Pub Date : 2024-10-11DOI: 10.1021/acssuschemeng.4c05754
Qinyu Wu, Muhammad Saeed, Jiaqi Wang, Xuejuan Ma, Shengfu Tong, Zongwei Mei
The proton exchange membrane water electrolyzer (PEMWE) is regarded as the most promising technique to convert intermittent renewable energy sources into clean and storable hydrogen through electrocatalytic water splitting. However, commercial electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are based on expensive platinum group metals (PGMs), which predominantly hinder the large-scale application of PEMWE. Single-atom electrocatalysts (SAECs) with atomic level dispersion of metal active sites can greatly minimize the usage amount of precious metals while keeping the efficient electrocatalytic activities. These advantages make SAECs attractive for their application in PEMWE. In this review, the mechanism of the HER and OER, together with general synthesis strategies of SAECs, was introduced and discussed. Subsequently, the recent development of SAECs based on (non)precious metals for acidic HER, OER, and overall water splitting is summarized, highlighted with the mechanism understanding between the electronic structure and electrocatalytic performance. Finally, the challenges and perspectives of SAECs for acidic water splitting are proposed.
质子交换膜水电解槽（PEMWE）被认为是通过电催化水分裂将间歇性可再生能源转化为清洁和可储存氢气的最有前途的技术。然而，用于氢进化反应（HER）和氧进化反应（OER）的商用电催化剂基于昂贵的铂族金属（PGM），这主要阻碍了 PEMWE 的大规模应用。单原子电催化剂（SAECs）具有原子级分散的金属活性位点，可在保持高效电催化活性的同时大大减少贵金属的用量。这些优势使得单原子电催化剂在 PEMWE 中的应用极具吸引力。本综述介绍并讨论了 HER 和 OER 的机理以及 SAECs 的一般合成策略。随后，总结了基于（非）贵金属的 SAECs 在酸性 HER、OER 和整体水分离方面的最新发展，重点介绍了电子结构与电催化性能之间的机理。最后，提出了用于酸性水分离的 SAECs 所面临的挑战和前景。
{"title":"Single-Atom Electrocatalysts for Water Splitting in Acidic Media","authors":"Qinyu Wu, Muhammad Saeed, Jiaqi Wang, Xuejuan Ma, Shengfu Tong, Zongwei Mei","doi":"10.1021/acssuschemeng.4c05754","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05754","url":null,"abstract":"The proton exchange membrane water electrolyzer (PEMWE) is regarded as the most promising technique to convert intermittent renewable energy sources into clean and storable hydrogen through electrocatalytic water splitting. However, commercial electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are based on expensive platinum group metals (PGMs), which predominantly hinder the large-scale application of PEMWE. Single-atom electrocatalysts (SAECs) with atomic level dispersion of metal active sites can greatly minimize the usage amount of precious metals while keeping the efficient electrocatalytic activities. These advantages make SAECs attractive for their application in PEMWE. In this review, the mechanism of the HER and OER, together with general synthesis strategies of SAECs, was introduced and discussed. Subsequently, the recent development of SAECs based on (non)precious metals for acidic HER, OER, and overall water splitting is summarized, highlighted with the mechanism understanding between the electronic structure and electrocatalytic performance. Finally, the challenges and perspectives of SAECs for acidic water splitting are proposed.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405013","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}
One promising solution for the development of greener chemical processes is the utilization of reversible CO2-switchable hydrophilicity solvents (CO2-SHSs) that offer an energy-friendly alternative to solvents with fixed solvation properties. The use of these solvents needs efficient interactions between the solvent and the trigger as mass transfer issues can significantly affect efficiency. In this study, a novel approach for fast investigation of SHS performances is proposed by employing 2-2-dibutylaminoethanol (DBAE) as a known CO2-SHS within a continuous microfluidic device made of poly(dimethylsiloxane) (PDMS). This method allowed the examination of mass transport in the phase change reaction and a considerable reduction of the time required for the phenomenon to occur to subminute time scales. A proof of concept is presented for the extraction of soybean oil from a soybean oil/DBAE mixture, which paves the way for the development of continuous microfluidic liquid–liquid extraction processes. In addition to this study, spectroscopic analyses conducted on DBAE under a CO2 atmosphere also revealed that water is unnecessary for initiating the switch of DBAE into a hydrophilic compound, implying the existence of an additional reaction pathway. This finding could extend the potential applications of DBAE as an SHS to hydrophilic solvents other than water.
