Orotic acid (OA) is an intermediate in de novo pyrimidine biosynthesis and a bio-based chemical of interest for nutraceutical, animal nutrition, and biomedical applications. Efficient fermentative OA production, however, remains constrained by carbon loss, insufficient nitrogen assimilation, product-associated stress, and energy-redox imbalance during high-titer production. This study constructed a high-performance Escherichia coli cell factory by coordinating product transport, carbon-nitrogen flux, and energy-redox metabolism. Deletion of the inward OA transporter dctA improved extracellular OA accumulation, while the introduction of a nonoxidative glycolysis (NOG) module, acetyl-phosphate recycling, and byproduct-pathway attenuation reduced overflow carbon loss. Nitrogen assimilation was strengthened by tuning heterologous ammonium transport and balancing NADPH supply. Adenylate metabolism reconstruction and microaerobically responsive expression of vgb and cyoABCDE increased intracellular ATP levels and promoted the NADH/NAD+ redox balance, supporting OA biosynthesis during mid-to-late-stage fed-batch fermentation. OA24 produced 214.2 g/L OA in 42 h in a 5-L bioreactor, with an apparent glucose-based yield of 0.70 g/g glucose and productivity of 5.10 g/L/h; relative to the initial strain Ora21, the yield and productivity increased by 20.7% and 34.2%, respectively. This work provides a carbon-efficient and high-intensity biomanufacturing strategy for OA and related pyrimidine chemicals.
{"title":"Coordinated Metabolic Strategies for Green and Efficient Orotic Acid Biomanufacturing in Escherichia coli","authors":"Changgeng Li,Runze Zhao,Ruihong Liu,Wenjing Fan,Tang'en Shi,Siyu Zhao,Ling Ma,Zichen Yu,Zhichao Chen,Haibo Xiong,Xin Liang,Qingyang Xu","doi":"10.1021/acssuschemeng.6c08632","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08632","url":null,"abstract":"Orotic acid (OA) is an intermediate in de novo pyrimidine biosynthesis and a bio-based chemical of interest for nutraceutical, animal nutrition, and biomedical applications. Efficient fermentative OA production, however, remains constrained by carbon loss, insufficient nitrogen assimilation, product-associated stress, and energy-redox imbalance during high-titer production. This study constructed a high-performance Escherichia coli cell factory by coordinating product transport, carbon-nitrogen flux, and energy-redox metabolism. Deletion of the inward OA transporter dctA improved extracellular OA accumulation, while the introduction of a nonoxidative glycolysis (NOG) module, acetyl-phosphate recycling, and byproduct-pathway attenuation reduced overflow carbon loss. Nitrogen assimilation was strengthened by tuning heterologous ammonium transport and balancing NADPH supply. Adenylate metabolism reconstruction and microaerobically responsive expression of vgb and cyoABCDE increased intracellular ATP levels and promoted the NADH/NAD+ redox balance, supporting OA biosynthesis during mid-to-late-stage fed-batch fermentation. OA24 produced 214.2 g/L OA in 42 h in a 5-L bioreactor, with an apparent glucose-based yield of 0.70 g/g glucose and productivity of 5.10 g/L/h; relative to the initial strain Ora21, the yield and productivity increased by 20.7% and 34.2%, respectively. This work provides a carbon-efficient and high-intensity biomanufacturing strategy for OA and related pyrimidine chemicals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-21DOI: 10.1021/acssuschemeng.6c08496
Rujia Chen,Kejia Wu,Xiudan Zhao,Yun Tian,Zhenping Cai,Jinrong Liang,Weilu Ding,Wentao Mu,Xuehui Li
The development of sustainable routes for polymer monomers is crucial for the chemical industry. Herein, we report a highly efficient and selective oxidative depolymerization strategy for converting lignin into diethyl maleate (DEM), a valuable precursor for polyaspartic polyurea resins. A series of iron oxide catalysts supported on commercial USY zeolites via a simple impregnation-calcination method were developed. Notably, the catalyst prepared using iron sulfate (Fe2(SO4)3) as the precursor exhibited superior performance, achieving a maximum DEM yield of 53.0 wt % and a selectivity of 72.4% from organosolv bagasse lignin, outperforming the iron nitrate- and chloride-derived catalysts by 29.2 and 31.9 wt % in yield, respectively. Comprehensive characterizations revealed that the unique highly dispersed Fe(SO4)x phases significantly increased the proportion of Fe3+ species and facilitated electron transfer across the support-iron interface. The synergistic interplay between sulfur-induced Brønsted acid sites and isolated octahedral iron sites was identified as the key factor driving the efficient cleavage of lignin linkages and subsequent oxidative ring-opening. By combining commercially available supports and earth-abundant metals, this work offers an environmentally viable pathway for lignin depolymerization into polymer monomers, demonstrating significant potential for industrial scalability.
