Pub Date : 2026-01-28DOI: 10.1021/acssuschemeng.5c12502
Mingyang Hu, Ying He, Yunying Wang, Hongzhi Du, Liang Wang, Jie Yang, Yun Liu
The methanolysis of polyethylene terephthalate (PET) to produce dimethyl terephthalate (DMT) and ethylene glycol (EG) is a promising route for sustainable PET valorization. Conventional metal-based catalysts often suffer from high cost, large loading, low processing capacity, and environmental concerns. Here, we report a nitrogen–sulfur codoped lignin-derived carbon catalyst (S–N@C-800 °C) for oxidative alcoholysis of PET. Under 180 °C and 30 min with a PET-to-catalyst ratio of 250:1, PET conversion reached 99.58%, with EG and DMT yields of 97.67 and 95.37%, respectively. Even at a 600:1 ratio (0.16% catalyst by mass), the system maintained high depolymerization efficiency, highlighting its performance under low catalyst usage and high solid loading. Characterization revealed strong correlations among activity, acid–base sites, nitrogen species, and vacancies. Mechanistic studies using electron paramagnetic resonance (EPR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that basic sites activate O2 to generate superoxide (·O2–), which reacts with methanol to form OOH· and CH3O-, while acidic sites activate carbonyl groups, forming carbocations that lower ester bond dissociation energy and facilitate nucleophilic attack. This metal-free, efficient, and environmentally benign catalytic system provides a practical strategy for PET recycling.
{"title":"Dual Active Sites of Metal-Free N,S-Doped Lignin-Derived Carbon Catalysts for Oxidative Esterification Depolymerization of Polyethylene Terephthalate","authors":"Mingyang Hu, Ying He, Yunying Wang, Hongzhi Du, Liang Wang, Jie Yang, Yun Liu","doi":"10.1021/acssuschemeng.5c12502","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12502","url":null,"abstract":"The methanolysis of polyethylene terephthalate (PET) to produce dimethyl terephthalate (DMT) and ethylene glycol (EG) is a promising route for sustainable PET valorization. Conventional metal-based catalysts often suffer from high cost, large loading, low processing capacity, and environmental concerns. Here, we report a nitrogen–sulfur codoped lignin-derived carbon catalyst (S–N@C-800 °C) for oxidative alcoholysis of PET. Under 180 °C and 30 min with a PET-to-catalyst ratio of 250:1, PET conversion reached 99.58%, with EG and DMT yields of 97.67 and 95.37%, respectively. Even at a 600:1 ratio (0.16% catalyst by mass), the system maintained high depolymerization efficiency, highlighting its performance under low catalyst usage and high solid loading. Characterization revealed strong correlations among activity, acid–base sites, nitrogen species, and vacancies. Mechanistic studies using electron paramagnetic resonance (EPR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that basic sites activate O<sub>2</sub> to generate superoxide (·O<sub>2</sub><sup>–</sup>), which reacts with methanol to form OOH· and CH<sub>3</sub>O-, while acidic sites activate carbonyl groups, forming carbocations that lower ester bond dissociation energy and facilitate nucleophilic attack. This metal-free, efficient, and environmentally benign catalytic system provides a practical strategy for PET recycling.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057121","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 : 2026-01-28DOI: 10.1021/acssuschemeng.5c11559
Yangyang Zhang, Xiaodong Xu, Siqi Ding, Qingxin Zhao, Jun Chang
Calcium sulfoaluminate (CSA) cement offers a strategic low-carbon alternative for seawater sea-sand concrete, reducing both CO2 emissions and freshwater demand. However, the ambiguous mechanisms governing seawater salts’ impact on its hydration kinetics and microstructural development hinder its practical engineering. This study systematically investigated the influence of three key seawater salts─NaCl (NC), Na2SO4 (NS), and MgCl2 (MC)─on the hydration kinetics and microstructural evolution of ye’elimite (the primary CSA cement clinker) compared to deionized (DI) water. Results revealed that seawater salts altered the hydration kinetics of C4A3 via a dual effect characterized by early-stage acceleration, followed by later-stage retardation. The NS system demonstrated the most pronounced dual effect, while the MC system had the least impact. Microstructural analysis revealed that these salts significantly modify phase evolution and crystal morphology. Specifically, the AH3 content ranked as MC > NS > DI > NC. AFm was present across all systems, with the highest content in DI and the lowest in NC, while AFt content shifted from an early-stage ranking of NC > MC > NS to a late-stage ranking of NC > NS > MC. Friedel’s salt formed only in Cl–-containing systems, with the highest concentrations consistently observed in the NC system. Furthermore, both NC and NS systems fostered larger AFt and AFm crystals compared to the DI system, while the MC system generated smaller crystals. While all salt systems increased the macropore volume, the NC and MC systems reduced micropores. Additionally, AH3 exhibited higher crystallinity in the NS/NC systems and the lowest in the MC system; the AH3 phase exhibited a comparatively stronger affinity for cations, with the adsorption following the order of Mg2+ > Ca2+ > Na+, while the uptake of anions by AH3 remained weak. These findings elucidate the fundamental mechanisms for the development of next-generation, low-carbon CSA-based composites.
