Marvin L. Richter, Eduardo Peris and Sergio Gonell
Reduction of carbonate salts by transfer hydrogenation, utilizing glycerol as a sacrificial hydrogen donor, to generate formate and lactate is an attractive reaction to produce value-added products from chemical waste. Iridium complexes have emerged as highly active catalysts for this transformation. Herein, we report the synthesis of a series of iridium(I) bis-carbonyl complexes, supported by neutral chelating bis-N-heterocyclic carbene (bis-NHC) ligands, which define 7-membered ring metallacycles. A rigid ortho-phenylene-bis(N-methylimidazol-2-ylidene (Ph-bis-mim) and a flexible ethylene-bis(N-methylimidazol-2-ylidene (C2H4-bis-mim) were utilized as chelating ligands. We performed a comparative study with the analogue complex bearing a bis-NHC with an imidazolium bridging group (1,3-dimethyl-imidazolium-4,5-bis(N-methylimidazol-2-ylidene), Im-bis-mim), and found that this positively charged ligand enables high selectivity towards the generation of formate, and high activity at low catalyst loadings. Our study reveals general design principles for iridium bis-N-heterocyclic carbene catalysts that can guide further designs for fast and selective carbonate transfer hydrogenation with glycerol at low catalyst concentrations.
{"title":"Impact of linking groups in chelating bis-carbene iridium catalysts for transfer hydrogenation of inorganic carbonates with glycerol","authors":"Marvin L. Richter, Eduardo Peris and Sergio Gonell","doi":"10.1039/D5GC05119C","DOIUrl":"https://doi.org/10.1039/D5GC05119C","url":null,"abstract":"<p >Reduction of carbonate salts by transfer hydrogenation, utilizing glycerol as a sacrificial hydrogen donor, to generate formate and lactate is an attractive reaction to produce value-added products from chemical waste. Iridium complexes have emerged as highly active catalysts for this transformation. Herein, we report the synthesis of a series of iridium(<small>I</small>) bis-carbonyl complexes, supported by neutral chelating bis-N-heterocyclic carbene (bis-NHC) ligands, which define 7-membered ring metallacycles. A rigid <em>ortho</em>-phenylene-bis(<em>N</em>-methylimidazol-2-ylidene (Ph-bis-mim) and a flexible ethylene-bis(<em>N</em>-methylimidazol-2-ylidene (C<small><sub>2</sub></small>H<small><sub>4</sub></small>-bis-mim) were utilized as chelating ligands. We performed a comparative study with the analogue complex bearing a bis-NHC with an imidazolium bridging group (1,3-dimethyl-imidazolium-4,5-bis(<em>N</em>-methylimidazol-2-ylidene), Im-bis-mim), and found that this positively charged ligand enables high selectivity towards the generation of formate, and high activity at low catalyst loadings. Our study reveals general design principles for iridium bis-N-heterocyclic carbene catalysts that can guide further designs for fast and selective carbonate transfer hydrogenation with glycerol at low catalyst concentrations.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 5","pages":" 2385-2394"},"PeriodicalIF":9.2,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098955","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}
Microalgae are a viable source for sustainable biofuel generation due to their quick growth and high energy content; nevertheless, commercialization is hindered by substantial production costs and energy requirements. This review offers a comprehensive assessment of microalgal biorefinery methods, encompassing biodiesel, biohydrogen, and biogas production, while evaluating their energy efficiencies, environmental impacts, and scalability. It discusses current developments in microalgal strain engineering (e.g., CRISPR-modified strains for enhanced lipid yields), process optimization (novel photobioreactor designs), and integration with waste treatment to highlight pathways for enhancing feasibility. Techno-economic and life cycle assessments demonstrate that microalgal biofuels can substantially decrease life-cycle CO2 emissions compared to fossil fuels; however, their economic viability is largely contingent upon co-product valorization and process optimization. Key challenges including biomass harvesting, genetic strain stability, and regulatory obstacles have been examined, while advanced PBRs (photobioreactors) and heterotrophic systems have been identified as better suited for co-product markets. Future deployment will hinge on integrating carbon capture strategies, synthetic biology breakthroughs, and process intensification to balance productivity with economic sustainability, and a strategic roadmap for future research is proposed to facilitate the commercialization of microalgae-based biofuels within a circular green economy.
