Covalent Organic Frameworks as Porous Pigments for Photocatalytic Metal-Free C–H Borylation DOI

Ananda Basak,

Suvendu Karak, Rahul Banerjee

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7592 - 7599

Published: March 21, 2023

Covalent organic frameworks (COFs) are highly promising as heterogeneous photocatalysts due to their tunable structures and optoelectronic properties. Though COFs have been used photocatalysts, they mainly employed in water splitting, carbon dioxide reduction, hydrogen evolution reactions. A few examples synthesis using metal-anchored COF were reported. Herein, we report stable β-keto-enamine-based for metal-free C–B bond formation Three different availed this purpose. Their photocatalysis performances monitored 12 substrates, like quinolines, pyridines, pyrimidines. All the showcase moderate-to-high yields (up 96%) depending upon substrate's molecular functionality. High crystallinity, a large surface area, low band gap, suitable position result highest catalytic activity of TpAzo COF. The thorough mechanistic investigation further highlights crucial role light-harvesting capacity, charge separation efficiency, current density during catalysis. light absorbance capacity plays critical catalysis maximized near COF's absorption maxima. high photostability as-synthesized offers reusability several (>5) cycles.

Language: Английский

Mechanistic analysis of multiple processes controlling solar-driven H2O2 synthesis using engineered polymeric carbon nitride DOI Creative Commons
Yubao Zhao, Peng Zhang, Zhenchun Yang

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 17, 2021

Abstract Solar-driven hydrogen peroxide (H 2 O ) production presents unique merits of sustainability and environmental friendliness. Herein, efficient solar-driven H through dioxygen reduction is achieved by employing polymeric carbon nitride framework with sodium cyanaminate moiety, affording a rate 18.7 μmol h −1 mg an apparent quantum yield 27.6% at 380 nm. The overall photocatalytic transformation process systematically analyzed, some previously unknown structural features interactions are substantiated via experimental theoretical methods. cyanamino group pyridinic nitrogen-coordinated soidum in the promote photon absorption, alter energy landscape improve charge separation efficiency, enhance surface adsorption dioxygen, create selective 2e − oxygen reaction surface-active sites. Particularly, electronic coupling interaction between surface, which boosts population prolongs lifetime active shallow-trapped electrons, experimentally substantiated.

Language: Английский

Citations

291
Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance DOI Creative Commons
Zhongshan Chen, Jingyi Wang, Mengjie Hao

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Feb. 27, 2023

Covalent organic frameworks (COFs) represent an emerging class of photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry construct a family isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties local pore characteristics COFs modulated using different linkers. The excited state electronic distribution transport pathways in are probed host experimental methods theoretical calculations at molecular level. One our developed (denoted as COF-4) exhibits remarkable electron utilization efficiency charge transfer properties, achieving record-high uranium extraction performance ~6.84 mg/g/day natural seawater among all techniques reported so far. This study brings new understanding operation COF-based guiding design improved photocatalysts for many applications.

Language: Английский

Citations

283
Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction DOI
Bin Han,

Xu Ding,

Baoqiu Yu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 7104 - 7113

Published: May 3, 2021

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed recent years. However, the of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine (denoted as CoPc-PI-COF-1 CoPc-PI-COF-2) have devised prepared through solvothermal reaction tetraanhydrides 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine 4,4′-biphenyldiamine, respectively. resultant CoPc-PI-COFs four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, excellent resistance 12 M HCl aqueous solution 20 days. Current–voltage curves reveal conductivity CoPc-PI-COF-2 value 3.7 × 10–3 1.6 S m–1, Due same Co(II) electroactive sites together similar porosity CO2 adsorption capacity CoPc-PI-COFs, cathodes made up carbon black display CO2-to-CO Faradaic efficiency 87–97% at applied potentials between −0.60 −0.90 V (vs RHE) 0.5 KHCO3 solution. comparison CoPc-PI-COF-2&carbon electrode, counterpart provides larger current density (jCO) −21.2 mA cm–2 associated its higher conductivity. This cathode also high turnover number frequency, amounting 277 000 2.2 s–1 −0.70 during 40 h measurement. present result clearly discloses potential 2D porous crystalline solids electrocatalysis.

Language: Английский

Citations

276
Integration of metal-organic frameworks and covalent organic frameworks: Design, synthesis, and applications DOI Creative Commons
Li Yang, Meghdad Karimi, Yun‐Nan Gong

et al.

