Wenjian Li , Xirui Li , Rong Huang , Xiangyuan Yao , Guo-Jun Deng , Fuhong Xiao
A novel heterogeneous cobalt–silicotungstate polyoxometalate catalyst (CoSiW-300) for the aerobic dehydrogenative aromatization of cyclohex-2-enones and amines is described. This method efficiently constructs both symmetric and unsymmetric 1,4-phenylenediamine derivatives in a single step from readily available precursors. Comprehensive characterization (XRD, FT-IR, XPS, Py-IR) confirmed the preservation of the Keggin-type structure and revealed the critical role of Lewis acid sites, whose strength and population are modulated by the calcination temperature. The CoSiW-300 catalyst demonstrated broad substrate scope, excellent functional group tolerance, and robust recyclability without significant loss of activity, underscoring its potential as a sustainable and economical alternative to noble–metal-based homogeneous systems.
{"title":"Heterogeneous Co-catalyzed dehydrogenative aromatization of cyclohex-2-enone and amines to 1,4-phenylenediamine","authors":"Wenjian Li , Xirui Li , Rong Huang , Xiangyuan Yao , Guo-Jun Deng , Fuhong Xiao","doi":"10.1039/d5gc05871f","DOIUrl":"10.1039/d5gc05871f","url":null,"abstract":"<div><div>A novel heterogeneous cobalt–silicotungstate polyoxometalate catalyst (CoSiW-300) for the aerobic dehydrogenative aromatization of cyclohex-2-enones and amines is described. This method efficiently constructs both symmetric and unsymmetric 1,4-phenylenediamine derivatives in a single step from readily available precursors. Comprehensive characterization (XRD, FT-IR, XPS, Py-IR) confirmed the preservation of the Keggin-type structure and revealed the critical role of Lewis acid sites, whose strength and population are modulated by the calcination temperature. The CoSiW-300 catalyst demonstrated broad substrate scope, excellent functional group tolerance, and robust recyclability without significant loss of activity, underscoring its potential as a sustainable and economical alternative to noble–metal-based homogeneous systems.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2041-2048"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043370","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}
Pietro Caboni , Andrea Porcheddu , Sándor B. Ötvös , C. Oliver Kappe
Amide bonds are among the most ubiquitous linkages in pharmaceuticals, agrochemicals, and materials, yet their synthesis is still dominated by solvent-intensive protocols. Mechanochemistry offers a sustainable alternative, but its scalability has remained a critical challenge. Here we demonstrate that amide bond formation can be translated into an industrially relevant process using a standard agitator bead mill. Through systematic optimization, we achieved efficient amidations over a broad substrate scope under liquid-assisted grinding with only minimal ethyl acetate. A 20-fold scale-up delivered productivities of up to 2.89 kg h−1, without excess reagents, added base, or bulk solvent, substantially reducing waste. The use of commercially available equipment that is available from lab to manufacturing-scale establishes bead milling as a practical, and environmentally responsible platform for scalable amide synthesis.
酰胺键是药物、农用化学品和材料中最普遍存在的键之一，但它们的合成仍然以溶剂密集型协议为主。机械化学提供了一种可持续的替代方案，但其可扩展性仍然是一个关键挑战。在这里，我们证明酰胺键的形成可以转化为一个工业相关的过程中使用标准搅拌珠磨机。通过系统优化，我们在液体辅助研磨的情况下，仅用最少的乙酸乙酯，在广泛的底物范围内实现了高效的酰胺化。20倍的放大生产效率高达2.89 kg h - 1，没有多余的试剂，添加碱，或散装溶剂，大大减少了浪费。从实验室到生产规模的商用设备的使用，使珠磨成为一种实用、环保的可扩展酰胺合成平台。
{"title":"Scalable mechanochemical synthesis of amides using bead milling technology","authors":"Pietro Caboni , Andrea Porcheddu , Sándor B. Ötvös , C. Oliver Kappe","doi":"10.1039/d5gc04764a","DOIUrl":"10.1039/d5gc04764a","url":null,"abstract":"<div><div>Amide bonds are among the most ubiquitous linkages in pharmaceuticals, agrochemicals, and materials, yet their synthesis is still dominated by solvent-intensive protocols. Mechanochemistry offers a sustainable alternative, but its scalability has remained a critical challenge. Here we demonstrate that amide bond formation can be translated into an industrially relevant process using a standard agitator bead mill. Through systematic optimization, we achieved efficient amidations over a broad substrate scope under liquid-assisted grinding with only minimal ethyl acetate. A 20-fold scale-up delivered productivities of up to 2.89 kg h<sup>−1</sup>, without excess reagents, added base, or bulk solvent, substantially reducing waste. The use of commercially available equipment that is available from lab to manufacturing-scale establishes bead milling as a practical, and environmentally responsible platform for scalable amide synthesis.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2049-2055"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043371","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}
