Green Chemistry最新文献

{"title":"Continuous production prototype for scaling up of graphene oxide/carbon nanotube composite synthesis towards efficient hydrogen storage†","authors":"Yunting Wang, Yudong Xue and Andreas Züttel","doi":"10.1039/D4GC04753B","DOIUrl":"https://doi.org/10.1039/D4GC04753B","url":null,"abstract":"<p >A continuous production prototype for scaling up the synthesis of a graphene oxide/multi-walled carbon nanotubes (GO/MWCNTs) composite as a hydrogen storage material has been proposed in this study. This prototype consists of an automatic feeding and mixing step wherein KMnO<small>₄</small> and graphite are individually fed into concentrated H<small>₂</small>SO<small>₄</small> and then mixed to form a graphite/oxidant mixture. Following this, the oxidation step involves oxidizing the graphite/oxidant mixture through two-step oxidation to produce a graphene oxide dispersion. Then, the composite synthesis step includes mixing, sonicating, and stirring the graphene oxide dispersion with a sonicated dispersion of MWCNTs to obtain the final product. As a result, the morphology and structure of the GO/MWCNTs composite synthesized by the large-scale method exhibit high similarity to those of the gram-scale sample. The GO/MWCNTs exhibited a 3D nanostructure composed of MWCNTs linked to the graphene oxide layers. The hydrogen storage test results, simulated to practical hydrogen storage tanks with large amounts of adsorbents, indicated that the hydrogen storage capacity of GO/MWCNTs can reach 3.1 wt% at ambient temperature and 50 bar. The analysis of life cycle impacts in terms of energy consumption, carbon footprint, cost, and environmental impact indicated that the proposed large-scale continuous production prototype is greener compared to other methods. Therefore, this approach holds great potential for industrial applications, paving the way for commercialization and facilitating the development of small storage units to explore the properties of the new storage system.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 3","pages":" 756-769"},"PeriodicalIF":9.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962926","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}

{"title":"Recovering lead and sulfur from spent lead paste by molten salt electrolysis: a clean and sustainable lead and sulfur loop†","authors":"Hongya Wang, Fengyin Zhou, Bingbing Wang, Muya Cai, Jingjing Zhao, Xinyu Li, Yongxin Wu, Xiaowei Liu, Xiang Chen, Dihua Wang and Huayi Yin","doi":"10.1039/D4GC05220J","DOIUrl":"https://doi.org/10.1039/D4GC05220J","url":null,"abstract":"<p >The sulfur transfer is key to obtaining greenness of recycling spent lead paste (SLP) since conventional recycling methods always involve generating secondary wastes such as sulfur oxides (SO<small>_<em>x</em></small>), sulfates, and sulfides. To address these challenges, we propose a combined process in which the SLP is first converted into lead sulfide (PbS) by carbothermic reduction, and then the resultant PbS is split into liquid lead (Pb) and sulfur vapor (S<small>_<em>x</em></small>) by molten salt electrolysis (MSE). The faradaic efficiency of MSE reaches 92.29% with a Pb recovery rate of 97.85%, and the liquid Pb and gaseous S<small>_<em>x</em></small> are respectively discharged from the bottom and top of the cell to allow the reaction to happen continuously. Compared with traditional methods, over 98.85% of SO<small>₂</small> emissions are reduced, and no sulfides and sulfates are generated. Furthermore, the energy consumption is only 0.32 kW h (kg-Pb)<small>⁻¹</small>, which demonstrates a 67% reduction compared to mainstream recycling processes using a 50 g-scale electrolyzer. Overall, we offer a clean sulfur transfer route to reduce secondary wastes and energy consumption, which will benefit the recovery and utilization of various sulfate wastes and raw materials with low environmental footprints.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1089-1101"},"PeriodicalIF":9.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993943","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}

