Pub Date : 2025-01-10DOI: 10.1021/acssuschemeng.4c06705
Sari Araki, Yasuaki Einaga
Boron-doped diamond (BDD) is an excellent functional electrode material used as a working electrode in the electrochemical reduction of CO2. Formic acid production with approximately 100% Faradaic efficiency has been achieved via CO2 reduction using BDD electrodes. In this study, we investigated the production performance stability during long-term electrolysis by focusing on ion transport in the electrolyte during electrolysis. Initially, we investigated the behavior of potassium ions (K+) and pH during long-term electrolysis in detail. A relationship was observed between the change in ion concentrations and formic acid production, crucial in formic acid production. Based on this knowledge, we successfully achieved stable formic acid production for an extremely long time (1264 h) by controlling ion transport. In addition to utilizing the durability of BDD electrodes as stable electrode materials, controlling ion transport has paved the way for the industrialization of formic acid production via CO2 reduction.
{"title":"Semipermanent Continuous Formic Acid Production from CO2 by Controlling Ion Transport Using Boron-Doped Diamond Electrodes","authors":"Sari Araki, Yasuaki Einaga","doi":"10.1021/acssuschemeng.4c06705","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06705","url":null,"abstract":"Boron-doped diamond (BDD) is an excellent functional electrode material used as a working electrode in the electrochemical reduction of CO<sub>2</sub>. Formic acid production with approximately 100% Faradaic efficiency has been achieved via CO<sub>2</sub> reduction using BDD electrodes. In this study, we investigated the production performance stability during long-term electrolysis by focusing on ion transport in the electrolyte during electrolysis. Initially, we investigated the behavior of potassium ions (K<sup>+</sup>) and pH during long-term electrolysis in detail. A relationship was observed between the change in ion concentrations and formic acid production, crucial in formic acid production. Based on this knowledge, we successfully achieved stable formic acid production for an extremely long time (1264 h) by controlling ion transport. In addition to utilizing the durability of BDD electrodes as stable electrode materials, controlling ion transport has paved the way for the industrialization of formic acid production via CO<sub>2</sub> reduction.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961323","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 : 2025-01-10DOI: 10.1021/acssuschemeng.4c08680
Han Zhang, Peng Tan, Xun-Qiang Wang, Kai-Li Gao, Lin-Bing Sun
CO2 adsorption in humid conditions has wide industrial uses, but the low uptake of adsorbents and the inferior efficiency of amines present a notable challenge for its development. Through the copolymerization of acrylamide (AAm), styrene (ST), and N-(3-(dimethylamino)propyl)methacrylamide (DMAPMA), we developed a thermoresponsive adsorbent with tunable amine sites. In a humid environment, the tertiary amines of the DMAPMA moiety keep an extended state and are exposed to the CO2 molecules at 20 °C. The optimal adsorption capacity is 3.78 mmol g–1 with 1 mol of amine reacting with 0.98 mol of CO2. This amine efficiency in adsorption surpasses that of various typical adsorbents. At 80 °C, the adsorption capacity decreases to 1.10 mmol g–1, with only 0.34 of the amine efficiency. The elevated temperature makes the AAm moiety form intramolecular H-bonds with the DMAPMA moiety; thus, the amines are shielded in the adsorbent’s particles. This change of amines couples with the feature of adsorption swing, making adsorbents have both the satisfied adsorption capacity and the convenience of desorption.
