Review
Chemistry, Multidisciplinary
Peng Gao, Liangshu Zhong, Buxing Han, Mingyuan He, Yuhan Sun
Summary: The concept of green carbon science aims to achieve carbon neutrality, which has gained global recognition and attention. The transition from fundamental research to practical applications in addressing the urgent need for carbon neutralization must be accelerated. This Review summarizes recent technological developments in the field of green carbon science, focusing on pilot tests, industrial demonstrations, and commercial applications beyond the laboratory stage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Chao Chen, Yves Gnanou, Xiaoshuang Feng
Summary: This research describes the design and synthesis of organoboron catalysts for the alternating ring-opening copolymerization (ROCOP) of CO2 with cyclic ethers. The performance of these catalysts was assessed by considering various parameters, such as the type of boron center, the distance between the boron center and the ammonium cation, and the size of the substituents of the cation. Among all the boron-based catalysts, borinane-based catalyst 5 showed the highest productivity in the copolymerization of CO2 and epoxides. Additionally, catalyst 5 could be easily recycled and used as a difunctional initiator. Density Functional Theory computation provided insights into the mechanism of the bifunctional catalyst-mediated CO2 copolymerization and highlighted the importance of the type of boron centers in the overall performance.
Article
Chemistry, Inorganic & Nuclear
Hassan A. Baalbaki, Kudzanai Nyamayaro, Julia Shu, Chatura Goonesinghe, Hyuk-Joon Jung, Parisa Mehrkhodavandi
Summary: Aluminum, gallium, and indium complexes were studied as catalysts for the copolymerization of CO2 and cyclohexene oxide. The indium complex exhibited higher conversion and selectivity compared to the aluminum and gallium analogues. The mechanism of the reaction and an off-cycle catalytic intermediate involving indium were investigated through experiments and structural characterization.
INORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Chunwei Zhuo, Han Cao, Huai You, Shunjie Liu, Xianhong Wang, Fosong Wang
Summary: A photothermal strategy was developed using visible light as an external stimulus for the copolymerization of carbon dioxide and epoxides. This strategy showed enhanced polymerization activity and demonstrated spatial-temporal control.
Article
Chemistry, Physical
Arron C. Deacy, Christopher B. Durr, Ryan W. F. Kerr, Charlotte K. Williams
Summary: Anhydride and epoxide ring opening copolymerisation can produce aliphatic, semi-aromatic, and functionalised polyesters through the use of heterodinuclear catalysts. These catalysts show high efficiency in forming ester linkages, but exhibit lower activity compared to certain previously reported catalysts. Further exploration of factors influencing synergic heterometallic combinations is needed.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Hong-Juan Lv, Shu-Cong Fan, Yu-Cheng Jiang, Shu-Ni Li, Quan-Guo Zhai
Summary: Efficient CO2 capture and conversion techniques are essential for global sustainable development. In this study, a novel bi-microporous Sc-MOF was designed and used for CO2 storage and catalytic conversion. The material showed high adsorption selectivity, large CO2 storage capacity, and high catalytic activity.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Polymer Science
Anjaneyulu Kummari, Sreenath Pappuru, Sourav Singha Roy, Debashis Chakraborty
Summary: A new environmentally benign synthesis of polyesters has been developed using molecular iodine and alkali metal alkoxides as dual catalytic systems for the ring-opening alternating copolymerization of phthalic anhydride and various epoxides. The reaction showed high conversion, good regioselectivity, and respectable TOF values. This methodology allows the regioselective fabrication of polyesters with diverse structures.
Article
Thermodynamics
Kai Zhang, Linyang Dan, Qiang Wang, Jian Li
Summary: This paper investigated the evaporation processes and heat transfer characteristics of CO2, CF4, and CO2/CF4 on different ZnO surfaces through molecular dynamics simulations. The study revealed that the evaporation response of CO2 has a delay effect compared to CF4, and the presence of CO2 promotes the evaporation of CF4.
