Metallophthalocyanine-based redox active metal–organic conjugated microporous polymers for OER catalysis

Singh, Ashish; Roy, Syamantak; Das, Chayanika; Samanta, Debabrata; Maji, Tapas Kumar

doi:10.1039/c8cc01291a

Cited by 64 publications

(50 citation statements)

References 30 publications

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“…Intense peaks at 1602 and 1605 cm −1 in TAPA‐OPE‐mix and TAPA‐OPE‐gly, respectively, are attributed to the imine bond (−C=N) and are characteristic of the formation of polymers. A peak at 2208 cm −1 corresponding to the alkyne bond (−C≡C−) confirms the presence of the OPE unit in both CMPs . Solid‐state 13 C‐NMR spectra demonstrate a distinguishing peak at 154.2 ppm for TAPA‐OPE‐mix and 155.2 ppm for TAPA‐OPE‐gly (Figure ), which is attributed to the imine carbon (−C=N) and confirms the formation of polymers.…”

Section: Resultsmentioning

confidence: 70%

“…Ap eak at 2208 cm À1 correspondingt ot he alkyne bond (ÀCCÀ)c onfirmst he presence of the OPE unit in both CMPs. [63] Solid-state 13 C-NMR spectra demonstrate ad istinguishing peak at 154.2 ppm for TAPA-OPE-mix and 155.2 ppm for TAPA-OPE-gly ( Figure 1), which is attributed to the imine carbon (ÀC=N) andc onfirms the formationo fp olymers. Notably,p eaks between 14-29 ppm and 58.2-70.4 ppm in TAPA-OPE-mix are attributed to the alkyl and glycol carbons, respectively,c onfirming unsymmetrical side-chain substitution in the polymer,w hereas symmetrical substitution of the glycol chain in the OPEu nit in TAPA-OPE-gly exhibits peaks at 58.3 and 70.9 ppm.…”

Section: Resultsmentioning

confidence: 83%

“…Synthesis of CMPs (TAPA‐OPE‐mix and TAPA‐OPE‐gly) : Both CMPs were synthesized through Schiff base condensation reactions using the reported procedure . We performed the CMP synthesis using a microwave reactor, which required significantly less time and gave impressive yields in comparison with the solvothermal method.…”

Section: Methodsmentioning

confidence: 99%

“…The synthetic procedure used for the synthesis of OPE-based dialdehydes (ALD1 and ALD2) was similar to that reported in the literature (detail is given in Supporting Information, Figures S1-S3). [63] However,b oth CMPs were synthesized using am icrowave synthesizer,a nd the detailed procedure is described below. Synthesis of CMPs (TAPA-OPE-mix and TAPA-OPE-gly):B oth CMPs were synthesized through Schiff base condensation reactions using the reported procedure.…”

Section: Experimental Section Synthesismentioning

confidence: 99%

“…Synthesis of CMPs (TAPA-OPE-mix and TAPA-OPE-gly):B oth CMPs were synthesized through Schiff base condensation reactions using the reported procedure. [63] We performed the CMP synthesis using am icrowave reactor,w hich required significantly less time and gave impressive yields in comparison with the solvothermal method. The OPE-based di-aldehydes, 4,4'-((2-(dodecyloxy)-5-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-1,4-phenylene)bis(ethyne-2,1diyl))dibenzaldehyde (ALD1) and 4,4'-((2,5-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-1,4-phenylene)bis (ethyne-2,1-diyl))dibenzaldehyde (ALD2), were used for the synthesis of TAPA-OPE-mix and TAPA-OPE-gly,r espectively.I nbrief, OPE-based dialdehyde (0.197 mmol) and 4,4',4''-triaminotriphenylamine (TAPA) (0.132 mmol) were taken together in am ixture of mesitylene (0.75 mL) and 1,4-dioxane solvent (0.5 mL).…”

Section: Experimental Section Synthesismentioning

confidence: 99%

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Bimodal Heterogeneous Functionality in Redox‐Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution

Singh

Verma

Samanta

et al. 2020

Chemistry A European J

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The designing and development of heterogeneous catalysts for conversion of renewable energy to chemical energies by electrochemical as well as photochemical processes is at the forefront of energy research. In this work, two new donor–acceptor‐based redox‐active conjugated microporous polymers (CMPs) (TAPA‐OPE‐mix and TAPA‐OPE‐gly) are synthesized through Schiff base condensation reaction using a microwave synthesizer. Notably, the asymmetric and symmetric bola‐amphiphilic nature of the OPE struts results in distinct nanostructuring and morphologies in the CMPs. Interestingly, both CMPs show impressive heterogeneous catalytic activity toward electrochemical O2 reduction and photocatalytic H2 evolution reactions, and therefore, act as bimodal electro‐ and photocatalytic porous organic materials. Furthermore, the redox‐active property of the CMPs is exploited for in situ generation and stabilization of platinum nanoparticles (Pt), and these Pt@CMPs exhibit significantly enhanced photocatalytic activity.