{"title":"Engineering Fe Species on USY Zeolite Support for the Oxidative Cleavage of Lignin to Bio-Based Diethyl Maleate","authors":"Rujia Chen,Kejia Wu,Xiudan Zhao,Yun Tian,Zhenping Cai,Jinrong Liang,Weilu Ding,Wentao Mu,Xuehui Li","doi":"10.1021/acssuschemeng.6c08496","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08496","url":null,"abstract":"The development of sustainable routes for polymer monomers is crucial for the chemical industry. Herein, we report a highly efficient and selective oxidative depolymerization strategy for converting lignin into diethyl maleate (DEM), a valuable precursor for polyaspartic polyurea resins. A series of iron oxide catalysts supported on commercial USY zeolites via a simple impregnation-calcination method were developed. Notably, the catalyst prepared using iron sulfate (Fe2(SO4)3) as the precursor exhibited superior performance, achieving a maximum DEM yield of 53.0 wt % and a selectivity of 72.4% from organosolv bagasse lignin, outperforming the iron nitrate- and chloride-derived catalysts by 29.2 and 31.9 wt % in yield, respectively. Comprehensive characterizations revealed that the unique highly dispersed Fe(SO4)x phases significantly increased the proportion of Fe3+ species and facilitated electron transfer across the support-iron interface. The synergistic interplay between sulfur-induced Brønsted acid sites and isolated octahedral iron sites was identified as the key factor driving the efficient cleavage of lignin linkages and subsequent oxidative ring-opening. By combining commercially available supports and earth-abundant metals, this work offers an environmentally viable pathway for lignin depolymerization into polymer monomers, demonstrating significant potential for industrial scalability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-21DOI: 10.1021/acssuschemeng.6c09509
Dehang Yang,Shuai Du,Shanshan Dai,Fengyuan Zhang,Songqi Ma
Recyclable epoxy thermosets and their carbon fiber-reinforced polymer composites (CFRPs) have faced three long-standing bottlenecks: complex synthesis and purification processes, inherently high viscosity incompatible with the industrial vacuum-assisted resin infusion (VARI) process—the dominant technology for manufacturing large wind turbine blades and aerospace composites—and incomplete recovery of individual composite constituents. While dynamic covalent bonds offer a promising route to epoxy recyclability, most existing recyclable epoxy systems fail to simultaneously overcome these hurdles. Herein, we report a green, scalable one-pot synthesis of a novel low-viscosity acetal epoxy resin (BCAE) that simultaneously addresses the synthesis, processing, and end-of-life recycling challenges of epoxy thermosets. This telescoped protocol eliminates intermediate purification steps, delivering BCAE with an ultra-low viscosity of 1.9 Pa·s at 25 °C—6.7-fold lower than commercial bisphenol A diglycidyl ether (DGEBA)—enabling diluent-free VARI fabrication of high-performance CFRPs. The cured BCAE networks exhibit dual recyclability: catalyst-free thermal reprocessability and mild acid-triggered degradation under ambient conditions. Most notably, we demonstrate a closed-loop monomer recycling combined with an open-loop upcycling system with key quantitative breakthroughs: carbon fibers are recovered with 96.7% strength retention in the regenerated composite, the benzaldehyde monomer is recycled to resynthesize BCAE with identical performance, and the tertiary amine polyol degradation product is upcycled as a high-value curing agent for commercial epoxies. Life cycle assessment confirms that closed‑loop recycling reduces CO2‑equivalent emissions by approximately 79% compared with incineration. This work provides a general and industrially viable strategy for sustainable thermoset composites, aligning perfectly with global carbon neutrality goals.
