Pub Date : 2025-01-16DOI: 10.1021/acssuschemeng.4c10171
Hiba Azim, Amy-Louise Johnston, Morag Nixon, John Luke Woodliffe, Romano Theunissen, Reshma Suresh, Subarna Sivapalan, Jack Bobo, Peter Licence
We illustrate the importance of early career perspectives and diverse partnerships to develop solutions and overcome key challenges to achieve the Sustainable Development Goals.
{"title":"Collaborating for Impact: Navigating Partnerships and Overcoming Challenges across the Sustainable Development Goals","authors":"Hiba Azim, Amy-Louise Johnston, Morag Nixon, John Luke Woodliffe, Romano Theunissen, Reshma Suresh, Subarna Sivapalan, Jack Bobo, Peter Licence","doi":"10.1021/acssuschemeng.4c10171","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10171","url":null,"abstract":"We illustrate the importance of early career perspectives and diverse partnerships to develop solutions and overcome key challenges to achieve the Sustainable Development Goals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"127 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986021","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 : 2025-01-16DOI: 10.1021/acssuschemeng.4c07538
Andrea Torre-Celeizabal, Francesca Russo, Francesco Galiano, Alberto Figoli, Clara Casado-Coterillo, Aurora Garea
Although membrane technology is widely used in different gas separation applications, membrane manufacturers need to reduce the environmental impact during the membrane fabrication process within the framework of the circular economy by replacing toxic solvents, oil-based polymers, and such by more sustainable alternatives. These include environmentally friendly materials, such as biopolymers, green solvents, and surfactant free porous fillers. This work promotes the use of environmentally sustainable and low toxic alternatives, introducing the novel application of cellulose acetate (CA) as a biopolymer in combination with dimethyl carbonate (DMC) as a greener solvent and different inorganic fillers (Zeolite-A, ETS-10, AM-4 and ZIF-8) prepared without the use of toxic solvents or reactants. Hansen Solubility Parameters were used to confirm the polymer–solvent affinity. Pure CA and mixed matrix membranes were characterized regarding their hydrophilicity by water uptake and contact angle measurements, thermal stability by TGA, mechanical resistance, ATR-FTIR and scanning electron microscopy before evaluating the gas separation performance by single gas permeability of N2, CH4, and CO2. Conditioning of the CA membranes is observed causing reduction of the CO2 permeability values from 12,600 Barrer for the fresh 0.5 wt % ETS-10/CA membrane to 740 Barrer for the 0.5 wt % ZIF-8/CA membranes, corresponding to 24% and 4.2% reductions in CO2/CH4 selectivity and 30% and 24% increase in CO2/N2 selectivity for the same membranes. The structure–relationship was evaluated by phenomenological models which are useful at low filler loading considering flux direction and particle shape and size but still fail to explain the interactions between the DMC green solvent and CA matrix and fillers that are influencing gas transport performance different than other CA membranes.
{"title":"Green Synthesis of Cellulose Acetate Mixed Matrix Membranes: Structure–Function Characterization","authors":"Andrea Torre-Celeizabal, Francesca Russo, Francesco Galiano, Alberto Figoli, Clara Casado-Coterillo, Aurora Garea","doi":"10.1021/acssuschemeng.4c07538","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07538","url":null,"abstract":"Although membrane technology is widely used in different gas separation applications, membrane manufacturers need to reduce the environmental impact during the membrane fabrication process within the framework of the circular economy by replacing toxic solvents, oil-based polymers, and such by more sustainable alternatives. These include environmentally friendly materials, such as biopolymers, green solvents, and surfactant free porous fillers. This work promotes the use of environmentally sustainable and low toxic alternatives, introducing the novel application of cellulose acetate (CA) as a biopolymer in combination with dimethyl carbonate (DMC) as a greener solvent and different inorganic fillers (Zeolite-A, ETS-10, AM-4 and ZIF-8) prepared without the use of toxic solvents or reactants. Hansen Solubility Parameters were used to confirm the polymer–solvent affinity. Pure CA and mixed matrix membranes were characterized regarding their hydrophilicity by water uptake and contact angle measurements, thermal stability by TGA, mechanical resistance, ATR-FTIR and scanning electron microscopy before evaluating the gas separation performance by single gas permeability of N<sub>2</sub>, CH<sub>4</sub>, and CO<sub>2</sub>. Conditioning of the CA membranes is observed causing reduction of the CO<sub>2</sub> permeability values from 12,600 Barrer for the fresh 0.5 wt % ETS-10/CA membrane to 740 Barrer for the 0.5 wt % ZIF-8/CA membranes, corresponding to 24% and 4.2% reductions in CO<sub>2</sub>/CH<sub>4</sub> selectivity and 30% and 24% increase in CO<sub>2</sub>/N<sub>2</sub> selectivity for the same membranes. The structure–relationship was evaluated by phenomenological models which are useful at low filler loading considering flux direction and particle shape and size but still fail to explain the interactions between the DMC green solvent and CA matrix and fillers that are influencing gas transport performance different than other CA membranes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986020","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 : 2025-01-16DOI: 10.1021/acssuschemeng.4c07408
