Pub Date : 2024-11-19DOI: 10.1021/acssuschemeng.4c06100
Aleksandra Zamljen, Blaž Likozar
As the world’s technological development shifts toward a sustainable energy future by harnessing renewable energy sources, ammonia is gaining recognition as a complementary green vector to hydrogen. This energy-dense carbon-neutral fuel is capable of overcoming hydrogen’s limitations in terms of storage, distribution, and infrastructure deployment. The biggest challenge to the global use of ammonia as an energy storage medium remains more efficient, readily deployable production of ammonia from abundant, yet intermittent, sources. Green decentralized ammonia production, which refers to the small-scale, localized ammonia production utilizing environmentally sustainable methods, offers a promising approach to overcoming the challenges of traditional ammonia synthesis. The process aims to minimize carbon emissions, increase energy efficiency, and improve accessibility to ammonia in remote regions. Ammonia separation using sorbent materials holds significant potential in green ammonia production, providing a viable alternative to conventional condensation-based separation methods, with particular benefits in improving energy efficiency. This perspective summarizes recent developments in the field of ammonia separation, focusing on newly developed sorbents for the integrated ammonia synthesis–separation process, particularly metal halides that could potentially replace a conventional ammonia condenser. The challenges and potential solutions are also discussed. Moreover, this perspective outlines the mechanism of ammonia absorption into metal halides with its kinetics and thermodynamics. The use of computational methods for the development of new materials is also described, thereby laying the foundations of green ammonia technology.
{"title":"Catalytic Reactor-Utilized Ammonia Adsorption, Absorption, and Storage Materials: Mechanism, Nanostructure, and Ab Initio Design","authors":"Aleksandra Zamljen, Blaž Likozar","doi":"10.1021/acssuschemeng.4c06100","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06100","url":null,"abstract":"As the world’s technological development shifts toward a sustainable energy future by harnessing renewable energy sources, ammonia is gaining recognition as a complementary green vector to hydrogen. This energy-dense carbon-neutral fuel is capable of overcoming hydrogen’s limitations in terms of storage, distribution, and infrastructure deployment. The biggest challenge to the global use of ammonia as an energy storage medium remains more efficient, readily deployable production of ammonia from abundant, yet intermittent, sources. Green decentralized ammonia production, which refers to the small-scale, localized ammonia production utilizing environmentally sustainable methods, offers a promising approach to overcoming the challenges of traditional ammonia synthesis. The process aims to minimize carbon emissions, increase energy efficiency, and improve accessibility to ammonia in remote regions. Ammonia separation using sorbent materials holds significant potential in green ammonia production, providing a viable alternative to conventional condensation-based separation methods, with particular benefits in improving energy efficiency. This perspective summarizes recent developments in the field of ammonia separation, focusing on newly developed sorbents for the integrated ammonia synthesis–separation process, particularly metal halides that could potentially replace a conventional ammonia condenser. The challenges and potential solutions are also discussed. Moreover, this perspective outlines the mechanism of ammonia absorption into metal halides with its kinetics and thermodynamics. The use of computational methods for the development of new materials is also described, thereby laying the foundations of green ammonia technology.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670425","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 : 2024-11-18DOI: 10.1021/acssuschemeng.4c07375
Huan Liu, Yang Yu
Developing renewable monomers for preparing polyesters with high UV shielding and hydrolytic degradability is a challenging topic. Herein, a ternary cyclic monomer (denoted as FBPC) containing one furan and two pyrrolidones was prepared by an aza-Michael addition reaction using biobased furan diamine and dimethyl itaconate (DMI). FBPC was melt polymerized with various diols to prepare homopolyesters with a number-average molecular mass (Mn) in the range of 22.4–30.3 kDa. The homopolyesters based on FBPC presented excellent UV shielding properties, with a maximum shielding cutoff of 398 nm, which is significantly superior to monofuran-based polyesters, such as poly(ethylene furanoate) (PEF) and poly(methyl 5-[(2-hydroxyethyl)-sulfanyl]furan-2-carboxylate) (pMSF). The hydrophilic pyrrolidone rings in FBPC enhance the hydrolytic sensitivity of the homopolyesters, giving them complete degradation within 130 days. Then, FBPC was copolymerized with poly(butylene terephthalate) (PBT) to prepare a series of copolyesters with Mn of 23.9–42.7 kDa. The UV shielding and hydrolytic degradation of PBT were significantly improved by adding a ternary cyclic monomer. In addition, FBPC was effective in toughening PBT without changing the thermal stability, and the toughness effect far exceeded those of other sugar-derived cyclic monomers. The mechanical, UV shielding, and hydrolytic degradation properties of the copolyesters can be adjusted depending on FBPC content. Overall, FBPC is an effective biobased precursor that can offer new solutions for improving polyester properties, including UV shielding and hydrolytic degradation.
