The development of a greener, more efficient, and economically attractive synthetic methodology is one of the challenging tasks for the sustainable progress of organic synthesis. In recent years, considerable effort has been carried out in search of more sustainable catalysts that aims to minimize the generation of waste through the use of easily recyclable material. Glass waste is an accessible and abundant resource but suffers with challenges in the recycling and disposal process; therefore, its reuse as a support for the growth of metallic nanoparticles is extremely attractive from an environmental as well as economic point of view. Considering this, herein we report the synthesis and characterization of glass waste tablets used for the self-support of metallic copper nanoparticles. The synthetic utility of this new material was explored as a catalyst for the A3 coupling reaction and access to biologically useful propargylamines as well as for the reduction of nitrophenol. Furthermore, due to the catalyst format, it was easily recovered using simple tweezers and reused without a significant loss of catalytic efficiency. In fact, the solvent-free approach, atom economy, ease of recycling, robustness, and efficiency make these tablets useful and environmentally suitable catalysts for A3 coupling and the reduction of nitrophenols.
{"title":"Waste Glass Tablets Cu(0)NP-Doped: An Easily Recyclable Catalyst for the Synthesis of Propargylamines and Nitrophenol Reduction","authors":"Nicoli Catholico, Sumbal Saba, Jamal Rafique, Fabián Ccahuana Ayma, Ricardo Schneider, Giancarlo V. Botteselle","doi":"10.1021/acssuschemeng.4c09871","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09871","url":null,"abstract":"The development of a greener, more efficient, and economically attractive synthetic methodology is one of the challenging tasks for the sustainable progress of organic synthesis. In recent years, considerable effort has been carried out in search of more sustainable catalysts that aims to minimize the generation of waste through the use of easily recyclable material. Glass waste is an accessible and abundant resource but suffers with challenges in the recycling and disposal process; therefore, its reuse as a support for the growth of metallic nanoparticles is extremely attractive from an environmental as well as economic point of view. Considering this, herein we report the synthesis and characterization of glass waste tablets used for the self-support of metallic copper nanoparticles. The synthetic utility of this new material was explored as a catalyst for the A<sup>3</sup> coupling reaction and access to biologically useful propargylamines as well as for the reduction of nitrophenol. Furthermore, due to the catalyst format, it was easily recovered using simple tweezers and reused without a significant loss of catalytic efficiency. In fact, the solvent-free approach, atom economy, ease of recycling, robustness, and efficiency make these tablets useful and environmentally suitable catalysts for A<sup>3</sup> coupling and the reduction of nitrophenols.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402014","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 : 2025-02-12DOI: 10.1021/acssuschemeng.4c04217
Pedro Y. S. Nakasu, Vinicius Piccoli, Antonio Ovejero-Pérez, Priyanka Kumar, Amir Al Ghatta, Susiana Melanie, Cariny Polesca, Leandro Martinez, Jason P. Hallett
This study investigates the utilization of squid pen waste through a biocompatible ionic liquid approach, focusing on choline acetate, [Ch][OAc]. This ionic liquid effectively extracts over 80 wt % of protein from squid pen waste. To optimize the extraction process, a factorial design of experiments was employed to achieve a protein recovery of 75% at an estimated purity of 86%, along with highly acetylated, crystalline β-chitin with a purity of up to 95%. The extracted protein was subsequently used to create biocomposite films from α- and β-chitosan, demonstrating impressive tensile strengths of 93.15 ± 7.9 and 83.5 ± 6.2 MPa, respectively, while maintaining hydrophilic properties (θwater < 90°). Molecular dynamics simulations revealed that the anion [OAc]− exhibits a stronger affinity for protein surfaces compared to other anions, while its combination with the cation [Ch]+ optimally facilitates protein recovery. A material mass balance indicated that from 1 kg of dry squid pen, 0.526 kg of protein and 0.34 kg of chitin were recovered. However, high solvent usage significantly impacts energy demands and CO2 emissions, generating approximately 4.27 kg of CO2 per kg of product, with 61% attributed to protein production. Technoeconomic analysis demonstrated that solvent costs account for nearly 65% of the minimum selling price of the protein, estimated at $9 kg–1, which decreases to $0.6 for each kilogram of coproduced β-chitin. Technoeconomic analysis showed that solvent costs comprise nearly 65% of the minimum selling price of the protein, which can reach $9 kg–1, but this price decreases to $0.6 for each kilogram of coproduced β-chitin. This research underscores the potential of squid pen waste as a valuable resource while highlighting the need for sustainable solvent management strategies.
