Pub Date : 2026-02-03DOI: 10.1021/acssuschemeng.5c13113
Yifan Liu, Xiangyue Wei, Shun Zhang, Xuan Zhao, Wenhao Xu, Lei Yan, Zijun Feng, Xuehui Liu, Yu-Zhong Wang, Shimei Xu
Polyester/cotton blends, which represent over 60% of the textile market, present a significant challenge for chemical recycling. Conventional solution acid hydrolysis suffers from high acid consumption and low solid/liquid ratios and results in severe equipment corrosion due to the acid-resistant nature of polyester. To address the limitation, we developed an in situ catalyst-loaded semidry acidic hydrolysis method for depolymerization of polyester/cotton blends. By leveraging hydrogen bonding between cotton and a phosphomolybdic acid (PMA) catalyst, the acidic catalyst is anchored onto the fabric, forming localized acid microreactors that facilitate the hydrolysis of polyester without requiring an additional aid solution. The semidry hydrolysis process cuts acid usage to 1/100 of conventional processes, increases the solid–liquid ratio by 3 times, and accelerates the reaction rate by 25 times, while achieving a TPA yield exceeding 94%. The corrosion is markedly suppressed. Both the impregnation solution and the used catalyst are recyclable, contributing to a more sustainable catalytic process. The study offers a sustainable and efficient strategy for recycling blended fabrics with a broad applicability.
{"title":"Semidry Acid Hydrolysis of Polyester/Cotton Blends through In Situ Catalyst Loading","authors":"Yifan Liu, Xiangyue Wei, Shun Zhang, Xuan Zhao, Wenhao Xu, Lei Yan, Zijun Feng, Xuehui Liu, Yu-Zhong Wang, Shimei Xu","doi":"10.1021/acssuschemeng.5c13113","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13113","url":null,"abstract":"Polyester/cotton blends, which represent over 60% of the textile market, present a significant challenge for chemical recycling. Conventional solution acid hydrolysis suffers from high acid consumption and low solid/liquid ratios and results in severe equipment corrosion due to the acid-resistant nature of polyester. To address the limitation, we developed an in situ catalyst-loaded semidry acidic hydrolysis method for depolymerization of polyester/cotton blends. By leveraging hydrogen bonding between cotton and a phosphomolybdic acid (PMA) catalyst, the acidic catalyst is anchored onto the fabric, forming localized acid microreactors that facilitate the hydrolysis of polyester without requiring an additional aid solution. The semidry hydrolysis process cuts acid usage to 1/100 of conventional processes, increases the solid–liquid ratio by 3 times, and accelerates the reaction rate by 25 times, while achieving a TPA yield exceeding 94%. The corrosion is markedly suppressed. Both the impregnation solution and the used catalyst are recyclable, contributing to a more sustainable catalytic process. The study offers a sustainable and efficient strategy for recycling blended fabrics with a broad applicability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"189 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101991","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c12750
Wenjin Ni,Jinfeng Fu,Wenxi Ouyang,Yanan Wei,Jian Liu,Zhengji Yi
The oxidative conversion of cyclohexylamine (CHA) is a sustainable route to cyclohexanone oxime, but its main byproduct, N-cyclohexylcyclohexanamine (N-CCA), largely diminishes the atom economy. Herein, an innovative strategy for the upcycling of N-CCA back to CHA using a non-noble bimetallic NiCu/MgAlO catalyst via reductive amination has been reported. The catalyst, synthesized by urea-assisted coprecipitation, achieved 99.8% N-CCA conversion with 99.6% CHA selectivity under mild conditions using ethanol as a green solvent. The process exhibits 99.4% atom utilization and outstanding catalytic stability. Critically, a quantitative green metrics analysis reveals remarkably low waste generation, with an reaction E-factor of 3.62 and a process mass intensity of 4.62, underpinning the sustainability of this waste-to-value strategy. Density functional theory calculations revealed that the reaction proceeds mainly through a hydrogenation-first pathway (with H2) followed by amination (with NH3). Compared to the Ni(111) and Cu(111), the NiCu(111) facet exhibited stronger adsorption-activation capability for N-CCA and a lower activation energy for the rate-determining step. This work provides a green and practical solution for enhancing the circularity of nylon-6 production.
