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Toward High Performance of Na4Fe3(PO4)2P2O7 Cathode via Constructing a Porous Structure for Sodium-Ion Batteries 通过构建钠离子电池用多孔结构实现 Na4Fe3(PO4)2P2O7 阴极的高性能
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-13 DOI: 10.1021/acssuschemeng.4c03547
Xiaochen Ge, Bowen Zhu, Liang He, Xu Wang, Yanqing Lai, Zhian Zhang
Sodium-ion batteries (SIBs) are a promising alternative to lithium-ion batteries for grid-scale energy-storage systems due to their low cost and abundant resource. Herein, Na4Fe3(PO4)2P2O7 with a porous structure was fabricated by a mechanochemical method. The porous structure and the uniform carbon coating layer of the material are beneficial to the electrolyte infiltration for better electron/ion transfer. The in situ and ex situ XRD analyses reveal that the cathode material undergoes an imperfect solid-resolution reaction during the charge/discharge process. The robust structural stability and high reversibility of the cathode material are attributed for the excellent rate performance and the long-term cycling life. The cathode material gives a high reversible capacity (124.5 mAh g–1 at 0.1 C), a superior rate performance (97.6 mAh g–1 at 50 C), and an excellent ultralong cycling life (capacity retention of 94.64% at 1 C after 1000 cycles and 93.98% at 10 C after 5000 cycles). Thus, the Na4Fe3(PO4)2P2O7 material with excellent electrochemical properties, low cost, and a simple synthesis method is a promising cathode electrode for SIBs.
钠离子电池(SIB)因其低成本和丰富的资源而成为电网级储能系统中锂离子电池的理想替代品。本文采用机械化学方法制备了具有多孔结构的 Na4Fe3(PO4)2P2O7。该材料的多孔结构和均匀的碳涂层有利于电解质的渗透,从而实现更好的电子/离子传输。原位和非原位 XRD 分析表明,阴极材料在充放电过程中发生了不完全的固溶反应。阴极材料的结构稳定性强、可逆性高,因此具有出色的速率性能和长期循环寿命。该阴极材料具有高可逆容量(0.1 摄氏度时为 124.5 mAh g-1)、卓越的速率性能(50 摄氏度时为 97.6 mAh g-1)和出色的超长循环寿命(1000 次循环后 1 摄氏度时容量保持率为 94.64%,5000 次循环后 10 摄氏度时容量保持率为 93.98%)。因此,Na4Fe3(PO4)2P2O7 材料具有优异的电化学性能、低成本和简单的合成方法,是一种很有前景的 SIB 阴极电极。
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引用次数: 0
AGREEMIP: The Analytical Greenness Assessment Tool for Molecularly Imprinted Polymers Synthesis AGREEMIP:分子印迹聚合物合成绿色分析评估工具
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-13 DOI: 10.1021/acssuschemeng.4c03874
Mariusz Marć, Wojciech Wojnowski, Francisco Pena-Pereira, Marek Tobiszewski, Antonio Martín-Esteban
Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years. However, although it is intuitively possible to design new green MIPs, it would be desirable to have a quantitative measure of the environmental impact of the changes introduced for their synthesis. In this regard, this work proposes, for the first time, a metric tool and software (termed AGREEMIP) to assess and compare the greenness of MIP synthesis procedures. AGREEMIP is based on 12 assessment criteria that correspond to the greenness of different reaction mixture constituents, energy requirements, and the details of MIP synthesis procedures. The input data of the 12 criteria are transformed into individual scores on a 0–1 scale that in turn produce an overall score through the calculation of the weighted average. The assessment can be performed using user-friendly open-source software, freely downloadable from mostwiedzy.pl/agreemip. The assessment result is an easily interpretable pictogram and visually appealing, showing the performance in each of the criteria, the criteria weights, and overall performance in terms of greenness. The application of AGREEMIP is presented with selected case studies that show good discrimination power in the greenness assessment of MIP synthesis pathways.