{"title":"One-Pot Green Synthesis of Low-Viscosity Acetal Epoxy Resins for Diluent-Free Industrial Processing and Closed-Loop Recycling of Carbon Fiber Composites","authors":"Dehang Yang,Shuai Du,Shanshan Dai,Fengyuan Zhang,Songqi Ma","doi":"10.1021/acssuschemeng.6c09509","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c09509","url":null,"abstract":"Recyclable epoxy thermosets and their carbon fiber-reinforced polymer composites (CFRPs) have faced three long-standing bottlenecks: complex synthesis and purification processes, inherently high viscosity incompatible with the industrial vacuum-assisted resin infusion (VARI) process—the dominant technology for manufacturing large wind turbine blades and aerospace composites—and incomplete recovery of individual composite constituents. While dynamic covalent bonds offer a promising route to epoxy recyclability, most existing recyclable epoxy systems fail to simultaneously overcome these hurdles. Herein, we report a green, scalable one-pot synthesis of a novel low-viscosity acetal epoxy resin (BCAE) that simultaneously addresses the synthesis, processing, and end-of-life recycling challenges of epoxy thermosets. This telescoped protocol eliminates intermediate purification steps, delivering BCAE with an ultra-low viscosity of 1.9 Pa·s at 25 °C—6.7-fold lower than commercial bisphenol A diglycidyl ether (DGEBA)—enabling diluent-free VARI fabrication of high-performance CFRPs. The cured BCAE networks exhibit dual recyclability: catalyst-free thermal reprocessability and mild acid-triggered degradation under ambient conditions. Most notably, we demonstrate a closed-loop monomer recycling combined with an open-loop upcycling system with key quantitative breakthroughs: carbon fibers are recovered with 96.7% strength retention in the regenerated composite, the benzaldehyde monomer is recycled to resynthesize BCAE with identical performance, and the tertiary amine polyol degradation product is upcycled as a high-value curing agent for commercial epoxies. Life cycle assessment confirms that closed‑loop recycling reduces CO2‑equivalent emissions by approximately 79% compared with incineration. This work provides a general and industrially viable strategy for sustainable thermoset composites, aligning perfectly with global carbon neutrality goals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-20DOI: 10.1021/acssuschemeng.6c04554
Wubin Wan,Xuejing Yang,Tianguo Wang,Cheng Luo,Chuitao Zeng,Xingxing Zhu,Xingyou Lang
Single-phase transition metal nitrides (TMNs) for alkaline hydrogen evolution reaction (HER) are limited by sluggish charge transfer kinetics, suboptimal adsorption, and restricted accessibility of active sites—intrinsic drawbacks of their electronic structure and conventional electrode architecture. Herein, we circumvent these obstacles by constructing a Ni4N/CoN heterostructure on nickel foam (Ni4N/CoN/NF) with two synergistic features: a built-in interfacial electric field (BIEF) and a hierarchical porous morphology. The work function difference between Ni4N and CoN generates a robust BIEF that drives directional electron transfer from Ni to Co, precisely tailoring the electronic configuration of Ni sites to optimize adsorption energy. Moreover, this hierarchical architecture, assembled from interconnected nanochains and nanosheets, simultaneously enhances active-site exposure, facilitates electron transport, and promotes efficient gas release. Benefiting from these synergistic advantages, the Ni4N/CoN electrode delivers an industrial-level current density of 1000 mA cm–2 at an overpotential of only 213 mV in alkaline media. Moreover, the combination of its robust interwoven nanochain architecture and strong interfacial electronic coupling endows the electrode with outstanding operational stability, sustaining continuous hydrogen evolution for over 500 h at the current density of 500 mA cm–2. This work presents a viable strategy for designing efficient and durable heterostructure electrocatalysts toward practical water electrolysis.
用于碱性析氢反应（HER）的单相过渡金属氮化物（TMNs）受到电荷转移动力学缓慢、吸附不理想以及活性位点可及性受限的限制，这些都是其电子结构和传统电极结构的固有缺陷。在此，我们通过在泡沫镍上构建Ni4N/CoN异质结构（Ni4N/CoN/NF）来规避这些障碍，该异质结构具有两个协同特征：内置界面电场（BIEF）和分层多孔形态。Ni4N和CoN之间的功函数差异产生了强大的BIEF，驱动从Ni到Co的定向电子转移，精确地调整Ni位点的电子配置以优化吸附能。此外，这种由相互连接的纳米链和纳米片组装而成的分层结构同时增强了活性位点暴露，促进了电子传递，并促进了有效的气体释放。得益于这些协同优势，Ni4N/CoN电极在碱性介质中过电位仅为213 mV时可提供1000 mA cm-2的工业级电流密度。此外，其强大的交织纳米链结构和强大的界面电子耦合相结合，使电极具有出色的操作稳定性，在500 mA cm-2的电流密度下持续500小时以上的析氢。本研究为设计高效耐用的异质结构电催化剂提供了可行的策略。
{"title":"Engineering Self-Woven Hierarchical Bimetallic Nitride Electrode with Built-In Interfacial Electric Field for Enhanced Alkaline Hydrogen Evolution","authors":"Wubin Wan,Xuejing Yang,Tianguo Wang,Cheng Luo,Chuitao Zeng,Xingxing Zhu,Xingyou Lang","doi":"10.1021/acssuschemeng.6c04554","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c04554","url":null,"abstract":"Single-phase transition metal nitrides (TMNs) for alkaline hydrogen evolution reaction (HER) are limited by sluggish charge transfer kinetics, suboptimal adsorption, and restricted accessibility of active sites—intrinsic drawbacks of their electronic structure and conventional electrode architecture. Herein, we circumvent these obstacles by constructing a Ni4N/CoN heterostructure on nickel foam (Ni4N/CoN/NF) with two synergistic features: a built-in interfacial electric field (BIEF) and a hierarchical porous morphology. The work function difference between Ni4N and CoN generates a robust BIEF that drives directional electron transfer from Ni to Co, precisely tailoring the electronic configuration of Ni sites to optimize adsorption energy. Moreover, this hierarchical architecture, assembled from interconnected nanochains and nanosheets, simultaneously enhances active-site exposure, facilitates electron transport, and promotes efficient gas release. Benefiting from these synergistic advantages, the Ni4N/CoN electrode delivers an industrial-level current density of 1000 mA cm–2 at an overpotential of only 213 mV in alkaline media. Moreover, the combination of its robust interwoven nanochain architecture and strong interfacial electronic coupling endows the electrode with outstanding operational stability, sustaining continuous hydrogen evolution for over 500 h at the current density of 500 mA cm–2. This work presents a viable strategy for designing efficient and durable heterostructure electrocatalysts toward practical water electrolysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-20DOI: 10.1021/acssuschemeng.6c07249
