Reinforced catalytic oxidation of polyoxometalate@charge transfer complex by on-site heating from photothermal conversion

Chen, Xiaofei; Yang, Aibing; Wang, Gengxin; Wei, Ming-Feng; Ning, Liu; Li, Bao; Wu, Lixin

doi:10.1016/j.cej.2022.137134

Cited by 23 publications

(9 citation statements)

References 53 publications

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“…Moreover, they used 3,3′,5,5′-tetramethylbenzidine (TMB) as the precursor of the photothermal center, a stable charge transfer (TMB CT ) complex with a strong NIR photothermal effect was obtained by one-step oxidation and encapsulated with the catalysis components Na 5 PMo 10 V 2 O 40 , Na 4 PMo 11 VO 40 , K 4 PW 11 VO 40 , or Na 3 PMo 12 O 40 through the electrostatic interaction, resulting in complexes with enhanced photothermal properties. 104 Meanwhile, they exist in the form of 4–6 nm oligomers in an aqueous solution, and show high conversion and selectivity for the oxidation of toluene derivatives to alcohols under mild conditions. In the latest study, they constructed POM-modified AuNR composites by combining the high catalytic activity of PW 12 and the NIR photothermal properties of Au nanorods through ligand replacement and electrostatic adsorption.…”

Section: Currently Developed Pom-based Framework For Photothermal Cat...mentioning

confidence: 99%

Polyoxometalate-based frameworks for photocatalysis and photothermal catalysis

Chen

Shi

et al. 2023

Nanoscale

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Section: Currently Developed Pom-based Framework For Photothermal Cat...mentioning

confidence: 99%

Polyoxometalate-based frameworks for photocatalysis and photothermal catalysis

Chen

Shi

et al. 2023

Nanoscale

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“…The catalytic activity of either component PMo 10 V 2 or TMB CT for toluene is far inferior to that of the nanocomposite catalyst, which means that the electrostatic interactions and in situ heating of the POMs by the NIR light‐activated TMB CT make it a stable reinforced catalyst. [ 112 ]…”

Section: Applications Of the Organic Photothermal Ctcsmentioning

confidence: 99%

Organic Charge‐Transfer Complexes for Near‐Infrared‐Triggered Photothermal Materials

Zheng

et al. 2022

Small Structures

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When light-absorbing materials are excited by visible or near-infrared (NIR) light, they will eventually come back to their original equilibrium state, and a part of the absorbed photon energy is released as heat through nonradiative transitions during this process. The heat is determined by absorption ability under excitation wavelength and photothermal conversion efficiency, which is strongly related to the radiative and nonradiative transition rates. A good photothermal material should have high photothermal conversion efficiency, suitable absorption spectrum, and high light absorption ability, and can be used for photoacoustic imaging, [1][2][3] cancer photothermal therapy, [4,5] seawater desalination, [6][7][8] lightdriven thermoelectric system, [9,10] and so on. Especially, the second infrared window (NIR-II, 1000-1700 nm) absorbed photothermal materials have received much attention in biological applications for weak light scattering, low tissue absorption, deep tissue penetration depth, and high maximum permission exposure (up to 1.0 W cm À2 under 1064 nm laser excitation). Up to now, varied photothermal materials can roughly be categorized into two parts: inorganic materials and organic counterparts. For the potential long-term toxicity of inorganic materials, organic counterparts possess low toxicity, easy structural modification, tunable properties, and abundant molecules, so organic photothermal materials have rapidly developed during the last two decades. Typical organic photothermal materials embrace porphyrin, [11] cyanine dyes, [12,13] diketopyrrolopyrrole, [5] polyaniline, [14] polypyrrole, [15] semiconducting polymers, charge-transfer complexes (CTCs), [16] and so on.Among them, the CTCs are composed of electron-donating (D) and electron-accepting (A) molecules, and formed once charge delocalization takes place between the D and A leading to an enhanced molecular polarization, [17] which can be described as [18] In 1973, a famous CTC (TTF-TCNQ) was first reported, which was made of tetrathiafulvalene and 7,7 0 ,8,8 0 -tetracyanoquinodimethane; the researchers found that the electrical conductivity of TTF-TCNQ was comparable with metals. [19] From then on, the electrical properties of CTCs have got much attraction,

