Article
Polymer Science
Xuhao Zhang, Jianyu Liu, Rui Qu, Hongyi Suo, Zhirong Xin, Yusheng Qin
Summary: Siloxane functionalized CO2-based polycarbonates were synthesized via terpolymerization of CO2, PO, and TMSO using a SalenCoCl/PPNCl catalyst system. By adjusting the ratio between TMSO and PO, the polycarbonates exhibited improved thermal, mechanical, and surface properties. The introduction of siloxane units increased the surface energy, leading to a water contact angle of 110 degrees. The micro-crosslinked structure formed by the hydrolysis and condensation of methoxysilane groups enhanced the mechanical strength.
Article
Chemistry, Physical
Karol Dyduch, Aleksandra Roznowska, Monika Srebro-Hooper, Bun Yeoul Lee, Artur Michalak
Summary: Density Functional Theory calculations were used to investigate the binding and ring-opening reaction of propylene oxide with a CO2/epoxide copolymerization catalyst. The results showed that the ring-opening of PO proceeds preferentially in the trans catalyst configuration, with a preference for (R)-PO ring-opening over (S)-PO ring-opening. The orientation of the N+-chains in the real catalyst plays a key role in the stereoselectivity of the reaction.
Article
Chemistry, Multidisciplinary
Wouter Lindeboom, Arron C. Deacy, Andreas Phanopoulos, Antoine Buchard, Charlotte K. Williams
Summary: Carbon dioxide copolymerization is a promising strategy for CO2 utilization, but the success depends on improving the catalysis. However, the relationship between catalyst structure and performance is not straightforward, which limits the ability to predict and enhance both catalytic activity and selectivity. In this study, a simple measure of a catalyst ground-state parameter, metal reduction potential, is shown to directly correlate with both polymerization activity and selectivity. This method has been successfully applied to compare the performance of 6 new heterodinuclear Co(III)K(I) catalysts for CO2 copolymerization, providing valuable insights for future catalyst discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Yao Chen, Wenchuan Wang, Dong Xie, Lili Wu, Chaocan Zhang
Summary: The binary catalyst of TPPAlCl-PPN+Cl- can effectively initiate the copolymerization of CO2, lactide, and epoxide, leading to the formation of multiblock poly(carbonate-co-lactide) products. The functionality and glass-transition temperature of the products can be easily adjusted by varying the copolymerization variables.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Polymer Science
Chao Chen, Yves Gnanou, Xiaoshuang Feng
Summary: We report the synthesis of commercially attractive low molar mass polycarbonate polyols obtained through CO2 and epoxide ring-opening copolymerization using borinane-based bifunctional organocatalysts and chain transfer agents. These catalysts exhibit high selectivity and productivity for both poly(cyclohexane carbonate) polyols and poly(ether propylene carbonate) polyols. The molar mass of the resulting polycarbonates can be precisely controlled, showing great potential for large-scale preparation of CO2-based polyols.
Article
Polymer Science
Yi-Ning Li, Han-Han Yang, Xiao-Bing Lu
Summary: This study demonstrates the asymmetric alternating copolymerization of CO2 and meso-epoxides to produce isotactic polycarbonates with main-chain chirality. The designed binaphthol-linked dinuclear aluminum complexes exhibit high enantioselectivity and activity in catalyzing the copolymerization. The length of the linked chains and steric hindrance on the ligand's phenolate moieties significantly affect the catalyst's performance.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Chemistry, Physical
Jonathan Schaefer, Hua Zhou, Eryn Lee, Nikola S. Lambic, Gursu Culcu, Matthew W. Holtcamp, Francis C. Rix, Tzu-Pin Lin
Summary: This study investigates the use of modified tertiary and quaternary phosphonium borane catalysts for CO2/epoxide copolymerization. The catalysts were analyzed using in situ Raman spectroscopy and a nonisothermal kinetic technique to evaluate their performance. The results showed that the substitution of phosphonium/borane groups and the tether length significantly affected the polymerization rates. Additionally, the tertiary phosphonium catalysts maintained high activity in the presence of excess di-alcohols.
