Pub Date : 2026-03-12DOI: 10.1021/acssuschemeng.5c10815
Wenwu Fu, Kai Zhang, Jun Zheng, Ming Zhang, Zhongrong Shen
Iron-based Prussian blue analogues (PBAs) are promising cathode materials for sodium-ion batteries owing to their low cost and high theoretical capacity. However, their practical capacity is often hampered by a high lattice water content and structural defects. While the use of complexing agents and elemental substitution can mitigate these issues, the subsequent difficulty in recovering these complexing agents raises costs and hinders industrial scalability. To address this challenge, we present a novel oxalate-assisted kinetic synthesis route. This method leverages the slow dissolution of metal oxalate precipitates to gradually release Fe2+ and Mn2+ ions, which then coordinate with ferrocyanide ions to form PBAs. This controlled release kinetics eliminates the need for extraneous complexing agents, enabling the preparation of high-sodium-content, low-defect PBAs. By optimizing the Mn/Fe ratio, we found that the sample with 20% Mn doping (PBA@20% Mn) delivers an excellent specific capacity of 115.5 mAh g–1 at 0.2 C and retains 85.6% of its initial capacity after 500 cycles at 5 C. Ex-situ XRD analysis reveals highly reversible (de)sodiation processes with no significant phase transitions, accounting for the superior cycling stability. Furthermore, the oxalate in the mother liquor can be filtered and reused to produce high-quality PBAs, thereby demonstrating a consistent closed-loop process. This work not only provides a strategy for synthesizing high-performance PBAs but also proposes a green, cost-effective pathway for their industrial production.
铁基普鲁士蓝类似物（PBAs）具有成本低、理论容量高等优点，是钠离子电池极具发展前景的正极材料。然而，它们的实际应用能力往往受到高晶格含水量和结构缺陷的阻碍。虽然使用络合剂和元素替代可以缓解这些问题，但随后回收这些络合剂的困难增加了成本并阻碍了工业可扩展性。为了解决这一挑战，我们提出了一种新的草酸盐辅助动力学合成路线。该方法利用金属草酸盐沉淀的缓慢溶解，逐渐释放出Fe2+和Mn2+离子，然后与亚铁氰化物离子配合形成PBAs。这种控制释放动力学消除了对外来络合剂的需要，使制备高钠含量，低缺陷的PBAs成为可能。通过优化Mn/Fe比，我们发现掺杂20% Mn （PBA@20% Mn）的样品在0.2 C时具有115.5 mAh g-1的优异比容量，并且在5 C下循环500次后仍保持其初始容量的85.6%。非原位XRD分析显示高度可逆的（de）酸化过程没有明显的相变，这是优越循环稳定性的原因。此外，母液中的草酸盐可以过滤并重复使用，以生产高质量的PBAs，从而证明了一个一致的闭环过程。这项工作不仅为合成高性能的PBAs提供了策略，而且为其工业生产提供了绿色，经济的途径。
{"title":"Oxalate-Assisted Kinetic Synthesis of High-Sodium, Low-Defect Mn/Fe Prussian Blue Analogues for Enhanced Performance in Sodium-Ion Batteries","authors":"Wenwu Fu, Kai Zhang, Jun Zheng, Ming Zhang, Zhongrong Shen","doi":"10.1021/acssuschemeng.5c10815","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10815","url":null,"abstract":"Iron-based Prussian blue analogues (PBAs) are promising cathode materials for sodium-ion batteries owing to their low cost and high theoretical capacity. However, their practical capacity is often hampered by a high lattice water content and structural defects. While the use of complexing agents and elemental substitution can mitigate these issues, the subsequent difficulty in recovering these complexing agents raises costs and hinders industrial scalability. To address this challenge, we present a novel oxalate-assisted kinetic synthesis route. This method leverages the slow dissolution of metal oxalate precipitates to gradually release Fe<sup>2+</sup> and Mn<sup>2+</sup> ions, which then coordinate with ferrocyanide ions to form PBAs. This controlled release kinetics eliminates the need for extraneous complexing agents, enabling the preparation of high-sodium-content, low-defect PBAs. By optimizing the Mn/Fe ratio, we found that the sample with 20% Mn doping (PBA@20% Mn) delivers an excellent specific capacity of 115.5 mAh g<sup>–1</sup> at 0.2 C and retains 85.6% of its initial capacity after 500 cycles at 5 C. Ex-situ XRD analysis reveals highly reversible (de)sodiation processes with no significant phase transitions, accounting for the superior cycling stability. Furthermore, the oxalate in the mother liquor can be filtered and reused to produce high-quality PBAs, thereby demonstrating a consistent closed-loop process. This work not only provides a strategy for synthesizing high-performance PBAs but also proposes a green, cost-effective pathway for their industrial production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439915","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 : 2026-03-12DOI: 10.1021/acssuschemeng.5c13241
Jinhyun Kim, Hye-Jin Jo, Hee-Jeong Cha, Jimin Kim, Han K. D. Le, Peidong Yang, Douglas S. Clark
Harnessing renewable energy to convert anthropogenic CO2 to valuable products is central to establishing a sustainable carbon cycle. Here, we present a continuous electrobiocatalytic platform for converting CO2 to Bioplastic by using an external water-splitting electrolyzer integrated with a two-stage cascade of continuous stirred-tank bioreactors (CSTBs) arranged in tandem, a system-level architecture that has not been previously reported. A proton exchange membrane (PEM) electrolyzer produces H2 for the acetogenic bacterium Sporomusa ovata, which fixes CO2 into acetate in CSTB 1, achieving a steady-state productivity of 293 ± 17 mg L–1 h–1. The acetate is continuously and directly supplied to CSTB 2 and subsequently metabolized by the facultative chemolithoautotroph Cupriavidus necator for the biosynthesis of poly(3-hydroxybutyrate) (PHB) biopolymers. Under steady-state conditions, the electrolyzer/CSTB 1/CSTB 2 system achieves a PHB productivity of 2.76 ± 0.24 mg L–1 h–1, which provides a quantitative benchmark for a fully continuous, electrolyzer-driven CO2-to-PHB process. This work presents an electromicrobial approach integrating environmental remediation with chemical syntheses from CO2 and H2O.
