Separation and Purification Technology最新文献_第4页

Design of mixed ionic liquid extractant and study on process intensification for separation of isopropanol and n-hexane from wastewater 设计混合离子液体萃取剂并研究从废水中分离异丙醇和正己烷的强化工艺

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-25 DOI: 10.1016/j.seppur.2024.129884

The separation of the ternary azeotrope system is still a topic worth studying. An effective method based on a mixed ionic liquids (ILs) extractant was proposed and applied to the separation of isopropanol (IPA), n-hexane (NH) and water (H₂O) systems. Firstly, the organic solvent and ILs with better separation effects for the two components of the ternary azeotropic system were screened out by relative volatility calculation, quantum chemistry and molecular dynamics calculation. Based on the synergistic effect of dimethyl sulfoxide (DMSO) and 1-ethyl-3-methylimidazolium thiocyanate ([EMIMSCN]), a mixed ILs extractant was designed. It was then applied to three extractive distillation (ED) processes. Aiming at the minimum total process cost and gas emission, an optimization strategy was designed to achieve multi-objective optimization of process flow, the optimal composition and dosage of the mixed extractant were determined. The process results showed that the total annual cost (TAC) and gas emissions from mixed extractive distillation (MED) were 795406.85 $/y and 1536.84 kg/y, and the process energy consumption was 1987.99 kW. Compared with the ED process with DMSO as an extractant, the MED process can save 40.05 % TAC and reduce 30.39 % gas emission and energy consumption. The mixed extractant was carefully studied, and the addition of ILs was analyzed to increase the relative volatility between IPA and H₂O separated by the extractant. The sensitivity analysis of the key variables of the MED process was carried out. The results show that the feed position of the extractant has the greatest influence on the objective function. Finally, the MED and the mixed extractive distillation under reduced pressure (RPMED) process were intensified, and the heat pump coupled thermal integrated Heat-integrated mixed extractive distillation (HPH-MED) process was determined to be the best process based on environmental pollution and energy consumption considerations. The TAC of the process is 767298.474 $/y, the gas emission is 753.84 kg/y, and the energy consumption of the process is 975.13 kW. Compared with the MED process, TAC is reduced by 3.53 %, and total gas emissions and energy consumption are reduced by 50.95 %.

三元共沸体系的分离仍然是一个值得研究的课题。本研究提出了一种基于混合离子液体（ILs）萃取剂的有效方法，并将其应用于异丙醇（IPA）、正己烷（NH）和水（H2O）体系的分离。首先，通过相对挥发度计算、量子化学和分子动力学计算，筛选出对三元共沸体系中两组分分离效果较好的有机溶剂和离子液体。基于二甲基亚砜（DMSO）和1-乙基-3-甲基咪唑硫氰酸盐（[EMIMSCN]）的协同效应，设计了一种混合ILs萃取剂。然后将其应用于三种萃取蒸馏（ED）工艺。以工艺总成本和气体排放量最小为目标，设计了一种优化策略来实现工艺流程的多目标优化，并确定了混合萃取剂的最佳成分和用量。工艺结果表明，混合萃取精馏（MED）的年总成本（TAC）和气体排放量分别为 795406.85 美元/年和 1536.84 千克/年，工艺能耗为 1987.99 千瓦。与以 DMSO 为萃取剂的 ED 工艺相比，MED 工艺可节省 40.05 % 的 TAC，减少 30.39 % 的气体排放和能耗。对混合萃取剂进行了仔细研究，并分析了添加 ILs 以增加萃取剂分离出的 IPA 和 H2O 之间的相对挥发性。对 MED 工艺的关键变量进行了敏感性分析。结果表明，萃取剂的进料位置对目标函数的影响最大。最后，强化了 MED 和减压混合萃取蒸馏（RPMED）工艺，并根据环境污染和能源消耗方面的考虑，确定热泵耦合热集成混合萃取蒸馏（HPH-MED）工艺为最佳工艺。该工艺的 TAC 为 767298.474 美元/年，气体排放量为 753.84 千克/年，能耗为 975.13 千瓦。与 MED 工艺相比，TAC 降低了 3.53%，气体排放总量和能耗降低了 50.95%。