在催化、传感和分离/样品制备等需要高选择性的领域,分子印迹技术已得到广泛应用。然而,根据绿色化学原理,获得分子印迹聚合物(MIPs)所需的各种步骤显然远非理想。为此,近年来有人提出了合成分子印迹聚合物的绿色替代方法。然而,虽然直观上可以设计出新的绿色 MIP,但最好能对合成过程中引入的变化对环境的影响进行量化测量。为此,这项工作首次提出了一种度量工具和软件(称为 AGREEMIP),用于评估和比较 MIP 综合程序的绿色程度。AGREEMIP 基于 12 项评估标准,这些标准与不同反应混合物成分的绿色程度、能源需求和 MIP 合成程序的细节相对应。这 12 项标准的输入数据被转换成 0-1 级的单项分数,然后通过加权平均计算得出总分。评估可通过用户友好型开源软件进行,该软件可从 mostwiedzy.pl/agreemip 免费下载。评估结果是一个易于解释的图形,具有视觉吸引力,显示了每个标准的表现、标准权重以及绿色程度方面的总体表现。本文介绍了 AGREEMIP 的应用,并选取了在 MIP 合成途径的绿色度评估中显示出良好辨别能力的案例研究。
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引用次数: 0
Synergistically Modulating the Bay and Amid Sites of a Perylene Diimide Cathode Interface Layer for High-Efficiency and High-Stability Organic Solar Cells 协同调节二亚胺培林阴极界面层的海湾和舯部位点,实现高效率和高稳定性有机太阳能电池
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c03854
Jianru Wang, Dan Zhou, Jianwei Quan, Senmei Lan, Fang Wang, Lin Hu, Wentian Wan, Yongfen Tong, Bin Hu, Ruizhi Lv, Haitao Xu, Zaifang Li, Lie Chen
Simultaneously enhancing the power conversion efficiency (PCE) and stability of organic solar cells (OSCs) is a pivotal issue to advance their commercial feasibility. The frequently used cathode interface layer (CIL) based on perylene diimide (PDI) derivatives usually causes some problems, such as unmatched surface energies (γs) with an active layer, strong aggregation, and poor stability. Herein, the bay and amide position synergistically benzoyl hydrazide-functionalized PDI-based CILs, namely PDI-4NOPN and PDINN-NOPN, have been designed and synthesized. Compared with PDI-4NOPN with a PCE of 14.85%, the PDINN-NOPN-applied OSCs display a higher PCE of 17.37% (PM6: BTP-eC9) with more excellent device stabilities under diverse conditions. Furthermore, PDINN-NOPN demonstrates an impressive level of insensitivity to thickness, maintaining a PCE over 92% even when the thickness is up to 19 nm, which is attributed to the powerful self-doping effect, superior work function (Wf) modulating capability, excellent morphology and proper crystallinity, and the low impedance of PDINN-NOPN. The inferior performance observed in PDI-4NOPN is ascribed to the decrease of electron cloud distribution resulting from an excess of carbonyl groups. Carbonyl groups intensify the electron-withdrawing characteristic of the benzoyl groups, consequently impeding the charge transfer process. Thus, collaboratively optimizing the bay and amid sites of PDI represents a practical approach for achieving high-efficiency, high-stability, and thickness-insensitive OSCs.
