Bimetallic metal–organic frameworks and MOF-derived composites: Recent progress on electro- and photoelectrocatalytic applications

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214264 - 214264

Published: Oct. 25, 2021

Language: Английский

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Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

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

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Metalloporphyrins as Catalytic Models for Studying Hydrogen and Oxygen Evolution and Oxygen Reduction Reactions

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(6), P. 878 - 892

Published: Feb. 22, 2022

ConspectusThe hydrogen evolution reaction (HER), oxygen (OER), and reduction (ORR) are involved in biological artificial energy conversions. H–H O–O bond formation/cleavage essential steps these reactions. In nature, intermediates the highly reactive short-lived, making their identification investigation difficult. catalysis, realization of reactions at considerable rates close to thermodynamic equilibria remains a challenge. Therefore, elucidation mechanisms structure–function relationships is fundamental significance understand develop catalysts.This Account describes our recent investigations on catalytic HER, OER, ORR with metalloporphyrins derivatives. Metalloporphyrins used nature for light harvesting, conversion, electron transfer, O2 activation, peroxide degradation. Synthetic metal porphyrin complexes shown be active We focused exploring study because they have stable tunable structures characteristic spectroscopic properties.For we identified three formation established correlation between processes hydride electronic structures. Importantly, provided direct experimental evidence bimetallic homolytic mechanism by using sterically bulky porphyrins. Homolytic HER has been long proposed but rarely verified coupling occurs spontaneously quickly, detection challenging. By blocking bimolecular through steric effects, stabilized characterized NiIII–H intermediate comparing behaviors Ni porphyrins without effects. therefore an unprecedented example control versus heterolytic tuning effects molecular catalysts.For water nucleophilic attack (WNA) high-valent terminal Mn-oxo natural oxidation. Mn tris(pentafluorophenyl)corrole, MnV(O) MnIV-peroxo chemical electrochemical OER Mn-based WNA mechanism. Moreover, demonstrated several catalyst design strategies enhance rate, including pioneering use protective axial ligands. studying Cu porphyrins, two metal-hydroxide radicals form bonds. Note that late-transition metals do not likely metal-oxo/oxyl.For ORR, presented improve activity selectivity, providing rapid electron-donating ligands, introducing hydrogen-bonding interactions, constructing dinuclear cooperation, employing porphyrin-support domino catalysis. Co atropisomers realize both two-electron four-electron representing unparalleled selectivity only modifying and/or structures.Lastly, developed graft various electrode materials different covalent The molecular-engineered exhibit boosted electrocatalytic performance, highlighting promising applications electrocatalysis. Taken together, this demonstrates benefits ORR. knowledge learned herein valuable development porphyrin-based catalysts also other material small molecule activation

Language: Английский

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Recent advances in electrocatalysis with phthalocyanines

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 12985 - 13011

Published: Jan. 1, 2021

Applications of phthalocyanines (Pcs) in electrocatalysis-including the oxygen reduction reaction (ORR), carbon dioxide (CO2RR), evolution (OER), and hydrogen (HER)-have attracted considerable attention recently. Pcs their derivatives are more attractive than many other macrocycles as electrocatalysts since, although they structurally related to natural porphyrin complexes, offer advantages low cost, facile synthesis good chemical stability. Moreover, high tailorability structural diversity mean have great potential for application electrochemical devices. Here we review structure composition Pcs, methods analogues, well applications Pc-based heterogeneous electrocatalysts. Optimization strategies materials electrocatalysis ORR, CO2RR, OER HER proposed, based on mechanisms different reactions. We also discuss structure/composition-catalytic activity relationships Pc order identify future practical applications. Finally, opportunities challenges use molecular discussed.

Language: Английский

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Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

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

Published: Nov. 4, 2021

The electrochemical CO2 reduction to high-value-added chemicals is one of the most promising and challenging research in energy conversion field. An efficient ECR catalyst based on a Cu-based conductive metal-organic framework (Cu-DBC) dedicated producing CH4 with superior activity selectivity, showing Faradaic efficiency as high ~80% large current density -203 mA cm-2 at -0.9 V vs. RHE. further investigation theoretical calculations experimental results indicates Cu-DBC oxygen-coordinated Cu sites exhibits higher selectivity over other two crystalline catalysts nitrogen-coordinated due lower barriers Cu-O4 during process. This work unravels strong dependence site coordination environment porous catalysts, provides platform for constructing highly selective catalysts.

Language: Английский

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Bioinspired Framework Catalysts: From Enzyme Immobilization to Biomimetic Catalysis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5347 - 5420

Published: April 12, 2023

Enzymatic catalysis has fueled considerable interest from chemists due to its high efficiency and selectivity. However, the structural complexity vulnerability hamper application potentials of enzymes. Driven by practical demand for chemical conversion, there is a long-sought quest bioinspired catalysts reproducing even surpassing functions natural As nanoporous materials with surface areas crystallinity, metal-organic frameworks (MOFs) represent an exquisite case how enzymes their active sites are integrated into porous solids, affording heterogeneous superior stability customizable structures. In this review, we comprehensively summarize advances MOFs catalysis, discuss design principle various MOF-based catalysts, such as MOF-enzyme composites embedded sites, explore utility these in different reactions. The advantages enzyme mimetics also highlighted, including confinement, templating effects, functionality, comparison homogeneous supramolecular catalysts. A perspective provided potential solutions addressing current challenges MOF catalysis.

