ChemSusChemPub Date : 2025-10-08DOI: 10.1002/cssc.202501667
Jeongin Ha, Hyeon Seok Kim, Hyunjung Kim, Yikyeom Kim, Surya Ayuati Ning Asih, Jae W Lee
{"title":"Modulating Oxygen Transfer via A-Site Doping in LaFeO<sub>3</sub> for Coke-Resistant Chemical Looping Steam Methane Reforming.","authors":"Jeongin Ha, Hyeon Seok Kim, Hyunjung Kim, Yikyeom Kim, Surya Ayuati Ning Asih, Jae W Lee","doi":"10.1002/cssc.202501667","DOIUrl":"https://doi.org/10.1002/cssc.202501667","url":null,"abstract":"<p><p>Chemical looping steam methane reforming (CL-SMR) is a promising technology for the simultaneous production of high-purity hydrogen and syngas without the need for external gas separation units. This study evaluates a series of A-site doped perovskite-type oxygen carriers, La<sub>0.8</sub>A<sub>0.2</sub>FeO<sub>3</sub> (A = Ca, Sr, Ba), to investigate the influence of alkaline earth metal doping on redox behavior and catalytic performance in CL-SMR. Substituting divalent cations at the A-site effectively promotes oxygen vacancy formation and enhances lattice oxygen transfer. Among the evaluated oxygen carriers, Sr-doped LaFeO<sub>3</sub> (La<sub>0.8</sub>Sr<sub>0.2</sub>FeO<sub>3</sub>) exhibits the most favorable performance. This is attributed to the optimal concentration of oxygen vacancies, which improved oxygen transfer, as confirmed by X-ray photoelectron spectroscopy, cerimetric titration, and O<sub>2</sub>-temperature programmed desorption. While undoped LaFeO<sub>3</sub> (LF) exhibits the highest methane activation, its limited oxygen mobility leads to severe coke formation. Enhanced oxygen transfer in La<sub>0.8</sub>Sr<sub>0.2</sub>FeO<sub>3</sub> effectively suppresses carbon deposition, while it shows the highest CO and hydrogen production. It achieves consistently high CO and H<sub>2</sub> yields (6.22-6.51 and 6.48-6.69 mmol/g<sub>cat</sub>, respectively) and demonstrates excellent stability over 50 redox cycles.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501667"},"PeriodicalIF":6.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145248973","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}
ChemSusChemPub Date : 2025-10-08DOI: 10.1002/cssc.202501104
Lennart Wichmann, Aleksei Sadykov, Pascal Seete, Bärbel Tengen, Peng Yan, Tom Boenke, Isidora Cekic-Laskovic, Sascha Nowak, Holger Althues, Stefan Kaskel, Martin Winter, Gunther Brunklaus
{"title":"Balancing Polysulfide Distribution in \"Anode-Free\" Lithium-Sulfide Batteries.","authors":"Lennart Wichmann, Aleksei Sadykov, Pascal Seete, Bärbel Tengen, Peng Yan, Tom Boenke, Isidora Cekic-Laskovic, Sascha Nowak, Holger Althues, Stefan Kaskel, Martin Winter, Gunther Brunklaus","doi":"10.1002/cssc.202501104","DOIUrl":"https://doi.org/10.1002/cssc.202501104","url":null,"abstract":"<p><p>Lithium-sulfide positive electrodes represent a promising alternative to established transition metal-based positive electrodes due to enhanced specific capacity and sustainability. While positive electrodes containing elemental sulfur require a lithiated negative electrode, lithium-sulfide can serve as the lithium reservoir and thus be paired with bare copper electrodes in \"anode-free\" or \"zero-excess\" cell concepts. This boosts energy density and avoids handling of thin lithium metal electrodes. While promising electrochemical performance of \"anode-free\" lithium-sulfide batteries has already been demonstrated, many reported cell configurations rely on nickel- instead of copper-based negative electrodes, undermining the enhanced sustainability bestowed by lithium-sulfide positive electrodes. Demonstrating a continuous reaction between copper electrodes and soluble polysulfide species, two approaches are evaluated that restrict the migration of polysulfide species. While both, in situ polymerization of an electrolyte additive as well as electrospinning of a polymer layer at negative electrodes, enable reversible operation of copper-based \"anode-free\" lithium-sulfide batteries, the former approach offers notably enhanced capacity retention. Counterintuitively, the quantification of polysulfide distribution throughout the individual battery components reveals less confinement within the positive electrode as beneficial for the overall reversibility. This demonstrates that a balance between positive and negative electrode reversibility is required to advance \"anode-free\" lithium-sulfide batteries.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501104"},"PeriodicalIF":6.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145249036","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}
