Pub Date : 2026-01-22Epub Date: 2026-01-28DOI: 10.1039/d5gc04925c
Mousumi Biswas , Shankab J. Phukan , Suraj Goswami , Jit Satra , Gaurav Gupta , Tarun Yadav , Ranjith Krishna Pai , Manas Roy , Somenath Garai
Amid the global energy crisis, green hydrogen emerges as a potent energy carrier, yet the hydrogen economy grapples with economic viability, low volumetric energy density, storage, and safety issues that hinder its direct utilization. In this context, ammonia serves as an efficacious hydrogen carrier owing to its excellent volumetric and gravimetric hydrogen density, ability to be stored at low pressures and ease of catalytic decomposition, enabling onsite H2 production without greenhouse gas emissions. The production of ammonia is primarily based on the Haber–Bosch process alongside electrochemical and thermochemical methods, while the decomposition of ammonia to hydrogen relies on thermal cracking, electro/photo-chemical, and plasma-assisted methods employing suitable catalysts, notably the extensively studied catalyst-assisted thermal cracking of NH3. The present review explores diverse synthetic routes for the synthesis of ammonia and its storage strategies, catalyst-driven decomposition, and challenges associated with the development of proficient catalysts. Furthermore, this review ruminates on strategies used by the scientific community to scale up cutting-edge reactor technology for green NH3 decomposition from early studies to the contemporary research outcomes, along with highlighting the bottlenecks to industrial entry and commercialization with respect to other hydrogen carriers, production and transport costs, and demand and supply constraints.
{"title":"Techno-economic insights into ammonia as a hydrogen vector: synthesis, cracking, storage, and supply chain solutions","authors":"Mousumi Biswas , Shankab J. Phukan , Suraj Goswami , Jit Satra , Gaurav Gupta , Tarun Yadav , Ranjith Krishna Pai , Manas Roy , Somenath Garai","doi":"10.1039/d5gc04925c","DOIUrl":"10.1039/d5gc04925c","url":null,"abstract":"<div><div>Amid the global energy crisis, green hydrogen emerges as a potent energy carrier, yet the hydrogen economy grapples with economic viability, low volumetric energy density, storage, and safety issues that hinder its direct utilization. In this context, ammonia serves as an efficacious hydrogen carrier owing to its excellent volumetric and gravimetric hydrogen density, ability to be stored at low pressures and ease of catalytic decomposition, enabling onsite H<sub>2</sub> production without greenhouse gas emissions. The production of ammonia is primarily based on the Haber–Bosch process alongside electrochemical and thermochemical methods, while the decomposition of ammonia to hydrogen relies on thermal cracking, electro/photo-chemical, and plasma-assisted methods employing suitable catalysts, notably the extensively studied catalyst-assisted thermal cracking of NH<sub>3</sub>. The present review explores diverse synthetic routes for the synthesis of ammonia and its storage strategies, catalyst-driven decomposition, and challenges associated with the development of proficient catalysts. Furthermore, this review ruminates on strategies used by the scientific community to scale up cutting-edge reactor technology for green NH<sub>3</sub> decomposition from early studies to the contemporary research outcomes, along with highlighting the bottlenecks to industrial entry and commercialization with respect to other hydrogen carriers, production and transport costs, and demand and supply constraints.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 3963-4005"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320715","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}
Pub Date : 2026-01-22Epub Date: 2026-02-10DOI: 10.1039/d5gc06782k
Lorenzo Rosa , Davide Tonelli
Ammonia production, central to global food and energy systems, is highly centralized and fossil-dependent, consuming ∼5% of global natural gas and creating supply chain risks due to long-distance transport. Decentralized, electrified Haber–Bosch systems offer a resilient alternative that can diversify supply and reduce emissions. This study develops an optimization model to assess the techno-economic feasibility of decentralized ammonia production across six representative locations (Brazil, India, China, the United States, Italy, and Ethiopia). We evaluate three configurations: autonomous (renewables only), grid-connected, and hybrid systems, under 2025 and 2045 cost scenarios. In 2025, decentralized systems remain uncompetitive, with levelized costs of ammonia often exceeding global market prices by more than 500 USD per tonnes in regions with low renewables potential. By 2045, declining renewables and electrolyzer costs narrow the premium: cost-effectiveness is achieved in the United States and Ethiopia, while China, Brazil, and India approach competitiveness with premiums of 175–435 USD per tonnes. Cost drivers vary by design: capital costs and financing conditions dominate autonomous systems, and electricity prices shape grid-connected plants. We show that coupling of intermittent renewables production, buffer capacities, operational flexibility of electrified Haber–Bosch reactors, and flexibility in ammonia demand are key to determining the cost of ammonia supply. High-pressure reactors and the thermal inertia of Haber–Bosch reactors can limit rapid ramping under variable renewable power, highlighting a core green chemistry challenge: current catalytic and reactor designs are poorly matched to fluctuating, low-carbon energy inputs, thus requiring high buffer capacities or a flexible demand. Sensitivity analyses indicate that higher conversion efficiency, lower specific energy use, and reduced dependence on hydrogen and battery storage or oversized renewable capacity are decisive for cost-competitiveness. These system-level results translate into quantitative design targets for green chemistry, indicating that catalysts, electrolyzers, and synthesis pathways that maintain high efficiency under dynamic and part-load operation are essential for sustainable nitrogen fixation. Overall, reductions in system-level cost and energy demand, and enhancements in operational flexibility and part-load operation are necessary to enable next-generation ammonia reactors that embody the principles of energy efficiency, waste minimization, and decentralized, safer chemical manufacturing to reach competitiveness for industrial-scale deployment.
