Simultaneously achieving a high recoverable energy density (Wrec) and efficiency (η) in dielectric ceramic capacitors is crucial for advancing energy storage applications. Herein, a design strategy is adopted that involves regulating the parameters of structure distortion (δ) and tolerance factor (t) in (Na0.5Bi0.5)TiO3 (BNT)-based relaxor ferroelectric ceramics. Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) is doped into the BNT matrix to maintain a large δ and enhance maximum polarization (Pmax), while BaZrO3 (BZ) is introduced to tune the t value close to unity, thereby improving η. To validate this strategy, (1–x)(0.75Na0.5Bi0.5TiO3-0.25Ba0.85Ca0.15Zr0.1Ti0.9O3)-xBaZrO3 (BNT-BCZT-xBZ) ceramics are fabricated and characterized. The optimized BNT-BCZT-0.15BZ sample exhibits excellent energy storage performance with an ultrahigh Wrec (∼10.31 J/cm3) and a high η (∼80.4%). Comprehensive structural and microstructural characterizations reveal that the multielement substitutions at both A- and B-sites result in the miniaturization of ferroelectric domains and form highly dynamic polar nanoregions (PNRs), which are crucial for the enhanced performance. Furthermore, the optimal ceramic demonstrates excellent frequency and temperature stability along with a fast charge–discharge speed (t0.9 ∼ 33 ns) and a high power density (∼391.9 MW cm–3). This work provides new perspectives for the development of dielectric energy storage materials.
{"title":"High Energy-Storage Performance and Superior Stability in Novel (Na0.5Bi0.5)TiO3-Based Relaxor Ferroelectric Ceramics by Regulating Structural Distortion and Tolerance Factor Parameters","authors":"Dandan Han,Yunfei Ma,Longxiao Duan,Yaosheng Liu,Pengfei Ma,Changhao Wang,Fanxu Meng","doi":"10.1021/acssuschemeng.6c00892","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00892","url":null,"abstract":"Simultaneously achieving a high recoverable energy density (Wrec) and efficiency (η) in dielectric ceramic capacitors is crucial for advancing energy storage applications. Herein, a design strategy is adopted that involves regulating the parameters of structure distortion (δ) and tolerance factor (t) in (Na0.5Bi0.5)TiO3 (BNT)-based relaxor ferroelectric ceramics. Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) is doped into the BNT matrix to maintain a large δ and enhance maximum polarization (Pmax), while BaZrO3 (BZ) is introduced to tune the t value close to unity, thereby improving η. To validate this strategy, (1–x)(0.75Na0.5Bi0.5TiO3-0.25Ba0.85Ca0.15Zr0.1Ti0.9O3)-xBaZrO3 (BNT-BCZT-xBZ) ceramics are fabricated and characterized. The optimized BNT-BCZT-0.15BZ sample exhibits excellent energy storage performance with an ultrahigh Wrec (∼10.31 J/cm3) and a high η (∼80.4%). Comprehensive structural and microstructural characterizations reveal that the multielement substitutions at both A- and B-sites result in the miniaturization of ferroelectric domains and form highly dynamic polar nanoregions (PNRs), which are crucial for the enhanced performance. Furthermore, the optimal ceramic demonstrates excellent frequency and temperature stability along with a fast charge–discharge speed (t0.9 ∼ 33 ns) and a high power density (∼391.9 MW cm–3). This work provides new perspectives for the development of dielectric energy storage materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506236","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 : 2026-03-25DOI: 10.1021/acssuschemeng.5c12264
Sudeshna Pal,Dipanjan Shaw,Prasanta Kumar Das
Carbonic anhydrase (CA) is an efficient enzyme for mitigating the emission of CO2. Herein, a Zn-coordinated supramolecular organohydrogel has been developed from histidine-containing dipeptide gelators to mimic the activity of CA for efficient CO2 capture and its conversion. By changing the headgroup at the C-terminal and protection at the N-terminal of phenylalanine–histidine dipeptides, organohydrogels were developed in DMSO/water in the absence and presence of Zn salts (Cl–, OH–, NO3–, OAc–). Gelation efficiency of gelators (G1–G4) varied from 1.0 to 10.0% w/v in different v/v compositions of DMSO–water. Gelation ability in the presence of varying Zn salts and their rheological studies showed that gelator G4 (Palm(C16)-Phe-His-OH) formed the most efficient organohydrogel along with all four Zn salts in 2:1 (v/v) DMSO–water, having a minimum gelation concentration (MGC) 0.8% w/v. The 1H NMR spectra, mass spectroscopy, elemental analysis in the XPS study, EPR, and FTIR studies confirmed the formation of Zn-coordinated organohydrogel of G4–ZnCl2 at a 3:1 mol ratio of the gelator and Zn salt. Lowering of MGC in the presence of Zn salt and the corresponding XRD analysis assured the contribution of the metal ion in improving the gelation