Two-Dimensional Lanthanide Metal–Organic Framework Heterostructures for Noninvasively Photoresponsive High-Security Photonic Barcodes DOI
Jiachen Wang, Tongjin Zhang, Zhenhua Gao

et al.

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: unknown

Published: April 26, 2024

Stimuli-responsive micro/nanoscale photonic barcodes show great capacity for encryption and anticounterfeiting technologies due to multiple authentications, yet their application is commonly restricted by invasive stimuli. Herein, we report noninvasive light-stimulated high-security based on spatially assembled photoresponsive two-dimensional (2D) 1,3,5-benzenetribenzoate (BTB)@Ln-MOF host–guest heterostructures. The photoluminescence (PL) spectra information BTB@Ln-MOF heterostructures could be precisely controlled the different wavelengths of ultraviolet (UV) light trigger. By using PL properties 2D as cryptographic primitives, resolved smart both spectral graphical coding are realized in materials. These results will pave an avenue development stimuli-responsive applications.

Language: Английский

Bulk Depolymerization of Methacrylate Polymers via Pendent Group Activation DOI
Rhys W. Hughes, Megan E. Lott, Isabella S. Zastrow

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6217 - 6224

Published: Feb. 21, 2024

In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk method exhibits exceptional efficiency, even high-molecular-weight polymers, including ultrahigh-molecular-weight (10

Language: Английский

Citations

36
Light-driven polymer recycling to monomers and small molecules DOI Creative Commons
Laura Wimberger,

Gervase Ng,

Cyrille Boyer

et al.

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

Published: March 20, 2024

Abstract Only a small proportion of global plastic waste is recycled, which most mechanically recycled into lower quality materials. The alternative, chemical recycling, enables renewed production pristine materials, but generally comes at high energy cost, particularly for processes like pyrolysis. This review focuses on light-driven approaches chemically recycling and upcycling waste, with emphasis reduced consumption selective transformations not achievable heat-driven methods. We focus challenging to recycle backbone structures composed mainly C‒C bonds, lack functional groups i.e., esters or amides, that facilitate e.g., by solvolysis. discuss the use light, either in conjunction heat drive depolymerization monomers via photocatalysis transform polymers valuable molecules. structural prerequisites these are outlined, highlighting their advantages as well limitations. conclude an outlook, addressing key challenges, opportunities, provide guidelines future photocatalyst (PC) development.

Language: Английский

Citations

35
Photocatalytic Upcycling and Depolymerization of Vinyl Polymers DOI Creative Commons
Kostas Parkatzidis, Hyun Suk Wang, Athina Anastasaki

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 11, 2024

Abstract Photocatalytic upcycling and depolymerization of vinyl polymers have emerged as promising strategies to combat plastic pollution promote a circular economy. This mini review critically summarizes current developments in the degradation including polystyrene poly(meth)acrylates. Of these material classes, polymethacrylates possess unique possibility undergo photocatalytic back monomer under thermodynamically favourable conditions, thus presenting significant advantages over traditional thermal strategies. Our perspective on formidable challenges potential future directions are also discussed.

Language: Английский

Citations

33
Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate) DOI
Kwangwook Ko,

David Lundberg,

Alayna M. Johnson

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9142 - 9154

Published: March 25, 2024

The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for introduction backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues selective deconstruction multiple classes vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize methacrylates an appreciable extent enable polymer deconstruction. Here, we overcome this challenge through design a new class benzyl-functionalized thionolactones (bDOTs). Guided detailed mechanistic analyses, find that radical-stabilizing substituents bDOTs enables markedly increased tunable methyl methacrylate (MMA). Through iterative optimizations molecular structure, specific bDOT, F-p-CF3PhDOT, is discovered efficiently MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, Mn > 120 kDa) low percentages F-p-CF3PhDOT (1.8 3.8 mol%) are prepared using industrially relevant bulk free radical conditions. thermomechanical properties dPMMA similar PMMA; former degrade fragments (<6.5 under mild aminolysis This work presents first example ring-opening capable nearly random MMA without possibility cross-linking provides workflow mechanism-guided future.

Language: Английский

Citations

18
Visible light–triggered depolymerization of commercial polymethacrylates DOI
Hyun Suk Wang, Mikhail Agrachev, Hongsik Kim

et al.

