimental findings jointly revealed Ni‐porphyrins facilitates generation highly reactive I species during catalytic process, effectively stabilizing reducing barrier formation key * COOH intermediate. As a result, gave production rates 24.7 38.8 mmol g −1 h as well selectivity toward 94.0% 96.4%, respectively, outperforming symmetric NiN 4 rate 6.6 82.8%). These offer microscopic insights into modulate activity by tuning rational design competent catalyst RR photocatalysis.

Language: Английский

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Structural Transformation of Copper-Coordinated COFs Drives Enhanced Multi-Carbon Selectivity in CO2 Electroreduction

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125131 - 125131

Published: Feb. 1, 2025

Language: Английский

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A review of the development of porphyrin-based catalysts for electrochemical CO2 reduction

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 470, P. 144249 - 144249

Published: June 22, 2023

Language: Английский

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CO₂ Conversion Toward Real‐World Applications: Electrocatalysis versus CO₂ Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(32)

Published: April 25, 2023

Abstract Electrochemical carbon dioxide (CO 2 ) conversion technologies have become new favorites for addressing environmental and energy issues, especially with direct electrocatalytic reduction of CO (ECO RR) alkali metal‐CO (M–CO batteries as representatives. They are poised to create economic drivers while also paving the way a cleaner more sustainable future humanity. Although still far from practical application, ECO RR has been intensively investigated over last few years, some achievements. In stark contrast, M–CO batteries, aqueous hybrid offer potential combine storage into an integrated system, but their research is in early stages. This article gives insightful review, comparison, analysis recent advances illustrating similarities differences, aiming advance development innovation. Considering crucial role well‐designed functional materials facilitating special attention paid rational design strategies components, such electrodes/catalysts, electrolytes, membranes/separators, at industrial level impact on conversion. Moreover, perspectives suggestions presented facilitate applications.

Language: Английский

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Confinement Effect and 3D Design Endow Unsaturated Single Ni Atoms with Ultrahigh Stability and Selectivity toward CO₂ Electroreduction

Small, Journal Year: 2023, Volume and Issue: 20(14)

Published: Nov. 16, 2023

Abstract Developing single‐atomic catalysts with superior selectivity and outstanding stability for CO 2 electroreduction is desperately required but still challenging. Herein, confinement strategy three‐dimensional (3D) nanoporous structure design are combined to construct unsaturated single Ni sites (Ni‐N 3 ) stabilized by pyridinic N‐rich interconnected carbon nanosheets. The agent chitosan its strong interaction g‐C N 4 nanosheet effective dispersing restraining their agglomeration during pyrolysis, resulting in ultrastable single‐atom catalyst. Due the effect advantage, such designed catalyst exhibits a nearly 100% remarkable CO, exceeding most reported state‐of‐the‐art catalysts. Specifically, Faradaic efficiency (FE maintains above 90% over broad potential range (‐0.55 ‐0.95 V vs . RHE) reaches maximum value of 99.6% at relatively low ‐0.67 V. More importantly, FE kept 95% within long‐term 100 h electrolyzing. Density functional theory (DFT) calculations explain high generation due energy barrier hydrogen evolution on Ni‐N This work provides new designing construction highly selective efficient conversion.

Language: Английский

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Copper-organic frameworks for electrocatalytic carbon dioxide reduction

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 517, P. 216021 - 216021

Published: June 19, 2024

Language: Английский

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Constructing Ionic Interfaces for Stable Electrochemical CO₂ Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(22), P. 14020 - 14028

Published: May 20, 2024

The electrochemical CO2 reduction reaction (CO2RR) has emerged as a promising approach for sustainable carbon cycling and valuable chemical production. Various methods strategies have been explored to boost CO2RR performance. One of the most includes construction stable ionic interfaces on metallic or molecular catalysts using organic inorganic cations, which demonstrated significant improvement in catalytic interface is instrumental adjusting adsorption behavior, influencing reactive intermediates, facilitating mass transportation, suppressing hydrogen evolution reaction, particularly under acidic conditions. In this Perspective, we provide an overview recent advancements building electrocatalytic process discuss application strategy improve performance catalysts. We aim convey future trends opportunities creating further enhance utilization efficiency productivity products. emphasis Perspective lies pivotal role catalysis, providing reference research critical field.

Language: Английский

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New Insight into the Electronic Effect for Cu Porphyrin Catalysts in Electrocatalytic of CO₂ into CH₄

Small, Journal Year: 2023, Volume and Issue: 20(2)

Published: Sept. 5, 2023

Perturbation of the copper (Cu) active site by electron manipulation is a crucial factor in determining activity and selectivity electrochemical carbon dioxide (CO

Language: Английский

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Tetraphenylporphyrin‐based Chelating Ligand Additive as a Molecular Sieving Interfacial Barrier toward Durable Aqueous Zinc Metal Batteries

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Sept. 29, 2023

Abstract The sustained water consumption and uncontrollable dendrite growth strongly hamper the practical applications of rechargeable zinc (Zn) metal batteries (ZMBs). Herein, for first time, we demonstrate that trace amount chelate ligand additive can serve as a “molecular sieve‐like” interfacial barrier achieve highly efficient Zn plating/stripping. As verified by theoretical modeling experimental investigations, benzenesulfonic acid groups on molecular not only facilitates its solubility selective adsorption anode, but also effectively accelerates de‐solvation kinetics 2+ . Meanwhile, central porphyrin ring expels free molecules from via chemical binding against hydrogen evolution, reversibly releases captured to endow dendrite‐free deposition. By virtue this non‐consumable additive, high average plating/stripping efficiency 99.7 % over 2100 cycles together with extended lifespan suppressed decomposition in Zn||MnO 2 full battery were achieved, thus opening new avenue developing durable ZMBs.

Language: Английский

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