Green Chemistry最新文献

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Green and efficient separation of vanadium and chromium from high-chromium vanadium slag: a review of recent developments 从高铬钒渣中绿色高效分离钒和铬：最新发展综述

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02192d

Weizao Liu , Zhenghao Wang , Wen Cao , Yanjie Liang , Sohrab Rohani , Yuntao Xin , Jinmao Hua , Chunlian Ding , Xuewei Lv

Vanadium(v) and chromium (Cr) are important strategic resources due to their outstanding physicochemical properties. Due to their similar physical and chemical properties, V and Cr are often associated and coexist in many minerals. This review highlights the significance of V and Cr extraction and separation from high-chromium vanadium slag, emphasizing the key separation techniques. Current strategies for vanadium–chromium separation include separation during the extraction process, that is selective extraction of one of the elements from the slag and co-extraction of vanadium and chromium into solution followed by separation of vanadium and chromium from the solution. Both strategies are pivotal for optimizing the extraction process and enhancing industrial applications. This comprehensive review provides insights into the separation methods, addressing the challenges and advancements in the field. The elucidation of the importance of vanadium and chromium, coupled with a detailed analysis of high-chromium vanadium slag and current separation techniques, contributes to the utilization of vanadium–titanium-bearing magnetite resources with a high content of chromium and also evolves the knowledge in this critical area.

钒（V）和铬（Cr）因其出色的物理化学特性而成为重要的战略资源。由于其相似的物理和化学性质，钒和铬经常伴生和共存于许多矿物中。本综述强调了从高铬钒渣中提取和分离钒和铬的重要性，并着重介绍了关键的分离技术。目前的钒铬分离策略包括在萃取过程中进行分离，即从钒渣中选择性地萃取其中一种元素，以及将钒和铬共同萃取到溶液中，然后从溶液中分离钒和铬。这两种策略对于优化萃取工艺和提高工业应用至关重要。本综述深入探讨了分离方法，探讨了该领域的挑战和进展。对钒和铬的重要性的阐释，加上对高铬钒渣和当前分离技术的详细分析，有助于利用铬含量高的含钒钛磁铁矿资源，同时也发展了这一关键领域的知识。

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引用次数: 0

Visible light-induced photocatalytic deoxyfluorination of benzyl alcohol using SF6 as a fluorinating reagent† 以 SF6 为氟化试剂，利用可见光诱导光催化苯甲醇的脱氧氟化反应

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03324h

Yi-Fan Zhang , Shan Zhu , Ya-Wen Zuo , Hang Liu , Ruo-Xing Jin , Xi-Sheng Wang

As fluorine atoms significantly strengthen the metabolic stability and bioavailability of organic molecules, benzyl fluoride is found as an essential skeleton in pharmaceuticals or biologically active molecules. Here, we employ sulfur hexafluoride (SF₆) as an efficient fluorinating reagent, achieving nucleophilic fluorination of widely available benzyl alcohols under visible LED light irradiation with a low dosage of photocatalyst 4CzIPN. The reaction is compatible with several substrate backbones and is not air- or moisture-sensitive, realizing the degradation and utilization of SF₆, a potent greenhouse gas resource.

氟原子能显著增强有机分子的代谢稳定性和生物利用度，因此氟化苄基是药物或生物活性分子中不可或缺的骨架。在此，我们采用六氟化硫（SF6）作为高效氟化试剂，在可见光 LED 光照射下，利用低剂量光催化剂 4CzIPN 实现了广泛存在的苄醇的亲核氟化反应。该反应与多种底物骨架兼容，对空气和湿气不敏感，实现了有效温室气体资源 SF6 的降解和利用。

引用次数: 0

Electrochemical oxidative dehydrogenation of hydrosilanes to generate silyl radicals: an efficient method for the construction of Si–O/Si–Si bonds utilizing a recyclable ionic liquid catalyst† 利用可回收离子液体催化剂对氢硅烷进行电化学氧化脱氢以生成硅基：一种构建 Si-O/Si-Si 键的高效方法

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02663b

Zhaoxin Wei , Ziren Chen , Fei Xue , Yuancheng Yue , Shaofeng Wu , Yonghong Zhang , Bin Wang , Yu Xia , Weiwei Jin , Chenjiang Liu