efficiency. The histidine moiety of gelators might have made efficient coordination with the metal center and can act as a mimic of the active site of metalloenzyme CA. Subsequently, the CA-mimicking activity of Zn-coordinated gels of G4 was monitored by measuring the hydrolysis of p-nitrophenyl acetate (p-NPA). Among all Zn-coordinated gels of G4 with varying Zn salts, G4–ZnCl2 exhibited the highest conversion rate (2.53 ± 0.05 μM/min), which was 2.14–6.17 times higher than those of other Zn salt-coordinated gels and 8.4–21 times higher than that of only gel or Zn salt. Importantly, GC-TCD experiments confirmed that G4–ZnCl2 can efficiently absorb ∼43% CO2 within its three-dimensional (3D) porous structure, which was further converted into CaCO3 upon addition of CaCl2. Hence, G4–ZnCl2 provides a sustainable platform that can both absorb and transform CO2.
{"title":"Histidine Tethered Dipeptide Based Zn-Coordinated Organohydrogel: Potential Biomimic for CO2 Capture and Conversion","authors":"Sudeshna Pal,Dipanjan Shaw,Prasanta Kumar Das","doi":"10.1021/acssuschemeng.5c12264","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c12264","url":null,"abstract":"Carbonic anhydrase (CA) is an efficient enzyme for mitigating the emission of CO2. Herein, a Zn-coordinated supramolecular organohydrogel has been developed from histidine-containing dipeptide gelators to mimic the activity of CA for efficient CO2 capture and its conversion. By changing the headgroup at the C-terminal and protection at the N-terminal of phenylalanine–histidine dipeptides, organohydrogels were developed in DMSO/water in the absence and presence of Zn salts (Cl–, OH–, NO3–, OAc–). Gelation efficiency of gelators (G1–G4) varied from 1.0 to 10.0% w/v in different v/v compositions of DMSO–water. Gelation ability in the presence of varying Zn salts and their rheological studies showed that gelator G4 (Palm(C16)-Phe-His-OH) formed the most efficient organohydrogel along with all four Zn salts in 2:1 (v/v) DMSO–water, having a minimum gelation concentration (MGC) 0.8% w/v. The 1H NMR spectra, mass spectroscopy, elemental analysis in the XPS study, EPR, and FTIR studies confirmed the formation of Zn-coordinated organohydrogel of G4–ZnCl2 at a 3:1 mol ratio of the gelator and Zn salt. Lowering of MGC in the presence of Zn salt and the corresponding XRD analysis assured the contribution of the metal ion in improving the gelation efficiency. The histidine moiety of gelators might have made efficient coordination with the metal center and can act as a mimic of the active site of metalloenzyme CA. Subsequently, the CA-mimicking activity of Zn-coordinated gels of G4 was monitored by measuring the hydrolysis of p-nitrophenyl acetate (p-NPA). Among all Zn-coordinated gels of G4 with varying Zn salts, G4–ZnCl2 exhibited the highest conversion rate (2.53 ± 0.05 μM/min), which was 2.14–6.17 times higher than those of other Zn salt-coordinated gels and 8.4–21 times higher than that of only gel or Zn salt. Importantly, GC-TCD experiments confirmed that G4–ZnCl2 can efficiently absorb ∼43% CO2 within its three-dimensional (3D) porous structure, which was further converted into CaCO3 upon addition of CaCl2. Hence, G4–ZnCl2 provides a sustainable platform that can both absorb and transform CO2.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506237","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}
Engineering the location of framework aluminum (AlF) within MFI zeolites offers an effective strategy to improve para-xylene (PX) selectivity in tandem CO2–toluene conversion. Here, a ZnZrOx catalyst for CO2 hydrogenation was combined with ZSM-5 zeolites featuring controlled AlF distributions for toluene methylation. Using distinct organic structure-directing agents (OSDAs), AlF was preferentially incorporated into the straight and sinusoidal channels, thereby enhancing Brønsted acid site density in these regions. Catalytic evaluation revealed that the conventional tetra-n-propylammonium-derived zeolite produced xylene isomers in the thermodynamic ratio (p-X 24.2%, m-X 49.5%, and o-X 26.3%). In contrast, the n-butylamine-derived zeolite increased PX selectivity to 39.3%, while the ethylenediamine-derived sample achieved 77.0% PX, with m-X and o-X suppressed to 5.3% and 17.7%, respectively. These enhancements are attributed to steric and diffusional constraints imposed by the channel topology. In situ DRIFTS confirmed that CO2 was first hydrogenated to methanol/methoxy intermediates over ZnZrOx, which subsequently diffused into the zeolite phase to react with toluene. These findings demonstrate that OSDA-directed Al location engineering is an effective approach for selective aromatic synthesis and highlight its potential in sustainable CO2 valorization.