{"title":"Synergistic NiCu Alloy Catalysis for the Sustainable Upcycling of N-Cyclohexylcyclohexanamine to Cyclohexylamine via Reductive Amination","authors":"Wenjin Ni,Jinfeng Fu,Wenxi Ouyang,Yanan Wei,Jian Liu,Zhengji Yi","doi":"10.1021/acssuschemeng.5c12750","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12750","url":null,"abstract":"The oxidative conversion of cyclohexylamine (CHA) is a sustainable route to cyclohexanone oxime, but its main byproduct, N-cyclohexylcyclohexanamine (N-CCA), largely diminishes the atom economy. Herein, an innovative strategy for the upcycling of N-CCA back to CHA using a non-noble bimetallic NiCu/MgAlO catalyst via reductive amination has been reported. The catalyst, synthesized by urea-assisted coprecipitation, achieved 99.8% N-CCA conversion with 99.6% CHA selectivity under mild conditions using ethanol as a green solvent. The process exhibits 99.4% atom utilization and outstanding catalytic stability. Critically, a quantitative green metrics analysis reveals remarkably low waste generation, with an reaction E-factor of 3.62 and a process mass intensity of 4.62, underpinning the sustainability of this waste-to-value strategy. Density functional theory calculations revealed that the reaction proceeds mainly through a hydrogenation-first pathway (with H2) followed by amination (with NH3). Compared to the Ni(111) and Cu(111), the NiCu(111) facet exhibited stronger adsorption-activation capability for N-CCA and a lower activation energy for the rate-determining step. This work provides a green and practical solution for enhancing the circularity of nylon-6 production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"81 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098127","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c09514
Yueyue Wang,Zexian Zhang,Xinyue Deng,Ran Liu,Xiang Xiao,Zimujun Ye,Yang Xu,Xianbao Wang,Tao Mei
Lithium–sulfur batteries (LSBs) have high energy density and low cost, but their lifespan is shortened by the shuttle effect of sulfur species (lithium polysulfides, LiPSs), restricting their applications. Herein, a novel composite material consisting of Ru nanoclusters with an average diameter of approximately 3.51 nm, embedded in microporous carbon nanospheres (Ru@NC), is facilely synthesized to combat the shuttle effect and improve sulfur’s redox kinetics. Experimental and theoretical studies show that the Ru@NC features a durable spherical structure with abundant exposed active interfaces, high porosity, and a dual lithiophilic and thiophilic Ru–N structure, enabling efficient restriction of LiPSs and facilitating rapid electron and ion transfer. As a result, the battery shows good rate capability and retains a capacity of over 1050 mAh g–1 at 0.5 C after the rate performance test. Moreover, the Ru@NC/S cathode in the LSB exhibits excellent stability, offering a capacity of over 728 mAh g–1 after 800 cycles at a 1 C rate with nearly 100% Coulombic efficiency. Even under an S loading of 5.0 mg cm–2, the Ru@NC/S-based Li–S pouch cell achieves a capacity of 1097 mAh g–1, retaining 536 mAh g–1 after 100 cycles at a current density of 0.5 C.
