Green Chemistry最新文献

{"title":"Electrochemical difunctionalization of indolizines with glyoxylic acid and halide salts†","authors":"Chenglong Feng ,&nbsp;Xin Liu ,&nbsp;Peipeng Zhang ,&nbsp;Meichao Li ,&nbsp;Zhenlu Shen","doi":"10.1039/d4gc06102k","DOIUrl":"10.1039/d4gc06102k","url":null,"abstract":"<div><div>A novel and sequential strategy for the synthesis of C3-formylated and C1-halogenated indolizines through electrochemical difunctionalization has been developed. This protocol proceeds smoothly without external oxidants or catalysts, and exhibits excellent functional group tolerance. A series of disubstituted indolizines are obtained under mild conditions (yield up to 81%). Scale-up reaction and further transformation of the product can confirm the practicality of this protocol. The developed process has been evaluated using green metrics to validate its sustainability. A possible mechanism for regioselective C–H formylation and halogenation of indolizines is elucidated by control experiments and cyclic voltammetry studies.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5119-5125"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908566","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":"Machine learning-driven design of single-atom catalysts for carbon dioxide valorization to high-value chemicals: a review of photocatalysis, electrocatalysis, and thermocatalysis","authors":"Xiangyu Wen ,&nbsp;Xiao Geng ,&nbsp;Guandong Su ,&nbsp;Yizheng Li ,&nbsp;Qidong Li ,&nbsp;Yuxuan Yi ,&nbsp;Lifen Liu","doi":"10.1039/d5gc00739a","DOIUrl":"10.1039/d5gc00739a","url":null,"abstract":"<div><div>The pressing need for carbon-neutral technologies has driven extensive research into photocatalytic, electrocatalytic, and thermocatalytic CO₂ reduction, with highly efficient single-atom catalysts (SACs) due to their atomically dispersed active sites, tunable coordination environments, and well-defined electronic structures. Recent advances in SACs have demonstrated enhanced activity, selectivity and stability through rational design strategies incorporating transition-metal-based single-atom sites, nitrogen-coordinated frameworks, and perovskite-, graphene-, or MOF-supports. Mechanistically, SACs facilitate CO₂ activation <em>via</em> optimized CO₂ adsorption, electronic-state modulation and selective stabilization of key intermediates, thus promoting tailored product formation. Despite significant progress, challenges remain in understanding the precise electronic effects governing intermediate binding and selectivity and suppressing metal aggregation under operando conditions. This review systematically integrates experimental findings with machine learning (ML)-assisted first-principles calculations, deep learning (DL) frameworks, and density functional theory (DFT) modeling to refine the performances of SACs. ML-driven Bayesian optimization accelerates catalyst discovery by correlating the synthesis parameters with reaction kinetics and thermodynamics. High-throughput experimental validation combined with multi-technique characterization elucidates the structure–activity relationships, providing insights into the electron transfer dynamics, coordination tuning, and catalytic site evolution. The integration of active learning algorithms enables self-optimizing SACs, dynamically adjusting synthesis and reaction conditions for superior selectivity and faradaic efficiency. By bridging predictive modeling with experimental validation, this review presents a comprehensive framework for the rational design of next-generation SACs, paving the way for high-efficiency conversion of CO₂ into valuable chemicals. The synergy between AI-driven catalyst discovery and mechanistic elucidation represents a paradigm shift toward viable and selective CO₂ valorization strategies.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 4898-4925"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908436","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":"Demystify the unique hydrogen spillover effect in electrocatalytic hydrogen evolution","authors":"Xiaodong Chen ,&nbsp;Xiaofei Wei ,&nbsp;Xingheng Zhang ,&nbsp;Jianye Wang ,&nbsp;Zhaojie Wang ,&nbsp;Shuxian Wei ,&nbsp;Siyuan Liu ,&nbsp;Bo Liao ,&nbsp;Zhe Sun ,&nbsp;Xiaoqing Lu","doi":"10.1039/d4gc05909c","DOIUrl":"10.1039/d4gc05909c","url":null,"abstract":"<div><div>Hydrogen spillover, involving the migration of active hydrogen species between high-affinity sites and weak adsorption sites on the catalyst surface, has recently garnered attention for its unique reaction mechanism and accelerated reaction kinetics. However, this migration process is thermodynamically unfavorable, as it necessitates overcoming significant interfacial barriers. Thus, hydrogen spillover is not commonly observed in hydrogen