Language: Английский

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Highly Curved Nanostructure‐Coated Co, N‐Doped Carbon Materials for Oxygen Electrocatalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(23), P. 12759 - 12764

Published: March 1, 2021

Abstract Nitrogen‐doped graphene could catalyze the electrochemical reduction and evolution of oxygen, but unfortunately suffers from sluggish catalytic kinetics. Herein, for first time, we report an onion‐like carbon coated Co, N‐doped (OLC/Co‐N‐C) material, which possesses multilayers highly curved nanostructures that form mesoporous architectures. These unique nanospheres are produced when surfactant micelles introduced to synthesis precursors. Owing combined electronic effect nanostructuring effect, our OLC/Co‐N‐C materials exhibit high bifunctional oxygen reduction/evolution reaction (ORR/OER) activity, showing a promising application in rechargeable Zn‐air batteries. Experimental results rationalized by theoretical calculations, curvature graphitic plays vital role promoting activities meta‐carbon atoms near N ortho/meta close pyridinic N.

Language: Английский

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Transformation of Porous Organic Cages and Covalent Organic Frameworks with Efficient Iodine Vapor Capture Performance

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(27), P. 12390 - 12399

Published: June 29, 2022

The reaction of 5,5′-([2,2′-bipyridine]-5,5′-diyl)diisophthalaldehyde (BPDDP) with cyclohexanediamine and [benzidine (BZ)/[2,2′-bipyridine]-5,5′-diamine (BPDA)], respectively, affords a nitrogen-rich porous organic cage BPPOC two two-dimensional (2D) covalent frameworks (COFs), USTB-1 USTB-2 (USTB = University Science Technology Beijing), under suitable conditions. Interestingly, single-crystal X-ray diffraction structure is able to successfully transform into (newly converted COFs denoted as USTB-1c USTB-2c, respectively) upon exchange the imine unit in by BZ BPDA. Such transformation also enables isolation analogous (USTB-3c USTB-4c) on basis an isostructural cage, BTPOC, which derived from 5,5′-([2,2′-bithiophene]-4,4′-diyl)diisophthalaldehyde (BTDDP) cyclohexanediamine. However, conventional solvothermal between BTDDP BPDA leads impure phase USTB-4 containing incompletely aldehyde groups due limited solubility building block. newly prepared have been characterized nuclear magnetic resonance spectroscopy, Fourier infrared scanning electron microscopy, transmission microscopy. In particular, absorb iodine vapor uptake 5.64 g g–1, breaking cage's (POC's) record value 3.78 g–1. Nevertheless, cage-derived exhibit improved adsorption capability comparison directly synthesized counterparts, highest 5.80 g–1 for USTB-1c. mechanism investigation unveils superiority nitrogen atoms sulfur POCs capture assistance definite crystal structures. This, combination porosity, synergistically influences capacity COFs.

Language: Английский

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Three-Dimensional Covalent Organic Frameworks with Ultra-Large Pores for Highly Efficient Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 3248 - 3254

Published: Jan. 31, 2023

Benefiting from their unique structural merits, three-dimensional (3D) large-pore COF materials demonstrate high surface areas and interconnected large channels, which makes these promising in practical applications. Unfortunately, functionalization strategies application research are still absent structures. To this end, a series of functional 3D stp-topologized COFs designed based on porphyrin or metalloporphyrin moieties, named JUC-640-M (M = Co, Ni, H). Interestingly, JUC-640-H exhibits record-breaking low crystal density (0.106 cm3 g-1) among all crystalline materials, along with the largest pore size (4.6 nm) COFs, area (2204 m2 g-1), abundant exposed moieties (0.845 mmol g-1). Inspired by characteristics photoelectrical performance, JUC-640-Co is utilized for photoreduction CO2 to CO demonstrates production rate (15.1 g-1 h-1), selectivity (94.4%), stability. It should be noted that has exceeded those reported COF-based materials. This work not only produces novel channels but also provides new guidance applications COFs.

Language: Английский

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Integrating Single Atoms with Different Microenvironments into One Porous Organic Polymer for Efficient Photocatalytic CO₂ Reduction

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

Published: July 8, 2021

Abstract The precise identification of single‐atom catalysts (SACs) activity and boosting their efficiency toward CO 2 conversion is imperative yet quite challenging. Herein, for the first time a series porous organic polymers designed prepared simultaneously, containing well‐defined M–N 4 O sites. Such strategy not only offers multiactive sites to promote catalytic but also provides more direct chance identify metal center activity. photoreduction results indicate that introduction salphen unit with Ni–N centers into pristine phthalocyanine‐based framework achieves remarkable generation ability (7.77 mmol g –1 ) high selectivity 96% over H . In combination control experiments, as well theoretical studies, moiety evidenced active site RR compared traditional moiety, which can be ascribed effectively reducing energy barrier, facilitating adsorption reaction radicals *COOH, improving charge transportation. This work might shed some light on designing efficient SACs reduction through modification coordination environments.

Language: Английский

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