{"title":"Fabrication of Thermoresponsive Adsorbents with High Amine Efficiency for Wet CO2 Capture: Coupling Responsiveness with Adsorption Swing","authors":"Han Zhang, Peng Tan, Xun-Qiang Wang, Kai-Li Gao, Lin-Bing Sun","doi":"10.1021/acssuschemeng.4c08680","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08680","url":null,"abstract":"CO<sub>2</sub> adsorption in humid conditions has wide industrial uses, but the low uptake of adsorbents and the inferior efficiency of amines present a notable challenge for its development. Through the copolymerization of acrylamide (AAm), styrene (ST), and <i>N</i>-(3-(dimethylamino)propyl)methacrylamide (DMAPMA), we developed a thermoresponsive adsorbent with tunable amine sites. In a humid environment, the tertiary amines of the DMAPMA moiety keep an extended state and are exposed to the CO<sub>2</sub> molecules at 20 °C. The optimal adsorption capacity is 3.78 mmol g<sup>–1</sup> with 1 mol of amine reacting with 0.98 mol of CO<sub>2</sub>. This amine efficiency in adsorption surpasses that of various typical adsorbents. At 80 °C, the adsorption capacity decreases to 1.10 mmol g<sup>–1</sup>, with only 0.34 of the amine efficiency. The elevated temperature makes the AAm moiety form intramolecular H-bonds with the DMAPMA moiety; thus, the amines are shielded in the adsorbent’s particles. This change of amines couples with the feature of adsorption swing, making adsorbents have both the satisfied adsorption capacity and the convenience of desorption.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"84 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961324","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 : 2025-01-05DOI: 10.1021/acssuschemeng.4c07557
Xiaorong Shi, Yongming Zhang, Yongsong Tan, Zhu Long, Chaoxia Wang
The irregular dendrite growth and unfavorable adverse reactions on the Zn anode has emerged as a non-negligible obstacle for broad deployment of aqueous zinc-ion batteries (AZIBs). Herein, a thin and robust separator (LFP1:1) composed of lyocell fibrillated fibers and polyethylene terephthalate (PET) fibers that features a light weight, cost effectiveness, and being mass-producible is developed by a paper-making method to inhibit the undesirable adverse reactions and achieve an exceptional stable Zn anode. The LFP1:1 separator offers abundant polar functional groups, small and uniform pore structure, and high mechanical strength, which is beneficial to constructing specific migration channels for Zn2+ and suppressing adverse reactions, promoting uniform Zn deposition, and resisting dendrite penetration. As verified by the experimental results, the Zn//Zn symmetric cell furnished with the LFP1:1 separator displays prolonged lifespan up to 1452 h in 3 M Zn(CF3SO3)2 electrolyte at 1 mA·cm–2 without dendrite or byproducts, which is superior than that with GF separator. Moreover, the assembled Zn//V2O5 full cell with the LFP1:1 separator also demonstrates an outstanding cycling stability with 77.8% capacity retention at 1 A·g–1 after 1000 cycles. This work sheds light on a promising and large-scale producible method for the development of advanced separator materials for high performance AZIBs.
{"title":"Thin and Robust Separator with Directed Zn2+ Migration Channel for a Stable and Dendrites-Free Zn Anode","authors":"Xiaorong Shi, Yongming Zhang, Yongsong Tan, Zhu Long, Chaoxia Wang","doi":"10.1021/acssuschemeng.4c07557","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07557","url":null,"abstract":"The irregular dendrite growth and unfavorable adverse reactions on the Zn anode has emerged as a non-negligible obstacle for broad deployment of aqueous zinc-ion batteries (AZIBs). Herein, a thin and robust separator (LFP<sub>1:1</sub>) composed of lyocell fibrillated fibers and polyethylene terephthalate (PET) fibers that features a light weight, cost effectiveness, and being mass-producible is developed by a paper-making method to inhibit the undesirable adverse reactions and achieve an exceptional stable Zn anode. The LFP<sub>1:1</sub> separator offers abundant polar functional groups, small and uniform pore structure, and high mechanical strength, which is beneficial to constructing specific migration channels for Zn<sup>2+</sup> and suppressing adverse reactions, promoting uniform Zn deposition, and resisting dendrite penetration. As verified by the experimental results, the Zn//Zn symmetric cell furnished with the LFP<sub>1:1</sub> separator displays prolonged lifespan up to 1452 h in 3 M Zn(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub> electrolyte at 1 mA·cm<sup>–2</sup> without dendrite or byproducts, which is superior than that with GF separator. Moreover, the assembled Zn//V<sub>2</sub>O<sub>5</sub> full cell with the LFP<sub>1:1</sub> separator also demonstrates an outstanding cycling stability with 77.8% capacity retention at 1 A·g<sup>–1</sup> after 1000 cycles. This work sheds light on a promising and large-scale producible method for the development of advanced separator materials for high performance AZIBs.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925191","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 : 2025-01-05DOI: 10.1021/acssuschemeng.4c09246
Zhixiong Yang, Bo Hu, Xiaotian Wang, Dmitry Selishchev, Gaoke Zhang
The development of high-performance photocatalysts is crucial for enabling efficient CO2 conversion in photocatalytic systems. Here, we developed a novel heterojunction (N-BON) composed of Ni-doped Bi4O5Br2 and NiCo2O4 for CO2 photoreduction with the help of simulated sunlight. The optimized 21N-BON composite exhibited the highest activity, producing 18.66 μmol·g–1·h–1 of CO with a selectivity of 95.7%, which represents a remarkable 2.15-fold and 4.75-fold increase in CO yield compared to the Bi4O5Br2/NiCo2O4 heterojunction and Ni-doped Bi4O5Br2, respectively. Photoelectrochemical testing, photoluminescence analysis, and theoretical calculations demonstrated that the enhanced performance of the 21N-BON composite is attributed to improved photogenerated carrier separation, driven by the synergistic effects of Ni-doping-induced spin polarization and the built-in electric field from heterojunction construction. Additionally, theoretical calculations and in situ DRIFTS analyses was used to clarify the CO2 reaction mechanisms on the photocatalyst surface, showing that Ni doping improved CO2 adsorption and promoted the formation of key reaction intermediates. This study offers important guidance for developing advanced photocatalysts for solar-driven CO2 reduction, contributing to sustainable energy solutions.