A highly efficient and sustainable approach was developed for the construction of Si–O/Si–Si bonds, through the electrochemical oxidative dehydrogenation of hydrosilanes with O-nucleophiles (e.g. phenols, naphthols, alcohols, and H₂O) or hydrosilane self-condensation. The protocol employs a highly electrically conductive and recyclable ionic liquid as a catalyst, thus eliminating the need for external electrolytes and hydrogen atom transfer (HAT) agents. The ionic liquid could be easily recovered and reused for at least eight cycles with consistent performance. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility (66 examples, up to 96% yield). Initial mechanistic studies show that silicon radicals are generated via the process of hydrogen atom transfer between bromine radicals and silanes, and KIE experiments demonstrate that Si–H bond cleavage is the rate-determining step of the reaction.

通过氢硅烷与 O 型亲核物（如酚、萘酚、醇和 H2O）的电化学氧化脱氢反应或氢硅烷自缩合反应，开发出了一种构建 Si-O/Si-Si 键的高效、可持续方法。该方案采用高导电性和可回收的离子液体作为催化剂，因此无需外加电解质和氢原子转移（HAT）剂。离子液体可轻松回收并重复使用至少八个周期，且性能始终如一。值得注意的是，这种电化学方法具有广泛的底物范围和较高的官能团兼容性（66 个实例，收率高达 96%）。初步的机理研究表明，硅自由基是通过溴自由基和硅烷之间的氢原子转移过程产生的，KIE 实验证明，Si-H 键裂解是该反应的决定性步骤。

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引用次数: 0

De novo synthesis of 6-6-5 fused systems through electrochemical decarboxylation and radical domino additions† 通过电化学脱羧和自由基多米诺加成从头合成 6-6-5 熔合体系

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03260h

Chengcheng Yuan , Guanru Liu , Wenjing Guan , Jinlin Hang , Zheng Fang , Chengkou Liu , Kai Guo

Highly complex fused systems are widely present in drug development. The direct electrosynthesis of fused systems through radical domino reactions features higher atom and step economy, using abundantly available starting materials and avoiding exogenous oxidants and reductants, and thus it has been in high demand and recognized as a green, powerful, and versatile synthetic tool but remains challenging because of the instability of the radical species under the electrolysis conditions and the inclusion of a quaternary ammonium salt. Herein, we developed a de novo electrosynthesis of 6-6-5 fused systems with two new rings constructed using a user-friendly undivided cell through decarboxylation and three-step radical addition under exogenous oxidant and quaternary ammonium salt free conditions. Excellent functional group, water and air compatibility was observed with good yields obtained.

高度复杂的融合体系广泛存在于药物研发中。通过自由基多米诺反应直接电合成融合体系具有更高的原子和步骤经济性，可利用丰富的起始材料，避免外源氧化剂和还原剂，因此需求量很大，被公认为是一种绿色、强大和多用途的合成工具，但由于自由基物种在电解条件下的不稳定性以及加入季铵盐，该方法仍具有挑战性。在此，我们开发了一种全新的电合成方法，在不含外源氧化剂和季铵盐的条件下，通过脱羧和三步自由基加成，利用用户友好型非分裂电池构建出带有两个新环的 6-6-5 融合体系。观察到了极佳的官能团、水和空气相容性，并获得了良好的产率。

引用次数: 0

Designing green chemicals by predicting vaporization properties using explainable graph attention networks† 利用可解释图注意网络预测汽化特性，设计绿色化学品

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc01994f

Yeonjoon Kim , Jaeyoung Cho , Hojin Jung , Lydia E. Meyer , Gina M. Fioroni , Christopher D. Stubbs , Keunhong Jeong , Robert L. McCormick , Peter C. St. John , Seonah Kim

Computational predictions of vaporization properties aid the de novo design of green chemicals, including clean alternative fuels, working fluids for efficient thermal energy recovery, and polymers that are easily degradable and recyclable. Here, we developed chemically explainable graph attention networks to predict five physical properties pertinent to performance in utilizing renewable energy: heat of vaporization (HoV), critical temperature, flash point, boiling point, and liquid heat capacity. The predictive model for HoV was trained using ∼150 000 data points, considering their uncertainties and temperature dependence. Next, this model was expanded to the other properties through transfer learning to overcome the limitations due to fewer data points (700–7500). The chemical interpretability of the model was then investigated, demonstrating that the model explains molecular structural effects on vaporization properties. Finally, the developed predictive models were applied to design chemicals that have desirable properties as efficient and green working fluids, fuels, and polymers, enabling fast and accurate screening before experiments.