{"title":"A new chemo-enzymatic approach to synthesize rare sugars using an engineered glycoside-3-oxidase†","authors":"André Taborda, Márcia Rénio, M. Rita Ventura and Lígia O. Martins","doi":"10.1039/D4GC04449E","DOIUrl":"https://doi.org/10.1039/D4GC04449E","url":null,"abstract":"<p >Rare sugars are monosaccharides and disaccharides highly valued for their unique properties and beneficial health effects. Their scarcity has led to inefficient extraction from natural sources, prompting the development of several chemical and enzymatic methods to improve their synthesis. In this study, we aim to optimize a regio- and stereoselective chemo-enzymatic process for synthesizing the rare sugar <small>D</small>-allose. We use a bacterial glycoside-3-oxidase that oxidizes <small>D</small>-Glc at the C2 or C3 position, depending on the presence of a C1 substitution, being converted into the respective keto-derivatives. Through protein engineering, we improve the enzyme's catalytic activity for <small>D</small>-Glc by 20-fold after seven rounds of directed evolution and increase its operational stability by 10-fold. The engineered enzyme uses 1-<em>O</em>-benzyl-<small>D</small>-glucoside as substrate, ensuring regioselective oxidation at the C3 position, followed by a stereoselective chemical reduction and deprotection step, affording <small>D</small>-allose with an overall yield of 81%. This innovative strategy represents a novel, straightforward approach for synthesizing <small>D</small>-allose, avoiding laborious, time-consuming purifications and complicated and lengthy protection–deprotection strategies. Importantly, it shows potential for synthesizing other rare C3 epimers of biomass sugars through eco-friendly and cost-effective processes, with applications in pharmaceuticals and food technology.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1044-1053"},"PeriodicalIF":9.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc04449e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-free stereoselective intramolecular oxyamination of alkynes using a robotic and rapid photocatalytic synthesis and screening system†","authors":"Jia-Min Lu, Yihui Mao, Qihang Guo, Chengcheng Zhong, Xian-Ge Gao, Qun Fang and Zhan Lu","doi":"10.1039/D4GC05100A","DOIUrl":"https://doi.org/10.1039/D4GC05100A","url":null,"abstract":"<p >A unique metal-free and 100% atom-economical method for intramolecular oxyamination of alkynes with high stereoselectivity <em>via</em> visible light photocatalysis is developed. Utilizing a robotic and rapid photocatalytic synthesis and screening system capable of anhydrous and oxygen-free flow synthesis, the standard reaction conditions were extensively investigated and optimized with reduced sample consumption, and an inexpensive and efficient organic photosensitizer was rapidly and successfully found. Starting from inexpensive, widely and readily available propargyl alcohol feedstock materials, single <em>Z</em> configuration 2-aminoprop-1-ene-1,3-diol derivatives could be obtained with good functional group compatibility and broad substrate scope. A possible mechanism involving a nitrogen radical process and nucleophilic attack was proposed based on the radical inhibition experiment and the cross-over experiment.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 3","pages":" 560-565"},"PeriodicalIF":9.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962909","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}

{"title":"Replacing polyacrylonitrile with Kraft lignin for sustainable carbon fiber manufacturing mitigates carbon emissions†","authors":"Shaokai Wang, Yan Zhang, Hairong Gao, Keda Jin, Can Ao, Luning Tian, Qingyao He, Baojun Yi, Ping Ai, Weiyu Cao, Yunqiao Pu, Yunjiang Cheng and Qiang Li","doi":"10.1039/D4GC04579C","DOIUrl":"https://doi.org/10.1039/D4GC04579C","url":null,"abstract":"<p >Although carbon fibers have been significantly sought after as the foundation of various advanced materials, their manufacturing is energy-intensive with high carbon emissions. Replacing the petroleum-derived polyacrylonitrile (PAN) precursor of carbon fibers with green biopolymers can potentially enhance the sustainability of the carbon fiber industry, but how this replacement can mitigate carbon emissions is still elusive. In this study, we performed a life cycle assessment (LCA) on the alternative of a plant-derived lignin biopolymer from biorefining waste for the replacement of PAN in carbon fiber production. Here, 50% of PAN was replaced with an industrial softwood Kraft lignin, and wet spinning was used for making lignin/PAN precursor fibers, followed by thermostabilization and carbonization. LCA study revealed that carbon fibers made from PAN could induce carbon emissions of 23.3 kg CO<small>₂</small>-eq per kg carbon fibers, while 50% replacement of PAN with lignin led to carbon emissions of 19.5 kg CO<small>₂</small>-eq per kg carbon fibers, representing a 16.3% reduction in carbon emissions. Analysis of the main contributions to carbon emissions from processing demonstrated that the preparation of spinning dopes had the highest carbon emission, followed by thermostabilization, wet spinning, and carbonization. Among the different production factors, consumed electricity generated the highest carbon emissions, followed by the precursor PAN. Among other environmental impacts, electricity represented the highest contributor, and the preparation of spinning dopes had the most environmental impacts. Further sensitivity analysis elucidated that increasing the spinning tow and carbon yield led to lower carbon emissions and other environmental impacts. All these results highlighted that using lignin instead of PAN could significantly mitigate carbon emissions for greener carbon fiber production.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1031-1043"},"PeriodicalIF":9.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993999","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}

