Sung Joon Park, Jia Ler Eng, Pethe Shreyas Dinesh, Darrell Jun Jie Tay, Natalia Yantara, Nripan Mathews
To commercialize perovskite solar cells and advance beyond lab-scale comparisons, understanding large-area film formation using slot-die coating is essential to improve film homogeneity. Adding high-boiling-point solvents like NMP to the perovskite ink extends film's processing window, but the effects of varying NMP levels on gas-quenched slot-die coatings remain unclear. This article examines how different NMP ratios impact film quality, showing that a moderate amount of NMP as a co-solvent reduces defects, as observed through photoluminescence, hyperspectral absorbance, and back-illuminated optical absorptions. However, the decreased vapor pressure with the addition of NMP impairs crystallization and film coverage, highlighting the need for balanced amounts. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis indicate that the most volatile option tested at DMF: NMP ratio of 8:1 yields the most homogeneous and compact films. Slot-die-coated devices fabricated with this optimized ratio were subsequently compared with using NMP as an additive to increase the volatility of the perovskite inks further. The additive method demonstrates improved performance and uniformity, suggesting that minimizing high-boiling-point solvents to maintain ink volatility supports effective large-area coatings and fabrication of perovskite solar cells. Furthermore, this article provides insights on important metrics to narrow down suitable perovskite inks for large-area coatings.
{"title":"Investigating the effects of a high boiling point solvent in slot die-coated halide perovskite solar cells.","authors":"Sung Joon Park, Jia Ler Eng, Pethe Shreyas Dinesh, Darrell Jun Jie Tay, Natalia Yantara, Nripan Mathews","doi":"10.1002/cssc.202402499","DOIUrl":"https://doi.org/10.1002/cssc.202402499","url":null,"abstract":"<p><p>To commercialize perovskite solar cells and advance beyond lab-scale comparisons, understanding large-area film formation using slot-die coating is essential to improve film homogeneity. Adding high-boiling-point solvents like NMP to the perovskite ink extends film's processing window, but the effects of varying NMP levels on gas-quenched slot-die coatings remain unclear. This article examines how different NMP ratios impact film quality, showing that a moderate amount of NMP as a co-solvent reduces defects, as observed through photoluminescence, hyperspectral absorbance, and back-illuminated optical absorptions. However, the decreased vapor pressure with the addition of NMP impairs crystallization and film coverage, highlighting the need for balanced amounts. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis indicate that the most volatile option tested at DMF: NMP ratio of 8:1 yields the most homogeneous and compact films. Slot-die-coated devices fabricated with this optimized ratio were subsequently compared with using NMP as an additive to increase the volatility of the perovskite inks further. The additive method demonstrates improved performance and uniformity, suggesting that minimizing high-boiling-point solvents to maintain ink volatility supports effective large-area coatings and fabrication of perovskite solar cells. Furthermore, this article provides insights on important metrics to narrow down suitable perovskite inks for large-area coatings.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402499"},"PeriodicalIF":7.5,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ram Kishan, Pooja Rani, Nidhi Duhan, T J Dhilip Kumar, C M Nagaraja
Photocatalytic conversion of CO2 into value-added chemicals offers a propitious alternative to traditional thermal methods, contributing to environmental remediation and energy sustainability. In this respect, covalent organic frameworks (COFs), are crystalline porous materials showcasing remarkable efficacy in CO2 fixation facilitated by visible light owing to their excellent photochemical properties. Herein, we employed Lewis acidic Zn(II) anchored pyrene-based COF (Zn(II)@Pybp-COF) to facilitate the photocatalytic CO2 utilization and transformation to 2-oxazolidinones. Notably, Zn-COF displayed absorption of visible light, with an optimal band gap of 1.8 eV, effectively catalyzing light-mediated functionalization of propargylic amines to 2-oxazolidinones under green conditions. Detailed experimental and theoretical mechanistic investigations demonstrated that light plays a crucial role in enhancing the efficacy of the photocatalyst, as it activates inert CO2 molecule to radical anion and thereby, lowers the energy barrier for its subsequent cyclization reaction with propargylic amine. Additionally, Zn-COF demonstrates promising catalytic performance utilizing dilute gas as the CO2 source. This is the first report regarding noble metal-free, Zn-COF exhibiting excellent photocatalytic carboxylative cyclization of CO2 with propargyl amines to prepare 2-oxazolidinones using dilute gas (13% CO2). This study offers a new direction for rationally constructing noble metal-free eco-friendly photocatalysts for achieving CO2 fixation reactions under eco-friendly conditions.