{"title":"Photocatalytic-Filler-Engineered Solid Polymer Electrolytes for High-Performance Flexible Lithium-Metal Batteries.","authors":"Rong-Hao Wang, Liang Yue, Jun-Hao Liu, Li-Feng Chen","doi":"10.1002/cssc.202501717","DOIUrl":"https://doi.org/10.1002/cssc.202501717","url":null,"abstract":"<p><p>Flexible all-solid-state energy storage devices, with their exceptional energy density and safety, have emerged as promising candidates for next-generation portable electronics. However, the development of solid polymer electrolytes (SPEs) that simultaneously achieve high ionic conductivity, mechanical resilience, and interfacial stability remains a significant challenge. Although incorporating functionalized inorganic fillers into polymer matrices has shown partial success in enhancing ion transport, the intrinsic limitations of traditional fillers-low room-temperature ionic conductivity-hinder their further application. To address this, a novel strategy inspired by photocatalytic design principles is proposed, which involves engineering photocatalytic active fillers to generate strong and stable photogenerated electric fields. These fields modulate interfacial charge distribution, promote segmental motion of polymer chains, and facilitate lithium (Li) salt dissociation, while simultaneously optimizing the Li<sup>+</sup> solvation structure and coordination environment. Importantly, this approach significantly minimizes anion recombination, effectively suppressing space charge layer formation and reducing Li<sup>+</sup> concentration gradients. This innovative concept provides a new approach for developing high-performance flexible lithium metal batteries.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501717"},"PeriodicalIF":6.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145249003","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}
ChemSusChemPub Date : 2025-10-08DOI: 10.1002/cssc.202501477
Xiangli Shi, Qiong Zhang, Zhanzhen Ma, Sirui Liu, Di Li, Deli Jiang
{"title":"Enhanced Charge Separation Endowed by Perylene Diimide Polymers Decorated N Vacancy on Carbon Nitride S-Scheme Heterojunction for Efficient Photocatalytic N<sub>2</sub> Fixation.","authors":"Xiangli Shi, Qiong Zhang, Zhanzhen Ma, Sirui Liu, Di Li, Deli Jiang","doi":"10.1002/cssc.202501477","DOIUrl":"https://doi.org/10.1002/cssc.202501477","url":null,"abstract":"<p><p>Designing effective photocatalyst with high charge carrier utilization for photocatalytic N<sub>2</sub> fixation is extremely crucial but remains a challenge. Hence, a novel p-phenylenediamine substituted perylenediimide (pPDI)/nitrogen vacancy-modified carbon nitride (NV-CN) S-scheme heterojunction photocatalyst, integrated with pPDI polymers and NV-CN, is synthesized. The introduction of bridged p-phenylenediamine units in the pPDI skeleton creates a strong built-in electric field, which can significantly enhance the separation and migration of charge. Additionally, the constructed S-scheme system greatly facilitates the interfacial photogenerated carrier separation and transfer. Meanwhile, the introduction of nitrogen vacancies into NV-CN acts as an electron trap to capture electrons, thus preventing the recombination of electron-hole pairs and significantly prolongs N<sub>2</sub> absorption capacity. Benefiting from these synergistic advantages, the optimized 10% pPDI/NV-CN heterojunction achieves a superior NH<sub>3</sub> yield of 8.83 mM g<sup>-1</sup> h<sup>-1</sup>, achieving 12.26 and 13.63 times increase over CN (0.72 mM g<sup>-1</sup> h<sup>-1</sup>) and PDI (0.65 mM g<sup>-1</sup> h<sup>-1</sup>), respectively. This article provides an innovative perspective for the synthesis of CN-based photocatalysts for the efficient N<sub>2</sub> reduction through the introduction of bridging p-phenylenediamine units, nitrogen vacancy modification, and the construction of S-scheme heterojunctions.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501477"},"PeriodicalIF":6.6,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145248964","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}
{"title":"Redox-Active Bis(arylimino)acenaphthene-Catalyzed Dehydrogenative Aerial Functionalization of Alcohols to N-Heterocycles Under Exposure of Visible Light.","authors":"Krishnendu Paramanik, Nilaj Bandopadhyay, Agnishwar Mangal, Sourabh Pal, Suraj Kumar Agrawalla, Chandra Shekhar Purohit, Bhaskar Biswas, Jasimuddin Ahmed, Hari Sankar Das","doi":"10.1002/cssc.202501498","DOIUrl":"https://doi.org/10.1002/cssc.202501498","url":null,"abstract":"<p><p>An environmentally benign, transition-metal-free catalytic method has been developed for the synthesis of important classes of bioactive N-heterocycles, including quinoline, quinazoline, and quinazolinone under exposure of blue light. In this method, benzylic alcohol derivatives are catalytically dehydrogenated to the corresponding aldehydes by a redox-active molecule known as bis(arylimino)acenaphthene (Ar-BIAN) under exposure of blue light, and subsequently they react with ketones, nitriles, and amide partners. By using aerial-O<sub>2</sub> as a terminal oxidant, a variety of heavily functionalized N-heterocycles have been successfully synthesized with good to excellent yields across 59 examples. The organocatalyst used in this method demonstrates high compatibility and selectivity compared to previously reported transition metal catalysts. A plausible mechanistic path for the current protocol by combining structural, electrochemical, and photophysical properties, spectroscopic results, various control experiments, and detailed theoretical calculations is proposed.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501498"},"PeriodicalIF":6.6,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243395","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}