Matter, Journal Year: 2021, Volume and Issue: 4(7), P. 2230 - 2265

Published: July 1, 2021

Language: Английский

Citations

262
Covalent organic frameworks for photocatalysis: Synthesis, structural features, fundamentals and performance DOI
Yun‐Nan Gong, Xinyu Guan, Hai‐Long Jiang

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 475, P. 214889 - 214889

Published: Oct. 15, 2022

Language: Английский

Citations

242
Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction DOI
Yanbiao Shi, Guangming Zhan, Hao Li

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(38)

Published: July 31, 2021

Abstract The objective of photocatalytic CO 2 reduction (PCR) is to achieve high selectivity for a single energy‐bearing product with efficiency and stability. bulk configuration usually determines charge carrier kinetics, whereas surface atomic arrangement defines the PCR thermodynamic pathway. Concurrent engineering structures therefore crucial achieving goal PCR. Herein, an ultrastable highly selective using homogeneously doped BiOCl nanosheets synthesized via inventive molten strategy presented. With B O 3 as both salt doping precursor, this new approach ensures boron (B) from into dual functionalities. Bulk mitigates strong excitonic effects confined in 2D by significantly reducing exciton binding energies, surface‐doped atoms reconstruct extracting lattice hydroxyl groups, resulting intimate B‐oxygen vacancy (B‐OV) associates. These exclusive B‐OV associates enable spontaneous activation, suppress competitive hydrogen evolution promote proton‐coupled electron transfer step stabilizing *COOH generation. As result, homogeneous B‐doped exhibit 98% ‐to‐CO under visible light, impressive rate 83.64 µmol g −1 h ultrastability long‐term testing 120 h.

Language: Английский

Citations

217
Metalated covalent organic frameworks: from synthetic strategies to diverse applications DOI
Qun Guan, Lele Zhou, Yu‐Bin Dong

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Language: Английский

Citations

214
Computation-based regulation of excitonic effects in donor-acceptor covalent organic frameworks for enhanced photocatalysis DOI Creative Commons
Yunyang Qian, Yulan Han, Xiyuan Zhang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 29, 2023

The strong excitonic effects widely exist in polymer-semiconductors and the large exciton binding energy (Eb) seriously limits their photocatalysis. Herein, density functional theory (DFT) calculations are conducted to assess band alignment charge transfer feature of potential donor-acceptor (D-A) covalent organic frameworks (COFs), using 1,3,5-tris(4-aminophenyl)triazine (TAPT) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) as acceptors tereph-thaldehydes functionalized diverse groups donors. Given discernable D-A interaction strengths pairs, Eb can be systematically regulated with minimum TAPT-OMe. Guided by these results, corresponding COFs synthesized, where TAPT-OMe-COF possesses best activity photocatalytic H2 production trend other is associated that calculated for pairs. In addition, further alkyne cycloaddition imine linkage greatly improves stability resulting TAPT-OMe-alkyne-COF a substantially smaller exhibits ~20 times higher than parent COF.

Language: Английский

Citations

212
Tuning Local Charge Distribution in Multicomponent Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Uranium Extraction DOI
Hui Yang, Mengjie Hao,

Yinghui Xie

et al.

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

Published: April 29, 2023

Optimizing the electronic structure of covalent organic framework (COF) photocatalysts is essential for maximizing photocatalytic activity. Herein, we report an isoreticular family multivariate COFs containing chromenoquinoline rings in COF and electron-donating or withdrawing groups pores. Intramolecular donor-acceptor (D-A) interactions allowed tuning local charge distributions carrier separation under visible light irradiation, resulting enhanced performance. By optimizing optoelectronic properties COFs, a uranium extraction efficiency 8.02 mg/g/day was achieved using nitro-functionalized multicomponent natural seawater, exceeding performance all reported to date. Results demonstrate effective design strategy towards high-activity with intramolecular D-A structures not easily accessible traditional synthetic approaches.

Language: Английский

Citations

195
Covalent organic frameworks towards photocatalytic applications: Design principles, achievements, and opportunities DOI
Sisi Liu, Mengfan Wang, Yanzheng He

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 475, P. 214882 - 214882

Published: Oct. 14, 2022

Language: Английский

Citations

156