{"title":"Noble-Metal-Free ZnII-Anchored Pyrene-Based Covalent Organic Framework (COF) for Photocatalytic Fixation of CO2 from Dilute Gas into Bioactive 2-Oxazolidinones.","authors":"Ram Kishan, Pooja Rani, Nidhi Duhan, T J Dhilip Kumar, C M Nagaraja","doi":"10.1002/cssc.202402535","DOIUrl":"https://doi.org/10.1002/cssc.202402535","url":null,"abstract":"<p><p>Photocatalytic conversion of CO2 into value-added chemicals offers a propitious alternative to traditional thermal methods, contributing to environmental remediation and energy sustainability. In this respect, covalent organic frameworks (COFs), are crystalline porous materials showcasing remarkable efficacy in CO2 fixation facilitated by visible light owing to their excellent photochemical properties. Herein, we employed Lewis acidic Zn(II) anchored pyrene-based COF (Zn(II)@Pybp-COF) to facilitate the photocatalytic CO2 utilization and transformation to 2-oxazolidinones. Notably, Zn-COF displayed absorption of visible light, with an optimal band gap of 1.8 eV, effectively catalyzing light-mediated functionalization of propargylic amines to 2-oxazolidinones under green conditions. Detailed experimental and theoretical mechanistic investigations demonstrated that light plays a crucial role in enhancing the efficacy of the photocatalyst, as it activates inert CO2 molecule to radical anion and thereby, lowers the energy barrier for its subsequent cyclization reaction with propargylic amine. Additionally, Zn-COF demonstrates promising catalytic performance utilizing dilute gas as the CO2 source. This is the first report regarding noble metal-free, Zn-COF exhibiting excellent photocatalytic carboxylative cyclization of CO2 with propargyl amines to prepare 2-oxazolidinones using dilute gas (13% CO2). This study offers a new direction for rationally constructing noble metal-free eco-friendly photocatalysts for achieving CO2 fixation reactions under eco-friendly conditions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402535"},"PeriodicalIF":7.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polyesters featuring a linear topology and in-chain 1,3-cyclobutane rings, synthesized via ring-opening polymerization (ROP) of 2-oxabicyclo[2.1.1]hexan-3-one (4R-BL, R = Bu, Ph) through a coordination-insertion mechanism, display excellent thermal and hydrolytic stability, making them promising candidates for sustainable circular materials. However, achieving diverse topological and stereochemical structures remains challenging. Herein, we demonstrate precise control over linear and cyclic topologies of these polyesters and the conformation of in-chain cyclobutane rings through anionic ROP of 4R-BL with appropriate catalysts or initiators. Using tert-butoxide (tBuOK) as the catalyst, low loading (0.05-0.1 mol%) produces high-molar-mass cyclic polyester P(4R-BL) (up to 571 kg/mol), whereas high loading (2 mol%) promotes transesterification and isomerization, ultimately yielding cyclic oligomers. Remarkably, the tetramer (4Ph-BL)4undergoes conformational turnover of the puckered cyclobutane rings and can be repolymerized into polymer P(4Ph-BL). This establishes a "monomer ⇄ polymer ⇄ tetramer" dual closed-loop life cycle, enhancing the potential for a circular material economy.
