Green Chemistry最新文献

{"title":"Tracking the hydrogen spillover of heterogeneous catalysts in hydrogenation: from formation, migration, and regulation to fate","authors":"Guangxun Sun, Peng Xue, Lei Wang, Xin Zhang, Guangzheng Sun, Zhidong Wang, Qian Zhang, Peng Zhang, Yunqi Liu and Yuan Pan","doi":"10.1039/D5GC02983J","DOIUrl":"https://doi.org/10.1039/D5GC02983J","url":null,"abstract":"<p >Hydrogen spillover is a critical factor in enhancing the hydrogenation of heterogeneous catalysts. However, understanding and orderly controlling spillover are still challenging. The structural design of heterogeneous catalysts significantly promotes hydrogen spillover, which affects the activity, selectivity, and stability of hydrogenation. However, to date, very few systematic reviews have tracked the period of hydrogen spillover in heterogeneous catalysis. Herein, we systematically reviewed the recent research progress on hydrogen spillover from formation and fate to regulation. A strengthening mechanism of hydrogen spillover in hydrogenation for the catalytic reaction process is proposed. In addition, targeted regulatory strategies for promoting hydrogen spillover are summarized <em>via</em> constitutive relationships to guide the development of highly efficient hydrogenation catalysts. Finally, the opportunities and challenges of hydrogen spillover are prospectively discussed, providing theoretical guidance for the catalytic hydrogenation methodology.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 38","pages":" 11739-11768"},"PeriodicalIF":9.2,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145184043","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":"The acetate anion promotes hydrolysis of poly(ethylene terephthalate) in ionic liquid–water mixtures","authors":"Maariyah Y. Suleman, Harriet L. Judah, Panagiotis Bexis, Paul Fennell, Jason P. Hallett and Agnieszka Brandt-Talbot","doi":"10.1039/D5GC02409A","DOIUrl":"https://doi.org/10.1039/D5GC02409A","url":null,"abstract":"<p >A circular plastic economy reduces raw material consumption and discourages pollution. Chemical recycling upgrades the quality of recyclate and is a complementary approach to thermomechanical recycling of plastic waste. This study investigated the use of aprotic and protic ionic liquids (ILs) as solvents for chemical recycling by the hydrolysis of the most common polyester plastic, poly(ethylene terephthalate) (PET). Combinations of three types of cations (aprotic 1-alkyl-3-methylimidazolium, protic 1-methylimidazolium and protic 1,5-biazocyclo-[4.3.0]non-5-enium) combined with a range of anions (acetate, chloride, methanesulfonate, hydrogen sulfate, methyl sulfate, trifluoromethanesulfonate and chlorozincate) were used to hydrolyse PET in the presence of 15 wt% water as the co-solvent and reagent. PET conversion under the screening conditions (180 °C, 3 h, 5% PET loading) varied between 1 and 100%, with ILs containing the acetate anion enabling &gt;97% PET conversion irrespective of the cation. Acidification with aqueous HCl recovered crude crystallised terephthalic acid (TPA). Significant crude yields (46–93%) were only observed for the acetate ILs. The purity of the crude TPA was 34–98%, with 1-ethy-3-methylimidazolium acetate, [C<small>₂</small>C<small>₁</small>im][OAc], and 1-methylimidazolium acetate, [C<small>₁</small>Him][OAc], yielding more and purer TPA than 1,5-biazocyclo-[4.3.0]non-5-enium acetate, [DBNH][OAc]. TPA solubility, PET conversion and TPA yield generally correlated well with increasing p<em>K</em><small>_a</small> and higher hydrogen bond acceptor strength of the IL anion, suggesting that the depolymerisation mechanism in the acetate IL water mixtures is base catalysed. The screening identifies aqueous mixtures of the (pseudo)-protic IL [C<small>₁</small>Him][OAc] as promising catalytic solvent component for the chemical recycling of PET at an industrially feasible temperature, due to high isolated TPA yields and purity achieved at a low solvent cost ($1.74–2.15 per kg). However, an effective separation approach for the monomers TPA and ethylene glycol from the solvent remains to be developed.