{"title":"Fractionation of Squid Pens with Ionic Liquids─An Upgraded β-Chitin and Shellfish Protein Production","authors":"Pedro Y. S. Nakasu, Vinicius Piccoli, Antonio Ovejero-Pérez, Priyanka Kumar, Amir Al Ghatta, Susiana Melanie, Cariny Polesca, Leandro Martinez, Jason P. Hallett","doi":"10.1021/acssuschemeng.4c04217","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04217","url":null,"abstract":"This study investigates the utilization of squid pen waste through a biocompatible ionic liquid approach, focusing on choline acetate, [Ch][OAc]. This ionic liquid effectively extracts over 80 wt % of protein from squid pen waste. To optimize the extraction process, a factorial design of experiments was employed to achieve a protein recovery of 75% at an estimated purity of 86%, along with highly acetylated, crystalline β-chitin with a purity of up to 95%. The extracted protein was subsequently used to create biocomposite films from α- and β-chitosan, demonstrating impressive tensile strengths of 93.15 ± 7.9 and 83.5 ± 6.2 MPa, respectively, while maintaining hydrophilic properties (θ<sub>water</sub> < 90°). Molecular dynamics simulations revealed that the anion [OAc]<sup>−</sup> exhibits a stronger affinity for protein surfaces compared to other anions, while its combination with the cation [Ch]<sup>+</sup> optimally facilitates protein recovery. A material mass balance indicated that from 1 kg of dry squid pen, 0.526 kg of protein and 0.34 kg of chitin were recovered. However, high solvent usage significantly impacts energy demands and CO<sub>2</sub> emissions, generating approximately 4.27 kg of CO<sub>2</sub> per kg of product, with 61% attributed to protein production. Technoeconomic analysis demonstrated that solvent costs account for nearly 65% of the minimum selling price of the protein, estimated at $9 kg<sup>–1</sup>, which decreases to $0.6 for each kilogram of coproduced β-chitin. Technoeconomic analysis showed that solvent costs comprise nearly 65% of the minimum selling price of the protein, which can reach $9 kg<sup>–1</sup>, but this price decreases to $0.6 for each kilogram of coproduced β-chitin. This research underscores the potential of squid pen waste as a valuable resource while highlighting the need for sustainable solvent management strategies.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143402012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To preliminarily validate the storage stability of CO2, SO2, and NOx within gas-bearing shale reservoirs, one representative shale and its surrounding rocks were exposed to CO2/flue gas at 30 MPa and 353.15 K for 60 days, and changes in their physical properties were investigated. Results indicated that the CO2/flue gas–H2O exposure raised sample complexity via mineral dissolution and precipitation. Mineral dissolution increased micropores of the roof rock, while precipitation decreased micropores of the shale and floor rock and mesopores of all samples. Thereinto, the flue gas–H2O exposure demonstrated higher influential degrees than those of the CO2–H2O exposure. Furthermore, the CO2–H2O exposure enlarged macropores of the surrounding rocks but narrowed those of the shale. The flue gas–H2O exposure oppositely affects macropores as the does, which is more conducive for fluid storage. Although the CO2–H2O and flue gas–H2O exposures transformed small-scale pores into medium- and large-scale pores/fractures, they reduced sample permeability by 62.51–86.43% and 65.47–90.21%, respectively. Such phenomena suggested stronger flue gas–H2O–shale interactions and a better sealing capability of the surrounding rocks for flue gas than for CO2. Overall, flue gas can react with shale/surrounding rocks more intensively than CO2, making shale reservoirs a promising geologic formation for the stable storage of CO2, SO2, and NOx.