{"title":"Microalgal biorefinery: innovations in sustainable biofuel production","authors":"Aparna Sharma , Syed Ejaz Hussain Mehdi , Suleman Shahzad , Fida Hussain , Sandesh Pandey , Woochang Kang , Sang-Eun Oh","doi":"10.1039/d5gc02940f","DOIUrl":"10.1039/d5gc02940f","url":null,"abstract":"<div><div>Microalgae are a viable source for sustainable biofuel generation due to their quick growth and high energy content; nevertheless, commercialization is hindered by substantial production costs and energy requirements. This review offers a comprehensive assessment of microalgal biorefinery methods, encompassing biodiesel, biohydrogen, and biogas production, while evaluating their energy efficiencies, environmental impacts, and scalability. It discusses current developments in microalgal strain engineering (<em>e.g.</em>, CRISPR-modified strains for enhanced lipid yields), process optimization (novel photobioreactor designs), and integration with waste treatment to highlight pathways for enhancing feasibility. Techno-economic and life cycle assessments demonstrate that microalgal biofuels can substantially decrease life-cycle CO<sub>2</sub> emissions compared to fossil fuels; however, their economic viability is largely contingent upon co-product valorization and process optimization. Key challenges including biomass harvesting, genetic strain stability, and regulatory obstacles have been examined, while advanced PBRs (photobioreactors) and heterotrophic systems have been identified as better suited for co-product markets. Future deployment will hinge on integrating carbon capture strategies, synthetic biology breakthroughs, and process intensification to balance productivity with economic sustainability, and a strategic roadmap for future research is proposed to facilitate the commercialization of microalgae-based biofuels within a circular green economy.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1852-1871"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043345","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}
Yonggui Liu , Kang Yan , Shiyu Peng , Zhilou Liu , Yuhu Li , Ruixiang Wang , Zhifeng Xu , Zhilin Liu , Zhongtang Zhang
Copper and selenium in copper anode slime are important strategic metals that exhibit favorable economic benefits for recovery and utilization. In this study, impurity-removed copper anode slime was taken as the research object, and a two-stage roasting process was proposed, which involved low-temperature sulfation roasting-water leaching for copper separation in the first stage and roasting for selenium evaporation in the second stage. This process enables the efficient and environmentally friendly separation of Cu and Se from impurity-removed copper anode slime. In the first-stage roasting, ammonium sulfate was utilized as an additive to convert Cu–Se and Cu–Te metal compounds into soluble sulfates, and the selective separation of Cu was achieved through water leaching. Under the conditions of a roasting temperature of 275 °C, 1.2-fold excess of (NH4)2SO4, oxygen-enriched concentration of 50%, and duration of 90 min, the leaching rate of Cu reached 94.07%. For the second-stage roasting of Cu-removed anode slime for selenium volatilization, the volatilization rate of Se reached 93.33% under the experimental conditions of a roasting temperature of 550 °C, oxygen-enriched concentration of 20%, duration of 90 min, and gas flow rate of 100 mL min−1. The two-stage roasting process realizes selective and efficient separation of Cu and Se, while the scattered metal Te is effectively enriched in the residue phase. Additionally, the use of strong acids is avoided throughout the process. The results can provide theoretical basis and technical support for the construction and optimization of a comprehensive recovery and utilization system of copper anode slime.
铜阳极泥中的铜和硒是回收利用具有良好经济效益的重要战略金属。本研究以除杂铜阳极泥为研究对象，提出了一种两阶段焙烧工艺，即低温硫化焙烧-第一阶段水浸铜分离，第二阶段焙烧硒蒸发。该工艺实现了铜阳极泥中铜和硒的高效、环保分离。在第一阶段焙烧中，以硫酸铵作为添加剂将Cu - se和Cu - te金属化合物转化为可溶性硫酸盐，并通过水浸实现Cu的选择性分离。在焙烧温度为275℃、（NH4）2SO4过量1.2倍、富氧浓度为50%、焙烧时间为90 min的条件下，Cu的浸出率可达94.07%。在焙烧温度550℃、富氧浓度20%、焙烧时间90 min、瓦斯流量100 mL min−1的试验条件下，除铜阳极泥的挥发硒第二阶段焙烧，硒的挥发率达到93.33%。两段焙烧工艺实现了铜、硒的选择性高效分离，而分散的金属Te在渣相得到有效富集。此外，在整个过程中避免使用强酸。研究结果可为铜阳极泥综合回收利用系统的建设和优化提供理论依据和技术支持。
