Green Chemistry最新文献

{"title":"Perspective on direct seawater electrolysis and electrodesalination: innovations and future directions for mining green X","authors":"Gun-hee Moon, Jonghun Lim, Byeong-ju Kim, Dong Suk Han and Hyunwoong Park","doi":"10.1039/D4GC04930F","DOIUrl":"https://doi.org/10.1039/D4GC04930F","url":null,"abstract":"<p >Molecular hydrogen (H<small>₂</small>) represents a sustainable and environmentally benign energy resource. Of the various methodologies that have been developed for H<small>₂</small> production, water electrolysis has garnered particular attention due to its ability to generate H<small>₂</small> without emitting CO<small>₂</small> or other pollutants, with seawater electrolysis receiving significant focus due to the abundance and accessibility of seawater. However, both direct and indirect seawater electrolysis technologies have a number of practical limitations, including the high energy consumption and maintenance costs associated with seawater desalination systems and the need for strong alkaline conditions. Nevertheless, indirect seawater electrolysis, which amalgamates desalination and water electrolysis processes by employing clean water produced by seawater reverse osmosis (RO) as the feed for water splitting, is currently considered more economical than direct electrolysis. Electrodeionization has also emerged as an alternative to conventional seawater RO due to its high energy efficiency and environmental advantages. In addition, the development of environmentally friendly processes to simultaneously extract high-value compounds from seawater and the brine produced as a by-product from seawater RO can mitigate the high process costs associated with seawater electrolysis and deionization. Recent advancements in seawater electrolysis technologies based on the chlorine evolution reaction (CER) have also been reported, with the generated chlorine harnessed as a resource in other processes. The CER and electrodeionization can be used in a diverse array of other applications, including chlorine-mediated electrochemical redox reactions, the desalination-coupled electrochemical production of acids and bases, resource recovery from seawater and brine, direct ocean CO<small>₂</small> capture, and reverse electrodialysis for green electricity production. In this perspective, we first compare the mechanisms, thermodynamics, and kinetics of the CER with those of the oxygen evolution reaction (OER). Subsequently, we introduce an array of electrodeionization technologies that can be seamlessly integrated with seawater electrolysis systems. We then describe the various applications of seawater electrolysis and electrodeionization technologies, before addressing the remaining challenges and offering insights into the future prospects for the electrochemical utilization of seawater resources.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 4","pages":" 982-1005"},"PeriodicalIF":9.3,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142993749","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":"Green and facile modification of mesoporous activated carbon for selective indium and gallium recovery from waste photovoltaic modules†","authors":"Wenxuan Wang, Xinhai Xu, Jie Li, Tao Liu, Hailong Wang and Yin Wang","doi":"10.1039/D4GC04204B","DOIUrl":"https://doi.org/10.1039/D4GC04204B","url":null,"abstract":"<p >With the increasing deployment and subsequent retirement of photovoltaic (PV) modules, it is urgent to selectively recover critical metals involved, such as indium (In) and gallium (Ga). Activated carbon, a widely used eco-friendly adsorbent for metal ions, often requires large amounts of toxic chemicals and complicated modifications to achieve selective adsorption. Herein, a novel adsorbent with outstanding ability for In and Ga recovery, phosphoryl-functionalized waste biomass-derived mesoporous activated carbon (P-PDA@MAC), was synthesized <em>via</em> a green and facile one-pot method. This approach eliminates the use of toxic organic reagents and enables functionalization at ambient temperature and pressure, aligning with the principles of green chemistry. Using ethyl phenylphosphinate (EPP) as a precursor, the obtained EPP–PDA@MAC exhibited superior adsorption capacity for In<small>³⁺</small> (125.1 mg g<small>⁻¹</small>) and Ga<small>³⁺</small> (140.7 mg g<small>⁻¹</small>) and high selectivity (SF<small>^X</small><small>_In</small> = 382.4, SF<small>^X</small><small>_Ga</small> = 239.0) over competing ions Al<small>³⁺</small>, Zn<small>²⁺</small>, Cd<small>²⁺</small>, Cu<small>²⁺</small>, and Mg<small>²⁺</small>. Surprisingly, this adsorbent demonstrated excellent reusability, maintaining adsorption efficiencies above 85% over 9 cycles in a static system and 98% over 50 cycles in a capacitive deionization system. The superior adsorption ability of EPP–PDA@MAC was ascribed to the abundant and stable phosphoryl groups, facilitated by the adhesive polydopamine coating and covalent phosphoryl-functionalization on the high surface area of MAC. Furthermore, a comparison of the adsorption ability, green metrics, and production costs with those of commercial adsorbents underscores the significant industrial application potential of EPP–PDA@MAC. The successful extraction of 99.9% In (purity = 97.79%) and Ga (purity = 90.40%) from waste copper indium gallium selenide PV modules by EPP–PDA@MAC highlights its potential and industrial viability for the circular economy.