{"title":"Physical Property Responses of Shale Matrix and Its Surrounding Rocks to CO2/Oxy-Coal Combustion Flue Gas Exposure: Implications for Fluid Storage Stability Assessment","authors":"Yi Xu, Zengmin Lun, Haitao Wang, Wenjin Hu, Xia Zhou, Chunpeng Zhao, Dengfeng Zhang","doi":"10.1021/acssuschemeng.4c06095","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06095","url":null,"abstract":"To preliminarily validate the storage stability of CO<sub>2</sub>, SO<sub>2</sub>, and NO<i><sub><i>x</i></sub></i> within gas-bearing shale reservoirs, one representative shale and its surrounding rocks were exposed to CO<sub>2</sub>/flue gas at 30 MPa and 353.15 K for 60 days, and changes in their physical properties were investigated. Results indicated that the CO<sub>2</sub>/flue gas–H<sub>2</sub>O exposure raised sample complexity via mineral dissolution and precipitation. Mineral dissolution increased micropores of the roof rock, while precipitation decreased micropores of the shale and floor rock and mesopores of all samples. Thereinto, the flue gas–H<sub>2</sub>O exposure demonstrated higher influential degrees than those of the CO<sub>2</sub>–H<sub>2</sub>O exposure. Furthermore, the CO<sub>2</sub>–H<sub>2</sub>O exposure enlarged macropores of the surrounding rocks but narrowed those of the shale. The flue gas–H<sub>2</sub>O exposure oppositely affects macropores as the does, which is more conducive for fluid storage. Although the CO<sub>2</sub>–H<sub>2</sub>O and flue gas–H<sub>2</sub>O exposures transformed small-scale pores into medium- and large-scale pores/fractures, they reduced sample permeability by 62.51–86.43% and 65.47–90.21%, respectively. Such phenomena suggested stronger flue gas–H<sub>2</sub>O–shale interactions and a better sealing capability of the surrounding rocks for flue gas than for CO<sub>2</sub>. Overall, flue gas can react with shale/surrounding rocks more intensively than CO<sub>2</sub>, making shale reservoirs a promising geologic formation for the stable storage of CO<sub>2</sub>, SO<sub>2</sub>, and NO<i><sub><i>x</i></sub></i>.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393252","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 : 2025-02-11DOI: 10.1021/acssuschemeng.4c08451
Divakar Arumugam, Tongxin Zhou, Sathya Narayanan Jagadeesan, Ranga Teja Pidathala, Lihua Zhang, AM Milinda Abeykoon, Gihan Kwon, Daniel Olds, Badri Narayanan, Xiaowei Teng
Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe3O4 and parasitic H2 gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe3O4 accumulation and H2 generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe3O4 → Fe(OH)2 → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH)2 phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe3O4, also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.
{"title":"Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive","authors":"Divakar Arumugam, Tongxin Zhou, Sathya Narayanan Jagadeesan, Ranga Teja Pidathala, Lihua Zhang, AM Milinda Abeykoon, Gihan Kwon, Daniel Olds, Badri Narayanan, Xiaowei Teng","doi":"10.1021/acssuschemeng.4c08451","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08451","url":null,"abstract":"Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe<sub>3</sub>O<sub>4</sub> and parasitic H<sub>2</sub> gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe<sub>3</sub>O<sub>4</sub> accumulation and H<sub>2</sub> generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe<sub>3</sub>O<sub>4</sub> → Fe(OH)<sub>2</sub> → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH)<sub>2</sub> phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe<sub>3</sub>O<sub>4</sub>, also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393253","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 : 2025-02-11DOI: 10.1021/acssuschemeng.4c08793
Lay Hiang Ling, Elvis Teng Chua, Bo Xue, Xinying Jia, Jeng Yeong Chow, Ren Liang Yang, Yan Ping Lim, Ping Han, Hao Xie, Choon-Hong Tan, Giang Kien Truc Nguyen, Wen Shan Yew
Fatty acid esters of hydroxy fatty acids (FAHFAs) are a newly discovered lipid class known for their potential anti-inflammatory and insulin-sensitizing properties. A sustainable and efficient synthesis route is essential to realize the potential of FAHFAs and enable cost-effective, large-scale production. Enzymatic synthesis, favored for its scalability and environmental impact, is the preferred approach. Candida (Moesziomyces) antarctica lipase A (CalA), previously known for its thermostability and limited ability to catalyze FAHFA esterification, was investigated along with its orthologues for their ability to produce a variety of FAHFAs. We developed a systematic workflow to identify uncharacterized enzymes for FAHFA synthesis from natural sources, using an automation-compatible method, leading to the discovery of several novel lipases capable of synthesizing diverse FAHFAs. Among these lipases, two newly discovered enzymes, CL20 and CL23, demonstrated superior performance in FAHFA biosynthesis, achieving faster and higher yields than the benchmark enzyme, CalA. Our work advances methodologies and processes critical for industrial FAHFA production and provides a foundation for sustainable commercial-scale synthesis via synthetic enzymology.