{"title":"Influence of Seawater-Derived Salts on Ye’elimite Hydration Kinetics and Microstructural Evolution: Toward Developing Sustainable Calcium Sulfoaluminate Cement-Based Materials","authors":"Yangyang Zhang, Xiaodong Xu, Siqi Ding, Qingxin Zhao, Jun Chang","doi":"10.1021/acssuschemeng.5c11559","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11559","url":null,"abstract":"Calcium sulfoaluminate (CSA) cement offers a strategic low-carbon alternative for seawater sea-sand concrete, reducing both CO<sub>2</sub> emissions and freshwater demand. However, the ambiguous mechanisms governing seawater salts’ impact on its hydration kinetics and microstructural development hinder its practical engineering. This study systematically investigated the influence of three key seawater salts─NaCl (NC), Na<sub>2</sub>SO<sub>4</sub> (NS), and MgCl<sub>2</sub> (MC)─on the hydration kinetics and microstructural evolution of ye’elimite (the primary CSA cement clinker) compared to deionized (DI) water. Results revealed that seawater salts altered the hydration kinetics of C<sub>4</sub>A<sub>3</sub> via a dual effect characterized by early-stage acceleration, followed by later-stage retardation. The NS system demonstrated the most pronounced dual effect, while the MC system had the least impact. Microstructural analysis revealed that these salts significantly modify phase evolution and crystal morphology. Specifically, the AH<sub>3</sub> content ranked as MC > NS > DI > NC. AFm was present across all systems, with the highest content in DI and the lowest in NC, while AFt content shifted from an early-stage ranking of NC > MC > NS to a late-stage ranking of NC > NS > MC. Friedel’s salt formed only in Cl<sup>–</sup>-containing systems, with the highest concentrations consistently observed in the NC system. Furthermore, both NC and NS systems fostered larger AFt and AFm crystals compared to the DI system, while the MC system generated smaller crystals. While all salt systems increased the macropore volume, the NC and MC systems reduced micropores. Additionally, AH<sub>3</sub> exhibited higher crystallinity in the NS/NC systems and the lowest in the MC system; the AH<sub>3</sub> phase exhibited a comparatively stronger affinity for cations, with the adsorption following the order of Mg<sup>2+</sup> > Ca<sup>2+</sup> > Na<sup>+</sup>, while the uptake of anions by AH<sub>3</sub> remained weak. These findings elucidate the fundamental mechanisms for the development of next-generation, low-carbon CSA-based composites.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070154","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 : 2026-01-28DOI: 10.1021/acssuschemeng.5c13676
Jialu Zhang, Nan Nan Xia, Fei He, Qin Wu
Cellulose is a green and renewable biobased material with immense potential, yet its application in self-healing materials is hindered by its inherent rigidity, which severely limits the molecular chain movement. To break through this limitation, we introduce an innovative design strategy: “Introduces a rigid-flexible synergy strategy by utilizing the flexible polymer network to drive the rigid cellulose network”. In this strategy, a hydroxyethyl cellulose-based composite material with a synergy network structure was successfully constructed by covalently bonding a rigid hydroxyethyl cellulose (HEC) backbone into a flexible polyurethane (PU) matrix containing dynamic disulfide bonds. The inherent thermodynamic incompatibility between HEC and the PU matrix leads to the formation of HEC-rich rigid domains that act as multifunctional cross-linking points, enhancing the mechanical integrity of the material. Upon damage, the high mobility of the flexible PU segments, coupled with the dynamic exchange of disulfide bonds, allows the entire network to rearrange and flow at the crack interface, leading to highly efficient healing. The anchored HEC domains provide structural stability during this process. The results show that the composite material not only maintains excellent mechanical properties but also achieves a self-healing efficiency of up to 96.6%, which is 3.7 times higher than that of the control group without disulfide bonds. Furthermore, this composite possesses outstanding thermal reprocessability. This research carves out a new path for high-performance hydroxyethyl cellulose-based smart materials and offers a promising material-based solution to tackle plastic pollution and advance sustainable development goals.