{"title":"Anionic ring-opening polymerization of 2-oxabicyclo[2.1.1]hexan-3-one: manipulating topology and conformation for circular polymer design.","authors":"Chaoqun Weng, Yanghaoyu Tan, Xiaoyan Tang","doi":"10.1002/cssc.202402667","DOIUrl":"https://doi.org/10.1002/cssc.202402667","url":null,"abstract":"<p><p>Polyesters featuring a linear topology and in-chain 1,3-cyclobutane rings, synthesized via ring-opening polymerization (ROP) of 2-oxabicyclo[2.1.1]hexan-3-one (4R-BL, R = Bu, Ph) through a coordination-insertion mechanism, display excellent thermal and hydrolytic stability, making them promising candidates for sustainable circular materials. However, achieving diverse topological and stereochemical structures remains challenging. Herein, we demonstrate precise control over linear and cyclic topologies of these polyesters and the conformation of in-chain cyclobutane rings through anionic ROP of 4R-BL with appropriate catalysts or initiators. Using tert-butoxide (tBuOK) as the catalyst, low loading (0.05-0.1 mol%) produces high-molar-mass cyclic polyester P(4R-BL) (up to 571 kg/mol), whereas high loading (2 mol%) promotes transesterification and isomerization, ultimately yielding cyclic oligomers. Remarkably, the tetramer (4Ph-BL)4undergoes conformational turnover of the puckered cyclobutane rings and can be repolymerized into polymer P(4Ph-BL). This establishes a \"monomer ⇄ polymer ⇄ tetramer\" dual closed-loop life cycle, enhancing the potential for a circular material economy.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402667"},"PeriodicalIF":7.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Multi-domain biological and environmental research highlights the efficacy of carbon quantum dots (CQDs) as a safer alternative to toxic metal-based quantum dots (QDs) and expensive conventional organic dyes, particularly in biomedical applications. CQDs are often functionalized by metal heteroatoms to improve their electron-donating properties and modify charge density, thereby enhancing their physicochemical characteristics. However, metal doping may re-introduce toxicity concerns similar to traditional QDs and further increase environmental risks. Thus, detailed ecotoxicology studies are necessary to understand the environmental impact of these CQDs in different organisms. To address this, we synthesized metal-doped CQDs (Mn, Fe, Cu and Ag) using microwave-assisted technique and conducted in-vitro experiments on diverse biological models belonging to different trophic levels, including bacteria (E. coli and B. subtilis), plants (Vigna radiata) and mammalian cells (mouse myoblast cells- C2C12). Results revealed that among all the CQDs explored, Ag-CQDs exhibited highest toxicity causing ~85% bacterial and 100% mammalian cell death even at 10 μg mL-1 and ~60% radicle growth inhibition after 5 days of exposure at 50 μg mL-1, whereas Mn-CQD showed the least toxicity. These findings contribute significantly to the critical need for determining optimal concentration ranges for metal-doped CQDs and enhance our understanding of their environmental implications.
