Green Chemistry最新文献_第7页

Deep eutectic solvents for efficient and sustainable recycling of spent lithium-ion batteries: fundamental research, process intensification, and future prospects 用于高效和可持续回收废锂离子电池的深度共晶溶剂：基础研究、工艺强化和未来展望

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-05-25 DOI: 10.1039/d6gc02403c

Yang Chen , Bi Luo , Jiangshuo Li , Xubiao Luo , Yefeng Zhou

The development of new energy vehicles has generated a surplus of spent lithium-ion batteries (LIBs), leading to an urgent need for recycling spent LIBs. Deep eutectic solvents (DESs), versatile green liquids, hold broad promise for recycling spent LIBs. This review summarizes the fundamental research progress of LIBs recycling via DESs in pretreatment, hydrometallurgy, and direct regeneration. However, the practical application of DESs is hindered by inherent drawbacks, including high viscosity and detrimental side reactions such as esterification between the hydroxyl and carboxyl groups in the DESs components. To bridge this gap, process intensification technologies for recycling LIBs using DESs are summarized. On the one hand, various process intensification technologies are being rapidly developed to improve the efficiency of DESs. These include chemical methods, such as the addition of cosolvents to improve mass transfer and reducibility, and the design of ternary DESs that integrate a hydrogen bond acceptor and a hydrogen bond donor to tailor solvent properties, as well as physical methods, such as microwave, ultrasound, high-pressure, and flash Joule heating. On the other hand, advanced computational approaches involving simulation and artificial intelligence are increasingly being adopted. These approaches empower the rational design of high-performance DESs. Moreover, to balance environmental friendliness and economic considerations, we focus on analyzing DESs recycling strategies and the methodological value of life cycle assessment for evaluating environmental and economic benefits. This review outlines and analyzes prospects, guiding the development of recycling technologies to achieve efficient and sustainable LIBs recycling.

随着新能源汽车的发展，废旧锂离子电池出现过剩，废旧锂离子电池的回收利用迫在眉睫。深共晶溶剂（DESs）是一种多功能的绿色液体，在回收废lib方面有着广阔的前景。综述了DESs法回收lib在预处理、湿法冶金和直接再生等方面的基础研究进展。然而，DESs的实际应用受到其固有缺陷的阻碍，包括高粘度和有害的副反应，如DESs组分中羟基和羧基之间的酯化反应。为了弥补这一差距，综述了利用DESs回收lib的过程强化技术。一方面，各种工艺强化技术正在迅速发展，以提高DESs的效率。这些方法包括化学方法，如添加助溶剂来改善传质和还原性；设计三元DESs，将氢键受体和氢键供体集成在一起，以调整溶剂性能；以及物理方法，如微波、超声波、高压和闪蒸焦耳加热。另一方面，涉及模拟和人工智能的先进计算方法越来越多地被采用。这些方法支持了高性能DESs的合理设计。此外，为了平衡环境友好和经济考虑，我们重点分析了DESs回收策略和生命周期评估的方法价值，以评估环境和经济效益。本文概述和分析了前景，指导回收技术的发展，以实现高效和可持续的锂离子电池回收。

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引用次数: 0

Establishing parameters for resonant acoustic mixing (RAM) chemistry using Buchwald–Hartwig amination as a model 以Buchwald-Hartwig胺化为模型建立共振声混合（RAM）化学参数

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-02-24 DOI: 10.1039/d6gc00784h

Lori Gonnet , Cameron B. Lennox , Tristan H. Borchers , Mohammad S. Askari , Alexander Wahrhaftig-Lewis , Stefan G. Koenig , Karthik Nagapudi , Tomislav Friščić

