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Rapid, selectivity, and reversibility absorption of SO2 via purine-based deep eutectic solvents and thermodynamic analysis 通过嘌呤基深共晶溶剂和热力学分析快速，选择性和可逆性吸收SO2

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2024-10-24 DOI: 10.1016/j.gce.2024.10.005

Yiru Zou , Chao Wang , Haiyan Ji , Peiwen Wu , Yanhong Chao , Xiaoxiao Yu , Zhendong Yu , Haiyan Liu , Zhichang Liu , Wenshuai Zhu

Since the advantages of simple preparation, low-priced, environmental friendliness, and high absorption capacity, deep eutectic solvents (DESs) are considered to have eminent application potential in terms of SO₂ absorption. However, the absorption rate, selectivity, and reversibility of DESs urgently need to be further improved to meet the requirements of industrialization. In this work, five purine-based DESs were designed and synthesized through the use of 1-ethyl-3-methylimidazolium chloride (EmimCl) as hydrogen bond acceptors (HBAs) plus 6-aminopurine (6-AmP), 6-hydroxypurine (6-HoP), and 6-chloropurine (6-ChP) as hydrogen bond donors (HBDs), respectively. The results indicated that the optimal molar ratio of HBAs to HBDs is 7:1, and the absorption capacity of EmimCl + 6-AmP-7 can reach up to 18.118 mol/kg, at 298.15 K and 1.0 bar. Notably, the present purine-based DESs not only achieve gas-liquid equilibrium within 40 s, but also exhibit outstanding reversibility (absorb-desorb more than 30 times) and remarkable selectivity of SO₂/CO₂. Furthermore, a reaction equilibrium thermodynamic model (RETM) equation was employed to investigate the absorption behavior by combining the absorption data under different SO₂ partial pressures and temperatures. Finally, Fourier-transform infrared (FT-IR) spectroscopy and ¹H nuclear magnetic resonance (NMR) were conducted to explore further the formation and SO₂ absorption mechanism of purine-based DESs. It is revealed that the former is mainly hydrogen bonding interaction among HBAs and HBDs, and the latter is mainly Lewis acid-base interaction plus strong charge-transfer interaction among DESs and SO₂. Based on the obtained data, it could be confirmed that the SO₂ absorption includes both physical and chemical absorption.

由于制备简单、价格低廉、对环境友好、吸附能力强等优点，深共晶溶剂（DESs）在吸收SO2方面具有突出的应用潜力。但是，DESs的吸收率、选择性和可逆性等方面还有待进一步提高，以满足工业化的要求。本文以1-乙基-3-甲基咪唑氯（EmimCl）为氢键受体（HBAs）， 6-氨基嘌呤（6-AmP）、6-羟基嘌呤（6-HoP）和6-氯嘌呤（6-ChP）为氢键给体（HBDs），设计并合成了5种嘌呤基DESs。结果表明，HBAs与HBDs的最佳摩尔比为7:1，在298.15 K和1.0 bar条件下，EmimCl + 6-AmP-7的吸收容量可达18.118 mol/kg。值得注意的是，基于嘌呤的DESs不仅在40 s内达到气液平衡，而且具有良好的可逆性（吸收-解吸30次以上）和SO2/CO2的选择性。此外，结合不同SO2分压和温度下的吸附数据，采用反应平衡热力学模型（RETM）方程对其吸附行为进行了研究。最后，利用傅里叶变换红外光谱（FT-IR）和1H核磁共振（NMR）进一步探讨嘌呤基DESs的形成和SO2吸收机理。结果表明，前者主要是HBAs与HBDs之间的氢键相互作用，后者主要是DESs与SO2之间的Lewis酸碱相互作用加强电荷转移相互作用。根据获得的数据，可以确定SO2的吸收包括物理吸收和化学吸收。