evolution reaction (HER) catalysis. A thorough understanding of hydrogen spillover is crucial for designing advanced HER catalysts with low-energy-barrier interfaces that facilitate hydrogen migration. In this review, we analyze the fundamental characteristics of hydrogen spillover and provide a comprehensive overview of its effects in the context of recent advances in HER. We summarize the various manifestations of hydrogen spillover observed in early HER catalysis and describe feasible physicochemical and electrochemical characterization methods to validate the occurrence of this phenomenon. Additionally, we discuss different strategies to modulate the kinetic barriers associated with interfacial hydrogen spillover in detail, which are essential for the efficient design and synthesis of advanced HER catalysts that leverage this effect. Finally, we present the challenges and future perspectives related to the hydrogen spillover effect in HER catalysis, offering guidance for expanding its application in catalytic reactions.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 4959-4985"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908438","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":"Catalytic alkaline hydrolysis of PET and BPA-PC waste in minutes at atmospheric pressure without microwaves or organic solvents†","authors":"Anshul Jain ,&nbsp;Stephen J. Connon","doi":"10.1039/d5gc01183c","DOIUrl":"10.1039/d5gc01183c","url":null,"abstract":"<div><div>Rapid hydrolysis of poly(ethylene terephthalate) (PET) waste usually requires organic cosolvents, high pressures or microwave irradiation, which can increase the environmental impact/expense/operational complexity of an emerging enabling technology for more sustainable plastic recycling. Using a combination of solute-derived boiling point elevation and phase transfer catalysis, operationally facile, rapid alkaline hydrolysis of PET and poly(bisphenol A carbonate) (BPA-PC) waste – from beverage bottles/textiles and compact discs respectively – is achievable in minutes (≤5 min for PET and 20 min for BPA-PC) at atmospheric pressure without the need for either microwaves or organic cosolvents. Dimethyldialkylammonium halides were found to be optimal catalysts at low loadings. The rapid, one-pot catalytic hydrolysis of a waste stream of both plastics followed by ready isolation of the terephthalic acid and bis-phenol A monomer units in excellent yields (without decomposition) is possible by selective protonolysis.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 4986-4994"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908439","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":"Supramolecular assisted O-acylation of carbohydrates†","authors":"Soumyadip Dey ,&nbsp;Debabrata Giri ,&nbsp;Adrita Nandy ,&nbsp;Abhijit Sau","doi":"10.1039/d5gc00499c","DOIUrl":"10.1039/d5gc00499c","url":null,"abstract":"<div><div>The acylation of hydroxy groups serves as one of the most employed protecting group strategies in carbohydrate chemistry. Here, we present a base-free, supramolecular assisted approach for the <em>O</em>-acylation of carbohydrates under mild conditions, using 18-crown-6 in combination with a catalytic amount of potassium fluoride. This sustainable and useful method successfully converted various functional groups containing carbohydrate hydroxy groups into <em>O</em>-acyl, <em>O</em>-benzoyl, and <em>O</em>-propionyl derivatives with up to 99% yields.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 4995-5000"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908453","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":"Evolution process of humins derived from cellulose by a humin extraction approach†","authors":"Xianda Li ,&nbsp;Zhongping Shao ,&nbsp;Haozhe Shan ,&nbsp;Li Liu","doi":"10.1039/d5gc00654f","DOIUrl":"10.1039/d5gc00654f","url":null,"abstract":"<div><div>Cellulose utilization has been seriously hindered by the formation of humins, while the humin structure remains challenging since unconverted cellulose and humins exist as a solid mixture. In this work, we developed a novel strategy to extract humins from unconverted cellulose and disclosed the structural evolution process of cellulose-derived humins for the first time. The key intermediate levoglucosan was successfully captured and identified, which significantly favors the formation of anhydro-sugars followed by polymerization due to its stability. By means of comprehensive HPLC-MS/MS, FT-IR, MALDI-TOF and SEM characterization studies, it was proposed that multiple elementary reactions were involved in the formation of cellulose-derived humins, including cellulose depolymerization, etherification, esterification, aldol condensation, dehydration and thermal oxidation. In the early stage, cellulose depolymerization results in glucose and levoglucosan (LG), which undergo etherification to form the early humins <em>via</em> a small molecule mechanism, accompanied by esterification and dehydration. In the later stage, <em>gluco</em>oligosaccharides especially with the LG end from cellulose depolymerization undergo etherification <em>via</em> an oligomer mechanism. Meanwhile, etherification of HMF and aldol condensation with LA take place prominently, together with dehydration and oxidation, resulting in the enhancement of CC and CO conjugation.