While Resonant Acoustic Mixing (RAM) has been proposed as a scalable methodology for environmentally-friendly synthesis, notably media-free mechanochemical synthesis, the underlying reaction environment and the parameters that govern reaction control, optimization, and scale-up remain poorly understood. Using the Buchwald–Hartwig amination as a model system, this study provides insight into the RAM reaction environment and establishes design parameters through a combination of systematic screening and multimodal, real-time in situ monitoring of reaction progress, temperature evolution, and the transformations of crystalline and non-crystalline bulk phases. The simultaneous application of benchtop infrared thermography, and fingerprint- and terahertz-region Raman (THz-Raman) spectroscopy enables the direct correlation of reactivity, thermal behaviour, and phase evolution. Specifically, this work identifies the filling ratio (φ), acceleration, and the amount of liquid additive (η) as critical parameters to design tunable and scalable (at least 100 mmol) reactivity under RAM conditions, in short timeframes. Real-time monitoring reveals that rapid Buchwald–Hartwig reactivity is associated with autogenous heating, and that φ and acceleration serve as parameters that can be used to control reaction kinetics and temperature evolution. By identifying experimentally accessible reaction control parameters and presenting a benchtop-only design for the simultaneous monitoring of temperature, reaction progress and evolution of transient bulk phases, this work provides a foundation for the rational design, control, and safety of chemistry under RAM conditions.

虽然共振声混合（RAM）已被提出作为一种可扩展的环保合成方法，特别是无介质机械化学合成，但潜在的反应环境和控制反应控制、优化和放大的参数仍然知之甚少。本研究采用Buchwald-Hartwig胺化作为模型系统，通过系统筛选和多模态实时现场监测反应过程、温度演变以及结晶和非结晶体相的转变，深入了解RAM反应环境并建立设计参数。同时应用台式红外热成像，指纹和太赫兹区域拉曼（太赫兹-拉曼）光谱可以直接关联反应性，热行为和相演变。具体来说，本研究确定了填充比（φ）、加速度和液体添加剂量（η）作为关键参数，以在短时间内设计可调和可扩展的（至少100 mmol） RAM条件下的反应性。实时监测显示，快速的Buchwald-Hartwig反应与自加热有关，φ和加速度可作为控制反应动力学和温度演变的参数。通过确定实验可获得的反应控制参数，并提出了一个仅限台式的设计，用于同时监测温度，反应过程和瞬态体相的演变，本工作为RAM条件下化学的合理设计，控制和安全奠定了基础。

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引用次数: 0

Concatenating microorganisms, chemical catalysts, and enzymes for the synthesis of ethyl formate from renewables 连接微生物、化学催化剂和酶，用可再生能源合成甲酸乙酯

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-09 DOI: 10.1039/d6gc02757a

Nina Klos , Christopher Weike , Philipp Demling , Andreas Sebastian Klein , Giancarlo Franciò , Lars M. Blank , Walter Leitner , Dörte Rother

Alternative chemical synthesis routes and the (re)utilization of CO₂ are crucial for the development of a circular bioeconomy. To establish sustainable production methods, concatenating various catalysts allows for leveraging the unique advantages of each catalyst type. During process development, however, the reaction conditions must be harmonized, the catalyst compatibility must be examined, bottlenecks must be identified, and thus the operating window for the best process mode must be found. Here, we present ethyl formate synthesis from glucose, which is achieved by concatenating three catalysts: the yeast Saccharomyces cerevisiae, a ruthenium catalyst, and a lipase in an immobilized enzyme formulation. This study identifies the parameters that require investigation when combining different catalyst types and integrating CO₂ as an alternative raw material. Parameters such as product stability across different reaction systems, product distribution in a two-phase system using different organic solvents, and catalyst compatibility were studied. Candida antarctica lipase B was identified as a suitable biocatalyst for the enzymatic esterification of formic acid and ethanol. The catalyst compatibility is shown. However, the aqueous phase, necessary for yeasts, conflicts with product stability and catalyst activity. The desired one-pot, one-step process could not be realized. As a consequence, the process can only be efficiently performed in two steps, because in a one-pot, one-step reaction, the product yield was low. The concept of a concatenated ruthenium-catalyzed hydrogenation and lipase reaction can also be adapted to other formate esters starting from CO₂.

替代化学合成路线和二氧化碳（再）利用对循环生物经济的发展至关重要。为了建立可持续的生产方法，串联各种催化剂可以利用每种催化剂的独特优势。然而，在工艺开发过程中，必须协调反应条件，必须检查催化剂相容性，必须确定瓶颈，因此必须找到最佳工艺模式的操作窗口。在这里，我们提出从葡萄糖合成甲酸乙酯，这是通过连接三种催化剂：酵母酿酒酵母，钌催化剂和固定化酶制剂中的脂肪酶实现的。本研究确定了在组合不同催化剂类型和整合二氧化碳作为替代原料时需要研究的参数。研究了产物在不同反应体系中的稳定性、产物在不同有机溶剂下的两相体系中的分布以及催化剂的相容性等参数。南极念珠菌脂肪酶B是一种适合于甲酸和乙醇酶催化酯化的生物催化剂。表明了催化剂的相容性。然而，酵母所必需的水相与产物稳定性和催化剂活性相冲突。期望的一锅一步工艺无法实现。因此，该过程只能在两个步骤中有效地进行，因为在一个锅，一步反应中，产物收率很低。串联钌催化加氢和脂肪酶反应的概念也适用于从CO2开始的其他甲酸酯。