对汽化特性的计算预测有助于绿色化学品的全新设计，包括清洁替代燃料、用于高效热能回收的工作液以及易于降解和回收的聚合物。在此，我们开发了化学可解释图注意网络，用于预测与可再生能源利用性能相关的五种物理特性：汽化热（HoV）、临界温度、闪点、沸点和液体热容量。考虑到其不确定性和温度依赖性，HoV 的预测模型使用了 150 000 个数据点进行训练。接下来，通过迁移学习将该模型扩展到其他属性，以克服数据点较少（700-7500 个）所带来的局限性。然后对模型的化学可解释性进行了研究，证明该模型可以解释分子结构对汽化特性的影响。最后，开发的预测模型被应用于设计具有理想特性的化学物质，如高效绿色工作液、燃料和聚合物，从而在实验前实现快速准确的筛选。

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引用次数: 0

Renewable lignocellulose based binders for advanced battery systems† 基于可再生木质纤维素的先进电池系统粘合剂

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02226b

Zhuzuan Chen , Shengzhi Li , Guangzhao Zhang , Yu Yang , Yong Qian

As a crucial component of batteries, the binder connects the granular active material and the conductive additive into a whole electrode and attaches to the surface of the current collector through a variety of interactions to maintain the electron/ion transport and the integrity of the electrode during the charge–discharge cycles. However, conventional binders are mostly synthetic polymers with single structures and properties and are not renewable, thus the development of multifunctional green renewable binders derived from biomass materials is attracting increasing attention. The distribution and function of lignocellulose in plants are similar to those of binders in electrodes. They strengthen the structure of the plants via hydrogen bonding, π–π conjugation, hydrophobicity, etc., and maintain the diffusion and transport of molecules, aligning with the criteria for the next generation of battery binders. In the context of the significant impact of binders on the performance of advanced battery systems, recent progress in research on lignocellulose derivative-based binders in various batteries is summarized. The research potential and challenges of lignocellulose and its derivatives as binder materials are discussed, with the hope of shedding light on the rational construction of robust and stable lignocellulose-based binders for high-energy-density batteries.

作为电池的重要组成部分，粘结剂将颗粒状活性材料和导电添加剂连接成一个整体电极，并通过各种相互作用附着在集流器表面，从而在充放电循环过程中保持电子/离子传输和电极的完整性。然而，传统的粘合剂大多是结构和性能单一的合成聚合物，不具有可再生性，因此开发从生物质材料中提取的多功能绿色可再生粘合剂越来越受到人们的关注。木质纤维素在植物中的分布和功能与电极中的粘合剂类似。它们通过氢键、π-π共轭、疏水性等加强植物的结构，保持分子的扩散和运输，符合下一代电池粘合剂的标准。鉴于粘合剂对先进电池系统性能的重要影响，本文总结了近期基于木质纤维素衍生物的粘合剂在各种电池中的研究进展。讨论了木质纤维素及其衍生物作为粘合剂材料的研究潜力和挑战，希望能为高能量密度电池合理构建坚固稳定的木质纤维素基粘合剂提供启示。

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引用次数: 0

Unraveling the secrets of harnessing a surfactant-modified strategy in organosolv pretreatment of lignocellulosic biomass for efficient fermentable sugar production† 揭开在有机溶胶预处理木质纤维素生物质过程中利用表面活性剂改良策略高效生产可发酵糖的秘密

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02775b

Guojie Song , Hui Zhang , Meysam Madadi , Zhixiangpeng Chen , Hao Wang , Ao Xia , Abdolreza Samimi , Chihe Sun , Xianzhi Meng , Arthur J. Ragauskas , Fubao Sun