{"title":"Tandem Electrolyzer–Chemostats for Synthesizing Bioplastics from CO2 and H2O","authors":"Jinhyun Kim, Hye-Jin Jo, Hee-Jeong Cha, Jimin Kim, Han K. D. Le, Peidong Yang, Douglas S. Clark","doi":"10.1021/acssuschemeng.5c13241","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13241","url":null,"abstract":"Harnessing renewable energy to convert anthropogenic CO<sub>2</sub> to valuable products is central to establishing a sustainable carbon cycle. Here, we present a continuous electrobiocatalytic platform for converting CO<sub>2</sub> to Bioplastic by using an external water-splitting electrolyzer integrated with a two-stage cascade of continuous stirred-tank bioreactors (CSTBs) arranged in tandem, a system-level architecture that has not been previously reported. A proton exchange membrane (PEM) electrolyzer produces H<sub>2</sub> for the acetogenic bacterium <i>Sporomusa ovata</i>, which fixes CO<sub>2</sub> into acetate in CSTB 1, achieving a steady-state productivity of 293 ± 17 mg L<sup>–1</sup> h<sup>–1</sup>. The acetate is continuously and directly supplied to CSTB 2 and subsequently metabolized by the facultative chemolithoautotroph <i>Cupriavidus necator</i> for the biosynthesis of poly(3-hydroxybutyrate) (PHB) biopolymers. Under steady-state conditions, the electrolyzer/CSTB 1/CSTB 2 system achieves a PHB productivity of 2.76 ± 0.24 mg L<sup>–1</sup> h<sup>–1</sup>, which provides a quantitative benchmark for a fully continuous, electrolyzer-driven CO<sub>2</sub>-to-PHB process. This work presents an electromicrobial approach integrating environmental remediation with chemical syntheses from CO<sub>2</sub> and H<sub>2</sub>O.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439922","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 : 2026-03-12DOI: 10.1021/acssuschemeng.5c11985
Jiaqi Cheng, Junting Yang, Ge Qi, Yuwei Ma, Jinxiao Bao, Qingchun Wang
This work presents a novel strategy for improving the anti-CO poisoning performance of Pt-based catalysts by coupling the electronic states of Mo 4d and Ce 4f to modulate the Pt electronic structure. The introduction of Mo into CeO2 creates a composite support (Mo-CeOx) that induces electron redistribution at the Pt/CeO2 interface, inducing the electronic structure modulation of Pt, thereby influencing the Pt–CO interaction. This electronic tuning not only enhances Pt’s CO tolerance but also promotes charge transfer and improves catalyst stability. Density functional theory calculations and experimental data reveal that Mo doping decreases the formation energy of oxygen vacancies, facilitating Pt stabilization and the generation of active sites. The resulting Pt/Mo-CeOx/rGO catalyst exhibits significantly enhanced methanol oxidation reaction activity, with a mass activity 4.67 times higher than that of the undoped counterpart, alongside excellent CO poisoning resistance and long-term stability. This work introduces a new paradigm for designing highly efficient and durable Pt-based catalysts by leveraging electronic state engineering, offering a powerful approach for tackling CO poisoning in electrocatalysis.