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引用次数: 0

Multidimensional engineering of Komagataella phaffii for efficient synthesis of retinal 多维工程化法菲小蛾高效合成视网膜

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-05 DOI: 10.1039/d6gc01294a

Jingnan Wang , Wenqi Ma , Yuxuan Xin , Jiayi Cui , Feng Guo , Yujia Jiang , Wankui Jiang , Fengxue Xin , Wenming Zhang , Min Jiang

Retinal is a fundamental molecule in the visual system and a critical regulator of skin health and cellular physiology. The sustainable production of retinal via engineered microbial cell factories offers a promising alternative to chemical synthesis. In this study, we established the biosynthetic pathway in Komagataella phaffii, providing the first experimental demonstration of the membrane-associated nature of β-carotene 15,15′-mono(di)oxygenase (BCMO). To maximize productivity, we implemented a multi-layered engineering strategy, including the amplification of key gene dosages, the balancing of NADPH cofactor supply, and the augmentation of precursor availability. Leveraging the unique sub-cellular architecture of K. phaffii, an anchoring motif from the peroxin PEX15 was used to achieve peroxisome surface display of BCMO. This spatial scaffolding effectively achieved in vivo enzyme immobilization, significantly enhancing catalytic activity. To harmonize cellular fitness with the oxygen-dependent requirements of BCMO, heterologous expression of Vitreoscilla hemoglobin (VHb) led to a 58.13% increase in biomass and a 17.32% improvement in retinal titer. In addition, we identified the Pdr5 transporter as a key mediator for retinal efflux, thereby alleviating intracellular cytotoxicity. The integration of surfactants facilitated the recovery of over 90% of intracellular retinal into the extracellular space, substantially reducing downstream processing complexity. Finally, utilizing glucose and methanol as carbon sources, the engineered strain achieved retinal titers of 764.22 mg L⁻¹ and 1406.69 mg L⁻¹ in a 5 L bioreactor, respectively. The methanol-derived titer represents the highest reported to date, underscoring the potential of K. phaffii as a versatile one-carbon biomanufacturing platform for industrial terpenoid biosynthesis.

视网膜是视觉系统的基本分子，也是皮肤健康和细胞生理的关键调节器。通过工程微生物细胞工厂可持续生产视网膜为化学合成提供了一个有前途的替代方案。在本研究中，我们建立了Komagataella phaffii的生物合成途径，首次通过实验证明了β-胡萝卜素15,15 ' -单（二）加氧酶（BCMO）的膜相关性质。为了最大限度地提高生产效率，我们实施了多层工程策略，包括关键基因剂量的扩增，NADPH辅助因子供应的平衡，以及前体可用性的增加。利用K. phaffii独特的亚细胞结构，利用来自过氧化物PEX15的锚定基元来实现BCMO的过氧化物酶体表面显示。这种空间支架有效地实现了体内酶的固定化，显著提高了催化活性。为了使细胞适应性与BCMO的氧依赖性需求相协调，异源表达玻璃体颤菌血红蛋白（VHb）导致生物量增加58.13%，视网膜滴度提高17.32%。此外，我们发现Pdr5转运体是视网膜外排的关键介质，从而减轻细胞内细胞毒性。表面活性剂的整合促进了超过90%的细胞内视网膜恢复到细胞外空间，大大降低了下游加工的复杂性。最后，利用葡萄糖和甲醇作为碳源，工程菌株在5l生物反应器中分别获得了764.22 mg L−1和1406.69 mg L−1的视网膜滴度。甲醇衍生的滴度是迄今为止报道的最高滴度，强调了法菲梭菌作为工业萜类生物合成的多功能单碳生物制造平台的潜力。