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引用次数: 0

Selective oxidation of organic pollutants by unactivated and carbonate-activated peroxymonosulfate (PMS): Mechanism, kinetics, and transformation pathway 未活化和碳酸盐活化过一硫酸盐（PMS）对有机污染物的选择性氧化：机理、动力学和转化途径

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129472

Although the activation mechanisms of peroxymonosulfate (PMS) by various homogeneous and heterogeneous catalysts have been reported, the chemistry of PMS in catalyst-free systems and its interaction with background oxygenated anions remains poorly understood. In this study, the unactivated PMS and carbonate-activated PMS (CO₃^2–/PMS) systems for removal of various organic pollutant (including oxytetracycline (OTC), metronidazole (MNZ), methylene blue (MB), and acid orange G (OG)) were investigated. The results showed that 74.5 %, 90.21 %, 1.22 %, and 2.25 % of OTC, MB, OG, and MNZ were removed, respectively within 180 min in the unactivated PMS system due to the formation of ·OH and ¹O₂. 95.88 %, 100 %, 100 %, and 6.09 % of OTC, MB, OG, and MNZ were removed, respectively in the CO₃^2–/PMS system, which is primary due to the generation of ¹O₂. The removal efficiencies of these four pollutants were significantly improved under alkaline conditions. In addition, the TOC removal rates were 21.88 % for MB and 26.53 % for OTC within 180 min in the CO₃^2–/PMS system. The presence of Cl⁻ and SO₄²⁻ can greatly enhance the OTC removal efficiency both in the unactivated and CO₃^2–/PMS systems. Through the high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis, OTC degradation products in the unactivated PMS and CO₃^2–/PMS systems were identified, revealing six different reaction mechanisms, including hydroxylation (+16 Da), decarbonylation (−28 Da), demethylation (−14 Da), secondary alcohol oxidation (−2 Da), deamination (−15 Da), and dehydration (−18 Da). This study provides insight into the reaction mechanism of catalyst-free PMS systems and may promote the application of unactivated PMS and CO₃^2–/PMS systems for the remediation of organic contaminated water.

尽管各种均相和异相催化剂对过氧化单硫酸盐（PMS）的活化机制已有报道，但人们对无催化剂体系中 PMS 的化学性质及其与背景含氧阴离子的相互作用仍知之甚少。本研究调查了未活化的 PMS 和碳酸盐活化的 PMS（CO32-/PMS）体系去除各种有机污染物（包括土霉素（OTC）、甲硝唑（MNZ）、亚甲基蓝（MB）和酸性橙 G（OG））的情况。结果表明，在未活化的 PMS 系统中，由于 -OH 和 1O2 的形成，OTC、MB、OG 和 MNZ 在 180 分钟内分别被去除 74.5%、90.21%、1.22% 和 2.25%。在 CO32-/PMS 系统中，OTC、MB、OG 和 MNZ 的去除率分别为 95.88%、100%、100% 和 6.09%，这主要是由于生成了 1O2。在碱性条件下，这四种污染物的去除率明显提高。此外，在 CO32-/PMS 系统中，180 分钟内 MB 和 OTC 的总有机碳去除率分别为 21.88% 和 26.53%。在未活化和 CO32-/PMS 系统中，Cl- 和 SO42- 的存在可大大提高 OTC 的去除效率。通过高效液相色谱-质谱（HPLC-MS）分析，确定了未活化 PMS 和 CO32-/PMS 系统中的 OTC 降解产物，揭示了六种不同的反应机制，包括羟基化（+16 Da）、脱羰基化（-28 Da）、脱甲基化（-14 Da）、仲醇氧化（-2 Da）、脱氨（-15 Da）和脱水（-18 Da）。这项研究深入揭示了无催化剂 PMS 系统的反应机理，可促进未活化 PMS 和 CO32-/PMS 系统在有机污染水体修复中的应用。

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引用次数: 0

Chemically bonded Co2P-Cu3P heterostructure nanoparticles on porous carbon framework as efficient hydrogen evolution/oxidation electrocatalysts 多孔碳框架上的化学键合 Co2P-Cu3P 异质结构纳米粒子作为高效氢气进化/氧化电催化剂