{"title":"Resource utilization of impurity-removed copper anode slime based on two-stage roasting: process optimization for selective separation and high-value recovery of copper and selenium","authors":"Yonggui Liu , Kang Yan , Shiyu Peng , Zhilou Liu , Yuhu Li , Ruixiang Wang , Zhifeng Xu , Zhilin Liu , Zhongtang Zhang","doi":"10.1039/d5gc05843k","DOIUrl":"10.1039/d5gc05843k","url":null,"abstract":"<div><div>Copper and selenium in copper anode slime are important strategic metals that exhibit favorable economic benefits for recovery and utilization. In this study, impurity-removed copper anode slime was taken as the research object, and a two-stage roasting process was proposed, which involved low-temperature sulfation roasting-water leaching for copper separation in the first stage and roasting for selenium evaporation in the second stage. This process enables the efficient and environmentally friendly separation of Cu and Se from impurity-removed copper anode slime. In the first-stage roasting, ammonium sulfate was utilized as an additive to convert Cu–Se and Cu–Te metal compounds into soluble sulfates, and the selective separation of Cu was achieved through water leaching. Under the conditions of a roasting temperature of 275 °C, 1.2-fold excess of (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>, oxygen-enriched concentration of 50%, and duration of 90 min, the leaching rate of Cu reached 94.07%. For the second-stage roasting of Cu-removed anode slime for selenium volatilization, the volatilization rate of Se reached 93.33% under the experimental conditions of a roasting temperature of 550 °C, oxygen-enriched concentration of 20%, duration of 90 min, and gas flow rate of 100 mL min<sup>−1</sup>. The two-stage roasting process realizes selective and efficient separation of Cu and Se, while the scattered metal Te is effectively enriched in the residue phase. Additionally, the use of strong acids is avoided throughout the process. The results can provide theoretical basis and technical support for the construction and optimization of a comprehensive recovery and utilization system of copper anode slime.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1986-2007"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043366","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}
Areti Moutsiou , Theodore A. Gazis , Luis A. Cipriano , Mert Can Ince , Ik Seon Kwon , Nicolò Allasia , Sadaf Fatima Jafri , Elisa Borfecchia , Lorenzo Mino , Martin Sterrer , Giovanni Di Liberto , Gianvito Vilé
The sustainable synthesis of biaryl skeletons via Ullmann-type C–C coupling remains a challenge in organic synthesis. Herein, we report a series of Pd single-atom catalysts supported on mesoporous graphitic carbon nitride (CNx) that promote the visible-light-driven homocoupling of aryl halides under ambient reaction conditions and with high efficiency and recyclability. Spectroscopic and microscopic analyses confirmed the atomic dispersion of Pd within CNx and elucidated its local coordination environment, while demonstrating that the structural framework of the support remained intact upon metal incorporation. Mechanistic studies combining operando X-ray absorption spectroscopy and density functional theory revealed a reversible, light-induced change in Pd coordination, that is linked to the catalytic turnover. Finally, techno-economic analysis and life cycle assessment validated the sustainability of the protocol, highlighting its reduced environmental footprint compared to conventional approaches. Collectively, these findings demonstrate that photoactive single-atom catalysts are a promising platform for efficient, stable, and sustainable biaryl synthesis, paving the way for more sustainable and efficient C–C coupling methodologies.
{"title":"Light-driven and green Ullmann homocoupling with a Pd single-atom catalyst","authors":"Areti Moutsiou , Theodore A. Gazis , Luis A. Cipriano , Mert Can Ince , Ik Seon Kwon , Nicolò Allasia , Sadaf Fatima Jafri , Elisa Borfecchia , Lorenzo Mino , Martin Sterrer , Giovanni Di Liberto , Gianvito Vilé","doi":"10.1039/d5gc04693a","DOIUrl":"10.1039/d5gc04693a","url":null,"abstract":"<div><div>The sustainable synthesis of biaryl skeletons <em>via</em> Ullmann-type C–C coupling remains a challenge in organic synthesis. Herein, we report a series of Pd single-atom catalysts supported on mesoporous graphitic carbon nitride (CN<sub><em>x</em></sub>) that promote the visible-light-driven homocoupling of aryl halides under ambient reaction conditions and with high efficiency and recyclability. Spectroscopic and microscopic analyses confirmed the atomic dispersion of Pd within CN<sub><em>x</em></sub> and elucidated its local coordination environment, while demonstrating that the structural framework of the support remained intact upon metal incorporation. Mechanistic studies combining <em>operando</em> X-ray absorption spectroscopy and density functional theory revealed a reversible, light-induced change in Pd coordination, that is linked to the catalytic turnover. Finally, techno-economic analysis and life cycle assessment validated the sustainability of the protocol, highlighting its reduced environmental footprint compared to conventional approaches. Collectively, these findings demonstrate that photoactive single-atom catalysts are a promising platform for efficient, stable, and sustainable biaryl synthesis, paving the way for more sustainable and efficient C–C coupling methodologies.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2008-2021"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043367","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}