{"title":"A Ternary Bio-Based Monomer toward the Polyesters with High UV Shielding and Water-Degradation Properties","authors":"Huan Liu, Yang Yu","doi":"10.1021/acssuschemeng.4c07375","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c07375","url":null,"abstract":"Developing renewable monomers for preparing polyesters with high UV shielding and hydrolytic degradability is a challenging topic. Herein, a ternary cyclic monomer (denoted as FBPC) containing one furan and two pyrrolidones was prepared by an aza-Michael addition reaction using biobased furan diamine and dimethyl itaconate (DMI). FBPC was melt polymerized with various diols to prepare homopolyesters with a number-average molecular mass (<i>M</i><sub>n</sub>) in the range of 22.4–30.3 kDa. The homopolyesters based on FBPC presented excellent UV shielding properties, with a maximum shielding cutoff of 398 nm, which is significantly superior to monofuran-based polyesters, such as poly(ethylene furanoate) (PEF) and poly(methyl 5-[(2-hydroxyethyl)-sulfanyl]furan-2-carboxylate) (pMSF). The hydrophilic pyrrolidone rings in FBPC enhance the hydrolytic sensitivity of the homopolyesters, giving them complete degradation within 130 days. Then, FBPC was copolymerized with poly(butylene terephthalate) (PBT) to prepare a series of copolyesters with <i>M</i><sub>n</sub> of 23.9–42.7 kDa. The UV shielding and hydrolytic degradation of PBT were significantly improved by adding a ternary cyclic monomer. In addition, FBPC was effective in toughening PBT without changing the thermal stability, and the toughness effect far exceeded those of other sugar-derived cyclic monomers. The mechanical, UV shielding, and hydrolytic degradation properties of the copolyesters can be adjusted depending on FBPC content. Overall, FBPC is an effective biobased precursor that can offer new solutions for improving polyester properties, including UV shielding and hydrolytic degradation.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"99 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670426","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}
Rechargeable aqueous zinc-ion batteries (RAZIB) are emerging as promising candidates for renewable energy storage devices, offering superior electrochemical performance, enhanced safety, and economic viability. However, the uncontrolled parasitic reactions and the growth of zinc dendrites resulting from nonuniform deposition impede the practical application of RAZIBs. Herein, inspired by the biological role of bamboo parenchymal cells (BPC), a biomimetic electrolyte additive was introduced to enhance the performance of RAZIBs. Abundant, readily extractable, and environmentally friendly BPC additives integrate the structural characteristics of inorganic materials and the advantages of organic materials. (1) BPC acts as the rich Zn2+ reservoir on the anode by adsorbing Zn2+ from the electrolyte, significantly mitigating concentration polarization. (2) The three-dimensional (3D) polyhedral structure of BPC provides numerous active sites to homogenize Zn2+ flux and inhibit two-dimensional (2D) diffusion on the anode. (3) BPC can suppress hydrogen evolution corrosion and guide Zn deposition toward smoother and denser crystal planes. Consequently, the symmetrical cells containing BPC can stably cycle over 3000 h with minimal voltage hysteresis, and the half-cells exhibit a high average Coulombic efficiency (99.67%) over 380 cycles at 5 mA cm–2. Our strategy demonstrates a zincophilic biomass material for constructing a uniformly zinc-rich and fast-transporting interface layer at the anode interface, paving the way for the sustainable utilization of biomass materials applied in the field of energy storage.