{"title":"Framework Al Location Engineering in MFI Zeolites for Tandem Catalytic Conversion of CO2 and Toluene to Para-Xylene","authors":"Yingjie Guan,Abel Xicola Escriche,Li He,Bin Zhou,Yuhao Song,Huilin Chen,Jisheng Yu,Xin Gao,Jinglong Pu,Dongxue Yi,Xuedong Zhu,Fan Yang","doi":"10.1021/acssuschemeng.6c01002","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c01002","url":null,"abstract":"Engineering the location of framework aluminum (AlF) within MFI zeolites offers an effective strategy to improve para-xylene (PX) selectivity in tandem CO2–toluene conversion. Here, a ZnZrOx catalyst for CO2 hydrogenation was combined with ZSM-5 zeolites featuring controlled AlF distributions for toluene methylation. Using distinct organic structure-directing agents (OSDAs), AlF was preferentially incorporated into the straight and sinusoidal channels, thereby enhancing Brønsted acid site density in these regions. Catalytic evaluation revealed that the conventional tetra-n-propylammonium-derived zeolite produced xylene isomers in the thermodynamic ratio (p-X 24.2%, m-X 49.5%, and o-X 26.3%). In contrast, the n-butylamine-derived zeolite increased PX selectivity to 39.3%, while the ethylenediamine-derived sample achieved 77.0% PX, with m-X and o-X suppressed to 5.3% and 17.7%, respectively. These enhancements are attributed to steric and diffusional constraints imposed by the channel topology. In situ DRIFTS confirmed that CO2 was first hydrogenated to methanol/methoxy intermediates over ZnZrOx, which subsequently diffused into the zeolite phase to react with toluene. These findings demonstrate that OSDA-directed Al location engineering is an effective approach for selective aromatic synthesis and highlight its potential in sustainable CO2 valorization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506233","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 : 2026-03-25DOI: 10.1021/acssuschemeng.6c00455
Lei Liu,Ye Yuan,Yuhang Shi,Lingzhun Meng,Zijian Li,Yuji Liu,Yongxing Tang,Wei Huang
The evolution of energetic materials science poses new challenges centered on developing advanced technologies and structures. A new azo-bridged compound with pyrazole and tetrazole moieties featuring nitro groups was synthesized by electrochemical homocoupling of C-amino pyrazole. Green and pollution-free, electrochemical preparation overcomes C-aminopyrazole’s high oxidative sensitivity, effectively avoiding competing pathways like overoxidation, ring degradation, and cleavage under oxidative conditions. The azo-linked four-heterocyclic molecule 3 exhibits encouraging properties as an insensitive energetic material. Compound 3 demonstrates good density (1.86 g/cm3), good detonation velocities (8643 m/s), low impact and friction sensitivity (IS > 40 J, FS > 360 N), and extremely high enthalpies of formation (1301.9 kJ/mol). Theoretical calculations revealed that the low sensitivity of C-linked azopyrazole derivative 3 arises from a reduced surface electrostatic potential and enhanced noncovalent interactions, while the disrupted π-conjugation accounts for its moderate thermal stability. This work provides an efficient green electrochemical synthesis methodology that effectively mitigates the high oxidative sensitivity of C-amino and offers a novel strategy for its coupling reactions in diverse research fields.