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129863

Exploring economical and efficient catalysts for hydrogen evolution/oxidation reaction (HER/HOR) is very crucial for water splitting and fuel-cells applications. Constructing transition metal phosphides heterostructures is a representative strategy to accelerate kinetics. Herein, we designed Co₂P-Cu₃P heterostructure particles on a porous carbon skeleton (Co₂P-Cu₃P/C) for the HER/HOR. The Co₂P-Cu₃P/C possesses a suitable specific surface area, an optimized electronic structure, and strong chemical bridge bonds (C-P-Co(Cu)) between porous carbon skeleton and Co₂P-Cu₃P nanoparticles, resulting in a substantial increase in its HER/HOR activity and enhanced stability. Therefore, Co₂P-Cu₃P/C only requires a low overpotential of 90 mV to reach a current density of 10 mA cm⁻² with a low Tafel slope of 53.5 mV dec^-1, and it can maintain the HER over long-term (72 h). Moreover, Co₂P-Cu₃P/C also has potential in applications due to its excellent HER performance. Furthermore, the Co₂P-Cu₃P/C exhibits a superior intrinsic activity of 1.19 mA cm⁻² and excellent durability (500 min) for the HOR. Density functional theory calculations indicate that the interfacial effect between Co₂P and Cu₃P at the heterogeneous interfaces contributes to the enhanced HER/HOR performance.

探索经济高效的氢进化/氧化反应（HER/HOR）催化剂对于水分离和燃料电池的应用至关重要。构建过渡金属磷化物异质结构是加速动力学的一种代表性策略。在此，我们在多孔碳骨架上设计了用于 HER/HOR 的 Co2P-Cu3P 异质结构颗粒（Co2P-Cu3P/C）。Co2P-Cu3P/C 具有合适的比表面积、优化的电子结构以及多孔碳骨架与 Co2P-Cu3P 纳米颗粒之间的强化学桥键（C-P-Co(Cu)），从而大幅提高了其 HER/HOR 活性并增强了稳定性。因此，Co2P-Cu3P/C 只需要 90 mV 的低过电位就能达到 10 mA cm-2 的电流密度和 53.5 mV dec-1 的低塔菲尔斜率，并能长期（72 小时）保持 HER。此外，Co2P-Cu3P/C 也因其优异的 HER 性能而具有应用潜力。此外，Co2P-Cu3P/C 还表现出 1.19 mA cm-2 的优异本征活性和出色的 HOR 耐久性（500 分钟）。密度泛函理论计算表明，异质界面上 Co2P 和 Cu3P 之间的界面效应有助于增强 HER/HOR 性能。

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引用次数: 0

Kinetic insights into energy-saving and low-carbon reactive distillation processes for the transesterification to dimethyl carbonate 节能低碳反应蒸馏工艺在酯交换制碳酸二甲酯过程中的动力学启示

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129745

The transesterification of propylene carbonate (PC) or ethylene carbonate (EC) to dimethyl carbonate (DMC) by using catalytic reactive distillation (RD) is a promising approach for carbon dioxide utilization. However, there is still scarcity of comprehensive comparison between the two RD processes. Hence, using the UNIQUAC model and kinetics calibrated by literature and our experiments, we conduct an extensive comparison of the two RD processes. Based on the kinetic insights, laboratory RD processes for both reactions are modeled, analyzed, and experimentally validated. Consequently, two RD processes designed to produce 60 ktpy of DMC are optimized and compared. The interplay and control factors between reaction and separation are elucidated and clarified via investigating variations of the actual chemical equilibrium constant profile compared with theoretical values along the reactive section at various pressures, liquid holdups, etc. The results reveal that the optimized EC RD process achieves almost 50 % reductions in both total annual cost and carbon dioxide emission compared to the PC RD process. This work facilitates the carbon neutrality and provides an essential guide for quantitatively assessing the two routes.