同时提高有机太阳能电池(OSC)的功率转换效率(PCE)和稳定性是推动其商业可行性的关键问题。常用的基于过二亚胺(PDI)衍生物的阴极界面层(CIL)通常会产生一些问题,如与活性层的表面能量(γs)不匹配、聚集性强、稳定性差等。本文设计并合成了苯甲酰肼功能化的畦位和酰胺位协同 PDI 基 CIL,即 PDI-4NOPN 和 PDINN-NOPN。与 PCE 为 14.85% 的 PDI-4NOPN 相比,应用 PDINN-NOPN 的 OSCs 的 PCE 高达 17.37%(PM6:BTP-eC9),并且在各种条件下具有更出色的器件稳定性。此外,PDINN-NOPN 对厚度的不敏感性也令人印象深刻,即使厚度达到 19 nm,其 PCE 仍能保持在 92% 以上,这归功于 PDINN-NOPN 强大的自掺杂效应、出色的功函数(Wf)调节能力、优异的形貌和适当的结晶度以及低阻抗。在 PDI-4NOPN 中观察到的较差性能是由于过量的羰基导致电子云分布减少。羰基增强了苯甲酰基的电子吸收特性,从而阻碍了电荷转移过程。因此,协同优化 PDI 的海湾和酰胺位点是实现高效率、高稳定性和对厚度不敏感的 OSC 的一种实用方法。
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引用次数: 0
Biocatalytic Synthesis of Two Furan-Based Amino Compounds 2-Acetyl-4-aminofuran and 3-Acetylamino-5-(α-aminoethyl)-furan from Chitin Resources 从甲壳素资源中生物催化合成两种呋喃基氨基化合物 2-乙酰基-4-氨基呋喃和 3-乙酰氨基-5-(α-氨基乙基)-呋喃
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c01435
Chaoqiang Wu, Xin Zhang, Wei Liu, Chengyong Wang, Qianqian Jiang, Feifei Chen, Quanzhen Liu, Fei Cao, Gaowei Zheng, Alei Zhang, Kequan Chen
Chitin, as the second most abundant biomass in nature, possesses 7 wt % biologically fixed nitrogen, and its direct valorization into valuable nitrogen (N)-containing chemicals is optimal. Herein, we report the biosynthesis of two specific furan-based amine compounds, 2-acetyl-4-aminofuran (2A4AF) and 3-acetylamino-5-(α-aminoethyl)-furan (3A5AEF), from chitin-derived 3-acetamido-5-acetylfuran (3A5AF) via biocatalytic deacetylation and reduction amination, respectively. An amidase (MmH) from Starkeya sp. and an R-selective aminotransferase (ATA117) from Arthrobacter sp. were obtained, which can, respectively, convert 3A5AF to 2A4AF with a yield of 79.3% (47.58 mM) and (R)-3A5AEF (enantiomeric excess (ee) value of >99%) with a yield of 84.0% (126 mM), respectively, under the optimal conditions. The biosynthesis efficiency of the two amines was high in comparison with chemical approaches. This work paves the way for green and efficient production of furan-based amino chemicals from inexpensive renewable chitin resources.
甲壳素是自然界中含量第二丰富的生物质,具有 7 wt % 的生物固定氮,将其直接转化为有价值的含氮(N)化学品是最佳选择。在此,我们报告了通过生物催化脱乙酰化和还原胺化,分别从甲壳素衍生的3-乙酰氨基-5-乙酰基呋喃(3A5AF)生物合成两种特定的呋喃基胺化合物,即2-乙酰基-4-氨基呋喃(2A4AF)和3-乙酰氨基-5-(α-氨基乙基)-呋喃(3A5AEF)。在最佳条件下,获得了来自Starkeya sp.的氨化酶(MmH)和来自Arthrobacter sp.的R-选择性氨基转移酶(ATA117),它们可分别将3A5AF转化为2A4AF(产率为79.3%(47.58 mM))和(R)-3A5AEF(对映体过量(ee)值为>99%),产率为84.0%(126 mM)。与化学方法相比,这两种胺的生物合成效率很高。这项工作为利用廉价的可再生甲壳素资源绿色、高效地生产呋喃基氨基化学品铺平了道路。
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引用次数: 0
Novel Carbonated Materials: The Synergistic Role of MgO in Partially Calcined Limestone 新型碳化材料:部分煅烧石灰石中氧化镁的协同作用
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c00544
Xinyu Zhou, Xiong Qian, Yukun Qin, Chuanlin Hu, Zhichao Liu, Fazhou Wang
The rise of modern Portland cement has relegated lime to a secondary role in the construction industry, now mainly used for repairing and restoring historical buildings. This study proposes an innovative application of partially calcined limestone (PCL) as a carbonated material. The impact of varying MgO dosages on the carbonation mechanism of PCL is explored. It is found that a 5% MgO dosage significantly enhances the 1 d compressive strength postcarbonation by over 84.7%. The critical role of hydrated MgCO3, produced from MgO, in the formation and crystallinity of CaCO3 is highlighted. However, it is observed that excessive MgO can impede carbonation, negatively impacting the mechanical properties and pore structure of the material. The presence of MgCO3·3H2O is noted to significantly influence the compressive strength of the carbonated material. Potential pathways for dolomite formation in PCL with different MgO dosages are suggested, indicating new possibilities for creating high-performance, low-carbon cementitious materials.