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引用次数: 0

Dual-functional SnS2–CuS heterostructure for zinc anode protection and conversion-type anode toward advanced aqueous zinc-ion batteries 双功能sns2 - cu异质结构用于锌阳极保护和转换型阳极

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-12 DOI: 10.1039/d6gc02132h

Shaoyan Huang , Shuling Liu , Sha Fan , Rui Su , Deliang Tian , Zili Deng , Jinbao Li , Jianbo Tong

Aqueous zinc-ion batteries (AZIBs) face critical challenges including poor cycling stability, zinc dendrite growth, and low zinc utilization. To address these issues, a multifunctional SnS₂–CuS heterostructure is proposed, serving both as a zinc anode protective layer in conventional AZIBs and a metal-free anode in rocking-chair zinc-ion batteries (RCZIBs). In AZIBs, the SnS₂–CuS heterostructure generates a synergistic effect between different phases. This effect improves interfacial charge transfer efficiency, guides the oriented deposition of Zn²⁺ along the (001) crystal plane of SnS₂, and optimizes Zn²⁺ migration kinetics. When deployed as the anode for RCZIBs, the elaborate heterostructure construction efficiently alleviates the severe volume expansion of CuS during repeated charge–discharge cycling, while interfacial charge polarization derived from heterogeneous coupling further accelerates the electrochemical reaction kinetics. To clarify the electrochemical mechanism, in situ XRD, in situ EIS, DRT analysis, and ex situ XPS are used to track phase transitions and interfacial dynamic processes. Density functional theory calculations also theoretically verify that the SnS₂–CuS heterostructure significantly enhances Zn²⁺ storage capability. Electrochemical tests show that the assembled RCZIB delivers a discharge specific capacity of 179.03 mAh g⁻¹ at 0.2 A g⁻¹, retaining 114.51 mAh g⁻¹ after 200 cycles. Moreover, it maintains 83.6% of its initial capacity after 1000 cycles at 1 A g⁻¹, demonstrating outstanding cycling stability. This study achieves the compatible application of the SnS₂–CuS heterostructure in both AZIBs and RCZIBs and highlights its considerable potential for next-generation high-performance energy storage systems.

水性锌离子电池（azib）面临着循环稳定性差、锌枝晶生长和锌利用率低等严峻挑战。为了解决这些问题，提出了一种多功能sns2 - cu异质结构，既可以作为传统azib中的锌阳极保护层，也可以作为摇椅锌离子电池（rczib）中的无金属阳极。在azib中，sns2 - cu异质结构在不同相之间产生协同效应。该效应提高了界面电荷传递效率，引导了Zn2+沿SnS2（001）晶面定向沉积，优化了Zn2+迁移动力学。当作为rczib的阳极时，精心构建的异质结构有效地缓解了cu在反复充放电循环过程中的严重体积膨胀，而非均相耦合产生的界面电荷极化进一步加速了电化学反应动力学。为了弄清电化学机理，采用原位XRD、原位EIS、DRT分析和非原位XPS对相变和界面动力学过程进行了跟踪。密度泛函理论计算也从理论上验证了sns2 - cu异质结构显著提高了Zn2+的存储能力。电化学测试表明，组装后的RCZIB在0.2 a g−1下的放电比容量为179.03 mAh g−1，在200次循环后保持114.51 mAh g−1。此外，它在1 A g−1下循环1000次后仍保持其初始容量的83.6%，表现出出色的循环稳定性。本研究实现了sns2 - cu异质结构在azib和rczib中的兼容应用，并突出了其在下一代高性能储能系统中的巨大潜力。

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引用次数: 0

Novel benzenesulfonamide-based ionic liquids for energy-efficient CO2 capture and conversion 新型基于苯磺酰胺的离子液体，用于节能CO2捕获和转化

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-09 DOI: 10.1039/d6gc01624c

Yangyang Jiang , Yuxin Liu , Yuanli Qi , Yurou Shao , Dong Wang , Benshuai Guo , Jingyan Zhao , Zhibin Zhou , Yuntao Lei , Lili Jin