锂硫电池具有能量密度高、成本低等优点，但由于硫离子（锂多硫化物，LiPSs）的穿梭效应导致其寿命缩短，限制了其应用。本文制备了一种由平均直径约为3.51 nm的Ru纳米团簇组成的新型复合材料，嵌入微孔碳纳米球（Ru@NC）中，可以很容易地对抗穿梭效应并改善硫的氧化还原动力学。实验和理论研究表明，Ru@NC具有持久的球形结构，具有丰富的暴露活性界面，高孔隙率，亲锂和亲硫双重Ru-N结构，能够有效地限制LiPSs，促进快速的电子和离子转移。因此，电池表现出良好的倍率能力，在0.5 C倍率性能测试后，电池容量保持在1050 mAh g-1以上。此外，LSB中的Ru@NC/S阴极表现出优异的稳定性，在1℃的倍率下，在800次循环后提供超过728 mAh g-1的容量，库仑效率接近100%。即使在5.0 mg cm-2的S负载下，Ru@NC/S锂电池也能达到1097 mAh g-1的容量，在0.5 C电流密度下循环100次后仍能保持536 mAh g-1。
{"title":"N-Doped Carbon-Anchored Ruthenium Nanoclusters for Enhanced Polysulfide Conversion Kinetics in High-Performance Lithium–Sulfur Batteries","authors":"Yueyue Wang,Zexian Zhang,Xinyue Deng,Ran Liu,Xiang Xiao,Zimujun Ye,Yang Xu,Xianbao Wang,Tao Mei","doi":"10.1021/acssuschemeng.5c09514","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09514","url":null,"abstract":"Lithium–sulfur batteries (LSBs) have high energy density and low cost, but their lifespan is shortened by the shuttle effect of sulfur species (lithium polysulfides, LiPSs), restricting their applications. Herein, a novel composite material consisting of Ru nanoclusters with an average diameter of approximately 3.51 nm, embedded in microporous carbon nanospheres (Ru@NC), is facilely synthesized to combat the shuttle effect and improve sulfur’s redox kinetics. Experimental and theoretical studies show that the Ru@NC features a durable spherical structure with abundant exposed active interfaces, high porosity, and a dual lithiophilic and thiophilic Ru–N structure, enabling efficient restriction of LiPSs and facilitating rapid electron and ion transfer. As a result, the battery shows good rate capability and retains a capacity of over 1050 mAh g–1 at 0.5 C after the rate performance test. Moreover, the Ru@NC/S cathode in the LSB exhibits excellent stability, offering a capacity of over 728 mAh g–1 after 800 cycles at a 1 C rate with nearly 100% Coulombic efficiency. Even under an S loading of 5.0 mg cm–2, the Ru@NC/S-based Li–S pouch cell achieves a capacity of 1097 mAh g–1, retaining 536 mAh g–1 after 100 cycles at a current density of 0.5 C.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098130","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c09418
Zi-cheng Tang,Ya-juan Zhou,Zi-jie Huang,Qin Wang,De-xiang Sun,Jing-hui Yang,Qing Lin,Xiao-dong Qi,Yong Wang
As advanced electronics evolve toward integration and miniaturization, phase change materials (PCMs) with efficient encapsulation and thermal management properties become critically imperative. Inspired by architectural frameworks, this work utilized the wood-derived carbon skeleton (CW) as the “layers” and the in situ grown carbon nanotubes (CNTs) as the “pillars”, successfully constructing a layer-pillar structured scaffold, denoted as CW@Ni-CNTs. This architecture enabled highly efficient encapsulation of polyethylene glycol (PEG). The resulting composite PCMs (CW@Ni-CNTs/P) exhibited exceptional thermomechanical stability, maintaining a shape retention ratio of 94.3% under 10 N load with less than 3% leakage after multiple thermal cycles. The interpenetrating network enhanced the thermal conductivity by 160.87% axially and 143.48% radially, while providing an electromagnetic interference (EMI) shielding effectiveness of 39.62 dB to PEG. Combined with high latent heat, the composite PCMs show stable thermal management in electronic devices. This hierarchically layer-pillar structural design offers an effective strategy for fabricating composite PCMs with integrated structural and functional properties.