现代波特兰水泥的兴起使石灰在建筑业中退居次要地位,目前主要用于修缮和修复历史建筑。本研究提出了部分煅烧石灰石(PCL)作为碳化材料的创新应用。研究探讨了不同氧化镁用量对 PCL 碳化机制的影响。研究发现,5% 的氧化镁用量可将碳化后 1 d 的抗压强度显著提高 84.7% 以上。由 MgO 生成的水合 MgCO3 在 CaCO3 的形成和结晶中的关键作用得到了强调。然而,观察发现过量的氧化镁会阻碍碳化,对材料的机械性能和孔隙结构产生负面影响。据指出,MgCO3-3H2O 的存在会显著影响碳化材料的抗压强度。研究提出了不同氧化镁用量的 PCL 中白云石形成的潜在途径,为创造高性能、低碳的水泥基材料提供了新的可能性。
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引用次数: 0
Research on Toughening Polylactic Acid by an Epoxy Soybean Oil Curing Network Based on Dynamic Cross-Linking 基于动态交联的环氧大豆油固化网络增韧聚乳酸的研究
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c03569
Feng Zhao, Ruilong Xu, Xu Zhang, Jiawang Zheng, Wei Liu, Shuai Zhao, Lin Li
In this study, our primary focus was the efficient synthesis of epoxidized soybean oil and anhydrous citric acid within a polylactic acid (PLA) matrix through a ring-opening reaction catalyzed by zinc acetate. Our objective was to establish a dynamic and reversible ester exchange network. Subsequently, we introduced the cured epoxidized soybean oil network into the PLA matrix through dynamic cross-linking, aiming to enhance the compatibility of epoxidized soybean oil within the PLA matrix. This process resulted in the preparation of a series of PLA composites characterized by improved toughness. We conducted a comprehensive analysis of the influence of various carboxyl/epoxy equivalent ratios (R values) on the mechanical properties, thermal characteristics, and chemical structures of the PLA composites. Our findings demonstrated that, during the dynamic cross-linking process, both epoxidized soybean oil and citric acid underwent ring-opening reactions and chain reactions with the PLA matrix, culminating in the formation of a well-defined network cross-linking structure. These chain reactions within the system significantly enhanced the internal compatibility of the blends. Our experimental results conclusively indicated that optimal toughness was achieved when the R value was set to 0.1, with the addition of 5 parts per hundred resin (phr). This configuration resulted in an elongation at break of 315% and an impact strength of 28.5 kJ/m2.
在这项研究中,我们的主要重点是通过醋酸锌催化的开环反应,在聚乳酸(PLA)基质中高效合成环氧化大豆油和无水柠檬酸。我们的目标是建立一个动态、可逆的酯交换网络。随后,我们通过动态交联将固化的环氧化大豆油网络引入聚乳酸基质,目的是提高环氧化大豆油在聚乳酸基质中的相容性。通过这一过程,制备出了一系列聚乳酸复合材料,其特点是韧性得到了改善。我们全面分析了各种羧基/环氧当量比(R 值)对聚乳酸复合材料机械性能、热特性和化学结构的影响。我们的研究结果表明,在动态交联过程中,环氧化大豆油和柠檬酸都与聚乳酸基体发生了开环反应和链反应,最终形成了明确的网络交联结构。系统内的这些链式反应大大提高了混合物的内部相容性。实验结果表明,当 R 值设定为 0.1,树脂添加量为百份之五(phr)时,韧性达到最佳。这种配置使断裂伸长率达到 315%,冲击强度达到 28.5 kJ/m2。
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引用次数: 0
Amine-Modified Polyacrylonitrile as Catalysts for the C–C Coupling of Furfural to High-Carbon Fuel Precursors 胺改性聚丙烯腈作为糠醛与高碳燃料前体的 C-C 偶联催化剂
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c03684
Xiaoxia Zheng, Yinwei Wang, Xiao Feng, Jieqi Cao, Xinbin Gong, Chun Gu, Xinhong Wang, Song Shi
With the deepening of the concept of sustainable development and the development of green chemistry, heterogeneous base catalysts have attracted widespread attention due to their particular strengths such as low corrosion, separability, and easy recovery. Here, we report various types of amine-modified polyacrylonitriles (PANs), which are found to be highly active in the C–C coupling process. Such catalysts are more active than homogeneous catalysts in upgrading biomass platform-derived molecules such as furfural to high-carbon fuel precursors. A highly selective C14 fuel precursor of 85% was obtained through the C–C coupling reaction of 2-butanone and furfural at a lower temperature. A precursor with a carbon number of 9–16 is obtained by coupling furfural with a C3–C6 carbon-based compound and has a high yield. In addition, we loaded 1,3-propanediamine onto polyacrylonitrile fibers (PANFs) and used it in the reaction of furfural and cyclohexanone with high yields. It provides a new idea for the heterogeneous base catalysis of the aldol condensation reaction.