{"title":"Toxicological Effects of Metal-Doped Carbon Quantum Dots.","authors":"Jyotsna Mishra, Tejas Suryawanshi, Neha Redkar, Rahul Kumar Das, Sumit Saxena, Abhijit Majumder, Kiran Kondabagil, Shobha Shukla","doi":"10.1002/cssc.202402056","DOIUrl":"10.1002/cssc.202402056","url":null,"abstract":"<p><p>Multi-domain biological and environmental research highlights the efficacy of carbon quantum dots (CQDs) as a safer alternative to toxic metal-based quantum dots (QDs) and expensive conventional organic dyes, particularly in biomedical applications. CQDs are often functionalized by metal heteroatoms to improve their electron-donating properties and modify charge density, thereby enhancing their physicochemical characteristics. However, metal doping may re-introduce toxicity concerns similar to traditional QDs and further increase environmental risks. Thus, detailed ecotoxicology studies are necessary to understand the environmental impact of these CQDs in different organisms. To address this, we synthesized metal-doped CQDs (Mn, Fe, Cu and Ag) using microwave-assisted technique and conducted in-vitro experiments on diverse biological models belonging to different trophic levels, including bacteria (E. coli and B. subtilis), plants (Vigna radiata) and mammalian cells (mouse myoblast cells- C2C12). Results revealed that among all the CQDs explored, Ag-CQDs exhibited highest toxicity causing ~85% bacterial and 100% mammalian cell death even at 10 μg mL<sup>-1</sup> and ~60% radicle growth inhibition after 5 days of exposure at 50 μg mL<sup>-1</sup>, whereas Mn-CQD showed the least toxicity. These findings contribute significantly to the critical need for determining optimal concentration ranges for metal-doped CQDs and enhance our understanding of their environmental implications.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402056"},"PeriodicalIF":7.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although microporous carbons can perform well for CO2 separations under high pressure conditions, their energy-demanding regeneration may render them a less attractive material option. Here, we developed a large-pore mesoporous carbon with pore sizes centered around 20-30 nm using a templated technical lignin. During the soft-templating process, unique cylindrical supramolecular assemblies form from the copolymer template. This peculiar nanostructuring takes place due to the presence of polyethylene glycol (PEG) segments on both the Pluronic® template and the PEG-grafted lignin derivative (glycol lignin). A large increase in CO2 uptake occurs on the resulting large-pore mesoporous carbon at 270 K close to the saturation pressure (3.2 MPa), owing to capillary condensation. This phenomenon enables a CO2/CH4 selectivity (SCO2/CH4, mol/mol) of 3.7 at 270 K and 3.1 MPa absolute pressure, and a swift pressure swing regeneration process with desorbed CO2 per unit pressure far outperforming a benchmark activated carbon (i.e., notably rapid decrease in the amount of adsorbed CO2 with decreasing pressure). We propose large-pore mesoporous carbons as a novel family of CO2 capture adsorbents, based on the phase-transition behavior shift of CO2 in the nanoconfined environment. This novel material concept may open new horizons for physisorptive CO2 separations with energy-efficient regeneration options.
{"title":"Nanoconfinement-Driven Energy-Efficient CO2 Capture and Release at High Pressures on a Unique Large-Pore Mesoporous Carbon.","authors":"Laszlo Szabo, Mizuki Inoue, Yurina Sekine, Ryuhei Motokawa, Yusuke Matsumoto, Thi Thi Nge, Edhuan Ismail, Izumi Ichinose, Tatsuhiko Yamada","doi":"10.1002/cssc.202402034","DOIUrl":"https://doi.org/10.1002/cssc.202402034","url":null,"abstract":"<p><p>Although microporous carbons can perform well for CO2 separations under high pressure conditions, their energy-demanding regeneration may render them a less attractive material option. Here, we developed a large-pore mesoporous carbon with pore sizes centered around 20-30 nm using a templated technical lignin. During the soft-templating process, unique cylindrical supramolecular assemblies form from the copolymer template. This peculiar nanostructuring takes place due to the presence of polyethylene glycol (PEG) segments on both the Pluronic® template and the PEG-grafted lignin derivative (glycol lignin). A large increase in CO2 uptake occurs on the resulting large-pore mesoporous carbon at 270 K close to the saturation pressure (3.2 MPa), owing to capillary condensation. This phenomenon enables a CO2/CH4 selectivity (SCO2/CH4, mol/mol) of 3.7 at 270 K and 3.1 MPa absolute pressure, and a swift pressure swing regeneration process with desorbed CO2 per unit pressure far outperforming a benchmark activated carbon (i.e., notably rapid decrease in the amount of adsorbed CO2 with decreasing pressure). We propose large-pore mesoporous carbons as a novel family of CO2 capture adsorbents, based on the phase-transition behavior shift of CO2 in the nanoconfined environment. This novel material concept may open new horizons for physisorptive CO2 separations with energy-efficient regeneration options.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402034"},"PeriodicalIF":7.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Efficient recovery of metals from secondary resources is essential to address resource shortages and environmental crises. The development of a cheap, environmentally friendly, and highly efficient recovery pathway is essential for resource retrieval. In this study, we propose a high-efficiency extraction approach utilizing bis(2,4,4-trimethylpentyl) phosphonic acid (Cyanex272) to recover cobalt from waste choline chloride/ethylene glycol (Ethaline) electrolyte containing Co(II) ions. By adjusting the water content of the system to modify the ligand of Co(II) ions, combined with pH adjustment, we achieved an extraction efficiency exceeding 99.9% for Co(II) ions. Subsequently, oxalic acid (OA) was added as a stripping agent to achieve a recovery efficiency of over 99.4% for cobalt. The extractant can be recycled more than 15 times after stripping. Impressively, more than 98.3% of the water-diluted Ethaline extraction raffinate was recovered through reduced pressure distillation while maintaining the structure of recovered Ethaline unchanged. This work provides an economical, efficient, and sustainable pathway for treating waste Ethaline electrolyte-containing metal ions.