Jiachen Fei , Kaizhi Wang , Ting Yang , Mugeng Chen , Zehui Sun , Chengguang Liu , Xinyue Liang , Chen Chen , Yongmei Liu , Guowei Wang , Heyong He , Yong Cao
Inspired by the platform-molecule concept central to modern biorefineries, we propose a polymer-editing approach based on backbone and side-chain modifications that activate inherent functional motifs in commodity plastics, enabling programmable cascade transformations to convert polymeric scaffolds into tailored small molecules, functional oligomers, and advanced materials. Using hydrogenated poly(ethylene terephthalate) (PECHD) as a paradigmatic “backbone-preedited” synthon, we efficiently transform waste PET into trans-enriched 1,4-cyclohexanedicarboxylic acid (CHDA), its mono- and diesters, and cycloaliphatic oligodiols that act as tunable precursors for degradable polyurethane elastomers. Mechanistic and kinetic studies indicate that the semi-rigid alicyclic backbone and ester linkages of PECHD promote specific reaction pathways, resulting in lower energy barriers for selective ester cleavage and facilitating efficient diverse hydrogenation–depolymerization cascades. Additionally, through side-chain editing, polystyrene (PS) is converted—via its hydrogenated intermediates—into cyclohexanone and polyethylene-like polyketones through tandem hydrogenation–oxidation. Collectively, this work establishes a flexible molecular editing strategy that enables stereoselective and catalytically programmable refunctionalization of polymer architectures, providing versatile, scalable, and sustainable design principles for a circular plastic economy.
{"title":"Hydrogenated polyethylene terephthalate as a versatile macromolecular platform synthon for waste plastic refineries","authors":"Jiachen Fei , Kaizhi Wang , Ting Yang , Mugeng Chen , Zehui Sun , Chengguang Liu , Xinyue Liang , Chen Chen , Yongmei Liu , Guowei Wang , Heyong He , Yong Cao","doi":"10.1039/d5gc05759k","DOIUrl":"10.1039/d5gc05759k","url":null,"abstract":"<div><div>Inspired by the platform-molecule concept central to modern biorefineries, we propose a polymer-editing approach based on backbone and side-chain modifications that activate inherent functional motifs in commodity plastics, enabling programmable cascade transformations to convert polymeric scaffolds into tailored small molecules, functional oligomers, and advanced materials. Using hydrogenated poly(ethylene terephthalate) (PECHD) as a paradigmatic “backbone-preedited” synthon, we efficiently transform waste PET into <em>trans</em>-enriched 1,4-cyclohexanedicarboxylic acid (CHDA), its mono- and diesters, and cycloaliphatic oligodiols that act as tunable precursors for degradable polyurethane elastomers. Mechanistic and kinetic studies indicate that the semi-rigid alicyclic backbone and ester linkages of PECHD promote specific reaction pathways, resulting in lower energy barriers for selective ester cleavage and facilitating efficient diverse hydrogenation–depolymerization cascades. Additionally, through side-chain editing, polystyrene (PS) is converted—<em>via</em> its hydrogenated intermediates—into cyclohexanone and polyethylene-like polyketones through tandem hydrogenation–oxidation. Collectively, this work establishes a flexible molecular editing strategy that enables stereoselective and catalytically programmable refunctionalization of polymer architectures, providing versatile, scalable, and sustainable design principles for a circular plastic economy.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2022-2033"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043368","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}
Zixin Zhao , Fujun Shang , Xi Liang , Zhi Liang , Qi Zhang , Xiaoyi Sun , Juan Li
The high utilization rate, processability and tunability of zinc powder make it a promising candidate for anodes in rechargeable zinc-ion batteries. However, a rough surface with a high surface area exacerbates corrosion and dendrite growth. Here, β-cyclodextrin (β-CD) was introduced into zinc powder slurry as a multi-functional modifier to optimize the interface and improve the cycling performance of the zinc powder anode through its unique cavity structure. First, β-CD greatly enhances interfacial compatibility with a contact angle of 23.0° through the hydrophilic hydroxyl groups, leading to an extremely low voltage hysteresis of 12 mV. Second, the anion CF3SO3− is revealed to be trapped inside the cavity of β-CD, impairing barriers for Zn2+ migration and significantly elevating the Zn2+ transference number to 0.72. The symmetrical Zn||Zn cell assembled with a β-CD modified zinc anode can achieve stable cycling for 210 h at a high depth of discharge (DOD) of 80%. At a low N/P value of 1.0, the full battery coupled with a ZnVO cathode exhibits a long cycle life of over 280 cycles. It provides a new strategy for the design of a highly stable zinc powder anode.
