Green Chemistry最新文献

{"title":"Adding value to terpenes: copper-catalyzed oxidation of α-pinene in water under micellar conditions†","authors":"Gilvan A. Correia ,&nbsp;Chris H. J. Franco ,&nbsp;Marina V. Kirillova ,&nbsp;Fabrice Gallou ,&nbsp;Alexander M. Kirillov","doi":"10.1039/d4gc06525e","DOIUrl":"10.1039/d4gc06525e","url":null,"abstract":"<div><div>The development of sustainable protocols for the conversion of renewables such as terpenes into value-added products is currently in high demand, which motivates the search for inexpensive and environmentally tolerable catalytic systems and reaction conditions. In the present study, three new prospective catalysts featuring mono-, di-, and tricopper(<span>ii</span>) cores were easily assembled in aqueous ethanol medium from copper(<span>ii</span>) ions, amino alcohol and carboxylic acid ligands. Their catalytic performance was evaluated in water under micellar conditions with 1% of PS-750-M surfactant, while studying the mild oxidation of α-pinene as an abundant, low-cost, and renewable feedstock. A water-soluble monocopper(<span>ii</span>) complex proved to be the most promising catalyst for the oxidation of α-pinene with <em>tert</em>-butyl hydroperoxide under micellar conditions, leading to high substrate conversion (87%) and good yields of the main products (<em>tert</em>-butylperoxy-2-pinene, verbenone, and pinene oxide). A partially water-soluble 1D coordination polymer based on dicopper(<span>ii</span>) units also showed a notable catalytic behavior. The effects of different reaction parameters and mechanistic features were investigated. This work opens up the use of micellar catalysis systems and aqueous-medium conditions for the oxidative functionalization of α-pinene and other terpene feedstocks into value-added products.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3178-3185"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06525e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632294","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":"Bioconversion of a lignin-derived biphenyl dimer into the strategic building block 5-carboxyvanillic acid in Pseudomonas putida KT2440†","authors":"Helena Gómez-Álvarez ,&nbsp;Carlos del Cerro-Sánchez ,&nbsp;Pablo Iturbe ,&nbsp;Virginia Rivero-Buceta ,&nbsp;Juan Nogales ,&nbsp;Timothy D. H. Bugg ,&nbsp;Eduardo Díaz","doi":"10.1039/d4gc06537a","DOIUrl":"10.1039/d4gc06537a","url":null,"abstract":"<div><div>The design of new biocatalysts for funneling lignin depolymerization-derived dimers into added-value compounds is nowadays a major challenge in biological lignin valorization. Biphenyl 5,5′-dehydrodivanillate (DDVA) is a model-lignin dimer that contains the C₅–C_5′ linkage commonly found in lignin depolymerization mixtures. In this work, the metabolic potential of the industrially relevant <em>Pseudomonas putida</em> KT2440 bacterial strain was broadened by expressing synthetic DNA modules encoding selected metabolic and transport steps from the well-characterized DDVA degradation pathway of the <em>Sphingobium lignivorans</em> SYK-6 strain. By employing this heterologous expression strategy, we successfully developed an unprecedented resting cell-based bioprocess to convert DDVA into 5-carboxyvanillic acid (5CVA), a promising building block for the production of innovative bio-based polymers. This proof-of-concept study underscores the essential role of the associated DDVA transport systems. Furthermore, the findings reveal that <em>P. putida</em> KT2440 serves as an effective bacterial chassis for biotechnological processes that require the uptake of substrates through specific TonB-dependent transporters.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3197-3206"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06537a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632296","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":"Bio-degradable, fully bio-based, thermally cross-linked superabsorbent polymers from citric acid and glycerol†","authors":"Jingying Chen ,&nbsp;Deelan Yen Chan ,&nbsp;TaoTao Yang ,&nbsp;Daniele Parisi ,&nbsp;Bart Reuvers ,&nbsp;Theo Veldhuis ,&nbsp;Francesco Picchioni ,&nbsp;Jing Wu ,&nbsp;Patrizio Raffa ,&nbsp;Cor Koning","doi":"10.1039/d4gc06323f","DOIUrl":"10.1039/d4gc06323f","url":null,"abstract":"<div><div>In this study, cross-linker free, fully bio-based, biodegradable superabsorbent polymers (SAPs) were synthesized from the multi-functional monomers citric acid (CA), monosodium citrate (MSC) and glycerol (GLY) by polycondensation and subsequent thermal self-cross-linking. All monomers (CA, MSC, GLY) used in this study were not only bio-based but also non-toxic. All of them contain more than two hydrophilic groups in one molecule, which shows great