{"title":"Toward Liquid–Liquid Extraction Using Switchable Hydrophilicity Solvents in Microfluidic Poly(dimethylsiloxane) Chips","authors":"Margaux Zollo, Thierry Tassaing, Jean-Baptiste Salmon, Yaocihuatl Medina-Gonzalez","doi":"10.1021/acssuschemeng.4c04907","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04907","url":null,"abstract":"One promising solution for the development of greener chemical processes is the utilization of reversible CO<sub>2</sub>-switchable hydrophilicity solvents (CO<sub>2</sub>-SHSs) that offer an energy-friendly alternative to solvents with fixed solvation properties. The use of these solvents needs efficient interactions between the solvent and the trigger as mass transfer issues can significantly affect efficiency. In this study, a novel approach for fast investigation of SHS performances is proposed by employing 2-2-dibutylaminoethanol (DBAE) as a known CO<sub>2</sub>-SHS within a continuous microfluidic device made of poly(dimethylsiloxane) (PDMS). This method allowed the examination of mass transport in the phase change reaction and a considerable reduction of the time required for the phenomenon to occur to subminute time scales. A proof of concept is presented for the extraction of soybean oil from a soybean oil/DBAE mixture, which paves the way for the development of continuous microfluidic liquid–liquid extraction processes. In addition to this study, spectroscopic analyses conducted on DBAE under a CO<sub>2</sub> atmosphere also revealed that water is unnecessary for initiating the switch of DBAE into a hydrophilic compound, implying the existence of an additional reaction pathway. This finding could extend the potential applications of DBAE as an SHS to hydrophilic solvents other than water.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405092","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 : 2024-10-11DOI: 10.1021/acssuschemeng.4c05300
Na Wang, Xiang Zhou, Youming Dong, Ying Zhang, Rong Liu, Haijiao Kang, Kaili Wang, Jianzhang Li
Natural mildew preventives, like citral, have great potential to protect bamboo from mildew, while their long-lasting antimildew performance is yet to be challenged owing to their oxidability and volatility. Inspired by biomimetic mineralization, in this work, citral@ZIF-67 particles were synthesized by encapsulating citral into a zeolite imidazolate framework-67 (ZIF-67) cage and introduced into a bamboo structure. Benefiting from the unique cage structure and large surface area of ZIF-67, it can encapsulate sufficient citral molecules. The encapsulation reduced the particle size of ZIF-67 due to the nucleation of citral. Furthermore, the surface area, pore size, and volume of citral@ZIF-67 particles gradually decreased with the increase in loading amounts of citral. ZIF-67 exhibited a certain antibacterial ability against E. coli and S. aureus. The encapsulation of citral can further enhance the antibacterial activity of ZIF-67. In addition, the citral@ZIF-67 showed slow-release performance that followed the Fickian diffusion mechanism. After the citral@ZIF-67 treatment, bamboo showed no mold spots on the surface with an infection grade of 0, which was retained, even though bamboo was conditioned at 50 °C and 85% relative humidity for 10 days. This proposed method can effectively improve the stability of natural mildew preventives and endow bamboo with long-term antimildew properties with low cost and minimized environmental impacts.