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 37","pages":" 11475-11490"},"PeriodicalIF":9.2,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/gc/d5gc02409a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100576","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":"Engineered Pseudomonas putida monoculture system for green synthesis of 7-methylxanthine","authors":"Bhagya Jayantha, Shuyuan Zhang, Ryan M. Summers, Gamini P. Mendis and Lahiru N. Jayakody","doi":"10.1039/D5GC02883C","DOIUrl":"https://doi.org/10.1039/D5GC02883C","url":null,"abstract":"<p >7-Methylxanthine (7-MX) is a clinically proven safe drug to treat myopia. The chemical synthesis of 7-MX is hindered due to low specificity, demanding sustainable biological production using renewable, cost-effective feedstocks. To this end, we systematically engineered robust <em>P. putida</em> EM42 to produce 7-MX using caffeine and glycerol in minimal salt media. Removing the transcriptional repressor (<em>glpR</em>), genome integration of heterologous <em>N</em>-demethylase and its reductase, <em>ndmABD</em>, and overexpression of native <em>fdhA</em> to balance the redox cofactors enabled the selective conversion of caffeine to 7-MX with 100% yield. We discovered a native transporter, <em>PP_RS18750</em>, that efficiently takes up caffeine, facilitating the conversion in glycerol-containing media. We achieved 9.2 ± 0.42 g L<small>⁻¹</small> of 7-MX in a 3-L bioreactor by process-level optimization, the highest titer reported to date. Our techno-economic analysis indicates that this novel engineered monoculture approach can produce pharmaceutical-grade 7-MX commercially for $328 per kg, with remarkably low <em>E</em>-factor and Process Mass Intensity (PMI) values, demonstrating the sustainable green valorization of caffeine into high-value methylated xanthine.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 37","pages":" 11365-11379"},"PeriodicalIF":9.2,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145100567","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":"Electrocatalytic oxidation of biomass-derived chemicals using non-precious metal catalysts: design strategies, performance characteristics and perspectives","authors":"Haoyun Wang ,&nbsp;Xiaoyun Li ,&nbsp;Chuanling Si","doi":"10.1039/d5gc00719d","DOIUrl":"10.1039/d5gc00719d","url":null,"abstract":"<div><div>Electrocatalytic oxidation of biomass-derived chemicals is emerging as a revolutionary strategy for replacing traditional thermocatalytic routes due to the advantages of renewable feedstocks, mild reaction conditions, and directional product tunability. The development of non-precious metal catalysts has not only greatly reduced catalyst costs, but also demonstrated unique selectivity advantages in specific reactions, which could be beneficial for large-scale industrial production. In this review, we summarized recent research progress on non-precious metal catalysts for the electrocatalytic oxidation of biomass-derived chemicals. Electrocatalysts for the oxidation of furfural, 5-hydroxymethylfurfural, glycerol and glucose were described in a detailed classification. In addition, the design strategies and performance characteristics of the catalysts are discussed, based on a comprehensive analysis of existing research results. Although non-precious metal catalysts show great potential in the field of biomass electrooxidation, there are still limitations in terms of their intrinsic activity, stability and cost trade-offs. Finally, we provide approaches and perspectives for subsequent studies in terms of their limitations, as well as an outlook on future trends.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10346-10371"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011364","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 synthesis of nitrogen-containing chemicals from biomass-derived carbonyls: catalytic strategies and mechanistic perspectives in multicomponent systems","authors":"Zhisen He ,&nbsp;Shanjian Liu ,&nbsp;Fernando Cardenas-Lizana ,&nbsp;Dongmei Bi ,&nbsp;Aimaro Sanna","doi":"10.1039/d5gc02853a","DOIUrl":"10.1039/d5gc02853a","url":null,"abstract":"<div><div>Nitrogen-containing chemicals (NCCs) are widely used in pharmaceuticals, agrochemicals, polymers, and fine chemicals. Traditional synthesis methods, based on fossil resources, pose sustainability and environmental challenges. Biomass and its derived carbonyl compounds (aldehydes, ketones), with high reactivity and structural diversity, show great potential in catalyzed amination/ammoniation for NCCs. Due to the limited systematic experimental studies on the competitive reaction mechanisms in complex multicomponent systems, there is a lack of understanding of the multicomponent reaction characteristics of biomass-derived aldehydes and ketones. By comparing the regulatory advantages and limitations of different catalytic systems in a multi-functional group environment, this review aims to identify the key factors influencing the competition and selectivity of nitrogen conversion pathways in aldehyde/ketone platform compounds. It focuses on key reaction mechanisms and strategies to control competing pathways in thermochemical conversion. It provides an in-depth analysis of the performance differences between homogeneous and heterogeneous catalysts in directed conversion. It also seeks to highlight the research priorities that need to be addressed in complex systems, based on existing reaction trends. Despite significant progress in optimizing reaction efficiency and selectivity, challenges remain in industrial applications. These include the complex functional group characteristics of biomass-derived aldehydes and ketones, system diversity, catalyst stability, and product separation costs. Future research should focus on the precise design of multifunctional catalysts, dynamic analysis of reaction pathways, and the development of multiscale reaction-separation coupling technologies. This review aims to promote the sustainable synthesis and large-scale application of biomass-based NCCs, supporting the low-carbon economy transition.