{"title":"Hierarchical Wood-Derived Carbon Scaffold with Layer-Pillar Structure Enabling Thermomechanical Stability and Bidirectional Thermal Conductivity in Phase Change Materials","authors":"Zi-cheng Tang,Ya-juan Zhou,Zi-jie Huang,Qin Wang,De-xiang Sun,Jing-hui Yang,Qing Lin,Xiao-dong Qi,Yong Wang","doi":"10.1021/acssuschemeng.5c09418","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c09418","url":null,"abstract":"As advanced electronics evolve toward integration and miniaturization, phase change materials (PCMs) with efficient encapsulation and thermal management properties become critically imperative. Inspired by architectural frameworks, this work utilized the wood-derived carbon skeleton (CW) as the “layers” and the in situ grown carbon nanotubes (CNTs) as the “pillars”, successfully constructing a layer-pillar structured scaffold, denoted as CW@Ni-CNTs. This architecture enabled highly efficient encapsulation of polyethylene glycol (PEG). The resulting composite PCMs (CW@Ni-CNTs/P) exhibited exceptional thermomechanical stability, maintaining a shape retention ratio of 94.3% under 10 N load with less than 3% leakage after multiple thermal cycles. The interpenetrating network enhanced the thermal conductivity by 160.87% axially and 143.48% radially, while providing an electromagnetic interference (EMI) shielding effectiveness of 39.62 dB to PEG. Combined with high latent heat, the composite PCMs show stable thermal management in electronic devices. This hierarchically layer-pillar structural design offers an effective strategy for fabricating composite PCMs with integrated structural and functional properties.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"87 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098131","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}
The utilization of renewable energy and mild synthesis conditions has recently garnered increased interest for the electrochemical conversion of 5-hydroxymethylfurfural (HMF) into high-value chemicals. However, the deep oxidation of the alcohol group (−OH) while protecting the aldehyde group (−CHO) of HMF made the selective electrooxidation to 5-formyl-2-furancarboxylic acid (FFCA) challenging. Herein, three overall operating factors (applied potential, temperature, and HMF concentration) governing partial and deep oxidation of the alcohol group of HMF were investigated; thereby, the selective formation of FFCA in borate electrolyte (pH 9.5) over CoOx electrocatalyst was achieved. At room temperature, the applied potential could regulate the partial to deep oxidation ratio of the −OH group of HMF, thereby allowing high selectivity of FFCA but leading to a low total Faradaic efficiency (FE) at the high applied potential. The temperature was the most significant factor affecting product distribution, causing both cathodic shifts in onset potential and deep −OH group oxidation, resulting in higher FFCA selectivity at high temperature. The HMF concentration was found to have an insignificant influence on the −OH group oxidation process but caused HMF electrooxidation (HMFOR) to be more effective. Accordingly, HMFOR on CoOx in a pH 9.5 electrolyte at 50 °C achieved a total FE of 70% and yielded FFCA as the main product with a selectivity of 60%. Our study provides insight into the simple approach to control the oxidation process of the −OH group of HMF, hence facilitating future research in this domain, especially in refining reaction conditions for the selective large-scale synthesis of targeted products.