{"title":"Enhanced Photocatalytic CO2 Reduction over Ni-doped Bi4O5Br2/NiCo2O4 Heterojunction: Synergistic Enhancement Effect between Spin Polarization and Built-in Electric Field","authors":"Zhixiong Yang, Bo Hu, Xiaotian Wang, Dmitry Selishchev, Gaoke Zhang","doi":"10.1021/acssuschemeng.4c09246","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09246","url":null,"abstract":"The development of high-performance photocatalysts is crucial for enabling efficient CO<sub>2</sub> conversion in photocatalytic systems. Here, we developed a novel heterojunction (N-BON) composed of Ni-doped Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub> and NiCo<sub>2</sub>O<sub>4</sub> for CO<sub>2</sub> photoreduction with the help of simulated sunlight. The optimized 21N-BON composite exhibited the highest activity, producing 18.66 μmol·g<sup>–1</sup>·h<sup>–1</sup> of CO with a selectivity of 95.7%, which represents a remarkable 2.15-fold and 4.75-fold increase in CO yield compared to the Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub>/NiCo<sub>2</sub>O<sub>4</sub> heterojunction and Ni-doped Bi<sub>4</sub>O<sub>5</sub>Br<sub>2</sub>, respectively. Photoelectrochemical testing, photoluminescence analysis, and theoretical calculations demonstrated that the enhanced performance of the 21N-BON composite is attributed to improved photogenerated carrier separation, driven by the synergistic effects of Ni-doping-induced spin polarization and the built-in electric field from heterojunction construction. Additionally, theoretical calculations and in situ DRIFTS analyses was used to clarify the CO<sub>2</sub> reaction mechanisms on the photocatalyst surface, showing that Ni doping improved CO<sub>2</sub> adsorption and promoted the formation of key reaction intermediates. This study offers important guidance for developing advanced photocatalysts for solar-driven CO<sub>2</sub> reduction, contributing to sustainable energy solutions.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142928999","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}
While the promising application prospects of soy protein adhesives (SPI) as green alternatives to formaldehyde-based resins, poor bonding strength and unsatisfactory water resistance restrict the practical application. Inspired by brown alga bionics and organic–inorganic hybridization system, a bionic and multifunctional soy protein adhesive (SPI-RA-BCNF-MMT) was prepared utilizing rosin acid derivative (RA), bamboo cellulose nanofiber (BCNF), and montmorillonite (MMT). Optimal formulation SPI-10RA-6BCNF-4MMT optimized by response surface methodology presented excellent dry and wet shear strengths (2.41 and 1.41 MPa), which were increased by 270% and 231% compared to pure SPI. Moreover, the strength of the modified adhesive far exceeded the China National Standard (0.70 MPa). Molecular docking strategy and finite element analysis also confirmed strong interactions within SPI-10RA-6BCNF-4MMT. In addition, SPI-10RA-6BCNF-4MMT exhibited exceptional water and organic solvent resistance, owing to the dense cross-linking structure. Remarkable coating properties enabled SPI-10RA-6BCNF-4MMT to be coated evenly in dry and wet environments. Furthermore, SPI-10RA-6BCNF-4MMT showed outstanding flame-retardant properties, improving safety in practical use. Meanwhile, life cycle assessment of SPI-10RA-6BCNF-4MMT revealed environmentally friendly features, such as low formaldehyde pollution and greenhouse gas emission. Therefore, this proposed green, multifunctional, and bionic adhesive demonstrated an eco-conscious alternative to traditional formaldehyde-based resins for the large-scale fabrication of wood composite materials.