{"title":"Sustainable Biosynthesis of Diverse Fatty Acid Esters of Hydroxy Fatty Acids (FAHFAs) for Industrial Production","authors":"Lay Hiang Ling, Elvis Teng Chua, Bo Xue, Xinying Jia, Jeng Yeong Chow, Ren Liang Yang, Yan Ping Lim, Ping Han, Hao Xie, Choon-Hong Tan, Giang Kien Truc Nguyen, Wen Shan Yew","doi":"10.1021/acssuschemeng.4c08793","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08793","url":null,"abstract":"Fatty acid esters of hydroxy fatty acids (FAHFAs) are a newly discovered lipid class known for their potential anti-inflammatory and insulin-sensitizing properties. A sustainable and efficient synthesis route is essential to realize the potential of FAHFAs and enable cost-effective, large-scale production. Enzymatic synthesis, favored for its scalability and environmental impact, is the preferred approach. <i>Candida (Moesziomyces) antarctica</i> lipase A (CalA), previously known for its thermostability and limited ability to catalyze FAHFA esterification, was investigated along with its orthologues for their ability to produce a variety of FAHFAs. We developed a systematic workflow to identify uncharacterized enzymes for FAHFA synthesis from natural sources, using an automation-compatible method, leading to the discovery of several novel lipases capable of synthesizing diverse FAHFAs. Among these lipases, two newly discovered enzymes, CL20 and CL23, demonstrated superior performance in FAHFA biosynthesis, achieving faster and higher yields than the benchmark enzyme, CalA. Our work advances methodologies and processes critical for industrial FAHFA production and provides a foundation for sustainable commercial-scale synthesis via synthetic enzymology.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143392909","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 : 2025-02-11DOI: 10.1021/acssuschemeng.4c08295
Dong Geon Lee, Su Hyeon Son, Won San Choi
This study explores the development and performance of hydrophobic ink contact-printed air-filtering (HAF) series masks (HAF and p-HAF), designed with a four-layer structure using PDMS-inked LEGO stamp contact printing. These masks demonstrate superior properties compared to commercial options like the N-95 mask, particularly in terms of removal efficiency, biodegradability, deodorization property, antibacterial property, and user comfort. The HAF mask, with its optimized hydrophilic outer surfaces and hydrophobic inner layer, maintains a low, consistent pressure drop, enhancing user comfort even in high humidity conditions. Notably, both HAF and p-HAF masks surpass textile deodorization standards, achieving deodorization rates of 83.9 and 87.1%, respectively, while effectively adsorbing odors and inhibiting bacterial growth. Furthermore, the masks exhibit outstanding recyclability over 50 cycles and show significant biodegradability in soil, with 24 and 35.4% decomposition in 10.7 weeks. This research suggests that the HAF mask is particularly suitable for humid environments and disposable applications, while the p-HAF is ideal for air filtration in air purifiers under everyday conditions.