{"title":"Electrochemical Homocoupling of C-Amino Pyrazole for Sustainable Synthesis of Azo-Linked Tetracyclic Insensitive Energetic Materials","authors":"Lei Liu,Ye Yuan,Yuhang Shi,Lingzhun Meng,Zijian Li,Yuji Liu,Yongxing Tang,Wei Huang","doi":"10.1021/acssuschemeng.6c00455","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00455","url":null,"abstract":"The evolution of energetic materials science poses new challenges centered on developing advanced technologies and structures. A new azo-bridged compound with pyrazole and tetrazole moieties featuring nitro groups was synthesized by electrochemical homocoupling of C-amino pyrazole. Green and pollution-free, electrochemical preparation overcomes C-aminopyrazole’s high oxidative sensitivity, effectively avoiding competing pathways like overoxidation, ring degradation, and cleavage under oxidative conditions. The azo-linked four-heterocyclic molecule 3 exhibits encouraging properties as an insensitive energetic material. Compound 3 demonstrates good density (1.86 g/cm3), good detonation velocities (8643 m/s), low impact and friction sensitivity (IS > 40 J, FS > 360 N), and extremely high enthalpies of formation (1301.9 kJ/mol). Theoretical calculations revealed that the low sensitivity of C-linked azopyrazole derivative 3 arises from a reduced surface electrostatic potential and enhanced noncovalent interactions, while the disrupted π-conjugation accounts for its moderate thermal stability. This work provides an efficient green electrochemical synthesis methodology that effectively mitigates the high oxidative sensitivity of C-amino and offers a novel strategy for its coupling reactions in diverse research fields.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506235","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 : 2026-03-25DOI: 10.1021/acssuschemeng.6c00030
Anton A. Stepnov,Brenna Norton-Baker,Esteban Lopez-Tavera,Ravindra R. Chowreddy,Vincent G. H. Eijsink,Gregg T. Beckham,Gustav Vaaje-Kolstad
Fast and sensitive analytical methods are the key to efficient screening of plastic-degrading enzymes. Here, we present a streamlined and affordable approach to assess the enzymatic deconstruction of insoluble synthetic polymers by blending them with a fluorescent dye, rhodamine 6G, and we evaluate this screening method using poly(ethylene terephthalate) (PET) as a model material. Our results indicate that enzymatic depolymerization of the rhodamine-doped PET can be observed in a high-throughput fashion by following release of the fluorophore. The fluorescence data obtained during the hydrolysis of rhodamine-doped PET by 14 PET hydrolases, produced with a robotic platform, correlated with the quantitative chromatographic analysis of PET degradation products. Remarkably, the use of the rhodamine-loaded PET substrate resulted in negligibly low background signals even when detecting PETase activity in crude cell lysates, suggesting suitability for screening of a wide variety of samples. Encouraged by these results, we next produced a selection of polyethylene- and nylon-based materials loaded with rhodamine 6G. While rapid leaching of fluorophore observed with nylon substrates limits the utility of the method for detecting nylonase activity, the rhodamine-loaded polyethylene showed promising performance in passive diffusion tests, indicating that this latter substrate may be used to screen for polyolefin-degrading enzymes.
{"title":"Production and Evaluation of Fluorophore-Doped Polymer Substrates to Screen for Plastic-Degrading Enzymes","authors":"Anton A. Stepnov,Brenna Norton-Baker,Esteban Lopez-Tavera,Ravindra R. Chowreddy,Vincent G. H. Eijsink,Gregg T. Beckham,Gustav Vaaje-Kolstad","doi":"10.1021/acssuschemeng.6c00030","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00030","url":null,"abstract":"Fast and sensitive analytical methods are the key to efficient screening of plastic-degrading enzymes. Here, we present a streamlined and affordable approach to assess the enzymatic deconstruction of insoluble synthetic polymers by blending them with a fluorescent dye, rhodamine 6G, and we evaluate this screening method using poly(ethylene terephthalate) (PET) as a model material. Our results indicate that enzymatic depolymerization of the rhodamine-doped PET can be observed in a high-throughput fashion by following release of the fluorophore. The fluorescence data obtained during the hydrolysis of rhodamine-doped PET by 14 PET hydrolases, produced with a robotic platform, correlated with the quantitative chromatographic analysis of PET degradation products. Remarkably, the use of the rhodamine-loaded PET substrate resulted in negligibly low background signals even when detecting PETase activity in crude cell lysates, suggesting suitability for screening of a wide variety of samples. Encouraged by these results, we next produced a selection of polyethylene- and nylon-based materials loaded with rhodamine 6G. While rapid leaching of fluorophore observed with nylon substrates limits the utility of the method for detecting nylonase activity, the rhodamine-loaded polyethylene showed promising performance in passive diffusion tests, indicating that this latter substrate may be used to screen for polyolefin-degrading enzymes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506234","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 : 2026-03-25DOI: 10.1021/acssuschemeng.5c13850
Francesco Del Prete,Francesca Sansone,Francesca Fortunato,Tiziana Esposito,Teresa Mencherini,Annamaria Di Serio,Domenico Ronga,Rita. P. Aquino