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 485-497"},"PeriodicalIF":9.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870227","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":"Green synthesis of poly ε-caprolactone using a metal-free catalyst via non-covalent interactions†","authors":"Shweta Sagar, Priyanku Nath, Shiva Lall Sunar, Aranya Ray, Mridula Choudhary, Alok Sarkar, Saurabh K. Singh and Tarun K. Panda","doi":"10.1039/D4GC04411H","DOIUrl":"https://doi.org/10.1039/D4GC04411H","url":null,"abstract":"<p >The ring-opening polymerization (ROP) of ε-caprolactone (CL) catalyzed by a metal-free initiator <em>N</em>,<em>N</em>′-dibutyl-<em>N</em>,<em>N</em>,<em>N</em>′,<em>N</em>′-tetramethylethane1,2-diammonium bromide [<small>^<em>n</em></small>BuMe<small>₂</small>NCH<small>₂</small>CH<small>₂</small>N<small>^<em>n</em></small>BuMe<small>₂</small>]Br<small>₂</small> (DBTMEDA)Br<small>₂</small> has been investigated. The catalyst (DBTMEDA)Br<small>₂</small> promotes polymerization under mild conditions without any external initiator. Polymerization was demonstrated in a controlled and living manner, producing PCLs with a precisely controlled molecular weight of up to 50 kDa with narrow polydispersity. Density Functional Theory (DFT) calculations indicated the involvement of a C–H⋯O type non-covalent interaction between DBTMEDA cations and the carbonyl group of ε-CL in the monomer activation step. Remarkably, DBTMEDA can also be easily recovered and reused for up to six consecutive cycles without an appreciable decrease in catalytic activity.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 2","pages":" 527-534"},"PeriodicalIF":9.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870238","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":"Efficient decomposition of a melamine–formaldehyde foam into melamine via selective disconnection of bonds†","authors":"Chaohui Yang, Xinyu Li, Hongyan Li, Chizhou Wang, Qianqian Xing, Xiaoliang Jia, Xiaojing Cui, Xianglin Hou and Tiansheng Deng","doi":"10.1039/D4GC04481A","DOIUrl":"https://doi.org/10.1039/D4GC04481A","url":null,"abstract":"<p >The precise disconnection of one type of chemical bond in polymers realizes high-yield recovery of valuable chemicals. In this study, we demonstrate a sustainable and efficient strategy to selectively cleave the specific sp<small>³</small>C–sp<small>³</small>N bond of a thermoset melamine–formaldehyde foam, by which valuable melamine of 99.5% purity was obtained with a yield of 95.3%.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 24","pages":" 11860-11865"},"PeriodicalIF":9.3,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc04481a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798167","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":"Halogen-bond-assisted radical remote difunctionalization of bicyclo[1.1.1]butane skeletons†","authors":"Hui Liu, Zhenda Fu, Xingwei Li and Songjie Yu","doi":"10.1039/D4GC05166A","DOIUrl":"https://doi.org/10.1039/D4GC05166A","url":null,"abstract":"<p >Transition-metal-free radical remote difunctionalization of bicyclo[1.1.1]butane skeletons in both two- and three-component fashions is presented. The reactions proceed <em>via</em> halogen-bond-assisted polyfluoroalkyl radical addition to newly designed 1-vinylbicyclo[1.1.1]pentanes, followed by strain-release-driven C–C bond cleavage to generate a strained cyclobutylmethyl radical. In the two-component reaction, iodine atom transfer to the resulting cyclobutylmethyl radical with polyfluoroiodides forms a broad array of strained 1,6-polyfluorocarboiodinated products, while boron atom transfer with bis(catecholato)diboron releases various strained 1,6-polyfluorocarboborylated products in the three-component reaction. This redox-neutral reaction features mild conditions, ease of operation, high atom economy, functional group tolerance, and a broad substrate scope, and offers a practical and sustainable approach for the synthesis of a range of challenging polyfluoroalkylated cyclobutane skeletons containing iodine and boron as versatile transformation handles for further useful derivatizations.