{"title":"Air-Filtering Masks Printed with Hydrophobic Ink: Comfortable Breathing and Semibiodegradable","authors":"Dong Geon Lee, Su Hyeon Son, Won San Choi","doi":"10.1021/acssuschemeng.4c08295","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08295","url":null,"abstract":"This study explores the development and performance of hydrophobic ink contact-printed air-filtering (HAF) series masks (HAF and p-HAF), designed with a four-layer structure using PDMS-inked LEGO stamp contact printing. These masks demonstrate superior properties compared to commercial options like the N-95 mask, particularly in terms of removal efficiency, biodegradability, deodorization property, antibacterial property, and user comfort. The HAF mask, with its optimized hydrophilic outer surfaces and hydrophobic inner layer, maintains a low, consistent pressure drop, enhancing user comfort even in high humidity conditions. Notably, both HAF and p-HAF masks surpass textile deodorization standards, achieving deodorization rates of 83.9 and 87.1%, respectively, while effectively adsorbing odors and inhibiting bacterial growth. Furthermore, the masks exhibit outstanding recyclability over 50 cycles and show significant biodegradability in soil, with 24 and 35.4% decomposition in 10.7 weeks. This research suggests that the HAF mask is particularly suitable for humid environments and disposable applications, while the p-HAF is ideal for air filtration in air purifiers under everyday conditions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393254","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 : 2025-02-11DOI: 10.1021/acssuschemeng.4c09699
Jucai Wei, Xu Wu
Water electrolysis is a powerful and environmentally friendly strategy for green H2 production. However, the kinetics and efficiency of this process suffer seriously from the sluggish oxygen evolution reaction. Here, we report a fully self-powered H2 production approach coupling a hydrogen evolution reaction with a sulfide oxidation reaction. Driven by a sulfidic spent caustic stream, the lab-scale flow reactor can deliver an open-circuit voltage of up to 0.44 V and a self-powered current density of up to 33.79 mA cm–2. A hybrid NiCu-doped MoS2 catalyst is prepared using a nickel–copper etching waste fluid, which can effectively catalyze sulfide oxidation and hydrogen evolution. The conversion efficiencies for waste chemical energy to electricity and H2 are >40% and >30%, respectively. This work strongly suggests a self-powered H2 production potential and ability by coupling water splitting with small-molecule waste treatments, with substantial benefits concerning energy conservation, waste treatment, and resource optimization.
{"title":"Self-Powered Water Electrolysis with Sulfide Waste as Consumable","authors":"Jucai Wei, Xu Wu","doi":"10.1021/acssuschemeng.4c09699","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09699","url":null,"abstract":"Water electrolysis is a powerful and environmentally friendly strategy for green H<sub>2</sub> production. However, the kinetics and efficiency of this process suffer seriously from the sluggish oxygen evolution reaction. Here, we report a fully self-powered H<sub>2</sub> production approach coupling a hydrogen evolution reaction with a sulfide oxidation reaction. Driven by a sulfidic spent caustic stream, the lab-scale flow reactor can deliver an open-circuit voltage of up to 0.44 V and a self-powered current density of up to 33.79 mA cm<sup>–2</sup>. A hybrid NiCu-doped MoS<sub>2</sub> catalyst is prepared using a nickel–copper etching waste fluid, which can effectively catalyze sulfide oxidation and hydrogen evolution. The conversion efficiencies for waste chemical energy to electricity and H<sub>2</sub> are >40% and >30%, respectively. This work strongly suggests a self-powered H<sub>2</sub> production potential and ability by coupling water splitting with small-molecule waste treatments, with substantial benefits concerning energy conservation, waste treatment, and resource optimization.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"55 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143392910","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 : 2025-02-11DOI: 10.1021/acssuschemeng.4c10045
Cameron L. Roman, Jonathan Lucas, James A. Dorman, Kerry M. Dooley
Due to an abundance of shale gas, manufacturers are interested in meeting increased demands for alkenes, especially n-alkenes, by the dehydrogenation of light alkanes. While the catalysts for these reactions have been studied for many years, alkene selectivity and deactivation remain challenging problems. This work addresses these problems by the substitution of a localized indirect heating method (radio-frequency induction heating, RF-IH) for more traditional process heating employing steam or burners (e.g., natural gas combustion). RF-IH has been applied to the dehydrogenation of n-butane to C4 alkenes by utilizing magnetically susceptible catalysts based on Fe/Fe3O4 susceptors. Magnetic core–shell catalysts with either Pt or V as active metals were synthesized to mimic typical n-butane dehydrogenation catalysts. For these catalysts, RF-IH operation resulted in significantly improved selectivity to alkenes and less deactivation when compared to conventional thermal heating, although the initial activities were not always as high as their thermally operated counterparts. These results provide motivation to continue investigating the effects of RF-IH and its benefits to certain heterogeneous catalytic processes.