{"title":"Highly efficient recovery of cobalt-ion containing waste deep eutectic electrolytes: a sustainable solvent extraction approach.","authors":"Jie Wang, Chaowu Wang, Qibo Zhang","doi":"10.1002/cssc.202402422","DOIUrl":"https://doi.org/10.1002/cssc.202402422","url":null,"abstract":"<p><p>Efficient recovery of metals from secondary resources is essential to address resource shortages and environmental crises. The development of a cheap, environmentally friendly, and highly efficient recovery pathway is essential for resource retrieval. In this study, we propose a high-efficiency extraction approach utilizing bis(2,4,4-trimethylpentyl) phosphonic acid (Cyanex272) to recover cobalt from waste choline chloride/ethylene glycol (Ethaline) electrolyte containing Co(II) ions. By adjusting the water content of the system to modify the ligand of Co(II) ions, combined with pH adjustment, we achieved an extraction efficiency exceeding 99.9% for Co(II) ions. Subsequently, oxalic acid (OA) was added as a stripping agent to achieve a recovery efficiency of over 99.4% for cobalt. The extractant can be recycled more than 15 times after stripping. Impressively, more than 98.3% of the water-diluted Ethaline extraction raffinate was recovered through reduced pressure distillation while maintaining the structure of recovered Ethaline unchanged. This work provides an economical, efficient, and sustainable pathway for treating waste Ethaline electrolyte-containing metal ions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402422"},"PeriodicalIF":7.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Selin Sariyer, Nilanka M Keppetipola, Ozlem Sel, Rezan Demir-Cakan
This contribution uses a rapid microwave-assisted hydrothermal synthesis method to produce a vanadium-based K1.92Mn0.54V2O5·H2O cathode material (quoted as KMnVOH). The electrochemical performance of KMnVOH is tested in an aqueous electrolyte, which exhibits a remarkable specific capacity of 260 mA·h g-1 at 5 C and retains 94% of its capacity over 2000 cycles. In contrast to the aqueous electrolyte, the KMnVOH electrode tested in the organic electrolyte provides a modest discharge capacity of 60 mAh⋅g-1 at C/10, and the electrogravimetric analysis indicates that the charge storage mechanism is solely due to non-solvated Zn2+ intercalation. In aqueous electrolyte tests, Zn species insertion, interfacial pH increase, and subsequent formation of Znx(OH)y(CF3SO3)2x-y·nH2O (ZHT) are supported by in-situ EQCM. Ex-situ XRD measurements also confirm the ZHT formation and its characteristic plate-like structure is observed by SEM. The ion diffusion coefficient values in aqueous and non-aqueous electrolytes are very similar according to the GITT analysis, while it is expected to be higher in aqueous electrolytes. These results may further emphasize the complex redox dynamics in the aqueous electrolyte, namely the difficulty of intercalation of bare Zn2+, strong Zn2+ solvation in the bulk electrolyte, solvent or proton intercalation, and ZHT formation.
