Green Chemistry最新文献

{"title":"Design of a cage–core–chain structure catalyst for deep catalytic oxidative desulfurization with enhanced substrate enrichment†","authors":"Ran Liu ,&nbsp;Chang Wang ,&nbsp;Xiangxiang Gao ,&nbsp;Chen Liu ,&nbsp;Jianmin Lv ,&nbsp;Yusheng Zhang ,&nbsp;Xinying Liu ,&nbsp;Ndzondelelo Bingwa ,&nbsp;Yali Yao ,&nbsp;Fa-tang Li","doi":"10.1039/d5gc00838g","DOIUrl":"10.1039/d5gc00838g","url":null,"abstract":"<div><div>Developing composite metal–organic framework (MOF) catalysts that integrate target molecule enrichment and reactive oxygen species generation to enhance oil–water biphasic desulfurization efficiency remains challenging. A “cage–core–chain” structured functional catalyst, [Bmim]PW@MIL-101(Fe), was designed by encapsulating a phosphotungstic acid (HPW) core inside an MIL-101(Fe) cage and grafting [Bmim]⁺ chains (hydrophobic ionic liquid groups) onto it. The W–O–Fe bond facilitates electron transfer, redistributes charge density, and activates peracetic acid. The Fe³⁺/Fe²⁺ redox cycle promotes the generation and transformation of reactive oxygen species, with singlet oxygen (¹O₂) as the primary oxidant. Density functional theory (DFT) calculations confirm charge density changes between core and shell, and active oxygen generation pathways. Additionally, the catalyst creates a micro-oil environment at the solid–oil–water interface, enhancing the enrichment of dibenzothiophene (DBT) and its interaction with reactive oxygen species, achieving nearly 3.5 times the DBT removal efficiency of MIL-101(Fe). This work provides a sustainable strategy for activating catalytic sites in MOFs with inherently low activity, offering an efficient desulfurization approach for cleaner fuel production.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5340-5358"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908529","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":"Sonochemistry and sonocatalysis: current progress, existing limitations, and future opportunities in green and sustainable chemistry†","authors":"Quang Thang Trinh ,&nbsp;Nicholas Golio ,&nbsp;Yuran Cheng ,&nbsp;Haotian Cha ,&nbsp;Kin Un Tai ,&nbsp;Lingxi Ouyang ,&nbsp;Jun Zhao ,&nbsp;Tuan Sang Tran ,&nbsp;Tuan-Khoa Nguyen ,&nbsp;Jun Zhang ,&nbsp;Hongjie An ,&nbsp;Zuojun Wei ,&nbsp;Francois Jerome ,&nbsp;Prince Nana Amaniampong ,&nbsp;Nam-Trung Nguyen","doi":"10.1039/d5gc01098e","DOIUrl":"10.1039/d5gc01098e","url":null,"abstract":"<div><div>Sonocatalysis is a specialised field within sonochemistry that leverages the interaction between ultrasound and solid catalysts to enhance the rate and selectivity of chemical reactions. As a non-traditional catalytic activation method, sonocatalysis can profoundly modify reaction mechanisms and unlock novel activation pathways that are not typically accessible through standard catalysis. This unique approach offers new opportunities for driving reactions under milder conditions while potentially improving selectivity and efficiency. This review highlights the recent progress of sonocatalytic applications in green chemistry and their contribution to the United Nations' Sustainable Development Goals (SDGs), including environmental remediation, sonotherapy, and biomass conversion. In these applications, we explore the underlying sonocatalytic mechanisms and the interaction between solid catalysts and ultrasound, which drive the enhanced reactivity. A key feature of this manuscript is its comprehensive analysis of the primary technical challenges in sonocatalysis, specifically its low energy efficiency and the complexity of reaction control. To address these hurdles, we examine various effective strategies, such as the incorporation of nanostructured catalytic cavitation agents and the design of advanced microfluidic sonoreactors. These innovations improve energy transfer, control bubble dynamics, and enhance catalytic activity under ultrasound. Furthermore, we implement molecular modelling to gain fundamental insights into the mechanisms fundamental to the effectiveness of sonocatalysts. This approach provides a deeper understanding of how nanostructured catalysts interact with ultrasonic fields, guiding the design of next-generation catalytic materials. The integration of nanostructured catalytic cavitation agents, microfluidic reactor technologies, and computational molecular modelling forms a trilateral synergistic platform that unlocks new potential in sonocatalysis. This multidisciplinary framework paves the way for significant advancements in green and sustainable chemistry, offering innovative solutions to global challenges in energy, health, and environmental sustainability.