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

Effective Iodine Adsorption by Nitrogen-Rich Nanoporous Covalent Organic Frameworks DOI
Hailian Li, De-Shan Zhang, Ke Cheng

et al.

ACS Applied Nano Materials, Journal Year: 2023, Volume and Issue: 6(2), P. 1295 - 1302

Published: Jan. 11, 2023

With the rapid development of nuclear industry, effective treatment radioactive iodine has currently become an urgent but challenging task. Herein, two covalent organic frameworks (COFs), TFBT-1 and TFBT-2, were successfully synthesized for adsorption. Structure analysis revealed that they are both nanoporous materials with one-dimensional channels derived from packing related two-dimensional frameworks. Iodine adsorption experiments demonstrated COF exhibit performance adsorption, a maximum amount upto 3.15 g g–1 2.60 TFBT-2. The results experimental analyses Fourier-transform infrared spectroscopy, X-ray photoelectron Raman spectroscopy clearly their high is attributed to strong interactions between adsorbed uniformly located abundant nitrogen sites in pores materials, which pre-introduced acylamides situ-generated Schiff base imine groups. present work by introducing nitrogen-rich into adsorbents can be achieved.

Language: Английский

Citations

74
Covalent organic frameworks for CO2 capture: from laboratory curiosity to industry implementation DOI
He Li,

Akhil Dilipkumar,

Saifudin Abubakar

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6294 - 6329

Published: Jan. 1, 2023

Synergistic developments of covalent organic frameworks and engineering processes can expedite the qualitative leap for net-zero carbon emissions.

Language: Английский

Citations

73
From Supramolecular Organic Cages to Porous Covalent Organic Frameworks for Enhancing Iodine Adsorption Capability by Fully Exposed Nitrogen‐Rich Sites DOI
Ke Cheng, Hailian Li, Jiarui Wang

et al.

Small, Journal Year: 2023, Volume and Issue: 19(34)

Published: May 10, 2023

In order to overcome the limitations of supramolecular organic cages for their incomplete accessibility active sites in solid state and uneasy recyclability liquid solution, herein a nitrogen-rich cage is rationally linked into framework systems four isoreticular covalent frameworks (COFs), that is, Cage-TFB-COF, Cage-NTBA-COF, Cage-TFPB-COF, Cage-TFPT-COF, are successfully synthesized. Structure determination reveals they all high-quality crystalline materials derived from eclipsed packing related two-dimensional frameworks. Since usually have high affinity toward iodine species, adsorption investigations carried out results show them display an enhancement capacities. Especially, Cage-NTBA-COF exhibits capacity 304 wt%, 14-fold higher than sample packed itself. The strong interactions between adsorbed species revealed by spectral analyses. This work demonstrates that, utilizing reticular chemistry strategy extend close-packed porous solids, inherent properties can be greatly exploited targeted applications.

Language: Английский

Citations

64
Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions DOI
Meng Lu, Shuai‐Bing Zhang, Mingyi Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 7, 2023

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+ /Fe(bpy)32+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer suitable band gap for highly photocatalytic hydrogen (H2 evolution. Rubpy-ZnPor COF achieved the highest H2 yield (30 338 μmol g-1 h-1 with apparent quantum efficiency (AQE) 9.68 %@420 nm, showed one best performances among all reported based photocatalysts. Furthermore, in situ produced was successfully tandem used alkyne hydrogenation ≈99.9 % conversion efficiency. Theoretical calculations reveal both photosensitizer units MCOFs can be photoexcited thus contribute optimal activity. This work develops general strategy shows great potential using multiple photosensitive materials field photocatalysis.

Language: Английский

Citations

62
Electrocatalytic Porphyrin/Phthalocyanine‐Based Organic Frameworks: Building Blocks, Coordination Microenvironments, Structure‐Performance Relationships DOI Creative Commons
Ning Lv, Qian Li, Huang Zhu

et al.

Advanced Science, Journal Year: 2023, Volume and Issue: 10(7)

Published: Jan. 4, 2023

Metal-porphyrins or metal-phthalocyanines-based organic frameworks (POFs), an emerging family of metal-N-C materials, have attracted widespread interest for application in electrocatalysis due to their unique metal-N

Language: Английский

Citations

59
2D Covalent Organic Framework for Water Harvesting with Fast Kinetics and Low Regeneration Temperature DOI
Chao Sun, Yuhao Zhu, Pengpeng Shao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 14, 2023

Atmospheric water harvesting represents a promising technique to address stress. Advanced adsorbents have been rationally designed achieve high uptake, yet their sorption kinetics and regeneration temperature greatly limit production efficiency. Herein, we demonstrated that 2D covalent organic frameworks (COFs), featuring hydrophobic skeleton, proper hydrophilic site density, 1D open channels significantly lowered the diffusion desorption energy barrier. DHTA-Pa COF showed uptake of 0.48 g/g at 30 % R.H. with remarkable adsorption rate 0.72 L/Kg/h (298 K) 2.58 (333 K). Moreover, more than 90 adsorbed could be released within 20 min 313 K. This kinetic performance surpassed reported porous materials boosted efficiency for multiple extraction cycles. It may shed light on material design strategy daily low-energy input.