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“…Catalytic oxidation of cyclohexene to yield 2-cyclohexene-1-ol and 2-cyclohexene-1-one has gained a colossal research interest owing to have a lot of potential of these products as useful intermediates in the manufacturing of other valuable chemicals . Many heterogeneous catalytic systems, e.g., mixed metal oxides, perovskites, polyoxometalates, metal–organic framework (MOF), zeolites, metalated g-C 3 N 4 , and covalent organic framework (COF), have been developed to explore the C–H functionalization of cyclohexene.…”

Section: Introductionmentioning

confidence: 99%

Experimental Validation and Computational Predictions Join Forces to Map Catalytic C–H Activation in Ferrocene Metalated Porous Organic Polymers

Boro

Paul

Tan

et al. 2023

ACS Appl. Mater. Interfaces

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In recent times, a self-complementary balanced characteristic feature with the combination of both covalent bonds (structural stability) and open metal sites (single-site catalysis) introduced an advanced emerging functional nanoarchitecture termed metalated porous organic polymers (M-POPs). However, the development of M-POPs in view of the current interest in catalysis has been realized still in its infancy and remains a challenge for the years to come. In this work, we built benzothiazolelinked Fe-metalated porous organic polymer (Fc-Bz-POP) using ferrocene dicarboxaldehyde (FDC), 1,3,5-tris(4-aminophenyl) benzene (APB), and elemental sulfur (S 8 ) via a template-free, multicomponent, cost-effective one-pot synthetic approach. This Fc-Bz-POP is endowed with unique features including an extended network unit, isolated active sites, and catalytic pocket with a possible local structure, in which convergent binding sites are positioned in such a way that substrate molecules can be held in close proximity. Prospective catalytic application of this Fc-Bz-POP has been explored in executing catalytic allylic "C−H" bond functionalization of cyclohexene (CHX) in water at room temperature. Catalytic screening results identified that a superior performance with a CHX conversion of 95% and a 2-cyclohexene-1-ol selectivity (COL) of 80.8% at 4 h and 25 °C temperature has been achieved over Fc-Bz-POP, thereby addressing previous shortcomings of the other conventional catalytic systems. Comprehensive characterization understanding with the aid of synchrotron-based extended X-ray absorption fine structure (EXAFS) analysis manifested that the Fe atom with an oxidation state of +2 in our Fc-Bz-POP catalytic system encompasses a sandwich structural environment with the two symmetrical eclipsed cyclopentadienyl (Cp) rings, featuring nearestneighbor (NN) Fe−C (≈2.05 Å) intramolecular bonds, as validated by the Fe L 3 -edge EXAFS fitting result. Furthermore, in situ attenuated total reflection-infrared spectroscopy (ATR-IR) analysis data for liquid-phase oxidation of cyclohexene allow for the formulation of a molecular-level reaction mechanistic pathway with the involvement of specific reaction intermediates, which is initiated by the radical functionalization of the allyl hydrogen. A deep insight investigation from density functional theory (DFT) calculations unambiguously revealed that the dominant pathway from cyclohexene to 2-cyclohexene-1-ol is initiated by an allyl-H functionalization step accompanied by the formation of 2-cyclohexene-1-hydroperoxide species as the key reaction intermediate. Electronic properties obtained from DFT simulations via the charge density difference plot, Bader charge, and density of state (DOS) demonstrate the importance of the organic polymer frame structure in altering the electronic properties of the Fe site in Fc-Bz-POP, resulting in its high activity. Our contribution has great implications for the precise design of metalated porous organic polymer-based robust catalysts, which will open a new av...

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Reinforced catalytic oxidation of polyoxometalate@charge transfer complex by on-site heating from photothermal conversion

Cited by 23 publications

References 53 publications

Polyoxometalate-based frameworks for photocatalysis and photothermal catalysis

Polyoxometalate-based frameworks for photocatalysis and photothermal catalysis

Organic Charge‐Transfer Complexes for Near‐Infrared‐Triggered Photothermal Materials

Experimental Validation and Computational Predictions Join Forces to Map Catalytic C–H Activation in Ferrocene Metalated Porous Organic Polymers

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