Emis Ingenito,Alexander Dömling
Miniaturized chemical synthesis through acoustic droplet ejection (ADE) is transforming reaction discovery by reducing material consumption and enabling highly parallelized, autonomous workflows. However, its application in organic synthesis has remained largely confined to DMSO and aqueous media, restricting solvent exploration and limiting broader process innovation. Often attributed to the intrinsic physics of acoustic transfer, these constraints may instead reflect historical calibration practices. Here, we establish a data-driven framework for expanding ADE-compatible solvent space toward a more applicable nanoscale reaction chemistry. Through systematic gravimetric analysis of 19 high-boiling organic solvents, including water and DMSO as reference fluids, we identify a broad operating window that supports accurate (deviation < 10%) and reproducible (RSD < 8%) dispensing using existing instrumentation. We further validate this framework via automated assembly of a 384-member Suzuki–Miyaura reaction library, where testing of N,N-dimethylformamide and a bio-based alternative solvent dimethyl isosorbide resulted in broad product formation across diverse substrates. This work decouples solvent choice from historical conventions and opens the route to a reaction-agnostic, solvent-flexible, and sustainable approach for high-throughput reaction discovery, enabling ADE workflows to transition from condition-constrained screening tools to general engines for sustainable, data-driven chemical exploration.
{"title":"Breaking Solvent Constraints Enables Sustainable Nanoscale Chemical Synthesis by Acoustic Droplet Ejection","authors":"Emis Ingenito,Alexander Dömling","doi":"10.1021/acssuschemeng.6c07249","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c07249","url":null,"abstract":"Miniaturized chemical synthesis through acoustic droplet ejection (ADE) is transforming reaction discovery by reducing material consumption and enabling highly parallelized, autonomous workflows. However, its application in organic synthesis has remained largely confined to DMSO and aqueous media, restricting solvent exploration and limiting broader process innovation. Often attributed to the intrinsic physics of acoustic transfer, these constraints may instead reflect historical calibration practices. Here, we establish a data-driven framework for expanding ADE-compatible solvent space toward a more applicable nanoscale reaction chemistry. Through systematic gravimetric analysis of 19 high-boiling organic solvents, including water and DMSO as reference fluids, we identify a broad operating window that supports accurate (deviation < 10%) and reproducible (RSD < 8%) dispensing using existing instrumentation. We further validate this framework via automated assembly of a 384-member Suzuki–Miyaura reaction library, where testing of N,N-dimethylformamide and a bio-based alternative solvent dimethyl isosorbide resulted in broad product formation across diverse substrates. This work decouples solvent choice from historical conventions and opens the route to a reaction-agnostic, solvent-flexible, and sustainable approach for high-throughput reaction discovery, enabling ADE workflows to transition from condition-constrained screening tools to general engines for sustainable, data-driven chemical exploration.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Traditional ambient-pressure drying of aerogels relies on minimizing capillary shrinkage to preserve nanoporous structures, yet this strategy inevitably compromises either processing efficiency or mechanical robustness. Here, we show that capillary shrinkage can instead be exploited as a controllable structural reconstruction process. Through a rapid composite solvent exchange strategy, effective solvent exchange is achieved within only 10 min, enabling regulated capillary stress to drive network rearrangement and pore-wall reinforcement during ambient-pressure drying while preserving an interconnected nanoporous architecture. The resulting cellulose aerogel fibers exhibit a density of 0.10 g·cm–3, an areal porosity of 82.15%, and a specific surface area of 90.67 m2·g–1, together with a tensile strength of 29.46 MPa and a toughness of 10.05 MJ·m–3, representing strength improvements of 135.1% and 280.6% over freeze-dried and supercritical-dried counterparts, respectively. Despite moderate network densification, the aerogel fabric maintains excellent thermal insulation, with a room-temperature thermal conductivity of 0.037 W·m–1·K–1, producing a temperature difference of 27.7 °C on a 100 °C hot plate. Our results establish controlled capillary reconstruction as a scalable structural engineering strategy for manufacturing mechanically robust nanoporous materials through ambient-pressure drying.