{"title":"Highly Efficient Anti-CO Poisoning Catalyst By Coupling Mo 4d–Ce 4f Electronic States to Regulate the Electronic Structure of Pt","authors":"Jiaqi Cheng, Junting Yang, Ge Qi, Yuwei Ma, Jinxiao Bao, Qingchun Wang","doi":"10.1021/acssuschemeng.5c11985","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11985","url":null,"abstract":"This work presents a novel strategy for improving the anti-CO poisoning performance of Pt-based catalysts by coupling the electronic states of Mo 4d and Ce 4f to modulate the Pt electronic structure. The introduction of Mo into CeO<sub>2</sub> creates a composite support (Mo-CeO<sub><i>x</i></sub>) that induces electron redistribution at the Pt/CeO<sub>2</sub> interface, inducing the electronic structure modulation of Pt, thereby influencing the Pt–CO interaction. This electronic tuning not only enhances Pt’s CO tolerance but also promotes charge transfer and improves catalyst stability. Density functional theory calculations and experimental data reveal that Mo doping decreases the formation energy of oxygen vacancies, facilitating Pt stabilization and the generation of active sites. The resulting Pt/Mo-CeO<sub><i>x</i></sub>/rGO catalyst exhibits significantly enhanced methanol oxidation reaction activity, with a mass activity 4.67 times higher than that of the undoped counterpart, alongside excellent CO poisoning resistance and long-term stability. This work introduces a new paradigm for designing highly efficient and durable Pt-based catalysts by leveraging electronic state engineering, offering a powerful approach for tackling CO poisoning in electrocatalysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"315 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393387","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}
To address the growing demand for efficient low-concentration CO2 capture from flue gas, functionalized ionic liquid (IL) hybrids─integrating ILs’ intrinsic CO2-philicity (specific functional group-CO2 interactions) and porous supports’ structural merits (high specific surface area, tunable pores, robust framework)─have emerged as promising adsorbents. In this work, a kind of novel polyamine IL (PIL) hybrid with narrowly distributed mesopores and ultrahigh IL loading over 70 wt % was fabricated by immobilizing the PIL triethyltetramine trifluoromethanesulfonate ([TETA][TfO]) onto a hydrophobic resin (XAD) featuring wide mesopores and a small fraction of macropores. At 313 K, 70 wt % [TETA][TfO]@XAD exhibited a high CO2 adsorption capacity of 3.09 mmolCO2/g-adsorbent at 1 bar and 2.35 mmol CO2/g-adsorbent at 0.15 bar. Notably, under simulated humid flue gas conditions (15 vol % CO2/5 vol % H2O balanced with N2), the PIL hybrid still could maintain a relatively stable adsorption capacity of 1.31 mmol CO2/g-adsorbent, which is comparable to that under dry flue gas conditions (1.24 mmol CO2/g-adsorbent, 15 vol % CO2 balanced with N2). Furthermore, after three consecutive adsorption–desorption cycles, the PIL hybrid maintained structural integrity and stable CO2 adsorption performance without significant attenuation under both dry and humid environments. The superior CO2 separation performance was attributed to the chemical interactions between CO2 and multiple amino groups (one secondary amine as well as two primary amines) of [TETA]+, coupled with the synergistic effect of the in situ-formed mesoporous structures. This work provides a feasible strategy for the rational design and development of mesoporous PIL hybrids for the efficient capture of low-concentration CO2 from flue gas.
{"title":"Mesoporous Polyamine Ionic Liquid Hybrids for Efficient Capture of Low-Concentration CO2 from Flue Gas","authors":"Bowen Li, Shuang Zheng, Guilin Li, Jiang Chang, Lu Bai, Yinge Bai, Xiangping Zhang, Shaojuan Zeng","doi":"10.1021/acssuschemeng.5c14182","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14182","url":null,"abstract":"To address the growing demand for efficient low-concentration CO<sub>2</sub> capture from flue gas, functionalized ionic liquid (IL) hybrids─integrating ILs’ intrinsic CO<sub>2</sub>-philicity (specific functional group-CO<sub>2</sub> interactions) and porous supports’ structural merits (high specific surface area, tunable pores, robust framework)─have emerged as promising adsorbents. In this work, a kind of novel polyamine IL (PIL) hybrid with narrowly distributed mesopores and ultrahigh IL loading over 70 wt % was fabricated by immobilizing the PIL triethyltetramine trifluoromethanesulfonate ([TETA][TfO]) onto a hydrophobic resin (XAD) featuring wide mesopores and a small fraction of macropores. At 313 K, 70 wt % [TETA][TfO]@XAD exhibited a high CO<sub>2</sub> adsorption capacity of 3.09 mmolCO<sub>2</sub>/g-adsorbent at 1 bar and 2.35 mmol CO<sub>2</sub>/g-adsorbent at 0.15 bar. Notably, under simulated humid flue gas conditions (15 vol % CO<sub>2</sub>/5 vol % H<sub>2</sub>O balanced with N<sub>2</sub>), the PIL hybrid still could maintain a relatively stable adsorption capacity of 1.31 mmol CO<sub>2</sub>/g-adsorbent, which is comparable to that under dry flue gas conditions (1.24 mmol CO<sub>2</sub>/g-adsorbent, 15 vol % CO<sub>2</sub> balanced with N<sub>2</sub>). Furthermore, after three consecutive adsorption–desorption cycles, the PIL hybrid maintained structural integrity and stable CO<sub>2</sub> adsorption performance without significant attenuation under both dry and humid environments. The superior CO<sub>2</sub> separation performance was attributed to the chemical interactions between CO<sub>2</sub> and multiple amino groups (one secondary amine as well as two primary amines) of [TETA]<sup>+</sup>, coupled with the synergistic effect of the in situ-formed mesoporous structures. This work provides a feasible strategy for the rational design and development of mesoporous PIL hybrids for the efficient capture of low-concentration CO<sub>2</sub> from flue gas.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393662","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}
Achieving a balance between high strength and toughness in biodegradable polymer fibers such as poly(vinyl alcohol) (PVA) remains a major challenge in sustainable materials design. Notably, TEMPO-oxidized cellulose nanofibers (TOCNF), featuring high aspect ratio, abundant surface hydroxyl and carboxyl groups, and excellent sustainability, serve as efficient reinforcing elements by constructing dense hydrogen-bonding networks and facilitating effective stress transfer. Here, we fabricated PVA/TOCNF composite fibers via wet spinning using a dimethyl sulfoxide (DMSO)–water mixed coagulation bath, which optimizes solubility and spinning viscosity. The synergistic combination of TOCNF–PVA hydrogen bonding and chain alignment during spinning significantly enhanced the mechanical properties. The resulting fibers exhibit remarkable ductility (elongation at break of 442.5%) and high tensile strength (131.4 MPa in the dry state and 3.12 MPa in the wet state) within an ultrashort coagulation bath residence time (∼4.57 s in total). Compared with pure PVA fibers, their dry and wet tensile strengths increased by 406% and 165%, respectively, effectively mitigating the drastic loss of strength under wet conditions. These biocompatible and biodegradable composite fibers provide a materials-design strategy for developing next-generation sustainable and flexible fibrous systems, with potential relevance to wearable and biomedical applications.