{"title":"Enhancing interface kinetics in zinc powder anodes via β-cyclodextrin modification toward zinc ion batteries with low N/P ratios","authors":"Zixin Zhao , Fujun Shang , Xi Liang , Zhi Liang , Qi Zhang , Xiaoyi Sun , Juan Li","doi":"10.1039/d5gc06263b","DOIUrl":"10.1039/d5gc06263b","url":null,"abstract":"<div><div>The high utilization rate, processability and tunability of zinc powder make it a promising candidate for anodes in rechargeable zinc-ion batteries. However, a rough surface with a high surface area exacerbates corrosion and dendrite growth. Here, β-cyclodextrin (β-CD) was introduced into zinc powder slurry as a multi-functional modifier to optimize the interface and improve the cycling performance of the zinc powder anode through its unique cavity structure. First, β-CD greatly enhances interfacial compatibility with a contact angle of 23.0° through the hydrophilic hydroxyl groups, leading to an extremely low voltage hysteresis of 12 mV. Second, the anion CF<sub>3</sub>SO<sub>3</sub><sup>−</sup> is revealed to be trapped inside the cavity of β-CD, impairing barriers for Zn<sup>2+</sup> migration and significantly elevating the Zn<sup>2+</sup> transference number to 0.72. The symmetrical Zn||Zn cell assembled with a β-CD modified zinc anode can achieve stable cycling for 210 h at a high depth of discharge (DOD) of 80%. At a low N/P value of 1.0, the full battery coupled with a ZnVO cathode exhibits a long cycle life of over 280 cycles. It provides a new strategy for the design of a highly stable zinc powder anode.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2056-2065"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043372","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}
Peroxydisulfate (PDS)-based advanced oxidation processes are promising for reclaimed water treatment; however, they are often hindered by high energy demands, costly and complex catalyst synthesis, and the requirement for external energy inputs. Commercially available materials, commercial catalytic iron powder (CCI) and MoS2 were selected to activate PDS (CCI/MoS2/PDS system) for the degradation of high-concentration dye wastewater (Acid Orange 7, AO7) within 5 minutes. CCI generates Fe2+ and Fe3+, while MoS2 facilitates the rate-limiting Fe3+/Fe2+ cycle. The reaction rate of the CCI/MoS2/PDS system is approximately 2 times higher than that without a co-catalyst. Therefore, the system can efficiently generate a variety of reactive species (e.g., radicals) for the degradation of organic wastewater. The primary active species responsible for the degradation of AO7 in the CCI/MoS2/PDS system was the sulfate radical (SO4˙−). Following both a small-scale continuous-flow experiment and a pilot-scale continuous-flow reactor equipped with a catalyst-filled column, the system maintained high efficiency and catalytic activity, enabling long-term, stable, and effective removal of AO7. Remarkably, the CCI/MoS2/PDS system has an operating cost of only US$ 0.16 per ton of wastewater, highlighting its great potential for large-scale industrial applications. This work provides valuable guidance for the development of green, low-cost and efficient PDS-activation systems for industrial wastewater treatment.
{"title":"MoS2-assisted iron-driven peroxydisulfate activation for green and sustainable water purification","authors":"Zi-Hang He , Wei-Lin Wang , Bin Li , Chang Liu","doi":"10.1039/d5gc04923g","DOIUrl":"10.1039/d5gc04923g","url":null,"abstract":"<div><div>Peroxydisulfate (PDS)-based advanced oxidation processes are promising for reclaimed water treatment; however, they are often hindered by high energy demands, costly and complex catalyst synthesis, and the requirement for external energy inputs. Commercially available materials, commercial catalytic iron powder (CCI) and MoS<sub>2</sub> were selected to activate PDS (CCI/MoS<sub>2</sub>/PDS system) for the degradation of high-concentration dye wastewater (Acid Orange 7, AO7) within 5 minutes. CCI generates Fe<sup>2+</sup> and Fe<sup>3+</sup>, while MoS<sub>2</sub> facilitates the rate-limiting Fe<sup>3+</sup>/Fe<sup>2+</sup> cycle. The reaction rate of the CCI/MoS<sub>2</sub>/PDS system is approximately 2 times higher than that without a co-catalyst. Therefore, the system can efficiently generate a variety of reactive species (<em>e.g.</em>, radicals) for the degradation of organic wastewater. The primary active species responsible for the degradation of AO7 in the CCI/MoS<sub>2</sub>/PDS system was the sulfate radical (SO<sub>4</sub>˙<sup>−</sup>). Following both a small-scale continuous-flow experiment and a pilot-scale continuous-flow reactor equipped with a catalyst-filled column, the system maintained high efficiency and catalytic activity, enabling long-term, stable, and effective removal of AO7. Remarkably, the CCI/MoS<sub>2</sub>/PDS system has an operating cost of only US$ 0.16 per ton of wastewater, highlighting its great potential for large-scale industrial applications. This work provides valuable guidance for the development of green, low-cost and efficient PDS-activation systems for industrial wastewater treatment.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1912-1923"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043347","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}