利用催化反应蒸馏（RD）将碳酸丙烯酯（PC）或碳酸乙烯酯（EC）酯化为碳酸二甲酯（DMC）是一种很有前景的二氧化碳利用方法。然而，目前仍缺乏对这两种 RD 工艺的全面比较。因此，我们利用 UNIQUAC 模型以及经文献和实验校准的动力学，对两种 RD 过程进行了广泛的比较。根据动力学见解，我们对两种反应的实验室 RD 过程进行了建模、分析和实验验证。因此，我们对设计用于生产 60 ktpy DMC 的两种 RD 工艺进行了优化和比较。通过研究在不同压力、液体截留等条件下，反应段的实际化学平衡常数曲线与理论值的比较变化，阐明并澄清了反应与分离之间的相互作用和控制因素。结果表明，与 PC RD 工艺相比，经过优化的 EC RD 工艺在年度总成本和二氧化碳排放量方面都减少了近 50%。这项工作有助于实现碳中和，并为定量评估这两种工艺提供了重要指导。

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引用次数: 0

A highly stable metal–organic framework via pore aromatization for efficient natural gas purification with record C3H8 and C2H6 uptake 通过孔隙芳香化实现高效天然气净化的高稳定性金属有机框架，具有创纪录的 C3H8 和 C2H6 吸收能力

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129824

Selective capture of C₃H₈ and C₂H₆ from CH₄ is extremely key in natural gas purification, but there is a trade-off between uptake and selectivity. Herein, we proposed a method for pore aromatization to build an ultramicroporous metal–organic framework Ni(ndc)(dabco)_0.5 with a robust structure and examine its separation performance for C₃H₈/CH₄ and C₂H₆/CH₄ mixtures. The pore walls of the material are composed of opposite and parallel naphthalene rings with a pore size of 6.0 Å and rich electronegative binding sites, and the overlapping areas between naphthalene rings form extremely strong potential energy overlaps. This MOF owns a record C₃H₈ and C₂H₆ uptake (91.4 and 46.5 cm³(STP) g⁻¹) in actual natural gas components at 298 K and 0.05 and 0.1 bar respectively with excellent C₃H₈ (119.0 cm³(STP) g⁻¹) and C₂H₆ (116.6 cm³(STP) g⁻¹) and 1.0 bar, presenting a strong binding ability toward C₃H₈ and C₂H₆. Meanwhile, the IAST-predicted C₃H₈/CH₄ (1947.4) and C₂H₆/CH₄ (42.6) selectivity is also superior to all adsorbents so far, only inferior to BSF-2, thus overcoming the aforementioned trade-off and setting a novel benchmark. The theoretical studies imply that the enhanced C₃H₈ and C₂H₆ adsorption performance is attributed to the aromatized ultramicropores modified by dense low-polarity naphthalene rings, causing a strong affinity for the two gases. Additionally, the breakthrough test proved that the C₃H₈/CH₄ and C₂H₆/CH₄ accompanied by C₃H₈/C₂H₆/CH₄ mixtures were fully separated at ambient temperature with superb recyclability. Accordingly, these results confirm the great potentiality of Ni(ndc)(dabco)_0.5 for natural gas purification.

从 CH4 中选择性捕获 C3H8 和 C2H6 是天然气净化的关键，但在吸收和选择性之间需要权衡。在此，我们提出了一种孔芳香化方法，以构建结构坚固的超微孔金属有机框架 Ni(ndc)(dabco)0.5，并考察了其对 C3H8/CH4 和 C2H6/CH4 混合物的分离性能。该材料的孔壁由相对平行的萘环组成，孔径为 6.0 Å，具有丰富的电负性结合位点，萘环之间的重叠区域形成了极强的势能重叠。在 298 K、0.05 和 0.1 bar 条件下，该 MOF 对实际天然气组分中 C3H8 和 C2H6 的吸收率分别达到了创纪录的 91.4 和 46.5 cm3(STP) g-1，其中 C3H8（119.0 cm3(STP) g-1）和 C2H6（116.6 cm3(STP) g-1）以及 1.0 bar 条件下的吸收率都非常好，显示出对 C3H8 和 C2H6 的强大结合能力。同时，IAST 预测的 C3H8/CH4 （1947.4）和 C2H6/CH4 （42.6）选择性也优于迄今为止的所有吸附剂，仅逊于 BSF-2，从而克服了上述权衡问题，树立了新的基准。理论研究表明，C3H8 和 C2H6 吸附性能的提高是由于芳香化超微孔被致密的低极性萘环修饰，从而对这两种气体产生了很强的亲和力。此外，突破试验证明，C3H8/CH4 和 C2H6/CH4 以及 C3H8/C2H6/CH4 混合物在常温下完全分离，具有极佳的可回收性。因此，这些结果证实了 Ni(ndc)(dabco)0.5 在天然气净化方面的巨大潜力。