Article
Chemistry, Multidisciplinary
Chinh Hoang Tran, Ha-Kyung Choi, Eun-Gyeong Lee, Byeong-Ryeol Moon, Wenliang Song, Il Kim
Summary: A series of Prussian blue analogs (PBAs) were investigated as heterogeneous catalysts for the fixation of carbon dioxide (CO2) to glycidol. Zn(II)-Co(III) PBA with a cubic crystal structure exhibited the highest catalytic activity, selectivity, and recyclability for the cycloaddition reaction. By using a Zn(II)-Co(III) double metal cyanide catalyst, branched polycarbonate polyols and linear polycarbonates with high carbonate content were produced via ring-opening copolymerization of CO2 and various epoxides. Mechanistic pathways were proposed combining experimental results with computational studies.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Polymer Science
Chunwei Zhuo, Xiaoxiao Yu, Yanhua Cheng, Shunjie Liu, Meifang Zhu, Xianhong Wang
Summary: Visual temperature sensors using fiber fluorescent imaging based on aggregation-induced emission (AIE)-functionalized CO2-based PPC have been developed. A three-in-one strategy involving AIE, chain transfer, and co-catalytic properties was used to synthesize AIEgen end-labeled PPC as a thermometer material. The fiber thermometer obtained by melt spinning converts the invisible temperature gradient information into different fluorescent colors visible to the naked eye. It enables high-resolution (±1°C, 10μm) multiscale temperature visualization applications in the range of -40 to 140 °C, including regional temperature detection and internal 1D/2D temperature mapping.
Article
Chemistry, Multidisciplinary
Kam C. Poon, Georgina L. Gregory, Gregory S. Sulley, Fernando Vidal, Charlotte K. Williams
Summary: Using CO2 to make polycarbonates through ROCOP reduces pollution in polymer manufacturing. Recent developments in catalysis allow for the copolymerization with biomass-derived monomers, but the resulting material properties are underinvestigated.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marc Martinez de Sarasa Buchaca, Felipe de la Cruz-Martinez, Luis F. F. Sanchez-Barba, Juan Tejeda, Ana M. M. Rodriguez, Jose A. Castro-Osma, Agustin Lara-Sanchez
Summary: Ring-opening copolymerization reactions of epoxides, carbon dioxide and cyclic esters using bimetallic chloride indium complexes as catalysts were conducted under mild reaction conditions. The catalysts exhibited high catalytic activity and selectivity in the absence of a co-catalyst, leading to the formation of poly(cyclohexene carbonate) (PCHC). Furthermore, polyester-polycarbonate copolymers poly(lactide-co-cyclohexene carbonate) (PLA-co-PCHC) were synthesized via a one-pot one-step route without the use of a co-catalyst. The copolymers showed different thermal properties by adjusting the CO2 pressure and monomer feed.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Amelie Fuchs, Stefan Mecking
Summary: This study reports an organometallic-mediated radical copolymerization method for carbon monoxide and ethylene, leading to the synthesis of keto-modified polyethylenes. The presence of carbon monoxide enhances the controlled character of the copolymerization by suppressing unfavorable termination pathways.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Luke Wylie, Gabriel Perli, Jocasta Avila, Sebastien Livi, Jannick Duchet-Rumeau, Margarida Costa Gomes, Agilio Padua
Summary: This study investigates the physical and chemical absorption of CO2 by ionic liquids based on imidazolium cations bearing oxirane groups through simulations and calculations. It shows that these ionic liquids have strong abilities for both physical and chemical absorption of CO2, with different energy barriers for the opening and closing reactions of the epoxide groups.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Polymer Science
David K. Tran, Ahmed Z. Rashad, Donald J. Darensbourg, Karen L. Wooley
Summary: The synthetic transformation of d-xylose into a four-membered cyclic ether enables reactions with carbon dioxide to produce linear polycarbonates through either one-step ring-opening copolymerisation (ROCOP) directly or sequential isolation of a preformed six-membered cyclic carbonate followed by ring-opening polymerisation (ROP).