INTERNATIONAL JOURNAL OF HEAT AND MASS TRANSFER
(2022)
Article
Chemistry, Multidisciplinary
Nazrul Hsan, Pradip K. Dutta, Santosh Kumar, Joonseok Koh
Summary: This study investigates the performance of chitosan-graphene oxide and arginine-based aerogels as CO2 capture and fixation materials. The results show that these materials have a higher CO2 capture capacity compared to pure chitosan.
JOURNAL OF CO2 UTILIZATION
(2022)
Article
Chemistry, Inorganic & Nuclear
Kaijie Ni, Louise N. Dawe, Amy A. Sarjeant, Christopher M. Kozak
Summary: In this study, a chromium(III) complex has been reported, which can effectively copolymerize carbon dioxide and cyclohexene oxide into a polycarbonate diol, and then be used to polymerize lactide to produce polycarbonate-block-polyester copolymers.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Mirtha A. O. Lourenco, Juqin Zeng, Pravin Jagdale, Micaela Castellino, Adriano Sacco, M. Amin Farkhondehfal, Candido F. Pirri
Summary: Novel electrocatalysts based on zinc oxide and biochars were prepared through a simple and scalable route for the electrocatalytic reduction of CO2. The study found that pyrolyzed chitosan with pyridinic- and pyridone-N species outperformed pyrolyzed brewed waste coffee in terms of CO selectivity and current density. The composite with 40.6 wt % of biochar showed the best performance, with high CO selectivity and electrode activity retention during long-term CO2 electrolysis.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Polymer Science
Peng Du, Yao Li, Xiao-Bing Lu
Summary: Asymmetric organocatalysis has been widely used in the synthesis of small chiral molecules, but its application in the synthesis of enantioenriched polymers is limited. This study presents a metal-free asymmetric catalytic copolymerization of meso-epoxides with CO2 using chiral organoboron-based bifunctional and binary catalysts. Although the enantioselectivities of the resulting copolymers are lower than those of metal-based catalyst systems, it is the first example of organocatalyzed synthesis of enantioenriched and perfectly alternating copolymers via asymmetric polymerization.
Article
Polymer Science
Ye Liu, Xiao-Bing Lu
Summary: Carbon dioxide (CO2) is a renewable building block for chemical synthesis, offering advantages like abundance, low toxicity, nonflammability, and availability. Incorporating CO2 into polymers provides desirable material properties and unique degradability under microbial conditions. This Perspective highlights recent advances, catalytic strategies, conceptual routes, and potential applications of CO2-derived polymers, while also discussing future challenges and new strategies for developing CO2-based polymers with desired performance and economic competitiveness comparable to petroleum-based materials.
Article
Polymer Science
Peng Du, Yao Li, Xiao-Bing Lu
Summary: This article presents a metal-free asymmetric catalytic copolymerization method for synthesizing enantioenriched and perfectly alternating copolymers. By using a chiral organoboron and a binary catalyst system, polycarbonates with controlled molecular weights and narrow dispersities can be efficiently synthesized at low catalyst loading over a broad temperature range.
Article
Nanoscience & Nanotechnology
Yanpeng Song, Yi Wang, Jiaqi Shao, Ke Ye, Qi Wang, Guoxiong Wang
Summary: In this study, a stable ZnS/ZnO interface structure was constructed by embedding ZnS nanoparticles onto the ZnO surface to enhance the performance and stability of CO2 electroreduction. The ZnS/ZnO interface exhibited a high maximum current density and CO Faradaic efficiency, remaining stable over a long period of time, demonstrating a promising catalyst for CO2 electroreduction.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Multidisciplinary Sciences
Ilaria D'Auria, Marina Lamberti, Raffaella Rescigno, Vincenzo Venditto, Mina Mazzeo
Summary: The zinc complexes with chelating phosphorous based pincer ligands were found to catalyze the ring-opening copolymerization of L-lactide and epsilon-caprolactone in the melt, resulting in high molecular weight copolymers with thermal properties strongly dependent on their composition.