{"title":"Improved Performance of Catalysts Containing Pt, Pt–Sn, and V in the Dehydrogenation of n-Butane by Radio-Frequency Induction Heating","authors":"Cameron L. Roman, Jonathan Lucas, James A. Dorman, Kerry M. Dooley","doi":"10.1021/acssuschemeng.4c10045","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c10045","url":null,"abstract":"Due to an abundance of shale gas, manufacturers are interested in meeting increased demands for alkenes, especially <i>n</i>-alkenes, by the dehydrogenation of light alkanes. While the catalysts for these reactions have been studied for many years, alkene selectivity and deactivation remain challenging problems. This work addresses these problems by the substitution of a localized indirect heating method (radio-frequency induction heating, RF-IH) for more traditional process heating employing steam or burners (e.g., natural gas combustion). RF-IH has been applied to the dehydrogenation of <i>n</i>-butane to C<sub>4</sub> alkenes by utilizing magnetically susceptible catalysts based on Fe/Fe<sub>3</sub>O<sub>4</sub> susceptors. Magnetic core–shell catalysts with either Pt or V as active metals were synthesized to mimic typical <i>n</i>-butane dehydrogenation catalysts. For these catalysts, RF-IH operation resulted in significantly improved selectivity to alkenes and less deactivation when compared to conventional thermal heating, although the initial activities were not always as high as their thermally operated counterparts. These results provide motivation to continue investigating the effects of RF-IH and its benefits to certain heterogeneous catalytic processes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"43 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143392912","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 : 2025-02-09DOI: 10.1021/acssuschemeng.4c07901
Deborah Pérez-Almada, Ángel Galán-Martín, María del Mar Contreras, Juan Miguel Romero-García, Eulogio Castro
Biorefineries are pivotal in advancing sustainability, yet most studies remain confined to laboratory scales, lacking comprehensive industrial-level analyses. In this work, the laboratory experiments are scaled up to design and assess the techno-economic and environmental implications of a multiproduct biorefinery system producing antioxidant extracts, lignin, and bioethanol from exhausted olive pomace, a residual biomass from olive oil extraction. Using process simulation and life cycle assessment, five scenarios were evaluated, varying in electricity sources (national mix, solar, wind, or olive biomass) and the heat and cooling sources (fossil natural gas or synthetic natural gas from capture CO2 and electrolytic hydrogen), with one scenario incorporating a carbon capture and storage (CCS) system. The CCS scenario showed the highest overall costs, 2.5 times higher than the base scenario (27.74 vs 10.99 $/functional unit), primarily due to the additional infrastructure and energy-intensive processes associated with CO2 utilization and storage. Despite higher costs, it achieved even a negative carbon footprint (−1.05 kg CO2eq per functional unit cradle-to-gate) and reduced impacts on ecosystem quality, resources, and human health. However, specific impacts like human noncarcinogenic and carcinogenic effects (40% and 60%) and ecotoxicity (up 70%) worsened. Notwithstanding economic barriers and environmental challenges, which can be alleviated by selling carbon credits and tailored policies and strategic decisions, these findings underscore the potential of integrating CCS into biorefinery schemes as a promising pathway to enhance environmental sustainability.
{"title":"Uncovering the Techno-Economic and Environmental Implications of a Multiproduct Biorefinery from Exhausted Olive Pomace","authors":"Deborah Pérez-Almada, Ángel Galán-Martín, María del Mar Contreras, Juan Miguel Romero-García, Eulogio Castro","doi":"10.1021/acssuschemeng.4c07901","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07901","url":null,"abstract":"Biorefineries are pivotal in advancing sustainability, yet most studies remain confined to laboratory scales, lacking comprehensive industrial-level analyses. In this work, the laboratory experiments are scaled up to design and assess the techno-economic and environmental implications of a multiproduct biorefinery system producing antioxidant extracts, lignin, and bioethanol from exhausted olive pomace, a residual biomass from olive oil extraction. Using process simulation and life cycle assessment, five scenarios were evaluated, varying in electricity sources (national mix, solar, wind, or olive biomass) and the heat and cooling sources (fossil natural gas or synthetic natural gas from capture CO<sub>2</sub> and electrolytic hydrogen), with one scenario incorporating a carbon capture and storage (CCS) system. The CCS scenario showed the highest overall costs, 2.5 times higher than the base scenario (27.74 vs 10.99 $/functional unit), primarily due to the additional infrastructure and energy-intensive processes associated with CO<sub>2</sub> utilization and storage. Despite higher costs, it achieved even a negative carbon footprint (−1.05 kg CO<sub>2</sub>eq per functional unit cradle-to-gate) and reduced impacts on ecosystem quality, resources, and human health. However, specific impacts like human noncarcinogenic and carcinogenic effects (40% and 60%) and ecotoxicity (up 70%) worsened. Notwithstanding economic barriers and environmental challenges, which can be alleviated by selling carbon credits and tailored policies and strategic decisions, these findings underscore the potential of integrating CCS into biorefinery schemes as a promising pathway to enhance environmental sustainability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"79 4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371567","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 : 2025-02-09DOI: 10.1021/acssuschemeng.4c08549