Article
Chemistry, Applied
Guillermo Penche, M. Pilar Gonzalez-Marcos, Juan R. Gonzalez-Velasco
Summary: This study reports the catalytic activity of four transition metal hexacyanoferrate(II) complexes in the ring-opening copolymerization of CO2 and propylene oxide for the first time. The complexes showed mild activity and produced polyethercarbonates with moderate CO2 content and random configuration. Among them, the Co-2[Fe(CN)(6)] complex exhibited high potential as a catalyst for CO2/PO ROCOP.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Adriana M. Navarro-Suarez, Milo S. P. Shaffer
Summary: Structural energy storage devices (SESDs), which can simultaneously store electrical energy and withstand mechanical loads, have great potential in reducing overall system weight in various applications. The development of true multifunctional materials is crucial for the realization of electrochemical SESDs, and the choice of device chemistries poses significant challenges.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Georgina L. Gregory, Hui Gao, Boyang Liu, Xiangwen Gao, Gregory J. Rees, Mauro Pasta, Peter G. Bruce, Charlotte K. Williams
Summary: Polymers with specific properties can help overcome challenges in all-solid-state batteries, resulting in improved capacity retention.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Arron C. Deacy, Antoine Buchard, Charlotte K. Williams
Summary: The study demonstrates the chemical recycling of aliphatic polycarbonates using a heterodinuclear [Mg(II)Co(II)] catalyst under solid-state conditions, showing high activity and selectivity. This approach is not only efficient but also allows for multiple reuses of the catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Arron C. Deacy, Andreas Phanopoulos, Wouter Lindeboom, Antoine Buchard, Charlotte K. Williams
Summary: A combined computational and experimental investigation was conducted on the catalytic cycle of carbon dioxide and propylene oxide ring-opening copolymerization. The study revealed the role of a Co(III)K(I) heterodinuclear complex in activating and stabilizing the intermediates, as well as the transient carbonate nucleophile provided by potassium. The results provided insights into the key steps and selectivity limitations of the catalytic cycle, aiding future catalyst design and optimization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Kam C. Poon, Georgina L. Gregory, Gregory S. Sulley, Fernando Vidal, Charlotte K. Williams
Summary: Using CO2 to make polycarbonates through ROCOP reduces pollution in polymer manufacturing. Recent developments in catalysis allow for the copolymerization with biomass-derived monomers, but the resulting material properties are underinvestigated.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Bradley E. Cowie, Lisa Hafele, Andreas Phanopoulos, Said A. Said, Ja Kyung Lee, Anna Regoutz, Milo S. P. Shaffer, Charlotte K. Williams
Summary: This work demonstrates the use of organometallic routes for the synthesis of copper(0/I) nanoparticles and emphasizes the importance of ligand selection to achieve desired material compositions. By reacting an organo-copper precursor with hydrogen, air or hydrogen sulfide, Cu, Cu2O or Cu2S nanoparticles can be obtained. Sub-stoichiometric amounts of protonated ligands are used to avoid excess contamination, and ligand exchange reactions reveal different coordination tendencies for copper(0) nanoparticles compared to Cu2O and Cu2S. This study highlights the potential of organometallic methods for well-defined nanoparticles and underscores the significance of ligand chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jamie T. T. Wilmore, Yuen Cheong Tse, Andrew Docker, Caspar Whitehead, Charlotte K. K. Williams, Paul D. D. Beer
Summary: A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles were synthesized with high yield using active metal template synthetic methodology. The dynamic macrocycle translocation is controlled by an inter-component co-ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin. The shuttling behavior can be inhibited by a neutral Lewis base, but can be tuned through rotaxane demetallation or subsequent metallation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fernando Vidal, Sevven Smith, Charlotte K. Williams
Summary: Boron-functionalized polymers have wide applications in opto-electronics, biology, and medicine. However, methods to produce boron-functionalized and degradable polyesters are rare. This study presents a controlled ring-opening copolymerization method to produce boron-functionalized polyesters. The resulting polymers have adjustable structures, molecular weights, and boron functionalities. The boronic ester-functionalized polymers are amorphous and have high glass transition temperatures and good thermal stability. The utility of this method is demonstrated by synthesizing fluorescent spherical nanoparticles. This versatile technology provides a platform for future explorations of degradable and functional polymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wouter Lindeboom, Arron C. Deacy, Andreas Phanopoulos, Antoine Buchard, Charlotte K. Williams