Lingxuan Sun , Jin Zhang , Haotian Zhai , Huangwei Xu , Mengmeng Liu , Qingsheng Qi , Jin Hou
Zeaxanthin, a high-value lipophilic xanthophyll carotenoid, has been extensively used in nutraceuticals, cosmetics and animal feed. Although its industrial demand is rising rapidly, the titer of microbial zeaxanthin production remains relatively low. Here, we systematically engineered the oleaginous yeast Yarrowia lipolytica to achieve the highest zeaxanthin production ever reported. To convert β-carotene into zeaxanthin, different β-carotene hydroxylases (CrtZ) were screened and the metabolic flux of β-carotene was strengthened in a β-carotene-producing strain. We then developed a protein-degron-mediated multi-copy integration strategy to elevate the expression of CrtZ and engineered the ferredoxin/ferredoxin oxidoreductase and redox cofactor regeneration to improve the catalytic efficiency of β-carotene hydroxylase. Liquid–liquid phase separation was then implemented to spatially co-localize the enzymes for mevalonate synthesis, accelerating mevalonate supply and boosting zeaxanthin production in Y. lipolytica. Combined with cultivation optimization, the engineered strain produced 6.9 g L−1 zeaxanthin in fed-batch cultivation, the highest reported titer to date. This study establishes an integrated metabolic engineering strategy that couples metabolic, redox and spatial engineering for high-level zeaxanthin production. The multi-copy integration and phase separated multienzyme condensate approaches developed here can also be used as versatile toolkits for metabolic engineering in Y. lipolytica.
玉米黄质是一种高价值的亲脂性叶黄素类胡萝卜素，在保健品、化妆品和动物饲料中有着广泛的应用。虽然其工业需求正在迅速上升，但微生物玉米黄质生产的滴度仍然相对较低。在这里，我们系统地改造了产油酵母解脂耶氏酵母，以达到有史以来最高的玉米黄质产量。为了将β-胡萝卜素转化为玉米黄质，筛选了不同的β-胡萝卜素羟化酶（CrtZ），并在β-胡萝卜素产生菌株中加强了β-胡萝卜素的代谢通量。然后，我们开发了一种蛋白质降解介导的多拷贝整合策略来提高CrtZ的表达，并设计了铁氧化还蛋白/铁氧化还蛋白氧化还原酶和氧化还原辅助因子再生来提高β-胡萝卜素羟化酶的催化效率。然后进行液-液相分离，使甲基戊酸合成酶在空间上共定位，加速了甲基戊酸的供应，促进了聚脂y菌玉米黄质的产生。结合培养优化，该工程菌株在投喂分批培养中产生6.9 g L−1的玉米黄质，是迄今为止报道的最高滴度。本研究建立了代谢、氧化还原和空间工程相结合的高产玉米黄质综合代谢工程策略。本文所建立的多拷贝整合和相分离多酶凝析方法也可作为多用途的工具，用于脂肪瘤菌的代谢工程。
{"title":"Metabolic, redox, and spatial engineering of Yarrowia lipolytica for high-level zeaxanthin production","authors":"Lingxuan Sun , Jin Zhang , Haotian Zhai , Huangwei Xu , Mengmeng Liu , Qingsheng Qi , Jin Hou","doi":"10.1039/d5gc06011g","DOIUrl":"10.1039/d5gc06011g","url":null,"abstract":"<div><div>Zeaxanthin, a high-value lipophilic xanthophyll carotenoid, has been extensively used in nutraceuticals, cosmetics and animal feed. Although its industrial demand is rising rapidly, the titer of microbial zeaxanthin production remains relatively low. Here, we systematically engineered the oleaginous yeast <em>Yarrowia lipolytica</em> to achieve the highest zeaxanthin production ever reported. To convert β-carotene into zeaxanthin, different β-carotene hydroxylases (CrtZ) were screened and the metabolic flux of β-carotene was strengthened in a β-carotene-producing strain. We then developed a protein-degron-mediated multi-copy integration strategy to elevate the expression of <em>CrtZ</em> and engineered the ferredoxin/ferredoxin oxidoreductase and redox cofactor regeneration to improve the catalytic efficiency of β-carotene hydroxylase. Liquid–liquid phase separation was then implemented to spatially co-localize the enzymes for mevalonate synthesis, accelerating mevalonate supply and boosting zeaxanthin production in <em>Y. lipolytica</em>. Combined with cultivation optimization, the engineered strain produced 6.9 g L<sup>−1</sup> zeaxanthin in fed-batch cultivation, the highest reported titer to date. This study establishes an integrated metabolic engineering strategy that couples metabolic, redox and spatial engineering for high-level zeaxanthin production. The multi-copy integration and phase separated multienzyme condensate approaches developed here can also be used as versatile toolkits for metabolic engineering in <em>Y. lipolytica</em>.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 2087-2097"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043375","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}
Jie Wu , Nathan Huang , Daniel Barker-Rothschild , Zhangmin Wan , Minke Yang , Xin Shu , Yi Hu , Joshua Booth , Oliver Evenden , Orlando J. Rojas , Kwang Ho Kim