Jord P. Haven, Simon Haanschoten, Leon Lefferts, Arian Nijmeijer, Aloijsius G. J. van der Ham, Jimmy A. Faria Albanese
The potential of applying ceramic proton-conducting electrolysis cell (PCEC) membranes in ethylene production processes was explored in this work. To this end, the techno-economics of a PCEC-assisted ethane dehydrogenation process were compared against the conventional ethane steam cracking (SC) process. The PCEC process required four to five times more electricity than the SC process. Consequently, fully renewable electricity needed to be utilized in the PCEC process to outcompete conventional SC in terms of carbon dioxide emissions. Notably, the PCEC process was financially and environmentally competitive with conventional SC only when achieving similar ethylene yields (ca. 50%). For an ethylene yield of ca. 25%, which is currently achievable using PCEC technologies, the capital investment and carbon emissions of the PCEC process were too excessive to outcompete electrified SC. The total energy usage, utility demand, and capital investment were substantially higher for the 25% ethylene yield PCEC case as compared to the 50% PCEC one, due to larger process streams and process units as a result of the lower single-pass yield. The results further highlighted that carbon emissions could be reduced from ca. 1.5 tCO2/tethylene to ca. 0.2 tCO2/tethylene when employing green electrified SC or PCEC processes instead of conventional fossil fuel-based SC, but only if fully renewable electricity was utilized. Moreover, a carbon tax of more than 100 USD/tCO2 would need to be imposed to make the green electrified SC and PCEC process more viable than their fossil-based counterparts. Lastly, technological challenges related to attainable ethylene yield, PCEC stability, large-scale sustainable production of PCECs, and the continuous availability of green electricity were identified as the main hurdles for the industrial implementation of PCECs for green ethylene production.
{"title":"Industrial Perspective of Electrified Ethylene Production via Membrane-Assisted Nonoxidative Dehydrogenation of Ethane","authors":"Jord P. Haven, Simon Haanschoten, Leon Lefferts, Arian Nijmeijer, Aloijsius G. J. van der Ham, Jimmy A. Faria Albanese","doi":"10.1021/acssuschemeng.4c08549","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08549","url":null,"abstract":"The potential of applying ceramic proton-conducting electrolysis cell (PCEC) membranes in ethylene production processes was explored in this work. To this end, the techno-economics of a PCEC-assisted ethane dehydrogenation process were compared against the conventional ethane steam cracking (SC) process. The PCEC process required four to five times more electricity than the SC process. Consequently, fully renewable electricity needed to be utilized in the PCEC process to outcompete conventional SC in terms of carbon dioxide emissions. Notably, the PCEC process was financially and environmentally competitive with conventional SC only when achieving similar ethylene yields (ca. 50%). For an ethylene yield of ca. 25%, which is currently achievable using PCEC technologies, the capital investment and carbon emissions of the PCEC process were too excessive to outcompete electrified SC. The total energy usage, utility demand, and capital investment were substantially higher for the 25% ethylene yield PCEC case as compared to the 50% PCEC one, due to larger process streams and process units as a result of the lower single-pass yield. The results further highlighted that carbon emissions could be reduced from ca. 1.5 t<sub>CO2</sub>/t<sub>ethylene</sub> to ca. 0.2 t<sub>CO2</sub>/t<sub>ethylene</sub> when employing green electrified SC or PCEC processes instead of conventional fossil fuel-based SC, but only if fully renewable electricity was utilized. Moreover, a carbon tax of more than 100 USD/t<sub>CO2</sub> would need to be imposed to make the green electrified SC and PCEC process more viable than their fossil-based counterparts. Lastly, technological challenges related to attainable ethylene yield, PCEC stability, large-scale sustainable production of PCECs, and the continuous availability of green electricity were identified as the main hurdles for the industrial implementation of PCECs for green ethylene production.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371568","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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