Yuanhui Yao, Kai Wei, Shuang Zhao, Haiqiao Zhou, Bin Kui, Genping Zhu, Wei Wang, Peng Gao, Wei Ye
Electrocatalytically converting nitrates in sewage to ammonia, which can not only achieve the purpose of eliminating sewage but also obtaining valuable ammonia, is an effective supplement to the traditional Haber–Bosch process. Although significant progress has been made in cathodic catalyst design, the overall ammonia electrolysis from nitrate reduction is still restricted by the anodic oxygen evolution heavily relying on noble-based catalysts. Herein, a bimetallic NiFe-MOF nanosheet array electrode is fabricated and serves as an efficient bifunctional catalyst for nitrate reduction and oxygen evolution reactions. The introduction of Fe to Ni-MOF facilitates the formation of a nanosheet structure with higher electrochemical active surface area, as well as provides synergetic NiFe sites. The NiFe-MOF electrode reaches a greatly enhanced ammonia yield rate of 0.94 mmol cm–2 h–1 and a Faradaic efficiency of 90.8% at the cathode and −0.6 V versus reversible hydrogen electrode, as well as an enhanced oxygen evolution reaction with a declined overpotential of 424 mV at 50 mA cm–2. As a bifunctional catalyst in the overall electrocatalysis, the performance of NiFe-MOF in the nitrate reduction reaction is comparable with that using Pt mesh as a counter electrode.
{"title":"Highly Efficient Bifunctional NiFe-MOF Array Electrode for Nitrate Reduction to Ammonia and Oxygen Evolution Reactions","authors":"Yuanhui Yao, Kai Wei, Shuang Zhao, Haiqiao Zhou, Bin Kui, Genping Zhu, Wei Wang, Peng Gao, Wei Ye","doi":"10.1021/acssuschemeng.4c07408","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07408","url":null,"abstract":"Electrocatalytically converting nitrates in sewage to ammonia, which can not only achieve the purpose of eliminating sewage but also obtaining valuable ammonia, is an effective supplement to the traditional Haber–Bosch process. Although significant progress has been made in cathodic catalyst design, the overall ammonia electrolysis from nitrate reduction is still restricted by the anodic oxygen evolution heavily relying on noble-based catalysts. Herein, a bimetallic NiFe-MOF nanosheet array electrode is fabricated and serves as an efficient bifunctional catalyst for nitrate reduction and oxygen evolution reactions. The introduction of Fe to Ni-MOF facilitates the formation of a nanosheet structure with higher electrochemical active surface area, as well as provides synergetic NiFe sites. The NiFe-MOF electrode reaches a greatly enhanced ammonia yield rate of 0.94 mmol cm<sup>–2</sup> h<sup>–1</sup> and a Faradaic efficiency of 90.8% at the cathode and −0.6 V versus reversible hydrogen electrode, as well as an enhanced oxygen evolution reaction with a declined overpotential of 424 mV at 50 mA cm<sup>–2</sup>. As a bifunctional catalyst in the overall electrocatalysis, the performance of NiFe-MOF in the nitrate reduction reaction is comparable with that using Pt mesh as a counter electrode.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"77 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986105","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 : 2025-01-15DOI: 10.1021/acssuschemeng.4c09344
Pilar Bernal-Ortega, Rafal Anyszka, Raffaele di Ronza, Claudia Aurisicchio, Anke Blume
The tire industry is in constant transformation toward the development of more sustainable products while maintaining high performance. Nowadays, one of the most used strategies is the implementation of the circular economy (CE) model, based on the reuse of products, recycling, and conservation of natural resources. One of the main goals of introducing the CE model is to reduce the amount of end of life tires (ELTs) that accumulate every year. For this, improvement in the recycling process of these products is of great importance. To face this challenge, this research aims to improve the recyclability of rubber by a novel approach to apply dynamic imine bonds for the silica–rubber coupling in tire tread compounds as an alternative to the state-of-the-art silica/silane covalent coupling. The formation of this new coupling using an imine bond was achieved by the reaction of an amine and different aromatic aldehydes. Rubber compounds with this new coupling system show a decrease in the wet grip indicator but improved mechanical performance, rolling resistance, superior fatigue behavior, and a high potential for recycling compared with the state-of-the-art compounds.