{"title":"Suppression of Zinc Dendrites by Bamboo-Inspired Additive for Aqueous Zinc Battery","authors":"Tong Ye, Haiqiang Ma, Shasha Tang, Zhinan Yang, Qinghui Yan, Liurui Zhang, Haiyong He, Yongbo Kuang","doi":"10.1021/acssuschemeng.4c05447","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c05447","url":null,"abstract":"Rechargeable aqueous zinc-ion batteries (RAZIB) are emerging as promising candidates for renewable energy storage devices, offering superior electrochemical performance, enhanced safety, and economic viability. However, the uncontrolled parasitic reactions and the growth of zinc dendrites resulting from nonuniform deposition impede the practical application of RAZIBs. Herein, inspired by the biological role of bamboo parenchymal cells (BPC), a biomimetic electrolyte additive was introduced to enhance the performance of RAZIBs. Abundant, readily extractable, and environmentally friendly BPC additives integrate the structural characteristics of inorganic materials and the advantages of organic materials. (1) BPC acts as the rich Zn<sup>2+</sup> reservoir on the anode by adsorbing Zn<sup>2+</sup> from the electrolyte, significantly mitigating concentration polarization. (2) The three-dimensional (3D) polyhedral structure of BPC provides numerous active sites to homogenize Zn<sup>2+</sup> flux and inhibit two-dimensional (2D) diffusion on the anode. (3) BPC can suppress hydrogen evolution corrosion and guide Zn deposition toward smoother and denser crystal planes. Consequently, the symmetrical cells containing BPC can stably cycle over 3000 h with minimal voltage hysteresis, and the half-cells exhibit a high average Coulombic efficiency (99.67%) over 380 cycles at 5 mA cm<sup>–2</sup>. Our strategy demonstrates a zincophilic biomass material for constructing a uniformly zinc-rich and fast-transporting interface layer at the anode interface, paving the way for the sustainable utilization of biomass materials applied in the field of energy storage.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"227 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142670427","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 : 2024-11-17DOI: 10.1021/acssuschemeng.4c04490
Xiyan Liu, Manxin Cao, Jun Wen, Yu Gong
The AlB2-type WB2-191 with only graphene-like flat boron layers is deemed to be an ideal electrocatalyst for hydrogen evolution. However, such investigation is severely hindered by the lack of facile synthesis methods for this type of WB2-191. Herein, we report the successful synthesis of AlB2-type WB2-191 by a one-step molten salt method via the reaction of WCl6 and NaBH4 in LiCl–KCl molten salt at 800 °C under atmospheric pressure. The as-synthesized WB2-191 presents a nanosheet structure, as demonstrated by the scanning electron microscope and transmission electron microscopy results with a large BET surface area of 63 m2/g. Such WB2-191 nanosheets exhibit remarkable hydrogen evolution reaction activity, delivering low overpotentials of 121 in 0.5 H2SO4 and 147 mV in 1.0 M KOH to drive 10 mA/cm2, which is superior to any previously reported binary tungsten borides. Furthermore, an outstanding stability was shown over 70 h of potentiostatic operations in both acidic and alkaline electrolytes.
{"title":"Facile Synthesis of Tungsten Diboride (WB2-191) in Molten Salt and Its Hydrogen Evolution Performance in Acidic and Alkaline Media","authors":"Xiyan Liu, Manxin Cao, Jun Wen, Yu Gong","doi":"10.1021/acssuschemeng.4c04490","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c04490","url":null,"abstract":"The AlB<sub>2</sub>-type WB<sub>2</sub>-191 with only graphene-like flat boron layers is deemed to be an ideal electrocatalyst for hydrogen evolution. However, such investigation is severely hindered by the lack of facile synthesis methods for this type of WB<sub>2</sub>-191. Herein, we report the successful synthesis of AlB<sub>2</sub>-type WB<sub>2</sub>-191 by a one-step molten salt method via the reaction of WCl<sub>6</sub> and NaBH<sub>4</sub> in LiCl–KCl molten salt at 800 °C under atmospheric pressure. The as-synthesized WB<sub>2</sub>-191 presents a nanosheet structure, as demonstrated by the scanning electron microscope and transmission electron microscopy results with a large BET surface area of 63 m<sup>2</sup>/g. Such WB<sub>2</sub>-191 nanosheets exhibit remarkable hydrogen evolution reaction activity, delivering low overpotentials of 121 in 0.5 H<sub>2</sub>SO<sub>4</sub> and 147 mV in 1.0 M KOH to drive 10 mA/cm<sup>2</sup>, which is superior to any previously reported binary tungsten borides. Furthermore, an outstanding stability was shown over 70 h of potentiostatic operations in both acidic and alkaline electrolytes.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"248 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665297","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}