{"title":"Cellulose-Induced Orientation Engineering for Strong and Tough Wet-Spun PVA Filaments","authors":"Yusi Huang,Han Wang,Sining Huang,Zhiguo Li,Chengyu Wang,Siqi Huan","doi":"10.1021/acssuschemeng.5c12541","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12541","url":null,"abstract":"Achieving a balance between high strength and toughness in biodegradable polymer fibers such as poly(vinyl alcohol) (PVA) remains a major challenge in sustainable materials design. Notably, TEMPO-oxidized cellulose nanofibers (TOCNF), featuring high aspect ratio, abundant surface hydroxyl and carboxyl groups, and excellent sustainability, serve as efficient reinforcing elements by constructing dense hydrogen-bonding networks and facilitating effective stress transfer. Here, we fabricated PVA/TOCNF composite fibers via wet spinning using a dimethyl sulfoxide (DMSO)–water mixed coagulation bath, which optimizes solubility and spinning viscosity. The synergistic combination of TOCNF–PVA hydrogen bonding and chain alignment during spinning significantly enhanced the mechanical properties. The resulting fibers exhibit remarkable ductility (elongation at break of 442.5%) and high tensile strength (131.4 MPa in the dry state and 3.12 MPa in the wet state) within an ultrashort coagulation bath residence time (∼4.57 s in total). Compared with pure PVA fibers, their dry and wet tensile strengths increased by 406% and 165%, respectively, effectively mitigating the drastic loss of strength under wet conditions. These biocompatible and biodegradable composite fibers provide a materials-design strategy for developing next-generation sustainable and flexible fibrous systems, with potential relevance to wearable and biomedical applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383741","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}
Electrochemical methanol upgrading (EMU) represents a sustainable and energy-efficient pathway for producing value-added formate, underscoring the urgent demand for EMU electrocatalysts with enhanced activity and stability. In this work, a multimetal Prussian blue analogue (PBA)/copper hydroxide nanoarray catalyst supported on copper foam (5-PBA/CH/CF) was synthesized via an anodization-self-sacrificial template approach. This strategy synergistically optimizes both active site density and intrinsic activity for efficient EMU to formate. The catalyst leverages multimetal synergy and catalytic ensemble effects to tailor electronic structures. The hierarchical PBA architecture not only exposes abundant high-valence active sites but also provides plentiful reactive sites for enhanced preoxidation, thereby enabling further enrichment of active species. This dual effect concurrently boosts catalytic activity and operational stability. Capitalizing on these structural merits, the 5-PBA/CH/CF catalyst delivers exceptional EMU performance, requiring only 1.355 V vs RHE to achieve 50 mA cm–2 current density while maintaining near 100% Faradaic efficiency (FE) across a broad potential window (1.3–1.5 V vs RHE). Moreover, stability testing over 96 h revealed significant current density enhancement coupled with excellent FE retention. This work establishes a new paradigm for designing highly efficient and ultrastable electrocatalysts for methanol valorization, and provides an efficient and durable catalyst for green electrosynthesis of value-added formate.