{"title":"Dynamic Imine Bonds in Tire Tread Compounds: A Pathway to a Circular Economy and Reduced Waste","authors":"Pilar Bernal-Ortega, Rafal Anyszka, Raffaele di Ronza, Claudia Aurisicchio, Anke Blume","doi":"10.1021/acssuschemeng.4c09344","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09344","url":null,"abstract":"The tire industry is in constant transformation toward the development of more sustainable products while maintaining high performance. Nowadays, one of the most used strategies is the implementation of the circular economy (CE) model, based on the reuse of products, recycling, and conservation of natural resources. One of the main goals of introducing the CE model is to reduce the amount of end of life tires (ELTs) that accumulate every year. For this, improvement in the recycling process of these products is of great importance. To face this challenge, this research aims to improve the recyclability of rubber by a novel approach to apply dynamic imine bonds for the silica–rubber coupling in tire tread compounds as an alternative to the state-of-the-art silica/silane covalent coupling. The formation of this new coupling using an imine bond was achieved by the reaction of an amine and different aromatic aldehydes. Rubber compounds with this new coupling system show a decrease in the wet grip indicator but improved mechanical performance, rolling resistance, superior fatigue behavior, and a high potential for recycling compared with the state-of-the-art compounds.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"74 2 Pt 2 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986023","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 : 2025-01-15DOI: 10.1021/acssuschemeng.4c08335
Xiaoyan Feng, Xuewu Gao, Xiaoyu Zhou, Mengke Li, Haifeng Ji, Yingchun Liu, Kai Liu, Dashan Qin, Yi Feng, Xiaojie Zhang
Aqueous zinc ion batteries (AZIBs) show significant advantages in the field of current energy storage. This work has focused on the binder, which is one of the components of the cathode, which enhances the electrochemical behavior of sustainable high-capacity batteries. The polyurea-containing diselenide or disulfide units have been synthesized as a binder for AZIBs, which are named PICSe and PICS. Compared with PVDF, the critical contents of polyurea binders are diselenide/disulfide units, which act as cofactors to coordinate with cation charge carriers, facilitate Zn2+ transfer, and improve redox kinetics. Furthermore, the binders achieve physical cross-linking through free-radical-mediated mechanisms and hydrogen bonding interactions, which result in high mechanical properties of the cathodes. Therefore, the resultant AZIBs based on a PICSe binder show that the discharge specific capacity can be stabilized at about 100 mA h g–1 after 500 cycles at 1 C, and the capacity retention rate is 84.9%.
{"title":"Advanced Polymeric Binders in Aqueous Zinc Ion Batteries: Dynamic Diselenide Bonds as Unique Cofactors for Improving Redox Kinetics","authors":"Xiaoyan Feng, Xuewu Gao, Xiaoyu Zhou, Mengke Li, Haifeng Ji, Yingchun Liu, Kai Liu, Dashan Qin, Yi Feng, Xiaojie Zhang","doi":"10.1021/acssuschemeng.4c08335","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08335","url":null,"abstract":"Aqueous zinc ion batteries (AZIBs) show significant advantages in the field of current energy storage. This work has focused on the binder, which is one of the components of the cathode, which enhances the electrochemical behavior of sustainable high-capacity batteries. The polyurea-containing diselenide or disulfide units have been synthesized as a binder for AZIBs, which are named PICSe and PICS. Compared with PVDF, the critical contents of polyurea binders are diselenide/disulfide units, which act as cofactors to coordinate with cation charge carriers, facilitate Zn<sup>2+</sup> transfer, and improve redox kinetics. Furthermore, the binders achieve physical cross-linking through free-radical-mediated mechanisms and hydrogen bonding interactions, which result in high mechanical properties of the cathodes. Therefore, the resultant AZIBs based on a PICSe binder show that the discharge specific capacity can be stabilized at about 100 mA h g<sup>–1</sup> after 500 cycles at 1 C, and the capacity retention rate is 84.9%.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"74 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981524","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}