{"title":"Citral Encapsulated into a Zeolite Imidazolate Framework-67 (ZIF-67) Cage via Biomimetic Mineralization as an Efficient Preservative for Long-Term Antimildew Efficacy of Bamboo","authors":"Na Wang, Xiang Zhou, Youming Dong, Ying Zhang, Rong Liu, Haijiao Kang, Kaili Wang, Jianzhang Li","doi":"10.1021/acssuschemeng.4c05300","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05300","url":null,"abstract":"Natural mildew preventives, like citral, have great potential to protect bamboo from mildew, while their long-lasting antimildew performance is yet to be challenged owing to their oxidability and volatility. Inspired by biomimetic mineralization, in this work, citral@ZIF-67 particles were synthesized by encapsulating citral into a zeolite imidazolate framework-67 (ZIF-67) cage and introduced into a bamboo structure. Benefiting from the unique cage structure and large surface area of ZIF-67, it can encapsulate sufficient citral molecules. The encapsulation reduced the particle size of ZIF-67 due to the nucleation of citral. Furthermore, the surface area, pore size, and volume of citral@ZIF-67 particles gradually decreased with the increase in loading amounts of citral. ZIF-67 exhibited a certain antibacterial ability against <i>E. coli</i> and <i>S. aureus</i>. The encapsulation of citral can further enhance the antibacterial activity of ZIF-67. In addition, the citral@ZIF-67 showed slow-release performance that followed the <i>Fickian</i> diffusion mechanism. After the citral@ZIF-67 treatment, bamboo showed no mold spots on the surface with an infection grade of 0, which was retained, even though bamboo was conditioned at 50 °C and 85% relative humidity for 10 days. This proposed method can effectively improve the stability of natural mildew preventives and endow bamboo with long-term antimildew properties with low cost and minimized environmental impacts.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405235","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 : 2024-10-10DOI: 10.1021/acssuschemeng.4c04227
Monalisa Chakraborty, Mariona Battestini Vives, Omar Y. Abdelaziz, Gunnar Henriksson, Rakel Wreland Lindström, Christian P. Hulteberg, Amirreza Khataee
Lignin is one of the most naturally occurring biopolymers on Earth and exists in a relatively large portion of the residual stream of the pulp and paper industry. Technical lignin is water-soluble, nontoxic, and rich in quinone-type groups; therefore, it could be a potential redox species for next-generation aqueous redox flow batteries (RFBs). Despite having attractive features, lignin does not show a reversible electrochemical behavior. Herein, we implemented a straightforward approach to modify the structure of soda-based lignin by oxidative depolymerization. The modified lignin showed good electrochemical activity through cyclic voltammetry with distinct redox peaks, which match lignin monomers, such as vanillin and acetovanillone. The modified lignin was used as the negolyte of the RFB setup with potassium ferrocyanide as the counterpart. The RFB was cycled for over 200 cycles with an average Coulombic efficiency of 91%. In addition, the modified lignin electrolyte maintained the (electro)chemical properties even after four months of storage, as proven by RFB tests.
{"title":"Lignin-Based Electrolytes for Aqueous Redox Flow Batteries","authors":"Monalisa Chakraborty, Mariona Battestini Vives, Omar Y. Abdelaziz, Gunnar Henriksson, Rakel Wreland Lindström, Christian P. Hulteberg, Amirreza Khataee","doi":"10.1021/acssuschemeng.4c04227","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04227","url":null,"abstract":"Lignin is one of the most naturally occurring biopolymers on Earth and exists in a relatively large portion of the residual stream of the pulp and paper industry. Technical lignin is water-soluble, nontoxic, and rich in quinone-type groups; therefore, it could be a potential redox species for next-generation aqueous redox flow batteries (RFBs). Despite having attractive features, lignin does not show a reversible electrochemical behavior. Herein, we implemented a straightforward approach to modify the structure of soda-based lignin by oxidative depolymerization. The modified lignin showed good electrochemical activity through cyclic voltammetry with distinct redox peaks, which match lignin monomers, such as vanillin and acetovanillone. The modified lignin was used as the negolyte of the RFB setup with potassium ferrocyanide as the counterpart. The RFB was cycled for over 200 cycles with an average Coulombic efficiency of 91%. In addition, the modified lignin electrolyte maintained the (electro)chemical properties even after four months of storage, as proven by RFB tests.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398490","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 : 2024-10-10DOI: 10.1021/acssuschemeng.4c06214