{"title":"Fast Preparation of Ultratough Cellulose Aerogel Fibers via One-Step Composite Solvent Exchange under Ambient Pressure Drying","authors":"Shasha Liu,Jingjing Yuan,Ling Nie,Zishan Xiong,Zhihao Zhao,Xinrui Hao,Xiong Qian,Jinfeng Wang,Weilin Xu,Kunkun Zhu","doi":"10.1021/acssuschemeng.6c10206","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c10206","url":null,"abstract":"Traditional ambient-pressure drying of aerogels relies on minimizing capillary shrinkage to preserve nanoporous structures, yet this strategy inevitably compromises either processing efficiency or mechanical robustness. Here, we show that capillary shrinkage can instead be exploited as a controllable structural reconstruction process. Through a rapid composite solvent exchange strategy, effective solvent exchange is achieved within only 10 min, enabling regulated capillary stress to drive network rearrangement and pore-wall reinforcement during ambient-pressure drying while preserving an interconnected nanoporous architecture. The resulting cellulose aerogel fibers exhibit a density of 0.10 g·cm–3, an areal porosity of 82.15%, and a specific surface area of 90.67 m2·g–1, together with a tensile strength of 29.46 MPa and a toughness of 10.05 MJ·m–3, representing strength improvements of 135.1% and 280.6% over freeze-dried and supercritical-dried counterparts, respectively. Despite moderate network densification, the aerogel fabric maintains excellent thermal insulation, with a room-temperature thermal conductivity of 0.037 W·m–1·K–1, producing a temperature difference of 27.7 °C on a 100 °C hot plate. Our results establish controlled capillary reconstruction as a scalable structural engineering strategy for manufacturing mechanically robust nanoporous materials through ambient-pressure drying.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alkaline water electrolysis urgently requires scalable, binder-free integrated bulk electrodes with high activity and robust stability at high current densities. High-entropy alloys (HEAs) are promising candidates for such electrodes, but conventional as-cast HEAs generally suffer from coarse grains, which limits their electrocatalytic performance. Herein, FeCrNiMoC0.3 HEA ribbons were fabricated as integrated electrocatalysts via melt-spinning rapid solidification. This metallurgical treatment refines matrix grains to an average size of 135.7 nm, uniformly disperses nanoscale carbides, induces FCC lattice expansion, and drives directional charge transfer from Fe/Cr/Ni to Mo without altering the phase composition. In 1.0 M KOH, the melt-spun ribbons (MSRs) exhibit enhanced bifunctional electrocatalytic performance. At 10 mA cm–2, the MSR electrode delivers overpotentials of 218 mV for the oxygen evolution reaction (OER) and 81 mV for the hydrogen evolution reaction (HER), with Tafel slopes of 30.8 and 55.4 mV dec–1, respectively. The two-electrode overall water splitting achieves 500 mA cm–2 at 2.03 V and runs stably for over 500 h. Grain and carbide refinement, accompanied by electronic modulation, an enlarged electrochemically active surface area, and reduced charge transfer resistance, collectively accounts for the enhanced performance. This work provides a facile and scalable metallurgical strategy to optimize carbide-containing binder-free bulk HEAs and offers a reference for understanding the microstructure–activity relationship of bulk alloy electrodes for alkaline water electrolysis.