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引用次数: 0

Understanding oxidation potential and degradation mechanism of acid-treated TiO2 coupled g-C3N4 S-scheme heterojunction photocatalyst for the removal of gaseous formaldehyde 了解酸处理二氧化钛耦合 g-C3N4 S 型异质结光催化剂在去除气态甲醛中的氧化潜能和降解机理

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129862

In this work, a step (S)-scheme heterojunction catalyst is synthesized by coupling acid-treated TiO₂ (ATT) with graphitic carbon nitride nanosheet (g-C₃N₄: GCN) and used for adsorption-photocatalytic removal of gaseous formaldehyde (FA: 100 - 500 ppm). The acid treatment of TiO₂ proves to be an effective approach for improving the surface porosity of ATT with more abundant active sites for efficient catalytic reactions. Similarly, the S-scheme heterojunction displays superior redox potential (i.e., availability of free e^- at conduction band of GCN (reduction potential of −0.485 eV/NHE) and free h⁺ at valance band of ATT (oxidation potential 2.79 eV/NHE)). As such, in a dynamic packed-bed flow reactor, the improved textural and optical properties of ATT-GCN (bed mass = 10 mg) offer outstanding adsorption and photocatalytic oxidation potential, effectively removing 86% of 200 ppm FA vapor at a reaction rate of 70.2 nmole mg⁻¹ min⁻¹ under slightly humidified conditions (e.g., 20% relative humidity (RH) and 21% O₂) when exposed to 32-W UV-A light source. Under these operational conditions, the ATT-GCN achieves the superior performance metrics (e.g., quantum yield of 5.1E-02 molec. photon^-1, space–time yield of 5.1E-03 molec. photon^-1 mg⁻¹, and specific clean air delivery rate of 515.4 L g^-1 h⁻¹). In-situ Kelvin probe microscope analysis of ATT-GCN postulates the formation of a strong built-in electric field to improve the separation of charge carriers. Considerations on the degradation pathway and intermediate dynamics with the aid of in-situ DRIFTS analysis suggest that the presence of water molecules (e.g., 20% RH) is beneficial for accelerating the oxidation and mineralization of FA molecules relative to a dry gas stream. The overall outcomes of this work are expected to help deliver new paths for the construction of advanced photocatalytic systems for upscaled applications toward air quality management.

本研究通过酸处理二氧化钛（ATT）与氮化石墨碳纳米片（g-C3N4: GCN）的偶联合成了一种阶跃（S）型异质结催化剂，并将其用于吸附-光催化去除气态甲醛（FA：100 - 500 ppm）。事实证明，对二氧化钛进行酸处理是提高 ATT 表面孔隙率的一种有效方法，可为高效催化反应提供更丰富的活性位点。同样，S 型异质结显示出卓越的氧化还原电位（即 GCN 传导带的自由 e-（还原电位 -0.485 eV/NHE）和 ATT 价带的自由 h+（氧化电位 2.79 eV/NHE））。因此，在动态填料床流动反应器中，ATT-GCN（床层质量 = 10 mg）的质地和光学特性得到了改善，具有出色的吸附和光催化氧化潜力，在轻微增湿条件下（如 20% 相对湿度 (RH) 和 21% 氧气），当暴露于 32-W UV-A 光源时，以 70.2 nmole mg-1 min-1 的反应速率，可有效去除 86% 的 200 ppm FA 蒸汽。在这些操作条件下，ATT-GCN 实现了卓越的性能指标（例如，量子产量为 5.1E-02 摩尔光子-1，时空产量为 5.1E-03 摩尔光子-1 毫克-1，特定洁净空气输送率为 515.4 升克-1 小时-1）。对 ATT-GCN 的原位开尔文探针显微镜分析表明，ATT-GCN 形成了一个强大的内置电场，以改善电荷载流子的分离。借助原位 DRIFTS 分析对降解途径和中间动态的考虑表明，相对于干燥气流，水分子的存在（如 20% 相对湿度）有利于加速 FA 分子的氧化和矿化。预计这项工作的总体成果将有助于为构建先进的光催化系统提供新的途径，从而扩大在空气质量管理方面的应用。