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 4926-4958"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908437","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":"Tuning the electronic structure of phosphonic acid-based deep eutectic solvents for synergistic catalytic oxidative desulfurization†","authors":"Lixian Xu ,&nbsp;Jie Yin ,&nbsp;Dongao Zhu ,&nbsp;Beibei Zhang ,&nbsp;Linhua Zhu ,&nbsp;Hongping Li ,&nbsp;Jing He ,&nbsp;Huaming Li ,&nbsp;Wei Jiang","doi":"10.1039/d5gc00327j","DOIUrl":"10.1039/d5gc00327j","url":null,"abstract":"<div><div>Deep eutectic solvents (DESs) hold immense potential in extraction-coupled oxidative desulfurization; however, their efficient utilization, in terms of catalytic activity and cycle-regeneration stability, remains a significant challenge. Herein, we propose a strategy for constructing bifunctional phosphonic acid-based DESs (PDESs) using zinc chloride (ZnCl₂) combined with organic phosphonic acids to achieve ultradeep desulfurization by inducing strong electronic interaction <em>via</em> coordination regulation. Through experimental and theoretical screening, the PDES ZnCl₂/phenylphosphinic acid (ZnCl₂/PIA = 1 : 2), demonstrating strong electron transfer capability and high adsorption energy for oxidants, exhibits remarkable catalytic performance towards the removal of heterocyclic thiophenes. Notably, PDESs can simultaneously function as extractants and catalysts, maintaining a desulfurization efficiency of up to 98.4% even after 12 consecutive cycles under mild conditions, which is much higher than that of previously reported DESs-based desulfurization systems. Furthermore, a possible reaction mechanism is proposed, wherein heterocyclic thiophenes are extracted by the ZnCl₂/2PIA PDES <em>via</em> strong interactions (<em>e.g.</em> hydrogen bonding, C–H⋯π and π⋯π) and are then rapidly oxidized by reactive oxygen radicals and peroxy acid in the presence of an oxidant. This study provides a feasible strategy for achieving strong electronic transfer <em>via</em> coordination regulation, aimed at developing high-performance DESs for deep desulfurization and other related application.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5051-5062"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908561","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":"Insights into the reductive catalytic deconstruction of lignin over ultralow-loading palladium–zinc catalysts derived from zinc imidazolate frameworks†","authors":"Yi-Hui Lv ,&nbsp;Qiang Wang ,&nbsp;Wen-Zheng Yin ,&nbsp;Xue-Jie Gao ,&nbsp;Ling-Ping Xiao ,&nbsp;Run-Cang Sun","doi":"10.1039/d4gc05467a","DOIUrl":"10.1039/d4gc05467a","url":null,"abstract":"<div><div>The development of high-performance noble metal catalysts at the atomic scale for the selective chemical catalytic conversion of lignin into monophenolic compounds is highly desirable but remains a challenge. Herein, we report a single-atom strategy to fabricate a highly active and stable hydrogenolysis catalyst containing an ultralow Pd content (0.1 wt%) using cobalt and zinc imidazolate frameworks as precursors. The resultant Pd–Zn@NC catalyst exhibits outstanding activity in the reductive catalytic deconstruction of lignin into aromatic compounds. The catalyst affords a phenol monomer yield of up to 49.6%, which surpasses that of commercial Pd/C. Notably, it demonstrates high selectivity towards unsaturated allyl monomers, reaching a maximum of 91% under optimized conditions. Mechanistic studies using β-<em>O</em>-4′ mimics reveal that the high dispersion of Zn contributes to the dissociation of hydroxyl groups, while the atomically dispersed Pd significantly enhances the hydrogenation performance. The synergistic interactions between Pd and Zn active sites activate the C–O bonds, thereby enhancing reductive aryl-ether scission in lignin.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 18","pages":"Pages 5091-5103"},"PeriodicalIF":9.3,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908564","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 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}