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引用次数: 0

Visible light-driven selective oxidative transformation of vicinal diols using ZnS-based photocatalyst in the presence of molecular oxygen 在分子氧存在下，利用zns基光催化剂进行邻二醇的可见光驱动选择性氧化转化

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2024-11-06 DOI: 10.1016/j.gce.2024.11.002

Ruichen Liu, Miao Wang, Jiaxin Zheng, Xinli Tong

The heterogeneous photocatalysis for the oxidative cleavage of C–C bond is significant to the transformation of biomass feedstock. In this work, a heterojunction photocatalyst based on the conductor ZnS and C₃N₄ (CN) material is prepared and employed in the aerobic oxidative cleavage reaction of vicinal diol under visible light irradiation. As a result, it is found that 3ZnS/CN catalyst obtained by a mechanical grinding method shows a high photocatalytic activity. In the photocatalytic oxidative cleavage process of 1-phenyl-1,2-glycol, more than 98.7% conversion of substrate with a 96.2% selectivity of benzaldehyde was attained using O₂ as oxidant. In addition, the photocatalyst recycling experiments exhibited that the 3ZnS/CN catalyst still kept a good activity and stability even after being recycled for 5 times. Finally, the active reaction intermediates were investigated by the control experiments and the relative electron paramagnetic resonance (EPR) detection. According to the obtained results and photocatalytic principle, the mechanism for the selective oxidative transformatioin of 1-phenyl-1,2-glycol has been proposed. It gives a promising approach for the catalytic utilization of biomass-based lignin and cellulose.

C-C键氧化裂解的非均相光催化作用对生物质原料的转化具有重要意义。本文制备了一种以ZnS和C3N4 （CN）材料为导体的异质结光催化剂，并将其用于邻二醇在可见光下的有氧氧化裂解反应。结果表明，机械研磨法制备的3ZnS/CN催化剂具有较高的光催化活性。在1-苯基-1,2-乙二醇光催化氧化裂解过程中，以O2为氧化剂，底物转化率达98.7%以上，苯甲醛选择性达96.2%。此外，光催化剂回收实验表明，3ZnS/CN催化剂在回收5次后仍保持良好的活性和稳定性。最后，通过对照实验和相对电子顺磁共振（EPR）检测对活性中间体进行了研究。根据所得结果和光催化原理，提出了1-苯基-1,2-乙二醇选择性氧化转化的机理。为生物质木质素和纤维素的催化利用提供了一条很有前途的途径。

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引用次数: 0

OFC: Outside Front Cover OFC：外封面

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2025-12-24 DOI: 10.1016/S2666-9528(25)00099-8

引用次数: 0

Advances and challenges in N2O valorization for alkane oxidative dehydrogenation to olefins 烷烃氧化脱氢制烯烃N2O气化研究进展与挑战

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2024-11-28 DOI: 10.1016/j.gce.2024.11.005

Yunshuo Wu , Xuanhao Wu , Haiqiang Wang , Zhongbiao Wu

Valorization of nitrous oxide (N₂O), a potent greenhouse gas, through the oxidative dehydrogenation of light alkanes such as methane and propane to produce light olefins (ethylene and propylene), presents a promising technique for both environmental mitigation and valuable chemical production. This review provides a systematic analysis of the differences between N₂O and O₂ as oxidants, emphasizing the distinctive advantages of N₂O as a mild oxidant for olefin production. It delves into key technologies, such as oxidative dehydrogenation of propane (ODHP) to propylene and oxidative coupling of methane (OCM) to ethylene, focusing on the underlying reaction mechanisms and recent advancements in catalyst development. A major challenge in these reactions is the trade-off between activity and selectivity. To address this, we propose an innovative strategy–redox center separation–to enhance catalytic performance. This comprehensive review offers valuable insights for the rational design of catalysts, advancing sustainable chemical engineering processes that utilize N₂O, while addressing critical environmental and industrial challenges.