Jun Xu , Fan Zhang , Minghua Gan , Yaoyao Liu , Mengqi Wang , Jianfeng Wen , Die Hu
The functionalization of the C(sp3)–H bond through an oxidative cross-dehydrogenative coupling strategy represents a challenging transformation in the field of organic chemistry. In continuation of our research interest in green oxidation of indoles, herein we further explore the direct functionalization of the C(sp3)–H bond at the benzylic position of unactivated 2-methylindoles promoted by a simple reagent, NCS or NBS, associated with nitrogen, oxygen, sulfur, and carbon nucleophiles, via an oxidative cross-dehydrogenative coupling strategy, forming C(sp3)–N, C(sp3)–O, C(sp3)–S, and C(sp3)–C bonds. Different from our previous approaches, this methodology was demonstrated to be a robust protocol consisting of chlorination or bromination and then SN2′ nucleophilic substitution processes, and exhibits a reasonably broad substrate scope and excellent functional group tolerance, thus enabling the late-stage functionalization of complex drugs, amino acids and natural products.
{"title":"Metal-free C(sp3)–H bond functionalization via oxidative cross-dehydrogenative coupling","authors":"Jun Xu , Fan Zhang , Minghua Gan , Yaoyao Liu , Mengqi Wang , Jianfeng Wen , Die Hu","doi":"10.1039/d5gc05120g","DOIUrl":"10.1039/d5gc05120g","url":null,"abstract":"<div><div>The functionalization of the C(sp<sup>3</sup>)–H bond through an oxidative cross-dehydrogenative coupling strategy represents a challenging transformation in the field of organic chemistry. In continuation of our research interest in green oxidation of indoles, herein we further explore the direct functionalization of the C(sp<sup>3</sup>)–H bond at the benzylic position of unactivated 2-methylindoles promoted by a simple reagent, NCS or NBS, associated with nitrogen, oxygen, sulfur, and carbon nucleophiles, <em>via</em> an oxidative cross-dehydrogenative coupling strategy, forming C(sp<sup>3</sup>)–N, C(sp<sup>3</sup>)–O, C(sp<sup>3</sup>)–S, and C(sp<sup>3</sup>)–C bonds. Different from our previous approaches, this methodology was demonstrated to be a robust protocol consisting of chlorination or bromination and then S<sub>N</sub>2′ nucleophilic substitution processes, and exhibits a reasonably broad substrate scope and excellent functional group tolerance, thus enabling the late-stage functionalization of complex drugs, amino acids and natural products.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1904-1911"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043344","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}
Haonan Guo , Zhuoya Ma , Xiangtao Yu , Xuyang Li , Ye Wang , Tiantian Song , Tao Yang , Xinmei Hou
Offshore wind power driving seawater electrolysis for hydrogen production is one of the key pathways toward large-scale green hydrogen generation. However, the mismatch between the fluctuating renewable energy supply and the electrolyzer load not only results in low wind power conversion efficiency but also causes damage to electrode and membrane materials, thereby severely affecting the stable operation of the electrolysis system. On the other hand, due to the complex composition of seawater, direct seawater electrolysis induces electrode corrosion, competing side reactions, and precipitate blockage, all of which present significant challenges to practical applications. Based on these issues, we provide a comprehensive review of the challenges and mitigation strategies of seawater electrolysis from the perspectives of offshore wind–electrolyzer coupling modes, seawater electrolysis technologies, and hydrogen storage methods. We first discuss the coupling patterns between offshore wind-power systems and electrolytic hydrogen production systems, followed by a systematic analysis of coupling strategies for different scenarios and conditions. Next, we address the bottlenecks in seawater electrolysis technologies and highlight the latest strategies for overcoming them. Effective design strategies for efficient and stable electrode and membrane materials, including hydrogen evolution catalysts, oxygen evolution catalysts, and electrolyzer membranes, are summarized in detail. Finally, we outline recent advances in mainstream hydrogen storage approaches, providing new insights into enabling the large-scale application of offshore wind coupled with seawater electrolysis for hydrogen production.