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5322-5331"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908527","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":"Highly efficient electro-epoxidation of olefins coupled with bromine recycling†","authors":"Haoqiong Zhu ,&nbsp;Menglu Cai ,&nbsp;Xiaozhong Wang ,&nbsp;Liyan Dai","doi":"10.1039/d5gc00148j","DOIUrl":"10.1039/d5gc00148j","url":null,"abstract":"<div><div>Organic electrosynthesis powered by renewable electricity has gained attention as a sustainable and economically advantageous method for diverse chemical transformations. Olefin epoxidation is a key reaction for producing multiple epoxides used as value-added fine chemicals and crucial industrial intermediates. The halohydrin-based method was previously utilized in large-scale productions. However, its reliance on corrosive reagents and substantial energy demands have led to a gradual transition towards more environmentally friendly methodologies, with electrosynthesis emerging as a significant alternative. In this study, we developed a Br₂/Br⁻-mediated electro-epoxidation strategy for olefins using a one-pot electrochemical cell. This method achieved an impressive yield of styrene oxide (97.5%) and Faraday efficiency (84.7%) at a high substrate concentration of 100 mM and exhibited high compatibility with an industrial-relevant current density (100 mA cm⁻²). Additionally, we developed a novel method to realize the electrolyte recyclability in a one-pot cell, ensuring ion regeneration and demonstrating strong feasibility for practical applications. Moreover, the current system exhibited exceptional stability for 23 cycles and demonstrated a broad scope for substrates. To further capitalize on these advantages, we successfully scaled up the production of styrene and cyclohexene into value-added products. These results underscore the methodological universality, economic viability, and sustainability of the developed system, highlighting its potential for industrial adoption.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5366-5375"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908531","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":"Selective catalytic depolymerisation of C-lignin into ethylcatechol using commercial Pd/C under hydrogen-free conditions†","authors":"Xuening Li ,&nbsp;Shuizhong Wang ,&nbsp;Guoyong Song","doi":"10.1039/d5gc00161g","DOIUrl":"10.1039/d5gc00161g","url":null,"abstract":"<div><div>The catalytic depolymerisation of catechyl lignin (C-lignin) represents a promising and sustainable approach for producing catechol monomers adorned with C3 side chains, but the selective production of ethylcatechol with a C2 side chain remains a significant challenge due to the intricate scission of vicinal C–O and C–C bonds. Herein, we demonstrate that Pd/C can effectively catalyse the cleavage of C_α–O, C_β–O and C_β–C_γ bonds in C-lignin under hydrogen-free conditions, resulting in the formation of ethylcatechol in a selective manner, with methanol acting as the primary hydrogen donor. By optimizing the reaction parameters, an impressive yield of 80.7 mol% of catechol monomers has been achieved, accompanied by a remarkable selectivity of 69% for ethylcatechol. Detailed investigations using model compounds suggest that a plausible reaction pathway involves the generation of caffeyl alcohol as a key intermediate by the synchronous cleavage of C_α–O and C_β–O bonds in benzodioxane linkages, followed by hydrogenation, dehydrogenation and subsequent decarbonylation reactions, enabling the efficient production of ethylcatechol. This study provides a practical and scalable route for transforming renewable C-lignin biopolymers into high-value-added ethylcatechol under an N₂ atmosphere, highlighting its potential for sustainable chemical production.