An integrated biorefinery model was developed and experimentally validated for the multiproduct valorization of Chlorella vulgaris biomass through the sequential and polarity-driven extraction of high-value bioactive fractions. The extraction of C. vulgaris biomass was based on integration of mechanical disruption with selective aqueous, ethanol-based, and alkaline extraction steps. Six different extraction sequences were applied to high-quality biomass cultivated in an indoor photobioreactor system to obtain polysaccharides (Po), pigments (Pi), and proteins (Pr). The resulting fractions were compared in terms of extraction yields, biochemical marker content, and postextraction residual biomass also characterized in term of morphology and solid state. The novelty of the work lies in a systematic comparison of all six possible extraction permutations within the polarity-driven cascade. Our results demonstrate that, among all configurations, the Po → Pi → Pr sequence provided the most balanced outcome, yielding 20.7% polysaccharides, 16.2% pigments, and 27.6% proteins. At the same time, 36% (w/w) of residual biomass was preserved, a significantly higher retention compared to the most existing strategies relying on lipid-first or fixed-sequence extraction schemes. The considerable residual biomass (36% w/w), retained after processing remains available for potential further valorization, including lipid extraction or agronomic reuse as a biostimulant. Biochemical integrity was maintained across all fractions, as confirmed by reference markers: 411.07 mg g–1 total carbohydrates (Dubois method), 392.53 mg g–1 proteins (Bradford assay), and 0.88 mg g–1 lutein (UV–Vis). Overall, the findings indicate that a rationally designed cascade biorefinery can maximize product recovery, minimize material losses, and preserve extract quality.
{"title":"Cascade Biorefinery of Chlorella vulgaris: Optimized Extraction Sequencing for Sustainable Whole-Biomass Valorization","authors":"Francesco Del Prete,Francesca Sansone,Francesca Fortunato,Tiziana Esposito,Teresa Mencherini,Annamaria Di Serio,Domenico Ronga,Rita. P. Aquino","doi":"10.1021/acssuschemeng.5c13850","DOIUrl":"https://doi.org/10.1021/acssuschemeng.5c13850","url":null,"abstract":"An integrated biorefinery model was developed and experimentally validated for the multiproduct valorization of Chlorella vulgaris biomass through the sequential and polarity-driven extraction of high-value bioactive fractions. The extraction of C. vulgaris biomass was based on integration of mechanical disruption with selective aqueous, ethanol-based, and alkaline extraction steps. Six different extraction sequences were applied to high-quality biomass cultivated in an indoor photobioreactor system to obtain polysaccharides (Po), pigments (Pi), and proteins (Pr). The resulting fractions were compared in terms of extraction yields, biochemical marker content, and postextraction residual biomass also characterized in term of morphology and solid state. The novelty of the work lies in a systematic comparison of all six possible extraction permutations within the polarity-driven cascade. Our results demonstrate that, among all configurations, the Po → Pi → Pr sequence provided the most balanced outcome, yielding 20.7% polysaccharides, 16.2% pigments, and 27.6% proteins. At the same time, 36% (w/w) of residual biomass was preserved, a significantly higher retention compared to the most existing strategies relying on lipid-first or fixed-sequence extraction schemes. The considerable residual biomass (36% w/w), retained after processing remains available for potential further valorization, including lipid extraction or agronomic reuse as a biostimulant. Biochemical integrity was maintained across all fractions, as confirmed by reference markers: 411.07 mg g–1 total carbohydrates (Dubois method), 392.53 mg g–1 proteins (Bradford assay), and 0.88 mg g–1 lutein (UV–Vis). Overall, the findings indicate that a rationally designed cascade biorefinery can maximize product recovery, minimize material losses, and preserve extract quality.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"337 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506238","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 : 2026-03-24DOI: 10.1021/acssuschemeng.6c00773
Mengyuan Shang, Lvlv Ji, Yanjun Wen, Tao Wang, Jianying Wang, Zuofeng Chen, Sheng Wang
Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions offers a promising alternative to the energy-intensive Haber–Bosch process for ammonia synthesis. However, the low solubility of N2 and high proton activity in aqueous electrolytes lead to limited yield rates and poor selectivity. Inspired by the structure and function of natural nitrogenase, here, we adopt a “Solid Catalysts with Ionic Liquid Layer” (SCILL) strategy to tailor the liquid microenvironment at the catalyst surface via ionic liquid (IL) coating. An IL of [P6,6,6,14][NTf2], with high N2 solubility and strong hydrophobicity, is immobilized onto a porous copper catalyst (Cu MFs). The resulting hydrophobic IL layer effectively reduces the local proton concentration and availability while simultaneously enriching and activating N2 at the catalytic interface. Compared to the pristine Cu MFs, the modified electrode ([P6,6,6,14][NTf2]@Cu MFs) exhibits a substantially improved NRR performance in 0.05 M H2SO4. This enhancement is further systematically corroborated through a combination of in situ characterizations and theoretical investigations.