{"title":"Microwave-Assisted Rapid Hydrothermal Synthesis of Vanadium-Based Cathode: Unravelling Charge Storage Mechanisms in Aqueous Zinc-Ion Batteries.","authors":"Selin Sariyer, Nilanka M Keppetipola, Ozlem Sel, Rezan Demir-Cakan","doi":"10.1002/cssc.202402445","DOIUrl":"https://doi.org/10.1002/cssc.202402445","url":null,"abstract":"<p><p>This contribution uses a rapid microwave-assisted hydrothermal synthesis method to produce a vanadium-based K1.92Mn0.54V2O5·H2O cathode material (quoted as KMnVOH). The electrochemical performance of KMnVOH is tested in an aqueous electrolyte, which exhibits a remarkable specific capacity of 260 mA·h g-1 at 5 C and retains 94% of its capacity over 2000 cycles. In contrast to the aqueous electrolyte, the KMnVOH electrode tested in the organic electrolyte provides a modest discharge capacity of 60 mAh⋅g-1 at C/10, and the electrogravimetric analysis indicates that the charge storage mechanism is solely due to non-solvated Zn2+ intercalation. In aqueous electrolyte tests, Zn species insertion, interfacial pH increase, and subsequent formation of Znx(OH)y(CF3SO3)2x-y·nH2O (ZHT) are supported by in-situ EQCM. Ex-situ XRD measurements also confirm the ZHT formation and its characteristic plate-like structure is observed by SEM. The ion diffusion coefficient values in aqueous and non-aqueous electrolytes are very similar according to the GITT analysis, while it is expected to be higher in aqueous electrolytes. These results may further emphasize the complex redox dynamics in the aqueous electrolyte, namely the difficulty of intercalation of bare Zn2+, strong Zn2+ solvation in the bulk electrolyte, solvent or proton intercalation, and ZHT formation.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402445"},"PeriodicalIF":7.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Federico Droghetti, Lucrezia Villa, Andrea Sartorel, Luca Dell'Amico, Albert Ruggi, Mirco Natali
Direct photochemical conversion of CO2 into a single carbon-based product currently represents one of the major issues in the catalysis of the CO2 reduction reaction (CO2RR). In this work, we demonstrate that the combination of an organic photosensitizer with a heptacoordinated iron(II) complex allows to attain a noble-metal-free photochemical system capable of efficient and selective conversion of CO2 into CO upon light irradiation in the presence of N,N-diisopropylethylamine (DIPEA) and 2,2,2-trifluoroethanol (TFE) as the electron and proton donor, respectively, with unprecedented performances (ΦCO up to 36 %, TONCO >1000, selectivity >99 %). As shown by transient absorption spectroscopy studies, this can be achieved thanks to the fast rates associated with the electron transfer from the photogenerated reduced dye to the catalyst, which protect the dye from parallel degradation pathways ensuring its stability along the photochemical reaction. These results point out how the profitable merging of molecular species based on cheap and abundant elements can have great potential to target efficient and selective transformations crucial for the conversion of solar energy into fuels.