碱水电解迫切需要可扩展的、无粘结剂的集成体电极，这些电极在高电流密度下具有高活性和强大的稳定性。高熵合金（HEAs）是这种电极的有希望的候选者，但传统的铸态HEAs通常存在粗大的晶粒，这限制了它们的电催化性能。采用熔融纺丝快速凝固法制备了FeCrNiMoC0.3 HEA带作为一体化电催化剂。这种冶金处理使基体晶粒细化到平均135.7 nm，均匀分散纳米级碳化物，诱导FCC晶格膨胀，并在不改变相组成的情况下驱动Fe/Cr/Ni向Mo的定向电荷转移。在1.0 M KOH条件下，熔融纺带（MSRs）表现出增强的双功能电催化性能。在10 mA cm-2下，MSR电极的析氧反应（OER）和析氢反应（HER）的过电位分别为218 mV和81 mV， Tafel斜率分别为30.8和55.4 mV / dec1。两电极整体水分解在2.03 V下达到500 mA cm-2，并稳定运行超过500小时。晶粒和碳化物的细化，伴随着电子调制，电化学活性表面积的扩大，电荷转移电阻的降低，共同导致了性能的增强。本研究为优化含碳化物无粘结剂大块HEAs提供了一种简便、可扩展的冶金策略，并为理解大块合金电极的显微结构-活性关系提供了参考。
{"title":"Melt-Spun FeCrNiMoC0.3 High-Entropy Alloy Ribbons: Microstructure Refinement for Enhanced Bifunctional Alkaline Overall Water Splitting","authors":"Tong Zhang,Guanglong Li,Zhen Wen,Wei Zhang,Shulin Dong,Siruo Zhang,Yingdong Qu","doi":"10.1021/acssuschemeng.6c07043","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c07043","url":null,"abstract":"Alkaline water electrolysis urgently requires scalable, binder-free integrated bulk electrodes with high activity and robust stability at high current densities. High-entropy alloys (HEAs) are promising candidates for such electrodes, but conventional as-cast HEAs generally suffer from coarse grains, which limits their electrocatalytic performance. Herein, FeCrNiMoC0.3 HEA ribbons were fabricated as integrated electrocatalysts via melt-spinning rapid solidification. This metallurgical treatment refines matrix grains to an average size of 135.7 nm, uniformly disperses nanoscale carbides, induces FCC lattice expansion, and drives directional charge transfer from Fe/Cr/Ni to Mo without altering the phase composition. In 1.0 M KOH, the melt-spun ribbons (MSRs) exhibit enhanced bifunctional electrocatalytic performance. At 10 mA cm–2, the MSR electrode delivers overpotentials of 218 mV for the oxygen evolution reaction (OER) and 81 mV for the hydrogen evolution reaction (HER), with Tafel slopes of 30.8 and 55.4 mV dec–1, respectively. The two-electrode overall water splitting achieves 500 mA cm–2 at 2.03 V and runs stably for over 500 h. Grain and carbide refinement, accompanied by electronic modulation, an enlarged electrochemically active surface area, and reduced charge transfer resistance, collectively accounts for the enhanced performance. This work provides a facile and scalable metallurgical strategy to optimize carbide-containing binder-free bulk HEAs and offers a reference for understanding the microstructure–activity relationship of bulk alloy electrodes for alkaline water electrolysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-20DOI: 10.1021/acssuschemeng.6c09525
Mingqian Yang,Bo Xu,Yue Wang,Yaolin Yi
CaO-based materials are promising sorbents for CO2 capture and represent the dominant reactive phase in Ca-rich alkaline industrial residues. Zinc is one of the most common metal impurities in CaO-based sorbents, yet its influence on the carbonation behavior of CaO remains less understood. Thus, this study investigates the effect of Zn (0–50,000 mg·kg–1) on CaO carbonation, combining phase evolution, structure–property relationships, surface chemistry, carbonate distribution, and density functional theory calculations, to establish a mechanistic framework linking atomic-scale CO2 activation to macroscopic carbonation behavior. Results showed that increasing Zn concentration progressively suppressed the carbonation reactivity of CaO. The CO2 uptake decreased from 0.528 to 0.478 gCO2·gsorbent–1 at 120 min, corresponding to a 9.4% reduction, while the initial carbonation during the chemically controlled stage was inhibited by approximately 30%. At a high Zn concentration (50,000 mg·kg–1), calcium zincate hydrate and zinc hydroxycarbonate formed, and carbonate crystallization shifted from continuous surface precipitation to discontinuous crystal growth, producing fewer but coarser carbonate crystallites. Zn delayed the hydroxyl-to-carbonate interfacial transformation and produced spatially heterogeneous carbonation domains. The weakened interaction between surface O 2p states and CO2-derived C 2p states reduced the electronic coupling at the adsorption interface and lowered the thermodynamic stability of adsorbed CO2. Thus, Zn-affected CaO carbonation through Zn-bearing secondary-phase formation, pore-network reconstruction, spatially heterogeneous interfacial conversion, and local electronic perturbation. This study provides mechanistic insights into Zn-affected gas–solid reactions and a theoretical basis for evaluating Zn-contaminated Ca-rich industrial residues for CO2 capture.