Covalent organic frameworks (COFs) have emerged as promising photocatalysts for the CO2 reduction reaction (CO2RR). Among various building components, metal phthalocyanines have gained significant attention owing to their excellent photochemical properties and well-defined M–N4 sites. Herein, tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine cobalt(II) (CoTAPc) are used as connection points to couple with bipyridine (bpy) for constructing an imine linked CoPc-bpy COF and then coordinated with Re(CO)3Cl to create a novel CoPc-Rebpy COF. It is found that there exists an intramolecular charge transfer from the CoPc to Rebpy units and then to Re center for CO2RR via Z-scheme molecular heterojunction mechanism. Under visible light illumination, the CoPc-bpy and CoPc-Rebpy COFs deliver CO yields of 3068 and 6680 μmol g–1 h–1, respectively. The significantly increased activity of CoPc-Rebpy COF can be ascribed to the synergistic effect of Re catalytic sites and the electron capture center provided by the CoPc unit. These findings present an effective strategy for COF-based photocatalysts for CO2RR.
共价有机框架(COFs)已成为二氧化碳还原反应(CO2RR)中前景广阔的光催化剂。在各种构建成分中,金属酞菁因其出色的光化学特性和明确的 M-N4 位点而备受关注。在本文中,2,3,9,10,16,17,23,24-八羧基酞菁钴(II)(CoTAPc)的四酸酐被用作连接点,与双吡啶(bpy)耦合以构建亚胺连接的 CoPc-bpy COF,然后与 Re(CO)3Cl 配位以创建新型 CoPc-Rebpy COF。研究发现,CoPc 与 Rebpy 单元之间存在分子内电荷转移,然后通过 Z 型分子异质结机制将电荷转移到 Re 中心,实现 CO2RR。在可见光照射下,CoPc-bpy 和 CoPc-Rebpy COFs 的 CO 产率分别为 3068 和 6680 μmol g-1 h-1。CoPc-Rebpy COF 活性的大幅提高可归因于 Re 催化位点和 CoPc 单元提供的电子捕获中心的协同效应。这些发现为基于 COF 的 CO2RR 光催化剂提供了一种有效的策略。
{"title":"Cobalt Phthalocyanine-Based Covalent Organic Framework with Bimetallic Synergistic Effect for Efficient Photocatalytic CO2 Reduction","authors":"Chenyang Luo, Yu Zhou, Yulai Guo, Xinming Li, Renjie Li, Tianyou Peng","doi":"10.1021/acssuschemeng.4c08044","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08044","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising photocatalysts for the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). Among various building components, metal phthalocyanines have gained significant attention owing to their excellent photochemical properties and well-defined M–N<sub>4</sub> sites. Herein, tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine cobalt(II) (CoTAPc) are used as connection points to couple with bipyridine (bpy) for constructing an imine linked CoPc-bpy COF and then coordinated with Re(CO)<sub>3</sub>Cl to create a novel CoPc-Rebpy COF. It is found that there exists an intramolecular charge transfer from the CoPc to Rebpy units and then to Re center for CO<sub>2</sub>RR via Z-scheme molecular heterojunction mechanism. Under visible light illumination, the CoPc-bpy and CoPc-Rebpy COFs deliver CO yields of 3068 and 6680 μmol g<sup>–1</sup> h<sup>–1</sup>, respectively. The significantly increased activity of CoPc-Rebpy COF can be ascribed to the synergistic effect of Re catalytic sites and the electron capture center provided by the CoPc unit. These findings present an effective strategy for COF-based photocatalysts for CO<sub>2</sub>RR.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"85 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665321","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 : 2024-11-16DOI: 10.1021/acssuschemeng.4c06264
Gonzalo Rodriguez-Garcia, Jon J. Kellar, Zhengtao Zhu, Erkan Aydin, Stefaan De Wolf, Ilke Celik
Perovskite/silicon tandem solar cells (PSTs) have emerged as promising photovoltaic (PV) technology that can exceed the theoretical power conversion efficiency limit of single-junction solar cells. To determine the future potential benefits of PSTs, it is crucial to accurately assess their environmental impacts and recyclability. Here, we present the first complete life cycle toxicity assessment of the PST panels. For this, we evaluated the toxicity of material procurement, manufacturing, and use stages and compared them with the toxicity of crystalline silicon PVs and CdTe PVs, as well as other electricity sources. For the end-of-life (EoL) stage, we developed three variants of panel recycling processes and compared their toxicity impacts with those of procuring the materials required to manufacture a new panel. We found that the life cycle toxicity of PV sin general is mainly driven by metal emissions. PSTs in particular emit more metals (and these are more toxic) than other PVs, but less than conventional sources of energy. A lower silver content─or more sustainable silver procurement─would be the first step toward making PSTs more environmentally sustainable. Concerning the EoL analysis, all proposed variants are less impactful than materials procured from the market. Their largest benefits can be found in the recovery of the bottom glass and crystalline silicon subcell, the copper cables, and the top glass.