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10372-10401"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011365","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":"Toward closed-loop hydrometallurgy: a critical review of wastewater reuse strategies for end-of-life LiFePO4 battery recycling","authors":"Jong-Won Choi ,&nbsp;Hyun-Woo Shim ,&nbsp;Hong-In Kim ,&nbsp;Sookyung Kim ,&nbsp;Duy Tho Tran ,&nbsp;Mooki Bae","doi":"10.1039/d5gc02987b","DOIUrl":"10.1039/d5gc02987b","url":null,"abstract":"<div><div>The rapid adoption of LiFePO₄ (LFP) batteries, driven by their safety and cost advantages, necessitates the development of sustainable recycling technologies tailored to their low-value composition. While hydrometallurgical methods enable efficient lithium recovery, they typically generate large volumes of wastewater, undermining both environmental and economic viability. This review critically examines recent advances in closed-loop hydrometallurgical recycling of end-of-life LFP batteries, with a particular focus on wastewater reuse strategies. A comprehensive classification of lixiviants, including inorganic acids, salt-based compounds, and alkaline and organic compound, is presented, highlighting wastewater reuse. Quantitative techno-economic simulations reveal that full wastewater reuse, starting from the second cycle, significantly reduces operational costs and enables positive net profit within four to five reuse cycles in regions with favorable energy and labor conditions. Despite these advancements, challenges such as impurity build-up, reagent stability, and limited long-term cycle testing remain. This review outlines current limitations and proposes future directions for scaling up closed-loop systems in alignment with the principles of green chemistry and circular hydrometallurgy.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10423-10443"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011367","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 visible light promoted cascade cyclization reaction via a PCET process: easy access to indolinone-fused polycycles","authors":"Yuxuan Han ,&nbsp;Jie Chen ,&nbsp;Hong Zhang ,&nbsp;Xiuling Cui","doi":"10.1039/d5gc03208c","DOIUrl":"10.1039/d5gc03208c","url":null,"abstract":"<div><div>An efficient protocol for the synthesis of indolinone-fused polycycles initiated by nitrogen-centered radicals (NCRs) has been developed. The amide radical was generated by proton-coupled electron transfer (PCET) under visible light. A series of indole[1,2-<em>b</em>]isoquinolinones were synthesized in up to 99% yield in “one-pot” construction of C–N/C–C bonds through cascade cyclization. This protocol features excellent step and atom economy, obviating the use of transition metals and Brønsted bases, offering a mild and efficient photochemical pathway to synthesize polycyclic indolinones.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10562-10566"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011375","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":"Ecotoxicity of binary mixtures of cholinium-based ionic liquids and salts to microalgae†","authors":"Fátima Jesus ,&nbsp;Joana L. Pereira ,&nbsp;Sónia P. M. Ventura ,&nbsp;João A. P. Coutinho ,&nbsp;Fernando J. M. Gonçalves ,&nbsp;Ana M. M. Gonçalves","doi":"10.1039/d5gc02838h","DOIUrl":"10.1039/d5gc02838h","url":null,"abstract":"<div><div>Due to the widespread use of ionic liquids (ILs) in various applications and their frequent combination with salts in processes or products, mixtures of ILs and salts are likely to be present in aquatic environments. The present study aimed to assess the combined ecotoxicity of mixtures of cholinium-based ILs (cholinium bicarbonate, benzyldimethyl(2-hydroxyethyl)ammonium chloride, cholinium bitartrate and cholinium dihydrogencitrate) and salts (potassium phosphate tribasic and sodium citrate dihydrate) to the microalga <em>Raphidocelis subcapitata</em>, a highly sensitive microalgal species. The 96 h-EC₅₀ values for the endpoint yield increased as follows: [Chol][DHCit] (EC₅₀ = 85.2 mg L⁻¹) &lt; [Chol][Bit] (EC₅₀ = 110.8 mg L⁻¹) &lt; [Chol][Bic] (EC₅₀ = 310.5 mg L⁻¹) &lt; [BzChol]Cl (EC₅₀ = 766.3 mg L⁻¹), generally following the expected increase of ecotoxicity