{"title":"Rigid-Flexible Synergy in Hydroxyethyl Cellulose-Polyurethane Composites Featuring Dynamic Disulfide Bonds for Highly Efficient Self-Healing","authors":"Jialu Zhang, Nan Nan Xia, Fei He, Qin Wu","doi":"10.1021/acssuschemeng.5c13676","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13676","url":null,"abstract":"Cellulose is a green and renewable biobased material with immense potential, yet its application in self-healing materials is hindered by its inherent rigidity, which severely limits the molecular chain movement. To break through this limitation, we introduce an innovative design strategy: “Introduces a rigid-flexible synergy strategy by utilizing the flexible polymer network to drive the rigid cellulose network”. In this strategy, a hydroxyethyl cellulose-based composite material with a synergy network structure was successfully constructed by covalently bonding a rigid hydroxyethyl cellulose (HEC) backbone into a flexible polyurethane (PU) matrix containing dynamic disulfide bonds. The inherent thermodynamic incompatibility between HEC and the PU matrix leads to the formation of HEC-rich rigid domains that act as multifunctional cross-linking points, enhancing the mechanical integrity of the material. Upon damage, the high mobility of the flexible PU segments, coupled with the dynamic exchange of disulfide bonds, allows the entire network to rearrange and flow at the crack interface, leading to highly efficient healing. The anchored HEC domains provide structural stability during this process. The results show that the composite material not only maintains excellent mechanical properties but also achieves a self-healing efficiency of up to 96.6%, which is 3.7 times higher than that of the control group without disulfide bonds. Furthermore, this composite possesses outstanding thermal reprocessability. This research carves out a new path for high-performance hydroxyethyl cellulose-based smart materials and offers a promising material-based solution to tackle plastic pollution and advance sustainable development goals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"40 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070188","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 : 2026-01-28DOI: 10.1021/acssuschemeng.5c12033
Eva González Carmona, Inge Schlapp-Hackl, Michael Hummel
Developing novel and sustainable processes for the production of bioplastics is crucial to addressing and mitigating the environmental challenges caused by the overconsumption of synthetic plastics. The old-fashioned linear “make-take-waste” consumption models are not environmentally sustainable and need to be transformed to circular systems to preserve natural resources. Therefore, in this study, we successfully recycled regenerated cellulose films into films and textile fibers via the Ioncell process. Films produced from dissolving pulp–ionic liquid (IL) solutions (cycle 0) were redissolved in ionic liquid to form recycled films and fibers within cycle 1. This process was repeated to showcase the recyclability of the cellulose within 2 recycling cycles. In both cycles, thin and highly transparent films have been produced that maintained the strength of the original films but improved the elongation at break (230–235 MPa, 10–13%). The fibers exhibit tenacities and elongations at break comparable to standard Ioncell fibers from virgin pulp (51.3–53.7 cN/tex, 9.2–11.6%). Additionally, a demonstration fabric was knitted from fibers of cycle 1. Overall, the results display the recyclability of the cellulosic films into high-quality products without any loss of quality.