{"title":"Comparative Life Cycle Toxicity Assessment of Perovskite/Silicon Tandem Photovoltaics","authors":"Gonzalo Rodriguez-Garcia, Jon J. Kellar, Zhengtao Zhu, Erkan Aydin, Stefaan De Wolf, Ilke Celik","doi":"10.1021/acssuschemeng.4c06264","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06264","url":null,"abstract":"Perovskite/silicon tandem solar cells (PSTs) have emerged as promising photovoltaic (PV) technology that can exceed the theoretical power conversion efficiency limit of single-junction solar cells. To determine the future potential benefits of PSTs, it is crucial to accurately assess their environmental impacts and recyclability. Here, we present the first complete life cycle toxicity assessment of the PST panels. For this, we evaluated the toxicity of material procurement, manufacturing, and use stages and compared them with the toxicity of crystalline silicon PVs and CdTe PVs, as well as other electricity sources. For the end-of-life (EoL) stage, we developed three variants of panel recycling processes and compared their toxicity impacts with those of procuring the materials required to manufacture a new panel. We found that the life cycle toxicity of PV sin general is mainly driven by metal emissions. PSTs in particular emit more metals (and these are more toxic) than other PVs, but less than conventional sources of energy. A lower silver content─or more sustainable silver procurement─would be the first step toward making PSTs more environmentally sustainable. Concerning the EoL analysis, all proposed variants are less impactful than materials procured from the market. Their largest benefits can be found in the recovery of the bottom glass and crystalline silicon subcell, the copper cables, and the top glass.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"17 6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642769","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 : 2024-11-15DOI: 10.1021/acssuschemeng.4c08054
Rainer Hippler, Martin Cada, Antonin Knizek, Martin Ferus, Zdenek Hubicka
A hollow cathode discharge with a copper nickel cathode (Cu50Ni50) was operated in an Ar/H2/N2 gas mixture. Optical emission spectroscopy revealed the formation of NH radicals, which serve as precursors for NH3 formation. Ion mass spectrometry showed the formation of NH3+ and NH4+ ions indicating NH3 formation. Gas samples taken at the exhaust of the vacuum system were analyzed by Fourier transform infrared spectroscopy. Clear evidence for NH3 formation was obtained from these measurements.