The capture and utilization of carbon dioxide (CO₂) from the post-combustion of fossil fuels has been identified as a highly effective strategy for reducing carbon emissions. Herein, a series of novel substituted benzenesulfonamide ionic liquids (BSA-ILs) were designed and synthesized via facile acid–base neutralization reactions for the purpose of achieving reversible CO₂ capture and catalyzing CO₂ chemical fixation. Addressing the inherently high viscosity of neat BSA-ILs (551.2–7785.7 mPa s), propylene carbonate (PC), a green product derived from CO₂ chemical fixation, was selected as a diluent to form BSA-IL mixed absorbents (BSA-IL-MAs). The optimized system exhibited a high CO₂ uptake capacity of 1.38 mol of CO₂ per mol BSA-IL, an excellent CO₂/N₂ selectivity of 18.36, and a remarkable 99.0% conversion of epichlorohydrin under mild, solvent-free, metal-free, halogen-free, co-catalyst-free and atmospheric pressure conditions. Meanwhile, the findings demonstrated a certain positive correlation between the CO₂ uptake capacity/conversion and the pK_a of the substituted BSA. Notably, the BSA-IL system retained nearly intact CO₂ capture performance and catalytic activity after five consecutive absorption–desorption and catalytic cycles, with an extremely low E-factor of 0.11. Spectroscopic characterization confirmed the formation of a new carbonyl moiety peak in CO₂-saturated BSA-ILs, indicating that chemisorption dominated the CO₂ uptake process. NMR investigations and DFT calculations further elucidated the interactions between BSA-ILs, CO₂ and epoxide substrates, validating the feasibility of the proposed reaction pathways. This work provides a sustainable, efficient and industrially feasible integrated platform for CO₂ capture and utilization, offering a paradigm for low-carbon catalytic conversion systems.

捕获和利用化石燃料燃烧后产生的二氧化碳已被确定为减少碳排放的一种非常有效的策略。本文设计并合成了一系列新型取代苯磺酰胺离子液体（BSA-ILs），通过酸碱中和反应实现了CO2的可逆捕获和催化CO2的化学固定。针对纯BSA-IL高粘度（551.2 ~ 7785.7 mPa s）的特点，选择CO2化学固定的绿色产物碳酸丙烯（PC）作为稀释剂制备BSA-IL混合吸附剂（BSA-IL- mas）。优化后的体系在温和、无溶剂、无金属、无卤素、无助催化剂和常压条件下，对环氧氯丙烷的转化率达到99.0%，CO2吸收率为1.38 mol / mol BSA-IL， CO2/N2选择性为18.36。同时，研究结果表明，取代BSA的CO2吸收能力/转化率与pKa之间存在一定的正相关。值得注意的是，在连续五次吸附-解吸和催化循环后，BSA-IL体系保持了几乎完整的CO2捕获性能和催化活性，e因子极低，为0.11。光谱表征证实在CO2饱和的BSA-ILs中形成了一个新的羰基片段峰，表明化学吸附主导了CO2的吸收过程。核磁共振研究和DFT计算进一步阐明了bsa - il、CO2和环氧化物底物之间的相互作用，验证了所提出的反应途径的可行性。本研究为二氧化碳捕集与利用提供了一个可持续、高效、工业上可行的综合平台，为低碳催化转化系统提供了一个范例。

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引用次数: 0

Integrating compartmentalized catalysis with low-energy recovery via a magneto-responsive water-in-water Pickering emulsion platform for sustainable biomanufacturing of 4-methyl-5-thiazoleethanol 通过磁响应水包水Pickering乳液平台，将区隔化催化与低能量回收相结合，实现4-甲基-5-噻唑乙醇的可持续生物制造

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-04 DOI: 10.1039/d6gc02039a

Weizhi Huang , Xiaoqi Ding , Sha Ao , Huaqiang Cao , Jia Hu , Xiaoqing Han , Shilin Liu