Summary: Carbon dioxide copolymerization is a promising strategy for CO2 utilization, but the success depends on improving the catalysis. However, the relationship between catalyst structure and performance is not straightforward, which limits the ability to predict and enhance both catalytic activity and selectivity. In this study, a simple measure of a catalyst ground-state parameter, metal reduction potential, is shown to directly correlate with both polymerization activity and selectivity. This method has been successfully applied to compare the performance of 6 new heterodinuclear Co(III)K(I) catalysts for CO2 copolymerization, providing valuable insights for future catalyst discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Antoine Buchard, Charlotte Williams
Summary: This study presents an efficient method for chemical recycling of waste Poly(L-lactic acid) (PLLA) using a commercial Sn(II) catalyst and nonvolatile commercial alcohol. The depolymerization of PLLA to yield pure L-lactide (L-LA) can be achieved at low temperatures, and the catalyst system shows outstanding activity and selectivity. Furthermore, the catalyst system can be recycled multiple times without loss of its catalytic productivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Francesca Fiorentini, Wilfred T. T. Diment, Arron C. C. Deacy, Ryan W. F. Kerr, Stephen Faulkner, Charlotte K. K. Williams
Summary: In this study, a series of heterodinuclear catalysts based on Co(III) combined with alkali and alkaline earth metals were evaluated for three different polymerization reactions. The results show that catalysts with lower Lewis acidity exhibit higher reaction rates and selectivity. These structure-performance correlations apply across different polymerization reactions and provide valuable insights for the future development of catalytic synergy.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wilfred T. Diment, Gloria Rosetto, Noura Ezaz-Nikpay, Ryan W. F. Kerr, Charlotte K. Williams
Summary: The utilization of an iron(iii)/potassium(i) catalyst in ring-opening copolymerization of epoxides and anhydrides without additives/co-catalyst demonstrates high catalytic efficiency, loading tolerance, thermal stability, and selectivity. This catalyst exhibits unparalleled rates using terpene-derived monomers, resulting in bio-derived, amorphous polyesters with a high glass transition temperature (>100 degrees C), making them suitable for future applications as thermoplastics, block polymer adhesives, and elastomers.
Article
Materials Science, Multidisciplinary
Gi Byoung Hwang, Joe Stent, Sacha Noimark, Ki Joon Heo, Alexander J. Macrobert, Christopher W. M. Kay, Enrico Salvadori, Charlotte K. Williams, Sebastian D. Pike, Milo S. P. Shaffer, Elaine Allan, Ivan P. Parkin
Summary: In this study, a white light-activated bactericidal coating consisting of acrylic latex, ZnO NPs and CV was produced. The CV-dyed samples showed intrinsic bactericidal activity against S. aureus and the presence of ZnO NPs significantly enhanced the bactericidal activity. It is expected that this technique could be used to maintain low pathogen levels on hospital surfaces.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Antoine Buchard, Charlotte Williams
Summary: A commercial Sn(II) catalyst combined with a commercial alcohol has been found to efficiently convert waste PLLA plastic into pure L-lactic acid at low temperatures. This catalyst system exhibits not only excellent catalytic activity and yield, but also significantly lower usage compared to previous catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Multidisciplinary
Hannah S. Leese, Miroslav Tejkl, Laia Vilar, Leopold Georgi, Hin Chun Yau, Noelia Rubio, Elisenda Reixach, Jan Buk, Qixiang Jiang, Alexander Bismarck, Robert Hahn, Milo S. P. Shaffer
Summary: Mechanical energy harvesting devices have been developed using novel printed nanocomposite dielectric inks and commercially available conductive elastomers to create a low cost, high performance embodiment of a variable capacitance mechanism. The use of nanoparticle polymer functionalisation improves the homogeneity and stability of the inks. These devices can scavenge low-frequency mechanical energy, providing high mechanical cycling stability and low leakage current.
MATERIALS ADVANCES
(2022)