{"title":"Generation of Ammonia in a Pulsed Hollow Cathode Discharge Operated in an Ar/H2/N2 Gas Mixture Detected by Fourier Transform Infrared","authors":"Rainer Hippler, Martin Cada, Antonin Knizek, Martin Ferus, Zdenek Hubicka","doi":"10.1021/acssuschemeng.4c08054","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08054","url":null,"abstract":"A hollow cathode discharge with a copper nickel cathode (Cu50Ni50) was operated in an Ar/H<sub>2</sub>/N<sub>2</sub> gas mixture. Optical emission spectroscopy revealed the formation of NH radicals, which serve as precursors for NH<sub>3</sub> formation. Ion mass spectrometry showed the formation of NH<sub>3</sub><sup>+</sup> and NH<sub>4</sub><sup>+</sup> ions indicating NH<sub>3</sub> formation. Gas samples taken at the exhaust of the vacuum system were analyzed by Fourier transform infrared spectroscopy. Clear evidence for NH<sub>3</sub> formation was obtained from these measurements.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"248 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643107","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}
Curing catalysts can accelerate cross-linking reactions but often deteriorate surface performance due to heterogeneous catalysis, which can be resolved by improved homogeneous dispersion of nanoscale catalysts and thus uniform catalysis of resin cross-linking reaction. Nonetheless, nanosizing solidified catalysts, typically organic small molecular crystals, presents challenges using conventional top-down and bottom-up methodologies. Herein, we present a straightforward approach to preparing nanocuring catalysts by leveraging the dry-water structure and obtaining high-performance low-temperature curing coatings. The stable dry-water structure, with microscale catalyst solution droplets surrounded with hydrophobic fumed silica, was formed. Confinement of fumed silica effectively limits the size of the organic catalyst crystals on the nanoscale by ensuring the low 2-eim content in the separated compartment. Coatings incorporating the obtained catalyst, cured at a lower temperature of 170 °C for 15 min, exhibit mechanical strength and chemical resistance compared to standard powder coatings cured at 190 °C for 15 min. Furthermore, with the improved uniform catalysis brought from the nanocatalyst, the low-temperature curing coatings demonstrate excellent surface performance, maintaining gloss levels comparable to the original powder coating film. This study delves into the mechanism of the dry-water structure, offering a facile approach for fabricating nanoscale curing catalysts and achieving high-quality surfaces in powder coating applications.
固化催化剂可以加速交联反应,但往往会因异构催化而导致表面性能下降,而改进纳米级催化剂的均匀分散,从而均匀催化树脂交联反应,则可以解决这一问题。尽管如此,使用传统的自上而下和自下而上的方法对固化催化剂(通常是有机小分子晶体)进行纳米化仍是一项挑战。在此,我们提出了一种利用干水结构制备纳米固化催化剂并获得高性能低温固化涂层的直接方法。通过疏水性气相法二氧化硅包围微尺度催化剂溶液液滴,形成了稳定的干-水结构。气相法二氧化硅的封闭作用可有效限制纳米级有机催化剂晶体的尺寸,确保分离区中的 2-eim 含量较低。与在 190 °C 下固化 15 分钟的标准粉末涂料相比,在 170 °C 下固化 15 分钟的较低温度下固化的含有所获催化剂的涂料具有更高的机械强度和耐化学性。此外,由于纳米催化剂的均匀催化作用得到了改善,低温固化涂料的表面性能极佳,可保持与原始粉末涂料膜相当的光泽度。这项研究深入探讨了干水结构的机理,为制造纳米级固化催化剂和在粉末涂料应用中实现高质量表面提供了一种简便的方法。
{"title":"Dry-Water-System Confined Fabrication of Nanocuring Catalysts for Superior Low-Cure Powder Coating","authors":"Xiao Lv, Haiping Zhang, Hui Zhang, Yuanyuan Shao, Jesse Zhu","doi":"10.1021/acssuschemeng.4c06792","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06792","url":null,"abstract":"Curing catalysts can accelerate cross-linking reactions but often deteriorate surface performance due to heterogeneous catalysis, which can be resolved by improved homogeneous dispersion of nanoscale catalysts and thus uniform catalysis of resin cross-linking reaction. Nonetheless, nanosizing solidified catalysts, typically organic small molecular crystals, presents challenges using conventional top-down and bottom-up methodologies. Herein, we present a straightforward approach to preparing nanocuring catalysts by leveraging the dry-water structure and obtaining high-performance low-temperature curing coatings. The stable dry-water structure, with microscale catalyst solution droplets surrounded with hydrophobic fumed silica, was formed. Confinement of fumed silica effectively limits the size of the organic catalyst crystals on the