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引用次数: 0

Metal-free carbon-dots nanozyme with oxidase-like activity as photocatalysts for highly efficient detection/reduction of Cr(VI) and antibacterial application 具有类似氧化酶活性的无金属碳点纳米酶作为光催化剂用于高效检测/还原六价铬和抗菌应用

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129852

Wastewater containing Cr(VI) and bacteria indicated significant challenges and threats to public health and ecological environments. Hence, it is necessary to construct novel method for detecting and treatment such wastewater. Non-metal-doped carbon dots nanozyme (TA-CDs) were effectively synthesized by one-pot hydrothermal method utilizing tartaric acid (TA) and L-tryptophan (L-trp) as ingredients. TA-CDs revealed excellent water solubility, optical stability, and biocompatibility. Particularly noteworthy, TA-CDs (150 μg/mL) exhibited outstanding light-responsive oxidase-like activity, efficiently generating

e^{-}

,

O_{2}^{∙ -}

and

{CO}_{2}^{∙ -}

. Furthermore, TA-CDs illustrated an exceptional linear relationship with Cr(VI) in an extensive detection range and low detection limits (0.51 μM), as well as high selectivity and anti-interference properties. Simultaneously, TA-CDs also demonstrated significant photocatalytic activity, achieving approximately 70.26 % reduction in 40 mg/L Cr(VI) and realized excellent antimicrobial performance (inhibition rates of 97.18 % and 82.67 % against E. coli and S. aureus, respectively). In short, this research not only provided a multifunctional carbon-dots nanoenzyme for recognition, photoreduction of Cr(VI), and photodynamic antibacterial application, but also offered novel strategy and methodology for detection and treatment of water containing heavy metals and microorganisms.

含有六价铬和细菌的废水对公众健康和生态环境构成了重大挑战和威胁。因此，有必要构建新型方法来检测和处理此类废水。以酒石酸（TA）和 L-色氨酸（L-trp）为原料，通过一锅水热法有效合成了非金属掺杂纳米碳点（TA-CDs）。TA-CDs 具有优异的水溶性、光学稳定性和生物相容性。尤其值得注意的是，TA-CDs（150 μg/mL）具有出色的光反应氧化酶样活性，能有效生成 e-、O2∙- 和 CO2∙-。此外，TA-CDs 与 Cr(VI) 在较宽的检测范围和较低的检测限（0.51 μM）内呈优异的线性关系，并具有高选择性和抗干扰性。与此同时，TA-CDs 还表现出显著的光催化活性，可使 40 mg/L 的六（七）铬减少约 70.26%，并具有优异的抗菌性能（对大肠杆菌和金黄色葡萄球菌的抑制率分别为 97.18% 和 82.67%）。总之，这项研究不仅提供了一种多功能碳点纳米酶，可用于识别、光还原六价铬和光动力抗菌，还为检测和处理含有重金属和微生物的水提供了新的策略和方法。

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引用次数: 0

Size sieving and electrostatic exclusion synergetic strategy for high efficiency recovery of superbase-derived ionic liquids via nanofiltration from the spinning process 尺寸筛分和静电排斥协同策略，通过纳滤从纺丝过程中高效回收超碱衍生离子液体

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129851

Superbase-derived ionic liquids (SILs) as the promising green solvents for cellulose spinning process should be urgently and deeply evaluated with respect to their recyclability. Herein, size sieving and electrostatic exclusion synergetic strategy was adopted for recycling four SILs ([DBUH][CH₃CH₂OCH₂COO], [DBUH][CH₃OCH₂COO], [DBNH][CH₃CH₂OCH₂COO], and [DBNH][CH₃OCH₂COO]) from aqueous solutions by the nanofiltration membranes (NF270 and NF90) at the first time. NF270 with larger pore and more negative charge was conducive to recycle SIL on account of a higher volume flux and the remarkably high IL rejection (＞95 %) compared to NF90. Rising the pressure and temperature played the positive role in the permeate flux of the membranes, whereas the elevated SIL concentration markedly decreased the electrostatic exclusion, leading to a decline in the recovery efficiency. Benefiting from the size sieving effect, the [DBNH][CH₃OCH₂COO] with small cation and anion structure could be recovered efficiently due to the high energy gap and big IL aggregates. Conversely, the strong electrostatic attraction was appeared between [DBUH][CH₃CH₂OCH₂COO] (low energy gap and high positive charge density) and the membranes, leading to a decline in recovery efficiency. Furthermore, the combination of nanofiltration and evaporation to recover SIL from spinning wastewater effectively reduced the total recovery cost (1.51 $/Kg) in comparison with the evaporation only. Insight gained from this work suggested a high-efficiency and economical approach could be used in the recovery of SILs with small cations and anions size via large pore nanofiltration membranes during the industrialized cellulose spinning process.