{"title":"Preparation of a Brown Alga-Inspired, Multifunctional, and Bionic Soy Protein Adhesive Based on Bamboo Cellulose Nanofiber and Rosin Acid","authors":"Yinchun Hu, Zhenyang Bao, Zhaoshuang Li, Renzhong Wei, Tonghua Ma, Xiaobing Xie, Guoen Yang, Yan Qing, Xingong Li, Yiqiang Wu","doi":"10.1021/acssuschemeng.4c09184","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09184","url":null,"abstract":"While the promising application prospects of soy protein adhesives (SPI) as green alternatives to formaldehyde-based resins, poor bonding strength and unsatisfactory water resistance restrict the practical application. Inspired by brown alga bionics and organic–inorganic hybridization system, a bionic and multifunctional soy protein adhesive (SPI-RA-BCNF-MMT) was prepared utilizing rosin acid derivative (RA), bamboo cellulose nanofiber (BCNF), and montmorillonite (MMT). Optimal formulation SPI-10RA-6BCNF-4MMT optimized by response surface methodology presented excellent dry and wet shear strengths (2.41 and 1.41 MPa), which were increased by 270% and 231% compared to pure SPI. Moreover, the strength of the modified adhesive far exceeded the China National Standard (0.70 MPa). Molecular docking strategy and finite element analysis also confirmed strong interactions within SPI-10RA-6BCNF-4MMT. In addition, SPI-10RA-6BCNF-4MMT exhibited exceptional water and organic solvent resistance, owing to the dense cross-linking structure. Remarkable coating properties enabled SPI-10RA-6BCNF-4MMT to be coated evenly in dry and wet environments. Furthermore, SPI-10RA-6BCNF-4MMT showed outstanding flame-retardant properties, improving safety in practical use. Meanwhile, life cycle assessment of SPI-10RA-6BCNF-4MMT revealed environmentally friendly features, such as low formaldehyde pollution and greenhouse gas emission. Therefore, this proposed green, multifunctional, and bionic adhesive demonstrated an eco-conscious alternative to traditional formaldehyde-based resins for the large-scale fabrication of wood composite materials.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The resource and environmental issues caused by discarded plastics make plastic recycling research increasingly urgent. Polyamide, one of the top five general engineering polymers, has yet to be thoroughly explored for its recycling performance or mechanism, particularly for aromatic polyamides. In this study, ferulic acid, a lignin derivative generated from bio sources, was used to synthesize diacids and photoresponsive aromatic polyamides that could be recycled via dual processes and had outstanding thermal and mechanical properties. On the one hand, UV-induced cycloaddition reactions occurred in photoresponsive groups, allowing polyamides to achieve the performance enhancement of the discarded materials by UV enhancement. The hydrolysis of amide bonds under alkaline circumstances, on the other hand, conferred degradability on ferulic acid-based polyamides. In addition, a simple acidification and filtration approach for extracting beginning monomers from degradation solutions was developed, resulting in closed-loop chemical recycling of ferulic acid-based polyamides. This work enriches the raw material library for the preparation of high-performance biobased polyamides and provides new ideas for the development of recyclable polyamides.
{"title":"In Situ Enhancive and Closed-Loop Chemical Recyclable High-Performance Aromatic Polyamides from Lignin-Derived Ferulic Acid","authors":"Yanlin Liu, Wanding Chen, Zhen Yu, Yajin Fang, Xiangyu Zhou, Yi Wang, Zhaobin Tang","doi":"10.1021/acssuschemeng.4c09354","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c09354","url":null,"abstract":"The resource and environmental issues caused by discarded plastics make plastic recycling research increasingly urgent. Polyamide, one of the top five general engineering polymers, has yet to be thoroughly explored for its recycling performance or mechanism, particularly for aromatic polyamides. In this study, ferulic acid, a lignin derivative generated from bio sources, was used to synthesize diacids and photoresponsive aromatic polyamides that could be recycled via dual processes and had outstanding thermal and mechanical properties. On the one hand, UV-induced cycloaddition reactions occurred in photoresponsive groups, allowing polyamides to achieve the performance enhancement of the discarded materials by UV enhancement. The hydrolysis of amide bonds under alkaline circumstances, on the other hand, conferred degradability on ferulic acid-based polyamides. In addition, a simple acidification and filtration approach for extracting beginning monomers from degradation solutions was developed, resulting in closed-loop chemical recycling of ferulic acid-based polyamides. This work enriches the raw material library for the preparation of high-performance biobased polyamides and provides new ideas for the development of recyclable polyamides.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924579","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 : 2025-01-03DOI: 10.1021/acssuschemeng.4c07528
Haining You, Cheng Yang, Zubang Liu, Huichun Xue, Song Guo, Yaxiong Tian, Tunmise Ayode Otitoju, Yuanli Liu
Aqueous magnesium-ion batteries (AMIBs) have garnered a lot of interest in future energy storage due to their high energy density, easy preparation, and excellent safety. Yet, the lack of a proper electrode material with high-capacity performance hinders its development. In this work, a facile heterojunction of VO2·xH2O@V2O5 (VOx) electrode with a nanobelt structure was synthesized by an electrochemical deposition process for AMIBs for the first time. The specific structure combines the advantages of layered V2O5 and tunnel-like VO2·xH2O, which shows excellent storage capacity and cycle stability. It shows high rate performances of 510 and 195.5 mAh g–1 at 0.05 and 5 A g–1, respectively, as well as a cycle performance of 100 mAh g–1 after 1000 cycles at 1 A g–1. Combining experimental characterization and theoretical calculations, we can show that the structured water in VOX can improve the conductivity and diffusion rate of Mg2+. The mechanism study reveals that VOX undergoes a cointercalation reaction of H+ and Mg2+ during the discharge process. This study not only highlights the role of structural water and heterogeneous design in enhancing Mg2+ diffusion in VOX materials but also offers a novel approach for preparing a high-performance AMIB system.