{"title":"Optimal design of decentralized ammonia production via electric Haber–Bosch systems","authors":"Lorenzo Rosa , Davide Tonelli","doi":"10.1039/d5gc06782k","DOIUrl":"10.1039/d5gc06782k","url":null,"abstract":"<div><div>Ammonia production, central to global food and energy systems, is highly centralized and fossil-dependent, consuming ∼5% of global natural gas and creating supply chain risks due to long-distance transport. Decentralized, electrified Haber–Bosch systems offer a resilient alternative that can diversify supply and reduce emissions. This study develops an optimization model to assess the techno-economic feasibility of decentralized ammonia production across six representative locations (Brazil, India, China, the United States, Italy, and Ethiopia). We evaluate three configurations: autonomous (renewables only), grid-connected, and hybrid systems, under 2025 and 2045 cost scenarios. In 2025, decentralized systems remain uncompetitive, with levelized costs of ammonia often exceeding global market prices by more than 500 USD per tonnes in regions with low renewables potential. By 2045, declining renewables and electrolyzer costs narrow the premium: cost-effectiveness is achieved in the United States and Ethiopia, while China, Brazil, and India approach competitiveness with premiums of 175–435 USD per tonnes. Cost drivers vary by design: capital costs and financing conditions dominate autonomous systems, and electricity prices shape grid-connected plants. We show that coupling of intermittent renewables production, buffer capacities, operational flexibility of electrified Haber–Bosch reactors, and flexibility in ammonia demand are key to determining the cost of ammonia supply. High-pressure reactors and the thermal inertia of Haber–Bosch reactors can limit rapid ramping under variable renewable power, highlighting a core green chemistry challenge: current catalytic and reactor designs are poorly matched to fluctuating, low-carbon energy inputs, thus requiring high buffer capacities or a flexible demand. Sensitivity analyses indicate that higher conversion efficiency, lower specific energy use, and reduced dependence on hydrogen and battery storage or oversized renewable capacity are decisive for cost-competitiveness. These system-level results translate into quantitative design targets for green chemistry, indicating that catalysts, electrolyzers, and synthesis pathways that maintain high efficiency under dynamic and part-load operation are essential for sustainable nitrogen fixation. Overall, reductions in system-level cost and energy demand, and enhancements in operational flexibility and part-load operation are necessary to enable next-generation ammonia reactors that embody the principles of energy efficiency, waste minimization, and decentralized, safer chemical manufacturing to reach competitiveness for industrial-scale deployment.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4103-4118"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320721","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}
Pub Date : 2026-01-22Epub Date: 2026-02-12DOI: 10.1039/d5gc05839b
Kavan Chauhan , Anjali Patel
In this study, an innovative approach was developed for the synthesis of γ-valerolactone (GVL), a highly versatile keto-lactone and a promising eco-friendly fuel additive. For that, a sustainable catalyst, nickel-exchanged 12-tungstophosphoric acid supported on neutral Al2O3, was synthesized and extensively characterized using EDX, NH3-TPD, BET, TGA, FT-IR, UV-Vis-NIR, XPS, 31P NMR, powder XRD, and TEM analyses. The catalytic activity was studied for the hydrogenation of levulinic acid using formic acid as an internal hydrogen source, which showcased its excellent performance by achieving 76% conversion and a high turnover number of 7451. Compared to existing research, 100% selectivity was demonstrated for GVL, a highly desired product, with an exceptionally high substrate-to-catalyst ratio of 4902. This not only emphasizes the efficiency of the catalyst but also highlights its superior catalytic activity and robust performance under mild reaction conditions, making it a more effective and sustainable option in comparison to previously reported catalysts. To determine the reaction order, detailed kinetic studies were conducted at various temperatures and over different reaction times (in hours). Additionally, this study presents the in situ reduction of Ni(ii) to Ni(0), which was confirmed through X-ray photoelectron spectroscopy. The catalyst stability was established via a hot filtration test, and its reusability over multiple catalytic cycles confirmed its robust heterogeneous nature. This work highlights the catalyst potential in advancing sustainable and renewable energy solutions, making significant strides toward green and cost-effective processes.
