N-Heterocyclic Carbene Moiety in Highly Porous Organic Hollow Nanofibers for Efficient CO2 Conversions: A Comparative Experimental and Theoretical Study DOI
Sudip Bhattacharjee, Anjana Tripathi, Rupak Chatterjee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 718 - 727

Published: Jan. 2, 2024

Global warming and climate change are two severe environmental dangers brought on by the steady rise in carbon dioxide (CO2) concentration atmosphere. Thus, order to reduce this problem, it is essential find an efficient material for high CO2 capture that can simultaneously exhibit good catalytic activity utilization into useful chemicals. Herein, we report synthesis of N-heterocyclic carbene-based porous organic polymers (NHC-01 NHC-02) using Friedel–Crafts reaction with imidazolium salt bi-phenyl. Among polymers, NHC-01 exhibited outstanding stability, flexibility, BET surface area (1298 m2 g–1). displayed a uptake capacity 2.85 mmol g–1 under 1.0 bar pressure at 273 K. NHC-01/02 has been utilized as metal-free organocatalyst conversion due its area, absorption capacity, bears NHC moiety network. selectively reduced methanol via hydrosilylation complete silane atmospheric pressure. Furthermore, catalyst also shows toward N-formylation reductive cyclization reactions, which showed yields up least four cycles. The mechanisms studied theoretical simulation density functional theory (DFT), intermediates have appropriate free energy level promote low barrier.

Language: Английский

Photocoupled Electroreduction of CO2 over Photosensitizer-Decorated Covalent Organic Frameworks DOI

Qiu‐Jin Wu,

Duan‐Hui Si,

Shihua Ye

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19856 - 19865

Published: Aug. 31, 2023

Introducing an external visible-light field would be a promising strategy to improve the activity of electrocatalytic CO2 reduction reaction (CO2RR), but it still remains challenge due short excited-state lifetime active sites. Herein, Ru(bpy)3Cl2 struts as powerful photosensitive donors were immobilized into backbones Co-porphyrin-based covalent organic frameworks (named Co-Bpy-COF-Rux, x is molar ratio Ru and Co species, = 1/2 2/3) via coordination bonds, for photo-coupled CO2RR produce CO. The optimal Co-Bpy-COF-Ru1/2 displays high CO Faradaic efficiency 96.7% at -0.7 V vs reversible hydrogen electrode (RHE) partial current density 16.27 mA cm-2 -1.1 RHE under assistance light, both which far surpassing values observed in dark. significantly enhanced mainly attributed incorporation donor with long concomitantly giant built-in electric Co-Bpy-COF-Ru1/2, efficiently accelerate photo-induced electron transfer from cobalt-porphyrin light. Thus, sites have longer lower rate-determining steps' energy occurring during actual process. This first work porphyrin-based COFs CO2RR, opening new frontier construction efficient electrocatalysts.

Language: Английский

Citations

52
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
Ionic Covalent Organic Frameworks in Adsorption and Catalysis DOI
Minghao Liu, Qing Xu, Gaofeng Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: April 2, 2024

The ion extraction and electro/photo catalysis are promising methods to address environmental energy issues. Covalent organic frameworks (COFs) a class of template construct absorbents catalysts because their stable frameworks, high surface areas, controllable pore environments, well-defined catalytic sites. Among them, ionic COFs as unique crystalline porous materials, with charges in the or along walls, have shown different properties resulting performance these applications those from charge-neutral COFs. In this review, current research progress based on for conversion, including cationic/anionic materials is reviewed terms synthesis strategy, modification methods, mechanisms adsorption catalysis, well applications. Finally, we demonstrated challenges future development design strategies

Language: Английский

Citations

31
Elaborate Modulating Binding Strength of Intermediates via Three‐component Covalent Organic Frameworks for CO2 Reduction Reaction DOI
Minghao Liu, Cheng‐Xing Cui, Shuai Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: Feb. 26, 2024

Abstract The catalytic performance for electrocatalytic CO 2 reduction reaction (CO RR) depends on the binding strength of reactants and intermediates. Covalent organic frameworks (COFs) have been adopted to catalyze RR, their abilities are tuned via constructing donor‐acceptor (DA) systems. However, most DA COFs single donor acceptor units, which caused wide‐range but lacking accuracy in modulating More elaborate regulation interactions with intermediates necessary challenge construct high‐efficiency catalysts. Herein, three‐component COF D‐A‐A units was first constructed by introducing electron‐rich diarylamine unit, electron‐deficient benzothiazole Co‐porphyrin units. Compared two‐component COFs, designed exhibit elevated electronic conductivity, enhanced reducibility, high efficiency charge transfer, further improving RR faradic 97.2 % at −0.8 V activity partial current density 27.85 mA cm −2 −1.0 exceed other COFs. Theoretical calculations demonstrate that sites suitable ability intermediates, benefit formation *COOH desorption *CO. This work offers valuable insights advancement multi‐component enabling modulated transfer improve activity.

Language: Английский

Citations

22
Engineering Copper‐Based Covalent Organic Framework Microenvironments to Enable Efficient CO2 Electroreduction with Tunable Ethylene/Methane Switch DOI
Qian Chen, Duan‐Hui Si,

Qiu‐Jin Wu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(24)

Published: Feb. 5, 2024

Abstract A microenvironment engineering strategy has been developed to switch the CO 2 electroreduction reaction (CO RR) selectivity from methane (CH 4 ) ethylene (C H by adjusting coordination microstructures of trinuclear copper cluster‐based metal‐covalent organic framework (MCOF). When Cu sites are oriented channels in Cu‐PyCA‐MCOF, is main product. Conversely, when coordinated with OH − and O molecules Cu‐PyCAOH‐MCOF nanosheets, product switches CH C 50.5% 200.2 mA cm partial current density at −1.2 V (vs RHE). This happens because can only contact active perpendicular cluster plane where Cu─Cu distance between them 3.2 Å, favoring efficient conversion through C─C coupling reaction. Operando infrared spectroscopy, situ X‐ray absorption near‐edge structure spectra, DFT calculations reveal that changing environments MCOFs significantly stabilizes key intermediates reduces energies RR. work offers an effective for enhancing RR performance toward products tuning microenvironments copper‐based electrocatalysts.