Alkaline-catalyzed organosolv pretreatment of lignocellulosic biomass affords excellent delignification, yielding a holocellulose-rich substrate for fermentable sugar production. However, complete lignin removal is impractical, and residual lignin also exacerbates negative effects on subsequent enzymatic hydrolysis. Herein, a novel strategy of developing surfactant-assisted organosolv pretreatment (Triton-X 100, AEO 9 and Tween 80) for in situ lignin modification was proposed to overcome this issue. The results indicated that the pretreated substrates showed considerable enzymatic hydrolyzability with a 15.7%–38.3% higher sugar yield compared to the control group without surfactants. Surfactants could graft on both residual and dissolved lignin through etherification, forming α-etherified lignin, though without significantly changing the component distribution and substrate-related properties. Quantum chemical calculations provided theoretical evidence of strong H-bonding and pronounced interaction energy between lignin and surfactants (maximally at −48.4 kcal mol⁻¹). In particular, this surfactant modification decreased the aliphatic –OH and phenolic –OH contents of residual lignin by 16.0%–22.4% and 13.8%–28.8%, respectively. The reduction of –OH groups mitigated non-productive adsorption between lignin and cellulases via H-bonding interaction, which exhibited a significant correlation with the increased enzymatic hydrolyzability (>−0.9). Overall, this study offers valuable insight into the fundamental understanding of the mechanism involved in lignin modification during surfactant-assisted pretreatment and lignin–enzyme interaction during enzymatic hydrolysis. The new findings underscore the potential application of surfactants in organosolv pretreatment to achieve a feasible approach for developing an efficient enzyme-mediated lignocellulosic sugar platform.

对木质纤维素生物质进行碱性催化的有机溶胶预处理可获得极佳的木质素脱除效果，从而产生富含全纤维素的底物，用于生产可发酵糖。然而，完全去除木质素并不现实，残留的木质素还会加剧对后续酶水解的负面影响。为解决这一问题，本文提出了一种新的策略，即开发表面活性剂辅助有机溶剂预处理（Triton-X 100、AEO 9 和 Tween 80），对木质素进行原位改性。结果表明，经预处理的基质显示出相当高的酶水解性，与未添加表面活性剂的对照组相比，糖产量提高了 15.7%-38.3%。表面活性剂可通过醚化作用接枝到残留和溶解的木质素上，形成α-醚化木质素，但不会显著改变木质素的组分分布和基质相关特性。量子化学计算从理论上证明了木质素与表面活性剂之间的强 H 键和明显的相互作用能（最大值为 -48.4 kcal mol-1）。特别是，这种表面活性剂改性使残留木质素中脂肪族 -OH 和酚类 -OH 的含量分别降低了 16.0%-22.4% 和 13.8%-28.8% 。-OH基团的减少通过H键相互作用减轻了木质素和纤维素酶之间的非生产性吸附，这与酶水解性的增加有显著的相关性（>-0.9）。总之，这项研究为从根本上理解表面活性剂辅助预处理过程中木质素改性以及酶水解过程中木质素与酶相互作用的机理提供了宝贵的见解。新发现强调了表面活性剂在有机溶胶预处理中的潜在应用，为开发高效的酶介导木质纤维素糖平台提供了可行的方法。

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引用次数: 0

Improving both activity and stability for direct conversion of cellulose to ethanol by decorating Pt/WOx with mononuclear NbOx† 用单核氧化铌装饰铂/氧化物，提高纤维素直接转化为乙醇的活性和稳定性

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03390f

Weixiang Guan , Chen Cao , Fei Liu , Aiqin Wang , Tao Zhang

Chemocatalytic conversion of cellulose to ethanol provides an alternative route for biofuel production with a theoretical carbon yield of 100%; however, it faces significant challenges of high catalyst cost and poor catalyst stability. In this work, we report a new strategy to decrease the use of expensive noble metals, by decorating mononuclear NbO_x on a low-Pt Pt/WO_x catalyst surface. The resulting 0.1Nb/0.5Pt/WO_x catalyst gave rise to an ethanol yield of 33.7% together with an ethylene glycol yield of 21.8%, and the noble metal efficiency reached 25.90 g_ethanol g_Pt⁻¹ h⁻¹, an increase by a factor of 2–10 compared to those in the literature. Moreover, the catalyst stability was significantly enhanced by the decoration of mononuclear NbO_x, allowing for recycling at least 7 times without obvious activity decay. Characterization revealed that Pt was highly dispersed at subnanometer and single atom scales, and modification with mononuclear NbO_x facilitated hydrogen spillover and created more oxygen vacancies on the WO_x surface upon hydrogen reduction, thus generating a higher density of Brønsted acid sites. This effect not only favored cellulose conversion to ethylene glycol but also promoted the hydrogenolysis of ethylene glycol to ethanol.

