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

Thermo-, Electro-, and Photocatalytic CO2 Conversion to Value-Added Products over Porous Metal/Covalent Organic Frameworks DOI

Qiu‐Jin Wu,

Jun Liang, Yuan‐Biao Huang

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(20), P. 2978 - 2997

Published: Sept. 26, 2022

ConspectusThe continuing increase of the concentration atmospheric CO2 has caused many environmental issues including climate change. Catalytic conversion using thermochemical, electrochemical, and photochemical methods is a potential technique to decrease simultaneously obtain value-added chemicals. Due high energy barrier however, this method still far from large-scale applications which requires activity, selectivity, stability. Therefore, development efficient catalysts convert different products urgent. With their well-engineered pores chemical compositions, surface area, elevated adsorption capability, adjustable active sites, porous crystalline frameworks metal-organic (MOFs) covalent organic (COFs) are materials for catalytic conversion. Here, we summarize our recent work on MOFs COFs thermocatalytic, electrocatalytic, photocatalytic describe structure-activity relationships that could guide design effective catalysts.The first section paper describes imidazolium-functionalized MOFs, liquid cationic with nucleophilic halogen ions, can promote thermocatalytically cycloaddition reaction epoxides toward cyclic carbonates at one bar pressure. A MOF takes role reservoir tackle low local concentrations in gas-liquid-solid heterogeneous reactions. Imidazolium-functionalized ions avoid use cocatalysts, leads milder more facile experimental conditions separation processes.In dealing electrocatalytic reduction (CO2RR), developed series conductive framework fast electron transmission capabilities, afford current densities outperform traditional COF have been reported. The intrinsically two-dimensional 2D nanosheets based fully π-conjugated phthalocyanine motif excellent transport capability were prepared, strong transporters also integrated into metalloporphyrin-based CO2RR. Cu2O quantum dots Cu nanoparticles (NPs) be uniformly dispersed MOFs/COFs synergistic and/or tandem electrocatalysts, achieve highly selective production CH4 or C2H4 CO2RR.A third efforts facilitate electron-hole photocatalysis. Our focus regulation coordination spheres fabrication architecture heterojunctions, engineering films reduction.Finally, discuss several problems associated studies consider some prospects

Language: Английский

Citations

176
Post-synthetic modification of covalent organic frameworks for CO2 electroreduction DOI Creative Commons
Minghao Liu, Shuai Yang, Xiubei Yang

et al.

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

Published: June 26, 2023

To achieve high-efficiency catalysts for CO2 reduction reaction, various catalytic metal centres and linker molecules have been assembled into covalent organic frameworks. The amine-linkages enhance the binding ability of molecules, ionic frameworks enable to improve electronic conductivity charge transfer along However, directly synthesis with is hardly achieved due electrostatic repulsion predicament strength linkage. Herein, we demonstrate reaction by modulating linkers linkages template framework build correlation between performance structures Through double modifications, states are well tuned, resulting in controllable activity selectivity reaction. Notably, dual-functional achieves high a maximum CO Faradaic efficiency 97.32% turnover frequencies value 9922.68 h-1, which higher than those base single-modified Moreover, theoretical calculations further reveal that attributed easier formation immediate *CO from COOH*. This study provides insights developing

Language: Английский

Citations

122
Boosting Electroreduction of CO2over Cationic Covalent Organic Frameworks: Hydrogen Bonding Effects of Halogen Ions DOI

Qiu‐Jin Wu,

Duan‐Hui Si, Qiao Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(7)

Published: Nov. 25, 2022

We present the first example of charged imidazolium functionalized porphyrin-based covalent organic framework (Co-iBFBim-COF-X) for electrocatalytic CO2 reduction reaction, where free anions (e.g., F- , Cl- Br- and I- ) ions nearby active Co sites can stabilize key intermediate *COOH inhibit hydrogen evolution reaction. Thus, Co-iBFBim-COF-X exhibits higher activity than neutral Co-BFBim-COF, following trend

Language: Английский

Citations

109
Large‐area Free‐standing Metalloporphyrin‐based Covalent Organic Framework Films by Liquid‐air Interfacial Polymerization for Oxygen Electrocatalysis DOI

Jiaqi Tang,

Zuozhong Liang, Haonan Qin

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Nov. 8, 2022

Synthesizing large-area free-standing covalent organic framework (COF) films is of vital importance for their applications but still a big challenge. Herein, we reported the synthesis large metalloporphyrin-based COF and oxygen electrocatalysis. The reaction meso-benzohydrazide-substituted metal porphyrins with tris-aldehyde linkers afforded at liquid-air interface. These can be scaled up to 3000 cm2 area display great mechanical stability structural integrity. Importantly, Co-porphyrin-based are efficient electrocatalytic O2 reduction evolution reactions. A flexible, all-solid-state Zn-air battery was assembled using showed high performance charge-discharge voltage gap 0.88 V 1 mA cm-2 under bent conditions (0° 180°). This work thus presents strategy synthesize functionalized quality uses in flexible electronics.

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
A porous metal-organic cage liquid for sustainable CO2 conversion reactions DOI Creative Commons
Chang He,

Yu‐Huang Zou,

Duan‐Hui Si

et al.

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

Published: June 7, 2023

Porous liquids are fluids with the permanent porosity, which can overcome poor gas solubility limitations of conventional porous solid materials for three phase gas-liquid-solid reactions. However, preparation still requires complicated and tedious use hosts bulky liquids. Herein, we develop a facile method to produce metal-organic cage (MOC) liquid (Im-PL-Cage) by self-assembly long polyethylene glycol (PEG)-imidazolium chain functional linkers, calixarene molecules Zn ions. The Im-PL-Cage in neat has porosity fluidity, endowing it high capacity CO2 adsorption. Thus, stored an be efficiently converted value-added formylation product atmosphere, far exceeds MOC nonporous PEG-imidazolium counterparts. This work offers new prepare catalytic transformation adsorbed molecules.

Language: Английский

Citations

70
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
Boosting CO2 Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework DOI
Lei Zou, Ziao Chen, Duan‐Hui Si

et al.

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

Published: Sept. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Language: Английский

Citations

54
Oxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy DOI Creative Commons

Hong‐Jing Zhu,

Duan‐Hui Si, Hui Guo

et al.

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

Published: Feb. 17, 2024

Abstract The direct use of flue gas for the electrochemical CO 2 reduction reaction is desirable but severely limited by thermodynamically favorable oxygen reaction. Herein, a photonicswitching unit 1,2-Bis(5’-formyl-2’-methylthien-3’-yl)cyclopentene (DAE) integrated into cobalt porphyrin-based covalent organic framework highly efficient electrocatalysis under aerobic environment. DAE moiety in material can reversibly modulate O activation capacity and electronic conductivity ring-closing/opening reactions UV/Vis irradiation. DAE-based with ring-closing type shows high Faradaic efficiency 90.5% partial current density −20.1 mA cm −2 at −1.0 V vs. reversible hydrogen electrode co-feeding 5% . This work presents an passivation strategy to realize electroreduction performance , which would inspire design electrocatalysts practical source such as from power plants or air.

Language: Английский

Citations

54
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