随着可持续发展理念的深入和绿色化学的发展,异相基催化剂因其低腐蚀性、可分离性和易回收性等特殊优势而受到广泛关注。在此,我们报告了各种类型的胺改性聚丙烯腈(PANs),发现它们在 C-C 偶联过程中具有很高的活性。在将糠醛等生物质平台衍生分子升级为高碳燃料前体方面,此类催化剂比均相催化剂更活跃。在较低温度下,通过 2-丁酮和糠醛的 C-C 偶联反应,可获得 85% 的高选择性 C14 燃料前体。通过糠醛与 C3-C6 碳基化合物的偶联反应,可获得碳数为 9-16 的前体,且收率较高。此外,我们还将 1,3-丙二胺负载到聚丙烯腈纤维(PANF)上,并将其用于糠醛和环己酮的反应,收率很高。这为醛醇缩合反应的异构碱催化提供了新思路。
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引用次数: 0
Unraveling the Textile Pollution Problem with Li5FeO4 as a Bifunctional Material for Hydrogen Production and COx Capture: From Glucose to Cotton Pyrolysis 用 Li5FeO4 作为制氢和二氧化碳捕集的双功能材料来解决纺织品污染问题:从葡萄糖到棉花热解
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c03359
Nan Wang, Carlos Hernández-Fontes, Wilmer Esteban Vallejo Narváez, Serguei Fomine, Heriberto Pfeiffer
Enhancing biomass pyrolysis to produce hydrogen, via catalysis and carbon oxides sorption, presents a potential energy solution while mitigating COx emissions. In the present work, Li5FeO4 was tested for the pyrolysis reaction of efficient hydrogen production from different biomass sources, such as glucose, cellulose, and various kinds of cotton. The pyrolytic process utilizes catalytic effects and COx sorption enhancements to provide maximum hydrogen production and minimum greenhouse gas emissions, in order to solve the resource utilization of textile biomass. Initially, a systematic glucose pyrolysis screening, as a model molecule, was conducted to analyze different conditioning parameters, such as heating rate (HR), biomass-to-catalyst ratio, and N2 flow rate. In the Li5FeO4 presence, the glucose pyrolytic temperature was reduced from 340 to 130–230 °C, and hydrogen production increased by 2.5–4.9 times. Furthermore, solid residue analyses verified that Li5FeO4 effectively captures carbon oxides, through the lithium carbonate formation. Complementarily, density functional theory explains how Li5FeO4 enhances hydrogen production by studying dissociation bond energies. Based on all these results, additional biomass substrates were tested in the Li5FeO4 presence, exhibiting efficient hydrogen generations. Complementarily, kinetic calculations showed that biomass pyrolysis activation energies were significantly reduced in the ceramic presence. This substantiates the efficacy of Li5FeO4 as a catalyst and carbon dioxide sorbent, particularly in the context of hydrogen production from textile cotton through the so-called sorption-enhanced mechanisms.