环境条件下的电催化氮还原反应（NRR）为氨合成的高能耗Haber-Bosch工艺提供了一个有希望的替代方案。然而，N2在水溶液中的溶解度低，质子活性高，导致收率有限，选择性差。受天然氮酶结构和功能的启发，我们采用了“固体催化剂与离子液体层”（SCILL）策略，通过离子液体（IL）涂层来定制催化剂表面的液体微环境。将具有高N2溶解度和强疏水性的[p6,6,14][NTf2] IL固定在多孔铜催化剂（Cu MFs）上。由此产生的疏水IL层有效地降低了局部质子浓度和可用性，同时富集和激活了催化界面上的N2。与原始Cu MFs相比，修饰电极（[P6,6,6,14][NTf2]@Cu MFs）在0.05 M H2SO4中表现出显著提高的NRR性能。通过原位表征和理论研究的结合，进一步系统地证实了这种增强。
{"title":"A Bioinspired Strategy for Enhancing Nitrogen Fixation Using Hydrophobic Ionic Liquids","authors":"Mengyuan Shang, Lvlv Ji, Yanjun Wen, Tao Wang, Jianying Wang, Zuofeng Chen, Sheng Wang","doi":"10.1021/acssuschemeng.6c00773","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00773","url":null,"abstract":"Electrocatalytic nitrogen reduction reaction (NRR) under ambient conditions offers a promising alternative to the energy-intensive Haber–Bosch process for ammonia synthesis. However, the low solubility of N<sub>2</sub> and high proton activity in aqueous electrolytes lead to limited yield rates and poor selectivity. Inspired by the structure and function of natural nitrogenase, here, we adopt a “<i>Solid Catalysts with Ionic Liquid Layer</i>” (SCILL) strategy to tailor the liquid microenvironment at the catalyst surface via ionic liquid (IL) coating. An IL of [P<sub>6,6,6,14</sub>][NTf<sub>2</sub>], with high N<sub>2</sub> solubility and strong hydrophobicity, is immobilized onto a porous copper catalyst (Cu MFs). The resulting hydrophobic IL layer effectively reduces the local proton concentration and availability while simultaneously enriching and activating N<sub>2</sub> at the catalytic interface. Compared to the pristine Cu MFs, the modified electrode ([P<sub>6,6,6,14</sub>][NTf<sub>2</sub>]@Cu MFs) exhibits a substantially improved NRR performance in 0.05 M H<sub>2</sub>SO<sub>4</sub>. This enhancement is further systematically corroborated through a combination of <i>in situ</i> characterizations and theoretical investigations.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506581","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 : 2026-03-24DOI: 10.1021/acssuschemeng.5c13628
Daniel Andrés-Sanz, Sara Arteche Echeverría, Carine Vergne-Vaxelaire, Fernando López-Gallego
β-Amino esters are key intermediates in pharmaceuticals, polymers, and semisynthetic proteins; however, their enantioselective synthesis remains challenging. Amine dehydrogenases (AmDHs) enable atom-efficient reductive amination (ARA) using ammonia, but their stability limits process intensification. We identified two AmDHs from Cystobacter fuscus (an engineered variant W145A) and Streptomyces sp. that asymmetrically aminate β-keto esters using NAD(P)H. Both enzymes were coimmobilized with their cofactor and glucose dehydrogenase (GDH) on agarose-based macroporous beads coated with cationic polymers, generating self-sufficient heterogeneous biocatalysts (ssHB) requiring no external NAD(P)H. The most productive systems operated in packed-bed reactors to aminate ethyl acetoacetate continuously, reaching 90% yield and >99% ee (S). Space-time yield achieved a maximum of 12.1 g L–1 d–1. Yields declined after 24 h, dropping below 20%. Reducing the ammonium concentration from 1 to 0.2 M improved operational stability 4.2 times at the expense of productivity, which decreased 9-fold. These results support the development of robust self-sufficient amine dehydrogenase immobilized systems for reductive amination at low ammonium levels without added cofactors.