{"title":"Chemical Recycling of Next-Generation Films into New Films and Textile Fibers","authors":"Eva González Carmona, Inge Schlapp-Hackl, Michael Hummel","doi":"10.1021/acssuschemeng.5c12033","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12033","url":null,"abstract":"Developing novel and sustainable processes for the production of bioplastics is crucial to addressing and mitigating the environmental challenges caused by the overconsumption of synthetic plastics. The old-fashioned linear “make-take-waste” consumption models are not environmentally sustainable and need to be transformed to circular systems to preserve natural resources. Therefore, in this study, we successfully recycled regenerated cellulose films into films and textile fibers via the Ioncell process. Films produced from dissolving pulp–ionic liquid (IL) solutions (cycle 0) were redissolved in ionic liquid to form recycled films and fibers within cycle 1. This process was repeated to showcase the recyclability of the cellulose within 2 recycling cycles. In both cycles, thin and highly transparent films have been produced that maintained the strength of the original films but improved the elongation at break (230–235 MPa, 10–13%). The fibers exhibit tenacities and elongations at break comparable to standard Ioncell fibers from virgin pulp (51.3–53.7 cN/tex, 9.2–11.6%). Additionally, a demonstration fabric was knitted from fibers of cycle 1. Overall, the results display the recyclability of the cellulosic films into high-quality products without any loss of quality.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"179 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057120","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 : 2026-01-27DOI: 10.1021/acssuschemeng.5c09022
Evan C. Wegener, Christopher D. Skory
Massoia lactone (ML) is a valuable chemical with a variety of uses that can be sourced from extracellular polyol lipids, called liamocins, produced by Aureobasidium pullulans. In this study, sustainability and safety considerations were used to guide the development of a new method for converting liamocins to ML that would be easily scalable and could be performed in a continuous flow reactor. Methyl ethyl ketone (MEK) and water are used as cosolvents, and biobased carboxylic acids (e.g., citric acid) are used as Brønsted acids to catalyze sequential hydrolysis and dehydration reactions. The acids exhibited salting-in effects on MEK–water mixtures, allowing for reactions to be performed in a single liquid phase. In batch reactors at 70 °C and atmospheric pressure, long reaction times (∼200 h) are required for the dehydration reaction to reach equilibrium and achieve yields approaching the apparent theoretical limit (∼0.668 g/gliamocins). In a plug-flow reactor at 150 °C and 500 psi, the apparent maximum yields (0.675 g/gliamocins) are seen at a residence time of 2 h. Overall, this work highlights the use of sustainability and safety criteria in the development of new technologies to produce valuable chemicals from renewable agricultural resources.
{"title":"Sustainable Synthesis of Massoia Lactone from Liamocin Polyol Lipids Produced by Aureobasidium pullulans","authors":"Evan C. Wegener, Christopher D. Skory","doi":"10.1021/acssuschemeng.5c09022","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09022","url":null,"abstract":"Massoia lactone (ML) is a valuable chemical with a variety of uses that can be sourced from extracellular polyol lipids, called liamocins, produced by <i>Aureobasidium pullulans</i>. In this study, sustainability and safety considerations were used to guide the development of a new method for converting liamocins to ML that would be easily scalable and could be performed in a continuous flow reactor. Methyl ethyl ketone (MEK) and water are used as cosolvents, and biobased carboxylic acids (e.g., citric acid) are used as Brønsted acids to catalyze sequential hydrolysis and dehydration reactions. The acids exhibited salting-in effects on MEK–water mixtures, allowing for reactions to be performed in a single liquid phase. In batch reactors at 70 °C and atmospheric pressure, long reaction times (∼200 h) are required for the dehydration reaction to reach equilibrium and achieve yields approaching the apparent theoretical limit (∼0.668 g/g<sub>liamocins</sub>). In a plug-flow reactor at 150 °C and 500 psi, the apparent maximum yields (0.675 g/g<sub>liamocins</sub>) are seen at a residence time of 2 h. Overall, this work highlights the use of sustainability and safety criteria in the development of new technologies to produce valuable chemicals from renewable agricultural resources.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057122","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}
We present a sustainable photoelectrochemical platform based on a silk-based photoelectrode functionalized with phenothiazine (PTZ). The PTZ–silk system enables selective benzylic C–H etherification under mild conditions. Structural and electrochemical characterization confirmed successful PTZ functionalization and an anodic half-wave potential (E1/2 = +1.09 V vs SSCE). The photoelectrochemical reactions deliver isolated yields of up to 89% (diphenylmethane) and can be recycled for 10 consecutive runs. Postcycling FT-IR supports operational stability, showing retention of key PTZ features with a gradual attenuation consistent with minor loss of surface-bound PTZ. Mechanistic experiments are consistent with a PTZ-mediated, photoinduced single-electron transfer pathway. This work demonstrates the potential of bioderived, heterogeneous catalysts for sustainable organic synthesis.