{"title":"Synthesis of next-generation biofuel additive, γ-valerolactone, via hydrogenation of levulinic acid in the presence of formic acid over nickel-exchanged 12-tungstophosphoric acid supported on neutral Al2O3 and its kinetics study","authors":"Kavan Chauhan , Anjali Patel","doi":"10.1039/d5gc05839b","DOIUrl":"10.1039/d5gc05839b","url":null,"abstract":"<div><div>In this study, an innovative approach was developed for the synthesis of γ-valerolactone (GVL), a highly versatile keto-lactone and a promising eco-friendly fuel additive. For that, a sustainable catalyst, nickel-exchanged 12-tungstophosphoric acid supported on neutral Al<sub>2</sub>O<sub>3</sub>, was synthesized and extensively characterized using EDX, NH<sub>3</sub>-TPD, BET, TGA, FT-IR, UV-Vis-NIR, XPS, <sup>31</sup>P NMR, powder XRD, and TEM analyses. The catalytic activity was studied for the hydrogenation of levulinic acid using formic acid as an internal hydrogen source, which showcased its excellent performance by achieving 76% conversion and a high turnover number of 7451. Compared to existing research, 100% selectivity was demonstrated for GVL, a highly desired product, with an exceptionally high substrate-to-catalyst ratio of 4902. This not only emphasizes the efficiency of the catalyst but also highlights its superior catalytic activity and robust performance under mild reaction conditions, making it a more effective and sustainable option in comparison to previously reported catalysts. To determine the reaction order, detailed kinetic studies were conducted at various temperatures and over different reaction times (in hours). Additionally, this study presents the <em>in situ</em> reduction of Ni(<span>ii</span>) to Ni(0), which was confirmed through X-ray photoelectron spectroscopy. The catalyst stability was established <em>via</em> a hot filtration test, and its reusability over multiple catalytic cycles confirmed its robust heterogeneous nature. This work highlights the catalyst potential in advancing sustainable and renewable energy solutions, making significant strides toward green and cost-effective processes.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4213-4224"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320731","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}
Pub Date : 2026-01-22Epub Date: 2026-02-16DOI: 10.1039/d5gc06349c
Leonie Sophie Häser , Sven Moos , Felix Egger , Keanu Birkelbach , Mirijam Zobel , Thomas Wiegand , Regina Palkovits
Covalent Triazine-based Frameworks (CTFs) find use in a wide range of applications from gas storage to catalysis, including photocatalytic applications. While this versatility renders them a highly interesting material class, most of their synthetic protocols require either long polymerization times, high temperatures, toxic reagents, large amounts of organic solvents, or a combination of these, making current synthesis methods less attractive with regard to the green chemistry principles. We herein present a fast and facile ball milling synthesis route towards highly functionalized CTFs addressing the drawbacks of existing synthesis approaches. As a result, polymeric triazine-based structures were received within 40 min of milling time without the need for toxic chemicals or inert gas conditions. High CTF yields of more than 80% were achieved after 5 h utilizing vibrational ball milling. The sustainability of the synthesis was further improved by adjusting the salt addition to cost-effective and harmless salts. Using a photocatalytic model reaction, potential structural motives and their impact on the photocatalytic performance were elucidated.