氧化亚氮（N2O）是一种强效温室气体，通过甲烷和丙烷等轻烷烃的氧化脱氢生产轻烯烃（乙烯和丙烯），是一种很有前途的技术，既可以缓解环境，又可以生产有价值的化学品。本文系统分析了氧化亚氮和氧化亚氮作为氧化剂的区别，强调了氧化亚氮作为一种温和氧化剂在烯烃生产中的独特优势。重点介绍了丙烷氧化脱氢制丙烯和甲烷氧化偶联制乙烯等关键技术，重点介绍了反应机理和催化剂的最新进展。这些反应的一个主要挑战是在活性和选择性之间进行权衡。为了解决这个问题，我们提出了一种创新的策略-氧化还原中心分离-以提高催化性能。这一综合综述为合理设计催化剂、推进利用N2O的可持续化学工程过程，同时解决关键的环境和工业挑战提供了有价值的见解。

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引用次数: 0

Single solvent synthesis of lithium-selective hydrogen manganese oxide (HMO)-based mixed matrix membranes 单溶剂合成锂选择性氢锰氧化物（HMO）基混合基质膜

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2025-03-29 DOI: 10.1016/j.gce.2025.03.005

Hafiz M. Saif , Amanuel G. Gebretatios , Rosa M. Huertas , Joao G. Crespo , Sylwin Pawlowski

The rising lithium-ion battery market drives lithium demand and requires efficient and selective lithium recovery methods from aqueous sources. Membrane technologies can address environmental and inherent efficiency issues in conventional lithium extraction methods. This study presents the synthesis of novel lithium-selective mixed matrix membranes (MMMs) by integrating 0–30 wt% of a lithium selective filler named hydrogen manganese oxide (HMO) into a sulfonated polyethersulfone (SPES)-Nafion polymer matrix. The membranes were produced by casting and thoroughly examined to assess their chemical, physical, morphological, thermal, and mechanical characteristics. The transport of lithium across membranes was evaluated in diffusion and electro-diffusion studies. The membrane containing 20 wt% of HMO exhibited the highest ideal selectivity values, which were 1.05 for Li⁺/K⁺, 1.20 for Li⁺/Na⁺, and 13.36 for Li⁺/Mg²⁺; and more than 97% increase in lithium-ion conductivity when compared with the control membrane without HMO. In diffusion experiments, the binary separation factors for Li⁺/K⁺, Li⁺/Na⁺, and Li⁺/Mg²⁺ were 0.71, 1.52, and 11.83, respectively, while under electro-diffusion conditions, the corresponding values were 0.82, 1.55, and 9.88. Above 20 wt% of HMO, membranes lose their separation capacity as HMO aggregates inside the membrane structure. The higher selectivity of membranes towards Li⁺ in the presence of Mg²⁺ is due to magnesium's larger hydrated radius and higher hydration energy compared to lithium. Overall, the prepared membranes demonstrated a promising potential for green lithium recovery. This study facilitates the advancement of sustainable lithium-selective MMM synthesis.

不断增长的锂离子电池市场推动了锂的需求，并要求从水源中高效、选择性地回收锂。膜技术可以解决传统锂提取方法的环境和固有效率问题。本研究提出了一种新型锂选择性混合基质膜（MMMs）的合成方法，将0-30 wt%的锂选择性填料称为氢锰氧化物（HMO）整合到磺化聚醚砜(spe)-Nafion聚合物基体中。这些膜是通过铸造生产的，并进行了彻底的检查，以评估它们的化学、物理、形态、热和机械特性。锂的跨膜运输在扩散和电扩散研究中进行了评估。含20 wt% HMO的膜对Li+/K+、Li+/Na+和Li+/Mg2+的理想选择性值分别为1.05、1.20和13.36；与未添加HMO的对照膜相比，锂离子电导率提高了97%以上。扩散条件下，Li+/K+、Li+/Na+和Li+/Mg2+的二元分离系数分别为0.71、1.52和11.83，电扩散条件下分别为0.82、1.55和9.88。超过20%的HMO，由于HMO聚集在膜结构内，膜失去了分离能力。在Mg2+存在的情况下，膜对Li+有更高的选择性是由于镁的水合半径比锂大，水合能也比锂高。总的来说，所制备的膜显示出绿色锂回收的良好潜力。该研究促进了可持续锂选择性MMM合成的发展。