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 256-263"},"PeriodicalIF":9.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825989","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":"Green aromatic aldehyde production from biomass via catalytic fractionation and ozonolysis†","authors":"Tianyu Ren, Peidong Li, Zhuo He, Xinfeng Pan, Yutao Yang, Yuhe Liao, Haiyong Wang, Yanbin Cui and Chenguang Wang","doi":"10.1039/D4GC04199B","DOIUrl":"https://doi.org/10.1039/D4GC04199B","url":null,"abstract":"<p >Herein, we propose a catalytic fractionation–ozonolysis strategy for producing aromatic aldehydes from biomass. Native lignin is selectively depolymerized into ∼30 wt% 4-methoxypropenyl-guaiacol/syringol over MoO<small>₂</small> at 160–180 °C, followed by ozonolysis yielding 20 wt% vanillin and syringaldehyde. This strategy is free of base and well preserves carbohydrate pulp.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 24","pages":" 11866-11872"},"PeriodicalIF":9.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc04199b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798168","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":"Enhancing sustainable energy production through co-polyamide membranes for improved pressure-retarded osmosis performance and environmental impact: synthesis and life cycle analysis†","authors":"Sadegh Aghapour Aktij, Mostafa Dadashi Firouzjaei, Mohsen Pilevar, Asad Asad, Ahmad Rahimpour, Mark Elliott, João B. P. Soares and Mohtada Sadrzadeh","doi":"10.1039/D4GC03963G","DOIUrl":"https://doi.org/10.1039/D4GC03963G","url":null,"abstract":"<p >This study investigates the application of innovative co-polyamide (Co-PA) membranes in the pressure-retarded osmosis (PRO) process. The Co-PA membranes were synthesized <em>via</em> a polycondensation reaction of a mixture of <em>m</em>-phenylenediamine (MPD) and piperazine (PIP) with trimesoyl chloride (TMC). Characterization using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed chemical modifications in the membranes, while Atomic Force Microscopy (AFM) demonstrated increased surface roughness with PIP incorporation. Results showed that incorporating 1.5 wt% PIP significantly improved PRO performance, achieving a remarkable power density of 10.22 W m<small>⁻²</small> and a 41.5% increase in water flux compared to the pristine TFC membrane. Additionally, XPS analysis demonstrated an increase in the degree of crosslinking, reducing reverse salt flux by 36.7%. A life cycle assessment of PRO systems was conducted to evaluate the environmental impact of the technology with developed membranes. The results confirm the environmental benefits of this novel membrane synthesis approach, indicating a reduction in cumulative energy demand (CED) and a shift towards more sustainable energy sources. This research highlights the potential of Co-PA membranes to revolutionize PRO technology, offering sustainable solutions for energy generation and water treatment. The findings contribute valuable insights into the environmental implications of PRO, which are essential for developing sustainable PRO systems.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 3","pages":" 586-606"},"PeriodicalIF":9.3,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962912","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 simple, efficient and selective catalyst for closed-loop recycling of PEF in situ towards a circular materials economy approach†","authors":"Shaowei Wu, Lu Li, Lei Song, Guannan Zhou, Lixin Liu, Hailan Kang, Guangyuan Zhou and Rui Wang","doi":"10.1039/D4GC03803G","DOIUrl":"https://doi.org/10.1039/D4GC03803G","url":null,"abstract":"<p >Developing plastics from biomass and performing chemical recycling are two essential strategies in circular materials economy. Herein, we present an innovative technique for the closed-loop, <em>in situ</em> chemical recycling of bio-derived poly(ethylene 2,5-furandicarboxylate) (PEF), utilizing the exceptional capabilities of monodisperse nano γ-Ga<small>₂</small>O<small>₃</small> with tunable oxygen vacancy density. This framework enables seamless cycling of bio-based plastics from polymerization to de-polymerization and re-polymerization, promoting a sustainable polymer economy. The introduction of oxygen vacancy defects in the structure of gallium oxide, a low toxicity and transparent metal oxide, is considered to be an effective strategy for improving catalytic activity. The polymerization process was controlled by using novel oxygen vacancy-defective Ga<small>₂</small>O<small>₃</small>, which catalyzed the reaction between bio-based 2,5-furandicarboxylic acid and ethylene glycol to produce high molecular weight PEF. (<em>M</em><small>_n</small> = 41 kg mol<small>⁻¹</small>). This PEF can then undergo efficient <em>in situ</em> glycolysis, achieving complete de-polymerization under moderate conditions without the need for external catalysts. The glycolysis derivatives of PEF can be directly re-polymerized to polyester rPEF, achieving a significant molecular weight (<em>M</em><small>_n</small> = 43 kg mol<small>⁻¹</small>) and a remarkable yield (93%). Notably, γ-Ga<small>₂</small>O<small>₃</small> with nano oxygen vacancy defects exhibits the ability to selectively de-polymerize PEF within composite material systems containing commercial PET. This research highlights the significant utility of a green catalyst in <em>in situ</em> closed-loop recycling processes.