我们提出了一种基于吩噻嗪功能化的丝基光电极的可持续光电电化学平台。PTZ-silk体系在温和条件下实现了选择性苯丙-氢醚化。结构和电化学表征证实了PTZ功能化的成功和阳极半波电位（E1/2 = +1.09 V vs SSCE）。光电化学反应的分离收率高达89%（二苯甲烷），并且可以连续循环10次。后循环FT-IR支持操作稳定性，显示出关键PTZ特征的保留，其逐渐衰减与表面绑定PTZ的轻微损失一致。机械实验与ptz介导的光诱导单电子转移途径一致。这项工作证明了生物衍生的多相催化剂在可持续有机合成方面的潜力。
{"title":"Silk-Derived Photoelectrode Enables Sustainable Benzylic Etherification via Photoelectrocatalysis","authors":"Hung-Chi Chen, Yu-Hao Liu, Pei-Chi Kuo, Chih-Hui Chou, Kai-Wun Jhang, Wan-Hsuan Shih, Way-Zen Lee, Chun-Jen Su, Chien-Wei Chiang","doi":"10.1021/acssuschemeng.5c12017","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12017","url":null,"abstract":"We present a sustainable photoelectrochemical platform based on a silk-based photoelectrode functionalized with phenothiazine (PTZ). The PTZ–silk system enables selective benzylic C–H etherification under mild conditions. Structural and electrochemical characterization confirmed successful PTZ functionalization and an anodic half-wave potential (<i>E</i><sub>1/2</sub> = +1.09 V vs SSCE). The photoelectrochemical reactions deliver isolated yields of up to 89% (diphenylmethane) and can be recycled for 10 consecutive runs. Postcycling FT-IR supports operational stability, showing retention of key PTZ features with a gradual attenuation consistent with minor loss of surface-bound PTZ. Mechanistic experiments are consistent with a PTZ-mediated, photoinduced single-electron transfer pathway. This work demonstrates the potential of bioderived, heterogeneous catalysts for sustainable organic synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048752","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}
Ammonia is essential for food production and emerging energy applications, yet its conventional Haber–Bosch synthesis is highly energy- and carbon-intensive. Nitric oxide (NO), with its weaker N–O bond compared to N2, offers a more accessible nitrogen feedstock, whether captured from flue gases or generated via air fixation. Direct hydrogenation of NO to NH3 offers a promising alternative, but product selectivity is difficult to control. Here we show that tuning the oxidation state of ruthenium provides a powerful means to direct this reaction. RuO2/TiO2, dominated by Ru4+ species, achieves over 75% NH3 selectivity at 250 °C under ambient pressure. This performance is 2.5 times higher than that of Ru/TiO2 and remains stable for 48 h of continuous operation. In situ spectroscopy and density functional theory reveal a complementary mechanism: Ru0 sites facilitate low-temperature NO activation, while Ru4+ sites stabilize key hydrogenation intermediates (*NH2/*NH2O). This stabilization likely shifts the rate-determining step from N–O cleavage to NH3 desorption, suppressing N–N coupling. These findings suggest a clear structure–function relationship in Ru-catalyzed NO hydrogenation and provide a design principle for selective, low-energy ammonia synthesis.