Jin Du, Hebin Liang, Yubin Zou, Bing Li, Xiao-yan Li, Lin Lin
The electroreduction of carbon dioxide (CO2) to high-value organic chemicals by the microbial electrosynthesis (MES) system relies heavily on the electrochemical properties of the electrode materials. In this work, CO2 reduction for acetate production was greatly boosted by decorating the carbon felt cathode using the Fe–Mn bimetallic oxides, using an enriched anaerobic mixed culture dominated by the homoacetogen Acetobacterium wieringae. In comparison with the unmodified carbon felt as the cathode in the MES reactor, modification with MnFe2O4 increased the acetate production rate from 28 to 78 g/(m2·d), higher than those with MnO at 59 g/(m2·d) and Fe2O3 at 62 g/(m2·d), and the relative abundance of A. wieringae increased dramatically from 51 to 87% in the biofilm. This was probably due to the mediated electron uptake via the redox cycles of Mn(III)/(II) and Fe(III)/(II), improved specific surface area, and enhanced hydrophilicity of the cathode, benefiting from the synergistic effect of Fe and Mn ions. Overall, this study provides a facile and promising electrode modification strategy for MES with Fe–Mn bimetallic oxides for efficient CO2 conversion and acetate production, bringing the world closer to achieving carbon neutrality.
通过微生物电合成（MES）系统将二氧化碳（CO2）电还原成高价值有机化学品在很大程度上依赖于电极材料的电化学特性。在这项工作中，通过使用铁锰双金属氧化物装饰碳毡阴极，并使用以均乙酸菌 Acetobacterium wieringae 为主导的富集厌氧混合培养物，大大提高了生产醋酸的二氧化碳还原能力。与未经改性的碳毡作为 MES 反应器的阴极相比，使用 MnFe2O4 进行改性可将醋酸生产率从 28 g/(m2-d) 提高到 78 g/(m2-d)，高于使用 MnO 的 59 g/(m2-d) 和 Fe2O3 的 62 g/(m2-d)。这可能是由于 Mn（III）/（II）和 Fe（III）/（II）的氧化还原循环促进了电子吸收，提高了比表面积，以及阴极亲水性的增强，受益于 Fe 和 Mn 离子的协同效应。总之，这项研究为使用铁锰双金属氧化物进行 MES 的电极改性提供了一种简便而有前景的策略，可用于高效的二氧化碳转化和醋酸盐生产，从而使世界离实现碳中和更近一步。
{"title":"Boosting Microbial CO2 Electroreduction by the Biocompatible and Electroactive Bimetallic Fe–Mn Oxide Cathode for Acetate Production","authors":"Jin Du, Hebin Liang, Yubin Zou, Bing Li, Xiao-yan Li, Lin Lin","doi":"10.1021/acssuschemeng.4c06214","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06214","url":null,"abstract":"The electroreduction of carbon dioxide (CO<sub>2</sub>) to high-value organic chemicals by the microbial electrosynthesis (MES) system relies heavily on the electrochemical properties of the electrode materials. In this work, CO<sub>2</sub> reduction for acetate production was greatly boosted by decorating the carbon felt cathode using the Fe–Mn bimetallic oxides, using an enriched anaerobic mixed culture dominated by the homoacetogen <i>Acetobacterium wieringae</i>. In comparison with the unmodified carbon felt as the cathode in the MES reactor, modification with MnFe<sub>2</sub>O<sub>4</sub> increased the acetate production rate from 28 to 78 g/(m<sup>2</sup>·d), higher than those with MnO at 59 g/(m<sup>2</sup>·d) and Fe<sub>2</sub>O<sub>3</sub> at 62 g/(m<sup>2</sup>·d), and the relative abundance of <i>A. wieringae</i> increased dramatically from 51 to 87% in the biofilm. This was probably due to the mediated electron uptake <i>via</i> the redox cycles of Mn(III)/(II) and Fe(III)/(II), improved specific surface area, and enhanced hydrophilicity of the cathode, benefiting from the synergistic effect of Fe and Mn ions. Overall, this study provides a facile and promising electrode modification strategy for MES with Fe–Mn bimetallic oxides for efficient CO<sub>2</sub> conversion and acetate production, bringing the world closer to achieving carbon neutrality.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398385","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 : 2024-10-10DOI: 10.1021/acssuschemeng.4c05339