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5184-5192"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908537","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 in situ synthesis of ZIF-8 membranes on the inner-surface of PESf hollow fibers and application in hydrogen separation†","authors":"Yifan Yang ,&nbsp;Tengfei Yang ,&nbsp;Lu Liu ,&nbsp;Hanhan Chen ,&nbsp;Wenxiu Zhang ,&nbsp;Shaomin Liu ,&nbsp;Xiaobin Wang","doi":"10.1039/d4gc06464j","DOIUrl":"10.1039/d4gc06464j","url":null,"abstract":"<div><div>Membrane separation technology is widely recognized as a sustainable option, but achieving green manufacturing for the membranes themselves remains a significant challenge. To ensure sustainable development, it is crucial to prepare membranes in accordance with the “12 principles of green membrane materials and processes”. The preparation of most metal–organic framework (MOF) membranes currently requires the use of certain of toxic organic solvents and appropriate metal sources in the synthetic solution. Developing defect-free internally-supported MOF membranes on polymeric hollow fibers (HFs) <em>via</em> an environmentally friendly green synthetic route represents a significant yet challenging task. In this study, a straightforward continuous flow growth method under organic solvent-free conditions and without external metal sources in the synthetic solution to synthesize zeolitic imidazolate framework-8 (ZIF-8) membranes on the inner surface of PESf(polyethersulfone)-ZnO-HFs was proposed. This approach facilitates the <em>in situ</em> formation of well-intergrown ZIF-8 membranes through the direct coordination of an aqueous solution of 2-methylimidazole (Hmim) with ZnO embedded within PESf-HFs. ZnO particles not only regulate the porosity of PESf-HFs but also serve as both metal sources and nucleation sites for ZIF-8 membrane formation. The recirculating flow process ensures a steady and uniform supply of Hmim aqueous solutions within the HFs, thereby optimizing the regulation of the heterogeneous nucleation rate and crystallization conditions for ZIF-8 crystals across the entire inner surface of the HFs. The resulting ZIF-8 membranes were thin and continuous, with a thickness of approximately 800 nm. The membrane demonstrated outstanding molecular sieving performance, achieving ideal selectivities of 23.1 for H₂/CH₄ and 13.6 for H₂/N₂ mixtures at a H₂ permeance of 3.56 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. Furthermore, this ZIF-8 membrane exhibited remarkable mechanical, thermal, long-term, and pressure stabilities, as well as excellent reproducibility and scalability. The method developed in this work eliminates the need for metals in the synthetic solution and avoids the formation of ZIF-8 crystals in solution, thereby substantially mitigating the environmental risks and economic costs associated with subsequent separation processes. This contribution paves the way for simple, cost-effective, scalable and environmentally friendly strategies for the design and synthesis of MOF membranes on the inner surface of HFs.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5282-5294"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908580","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 metal recovery and electrocatalyst fabrication from spent lithium-ion batteries via green solvent extraction†","authors":"Mingfei Chen ,&nbsp;Yaping Wang ,&nbsp;Yixin Zhou ,&nbsp;Bin Guo ,&nbsp;Li Wang ,&nbsp;Jinsheng Liang","doi":"10.1039/d5gc00073d","DOIUrl":"10.1039/d5gc00073d","url":null,"abstract":"<div><div>The accelerated production of lithium-ion batteries (LIBs) causes the decommissioning tide of spent LIBs. Therefore, developing a sustainable battery recycling strategy can minimize environmental pollution and save valuable resources. We present an easy and innovative method to transform spent LiNi_{1−<em>x</em>−<em>y</em>}Co_<em>x</em>Mn_<em>y</em>O₂ (NCM) cathodes into nickel cobalt sulfide (NCS) electrocatalysts for the oxygen evolution reaction (OER). This process involves separating metal ions using green and reusable deep eutectic solvents (DESs), which play multiple roles of a leaching agent, metal source and template, simplifying the multi-stage metal separation process and reducing contamination and waste. Then, NCS clings to carbon fiber paper (CFP) using thioacetamide. The prepared NCS electrode presents a hollow nanorod array structure with rich active sites and high surface hydrophilicity, which can be engineered by adjusting the heating conditions <em>via</em> the Ostwald ripening mechanism. The NCS electrode exhibits satisfactory OER performance, featuring a modest overpotential (<em>η</em>₁₀ = 248 mV at 10 mA cm⁻²), small charge-transfer resistance (2.4 Ω), a Tafel slope of 67.74 mV dec⁻¹, and stable operation for 125 hours. The new recovery technology in this work presents an instructive and feasible approach for recycling spent LIBs into multimetallic sulfide OER electrocatalyst materials.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5126-5135"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908501","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}