电化学甲醇升级（EMU）代表了一种可持续和节能的生产增值甲酸的途径，强调了对具有更高活性和稳定性的EMU电催化剂的迫切需求。本文采用阳极氧化-自牺牲模板法合成了泡沫铜负载的多金属普鲁士蓝类似物(PBA)/氢氧化铜纳米阵列催化剂（5-PBA/CH/CF）。该策略协同优化了活性位点密度和内在活性，以实现高效EMU的形成。该催化剂利用多金属协同作用和催化系综效应来定制电子结构。层次化的PBA结构不仅暴露了丰富的高价活性位点，而且为增强预氧化提供了丰富的活性位点，从而使活性物质进一步富集。这种双重作用同时提高了催化活性和操作稳定性。利用这些结构优点，5-PBA/CH/CF催化剂提供了卓越的EMU性能，仅需1.355 V vs RHE即可实现50 mA cm-2电流密度，同时在宽电位窗口（1.3-1.5 V vs RHE）内保持接近100%的法拉第效率（FE）。此外，超过96小时的稳定性测试表明，电流密度显著增强，并具有良好的FE保留。本研究为设计高效、超稳定的甲醇增值电催化剂开辟了新思路，为绿色电合成增值甲酸酯提供了一种高效、耐用的催化剂。
{"title":"A Self-Sacrificial Templated Route to Fabricate Multimetal Prussian Blue Analogue/Cu(OH)2 Nanoarray for Promoted Electrochemical Methanol Upgrading","authors":"Zhuangzhuang Ren,Ruihao Wang,Yuhan Chen,Yameng Wang,Jiayi Kuang,Fengcai Lei,Xu Sun,Shanshan Liu,Junfeng Xie","doi":"10.1021/acssuschemeng.5c10546","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10546","url":null,"abstract":"Electrochemical methanol upgrading (EMU) represents a sustainable and energy-efficient pathway for producing value-added formate, underscoring the urgent demand for EMU electrocatalysts with enhanced activity and stability. In this work, a multimetal Prussian blue analogue (PBA)/copper hydroxide nanoarray catalyst supported on copper foam (5-PBA/CH/CF) was synthesized via an anodization-self-sacrificial template approach. This strategy synergistically optimizes both active site density and intrinsic activity for efficient EMU to formate. The catalyst leverages multimetal synergy and catalytic ensemble effects to tailor electronic structures. The hierarchical PBA architecture not only exposes abundant high-valence active sites but also provides plentiful reactive sites for enhanced preoxidation, thereby enabling further enrichment of active species. This dual effect concurrently boosts catalytic activity and operational stability. Capitalizing on these structural merits, the 5-PBA/CH/CF catalyst delivers exceptional EMU performance, requiring only 1.355 V vs RHE to achieve 50 mA cm–2 current density while maintaining near 100% Faradaic efficiency (FE) across a broad potential window (1.3–1.5 V vs RHE). Moreover, stability testing over 96 h revealed significant current density enhancement coupled with excellent FE retention. This work establishes a new paradigm for designing highly efficient and ultrastable electrocatalysts for methanol valorization, and provides an efficient and durable catalyst for green electrosynthesis of value-added formate.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383746","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 : 2026-03-11DOI: 10.1021/acssuschemeng.5c14235
Jiancheng Qian, Jia Yang, Baohong Wei, Baoqiang Xu, Dachun Liu, Bin Yang, Wenlong Jiang, Yifu Li
The conventional pyrometallurgical production of antimony is energy-intensive and heavily reliant on carbon, resulting in significant CO2 emissions and environmental toxicity concerns. Herein, we engineer a transformative electrolytic process that simultaneously addresses energy efficiency and environmental impact. This process leverages the unique properties of antimony oxide (Sb2O3), which serves as a self-sustaining, fluoride- and chloride-free electrolyte at 800 °C. Furthermore, we introduce carbon dioxide (CO2) not as a waste gas, but as a process-intensifying mediator. Under a 1 atm CO2 atmosphere, the dissolved gas drastically enhances anode bubble dynamics and initiates a strengthening cycle, enabling a dual-path (electrochemical and chemical) reduction mechanism. This engineered system achieves a landmark 937% increase in production rate and reduces the specific energy consumption to 52.35 kW·h/t-Sb. Most significantly, compared with the energy consumption of traditional smelting, the total carbon consumption of this process is only 57.95 kgce/t-Sb, representing a reduction of approximately 84.5% compared to conventional pyrometallurgy (304.44 kgce/t-Sb). Synergy with eutectic carbonate salts (e.g., K2CO3–Li2CO3) further intensified the process. Our work exemplifies how chemical engineering principles can be harnessed to create a quantifiably more sustainable and industrially viable metal production pathway, turning a greenhouse gas into a key process ingredient for green metallurgy.