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引用次数: 0

Sublimation crystallization: from mechanism to applications 升华结晶：从机理到应用

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2025-02-21 DOI: 10.1016/j.gce.2025.02.001

Sai Wang , Yuntian Xiao , Yitian Su , Yongkang Liu , Shanshan Feng , Hongchen Cao , Ling Zhou , Qiuxiang Yin

Sublimation crystallization, a solvent-free purification technique, has emerged as a sustainable strategy in materials science for producing high-purity substances and advanced functional materials. This review delves into the thermodynamic and kinetic principles governing sublimation crystallization, such as vapor pressure, temperature, and molecular interactions, which play crucial roles in phase transitions and crystal growth. We then explore its practical applications in the separation and purification of materials, the preparation of high-quality single crystals, polymorph and cocrystal screening, and the fabrication of thin films and semiconductor devices. By clarifying the processes and mechanisms involved, this review aims to provide insights into how sublimation crystallization optimizes separation and purification techniques while enhancing material properties as a secondary benefit. This work also outlines future directions and challenges for refining high-efficiency purification methods and advancing sustainable chemical engineering technologies.

升华结晶是一种无溶剂的纯化技术，已成为材料科学领域生产高纯度物质和先进功能材料的可持续发展战略。本文综述了控制升华结晶的热力学和动力学原理，如蒸汽压、温度和分子相互作用，它们在相变和晶体生长中起着至关重要的作用。然后探讨其在材料的分离和纯化、高质量单晶的制备、多晶和共晶筛选、薄膜和半导体器件的制造等方面的实际应用。通过阐明所涉及的过程和机制，本文旨在深入了解升华结晶如何优化分离和纯化技术，同时提高材料性能作为次要优势。本工作还概述了提炼高效净化方法和推进可持续化学工程技术的未来方向和挑战。

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引用次数: 0

Engineering nano-trap distribution in metal-organic frameworks enables boost of SF6/N2 separation 工程纳米陷阱分布在金属有机框架可以促进SF6/N2分离

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2025-01-10 DOI: 10.1016/j.gce.2025.01.004

Yan-Long Zhao, Yabo Xie, Xin Zhang, Xiang-Yu Li, Xuefeng Bai, Jian-Rong Li

Separating/capturing SF₆, having the strongest global warming potential, from exhaust gas with low concentration (1%–10%) in the power industry is significant for both greenhouse gas emission control and SF₆ recycling and reutilization. In this study, we achieved highly efficient SF₆/N₂ separation under different SF₆ concentrations (1% and 10%) using two homologous metal-organic frameworks, Ni-bpz and Zn-bpz. This outcome underscores the effectiveness of rational nano-traps distribution engineering for targeted separation applications. The molecular simulation suggests that an SF₆ molecule interacts with a single nano-trap in Zn-bpz. At the same time, it is efficiently confined by two adjacent nano-traps in the parallel distribution of Ni-bpz. Consequently, exceptional SF₆/N₂ selectivity for 1/99 and 10/90 mixtures have been respectively achieved in Ni-bpz (516, SF₆/N₂ = 1/99) and Zn-bpz (608, SF₆/N₂ = 10/90) at 298 K and 1 bar. In dynamic breakthrough experiments, Ni-bpz exhibits a record pure N₂ (≥ 99.99%) productivity (1496 mL/g) for an SF₆/N₂ (1/99) gas mixture. Moreover, both MOFs demonstrate excellent water resistance across multiple cycles, suggesting their high promise for practical application.