将二氧化碳直接光化学转化为单一碳基产物是目前二氧化碳还原反应(CO2RR)催化过程中的主要问题之一。在这项工作中,我们证明了有机光敏剂与七配位铁(II)配合物的结合可以获得一种不含惰性金属的光化学体系,在 N. N. 二异丙基乙胺(2、N-二异丙基乙胺(DIPEA)和 2,2,2-三氟乙醇(TFE)分别作为电子和质子供体的情况下,在光照射下能够高效、选择性地将 CO2 转化为 CO,其性能达到了前所未有的水平(ΦCO 高达 36%,TONCO > 1000,选择性 > 99%)。正如瞬态吸收光谱研究表明的那样,这要归功于从光生成的还原染料到催化剂之间的电子转移速度快,从而保护了染料免受平行降解途径的影响,确保了其在光化学反应过程中的稳定性。这些结果表明,基于廉价和丰富元素的分子物种的有利合并具有巨大的潜力,可以实现高效和选择性的转化,这对于将太阳能转化为燃料至关重要。
{"title":"Boosting Light-Driven CO<sub>2</sub> Conversion Into CO by a Polypyridine Iron(II) Catalyst Using an Organic Sensitizer.","authors":"Federico Droghetti, Lucrezia Villa, Andrea Sartorel, Luca Dell'Amico, Albert Ruggi, Mirco Natali","doi":"10.1002/cssc.202402627","DOIUrl":"10.1002/cssc.202402627","url":null,"abstract":"<p><p>Direct photochemical conversion of CO<sub>2</sub> into a single carbon-based product currently represents one of the major issues in the catalysis of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). In this work, we demonstrate that the combination of an organic photosensitizer with a heptacoordinated iron(II) complex allows to attain a noble-metal-free photochemical system capable of efficient and selective conversion of CO<sub>2</sub> into CO upon light irradiation in the presence of N,N-diisopropylethylamine (DIPEA) and 2,2,2-trifluoroethanol (TFE) as the electron and proton donor, respectively, with unprecedented performances (Φ<sub>CO</sub> up to 36 %, TON<sub>CO</sub> >1000, selectivity >99 %). As shown by transient absorption spectroscopy studies, this can be achieved thanks to the fast rates associated with the electron transfer from the photogenerated reduced dye to the catalyst, which protect the dye from parallel degradation pathways ensuring its stability along the photochemical reaction. These results point out how the profitable merging of molecular species based on cheap and abundant elements can have great potential to target efficient and selective transformations crucial for the conversion of solar energy into fuels.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402627"},"PeriodicalIF":7.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143045102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yibo Song, Anni Li, Haiyang Cui, Luxuan Wu, Bo Zhou, Xiujuan Li
Beyond directed evolution, ancestral sequence reconstruction (ASR) has emerged as a powerful strategy for engineering proteins with superior functional properties. Herein, we harnessed ASR to uncover robust PET hydrolase variants, expanding the repertoire of PET-degrading enzymes and providing deeper insights into the underlying mechanisms of PET hydrolysis. As a result, ASR1-PETase, featuring a unique cysteine catalytic site, was discovered. Despite having only 19.3% sequence identity with IsPETase, ASR1-PETase demonstrated improved PET degradation efficiency, with a finely-tuned substrate-binding cleft. Comprehensive experimental validation, including mutagenesis studies and comparisons with six state-of-the-art PET hydrolases, combined with microsecond-scale molecular dynamics (MD) simulations and QM-cluster calculations, revealed that ASR1-PETase's C161 catalytic residue assisted with the wobbled H242 can simultaneously cleave both ester bonds of BHET-a feature not commonly observed in other PET hydrolases. This mechanism may serve as the primary driving force for accelerating PET hydrolysis while minimizing the accumulation of the intermediate MHET, thereby enhancing the efficiency of TPA production.