{"title":"Macroscopic-to-Atomic Mechanism of Zinc Effects on CaO Carbonation","authors":"Mingqian Yang,Bo Xu,Yue Wang,Yaolin Yi","doi":"10.1021/acssuschemeng.6c09525","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c09525","url":null,"abstract":"CaO-based materials are promising sorbents for CO2 capture and represent the dominant reactive phase in Ca-rich alkaline industrial residues. Zinc is one of the most common metal impurities in CaO-based sorbents, yet its influence on the carbonation behavior of CaO remains less understood. Thus, this study investigates the effect of Zn (0–50,000 mg·kg–1) on CaO carbonation, combining phase evolution, structure–property relationships, surface chemistry, carbonate distribution, and density functional theory calculations, to establish a mechanistic framework linking atomic-scale CO2 activation to macroscopic carbonation behavior. Results showed that increasing Zn concentration progressively suppressed the carbonation reactivity of CaO. The CO2 uptake decreased from 0.528 to 0.478 gCO2·gsorbent–1 at 120 min, corresponding to a 9.4% reduction, while the initial carbonation during the chemically controlled stage was inhibited by approximately 30%. At a high Zn concentration (50,000 mg·kg–1), calcium zincate hydrate and zinc hydroxycarbonate formed, and carbonate crystallization shifted from continuous surface precipitation to discontinuous crystal growth, producing fewer but coarser carbonate crystallites. Zn delayed the hydroxyl-to-carbonate interfacial transformation and produced spatially heterogeneous carbonation domains. The weakened interaction between surface O 2p states and CO2-derived C 2p states reduced the electronic coupling at the adsorption interface and lowered the thermodynamic stability of adsorbed CO2. Thus, Zn-affected CaO carbonation through Zn-bearing secondary-phase formation, pore-network reconstruction, spatially heterogeneous interfacial conversion, and local electronic perturbation. This study provides mechanistic insights into Zn-affected gas–solid reactions and a theoretical basis for evaluating Zn-contaminated Ca-rich industrial residues for CO2 capture.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-20DOI: 10.1021/acssuschemeng.6c08592
Li Deng,Jinfeng Li,Dongming Wang,Ruikai Qi,Siqi Zhang,Mingbin Gao,Xiaofeng Lu
Electrochemical transformation of nitrate (NO3–) into ammonia (NH3) offers an environmentally sustainable pathway to complete the nitrogen cycle, enabling both green NH3 synthesis and NO3– pollution remediation. Herein, we propose an in situ synergistic reconstruction strategy for fabricating a Cu2O@Co-carbon nanofibers (CNFs) pre-electrocatalyst, integrated with the glycerol oxidation reaction (GOR) to replace the energy-intensive oxygen evolution reaction (OER), thereby significantly reducing energy consumption toward electrocatalytic NO3–-to-NH3 conversion. The potential-dependent reconstruction gives rise to coexisting Co0 and Co(OH)2 species together with active Cu sites. Electrochemical measurements and density functional theory (DFT) calculations support their complementary roles in *H generation and NO3– activation, respectively, thereby promoting the NO3RR while suppressing competing reactions. The resulting catalyst delivers an exceptional NH3 yield rate of 61.0 mg cm–2 h–1 at industrial-level current density, manifesting outstanding catalytic performance. This study offers a novel design principle and a reliable strategy for developing high-efficiency non-noble-metal-based bifunctional electrocatalysts and advanced coupled electrochemical systems.