{"title":"Accessing photocatalytically active covalent triazine-based frameworks by ball milling: a fast and facile synthesis method","authors":"Leonie Sophie Häser , Sven Moos , Felix Egger , Keanu Birkelbach , Mirijam Zobel , Thomas Wiegand , Regina Palkovits","doi":"10.1039/d5gc06349c","DOIUrl":"10.1039/d5gc06349c","url":null,"abstract":"<div><div>Covalent Triazine-based Frameworks (CTFs) find use in a wide range of applications from gas storage to catalysis, including photocatalytic applications. While this versatility renders them a highly interesting material class, most of their synthetic protocols require either long polymerization times, high temperatures, toxic reagents, large amounts of organic solvents, or a combination of these, making current synthesis methods less attractive with regard to the green chemistry principles. We herein present a fast and facile ball milling synthesis route towards highly functionalized CTFs addressing the drawbacks of existing synthesis approaches. As a result, polymeric triazine-based structures were received within 40 min of milling time without the need for toxic chemicals or inert gas conditions. High CTF yields of more than 80% were achieved after 5 h utilizing vibrational ball milling. The sustainability of the synthesis was further improved by adjusting the salt addition to cost-effective and harmless salts. Using a photocatalytic model reaction, potential structural motives and their impact on the photocatalytic performance were elucidated.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4292-4301"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320730","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}
Pub Date : 2026-01-22Epub Date: 2025-12-03DOI: 10.1039/d5gc03823e
Peng Chen , Ming Zou , Yu Zhang , Niuniu Li , Ruoqi Li , Lijuan Liang , Zhenguo Zhang , Teck-Peng Loh , Zhenhua Jia
Dithioacetals are essential building blocks in organic synthesis, materials development, and drug discovery. Despite their utility, existing synthetic methods often depend on organic solvents and transition metal catalysis under harsh conditions, limiting their sustainability and biological compatibility. In this work, we present an ultrafast, triaryl carbenium ion-pair-catalyzed thiol-acetalization protocol in water. Using a variety of aldehydes, ketones and isatins with thiols as coupling partners, the reaction proceeds under mild, metal-free conditions to deliver thioacetals in excellent yields (up to 99%) and with broad substrate scope. The method tolerates diverse functional groups and enables late-stage functionalization of natural products, amino acid derivatives, and small-molecule drugs. Moreover, the thiol-acetalization proceeded efficiently with catalyst loadings as low as 1.0 mol% and was scalable to a gram level. Furthermore, the biocompatibility, mild conditions, and rapid features make this approach well-suited for potential use in bioconjugation and biomolecule derivatization.
{"title":"Biocompatible ultrafast thiol-acetalization enabled by triaryl carbenium ion-pair","authors":"Peng Chen , Ming Zou , Yu Zhang , Niuniu Li , Ruoqi Li , Lijuan Liang , Zhenguo Zhang , Teck-Peng Loh , Zhenhua Jia","doi":"10.1039/d5gc03823e","DOIUrl":"10.1039/d5gc03823e","url":null,"abstract":"<div><div>Dithioacetals are essential building blocks in organic synthesis, materials development, and drug discovery. Despite their utility, existing synthetic methods often depend on organic solvents and transition metal catalysis under harsh conditions, limiting their sustainability and biological compatibility. In this work, we present an ultrafast, triaryl carbenium ion-pair-catalyzed thiol-acetalization protocol in water. Using a variety of aldehydes, ketones and isatins with thiols as coupling partners, the reaction proceeds under mild, metal-free conditions to deliver thioacetals in excellent yields (up to 99%) and with broad substrate scope. The method tolerates diverse functional groups and enables late-stage functionalization of natural products, amino acid derivatives, and small-molecule drugs. Moreover, the thiol-acetalization proceeded efficiently with catalyst loadings as low as 1.0 mol% and was scalable to a gram level. Furthermore, the biocompatibility, mild conditions, and rapid features make this approach well-suited for potential use in bioconjugation and biomolecule derivatization.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4029-4035"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320718","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}
With the finite nature of fossil resources, rising energy demands, and the environmental impact of conventional battery materials, the shift toward bio-based materials in energy storage systems has become crucial. Lignin, the second most abundant polymer in nature and a by-product of paper & pulping and ethanol production facilities, has attracted significant research interest due to its inherent benefits, including high carbon content, renewability, robust structure, and low cost. This critical review provides a comprehensive and comparative analysis of recent advances in the incorporation of lignin into lithium-ion battery components, including anodes, cathodes, binders, separators, and electrolytes. Beyond summarizing reported electrochemical performance, this review critically examines how lignin source, structural heterogeneity, molecular weight distribution, functional group chemistry, and fractionation strategies govern structure–property–performance relationships across different battery components. Lignin-derived hard carbons have demonstrated competitive anode capacities, reaching up to 602 mAh g−1 in silicon–lignin composites, while lignin-based cathode systems exploit quinone-type redox activity in hybrid architectures. In non-active components, lignin-based binders and separators offer clear advantages through aqueous processability, strong adhesion, enhanced thermal stability, and improved electrolyte affinity, whereas lignin-containing polymer and gel electrolytes exhibit ionic conductivities up to 10−3 S cm−1 at room temperature. Sustainability considerations, including life-cycle assessment, solvent replacement, recycling compatibility, and emerging commercialization efforts, are critically evaluated to contextualize lignin's realistic industrial potential. Despite these advances, challenges related to intrinsic conductivity, structural variability, interfacial stability, and long-term cycling still remain unsolved. This review identifies key research directions, such as controlled fractionation, targeted functionalization, and hybrid material design, required to bridge performance gaps and enable scalable, low-carbon lithium-ion battery technologies. To achieve commercialization, the lignin-derived batteries should have 1000 stable cycles, and over 250 Wh kg−1 energy density, and cost less than $100 k−1 Wh−1.