{"title":"Heterojunction of Vanadium Oxide Nanobelts for Aqueous Magnesium-Ion Batteries","authors":"Haining You, Cheng Yang, Zubang Liu, Huichun Xue, Song Guo, Yaxiong Tian, Tunmise Ayode Otitoju, Yuanli Liu","doi":"10.1021/acssuschemeng.4c07528","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07528","url":null,"abstract":"Aqueous magnesium-ion batteries (AMIBs) have garnered a lot of interest in future energy storage due to their high energy density, easy preparation, and excellent safety. Yet, the lack of a proper electrode material with high-capacity performance hinders its development. In this work, a facile heterojunction of VO<sub>2</sub>·<i>x</i>H<sub>2</sub>O@V<sub>2</sub>O<sub>5</sub> (VO<sub>x</sub>) electrode with a nanobelt structure was synthesized by an electrochemical deposition process for AMIBs for the first time. The specific structure combines the advantages of layered V<sub>2</sub>O<sub>5</sub> and tunnel-like VO<sub>2</sub>·<i>x</i>H<sub>2</sub>O, which shows excellent storage capacity and cycle stability. It shows high rate performances of 510 and 195.5 mAh g<sup>–1</sup> at 0.05 and 5 A g<sup>–1</sup>, respectively, as well as a cycle performance of 100 mAh g<sup>–1</sup> after 1000 cycles at 1 A g<sup>–1</sup>. Combining experimental characterization and theoretical calculations, we can show that the structured water in VO<sub>X</sub> can improve the conductivity and diffusion rate of Mg<sup>2+</sup>. The mechanism study reveals that VO<sub>X</sub> undergoes a cointercalation reaction of H<sup>+</sup> and Mg<sup>2+</sup> during the discharge process. This study not only highlights the role of structural water and heterogeneous design in enhancing Mg<sup>2+</sup> diffusion in VO<sub>X</sub> materials but also offers a novel approach for preparing a high-performance AMIB system.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"55 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924581","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}
A novel mechanochemical approach is described for chloride-templated head-to-tail macrocyclization of a pentapeptide and a hexapeptide. This straightforward method allows the solvent-free preparation of cyclopeptides with yields comparable to solution-based approaches without the need for high dilution of the reaction mixture and with significantly reduced reaction times and organic waste amount.