{"title":"Ancestral Sequence Reconstruction and Comprehensive Computational Simulations Unmask an Efficient PET Hydrolase with the Wobbled Catalytic Triad.","authors":"Yibo Song, Anni Li, Haiyang Cui, Luxuan Wu, Bo Zhou, Xiujuan Li","doi":"10.1002/cssc.202402614","DOIUrl":"https://doi.org/10.1002/cssc.202402614","url":null,"abstract":"<p><p>Beyond directed evolution, ancestral sequence reconstruction (ASR) has emerged as a powerful strategy for engineering proteins with superior functional properties. Herein, we harnessed ASR to uncover robust PET hydrolase variants, expanding the repertoire of PET-degrading enzymes and providing deeper insights into the underlying mechanisms of PET hydrolysis. As a result, ASR1-PETase, featuring a unique cysteine catalytic site, was discovered. Despite having only 19.3% sequence identity with IsPETase, ASR1-PETase demonstrated improved PET degradation efficiency, with a finely-tuned substrate-binding cleft. Comprehensive experimental validation, including mutagenesis studies and comparisons with six state-of-the-art PET hydrolases, combined with microsecond-scale molecular dynamics (MD) simulations and QM-cluster calculations, revealed that ASR1-PETase's C161 catalytic residue assisted with the wobbled H242 can simultaneously cleave both ester bonds of BHET-a feature not commonly observed in other PET hydrolases. This mechanism may serve as the primary driving force for accelerating PET hydrolysis while minimizing the accumulation of the intermediate MHET, thereby enhancing the efficiency of TPA production.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402614"},"PeriodicalIF":7.5,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143045087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The advancement of photocatalytic technology for solar-driven hydrogen (H2) production remains hindered by several challenges in developing efficient photocatalysts. A key issue is the rapid recombination of charge carriers, which significantly limits the light-harvesting ability of materials like BiOCl and Cu2SnS3 quantum dots (CTS QDs), despite the faster charge mobility and quantum confinement effect, respectively. Herein, a BiOCl/CTS (BCTS) heterostructure was synthesized by loading CTS QDs onto BiOCl 2D nanosheets (NSs), that demonstrated excellent photocatalytic activity under visible light irradiation. The improved hydrogen generation rate (HGR) was primarily due to an interfacial Bi-S bond formation, which facilitates the creation of direct Z-scheme heterojunction and an internal electric field at the interface, promoting efficient charge transfer between BiOCl and CTS. Moreover, due to the amalgamation of Bi-S bond formation and interfacial electric field, the optimized BCTS-5% heterostructure exhibited a high HGR of 8.27 mmol g-1 h-1, and an apparent quantum yield (AQY) of 61 %, ~4 times higher than pristine BiOCl. First-principle density functional theory (DFT) calculations further revealed the presence of a Bi-S bond with a bond length of ~2.85 Å and a minimal work function of 2.37 eV for the heterostructure, both of which are critical for enhancing H2 generation efficiency.
{"title":"Bi-S Bond Mediated Direct Z-Scheme BiOCl/Cu<sub>2</sub>SnS<sub>3</sub> Heterostructure for Efficient Photocatalytic Hydrogen Generation.","authors":"Dipendu Sarkar, Maitrayee Biswas, Swarup Ghosh, Joydeep Chowdhury, Biswarup Satpati, Srabanti Ghosh","doi":"10.1002/cssc.202402655","DOIUrl":"10.1002/cssc.202402655","url":null,"abstract":"<p><p>The advancement of photocatalytic technology for solar-driven hydrogen (H<sub>2</sub>) production remains hindered by several challenges in developing efficient photocatalysts. A key issue is the rapid recombination of charge carriers, which significantly limits the light-harvesting ability of materials like BiOCl and Cu<sub>2</sub>SnS<sub>3</sub> quantum dots (CTS QDs), despite the faster charge mobility and quantum confinement effect, respectively. Herein, a BiOCl/CTS (BCTS) heterostructure was synthesized by loading CTS QDs onto BiOCl 2D nanosheets (NSs), that demonstrated excellent photocatalytic activity under visible light irradiation. The improved hydrogen generation rate (HGR) was primarily due to an interfacial Bi-S bond formation, which facilitates the creation of direct Z-scheme heterojunction and an internal electric field at the interface, promoting efficient charge transfer between BiOCl and CTS. Moreover, due to the amalgamation of Bi-S bond formation and interfacial electric field, the optimized BCTS-5% heterostructure exhibited a high HGR of 8.27 mmol g<sup>-1</sup> h<sup>-1</sup>, and an apparent quantum yield (AQY) of 61 %, ~4 times higher than pristine BiOCl. First-principle density functional theory (DFT) calculations further revealed the presence of a Bi-S bond with a bond length of ~2.85 Å and a minimal work function of 2.37 eV for the heterostructure, both of which are critical for enhancing H<sub>2</sub> generation efficiency.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402655"},"PeriodicalIF":7.5,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143045100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}