potential to be used in the production of SAPs. The structure, water absorbance capacity and biodegradability of the resulting SAPs were investigated in detail. Upon removal of the soluble fraction, the SAPs have a gel content of approximately 60% and exhibit a maximum absorption capacity of deionized water of 24 ± 2 g g⁻¹. Moreover, the prepared SAPs show good biodegradability at 25 °C (40% biodegradability after 28 days) in an activated sludge-containing medium and are accordingly promising eco-friendly materials for potential use in our environment, not generating persistent microplastics like commercial non-biodegradable SAPs based on neutralized polyacrylic acid and polyacrylamides. Therefore, the bio-based SAPs described in this paper have promising application potential for the sustainable chemical industries including hygiene products and agricultural products, <em>e.g.</em> controlled-release fertilizer coatings and soil improvers.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3234-3247"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc06323f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632299","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":"Regulating the bubble-water/catalyst interface microenvironment for accelerated electrosynthesis of H2O2via optimizing oxygen functional groups on carbon black†","authors":"Yuanyuan Zhang ,&nbsp;Xuan Zheng ,&nbsp;Hui Su ,&nbsp;Yun Ling ,&nbsp;Rong Guo ,&nbsp;Maosheng Zhang ,&nbsp;Qingxiang Wang ,&nbsp;Li Niu","doi":"10.1039/d4gc06493c","DOIUrl":"10.1039/d4gc06493c","url":null,"abstract":"<div><div>The selective electrosynthesis of hydrogen peroxide (H₂O₂) <em>via</em> the oxygen reduction reaction (ORR) holds significant promise for sustainable chemical production. In this study, we optimized the oxygen functional groups on carbon black (CB) to modulate the bubble-water/catalyst interface microenvironment, thereby enhancing the electrosynthesis of H₂O₂. A simple hydrothermal method was employed to functionalize the carbon black surface, and the oxygen content was systematically adjusted by varying the temperature and time. The electrochemical performance of the resulting catalysts was evaluated, with CB-85-6 h demonstrating the highest H₂O₂ productivity (3302.23 mmol g_cat⁻¹ h⁻¹) and selectivity (90.1%). EDS, XPS, Raman spectroscopy, and contact angle analysis demonstrated that the introduction of oxygen functional groups enhanced the surface hydrophobicity, facilitating the adsorption and activation of oxygen. Density functional theory (DFT) calculations further confirmed that the COOH at the edge of graphene, C–O–C at the basal 2 and CO at the edge optimize the binding energy of the reaction intermediates, improving both the selectivity and efficiency of H₂O₂ production. This work provides valuable insights into the design of highly efficient catalysts for electrocatalytic H₂O₂ synthesis.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3315-3325"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632306","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":"Synthesis and characterisation of polycarbonates from spent lithium battery electrolytes†","authors":"Haiyue Wang ,&nbsp;Lili Deng ,&nbsp;Bing Fang ,&nbsp;Xiaolong Li ,&nbsp;Liying Guo ,&nbsp;Rongrong Zheng","doi":"10.1039/d4gc05418k","DOIUrl":"10.1039/d4gc05418k","url":null,"abstract":"<div><div>With spent lithium batteries piling up, the green and high-value utilisation of spent lithium-ion batteries (s-LIBs) becomes increasingly crucial. To address this issue, it is essential to prepare high-value copolycarbonates using s-LIBs. In this study, a range of copolycarbonates of isosorbide (ISB), bisphenol A (BPA), and s-LIBs were synthesised using 1,3-(<em>p</em>-toluic acid zinc salt)Im ZnCl₃ as a catalyst. In this way, high molecular weight copolycarbonates (PIBs) (<em>M</em>_w = 57 000–110 000 g mol⁻¹) were obtained. By introducing thermally stable and flexible ISB units, the thermal stability of copolycarbonates was enhanced, and the flexibility of polymer chains was improved. This study showcased the potential for developing environment-friendly soft polycarbonates that can overcome the inherent brittleness of BPA polycarbonates.