{"title":"Rewiring the NO-Hydrogenation Pathway via Ru Oxidation State: RuO2/TiO2 Delivers Low-Temperature, High-Selectivity NH3 Synthesis","authors":"Dan Cui, Huan Liu, Xia Zhou, Peipei Wang, Keke Pan, Feng Yu","doi":"10.1021/acssuschemeng.5c11518","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11518","url":null,"abstract":"Ammonia is essential for food production and emerging energy applications, yet its conventional Haber–Bosch synthesis is highly energy- and carbon-intensive. Nitric oxide (NO), with its weaker N–O bond compared to N<sub>2</sub>, offers a more accessible nitrogen feedstock, whether captured from flue gases or generated via air fixation. Direct hydrogenation of NO to NH<sub>3</sub> offers a promising alternative, but product selectivity is difficult to control. Here we show that tuning the oxidation state of ruthenium provides a powerful means to direct this reaction. RuO<sub>2</sub>/TiO<sub>2</sub>, dominated by Ru<sup>4+</sup> species, achieves over 75% NH<sub>3</sub> selectivity at 250 °C under ambient pressure. This performance is 2.5 times higher than that of Ru/TiO<sub>2</sub> and remains stable for 48 h of continuous operation. In situ spectroscopy and density functional theory reveal a complementary mechanism: Ru<sup>0</sup> sites facilitate low-temperature NO activation, while Ru<sup>4+</sup> sites stabilize key hydrogenation intermediates (*NH<sub>2</sub>/*NH<sub>2</sub>O). This stabilization likely shifts the rate-determining step from N–O cleavage to NH<sub>3</sub> desorption, suppressing N–N coupling. These findings suggest a clear structure–function relationship in Ru-catalyzed NO hydrogenation and provide a design principle for selective, low-energy ammonia synthesis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070189","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}
Electrolytic water splitting for hydrogen production remains a significant challenge, highlighting the urgent need for high-performance and economically viable electrocatalysts for the hydrogen evolution reaction (HER). In this study, a Ni2P/CoSe Mott–Schottky heterojunction was fabricated on carbon fiber paper (CFP), serving as an efficient HER electrocatalyst in alkaline media. The radially aligned CoSe hollow nanoneedles enable the uniform anchoring of Ni2P quantum dots, forming tightly coupled heterointerfaces between discrete quantum domains and the conductive scaffold, thereby increasing the density of interfacial active sites. Discretely dispersed semiconducting Ni2P on metallic CoSe induces interfacial charge polarization via quantum confinement effects, thereby generating a strong built-in electric field (BIEF) at the interface that drives electron transfer from Ni2P to CoSe. This field promotes interfacial charge redistribution and intrinsically activates the catalytic sites. Density functional theory (DFT) calculation reveals that interfacial charge redistribution between Ni2P and CoSe generates electron-deficient Ni sites and electron-rich Co sites, which respectively optimize H2O adsorption/dissociation and H* adsorption, thereby enhancing the HER activity. As a result, the 2-Ni2P/CoSe/CFP catalyst exhibits outstanding HER performance with a low overpotential of 186 mV at 1000 mA cm–2 and <1% loss after 300 h. Using 2-Ni2P/CoSe/CFP as the cathode, an AEM-WE device exhibits a low cell voltage of 1.74 V at 1000 mA cm–2 and a long-term stability for 500 h.