Simultaneously achieving compartmentalized catalysis and low-energy recovery remains a significant challenge in conventional liquid fermentation. To address this issue, citrate-functionalized Fe₃O₄ nanoparticles were utilized to construct a water/water (W/W) Pickering emulsion system. A recombinant Bacillus amyloliquefaciens strain was engineered for 4-methyl-5-thiazoleethanol (MTE) biosynthesis through competing pathway knockout (ΔylmB) and site-directed mutagenesis of TenA (Y113A/F169A). In liquid fermentation, the engineered strain (ΔylmB/pHY-BaTenA^Y113A/F169A) achieved a 6.80-fold increase in MTE production (from 273.67 mg·L⁻¹ to 1862.05 mg·L⁻¹). When cultivated in the magneto-responsive W/W Pickering emulsion under optimized conditions, the MTE yield was increased to 3061.14 mg·L⁻¹, representing a 20.47% improvement over the Fe₃O₄ nanoparticle-free control. This enhancement was attributed to the stable compartmentalized micro-environment of the aqueous two-phase system, which promoted bacterial proliferation and sustained catalytic activity. Notably, the interfacial Fe₃O₄ nanoparticles enabled gentle magnetic separation, achieving supernatant clarification (OD₆₀₀ = 0.27 ± 0.04) comparable to that of high-speed centrifugation (0.20 ± 0.02). Magnetically harvested bacteria readily resumed normal growth in fresh media, and the nanoparticles could be reused for two cycles, retaining 47.80% of their saturation magnetization and supporting a sustained MTE yield of 2968.88 mg·L⁻¹. A magneto-responsive aqueous two-phase system was developed to couple compartmentalized biosynthesis with low-energy bacterial recovery. This integrated platform would provide a circular and sustainable strategy for biomanufacturing high-value compounds.

同时实现区隔化催化和低能量回收仍然是传统液体发酵面临的重大挑战。为了解决这一问题，利用柠檬酸盐功能化的Fe3O4纳米颗粒构建了水/水（W/W） Pickering乳液体系。通过竞争途径敲除（ΔylmB）和定点诱变TenA (Y113A/F169A)，设计了一株重组解淀粉芽孢杆菌菌株，用于4-甲基-5-噻唑乙醇（MTE）的生物合成。在液体发酵中，工程菌株（ΔylmB/pHY-BaTenAY113A/F169A）的MTE产量增加了6.80倍（从273.67 mg·L−1增加到1862.05 mg·L−1）。在此条件下，MTE产率达到3061.14 mg·L−1，比无Fe3O4纳米颗粒对照提高了20.47%。这种增强归因于水两相体系稳定的区隔微环境，促进了细菌的增殖和持续的催化活性。值得注意的是，界面Fe3O4纳米颗粒实现了温和的磁分离，实现了上清澄清（OD600 = 0.27±0.04），与高速离心（0.20±0.02）相当。磁性收获的细菌很容易在新鲜培养基中恢复正常生长，纳米颗粒可以重复使用两个循环，保留47.80%的饱和磁化强度，并支持2968.88 mg·L−1的MTE产率。开发了一种磁响应双水相系统，将区隔生物合成与低能量细菌回收结合起来。这个综合平台将为高价值化合物的生物制造提供循环和可持续的战略。

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引用次数: 0

Greening water-lean solvents for CO2 capture: replacing toxic 1-methyl-2-pyrrolidone with high-performance eco-friendly cosolvents 用于CO2捕获的绿色水溶剂：用高性能环保助溶剂取代有毒的1-甲基-2-吡咯烷酮

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-04 DOI: 10.1039/d6gc02196d

Huilin Li , Xuechong Ding , Teng Zhou

Water-lean solvents are promising alternatives to aqueous amines for post-combustion CO₂ capture due to their lower regeneration energy. However, the majority of state-of-the-art water-lean solvents rely on 1-methyl-2-pyrrolidone (NMP) as the organic cosolvent, whose reproductive toxicity poses a serious barrier to large-scale deployment. This study proposes a systematic strategy to identify green, low-toxicity replacements for NMP in water-lean solvents. Based on COSMO-RS σ-profile similarity calculation, 20 high-potential candidates were first identified from 2562 organic solvents. Subsequent environmental, health, and safety (EHS) evaluations, combined with physicochemical property filtering, narrowed the selection to two green cosolvents: methylaminoacetaldehyde dimethyl acetal (MAADMA) and 3-methoxy-1-butanol (MOB). These two candidates and NMP were then experimentally validated in combination with three representative amines (EMEA, DMEDA, and DMPDA) at 5 wt% water content. Among all tested systems, the EM-A-5H solvent (30% EMEA/65% MAADMA/5% H₂O) showed the best performance, with a remarkable cyclic capacity of 0.86 mol CO₂ per mol amine and a regeneration efficiency of 93.6%. Importantly, EM-A-5H achieved a total regeneration energy of 2.20 GJ per t CO₂, 41% lower than conventional 30 wt% MEA and 15% lower than the NMP-based counterpart solvent. It also exhibited an excellent stability and satisfactory viscosity over seven absorption–desorption cycles without performance degradation. This work offers a systematic and practical approach for the rational design of eco-friendly, high-performance water-lean solvents for CO₂ capture.