{"title":"A CO2-Strengthened, Self-Sustaining Electrolyte Strategy for Antimony Production","authors":"Jiancheng Qian, Jia Yang, Baohong Wei, Baoqiang Xu, Dachun Liu, Bin Yang, Wenlong Jiang, Yifu Li","doi":"10.1021/acssuschemeng.5c14235","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c14235","url":null,"abstract":"The conventional pyrometallurgical production of antimony is energy-intensive and heavily reliant on carbon, resulting in significant CO<sub>2</sub> emissions and environmental toxicity concerns. Herein, we engineer a transformative electrolytic process that simultaneously addresses energy efficiency and environmental impact. This process leverages the unique properties of antimony oxide (Sb<sub>2</sub>O<sub>3</sub>), which serves as a self-sustaining, fluoride- and chloride-free electrolyte at 800 °C. Furthermore, we introduce carbon dioxide (CO<sub>2</sub>) not as a waste gas, but as a process-intensifying mediator. Under a 1 atm CO<sub>2</sub> atmosphere, the dissolved gas drastically enhances anode bubble dynamics and initiates a strengthening cycle, enabling a dual-path (electrochemical and chemical) reduction mechanism. This engineered system achieves a landmark 937% increase in production rate and reduces the specific energy consumption to 52.35 kW·h/t-Sb. Most significantly, compared with the energy consumption of traditional smelting, the total carbon consumption of this process is only 57.95 kgce/t-Sb, representing a reduction of approximately 84.5% compared to conventional pyrometallurgy (304.44 kgce/t-Sb). Synergy with eutectic carbonate salts (e.g., K<sub>2</sub>CO<sub>3</sub>–Li<sub>2</sub>CO<sub>3</sub>) further intensified the process. Our work exemplifies how chemical engineering principles can be harnessed to create a quantifiably more sustainable and industrially viable metal production pathway, turning a greenhouse gas into a key process ingredient for green metallurgy.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393392","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}
Production of jet fuels from renewable biomass is key to decarbonizing the aviation sector. In this work, valorization of the aromatic macromolecule lignin in plant biomass toward monocyclic and fused bicyclic alkanes was proposed. The lignin was first depolymerized toward prop-1-enyl-substituted monomers with high selectivity (>70%) using ethanol as the solvent in the absence of external H2. Alkylation of these monomers with hemicellulose-derived 2-methylfuran using solid acids such as Amberlyst 35 generated alkylation products (yield >80%) along with a small amount of dimers. The alkylation products can be hydrodeoxygenated toward monocyclic alkanes using Ru/C and zeolites, where the product distribution can be controlled by the microporosity of the zeolite. C14 is the major product using Ru/C and mordenite (MOR). The Friedel–Crafts dealkylation of the alkylation products can occur by using Beta and Y zeolites, leading to the formation of more C9. Using the same acid catalyst (i.e., Amberlyst 35) can almost quantitatively convert these monomers toward dimers, which can be hydrodeoxygenated toward fused bicyclic alkanes in the presence of hydrogenation catalysts and zeolites. However, the product distribution can be determined by the activity of the hydrogenation catalyst. C18 was obtained with high yield (>90%) using Pd/C and zeolites such as MOR and alkaline-treated Beta zeolite (Beta-AT). However, C12 was the dominant product (yield of 77.5%) using Raney Ni and alkaline-treated Beta-AT. This work paves a new way for the production of high-density cycloalkanes from recalcitrant lignin.
{"title":"Synthesis of Jet Fuels from Propenyl-Substituted Phenolic Monomers of Lignin","authors":"Haibin Gou,Yu Liu,Shuaihao Sun,Haiyun Huang,Chenguang Wang,Haiyong Wang,Yuhe Liao","doi":"10.1021/acssuschemeng.5c11618","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11618","url":null,"abstract":"Production of jet fuels from renewable biomass is key to decarbonizing the aviation sector. In this work, valorization of the aromatic macromolecule lignin in plant biomass toward monocyclic and fused bicyclic alkanes was proposed. The lignin was first depolymerized toward prop-1-enyl-substituted monomers with high selectivity (>70%) using ethanol as the solvent in the absence of external H2. Alkylation of these monomers with hemicellulose-derived 2-methylfuran using solid acids such as Amberlyst 35 generated alkylation products (yield >80%) along with a small amount of dimers. The alkylation products can be hydrodeoxygenated toward monocyclic alkanes using Ru/C and zeolites, where the product distribution can be controlled by the microporosity of the zeolite. C14 is the major product using Ru/C and mordenite (MOR). The Friedel–Crafts dealkylation of the alkylation products can occur by using Beta and Y zeolites, leading to the formation of more C9. Using the same acid catalyst (i.e., Amberlyst 35) can almost quantitatively convert these monomers toward dimers, which can be hydrodeoxygenated toward fused bicyclic alkanes in the presence of hydrogenation catalysts and zeolites. However, the product distribution can be determined by the activity of the hydrogenation catalyst. C18 was obtained with high yield (>90%) using Pd/C and zeolites such as MOR and alkaline-treated Beta zeolite (Beta-AT). However, C12 was the dominant product (yield of 77.5%) using Raney Ni and alkaline-treated Beta-AT. This work paves a new way for the production of high-density cycloalkanes from recalcitrant lignin.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383748","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 : 2026-03-11DOI: 10.1021/acssuschemeng.6c00243
Xiaolong Fan,Chong Li,Zhongyi Zhang
The improper disposal of lithium batteries is leading to increasingly severe and unavoidable pollution, as their daily use becomes more widespread and frequent. As a conventional cathode binder, poly(vinylidene fluoride) (PVDF) is difficult to degrade, leading to long-term environmental pollution from discarded batteries. Herein, a novel fluorine-free cathode binder (denoted as EMTO) was designed for degradation by environmental microorganisms. This innovative binder features an organic polymer derived from natural-product-based molecules with polysiloxane. This composition imparts exceptional adhesive strength and antioxidant properties that help to enhance the cycle performance of batteries. The sterically hindered phenolic motif in the as-developed binder can effectively reduce the chemical degradation of electrolyte by capturing singlet oxygen (1O2), thereby extending the battery cycle stability. Galvanostatic Intermittent Titration Technique (GITT) tests reveal that the lithium iron phosphate (LiFePO4) cathode integrated with this binder demonstrates superior Li+ diffusion coefficients. Both half cells and full cells with EMTO as the cathode binder demonstrate higher cycling stability than those with PVDF as the binder. Impressively, the discharge specific capacity of the EMTO binder-based full cell remains stable at 160 mAh g–1 for over 240 cycles. Furthermore, microbial culturing experiments indicate that Aspergillus niger can effectively colonize the binder membrane and degrade its organic components. This unique feature allows the EMTO binder to re-enter the ecosystem innocuously, conducive to advancing environmental protection and sustainable development.