超碱衍生离子液体（SILs）作为纤维素纺丝工艺中极具前景的绿色溶剂，其可回收性亟待深入评估。本文首次采用尺寸筛分和静电排斥协同策略，利用纳滤膜（NF270 和 NF90）从水溶液中回收了四种 SIL（[DBUH][CH3CH2OCH2COO]、[DBUH][CH3OCH2COO]、[DBNH][CH3CH2OCH2COO]和 [DBNH][CH3OCH2COO]）。与 NF90 相比，NF270 孔径更大，带负电荷更多，因此体积通量更大，对 IL 的截留率明显更高（＞95%），有利于回收 SIL。压力和温度的升高对膜的渗透通量起到了积极作用，而 SIL 浓度的升高则明显降低了静电排斥，导致回收效率下降。得益于尺寸筛分效应，阳离子和阴离子结构较小的[DBNH][CH3OCH2COO]由于能隙大、IL聚集体大而得到了有效回收。相反，[DBUH][CH3CH2OCH2COO]（能隙低、正电荷密度高）与膜之间出现了强烈的静电吸引，导致回收效率下降。此外，纳滤和蒸发相结合从纺丝废水中回收 SIL 与仅蒸发相比，有效降低了总回收成本（1.51 美元/Kg）。这项工作的启示是，在工业化纤维素纺丝过程中，可以采用一种高效、经济的方法，通过大孔径纳滤膜回收阳离子和阴离子尺寸较小的 SIL。

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引用次数: 0

Biphase TiO2Zn-tetracarboxy-phthalocyanine twin S-scheme heterojunction nanowires with efficient charge transfer and CO2 photocatalytic conversion 具有高效电荷转移和二氧化碳光催化转化功能的双相 TiO2（锌-四羧基酞菁）孪生 S 型异质结纳米线

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129870

Constructing heterojunction photocatalysts with proper charge transfer channels has been confirmed to be a promising strategy for CO₂ photoreduction into chemical fuels. However, promoting photoinduced charge separation in traditional heterojunction catalysts still remains a big obstacle for practical applications. In this work, the TiO₂(B)-AnataseZnTcPc twin S-scheme heterojunctions are designed and constructed by loading Zn (II) tetracarboxy phthalocyanine (ZnTcPc) on the prepared TiO₂(B)-Anatase biphase TiO₂ nanowires by self-assemble strategy. The TiO₂(B)-AnataseZnTcPc twin S-scheme heterojunctions effectively promote charge transport across the multi-heterointerfaces and enhance visible light absorption and CO₂ adsorption. Thus the optimized hybrid photocatalyst exhibits a remarkable photocatalytic CO₂ reduction performance, and the CO yield reaches 237.8μmol g⁻¹h⁻¹. The CO₂ photoreduction mechanism and charge transfer properties in the twin S-scheme heterojunction are also investigated and characterized. This research offers a viable approach to enhancing the heterojunction system for excellent photocatalytic performance.