l-Asparagine (l-Asn) is an important amino acid with broad applications in food, medicine, fine chemicals, and environmental protection. However, its industrial production is limited by the high cost of raw materials and the low catalytic efficiency of enzymes. In this study, a three-enzyme cascade pathway (FDN) was designed to produce l-Asn, using fumaric acid as the raw material. Within this pathway, EcAsnA was identified as the rate-limiting enzyme and was subsequently engineered using a product rescue strategy to reduce product inhibition by opening the closed gate. The optimal mutant, L109 K/K58R, exhibited a 6.61-fold reduction in product inhibition and a 4.24-fold improvement in catalytic efficiency. This mutant was then integrated into Escherichia coli along with the other two enzymes to construct the optimal recombinant strain E. coli 17. Using diatomite-glutaraldehyde cross-linking immobilized E. coli 17 as a biocatalyst, 267.74 g of l-Asn (with 5.35 g·L–1·h–1 STY, > 99% ee) was produced across 50 batch feedings in 1 L reaction volume. The purity of l-Asn exceeded 99% after isolation and purification. This study demonstrates the effective integration of cascade reaction design, enzyme engineering, and cell immobilization, providing a promising approach for synthesizing high-value products from cost-effective substrates.
{"title":"Efficient Synthesis of l-Asparagine by an Immobilized Three-Enzyme Cascade Reaction System","authors":"Ran Wang, Wei Song, Hangyuan Xu, Jian Wen, Wanqing Wei, Zhaoyang Chen, Guipeng Hu, Cong Gao, Xiaomin Li, Jia Liu, Jing Wu","doi":"10.1021/acssuschemeng.4c08590","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08590","url":null,"abstract":"<span>l</span>-Asparagine (<span>l</span>-Asn) is an important amino acid with broad applications in food, medicine, fine chemicals, and environmental protection. However, its industrial production is limited by the high cost of raw materials and the low catalytic efficiency of enzymes. In this study, a three-enzyme cascade pathway (FDN) was designed to produce <span>l</span>-Asn, using fumaric acid as the raw material. Within this pathway, <i>Ec</i>AsnA was identified as the rate-limiting enzyme and was subsequently engineered using a product rescue strategy to reduce product inhibition by opening the closed gate. The optimal mutant, L109 K/K58R, exhibited a 6.61-fold reduction in product inhibition and a 4.24-fold improvement in catalytic efficiency. This mutant was then integrated into <i>Escherichia coli</i> along with the other two enzymes to construct the optimal recombinant strain <i>E. coli</i> 17. Using diatomite-glutaraldehyde cross-linking immobilized <i>E. coli</i> 17 as a biocatalyst, 267.74 g of <span>l</span>-Asn (with 5.35 g·L<sup>–1</sup>·h<sup>–1</sup> STY, > 99% ee) was produced across 50 batch feedings in 1 L reaction volume. The purity of <span>l</span>-Asn exceeded 99% after isolation and purification. This study demonstrates the effective integration of cascade reaction design, enzyme engineering, and cell immobilization, providing a promising approach for synthesizing high-value products from cost-effective substrates.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"118 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986024","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 : 2025-01-15DOI: 10.1021/acssuschemeng.4c08648
Samantha P. Bunke, Kindle S. Williams, William A. Tarpeh
Low-impact, closed-loop recycling of plastics is crucial to sustainably managing these ubiquitous and resource-intense materials. Our approach aimed to improve chemical recycling by integrating it with electrochemical processes to generate reactants electrochemically and depolymerize plastic in situ, with the objective of reducing both costs and environmental impacts. We investigated electrochemically mediated alkaline hydrolysis and methanolysis of poly(ethylene terephthalate) (PET) to achieve the following advantages over conventional methods: access to more extreme reactivity from applying an electrochemical driving force, application of more moderate operating conditions, and process intensification. Total PET conversion and product yields were measured to systematically investigate the performance effects of the catholyte methanol content, anolyte buffering, and temperature. Leveraging these insights to improve experimental conditions, we achieved 45 mol % PET conversion in 5 h at ambient pressure and relatively moderate temperature (50 °C) in 0.1 M NaClO4 (100 mol % methanol) catholyte and 0.1 M Na3PO4 anolyte.