随着化石资源的有限性、不断增长的能源需求以及传统电池材料对环境的影响，在储能系统中向生物基材料的转变变得至关重要。木质素是自然界中含量第二丰富的聚合物，也是造纸和乙醇生产设备的副产品，由于其固有的优点，包括高碳含量、可再生、坚固的结构和低成本，引起了人们极大的研究兴趣。这篇重要的综述对木质素在锂离子电池组件（包括阳极、阴极、粘合剂、分离器和电解质）中的应用的最新进展进行了全面和比较分析。除了总结已报道的电化学性能外，本文还批判性地研究了木质素来源、结构异质性、分子量分布、官能团化学和分选策略如何影响不同电池组件的结构-性能-性能关系。木质素衍生的硬碳在硅-木质素复合材料中表现出具有竞争力的阳极容量，达到602 mAh g−1，而木质素基阴极系统在混合结构中利用醌型氧化还原活性。在非活性组分中，基于木质素的粘合剂和分离器具有明显的优势，可水溶液加工、强附着力、增强热稳定性和改善电解质亲和力，而含有木质素的聚合物和凝胶电解质在室温下的离子电导率高达10−3 S cm−1。可持续性考虑因素，包括生命周期评估、溶剂替代、回收兼容性和新兴的商业化努力，都经过严格评估，以确定木质素的现实工业潜力。尽管取得了这些进展，但与固有电导率、结构可变性、界面稳定性和长期循环相关的挑战仍未得到解决。本综述确定了关键的研究方向，如控制分馏法、目标功能化和混合材料设计，这些都是弥合性能差距和实现可扩展的低碳锂离子电池技术所必需的。为了实现商业化，木质素衍生电池应该具有1000个稳定循环，超过250 Wh kg - 1的能量密度，成本低于100美元k - 1 Wh - 1。
{"title":"Lignin-enabled Li-ion battery components: recent advances and outlook","authors":"Enoch Abeeku Aidoo , Pedram Fatehi","doi":"10.1039/d5gc05761b","DOIUrl":"10.1039/d5gc05761b","url":null,"abstract":"<div><div>With the finite nature of fossil resources, rising energy demands, and the environmental impact of conventional battery materials, the shift toward bio-based materials in energy storage systems has become crucial. Lignin, the second most abundant polymer in nature and a by-product of paper & pulping and ethanol production facilities, has attracted significant research interest due to its inherent benefits, including high carbon content, renewability, robust structure, and low cost. This critical review provides a comprehensive and comparative analysis of recent advances in the incorporation of lignin into lithium-ion battery components, including anodes, cathodes, binders, separators, and electrolytes. Beyond summarizing reported electrochemical performance, this review critically examines how lignin source, structural heterogeneity, molecular weight distribution, functional group chemistry, and fractionation strategies govern structure–property–performance relationships across different battery components. Lignin-derived hard carbons have demonstrated competitive anode capacities, reaching up to 602 mAh g<sup>−1</sup> in silicon–lignin composites, while lignin-based cathode systems exploit quinone-type redox activity in hybrid architectures. In non-active components, lignin-based binders and separators offer clear advantages through aqueous processability, strong adhesion, enhanced thermal stability, and improved electrolyte affinity, whereas lignin-containing polymer and gel electrolytes exhibit ionic conductivities up to 10<sup>−3</sup> S cm<sup>−1</sup> at room temperature. Sustainability considerations, including life-cycle assessment, solvent replacement, recycling compatibility, and emerging commercialization efforts, are critically evaluated to contextualize lignin's realistic industrial potential. Despite these advances, challenges related to intrinsic conductivity, structural variability, interfacial stability, and long-term cycling still remain unsolved. This review identifies key research directions, such as controlled fractionation, targeted functionalization, and hybrid material design, required to bridge performance gaps and enable scalable, low-carbon lithium-ion battery technologies. To achieve commercialization, the lignin-derived batteries should have 1000 stable cycles, and over 250 Wh kg<sup>−1</sup> energy density, and cost less than $100 k<sup>−1</sup> Wh<sup>−1</sup>.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 3911-3935"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320712","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}
Pub Date : 2026-01-22Epub Date: 2026-01-21DOI: 10.1039/d5gc06993a
Xinyue He , Weizhuo Xu , Guohao Xu , Wei Wang , Xin Bi , Bingjie Zhou , Jianfei Song , Wei Liu
Methanol is a promising hydrogen carrier for sustainable hydrogen production, but conventional electrocatalytic methanol oxidation for the hydrogen evolution reaction (HER) is limited by sluggish kinetics and susceptibility to catalyst poisoning. We developed a novel bifunctional Pt/Super-Electrically Activated Carbon (SEAC) catalyst coupled with a synergistic H3PMo12O40 (PMo12) and H4SiW12O40 (SiW12) system for hydrogen production from methanol. The integrated PMo12–SiW12 system can operate at a low voltage of 0.89 V to achieve 1 A cm−2, reducing energy consumption to 1.73 kW h Nm−3 H2, which is only 38.02% of that for conventional alkaline water electrolysis. This PMo12–SiW12 mediated approach can also be extended to other organic hydrogen carriers like ethanol, offering a low-cost, energy-efficient pathway for sustainable hydrogen production.