{"title":"An upcycling strategy for polyamide 6: preparing thermoplastic polyamide elastomers from glycolysates produced by controlled degradation†","authors":"Ji Lan, Cong Deng, Ze-Yong Zhao and Yu-Zhong Wang","doi":"10.1039/D4GC03815K","DOIUrl":"https://doi.org/10.1039/D4GC03815K","url":null,"abstract":"<p >Polyamides (PAs) represent a class of polymers conducive to chemical recycling, where the amide group acts as a reactive site for degradation agents. However, the inherent stability of the amide group means that chemical recycling of PAs often necessitates stringent conditions, such as high temperatures and pressures, significantly hindering advancements in PA chemical recycling. Moreover, the effectiveness of chemically recycling polyamides into monomers or oligomers—essential components for subsequent polymer synthesis—has not been conclusively verified through comprehensive research. Here, we present the first demonstration of a method for the upcycling of PA6 into high-performance PA derivatives. In the proposed method, PA6 is first degraded into oligomers with reactive end groups <em>via</em> glycolysis, with the reactivity of the resulting glycolysates subsequently verified. This oligomer acts as an intermediate in thermoplastic polyamide elastomer (TPAE) synthesis, facilitating direct integration with flexible polyethylene glycol oligomers into TPAE without requiring further degradation to monomers. The mechanical properties of the resultant TPAEs are commensurate with those previously reported for PA6-based TPAEs. By fine-tuning the reaction time and catalyst concentration, it is possible to control the molecular weight of the PA6 glycolysates, thus adjusting the TPAE's mechanical properties. This study presents an innovative approach that seamlessly combines the degradation process of PA6 with the synthesis pathway of TPAE, thus achieving the cost-effective upcycling of PA6 into TPAE.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1183-1193"},"PeriodicalIF":9.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993933","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}

{"title":"Advances in photocatalytic carboxylation of C(sp3)–H bonds with CO2: a sustainable strategy for CO2 fixation","authors":"A. John David and Anjan Das","doi":"10.1039/D4GC04956J","DOIUrl":"https://doi.org/10.1039/D4GC04956J","url":null,"abstract":"<p >Carbon dioxide (CO<small>₂</small>) is well recognized as a sustainable C<small>₁</small> synthon for producing a variety of carboxylic acid derivatives, including important natural and synthetic amino acids. In recent years, the inertness and high stability of the CO<small>₂</small> molecule have been successfully overcome through various stoichiometric and catalytic methods. Among these, visible-light-induced photoredox catalysis has emerged as a popular and effective approach, offering a greener and more sustainable solution. Various carboxylation reactions involving C(sp3)–H, C(sp2)–H, C(sp)–H, and Ar–X have been successfully developed by using a suitable photocatalyst under visible light excitation. In this mini review, we explore recent progress in carboxylation reactions through the functionalization of C(sp3)–H bonds specifically in various organic molecules using molecular CO<small>₂</small> through photocatalysis including organo-photocatalysts, homogeneous photocatalysts and heterogeneous photocatalysts along with their application in the development of bioactive molecules such as (±)-clopidogrel, (±)-tirofiban intermediate and <small>DL</small>-DOPA.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 851-862"},"PeriodicalIF":9.3,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993936","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}

{"title":"Atom-economical and workup-free multiparticipation of p-TsOH in yne-ynamide skeletal reshuffle: access to regiospecific, chemospecific, and stereospecific (E)-alkenyl sulfonate/ketone-tethered indoles†","authors":"Mohana Reddy Mutra, T. L. Chandana and Jeh-Jeng Wang","doi":"10.1039/D4GC05876C","DOIUrl":"https://doi.org/10.1039/D4GC05876C","url":null,"abstract":"<p >Transition metal-free organic transformations that do not involve/generate hazardous waste are of great interest in organic synthesis. In this regard, <em>p</em>-toluenesulfonic acid monohydrate (<em>p</em>-TsOH·H<small>₂</small>O) is an ecofriendly reagent for efficiently synthesizing diverse heterocyclic compounds. Using <em>p</em>-TsOH·H<small>₂</small>O as a multipurpose reagent, we synthesized highly substituted, sensitive, stereospecific alkenyl sulfonate/ketone derivatives from the same precursors (yne-ynamides) <em>via</em> skeletal rearrangement. This strategy is notable because it is transition metal- and additive-free, atom-economical, scalable, operationally simple, regioselective, and chemoselective. Furthermore, it avoids tedious workup procedures, has a broad substrate scope, uses environmentally friendly and commercially available <em>p</em>-TsOH·H<small>₂</small>O, and prevents hazardous waste generation. The alkenyl sulfonate synthesis is an acceptable green and economical organic synthesis process based on green chemistry metrics (<em>E</em>-factor of 1.72) and EcoScale (64.5 on a scale of 0–100). Moreover, this protocol demonstrates further synthetic transformations of the synthesized ketone products.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 1062-1072"},"PeriodicalIF":9.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993941","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}