{"title":"Advances in offshore wind-power coupled seawater electrolysis for hydrogen production: mode selection, system innovation, and materials design","authors":"Haonan Guo , Zhuoya Ma , Xiangtao Yu , Xuyang Li , Ye Wang , Tiantian Song , Tao Yang , Xinmei Hou","doi":"10.1039/d5gc05469a","DOIUrl":"10.1039/d5gc05469a","url":null,"abstract":"<div><div>Offshore wind power driving seawater electrolysis for hydrogen production is one of the key pathways toward large-scale green hydrogen generation. However, the mismatch between the fluctuating renewable energy supply and the electrolyzer load not only results in low wind power conversion efficiency but also causes damage to electrode and membrane materials, thereby severely affecting the stable operation of the electrolysis system. On the other hand, due to the complex composition of seawater, direct seawater electrolysis induces electrode corrosion, competing side reactions, and precipitate blockage, all of which present significant challenges to practical applications. Based on these issues, we provide a comprehensive review of the challenges and mitigation strategies of seawater electrolysis from the perspectives of offshore wind–electrolyzer coupling modes, seawater electrolysis technologies, and hydrogen storage methods. We first discuss the coupling patterns between offshore wind-power systems and electrolytic hydrogen production systems, followed by a systematic analysis of coupling strategies for different scenarios and conditions. Next, we address the bottlenecks in seawater electrolysis technologies and highlight the latest strategies for overcoming them. Effective design strategies for efficient and stable electrode and membrane materials, including hydrogen evolution catalysts, oxygen evolution catalysts, and electrolyzer membranes, are summarized in detail. Finally, we outline recent advances in mainstream hydrogen storage approaches, providing new insights into enabling the large-scale application of offshore wind coupled with seawater electrolysis for hydrogen production.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1872-1903"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043346","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}
Renxing Huang , Zeping Zhang , Chengcheng Sang , Weitao Gao , Yiming Bai , Yinghe Huang , Yuxing Shi , Yonghuan Li , Lianguo Sun , Cheng Wang , Jun Gu , Tao Yu
Improving the intrinsic activity of surface iridium sites without sacrificing stability remains a critical challenge, as conventional strategies often enhance one property at the expense of the other. Here, we report a hydroxyl radical (˙OH)-driven synthesis strategy that spontaneously converts Ir(OH)63− into sub-2 nm rutile-phase IrO2 nanocrystals in aqueous solution at 90 °C via a thermodynamically favorable radical-oxidation pathway (ΔG° = −257.05 kJ mol−1). The nanoscale confinement induces lattice contraction and shortens Ir–O bonds, thereby elevating the intrinsic activity of surface Ir sites, while the stabilized rutile framework with robust [IrO6] octahedra effectively suppresses Ir dissolution. The obtained IrO2 catalyst exhibits a mass activity of 135 A g−1 and a turnover frequency (TOF) of 0.254 s−1 at an overpotential of 320 mV, outperforming commercial IrO2 by 92% and 66%, respectively. When integrated into a PEMWE anode with a low Ir loading of 0.3 mg cm−2, the single cell achieves an industrial-relevant current density of 3.0 A cm−2 at 1.89 V and operates stably for over 500 h. This work not only offers a practical solution to the activity-stability dilemma in PEMWE catalyst design, but also presents a novel, and low-temperature synthetic platform for metal oxides.