{"title":"Factors Affecting the Selective 5-Hydroxymethylfurfural Electrooxidation to 5-Formyl-2-furancarboxylic Acid over Amorphous CoOx Catalyst","authors":"Giang-Son Tran,Ngoc-Han Nguyen,Mayongga Heriz Febrada,Chia-Ying Chiang","doi":"10.1021/acssuschemeng.5c12123","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12123","url":null,"abstract":"The utilization of renewable energy and mild synthesis conditions has recently garnered increased interest for the electrochemical conversion of 5-hydroxymethylfurfural (HMF) into high-value chemicals. However, the deep oxidation of the alcohol group (−OH) while protecting the aldehyde group (−CHO) of HMF made the selective electrooxidation to 5-formyl-2-furancarboxylic acid (FFCA) challenging. Herein, three overall operating factors (applied potential, temperature, and HMF concentration) governing partial and deep oxidation of the alcohol group of HMF were investigated; thereby, the selective formation of FFCA in borate electrolyte (pH 9.5) over CoOx electrocatalyst was achieved. At room temperature, the applied potential could regulate the partial to deep oxidation ratio of the −OH group of HMF, thereby allowing high selectivity of FFCA but leading to a low total Faradaic efficiency (FE) at the high applied potential. The temperature was the most significant factor affecting product distribution, causing both cathodic shifts in onset potential and deep −OH group oxidation, resulting in higher FFCA selectivity at high temperature. The HMF concentration was found to have an insignificant influence on the −OH group oxidation process but caused HMF electrooxidation (HMFOR) to be more effective. Accordingly, HMFOR on CoOx in a pH 9.5 electrolyte at 50 °C achieved a total FE of 70% and yielded FFCA as the main product with a selectivity of 60%. Our study provides insight into the simple approach to control the oxidation process of the −OH group of HMF, hence facilitating future research in this domain, especially in refining reaction conditions for the selective large-scale synthesis of targeted products.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098126","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c11384
Eun Ji Son, Hyun Wook Kang, Joo Yong Shin, Min Je Hong, Si Eun Baek, Jin Hui Park, Ju Min Kim, Nakwon Choi, Tae Soup Shim
Industrial plastic waste remains a major environmental concern, particularly in short-lifecycle applications such as prototyping and disposable 3D printing. Although biodegradable polymers offer a promising alternative, their inherently weak mechanical properties hinder widespread adoption. In this study, we present an eco-consciously engineered 3D printing ink composed of cellulose acetate (CA) and muscovite, which forms robust brick-and-mortar microstructures via direct ink writing. The ink exhibits optimized rheological properties and thixotropy, enabling stable extrusion and high structural fidelity during printing. Following printing, CA is converted into cellulose through alkaline treatment, resulting in fully compostable composites. The resulting cellulose–muscovite structures achieve a flexural modulus of up to 6.74 GPa with 20 wt % muscovite, substantially higher than that of polylactic acid (PLA, ∼2.4–4.9 GPa) and comparable to conventional synthetic plastics. The ink also supports versatile processing, including thin-film fabrication and surface coloration, thereby expanding its potential applications. By combining high mechanical performance, end-of-life compostability, and material circularity, this approach offers a scalable and sustainable solution for reducing plastic waste in temporary or short-lifecycle 3D printed structures.
{"title":"Sustainable Design of Biocompatible and Mechanically Robust Inks for Direct Ink Writing of Brick-and-Mortar Structures","authors":"Eun Ji Son, Hyun Wook Kang, Joo Yong Shin, Min Je Hong, Si Eun Baek, Jin Hui Park, Ju Min Kim, Nakwon Choi, Tae Soup Shim","doi":"10.1021/acssuschemeng.5c11384","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c11384","url":null,"abstract":"Industrial plastic waste remains a major environmental concern, particularly in short-lifecycle applications such as prototyping and disposable 3D printing. Although biodegradable polymers offer a promising alternative, their inherently weak mechanical properties hinder widespread adoption. In this study, we present an eco-consciously engineered 3D printing ink composed of cellulose acetate (CA) and muscovite, which forms robust brick-and-mortar microstructures via direct ink writing. The ink exhibits optimized rheological properties and thixotropy, enabling stable extrusion and high structural fidelity during printing. Following printing, CA is converted into cellulose through alkaline treatment, resulting in fully compostable composites. The resulting cellulose–muscovite structures achieve a flexural modulus of up to 6.74 GPa with 20 wt % muscovite, substantially higher than that of polylactic acid (PLA, ∼2.4–4.9 GPa) and comparable to conventional synthetic plastics. The ink also supports versatile processing, including thin-film fabrication and surface coloration, thereby expanding its potential applications. By combining high mechanical performance, end-of-life compostability, and material circularity, this approach offers a scalable and sustainable solution for reducing plastic waste in temporary or short-lifecycle 3D printed structures.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098128","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c10236