ChemSusChemPub Date : 2025-10-06DOI: 10.1002/cssc.202501383
Chloe Tolbert, Caleb Stetson, Denis Prodius, Christopher Orme, David Appy, Ikenna Nlebedim, Aaron D Wilson
{"title":"Lanthanide Sulfate Recovery by Synergistic Dimethyl Ether and Na<sub>2</sub>SO<sub>4</sub> Fractional Crystallization.","authors":"Chloe Tolbert, Caleb Stetson, Denis Prodius, Christopher Orme, David Appy, Ikenna Nlebedim, Aaron D Wilson","doi":"10.1002/cssc.202501383","DOIUrl":"https://doi.org/10.1002/cssc.202501383","url":null,"abstract":"<p><p>Lanthanides (Lns) are important to many technologies including magnets used in high-efficiency traction motors and generators. While commonly occurring in the environment and industrial waste streams, Ln are generally present at low concentrations. This work demonstrates synergistic Ln recovery from an aqueous magnet leachate to single ppm concentrations using Na<sub>2</sub>SO<sub>4</sub> addition and subsequent dimethyl ether-driven fractional crystallization (DME-FC) treatment. It is found that combining DME-FC with low concentrations of Na<sub>2</sub>SO<sub>4</sub> (≈0.1 M) results in synergistic isolation of Lns while making use of Na<sub>2</sub>SO<sub>4</sub>, an excessive byproduct of hydrometallurgical metal production. Combined Na<sub>2</sub>SO<sub>4</sub> + DME reduces Ln metal ion (Pr, Nd, Sm, Gd, Dy, and Ho) solubilities by 700-27,000x with final concentrations ranging from 2 ppm to 200 ppm. Separately, Na<sub>2</sub>SO<sub>4</sub> 0.1 M provides a 10-200x reduction and DME provides a 90-1,400x reduction in Ln solubilities. Final Ln concentrations of the combined process are 99.8% lower than what is achieved with each individual process.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501383"},"PeriodicalIF":6.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145231088","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}
ChemSusChemPub Date : 2025-10-06DOI: 10.1002/cssc.202501531
Sahil D Patel, Stefan J Hill, Cameron C Weber
{"title":"Enhancing the Efficiency of Switching Switchable Hydrophilicity Solvents Using Continuous Flow Approaches.","authors":"Sahil D Patel, Stefan J Hill, Cameron C Weber","doi":"10.1002/cssc.202501531","DOIUrl":"https://doi.org/10.1002/cssc.202501531","url":null,"abstract":"<p><p>CO<sub>2</sub>-switchable hydrophilicity solvents, hydrophobic amines which reversibly react with water and CO<sub>2</sub> to form water miscible solvents, are promising nonvolatile alternatives to conventional organic solvents while offering improved solute separation compared to neoteric solvents such as ionic liquids and deep eutectic solvents. A significant limitation of switchable hydrophilicity solvents is the slow rate of the switching process, which can lead to evaporative losses even of the nonvolatile solvent used as well as incurring a significant energy cost. The lengthy switching procedure can also affect the purity of compounds that possess poor thermal stability. This article details the use of a vortex fluidic device in both batch and continuous flow modes to enhance the efficiency of reactions between the amine switchable hydrophilicity solvent, water, and CO<sub>2</sub>, substantially reducing the required reaction time. The ability of the vortex fluidic device to enable the reverse switching process is tested and discussed, along with the implementation of a continuous flow methodology capable of substantially reducing switching times. These results highlight the potential of this strategy to increase the throughput of CO<sub>2</sub>-switchable hydrophilicity solvent transformations in both directions, with the potential to scale this approach discussed.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501531"},"PeriodicalIF":6.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145231099","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}
ChemSusChemPub Date : 2025-10-06DOI: 10.1002/cssc.202501571
Yaxin He, Xianglang Sun, Nan Li, Zonglong Zhu, Zhong'an Li