随着锂电池的日常使用越来越广泛和频繁，对锂电池的不当处理导致了日益严重和不可避免的污染。聚偏氟乙烯（PVDF）作为传统的阴极粘结剂，其降解难度较大，废旧电池对环境造成长期污染。本文设计了一种新型的无氟阴极粘合剂（EMTO），用于环境微生物的降解。这种创新的粘合剂的特点是有机聚合物来源于天然产物为基础的分子与聚硅氧烷。这种成分赋予卓越的粘接强度和抗氧化性能，有助于提高电池的循环性能。所开发的粘合剂中的位阻酚基序可以通过捕获单线态氧（1O2）有效地减少电解质的化学降解，从而延长电池的循环稳定性。恒流间歇滴定技术（git）测试表明，与该粘合剂集成的磷酸铁锂（LiFePO4）阴极具有优异的Li+扩散系数。EMTO作为阴极粘合剂的半电池和全电池都比PVDF作为阴极粘合剂的电池表现出更高的循环稳定性。令人印象深刻的是，基于EMTO粘合剂的全电池的放电比容量保持稳定在160 mAh g-1，超过240次循环。此外，微生物培养实验表明，黑曲霉可以有效地定殖粘结剂膜并降解其有机成分。这种独特的特性使EMTO粘合剂能够无害地重新进入生态系统，有利于促进环境保护和可持续发展。
{"title":"A Fluorine-Free and Biodegradable Cathode Binder toward LiFePO4-Based Lithium Batteries","authors":"Xiaolong Fan,Chong Li,Zhongyi Zhang","doi":"10.1021/acssuschemeng.6c00243","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00243","url":null,"abstract":"The improper disposal of lithium batteries is leading to increasingly severe and unavoidable pollution, as their daily use becomes more widespread and frequent. As a conventional cathode binder, poly(vinylidene fluoride) (PVDF) is difficult to degrade, leading to long-term environmental pollution from discarded batteries. Herein, a novel fluorine-free cathode binder (denoted as EMTO) was designed for degradation by environmental microorganisms. This innovative binder features an organic polymer derived from natural-product-based molecules with polysiloxane. This composition imparts exceptional adhesive strength and antioxidant properties that help to enhance the cycle performance of batteries. The sterically hindered phenolic motif in the as-developed binder can effectively reduce the chemical degradation of electrolyte by capturing singlet oxygen (1O2), thereby extending the battery cycle stability. Galvanostatic Intermittent Titration Technique (GITT) tests reveal that the lithium iron phosphate (LiFePO4) cathode integrated with this binder demonstrates superior Li+ diffusion coefficients. Both half cells and full cells with EMTO as the cathode binder demonstrate higher cycling stability than those with PVDF as the binder. Impressively, the discharge specific capacity of the EMTO binder-based full cell remains stable at 160 mAh g–1 for over 240 cycles. Furthermore, microbial culturing experiments indicate that Aspergillus niger can effectively colonize the binder membrane and degrade its organic components. This unique feature allows the EMTO binder to re-enter the ecosystem innocuously, conducive to advancing environmental protection and sustainable development.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"127 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383739","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 : 2026-03-11DOI: 10.1021/acssuschemeng.5c12448
Yong Zhou,Yiyang Zhou,Jiamei Liu,Bin Yang,Yang Gao,Yingjie Hua,Bing Li,Xiaoyang Liu
To enable the large-scale implementation of the hydrogen evolution reaction (HER) in alkaline electrolytes, obtaining highly active and economical electrocatalysts remains a crucial requirement. In this work, ultrafine Ni–Ru alloy nanoclusters and atomically dispersed Ru–N4 and Ni–N4 sites were successfully anchored on nitrogen-doped hollow mesoporous carbon spheres (NHMCS) via a microwave-assisted solvothermal method within 15 min, yielding Ni–Ru bimetallic catalysts (NixRuy/NHMCS). In 1.0 M KOH, the NiRu4/NHMCS-900 catalyst delivered outstanding HER performance, characterized by a record-low overpotential of 9.3 mV at 10 mA cm–2. This value is notably lower than that of the commercial Pt/C catalysts. Moreover, the catalyst demonstrated remarkable stability over 100,000 cycles and sustained performance during 120 h of continuous operation. X-ray absorption fine structure (XAFS), in situ Raman spectroscopy, and density functional theory (DFT) calculations collectively demonstrate that the outstanding HER activity is governed by the synergy of Ni–Ru bimetallic sites and the reverse hydrogen spillover effect (HSE) between the NHMCS and metal clusters. Specifically, nitrogen sites in NHMCS initially adsorb H2O molecules, which then dissociate into N–H intermediates. The resulting adsorbed hydrogen atoms (Had) migrate to adjacent Ru sites, forming Ru–H intermediates that subsequently evolve into H2 gas. Simultaneously, Ni sites interact with hydroxyl groups to form Ni–OH species, modulating the electronic structure and stabilizing key intermediates. Additionally, the porous NHMCS architecture and strong metal–support interactions (MSI) prevent the aggregation of Ni–Ru clusters, further enhancing structural integrity. This study offers new insights into designing high-performance HER catalysts by harnessing reverse hydrogen spillover and bimetallic synergy.