{"title":"Rapid and Green Anion-Assisted Mechanochemical Peptide Cyclization","authors":"Mirko Duvnjak, Nikolina Vidović, Krunoslav Užarević, Gordan Horvat, Vladislav Tomišić, Giovanna Speranza, Nikola Cindro","doi":"10.1021/acssuschemeng.4c03309","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c03309","url":null,"abstract":"A novel mechanochemical approach is described for chloride-templated head-to-tail macrocyclization of a pentapeptide and a hexapeptide. This straightforward method allows the solvent-free preparation of cyclopeptides with yields comparable to solution-based approaches without the need for high dilution of the reaction mixture and with significantly reduced reaction times and organic waste amount.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917026","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 : 2025-01-03DOI: 10.1021/acssuschemeng.4c07297
Linshu Shan, Yang Liu, Yang Chen, Xinjie Zhang, Haizhong Dai, Dahai Xu, Bingzhe Yu, Yi Zhang, Shaowei Chen, Ting He, Xiaoping Ouyang
Carbon-based nanocomposites with atomically dispersed transition metals have been found to exhibit excellent electrocatalytic activity toward the oxygen evolution reaction (OER). Yet, the low metal loads and severe electrooxidation of carbon greatly limit the activity and stability. Reducing the pyrolysis temperature can weaken the aggregation of metal atoms, and using carbon aerogel as a 3D scaffold can maximize accessible metal sites. Simultaneously, a lower pyrolysis temperature can provide a higher oxygen content for the carbon substrate and enhance resistance against electrooxidation. Herein, carbon aerogels embedded with Fe–Ni dual atom centers (NCA/FeNi-500) are synthesized by controlled pyrolysis at 500 °C of a chitosan hydrogel composite along with FeCl3 and NiCl2. With an atomically dispersed metal loading of 4.35 wt %, NCA/FeNi-500 exhibits a remarkable OER catalytic activity in both alkaline water and simulated alkaline seawater, featuring a low overpotential of only +294 and +306 mV to reach the current density of 10 mA cm–2, respectively, along with excellent long-term stability during overall water splitting, a performance much better than those with commercial RuO2. First-principles calculations show that adjacent NiN4 sites effectively promote the OER kinetics at FeN4 sites by reducing the energy barrier of O–O formation. This is also manifested in alkaline saline water splitting.
{"title":"High-Density Iron–Nickel Dual Sites in Carbon Aerogels as Effective Alkaline Water/Seawater Oxidation Electrocatalysts","authors":"Linshu Shan, Yang Liu, Yang Chen, Xinjie Zhang, Haizhong Dai, Dahai Xu, Bingzhe Yu, Yi Zhang, Shaowei Chen, Ting He, Xiaoping Ouyang","doi":"10.1021/acssuschemeng.4c07297","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07297","url":null,"abstract":"Carbon-based nanocomposites with atomically dispersed transition metals have been found to exhibit excellent electrocatalytic activity toward the oxygen evolution reaction (OER). Yet, the low metal loads and severe electrooxidation of carbon greatly limit the activity and stability. Reducing the pyrolysis temperature can weaken the aggregation of metal atoms, and using carbon aerogel as a 3D scaffold can maximize accessible metal sites. Simultaneously, a lower pyrolysis temperature can provide a higher oxygen content for the carbon substrate and enhance resistance against electrooxidation. Herein, carbon aerogels embedded with Fe–Ni dual atom centers (NCA/FeNi-500) are synthesized by controlled pyrolysis at 500 °C of a chitosan hydrogel composite along with FeCl<sub>3</sub> and NiCl<sub>2</sub>. With an atomically dispersed metal loading of 4.35 wt %, NCA/FeNi-500 exhibits a remarkable OER catalytic activity in both alkaline water and simulated alkaline seawater, featuring a low overpotential of only +294 and +306 mV to reach the current density of 10 mA cm<sup>–2</sup>, respectively, along with excellent long-term stability during overall water splitting, a performance much better than those with commercial RuO<sub>2</sub>. First-principles calculations show that adjacent NiN<sub>4</sub> sites effectively promote the OER kinetics at FeN<sub>4</sub> sites by reducing the energy barrier of O–O formation. This is also manifested in alkaline saline water splitting.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142916827","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 : 2025-01-03DOI: 10.1021/acssuschemeng.4c09394
Bo Sun, Luchen Wang, Chunhu Li, Xiangchao Meng
To address the challenge of designing a highly reactive and stable bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), a hydrophilic Fe-CoPx nanorod array on nickel foam (NF) was designed and prepared in this work. The modulation of a d-band center of Co by adding Fe effectively optimized the adsorption energy of intermediates. The synergistic effect of the bimetallic active sites significantly enhanced the electrocatalytic performance for both reactions. In alkaline seawater, Fe-CoPx/NF exhibited excellent HER (−32 mV at −10 mA cm–2) and OER (216 mV at 10 mA cm–2) activities, maintaining stability for over 100 h at 100 mA cm–2. For overall seawater electrolysis, the catalyst achieved a low cell voltage of 1.54 V at 10 mA cm–2, outperforming the conventional RuO2∥Pt/C electrode (1.58 V at 10 mA cm–2). Additionally, in a simulated industrial flow cell, the catalyst operated stably for over 200 h at 100 mA cm–2, indicating its strong potential for practical applications. This study introduced a simple synthesis method for bimetallic phosphides, providing a new avenue for the design of high-performance bifunctional catalysts for seawater electrolysis.
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