Gan Yu,Wen Zhao,Hao Zeng,Chengsheng Yang,Yanran Cui,Lei Nie,Zhenglong Li
Lewis-acid molecular sieves are essential catalysts for transforming biomass-derived platform molecules into valuable chemicals. However, the Brønsted acidity arising from incorporated Lewis metals has been rarely reported and remains poorly understood. Using Zr-SBA-16 as a model catalyst, we discovered that the open site Zr centers ((Si–O)3–Zr–OH) exhibit an atypical Brønsted acidity, distinct from the conventional Brønsted acidity arising from Al atoms in the Si–OH–Al framework of zeolites. In a model reaction of ethanol conversion to butenes, these unique Zr centers concurrently catalyze the dehydration of ethanol and promote the C–C coupling of acetaldehyde. Upon selective poisoning with potassium acetate, these open site Zr species were converted into enclosed (Si–O)3-Zr-OK configuration, which suppressed both ethanol dehydration and acetaldehyde C–C coupling activities. Thus, an optimum level of potassium doping was found to achieve the balance of ethanol dehydration and C–C coupling activity. With this, 85% C3+ olefin selectivity at ∼98% ethanol conversion was achieved over the Cu-loaded Zr-SBA-16 catalyst in ethanol upgrading to butene-rich C3+ olefins. The discovery of the Brønsted acidity over Zr-SBA-16 provides a new perspective on the acidity of heteroatom-incorporated molecular sieve materials.
{"title":"Regulating the Atypical Brønsted Acidity of Zr-SBA-16 Catalysts for Selective Ethanol Conversion to Butene-Rich C3+ Olefins","authors":"Gan Yu,Wen Zhao,Hao Zeng,Chengsheng Yang,Yanran Cui,Lei Nie,Zhenglong Li","doi":"10.1021/acssuschemeng.5c10236","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10236","url":null,"abstract":"Lewis-acid molecular sieves are essential catalysts for transforming biomass-derived platform molecules into valuable chemicals. However, the Brønsted acidity arising from incorporated Lewis metals has been rarely reported and remains poorly understood. Using Zr-SBA-16 as a model catalyst, we discovered that the open site Zr centers ((Si–O)3–Zr–OH) exhibit an atypical Brønsted acidity, distinct from the conventional Brønsted acidity arising from Al atoms in the Si–OH–Al framework of zeolites. In a model reaction of ethanol conversion to butenes, these unique Zr centers concurrently catalyze the dehydration of ethanol and promote the C–C coupling of acetaldehyde. Upon selective poisoning with potassium acetate, these open site Zr species were converted into enclosed (Si–O)3-Zr-OK configuration, which suppressed both ethanol dehydration and acetaldehyde C–C coupling activities. Thus, an optimum level of potassium doping was found to achieve the balance of ethanol dehydration and C–C coupling activity. With this, 85% C3+ olefin selectivity at ∼98% ethanol conversion was achieved over the Cu-loaded Zr-SBA-16 catalyst in ethanol upgrading to butene-rich C3+ olefins. The discovery of the Brønsted acidity over Zr-SBA-16 provides a new perspective on the acidity of heteroatom-incorporated molecular sieve materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098129","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 : 2026-02-02DOI: 10.1021/acssuschemeng.5c10711
Eriko Yamada, Christof Brändli, Hirotaka Ejima
The incorporation of small, rigid fillers can effectively reduce stress concentrations in the materials. Nanocellulose has attracted significant attention as a biobased nanofiller due to increasing environmental concerns. To improve its compatibility with matrix materials, surface hydrophobization of nanocellulose is essential; however, achieving this without complex processes remains a challenge. In this study, we demonstrate a facile and reversible surface modification of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanocrystals (CNCs) via metal-phenolic networks (MPNs). The CNCs derived from tunicates were coated with MPNs formed from tannic acid (TA) and Fe3+ in water. Following the MPN coating, octadecylamine (ODA) was covalently bonded to TA, increasing the CNC surface hydrophobicity. ODA was attached at the 3-position of the galloyl moiety of TA. After modification with ODA, the CNCs became nondispersible in water but dispersible in organic solvents including ethanol. The surface coverage of CNCs, estimated using a quartz crystal microbalance (QCM), was 86%. Treatment with HCl solution effectively disassembled the coating, and inductively coupled plasma mass spectrometry (ICP-MS) analysis confirmed that more than 95% of Fe3+ was removed from the CNC surfaces. These results highlight the potential of MPNs as primer layers for the reversible surface modification of nanocellulose.