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3272-3283"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632302","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":"Gas-induced modulation of carbon nitride morphology through a green one-step calcination strategy†","authors":"Jie Wu ,&nbsp;Zheng Liu ,&nbsp;Mengjie Li ,&nbsp;Jinjuan Zhao ,&nbsp;Shuwen Li ,&nbsp;Honglei Yang","doi":"10.1039/d4gc05794e","DOIUrl":"10.1039/d4gc05794e","url":null,"abstract":"<div><div>Considering that graphitic carbon nitride (g-C₃N₄) has been employed as a photocatalytic material, multidimensional morphology modulation is of particular importance as the most effective method for increasing the specific surface area and enhancing the catalytic properties among all modifications. This work focuses on the development of a facile and green synthesis strategy for multidimensional carbon nitride, and the catalytic properties of the prepared materials were evaluated by utilizing Cr(<span>vi</span>) reduction as a model reaction. Ultimately, following the optimization of the preparation conditions such as calcination temperature and heating rate, the sample TCN-5, a conical tubular carbon nitride material with sea urchin-like stacking, was fabricated through the simple one-step calcination of melamine. The material exhibits the most optimal photocatalytic activity owing to its distinctive one-dimensional structure and exhibits enhanced light-sensing and mass transfer capabilities. Furthermore, the theory of gas-induced modulation in the morphology and structure of carbon nitride is further proposed. Briefly, the ammonia gas produced by precursor polymerisation affects the molecular structure at the microscopic level by altering the particle stacking density and exerts an influence on the morphology of the sample at the macroscopic level through the pushing and stripping effect of the gas. This work provides substantial evidence and theoretical guidance for the optimized modification of carbon nitride, presenting a new way for developing advanced carbon nitride materials and beyond.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3293-3302"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632304","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":"One material for many uses: facile construction of hydrogel sensors with strong anti-damage, anti-freezing, and anti-drying properties, cancer-killing ability and biocompatibility†","authors":"Jingwen Lan ,&nbsp;Rukuan Liu ,&nbsp;Yiming Gong ,&nbsp;Sisi Liu ,&nbsp;Zhihong Xiao ,&nbsp;Airong Xu","doi":"10.1039/d4gc06197g","DOIUrl":"10.1039/d4gc06197g","url":null,"abstract":"<div><div>Conductive hydrogels promise great application prospects in future flexible sensor areas. However, great challenges remain in successfully constructing a green hydrogel sensor with efficient synergy from various advantages simultaneously using green starting chemicals via a one-step green procedure. In this work, these challenges were overcome via a superhydrogen-bond network (SHBN) strategy, by which a novel polyvinyl acetate/tannic acid/graphene oxide (PVA/TA/GO) hydrogel was readily constructed and successfully synergized robust mechanical properties (e.g., supporting an 80 kg boy) with strong anti-damage (a hydrogel with a pre-drilled hole was not fractured at 300% strain), anti-freezing (strong mechanical performance, good electrical conductivity, strain sensitivity and stable signal output capacity were retained even at extremely low temperatures when performing real-time tasks) and anti-drying ability (after exposure to air for three months, the hydrogel did not dry out and retained excellent mechanical/anti-freezing performance similar to that of the original hydrogel). The easy construction (one-step freezing) of the hydrogel and its significantly strengthened mechanical properties and excellent anti-freezing/anti-drying ability mainly result from the SHBNs between the hydroxyls on PVA and the hydroxyls on TA/GO/glycerol. Moreover, no toxic/volatile starting chemicals were used in the preparation or discharged into the surrounding environment. More attractively, the hydrogel possesses both cancer-killing ability and biocompatibility. Another impressive facet is that after being assembled into a hydrogel sensor, it can satisfactorily recognize various motion signals. Therefore, the SHBN strategy, which unites diverse outstanding advantages in a single material, opens up a new avenue for designing new high-performance hydrogels for application even in extremely low-temperature or dry environments.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3303-3314"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632305","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 synthesis of high molecular weight semi-aromatic polyamides with biobased furans over metal-free ionic liquids†","authors":"Jian Feng ,&nbsp;Dongxia Yan ,&nbsp;Chunrui Rong ,&nbsp;Lingzhi Yu ,&nbsp;Jiabao Li ,&nbsp;Jiayu Xin ,&nbsp;Xingmei Lu ,&nbsp;Qing Zhou ,&nbsp;Ziqing Wang ,&nbsp;Zhong Wei","doi":"10.1039/d4gc06245k","DOIUrl":"10.1039/d4gc06245k","url":null,"abstract":"<div><div>Dimethyl furan-2,5-dicarboxylate (DMFDC) is a biobased monomer that can potentially serve as an alternative to terephthalic acid. It has been widely used in the