由于其较低的再生能量，水稀薄溶剂是有希望的替代水胺的燃烧后二氧化碳捕获。然而，大多数最先进的水溶剂依赖于1-甲基-2-吡咯烷酮（NMP）作为有机共溶剂，其生殖毒性对大规模部署构成严重障碍。本研究提出了一个系统的策略，以确定绿色，低毒性的替代品NMP在水稀薄的溶剂。通过cosmos - rs σ-剖面相似度计算，从2562种有机溶剂中筛选出20种高潜力候选溶剂。随后的环境、健康和安全（EHS）评估，结合理化性质过滤，将选择范围缩小到两种绿色助溶剂：甲胺乙醛二甲基缩醛（MAADMA）和3-甲氧基-1-丁醇（MOB）。然后在5 wt%含水量下，将这两种候选胺和NMP与三种代表性胺（EMEA， DMEDA和DMPDA）联合进行实验验证。在所有测试体系中，EM-A-5H溶剂（30% EMEA/65% MAADMA/5% H2O）表现最好，其循环容量为0.86 mol CO2 / mol胺，再生效率为93.6%。重要的是，EM-A-5H实现了2.20 GJ / t CO2的总再生能量，比传统的30 wt% MEA低41%，比基于nmp的对应溶剂低15%。在7次吸附-解吸循环中，它也表现出优异的稳定性和令人满意的粘度，而性能没有下降。这项工作为合理设计环保、高性能的低水溶剂用于二氧化碳捕获提供了系统和实用的方法。

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引用次数: 0

A green versatile platform for synthesising renewable ether-based thermoplastic elastomers 合成可再生醚基热塑性弹性体的绿色多功能平台

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-09 DOI: 10.1039/d6gc00989a

Sungkwon Yoon , Charlie Bateman , James J. C. Busfield , Peter J. Martin , Biqiong Chen

Ether-based polymers are commonly used in diverse applications. However, it is challenging to synthesise polyethers with more than five methylene groups in their repeating units from cyclic ethers, which limits the molecular design of ether-based polymers. Creating a new synthesis pathway to enabling green chemistry and flexible design of their molecular structures is, therefore, highly desired. Here, a green versatile platform is presented for synthesising renewable ether-based thermoplastic elastomers (TPEs) with broad and tuneable properties. An organic acid catalyst is used to synthesise a long-chain polyether diol from a fatty acid diol via a S_N2 reaction. This biobased, renewable polyether diol then serves as a universal platform for the synthesis of a wide spectrum of TPEs including thermoplastic polyurethanes, poly(urethane urea)s and poly(ether ester) elastomers, with controllable mechanical properties, excellent transparency and chemical resistance. The structure–property relationships, processability, and sustainability of these TPEs are also reported. The synthesis of these biobased TPEs can be readily scaled up, and different types of products are manufactured from the elastomers. This work provides a viable synthesis strategy to overcoming the limitations of the molecular design facing existing ether-based polymers, while enabling the sustainable manufacture of renewable ether-based TPE materials and products.

醚基聚合物通常用于各种应用。然而，从环醚中合成重复单元中含有超过五个亚甲基的聚醚具有挑战性，这限制了醚基聚合物的分子设计。因此，迫切需要创造一种新的合成途径，以实现绿色化学和灵活的分子结构设计。本文提出了一种绿色多功能平台，用于合成具有广泛可调性能的可再生醚基热塑性弹性体（tpe）。采用有机酸催化剂，通过SN2反应由脂肪酸二醇合成长链聚醚二醇。这种生物基可再生聚醚二醇可以作为合成各种tpe的通用平台，包括热塑性聚氨酯、聚（聚氨酯尿素）和聚（醚酯）弹性体，具有可控的机械性能、优异的透明度和耐化学性。还报道了这些tpe的结构-性能关系，可加工性和可持续性。这些生物基tpe的合成可以很容易地扩大规模，并从弹性体制造不同类型的产品。这项工作为克服现有醚基聚合物分子设计的局限性提供了一种可行的合成策略，同时使可再生醚基TPE材料和产品的可持续制造成为可能。