β-氨基酯是药物、聚合物和半合成蛋白质的关键中间体；然而，它们的对映选择性合成仍然具有挑战性。胺脱氢酶（AmDHs）能够利用氨进行原子高效的还原性胺化（ARA），但其稳定性限制了过程的强化。我们从fuscus Cystobacter（一种工程变体W145A）和Streptomyces sp.中鉴定出两种AmDHs，它们使用NAD(P)H不对称地胺化β-酮酯。这两种酶与其辅助因子和葡萄糖脱氢酶（GDH）共同固定在涂有阳离子聚合物的琼脂糖基大孔珠上，产生不需要外部NAD(P)H的自给自足的非均相生物催化剂（ssHB）。最高产的系统在填充床反应器中连续胺化乙酰乙酸乙酯，收率达到90%，ee (S)达到99%。时空产率最高可达12.1 g L-1 d-1。24 h后产量下降，降至20%以下。将氨浓度从1 M降低到0.2 M，操作稳定性提高4.2倍，但生产率降低了9倍。这些结果支持开发强大的自给自足的胺脱氢酶固定系统，用于在低铵水平下不添加辅助因子的还原性胺化。
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Pub Date : 2026-03-23DOI: 10.1021/acssuschemeng.5c13044
Xuemei Xiao, Wei Shao, Xiaoman Ye, Sheng Liu
The practical deployment of aqueous zinc-ion batteries is severely hindered by parasitic reactions and dendrite growth at the zinc metal anode, making advanced electrolyte engineering a critical pursuit. In this work, an efficient camphor-derived electrolyte additive, sodium camphorsulfonate, was developed to significantly improve the electrochemical performance of aqueous zinc-ion batteries by synergistically regulating the Zn2+ ion solvation microenvironment and directing the strong Zn(002) deposition texture. The efficacy of the trace sodium camphorsulfonate additive is demonstrated by an ultralong cycling lifespan of 7450 h and a cumulative plated capacity of 11.2 Ah cm–2 for Zn||Zn symmetric cells (3 mA cm–2, 1 mAh cm–2), and is further corroborated by the 72.5% capacity retention of Zn||V2O5·nH2O full cells after 2000 cycles at 2 A g–1. This study establishes a paradigm for harnessing natural compounds in electrolyte engineering, thereby guiding the development of sustainable, high-performance batteries.
锌金属阳极的寄生反应和枝晶生长严重阻碍了水性锌离子电池的实际部署，这使得先进的电解质工程成为一个关键的追求。本研究开发了一种高效的樟脑衍生电解质添加剂——樟脑磺酸钠，通过协同调节Zn2+离子溶剂化微环境和引导强Zn（002）沉积织体，显著改善了水性锌离子电池的电化学性能。微量樟磺酸钠添加剂对Zn||锌对称电池（3 mA cm-2, 1 mAh cm-2）的超长循环寿命为7450 h，累计镀容量为11.2 Ah cm-2，在2 a g-1下循环2000次后，Zn||V2O5·nH2O充满电池的容量保持率为72.5%。这项研究为在电解质工程中利用天然化合物建立了一个范例，从而指导了可持续、高性能电池的发展。
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Pub Date : 2026-03-23DOI: 10.1021/acssuschemeng.6c00517
Zikun Yang, HaoZe Liu, Xihui Yang, Anyu Zhang, Sha Sa, Zhao Wang
Herein, a universal low-temperature plasma method is developed to rapidly convert metal–organic frameworks into highly active photocatalysts for hazardous antibiotic degradation within minutes. Using Hong Kong University of Science and Technology-1 (HKUST-1) as a model precursor, plasma-induced ligand removal simultaneously triggers in situ redox reconstruction, yielding a Cu@Cu2O/CuO core–shell heterostructure with abundant heterointerfaces. The optimized catalyst (HKUST-1-D-10) exhibits enhanced surface area (7.49 m2·g–1 vs 4.40 m2·g–1 for thermally derived HKUST-1-C-550), narrowed bandgap (1.56 eV vs 1.84 eV), and prolonged charge carrier lifetime (2.52 ns). It achieves 99.4% tetracycline degradation within 20 min under visible light, 4.1 times higher than HKUST-1-C-550, and remains at 97% after four cycles. Experimental and density functional theory calculations reveal strong internal electric fields at the Cu/Cu2O and Cu2O/CuO interfaces, constructing an efficient S-scheme charge transfer pathway. This architecture preserves highly reactive electrons and holes, while metallic Cu serves as an electron sink to suppress recombination and stabilize Cu2O. Reactive species identification confirms the dominant roles of superoxide radicals and holes. Degradation pathway and toxicity assessments demonstrate progressive detoxification of tetracycline intermediates. The plasma strategy is further validated on Zeolitic Imidazolate Framework-8 (ZIF-8) and Materials of Institute Lavoisier-125(Ti) (MIL-125-Ti), highlighting its general applicability for hazardous pollutant remediation.