在不牺牲稳定性的情况下提高表面铱位点的固有活性仍然是一个关键的挑战，因为传统的策略通常是以牺牲另一种性质为代价来提高一种性质。在这里，我们报道了一种羟基自由基（˙OH）驱动的合成策略，该策略通过热力学有利的自由基氧化途径（ΔG°=−257.05 kJ mol−1），在90°C的水溶液中自发地将Ir(OH)63−转化为亚2 nm的金红石相IrO2纳米晶体。纳米级约束诱导晶格收缩并缩短Ir - o键，从而提高表面Ir位点的固有活性，而具有鲁棒[IrO6]八面体的稳定金红石框架有效抑制Ir溶解。在过电位为320 mV时，IrO2催化剂的质量活性为135 a g−1，周转频率（TOF）为0.254 s−1，分别比商用IrO2高92%和66%。当集成到低Ir负载为0.3 mg cm - 2的PEMWE阳极中时，单个电池在1.89 V下实现了工业相关的3.0 a cm - 2电流密度，并稳定运行超过500小时。该工作不仅为PEMWE催化剂设计中的活性-稳定性难题提供了实用的解决方案，而且为金属氧化物的低温合成提供了一个新的平台。
{"title":"Radical-driven nano-crystalline IrO2: resolving the activity-stability trade-off in acidic OER","authors":"Renxing Huang , Zeping Zhang , Chengcheng Sang , Weitao Gao , Yiming Bai , Yinghe Huang , Yuxing Shi , Yonghuan Li , Lianguo Sun , Cheng Wang , Jun Gu , Tao Yu","doi":"10.1039/d5gc04748j","DOIUrl":"10.1039/d5gc04748j","url":null,"abstract":"<div><div>Improving the intrinsic activity of surface iridium sites without sacrificing stability remains a critical challenge, as conventional strategies often enhance one property at the expense of the other. Here, we report a hydroxyl radical (˙OH)-driven synthesis strategy that spontaneously converts Ir(OH)<sub>6</sub><sup>3−</sup> into sub-2 nm rutile-phase IrO<sub>2</sub> nanocrystals in aqueous solution at 90 °C <em>via</em> a thermodynamically favorable radical-oxidation pathway (Δ<em>G</em>° = −257.05 kJ mol<sup>−1</sup>). The nanoscale confinement induces lattice contraction and shortens Ir–O bonds, thereby elevating the intrinsic activity of surface Ir sites, while the stabilized rutile framework with robust [IrO<sub>6</sub>] octahedra effectively suppresses Ir dissolution. The obtained IrO<sub>2</sub> catalyst exhibits a mass activity of 135 A g<sup>−1</sup> and a turnover frequency (TOF) of 0.254 s<sup>−1</sup> at an overpotential of 320 mV, outperforming commercial IrO<sub>2</sub> by 92% and 66%, respectively. When integrated into a PEMWE anode with a low Ir loading of 0.3 mg cm<sup>−2</sup>, the single cell achieves an industrial-relevant current density of 3.0 A cm<sup>−2</sup> at 1.89 V and operates stably for over 500 h. This work not only offers a practical solution to the activity-stability dilemma in PEMWE catalyst design, but also presents a novel, and low-temperature synthetic platform for metal oxides.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2077-2086"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043374","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}
Mujing Huang , Fanxun Lv , Yi Lv , Jiajun Yan , Chenlu Xie
The direct conversion of CH4 into transportable liquid chemicals under ambient conditions is a fundamental goal for sustainable chemistry. However, existing approaches to valuable derivatives like methanesulfonic acid (CH3SO3H) and methyl bisulfate (CH3SO4H) typically rely on corrosive acids and complex metal catalysts. Here, we report a catalyst-free, photochemical strategy for CH4 conversion in a purely aqueous phase under ambient conditions, yielding C–S products (CH3SO3H and CH3SO4H), alongside valuable C–C coupled products (CH3COOH and CH3COCH3). Using potassium peroxydisulfate as a simple precursor, photochemically generated sulfate radicals (SO4˙−) serve a dual role of mediating C–H bond activation via secondary ˙OH species from water oxidation, and acting as the sulfur source. A liquid product selectivity of 90% was achieved, and CH4 conversion of 3.5% was demonstrated in a photochemical flow reactor at ambient pressure. Mechanistic studies reveal that CH3SO4H is a key intermediate, whose subsequent reaction with a ˙CH3 radical not only forms the C–S product but also generates a methoxy radical to initiate C–C coupling. By harnessing sulfate radical reactivity in water, this work provides a simple and effective route for methane valorization under exceptionally mild conditions.
