Rational design of nitrogen and fluorine co-doped metal-free porous carbons electrocatalysts for highly efficient oxygen reduction and zinc-air batteries DOI Creative Commons

Linqiang Li,

Na Qin,

Huayun Ma

et al.

Carbon Neutrality, Journal Year: 2025, Volume and Issue: 4(1)

Published: Jan. 6, 2025

Abstract The oxygen reduction reaction (ORR) is an important in fuel cells and metal air batteries. affected by slow kinetics the use of high-priced resource-scarce platinum-based catalysts. Therefore, there urgent need to develop cost-effective nonprecious catalysts for ORR replace Pt-based In this study, we used two-dimensional covalent organic frameworks (recorded as TF-COFs) precursors produce a metal-free nitrogen fluorine-co-doped porous carbon catalyst TF-800, TF-900, TF-1000, TF-1100). TF-1000 had high initial potential (0.90 V) half-wave (0.83 alkaline medium, indicating good catalytic activity. addition, stability was better than that commercial Pt/C (20%). This mainly because has specific surface area, fluorine atoms it have dispersion synergistic effects on polarization adjacent atoms. also shows excellent performance zinc-air based batteries, battery observed: peak power density reached 216.66 mW·cm –2 , capacity 752.86 mAh·g –1 at 10 mA·cm long-term charge–discharge demonstrated. work provides inspiration new strategies prepare future

Language: Английский

Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable H2O2 electroproduction DOI Creative Commons

Qianjun Zhi,

Rong Jiang, Xiya Yang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 23, 2024

Realization of stable and industrial-level H

Language: Английский

Citations

61
Optimization Strategies of Covalent Organic Frameworks and Their Derivatives for Electrocatalytic Applications DOI
Liyuan Xiao, Zhenlü Wang, Jingqi Guan

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(11)

Published: Nov. 27, 2023

Abstract Covalent organic frameworks (COFs) are crystalline porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in field electrocatalysis. The precise control channel/dopant positions highly ordered network structures COFs provide an ideal material system applications advanced In this paper, topological structure design synthesis methods reviewed detail, their principles deeply analyzed. addition, derivatives electrocatalysis systematically summarized optimization strategies proposed. Finally, application prospects challenges may encountered future prospected, providing helpful guidance research.

Language: Английский

Citations

55
Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction DOI
Xuewen Li, Shuai Yang, Minghao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 28, 2023

Metal-free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms groups linked by imine bonds were used create catalytic COFs. However, roles of linkages COFs in ORR not investigated. In this work, linkage engineering has modulate behaviors. single sites while avoiding other possible sites, we synthesized from benzene units bonds, such as imine, amide, azine, oxazole bonds. Among these COFs, oxazole-linkage enables with highest activity, which achieved a half-wave potential 0.75 V limited current density 5.5 mA cm-2 . Moreover, oxazole-linked COF conversion frequency (TOF) value 0.0133 S-1 , 1.9, 1.3, 7.4-times that azine-, amide- imine-COFs, respectively. The theoretical calculation showed carbon atoms facilitated formation OOH* promoted protonation O* form OH*, thus advancing activity. This work guides us on are suitable for ORR.

Language: Английский

Citations

51
Charging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction DOI Creative Commons
Xiubei Yang,

Qizheng An,

Xuewen Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 29, 2024

Abstract Covalent organic frameworks (COFs) are ideal templates for constructing metal-free catalysts the oxygen reduction reaction due to their highly tuneable skeletons and controllable porous channels. However, development of active sites within COFs remains challenging limited electron-transfer capabilities weak binding affinities intermediates. Herein, we constructed catalytic centres by modulating electronic states pyridine nitrogen atoms incorporated into COFs. By incorporating different units (such as pyridine, ionic imidazole units), tuned various properties including dipole moments, reductive ability, hydrophilicity, towards Notably, COF ( im -PY-BPY-COF) exhibited greater activity than neutral (PY-BPY-COF) ion -PY-BPY-COF). Specifically, -PY-BPY-COF demonstrated a half-wave potential 0.80 V in 0.1 M KOH, outperforming other Theoretical calculations situ synchrotron radiation Fourier transform infrared spectroscopy confirmed that carbon rings improved facilitating intermediate OOH* promoting desorption OH*. This study provides new insights design metal-like catalysts.

Language: Английский

Citations

43
Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis DOI Creative Commons
Ziqi Zhang, Zhe Zhang, Cailing Chen

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 22, 2024

Abstract Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to unique nanoscale pore configurations, stable periodic structures, abundant coordination sites high surface area. This work aims construct a non-thermodynamically Pt-N 2 active site by electrochemically modifying platinum (Pt) single atoms into fully conjugated 2D COF conductive agent-free pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition maximizing atomic utilization, single-atom catalysts with definite structures can be used investigate catalytic mechanisms structure-activity relationships. this work, in-situ characterizations theoretical calculations reveal that nitrogen-rich graphene analogue not only exhibits favorable metal-support effect Pt, adjusting binding energy between Pt H* intermediates forming instead of typical 4 environment, but also enhances electron transport ability structural stability, showing both conductivity stability in acidic environments.