{"title":"Dual Metal-Active Phase for Significantly Enhanced Nitrate-to-Ammonia Electrocatalysis from Dynamic Reconstruction of a CuCo-Based Catalyst","authors":"Li Deng,Jinfeng Li,Dongming Wang,Ruikai Qi,Siqi Zhang,Mingbin Gao,Xiaofeng Lu","doi":"10.1021/acssuschemeng.6c08592","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08592","url":null,"abstract":"Electrochemical transformation of nitrate (NO3–) into ammonia (NH3) offers an environmentally sustainable pathway to complete the nitrogen cycle, enabling both green NH3 synthesis and NO3– pollution remediation. Herein, we propose an in situ synergistic reconstruction strategy for fabricating a Cu2O@Co-carbon nanofibers (CNFs) pre-electrocatalyst, integrated with the glycerol oxidation reaction (GOR) to replace the energy-intensive oxygen evolution reaction (OER), thereby significantly reducing energy consumption toward electrocatalytic NO3–-to-NH3 conversion. The potential-dependent reconstruction gives rise to coexisting Co0 and Co(OH)2 species together with active Cu sites. Electrochemical measurements and density functional theory (DFT) calculations support their complementary roles in *H generation and NO3– activation, respectively, thereby promoting the NO3RR while suppressing competing reactions. The resulting catalyst delivers an exceptional NH3 yield rate of 61.0 mg cm–2 h–1 at industrial-level current density, manifesting outstanding catalytic performance. This study offers a novel design principle and a reliable strategy for developing high-efficiency non-noble-metal-based bifunctional electrocatalysts and advanced coupled electrochemical systems.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"413 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218814","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Irreversible phase transition and lattice-oxygen loss above 4.0 V cause rapid capacity decay in high-capacity O3-type layered cathodes for sodium-ion batteries (SIBs). Herein, a novel high-entropy layered cathode of Na0.95Li0.05Ni0.3Fe0.1Mn0.3Zn0.05Ti0.2O2 (LNFMZT) with regulated lattice oxygen through a high-entropy configuration and multi-element compositional regulation is successfully synthesized by a high-temperature solid-state method. We show that high-entropy modification stabilizes the single-phase structure, expands Na+ diffusion pathways, and optimizes the transition-metal (TM)–O coordination environment. The LNFMZT delivers a high initial capacity (163.7 mAh g–1 at 0.1 C) and good cycling stability (64.0% retention over 250 cycles at 1 C) at a high-voltage window of 2.0–4.2 V. Combining in situ and ex situ experimental characterizations, we find that a high-entropy layered cathode exhibits reduced charge-transfer resistance, enhanced Na+ diffusion dynamics, good reversibility of lattice oxygen redox, and smoother O3-P3-OP2 evolution, which greatly improve the structural integrity and electrochemical durability. This work underscores the critical role of high-entropy modification in coupling lattice oxygen stability with phase transition reversibility for advanced SIB cathodes.
不可逆相变和4.0 V以上的晶格氧损失导致高容量o3型钠离子电池层状阴极容量快速衰减。本文采用高温固相法，通过高熵结构和多元素组成调控，成功地合成了一种新型高熵层状阴极Na0.95Li0.05Ni0.3Fe0.1Mn0.3Zn0.05Ti0.2O2 （LNFMZT）。研究表明，高熵改性稳定了单相结构，扩展了Na+扩散途径，并优化了过渡金属(TM) -O配位环境。LNFMZT在2.0-4.2 V的高电压窗口下提供高初始容量（0.1 C时163.7 mAh g-1）和良好的循环稳定性（在1 C下250次循环保持64.0%）。结合原位和非原位实验表征，我们发现高熵层状阴极具有电荷转移电阻降低、Na+扩散动力学增强、晶格氧氧化还原可逆性好、O3-P3-OP2演化更平稳等特点，大大提高了结构完整性和电化学耐久性。这项工作强调了高熵修饰在高级SIB阴极晶格氧稳定性与相变可逆性耦合中的关键作用。
{"title":"Regulation of Lattice Oxygen and Phase Transition in O3-Type High-Entropy Layered Sodium-Ion Cathodes","authors":"Ruyi Liu,Ziyao Zhao,Xinwang Niu,Xuyang Zhao,Shuhan Zhu,Fan Bu,Zongyu Guan,Guoyao Pang,Feixiang Ding,Xin Xia,Feng Ye,Biwei Xiao,Chao Xu","doi":"10.1021/acssuschemeng.6c05438","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c05438","url":null,"abstract":"Irreversible phase transition and lattice-oxygen loss above 4.0 V cause rapid capacity decay in high-capacity O3-type layered cathodes for sodium-ion batteries (SIBs). Herein, a novel high-entropy layered cathode of Na0.95Li0.05Ni0.3Fe0.1Mn0.3Zn0.05Ti0.2O2 (LNFMZT) with regulated lattice oxygen through a high-entropy configuration and multi-element compositional regulation is successfully synthesized by a high-temperature solid-state method. We show that high-entropy modification stabilizes the single-phase structure, expands Na+ diffusion pathways, and optimizes the transition-metal (TM)–O coordination environment. The LNFMZT delivers a high initial capacity (163.7 mAh g–1 at 0.1 C) and good cycling stability (64.0% retention over 250 cycles at 1 C) at a high-voltage window of 2.0–4.2 V. Combining in situ and ex situ experimental characterizations, we find that a high-entropy layered cathode exhibits reduced charge-transfer resistance, enhanced Na+ diffusion dynamics, good reversibility of lattice oxygen redox, and smoother O3-P3-OP2 evolution, which greatly improve the structural integrity and electrochemical durability. This work underscores the critical role of high-entropy modification in coupling lattice oxygen stability with phase transition reversibility for advanced SIB cathodes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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