电解水裂解制氢仍然是一个重大挑战，迫切需要高性能和经济可行的析氢反应（HER）电催化剂。本研究在碳纤维纸（CFP）上制备了Ni2P/CoSe Mott-Schottky异质结，作为碱性介质中高效的HER电催化剂。径向排列的CoSe空心纳米针能够均匀锚定Ni2P量子点，在离散量子域和导电支架之间形成紧密耦合的异质界面，从而增加界面活性位点的密度。金属CoSe上离散分散的半导体Ni2P通过量子约束效应诱导界面电荷极化，从而在界面处产生强大的内置电场（BIEF），驱动电子从Ni2P向CoSe转移。该场促进了界面电荷的重新分配，并从本质上激活了催化位点。密度泛函理论（DFT）计算表明，Ni2P和CoSe之间的界面电荷重分配产生了缺电子的Ni位点和富电子的Co位点，分别优化了H2O吸附/解离和H*吸附，从而提高了HER活性。结果表明，2-Ni2P/CoSe/CFP催化剂表现出优异的HER性能，在1000 mA cm-2时过电位为186 mV， 300 h后损耗为<；1%。使用2-Ni2P/CoSe/CFP作为阴极，AEM-WE器件在1000 mA cm-2时电池电压低至1.74 V，长期稳定性为500 h。
{"title":"Ni2P/CoSe Mott–Schottky Heterointerfaces with Electron Redistribution for Alkaline Hydrogen Evolution at Ampere-Level Current Densities","authors":"Xuetong Wang, Wenwen Zheng, Jinjie Fang, Jiaxia Zhou, Xiaoman Tang, Meng Zhao, Haozong Zhong, Guojing Wang, Xiaojie Li, Yuanzhi Zhu","doi":"10.1021/acssuschemeng.5c09260","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09260","url":null,"abstract":"Electrolytic water splitting for hydrogen production remains a significant challenge, highlighting the urgent need for high-performance and economically viable electrocatalysts for the hydrogen evolution reaction (HER). In this study, a Ni<sub>2</sub>P/CoSe Mott–Schottky heterojunction was fabricated on carbon fiber paper (CFP), serving as an efficient HER electrocatalyst in alkaline media. The radially aligned CoSe hollow nanoneedles enable the uniform anchoring of Ni<sub>2</sub>P quantum dots, forming tightly coupled heterointerfaces between discrete quantum domains and the conductive scaffold, thereby increasing the density of interfacial active sites. Discretely dispersed semiconducting Ni<sub>2</sub>P on metallic CoSe induces interfacial charge polarization via quantum confinement effects, thereby generating a strong built-in electric field (BIEF) at the interface that drives electron transfer from Ni<sub>2</sub>P to CoSe. This field promotes interfacial charge redistribution and intrinsically activates the catalytic sites. Density functional theory (DFT) calculation reveals that interfacial charge redistribution between Ni<sub>2</sub>P and CoSe generates electron-deficient Ni sites and electron-rich Co sites, which respectively optimize H<sub>2</sub>O adsorption/dissociation and H* adsorption, thereby enhancing the HER activity. As a result, the 2-Ni<sub>2</sub>P/CoSe/CFP catalyst exhibits outstanding HER performance with a low overpotential of 186 mV at 1000 mA cm<sup>–2</sup> and <1% loss after 300 h. Using 2-Ni<sub>2</sub>P/CoSe/CFP as the cathode, an AEM-WE device exhibits a low cell voltage of 1.74 V at 1000 mA cm<sup>–2</sup> and a long-term stability for 500 h.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057123","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 : 2026-01-27DOI: 10.1021/acssuschemeng.5c12381
Zahra Najafi, Leyla Nesrin Kahyaoglu
Multifunctional and biodegradable smart packaging films were developed here using pectin, phycocyanin rich Spirulina (PCS) extract and citric acid derived carbon dots (CDs). The physicochemical, active and intelligent properties of the films were systematically examined as a function of CD concentration. Incorporation of CDs enhanced tensile strength from 10.88 to 17.70 MPa, increased crystallinity and thermal stability and maintained high biodegradability (above 80% mass loss after 28 days in soil). The addition of CD enhanced antioxidant activity (from 12.8% to 39.5% ABTS scavenging) and imparted concentration dependent antimicrobial activity against E. coli and S. aureus. The PCSP/CD12.5 film displayed a distinct colorimetric response to ammonia vapor, displaying a linear ΔE–NH3 correlation (R2 = 0.93) within the range of 0–50 mg N/100 g and a detection limit of 9.04 mg N/100 g, and exhibited colorimetric stability over two months of storage. In real food trials, the PCSP/CD12.5 film enabled effective visual tracking of fish freshness at 23 °C with color changes closely correlating to increases in TVB-N (from 13.3 to 36.2 mg N/100 g) and TVC (from 4.5 to 7.4 log cfu/g) during storage. These results demonstrate that PCSP/CD films effectively integrate active and intelligent functionalities thereby extending the application of pigment and protein complexes.