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 179-189"},"PeriodicalIF":9.3,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825765","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":"DIPEA-induced Si–H activation of siloxane for hydrosilylation polymerization via metal-free photocatalysis†","authors":"Hangcen Xie, Rui Xu, Bin Huang, Pingping Lou, Hua-Feng Fei and Zhijie Zhang","doi":"10.1039/D4GC04501G","DOIUrl":"https://doi.org/10.1039/D4GC04501G","url":null,"abstract":"<p >Although metal-free hydrosilylation of siloxanes is essential for the industrial preparation of organosilicon compounds due to its unique advantages, such as the avoidance of the use and residue of precious metals, efficient metal-free silicon hydrogenation reactions are still rare. Herein, we report a straightforward visible light-driven metal-free hydrosilylation reaction based on siloxanes and silicon vinyl groups, catalyzed by the synergistic effect of the organic photooxidation catalyst 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile and the base <em>N</em>,<em>N</em>′-diisopropylethylamine, which undergo electron transfer and selectively induce Si–H activation during catalysis. After optimization, the silicon vinyl conversion rate in the hydrosilylation reaction exceeded 99% without using any traditional hydrogen atom transfer reagents. Mechanistic studies based on experimental data and theoretical calculations revealed that the reaction proceeds through a free radical reaction and is thermodynamically feasible. The proposed methodology efficiently affords linear polymer formation <em>via</em> a stepwise growth approach. Furthermore, it can crosslink commercial high-molecular-weight polyvinyl silicone oil with disiloxane, realizing the gelation of the material.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 155-162"},"PeriodicalIF":9.3,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142826078","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":"Sustainable pretreatment of blood samples using hydrophobic eutectic solvents to improve the detection of bisphenol A†","authors":"Cariny Polesca, Helena Passos, Ana C. A. Sousa, Nguyen Minh Tue, João A. P. Coutinho, Tatsuya Kunisue and Mara G. Freire","doi":"10.1039/D4GC03396E","DOIUrl":"https://doi.org/10.1039/D4GC03396E","url":null,"abstract":"<p >Bisphenols, and mostly bisphenol A (BPA), are widely used in many consumer products. Due to its toxicity, BPA presents a noteworthy risk to the environment and human health. Despite these concerns, monitoring BPA proves challenging, particularly in highly complex matrices such as blood, because extraction and clean-up require multiple steps, the use of volatile organic solvents, and associated high costs. To overcome these limitations, this work discloses a novel, one-step and sustainable pretreatment technique of blood samples using hydrophobic eutectic solvents (HES). Systems composed of different HES, including thymol : menthol, benzyl alcohol : cyclohexanol, and decanoic acid : trioctylphosphine oxide at various mole ratios, combined with potassium citrate buffer aqueous solutions at different volume ratios, were carefully evaluated as three-phase partitioning (TPP) systems. The high performance of the HES-based systems for the pretreatment of blood samples was confirmed with liquid chromatography–tandem mass spectrometry (LC-MS/MS) analysis, with a BPA recovery of (98 ± 3)% in the HES-rich phase, and with the interfering biological material precipitating at the liquid–liquid interphase. The green nature of the developed method was assessed using the Analytical GREENess Metric (AGREE) and the AGREE metrics of environmental impact of sample preparation (AGREEprep), scoring 0.59 and 0.63, respectively. The high pretreatment performance offered by HES-based TPP systems with respect to blood samples, combined with their greener credentials, paves the way for their application in a variety of biomonitoring studies.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 1","pages":" 200-208"},"PeriodicalIF":9.3,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825767","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}