nanoscale by ensuring the low 2-eim content in the separated compartment. Coatings incorporating the obtained catalyst, cured at a lower temperature of 170 °C for 15 min, exhibit mechanical strength and chemical resistance compared to standard powder coatings cured at 190 °C for 15 min. Furthermore, with the improved uniform catalysis brought from the nanocatalyst, the low-temperature curing coatings demonstrate excellent surface performance, maintaining gloss levels comparable to the original powder coating film. This study delves into the mechanism of the dry-water structure, offering a facile approach for fabricating nanoscale curing catalysts and achieving high-quality surfaces in powder coating applications.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637524","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 : 2024-11-15DOI: 10.1021/acssuschemeng.4c08240
Florent J. Dubray, Vladimir Paunovic, Jeroen A. van Bokhoven
To reduce the aviation industry’s greenhouse gas emissions, sustainable aviation fuel (SAF) is needed. Therefore, a methanol-to-SAF process comprising (i) methanol to olefin (MTO), (ii) olefin oligomerization, and (iii) olefin hydrogenation reaction steps is a promising route. The olefin oligomerization step is responsible for resulting SAF properties and needs to be optimized in concert with the previous MTO step. For this purpose, a kinetic model using a total of seven kinetic parameters was designed from a limited number of experimental measurements, allowing us to successfully describe the oligomerization reactivity of various olefin mixtures over an acid catalyst in flow. This inexpensive model predicted optimal reaction conditions and feed compositions, resulting in product mixtures with properties matching those of conventional Jet-A1 aviation fuel. To maximize SAF-range products, a feed composed of C4 and C5 olefins is most desirable, while controlled C3, C6, and C7 olefin cofeeding and C4/C5 olefin feed ratio are required to finely tune the SAF product composition. This modeling approach allows for efficient process optimization directed toward the synthesis of SAF with controlled properties and composition. Additionally, precise MTO–olefin compositions can be predicted for the optimal production of high-quality SAF, pointing toward the development of an efficient overall methanol-to-SAF process.
为减少航空业的温室气体排放,需要可持续航空燃料(SAF)。因此,由 (i) 甲醇制烯烃 (MTO)、(ii) 烯烃低聚和 (iii) 烯烃加氢反应步骤组成的甲醇制 SAF 工艺是一条很有前景的路线。烯烃低聚反应步骤决定了 SAF 的性能,需要与之前的甲醇制烯烃(MTO)步骤协同优化。为此,我们根据有限的实验测量数据设计了一个动力学模型,共使用了七个动力学参数,从而成功地描述了各种烯烃混合物在酸催化剂上的流动低聚反应性。这一廉价模型预测了最佳反应条件和进料成分,使产品混合物具有与传统 Jet-A1 航空燃料相匹配的特性。为了最大限度地获得 SAF 系列产品,最理想的进料成分是 C4 和 C5 烯烃,同时需要控制 C3、C6 和 C7 烯烃的共进料和 C4/C5 烯烃的进料比,以微调 SAF 产品成分。这种建模方法可实现高效的工艺优化,以合成具有可控性质和成分的 SAF。此外,精确的 MTO 烯烃成分可以预测出高质量 SAF 的最佳产量,从而指向高效的甲醇-SAF 整体工艺的开发。
{"title":"Optimization of Sustainable Aviation Fuel Production through Experiment-Driven Modeling of Acid-Catalyzed Oligomerization","authors":"Florent J. Dubray, Vladimir Paunovic, Jeroen A. van Bokhoven","doi":"10.1021/acssuschemeng.4c08240","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c08240","url":null,"abstract":"To reduce the aviation industry’s greenhouse gas emissions, sustainable aviation fuel (SAF) is needed. Therefore, a methanol-to-SAF process comprising (i) methanol to olefin (MTO), (ii) olefin oligomerization, and (iii) olefin hydrogenation reaction steps is a promising route. The olefin oligomerization step is responsible for resulting SAF properties and needs to be optimized in concert with the previous MTO step. For this purpose, a kinetic model using a total of seven kinetic parameters was designed from a limited number of experimental measurements, allowing us to successfully describe the oligomerization reactivity of various olefin mixtures over an acid catalyst in flow. This inexpensive model predicted optimal reaction conditions and feed compositions, resulting in product mixtures with properties matching those of conventional Jet-A1 aviation fuel. To maximize SAF-range products, a feed composed of C<sub>4</sub> and C<sub>5</sub> olefins is most desirable, while controlled C<sub>3</sub>, C<sub>6</sub>, and C<sub>7</sub> olefin cofeeding and C<sub>4</sub>/C<sub>5</sub> olefin feed ratio are required to finely tune the SAF product composition. This modeling approach allows for efficient process optimization directed toward the synthesis of SAF with controlled properties and composition. Additionally, precise MTO–olefin compositions can be predicted for the optimal production of high-quality SAF, pointing toward the development of an efficient overall methanol-to-SAF process.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643108","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 : 2024-11-15DOI: 10.1021/acssuschemeng.4c06550