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引用次数: 0

An AE/Fe-MOF/PVDF heterojunction self-cleaning photocatalytic membrane for rapid electron transfer to enhance photo-Fenton degradation of tannic acid 一种用于快速电子转移的AE/Fe-MOF/PVDF异质结自清洁光催化膜以增强单宁酸的光fenton降解

IF 10.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2026-06-29 Epub Date: 2026-06-12 DOI: 10.1039/d6gc02278b

Jiajia Li , Yulu Liu , Manhua Chen , Keke Cao , Rongqiang Zhang , Nan Zhang , Zhi Li , Qi Qiang , Yuping Tang , Qizhao Wang

As the traditional Chinese medicine (TCM) industry develops at a fast pace, its wastewater discharge has become an increasingly severe environmental problem. Membrane technology has been applied in the treatment of TCM wastewater; however, the high concentration of macromolecular organics, such as tannic acid, pectin, and protein, readily triggers severe pore blockage and fouling of polyvinylidene fluoride (PVDF) separation membranes. To address these challenges, this study innovatively integrates the natural photosensitizer aloe-emodin (AE) with an Fe-MOF to construct an AE/Fe-MOF type-I heterojunction photocatalyst directly immobilized onto a PVDF membrane substrate. Under visible-light irradiation with H₂O₂, the fabricated AE/Fe-MOF/PVDF membrane achieves 87.29% degradation efficiency toward tannic acid (TA) within 90 minutes. It also exhibits excellent removal performance for simulated TCM wastewater derived from Rheum officinale Baill. and Polygonum cuspidatum Sieb. et Zucc., achieving chemical oxygen demand (COD) removal rates of 74.44% and 96.61%, respectively. Furthermore, the AE/Fe-MOF/PVDF membrane demonstrates remarkable self-cleaning capability, achieving a flux recovery ratio (FRR) of up to 96.5% following in situ photo-Fenton degradation, which is far superior to conventional hydraulic cleaning (65.7%). Stable filtration performance is maintained across multiple filtration–cleaning cycles. Mechanistic investigations reveal that the AE/Fe-MOF type-I heterojunction enhances the spatial separation of photoinduced carriers and accelerates the Fe³⁺/Fe²⁺ redox cycle, thereby synergistically driving a sustained and efficient photo-Fenton process that enables simultaneous pollutant degradation and in situ membrane fouling mitigation. This work not only provides a novel heterojunction-based self-cleaning photocatalytic membrane for the efficient treatment of TCM wastewater but also deepens the understanding of the synergistic mechanism between charge transfer and the iron cycle in natural photosensitizer and MOF hybrid systems.

随着中药产业的快速发展，其废水排放已成为日益严重的环境问题。膜技术已应用于中药废水的处理；然而，高浓度的大分子有机物，如单宁酸、果胶和蛋白质，很容易引发严重的孔堵塞和聚偏氟乙烯（PVDF）分离膜的污垢。为了解决这些挑战，本研究创新地将天然光敏剂芦荟大黄素（AE）与Fe-MOF结合，构建了AE/Fe-MOF型异质结光催化剂，直接固定在PVDF膜基质上。在H2O2可见光照射下，制备的AE/Fe-MOF/PVDF膜在90分钟内对单宁酸（TA）的降解效率达到87.29%。对大黄模拟中药废水也表现出优异的去除效果。虎杖和虎杖。调查。，化学需氧量（COD）去除率分别为74.44%和96.61%。此外，AE/Fe-MOF/PVDF膜表现出显著的自清洁能力，在原位光- fenton降解后，通量回收率（FRR）高达96.5%，远远优于传统的水力清洗（65.7%）。在多个过滤-清洗循环中保持稳定的过滤性能。机制研究表明，AE/Fe-MOF i型异质结增强了光诱导载流子的空间分离，加速了Fe3+/Fe2+氧化还原循环，从而协同驱动持续高效的光- fenton过程，实现污染物降解和原位膜污染的同时缓解。本研究不仅为中药废水的高效处理提供了一种新型的基于异质结的自清洁光催化膜，而且加深了对天然光敏剂和MOF混合体系中电荷传递与铁循环协同机制的理解。

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引用次数: 0