Xiaojing Wu, Rui Zhang, Hanbing Wang, Xujing Sun, Ning Luo, Dongjiang You, Lingyu Du, Yunming Li, Litao Kang
Despite showing low cost, inherent safety, and high suitability, the rechargeable Zn–I2 aqueous batteries are still seriously suffering from self-discharge and energy density issues stemming from I2 dissolution, polyiodide shuttling, and low I2 mass loading. Herein, we develop a novel polyquaternium-10 (P10, a cationic cellulose)-based binding system to simultaneously circumvent these issues. The water-borne P10 binder can suppress I2 dissolution and polyiodide shuttling by not only adsorbing polyiodides via its quaternary ammonium groups and oxygen heteroatoms but also eliminating the use of toxic, expensive, and I2-dissolving organic solvents (e.g., N-methylpyrrolidone, NMP), enabling a facile and green cathode-fabricating process. More importantly, the P10 binder is conducive to the preparation of thick cathode coatings with high I2 mass loadings, thanks to its high elasticity and mechanical toughness after swelling by the electrolyte. As a result, Zn–I2 batteries prepared with the P10 binder demonstrate much better anti-self-discharge performance than those prepared with conventional PVDF binders (capacity retention: 84 vs 63% after 200 h of open-circuit storage). Even at an ultrahigh I2 mass loading of 14.5 mg cm–2, the batteries can still deliver significant specific capacity (216 mAh g–1) and cyclability (96.8% capacity remained after 385 cycles). This binder should be highly compatible with other performance-improving strategies, providing a green yet affordable approach for the construction of high-performance Zn–I2 aqueous batteries.
{"title":"Building a High-Performance Zn–I2 Battery with a Green and Affordable Cationic Cellulose Binder","authors":"Xiaojing Wu, Rui Zhang, Hanbing Wang, Xujing Sun, Ning Luo, Dongjiang You, Lingyu Du, Yunming Li, Litao Kang","doi":"10.1021/acssuschemeng.4c05339","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05339","url":null,"abstract":"Despite showing low cost, inherent safety, and high suitability, the rechargeable Zn–I<sub>2</sub> aqueous batteries are still seriously suffering from self-discharge and energy density issues stemming from I<sub>2</sub> dissolution, polyiodide shuttling, and low I<sub>2</sub> mass loading. Herein, we develop a novel polyquaternium-10 (P10, a cationic cellulose)-based binding system to simultaneously circumvent these issues. The water-borne P10 binder can suppress I<sub>2</sub> dissolution and polyiodide shuttling by not only adsorbing polyiodides via its quaternary ammonium groups and oxygen heteroatoms but also eliminating the use of toxic, expensive, and I<sub>2</sub>-dissolving organic solvents (e.g., <i>N</i>-methylpyrrolidone, NMP), enabling a facile and green cathode-fabricating process. More importantly, the P10 binder is conducive to the preparation of thick cathode coatings with high I<sub>2</sub> mass loadings, thanks to its high elasticity and mechanical toughness after swelling by the electrolyte. As a result, Zn–I<sub>2</sub> batteries prepared with the P10 binder demonstrate much better anti-self-discharge performance than those prepared with conventional PVDF binders (capacity retention: 84 vs 63% after 200 h of open-circuit storage). Even at an ultrahigh I<sub>2</sub> mass loading of 14.5 mg cm<sup>–2</sup>, the batteries can still deliver significant specific capacity (216 mAh g<sup>–1</sup>) and cyclability (96.8% capacity remained after 385 cycles). This binder should be highly compatible with other performance-improving strategies, providing a green yet affordable approach for the construction of high-performance Zn–I<sub>2</sub> aqueous batteries.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398384","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 : 2024-10-10DOI: 10.1021/acssuschemeng.4c06975
Chang-An Xu, Wenzi Liang, Shaoheng Yang, Yang Hu, Zhuohong Yang, Hao Pang