Language: Английский

Citations

20
Ionic Covalent Organic Frameworks in Adsorption and Catalysis DOI
Minghao Liu, Qing Xu, Gaofeng Zeng

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(22)

Published: April 2, 2024

Abstract The ion extraction and electro/photo catalysis are promising methods to address environmental energy issues. Covalent organic frameworks (COFs) a class of template construct absorbents catalysts because their stable frameworks, high surface areas, controllable pore environments, well‐defined catalytic sites. Among them, ionic COFs as unique crystalline porous materials, with charges in the or along walls, have shown different properties resulting performance these applications those from charge‐neutral COFs. In this review, current research progress based on for conversion, including cationic/anionic materials is reviewed terms synthesis strategy, modification methods, mechanisms adsorption catalysis, well applications. Finally, we demonstrated challenges future development design strategies

Language: Английский

Citations

18
Rapid charge transfer in covalent organic framework via through-bond for enhanced photocatalytic CO2 reduction DOI
Lijuan Gong,

Li-Yao Liu,

Shao–Shuai Zhao

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 458, P. 141360 - 141360

Published: Jan. 6, 2023

Language: Английский

Citations

37
Bifunctional Catalysts with Core–Shell Distributed ZrO2 and Co Nanoparticles Derived from MOF-on-MOF Heterostructures for Economical One-Pot Tandem CO2 Fixation DOI

Ze Qin,

Liyu Chen, Yingwei Li

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8372 - 8383

Published: June 8, 2023

The N-formylation of aryl amines with CO2 is an emerging strategy to simultaneously reduce carbon emission and produce high-value formamides. Considering that are usually produced from the hydrogenation their corresponding nitroarenes in chemical industry, one-pot tandem hydrogenation–formylation formamides obviously a much more economical but still unexploited for efficient fixation. Herein, we report rational synthesis bifunctional catalysts core–shell distributed ZrO2 Co nanoparticles (NPs) controlled pyrolysis ZIF-67-on-UiO-66 heterostructure this reaction. To fabricate such MOF-on-MOF heterostructures, develop facile surfactant-assisted seed ZIF-8 nuclei on UiO-66 surface, followed by successful growth thickness-controlled ZIF-67 shell UIO-66 core. Based further pyrolysis, highly mesoporous derivants NPs can be obtained, which reductive Lewis basic serve as active sites CO2, respectively, due favorable electronic structures good mass diffusion reactants/intermediates. Impressively, optimized catalyst achieves higher yield N-(4-methoxyphenyl)formamide (99.5%) than its ZrO2/C (0%), Co-NC (14.1%), physically mixed counterparts (52.3%) between 4-nitroanisole recyclability broad substrate scope, shedding light design fixation

Language: Английский

Citations

34
Molecular Engineering of Metal–Organic Layers for Sustainable Tandem and Synergistic Photocatalysis DOI
Yingjie Fan, Haifeng Zheng, Steven Labalme

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4158 - 4165

Published: Feb. 8, 2023

Metal–organic layers (MOLs), a monolayered version of metal–organic frameworks (MOFs), have recently emerged as novel two-dimensional molecular material platform to design multifunctional catalysts. MOLs inherit the intrinsic tunability MOFs and yet more accessible modifiable building blocks. Here we report engineering six via modulated solvothermal synthesis between HfCl4 three photosensitizing ligands followed by postsynthetic modification with two carboxylate-containing cobaloximes for tandem synergistic photocatalysis. Morphological structural characterization transmission electron microscopy atomic force compositional analysis inductively coupled plasma-mass spectrometry nuclear magnetic resonance spectroscopy establish flat nanoplates periodic lattice structure hexagonal symmetry. The efficiently catalyze dehydrogenative coupling reactions Heck-type reactions. most active MOL catalyst was used gram-scale vesnarinone, cardiotonic agent, in 80% yield turnover number 400 eight consecutive reaction cycles without significant loss activities.

Language: Английский

Citations

30
Modulating Electrochemical CO2 Reduction Performance via Sulfur-Containing Linkages Engineering in Metallophthalocyanine Based Covalent Organic Frameworks DOI
Xiubei Yang, Xuewen Li, Minghao Liu

et al.

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(6), P. 1611 - 1618

Published: May 1, 2023

Covalent organic frameworks (COFs) with metallophthalocyanine (MPc) units provide new opportunities for the design of advanced materials attractive electrical properties. However, limited synthetic linkage chemistry hinders their further exploration. Herein, we demonstrated heterocycles strategy-based engineering to fabricate two novel MPc-based COFs thiomorpholine and dithiine linkages. More S atoms in dithiine-linked CoPc-DSDS-COF contributed higher conductivity (0.78 mS cm–1) reductive ability than those thiomorpholine-linked CoPc-DNDS-COF (0.62 and, thus, result activity a partial current density CO 30.42 mA cm–2 at −1.0 V vs RHE selectivity toward CO2 reduction Faradaic efficiency 96.5% −0.9 V. Additionally, theoretical calculation revealed linkages showed better suppressing competing hydrogen evolution reaction This work gives us insight into catalytic via strategic atomic level.

Language: Английский

Citations

30