{"title":"Sulfate radical-mediated methane conversion to C–C and C–S products in water","authors":"Mujing Huang , Fanxun Lv , Yi Lv , Jiajun Yan , Chenlu Xie","doi":"10.1039/d5gc05500h","DOIUrl":"10.1039/d5gc05500h","url":null,"abstract":"<div><div>The direct conversion of CH<sub>4</sub> into transportable liquid chemicals under ambient conditions is a fundamental goal for sustainable chemistry. However, existing approaches to valuable derivatives like methanesulfonic acid (CH<sub>3</sub>SO<sub>3</sub>H) and methyl bisulfate (CH<sub>3</sub>SO<sub>4</sub>H) typically rely on corrosive acids and complex metal catalysts. Here, we report a catalyst-free, photochemical strategy for CH<sub>4</sub> conversion in a purely aqueous phase under ambient conditions, yielding C–S products (CH<sub>3</sub>SO<sub>3</sub>H and CH<sub>3</sub>SO<sub>4</sub>H), alongside valuable C–C coupled products (CH<sub>3</sub>COOH and CH<sub>3</sub>COCH<sub>3</sub>). Using potassium peroxydisulfate as a simple precursor, photochemically generated sulfate radicals (SO<sub>4</sub>˙<sup>−</sup>) serve a dual role of mediating C–H bond activation <em>via</em> secondary ˙OH species from water oxidation, and acting as the sulfur source. A liquid product selectivity of 90% was achieved, and CH<sub>4</sub> conversion of 3.5% was demonstrated in a photochemical flow reactor at ambient pressure. Mechanistic studies reveal that CH<sub>3</sub>SO<sub>4</sub>H is a key intermediate, whose subsequent reaction with a ˙CH<sub>3</sub> radical not only forms the C–S product but also generates a methoxy radical to initiate C–C coupling. By harnessing sulfate radical reactivity in water, this work provides a simple and effective route for methane valorization under exceptionally mild conditions.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2034-2040"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043369","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}
Kexin Wei , Siyuan Sun , Fan Yang , Yang Sun , Junpu An , Yongfeng Li
Carbon-based free-standing catalysts can be directly used in rechargeable zinc–air batteries while maintaining a high mass transfer level, making them highly promising as electrodes to catalyze oxygen reduction reaction/evolution reaction (ORR/OER). However, the existing complex preparation processes and limited conductive pathways remain challenges for their further application. Herein, a FeS/Fe3C nanoparticle-embedded and graphene nanosheet-doped carbon catalyst with a free-standing and amorphous porous carbon structure (FeS/Fe3C@CP) is easily synthesized by a simple solute precipitation strategy, in which the well-connected porous carbon and composite graphene nanosheets construct a conductive network extending in all directions. The result of electrochemical impedance spectroscopy (EIS) highlights the lower resistance of FeS/Fe3C@CP in the electron transfer process than that of the electrode synthesized by electrostatic spinning using the same raw material, which confirms that electrons are rapidly transported in this conductive network. The obtained FeS/Fe3C@CP possesses bifunctional catalytic activity and exhibits a half-wave potential (E1/2) of 0.89 V (vs. RHE) for the ORR and a potential of 1.40 V at a current density of 10 mA cm−2 (E10) for the OER. Further, in liquid ZAB applications, the FeS/Fe3C@CP exhibits a power density of 125 mW cm−2, which is better than that of a commercial Pt/C and RuO2 mixture. DFT analysis shows that the ORR adsorption/desorption process occurring on iron atoms in the FeS/Fe3C heterojunction has a smaller energy barrier than that on single FeS or Fe3C nanoparticles. This research lays a practical foundation for the design and synthesis of free-standing carbon catalysts with rich conductive networks.