通过催化和碳氧化物吸附来提高生物质热解产氢,是一种潜在的能源解决方案,同时还能减少二氧化碳的排放。本研究测试了 Li5FeO4 在不同生物质(如葡萄糖、纤维素和各种棉花)热解反应中的高效制氢能力。该热解过程利用催化效应和 COx 吸附增强效应提供最大的氢气产量和最小的温室气体排放,以解决纺织生物质的资源利用问题。首先,以葡萄糖热解为模型分子进行了系统筛选,分析了不同的调节参数,如加热速率(HR)、生物质与催化剂的比例和 N2 流量。在 Li5FeO4 存在的情况下,葡萄糖热解温度从 340 ℃ 降至 130-230 ℃,产氢量增加了 2.5-4.9 倍。此外,固体残留物分析验证了 Li5FeO4 能通过碳酸锂的形成有效捕获碳氧化物。此外,密度泛函理论通过研究解离键能解释了 Li5FeO4 如何提高氢气产量。基于所有这些结果,在 Li5FeO4 存在的情况下测试了其他生物质基质,结果表明这些基质能高效产生氢气。此外,动力学计算表明,在陶瓷存在的情况下,生物质热解活化能显著降低。这证实了 Li5FeO4 作为催化剂和二氧化碳吸附剂的功效,特别是在通过所谓的吸附增强机制从纺织棉制氢的情况下。
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引用次数: 0
Shrimp Shell-Derived Chitin Nanofibers as Shale Inhibitors in Water-Based Drilling Fluids 虾壳衍生甲壳素纳米纤维作为水基钻井液中的页岩抑制剂
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c01228
Jingping Liu, Yecheng Li, Kaihe Lv, Jinsheng Sun, Ziyan Li, Liyao Dai, Haokun Shen, Zhibo Wen, Xinyue Liu, Chaozheng Liu, Mei-Chun Li
To address shale wellbore instability and promote sustainable development in the oil and gas drilling industry, chitin nanofibers (ChNFs) were extracted from shrimp shells and employed as environmentally friendly shale inhibitors for the first time. Two types of ChNFs, namely, 2,2,6,6-tetramethylpiperidinooxy (TEMPO)-mediated oxidized ChNFs (T-ChNFs) and deacetylated T-ChNFs (DT-ChNFs), were prepared through TEMPO-mediated oxidation of shrimp shell-derived chitin and partial deacetylation of obtained T-ChNFs, respectively. Due to the abundance of hydroxyl, carboxyl, and amide groups, both T-ChNFs and DT-ChNFs formed hydrogen bonds with clay particles, adsorbed on the shale surface, and thereby demonstrated superior shale inhibition capacity than the conventional shale inhibitor potassium chloride (KCl). Moreover, T-ChNFs and DT-ChNFs were capable of replacing interlayer water through intercalation, effectively inhibiting water invasion into the interlayer. DT-ChNFs with positive charges on the surface exhibited enhanced shale inhibition properties due to more effective adsorption on the shale surface through electrostatic interactions. Additionally, T-ChNFs and DT-ChNFs showed favorable compatibility with bentonite water-based drilling fluids (BT-WDFs). The addition of ChNFs significantly improved the rheological properties of the BT-WDFs without compromising their filtration properties. In contrast, the inclusion of KCl in BT-WDFs resulted in a substantial decline in filtration performance.