Science, Journal Year: 2025, Volume and Issue: 387(6736), P. 874 - 880

Published: Feb. 20, 2025

The reversion of vinyl polymers with carbon-carbon backbones to their monomers represents an ideal path alleviate the growing plastic waste stream. However, depolymerizing such stable materials remains a challenge, state-of-the-art methods relying on "designer" that are neither commercially produced nor suitable for real-world applications. In this work, we report main chain-initiated, visible light-triggered depolymerization directly applicable commercial containing undisclosed impurities (e.g., comonomers, additives, or dyes). By in situ generation chlorine radicals from solvent, near-quantitative (>98%) polymethacrylates could be achieved regardless synthetic route radical ionic polymerization), end group, and molecular weight (up 1.6 million daltons). possibility perform multigram-scale depolymerizations confer temporal control renders methodology versatile general recycling.

Language: Английский

Citations

5
Photochemical upcycling and recycling of plastics: achievements and future opportunities DOI Creative Commons
Olga G. Mountanea,

Elpida Skolia,

Christoforos G. Kokotos

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(15), P. 8528 - 8549

Published: Jan. 1, 2024

Recent developments in the photochemical upcycling and recycling of plastics.

Language: Английский

Citations

12
Chemical recycling of bromine-terminated polymers synthesized by ATRP DOI Creative Commons
Stella Afroditi Mountaki, Richard Whitfield, Kostas Parkatzidis

et al.

RSC Applied Polymers, Journal Year: 2024, Volume and Issue: 2(2), P. 275 - 283

Published: Jan. 1, 2024

Efficient, fast and versatile depolymerization of bromine-terminated polymers.

Language: Английский

Citations

9
Photoiniferter Polymerization: Illuminating the History, Ascendency, and Renaissance DOI
Rhys W. Hughes, Megan E. Lott,

Rebecca A. Olson S

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: 156, P. 101871 - 101871

Published: Aug. 22, 2024

Language: Английский

Citations

9
Enhancing photothermal depolymerization with metalloporphyrin catalyst DOI Creative Commons

Gervase Ng,

Stuart W. Prescott, Almar Postma

et al.

Journal of Polymer Science, Journal Year: 2024, Volume and Issue: 62(17), P. 3920 - 3928

Published: May 22, 2024

Abstract The ability to revert polymers their original monomers represents a crucial chemical recycling technique, promoting sustainability and offering the chance convert used materials into valuable products. In recent years, numerous studies have explored use of synthesized via reversible deactivation radical polymerization (RDRP) techniques facilitate efficient depolymerization reactions. Herein, we report photocatalyst, zinc tetraphenylporphyrin (ZnTPP), along with light irradiation accelerate prepared by addition‐fragmentation chain transfer (RAFT) polymerization. We explore various parameters affecting efficiency, including solvents, reaction temperature (80, 100, 120°C), presence photocatalysts (ZnTPP Eosin Y), type RAFT end‐groups, namely trithiocarbonate, dithiobenzoate, 1 H ‐pyrazole‐1‐carbodithioate. For instance, when PMMA was diluted 25 mM in 1,4‐dioxane heated 120°C under green ZnTPP (200 ppm), rapid exceeding 70% occurred within h. Without ZnTPP, similar conditions, required over 8 h achieve slightly lower yield. Furthermore, this method confers moderate oxygen tolerance system, enabling proceed without need deoxygenation, albeit at rate consequently lesser monomer recovery (31%).

Language: Английский

Citations

7
Thermal Solution Depolymerization of RAFT Telechelic Polymers DOI Creative Commons
Nethmi De Alwis Watuthanthrige, Richard Whitfield, Simon Harrisson

et al.

ACS Macro Letters, Journal Year: 2024, Volume and Issue: 13(7), P. 806 - 811

Published: June 10, 2024

Thermal solution depolymerization is a promising low-temperature chemical recycling strategy enabling high monomer recovery from polymers made by controlled radical polymerization. However, current methodologies predominantly focus on the of monofunctional polymers, limiting material scope and pathways. Herein, we report telechelic synthesized RAFT Notably, observed significant decrease in molecular weight (Mn) during recovery, which contrasts minimal Mn shift polymers. Introducing Z groups at center or both ends polymer resulted distinct kinetic profiles, indicating partial bifunctional as supported mathematical modeling. Remarkably, featuring R-terminal showed up to 68% improvement overall conversion compared their analogues, highlighting potential these materials circular economy.

Language: Английский

Citations

7