Softwood Kraft lignin was esterified with palmitic anhydride to produce palmitoylated lignin (p-lignin). Structural analyses by FTIR and quantitative 31P NMR confirmed high degrees of hydroxyl substitution (71% aliphatic and 82% phenolic). Thermal measurements revealed marked plasticization, with the glass transition temperature shifting from 170 °C to 61 °C. The p-lignin resulting from the modification was more hydrophobic, as confirmed by reduced dynamic vapor sorption and molecular dynamics simulations showing lower hydration free energy and significantly stronger binding free energy. When applied from acetone solution onto paper, p-lignin produced coatings with water contact angles (WCA, 1 min) exceeding 150°, although low-temperature curing (80 °C) was required to achieve adequate adhesion. In contrast, waterborne colloidal suspensions of p-lignin particles, prepared via solvent-shift and stabilized with hydroxyethyl cellulose (HEC), could be sprayed directly onto paper to yield uniform coatings with WCA values above 130° (1 min) and strong adhesion, without any need for post-treatment. The coatings greatly enhanced filter paper's mechanical performance, with dry and wet tensile strength increasing by 65% and 400%, respectively. Using palmitic groups (C16) as a model, we show that grafting long hydrocarbon chains onto lignin imparts durable hydrophobicity and mechanical reinforcement, highlighting palmitoylated lignin as a promising bio-based coating for sustainable applications.
{"title":"Hydrophobic and mechanically reinforcing coatings from palmitoylated lignin via waterborne spraying","authors":"Jie Wu , Nathan Huang , Daniel Barker-Rothschild , Zhangmin Wan , Minke Yang , Xin Shu , Yi Hu , Joshua Booth , Oliver Evenden , Orlando J. Rojas , Kwang Ho Kim","doi":"10.1039/d5gc05423k","DOIUrl":"10.1039/d5gc05423k","url":null,"abstract":"<div><div>Softwood Kraft lignin was esterified with palmitic anhydride to produce palmitoylated lignin (p-lignin). Structural analyses by FTIR and quantitative <sup>31</sup>P NMR confirmed high degrees of hydroxyl substitution (71% aliphatic and 82% phenolic). Thermal measurements revealed marked plasticization, with the glass transition temperature shifting from 170 °C to 61 °C. The p-lignin resulting from the modification was more hydrophobic, as confirmed by reduced dynamic vapor sorption and molecular dynamics simulations showing lower hydration free energy and significantly stronger binding free energy. When applied from acetone solution onto paper, p-lignin produced coatings with water contact angles (WCA, 1 min) exceeding 150°, although low-temperature curing (80 °C) was required to achieve adequate adhesion. In contrast, waterborne colloidal suspensions of p-lignin particles, prepared <em>via</em> solvent-shift and stabilized with hydroxyethyl cellulose (HEC), could be sprayed directly onto paper to yield uniform coatings with WCA values above 130° (1 min) and strong adhesion, without any need for post-treatment. The coatings greatly enhanced filter paper's mechanical performance, with dry and wet tensile strength increasing by 65% and 400%, respectively. Using palmitic groups (C16) as a model, we show that grafting long hydrocarbon chains onto lignin imparts durable hydrophobicity and mechanical reinforcement, highlighting palmitoylated lignin as a promising bio-based coating for sustainable applications.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1924-1934"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043348","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}
Yang Wang , Xiang Luo , Man Zhou , Xiaojie Yu , Li Chen , Lina Wu , Cunshan Zhou
Excessive sugar consumption is fueling a global health crisis, creating demand for sustainable, zero-calorie sweeteners. Rebaudioside M (Reb-M), a high-intensity sweetener with a sucrose-like taste, is attractive. However, current supply depends on low-abundance leaf extraction and in vitro enzymatic glycosylation, limited by low titers/space–time yields, costly cofactors and enzyme purification, and inefficient atom utilization with significant byproduct streams. Here, we established for the first time an integrated E. coli whole-cell cascade co-expressing UGT76G1 variant and Glycine max sucrose synthase (GmSuSy), enabling in situ UDP-glucose regeneration from sucrose to drive Reb-D conversion into Reb-M. Process bottlenecks were overcome through expression regulation (multi-copy UGT76G1, RBS engineering of GmSuSy, and medium/induction optimization) and process engineering (permeabilization-assisted transport and reaction condition refinement). A fed-batch strategy further intensified performance, delivering 30.6 g L−1 Reb-M with 95.9% conversion, ranking among the highest levels reported to date. Importantly, this study also demonstrates the first conversion of the fructose byproduct into value-added d-allulose (2.97 g L−1) using a d-tagatose 3-epimerase module, thereby improving atom economy and sustainability. This approach offers a generalizable strategy to address fructose byproduct accumulation in multi-enzyme cascade reactions. Together, these advances establish a greener and more economical route to Reb-M at industrially relevant titers, highlighting both efficiency and green chemistry principles.