为解决页岩井筒不稳定问题,促进油气钻井行业的可持续发展,首次从虾壳中提取甲壳素纳米纤维(ChNFs),并将其用作环境友好型页岩抑制剂。通过TEMPO介导的虾壳甲壳素氧化和T-ChNFs的部分脱乙酰化,分别制备了两种类型的甲壳素纳米纤维,即2,2,6,6-四甲基哌啶氧(TEMPO)介导的氧化甲壳素纳米纤维(T-ChNFs)和脱乙酰化甲壳素纳米纤维(DT-ChNFs)。由于含有丰富的羟基、羧基和酰胺基,T-ChNFs 和 DT-ChNFs 都能与粘土颗粒形成氢键,吸附在页岩表面,从而表现出比传统页岩抑制剂氯化钾(KCl)更优越的页岩抑制能力。此外,T-ChNFs 和 DT-ChNFs 还能通过插层作用取代层间水,有效抑制水侵入层间。表面带正电荷的 DT-ChNFs 通过静电作用更有效地吸附在页岩表面,从而增强了页岩抑制性能。此外,T-ChNFs 和 DT-ChNFs 与膨润土水基钻井液(BT-WDFs)具有良好的兼容性。ChNFs 的加入大大改善了 BT-WDFs 的流变特性,而不会影响其过滤特性。相反,在 BT-WDF 中加入 KCl 会导致过滤性能大幅下降。
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引用次数: 0
A Preblocking Strategy with Rapid Immobilization of Nitrile Hydratase and Precise Control of Hydrophobic Microenvironment for High Regioselective Amide Transformation 快速固定腈水解酶并精确控制疏水性微环境的预阻塞策略,实现高区域选择性酰胺转化
IF 8.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-12 DOI: 10.1021/acssuschemeng.4c01723
Jicheng Dong, Xuesong Wu, Wenyan Weng, Fang Cheng, Lijun Zhang, Chunmei Li, Li Wang, Changhai Liang, Gang Cheng
The control over enzyme immobilization and its microenvironment at the molecular level is deemed crucial. In this study, a “preblocking” method was performed through the use of natural polymer agarose resins after activation by phenyl-, methyl-, and ethyl-vinyl sulfones combined with divinyl sulfones prior to the specific immobilization of a his-tag fused recombinant nitrile hydratase (ReNHase). This technique primarily allows for the establishment of a hydrophobic microenvironment to enhance the immobilization and mass transfer and avoid inactivation caused by traditional backfilling. The purified ReNHase showed specific activity and regioselectivity of adiponitrile in an aqueous solution as 28.43 U·mg–1 and 90.2%, respectively. Increasing the density of hydrophobic groups promotes the adsorption extent and immobilization yield of ReNHase. Optimized DVS:PVS 1:4 hydrophobic microenvironment could finish immobilization in 4h. Eminent expressed activity and regioselectivity of 94.6% and 93.9% was exhibited, respectively. The approach demonstrated exceptional selectivity in the biotransformation at the molecular level. Furthermore, the method was found to preserve enzymatic activity over seven cycles and exhibited significantly enhanced resilience to variations in the temperature and substrate concentration. The ReNHase@DVS:PVS 1:4 still retained 98% of the maximum activity, while ReNHase only retained 64% of activity at 55 °C. The ReNHase@DVS:PVS 1:4 still retained 55% of the maximum activity, while ReNHase was completely inactive at 200 mM adiponitrile. A packed-bed reactor was constructed, where the biotransformation of 5.64 g of 5-cyanovaleramide was carried out continuously for 48 h at a flow rate of 0.60 mL/min, achieving a peak space-time yield reported to be 0.93 mol·h–1·L–1. The “preblocking” technique developed in this study is anticipated to provide new methodology in the catalysis of hydrophobic substrates.
在分子水平上控制酶的固定及其微环境被认为是至关重要的。在本研究中,使用天然聚合物琼脂糖树脂,通过苯基、甲基和乙基乙烯基砜与二乙烯基砜活化后,采用 "预阻塞 "方法,对融合 his 标记的重组腈水解酶(ReNHase)进行特定固定。这种技术主要是建立疏水性微环境,以加强固定和传质,避免传统回填造成的失活。纯化的 ReNHase 在水溶液中对己二腈的比活度和区域选择性分别为 28.43 U-mg-1 和 90.2%。增加疏水基团的密度可提高 ReNHase 的吸附范围和固定化率。优化后的 DVS:PVS 1:4 疏水微环境可在 4 小时内完成固定化。其表达活性和区域选择性分别达到了 94.6% 和 93.9%。该方法在分子水平的生物转化中表现出了卓越的选择性。此外,该方法还能在七个周期内保持酶活性,并对温度和底物浓度的变化表现出显著的适应性。ReNHase@DVS:PVS 1:4 仍保留了 98% 的最大活性,而 ReNHase 在 55 °C 时仅保留了 64% 的活性。ReNHase@DVS:PVS 1:4 仍保留了 55% 的最大活性,而 ReNHase 在 200 mM 己二腈条件下完全失去活性。我们建造了一个填料床反应器,以 0.60 mL/min 的流速对 5.64 g 5-氰基戊酰胺连续进行了 48 小时的生物转化,据报道,达到的峰值时空产率为 0.93 mol-h-1-L-1。本研究开发的 "预阻塞 "技术有望为催化疏水性底物提供新的方法。
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