构建具有适当电荷转移通道的异质结光催化剂已被证实是将二氧化碳光还原成化学燃料的一种前景广阔的策略。然而，在传统异质结催化剂中促进光诱导电荷分离仍然是实际应用的一大障碍。在这项工作中，通过自组装策略在制备好的TiO2(B)-Anatase双相TiO2纳米线上负载四羧基酞菁锌（Zn (II) tetracarboxy phthalocyanine，ZnTcPc），设计并构建了TiO2(B)-Anatase/ZnTcPc双S型异质结。TiO2(B)-Anatase/ZnTcPc双S型异质结有效地促进了电荷在多异质界面上的传输，增强了对可见光的吸收和对二氧化碳的吸附。因此，优化后的混合光催化剂具有显著的光催化 CO2 还原性能，CO 产率达到 237.8μmol g-1h-1。此外，还研究并表征了孪生 S 型异质结中的二氧化碳光催化机理和电荷转移特性。这项研究为提高异质结系统的光催化性能提供了一种可行的方法。

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引用次数: 0

Nanoconfinement effect on the miscible behaviors of CO2/shale oil/surfactant systems in nanopores: Implications for CO2 sequestration and enhanced oil recovery 纳米孔隙对二氧化碳/页岩油/表面活性剂系统混溶行为的纳米强化效应：对二氧化碳封存和提高石油采收率的影响

IF 8.1 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology

Pub Date : 2024-09-24 DOI: 10.1016/j.seppur.2024.129826

Currently, CO₂ flooding is the most promising carbon capture, utilization, and storage (CCUS) technology in the energy industry. Understanding the nanoconfinement effect on the CO₂-oil miscible process is crucial for accurately determining the minimum miscibility pressure (MMP) of CO₂/oil in shale reservoirs. In this study, we conducted molecular dynamics (MD) simulations to investigate the effects of pore size, surfactants, and pore type on the MMP of nanoconfined CO₂/shale oil/surfactant systems. Validations against experimental data show a deviation of 2.98 % in the CO₂ MMP. The MMPs under nanoconfinement are found to be significantly lower than those in bulk phase conditions (up to 22.94 %). The simulation results reveal that decreasing pore size can enhance the miscibility of CO₂ and oil by increasing the CO₂ adsorption ratio, improving CO₂-surfactant interactions, and inhibiting the tendency of CO₂ molecules to self-aggregate. The enhancement of CO₂-oil miscibility caused by surfactants is ranked by CFP > SF > SDS according to the mixing degrees (D_mix) and the spatial distribution of CO₂ around surfactant molecules. In addition, pore type exhibits various abilities in influencing the MMP, owing to their different mineral surface properties and ability to influence CO₂-surfactant interactions. Nanopores with stronger hydrophobicity and a denser CO₂ distribution around surfactant molecules have lower MMPs. The results show that the order of MMP in terms of pore types is Quartz < Kaolinite < I/M clay. This study elaborates the micro-mechanisms of surfactant-assisted CO₂-oil miscibility under nanoconfinement, offering valuable insights for effectively designing CO₂ miscible flooding in shale oil reservoir development.

目前，二氧化碳淹没是能源行业最有前途的碳捕集、利用和封存（CCUS）技术。要准确确定页岩储层中二氧化碳/石油的最小混溶压力（MMP），了解纳米掺混对二氧化碳/石油混溶过程的影响至关重要。在这项研究中，我们进行了分子动力学（MD）模拟，以研究孔径、表面活性剂和孔隙类型对纳米致密二氧化碳/页岩油/表面活性剂体系的最小混溶压力的影响。根据实验数据进行的验证表明，二氧化碳 MMP 偏差为 2.98%。纳米强化条件下的 MMP 明显低于体相条件下的 MMP（最高达 22.94%）。模拟结果表明，减小孔径可以通过提高二氧化碳吸附率、改善二氧化碳与表面活性剂的相互作用以及抑制二氧化碳分子的自聚集趋势来提高二氧化碳与油的混溶性。根据混合度（Dmix）和表面活性剂分子周围 CO2 的空间分布，表面活性剂对 CO2 与油的混溶性的增强作用按 CFP > SF > SDS 排序。此外，由于矿物表面性质和影响二氧化碳-表面活性剂相互作用的能力不同，孔隙类型对 MMP 的影响也各不相同。疏水性更强、表面活性剂分子周围二氧化碳分布更密集的纳米孔隙，其 MMP 值更低。结果表明，按孔隙类型划分，MMP 的顺序为石英、高岭石、I/M 粘土。本研究详细阐述了纳米融合条件下表面活性剂辅助二氧化碳与油混溶的微观机制，为页岩油藏开发中有效设计二氧化碳混溶淹没提供了宝贵的见解。

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引用次数: 0