with increased hydrophobicity. Both CA and IA models could describe the observed ecotoxicity, but a better fit was achieved with the CA model, with antagonistic interactions observed in 5 of the 8 tested mixtures. The salt K₃PO₄ was found to be less ecotoxic than NaCit·2H₂O and, simultaneously, to promote stronger antagonism, and is thus recommended to be used in future processes or product design with cholinium-based ILs, hence supporting the advancement of green chemistry. Synergism was not significant in any mixture, despite being observed under specific conditions, particularly when the IL was dominant in the mixture and above 1 TU. The antagonism observed for most of the mixtures, associated with the hormesis observed for all mixtures, suggests that mixtures of ILs and salts will likely be less environmentally hazardous than predicted based on their individual toxicities. Since ILs commonly present high water solubility and good stability, further studies addressing the effects of mixtures with ILs should be performed, contributing to improving the risk assessment of ILs.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10664-10672"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011388","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":"Electrochemical iron-catalyzed difunctionalization of olefins: efficient and sustainable access to β-heteroarylated esters","authors":"Binbin Chen ,&nbsp;Jun Xu ,&nbsp;Zeyi Wang ,&nbsp;Ling Yang ,&nbsp;Qianyuan Liu ,&nbsp;Pengfei Zhang","doi":"10.1039/d5gc02319j","DOIUrl":"10.1039/d5gc02319j","url":null,"abstract":"<div><div>Aliphatic esters are fundamental components of biologically active compounds and serve as flexible chemical intermediates in pharmaceutical synthesis. Yet, their preparation from readily accessible olefins has been fraught with challenges. In this work, we introduce an electrochemical iron-catalysis strategy for difunctionalization of olefins to produce β-heteroarylated esters. This method aligns with green chemistry principles by eliminating the need for numerous sacrificial and hazardous reagents. Additionally, it demonstrates broad compatibility with diverse olefins and heteroarenes. Its practicality is further highlighted by product derivatizations and late-stage functionalizations of pharmaceutically relevant molecules. Mechanistic insights reveal a radical-based pathway is involved. We hope this approach can become an invaluable tool for aliphatic ester synthesis, offering substantial potential for drug discovery initiatives.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10656-10663"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011396","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":"Mechanochemical induced interfacial wetting and radical synergism for enhanced gallium recovery from waste gallium nitride","authors":"Lanbin Wang ,&nbsp;Beikai Zhang ,&nbsp;Chaocheng Zeng ,&nbsp;Jiadong Yu ,&nbsp;Jinhui Li","doi":"10.1039/d5gc03311j","DOIUrl":"10.1039/d5gc03311j","url":null,"abstract":"<div><div>Gallium nitride (GaN), a critical third-generation semiconductor material, faces significant recycling challenges due to its increasing waste generation, which poses a threat to global Ga resource security and environmental sustainability. Traditional hydrometallurgical or pyrometallurgical GaN recycling methods often suffer from low efficiency, high energy consumption, or secondary pollution. This study introduces a mechanochemical induced interfacial wetting and radical strategy, integrating mechanical activation with <em>in situ</em> radical generation in a low-water-consumption system for Ga recovery. Mechanical force promotes the generation of fresh surfaces, introduces lattice defects, and disrupts the surface passivation layer, thereby altering the surface properties of GaN to enhance hydrophilicity. Combined with pre-wetting treatment, it improves the mass transfer efficiency of OH⁻ at the solid–liquid interface. Mechanical energy also promotes the generation of ˙OH and ˙O₂⁻ radicals derived from Na₂O₂, with density functional theory (DFT) confirming that the dissociation energy barrier of Ga–N bonds is reduced from 4.31 eV to 3.15 eV. Under optimized conditions, this approach achieves a Ga leaching efficiency of 96.67%, yielding high-purity Ga₂O₃. Life cycle assessment (LCA) demonstrated 38.59% lower carbon emissions and 84.61% reduced water consumption compared to traditional methods. This synergistic system provides a green and efficient pathway for the recycling of inert semiconductors by combining mechanochemical interfacial wetting with radical-driven chemical oxidation.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 35","pages":"Pages 10837-10850"},"PeriodicalIF":9.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145011405","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}