甲醇是一种很有前途的可持续制氢载体，但传统的电催化甲醇氧化析氢反应（HER）受动力学缓慢和催化剂中毒的限制。我们开发了一种新型的双功能Pt/超级电活性炭（SEAC）催化剂，与H3PMo12O40 （PMo12）和H4SiW12O40 （SiW12）协同系统偶联，用于甲醇制氢。集成的PMo12-SiW12系统可以在0.89 V的低电压下工作，达到1 a cm−2，将能耗降低到1.73 kW h Nm−3 H2，仅为传统碱水电解的38.02%。这种PMo12-SiW12介导的方法也可以扩展到其他有机氢载体，如乙醇，为可持续制氢提供了一种低成本、节能的途径。
{"title":"Rational design of a PMo12–SiW12 coupled catalytic system toward energy-efficient methanol-to-hydrogen conversion","authors":"Xinyue He , Weizhuo Xu , Guohao Xu , Wei Wang , Xin Bi , Bingjie Zhou , Jianfei Song , Wei Liu","doi":"10.1039/d5gc06993a","DOIUrl":"10.1039/d5gc06993a","url":null,"abstract":"<div><div>Methanol is a promising hydrogen carrier for sustainable hydrogen production, but conventional electrocatalytic methanol oxidation for the hydrogen evolution reaction (HER) is limited by sluggish kinetics and susceptibility to catalyst poisoning. We developed a novel bifunctional Pt/Super-Electrically Activated Carbon (SEAC) catalyst coupled with a synergistic H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub> (PMo<sub>12</sub>) and H<sub>4</sub>SiW<sub>12</sub>O<sub>40</sub> (SiW<sub>12</sub>) system for hydrogen production from methanol. The integrated PMo<sub>12</sub>–SiW<sub>12</sub> system can operate at a low voltage of 0.89 V to achieve 1 A cm<sup>−2</sup>, reducing energy consumption to 1.73 kW h Nm<sup>−3</sup> H<sub>2</sub>, which is only 38.02% of that for conventional alkaline water electrolysis. This PMo<sub>12</sub>–SiW<sub>12</sub> mediated approach can also be extended to other organic hydrogen carriers like ethanol, offering a low-cost, energy-efficient pathway for sustainable hydrogen production.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4036-4047"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320714","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}
Pub Date : 2026-01-22Epub Date: 2025-11-26DOI: 10.1039/d5gc04714e
Isabel Hortal-Sánchez , Faysal Ibrahim , Edgard A. Lebrón-Rodríguez , Fabiola Y. Rodríguez-Rodríguez , Grace Gooley , Ruining Ma , Matias Alvear , Ive Hermans , Nelson Cardona-Martínez
Difructose anhydride (DFA) is a highly valuable compound, traditionally obtained from inulin or sucrose through enzymatic routes. This work reports a novel eco-efficient process for DFA production from abundantly available fructose in a biomass-derived solvent over a commercial Brønsted acidic beta zeolite. A systematic evaluation of the reaction conditions led to the observation that gamma-valerolactone (GVL) is the most selective solvent giving a DFA yield of 75% under mild reaction conditions. The addition of water as a co-solvent (to improve fructose solubility) suppresses the catalytic activity. Reagent and solvent partitioning was investigated using ssNMR, utilizing the residual dipolar couplings of adsorbed species in the zeolite pores in contrast to the bulk environment. By utilizing a cross-polarization pulse sequence to observe these absorbed species and a direct polarization to observe all species in the sample, we obtained the ratio of the absorbed species to overall species in each sample at varying water content in the reaction mixture. Using this approach, we observed that at the ≥10 volume% water content mark, fructose is no longer able to enter the zeolite pores, coinciding with reaction conditions where DFA is no longer produced. The results of this study illustrate the importance of substrate and solvent partitioning on liquid phase reactions over microporous catalysts.