{"title":"Sensing of Fish Freshness Using Smart Pectin Films Incorporated with Spirulina Extract and Carbon Dots","authors":"Zahra Najafi, Leyla Nesrin Kahyaoglu","doi":"10.1021/acssuschemeng.5c12381","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12381","url":null,"abstract":"Multifunctional and biodegradable smart packaging films were developed here using pectin, phycocyanin rich <i>Spirulina</i> (PCS) extract and citric acid derived carbon dots (CDs). The physicochemical, active and intelligent properties of the films were systematically examined as a function of CD concentration. Incorporation of CDs enhanced tensile strength from 10.88 to 17.70 MPa, increased crystallinity and thermal stability and maintained high biodegradability (above 80% mass loss after 28 days in soil). The addition of CD enhanced antioxidant activity (from 12.8% to 39.5% ABTS scavenging) and imparted concentration dependent antimicrobial activity against <i>E. coli</i> and <i>S. aureus</i>. The PCSP/CD12.5 film displayed a distinct colorimetric response to ammonia vapor, displaying a linear Δ<i>E</i>–NH<sub>3</sub> correlation (<i>R</i><sup>2</sup> = 0.93) within the range of 0–50 mg N/100 g and a detection limit of 9.04 mg N/100 g, and exhibited colorimetric stability over two months of storage. In real food trials, the PCSP/CD12.5 film enabled effective visual tracking of fish freshness at 23 °C with color changes closely correlating to increases in TVB-N (from 13.3 to 36.2 mg N/100 g) and TVC (from 4.5 to 7.4 log cfu/g) during storage. These results demonstrate that PCSP/CD films effectively integrate active and intelligent functionalities thereby extending the application of pigment and protein complexes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057125","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}
In recent years, extensive research has been devoted to the synthesis or modification of epoxy resins from biomass-derived feedstocks. However, realizing closed-loop recyclability, using fully renewable raw materials, and preserving key material properties remain open and persistent challenges in epoxy resin development. Herein, we propose a strategy involving the use of biomass-derived tung oil (TO) as the primary raw material and employing dynamic covalent ester-exchange chemistry to prepare a highly mechanically robust, recyclable, and reprocessable tung oil epoxy resin (ECAT-ME) vitrimer. The ECAT-ME vitrimer consists of a covalent adaptable network based on an associative mechanism, exhibiting tensile and compressive strengths of 11.87 and 17.45 MPa, respectively. Following six pulverization–melting–cooling cycles, the material retained tensile and compressive strengths of 6.99 and 8.92 MPa, respectively. This recyclable, high-performance biobased epoxy resin lays the foundation for the sustainable development of functional composites.
{"title":"Recyclable and Reprocessable Tung Oil-Based Epoxy Resin with High Mechanical Strength","authors":"Yinghao Wu, Xin Zhao, Chunlei Jiao, Haigang Wang, Ming Wei, Jian Li, Yanjun Xie, Shaoliang Xiao","doi":"10.1021/acssuschemeng.5c10423","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10423","url":null,"abstract":"In recent years, extensive research has been devoted to the synthesis or modification of epoxy resins from biomass-derived feedstocks. However, realizing closed-loop recyclability, using fully renewable raw materials, and preserving key material properties remain open and persistent challenges in epoxy resin development. Herein, we propose a strategy involving the use of biomass-derived tung oil (TO) as the primary raw material and employing dynamic covalent ester-exchange chemistry to prepare a highly mechanically robust, recyclable, and reprocessable tung oil epoxy resin (ECAT-ME) vitrimer. The ECAT-ME vitrimer consists of a covalent adaptable network based on an associative mechanism, exhibiting tensile and compressive strengths of 11.87 and 17.45 MPa, respectively. Following six pulverization–melting–cooling cycles, the material retained tensile and compressive strengths of 6.99 and 8.92 MPa, respectively. This recyclable, high-performance biobased epoxy resin lays the foundation for the sustainable development of functional composites.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"51 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057124","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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