Zahra Saeb, Soheila Shokrollahzadeh, Yasamin Bide
The effectiveness of the membranes is largely influenced by the characteristics of the additives. This study introduces a novel approach to the fabrication of loose nanofiltration (LNF) membranes by utilizing deep eutectic solvents (DESs) as innovative pore formers. For the first time, we systematically investigated the combined effects of DES hydrophilicity and molecular mass on membrane morphology during the phase inversion process. Four distinct polysulfone (PSF)-based LNF membranes with the same nature and different hydrophilicity and molecular mass were synthesized to elucidate the thermodynamic and kinetic parameters influencing casting solution behavior. Our analysis reveals that an increase in DES molecular mass correlates with elevated thermodynamic parameters, while viscosity increases contribute to enhanced kinetic hindrance during membrane formation. Furthermore, the study demonstrates that higher hydrophilicity in DES additives not only reduces thermodynamic instability but also encourages the formation of finger-like pores throughout the membrane’s structure. The synthesized membranes exhibited superior separation performance, achieving over 86% rejection of Congo red dye and less than 3% rejection of sodium ions. These findings present a promising strategy for designing membranes with the desired performance for salt–dye separation, mitigating water waste, and improving sustainability.
膜的效果在很大程度上受添加剂特性的影响。本研究介绍了一种利用深共晶溶剂(DES)作为创新孔形成剂来制造疏松纳滤膜(LNF)的新方法。我们首次系统地研究了相反转过程中 DES 亲水性和分子质量对膜形态的综合影响。我们合成了四种性质相同、亲水性和分子质量不同的基于聚砜(PSF)的 LNF 膜,以阐明影响浇铸溶液行为的热力学和动力学参数。我们的分析表明,DES 分子质量的增加与热力学参数的升高有关,而粘度的增加则有助于增强膜形成过程中的动力学阻碍。此外,研究还表明,DES 添加剂中较高的亲水性不仅能降低热力学不稳定性,还能促进整个膜结构中指状孔的形成。合成的膜具有优异的分离性能,对刚果红染料的截留率超过 86%,对钠离子的截留率低于 3%。这些发现为设计具有所需性能的盐染分离膜、减少水资源浪费和提高可持续发展能力提供了一种可行的策略。
{"title":"Design of Loose Nanofiltration Membranes by Tailoring Hydrophilicity and Molecular Mass of Deep Eutectic Solvent Additives: Thermodynamics and Kinetics of Phase Inversion","authors":"Zahra Saeb, Soheila Shokrollahzadeh, Yasamin Bide","doi":"10.1021/acssuschemeng.4c06550","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06550","url":null,"abstract":"The effectiveness of the membranes is largely influenced by the characteristics of the additives. This study introduces a novel approach to the fabrication of loose nanofiltration (LNF) membranes by utilizing deep eutectic solvents (DESs) as innovative pore formers. For the first time, we systematically investigated the combined effects of DES hydrophilicity and molecular mass on membrane morphology during the phase inversion process. Four distinct polysulfone (PSF)-based LNF membranes with the same nature and different hydrophilicity and molecular mass were synthesized to elucidate the thermodynamic and kinetic parameters influencing casting solution behavior. Our analysis reveals that an increase in DES molecular mass correlates with elevated thermodynamic parameters, while viscosity increases contribute to enhanced kinetic hindrance during membrane formation. Furthermore, the study demonstrates that higher hydrophilicity in DES additives not only reduces thermodynamic instability but also encourages the formation of finger-like pores throughout the membrane’s structure. The synthesized membranes exhibited superior separation performance, achieving over 86% rejection of Congo red dye and less than 3% rejection of sodium ions. These findings present a promising strategy for designing membranes with the desired performance for salt–dye separation, mitigating water waste, and improving sustainability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637563","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}