{"title":"The catalytic conversion of fructose to difructose anhydride","authors":"Isabel Hortal-Sánchez , Faysal Ibrahim , Edgard A. Lebrón-Rodríguez , Fabiola Y. Rodríguez-Rodríguez , Grace Gooley , Ruining Ma , Matias Alvear , Ive Hermans , Nelson Cardona-Martínez","doi":"10.1039/d5gc04714e","DOIUrl":"10.1039/d5gc04714e","url":null,"abstract":"<div><div>Difructose anhydride (DFA) is a highly valuable compound, traditionally obtained from inulin or sucrose through enzymatic routes. This work reports a novel eco-efficient process for DFA production from abundantly available fructose in a biomass-derived solvent over a commercial Brønsted acidic beta zeolite. A systematic evaluation of the reaction conditions led to the observation that gamma-valerolactone (GVL) is the most selective solvent giving a DFA yield of 75% under mild reaction conditions. The addition of water as a co-solvent (to improve fructose solubility) suppresses the catalytic activity. Reagent and solvent partitioning was investigated using ssNMR, utilizing the residual dipolar couplings of adsorbed species in the zeolite pores in contrast to the bulk environment. By utilizing a cross-polarization pulse sequence to observe these absorbed species and a direct polarization to observe all species in the sample, we obtained the ratio of the absorbed species to overall species in each sample at varying water content in the reaction mixture. Using this approach, we observed that at the ≥10 volume% water content mark, fructose is no longer able to enter the zeolite pores, coinciding with reaction conditions where DFA is no longer produced. The results of this study illustrate the importance of substrate and solvent partitioning on liquid phase reactions over microporous catalysts.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4019-4028"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320717","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}
Pub Date : 2026-01-22Epub Date: 2025-12-08DOI: 10.1039/d5gc05054e
Donato Calabrese , Guiyeoul Lim , Parsa Nayyara , Megan E. Wolf , Paul R. F. Cordero , Lindsay D. Eltis , Lars Lauterbach
Lignin is an abundant and renewable source of aromatic compounds, yet its utilization remains limited due to its recalcitrance and heterogeneity. Recent developments have enabled the catalytic fractionation of lignin into low molecular weight aromatics, which may be transformed into higher-value compounds. Here, we present a scalable biocatalytic platform for the selective O-demethylation of lignin-derived aromatic compounds, which integrates an O2-tolerant, NAD+-reducing soluble hydrogenase from Cupriavidus necator for cofactor regeneration and NADH-dependent cytochromes P450 and Rieske-type monooxygenases. The process was implemented in a closed-loop flow system featuring dialysis membrane-entrapped multi-enzyme modules. H2 and O2 were precisely supplied via gas addition modules powered by water electrolysis. This configuration achieved >99% substrate conversion, high atom efficiency, and effective real-time management of the inhibitory byproduct formaldehyde. The hydrogenase-based cofactor regeneration system exhibits robust tolerance to formaldehyde and is adaptable to a broad range of gas-dependent biocatalytic processes, thereby advancing green, resource-efficient chemical production from renewable biomass.