{"title":"Electrochemically Mediated Alkaline Hydrolysis and Methanolysis of Poly(ethylene terephthalate) (PET)","authors":"Samantha P. Bunke, Kindle S. Williams, William A. Tarpeh","doi":"10.1021/acssuschemeng.4c08648","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08648","url":null,"abstract":"Low-impact, closed-loop recycling of plastics is crucial to sustainably managing these ubiquitous and resource-intense materials. Our approach aimed to improve chemical recycling by integrating it with electrochemical processes to generate reactants electrochemically and depolymerize plastic <i>in situ</i>, with the objective of reducing both costs and environmental impacts. We investigated electrochemically mediated alkaline hydrolysis and methanolysis of poly(ethylene terephthalate) (PET) to achieve the following advantages over conventional methods: access to more extreme reactivity from applying an electrochemical driving force, application of more moderate operating conditions, and process intensification. Total PET conversion and product yields were measured to systematically investigate the performance effects of the catholyte methanol content, anolyte buffering, and temperature. Leveraging these insights to improve experimental conditions, we achieved 45 mol % PET conversion in 5 h at ambient pressure and relatively moderate temperature (50 °C) in 0.1 M NaClO<sub>4</sub> (100 mol % methanol) catholyte and 0.1 M Na<sub>3</sub>PO<sub>4</sub> anolyte.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981528","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 : 2025-01-15DOI: 10.1021/acssuschemeng.4c08516
Xin-Mian Chen, Hong-Yi Li, Cheng-Chao Wei, Jie Cheng, Jiang Diao, Bing Xie, Fusheng Pan
Vanadium slag with high calcium and phosphorus contents (HCPVS) is considered an inadequate raw material for vanadium extraction. Existing vanadium extraction techniques are incapable of efficiently extracting vanadium from HCPVS due to the severe interference of phosphorus and silicon impurities. This study proposed selective chemical etching to remove phosphorus and silicon prior to vanadium extraction under mild conditions. Results showed that the (Mn,Fe)V2O4 spinels in HCPVS were enveloped by a silicate matrix comprising Ca2SiO4–Ca3(PO4)2 and CaFeSiO4. Chemical etching with 1.5 mol/L hydrochloric acid for 30 min effectively removed the silicate matrix, yielding the etched slag for further processing. The etched slag underwent magnesiation roasting at a Mg/V molar ratio of 1.0 for 60 min at 1173 K. Subsequent leaching with sulfuric acid at pH 3.5 and 313 K for 10 min yielded a vanadium extraction efficiency of 93.2%. V2O5 with a purity of 98.6% was obtained after ammonium precipitation and calcination. The resulting leaching residue and wastewater are recyclable, demonstrating the proposed vanadium extraction process as environmentally friendly and sustainable. This study sheds light on a novel way for sustainable resource extraction from low-grade ores.
{"title":"Selective Chemical Etching of Vanadium Slag Enables Highly Efficient and Clean Extraction of Vanadium","authors":"Xin-Mian Chen, Hong-Yi Li, Cheng-Chao Wei, Jie Cheng, Jiang Diao, Bing Xie, Fusheng Pan","doi":"10.1021/acssuschemeng.4c08516","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08516","url":null,"abstract":"Vanadium slag with high calcium and phosphorus contents (HCPVS) is considered an inadequate raw material for vanadium extraction. Existing vanadium extraction techniques are incapable of efficiently extracting vanadium from HCPVS due to the severe interference of phosphorus and silicon impurities. This study proposed selective chemical etching to remove phosphorus and silicon prior to vanadium extraction under mild conditions. Results showed that the (Mn,Fe)V<sub>2</sub>O<sub>4</sub> spinels in HCPVS were enveloped by a silicate matrix comprising Ca<sub>2</sub>SiO<sub>4</sub>–Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> and CaFeSiO<sub>4</sub>. Chemical etching with 1.5 mol/L hydrochloric acid for 30 min effectively removed the silicate matrix, yielding the etched slag for further processing. The etched slag underwent magnesiation roasting at a Mg/V molar ratio of 1.0 for 60 min at 1173 K. Subsequent leaching with sulfuric acid at pH 3.5 and 313 K for 10 min yielded a vanadium extraction efficiency of 93.2%. V<sub>2</sub>O<sub>5</sub> with a purity of 98.6% was obtained after ammonium precipitation and calcination. The resulting leaching residue and wastewater are recyclable, demonstrating the proposed vanadium extraction process as environmentally friendly and sustainable. This study sheds light on a novel way for sustainable resource extraction from low-grade ores.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986019","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 : 2025-01-15DOI: 10.1021/acssuschemeng.4c08871
Padma Priya V. R., Sugapriya S., Antony Haritha Mercy A., Natarajan K., Ramesh Kataria, Ganesh Chandra Nandi
Herein, we present a metal-/catalyst-free, novel approach for S-sulfoximination of sulfenamide. The electrooxidative reactions of sulfenamides and sulfoximines are fast, high-yielding, atom-economical (99.5%), broad-substrate-tolerant, and free from supporting electrolytes. The protocol is ecofriendly and shows wider substrate tolerance than previous reports. The drug-attached sulfenamide (levetiracetam) and sulfoximine (albendazole) also undergo the reaction efficiently. A possible mechanistic pathway is proposed. Fascinatingly, the target products are also obtained via a photochemical approach in the presence of photocatalyst eosin Y.