At present, the dielectric constant of anticorrosion coatings is relatively high, which limits its application in electronic devices, and the epoxy curing agent currently used is mostly from fossil resources, which is not conducive to sustainable development. Therefore, a vanillin-based active ester curing agent (VAEI) containing an imine bond was prepared by the esterification reaction and amine aldehyde condensation reaction. Subsequently, VAEI and amino curing agents cured the epoxy resin to prepare a coating with antibacterial properties, low dielectric, and corrosion resistance. The results showed that when the content of VAEI was 5 wt %, its anticorrosion properties were basically equivalent to that of the coating prepared by the pure amino curing agent. When the content of VAEI was 14 wt %, the impedance modulus of the coating was as high as 1.00 × 109 Ω cm2 after soaking in salt water for 150 days, which was 2 orders of magnitude higher than that of the control group. In addition, the dielectric constant of the coating at 10 MHz decreased from 4.16 to 3.64, and it also exhibited excellent antibacterial properties against Escherichia coli (7.0%) and Staphylococcus aureus (19.6%). This work expands the added value of vanillin and provides a reference for the preparation of various performance coatings.
{"title":"Preparation of a Vanillin-Based Active Ester Curing Agent and the Low Dielectric, Antibacterial, and Anticorrosion Properties of Its Coatings","authors":"Chang-An Xu, Wenzi Liang, Shaoheng Yang, Yang Hu, Zhuohong Yang, Hao Pang","doi":"10.1021/acssuschemeng.4c06975","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06975","url":null,"abstract":"At present, the dielectric constant of anticorrosion coatings is relatively high, which limits its application in electronic devices, and the epoxy curing agent currently used is mostly from fossil resources, which is not conducive to sustainable development. Therefore, a vanillin-based active ester curing agent (VAEI) containing an imine bond was prepared by the esterification reaction and amine aldehyde condensation reaction. Subsequently, VAEI and amino curing agents cured the epoxy resin to prepare a coating with antibacterial properties, low dielectric, and corrosion resistance. The results showed that when the content of VAEI was 5 wt %, its anticorrosion properties were basically equivalent to that of the coating prepared by the pure amino curing agent. When the content of VAEI was 14 wt %, the impedance modulus of the coating was as high as 1.00 × 10<sup>9</sup> Ω cm<sup>2</sup> after soaking in salt water for 150 days, which was 2 orders of magnitude higher than that of the control group. In addition, the dielectric constant of the coating at 10 MHz decreased from 4.16 to 3.64, and it also exhibited excellent antibacterial properties against <i>Escherichia coli</i> (7.0%) and <i>Staphylococcus aureus</i> (19.6%). This work expands the added value of vanillin and provides a reference for the preparation of various performance coatings.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398387","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 : 2024-10-10DOI: 10.1021/acssuschemeng.4c03193
Adriano Leão, Marie Collin, Swarali Ghodkhande, Arnaud Bouissonnié, Xin Chen, Benjamin Malin, Yiming Liu, Geanna Hovey, Jagannathan Govindhakannan, Erika La Plante, David Jassby, Torben Gädt, Lorenzo Corsini, Dante Simonetti, Fabian Rosner, Gaurav Sant
Limestone (calcite, CaCO3) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (∼800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO2(g)) emissions and energy use, i.e., ∼1 tonne [t] of CO2 and ∼1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO3 as a Ca source to make hydrated lime (portlandite, Ca(OH)2) at ambient conditions (p, T)─while nearly eliminating process CO2(g) emissions (as low as 1.5 mol. % of the CO2 in the precursor CaCO3, equivalent to 9 kg of CO2(g) per t of Ca(OH)2)─within an aqueous flow-electrolysis/pH-swing process that coproduces hydrogen (H2(g)) and oxygen (O2(g)). Because Ca(OH)2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO3 and complexation of Ca2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO3–) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH)2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO3), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO3, 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ∼2 MWh of electrical energy are required to produce 1 t of Ca(OH)2, with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO2 mineralization via Ca(OH)2 carbonation.