Language: Английский

Citations

59
Composite materials based on covalent organic frameworks for multiple advanced applications DOI Creative Commons
Jia Chen, Yuting Wang, Yong‐Liang Yu

et al.

Exploration, Journal Year: 2023, Volume and Issue: 3(3)

Published: May 23, 2023

Covalent organic frameworks (COFs) stand for a class of emerging crystalline porous materials, which are ingeniously constructed with units through strong covalent bonds. Their excellent design capabilities, and uniform tunable pore structure make them potential materials various applications. With the continuous development synthesis technique nanoscience, COFs have been successfully combined variety functional to form COFs-based composites superior performance than individual components. This paper offers an overview different types reported so far, particular focus on applications composites. Moreover, challenges future prospects presented. We anticipate that review will provide some inspiration further

Language: Английский

Citations

55
Non‐Interpenetrated 3D Covalent Organic Framework with Dia Topology for Au Ions Capture DOI
Minghao Liu,

Hui‐Yuan Kong,

Shuai Bi

et al.

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

Published: April 23, 2023

Abstract The 3D covalent organic frameworks (COFs) have attracted considerable attention owing to their unique structural characteristics. However, most of COFs interpenetration phenomena, which will result in decreased surface area and porosities, thus limited applications molecular/gas capture. Developing with non‐fold is challenging but significant because the existence non‐covalent interactions between adjacent nets. Herein, a new COF (BMTA‐TFPM‐COF) dia topology for Au ion capture first demonstrated. constructed exhibits high Brunauer–Emmett–Teller 1924 m 2 g −1 , pore volume 1.85 cm 3 . abundant cavities as well exposed CN linkages due non‐interpenetration enable absorb 3+ capacity (570.18 mg ), selectivity (99.5%), efficiency (68.3% adsorption maximum 5 min). This work provides strategy design

Language: Английский

Citations

52
Realizing Photocatalytic Overall Water Splitting by Modulating the Thickness‐Induced Reaction Energy Barrier of Fluorenone‐Based Covalent Organic Frameworks DOI

Rongchen Shen,

Chaochao Qin,

Lei Hao

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(39)

Published: July 24, 2023

Direct photocatalytic hydrogen and oxygen evolution from water splitting is an attractive approach for producing chemical fuels. In this work, a novel fluorenone-based covalent organic framework (COF-SCAU-2) successfully exfoliated into ultrathin three-layer nanosheets (UCOF-SCAU-2) overall (OWS) under visible light. The structures of UCOF-SCAU-2 greatly enhance carrier separation, utilization efficiency, the exposure active surface sites. Surprisingly, exhibits efficient OWS performance, with rates reaching 0.046 0.021 mmol h-1 g-1 , respectively, visible-light irradiation, whereas bulk COF-SCAU-2 shows no activity OWS. Charge-carrier kinetic analysis DFT calculations confirm that reducing thickness COF increases number accessible sites, reduces distance charge migration, prolongs lifetimes photogenerated carriers, decreases Gibbs free energy rate-limiting step compared to nonexfoliated COFs. This work offers new insights effect layer COFs on

Language: Английский

Citations

51
Covalent Organic Frameworks for Extracting Water from Air DOI
Chao Sun, Dafei Sheng, Bo Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: March 27, 2023

Water scarcity is becoming an increasingly pressing issue due to global population growth and industrialization. One effective approach addressing this sorption-based atmospheric water harvesting (SAWH). Covalent organic frameworks (COFs) are a type of porous crystalline material that have emerged as promising sorbents for their high surface area, tunable pore size, customizable chemistry. In mini-review, we provide overview the different types COFs, structural characteristics, diverse linkage chemistries used construct them. Then, summarize recent advances in using COF-based harvesting, including strategies controlling sorption properties optimizing performance terms thermodynamics dynamics. Finally, discuss prospects challenges associated with improving efficiency SAWH systems.

Language: Английский

Citations

46