碳基独立式催化剂可直接用于可充电锌-空气电池中，同时保持较高的传质水平，作为催化氧还原/演化反应（ORR/OER）的电极具有很大的应用前景。然而，现有复杂的制备工艺和有限的导电途径仍然是其进一步应用的挑战。本文采用简单的溶质沉淀法制备了具有独立非晶多孔碳结构的FeS/Fe3C纳米颗粒嵌入和掺杂石墨烯纳米片的碳催化剂（FeS/Fe3C@CP），其中多孔碳和复合石墨烯纳米片连接良好，形成了一个向四面延伸的导电网络。电化学阻抗谱（EIS）结果表明，FeS/Fe3C@CP在电子传递过程中的电阻低于使用相同原料的静电纺丝合成的电极，这证实了该导电网络中电子的快速传递。所得的FeS/Fe3C@CP具有双功能催化活性，ORR的半波电位（E1/2）为0.89 V（相对于RHE）， OER在电流密度为10 mA cm−2 （E10）时的电位为1.40 V。此外，在液体ZAB应用中，FeS/Fe3C@CP的功率密度为125 mW cm−2，优于商用Pt/C和RuO2混合物。DFT分析表明，在FeS/Fe3C异质结中，发生在铁原子上的ORR吸附/解吸过程比在单个FeS或Fe3C纳米颗粒上的吸附/解吸过程具有更小的能垒。本研究为设计和合成具有丰富导电网络的独立碳催化剂奠定了实践基础。
{"title":"Engineering FeS/Fe3C nanoparticle-embedded free-standing porous carbon with numerous conductive pathways to enhance electron transfer for oxygen electrocatalysis in rechargeable zinc–air batteries","authors":"Kexin Wei , Siyuan Sun , Fan Yang , Yang Sun , Junpu An , Yongfeng Li","doi":"10.1039/d5gc05165g","DOIUrl":"10.1039/d5gc05165g","url":null,"abstract":"<div><div>Carbon-based free-standing catalysts can be directly used in rechargeable zinc–air batteries while maintaining a high mass transfer level, making them highly promising as electrodes to catalyze oxygen reduction reaction/evolution reaction (ORR/OER). However, the existing complex preparation processes and limited conductive pathways remain challenges for their further application. Herein, a FeS/Fe<sub>3</sub>C nanoparticle-embedded and graphene nanosheet-doped carbon catalyst with a free-standing and amorphous porous carbon structure (FeS/Fe<sub>3</sub>C@CP) is easily synthesized by a simple solute precipitation strategy, in which the well-connected porous carbon and composite graphene nanosheets construct a conductive network extending in all directions. The result of electrochemical impedance spectroscopy (EIS) highlights the lower resistance of FeS/Fe<sub>3</sub>C@CP in the electron transfer process than that of the electrode synthesized by electrostatic spinning using the same raw material, which confirms that electrons are rapidly transported in this conductive network. The obtained FeS/Fe<sub>3</sub>C@CP possesses bifunctional catalytic activity and exhibits a half-wave potential (<em>E</em><sub>1/2</sub>) of 0.89 V (<em>vs.</em> RHE) for the ORR and a potential of 1.40 V at a current density of 10 mA cm<sup>−2</sup> (<em>E</em><sub>10</sub>) for the OER. Further, in liquid ZAB applications, the FeS/Fe<sub>3</sub>C@CP exhibits a power density of 125 mW cm<sup>−2</sup>, which is better than that of a commercial Pt/C and RuO<sub>2</sub> mixture. DFT analysis shows that the ORR adsorption/desorption process occurring on iron atoms in the FeS/Fe<sub>3</sub>C heterojunction has a smaller energy barrier than that on single FeS or Fe<sub>3</sub>C nanoparticles. This research lays a practical foundation for the design and synthesis of free-standing carbon catalysts with rich conductive networks.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2098-2108"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043376","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}
Indrajit Karmakar , Xiang-Wei Huang , Hsiu-Te Hung , Rekha Bai , Ci-Yang Sun , Chien-Wei Chiang , Chin-Fa Lee
We report an electrochemical sulfinylation protocol that drives a skeletal rearrangement of Baylis–Hillman adducts, enabling the late-stage synthesis of methyl (Z)-3-(aryl/heteroaryl)-2-[(aryl/alkyl)sulfinyl]methyl acrylates. The transformation merges sulfenylation with a framework rearrangement, proceeds in an undivided cell with inexpensive KI as electrolyte and redox mediator, and requires no metals or external oxidants. Under mild conditions, the method delivers good to excellent yields across diverse substrates and can be scaled efficiently. Control experiments, EPR spectroscopy, and 18O-labeling confirm a radical pathway with intramolecular oxygen transfer, while DFT studies delineate the stepwise mechanism. This work establishes a green and general strategy for accessing sulfoxide-containing scaffolds through electrochemically induced skeletal reorganization.