production of biobased polyesters and polyamides. This study synthesized a series of poly(butylene furanamide) (PA4F) with DMFDC and 1,4-butanediamine (BDA) through consecutive prepolymerization and melt polycondensation using ionic liquids (ILs) based on 1-butyl-3-methylimidazolium. The relationship between anions of ILs and the number-average molecular weight (<em>M</em>_n) of PA4F was systematically investigated, and the results show that [Bmim][H₂PO₄] exhibits the best catalytic activity. PA4F with a <em>M</em>_n of 27 kg mol⁻¹ catalyzed by it showed a high glass transition temperature of 151 °C and a high elastic modulus of 3.7 GPa, which are the highest values reported to the best of our knowledge. NMR analysis and DFT calculations show that the strong interaction between [Bmim][H₂PO₄] and the substrate facilitates the polymerization reaction. Furthermore, it was found that the prepolymerization stage plays a crucial role in molecular weight growth. The hydrolysis of diester increases with the increase of the prepolymerization temperature and time, leading to a higher proportion of the furan dicarboxylic acid terminated segment in the oligomer, which greatly increases the possibility of decarboxylation and triamine formation in the polycondensation stage, thus further limiting the molecular weight growth of PA4F. The impact of the prepolymerization process was analyzed in detail by TG, DSC, ESI-MS, MALDI-TOF MS, and 2D NMR.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3335-3345"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632308","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":"Batch and flow synthesis of sulfides and sulfoxides using green solvents and oxidant through visible-light photocatalysis†","authors":"Jin Park ,&nbsp;Su Hyeon Kim ,&nbsp;Jun-Young Cho ,&nbsp;Shafrizal Rasyid Atriardi ,&nbsp;Jae-Young Kim ,&nbsp;Hanifah Mardhiyah ,&nbsp;Boyoung Y. Park ,&nbsp;Sang Kook Woo","doi":"10.1039/d4gc05769d","DOIUrl":"10.1039/d4gc05769d","url":null,"abstract":"<div><div>Herein, we report an environmentally friendly, one-pot, scalable method for the synthesis of sulfides and sulfoxides <em>via</em> photocatalyzed C–C bond-formation and oxidation. Employing mild photoredox conditions, green solvents, and oxygen as the oxidant, the approach is sustainable and efficient. The integration of a microreactor-based flow system enabled large-scale production, addressing the typical scalability issues of photocatalytic and liquid–gas phase reactions. Mechanistic studies confirmed that C–C bond formation occurs <em>via</em> an α-thiomethyl radical through a single-electron transfer (SET) pathway, while oxidation involves both SET and energy transfer (EnT) mechanisms.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3284-3292"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d4gc05769d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632303","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":"Synergism between the gradient dilution work function and the Janus electronic state of Pt-CoPxBr1−x for boosting alkaline seawater electrolysis†","authors":"Lei Jin ,&nbsp;Hui Xu ,&nbsp;Kun Wang ,&nbsp;Yang Liu ,&nbsp;Jie Chen ,&nbsp;Xingyue Qian ,&nbsp;Haiqun Chen ,&nbsp;Guangyu He","doi":"10.1039/d4gc05668j","DOIUrl":"10.1039/d4gc05668j","url":null,"abstract":"<div><div>The hydrogen spillover (HSo) effect of metal-supported electrocatalysts <em>via</em> electronic interactions can remarkably influence their performance in the hydrogen evolution reaction (HER). It needs electron-rich supporting metals to promote the adsorption/spillover of protons. However, this electron-enrichment region on metals will make the HSo-HER course contradict the electron-donating oxygen evolution reaction (OER), particularly in proton-poor alkaline seawater electrolytes. Herein, we have demonstrated the gradient dilution work function (<em>Φ</em>) of a Pt-CoP_<em>x</em>Br_{1−<em>x</em>} nanocone <em>via</em> the introduction of Br and rich P vacancies, and the Pt atoms are confirmed with Janus electron-deficient and electron-rich states in the interface and tip regions by the lightning-rod effect, which promotes the HSo-HER course and OER course. As a result, Pt-CoP_<em>x</em>Br_{1−<em>x</em>} exhibits outstanding HER and OER activities in alkaline seawater solution, also displaying a low cell voltage. This work emphasizes that synergies between gradient regulation <em>Φ</em> and the Janus electronic state are fundamental in rationalizing efficient metal–support alkaline seawater electrocatalysts.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 12","pages":"Pages 3355-3362"},"PeriodicalIF":9.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632310","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}