{"title":"ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production","authors":"Adriano Leão, Marie Collin, Swarali Ghodkhande, Arnaud Bouissonnié, Xin Chen, Benjamin Malin, Yiming Liu, Geanna Hovey, Jagannathan Govindhakannan, Erika La Plante, David Jassby, Torben Gädt, Lorenzo Corsini, Dante Simonetti, Fabian Rosner, Gaurav Sant","doi":"10.1021/acssuschemeng.4c03193","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c03193","url":null,"abstract":"Limestone (calcite, CaCO<sub>3</sub>) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (∼800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO<sub>2(g)</sub>) emissions and energy use, i.e., ∼1 tonne [t] of CO<sub>2</sub> and ∼1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO<sub>3</sub> as a Ca source to make hydrated lime (portlandite, Ca(OH)<sub>2</sub>) at ambient conditions (<i>p</i>, <i>T</i>)─while nearly eliminating process CO<sub>2(g)</sub> emissions (as low as 1.5 mol. % of the CO<sub>2</sub> in the precursor CaCO<sub>3</sub>, equivalent to 9 kg of CO<sub>2(g)</sub> per t of Ca(OH)<sub>2</sub>)─within an aqueous flow-electrolysis/pH-swing process that coproduces hydrogen (H<sub>2(g)</sub>) and oxygen (O<sub>2(g)</sub>). Because Ca(OH)<sub>2</sub> is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The <b>Zero CA</b>rbon <b>L</b>ime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO<sub>3</sub> and complexation of Ca<sup>2+</sup> under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO<sub>3</sub><sup>–</sup>) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH)<sub>2</sub> from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO<sub>3</sub>), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO<sub>3</sub>, 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ∼2 MWh of electrical energy are required to produce 1 t of Ca(OH)<sub>2</sub>, with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO<sub>2</sub> mineralization via Ca(OH)<sub>2</sub> carbonation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398586","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}
Protein-based nanomaterials are among the most promising materials for gas adsorption due to their green properties and high surface area. However, the performance of these materials is susceptible to variations in temperature. This study examined the effects of postheat treatment (40 °C, 0–9 h) on the dynamic network valence bonds of zein nanofibers (zeinNFs) and their ethylene adsorption performance using theoretical simulations and experimental studies. With increasing durations of postheat treatment, up to 9 h, the diameter of zeinNF-9 reduced by 42.11%, the structure of the zein protein stretched, the total sulfhydryl groups increased by 13.03%, and the ethylene adsorption efficiency increased to 7.05 ± 0.05 mg/m3/h. Furthermore, incubation of TaiPo pear with zeinNF-9 for 20 days resulted in the most effective preservation performance. The above results demonstrate that zeinNF-9 is a highly efficient and environmentally friendly material for ethylene adsorption. These characteristics render it greatly promising for practical applications in fruit preservation.