{"title":"H2-driven biocatalytic O-demethylation of lignin derived aromatics in a closed-loop flow system powered by water electrolysis","authors":"Donato Calabrese , Guiyeoul Lim , Parsa Nayyara , Megan E. Wolf , Paul R. F. Cordero , Lindsay D. Eltis , Lars Lauterbach","doi":"10.1039/d5gc05054e","DOIUrl":"10.1039/d5gc05054e","url":null,"abstract":"<div><div>Lignin is an abundant and renewable source of aromatic compounds, yet its utilization remains limited due to its recalcitrance and heterogeneity. Recent developments have enabled the catalytic fractionation of lignin into low molecular weight aromatics, which may be transformed into higher-value compounds. Here, we present a scalable biocatalytic platform for the selective <em>O</em>-demethylation of lignin-derived aromatic compounds, which integrates an O<sub>2</sub>-tolerant, NAD<sup>+</sup>-reducing soluble hydrogenase from <em>Cupriavidus necator</em> for cofactor regeneration and NADH-dependent cytochromes P450 and Rieske-type monooxygenases. The process was implemented in a closed-loop flow system featuring dialysis membrane-entrapped multi-enzyme modules. H<sub>2</sub> and O<sub>2</sub> were precisely supplied <em>via</em> gas addition modules powered by water electrolysis. This configuration achieved >99% substrate conversion, high atom efficiency, and effective real-time management of the inhibitory byproduct formaldehyde. The hydrogenase-based cofactor regeneration system exhibits robust tolerance to formaldehyde and is adaptable to a broad range of gas-dependent biocatalytic processes, thereby advancing green, resource-efficient chemical production from renewable biomass.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4006-4018"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320716","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}
Pub Date : 2026-01-22Epub Date: 2026-02-11DOI: 10.1039/d6gc00485g
Ivana Mendonça , Filipa Rodrigues , Marisa Faria , Juan L. Gómez Pinchetti , Artur Ferreira , Nereida Cordeiro
Bound extracellular polymeric substances (B-EPS) are extracellular polysaccharides tightly attached to cyanobacterial and microalgal cell surfaces, representing a high-value class of biopolymers with industrial potential. Selective extraction is technically challenging due to strong adhesion to the cell wall and potential co-extraction of soluble EPS. Conventional methods can be chemically aggressive and may involve high energy and/or solvent inputs, making solvent-free extraction routes desirable. In this work, four hydrothermal extraction techniques (reflux, autoclave, ultrasonic bath, and microwave) were evaluated for their ability to recover B-EPS from the marine cyanobacterium Chroococcus submarinus (BEA 1200B), followed by a harmonised ultrafiltration step. Each method was assessed for extraction efficiency and its impact on bulk descriptors (inorganic carry-over, ATR-FTIR, zeta potential, and thermal profiles) and morphology. Among the methods tested, autoclave extraction demonstrated the highest performance, yielding up to 2.5 times more B-EPS than the other methods and showing reduced inorganic carry-over after purification. Across all methods, the purified B-EPS fractions exhibited broadly comparable bulk profiles under the applied analytics. Response Surface Methodology (RSM) applied to the autoclave system identified temperature and extraction time as key variables; optimal conditions (biomass-to-solvent ratio 1 : 20 (w/v), 130 °C, 16 min) enabled >90% recovery. Coupling autoclave extraction with solvent-free ultrafiltration avoids solvent precipitation and the use of hazardous reagents, enabling desalting and removal of low-molecular-weight components. Using a photosynthetic marine strain supports seawater cultivation and biogenic CO2 uptake, aligning the workflow with carbon-mitigation goals.
{"title":"Towards scalable production of bound extracellular polymeric substances (B-EPS): autoclave hydrothermal extraction coupled with solvent-free ultrafiltration","authors":"Ivana Mendonça , Filipa Rodrigues , Marisa Faria , Juan L. Gómez Pinchetti , Artur Ferreira , Nereida Cordeiro","doi":"10.1039/d6gc00485g","DOIUrl":"10.1039/d6gc00485g","url":null,"abstract":"<div><div>Bound extracellular polymeric substances (B-EPS) are extracellular polysaccharides tightly attached to cyanobacterial and microalgal cell surfaces, representing a high-value class of biopolymers with industrial potential. Selective extraction is technically challenging due to strong adhesion to the cell wall and potential co-extraction of soluble EPS. Conventional methods can be chemically aggressive and may involve high energy and/or solvent inputs, making solvent-free extraction routes desirable. In this work, four hydrothermal extraction techniques (reflux, autoclave, ultrasonic bath, and microwave) were evaluated for their ability to recover B-EPS from the marine cyanobacterium <em>Chroococcus submarinus</em> (BEA 1200B), followed by a harmonised ultrafiltration step. Each method was assessed for extraction efficiency and its impact on bulk descriptors (inorganic carry-over, ATR-FTIR, zeta potential, and thermal profiles) and morphology. Among the methods tested, autoclave extraction demonstrated the highest performance, yielding up to 2.5 times more B-EPS than the other methods and showing reduced inorganic carry-over after purification. Across all methods, the purified B-EPS fractions exhibited broadly comparable bulk profiles under the applied analytics. Response Surface Methodology (RSM) applied to the autoclave system identified temperature and extraction time as key variables; optimal conditions (biomass-to-solvent ratio 1 : 20 (w/v), 130 °C, 16 min) enabled >90% recovery. Coupling autoclave extraction with solvent-free ultrafiltration avoids solvent precipitation and the use of hazardous reagents, enabling desalting and removal of low-molecular-weight components. Using a photosynthetic marine strain supports seawater cultivation and biogenic CO<sub>2</sub> uptake, aligning the workflow with carbon-mitigation goals.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 9","pages":"Pages 4152-4163"},"PeriodicalIF":9.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320725","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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