{"title":"Electrooxidative S-Sulfoximination of Sulfenamide: A Metal-/Catalyst-Free Green Approach","authors":"Padma Priya V. R., Sugapriya S., Antony Haritha Mercy A., Natarajan K., Ramesh Kataria, Ganesh Chandra Nandi","doi":"10.1021/acssuschemeng.4c08871","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08871","url":null,"abstract":"Herein, we present a metal-/catalyst-free, novel approach for <i>S</i>-sulfoximination of sulfenamide. The electrooxidative reactions of sulfenamides and sulfoximines are fast, high-yielding, atom-economical (99.5%), broad-substrate-tolerant, and free from supporting electrolytes. The protocol is ecofriendly and shows wider substrate tolerance than previous reports. The drug-attached sulfenamide (levetiracetam) and sulfoximine (albendazole) also undergo the reaction efficiently. A possible mechanistic pathway is proposed. Fascinatingly, the target products are also obtained via a photochemical approach in the presence of photocatalyst eosin Y.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986022","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}
Acetoin, a promising bio-based platform chemical, is mainly produced through chemical synthesis. Given the increasing attention to nonrenewable resources, developing safe and efficient microbial technologies for acetoin production is necessary. This study redirected more carbon flux to acetoin synthesis by deleting nonessential functional genes in Bacillus subtilis. Subsequently, based on spatial modulation engineering, the biological regulatory elements and DNA scaffold were used to enhance the co-catalytic capacity of key enzymes in the acetoin synthesis pathway. To increase the level of reducing the power of cells in the specific period, the logic gate circuit was built to regulate intracellular cofactor levels and metabolic fluxes distribution. Moreover, through fed-batch fermentation at a 5 L fermenter scale, the maximum acetoin titer achieved was 97.5 g/L, with a production rate of 1.81 g/L/h. To our knowledge, this is the highest acetoin fermentation titer reported for B. subtilis. This study significantly enhanced acetoin production in B. subtilis, offering new insights for the industrial production of bio-based platform chemicals and demonstrating broad application potential.
{"title":"Efficient Acetoin Production in Bacillus subtilis by Multivariate Modular Metabolic Engineering with Spatiotemporal Modulation","authors":"Qiang Wang, Teng Bao, Mengkai Hu, Meijuan Xu, Zhiming Rao, Xian Zhang","doi":"10.1021/acssuschemeng.4c06511","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06511","url":null,"abstract":"Acetoin, a promising bio-based platform chemical, is mainly produced through chemical synthesis. Given the increasing attention to nonrenewable resources, developing safe and efficient microbial technologies for acetoin production is necessary. This study redirected more carbon flux to acetoin synthesis by deleting nonessential functional genes in <i>Bacillus subtilis</i>. Subsequently, based on spatial modulation engineering, the biological regulatory elements and DNA scaffold were used to enhance the co-catalytic capacity of key enzymes in the acetoin synthesis pathway. To increase the level of reducing the power of cells in the specific period, the logic gate circuit was built to regulate intracellular cofactor levels and metabolic fluxes distribution. Moreover, through fed-batch fermentation at a 5 L fermenter scale, the maximum acetoin titer achieved was 97.5 g/L, with a production rate of 1.81 g/L/h. To our knowledge, this is the highest acetoin fermentation titer reported for <i>B. subtilis</i>. This study significantly enhanced acetoin production in <i>B. subtilis</i>, offering new insights for the industrial production of bio-based platform chemicals and demonstrating broad application potential.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981523","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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