{"title":"Interactions, properties and lipid digestibility of attractive Pickering emulgels formed by sequential addition of oppositely charged nanopolysaccharides†","authors":"Shasha Guo, Jun Li, Xingxiang Ji, Wenjuan Jiao, Zhangmin Wan, Luyao Huang, Xun Niu, Junhua Xu, Ying Liu, Jianan Zheng, Bin Li, Long Bai, Yi Lu and Orlando J. Rojas","doi":"10.1039/D4GC05700G","DOIUrl":"https://doi.org/10.1039/D4GC05700G","url":null,"abstract":"<p >Emulsion gels (emulgels) have emerged as cost-effective and versatile platforms in formulation engineering. In this study, we introduce Attractive Pickering Emulgels (APEGs), stabilized by the synergistic action of two oppositely charged green nanoparticles, <em>e.g.</em>, chitin nanofibers (ChNF) and cellulose nanocrystals (CNC). The CNC, featuring anionic sulfate half-ester groups, and the cationic ChNF, possessing amine groups, form adhesive bridging networks within the continuous aqueous phase, effectively inhibiting oil droplet coalescence. This network supports micro-clustering, significantly increasing the effective droplet volume fraction by entrapping substantial amounts of the continuous phase. Consequently, the emulgels demonstrate a robust viscoelastic response and effectively modulate lipid digestibility, as evidenced by a 30% reduction in free fatty acid (FFA) release at high oil fractions (70 wt%) during <em>in vitro</em> digestion. The stabilization mechanism relies on noncovalent interactions and nanoparticle coassembly, validated through quartz crystal microgravimetry and molecular dynamics simulations. APEGs present significant potential for advancing sustainable nanotechnologies in pharmaceutical, food, and health formulations.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 3","pages":" 650-659"},"PeriodicalIF":9.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962917","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}

{"title":"Interfacial engineering of a CoSe@NiFe heterostructure electrocatalyst for high-efficiency water and urea oxidation†","authors":"Xinyue Yu, Wenlu Zhang, Lijuan Ma, Jingxiao Tang, Wenbo Lu, Jisen Li, Jinjun Zhang and Xiaohu Xu","doi":"10.1039/D4GC05278A","DOIUrl":"https://doi.org/10.1039/D4GC05278A","url":null,"abstract":"<p >Electro-oxidation reactions as critical half-reactions in both overall and assisted water electrolysis play a pivotal role in realizing highly effective and energy-saving hydrogen generation and achieving simultaneous wastewater degradation. Herein, we synthesize a porous and hierarchical CoSe@NiFe/NF heterostructure electrocatalyst constructed by coupling uniform CoSe nanosheets with well-dispersed Ni(OH)<small>₂</small> and Fe<small>₂</small>O<small>₃</small> spherical nanoparticles <em>in situ</em> grown on a Ni foam (NF) substrate <em>via</em> a facile and scalable two-step method (<em>i.e.</em>, electrodeposition and hydrothermal treatment). Differing from its monophasic counterpart, the CoSe@NiFe/NF electrode possesses impressive multifunctional electrocatalytic activity, exhibiting low potentials of 1.46, 1.36, 1.38 and 1.38 V at 100 mA cm<small>⁻²</small> for the oxygen evolution reaction (OER), urea oxidation reaction (UOR), methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR), respectively. Excitingly, the durability is higher than 90 h at high current densities of 400 and 100 mA cm<small>⁻²</small> for the OER and UOR, respectively, without obvious attenuation. <em>In situ</em> Raman spectroscopy and <em>ex situ</em> characterization unveiled the surface self-reconstruction of Ni(OH)<small>₂</small> and Fe<small>₂</small>O<small>₃</small> to evolve Ni(Fe)-oxyhydroxides as the real active substances for the OER. Moreover, density functional theory (DFT) calculations further reveal that the reconstructed heterogeneous interface can regulate the intrinsic electronic structure and optimize the adsorption/desorption of reaction intermediates, thereby accelerating charge transfer and facilitating the reaction kinetics during the OER. Interestingly, the asymmetric electrolyte cell (CoSe@NiFe/NF||Pt/C/NF) needs cell voltages of only 1.44 and 1.40 V to drive a current density of 100 mA cm<small>⁻²</small> for overall water and urea splitting with long-term durability for more than 20 h. This study not only provides valuable insights into the intricate mechanisms governing electrocatalysis but also presents a facile and efficient scheme for constructing multifunctional all-in-one electrocatalysts tailored for sustainable green hydrogen production.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 3","pages":" 731-742"},"PeriodicalIF":9.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962924","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}