纤维素到乙醇的化学催化转化为生物燃料的生产提供了另一条途径，其理论碳收率可达 100%；然而，它面临着催化剂成本高和催化剂稳定性差的重大挑战。在这项工作中，我们报告了一种减少使用昂贵贵金属的新策略，即在低铂 Pt/WOx 催化剂表面装饰单核 NbOx。所得到的 0.1Nb/0.5Pt/WOx 催化剂的乙醇产率为 33.7%，乙二醇产率为 21.8%，贵金属效率达到 25.90 gethanol gPt-1 h-1，与文献相比提高了 2-10 倍。此外，通过单核氧化铌的装饰，催化剂的稳定性显著提高，至少可以循环使用 7 次而不会出现明显的活性衰减。表征结果表明，铂在亚纳米和单原子尺度上高度分散，用单核氧化铌修饰可促进氢溢出，并在氢还原时在 WOx 表面产生更多的氧空位，从而产生更高密度的布氏酸位点。这种效应不仅有利于纤维素转化为乙二醇，还能促进乙二醇氢解为乙醇。

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引用次数: 0

Preparation of methyl ethyl ketone from biomass-derived levulinic acid using a metal-free photocatalytic system and life cycle assessment study† 利用无金属光催化系统从生物质衍生的乙酰丙酸制备甲乙酮及生命周期评估研究

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc02798a

Meng-Xiang Shen , Chen-Qiang Deng , Jie Yang , Jin Deng

Levulinic acid (LA) is derived from lignocellulosic biomass and can undergo various chemical transformations to produce high-value chemicals. However, there are limited studies on C–C bond cleavage in LA. Methyl ethyl ketone (MEK) is a high-quality solvent with a wide range of industrial applications, traditionally produced from petroleum-derived n-butene. Here, we report a method for the production of MEK from LA using a metal-free photocatalytic system. Using acridine compounds as photosensitizers and thiophenols as hydrogen transfer reagents, high selectivity and yield of MEK are achieved under mild reaction conditions, and the reaction time is significantly shortened using a microchannel continuous flow photoreactor. Additionally, life cycle assessment indicates that this method has lower carbon emissions than other MEK production methods from LA. This catalytic system provides a green and efficient method to produce MEK from bio-based platform molecule LA, which meets the requirements of sustainable development.

乙酰丙酸（LA）来源于木质纤维素生物质，可通过各种化学转化生产高价值化学品。然而，关于左旋乙烯酸中 C-C 键裂解的研究还很有限。甲基乙基酮（MEK）是一种具有广泛工业用途的优质溶剂，传统上由石油衍生的正丁烯生产。在此，我们报告了一种利用无金属光催化系统从 LA 生产 MEK 的方法。利用吖啶化合物作为光敏剂，噻吩酚作为氢转移试剂，在温和的反应条件下实现了 MEK 的高选择性和高产率，并且利用微通道连续流光反应器大大缩短了反应时间。此外，生命周期评估表明，这种方法的碳排放量低于其他利用 LA 生产 MEK 的方法。该催化系统为从生物基平台分子 LA 生产 MEK 提供了一种绿色高效的方法，符合可持续发展的要求。

引用次数: 0

anti-Dihydroxylation of olefins enabled by in situ generated peroxyacetic acid† 利用原位生成的过氧乙酸实现烯烃的反二羟基化

IF 9.3 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Green Chemistry

Pub Date : 2024-09-30 DOI: 10.1039/d4gc03540b

Michael Tapera , Mohit Chotia , Jan Lukas Mayer-Figge , Adrián Gómez-Suárez , Stefan F. Kirsch

Herein, we report a general and green protocol for the anti-dihydroxylation of unactivated alkenes. Combining H₂O₂ and acetic acid at 50 °C results in the formation of peroxyacetic acid, which enables the efficient synthesis of a wide range of anti 1,2-diols in moderate to good yields without the need for hazardous solvents or expensive transition metals as catalysts.

在此，我们报告了一种用于未活化烯烃反二羟基化的通用绿色方案。将 H2O2 和乙酸在 50 °C的温度下结合会生成过氧乙酸，过氧乙酸能以中等到良好的产率高效合成各种抗 1,2-二醇，而无需使用有害溶剂或昂贵的过渡金属作为催化剂。

引用次数: 0

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