{"title":"Reversible Surface Functionalization of Cellulose Nanocrystals Mediated by Metal-Phenolic Networks","authors":"Eriko Yamada, Christof Brändli, Hirotaka Ejima","doi":"10.1021/acssuschemeng.5c10711","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c10711","url":null,"abstract":"The incorporation of small, rigid fillers can effectively reduce stress concentrations in the materials. Nanocellulose has attracted significant attention as a biobased nanofiller due to increasing environmental concerns. To improve its compatibility with matrix materials, surface hydrophobization of nanocellulose is essential; however, achieving this without complex processes remains a challenge. In this study, we demonstrate a facile and reversible surface modification of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanocrystals (CNCs) via metal-phenolic networks (MPNs). The CNCs derived from tunicates were coated with MPNs formed from tannic acid (TA) and Fe<sup>3+</sup> in water. Following the MPN coating, octadecylamine (ODA) was covalently bonded to TA, increasing the CNC surface hydrophobicity. ODA was attached at the 3-position of the galloyl moiety of TA. After modification with ODA, the CNCs became nondispersible in water but dispersible in organic solvents including ethanol. The surface coverage of CNCs, estimated using a quartz crystal microbalance (QCM), was 86%. Treatment with HCl solution effectively disassembled the coating, and inductively coupled plasma mass spectrometry (ICP-MS) analysis confirmed that more than 95% of Fe<sup>3+</sup> was removed from the CNC surfaces. These results highlight the potential of MPNs as primer layers for the reversible surface modification of nanocellulose.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097824","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 : 2026-02-01DOI: 10.1021/acssuschemeng.5c08634
Kimberly Ogden, Harvis Saka
This study presents a detailed carbon balance analysis of guayule (Parthenium argentatum), a drought-tolerant shrub with significant potential for carbon credit (CC) generation through its biomass-derived products. Guayule biomass was fractionated into rubber, resin, and bagasse, with further processing of resin into terpenes and residuals and bagasse into biofuels and particle board. The carbon content was quantified using elemental analysis and gas chromatography–mass spectrometry, and conversion pathways were evaluated using literature data. Results indicate that up to 3.2 CCs/ha can be allocated to rubber, 6 CCs/ha to resin-based products, and 24 CCs/ha to biofuels, with an additional 17 CCs/ha credited to growers using no-til practices and biochar application. This analysis provides a transparent framework for tracking carbon through the guayule supply chain, supporting accurate CC allocation and helping to prevent double counting. The findings offer practical insights into how mass balance analysis enhances emissions trading systems and advances sustainable agricultural practices.