{"title":"Electrochemical sulfinylation-driven skeletal rearrangement of Baylis–Hillman adducts†","authors":"Indrajit Karmakar , Xiang-Wei Huang , Hsiu-Te Hung , Rekha Bai , Ci-Yang Sun , Chien-Wei Chiang , Chin-Fa Lee","doi":"10.1039/d5gc05810d","DOIUrl":"10.1039/d5gc05810d","url":null,"abstract":"<div><div>We report an electrochemical sulfinylation protocol that drives a skeletal rearrangement of Baylis–Hillman adducts, enabling the late-stage synthesis of methyl (<em>Z</em>)-3-(aryl/heteroaryl)-2-[(aryl/alkyl)sulfinyl]methyl acrylates. The transformation merges sulfenylation with a framework rearrangement, proceeds in an undivided cell with inexpensive KI as electrolyte and redox mediator, and requires no metals or external oxidants. Under mild conditions, the method delivers good to excellent yields across diverse substrates and can be scaled efficiently. Control experiments, EPR spectroscopy, and <sup>18</sup>O-labeling confirm a radical pathway with intramolecular oxygen transfer, while DFT studies delineate the stepwise mechanism. This work establishes a green and general strategy for accessing sulfoxide-containing scaffolds through electrochemically induced skeletal reorganization.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2109-2122"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043377","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}
Robert A. Dagle , Nickolas Riedel , Zhibin Yang , Johnny Saavedra Lopez , Alia Cooper , Michael Thorson , Louis Edwards Caceres-Martinez , Wan Tang Jeff Zhang , Hilkka I. Kenttämaa , Gozdem Kilaz , Joshua Heyne , Ralph Gillespie
This study introduces two novel alcohol-to-jet catalytic pathways, both yielding a cycloalkane-rich liquid product with the potential to enhance fuel performance beyond current synthetic jet blendstocks. The process begins with ethanol-derived butene, which is converted into gasoline-range aromatics. The resulting aromatic intermediate is then upgraded into the jet-range fraction through two distinct approaches: alkylation, which produces alkyl-substituted aromatics, and hydroalkylation, which generates dual-ring cyclic compounds. Both products undergo selective hydrogenation, demonstrating minimal product loss due to undesirable cracking or ring-opening reactions. After distillation into the jet-range fraction, the alkylated and hydroalkylated products meet ASTM D7566 specifications for ethanol-to-jet blendstock, and with energy density increases of 1.5% and 4.8%, respectively, compared to a petroleum jet fuel baseline. Furthermore, both routes offer the potential for reduced hydrogen requirements compared to more established acyclic alkane pathways. While further process optimizations are necessary to improve carbon efficiency and economic feasibility, these results highlight the potential for synthetic jet blendstocks to surpass conventional petroleum fuels in energy density. Additionally, these blendstocks demonstrate favorable O-ring swelling characteristics, complementing existing ASTM D7566 synthetic paraffinic (SPK) pathways. Moreover, their higher smoke point compared to conventional jet fuel suggests improved combustion quality and reduced particulate emissions.
{"title":"High energy content bi- and mono-cycloalkane and iso-alkane jet blending mixtures derived from ethanol","authors":"Robert A. Dagle , Nickolas Riedel , Zhibin Yang , Johnny Saavedra Lopez , Alia Cooper , Michael Thorson , Louis Edwards Caceres-Martinez , Wan Tang Jeff Zhang , Hilkka I. Kenttämaa , Gozdem Kilaz , Joshua Heyne , Ralph Gillespie","doi":"10.1039/d5gc03955j","DOIUrl":"10.1039/d5gc03955j","url":null,"abstract":"<div><div>This study introduces two novel alcohol-to-jet catalytic pathways, both yielding a cycloalkane-rich liquid product with the potential to enhance fuel performance beyond current synthetic jet blendstocks. The process begins with ethanol-derived butene, which is converted into gasoline-range aromatics. The resulting aromatic intermediate is then upgraded into the jet-range fraction through two distinct approaches: alkylation, which produces alkyl-substituted aromatics, and hydroalkylation, which generates dual-ring cyclic compounds. Both products undergo selective hydrogenation, demonstrating minimal product loss due to undesirable cracking or ring-opening reactions. After distillation into the jet-range fraction, the alkylated and hydroalkylated products meet ASTM D7566 specifications for ethanol-to-jet blendstock, and with energy density increases of 1.5% and 4.8%, respectively, compared to a petroleum jet fuel baseline. Furthermore, both routes offer the potential for reduced hydrogen requirements compared to more established acyclic alkane pathways. While further process optimizations are necessary to improve carbon efficiency and economic feasibility, these results highlight the potential for synthetic jet blendstocks to surpass conventional petroleum fuels in energy density. Additionally, these blendstocks demonstrate favorable O-ring swelling characteristics, complementing existing ASTM D7566 synthetic paraffinic (SPK) pathways. Moreover, their higher smoke point compared to conventional jet fuel suggests improved combustion quality and reduced particulate emissions.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1935-1950"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043349","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}