从电力行业低浓度（1%-10%）废气中分离/捕集全球变暖潜势最强的SF6，对于控制温室气体排放和SF6回收再利用都具有重要意义。在本研究中，我们利用Ni-bpz和Zn-bpz两种同源金属有机骨架，在不同SF6浓度（1%和10%）下实现了SF6/N2的高效分离。这一结果强调了合理的纳米捕集器分布工程在定向分离应用中的有效性。分子模拟表明，SF6分子与Zn-bpz中的单个纳米陷阱相互作用。同时，在Ni-bpz的平行分布中，它被两个相邻的纳米陷阱有效地限制。因此，在298 K和1 bar条件下，Ni-bpz （516, SF6/N2 = 1/99）和Zn-bpz （608, SF6/N2 = 10/90）对SF6/N2的选择性分别为1/99和10/90。在动态突破实验中，Ni-bpz在SF6/N2（1/99）气体混合物中表现出创纪录的纯N2（≥99.99%）产率（1496 mL/g）。此外，这两种mof在多次循环中都表现出优异的耐水性，这表明它们具有很高的实际应用前景。

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引用次数: 0

Efficient capture of thorium ions by the hydroxyl-functionalized sp2c-COF through nitrogen-oxygen cooperative mechanism 羟基功能化的sp2c-COF通过氮氧协同机制高效捕获钍离子

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2024-11-01 DOI: 10.1016/j.gce.2024.10.008

Long Chen , Zhanjun Zhang , Songtao Xiao , Xinyan Li , Shangjie Zhao , Yaolin Zhao , Chenxi Yu , Zhaoning Feng , Ke Ma , Xiaojuan Liu , Xiaofan Ding , Jing Zhao , Jinping Liu

Since the continuous development of nuclear energy, substantial amounts of radioactive thorium wastewater are inevitably produced. The discharge of radioactive thorium wastewater not only pollutes the natural environment but also endangers human health. Due to its affordability, simplicity, and high effectiveness, the adsorption method has emerged as the most often used method for treatment. Covalent organic framework (COF) materials are excellent adsorbents with various characteristics, including superior chemical stability, design flexibility, and various architectures, and thus are widely used in separating radioactive nuclides. Herein, we synthesized two structurally similar COFs that vary in their pore dimensions and the connectivity of their modules. After incorporating hydroxyl groups into the structure of Tb-TMT formed by benzene-1,3,5-tricarbaldehyde (Tb) and 2,4,6-trimethyl-1,3,5-triazine (TMT), the uptake capacity of thorium ions is significantly enhanced. The differences in solution pH, contact time, initial concentration, and competitive ion experiments between the materials before and after hydroxyl functionalization were studied. Additionally, the research assessed their reuse capabilities. In this research, the Hb-TMT exhibits an outstanding adsorption capacity for Th(IV) ions, with a remarkable adsorptive capacity reaching 543.5 mg g⁻¹, and it showes good uptake efficiency within 5 min with excellent selectivity (K_d = 1.2 × 10⁴). After three cycles of regeneration, Hb-TMT still maintains a high level of adsorption capacity for Th(IV) (> 80%) and has good reusability. Furthermore, the role of nitrogen-oxygen synergistic effect on hydroxyl-functionalized COF is highlighted by density functional theory (DFT) calculations. This study provides fresh insights for choosing functional groups in functionalized COFs, specifically for radionuclide adsorption.