{"title":"The Multiple Roles of Nonfullerene Acceptors in Advancing Perovskite Solar Cells.","authors":"Yaxin He, Xianglang Sun, Nan Li, Zonglong Zhu, Zhong'an Li","doi":"10.1002/cssc.202501571","DOIUrl":"https://doi.org/10.1002/cssc.202501571","url":null,"abstract":"<p><p>Perovskite solar cells (PSCs) have now achieved power conversion efficiencies exceeding 27%, benefiting from rapid advancements in device processing and materials. However, challenges in processability and stability remain key barriers to their commercialization. Nonfullerene acceptors (NFAs) have garnered significant attention in perovskite research due to their high electron mobility, hydrophobicity, multiple defect-passivating functional groups, and complementary absorption in the near-infrared region. This review systematically summarizes the roles of NFAs in PSCs as electron transport layers, bulk-heterojunction layers, and interface layers. Finally, design principles are proposed for future NFA materials tailored for highly efficient and stable PSCs, paving the way for the commercialization of PSCs.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501571"},"PeriodicalIF":6.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145231053","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}
ChemSusChemPub Date : 2025-10-06DOI: 10.1002/cssc.202501905
Enrico Lanaro, Thirusangumurugan Senthamarai, Stephen K Hashmi, Arjan W Kleij
{"title":"Enabling a Diversity-Oriented Catalytic Atom Looping of a Biobased Polycarbonate.","authors":"Enrico Lanaro, Thirusangumurugan Senthamarai, Stephen K Hashmi, Arjan W Kleij","doi":"10.1002/cssc.202501905","DOIUrl":"https://doi.org/10.1002/cssc.202501905","url":null,"abstract":"<p><p>Herein, it is demonstrated that biobased poly(menthene carbonate) (PMC) can be conveniently used to enable catalysis-promoted atom looping thereby creating functionalized synthons and new types of repolymerizable monomers. The biobased polycarbonate undergoes chemoselective depolymerization in the presence of a bicyclic guanidinium providing under distinct reaction conditions and concentrations high-yield and selective access to either menthene oxide (MO), menthene carbonate (MC), or menthene diol (MD). These latter depolymerization products further enable the valorization of the original polymer atoms into several functionalized, partially biobased building blocks by integrating a monomer-and-molecular loop approach. As a proof-of-principle, four distinct scaffolds were converted into novel (bifunctional) monomers with potential to create a wider series of macromolecules. This work exemplifies a unique and holistic catalytic reuse of polymer atoms accommodating an on-demand preparation of fine-chemical precursors, repolymerizable monomers, and new monomer precursor designs.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501905"},"PeriodicalIF":6.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145231058","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}
ChemSusChemPub Date : 2025-10-06DOI: 10.1002/cssc.202501549
Kun Zhao, Hao Wu, Wenfang Feng, Michel Armand, Zhibin Zhou, Heng Zhang
{"title":"Coupling Graphite with Lithium Terephthalate Organic Electrode in Solid Polymer Electrolytes.","authors":"Kun Zhao, Hao Wu, Wenfang Feng, Michel Armand, Zhibin Zhou, Heng Zhang","doi":"10.1002/cssc.202501549","DOIUrl":"https://doi.org/10.1002/cssc.202501549","url":null,"abstract":"<p><p>Organic electroactive materials (OEMs) are featured with superior structural designability and ready accessibility from biomass or industrial plastics recycling, and they have emerged as important building blocks for future battery technology. Coupling OEMs with nonvolatile solid electrolytes offers the possibility for improving the technological sustainability and inherent safety of rechargeable batteries. This report delves into the representative carbonyl-based OEM, lithium terephthalate (Li<sub>2</sub>C<sub>8</sub>H<sub>4</sub>O<sub>4</sub>, LTPA), and prevailing graphite anode, and systematically investigates their fundamental properties with polyether-based electrolytes utilizing two sulfonimide anions (i.e., bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide), aiming to elucidate the unique features of OEMs and its synergy with salt anions. Results show that LTPA suffers from poor electronic conductivity in polymer electrolytes, while parasitic side reactions and cointercalation of low-molecular-weight compounds handicap neat graphite materials. Surprisingly, blended composite electrodes comprising graphite and a small portion of LTPA exhibit higher Coulombic efficiency and better capacity retention over continuous cycles, with significant improvement in the electrochemical utilization degree of graphite. The synergy between OEMs and classic graphite electrode materials in polymer electrolytes may spur the architectural design of solid-state batteries, and promote the realization of more sustainable battery technology in the near future.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202501549"},"PeriodicalIF":6.6,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230968","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}