Article
Chemistry, Multidisciplinary
Federica Santulli, Marina Lamberti, Mina Mazzeo
Summary: A simple zinc catalyst has been found to exhibit high activity in both the synthesis and degradation of polylactide, showing one of the highest activities in ring-opening polymerization of lactides even under industrial conditions. The same complex also proved to be efficient in depolymerization of polylactide by alcoholysis at room temperature and without solvent, reducing costs and environmental impact.
Article
Chemistry, Analytical
Maria Strianese, Viktoriia Vykhovanets, Naym Blal, Daniela Guarnieri, Alessandro Landi, Marina Lamberti, Andrea Peluso, Claudio Pellecchia
Summary: The authors investigated the interaction between a set of fluorescent zinc complexes and H2S, showing that HS- binds to the zinc center of the complexes, enabling them to function as sensors by a coordinative-based approach. Color changes were observed when treating the systems with HS-, indicating that the fluorescence responses are affected by the presence of HS-, which is related to changes in energy level and coupling of excited states according to computational study. The results demonstrate the potential of these systems as HS-/H2S colorimetric and fluorescent sensors, with paper-strip-based sensing experiments showing promise for applications in complex biological fluids.
Article
Chemistry, Physical
Federica Santulli, Giuseppe Gravina, Marina Lamberti, Consiglia Tedesco, Mina Mazzeo
Summary: Homoleptic and heteroleptic zinc and magnesium complexes with phenoxy-imine pyridine ligands were synthesized and characterized. Various structural parameters were investigated to identify design elements for improving catalytic activity in the ring opening polymerization of lactide and the degradation reaction of polylactide. Zinc catalysts exhibited high efficiency and control degree, while magnesium catalysts showed lower activity and weaker control degree. The most active complexes in the ring opening polymerization also exhibited high efficiency in the degradation reaction.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Physical
Federica Tufano, Federica Santulli, Fabia Grisi, Marina Lamberti
Summary: Two zinc complexes with NHC ligands were synthesized and studied for their behavior in the Ring-Opening Polymerization of lactides, showing efficiency as initiators with molecular weights dependent on cocatalysts. Microstructural analysis revealed enriched heterotactic PLA, with kinetic parameters compared between different conditions and reactions showing pseudo-first-order dependence on monomer concentration. Reactivity studies aimed to uncover the active species in polymerization processes with different catalytic systems, including zinc complexes alone or in combination with neutral or ionic cocatalysts.
Article
Chemistry, Physical
Federica Santulli, Marina Lamberti, Andrea Annunziata, Rita Chiara Lastra, Mina Mazzeo
Summary: Simple and commercially available metal amides were investigated as catalysts for the depolymerization of commercial polyesters via alcoholysis, and Zn, Mg, and Y amides showed the highest activities. The temperature had different effects on the activities of different metal amides, with Zn amide performing well at high temperatures, while Mg and Y amides showed a significant decrease. Additionally, Zr amide was found to be the best catalyst in the glycolysis of polyethylene terephthalate (PET), reaching activities comparable to the best metal catalysts reported in the literature. These studies provide new opportunities for sustainable plastic recycling and contribute to the design of a circular economy model in the plastic industry.
Article
Chemistry, Inorganic & Nuclear
Maria Strianese, Gerard Joseph D'Auria, Marina Lamberti, Alessandro Landi, Andrea Peluso, Antonio Varriale, Sabato D'Auria, Claudio Pellecchia
Summary: In this study, we used various spectroscopic techniques to investigate the interaction pathway between a newly synthesized family of zinc complexes and HS-. Computational analysis on the TD-DFT level revealed the fluorescence properties of these complexes and their different responses to HS-. Time-resolved fluorescence experiments demonstrated the potential of these systems to be used as HS- fluorescent sensors.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Federica Santulli, Filippo Bruno, Mina Mazzeo, Marina Lamberti
Summary: We synthesized new hexadentate ligands with imine and pyridine nitrogen neutral donors, which have two coordinative pockets to promote the formation of bimetallic complexes. The bimetallic complexes S-1 and rac-1 were obtained by reacting the enantiomerically pure and racemic ligands with two equivalents of zinc amide precursor. Both complexes showed high activity in the polymerization of lactides under various reaction conditions and remained active even in technical grade melted lactide, demonstrating the robustness of the catalysts. Complex S-1 allows the production of linear or purely macrocyclic PLAs by back-biting reactions, depending on the reaction conditions. Mechanistic studies in NMR-scale solution were conducted to understand the active species in the polymerization process.