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Section: Resultsmentioning

confidence: 70%

Section: Resultsmentioning

confidence: 83%

Section: Methodsmentioning

confidence: 99%

Section: Experimental Section Synthesismentioning

confidence: 99%

Section: Experimental Section Synthesismentioning

confidence: 99%

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Bimodal Heterogeneous Functionality in Redox‐Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution

Singh

Verma

Samanta

et al. 2020

Chemistry A European J

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Conjugated Porous Polymers: Ground‐Breaking Materials for Solar Energy Conversion

Barawi

Collado

Gomez‐Mendoza

et al. 2021

Advanced Energy Materials

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poor applicability for movable applications. Therefore, the development of new technologies to store renewable energy is really important to achieve the transition to a greener energy system. [3] Although new battery technologies will likely meet the need for cost-effective energy storage (1-3 days) for short time scales, fuels are the only effective option for longerterm, seasonal storage, and long-distance transportation applications. [4] Collecting and loading solar energy into electric power and more interestingly directly into valuable chemicals and fuels, as nature does through photosynthesis, is a highly desirable approach to solve this challenge. Since Honda and Fujishima [5] discovered the possibility to emulate this natural phenomenon using TiO 2 as photocatalyst more than 40 years ago, the scientific community has been trying to overcome the challenges hindering the commercialization of water splitting and CO 2 reduction. [6,7] During the past years, a large variety of systems have been proposed to drive the so-called artificial photosynthesis (AP), most of them based on inorganic semiconductors (ISs), usually metal oxides and metal chalcogenides. IS are able to absorb part of the solar spectrum and promote charge separation into electron and holes. In fact, there is a lot of recent work in the literature reviewing the use of ISs as photoabsorbers in photocatalytic, photoelectrochemical (PEC), and photovoltaic (PV) systems. [8,9] The achievements and improvements performed in this area have been always enormous. In this sense, among the huge number of materials explored, TiO 2 has been by far the most investigated until now due to its unique properties: high photoactivity and chemical stability, availability, and nontoxicity. [10,11] However, some ISs, and TiO 2 in particular, present well-known shortcomings in terms of low light absorption in the visible part of solar spectrum and fast charge recombination that limits electron donor-acceptor process. Therefore, the energy conversion efficiency achieved until now is still low. The improvement of this efficiency relies on the use of new materials that are able to harvest solar light and active toward CO 2 /N 2 reduction and water splitting. The most successful strategies to improve the photocatalyst performance so far have been: i) the modification of the optoelectronic properties of TiO 2 or other ISs, [12] ii) the use of organic materials as semiconductors, Solar energy conversion plays a very important role in the transition to a more sustainable energy system. In this sense, so many systems have been proposed to drive artificial photosynthesis, most of them based on inorganic semiconductors, and the achievements performed continue every day. However, most of these systems present well-known shortcomings as low light absorption, fast charge recombination, and lack of tunability, thus limiting their efficiency. The use of organic polymers in general and conjugated porous polymers (CPPs) in particular, opens the door to a multitude of new possibilities...

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Tailoring Bond Microenvironments and Reaction Pathways of Single‐Atom Catalysts for Efficient Water Electrolysis

Zheng

Zhu

et al. 2022

Angewandte Chemie

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Single-atom sites (SASs) are commonly stabilized and influenced by neighboring atoms in the host; disclosing the structure-reactivity relationships of SASs in water electrolysis is one of the grand challenges originating from the tremendous wealth of support materials with complex structures. Through a multidisciplinary view of the design principles, synthesis strategies, characterization techniques, and theoretical analysis of structure-performance correlations, this timely Review is dedicated to summarizing the most recent progress in tailoring bond microenvironments on different supports and discussing the reaction pathways and performance advantages of different SAS structures for water electrolysis. The essence and mechanisms of how SAS structures influence electrocatalysis and the critical requirements for future developments are discussed. Finally, the challenges and perspectives are also provided to stimulate the practical, widespread utilization of SAS catalysts in water-splitting electrolyzers.

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Metallophthalocyanine-based redox active metal–organic conjugated microporous polymers for OER catalysis

Cited by 64 publications

References 30 publications

Bimodal Heterogeneous Functionality in Redox‐Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution

Bimodal Heterogeneous Functionality in Redox‐Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution

Conjugated Porous Polymers: Ground‐Breaking Materials for Solar Energy Conversion

Tailoring Bond Microenvironments and Reaction Pathways of Single‐Atom Catalysts for Efficient Water Electrolysis

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