随着核能的不断发展，不可避免地产生了大量的放射性钍废水。放射性钍废水的排放不仅污染自然环境，而且危害人体健康。由于其经济、简单、高效，吸附法已成为最常用的处理方法。共价有机骨架（COF）材料是一种优异的吸附剂，具有优异的化学稳定性、设计灵活性和多种结构，广泛应用于放射性核素的分离。在此，我们合成了两种结构相似的COFs，它们的孔隙尺寸和模块的连通性不同。在由苯-1,3,5-三乙醛（Tb）和2,4,6-三甲基-1,3,5-三嗪（TMT）组成的Tb-TMT结构中加入羟基后，钍离子的吸收能力显著增强。研究了羟基功能化前后材料在溶液pH、接触时间、初始浓度和竞争离子实验等方面的差异。此外，该研究还评估了它们的重用能力。在本研究中，Hb-TMT对Th（IV）离子表现出了出色的吸附能力，吸附量达到543.5 mg g - 1，在5 min内表现出良好的吸附效率，具有良好的选择性（Kd = 1.2 × 104）。经过三次循环再生后，Hb-TMT对Th（IV）仍保持较高的吸附量（> 80%），且具有良好的可重复使用性。此外，通过密度泛函理论（DFT）计算强调了氮氧协同效应在羟基功能化COF中的作用。该研究为功能化COFs中官能团的选择，特别是放射性核素吸附提供了新的见解。

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引用次数: 0

Two-step preparation of asphalt-based porous carbon adsorbent with superior C2H6/CH4 selectivity for ethane recovery from natural gas 两步法制备具有优异C2H6/CH4选择性的沥青基多孔碳吸附剂用于天然气乙烷回收

IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2024-11-01 DOI: 10.1016/j.gce.2024.10.007

Jinhui Liu , Xiaolong Sun , Fei Teng , Qibin Xia , Zhong Li , Ying Wu , Xin Zhou

Efficient recovery of ethane (C₂H₆) from natural gas is of industrial importance, yet it poses considerable challenges. Herein, we report the two-step green preparation of asphalt-based carbon adsorbent Asphalt-based Carbon adsorbents (AsCs) with exceptional C₂H₆/CH₄ selectivity and high capacity, where the KOH usage can be significantly reduced by 75% than conventional chemical activation processes. More importantly, the resulting AsC-0.75-900 exhibits exceptional C₂H₆/CH₄ separation performance with the ideal adsorbed solution theory (IAST) selectivity of 30.74 and C₂H₆ capacity of 4.53 mmol/g at 298 K and 100 kPa. Notably, even at the low pressure of 10 kPa, its C₂H₆ uptake remains high at 2.25 mmol/g, comparable to many advanced metal-organic frameworks (MOFs). Molecular simulation was used to elucidate the adsorption mechanism. Fixed-bed experiments further demonstrate dynamic separation performance, achieving complete separation of a C₂H₆/CH₄ binary mixture (10:90, v/v) at ambient condition. In addition to superior separation performance, AsC-0.75-900 offers inherent structural stability and cost-effectiveness, positioning it a highly promising candidate for C₂H₆ recovery from natural gas.

从天然气中高效回收乙烷（C2H6）具有重要的工业意义，但也面临着相当大的挑战。在此，我们报告了两步绿色制备沥青基碳吸附剂的沥青基碳吸附剂（AsCs）具有优异的C2H6/CH4选择性和高容量，其中KOH的使用可以比传统的化学活化工艺显著减少75%。更重要的是，所得AsC-0.75-900在298 K和100 kPa条件下的理想吸附溶液理论（IAST）选择性为30.74，C2H6容量为4.53 mmol/g，具有优异的C2H6/CH4分离性能。值得注意的是，即使在10 kPa的低压下，其C2H6吸收量仍高达2.25 mmol/g，与许多先进的金属有机框架（mof）相当。采用分子模拟方法对吸附机理进行了研究。固定床实验进一步验证了动态分离性能，在常温条件下实现了C2H6/CH4二元混合物（10:90,v/v）的完全分离。除了卓越的分离性能外，AsC-0.75-900还具有固有的结构稳定性和成本效益，使其成为从天然气中回收C2H6的极具前景的候选材料。

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引用次数: 0

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IF 7.6 Q1 ENGINEERING, CHEMICAL

Green Chemical Engineering

Pub Date : 2026-06-01 Epub Date: 2025-12-24 DOI: 10.1016/S2666-9528(25)00107-4

引用次数: 0

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