Advancing sustainability and catalysis in synthetic organic processes has emerged as a central theme, driven by pressing environmental challenges associated with the manufacture of fine chemicals, pharmaceuticals, agrochemicals, and functional materials. At the core of this shift is the growing use of alternative reaction media, particularly water, and the adoption of energy-efficient processes, owing to their inherent advantages and superior environmental performance. In this context, we report a water-assisted olefin isomerization-Michael addition cascade reaction of functionalized β,γ-unsaturated olefins with amines in aqueous SDS micelles (2% w/w). The reaction proceeds at room temperature without the need for additional catalysts, additives, or activators, and demonstrates a broad substrate scope with excellent yields and functional group tolerance. Process scalability, recyclability of the aqueous micelles, 100% atom economy, and a low E factor further underscore the sustainability and efficiency of this methodology. Mechanistic studies establish that water plays a central role in enabling the amine-assisted olefin isomerization (β,γ → α,β) followed by Michael addition, likely through stabilization of reactive intermediates via water-mediated hydrogen-bonding networking. The resulting nitrile-containing piperazine derivatives were evaluated for antifungal activity. Compounds and demonstrated promising antifungal activity, showing molecular synergy with fluconazole and inducing ROS-mediated fungal growth inhibition, an important mechanistic strategy for combating fungal infections. Furthermore, these compounds demonstrated efficacy against a rapidly growing, drug-resistant clinical strain of Candida auris, a pathogen ranked as a critical priority by the WHO. Overall, our findings reaffirm the growing importance of sustainable chemistry in shaping the future of drug discovery and development.
{"title":"Olefin isomerization-Michael addition cascade in aqueous micelles: a new piperazine-based antifungal chemotype","authors":"Divita Kumar , Anil Shaha , Samruddhi Chavhan , Jourawar Singh , Jenali Bhavsar , Sapan Borah , Dinesh Kumar","doi":"10.1039/d5gc06424d","DOIUrl":"10.1039/d5gc06424d","url":null,"abstract":"<div><div>Advancing sustainability and catalysis in synthetic organic processes has emerged as a central theme, driven by pressing environmental challenges associated with the manufacture of fine chemicals, pharmaceuticals, agrochemicals, and functional materials. At the core of this shift is the growing use of alternative reaction media, particularly water, and the adoption of energy-efficient processes, owing to their inherent advantages and superior environmental performance. In this context, we report a water-assisted olefin isomerization-Michael addition cascade reaction of functionalized β,γ-unsaturated olefins with amines in aqueous SDS micelles (2% w/w). The reaction proceeds at room temperature without the need for additional catalysts, additives, or activators, and demonstrates a broad substrate scope with excellent yields and functional group tolerance. Process scalability, recyclability of the aqueous micelles, 100% atom economy, and a low <em>E</em> factor further underscore the sustainability and efficiency of this methodology. Mechanistic studies establish that water plays a central role in enabling the amine-assisted olefin isomerization (β,γ → α,β) followed by Michael addition, likely through stabilization of reactive intermediates <em>via</em> water-mediated hydrogen-bonding networking. The resulting nitrile-containing piperazine derivatives were evaluated for antifungal activity. Compounds and demonstrated promising antifungal activity, showing molecular synergy with fluconazole and inducing ROS-mediated fungal growth inhibition, an important mechanistic strategy for combating fungal infections. Furthermore, these compounds demonstrated efficacy against a rapidly growing, drug-resistant clinical strain of <em>Candida auris</em>, a pathogen ranked as a critical priority by the WHO. Overall, our findings reaffirm the growing importance of sustainable chemistry in shaping the future of drug discovery and development.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1951-1959"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043350","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}
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