{"title":"Self-Modification of Dynamic Network Valence Bonds in ZeinNFs via Post-Heat Treatment: Preparation of an Efficient and Environmentally Friendly Ethylene Adsorbent","authors":"Xin Fan, Jinghua Zhao, Huayin Pu, Lingshuang Rong, Lu Chang, Wenqiang He, Yiyu Wang, Junrong Huang","doi":"10.1021/acssuschemeng.4c06066","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06066","url":null,"abstract":"Protein-based nanomaterials are among the most promising materials for gas adsorption due to their green properties and high surface area. However, the performance of these materials is susceptible to variations in temperature. This study examined the effects of postheat treatment (40 °C, 0–9 h) on the dynamic network valence bonds of zein nanofibers (zeinNFs) and their ethylene adsorption performance using theoretical simulations and experimental studies. With increasing durations of postheat treatment, up to 9 h, the diameter of zeinNF-9 reduced by 42.11%, the structure of the zein protein stretched, the total sulfhydryl groups increased by 13.03%, and the ethylene adsorption efficiency increased to 7.05 ± 0.05 mg/m<sup>3</sup>/h. Furthermore, incubation of TaiPo pear with zeinNF-9 for 20 days resulted in the most effective preservation performance. The above results demonstrate that zeinNF-9 is a highly efficient and environmentally friendly material for ethylene adsorption. These characteristics render it greatly promising for practical applications in fruit preservation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385845","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 : 2024-10-09DOI: 10.1021/acssuschemeng.4c05739
Anton Bjurström, Antonella Scotto di Uccio, Sirui Liu, Anna J. Svagan, Shuvra Singha, Alessandra Cesaro, Stefano Papirio, Silvio Matassa, Mikael S. Hedenqvist
The majority of plastics used today are produced from nonrenewable resources, and, depending on the end-of-life management, they may end up in landfills or in nature, giving rise to microplastic pollution. A potential way of minimizing this is to use proteins, preferentially recovered from organic waste and residues, to make plastics. In line with this, we explored here the potential of protein-based bioplastics sourced from single-cell protein (SCP). Films of glycerol-plasticized SCPs (grown by recovering carbon from cheese whey and nitrogen from anaerobic digestate) were produced by compression molding. Electron microscopy revealed a structure of intact cells and the presence of cracks/voids, and the mechanical properties indicated a rather poor cohesion between the cells, despite the high-temperature treatment in the pressing stage. The resulting structure yielded a material that could absorb a sizable amount of both nonpolar (rapid capillary uptake) and polar liquids. The anaerobic biodegradation of the SCP films demonstrated that full biodegradability (100%) and high specific biomethane productions (471 ± 8 mL/gram of volatile solids) could be attained within operating conditions that are typical of anaerobic digestion processes in the treatment of food waste. Overall, this study highlights the potential and also the challenge of using SCP as an alternative bioplastic material in food packaging and edible coatings.
{"title":"Single-cell Protein Bioplastic Films from Recovered Nitrogen and Carbon with High Anaerobic Biodegradability and Biogas Potential at End-of-Life","authors":"Anton Bjurström, Antonella Scotto di Uccio, Sirui Liu, Anna J. Svagan, Shuvra Singha, Alessandra Cesaro, Stefano Papirio, Silvio Matassa, Mikael S. Hedenqvist","doi":"10.1021/acssuschemeng.4c05739","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05739","url":null,"abstract":"The majority of plastics used today are produced from nonrenewable resources, and, depending on the end-of-life management, they may end up in landfills or in nature, giving rise to microplastic pollution. A potential way of minimizing this is to use proteins, preferentially recovered from organic waste and residues, to make plastics. In line with this, we explored here the potential of protein-based bioplastics sourced from single-cell protein (SCP). Films of glycerol-plasticized SCPs (grown by recovering carbon from cheese whey and nitrogen from anaerobic digestate) were produced by compression molding. Electron microscopy revealed a structure of intact cells and the presence of cracks/voids, and the mechanical properties indicated a rather poor cohesion between the cells, despite the high-temperature treatment in the pressing stage. The resulting structure yielded a material that could absorb a sizable amount of both nonpolar (rapid capillary uptake) and polar liquids. The anaerobic biodegradation of the SCP films demonstrated that full biodegradability (100%) and high specific biomethane productions (471 ± 8 mL/gram of volatile solids) could be attained within operating conditions that are typical of anaerobic digestion processes in the treatment of food waste. Overall, this study highlights the potential and also the challenge of using SCP as an alternative bioplastic material in food packaging and edible coatings.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":8.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385196","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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