{"title":"Carbon Allocation throughout the Supply Chain: Test Case Guayule","authors":"Kimberly Ogden, Harvis Saka","doi":"10.1021/acssuschemeng.5c08634","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c08634","url":null,"abstract":"This study presents a detailed carbon balance analysis of guayule (<i>Parthenium argentatum</i>), a drought-tolerant shrub with significant potential for carbon credit (CC) generation through its biomass-derived products. Guayule biomass was fractionated into rubber, resin, and bagasse, with further processing of resin into terpenes and residuals and bagasse into biofuels and particle board. The carbon content was quantified using elemental analysis and gas chromatography–mass spectrometry, and conversion pathways were evaluated using literature data. Results indicate that up to 3.2 CCs/ha can be allocated to rubber, 6 CCs/ha to resin-based products, and 24 CCs/ha to biofuels, with an additional 17 CCs/ha credited to growers using no-til practices and biochar application. This analysis provides a transparent framework for tracking carbon through the guayule supply chain, supporting accurate CC allocation and helping to prevent double counting. The findings offer practical insights into how mass balance analysis enhances emissions trading systems and advances sustainable agricultural practices.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"90 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098333","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 : 2026-02-01DOI: 10.1021/acssuschemeng.5c12587
Yuqi Zhang, Kaidi Zhang, Jiamin Dong, Dan Wu, Jieli Li, Zhuzi Chen, Liying Yao, Rong Jiang, Gongjun Yang, Shunli Ji
The ecological and life-health risks posed by excessive humic acid (HA) accumulation and persistent antibiotic contamination are urgent challenges requiring synergistic solutions. Herein, based on the amide reactions between the numerous carboxyl functional groups of biobased HA and the hollow mesoporous Fe3O4–NH2 nanoparticles, the multifunctional magnetic nanocomposite (Fe3O4@HA) was developed to overcome these challenges. Based on the synergistic advantages of the components, a green and economically Fe3O4@HA-based magnetic dispersive solid-phase extraction method was first constructed for the enrichment and detection of fluoroquinolone antibiotics (FQs) in three complex matrices. Satisfactory recovery rates were shown over a wide concentration range (0.005–50 μg·L–1). Particularly, thanks to the protective and well-dispersed nature provided by HA, Fe3O4@HA exhibits long-lasting and excellent degradation ability for antibiotics, while effectively reducing the leakage of Fe ions. Notably, the spent Fe3O4@HA serves dual environmental benefits, preventing secondary pollution through magnetic recovery and acting as a nutrient-rich soil amendment. This “three-birds-with-one-stone” strategy provides a feasible solution for eliminating the hazards of excessive HA, establishes a sustainable platform for long-term antibiotic monitoring and removal, and realizes agricultural reuse as well as the circular economy. This work is of great significance for promoting the rational use of renewable resources and sustainable development.
{"title":"Magnetic Trinity Platform Based on Renewable Humic Acid for Closed-Loop Management of Antibiotics via Adsorption-Detection-Catalytic Degradation Synergy","authors":"Yuqi Zhang, Kaidi Zhang, Jiamin Dong, Dan Wu, Jieli Li, Zhuzi Chen, Liying Yao, Rong Jiang, Gongjun Yang, Shunli Ji","doi":"10.1021/acssuschemeng.5c12587","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12587","url":null,"abstract":"The ecological and life-health risks posed by excessive humic acid (HA) accumulation and persistent antibiotic contamination are urgent challenges requiring synergistic solutions. Herein, based on the amide reactions between the numerous carboxyl functional groups of biobased HA and the hollow mesoporous Fe<sub>3</sub>O<sub>4</sub>–NH<sub>2</sub> nanoparticles, the multifunctional magnetic nanocomposite (Fe<sub>3</sub>O<sub>4</sub>@HA) was developed to overcome these challenges. Based on the synergistic advantages of the components, a green and economically Fe<sub>3</sub>O<sub>4</sub>@HA-based magnetic dispersive solid-phase extraction method was first constructed for the enrichment and detection of fluoroquinolone antibiotics (FQs) in three complex matrices. Satisfactory recovery rates were shown over a wide concentration range (0.005–50 μg·L<sup>–1</sup>). Particularly, thanks to the protective and well-dispersed nature provided by HA, Fe<sub>3</sub>O<sub>4</sub>@HA exhibits long-lasting and excellent degradation ability for antibiotics, while effectively reducing the leakage of Fe ions. Notably, the spent Fe<sub>3</sub>O<sub>4</sub>@HA serves dual environmental benefits, preventing secondary pollution through magnetic recovery and acting as a nutrient-rich soil amendment. This “three-birds-with-one-stone” strategy provides a feasible solution for eliminating the hazards of excessive HA, establishes a sustainable platform for long-term antibiotic monitoring and removal, and realizes agricultural reuse as well as the circular economy. This work is of great significance for promoting the rational use of renewable resources and sustainable development.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098328","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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