Article
Biochemistry & Molecular Biology
Federica Santulli, Ilaria Grimaldi, Daniela Pappalardo, Marina Lamberti, Mina Mazzeo
Summary: Chromium and aluminum complexes with salalen ligands were studied as catalysts for the ring-opening copolymerization (ROCOP) of succinic (SA), maleic (MA), and phthalic (PA) anhydrides with various epoxides. Their performance was compared to traditional salen chromium complexes. When used with 4-(dimethylamino)pyridine (DMAP) as the cocatalyst, all catalysts achieved a completely alternating enchainment of monomers to obtain pure polyesters. Switch catalysis allowed the same catalyst to combine the ROCOP of propylene oxide and maleic anhydride with the ring-opening polymerization (ROP) of glycolide (GA) in a one-pot procedure, resulting in a diblock polyester with precise composition.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Analytical
Maria Strianese, Giovanni Ferrara, Viktoriia Vykhovanets, Naym Blal, Daniela Guarnieri, Alessandro Landi, Marina Lamberti, Andrea Peluso, Claudio Pellecchia
Summary: In this study, a new family of fluorescent zinc complexes with extended pi-conjugated systems was synthesized and characterized. The complexes were investigated for their potential use in high-performance H2S sensing devices. The immobilization of the complexes into a polymeric matrix for solid-state portable devices was also explored. The results demonstrated that the complexes could be successfully applied in fast, simple, and cost-effective H2S sensing devices.
Article
Biochemistry & Molecular Biology
Ilaria Grimaldi, Federica Santulli, Marina Lamberti, Mina Mazzeo
Summary: Salen, Salan, and Salalen chromium (III) chloride complexes have been studied as catalysts for the ring-opening copolymerization reactions. The salan and salalen complexes showed high activity in the production of polycarbonates, while the salen complex exhibited the best performance in the copolymerization of phthalic anhydride with the epoxides. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures, and all chromium complexes showed high activity in the chemical depolymerization of polycyclohexene carbonate.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Federica Tufano, Federica Tufano, Mariachiara Cozzolino, Ilaria D'Auria, Maria Strianese, Mina Mazzeo, Marina Lamberti
Summary: In this study, mono- and bimetallic complexes based on zinc were used for the synthesis of sustainable aliphatic and semi-aromatic polyesters. The bimetallic complexes showed higher activity and better control of polymerization processes compared to the monometallic complexes, highlighting the importance of cooperation between the two zinc centers in polyester synthesis.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Maria Strianese, Stefano Brenna, G. Attilio Ardizzoia, Daniela Guarnieri, Marina Lamberti, Ilaria D'Auria, Claudio Pellecchia
Summary: This study investigates the interaction of a family of fluorescent zinc complexes with HS-, showing the potential of these complexes to be used as HS-/H2S fluorescent sensors and probes for detecting H2S in living cells. Computational analysis based on TD-DFT was performed to shed light on the species formed in solution and elucidate the photophysical properties of the sensing constructs. Preliminary bio-imaging experiments indicate the promising potential of this class of compounds for H2S detection in living cells.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Maria Strianese, Daniela Pappalardo, Mina Mazzeo, Marina Lamberti, Claudio Pellecchia
Summary: Metalloporphyrins have great potential as optical probes and catalysts for sustainable polymers due to their flexibility in synthetic modifications of the porphyrin ring.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Maria Strianese, Daniela Pappalardo, Mina Mazzeo, Marina Lamberti, Claudio Pellecchia
DALTON TRANSACTIONS
(2020)