Language: Английский

Citations

42
Engineering organic polymers as emerging sustainable materials for powerful electrocatalysts DOI
Xun Cui, Mingjie Wu,

Xueqin Liu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1447 - 1494

Published: Jan. 1, 2024

A comprehensive overview on organic polymers as electrocatalysts is summarized. By presenting the engineering strategies, insightful understandings, challenges, and perspectives, we hope this review can provide valuable references for readers.

Language: Английский

Citations

41
Positional Thiophene Isomerization: A Geometric Strategy for Precisely Regulating the Electronic State of Covalent Organic Frameworks to Boost Oxygen Reduction DOI
Qian Wang, Chao Wang,

Kunpeng Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 13, 2024

Abstract With the oxygen conversion efficiency of metal‐free carbon‐based fuel cells dramatically improved, building blocks covalent organic frameworks (COFs) raised principal concerns on catalytic active sites with indistinct electronic states. Herein, to address this issue, we demonstrate COFs for reduction reaction (ORR) by regulating edge‐hanging thiophene units, and molecular geometries are further modulated via positional isomerization strategy, affording isomeric COF‐α 2‐substitution COF‐β 3‐substitution frameworks. The states intermediate adsorption ability well‐regulated through geometric modification, resulting in controllable chemical activity local density π‐electrons. Notably, introduction units different substitution positions into a pristine pure COF model COF‐Ph achieves excellent half‐wave potential 0.76 V versus reversible hydrogen electrode, which is higher than most those or metal‐based electrocatalysts. Utilizing combination theoretical prediction situ Raman spectra, show that skeleton ( ) can induce dangling unit activation, accurately identifying pentacyclic‐carbon (thiophene α‐position) adjacent sulfur atom as sites. results suggest groups suitable ORR promising geometry construction.

Language: Английский

Citations

31
Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks DOI
Yaqin Wang, Zelong Qiao, Han Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 16, 2024

Covalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two-dimensional (2D) COFs, while the 3D counterparts rarely explored due to their non-conjugated derived from sp

Language: Английский

Citations

25
Rational Design of Organic Electrocatalysts for Hydrogen and Oxygen Electrocatalytic Applications DOI Creative Commons
Ruiqi Cheng,

Xiaoqian He,

Kaiqi Li

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 8, 2024

Abstract Efficient electrocatalysts are pivotal for advancing green energy conversion technologies. Organic electrocatalysts, as cost‐effective alternatives to noble‐metal benchmarks, have garnered attention. However, the understanding of relationships between their properties and electrocatalytic activities remains ambiguous. Plenty research articles regarding low‐cost organic started gain momentum in 2010 been flourishing recently though, a review article both entry‐level experienced researchers this field is still lacking. This underscores urgent need elucidate structure–activity relationship design suitable electrode structures, leveraging unique features like controllability compatibility real‐world applications. classified into four groups: small molecules, oligomers, polymers, frameworks, with specific structural physicochemical serving activity indicators. To unlock full potential five strategies discussed: integrated surface property modulation, membrane technologies, electrolyte affinity regulation, addition anticorrosion species, all aimed at enhancing charge efficiency, mass transfer, long‐term stability during reactions. The offers comprehensive overview current state practical applications, bridging gap paving way future developments more efficient

Language: Английский

Citations

16
Zipper‐Like Interlocked Heterostructure of NiFe Layered Double Hydroxide‐WN for Super‐Stable Oxygen Evolution over 4500 h DOI

Minghui Xing,

Zelong Qiao,

Shaoke Zhu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 22, 2024

Abstract The nickel‐iron based materials are widely studied as excellent oxygen evolution reaction (OER) electrocatalysts. However, its relatively poor OER stability limits practical applications. Herein, a zipper‐like interlocked heterostructure of NiFe layered double hydroxide (LDH)‐WN is constructed. LDH‐WN exhibits not only ultrahigh activity 228 mV overpotential at current density 50 mA cm −2 , but also extremely long‐term over 4500 h and 550 an industrial ≈350 which ascribed to special structure. Moreover, in situ Raman confirms that the presence WN can efficiently achieve LDH reconstruction slower metal dissolution during OER, therefore boosts stability. DFT calculations reveal increase *O adsorption capability conductivity layer, anchor atoms layer improve energy barrier. In short, this work presents new method constructing Ni‐Fe‐based catalysts, would accelerate application.

Language: Английский

Citations

16