为了使碱性电解质中析氢反应（HER）的大规模实施，获得高活性和经济的电催化剂仍然是一个至关重要的要求。在这项工作中，通过微波辅助溶剂热方法，在15分钟内成功地将超细Ni-Ru合金纳米团簇和原子分散的Ru-N4和Ni-N4位点锚定在氮掺杂中空介孔碳球（NHMCS）上，制备了Ni-Ru双金属催化剂（NixRuy/NHMCS）。在1.0 M KOH条件下，NiRu4/NHMCS-900催化剂表现出优异的HER性能，在10 mA cm-2下的过电位低至创纪录的9.3 mV。该值明显低于商用Pt/C催化剂。此外，该催化剂在10万次循环中表现出卓越的稳定性，在120小时的连续运行中表现出持续的性能。x射线吸收精细结构（XAFS）、原位拉曼光谱和密度泛函数理论（DFT）计算共同表明，优异的HER活性是由Ni-Ru双金属位的协同作用以及NHMCS和金属团簇之间的反向氢溢出效应（HSE）控制的。具体来说，NHMCS中的氮位点最初吸附H2O分子，然后解离成N-H中间体。由此产生的吸附氢原子（Had）迁移到相邻的Ru位点，形成Ru - h中间体，随后演变成H2气体。同时，Ni位点与羟基相互作用形成Ni - oh基团，调节电子结构，稳定关键中间体。此外，多孔NHMCS结构和强金属支撑相互作用（MSI）防止了Ni-Ru团簇的聚集，进一步提高了结构的完整性。该研究为利用反向氢溢出和双金属协同作用设计高性能HER催化剂提供了新的见解。
{"title":"Boosting Alkaline Hydrogen Evolution via Synergistic Reverse Hydrogen Spillover and Metal–Support Interactions in Ni–Ru Alloy Clusters on Nitrogen-Doped Carbon","authors":"Yong Zhou,Yiyang Zhou,Jiamei Liu,Bin Yang,Yang Gao,Yingjie Hua,Bing Li,Xiaoyang Liu","doi":"10.1021/acssuschemeng.5c12448","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12448","url":null,"abstract":"To enable the large-scale implementation of the hydrogen evolution reaction (HER) in alkaline electrolytes, obtaining highly active and economical electrocatalysts remains a crucial requirement. In this work, ultrafine Ni–Ru alloy nanoclusters and atomically dispersed Ru–N4 and Ni–N4 sites were successfully anchored on nitrogen-doped hollow mesoporous carbon spheres (NHMCS) via a microwave-assisted solvothermal method within 15 min, yielding Ni–Ru bimetallic catalysts (NixRuy/NHMCS). In 1.0 M KOH, the NiRu4/NHMCS-900 catalyst delivered outstanding HER performance, characterized by a record-low overpotential of 9.3 mV at 10 mA cm–2. This value is notably lower than that of the commercial Pt/C catalysts. Moreover, the catalyst demonstrated remarkable stability over 100,000 cycles and sustained performance during 120 h of continuous operation. X-ray absorption fine structure (XAFS), in situ Raman spectroscopy, and density functional theory (DFT) calculations collectively demonstrate that the outstanding HER activity is governed by the synergy of Ni–Ru bimetallic sites and the reverse hydrogen spillover effect (HSE) between the NHMCS and metal clusters. Specifically, nitrogen sites in NHMCS initially adsorb H2O molecules, which then dissociate into N–H intermediates. The resulting adsorbed hydrogen atoms (Had) migrate to adjacent Ru sites, forming Ru–H intermediates that subsequently evolve into H2 gas. Simultaneously, Ni sites interact with hydroxyl groups to form Ni–OH species, modulating the electronic structure and stabilizing key intermediates. Additionally, the porous NHMCS architecture and strong metal–support interactions (MSI) prevent the aggregation of Ni–Ru clusters, further enhancing structural integrity. This study offers new insights into designing high-performance HER catalysts by harnessing reverse hydrogen spillover and bimetallic synergy.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"79 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383742","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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