过度的糖消费正在加剧全球健康危机，催生了对可持续、零卡路里甜味剂的需求。雷鲍迪糖苷M （Reb-M）是一种具有类似蔗糖味道的高强度甜味剂，很有吸引力。然而，目前的供应依赖于低丰度的叶片提取和体外酶糖基化，受低效价/时空产率、昂贵的辅因子和酶纯化以及低效的原子利用和大量副产物流的限制。在这里，我们首次建立了一个整合的大肠杆菌全细胞级联共表达UGT76G1变体和Glycine max蔗糖合成酶（GmSuSy），使蔗糖的原位udp -葡萄糖再生能够驱动Reb-D转化为Reb-M。通过表达调控（多拷贝UGT76G1、GmSuSy的RBS工程、培养基/诱导优化）和工艺工程（渗透辅助转运和反应条件优化）克服工艺瓶颈。进料批次策略进一步增强了性能，提供30.6 g L−1 Reb-M，转化率为95.9%，是迄今为止报道的最高水平。重要的是，该研究还首次证明了使用d -塔格糖3-epimerase模块将果糖副产物转化为增值的D-allulose (2.97 g L−1)，从而提高了原子经济性和可持续性。这种方法为解决多酶级联反应中果糖副产物的积累提供了一种可推广的策略。总之，这些进步为工业相关滴度的Reb-M建立了一条更环保、更经济的途径，突出了效率和绿色化学原则。
{"title":"An efficient whole-cell platform for Rebaudioside M biotransformation: cascade design, expression regulation, process engineering","authors":"Yang Wang , Xiang Luo , Man Zhou , Xiaojie Yu , Li Chen , Lina Wu , Cunshan Zhou","doi":"10.1039/d5gc04865f","DOIUrl":"10.1039/d5gc04865f","url":null,"abstract":"<div><div>Excessive sugar consumption is fueling a global health crisis, creating demand for sustainable, zero-calorie sweeteners. Rebaudioside M (Reb-M), a high-intensity sweetener with a sucrose-like taste, is attractive. However, current supply depends on low-abundance leaf extraction and <em>in vitro</em> enzymatic glycosylation, limited by low titers/space–time yields, costly cofactors and enzyme purification, and inefficient atom utilization with significant byproduct streams. Here, we established for the first time an integrated <em>E. coli</em> whole-cell cascade co-expressing UGT76G1 variant and <em>Glycine max</em> sucrose synthase (<em>Gm</em>SuSy), enabling <em>in situ</em> UDP-glucose regeneration from sucrose to drive Reb-D conversion into Reb-M. Process bottlenecks were overcome through expression regulation (multi-copy UGT76G1, RBS engineering of <em>Gm</em>SuSy, and medium/induction optimization) and process engineering (permeabilization-assisted transport and reaction condition refinement). A fed-batch strategy further intensified performance, delivering 30.6 g L<sup>−1</sup> Reb-M with 95.9% conversion, ranking among the highest levels reported to date. Importantly, this study also demonstrates the first conversion of the fructose byproduct into value-added <span>d</span>-allulose (2.97 g L<sup>−1</sup>) using a <span>d</span>-tagatose 3-epimerase module, thereby improving atom economy and sustainability. This approach offers a generalizable strategy to address fructose byproduct accumulation in multi-enzyme cascade reactions. Together, these advances establish a greener and more economical route to Reb-M at industrially relevant titers, highlighting both efficiency and green chemistry principles.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"28 4","pages":"Pages 1972-1985"},"PeriodicalIF":9.2,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146043365","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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