本文开发了一种通用的低温等离子体方法，可以在几分钟内将金属有机框架快速转化为高活性光催化剂，用于有害抗生素的降解。以香港科技大学1号（HKUST-1）为模型前体，等离子体诱导的配体去除同时触发原位氧化还原重建，产生具有丰富异质界面的Cu@Cu2O/CuO核壳异质结构。优化后的催化剂（HKUST-1-D-10）表面积增大（7.49 m2·g-1 vs 4.40 m2·g-1），带隙缩小（1.56 eV vs 1.84 eV），载流子寿命延长（2.52 ns）。在可见光下，它在20分钟内达到99.4%的四环素降解，比HKUST-1-C-550高4.1倍，并且在四个循环后仍保持在97%。实验和密度泛函理论计算表明，Cu/Cu2O和Cu2O/CuO界面处存在强大的内部电场，构建了有效的S-scheme电荷转移途径。这种结构保留了高活性电子和空穴，而金属Cu作为电子汇抑制复合和稳定Cu2O。活性物质的鉴定证实了超氧自由基和空穴的主导作用。降解途径和毒性评估表明四环素中间体具有逐步解毒作用。等离子体策略在沸石咪唑酸框架-8 （ZIF-8）和材料研究所拉瓦锡-125(Ti) （MIL-125-Ti）上进一步验证，突出了其对有害污染物修复的一般适用性。
{"title":"Plasma-Synthesized MOF-Derived Cu@Cu2O/CuO Photocatalysts for Rapid Tetracycline Degradation","authors":"Zikun Yang, HaoZe Liu, Xihui Yang, Anyu Zhang, Sha Sa, Zhao Wang","doi":"10.1021/acssuschemeng.6c00517","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c00517","url":null,"abstract":"Herein, a universal low-temperature plasma method is developed to rapidly convert metal–organic frameworks into highly active photocatalysts for hazardous antibiotic degradation within minutes. Using Hong Kong University of Science and Technology-1 (HKUST-1) as a model precursor, plasma-induced ligand removal simultaneously triggers in situ redox reconstruction, yielding a Cu@Cu<sub>2</sub>O/CuO core–shell heterostructure with abundant heterointerfaces. The optimized catalyst (HKUST-1-D-10) exhibits enhanced surface area (7.49 m<sup>2</sup>·g<sup>–1</sup> vs 4.40 m<sup>2</sup>·g<sup>–1</sup> for thermally derived HKUST-1-C-550), narrowed bandgap (1.56 eV vs 1.84 eV), and prolonged charge carrier lifetime (2.52 ns). It achieves 99.4% tetracycline degradation within 20 min under visible light, 4.1 times higher than HKUST-1-C-550, and remains at 97% after four cycles. Experimental and density functional theory calculations reveal strong internal electric fields at the Cu/Cu<sub>2</sub>O and Cu<sub>2</sub>O/CuO interfaces, constructing an efficient S-scheme charge transfer pathway. This architecture preserves highly reactive electrons and holes, while metallic Cu serves as an electron sink to suppress recombination and stabilize Cu<sub>2</sub>O. Reactive species identification confirms the dominant roles of superoxide radicals and holes. Degradation pathway and toxicity assessments demonstrate progressive detoxification of tetracycline intermediates. The plasma strategy is further validated on Zeolitic Imidazolate Framework-8 (ZIF-8) and Materials of Institute Lavoisier-125(Ti) (MIL-125-Ti), highlighting its general applicability for hazardous pollutant remediation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506536","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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